Metallography and Microstructure in Ancient and Historic Metals

MEALLOGAHY AND AN D MCRORUCURE OF NCEN AND AN D ORC MEAL

MEALLOGHY AND AN D MCRORUCURE OF NCEN AND AN D ORC MEAL

DAV  SCOTT SCO TT

H GET CONSERVATON NSTUE HE J PAU GETT MUSEU IN SSOTO T TP OOS

Ft a bak : Phtmgaph f a Wtz stl pll fm th Da g fIa Th stl s hyput a as, a was ma  a ubl pss Vs appa ak Th palt appas  a  ay f ls u t ffs  spag Th  wht ls a mtt; th asal lght paths a h  phsphus Ths ubl stl s a hgh-qualy put f at hst sga Cl tf tt th  sl a x420

Cts: Fgus 73-74 Cutsy f h Ama Sy f Tstg a Matals; Fgus 106, 45 148, 62 t Dll htgaphy Dpatmt, 1-812-20 Isttut f Ahagy, Ahagy, L L  Fgus 1-812-20 264055198-212 264055198-212 aw by Jat Spha quz; Fgus 198-212 Cutsy f th ta tal Cpp Rsah a Dlpmt Assat; Fgus 75-80 Ds Kly; C, Plats 1-20 Fgus 9-11 21-25, 4154: Da A Stt

ublats Cat Ia Akff GC Et Ia Ak Thal Dawg: Jat Spha Equz Dsg: Maquta Stal Dsg, Ls Agls, Calfa Typgaphy FamMak / Ab Gaam a Gll Sas tg T Wah ss, Lt

©

1991 h J aul Gtty ust

All ghts s Publsh  assat wth Ahtyp Bks whh akwg a gat fm th Cmmss f Eupa Cmmuts Pt  Sgap Lbay f Cgss CatalgugPublat Data Stt, Da A Mtallgaphy a mstutu f at a hst mtals/ Da A Stt p m Ilus bbgaphal fs a x ISBN 0892361956 (pbk) 1. Mtallgaphy 2 AllysMtalgaphy 3 Mtallgaph spms 4 At bjtsCsat a stat I T TN690S34 1991 669'95dc20

9119484

CP

H G CONSRVAO N e Gey Cseva Isue a eag ga f e e . Paul Gey us was ceaed  1 8  addess e cseva cseva  eeds eeds f u culual eage e Isue cducs wld wde edsclay  edsclay fessa fessa gas  scec eseac ag, ad dcuea. dcuea . s s acclsd ug a cba f use jecs ad cllabave veues w e gaas  e ad abad. Secal acves suc as ed jecs ea ea al cfeeces, ad ublcas sege e le f e Isue

USA

ALE OF ONTENT

ewd Pefae Lst  f Cl Plates and gues Cl Plates

IX XI Xlli 

e Natue  f Metals Metals 5



e Mstutue f Anent Metas

3

wased Mateas

11

4

e Mstutue f n Bnes

5

5

Ntes n te Stutue f Cabn Steels

3

6

Matenste n wabn wabn Steels

33

7

e eeng f Matenste

35

8

Stutue and Petes f Cast In

37



Cded Mstutues

43

10

Reeted Plaed Lgt Msy

4

11

Gan Ses f Anent Anent Metas

51

1

Metalgay and Anent Metals

57

13

Metallga Salng f Metals

61

14

Muntng and Peang Seens

63

15

Redng Results

6

16

Etng Etng and Etng Slutns

6

17

Muntng Resns

75

8

Madness estng

77

A

Aendx: Cn Mstutual Saes

7

B

Aendx: Mstutue Mstutue f Cded Cded Metals

81

C

Aendx: Madness Values f D ffeent Allys and Metals

8

D

Aendx: Allys Used n Antquty

84

E

Aendx: es and enques n Anent Metalwkng

85



Aendx: Metallga Studes

86

G

Aendx: Pase Dagas

11

Glssay

1 3

Bblgay

1 47

ndex

151

OWORD

Ifat Ifat abut te stuctue f ateals ateals ad teclgy f aufactue aufactue f acet ad s tc bject s ad atfacts atfacts ca pvde sgt t te date place f g ad pbable use vestgats f stuctue ay as be vey ptat f dcuetat pesevat stat egy  csevat teatet   ay decades bjects f a vaety  f ateals ad datg f pesty p esty t te peset ave bee s cetf cetf cally cally studed stud ed ay f te by etallgapc tecques Mst f te esults ae scatteed tugut te teatal lteatue ae se tes accessble ad fte t publsed at al equetly te eed as bee expessed  atal ad teatal eetgs t cllect fati fati  ceta types f bects  classes f ateals  e pace ad t ake t av aable as a database  publcat s vlue s a attept t pvde a easued aut f f f at egadg te tecques f etallga py as tey appy t acet ad stc etals It s llustated llus tated wt ay exaples f dff dffeet types f cstuctue daw daw f f avd Sctts ay yeas yeas f  f expeece  ts  eld f study e pe tat te peset vlue develped wt te gudace f  ak eusse Ass c ate ect gas GC wl be a usefu bk f studets csevats csevat sc etsts ad wkes  te aea f etalgapy etalgapy especally tse seekg t udestad te atue f cstuctue as t apples t acet ate als e bk s  s te st  a sees f efeece efeece wks tat te Getty Csevat sttute s publsg pub lsg  ateas used  csevat ad teclgy teclgy e Getty Csevat sttu te ad te te ] aul Getty Museu ave bee vlved vlved cllabatvely cll abatvely wt ts wk ad peset ts vlue as cpublses

Miguel Angel Corzo Director  The Get Conservation Institute Marina del Rey Calia

PREFACE

Ts bk beg a as a seres f labrary labrary es ad e aur pes a  e prcess f  f rewr g ad egrag e rgal ex as bee redered re accessble. Tere are ay sudes f ace ad src ealwrk publsed  e leraure bu  s re dcul  d a geeral accu f eallgrapc ecques ad a erprea erprea  f crsrucure wre prarly fr e csera sce s ad cserar. Ts bk aeps  ll s gap by pvdg a gude  e srucure f eas r e ae ras scece perspecve   s als useful useful  explre e ways  wc ays ave bee used  ace ealwrk. Tere are ay reass fr fr s udyg e srucure  f eals. eals. Te prper csera csera f bjecs requres r sees eables e cser var  b serve serve crsrucure. Ivesgave Ivesgave sudes ay be ecessary  rder  assess e degree f crrs r  r ebrle e f a bjec A ew cserva cserva reae ay ave ave pca pc a s fr fr e presea pr esea f eallgrapc s ruc ure Cyr Cy r Saley S saes a e erarcy f srucure ca be exaed a ay dff dffere levels faggrega faggrega ad a e crpra f eprcal experece f aerals  a ere ca fraewrk fraewrk as eabed aerals scece  apprecae e effecs effecs  f srucu sr ucure re  prperes prp eres ad eve eve e arsc quales  f aerals I s ceraly ceraly rue a ealgrapc srucures eselves are fe fe vsually cpellg b   a scec ad ad a arsc sese Meals are eresg aerals sce er prperes ca be ap ulaed  ay ways. By cbg eals, by eag ad quecg by akg e lqud ad casg e r by wrkg wrkg e  sape w a aer r a lae, ey allw a plascy f vee wle beg saped sap ed ad a aly f fr we a prcess s cpleed Te srucure f e b k suld ave ave a wrd f explaa explaa ere. Te apprac a as bee ake s  descrb e bre br ey wa eals are ad  dscuss pase dagras ad e kds f srucures  be fud  dff d ffere ere ad releva relev a allys befre prceedg  deal w e praccal applca f s kwledge: e saplg ad prepara

f saples fr eallgrapc sudy. Te quaave erprea f aly pase dagras as  bee cluded ere ad  geeral ae aca ce as bee kep  a u. Te praccal fra fra   e ex als cludes deals  ecg slus ad sr accus f crardess crardess ad e gra se f eals. Tere s a legy appedx )  wc wc exaples f dff dffere ypes  f allys ad  crsrucur crs rucures es are gve draw fr sudes carred u by e aur Ts appedx s  cpreesve, bu  s  ped a e reader wll d  eresg eresg ad frave. Te aalycal daa a ave bee preseed  e bk are qued wu a dscuss f w e resuls ave bee baed Tere are ay accus f aalycal aalycal eds ad ec ques suc as elecr crprbe aalyss, ac absrp specrpey, specrpey, duc duc vely cuped plasa ass specrery ad ray urescece aalyss, aalyss, ad e  r re f ese ecques are e prcpal eds by wc e resuls qued  e ex ave bee baed I was  e a f e prese ex  eer  dea l ccerg e cecal aalyss aalyss f eals. Slarly alug crrs ad cr rs prducs are fe esseal cpes cpes  f ace ace eals, ere ere s  dealed dscuss f e aure f crrs prducs gve sce   d s w uld add subs aaly  e leg f e e bk Te sel g casg ad wrkg f e als s as  cvered  deal by e ex alug e glssary des pr vde se fra fra  ad c ers used  descrbg eals ad ealwrkg prcesses

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Acknowledgments Te aur au r s  s very graeful graeful  e saff f e Gey Cseva Isue Publcas Depare fr seeg e auscrp rug fr edg  prg  parcular  Ira Averkeff fr er ugul ad dedcaed ed ral wrk. Jae Erque was respsble fr redrawg redrawg e rgal gures Des Keeley Keeley k k e pgraps pgraps  Caper Caper 1  , ad Mar qua Saeld dreced e verall desg desg Na

ly, F ak esse, Asscate ect   gas, ad a  a Aeke Aeke, lcats lcat s Cdat, st e  e taked   te ets as ad st e at s als gate gate t Se S e Scls Sc ls ess   assstace asss tace wt te cat   te st es  te text text Seeal  te te tcgas t cgas take y te at wd t ae ae ee ssle ssl e wtt te e ad assstace ded y t se w ae geesy deted deted sales  te t te case  atcla I wd lke t tak  Nge See ey, e ead   te eatet  Csea Csea t ad Mateals Scece, Isttte Ist tte  Acae gy, d, cety S ey ey  Csea Csea t, Natal st, d aes Back, Iteata Iteatall Acadec ects, d;  Rdey Cg, ely Reseac Asscate, eatet  Cseat Cseat ad Mateals Sc ece, d, ad e e stdet s  te eatet, eatet, Nl Se, eate Bs, B  ae,  aagkaa Ratak, Nayl Gad,  Adlasl Vatadst agg, ad ae te I wld lke t ge taks t te lwg lwg ees  te sta sta at te sttte Acaegy  Acaegy  awck Bay, Reade  St Aeca esty ete  e, ead  ead    te tgay eatet; ad Stat adlaw, Se tgac ecca At te Gety Cseat sttte I wd lke t tak,  addt, y secetay secetay Rt Feda, w as caed  t ay etyg etyg ad eatt eattg g s  cect  wt te eaa t   te asct; asc t;  Nee Agew, Agew, ect  Seca Seca ects ad Mcael Scl g, Asscate Asscate Scetst F te  a Getty Mse  a st gate t ey day, ead  te eatet eatet   Attes Attes Cse Cse at at ad da Sta ss, Asscate Cseat, eatet  ecate Ats ad Scl te Cseat

D. DavdA. So  Hea Mueum Seve The Ge Conevaon Inue

OLOR PE AND GURE

Plae I. Secio fom a Lisa  dagge hadle. Plae 2. agme of cooso cs  fom a Chese cas o lio. Plae 3. Seco fom a odoo  boe scle Pae 4. agme of a bass  medalio fom he La Peose  shweck off he coas of Asaia. Pae 5. Roma mio fom  Caeby. Pae . Cooded seco of a  Roma icese be. Plae . Cas io fagme fom  9hcey scaes. Plae 8. Seco fom a highi  boe vesse fom hailad. Plae 9. Secio fom a Geek Hem  of abo 120 Plae 0. aa o Age dagge  hi. Plae I Seco of a slamic  kwe. Plae 2. Seco of a cooded cas  o caoba fom he owe of  Lodo. Plae 3. Seco of a cas o  caobal om Sada Case. Plae 4 Secio of a hghi boe  boe  mio fom Java Plae 15. Seco fom a sma dia  Woo igo. Plae . Seco fom a Jaaese  swod blade. Pae . Lae Boe Age swod  fom Paesie. Pae 8. Poished ad eched seco  of a lae medieva dia ic coi. Pae 19 Secio of a sma Lisa  ceemoia axe fom a. Pae 20 Secio fom iside he  base of a Geek Hem. ig. !. Coseacked hexagoal i  cel sce. ig. 2. aceceeed cbc i ce. ig. 3. Bodyceeed cbic  cel. ig. 4. Gah of eaosh  bewee sess ad sa. ig. 5a b. Sess ad sa elaio  fo CC,BCC CC,BCCad ad CP H; sess sess ad  sai fo iesiia maeias. ig. . A edge disocaio.

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ig . Pog Pogess essive ive moveme of a  edge dslocaio ig 8. Dede ams ig. 9. Poished ad eched view  of a secio hogh a "Daiesy "Daiesye  e  ecoa fom Ace Coombia. ig. 0. Poished seco of a sma  cas fog fom he  aoa aoa aea of  Coomba. ig. a-f. a-f. Some micosca  feaes i soid soio CC  meas. g. 2. Relaioshi bewee sige hase sces  CC meas. ig. 3. Secio hogh coe aoy  axe fom a showig wied  gas. ig 14. wied gas of god coe aloy shee. ig. 5. wi aes i dia ic  co  g. . wi aes  ic g. . wi aes i ic g. 8. Phase diagam fo he gold sive sysem. ig. 9. Eecc dagam of sive coe aloy. ig. 20 Eecicye  micosces. ig. 2 Dediic   0% Ag 40% C cas aloy ig. 22. 0% Ag 40% C eched i  oassim dichomae. g. 23. 0% Ag 40% C cas aoy  isaig eecic . g. 24. Woo see igo fom da  gs. 25a,b 25a,b ad �  micosces. ig. 2 Eecc  ad �. ig 2. Eecc ad dedies g. 28. bos sce  woked  wohase aloy. ig. 29. ad  eecoid. g. 30. ocabo hase diagam. g 3a-d. 3a-d. Beakdow of  gas. ig. 32. Cemeie ad eaie. ig. 33. Coei hase diagam. ig. 34. � eiecic. ig. 35. hase gais. ig. 3. Coeic hase diagam ig. 3. � gas gas  coec. coec. ig. 38. Discoios eciiaio 

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i AgC ig. 39 CA hase diagam. g. 40 CPb hase diagam g. 4 Cas oggle  fom a. ig. 42. Chiese casboe icese  be. ig 43. A smal mio of bea eched boe fom Smaa. ig 44 Highi boe mio  fom Java ig. 45 Cas highi eaded boe  of 22% i,% i,% leadad leadad 2% coe. ig. 4. Laboaoy eched aoy  of 24% i, i,% % coe igs. 4-50 Jaaese swod blade  fagme. ig 5 Paay Widmase  see. ig 52. Gai boday sce  wh sbga feaes. ig. 53. Gai sie of kife edge. ig. 54. Baded sce of a  eched swod blade. ig. 55. Pa of he eeC hase  diagam. ig. 5. See il fom id of a  Woo ccible, Decca aea of  dia. ig 5 Medieval kfe bade fom  Adigey,Sssex Adigey, Sssex Eglad. ig 58. Phoomicogah of kis  fom dia igs. 59,0 59,0 ech cseel bead. ig  Pa of he eeC hase  diagam fo cas io ig. 2a- ake gahie i cas  o. ig. 3. 8hcey cas io scaes. ig 4 Cas io caobal fom  he owe of Lodo ig. 5. yica vaaios i he  esevaio of sface deai i  ace mealc afacs. ig . Moed ad oished  secio hogh a boe od  fagme g.  Dawg of he coss secio  of a boe od fagme g 8a-d. Exame Examess of cooso of  godcoe aloys. igs. 9,0. 9,0. Lisa ceemoa 

axe. g. . Secio of a cooded  fagme fom a Ecadoia gided  coe ceemoal axe. g. 2. Nomogah fo gai sie ig. 3. yica sadad fo  esimaig he aseiic) ga sie  of see. g. 4. yica sadad fo  esimaig he aseiic) gai sie  of aealed ofeos maeias  sch as bass,boe, boe,ad ad icke  sive ig. 5. Moig sma secimes ig.  Gidig moed samles. ig. . Poishig moed sames. ig 8. Samle soage. ig. 9. Examia Examiao o by oaied  igh micoscoy. ig. 80. Use of iveed sage  meagica micoscoe. ig. 8. Dawig of a axe showig  ideal ocaio of same cigs. ig. 82. wo sames of moed  wie o od. ig. 83a-c. Holdig sma sames ig. 84a-d. Embeddig smal samles g. 85. Shaes of feie i ow cabo sees ig. 8. Commo desciive  micosca ems gs 8-89. Base sivecoe aloy  coi fom wese dia. igs. 90-93 slamic iad kwe  cas i a coeicead aoy. igs 94-9. Cas boe aowhead  fom Paesie. igs. 9-99. Paesie boe swod. ig. 100. Roma wogh io. igs. 0-03. Coombia god coe aloy shee. igs. 0405. 0405. Ecadoia coe aloy ose oame. igs. 0-108. Cas aseica coe  axe fom Ecado. igs. 09 10. Chese boe  icese be. ig. . ha boe cas bel. igs 213 213 Lisa dagge  hadle igs. 4 5 agme of a ha 

bronze containe Figs16,17. Figs16,17. Columbian cas Si ear ornamen. Figs I-120. Cas on cannonba  fom Sandal Castle Figs 21,22 Bronze Age copper  ngo from Hampshe Engand Figs 23-25. Roman brass con Fgs 12627. Tha bonze  conainer fragmen. Fgs 128-30 God neckace bead  rom Colombia. Figs 31-133 Gold alloy nai and  god ear spool. Figs. 34,135. 34,135. Tang and blade  secon. Figs 1363. ron knfe. Fg 38 Roman coppe aoy coin Figs 13940. 13940. Roman iron na. Figs. 41-44 Naive coppe fom  he Great Lakes region in North Ameica Fgs 45-4. Head of a oggle oggl e pn  rom ran Fgs. 1485. Javanese ron bade. Fgs. 52 53 Bronze ae fagment  from ran Figs. 54,55. 54,55. Laboraory cast  60:40 bass. Figs 156-59 Glded siver earng  from Jordan Figs 60 161. Fragmen of a brass  medallon rom Asralian  shipwreck Fgs 162-164 162-164 Fragmen of a smal  Si ear ornamen Fig 65 Roman mror ragment. Fig 66. Roman bonze grine Fig 167. Roman bonze  mcrostrucre Fig 68 Renaissance silver basin  from Genoa Fig 69. Part o soder bob rom a  repar o he ote adial pane o the  Renaissance siver basin Fig 170. Section hough he  Renassance siver basin Fig. 1 Overal vew of a coe  diled pug from he silver basn Fg 72 Par of he siver shee  etched n acidied poassim  dichromae

Fig 3. Section o a circlar  braceet rom Thaand. Fg 14. Strctre o he ccuar  bracee fom Thaiand afer etchng  in alcoholic errc chode Fig. 5 High magnicaon of  cicuar baceet om Thaiand  Thaiand  showing redeposied redeposied copper,copper  sulde ncsions ncsionsand bonze metal. Fig. 6 Secon throgh a Roman  bronze bowlghy bowlghy eched n  acoholc eic choride. Fig.  Early medeva bass sheet  eched n alcohoic ferric chloride  and potassim dchromate. Fg 7. Recystalzed and heavily  worked gan strucue of brass sud. Fg 19. Microsrcture o  RomanoGreek ron arowhead arowhead Fig 180 Unusual corosion paten  throgh Byzantine bronze bade Fig I Heavly eched view of  Byzantne leafshaped bade Fig 182. Coroded iron knie bade  rom medieval Brain Fg 83. on knfe bade showing a  weld where diferen peces o ron  have been joned togeher Fig. 84. owcarbon seel area of  medieval medieval ron knie bade Fig. I5. Section o panpipes eched  in cyande/persfae Fig. 6 Fragmen of Byzantne iron  dagge blade showing par of he  edge Fg 8. Ovea vew o he Roman  coin o Victorenus etched in  acohoic feic choide Fg 8 Gan sucue of he  Roman con of Vcor en en us. Fg I9. Mcrosrctre of grey cas  ron of he eary 20th cenuy. Fg 190 Grey cas ion showing  graphite lakes and pearlitic nl Fig. 9 Gey cas iron showing the  cast srcre of the ironcarbon  aoy Fig. 92. Graphie akes n a ferrite  maix with an nl o pearle  conaning some steadie paches. Fig 93. Whie cas on showing  ong cementie lahs an sma 

gobar regon of peaite Fig 194 Whe cast iron etched in  Makam's Makam's reagen and picral Figs 19596. 19596. Tin ngot rom  Cornwal. Fig. 9 Tensile poperties impac  vaue,and vaue,and hardness o wrought  coppen aloys. Fig. 98. Coppen system. Fig. 99. Pa of he copperin  dagam under dferen condiions Fg 200. Coppearsenc system Fg 20 Copperead binary sysem Fig 202 Copperiron bnary system. Fg 203 Coppergold binay  system Fig. 204 Copperantmony bnay  sysem. Fg 205. Copperslver binary  system Fg. 206. Coppenicke bnay  system Fg. 207 Copperznc binary sysem Fg 208. roncarbon system. Fg 209 a. Leadin system  (pewers) b Godsver sysem Fg 210 Coppersivegod ternay  ternay  liqidus Fig 2  Coppersivegod ternay  soids Fig 22 Coppenead ernay  sysem.

1

igre I  Cloe-ed hego hego  ui t ell ell truur e Ato g for for of



HE AUR OF MEAL

Metas ae a aggegat aggegat f ats ats tat aat f ecuy ae sld at  teeatue ese ats ae eld tgete y etallc ds tat esut f sag avalale elec ts A egatve elect d evades te stuctue ad eat ad electcty ca e c ducted tug t ug te etal y te fee veet f elects e egatve elect d su uds te stve s tat ake u te cystal stuctue f te eta ee ae tee c tyes tyes  f lattce stuctue tat etals eg t clseacked exagal faceceteed faceceteed cuc ad dyceteed cuc

etal etal s  s cled vey adly as  slat cg te a cystae stuctue ca e su essed I  slat clg etal dets ae cled vey uckly etwee clled eta lates ad te stuctue tat deves s sla t glassa ad aageet f ats ate ta a cystale cystale aay I  te usua cystalle state etal wll css t f a ue f dscete gas e eta s te efeed efeed t as eg  y cystale A tat ety f etals etals s tat tey udeg  astc def d efat at we stetced  aeed s s lustated y a stesssta daga usg ug s Mduus M)

Cos-Packd Hxagona (CPH) Mdels f cystal stuctues ca e ade u f sees stacked  clseacked layes w aageets ae ssle e eg exaga ad te te cuc  asc stuctue  te clseacked exagal syste te sees eeat te sae st s t evey secd aye aye ABABAB    g





igure e-etered uit A CC ruure h four four to er ui ell d  to ig ftor of i ot ele et ryl





 strss tran

lowrbo ee

FacCntrd Cubic (FCC) Layes Layes ca e ult u lt u s tat te td aye aye f sees sees des t ccu y te sae st as te sees  te st w te stuctu e eeats evey td aye ABCABCABC  )  CC etals ted  t e ductle  e  ca e ecacaly defed defed daw ut t we   aeed t seet) Exales ae lead lead auu ce slve gd ad ckel g  

BodyCntrd Cubic (BCC)

gure 3 Bodyetered Bodyetered ubi ui el A BCC etl  two o er u ell d  t to oi i ig for of i eleetl rytl rytl BCC etl re boh dutil e d trog trog eg eg ro hroi u  ugte ugte d oybdeu 

YM=

la appl  crsssctnal ara  chang n lngth rgnal lnh

Ate Ate c c  tye fud fud  ay etals te dyceteed cuc stuctue s less csely acked ta te CC  CP st uctues ad as ats at te ces ad e at at te cete f te te cue Te ats at a t te ces ae saed wt eac adg cue g 3 te etas tat  atuty ave etey dffeet lattce stuctues f exale asec aty ad sut ae e da ad day t s  dyceteed dyceteed tetagal Metals ae cystalle slds ude al cdts fwkg f wkg ad etg weve f a

oer

tr  igure  elti o bewee re re d ri

Befe Befe lastc defat ccus ateas def def y te elast c veet f ats tat ld te stuctue tgete s eastc defa t ccus  etas ad  te ateas suc  as gass wc ave  aty t def at   teeatue Glass wl stetc y elastc defa t ad te eak Metals ca de as t cally ecause ecause aes f ats ca sl as t eac te t duce veet s kd  f ve et cat take ace  a glassy stuctue e etals suc as ue ce   ae stetced tey wl eak  actue ut ly afte a ceta aut f lastc defat defat as ccued see gs , a )

he Natu Nat u oMta 2

Figue a, ght Stess a stain elationshi elationshi p fo fo FCC BCC, an CP etals copae with gass a a typical polye An i cease in iteato iteato c spacgs is esposib esposib le fo eastic behavo, whil e pastc oveet esuts fo fo i socatios gvig ise to to sl ip When this plastic ove ent ca o longe occu factu factue e wi ll tae tae place igue b, below Stess a stan fo  ntestitia ntestitia ateas Itestitia eleets ae ae sall i n size, such as cabo, a ca be is ete ete ito the lattice spacing of soe eta ls such as steel whch is a itesttial aloy of ion a cabo Ite stitials ten to es ie at the base of s ocatios a ancho the When sli p occus cabon is left behin an the slocation is h el until soe hig he stess stess is eache When the stess facto facto i s eache a eoous u be of of isoca tons occu that ca ow ove at a lowe stess stess tha tha oigi nall y euiehence the two yiel points

Hadne

Dlocaton

e adness f a eta is easued by its esistance  indentatin e etal is indented unde a knwn lad using a sall steel ball as in te Binel test) test)  a squaebased diand yaid as in te Vickes test). In te Vickes test te esult is given as te Diand Pyaid Nube DPN  )

It is ae f cystals t ave a efect atic stuc tue tee ae usually iefectins esent. In etals edge dislcatins a nd scew dislcatins ae te st itant faults see igs 6, 7) ese cystal faults faults enable en able def d efat atin in t take lace at lwe alied stess by sli tan wuld be ssible if te lattice stuct ue was efect. efect. en

   BCC (eg Fe)    typica aophous polye (eg polystyee) polystyee)

factue poits poi ts

typcal bittle ateial (eg, glass)

VQ  

     

CP (eg Zn)

! FCC (eg, Cu)

 stain E on eform aton plastic deformat

CC BCC Factue

efoaton

I

uppe yiel yiel poi nt

Cu substitutioally alloye eg CuSn

Cu una loye loye

stain



ntestital alloy eg, eC

h Nau oM 

Notes

a etal s defed te sl takes lace utl a tagle f dslcats bulds u wc evets ay fute wkg .e. dslcat etage et As etal s wked, sl laes bece tcke ad ble . f te etal s wked fufute, t ust be aealed eated u t bg abut ecystallat. Befe aealg te etal ca be sad t be wkadeed. wkadeed. kadeg s acclsed by f exale a eg at  teeatue s ceases te etal adess value but deceases ductlty

 e atc ackg fact s a easue f te

2

sace actually used by te ats  te lattce.  ad FCC lattces ae ae bt 0 wle te B etals ave a lwe lwe fact fact f 0 68  A ete l l f te te lattce wuld wuld be 1 00  Ductlty s e used  te sese f tesle tesle veet .e . stetcg ad alleablty alleablty s used f f ablty t be wked wked  e , aeg.



Fige his ige shows an exta plae o atos is ete i the oignal lattice lattice The plae o the ege islocation a its  iecton o oveet ae ae pep eni cula cul a to to the sip plae

7

ege islocatio

cystal attice

gue Pogessive Pogessive o veet o an ege i slocatio showig slip









cystal lattice lattice aer sli p ege islocation

oveet though cystal

2 HE MCRORUCURE OF NCEN MEAL

There are two bac mean o f manipulating met a they can be cat or worked. All the variou method by whch cating and workng are car ried out cannot be examned here n detal, but the dif di fferent type o f tructure are decribed. decri bed.

Castng

tetiay seoay a



iay a igue



Deite as

here are eentially three type of mcrotructure mcrot ructure that can are during the catng and cooling of a melt in a mold reardle of the exact nature of the technology nvolved. nvolved. Mo t ancent metal are mpure or are delberate alloy of two or more metal uch a copper and tn (bro nze) or copper and zinc (bra) . Th e fact fact that they are impure  an mportant one for the knd of crytal growth that can occur  o a large extent dependent dependent on the purity of the metal metal Th i one reaon reaon why the great maorty of ance nt cating how a den drtic tructure endrte look lke tny fernlike growth cattered at random throughout the metal They grow larger until they meet each other Sometme outlne of grain form form between them, and the rate at whch the meta i cooled nuence ence their ie Uually a microcope mut be employed to make dendrite dendrite vble, b ut on obect that have cooled lowly, lowly, the dendrte have alo formed formed lowy and may be vble to the naked naked eye or under a binocular bench mcrocope at low magn magncaton (x  or x0 ) he fater fater the rate of cooling, the maller the dendrte. t  po ible to meaure the pacing between dendrte arm f they are well formed and to compare the pacing obtained from thoe from known alloy cat n dff dfferent mold mol d or o r under unde r di fferent cond co nd ton. ton . Arm of dendrite are uually referred referred to a prmary prmary econdary econdary or tertiary Fig. 8) . t may be o f interet to record dendrtic arm pacing for comparatve purpoe even if condi ton are not preciely known or there  a lack of background nformation nformation  n the metallurgcal lt erature. endrite may be rather fuzzy or rounded rounded n outl ne or qu te harp and well well dened, dened, dependn g on the nature of the alloy and the cooling condton of the melt. melt. endritc growth  actually one form of egregaton that can occur durng catng t i a egregaton

pheno menon that often are n mpure metal or alloy becaue one of the conttuent uually ha a lower melting point than the other. For exam exam ple conider co nider the th e cooling coolin g of an aloy of copper and tn. tn. Copper Copper melt melt at at 1 083 °C and tin tin at 3 °C. When the alloy cool and begn to olid by dendrtic dendr tic egregation the rt part of the dendrte arm to form are rcher n copper nce th con tituent olde rt , whle the outer part of the arm are rcher in tin. The reult i that there  a compotonal compo tonal gradient g radient from from the nn er regon of a dendrtc arm to the outer urface. urface. Such dendrte are uualy referred to a cored Corng i a com mon feature in catng of brone arenca cop per debaed lver etc. t i uualy neceary to etch a polhed ecto n of the metal to nvetigate whether corng  preent or not. ependng on the amount and nature of the alloyng conttuent preent, the remanng uid n the nterdendrtic channel or pace wll the n olid olid  to form form a df d f ferent phae of the partcular alloy alloy ytem. ytem. A phae  any homogen eou tate of a ubtance that ha a denite denite compoit ion. n practce th denton mut be interpreted a lttle ooely ooely becaue very often ancent metallc ytem are not fully in equilibum condition which mean that the proporton and even the compoton of the indvdual phae that are preent n an alloy may not match the prece vaue that can be determned from from a phae diagram. The ub ect of phae and pha e diagram diagram wll be taken taken up later n th ecton endrte, then, dominate the world of ancient ancient cating cating ee Fg. Fg.  1 0) b ut there are occaion when oth er type of egrega egrega ton occur n addtio n to dendrtc dendrt c egregaton or when coong condton gve re to completely diff different tructure truct ure he other prncpal type of egregation are normal egregaton and nvere egregaton Nor mal egregaton egregaton occur when the lower melting pont contituent i concentrated concentrated toward toward the inner par of the mold, while nvere egrega egrega tion often aocated wth alloy of copper con taning arenic antimony o r tncan puh the alloy ng element to the ex teror tero r of the urf ur face of the mold . nvere egregato egregatonn may be reponble

h Micotucu Micotucu oAn Ancin cintt Ma 6

Figue 9 ight ight Po lishe a uetche sectio though a Daie -style pectoal fo aciet Colo bia Magificat Magificato o (  60) shows selective coosio of the ete as  Note the vey oue i pessio of the eitic shapes The aloy is a 1 8% gol % % silve 68% coppe alloy cas t by by the ostwa pocess ige 1 0 a ight Polshe sectio of a s all cast o ogg fo the aioa aea of of Colo bia showig ieet eitic stucte Hee he agiicatio agiicatio i s 80 a the secto has bee etche with pota potassiu ssiu cyaie/a cyaie/aoiu oiu  pesu lfate lfate etchat

for some of the slvery coatgs occasoally reported  the lterature such as the atmoy coatgs o some cast Egypta copper obects (k ad Kopp Kopp 1 933) . Copper lead or gold gold castgs ca occasoally be relatvely free of mpurtes ad o slow coolg o dedrtes may be vsble. Uder these crcumstaces the metal may cool ad produce a equaxal, hexagoal gra structure. A equaxed hexagoal crystal structure, structure,  whch all the gras are roughly the same sze, radomly oreted ad roughly hexag oal  secto correspods to a deal model of a metallc gra gra or crystal.  t s the arragemet of separate growg crystals that meet as they grow that gves the hexagoal ature to the deal struc ture sce ths results  the least eergy requre met. t s a equlbr um structure for for ths reaso, whch the dedrtc structure s ot (see g. 1 1 ). Oe result result of ths s that that t may may be pos sble to o bta a equaxed hexagoal hexagoal gra structure by extesve aealg o f the orgal dedrtc structure. O the other had a de drtc structure caot be obtaed by aealg a equed gra structure. Cast metals that do ot show a dedrtc structure ca be qute df cult to etch ad t may be dcult to develop ay structure apart from from the vsble clusos ad ay porosty  the metal. Cast metals ofte dsplay characterstc sphercal sphercal holes o r porosty whch ca be due to dssolved dssolved gases  the melt or to terdedrtc holes ad chaels that have ot bee kept lled wth metal durg soldcato. the metal cools, the dssolved gases exsolve, exsolve, creatg reactos wth the metal tself to form oxdes (for example example the producto of cuprous oxde [Cu the copper eutectc  acet



castgs) or causg gas porosty  the mtal. The thrd type of structure whch s partcularly asso cated wth chll castgs s columar columar growth. Chll castgs are formed whe metal cools quckly o beg poured to a mold.  ths type of structure struct ure log arrow crystals form form by selec tve growth alog a oretato toward the ce ter of the mold. They may meet each other ad thus completely llll the mold. t s rare to d ths type ofstructure  acet metals although some gots may show columar growth.

Wog Workg refers to a method or combato of methods for chagg the shape of a metal or a alloy by techques techques such as hammerg turg rasg drawg, etc. A l st of useful useful terms s gve  Appedx E. ur ther detals ca be fod fod  may of the the texts metoed   the bblography, especally especally those by Utracht ( 1 95 ) ad Maryo (1971 The tal gra structure of a homogeeous alloy ca be cosdered as equaxed hexagoal gras. Whe these gras are deformed by ham merg they become atteed (ther shape s altered altered by slp d slocato movemet ad the geerato of dslocatos as a resul t of workg) workg) utl they are too brttle to work ay further. At ths pot the gras are sad to be fully work hardeed. f further further shapg or hammerg of the the metal metal s requred the the metal metal must be aealed  order to restore ductlty ad malleablty. malleablty. ur ther deformat deformato o of the metal by hammerg may the lead to workh ardeg aga ad f further shapg s requred the aother aealg oper ato ca be carred out. May obects have to be

Th Miout Mioutu u oAnint Ani nt Ma 7

shaped by cycles of workng and annealn g n order to acheve sufcent deformaton of the startng materal whch may be a cast blank or ngot of metal metal that must b e cut or shaped nto ndvdual artfacts. ypcaly annealng temper atures would be n the range of 00800 °C for for copperbased copper based alloys ro n and steel. f the metal s an alloy then strctly the type of annealng anneal ng oper aton should be speced process anneal stress relef annea annea sold soluton anneal anneal etc. me s an mportant factor factor as well too lengthy an anneal may lead to gran growth and a weakenng weakenng o f the structure of the artfact; artfact; too short an anneal and heterogenety heterogenety and resdua stresses may not be emnated sucently here are other practcal problems assocated wth annealng dependng on the metal concerned; for exampe when debased slver alloys usually slvercopper alloys) are annealed by heatng n ar they are able to undergo nterna oxdaton. A black skn of cuprc oxde forms forms Cu O) overlyng overlyng a subscale of cupr ous oxd e Cu) w hle oxygen can dff dffuse nto the alloy attackng the readly oxdzed cop perrch phase and producng nternal cuprte embedded  n a sverrch matrx for further further detals detals see Charl Charles es and Leake 1 97; Smth 1 97 1  igur iguree I I   Soe So e irotruturl i rotruturl eture eture in oid oution  CC etl  Cored grin with rennt dendriti  truture truture b Codwored ored grin  ul ly nneed nneed hoogeneou hegonl equied grin d Coldwored nneled  el el with ttened ttened grn  e Anneed ter ter old-wor ing howing twinned grin  Col dwored ter ter nneng howing ditorted twn lne nd trin line i n the grn

Schweer Schweer and and Meyer Meyerss 1 978 ). Coldworkng and annealng ca n be com bned nto on e operaton by hotworkng he obect to be worked s heated to near red heat and then mmedately hammered out. he two pro cesses namely coldworkng followe followedd by anneal ng and hotworkng wll gve essentally essentally the same mcrostructur mcros tructur e of worked and recrystalzed grans s o t s always always not possble to know f cold workng and anneang has been used n a partc ular case although there may be other ndcatons that have a bearng on the nterpretaton o f the resultng resultng structure structure see see gs. 1 1af 1af 1 ) Some metals such as ro n usually must be worked nto shape whe they are red hot he forgng forgng of wrought wrought ron whch contans slag globules as mpurtes produces a worked worked structure n whch the slag gradually becomes elongated or strung out nt o slag strngers along the length o f the obect.  t s mportant to note that most nclusons n ancent metals do no t recrystale recrystale as as a result of hot workng or workng and anneang they ether are broken up nto smaler partcles partcles or they are lattened out as the workng process proceeds acecentered cubc metals except for aumnu m recystall recystallze ze by a twnnng process

he Mirostrutur oAnc Ancent ent Meta 8

 

Figure Reltionhi etween etween ingle he tutu tuture re in  CC etl ued in ntiqity.

orig inl t teril howng dendriti egregtion egregtion

oldwored ol dwored ditorted ditorted dendrite

eteniv etenivee nnel ing wil l reove th e egregte egregtedd nd ored trtre

deored grin with oe trn ine evident on hevy woring equ i-ed hegonl grin

       �       � hot-woing nneling

nneling

wored wored deored gr in now howing ent twin nd trin line

1

rerytlli rerytlli zed nd twinned grin wth trin li ne ent nd tright twin line withi n grin

reytlli reytlli ed nd twinned grin with tright twin li ne grin ize uuly ller.

New rtal rtal that gr ow followng followng the an nealn g of oldworked faeentered ub metal uh a gold opper lver and ther allo produe the eff effet of a mrro r reeton plane wthn the r r tal wth the reult that paralel traght lne an be een n ethed eton traverng part or all of the ndvdual gran ofthe of the metal metal (Fg 1 ) After After annealng the twn lne n the rtal are per

fetl traght the ma not run omplete through ever gran but the are are traght. f the gran are ubequent deformed then the twn lne wl alo be deformed deformed n polhed and ethed ethed pemen the appear a ghtl urved urved lne n heavl worked metal lp of rtal plane an our n ndvdua rtal reultng n a ere of parallel parallel movement that an be een n

h Mi h Miuu uu An i in n Ma 9

etche ecton a a ere of ne lne n ome of the gran. hee lne are cale lp ban or tran lne Another feature that may how that metal ha been healy worke  the preence of a brou morphoogy n the mcrotructure h may occur when gran hae been lattene ou t by hammerng proucn g an elongate tructure commonly ecr be a a "texture e ffect. ect . When th metal  anneale to prouce a recrytalle gran tructure the recrytallze materal may tl how a preferre orentaton or a brou nature h  a n extreme example of the fact fact that recrytallze gran are not foun to be com pletely ranomly ranomly orente. epenng on the amount o f colworkng that the metal ha recee t wll be able to recytalze at ucce ely lower temperature whch are markely fferent fferent for partcular metal. For exampe healy worke pure copper  capable of recry tallzng at 10  ron at 560 °C znc at 10  tn tn at  1   an lea lea at 1  C h  why metal lke pure pure lea can be bent back an forth at room temperature wthout workharenng workharen ng they are eff effectely beng hot hot  worke at room t emperature. Aloyng eement eement an mpurte wl w l of coure affect affect recrytallzaton temperature temper ature a wll gran e an the egree

iu iu 1 3 hoomi oah oah o a sion houh houh a o alloy a om om  an showin wnn ains a a hin wih i hloi soluion (ao 300). o ha h oosiy in h mal has no bn lm ina by woin

of coworkng coworkn g he percentage of eformaton eformaton or egree of colwork  uually expree n term of reuc ton of heght of the pecmen h. h

 oldwork



initial 

h worked 



 hta . 

 1 00

t  often cult to remoe the egregaton that occur urng the catng operaton an many ancent obect that were worke to hape from a cat ngot  tl how ome corng or remnant enrtc tructure een though the obect wa ubequently worke worke to hape. Varaton  n compoton are n ot conne by th e new worke worke gran tructure an appear upermpoe upon the gran gran when the the pecmen  etche (g. 1 3 1) he kn of twnnng occurrng n CP met al  hown by the tructure of the nan nc con n gure 1 5 Whle lp an twnnng twnnng are the man metho by whch nc crytal crytal accommo ate platc eformaton eformaton there are tuaton n whc h nether o f thee thee eent eent can occ ur rectly h can happen when znc crytal are com pree parale to the baal plane or where crytal are retrane from from moement  uch a n

u  4 Twinn ains o ol-o alloy sh  om isa ni Colombi a si o Naio. Coosion whih aas y h oulins win ains o h ysals wihou hin. Siaons houh h son a u o sliv oosion as a sul o saon saon n h wo wo alloy al loy h saion saion is  u o unqual isibuion isibuion o o o an ol in h hamm sh Ann alin wins a sah shown ha annal n was h inal sa in manu au.   20.

Thee Micstucture ofAncie Th fAncient nt Metal 10

1165,

Fgure right r ight wn wn planes i n Indian zinc coin. coin. Figure zinc.

far f ar right right Twin planes  n

basal pa nes bend plane

the usual poycrystaline poycrystaline solid U nder these con dtions , stress can be relieved by the movement of the basa plan e axis The axes axes of the bend ae con tained in a bend plan e which bisects the included ange of bend bend and which has no dened crystallocrystallographic indices he bending mechanism involves slip, since individual basal planes must move elaive to each other for bending to occu Although in some cases the volume v olume of metal involved in a series se ries of bends is sucient to pro duce macroscopic kinks bending often occurs around ar ound a very large n umbe o f closely spaced pa ale axes g iving the e ffect of o f a curve When such deformed structues ae anneaed close to the melting melting point , a coalescence coalescence of the the ne bend seg ments ments into coars coarser er units units occurs occurs (Figs 1 6 1 7).

bend pane tWn n ZnC C rysta

        _ basa pane

Figre

17.

Twin T win panes n nc

3 WO-HAED MATERAL

Apart from from compoton compo tonal al varaton produced by egregato egregatonn o r by n cluon, the varete varete of mcrotructure produced by the preence of two or more phae n metal have have not been dcued. Some reaon why more than one phae can be preent are dcued n the folowng ecton:

1

2 3.3.4. 55 

Eutectc tructure Eutectod tructure Pertectc tructure Wdmanttten tranformaton contnuou precptaton  n termetallc compound formaton Immcble tructure When two or more) meta are mxed mxed together to form an alloy there are a number of dfferent poblte regardng ther mutual ou blty Uually a phae dagram dagram (or equlbrum dagram a t  ao known)  mployed mployed It  eentally a map that can be ued to predct what phae hould be preent n the alloy at equb rum t  mpor tant to tre tre that dagram dagram uually only refer refer to very lowly lowl y cooled melt whc h rarely occur n archaeologcal materal.  h doe not mean that t  uele uele to conult phae da gram t mean that the nformaton mut be Fi  8 has iaam o h ol-silv sysm No ha boh mals a oly sol bl in ah oh

nterpreted wth cauton and preferably after experence experence wth ancent alloy ganed by mcro copca examnaton. When two metal are mxed together there are three man poblte. he rt  a old alloy howng complete od  olublty of two two metal.  example  the range of o f aloy formed between  lver and gold. Gold  oluble n lver and lver  oluble n gold he phae dagram that reult from th knd o f alloy how how ut one od phae preent at all temperature up to the oldu. he odu lne eparate the regon o f old metal from the paty tage of oldcaton at tempera ture above th lne A the temperature re the alloy pa through a paty emold regon n whch whch ome lqud  preent preent n equ brum wth ome old. h contnue to the lqudu lne and above th ne the alloy  preent a a lqud met he lqudu  ne eparate eparate the paty tage tage from the lqud melt above Fg 18 In coolng from from the molten tate the alloy undergoe the folowng tranton:

where

 

L

L La



lqud and

a



a

od.

min on  o u ol

1050

000

950

0% ol 1 00% silv

soli soluion



50% ol 50% silv

1 00% 00% ol 0% silv

wphaed w phaed Mateia 12

f no corng or other form o f egregaton are reent then the mcrotructure wl be a collec ton of equaxed equaxed hexagonal hexagonal gran of unform unform comotonthere comotonthere wll be only one hae reent he econd oblty  that a old alloy can how only artal olubl ty of the metal n each other. One exame  ver and coer. There are three rnca tye of hae dagram that can are from from th tuaton he mot common  the eutectc tye tye econd  the eutectod and thrd  the ertectod. The thrd oblty  that the two metal are comletely mmcble n each other

vare of coure deend ng on the nature of the alloyng conttuentthe conttuentthe lqud melt ae to old whch  twohaed and cont of ne late late o f alha hae and beta hae nterered n each each other other (ee (ee Fg. Fg.  13 5a b)  here  a large area where aha hae coex t wth lqud and a mlar regon where beta hae coext wth lqud (F g. 1 9) . f an alloy of comoton B  cooled down from the melt then the folowng tranton wll occur

L t   L t + e L (  e + �

where t = temerature.

Eutectc Stuctu S tuctue e

  (e + �.

The nal old tructure therefore therefore cont of The orgnal alha wll b e reent a ether gran of alha alha old oluton or a dendrte of the the rmary alha whch wll robaby b e cored. he nllng around the aha gran wll then con  t of o f the alha beta eutectc a a ne nter ered mxture and under the mcrocoe n etched ecton wll loo omethng e Fgure 0a.

Slvercoer alloy are examle of the eutectc tye and have the folowng charactertc the olublty o f coer n lver and of lver lver n co er fall a the temerature fall (th  a general charactertc for mot aloy) and there  one temerature at whch the lqud melt can a drectly to old The eutectc ont. At th ar tcular comoton and temeraturewhch

+

Figue  9 Euei he he gm gm of ileoe lloy.



!

euei oi lloy C

lloy B

omoiion

w-phad aa 

gue 20a b Eutetitye mitutue.

infill f alha

+ beta euteti

dendite f alha ualy ed

a

Figue Figue 2 1  middl e left. he feat feathe heyy natue natue f dendti

 in a 60% Ag 40% Cu ally that ha been at. Ethed 

n taium dh mate mate x35. Whil e the dendite an be een lea ly at thi magn ifiatin the euteti �  annt be een infill f

+

igue 2 3 bttm bttm eft eft 60% Ag 40% Cu al y il utatng ng the natue f the eteti infil in whi h the e -h hae ethe da and the ilve-ih �  hae ethe light Elet n- be analyi f ne ne f the dendti  am that aea hee a da glbue give an analyi f 92% Cu 8% Ag ending ending vey well in mtin t the ft ld fmed fm the met in the hae diagam f Cu-Ag ethed n alhl eC and taium di hmate x 1 60



alha

+ beta euteti

gain gain f aha b

igue 22 midd le ight The ame ame ally a a gue 2 1  60% Ag Ag 40% Cu ethed i n taium dihmate di hmate x I 00 he  euteti hae i jut beginn ing t be elved int a fine ee f line in the etin



Figue 24 bttm ght Wt tee ingt fm I ndia nd ia hwing fagmen fagment t f ementite needle with an i nfi l f eutetid eaite FeC x300) ethed in nita. Wtz Wtz teel ingt ingt fm Ind ia wee high-abn tee (ften (ften ve 08% abn at in u ibl e and u ed f the manufatue f wd bade and t he qual ity dut du t he he eutetid may be im ila  t the euteti

 +

Tw-phasedaea 4

he coolng rae deermnes wheher he org na alpha phase s presen as dendres or as hex agona grans Usually n archaeoogcal maerals he prmary alpha wl be dendrc and cored; aer workng and annealng may remove den drc segregaon and and grans o falpha may become more apparen  s beyond he scope of hs ex o provde a quanave nerpreaon of he phase dagram, bu wha can be sad s ha as he euecc pon s approached here wll be corre spondngly less nal phases of apha apha or bea As he area of alpha s approached here wll be ess euecc presen and more alpha As he alloys approach he bea sde o f he dagram he same varaon s found he alloys are progres svely rcher n bea and have ess euecc n wo phase alloys where dendrc segregaon has occurred he prop oron o f he he w phases wl no be q e wha  shoud be a full full equlbrum he aloy aloy a composon A (g 1 9 wl have have a slghly dfferen composon n erms of he dsrbuon of he wo phases As  cools down he followng sequence should occur

L (   (   L (  �

he resulng srucure wll hen be alpha grans wh a hn lm of bea surroundng  hem, or alpha dendres wh a frnge frnge of bea (g   5 

a

a

a a 



ala en rtes rtes usa y core

igure 25ab an � micro structures A tyical eutecic alloy microstructure

igure 26 Eutectic

A he euecc composon he qud qud me passes drecly o so d and deally deally wll conss of a ne nermxed marx of alpha and bea phase (g 6. A feaure of he mcrosrucre of euecc ype aloys s ha  here may be a depeon of par of he euecc phase near he grans or dendres or example, suppose he orgnal dendres are alpha phase wh an nll of alpha bea euecc Some euecc alpha consuen can mgrae and on he dendr c alpha wh ch wll leave a frnge frnge surroundng he dendres appearng o conan a more homogeneous zone before euecc nllng s reached (g . One of he neresng changes ha can occur when a wophased aloy s worked s ha eher one or boh phases can become elongaed or sru ng ou mu ch lke slag srngers n wrough ron, along he drecon of he workng of he alloy Slag srngers are he brokenup remnans of slag nclusons n wrough ron ha become elongaed upon hammerng he ron o shape n heory one wold expec he process of workng workng and anneang o remove any orgna dendrc segregaon and o produce worked and recrysal lzed grans grans wh a euecc nll , dependng on he composon of he he orgnal raw ngo ow ever  s ofen ofen very dfcu dfcull o remove he nal dendrc srucure and nsead he mcrosruc

+

some alha beta eutectic because because of nonequil ibriu cooling

eutectic mx wil consst only of aha



bea

alha grains

eta flms between grains

Twphad aa 5

7 

Figre right Etectic a ertes i a tyical eutectic alloy

eutectic

Figue far ight ight ibr ous strcture i a tyical heaviy wore two-hase aloy. etectc etectc hase fil l

eutectic elete n alha ear enrites

elogate elogate en ritic rem ats ats

 

Fige 2 an eutectoi in a ti bronze aloy. core alha en rtes rtes light ble eutectoi where elta hase has the comosition C   Sn

  

ture tend to onit of elongated elongated ribbon of one phae with the euteti inbetween The lengthtobreadth ratio of thee elongated elongated tringer then give ome idea of the extent to whih the alloy ha been hammered outvery thin tringer ug geting more evere deformation during manu fature Sometime aloy alo have a brou quality or the ame reaon ig 8) Common example ofimpe of impe euteti ytem ytem in anent metal are thoe of debaed ilver arti fat, whih are uually ilveropper alloy and oft oder whih are leadtin aloy

Eutectod S tructures tructures he eutetoid phae i imilar to the eueti truture the prinipal differene being that the eutetoid reation our when an already exit ing olid olutio n tranform tranform into two ditint phae The type type of phae diagram that give rie to eutetoidtype tranformation are neearily more omplex beaue there are erie o f hange in the olid a it ool to room temperature There are two important eutetoid tranformation in arhaeologia metal: thoe in tin bronze and in arbon teel for one example ee ig ) The form the eutetoid take in bronze and teel i

not the ame In br onze the eutetoid ontitu ent i made u p of the the two phae, alpha the opperrih olid olution of tin i n opper) and delta an intermetalli ompound of xed om poition, poition, CS n) hi eutetoid phae begin to appear in the mirotruture between about 5% to 1 5% tin and above) depending on the ooling ondition o f the alloy It i a light blue, hard and brittle material that often ha a agged appearane he truture i often haped by grain bounday edge and the blue delta phae often ontain mall iland of alpha phae di pered through it ig 9)  If there i a lot of thi eutetoid phae preent, the bronze i difult to work work Proper annealing o f bronze with with up to about  % tin will reult in a homogeneou olid olution o f alpha grain that an then be worked to hape muh more readily beaue beaue the hard and brittle eutetoid ha been eliminated Eutetoid in the bronze ytem ytem originate from a omplex erie of hange that are not delineated in detail here, b ut are ummarized a follow

1.

passes through the th e alpha The alloy passes region as it cools.

+

l iquid

Tw-phad aras 6



34 55

t reache reache a tranton tranton at about 798 C and a pertectc tranformaton occur A beta ntermedate old oluton eult On coolng to about 586 the beta phae tranform tranform to gamma At 50 C the gamma old oluton tran form to the nal old mxture of alpha deta eutectod.

dc



Becaue the eutectod n the coppert n y tem  rather dfcult to follow, mot textbook on the ubect ntroduce the dea of eutectod tranformaton by lookng at the phae formed when carbon  added to ron to produce tee, and  the carbon content ncreae cat ron Mot ancent teel were made from ron con tanng up to about 1 % carbon, although n ot only  the carbon content of many many ancent art fact very varable n dfferent part of the ame obect but many of them ony contan about 0. 10. 5% carbon. Thee lowcar lowcarbon bon tee tee were were however very very mportant product and could be ued to produce excellent excellent edged tool The eutectod  formed when the autente old oluton (gamma phae) decompoe at about 77 C to form form the two new old old phae, ferrte and cementte he comb naton of thee Figue  0 Sgnifcant region on o f the ironcarbon hase agram

two conttuent a a ne colecton of mal plate  caled pearlte he name ferrte  gven to the pure ron alpha phae gran, whle cement te (eC)  another very hard and brttle contt uent, a compound of xed proporton beween ron and carbon Conder the coolng of an aloy from from above 900 C, n the autentc regon of the phae da gram wth an average content of carbon repre ented by the lne for aloy A n gure 30 coolng proceed autente (gammaphae) (gammaphae) gran wl eparate out and a the temperat ure fall fall fer rte begn to eparate from the autente at the gran boundare o a the temperature fall the gamma phae phae become rcher n carbon and the ferrte loe carbon untl t reache a low of 003% carbon whle the autente autente reache reache the eutectod eutectod compoton at 08 % carbon the temperature temperature fal fal below 77 C the autente decompoe by a eutectod reacton nto ferrte  cementte The change can be repreented a ymbol

A

A

a a  a +  a

Aoy A  

Fe C)

alloy A

Y

l

austentite

 austentte  cementte

earlite + cementite

o

2



% carbon

at about 80  C) beLow

7 C)

Two-phased Material 17

Figure Figure 3 1 ad Breakdown of grains in the iron-carbon system

y

grains g rains (above 850°)

y y y

grains (about (about 727 727 °C)

a

FeC F eC eutectod

+

gains at at gains

grains grains (abot 800°)

a

or as a series o drawings at di dierent temperatures on the way to room temperature (Fig. 31ad) The cooling o alloy B, shown on the portion o the ioncarbon phase diagam (Fig . 30), ollows a line leading through the eutectoid point with a composition o 0.8% cabon. Fo this particular alloy the microstructure, microstruc ture, i cooled slowly, slowly, would consist o an intimate mixture o pearlite (alpha FeC) FeC) . I n the case o the ironcabon eutectoid, the i nitial appeaance is very similar to that o o  the eutectic mixture drawn peviously p eviously (Fig . 26 ) I the the rate o cooling cooling o alloys alloys contain ing pearlite as a constituent inc reases reases then the spacing between eutectoid constituents becomes progessively fne I the cooling rate is very ast ast then the true natue o the phases that might orm on a phase diagam cannot be shown because nonequilibrium cooling conditions would be involved. What happens hap pens in steels in ast ast cooling is very important, and new phases, such as matensite, can orm, which has an extremely hard and brittle needlelie needlelie structure (see Chapters 6 an d 7)  he cooling o alloy alloy C ( Fig . 30 ) whose position is shown o n the phase diagram, produces a di dierent b ut analogou an alogouss series o tansormati tansormations ons rom the austenitic egion:

°C) (beow 727 °C)

he fnal structue will usually consist o cementite flms or a continuous cementite network between between the pearlite egions (Fig. 32).

+

Aloy

Y

Y

Y

Fe3 C 

Fe3 C 

+ (a + C -+ 

F3Cj F3Cj

+

Fe3 C 

pearlit e eutectod eutectod

Figure 32 Cementite Cementite and pearlte.

Peritectic Structures

Peritectic stuctures arise rom rom a type o o  transor transor mation that may seem ather peculia at st sight. t is unus ual in the sense that a liquid reacts with an existing solid phase to orm a new solid phase. An examp le can b e taken rom rom pat o the coppertin phase diagram (Fig. 33) to illustrate the typical shape o the phase system in peritectic alloys loy A cools down rom rom the me lt with abo ut  8 % tin content. Ignoring o o the moment the complications produced by coring, as alloy A cools cools down, initially an alphaphase solid solution o tin i n copper separates separates out, while the liquid

w-phaed aeras w 8

Figre 33 Coer-tin hase iagra.

20% S

h  lef ge pogrevely rcher n n. A rec on now occur  bou bou 800 °C beween beween h lq ud nd he lph phe whch produce  new phe be Snce lloy A occur n he lph be regon of he dgrm ll of he nrch lq ud wll be ued up before before he lph ph e  com pleey dolved, nd he lloy wll hen con  of ph be cryl: cryl:

compleey convered convered o  new grn rucur e of be grn:





Aoy A

 a

 a  a

iquid iquid (inrich) iquid (in (inrich) rich) � na srucure � grains

Ofen he perecc econ gve re o precp on of he new be phe boh whn he lph cy nd lo  he grn boundre o h he lph h rher rounded conour (g. 3. An loy of compoon B on he phe d grm g. 33) r o old by producon of ph phe grn bu hee grn hen rec rec wh he remnng lqud lqud  bou 800 °C nd re

a an  ertectic Figure 35, far ight. E hase grains. Figre 3, right

 a



A o oy B iquid iqui d iquid (inrich) iquid (in (inrich) rich) �

a+

na srucure srucu re � grains grains

One of he dfcule dfcule of he he per ecc rec rec on  h h   rely rely poble o ge complee converon of lph grn no be becue lph grn become covered wh  cong of be  hey rnform rnform nd he lm o f be hen preven he dff dffuon of nrch lqud o he lph  grn. he reul  h here  very ofen ofen  core of lph grn ef even f he phe dgrm ugge h ll he mer hould hve been convered o he econd phe. A complced exmple  gven by he nl ruc ure reulng from from n lloy conn ng 70% n nd 30% copper S ome of hee lloy were ued uully wh bou 0% n  he lloy specuum  whe lloy ued nce Romn me for for he producon of mrror. In

remaing alha hase grains grains eutectic eutectic ( Sn 

beta rouce b eritectc transormaton



(eta (eta hase coating (CuS n eventng eritectic reactio

wphasedaea 9

theory th alloy hould imply be a mixture of the eutectic (eta and tn) however thee alloy often how a nonequb rum tructure wth ep lon phae gran (Cun) coated wth eta () phae phae gran (Cu n)  n a eutectc mixture of ( n g. 35) Many of the mirror ued in Roman time were ether made ung hightn leaded brone wi th t n content of 0% and lead variable (typicay 5 1 % ) o r they they were made made wth a more common owtin brone alloy whch wa then tinned on the urface to produce the dered coor. There are other un uual feature feature n th e coppertin ytem ytem (ee (ee Fig 1 98  99) uch a that hown by the cooln g of an alloy with abou t 1 % tn urng coolng of th alloy gamma () phae crytal tart to eparate out at a tempera ture ture of about about 7 1 5 °C. At lghly lghly below below 700 °C freeng i compete and al the qud  tran formed to gamma olid phae At about 650 C the eta () phae tart to form from the gamma () () unt a temperature of 60 C  reached At abou t 60 60 °C the redual gamma () decompoe decompo e to form form mu ltaneouy the lqui d eta () phae phae

£





igue 36 Copezinc pase iagam



C

A olid alloy melt a a reult of coolng durng thee phae changea changea rather un que occurrence An alloy ytem of nteret nteret n whch a ere of pertectic tranformaton tranformaton can occ ur  th e copperinc copperinc yte ytem m (bra; ee g 0) . Mot copperinc alloy of antquity were made by a cementaton proce that had had a an upper lm t a nc content of about 8 % Znc ore wa wa mxed wth copper ore and the two were melted together drecly o that the nc wa aborbed nto the copper during reducton thu avodng o of nc whch whch bol at 907 C Mot ancient inc alloy therefore therefore poeed an alpha phae or cored dendrtic tructure. owever metallc nc wa alo produced; for example an all oy contan ing 87 % nc wa reputedly found found  n prehtorc ruin i n Tranylvana Tranylvana whle in ancent nda and China metal lc nc wa produced he brae are generally divded nto three categore categore depending on the phae type alpha brae wth up to about 3 5% nc; alpha beta brae brae wth between between 35% and 6.6 % inc; and beta brae brae wth betwee betweenn 66% and 5 0.6 % nc A nc content  ncreae ncreae the brt le  phae begin to appear and thu alloy wth wth more than



iqui alloy A alloy B

000

00

800

700

1 00% 00% Cu 0% n

20% n

0% n

Twphased aera 20

50% znc are generall generall avoded avoded Beta � �  phae brae are ver much harder than the alpha and can wthtand ver lttle coldworkng coldworkng he beta phae begn to often often at about 0 °C (a the lat tce change from an ordered to a dordered tate and at about 800 °C t become much eaer to work. The alpha brae whch nclude mot of the ancent pecmen are much bett er when the are coldworked and annealed rather than hotworked becaue f hotworked mpur te tend to egregate egregate at the gran b oundare and make the b ra ver weak weak hee tpe of tructure are eentall m lar to the poblte gven for the ecton of the coppertn dagram examned examned bre earler (g . 33  An allo of compoton A wll havng paed below below the lqudu lne begn to precp tate out alpha gran, whch are then partall attacked and converted to beta durng oldca ton o that the reultng tructure tructure cont of alpha beta gran gran (Fg . 36 .



Wdmansttten Tansfomatons Tansfomatons he copperznc allo ma appl to a bref d cuon of the Wdmanttten tranformaton. tranformaton. he Wdmanttten Wdmanttten tructur e reult from from the precptaton of a new old phae wthn the gran of the the extng old phae.  t  thu qute df d fferent from the martentc martent c tranformat tranformat on whch  eentall a nglephaed tructure uu all occurrng a a nonequlbrum co mponent of quenched allo. Martente  a collecton of n e nterectng needle that can form  n allo cooled ver quckl. quckl. Uuall the allo  quenched b

plungng  t nto water or ol from from a red heat  n contrat, the Wdmanttten precptaton  the reult of one old phae at a hgh temperature decompong nto two old ph ae ae at a lower temperature Th precptaton uuall occur at the gran b oundare of the the ntal crtal crtal and a plate or needle wthn the gran themelve, whch have a partcular orentaton dependng on the crtallographc tructure of the orgnal cr tal n the cae of allo B (g. 36 , a mxture of about 5 8% copper and % znc we can follow follow the precptaton of the alpha old oluton from the beta hgh temperature regon n Fgure 3a the beta gran are are hown a the would appear at at about 8 00 °C o r f the allo wa uddenl quenched n water whch would prevent t from from decompong nto the alpha beta beta regon The appearance of the gran   ut a homogeneou old oluton of beta beta gran F gure 3b how the nature of the Wdmanttten Wdmanttten pre cptaton upon coolng to room temperature. f the tructure  annealed or heated to about 600 °C then t can become qute coare and the alpha phae ma grow nto large crtal wth the back ground becomng a ne mxture of alpha beta. Wdmanttten tructure alo occur n ancent teel a a reult of the workng proce proce o r delberate delberate he at treatment ued dur ng manufac manufac ture. Ver often Wdmanttten precptaton  onl partall carred carred through thr ough the gran gran o that a agged eff effect  produ ced. t  ueful ueful to return r eturn to the roncarbon dagram (g 30 at th tage n order to dene a few common term Steel





Figre 37 � grai i coe- inc

 origial origial � grai grai at at 800 800 C

origia � gain bouarie

matrix robably mi x of

�

wphasedaea 2

contanng contanng l carbon than th amount ndd to mak th utctod tructur comlt ar calld hypoeu po euecoid ecoid sees s ees whra tho contanng car bon  n xc of th utctod comoton (and u to  7% carbon) ar uually calld hypereuec Th uctod comoton tlf occur oid sees Th at 08 % carbon n hyoutctod tl tl thr wll gnrally b mor frrt frrt than  rqurd and th  calld th proeuecoid (or fr) rrie n hyr hyr utctod tl thr wll gnrally b too much cmntt to form form a comlt utctod an d th  calld p roeuecoid roeuecoid cemenie cemen ie Proutctod Prout ctod frrt occur n vral dff dffrnt ha n th lowr carbon tl tl of antquty antquty t  charactrtcally found a xtnv ara among cattrd land of arlt h accordng to Samul Samul ( 1 980 ) hould b call calldd massedrrie massedrrie  n tl narng utctod comoton t h frrt frrt  uually foun foundd a thck th ck lm locatd at what wr orgnally th auseniic grains grains Th  calld oun d grain grainb boun oun  rrie rrie Frrt may alo b found n th form form o f broad ndl whch can b c ton of lat of frrt frrt occurrn occ urrngg a a Wdman tttn attrn wthn th arlt A dcrtv chm for om o m of o f th varou varo u form of frrt rr t ha bn dvlod by ub (n Samul 1980;  Andx A for for nam of o f frrt ha n low l ow car bon tl tl and a gloary gloary of trm)

Dsconnuous Prcpaon



Anothr ty of ha ha arato n of mortanc  dcontnuou rctaton A good good xaml  aff affordd by cor lvr aloy ud n antqu an tqu ty

Vry oftn th lvr wa dbad to  om xtnt wth cor artly to mak th alloy hardr and alo to rduc th amoun t of lvr bad lvr obct thn oftn cont of lvrrch gran n whch th cor ha not yt bgun to arat arat out a t hould accordng to th ha dagram Th oluton of cor n th lvr gran  thrfor n a mtatabl tat and can b rc tatd tatd lowly wth wth tm at th gran boundar Prctaton of th natur  calld dcontnu ou whn t occur at th gran bou ndar h ntal ntal art o f th ha dagram  hown blow (Fg 38) A tycal lghtly dbad lvr alloy  hown by alloy A on th lvrcor ha dagram Not that t cut acro th � ha rgon whr t cool down down to room tmratur. t can xt a a a homognou old ol uton alha ha btwn btwn tmratur tmratur t and t Whn th alloy gt to t  th dcomoton of art of th old oluton nto bta may not occur and ntad a mtatabl mtatabl old oluton wll rult  h cor rch ha may rctat out vry lowly at room tmratur tmratur  and Schwzr Schwzr and Myr Myr ( 1 978) uggt that th dcontnuou rctaton of cor can b ud to tablh th  authntcty of ancnt lvr Thy Th y xtraolat xtraolat from from xrmntal xrmntal  data to gv a growth growth rat of about 1 0 mcron r yar for for th rat o f rctaton h knd of growth can lad to agmbrttlmnt of ancnt mtal mtal homon and Chattr Chattr  ( 1 95) alo found that lad formd formd at th gr an boundar bou ndar of mur lvr and ld to mbrttlmnt



Figue Discotiuous recitatio i AgC T C

 00% Ag

 00% Cu

Twh whasd asd ara 22

Intemetllic Compound Fomton When some metals are mxed together they can form phases that are essentaly lke ordnary chemcal substanc s ubstances es n that they are effectvely effectvely compounds of xed composton An example s the goldcopper alloys hese alloys alloys were used  n antquty  especally especally n the more base copperrch compostons  n South Amerca hs alloy was known as tumbaga and was used wdey bot h for for castngs and for hammered sheework often beng nshed by a depleton gldng process (echtman 1973 Scott 1983; see g 39) h e dagram dagram shows that copper and gold are completely souble n each other wth a eutectctype low metng pont whch occurs at a composton ston of 80 1 % gold at at 9 1 1 °C he he rounded rounded shapes at the b ottom o f the dagram show the regons where the ordered phases can form here are essentaly three dfferent ordered compos tons: CAu CuAu and CuAu CuAu can form beween about 8 5% to 9% gold It s a superlattce formed by a pertetod (a sold state

pertectc reacton) at about 0 °C (Rhnes Bond and Rummel Rummel 1 95 5)  CAu can can form form beween 50% and 50 8% gold CuAu can can form form beween 70% to 85% gold Ordered phases such as these have to be ds tngushed from from those phases normaly called ntermetallc ntermetallc componds In termetalc termetalc com pounds are usualy represented on the phase da gram by a straght ne that passes down vertcaly as the temperature falls here may be wo such lnes close together that mark out a rectanguar block on the phase dagram showng the areas over whch the ntermetalc compound may form orm  he o rdered phases are rather df d fferent because they may be formed over wder compostonal lmts they do not show vertcal vertcal phase boundares  n the form form of straght straght lnes and they may pass easly beween ordered regons and ds ordered regons owever these ordered phases are usualy harder than the d sordered alloy of the same composton and they may make the process of

Fgure 3 Cu-Au ase agam.

T C



1 00% 00% Cu

CuA

1 00% 00% Au

Tw-phae Mateia 23

workng and annealng to hape more dcult. For example the quenched alloy n the gold copper ytem ytem beween beween about 8 5% gold and 5 0% gol d are ofter ofter than t he alloy that are allowed to cool lowly n ar. Th  the oppote of the tu aton that ext n alloy uch a ron and carbon where the materal i dramatcally hardened by quenchng becau e of the formaton of new phae martente The reaon why goldcopper alloy are ofter i that the quenchng proce up pree the formaton o f the ordered ph ae whch need ome tme to form and t  thee ordered phae that gve re to higher hardne value and to the dculty ometme experenced n the workng of thee goldcopper goldc opper alloy. South Amer can Ind an n lowland Colomba for for example ued water quenching after annealng n order to make the alloy eaier to work to hape and to avod embrttlement There are many example of ntermetallc compound uch a cementte (FeC whch contan 66% carbon and the delta phae n bronze whch  an intermetallc compound of the formula C  Sn  

mmscble Stuctues n ome cae metal may be completely nolu ble n each other. Example Example o f th type of mcro tructure are hown by the alloy of copper and lead zinc and lead and ron an d copper A the temperature fall from from the melt of thee mutually mutual ly noluble metal one ofthem of them wll be precptated

uually a globul e of one phae n gran of the hgher melting pont metal An example  leaded copper hown n Figure 0. The dagram dagram how that t he mcrotructure cont of wo wo dtnct phae and that the copper gran that form wll contan globule of lead. Practically all the copper wll old before the leadcopper eutectc form. Thi leadcopper eutectc  for all practcal purpoe pure lead a t conit conit of 999% lead and 0 1 % copper Th mean that the lead  egregated whle the olidi caton proce  takng place Ordnarly the eparaton of lead globule would be expected expected to reult n mave egregaton and and an unuable materal would reult There  a monotectc reac ton at at 95 5 whch occur when the lqud from which the copper  eparatng out reache a compoton of3 6% lead. lead. At thi pont a new liq ud form form that contan about 8 % lead. Thi new lqud  heave than the rt lqud and o t tend to nk under gravty owever n prac tce the gro egregation i lmted by the forma ton of a denditc tructure upon cating n the copperrch alloy and wth a hgh cooling rate the lead  nely dpeed among the dendrte Wth very hgh lead content alloy the two lq ud that eparate out form form an emulon when they are cooled from from about 1 000 °C (Lord 1 99  Th emulon reult n a dvon nto vey ne droplet o that gro eparaton cannot occur Wth leaded copper bra or bronze alloy the lead uually occur a mall nely dpered

c

igue 40 Cu-Pb phase phase diaga. p o i nt C u 84 .5 ° c 1 084.5

Cu

+

36 Cu

eltng pont Pb (3275 (3275 °C)

Cu



_

--

_

 -

two two lqu ds 95 C

    87

iqud

3 26 26  C Cu



Pb (eutei of 999% Pb 0.  % Cu )

Pb

wpha Mateia 24

hercal globle cattered cattered at the the gra bod are ad wth the gra themelve themelve Lead ha the eff effect o f makg the alloy of coer eae r to cat t ca for examle, mrove the dty of the alloy  the melt ead alo make coer alloy eaer to work ce the lead act a a  area o f weake betwee betwee the gra. h  of o ractcal ractcal  e f the allo y  e d for for the ma fac tre of dagger or word blade ce they wll be weakeed by the clo oflead, bt t  adva tageo for for the rodct r odcto o of cat obect t  ot trctly tre that that ro  olble  coer the hae dagram dagram  more comlex tha that, althogh the ed relt o f admxtre of coer wth mall amot of ro  the reece of mall dedrte or globle of ro mxed wth the coer gra. he hae dagram  gve  Aedx G  th book he coolg of a 6% ro   coer alloy  examed by Cooke ad Achebre Achebreer er (  95)  A the 9% coer ad ad 6% ro alloy cool, t reache the lqd at abot 115 C ad old gamma ro beg to earate earate ot h gamma ro wll cota abo t 8 3% coer  old olt o. A the temeratre temeratre fall, mo re of the gamma ro rch rc h hae earate tl at 1095 C the rectatg ro cota abot 8 5 % coer At the coerrch de of the

dagram the comoto of the tll lqd co er follow follow the lqd tl at 1 095 C the co er wll cota omethg lke 3% ro   olto. At 1 08 .5 C, a ertect ertectcc reacto reacto wll wll occr betwee the lqd a d the rectated gamma gamma hae to gve a old olto of 96% co er ad % ro h mea that gve a vey low low co olg rate the alloy alloy hold cot o f a old olto (eta  hae) of 96% coer ad % ro wth redal gamma () ro artcle A the temeratre fall, the coer  gradally rectated ot of the alha ro ad at the ame tme the eta () hae loe ro  acet ecme, ecme , o far far o evdece ha come to lght to gget that the ertectc reacto had occrred Becae of the reece o f alhahae alhahae ro (fer (fer rte), the coer alloy alloy cotag ro are ally ferromagetc ad ca ometme be cked  wth a maget. Care mt be take whe grdg ad ol hg leaded alloy to ere that lead globle do ot dro ot (wthot otce beg take of ther extece)  the roce f they do fall fall ot, they leave leave mall hercal hole ad t may the become vey dclt to dtgh betwee oroty de to catg defect defect ad lead cl o a a alloyg cottet, ce both aear a hole  the olhed ecto.

(e

4 HE MCRORUCURE OF N BRONZE

Some o f the the features features to be found n alloys alloys o f cop per and tn commonly referred referred to as brone or more correctly as tn br one have been dscussed n prevous chapters The phase dagram for the coppertn system s rather complex and cannot be dscussed fully fully here and the one gven n ths book gnores the owtemperature phase eld of the alpha epslon £ phase regon regon Fg 33 and Fgs 1 98  99 n Appendx Appendx G). hs s because the £ phase never appears n bro nes of up to abou  8% tn that have been manufactured manufactured by conventonal means Thousands o f hours of annealng are necessary n order to make the £ phase appear and of course such condtons never occur even n modern brones Despte ths common forms o f equlbrum dagrams contan no clue that equlbr um s practcaly practcaly never attaned Even more surprsngly some modern metallurgcal textbooks appear to be unknowledgeable unknowledgeable on th e subect and mantan that an aloy wth % tn wl decompose on co ol ng from from the usual alpha delta regon to gve alpha and eta wthout dfculty! dfculty! Tn brones may convenenty be dvded nto two regons lowtn brones and hghtn brones Lowtn brones are those n whch the tn content s less than than 1 7% hs s the maxmum theoretca lmt o f the solublty o f tn n the copperrch copperrch sod soluton n practce the usual lmt of sold soluton s nearer to 1 4% although t s rare to nd a brone wth ths tn content n a homogeneous sngle phase When a tn brone s cast the alloy s exten exten svely segregated usualy wth cored dendrtc growth and an nll of the the alpha delta eutectod surrounds the dendrt c arms The center of the dendrte arms are copperrch snce copper has the hgher meltng pont a nd the successve successve growth of the arms resuts n the deposton of more t n At lowtn contents for example between  and 5%  t may be possble for all the tn to b e absorbed nto the dendrtc growth Ths vares consderaby dependng on the cooln g rate of the brone a nd the knd of castng nvolved f th e coolng rate s vey slow there s a greater chance chance of reachng reachng equlbru m and the amou nt

   

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of nterdendrtc nterdendrtc delta phase wll be much reduced reduced or dsappear entrely owever owever at t n contents of about 1 0% t s very unusual n cast ngs from from antquty antquty to get absorpton of all all the delta phase and the dendrtes wll usualy be sur rounded by a matr x of the the alpha delta eutec tod As the tn content ncreases the proporton of nterdendrtc eutectod also ncreases  f a homo geneous coppertn alloy s worked by hammerng and annealng then the typcal features seen n facecentered cubc metals wl be developed; namey anneang twns stran lnes progres svely ner grans as a result of workng workng a nd at tened grans f left n the worked condton as dscussed dscuss ed earler The same features features wll develop f the aloy s twophased athough the eutectod s rather brttle and may be broken up to some extent The usua mcrostructure shows the pres ence of small sands of alpha delta eutectod between the recystaled grans o f the alpha sol d soluton f corng n the orgnal cast ngot was pronounced then ths may be carred over over n the worked aloy as a fant or "ghost dendrtc pat tern supermposed upon the recrystall recrystalled ed grans When a brone secton s etched wth ferrc cho rde ths dfference n alloy composton due to corng cor ng may only be app arent as vague d erences erences n shadng of the alloy and a dendrtc outne of the shadng may be vey dcult to see Some experence experence n the examnaton ofbrones of brones must be deveoped so t hat a worker can df d ffferentate between between uneven etchng an d uneven colorng of the specmen surface due to corng Apart from from compcatons ntroduced by other alloyng elements such as nc the struc tural features features seen n most lowtn brones are the followng

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J

2 3

omogeneous brones n whch all the tn has dssolved wth the copper and whch do not dsplay corng or resdual cast features. Cored brones n whch there s an unequa dstrbuton dstrbuton of copper copper and t n but no eutec tod phase present Brones n whch both the alpha phase and

e suu   n Bn 2

4

the eueoid phae are preent. Bronze n whih the alpha phae i exten ively ored and where the euteoid phae i preent.

Mot anient alloy have le le than 1 7% tin . At thi level of n onen bronze an be old worked and annealed; however, if the tin ontent  beween 1 % and 1 9% it ha been found found that the alloy i unworkable it an nether be hot worked nor oldworked. A lm of delta form and th brittle phae then oat the grain bound arie with the reul that the alloy break up no piee. However However above 1 9% tin th e bronze bronze an be hotworked. hotworked. Bell  and mirror in antiq uity were ofen ofen made of ternay ternay tin bron ze onitin oni tingg ofabout of about 05% tin 1 0% lead, the remainde remainderr being opper. Alloy Alloy of th type were almot invariably invariably at. B inary tin bronze ontaining more than 1 7% tin often often have about 3% tin whih orrepond orrepond loely o the equilib rium value of he beta phae of the bronze ytem, whh ha been mentioned in onnetion with periteti tranformaion. tranformaion. Above 586 °C a bronze in the beta region an be readily worked wherea ifallowed if allowed o ool lowly o roo m temper ature he bronze would deompoe into alpha and delta and be impoible o work. On e advan advan tage of beta bronze i hat the beta phae an be retained by quenhing A omplete aount of thi proe proe i quite omplex b u on e ofthe ofthe mot mportant poin  i hat the beta phae i retained by quenhing a a truture of marteniti marteniti nee dle. Thi quenhed quenhed beta bronze i very hard bu t a lot le britt le than the ame bronz e lowly lowly ooled o the alpha euteoid room temperature form. Apart from from a few at gur ine the maor ty of artifat artifat of beta bronze ompoition were made by the following erie of operation he alloy wa wa made up a aurately a the tehnol ogy of the time allowed a blank wa then at in the approximate form of the deired obet, and the obet wa haped by howorking at a tempera ture of abou 6 50 °C At the end of he working proe  the alloy wa uni formly reheated o abou t the ame temperature and wa then rapidly quenhed o preerve the hightemperature

phae and o produe a marteniti truture). Hammer mark and oxde ale ould then be removed by grinding with abraive of variou grade, often on a imple lathe, and then the obet wa polihed Surfae deoration, if preent wa ut into the urfae urfae with drill o r an abraive wheel before nal polihing Although ert ain veel veel made from from th i alloy poeed interetng interetng muial propertie the prin  ple reaon for for it ue in region where tin wa plentiful, wa it olor The olor of typial beta bronze reemble gold Beta bronze were rt found in ndia an d Thailand from from the early en turie and they pread lowly o the Near Eat. The lami alloy white bronze, sadruy, i an example of a hight in alloy. t wa alo found found in Java and Korea but when bra beame more widely widely known, hightin bro nze ue beame muh more limited The alloy known a specuLum, whih may on tain up o about 3 5% tin i aid by ome o have have been ued by the Roman for for the manufa m anufature ture of mirror However, Roman mirror were often made by tinning; the alloy itelf wa often a low tin bronze At high level of tin uh a thoe enountered in tinned urfae the following intermetalli phae of the oppertin ytem ytem mu be onidered aref arefully ully ( 1 ) the delta ) phae whih ha already been diued diu ed  Cu   Sn ontaining about 36% ti n; ) t he epilon epilon ) phae phae CSn ontaining about about 38 % tin; (3) the eta ) phae phae ontain ontaining ing 61 0% tin, CSn Here , in t inned urfae, urfae, the epilon phae doe appear and i important in undert anding the mirotruture. When tin i applied o bronze, layer layer of both the eta and the epi lon phae an develop by interd iff iffuion between the bronze and the molten tin, whih then an develop layered truture in the following equene urfae tin eta phae epilon pha e ubtrate bronze. Under the optial miroope, tin i light and ilvery ilvery in appearane the eta ompoun d i lightly more greyblue greyblue in olor, the epilon phae i the darket grey greyblue blue and the delta i light blue. The range of feature feature that may form form o n tinned urfae urfae i ompliated: CSn i ommon and i



8'

he Mirtructure in Bne 27



often msdescrbed as tn see Meeks 986). Many tn bronzes are leaded. Wth lowtn bronzes ypcally castngs the lead does not aloy wth the copper or tn and occurs as small globues throughout the sruct ure. S ome gravy gravy segregaton segregaton may take the lead down down to the base o r bottom of the castng but generally n cast structures the ds rbuton s ne and random. Wth a hgher percentage percentage of tn the structure may become dcut to understand f lead lead s present as well. Ths s especally true fthe f the bronzes are quenched. There are severa Roman mrrors made n bronzes approxmatng to 2.7% tn 3. 2% lead, and 73. 7% copper. When quenched quenched from ntermedate temperatures, a very ne part ce matrx develops that s dcult to resolve under the optcal mcroscope. hs s due to the very ne dsperson of the lead and the develop ment o f a Wdmansttten Wdmansttten sructure n the bronzes. f quenchng of brones of beta compos ton s not sucent to retan beta, then decompo ston ston nto nt o a Wdmansttten sructure of ofne alpha and delta may may occur. Some Roman m rrors have ths knd of sructure. he stuaton s even even more compcated  n fact, fact, because n leadedtn bronzes the meltng pont s of the alloys alloys are much lower than n the bnary system. system. he ternay phase da Fige  1  gh. gh. Cas og ogge ge pn fo Ian Bonze wih 3 7% i and  3% aseni. aseni. Eh FeCI FeCI x 120 Fig e 2 fa fa gh Chi ese as one inese bn e of of e 1 9h enuy Bonze wi 8% i and % lea Eh: FeCI  x80

gram shows that the presence of wo lquds for many compostons composton s above above 73 °C may prevent prevent quenchng from from temperatures hgh enough enough to retan beta (see Appendx G Fg 2 2 . Fgure  shows a secton through a cast toggle pn from from Iran  etched n FeCl FeCl  at x50. he net work of the eutectod can cearly be seen n the nterdendrtc regons. he togge pn has a composton of92.3% copper, 3.7% tn 0.6% znc, znc, 0.% 0. % ron and 1 .3% .3 % arsenc. Note Note that that the the phase (the copperrch component appears lght n color except near the eutectod where some cor ng occurs. The corng looks as though some of the tn s beng depeted n the regon o f the eutectod as some tn from the sold soluton regon mgrates to on up wth he darker regons around the phases are copperrch compared to the rest o f the bronze. The bronze sructure of the ncense burner n Fgure 2 s atypcal consstng of small polygo polygo na grans wth patches of the eutectod beween them and nterspersed wth small globules oflead. hs leaded bro nze mus t have been cast followed followed by an anneang process durng manufacture see Fgs. Fgs. 1 09, 1 1 0 n Append Appendxx F . There There are are ver veryy fe few traces of wnned gran s present present and these are not as promnent as the corng that stl remans from

J

J a+ 0

a

a+ 0

a  a

a+0

e Mr/re / in Brne 28

igue 43 top top ight A sall  io of eta-quenhe d oze fo ata fo ota Cna a 1 0th entuy AD AD tadig oplex x150 igue 44 top fa ight A high tin onze i o fo ava showing the lassi developet of the the etaquehed etaquehed onze stutue stutue in the iostutue iostutue x 1 30 igue 45 elow ight Cast high tn leaded oze of opositio 22% tin; 6% ead and 72% oppe showing stutue afte afte ethig i aloholi  eCI x80 x80 igue 46 elow fa ight Laoatoy quen hed aloy of oposition 24% ti 76% oppe that has een quenhed i  old wate at 650 °C showing a ine netwo netwo of  needles he  phase in this sape oupies the stutue opetely with onl y a few few gloules of oppe oxide pesent as as an i puity x 1 80

the cat metal. The broe mirror i  igure 43 ha lightly e tha the required amout of ti to make a com plete beta phae throughout throughout ad mall ilad of phae ca be ee that ofte follow the previou grai boudarie of the the high temperature  grai before before quechig the alloy. The type o f  eedle developed here i ometime mitake for trai lie i i  a copper alloy but the cotext ad type of lie to be ee i u mitakable I t i etched with eC eC at x 1 50; about 5% ti ti  .5% copper copper The ilad that are alo preet i may of the highti beta broze uch a the mirror i ig ure 43 are ometime wied a a reult of hot workig the broze before before quechig. The mirror

a

a

poee poee a highly lutro u dark gree patia. epite beig a metatable phae beta br oze remai quite table after thouad of year of burial. igure 45 ad 46 are example oflaboratory made broze broze igot igot origially origi ally produced to tudy the tructural apect of aciet alloy or example igure 45 wa cat i a highti leaded broe to replicate ome of the tructure that were fou foudd i a erie of Roma mirror. igure 46 illutrate il lutrate the microtructure for for a labor atory prepared alloy made made from from a igot of 4% ti  6% copper queched i cold water water at 650 °C The tructure of thi  alloy alloy coit of a e iterlockg ework of  eedle.

The Micrtructure Tn Brne 29

gue 7 top ght Japanes e swod bad e fagent fagent of the 1 8th entuy ose to the ente of the blade showng folds  n the fete ga stutue as a  esult of the fogg fogg opeatos used to ae the blade th: ntal x 1 50. gue 8 top fa ght apaese swod bla de fagent fagent lose to the uttng edge showg ath aten ste whh has bee tepeed Note the geat dffeene  st tue betwee the ente ad uttng tp of the swod Eth pa; x300 gue 9 below ght at of the seton of a Japanese swod blad e showng tanston one ea to ttng edge whee tooste vey fne esolvable peate) nod es a be seen togethe togethe wth Wd ansttten pealte Eth pal x220 gue 50 beow fa fa ght Japanese swod blade seton futhe ba fo the uttg edge and lose to the the ente than ge 8 He e the whte phase s pe fete gans wth a nf ll of the eutetod eutetod pealte fne gey oes) Note the two-phased two-phased slag stnges n the seton Eth pal x220

5

OE ON HE SRUCURE OF ARON SEEL

h ty ofruc of ructur tur n n n gur 5 1 , blow, n lowcarbon tl, could ar from hat ratmnt n th  rgon of th ha dagram At room tmratur, th tructur wll b frrt ar t and aftr hatng th wll bcom:

+

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and aftr coolng th gamma ha wll rvrt to:

igue 52 G ai bo uda stutue with subgai eatues



urng coong om o f th th frrt wll tak a Wdmantttn Wdmantttn ructur. ete ()

alha C. h cton n gur 5 3 how mall gran z n th cut tng dg and a largr gran z n th body of a knf knf hr    om tmrd t mrd mar tnt on th dg

slightl Wid astte astte  sall gais at edge

ige 5   Patal Widasttt Widasttte e steel

f th coolng rat  vry fat fat thn martnt can form form Evn f th coong rat   too lo w for for th tranformaton to occur th roorton of arlt an d frrt frrt n th old wll no t b rnt n qulbrum amount h rnc rnc of mor mor arl t than frrt frrt wll lad to an ovrtmaton of th th carbon contnt h tructur n gur 5 how gran boundary cmntt cmntt (C) wth a ubgran tructur o f cmntt cmntt arlt How can th ty of ructur ar? Whn coolng down an aloy from th gamma  rgon, th alloy con tan mor than 08% carbon Uon dcomo ton o f th gamma ha, C wl b  formd formd at th orgnal aut ntc gran bou ndar aftr aftr cool ng from from tmratur abov 900 C If th aloy, tycally tycally wth about 1 2 % carbon contnt,  coold down and thn ubquntly rhatd rhatd to abou 800 C (n th th gamma gamma alha C rgon ), thn mor C wll b formd formd on a nr ca, whl th orgnal autntc gran bound ar wl b rrvd, rrvd, o that on ubqunt coong, th gamma ha ha wll dcomo to

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+

age gas s i  bod o i e

igue 53 Gai size size o ie ie edge

h ty of tructur cannot orgnat from hatng hatng t h t  of th blad blad follow ollowdd by qunch ng. If th t wa mad by hat ratmnt from from th am mtal thn th gran tructur tructur would b argr h ndcat ndcat that th cutt ng dg mut hav hav bn u  n at om ont du rng manu fac tur; t could no t hav bn mad n on c Whn tchng qunchd tructur, om ara of th martnt may tch rathr darkr than othr h can b du to tmrng tmrng of th martnt or, f fuzzy nodular ha aar, t coul d b du to t h rnc of troot root atch aar bcau th coolng rat  not qut fat fat nough to roduc a martntc truc tur hr  o ftn co nfuon nfuon btw n th trm troot and orbt It  bttr to rrv th trm orbt for ructur rultng from qunchng folowd by hat ratmnt (for xaml, martn t gong to orbt uon hatng). root hould b ud for for ructur rultng from from th rd coong of a carbon tl, but not fat

Stuctue abn Ste 32

enough for the producton of martenste martenste n the banded structure of the quenched sword blade n gure 5, the queston arses as to why f the whoe structure has been quenched, are there some areas of martenste and some that are apparenly on ly a mxtur e of ferrte ferrte pearlte There are two possble reasons for the structural dff dfferences rst  the t he dfference dfference may be b e due to carbon content The amount of carbon carbon present wll aff affect the producton producto n o f martenste when the heated heated alloy s quenched t  s possble that the carbon content n the ne ferrte pearlte regons regons s not sufcent sufcent to produce martenste Second, the shft may be due to other aloy ele ments n the regons concerned, whch would be apparent wth further analyss

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+

igue 54 54 Baded stte of a quehed swod swod blade osistg of vey fie peate ad alte ate bads bad s of atesite

n gure 55   f the alloy s of composton A then the structure wl consst ofalpha ofalpha at the gran boundares wth pearlte nl, but f the aloy aloy s of composton B  the n the structure structure wll be cement cement te at the gran boundares wth an nl o f pear te Smal changes changes n the drecton ofB make ltle dff dfference to the vsble amount amoun t of cementte cementt e at the gran boundares but a smal movement movement n the drecton ofA of A makes a arge dfference n the amount of apha at the gran bou ndares

A

   ateste (

Smlarly  f n a homogeneous specmen the coolng rate s not sucenly hgh to produce a totally martenstc structure then t s possble to get a seres of transtons between martenste rooste ferrte ferrte and n e pearlte wth ncpenly Wdmansttten ferrte between the pearlte regns

     

B

8% 8% C igue 55 Pat Pat of the e-eC phase daga.

6 MARENE N OW-CARON SEEL

Martete  a ver hard eedlelke ottuet of tee that form whe teel are quehed  water or other lqu d at room temperature temperature A teel artfat  uuall heated up to the autete rego of the phae dagram, abou 8009 50 °, the qukl pluged to old water, thu form g the extremel extremel hard martete ottuet Some of the harde ad brttlee ould the be removed to varou degree b temperg, uu all at temperature temperature betwee 00 ad 500 °C Utempered martete  dfult to eth  pral, pral, b ut t a be ethed ethed  tal or odum bulte here ar e two eetal tpe of marte te lath ad plate Mot teel below a arbo otet of 06% gve lath martete he d vdual lath aot be reolved b optal mro op eve eve at x1 000 , ad what a be ee ee  a aggregato aggregato of mall mall lath budle he umber of poble oretato for the growth of lath mar tete wth the paret autete gra are le umerou tha thoe  plate martete, whh beome the domat ottuet a arbo o tet reae ath martete ha a more regular

appearae  eto tha the plate form Mxture oflath ad plate martete our  teel up to about 1 % arbo , whl e the plate plate form predomate over 1 % arbo Sometme darker darker ethg etwork etwork   bulte or tal are ompoed of plate martete he harde of martete  determed b t arbo otet whh a var from from about abo ut 300   at 0. 1 % arbo up to about 900  at 06% arbo Ma aet artfat, however, were made uder poorl otrolled odto, ad the martete ma have tempered telf a the heated teel ooled dow to room tempera ture; th  kow a elftemperg empered martete reat muh more qukl to ethat tha the utempered varet, ad pral ethat a be ued readl, a a bulte, although aordg to Samuel  1 980) there  ol a lght lght hage  the repoe to ta urg the quehg proe t  alo po ble to reta ome o f the hghtemperature aute aute te phae Autete a ofte be made apparet wth Vllela' ethat

7

HE EPERING EPERI NG OF MARTENSITE

Ahough  he empering process simpy involves heaing he quenched arifac o emperaures ha may may lie lie bewee beweenn 1 00 and 600 °C, he processes involved are are quie sube and complex; for for exaple exaple a paricular form form of carbde, epsilon E)carbide fors fors when seels conani ng ore han 0.2% carbon are empered between between 1 00 and 25 0 °C while if he emperng emperng is carried carried ou beween 250 and 700 cemenie cemenie is fored insead of Ecarbide in he  he form form of small small paes of spheroidal paricles. I is dcul o see any ne deail deail o f hese changes changes u sng opical mcroscopy. Precipaon o f Ecarbdes can on y be deeced ndirecly since hey ech mor e darkly han

unempered marensie. Smiarly Smiarly he formaion o f ceenie a higher empering emperaures (e.g . 500 °C) gives gives dark darker er eching eching regon regons s and someimes a moled appearance can be seen a high magnicaion magnicaion a x  OOOx2000. OOOx2000. When eperng eperng is carrie carried d ou a 400 °C or high er carbon is removed removed fro fro he marensie and grains of ferrie ferrie can sar o form. These can be plaelike pla elike bu  he morphology can barely be seen under he opical mcroscope. he hardness hardness of o f epered epered marensi e decreases as he empering emperaure rises and he nu ence ha carbon conen has on he hardness of epered eper ed srucures decreases decreases considerably.

Figure 56. A goodquality stee pr ill from the lid of a Wootz Wootz cruci ble found in the Deccan area of Ind ia The pll had become embedded n the crucble li nng probaby d uring agitation agitation to test that a molten poduct had been produced he carb on content content of of the prill is over 08%. 08%. The area shown n t he photomicrograph, photomicrograph, etched wth nital at x65 shows some ferrte at prior austentic grain grain boundar ies wth cementite needles and fine pearlite as the dark phase which is not resoved at this magnfication magnfication

Figure 57 Martensite nee dles i n the cutting edge of of a medieva  knife blade from from Ardingl e y Sussex England Etched n picral at x380 magnfication magnfication he needl es are only just resovabe at this magnifcaton c aton he overall effect effect s however, typica for martensite i n lowcar bon steels; compae ths with martensite martensite seen i n the cutsteel bead shown in Figure 59 This i s lath martenste. martenste.

dc,

 prng n 3

Figue 58 Photoogaph Photoogaph of pat of of a sall is fo di a showig the high abo otet of the blade Boe fagets fagets of eetite eetite eed es ou as white agula fagets fagets thoughout the setio oieted aog the dietio of woig of the blade The da bagoud bagoud is fiely divded peal ite wth patialy o slag otet. otet. Eth ital  1 50



Fgue 60 Feh ut-steel bead of the 1 8th ety showg well developed plate atesite at a agifato  of x20 ethed ethed i pi al he abo otet of the ut-stee ut-stee bead  s about  2% abo a vey high abo steel opaed with ost othe Euopea poduts of the tie

Figu e 59. A oss setio though a 1 8th ety ety eh ut steel bead sho wig pat of the suppo t wie (ete ad the otagoal faeted faeted bead i se tio Lightly ethed x20

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

STRUCTURE AND PROERTIE OF AT RON

I i s emakabe emakabe a acie Ciese mealsms i e Ha Wei peod (206 534 ) ad i e Wese Ha dyasy (06 4 ) wee aleady poduci speodal ape cas io J us as emakable emakable ae wieea wieea maleable cas ios fom e Povce ofHbe dai o e Wai Wai Saes peiod of 452 2 1 (Hoye ad J uemi 1  3)  Ealy appaaus appaaus fo fo povidi ecie ecie bass of ai eabled e aai me of ve veyy i empeaues Te commecal poducio of cas o i e Wes did o commece ul e 13 ceuy cosideably ae Bu wa is cas io ad wa ae e df df fee micosuces associaed wi s mae al? Cas ios ave  peceaes of cabo cabo eae a a % bu eeally eeally less less a 5%ad ae casabe casabe solely becase ey ca ca b e kep i  a lid sae a empeaues as ow as abou 1 1 4 °C (w a cabo cabo coe of 45%) Cas ios ae d if ifcu o desc ibe fuly fuly wiou so me aalyses aalyses fo fo ad dioal alloyi  elemes  a ae ofe pese besides cabo ad a ca cae cosideably bo e pysical popeies ad e micosucue Peseday cas io poduced i a blas fu ace is esseially esseially pi io ad may coai sili co sulfu pospous maaese ickel ad comium i addiio  o cabo ad eac of ese elemes elemes poduces caes i mcosucue Te mos impoa alloyi addiios o impuies as fa fa as acie ad isoical peod cas os ae coceed ae silico sulfu sulfu ad pospous Te special popeies of cas ios may be smmazed as folows

AD AD 

AD

 

   

Tey may may be cas io sape i mold s Tey ave ood uidy ad we cabo is pecpiaed pecpiaed ey expad o coo li ad us ake a ood ood mold impessio  Tei mei poi is low o e ode of 1200 1200 °C °C Tey ave ave ood wea popeies s ce apie is a ood lubca Tey ave a  dampi capaciy Tey ave a easoable se i compesso aou ey ae ae weak weak i esi o





Tey ca be mixed wi wou o a d eaed o po duce a seel by lowei e ca bo coe Gey cas ios may coode badly ad ey pese dicul pobems fo fo e coservao

Tee ae ee picipa oups of cas cas io  ey ey cas io wie cas io ad moled cas io (mied aeas of we ad ey) ey)  e ey cas ios ee is fee apie i e sucuesome of e cabo bei ejeced ejeced fom soluio ad solidii as lakes ofapie of apie I wie cas ios all e cabo occus as cemeie I e moled mixed oup bo apie akes ad cemei e ca be fou fou d i di ffee eios of e same sample somemes delibeaey made made by cilli pa o f e mold ad iceas e cooi ae wic favos ceme ie fomaio Tee ae two impo a facos iueci e fomaio fomaio of apie ad cemeie solidi caio ae ad composio Sice e ioca bo pase diaam diaam (i 30 ) i copoai feie feie ad apie as sable poducs is e eaes o euilibium slow cooli favo favoss apie poducio wile apid coo i favo favoss e measable feie ad cemeie sysem Te mos impoa  elemes i cas ios ae cabo ad sil ico a i co e of eie fa favo i apie fomaio fomaio Oe alloyi o impu iy elemes a sabilie apie ae ickel alumiium coppe ad iaium Maaese sabilizes cemeie aou  e siuai o is moe complicaed if sulfu sulfu is pese as well Sulfu Sulfu sabilies cemeie as well bu sulfu also as a s o af afi ty fo fo maaese ma aese ad foms maaese maaese sulde paicles if bo ele mes ae pese Ti s compoud  as a esul as lile iuece o cabo Pimay addiios fo eample of sulfu o a io wi a i maaese coe  ed o sabilize apie fomaio fomaio Pospou s acs cemicaly o pomoe cabide fomaio fomaio bu e pesece of pospous poduces a eay pospide euecic euecic (seadie) bewee feie feie (usually wi some pospous coe)  ceme ie ad io pospide Fe Fe  P FeC) is

a +

+

Sruur nd Prp Prprs rs 0/s rn 38

+

tenay tenay eutecic eutecic melts at 60 °C and and us is te last constituent to soidi Tis esults in te eC solidiing slowly and alows any silicon pesent to pomo te gapit e fomation fomation Wi t low amounts of pospous about 0  1 %) gapite can acualy be enanced ate tan destabilized. icke, ike silicon, dissolves easily in feite feite and aso acts to stabilie gapite Because of te compexities intoduced by aloying elements beside cabon a cabon euiva lent vaue CE) is often uoted instead: E  oa 

+ +

(Si  3

-

Tis CE value may en be used to detemine wee an ion is ypoeutectic o ypeeutectic ypeeutectic In genea, te lowe te CE value, te geate te endency fo an ion o solidi as a wite cast ion o as a mottled ion. Ions t at ae ypeeutectic cabon euiva lent moe tan 443%) wil pecipitate kis gapite  on solidicaion wit nomal cooling ates Hypeeutectic Hypeeutectic cast ions solid i by diect fomation omatio n of o f gapite fom te melt me lt in te fom fom ofkis, wic as a low density and and can ise to t e suface. Wen entapped by metal it genealy appeas as long wavy o umpy akes. Tis pase is pecipitated ove a ange of tempeaues tat will be examined examined wit te aid of a pase diagam diagam ig. 61) late in tis section sating at te liuidus su face face and continuing unt il te emaining melt i s at te eutectic point wen cystallizacystallization of gapite and austenite occus. Tis eutectic gapite in ypeeutectic cast ions is usually ne tan pimay kis gapite. As an example of te application of te CE fomula conside a wite cast in fom Nang Yang City, City, Henan ovince, Ci na dating fom fom te Easten Han dynasty 4 40 0 ) Te Te object is a cauldon wit te following elemental analysis: C 4% Si 014%, Mn 00%, S 0 06% ,  046% Hongye Hongye and Jueming 13)

D

E  419

+

014

+

3

048

39

Tis CE value places te Han cauldon in te ypeeutectic ypeeutectic egion altoug since te ledebuite eutectic occus at 43% cabon at a tem peatue peatue of 1 140 C)  te alloy alloy is uite close close to te eutectic egion egion . edebuite i s a eutectic com pising ion cabide and austenite

Mcostuctul Consttuents Te constituents apat apat fom fom gapite and tansfomed ledebuite ae simi la to steels and i n a typical gey cast ion would include gapite lakes as well as v aying amounts of feite feite a nd pealite. Te feite feite may be ade tan in odinay steels steels because of te silicon content. Te usual wite cast ion constituents ae pealite and cementite. Te gey cast ions may ave te following constituents:



lake gapite fomed fomed duing solidi cation can detemine te popeties of te ion by its sape, size, uantity and distibution. Gapite akes ae usualy found in te following foms: foms: andomly distibuted denditic o osette. 2. ealite wic may vay in composition be tween tween 0 5 and 0 % because because of alloy alloy content 3 Steadite, te tenay pospide eutectic pevi ously discussed. 4 ee feite, feite, wic appeas in appeciable amounts only in lowstengt cast cast ions. Te feite is usually ounded in appeaance com paed wit steadite o cementite because it pecipitates fom fom te austenite soli d soution ate tan fom fom a liu id It is often often found found in association wit gapite akes. ee cement ite is unusual in gey cast ions. epaation of gey cast io ns by metallo gapic polising can give ise to poblems because te gapite akes akes may be smeaed o emoved emoved pefeentially pefeentially upon po lis ing Vey co oded gey gey cast io ns can a lso be vey difcult difcult to etain in a plas tic mount because tey may consist ofl ittle moe tan a loose mass of in oxides in a gapite matix. Tese ave a tendency to lose pat of te fiable fiable s uface uface upon polis ing wi t te conseuent diculty of obtaining a good polis

Stuue an a n Ppetie a a n 39

ess crrded specimens p lished with diamnd abrasives abrasives usually d nt present majr diculties A gd test t determine if graphite is pl ished crrectly is t eamine the sample in  reected ected plarized light. Grap hite is anis trpic and ehibits reectin plechrism  When eamined under rdinary bright eld eld il lumina tin with unplarized light grap hite akes kes appear t have a un ifrm ifrm brwnishgrey clr. f the same sample is then eamined under plane plar ized light sme graphite akes kes appear light sme dark and sme have an intermediate clr If the sample is rtated 0° the akes frmerly dark becme light. The relatinship between between the plane f plarizatin plarizatin f the incident light an d the psi tin f maimum maimum r mini mum brightness is such that when the plane  f plarizatin plarizatin is at right angles t the graphite akes kes they appear dark and when parallel they appear light elsn 1  5)  f the same sample is eamined eamined under plarized light between crssed crssed plars upn rtatin thrugh 360° each graphite ake will lighten fur times this is epected frm the heagnal anistrpy anistrpy f graphite Picral is prbably the best etchant fr fr pre dminantly pearlitic grey malleable malleable and du ctile irns. Picral des nt damage graphite which nital can but fr ferritic ferritic grey cast irns nital i s prefer prefer able If the irn is sufciently sufciently belw the euectic value has a very lw silicn silicn c ntent an d cntains appreciable carbide stabilizers r if the cling rate is fast fast then instead  f graphite akes slidi  catin ccurs by frmatin frmatin  f austenite dendrites. Meanwhile the interdendritic regins slidi as ledeburite a eutectic miture f irn carbide and austenite. In appearance ledeburite etched etched in nital wuld cnsist flig ht etching cementite in a backgrund backgru nd f unreslved and t ransfrmed ransfrmed auste auste  nite which usually appears as dark etching pearlite cast irn cls the austenite transfrms transfrms t ferrite and cementite The structure f a white cast irn at rm temperature therefre usually cnsists f primary dendrites f pearlite with interdendritic transfrmed transfrmed ledeb urite.

A

Heat Teatment of Cast Ion Castings prduced in white white cast irn can be made malleabl malleablee t sme etent by a numbe r f tech tech niues Tw such methds are knwn as white heart and blackheart. These names refer t the respective fractures  f the di fferent irns after after annealing the whiteheart variey variey being white and crystalline due t the presence f pearlite and the blackheart being grey r black due t graphite I n whiteheart structures annealing idizes sme f the carbn pr ducing a ferrite ferrite structure that grad ually changes t a steellike mass f ferrite and pearlite pearlite with interspersed ndules ndules f  f graphite. In blackheart structures the heat treatment des nt result in much carbn idatin and depending n ther allying cnstituents such as silicn and sulfur the cementit e may break break dwn t graphite aggregate aggregate ndules in a matri f ferrite and pearlite

Tempe Cabon Nodules When cast irn is in the white cnditin anneal ing at temperatures temperatures in the range range f 005 0 °C may prduce graphite nucleati n. At this temper ature white cast irn usually cnsists f a eutectic matri f cementite austenite and if many many impu rities are present inclusins ucleatin fgraph f graph ite then ccurs at the austenite/cementite interfaces interfaces and at in clusin s. Cementite gradually disslves in the austenite and the carbn diffuses t the graphite nuclei t prduce ndules. This kind  f prcess f heat treatment appears appears t b e respnsible fr fr the spheridal graphite cast ir ns made in ancie nt China. Ancient Chinese smiths culd cast a white cast irn an d then by high temperature temperature heat treatment prduce sp heridal graphite The graphite is slightly plygnal in shape bu t in all ther respects is the same as the spheridal graphite cast irn prduced tday by allying a variey f elements such as cerium r magnesium with cast ir n. The se allying ele ele ments d nt ccur in ancient ancient Chinese eamples Analysis by SEM indicates that spheri dal graph ite nuclei are latent i n white cast irns having car bn lw silicn and the reuired rati rati f manganese t sulfur.

Stuctu Stuct u an a n Popt oat oat on 4

 the crotructure of a tcal cat ro whch cool ow quckl quckl the oeq ulbru hae FeC te to reoate the equb ru cottuet  free grahte e AB ha bee raw o the roro  carbe agra that rereet the coolg of a tcal cat ro (Fg 6 1 )  At teerat teerature ure t the qu ateral tart to ol a autete gra or rather e rte tart to for for urroue  urroue b lqu  A the teerature teeratur e fa fa th q u cool a  reace the tage at wch a le eutectc ecooto occur T eutectc  calle eeburte a co t o f autete autete  FeC

L  Y  L (enrte of  n qu At t  +   Fe C  + y  Fe

At t

A the teerature fall fall betwee t a t o  the grah o the caro cotet of the autete ecreae a ore FeC  rectate fro

both o f te cottuet cottuet reet at t At t tj

Fej C Y  ((  Fej



 (+Fe (+Fejj C + [( + Fej Fej   Fej

Fa F a a cool g rocee at t tel f al of the autete te to ecooe to earlte Th ea that the al chage ca be rereete a

FejC  [(  Fej Fej C  Fej  Y (+ FejC ( + Fe Fej   FejC FejC  e + FejC  FejC  FejC

At tj

Th ere of reacto lea to te forato of tcal whte cat ro There  a fferet ere of hae cage that a occur f low coog  carre out o r f there there are allog ato uch a lco ae to table the forato of grahte The ere of chage chage that take lace at t t  a t are the ae excet where FeC occur  the ae reatoh reatoh  t  relace

igue 6   Pt Pt o eeC phse dg o st io

B

D

Structure and a nd Properties o/Ct o/Ct Irn 41

n Fgur e 6  wold wold then be represented represented by: by:

with graphite graphite (G : Y + L2 tl LI  Y + (Y + G) At t2 Y + L  tr t3 Y + (Y + G)  Y  G + f(y + G + G} At t3 y + G + f(y + G) + G} 

Fe3C +  tx LI  ,C + (y (y +  At ty Fe3 C + L2  Fe  � y- tz Fe3C + (y(y + Fe At ty-

At

At

y+G+G+y+G+G+G

In practce the last stage never fully takes pace. More typically the rst phase change is from aus tenite to austenite + graphite but the astente is much more ikely to precipitate FeC. The phases at t then become: At

t3 Y + G + f(y + G) + G} 

(a + Fe C) + G + (a + Fe C) +

G+ G

This should lead to dendrites of pearlte n a matrix of o f ferrite and g raphite which is most ikely in grey cast cast iron  Above Above a carbon content o f 4% the primary reaction reaction would be decomposition o f the iquid to form FeC and edebrite (austenite + FeC). The The phase changes pon fast coolng o f an alloy shown

Fe3 Fe3 C (+ y) + f(y f(y + Fe3 

Fe3 C}  Fe3C

White cast irons wth a total carbon content of over 4% tend to be extremey hard with no elongation at al and are not normally used in the fast cooed state With sow cooling very arge graphite akes can form, and it s possible to get qute a arge difference difference in the size o f these akes depending on where they form in reaton to the phase dagram. Graphite formed wth a carbon content of 3% can be quite smal whereas whereas wth a carbon carbon content con tent of 5% the akes can be enormous Fig. 62) Although cast iron metalurgy was we deveoped in China, isolated examples of cast iron do occur in other Od Word contexts for example the 1 st century nd from the cass c excava excava tions of Bs Bs heFox heFo x at Heng istbury istb ury Head and also from the Roman perod cast iron from Wlders

A.D.

Figure 62 lake lake graphte in cast ron  From ISO Standard R 9451 969(E). 969(E). x 00 a Flake graphte b Crabtye grahite grahite c Quas ake graphite d Arega Aregate te or temer carbon e  rregular o ope-type odes f Nodular or sheroidal grahite

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SY"re nd Propere o/t Iron 42

66 

igue Cast ion sal es fo the 1 8th entuy entuy ypia ypia exaple fo Englad sho wing the gaphite faes faes suo nded by white bodes fete) The gey infill is pealte whih has vaiable spaig while whi le the white spotty spotty phase i s the tenay euteti steadite Ethed i ita; x90 igue 64 Heavily ooded faget faget of a ast on  anon ball fo fo the Towe of London  8th entuy Note sevee oosion of the feite feite egions a ound the ouse gaphite flaes ad oosion of peaite egios thoughout the stutue T he two phases phas es that have have suvived suvive d best ae the steadite euteti the the fie spotty ateial) and the eetite eetite laths the long white ystals) ystals ) Uethed x40

pool, anasire Bo of ese piees were of grey as iron e Hengisbury exaple ad an analysis of C 3.4% Mn r Si 0.3%, P 0.1%, S 0. 03 5%, wile e speien fro fro Wilderspool Wilderspool gave gave C 3.3%, Mn 0.403% Si  .05% , P 0.76%, S 0.4%. Many of  e Cinese exaples exaples ave ave lower silion onen an ese ranging fro fro 0.0 % o 0.  % in e exaples exaples publised by Hongye and and J ueing in 1  3. Te Cinese exaples exaples span a onsiderable onsiderabl e range of diff differen aerial as an be seen fro e following: 





An axe fro fro e Warring Saes period ( 45  1 ) exavae exavaedd fro fro e s ie o fon glu san Huangsie Ciy Hubei Provine, was found o be an exape of a wieear al leable as iro n wi  i perfe perfe dearburizaion and a oal arbon onen a varies varies fro 0. 7 o  .5 %. Te analysis for for is axe gave gave C 07. 07. 5% Si 0. 1 3%, Mn 0.05 %, S 0.01 6%, P 0. 10%. An exaple of a o led as iron is provided provided by a aer fro e sae sie wi e fo lowing anal analysis ysis C 4.05%; Si 0. 1 %; Mn 0.05% 0.05% S 0.01% P 0.1 5%. A wie as iron was found a Ceng ou Ciy Henan Provin e Tis blok daes o e Easern Han dynasty 40 ) and gave e follow following ing anay anaysis sis C 3. 7%, Si 0. % , Mn 0.30%, S 0.07% P 0.64%.  exaple of as as iron wi speroi dal grap ie was found found i n e iron worksop a Tries enggou daing  o e Wesern Han dynasy dynasy 06 4 ) . Tis sie is loaed in Gong County, Henan Provine an d gave gave e

BC

..



B.C..

follow ollowing ing analys analysis is C  . , Si 0 . 1 6 Mn 0 .04, S 0.04, P 0..

Notes





3.

is grapie is e grapie a separaes fro olen as iron as soon as i ools o e solid I ay soeies loa on op of e oen alloy Anisoropi subsanes do no ave e sae pysial properies in all direions of e aerial Reeion pleorois resls fro differen ineraions in anisoropi solids wen viewed nder polaried lig eneraly pleoroi sbsanes will sow soe olor variaion on roaion roaio n wen wen viewed viewed nder nde r polaried lig

9 ORRODED MICRORUCURE

Many anent objets are of ourse overed wth orroson produts that may have orgnated at the tme of manufature f the objet had been delberately delberately patnated for eample), or th ey may have arsen fr from orroso n durng bur al or n t he atmosphere Many books o n the subj et of orro son do not dsuss the types of strutures that our n anent metals. Often they are are subjeted to several dfferent orroson proesses resultng n a nearly omposte materal onsstng of metall remnants and mneral alteraton prod uts. or mally orroson produes a budup of nsoluble produt s both wthn and overlyng the orgnal metal volume. Corroson produts may be very nformatve ndeed they may be all that s left of the orgnal objet herefore orroson produts sho uld n ot b e leaned from from the surfae surfae of antutes before before metallograph metallograph eamnaton Loose materal sol and sol and mneral onre tons usually shou ld be removed beause beause ontnual loss of them durng poshng poshng ould reate reate a very badly srathed surfae surfae unsutabl unsu tablee for for mro m ro sop eamnaton  t s generally possble to pol sh orroded samples n muh the same way as more robust spemens although fthe f the materal s very frable frable vauum mpre gnaton wth a low vsosty epoy resn should be onsdered before mountng or the whole sample ould be mounted n resn under vauum vauum t  s mos t mportant to eamne all feature featuress of orroson produts b efore efore ethng the spemen sne many orroson pro duts are severey attaked by the hemals used to eth meta sur faes: they ould be dssolved ompetely. Under normal brghteld reeted lght mrosopy most orroson rusts have a grey olor. Eamna ton under reeted polarzed lght yelds a great deal of valuable nformaton. nformaton. The polarzer n reeted lght mrosopes s usually housed n the hamber of the the lght soure an d an be rotated whle the analyzer s plaed n a speal holder n front ofthe of the eyepee turret turret By adjustng one or bot h of the polarng elements the "true olors o f orroson produts an often be revealed. ot only does ths ad onsderably n the nterpretaton of many mrostrutures mrostrutures b ut

als o many rystalne rystalne and othe r morphologal detals are revealed learly. t should be remembered that the nt erfae erfae of nterest nterest may not j ust be between the metal and the prmary or urrently estng) orroson produts. mpo rtant nformaton nformaton may also be preserved n so me other nterfaal nterfaal event between layers of orroson orros on produts of o f dfferent dfferent ompos  ompos ton or struture Corroson produts may pseudomorphay pseudomorphay replae the metal struture that prevousy ested That s to say the strutural orentaton for for eample dendrt struture o f the the metal s preserved n the orroson produts that have replaed t One of the ways n whh ths an happen s by eptaal growth Ths means n general terms the regular orentaton o f a partular growth growth on a rystalne rystalne substrate. Most anent hemal orroson proesses wh h are best modeled by eletrohemal reatons) f they produe strutural nformaton preserved n the orroson produts do so by hemoeptay hs s a subdvson of the eptay struture Chemoeptay Chemoe ptay an be dened as a proess leadng to the growth of rystalne regularly orented reaton ayers on a materal resultng from a hemal reaton between ths ntal substane and any other substane. Eamples Eamples o f layers layers formed from suh a proess are uprte C) growng on the surfa surfaee or nto the metal grans themselves and Ag, the ntal thn lm that an form on slver objets. Valuable nformaton an sometmes be retreved from from orroded orro ded metall fragments; parts of the the struture may reman unorroded or there may be pseudomorph replaement replaement of the phases by orroson produts Append B llustrates some of the types of orroson found found n anent spemens Evdene of the authentty of an artfat an be obtaned from metallograph eamnaton of small small hps of orroded orroded metal n opper alloys the presene of ntergranular ntergranular orro son ntragranular orroson orroded slp lnes twn lnes or uprte net to the metal woud be very sgnant.  t s etremely dfult dfult to produe oherent uprte layers layers by artal orroson

re Micsrucue 44

ove sho peiods of ime and i  is also paially impossible o fake he peneaion of upie aong seleive planes planes in he ysal, suh as win bands o slip lines If he oosion poess has no ompleely disuped he oiginal volume of he meal bu has peseved some inefae beween inenal and exenal exenal oosion, hen his dison inuiy may be eognized as peseving infoma ion elaing o he oigina sufae of he aifa When ooded samples ae mouned fo pol ishing, he dif di fuly of pepaing sah fee su faes is eviden  Abasive pail es feuenly feuenly an beome beome embedded embedded in he oosion podus Duing poli shing some o f hese paies may be eleased, eleased, poduing sahes on he mea l Po longed polishing wih inemien ehing o

igue 6 pia vaatio  the peevatio o ae ae deai l a a eult o oo o a Peevatio o hape  ooo b Di p to o uae b ooio  oud etal with patia

emove smeaed smeaed maeal, o  ulasoni leaning in bahs of aeone o alohol, may podue a be e nish On e dange is ha small speimens will beome ounded a he edges and pa o f he he o osion us o  he edges of he mealli onsiu ens may hen be ou of fous miosopially ompaed wih he emaining polished sufae The polishing hadness ofoosion of oosion podus and he meal fom whih hey have fomed fomed i s usually usual ly uie diffeen Sufae elief effes ae heefoe ommon when examinin examinin g ooded samples samples  has been found ha a muh shape pesevaion of deail in oosion podus is ahieved ahieved by using diamond polishing ompounds ahe han alumina ompounds Figs 656) 

eah eal quatz ga et

orig or igina ina l coin oi n

ae

eoda ooo podut od etal

ooo pod ut ut

eath i eal qatz gai et et

oigal o ae

oud eta eta

eoda ooi o podut

or ig  na l s u rface

"pata "pata (oi de lde geae geae laue et.) oud etal

9 ORRODED MCRORUCURE

May aie objes ae, o f ouse, oveed oveed wi oosio podus ha may ave ave oiiaed a e ime o f maufa maufaue ue if e obje ad bee deibeaey deibeaey paiaed, fo exampe), o ey may ave ave aise fom fom oosio du i buia o  i e amospee. May books o e subje of oo oo sio do o disuss e ypes of suues a ou i aie meas. Ofe Ofe ey ae subjeed o sevea diffee oosio poesses, esui i a eay omposie maeia osisi of meai emas ad miea aeaio podus. omay oosio podues a buidup of isoube podus, bo wii ad oveyi oveyi e oiia mea voume Coosio podus may be vey ifomaive ideed, ey may be a a is ef of e oiia obje Teefoe, oosio podus soud o be eaed fom e sufae ofaiui of aiui ies be foe meaoapi examiaio. oose maeia, soi, ad soi ad miea oe ios usuay soud be emoved beause beause oi ua oss of em em dui poisi oud eae a vey bady saed sufae sufae usuiab us uiab e fo fo mio mi o sopi examiaio. I is eeay possibe possibe o po is ooded sampes i  mu e same way as as moe moe  obus speimes, ahou if e e maeia is vey fiabe, vauum impeaio wi a ow visosiy epoxy epoxy esi soud be osideed be foe moui, o e woe sampe oud be moued i  esi ude vauum. vauum. I is mos impoa  o examie examie a fea feaues ues of oosio podus befoe befoe ei e speime, sie may oosio podus ae seveey seveey aaked by e emias used o e mea su faes ey oud b e dissoved ompeey. Ud e oma bied eeed eed i miosopy mos oosio uss ave a ey ey oo. Examiaio ude eeed poaied i yieds a ea dea of vauabe ifomaio ifomaio . Te poaize i eeed i miosopes miosopes is usuay oused i e ambe ambe o f e e i soue soue a d a be oaed, wie e aayze is paed i a speia ode i fo of e eyepiee eyepiee ue. By adjusi oe o bo o f e poaizi eemes, e " ue oos of oosio podus a ofe ofe be eveaed eveaed o o y does is aid osideaby i e i epeaio of may miosuues bu

aso may ysaie ad oe moph ooia ooia deais ae eveaed eay. I soud be emembeed a e iefae of iees may o jus be bewee e mea ad e pimay o uey exisi) oosio podus Impoa i fomaio may aso be peseved i some oe iefaia eve bewee ayes of oosio oos io podus p odus of diff diffee omposi omp osi io o suue. suue. Coosio podus may pseudomopiay epae epae e meai s uue a peviousy exised Ta is o say, e suua oieaio fo fo exampe, dedii suue) of he mea mea is peseved i e oosio podus a ave ave epaed i. Oe of e ways i wi is a appe is by epiaxia ow. Tis meas, i  eea eea ems, e eua oieaio of a paipaiua ow ow o a ysaie subsae M os aie emia oosio poesses wi  ae bes modeed by eeoemia eaios), if ey podue suua i fomaio fomaio peseved peseved i e oosio pod us, do s o by emoepiaxy emoepiaxy Tis is a subdivisio of he he epiaxy suue. Cemoepiaxy a a be deed as a p oess eadi o e ow of ysaie, ysaie, euay euay oieed eaio ayes o a maeia esui fom a emia eaio bewee bewee his i iia su bsae ad ay oe subsae. Exampes of ayes fomed fom suh a poess ae upie CuO) owi o e sufae sufae o io e mea ais emseves, ad AO, e iiia i m a a fom o sive objes. Vauabe ifomaio ifomaio a someimes be eieved fom fom ooded mea i fames fames pas p as of e suue may emai uooded, o  ee may be pseudomopi epaeme of e phases by oosio podus. Appedix B iusaes some of e ypes of oosio foud i aie speimes. Evidee of e aueiiy of a aifa a be obaied fom meaoapi examiaio of sma ips of ooded ooded mea.  oppe aoys, he pesee of ieaua ieaua oo sio , i aaua aaua oosio, ooded ooded sip ies, wi ies, o upie ex o e mea woud be vey siia siia I is exemey diu o po due oee upie ayes ayes by aiia oosio

Corroded Corrode d Mcotrucure Mco trucure 

igur 66a, top ight ight Com pltly corrodd bronz  pin rom alsti n Th dark longatd phas ar ar original co ppr sulid inclusions rom th word word and annald pi n prsrving prsrving thir origin a location in th corrosion products rom th ir prsrvation prsrvation it is po ssib to dd uc that th objct was not cast, but workd vn though though no mtal rmains 25 Figur  66b top ar right. Part o a corrodd bronz  rod rom Iran. h origina  s urac urac o th rod s prsrvd in corrosion products only, but th circular cross sction is clar 50. gur 66c, midd  right Comptly m inralizd inralizd silvr disk radiating crystals crystals o silvr chlori d and patchs o silvr sulid dark) prsrv th shap o th obct wth som di stortion stortion 65 igur 66d, mi ddl  ar right Mul tip corrosion layrs layrs sim ilar to Lisgang rings i n a bronz ragmnt ragmnt rom rom Iran. h pr odic od ic prcipitation o cuprit and malachit rsult in ths nly bandd corrosion structur in whi ch suac suac outln is not prsrvd prsrvd in corroson.   00

outr aras aras contain som Sn, CI Ca,  and Cu imm diaty adacnt to th surac

som rgions o o high Ca contnt contnt soil mi nral incusions)

orginal surac surac o th objct

igur 67. Drawing o th cross sction o  a bronz  rod ragmnt Th location o th th ctron mi cro prob in scan s i lustratd. lustratd. A, C, and D in dicat aras o analysis Th l n scan was startd startd approi matly at position I and was trminatd at positon 2.

B

compact ayrs that ar princi paly cuprit and tin oid i n sgrgatd sgrgatd aras only trac amounts o tn in th outr corrosion crust

bronz mtal grans containing 95% tin

Coodd Cood d Miosue 6

gur 68ad ampls o corrosion o godcoppr alloys

Top lt a.a. Sht Sht goldcoppr a lloy rom th Sirra Nvad a d Santa Santa Mata, Colomb ia A ragmnt ragmnt o a larg Tairon a sht sht with dplti on gildd s uracs uracs h composti on is 1 5.2% gold 65.4% coppr coppr and 0.6% silvr Th structur consists largly o dark gry corros ion products, mostly cuprit with god and porosity sn as black hols) as a rsult o corrosion Th sound mtal mtal i s whit Untchd  60

Fragmnt o a Top right, b Fragmnt Tairona ar ornamnt ornamnt 396% gol d, 348% coppr, and 25% silvr n th untchd condition at a magniication o   60, tnsv cracking cracking can b sn Cracking rsults rom voum changs upon corrosion. Som cracks run just und r th su rac rac o th alloy Dpltiong ilding has cratd a gold -nrichd -nr ichd lay mor mor rsstant to mb rittlmnt than th und rlying layr layr

ottom lt c Cross scti on o a corrodd goldcoppr alloy sht rom th Tairona ara o Colom bia. Th composition o th sht is 596% gold, 1 94% coppr, and and 7 1 % silvr, th low total rlcting rlcting intrnal corrosion and tnsiv convrsion to cuprt Th polish d sction shows th cor cor rodd alloy with a n umb r o in lamlla o sound mtal rmnants rmnants that appar bright Th sht has bn bn d pltiongidd and th consi stnt goldrich su rac rac can b b sn clar ly on th top o th sction Untchd   60

ottom ottom right, d  nlargd viw o igur 68c, 300 Etchd Etchd i n alco holi c rric chlori d, rvalng a in ntwork o o cracks runn ing through th alloy Som cracks in th princ ipally cu prit matri ar rlatd rlatd to th orignal mic rostruc rostruc tur, sinc a twin can b sn in on grain ara and so m o th th cracks appar to b ollo ollo wing grain boundaris. Somtims th crack crack ing appars to b unr latd to th grain structur but hr thr is som psudomorp hic rtntion

Crrded Mrtruture 7

gur 69, top uristan crmonial a showing ntrdndritc poro sty dark) with wll dvopd dndrits. tch CI  30 igr 0, mid dl s ig 69) dpositd coppr rsulting rom in-d pth corrosion tch tch CI  I. igur igur 7 1  bottom bottom ction o a corrodd ragmnt ragmnt rom an cuadorian gildd co ppr crmonal a, rom rom Pindii g Canton Azogus Azogus cuador A gol d surac surac can just b sn as a thi n bright ln at h top o th sction his a was gldd by h lctrochmcal rplacmnt platng tchniqu dscri bd by chtm chtman an   982) Th phoo phoo mic rograph il lstrats h traord traord inary prciptation o coppr as a rsu t o o h h corrosio corr osio n o th a h rdpositd coppr outlins aras o rmainng uncorrodd alloy, alloy, which is narly pur coppr coppr  1 20

e samples ilustrated in igures 670 see als als Plate Plate 1 0 and igs 1 1 2, 1 1 3), taken taken frm te brken end  f a ilt f a uristan eremnial blade sw a welldevelped dendrti struture nsisting f an dendrit dendrit  system wit te usual eutetid inll swing tat te te it is n te asast nditn Tere s sme prsity present in te setin resulting frm interden drit les w uld be due eiter t rapid slidiatin n te mld r t gas evutin evutin in te asting Te ilt setin as distint pper glbules wi r ignate frm rrs in eff effets witin te br ne struture and ur ur mst prbably in te frmer frmer eutetd spaes tat are attaked seletively in tis partiular brne in a bural envrnment Te disslutin  f te euteeutetd smetimes leads t prepitatin f pper as ere) smewat akin t te press f deiniatin deiniatin n brass e pper gbules ften ften display twnned gran strutures barely vis ible ere at 150.

e

e



1 0 EFLECED POLARIZED IGH MICROCOY

oarized iuminatio n or or the eamination o anient metai ampe ha many many appiation In brighted unpoarized iumination many nonmeai inuion orroion produt buria onretion oi minera ore materia et appear a variou hade hade o  grey By uing poarized iumination and rotating the poarizer and anayzer anayzer unti mot or a normay inident ight i euded ne oor dierentiation beome poibe between many o the minera phae aoiated with anient meta Some o  the the meta themeve ao give rie to oored eet under poarized iumination i they are are opiay aniotropi ie  i they they have have two or three prinipa rerative indie Some eampe eampe o  aniotropi meta are antimony tin and zin n addit ion ome aoy aoy may ao pro due aniotropi eet uh a prior auteniti grain boundarie i n marteniti ee betagrain betagrain ruture in hightin bronze dierent reetiv itie in dupe aoy and train or ip marking within grain Mo t o the ommon meta o antiuity uh a iron opper iver god ead and nike are optiay iotropi ine they y taized in the ubi ytem and are eiher body entered ubi in the ae o aphairon) or ae entered ubi a in opper iver god nike and ead) Neverthee even optiay ioropi meta have grain boundarie and optia eet with or or eampe at meta do our ath ough they rarey provide new inormation inormation Wih ompetey ean and unorroded am pe here may be itte advantage in the ue o poarized ight miroopy miroopy However However hi  i rare among anient meta whih ypiay have both nonmeai inuion and orroion produt preent an d oten vauabe in ormation an be gained by eamining them in poarized poarized ight Void that appear dark in unpo arized arized iumination ugget or eampe that they may be ed with uartz or aite ahough the hemia identity o the materia eamined eamined i  no t eay o etabih In at there i no traightoward guide to he h e identit y o any materia o thi kind he bet mean o  identi identiation i by Xray didiration ration eetronmiroprobe anayi anning

eetron miroopy or tranmiioneetron miroopy he prinipa advantage gained by uing poarized poarized iu mination are the viua mani etation o the morphoogy and the ditrib ution o orroion produ  by oor and ryta ryta ize There are o me oor e et that an b e een i the tage or peimen i rotated Coor hange i due to peohroima the vibrationa diretion o the poarized ight i atered atered by rotation o the reuting oor o the oberved aniotropi mate ria wi ao hange Grain boundarie in mea twin ine and ip pane p ane may reat di dierenty even in  otropi otr opi materia uh a opper or owtin bronze Dendriti truture truture hat have preerred preerred orienation o growth growth may ao how hiaro uro e eet in poihed etion Care mut be taken to avoid inerene rom the abene o an epeted reaion to poarized iuminat ion: the onomitant abene o the ub tane ought or eampe uprite whih i uu ay a iverred iverred oor in miner a orm orm under maroopi ondiion i epeed epeed to appear aretred aretred under the miroope uing poihed etion with poarized poarized iumin ation Oten Oten thi i how it ook however however ome ma uprite inu ion give no br ight ooration beaue the orien tation o the ryta ryta i not produin g anioropi ee in that partiuar poition Ahough it i not utomary o ue rotating tage with meta urgia miroope une the tage i an inverted one i t may be ueu ueu to hange the tage i muh muh poarized poarized igh work i to b e arried out Maive orroion uh a that preerving the urae deai on a opper aoy artia wi uu ay produe a wide range o oor he  oor oberved oberved with opper orro ion produt i very imiar to the oor uuay aoiated with the minera onerned a evidened by uprite he ame imiation ha appy to viua identia tion appy to hi type o miroopi eamina tion t woud not be poibe or or eampe to know that a green minera een under poarized ight wa maahie It i ao no poibe to ay with a minera uh a uprite that the materia i oey ompoed o uprite beaue a arered

Reted Poarzed Lght Mpy 0

colo is visible unde po aized aized lig: ee may may be composiional vaiaions o oe mineals pesen in addiion, suc as sannic oxide, wic ale e sad o e e colo Tus e analys can no deec e pesence o mineas by is means alon aloug polaied polaied lig micoscopy used in conjuncio n wi eleconmicopobe analysis analysis can give vey use useul ul inomaion inomaion Sco  6  Slags and oe maeials, suc as mae speiss, cemens cemens  and plas es, can also als o be examined e eec ively by eeced polaized lig Ancien pase and cemens ae usualy ne gained o conain negained negai ned aggegaes aggegaes wic makes makes examinaion examinai on dicul in in secion usualy 30 micons ick Moe inomaion inomaion can be gained abou e cysalline and glassy pases in many slags unde polaized polaized lig, aloug mineal idenicaion is no usually possible An idea o e possible ange ange o colo can be sown by looking a slag composed o coppe sudes mae in globula om, suounded by magneie and ayalie cysals in a dak glassy maix In un polaized lig , e coppe suldes appea gey e ayalie las will be a dieen sade o gey e magneie is wie, and e glassy maix is dak gey Unde polaized polaized illumi naion, e coppe suldes es ae lig blue, e magneie is back, e ayalie is gey, and e maix can av e vaious e eecs, bu can appea anslucen and glassy Cysal size in cemens and plases can be evealed by polaized lig examinaion, as can colo vaiaion, and ay eed mineal assemblages , as ae commonly ou ound nd in wall painings pain ed esseae o poy  comed maeials



Notes





Fo moe inomaion inomaion on e sucue o  slags and oe meal bypoducs see Bacmann   2) wee many slag slag sucues sucues ae ae illus aed, bo in colo and blackandwie o ue ue in in omaion on polaized lig micoscopy aloug lile inomaion as been publised on ancien meas, ee o e woks menioned in e bibliogapy by McCone e al 174 and Wincell 164)

Gran S of Annt Mta 

Hil iards cicular intercept method can also be used In this techniue a photomicrograph of known magnication is selected and a circle, drawn on a shee of plastic plastic of diameter diameter  0 cm o 0 cm, is placed over the photomicrograph. The circle should intersect more than si gain boun d aries for for the method to give a reliable grain size

estimaion. The circle is used unil at least 35 grain boundary ntersections have been counted. One o f the advantag advantages es o f the the circula ntercept method is that it is easie to appy to deformed structures A nomograph for the graphica solu tion of the Hilliard method is given in Figure .

gue 73  Typial standad o estimatng estimatng the austeniti) gan size o steel hotomi ogaphs o samples abuized at 1 700 930 o 8 hous and slowy ooled to develop the ementit e netwo o Samans Samans  1 963) th th nital



f

.

no I g an size

no 2 gain size

no 3 gain size

no 4 gain size

no 5 gain size

no 6 gain size

no 7 gain size

no 8 gain size

Gai iz oi oi Mta 

·

yc sndrd or gr 74 yc  sz   nnld simng gr nonrrous mrs sc h s rss ronz nd nnii ck l ssl vr Acul dimr o vrg vrg g rn is nod 75

0

000 mm

0025 mm

0035 mm

0065 mm

0090 mm

0 20 mm

0  50 mm

0200 mm

Gai i oit Mta 4

Figur Figur 75 right Mounting sm all spcimns in silcon rubbr cups. Embdding rsin usd hr was uhlr poid sin which sts in about hours



igur 76, blow Grindng th mountd sampl on wt silcon carbid paprs usualy papr s o 24 600 600 grit ar mployd 

Crai ie oAciet Meta 

Figur 77 right olishin g th th mountd mountd sampl Hr uhl r Mastrt Mastrt loth loth i s bi ng usd with I m iron diamond spray abrasiv and lapping oil lubriant Figur 78 blow Sampl  storag storag and sltio n is bst arrid out in spially pu rhasd mtallography mtallography storag storag abi nts ays an b obtaind in a varity o diamtrs dia mtrs or storag storag o dint siz  mounts. Most o th sampls hr ar I  /4 dam tr polystr polystr or poy mountd samp ls that hav labls mbdd d n plasti on th ba or or asy idntiiation 

Gai i oAi Ma 56

igur 79, right Eamination o pigmnts or corrosio products o mtals can b bst achivd by polarizd light mic roscopy roscopy his mic roscop can can also b usd or rlct rlctd d i lu miatio s o that moutd sampls can b amid Figur 80, bow U s o th invrtd stag stag mtal mtal urgica mic roscop in which th spcimn is pacd on top o th mi croscop croscop stag stag as ilu stratd stratd hr. Th mic roscop il lustratd lustratd is th th Ni kon piphot attachd attachd to a vid o camra, a 35mm camra back, ad ad a 4  5 color or blac-and-whit oaroid ilm back Dark ild and rlctd ctd polari zd l ight ar both vry usul aturs o this mtallograph

1 2 MEALLOGHY AND NCIEN MEAL

Metallogapy Metalloga py off offes one of te ost usef useful ul means fo fo te exaination of ancient etas I t is te study of pol sed sections of etallic etallic mate als using a special icoscope tat eects ligt passing toug te objective lens onto te speci en suface Te eected ligt passes bac toug te objective to te eyepiece wic enables te s uface uface stuctue of te section o be sudied sud ied see  g  0 fo fo a typical example of a etalugcal icoscope) Reected igt cos copy is used fo etallogapic exaination because etals etals cannot tansit igt in tin sec tions i n te sae way as ceaic o ine a ate ials Apat fo gold foil wic if vey tin can tanst a geens ligt toug gain boundaies etals ae opaue substances It is usually necessa to tae a saple wic can be uite sal fo te object being stu died I t is possbe to p ois a sma aea of a elatively elatively at suface suface on an object using a inidi ll and ne polising discs but ts etod is uite dicult dicult Wit any antiuiti anti uities es usef u sefu u n foation oat ion can be  obtaned fo saples as sall as 1   wic can be eoved fom te object wit a inial amount of daage daage So e etods of sapling applicable to ancient atea ae listed in Cap te 1 3 . Te sape itself need not be etalic co osion po ducts pa int layes coe ateial fo fo castngs niel o deteoated enaes patinations and an aay aay of ote copositional ateials ateials ae of consdeable inteest Exaination wit a et augcal icoscope is often a useful st step in caacteing a paticua coponent of an object Soe typical etallogapc etallogapc euipment is sown in Figues 50 Metallogapy Metallogapy is ten  an impotant tool tat may povde clues to te fabication tecnology of te object o  ay assist in answeing ues tions tat ase dung te teatment teatment of an object by a consevato It ay be possible to povde nfoation nfoation o n te followng followng ange of topics

1.

e anufactu anufactung ng pocesses used to poduce te obect  o exaple wete cast into a old o woed to sape by aeing and annealng



3

4

e temal isto ofte of te object uencing and tempeing pocesses may poduce de nite canges in te icostuctue ta can be seen in section e natue of te meta o aloy eployed to ake te object o exaple any debased silve objects ae made fo silvecoppe al loys and bot constit uents ae clealy visible in te polised and etced secion; tey sow up as a coppeic pase and as a silveic pase Soeties it may be vey vey dcult to obtain any idea of composit ion fo fo looki ng at te icostucue and ee additional evidence must be obtained using a suitable ana lytical metod On e way of doing tis if a saple as been taken and aleady mounte d is to ti te plastic ou nt and place te sample i n an Xay uoescence analye analye XRF XRF ) e natue of coosion poducts  Mu c use ful and vaied infoaion infoaion can be obtained fom cooded fagments agments o  pieces of coo sion custs Fo example tee may be esidu al etallic stucues wiin te coosion layes pseudo mopic eplacement o f metal gains by coosion poducts te existence of gilded layes layes o ote su face face nises w itin te coosion layes, pseudomop ic eplace men o f oganic bes o negaive pseudomopic casts of bes unusual opo log of te te coosion poducs teselves and canges bougt about by metods ofconse of conse vation t soud be noed tat te scanning electon ico scope i s a ver poweful poweful tool fo any of tese investigations in addition to optical icoscopy

Te pincipal diculties wi etallogapy applied to ancient ateial lie in e pobems associated wit sapling t e object and te selec tion o f te sample If any any damage damage is to be caused te owne sould always always be consulted st so tat necessay necessay peission is obtained fo fo e wok I t sould b e ade clea clea to te owne wete te saple can be etuned wen te examination examination i s copeted and t e ind o f infomation infomation t at te saple is expected to povide e owne sould

Mog Mo gpy py n A n nnt nt M 8

igur 8   right Drawing o an a showing th idal location o two two samp s rmovd or mtalo  graphc amination. Not that that on o th cuts o th Y sction should b at right angls to th principa prin cipa l sids o th objct to to aid itrprtation o any di rctional charactristic s o th mi cro structur. igur 82  a right. wo samp ls o wir or rod mountd i n dint dint di rctions to to obtain strctural inormation lat ing to to lngth and cross sctio n Thr a otn otn dnt dnt or diagnostic aturs aturs vis ibl  n on sction that may not b appart in th othr.

eceive a copy of any witten epot tat is pepaed as a esul o f te exaination togete togete wit any potoicogaps of te stucue clealy identied identied wi e agnication of te pint te etcing etcing soltion sed and te laboatoy nbe assigned to te saple It a y be necessay necessay to exaine caefuly a goup of objects in te useu o laboatoy befoe coing to a deci sion as to te nube of saples saples to be taen o te objects fo fo wic it a y be peissible to take take a saple If te daag daagee is su c at it can be epaied epaied by l ing te aea concened concened te owne sould be given te option of deciding wete o not to ave te te object gaplled It is pef p efeabe eabe to ll sall oles o issin g cones wit wit a syntetic esin coloed to atc te su face coo o f te obect obec t A faiy faiy viscous epoxy esin c an be used fo tis pupose and can be cooed wit powde pigens  In any seu collecions tee ae exa ples wee lage slices pieces o dillings ave been taken o o etaic ant iuities causing goss daage to te objects concened Missing pats ae soeties lled wit unsuitable ateials suc as Plasticine noally a ixtue based on ptty witing and inseed oil  wic usually ceates sevee coosio n of exposed etal s faces ove a peiod of yeas yeas in te useu collection Sulfucontaining Sulfucontaining lles su c as Plasticine sould neve be used fo fo ount ing display o gapll ing of eallic objects Geat ipoveents in etallogapic etallogapic tecniues ove te last 20 yeas

ean tat it is no longe necessary to eove as uc saple bulk fo fo te object as any ealie investigations euied Te extent of te daage is teefoe teefoe geatly educed educed indeed, wit  uc cooded etalwok o fagenta fagentay y objects te loss ay be insignic ant and te esulting in fo ation ay be very ipotant indeed Te only difculty difculty wit taking sall saples is te p oble o f te epesentative epesentative natue o f te saple copaed wit te oveall stuctue of te object It does not follow fo exaple tat because te aea sapled sows an undistoted denditic stuctue indicating tat te piece was cast tat te wole of te object will eveal te sae stuctue Obviously tee ae cases cases in wic tis diculty would be very unlikely to occu: woked t in seetetal pieces of wie sall ites of jewely jewely and so on but wit atifacts suc as aes knives swods lage castings etc , it ay pesent a very difcult difcult poble If a copete intepetation o f te etallogapic stuctue of an atifact atifact suc as an ae is euied ten it is alost essential to take sapes fo te te ae ae Fig 8 1 ) Anote exaple exaple i s tat of a piece of wie o od wee bot te longitud inal and tansvese sections sections ae of potential inteest Hee te sections can be obtained fo a single saple by cutting te wie into pieces and ounting te in a old Fig 8 ) T e pocedues fo fo p epaing etallogapic saples ae a s follows:

fO

fO

fO

mold

J I cm

wir longtudinal sction

wir transvrs sction

Metaoaphy andAnce and Ancent nt Meta Meta 9

1

2 334  6

8



9

Selecting te sample Mounting te sample in a syntetic resin cast into a small mold Prelimin ary grinding of te embedded sample Polising, using rotary discs impregnated wit alumina or diamond powders powders Examining te polised section wit wit a metal lurgical microscope Etcing wit a suitable etcing solution Preparing a written report Do in g potomicrograpy an d drawings, drawings, if re uired, o f te section to sow microstructural details Employing an orderly system system of sample stor age and documentation

Note



Fo r eape, Araldite Araldite 5 can can be used wi good uaiy artists powder pigens ied ino e resin and ardener ardener itre I f a issing piece is being gaplled and it is reuired at te restoraion can be removed at a later ime ten te etal srace can be coated in te area to be lled wit a reversible reversible syneic syne ic resin suc as araloid araloid B brused on as a 1 % solution in toluene applied in two coas. is sold ensre at te ll can can be reoved ifit if it is no no  eyedin eyedin by soaking in i n acetone for for a few few in utes.

1 3 MTALLOGHIC SALING OF MTAL

There are fte fte evere retriti   the ua tity f metal that a be remved frm a artifat fr metallraphi metallraphi examiati O the ther had, eve a very mall mall ample, maller tha 1 mm  if eeary, a be muted ad plihed fr examiati, althuh reat are ha t be exer ied at all all tae f prepar ati It i muh eaier t wrk with larer ample, althuh by mueum  tadard ample f3 mm are already uuualy lare, ule whle artifat r ubtatial framet are available fr etii There are a umber f riteria riteria that ample huld meet



The bjet hud b e phtraphed r draw befre the ample i take Thi i epeially imprtat if the dimei f the the bjet are fudametally altered by the material



3. 4

removed.



3 4

The mirtru ture f the ample huld  t be altered altered i the pre f remval remval The ample huld be repreetative f the bjet a a whe r  f a eeted feature feature r area f the bjet The rietati f the ample ample i relatihip t the etire bjet huld be arefull arefullyy rerded ad if it i t bviu where the ample wa take frm, the piti  the bjet ered huld be marked  a phtraph r drawi f the bjet.

There are a u mber f pibilitie fr remv i a ampe depedi, depedi, ievitaby,  the ature f the bjet ad  the meta r ally fwhih f whih it i mped

1

A hakaw with a etthed blade a be ued t ut lare lare ample hwever, hih heat eerated eerated by friti friti duri ut ti a alter the riial mirtruture The bade huld be led peridialy i water r ethal Remvi a ampe will uualy etail iderable l f lid a e pwder. Th i pw der a be kept fr aalytial purpe althuh i t may  t be mpletely free free frm frm tamiati. It a be ued, fr fr exampe, exampe, t

5

prvide Xray ureee aalyi fr fr majr maj r tituet A e jeweller aw may be emplyed Thee are eaily brke if they et weded i the t he u,  a blade mu t be eleted that i  uf ufietly rbut fr fr the jb at had It i the pib le t remve very mall mall peime uite au ratey, fte with miima damae t the bjet ered. A hllwre drill bit a b e ued t remve a re that a the be m u ted fr fr examiati. While y rbut  r thiketied thiketied bet wuld urvive thi tehiue, it i metime the ly way a metallraphi metallraphi ample a be take A waferi blade a be ued t ut a thi lie r remve remve a mall Vhaped eti frm frm the bjet Oe uit able mahie fr fr thi pur pe i the Buehler " Imet diamd waferwaferi mahie with a utti blade iti f a iled pper dik i mpreated mpreated with diamd pwder al it irumferee irumferee The priipal prblem with thi mahie i the ihere t diulty diulty f hldi lare r irreular artifat, althuh a variety f lamp are prvided fr fr thi  purpe. If a bjet a be h eld eurey eurey ad rieted rieted i the prper direti, the the mahie i extremey extremey ueful. ueful. t ly a the leth a d direti f the ut be preiely preiely trled, but the peed ad weiht applied t the ut ti blade a be adjuted The pper blade dut eerated eerated heat t the il bath  that the rik  f ay mirtrutural mirtrutural alterati i eliible riable materia may break al lie f weake, ryta plae, frature, et ad huld t be ut ui thi mahie, ie travere travere preure preure  the blade i m ti wuld reut i raki raki r hippi  f the the diamdimpreated diamdimpreated utt i ede, whih wuld be tly apprximately apprximately $300 eah i 1989) With thi  heet r ueve ede ede i t may be

Metogri Sming of Me 2

poss be o beak off a small piece possbe pie ce of meal by caefl cae flly ly gipping he a ea o b e sampled wih a pai oflongnosed plies  medical foceps foceps o ne weezes. weezes. Sin ce many ancie n shee me als ae cooded o ohewise embiled he ack of pasic defomabi defomabiliy liy o f he maeial may assis in allowng he emoval of a sam pe since sligh and ca caefu efuly ly applied pesse may enable he emova of vey small pieces. p ieces. 6  A scalpel scalpel may be sed unde a binocula mcoscope. This  echniue may enable he emoval emo val of sma pieces of coosion podcs o meal fo fo subseuen examinaion . I is occasionally possibe o deach a specimen nde he mcoscope by paien chisellng wih a scapel. Some defomaion defomaion o f he spec ien may esu bu his zone can usualy be elmnaed in  he ginding sage o alena ively one o f he undefomed undefomed sides po lished A boen jeweles saw bade hed  n a vibo ool can be used. Thee ae a numbe o f appli caions fo fo his echniue whch allows he emova of smal peces fom hollow shee wok loswax loswax casings cavies ec. since he vibaoy acion acion o f he blade in combina ion wih a genle sawing acion is no as lim iin g as using he blade igidly held in is us ual fame. A boken bade abo 35 cm in engh s saisfacoy.



 4 MOUNTING AND AND PREA PREAR RING S ECIEN

One a sample is remved remved frm frm an arifa arifa i mu s be mun ed and prepared fr fr examinain under a meallurgial mirspe. Befre Befre e sample is plaed i n a m ld, i suld b e degreased greased rugly in aene r eanl and dried. Tis is espeially impran i f e sample as been u in a Bueler wafering wafering maine. Very small sam ples piees  f in wire,  r in see may reuire pysial suppr a e mun ing sage erwise erwise wen ey are embedded embedded in resin and e blk is grund and plised, ere will be n nrl ver e mea s urfae urfae expsed  view. Tere are a number f ways ways in wi is an b e aieved: aieved:

1

2.

3

A small brass jig, speially made fr e purpse f lding lding speimens, an be used ig. 3a) . Te pu rpse f e jig is  alw e e speimen  be b e aaed  a pik wi a very small amun f aryli r nirelulse adesive. Te aaed speimen and sik an en be rigidly eld in  e jig and anged r psiined as reuired in e mld. Similarly, e speimen an be muned  n a pik and en suppred wi mre piks r maes laid arss e mld as swn swn in igure 3 b.   is f urse, pssible  suppr mre an n e sample in e same mld using is eniue bu e sampes are mu mre likely  mve in e mld wen resin is pured in, and simulaneus plis ing f w r mre very small samples is mu mre liabl e  resul in e lss f e e embedded embedded speimens ne e blk as been grund and plised Sme exs sugges adering e sample  e bm f e e mld wi adesive r suppr ing e sample wi a paper lip. Tese me ds an be used bu ave disadvanages. r example  e adesive adesive may resul in slig  unevenness in e resin layer surrundi ng e edge f e sample wi lss  f gd edge reenin r e p aper lip may inerfere inerfere wi e plising fvery f very sf sf meas i f i is in n a wi  e resin surfae surfae

4.



6

A disk f asugened asugened wax r a small uan iy f mlen beeswax an be pured ver e bm f e mld Wen se in p siin , e speimen an be parially embedded befre befre e resin is pured in  e mld. Wen se and remved frm e mld e speimens will sand in slig relief and will ave  be arefuly grund befre plising. Tis eniue is inadvisable fr very brile maerials. f e sample will be subjeed  elerlyi r eleremial eleremial plising, i an be sup pred by a piee fwire f wire in e mld using e ig med deailed deailed in N 2. T e wire wire an an be aaed aaed  e speimen using "a ua dag r sme simia r nduing pain applied in w r mre as  effe gd elerial na Te wire is u  allw abu 35 m exess abve e e p f e mld ig. 3b ). arger speimens, espeially if ey ave been u, an usually be muned direly by plaing plaing em in e reuired psiin in e mld. f e embedding resin is en  en pured pu red aref arefully ully,, e speimen suld n mve in is psi in a e bm  f e mld

Emedding the Samle Tere are a numb er f prprieary synei synei resins n e marke a are designed as embedding maerias fr fr meallgrapi speimens. pxy, plyeser, and aryli resins are e ms mmn r ruine use, "Sandip "Sandipas as  1  1  plyes plyeser er embedding resin an be used wi perxide aays aays "Sandiplas "Sandiplas  1 2.  One drp per ml f aalys aalys is sirred in e resin wi begins  gel afer afer abu ve minues and and us mus mu s be used prmply. if i feen m f resin is sufien sufien  ll Mease Mease r Bueer 1 in diame diameer er r 1   in diameer mlds wi are made fpyeyle f pyeylene ne r r silin rubber. Curing is bes arried u a rm emperaure samples an be remved frm e mld afer wfur urs, bu d n aain eir maximum ardness unil abu eig urs. Man ufaurers sae a e sligy siky surfae n

Monng and Preparing Speiens



e se esin is due o oidaion eaions wi an be min imized by oveing e mold wile  e esin ses Tis oweve is aely a seious poblem pob lem and e esin gives saisfaoy saisfaoy edge edge eenio e enionn and low poosiy upon uing Wi many aaeologial aaeologial maeials e majo pobem is o aieve good edge eenion. Figure 83 Holding smal samples Top a Use o one type o mounting jig to hold small samples n a set position Middl e b Use o toothpic toothpic suppo rt over mold to attach to to sampes ottom ottom c Use o wa wa embeddin g method only sitabe o small sampes

Tee ae a numbe of ways in wi is pob lem an be akled. akled. One meod is o use an epoy mouning sysem a as ow visosiy ompaed wi polyeses polyeses and o add a lle of speially gaded gaded blak alumin a ganules Tese ae ollow alumina spees wose adness an be maed o a of e maeial maeial o be moun ed.

adjustng screw sample held wth HMG or other suitable cell ulose o acrylic adhesive

matchstic matchstic o toothpic toothpic slicon ubber mold

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 brass mounting ig

wood

Use o one type o mounting jig to hod smal sampes in a set position position

toothpics

sample held with with H MG adhesive or other suitable cel ulos e or acrylic adhesive Use o toothpic toothpic su ppot over mold to attach attach to sa mples

 :� g

Use o wa embedding method method Only suitable or smal samples

" m p l

Mountng and Prepang Speens 65

They also povid e ood ede eenion  alhouh hey ae ae imeonsumin o use. If he mealloaphi sample is embedded a an anle in he mold some of he sufae sufae aea of he sample will appea o be eae upon ind n and polishin his ehniue an be used used o povide a man ied view of sufae sufae layes o ohe  feaues ha mih pove diful o see in se on The sample when embedded a an anle anle is known as a ape seon Ohe ways of solvn he pob lem inlude eleoly eleoly deposiion of poeive poeive mealli oa ins suh as nikel o  he use of eleoless eleoless dep osiion soluons Cae howeve should be exeised exeised when u sin hese mehods si ne a o oded sample is pemeable pemeable o he peneaion o f applied layes and hey will eae a visually onfusin esul A label should be inopoaed no he op o f he esn ivin a leas he aboaoy numbe so ha samples an be popely iden ed. Anohe mehod of embeddin vey small samples whih i s ofen used fo fo pa n oss se ions, involves he use of a eanua mold half lled wih esin Fi 8 The sample is aefully

lad on o n he esin e sin su fae nex o one ede of he mold and he mold is hen ompleely lled wih esn, embeddin he sample wihou need of a suppo sik.

Gndng One mouned and se he esin blok mus be ound a The sandad poedue a hi s s ae ae s o use we slon abde papes wih poes sively sively ne ne i size sizess ( 1 0 0 00 600 ) The sample mus be held so ha i does no ok o move ou of one ndin plane ohewise i will be vey diul o ob ain an opially op ially a sufae sufae San wih he oase i pape he sample s moved bakwads and fowads fowads ove he pape unil a unfom unfom ound nsh is obaned. I is hen aefu aefully lly washed washed und e un nin wae examined oaed 90° and ound on he nex ade of pape Ths poess s hen epeaed epeaed wih he ne wo ndin papes oain he spei men 90° on eah pape. I s vey impoan o elminae ompleely he sahes fom he pe vious indin beause hey wll no be emoved by polishn Wih vey impoan speimens a fesh fesh sip

igr 84 mbdding smal sampls.

slicon ubr mold

al ll ll wit rs and al ow o st

intoduc samls and ill wh mo rsn

rmov mountd blocs rom rom mol d

Mnting and Preparng Speen 66

of gindng gin dng pape so uld be used and suessively suessively onge gnding imes ae neessay neessay as as e pape beomes ne is ensues ooug emoval of defomed defomed maeal ma eal a e  e speimen suf su fa aee bef be foe polising. e ualiy of 600 gi pape seems o vay and fany f any lage lage pailes ae pesen ey wll pod ue sufae sufae saes diful diful o emove lae e ae aken wi meallogapi pepa aion of sof meals su as gold alloys zin aloys o some oppe alloys as o be mu moe igoous an s neessay wi ion sees o as ion speimens in aaeoogial onexs onexs

Poshng o mos anien meas e bes esuls ae o be obained by polsing on diamondimpegnaed oay oay polsin g weels weels lub aed wi minea oil. Diamond powdes ae usualy supplied supplied as ubes of pase o n aeosol ans in an oil based suspensio n. e usual ange of diamond powde sizes ae: six mions ·one mion and oneua e mion Some of e polising an be aied ou auomaially using vaiey of maines maines o pol sin g aamens Handnising oweve is usually pefeable fo bes esuls w one mion mion o  oneuae mion diamond pase Polising wi diamond powdes podues less ounding o f sufae sufae deails an i s appaen appaen  wen using alumina alumina alumina o magnesium oxide pases Al umna umn a ofen ofen an be used fo fo less deailed wo and is feuenly saisfaoy fo e pepa aon of ion and seel alloys. Magnesum oxide as o be used fes as i undegoes amospei abonaion and e esuling magnesum a bonae a s fomed may ave a oase ysal fom. Polising is aied aied ou by oldng e spei spei men agains e oaing polising lo I is di ful o uan ow mu pessue mus be used: oo lile pessue eads e ae of polis ing and may esul in some pi ing o f e sufae sufae oo mu pessue may diso e sufae e oe poising pessue vaes wi diffeen meals and an only be leaed oug expei ene Afe Afe inial polising o n six mion diamond



pase e sample so uld be wased in wae insed in eanol o aeone and died I an en be poised o n one mion diamond fo fo a leas leas ve ve minues. o many ouine puposes is is suen and e sample sould en be aefully wased o emove all aes of poising ompound and oi befoe befoe i  is eady eady fo fo examinaon unde e mealugial miosope o vey igualiy wok wok nis by nal nal polis ing on oneuae mion diamond Eeolyi o eleomeanial eleomeanial polsin g an be employed fom fom e g indin g sage and may give a moe pefe pefe nis  an a  obainable fom andpolisin g Dis advanag advanages es ou wi many aaeologial aaeologial samples be ause o f e exensive exensive oosio n a  ey may ave unde gone e pesene of ese oosion podus means a loal anode/aode eaions may ou wi exessive sample disso luion as a esul. esul . f one pase of a wopase alloy is slig ly ooded i  may be pefeenially pefeenially aaked a an aeleaed ae Meania meods ae geneally pefeable unless ee is a paiula eason fo e us e of oe eniues. o example ganulaed gold spees diul o e wee poised and eed a e same same ime using an eleomeanial eleomeanial polising en ue on an adapaion of e Sues "Auopol maine. A fesl feslyy polised se ion soul d be examined meallogapially meallogapially as soon as possible: some sufaes aes anis  apidly and will  ave o b e epol ised Anien meal samples sould alway alwayss be examined in e polised sae o begin wi sine ee may be many feaues feaues aleady aleady visibe unde e miosope

Rerdng Resu 68

graphi mirspe Care shud be taken nt t  nfuse nfuse ntes made n speimens under diff different nditins f pi sh r ething beause it may be very very diut ater t reprdue eaty the eamined surfae As if arefu arefu nte f the speimen nu mber is nt kept t  t may beme very diut t estabish whh speimen had been eamined The same are shud be appied t the phtgraphi rerding

6

TCHINGAND TCHING SOLUTION

A satisfatry metagraphi speimen fr ma rspi r mirspi investigatin must present a representative representative pane area f the maeria T distingu ish the struure eary eary this area must be free frm frm d efets efets aused  aused by b y su rfa rfaee defrdefrmatin wed materia materia s mears) puking f the surfae puut), and surfae srathes n er tain speimens edges must be wepreserved in rder t investigate investigate giding tinning  et Even fr fr rutine examinatin, p r speimen preparatin an resut in prbems beause the bservatin r nusins may nt be vaid interpretatins f th e visua evidene. ished mea sur faes d nt revea detais f struure  n rer t examine examine grain bunaries ther phases phas es an a n eff effets f aying ayi ng aditins aditi ns he h e pished meta surfae must be attaked with seeed hemia reagents that wi revea dier enes in grain rienatin and mirstruture There are tree ways ways in whi ething a pis hed meta surfae an be arried ut

1



33

With hemia hemia reagents either as a sutin  r as a gas With eetryti eetryti ething, by appying sma AC r DC urrents t the speimen immersed in an eetryte eetryte With eetrmehania ething whih is a mbinain  f andi dissutin in an eetryte eetryte and mehania pi shing f the spemen

This setin deas wih ething sutins that are apprpriate fr arhaegia metas. The pished pis hed meta surf s urfae ae must be free f a traes f i frm pishing and f pishing pishing mpunds grease, and parties f dirt The usua predure is  pur a sma uant ity f ething sutin int a sma petri r rysaizing dish s that the speimen an be immersed fr a few sends r min utes as neessary neessary S me sutins need  be freshy mixed befre befre ea h use s ine they either underg very rapid hemia reatin suh as sutins  f ptassium ptassium yanide mixed with ammnium persufae) persufae) r they swy deterirate deterirate suh as sutin s mixed with hydrgen perx perx

ide) One the surfae f the sampe has been expsed expsed t the ething sut in i t shud nt be uhed it an b e dried after after rinsing i n ethan r aetne by p aing it i n frnt frnt  f a speimen drier fr a few sends Smetimes at this stage, very bvius sainin g f the speimen speimen urs arund the edges where where it meets the resin munt This i s a nseuene f he ethant seeping dwn any ne rak that may be present presen t and then being drawn t the surfae upn drying Sme speimens reuire nsiderabe are if this prb em is t be avided r exampe it may be ps ibe t dry the sampe mre swy swy in air r t dry it u sing a stream  f d air After After the sampe has been ethed, it is imp rtant t examine it immediaey immediaey as stred and ethed speimens an rapidy beme arnished, and this b sures the surfae surfae detai the ehant is t rying t revea revea The sampe, sampe, i fvery deiate shud be eveed eveed in suh a way ha the impat f the eveer des des n t fa fa nt the ethed surfae f the meta Damage t the s urfae urfae struture an res ut i f he eveer is depressed int s ft ft ays suh as gd and siver Sund metagraphi prinipe ditates that a speimens shud be examined in an unehed nditin befre preeding t the ethed examinatin This is party beause ething wi ften ften dissve ut any inusins that may be present this wud mean repishing the entire speimen), and party beause ehing ehing may nt be ne essary wih sme arhaegia materias f the speimen is twphased r has surfae surfae enrih ment r ther visibe features, features, a this sh ud be nted in the unethed nditin be fre preeding t ething

Ethat fo o, t, d at io Na 100 m ethan, CHH 2 m niri aid HN  cra 00 m ethan CHH  g piri aid aid CH{OH ){N)

Etching and Ethng utn 70

This is the most common etchant fo fo woght ion and on cabon steels Often usefl fo ion and heatteated heatteated steels pealite and matensite eC is stained a light yelow ta and pial can be mixed mixed togethe togethe in 1 : popoton



Oberhor  reagent 500 ml dstlled wate wate H 500 ml ethano C H OH 42 l hydochloc acd, HC 30 g feic choide eC 05 g stannos stannos chloide chloide SnC add HCl last last

 

Afte etching the section shold be nsed in a 4: 1 mxte of ethano ethano and hydochloic acid Usefull fo Usefu fo steels steel s and fo fo segegation segegatio n studies stu dies in ions eg asenic segegation Heyn  reagent 0 m distied wate H 0 g coppe II ammonium chloide, chloide, CuCH

Coppe  pecipitates pecipitates m st be wiped fom the s face with distilled dis tilled wate o  washed offwith disdi stilled till ed wate wate  fom fom a wash bot tle Usef Useful ul fo fo phos ph os phous segegaton segegaton i n stee Kemm  reagent 50 ml satated satated aueous solution o f sodim thiosulfate, thiosulfate, a S 1 g potassiu m metabislfate metabislfate KS

Phosphous segegation in ca st steels and cast ons Baumann Bauman n  print oution 100 ml distilled wate H 5 m sulfuic acid HS

Sive bomide pape is satuated with the solution and mly pessed pessed against against the specmen sface Afte one to ve minutes, inse and x with a soluton of 6 g aS in 1 00 m H  Wash and dy Usefl fo veication aangement and distibut ion of ion and manganese sulde inclusons Beraha  reagent 100 ml distiled wate, H

24 g sodum thiosulfate aS  3 g ctic ctic acid acid CH COHCH COOH  H   g cadmim chloide CdCl  2H Us e fo fo 040 seconds C hemicals must be dissolved in the seuence give n Each constit uent must dissolve befoe befoe adding the next Stoe i n the dak dak unde 0 °C i lte befoe befoe use Solution emains active fo fo only fou fou h ous Used as a t int etchant etchant fo fo ion and cabon steels e ite is staned bown o violet Cabides, phosphides and ntides may be only lightly stained With Beahas eagent, feite feite is coloed bu t cementite is not, so that both poeutectoid cementite and cementite in pealite ae in sto ng contast to the feite which can make even thin lms of cementite easily visible Akaine sodium picrate  g picic picic acid acid CHOH   5 g sodium hydoxide aOH 100 ml distlled wate H

This soluton is useful fo distinguishng between between ion cab ide and feite feite in steels It can be used as a boiling sol ution fo ten minutes o longe if euied The ion cabide eC s dakened by the eagent whle feite s unaf fected Etching in this solution may povide a good indicato n of pealite pealite lamellae spacing Beauard Beauard reag reagen entt 0 g sodium bisulte, aHS aHS  1 00 m distiled wate wate H

To ense that the specimen i s evenly wetted it is often a good idea to etch in nital fo two to fo seconds befoehand Beaujads eagent can then be used fo 1 05 seco nds the th e suf su face should be vey caefully washed and died othewise the deposited suface suface lm will be dis tubed The eagent poduces good contast between fe ite gains and between lghtly tempeed matenste and feite as well as delineating cementite netwoks The eagent woks by depositing a complex oxidesuldesulfate lm on the metal suface suface n vaious shades of bown

Ehng and Ehng Souon 7

Dmehy Dm ehygom gomee ncke nck e es Some anien seels onain nikel as an impoan impuiy. A simple es is o ake a nikel nikel pin  by pessing a bloi ng pape soaked soaked in dimeylglyoxime dimeylglyoxime agains e polis ed seion wen e nikeli aeas ae evealed by bown saining on e bloing pape. Vea  reagen 1 g pii pii aid aid CH CH OH ) 100 ml eanol CHH 5 ml ydoloi aid HC

A eagen a an be used 540 seonds and eveals lealy lealy e needles of pae maensie. I is useful fo exposing e ausenii gain size of uened and empeed seels if is feaue is a all disenible.



Wheey mehod 5 g silve niae Ag 100 ml disilled wae, H

A eniue fo evea evealing ling sude in lusions in seel and oe aloys. aloys. Soak e polisin g lo in e fesly fesly pepaed pepaed solu ion.  e lo is en wased o emove al exess soluion . Te pol ised sufae sufae of e sample is en ub bed ae fully ove e pepaed su fae fae of e lo . Any sulde inlusions a ae ae pesen soud be sained a dak bown

Etcnts for gold lloys See ammoni um pesulfaepoassium pesulfaepoassium yanide yanide p. 2 used fo silve alloys. A vey usefu solu ion fo a wide ange o f gold alloys. Aua rega 40 ml nii aid, H  60 ml ydoloi aid, HC

Used fo a few seonds o up o one minue Use fes fes Aua egia is a song oxid izing solu ion and igly CORROSVE. CORROSVE. In mos aoys aoys i povides gain onas. Hydrogen ydrogen perode pe rode / ron  ron (II chorde 100 ml disilled wae H 100 ml ydogen peoxide, H 32 g fei fei loide  eCl 

Someimes useful fo vaiable aa gold jewely alloys and AuCuAg aloys.

Etcnt for tn Ammon Amm onum um posud posude

A sauaed aueous aueous solu ion of ammonium polysulde. Use fo 2030 minues . Wipe o ff wi oon wool afe eing. Can be used fo al ypes of in alloys. i al o pial an also be used see eans fo ion see and as ion)

Etcnts for znc in aloys ae diful o pepae meani aly ake miosuues ae ommon beause defomaion is diful o peven



ameron reagen 100 ml disilled wae H 20 g omi oxide C  1  5 g sodium sulfae, sulfae, aS anydous) o 35 g sodium sulfae, aS  10H

Can be used fo seonds o minues.  concenraed H n dsed waer 50 ml on. ydooi aid HC 50 ml disilled wae H

Tis so ui on is someimes useful useful fo fo swab appliaion as wel as immesion.

Etcnts for led lloys Gcero echan 4 m gyeol HOCHCHOHCHH  ml glaial aei aid CH COOH  m nii aid H 

Use fes only Gives gain bounday on as ial an also be used see eans fo ion see and as ion). Gaca Gaca acec ace c acd  5 m glaial aei aid CHC OOH 20 ml nii  aid, aid, H 

Usefu fo lead soldes and PbSn alloys. If difuly difuly is expeiened in e pepaa ion of lead alloys alloys a good eniue is o y nisin g e pol ising wi ne alumina powde o 1/4



Ethng nd Ethng tn



mion) upended in ditilled wate wit a 1 % olution of aueou ammonium aetate. aetate.

Echans fo coe alloys Aqueous rri hlorid hloride wate H  1 20 ml ditilled wate ydoloi aid HC l 30 ml ydoloi 1 0  fei loide FeCl 

odue gain ontat. Vey ueful fo all oppe ontaining alloy u a te aenial oppe, bonze bae et. Eting time i given a a few few minute in ome book but anient metal et fate. Redue time to 3-5 eond at t. Aloholi rri hloride hloride etanol CH OH 1 20 ml etanol aid H C 30 ml ydoloi aid 1 0  fei loide FeCl

Same a aueou fei loide exept tat tee may be ome advantage advantage in uing an alo oli olution le taining fo fo example). Aqueous ammonium persute 1 00 ml ditilled wate H 10 g ammonum peulfate, H)S 

Only a few eond ae n eeay eeay fo all tee etant unle peied to te ontay. Po due gain ontat. Mut b e ued fe fe will not keep.

feiyanide de FeC N) 5 g potaium feiyani wate H  1 00 ml ditilled wate Ti etan an be ued to daken ome peipitate u a C C  P wi may oexit wit alpa delta eutetoid. CP an be een a a puple pup le ade againt te vey pale blue o f e delta pae. Afte Afte eting in FeC   te ditintion i lot. Some difultie may be oveome by uing a elatively elatively ig amount of aueou ammonia i n te nal poli e.g.  5% HH).

+

Echans fo oxde ayes on on Solution 1 wate H   0 ml diilled wate 5 ml 1 % niti aid HN oluion 5 ml 5 % iti aid CHCOHCHCOOH) olution 5 ml 5 % aueou tioglyolli aid HOCH HOCH  COS COSH H

Swab fo 15-60 eond. Ete Fe   Fe  i not attaked. Solution 2 wate H and 1 5 ml ditilled wate 5 ml fomi aid HCOOH oluion a) 1 5 ml H and uoboi aid F B  oluion b) 5 ml uoboi

Swab fo ve eond wit olution a) fol lowed by oluion b) fo two eond. Ete Fe Fe only.

Saturated Saturat ed soluti sol ution on ofhrom h romiu ium m I I oxide

Comium VI) oxide olution ould be andled wit geat ae. Mixtue of C and an d ogani may be EXPOSIVE. Gain b ounday etant. A mmon mm onia ia// hydr hydrog ogen en peroxide 2 5 ml ditiled wate H 25 ml ammonium ydoxde HH 52 5 ml ydogen ydogen peoxide H 

Make up and ue fe fe only . Adding lage amount o f H eate eate bette gain ontat adding le H eate bette gain bou nday eting.  potas po tassi sium um rriyan rriyanide ide

Echans fo slve alloys Aided potassium dihromate  0 ml ulfui aid HS atuated 1 00 ml potaium diomate atuated C in wate NC oluti on 2 ml odium loide atuated NC

Dilute  :  wit ditilled wate befoe befoe ue. Can alo be ued witout t e ulfui ulfui aid addition. Ueful fo ilve and oppeilve alloy. Am monium moni um persute / potassium potassium yanide yanide wate H an d  00 ml ditilled wate peulfate H S  a) 10 g ammonium peulfate 1 00 ml H and

Echng and Echng Sun 73

0 g poassium yanide CN b) POSON Soluions a) and b) mus be mixed before used in he proporion    Afer Afer use ush down he sink wih pleny of waer. Never mix wih aids aids The solu ion of poassi um yanide yanide is POI SON OUS  Also useful useful for for gold alloys silver aloys opper alloys. Make up he pe rsulfae rsulfae sou ion jus  before before use

I

Ammonia hydrogen peroxide 50 ml ammonium hydroxide NHH 50 ml hydrogen peroxide H

Mus  be used fresh. Aided thiourea 0% aueous soluion of hiourea SCNH 5 0 drops o f eiher niri niri aid HN or hydrohlori hydrohlori aid HC 

ntfnc m tchants fo colo cts I is someimes useful o invesigae he applia ion o f olor meallography o anien mealli obje speimens. One of he poenia advan ages o inerferene lm meallography is ha oring and segregaion may be reveaed reveaed when onvenional meallographi ehniues fail Coor meallography may also b e us ed o enhane he visual appreiaion o f mirosruural mirosruural fea fea ures. Fur her deals onerning he ehniues whih may be employed an be found in Yakowi   70)  Peo Peow w and and Exne Exnerr   5 ) and Phillips   7  ) . Some of he he useful useful reipes reipes are se ou below In rfrnc rfrnc chans for coppr aos

Aid A ided ed seLen seLeni i aid a id 2 ml 35% hydrohlori aid HC 05 ml seleni aid HSe 300 ml ehano CHOH

his soluion an be used afer afer rs ehing he polished sample for a few seonds in a 0% soluion solu ion of ammoniu ammo nium m persulfae Dy afer afer eh eh ing in persulfae before using he seleni aid ehan

I

Aided thiosute aetate  2 g sodium hiosulfae hiosulfae NaS  5H  .2 g lead lead aeae aeae PbCH COO  3H  .5 g iri aid CH   H H  50 ml disilled disilled waer waer H 

Use afer afer rs preehing wih a mmonium persulf persu lfae. ae. A very useful useful ehan e han  for for op per alloys bu mus be made made up fresh fresh as he soluion wil no  keep. Dissolve he hiosulfae before adding he oher ingrediens Bes made by plaing he prepared soluion so luion in a refrigeraor refrigeraor for wenyfou wenyfourr hou rs when a lear lead lead hi osulfae osulfae solui on should form wih a sulfur sulfur preipiae

I

Aid A ided ed sute hromi oxide 50 g hromium rioxide Cr 5 g sodiu m sulfae sulfae NaS 425 ml 35% hydrohlori aid HCl 25 0 ml disilled waer waer H nrfrnc chans for iron, s, and cas ron

 g poassium meabisue S  00 ml disilled waer H This ehan is u seful seful for boh arbon and alloy seels. 2 g sodium molybdae NaMo  2H 200 ml disiled waer H Aidi Aidi o pH 2.5 o 3 us ing dilue niri  aid aid Useful for as irons afer rs preehing wih nial 0 g sodium hiosulfae hiosulfae NaS NaS   5H 75 g iri aid CH   . H 5 g admium hloride CdCl  2H 25 0 ml disilled waer waer H  Useful for as iron an d seels wihou preUseful ehing Mus  be freshly freshly made. This soluion will no keep longer han a week. Saturated Saturated thiosute soLution 00 ml sauraed sodium hiosulfae waer NaS . 5H in disiled waer 2 g poassium meabisule S

Can be made up fresh and used for as iron and seel alloys

hng (nd Etchng Sutns 4

Seleni Seleni aid soluion 1 0 l 3 5 hydochloc acid HC 4  selenic acid HSe ethano CHO H 200 20 0 l ethano

Can be used fo fetic and aenstic stees nrfrnc chans for aumnum aos

Mobdae Mobdae / buoid buo idee 2 g sodiu olybdate aMo  2H hydochloic acd HC  5 l 3 5 hydochloic bioide H H 1 g aoni bioide 1 00  distiled wate, H

Can be sed fo fo etching both a luniu  and titaniu alloys

Note on ue of thee eagent fo colo etchng and tntng of coe allo Peetchng which is soeties necessay, should be caed out with  0 aoniu pesufate soution afte whch selenic acd etchant o thiosul thios ulate/acetate ate/acetate etchant can be eployed. In eithe case it can be df d fcult to fo fo ow the change of colos colos in vey sal sap es. The peetched saple shoud be esed n the ntefeence etchant and the colo change obseved. The seuence of co os should be fo fo yllow oange ed violet violet b e and nally bight slve. slve. Etching should not be alowed to contin ue beyond the blue o violet stage Choc acid/slfate acid/slfate etchant should b e used withot peetchng and s useful fo ipoving gain conast The tho sufate/ac sufate/acetate etate etchant fo exaple when used on an bass esults in the th e gains tunng lght geen while the gains becoe oangeyelow Wth a 5 cast tin bonze the denditic egions ae coloed coloed bu e yelow o bown bown dependng on oentation the eutectoid can also be cooed bown in the thiosufate/acetate etchant afte peetching in aoni pesulfate) pesulfate)

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 7 MOUNTING IN

Moun ng esns come in diff diffeen ypes and some som e manufacue ma nufacuess offe offe seveal seve al gades fo dif d ifffeen puposes Te mos suiable ae epoxy o polyese polyese esns a ave ave been specially adaped fo meallogapy meallogapy o mouni ng of small speci mens  Two suiable esins used by e auo ae gven as examples one an epoxy esin and e oe a polyese

poxide Manufacued Manufacued by Buele Ld 4 1 Waukegan Waukegan Road, O Box 1 Lake Buff Ilinois 60044, USA Epoxide Epoxide 20 30032 wi ade adene ne 20   3200 , is a coldmouning epoxy epoxy esin syse sysem m wic s excelen fo almos clea mouns fo meallogapc meallog apc samples Te esin adees well well o sampls and sows a vey low snkage ae dung cuing I ses in abou eig ous a oom empeaue Aloug e seng ime can be inconvenien  is bee o wai fo fo oomem peaue cuing an o speed up e pocess by cung in an oven a a ge empeaue sink age would would be moe likely o o occu Buele Ld aso manuf man ufacues acues a comple e ange of good ual iy mealogapic euipmen and many oe esi n ypes

Polyeste Scandiplas 01 U Disibuo: Hadene 1 % Scandipas 102 Manufacued Manufacued by olaon Euipmen L d, 6062 Geenil Cescen Holywell Indusial Esae, Wafod, Wafod, H efodse, efodse, U . Tis polyese esin, wic s geen can be used as an embedding esin fo sample examinaion in eeced lig o as an adesive fo some applica applicaions ions Scandipas Scandipas   0 1 s used wi wi a pe pe oxide oxide caays, caays, Scandplas Scandplas   02 One dop of caalys is added fo fo eac millili e of esin S iing soud b e caed ou  caefully caefully and no  violenly so a ai bubbles ae no incopoaed ino e esin Te poyese mus be used wiin six o

eig minues i can acieve a wokable adness afe afe 45 minues Te polymeizaion of e esin can be accel accelea eaed ed by eaing o o abou 45 °C I n fac, e manufacues ecommend eaing because exended adening ime a oom em peaue may esul in some s uface uface oxidaion, wc can lead o inco mplee polymeizaion and a oweed cemical esisance of e cued esin, aloug is is ae Si mialy o avoid a acky acky suface on e se esin, i sould emain in e mod uni i  cools down o oom empeaue Tis pevens oxidaion eacions a e suface suface of e o  esin  Because of excessive excessive ea genea on, e esin sould no be cued in a dying oven o any simila closed conaine Te sample sould be oougly cleaned cleaned and degeased degeased is will aid i n e adesio n of e polyese polyese esin esin o e sample Scandiplas Scandiplas  1 0 1 will cue fully fully afe afe eig  ous and can b e gound and pois ed o give a pe fecly adeuae mouning maeial Te m anufacue anufacue mainains a ee will be a complee absence of ai bub bles in e cued esin bu  is i s no always always e case n any even cae cae mus be aken wen poui ng e esin ino e mold so a ai bubbles do no become ap ped on e suface suface of e sample since ey will in efee efee wi e pod ucion la e of a scacfee suface by eaining abasive paicles o ensue paiculaly good edge eenion of e sample a small amoun of e esin can s s be made up and poued ino e boom of e mold o fom fom a laye abou 1 2 mm deep Once is laye as as cued, e mold is en lled up in e usual way o fue deails concening e mods and sample pepaaion see Cape , p 43 ) Te bes molds ae ae made ofsilicon ofsilicon ubbe olaon Euipmen supplies Scandifom embed ding molds wic ae excellen fo fo  is pupose as e Scandiplas esin i s easily emoved emoved fom fom e silicon ubbe suface suface Scandipl Scandiplas as 1 0 1 is no suiable fo vacuum impegnaion, and i f a vacuumpoing ecniue is necessay necessay a lowvscosiy epoxy esin is pef p efeable eable

1  MICRO MIC ROHA HARDNE RDNE ETING

Meals are raher differen fr ineras in ha Mhs sale f hardness ann be sed arael  assess he hardness f a ea Usall ehds s be sed ha defr he eal eal in a hardnessesing ahine nder a erain ad epling a speial shaped indener  press in he s rfae rfae f he eal. An earl ehd avidin g he need fr defr defr ain a he s rfae rfae was  drp a seel ball n he srf sr fae f he bje and easre he dis ane ha he ball rebnded afer afer ipa. Alhgh his devie aled he serspe is nw a hisr ial risi se earl arhaelgial arhaelgial reprs refer refer  his ehd  f hardness esing hs is enin here. Brinell hardness esing (H ) was he rs ehd  nd niversal aepane. Wih his ehniqe a seel bal f knwn diaeer diae er is fred fred in a eal srfae nder a erain applied lad. The diaeer f he ipressin ipr essin lef lef n he srf s rfae ae an be easred arae and a sale f hardness allaed. allaed. S bseqen indsrial develp develp ens have brgh her sales and ehds in perain sh as he Rkwell Rkwell ehd (H) he Knp ehd (H) and he Vikers ehd (H) . The nl si able sales sales fr fr arhaelgial eas are he Brinel and he Vikers sales. The Vikers ehd ilizes a frsided 136°, diand praid indener and he resls f he sale are are seies qed as DPN nbers (fr Diand Praid Nber). his is he sae as he H  ere ere being a di fferen abbreviain fr fr he resl . he Bri ne and Vik ers saes are rghl he sae alhgh fr arae wrk he d iff iffer and a able  f eqivalens eqivale ns s be resred  fr se parisns (see The Meta Meta Handbook an dbook h Edi in fr fr he s reen infrain) infrain) . Marspi sale hardness ess leave ipressins in ea ha an be seen wih he naked eein s anien eals snd ea is n fnd a he iediae srfae and hardness es ing s sal be arried  n a ir raher han a ar level n a plished and ned sein sing a speial irhardness ir hardness esing ahine. Mirhar dness esers sall perae

n he Vikers sale and are availabe as aahens fr invered sage ealrgia irspes sh as he Vikers eallrgial irspe r as aahens fr sage ir spes ha se reeed ligh. One sh ins ren is he MCrn e w w level ir hardness eser whih an be aahed  he Vikers eallrgial irspe. r readings readings  f he he hardness f a sape are aken  he saple s be n ed in ebedding resin in a 1 " r 1  1  4 " d and he srfae s be plished herwise he ipressin f he he indener a n be visible. The exa relainship b eween eween he ararhardness and he irhardness irhardness f a parilar saple a be dif  pare bease f a nber f pliains pliains ha ha a a arise. One eaple eaple is grain size if he he irhardness inden ain fals arss nl ne r  w grains i a n pa re wih a arhardness arhardness reading whih averages he resl f defra defrain in ver an grains and grain bndaries.

ENDIX EN DIX 

OON MICROTRUCTUL SHE

Figur 85. Shaps of r in low carbon sts sts 

gur 86. Common dscri ptiv trms

grain boundary allotriomorphs allotriomorphs quad qu ad hagona hagona grains

Widmansttt Widm anstttn n sid pl ats annaing twin

Wid manstttn ma nstttn sawtth strain lins sl sl ip lins)

idiomorphs

mchanical twinning

ntracyst ntracystali ali n a so known as transgranuar) crac k intrgranul ar Widm anstttn anstttn pl ats

intrcryst intrcrystai ai n crac) massd frrit

o

polygona

acicuar

dndritic

Appndx A

bandd

nta

ibos

GC

siorm

c  nodlar

tripl pont

o

disontinos disontinos p ipi

•

matnst ndl-ik)

o I  mnar grains

botryoidal

   rhomboidal   ang lar ragmnts

AENDX B

MROTRUTURE OF ORRODED METAL

intergranula intergranula orrosion

intragranular intragranular orrosion

pitting orrosion

uniorm orrosion through metal

stress-ang oroson seetve oosio n

 seletve orosion (parting) orrosin po duts over the origina srae srae avtation avtation orroso n

slip li nes outined by orrosion

twin lines outlined by orrosion orrosion

warty orrosion

remnant remnant metali metali grains in a mass o orros ion

orrosion produts and dis rupion o the su rae rae

AENDIX C

MICROHARDNE VALUE OR IERENT LLOY AND METAL

The vale given in e abe bew r he vari an in icr ardne  e  he cpper baed all lae he advanage  ing in brnze r r ba ning hard aeria Te ncreae n e Brinel hardne r r arenca cp per in  e range  3 arenic i  e n er e ince e prpr n  arenic inclded in e all bend he 3 leve ha relaivel ile e eec n  n e  e abili abil i  he all  be hardened an rhe rherr b wrking. Thi  in cnra  he in brnze where where increaing an   in prdce ccevel harder al when he are cdwrked An even greaer eec i niced when he n brnze are cpared wih lwnccnen bra and cprn cp rn ickel all b   whch are n grea ardened b cdwrking a e 50 redcin eve. Thee gre have a pracical iprance The clr  he prdc pn ca ng a be rngl a aeced b invere egregain  arenic  he  race race  he ld b a ar a reng h r hardne i cncerned here i li le r n advan advan age in having  arenic in he al cpared wih 3 arenic.  d be brne i n ind r r a pracical pn  view ha  i ver dicl dicl  cpare he rel  hardne e n ancen al where d i ieren hardn e cale have been ed. The cae ed d awa be peced and he ae cale epled whenever p ible r all cparin wh  iilar aeral aeral i n dieren dieren degree degree  wrkng r c p in. The llwin llwin g li give e vale r range r e icrardne  aeral  inere in he Vcker Vcker cale cale (H  whch i ne  he  generall e cale.

ea  A pre cpper ca 050 pre cpper wrked and annald 5060 pre cpper cd wrked 0020 7030 bra annealed 5065 030 bra cld wrked 20160 gneal ca ca 650  8 arenic arenic cpper cpper ca 8  . 8 arenic arenic cpper wrkd wrkd 650 2.6 arenic cpper ca 6570 2.6 arenic cpper wrked 5060 ca eaded eaded brnze brnze  0n 5 Pb 0 ca eaded brnze 10n 0 Pb 65 ca leaded leaded brnze brnze n  5P b 60 pr e ead ead 36 pre in 60 pre alini 22 pre lver ca 530 iver wrk hardened 80 20 cpper 80 ilver anneaed 550 0 cpper 60 lver annealed 550 60 cpper 0 lver annealed 650 80 cpper 20 lver annaled 650 1 2 n brne l l wrked wrked 220 0.5 C eel waer qenched 56 5 6 0. 5 C eel eel anneale annealedd 00 C 8 0.5 C eel annealed pearie  8 0. 55  C eel waer waer qenche qenchedd 86 8 6 0. C eel waer qenced 65 0.3 C ee nralzed 323 03 C ee waer qenched 83 6 ancien e epered arenie 535 ancen arrwhead epered arenie 3 0 knie bade epered arenie 2 0 ancen aw errie  85 rie chiel erre  2 axe pearlie and errie 26 ckle pearlie and errie 

endx 8

Hardnee f  f e ip an aly n he Brinel Scale (H in he 50 redcin cd red (i.e. wrked cndiin and in anneaed cndiin. 

 Reduction

H

Annealed

Brnze   Sn 2 Sn 3 Sn 4 Sn 5 Sn 6 Sn  Sn 8 Sn

 10 5 1 30 1 40  60 178 1 0 15

Arenical cpper A 2 A 3A 4 A 5 A 6 A  A 8 A

1 18 1 38 1 44 1 46 1 48 1 48 1 4  50

50 5 52 53 54

Cprn icke ally ally Ni 2 Ni 3  Ni 4 N i 5  Ni 6 N i  N i 8 Ni

1 02 1 04 1 08  0 1 12 1 14 11 21

52 525

Bra aly wih lw zinc cnen 1 02   Zn 1 04 2  Zn 1 06 3  Zn 1 07 4 Zn 1 0 5 Zn 1 12 6  Zn  14  Zn 1 8 8 Zn

50 52

54 59

62 2 80 82

55

56 58

53

54 55

56 5 58 51 5.5 52 52.8 53

54

55 56



AENDX D

LLOY ED N NTQUTY

Coe

Ion

pperin (brnze) als igin brnzes s as sadr and spe)

irnnikel (eeri/nsal res) irn pls slag (wrg irn)

pperarseni pperarseni (arsenial (arsenial pper r arseni brnze)

Ion Ion Cabon abo n A lloys oys

gre as irn (free C)

pperann

wie as ir n (n free free C)

pperzin (brass)

Steels

ppersilver (sibi)

pereei (>0.8

ppergd (aga sakd)

p pe ee e i i « 0.8)

pprzinead (bidri)

irnnirgen irnnirgen (niriding)

pperzinin (laen seies P)

irndrgen (ebrileen n seels)

pperprs ide pperinarsen

Lead leadin (s f f slders, anien pewers)

ppernikel (prniel)

leaded brnzes brasses e.

Gold

eadgld (fr gilding)

glderr (aagas) gdpper (aga)

Tn

gldsiver (eer)

inead (anien pewers) pewers)

gdplain (sinred as)

inanin  (dern pewers)

gldirn (Egpian rse glds)

inpper inpper (e. g. aings aings s as CSn)

gldlead (seies sed fr gilding)

Slve siverpper silvergd siverlead (seies fr pelain) siversilver siversilver x ide siver n irn (exape f gaa ada)

APPENDIX E

ERS AND ECHNIQUES IN NCIENT METALWORKING

Joining Techniques

Casting and Working Techniques

Mechanical MechanicalJoins

Casting

rImpIng overlapping overlapping s eam overlapping sheets riveting taband-slot Metallu Metallu rgicalJoins Join s brazing hard soldering fusing fusing welding (2 parts ocaly heated) fusion weld ler of same composition in sol id state ller of same composition in liquid state pressure welding (solid state) reaction soldering (as in granulation) sof sodering

Surface Surface Treatment Techniques Suce Coloration Coloration chemical solution treatments gold powder powder in binding medium pigments pigme nts and dyestuff dyestuffs Suce Coatings amalgam gilding arsenic coatings fusion giding goldiron alloys alloys gold or siver siver electrochemical electrochemical depositio n leaf giding platinum coatings silver coatings over copper tin coatings Sufce Enrichment depletion gildin g of AuCu AuCu aloys depletion silvering of Ag-Cu aloys gravity segregation inverse segregation natural corrosive processes seective surface etching selective s urface urface removal

casting on lostwax soid over a core from a master matrix other renements (e.g., mod carving) centrifuga casting open mold piece mold twopiece multipiece slush casting Working annealing chasing coldworking drawing engraVIng ling hotworking machining turnng drilling boring miling pIercIng punching quenching raSIng repouss spInnIng stamping tempering

AENDIX F

METALLOGAHIC STUDE

This setin ntains a iselan f itr tres ith a liited an f infratin infratin n erning the psiti n f the the bjets sdied Mst  f the the irstrtes hae been hsen bease the are f gd qalit and illstrate a ide range f featres seen in anient talli als, an f hih hae n de eqi alent. t d be ideal if the setin setin inlded repreentatins f the fl range f irstr tres t be fnd in anient and histri etal rk bt this is e dift dift t ahie. ahie. The seletin that flls is therefre sehat arbi trar trar b t inldes a gd range f pper pper as

irn and st and  xapes f siler and gld al e e ndbook l  pblihd b the erian Siet fr Mta inld an irstrtres reeant th td f anin tal and th th ditin has ben expanded t er preis etal h a ilr s that the text is re efl a bradr adi ne n rder t ake this appendix aibl aibl exapes are indxed ith rgard tpe f irtrtr all bet and perid r pr pr nane These appear in itali tpe in the indx at at the bak f this le.

t

t

t

Slvecoppe lloy con

Figue 87 Base silve-coppe aloy coin o anagu pta Westen Inia c AD. 470. 470. I I mm.

This is a ate and degraded fr fr f the drah hse rigins a be traed bak er 600 ears t the nd Greek kings his his in bears bears the kings head n the berse side and a re altar n the reerse. reerse. t is sall, thik, and strk in a hdebased hdeb ased silerpp er al that as alst ertain srfaeenrihed b piing reslting in pper depletin at the ter srfaes srfaes n the nethed n ethed nditin the phase natre f the in an be seen althgh it bees h re eident pn ething in either ptassi  dihrate r ferri ferri hlride. The dendrites, hih are silerrih, are nt n tins indiating a rather l siler ntent abt 1 8% anags anags t ther str siler siler pper all all ins . The silerrih phase is eln gated and attened attened ang the ength  f the in. As the ntrs fll fll the depressins in the srfae srfae sggesting the in as strk hile ht. he rrsin is qite liited and des nt extend h bel the s rfae rfae int the interir f the all.

Fge 88 top ow magncatio magncatio sowg pat o te stuc s ace. ace. No te te cu vatue in te stc tue as a esult o eomatio. eomatio. tc: tc: FeCI ; 32. Figue 89 bott bottom. om. T e coppe- c gais can now be see wt te attee attee emats o te sve c  c pase passig along te egt o te coi. Note te entic emnats ae ae not cotiuous but occu as iscete eogate eogate plates. Fom smla c ast a woe sectios te sl ve cotet ca be ogly estimate at abot 1 20% 20% tc: tc: FeCI; 1 2 3 



ppndix 87

slamc nlad nell cast n a coppe tn-nc-ead tn-nc-ead alloy he inla n his ne inlaid inkwell has been arried  in silver pper rk asphal asphal and prb ab grnd qarz.  was ade in he easern Iranian prvine f Khrasan Khrasan prbab i n Hera dring he perid fr fr he lae 1 2h hrgh earl 1 3h enr he inkwell easres 103  high (wih id) and has a diaeer f apprxiael 80 . he psii n f he he ea sed in he anfare was fnd  be: pper 65 in 5 zin 20 lead 10 wih saller ans f irn and siver. A saple aken fr he ri f he bd f he inkwell was reved sing a ne jeweler's saw. Alhgh here are fr fr ajr  nsiens he all an be nside red a ernar ix f pper zin and in bease lead is iisibe in pper. here is a rand saer flead glbes visible in he plished sein. he sein ehes well wih alhi ferri hride and reveas a red srre  he grains shwing ha he inkwel has been as  shape. he inner areas f eah grain are riher in per and h e er areas areas riher in zin and in. Als eviden in his sein are a nber  f hles ha are de  se prs i presen in he asing he prinen ring shws ha he inkwell i nkwell was n exensivel wrked r annealed flwing fabriain. Hwever se srain lines an be seen near he srfae sg gesing se nal wrking in he asas asas ndi in prbabl de  hasing f he srfae  reeive reeive he inlaid eal eal srips srips (see Plae Plae 1 1  .



Figur 90 abov. abov. Isla mic nla id n kwll rom th astrn astrn ran ian provinc o hurasan. Fgur 9 1 , top righ right. t. Coring is vdnt, as ar som globu s o lad h largr dark hols ar porosity in th alloy Th structur is dicult to to intrprt ully bcaus o coring Som strain l ins ar visi bl nar bottom right). right). tch FC; 63. Figur 92 midd l right. Ovrall viw o o th sction at at 2 1 tchd in alcoholic FCl showing coring ad gobuls gobuls and com pl structur Figur 93, bottom right. Som o th scond pha s aras may b gamma phas rom th coppr-tin zinc systm which appars as light colord rgons in th pctur Th lad gobu s appar dark gry. tch: tch: FC FC 4  .



Appendx F 88

Cst onze owhed

Figure 94 Dawig o cast broze broze arowhea ro ro Palest e

Fgure 97. Dawig o ate roze Age swor Etch FeC 

This arrwhead is fr Palesine and was exca vaed vaed by Sir linders Perie beween beween  30 and 1 38 fr he sie a Tell Ajjl. Dring his exca vains Perie fnd any arifacs assciaed wih bi dings and graves daing  he early  h Dynasy. This arrwhead arrwhead as well as he Palesinian brnze swrd (belw) were fnd fnd dring he excavains. The cpsi in f he he arrwhead arrwhead is a ernary cpperinarsenic ally wih se lead presen (Gha (Ghand nd rr 1 8 1)  Sn .86 Pb  .4 As 3 8 Zn 0 .8 5 he reaind reainder er cpper. cpper. The arrwhead arrwhead is 30  in lengh and rianglar in shape wih hree ns and a hle fr he sck e n he ang. The icrsrcre f he arrwhead can eas ily be bs ered afer afer eching ech ing i n ferric ferric chlride ch lride fr 35 secnds. secnd s. The cenral reg in f he arrwhead as well well as he hree ns which are seen here in sec in all have he sae sae ndisred cas dendriic paern. This is clear evidence ha he arrwhead arrwhead was cas in a ld direcly  shape and ha he ns were n beaen  r wrkhardened afer anfacr anfacre. e. A lw agnicain  very lng and ney develped dendries can be seen geher wih se f he he inerdendriic eecid in ll. The eecid iself is dicl  reslve se srcre becing apparen a x600.

 

Fgure 95, top F e very ong a u storte storte coppe rich e rites wth wth eutecto ill o phases betwee betwee the the ars Note the occasoa iteer itc pores Etch: Etch: FeC 32.



Figure 96 botto botto he e ritc stucture is clear a the occasioa  eutecto eutecto aeas are oe esove at this agiicatio tha at 32 Etch FeCI  65.

Plestnn onze swod This swrd is daed  he Lae Brnze Age.  has an inac ang recanglar in crss secin and a blade blade ab 28 5  lng and 3 1  wide wide a he axi widh. There is a prnnced idrib (see "Cas brnze arrwhead arrwhead abve fr a brief backgrnd reference). The swrd swrd is cpsed f Sn 8 .20  Pb 02 As 0.66 Zn 1 .2 he rea reainde inderr cp cp per. n he neched sae se grain grain bndaries are eviden as well as qie large b irregarly disrib ed pres. There are n visible slde r xide inclsins presen in his secin. Eching

� in alchic ferric chlride reveals he grain src re  be raher variable. variable. Tward he cing edge f he swrd he grains appear qi e large pssibly fr verannealing dring se sage in is wrking. Tward he idrib he grain size is saler b sill raher variable in size. S f he grains are cleary winned wih sraigh win

ppend



89

Figur e 98 ight. Overall view showing interrystallin interrystallin e raks, lage gains and some porosity in the setion Unethed; 30. Figure 99, ar rght erystallzed lzed grain s trt e with tw nned ystas and orrosion along sl ip bands. th FeCI 62

ines, s hwing ha he swrd was was nished b a na annealing perain. The dark dark hik ines ha i ne s f he grain bndaries are de  rrsin advaning hrgh he a in an inergranar fr f aak The pper has as rrded ang si p panes wihin wihin he grains, 

ini ng an an s ip bands in se pas f he he srre The exen  f hese sip bands sggess ha he na annealin g perain was n sfien sfien  reve he sresses sresses wihin a l he grains as a res f wrking he swrd  shape (see Pae 1 )

Roman wought on This sape is a sein fr a arge Ran bi e (bar) f irn ab  25 x  x   and weighing weighing ab 6 kg.  represens he priar frging frging f he b Dring his sage f prdin prdin s f he inrpraed sag was sqeezed sqeezed  and he irn was nsidaed in preparain fr rade r anfare in fnina aifas As wih he b, his irn an have varing varing degrees degrees f arbrizain. arbrizain. rging an reve r inrde arbn depending n he area f he frge  whih he irn is expsed ear he  ere (bas  f air) ndiins are re ndive  xidizain and arbn is s r he sr re Variabe arbn nen an be advana ges when irn is rged, sine ferrie regins (warbn areas) are aeabe and easi wrked, whie pearii regins are gher.

Figure 1 00. View showing variabe variabe grain size o the wrought ron wth etensive sag partiles and som e arger slag ragments. Note that the slag i s a twophased material and typialy onsists o wstite FeO) as rounded dendri t shapes n a glassy mati. mati. th: nita; 83.

Appndx F 90

Goldcoppe o sheet

mbg

gur gur  0 I . DplionDplion-gild gilddd disc o alloy showng ma god and burn ishd gold su rac dsgn mad by s urac-ching urac-ching h nrichd gold ar ar dplion gilding. Fro h Municpi o o Pupas i n h Dparmn o Naro souhn Colomba and probaby das rom h iara priod, abou I 01 2h cnury D .

This ragen is a ilar dis appxiaely 1 1 0  in diaeer. diaeer. These gdpper alys alys are saly reerred  as mbaga allys y were sally nished nished by a depein giding pr ess. Tis pariar ragen has deepyellw red saes wi se paes  prplebrwn saining . A ila he has been piered piered hrgh he see whih shws se ne srae srahes srahes in he eal eal srr nding he hle. These srahes srahes prba bly arse as a res  n n isin g e piered he when eal brrs were reved wih an abrasive. Analysis  snd eal grains wih an elen irprbe

analyze analyze veal vealed ed a psiin   ab 80. 6 ppe ppe  7.   gd and 2.6 siv Th pished sein sws a ypia wred shee wi sall gains and a   inganlar rsin. The grains an b ehed wih di ly in an ani pesae and passi yanide ixre ha shws he nare  he gldenrihed srae as wl. e grains ae winnd wih s  e win ines being sraig b a ew ew are n. Thre ae s prie insins as wel wel as pi laelae rnning alng e eng h  he sein whi as appeas  be vey evn evn in hinss (see S  8 3 .

Figur 1 02. h dplon-gldd sucur on h su ac ac o h wod sh  s carly dn. Th chan has l h god- rch suac suac largly u naac naac wh  chng h grains which ar now sib  as rcrys rcrys allzd wih sraigh win li ns Th aoy is sing phasd ch KCN (NHS 200.

gur 1 03 No h y y n hcnss o h sh an h smal globls o cpri cpri  ha can can b sn olowng so  o h gran bouai s h a longa longa l a a rgions ar causd causd by so corroso o o cupr dng bur a Unchd x64

cudon coppelo noseng The bje is ne  seveal ea nds r he senday hiney rn bial a La Cpaia Ls Ris pvine Eadr .  is   ineediae size in e lein  nse rnaens  is brial  he lae Milagr pase. The sein hgh he nse naen shws a e pper inrpraes a nsiderabe an  prs xide insi ns ha rn alng he eng  e bje i n a s iaed r r ypia  wred p per. The nsering as n is side srae a very very hik hik (ab 0. 1  1 000 irns irns aing aing

 a wphased siverppe ay There is a very ear dearain bween  appied appied silver aing and e pper bdy  h nsering. The pised sein was eed eed in ali eri eri hride es ling in a wel ed winned rysa s re wih peey peey sraig win lines in e ppr gains. The grains near  ener  he nseing are i large large wih prinen  winnin g (ASTM (ASTM grain sie nber 2 3) while n he r srae sraess  e nseing wih have reeived sligy greaer

ld





Cast asencal coppe axe

ue  06 above above ma coppe ae om Guayas cuad o. 70 mm ue  07 op h The suc suce e is s isny clean Thee s he eeced poo siy o a cas meal b no ode o sulide sulide ncus ons The sble shadi n passn acoss acoss he ains s ue o esiual coin o he casn ha ha pesss d espie he wnned ains which ae ceay visib le ch eCI 32 u e 1 08 boom boom ih. Noe ha he win l nes ae sah showin ha an annealin pocess was pobably he inal sae sae in manu acue. The eaively lae ains he absence o sain  nes and und isoed isoed poosiy in dicae ha he amon o wokin  was no eensive ch: eCI 65.

Sipe aes f his kind were were n n nly in any pars  f he ew Wrld Wrld b  as hrgh he Old Wrld and he ehds f prdi n and anfare anfare are essenially he sae. Many f hese hese aes were ade ade by asing in siple pen lds. The lds heseves ld be ade f sne lay r ea  is se ies pssible  bain evidene fr fr he p siin f asng by eallgraphi eainain. r eaple slag and drss ay be segregaed segregaed  he p s rfae rfae f an pen ld asing wih he resl ha ne side viewed viewed in sein l ks qie lean while he her ay nain re ide inlsins and grss ip riies in  he fr fr f debris r slag. Th is is n  he ase wih his ae alhgh alh gh we knw fr fr her h er eaples h a aes were were as hriznally in nepiee ds. Bshnell ( 1 5 8) believe believess ha he ae is fr fr he Mane perid Spergraphi analyses analyses shwed ha he  he ae was was ade f arsenial arsenial pp er wih ab 1  arseni nen. The her ele ens deeed were presen ny in very sall ans (all less han 0.05 These were ani ny bish irn lead anganese nikel and in.  is dil dil  as pper in pen lds wih  eensive eensive idain rring and ye  he irsrre f his ae is rearably lean: here are n prs ide inlsins  be seen. The ae has been asha as fr h e  ha is evid en fr paern f dis rib in i n f pr siy as wel wel as fr fr he rin g resling fr fr dendrii segregain. Cring rs as sbe pahes f darker darker ehing aerial ha ignres he grain srre and is

learly eviden eviden pn ehing. The fa fa ha he ae has a rerysallized grain srre wih win lines as well as as ring and viral y ndis rbed prsiy indiaes ha i  was was nished by a wrking wrking and annealing press prbably  ip rve rve he shape f he ae raher han  wrk i eensively. eensively. The grains have sraigh win ines indiaing ha he na press was eiher hwrking r an annealing perain. The ahieveen f asing asing he pper aly in a ld and aing an ae like his wih n apparen ide r slde i nsins presen de nsraes nsiderable ealrgial skill.



ppendix F

Chnese nze ncense une The ragen nted r td hw a r etin thrgh the lid  the inene rneThe aple hw an ndi trted at trtre with a air ant  delta tinrih etetid

gur   0 Th outi n o o th qui-ad structur can b clarly sn h utctoid utctoid phas occup is th grain bound aris or th most part part with smal cuprit inc uso ns scattrd scattrd through th sction Thi s structur is u nusual or a normal cast bronz bronz and ind icats annaling tchd tchd in alcoholc CI 98

 

igur igur 1 09 Chins  9th cntury cntury ancstral incns burnr usua ly placd on th ancstral ancstral tabl Hight 90 m

Th nze cst ell A rnze ell r Ban Dn Ta Phet (ee Rajpitak 1  83) with a th rae rae and dark green patina at  the lt wa pre The p itin itin ii C 85 Sn 3.5 P 1 5. 5 A A 0 1 , , Ag 03  Ni 0. 1   C 0 .0 1 . . he ir ir trtre hw the ell wa at at in n e piee.  t ha a are dendriti trtre with extenive extenive prit whih whih i evident in the etin igur I  I  Not th arg coars coars dndrits th tnsiv corroson spcially toward th bottom and th sgrgation sgrgation o th lad and tin to th intrd ndrtic aras tch tch CI  35

m



9

stn dgge dgge hndle The arials sed t ake the hande and blade were welhsen. The n nent f the hande s abt 0% whie the hil  f the bade has has a tin ntn f a   5% . The astingn astingn f the hand er the nished lade nled he se  f a la la ld l  arn d the bade int whh ltn brnze was red. It s irtan that the al sed in asng n has a lwe lting in than he etal t be inrated n the astn rd. Thi s was was faltaed n ths ase b the aref seletin f aerals. he blade has a wked wked irstrtre t he strtre f the hit nrrated nt he handle s an anneaed asting. asting. Te hi t s eqi axed aed with the heai denditi str e f he handle. The redested e hat rs in the rei etween he w nents a hae been ased  w xgen aalailit n  sie a nirnents. That sr f sitatin wd be deal fr this fr f rrsnrede sin henena A sigh tena gradien d als be set  beween the w nents thesees ha is eween the hil and the blade. Redsied er als elaes delta n h egins egins n the hit (see Plate  0 and gs. 670 670 .

Fig I 1 2 agmt o a ista bad om om I an C 766% Sn 208% Pb 09% N i 05%. Th handl  was was cast cast on in a tn- ich bonz aalyss o th dagg dagg hilt yld d C 836% Sn  35%  0.3% Pb 08% As 0.4% 0.4% Ni 0.6% gth 89 m 

Fig I 1 3 Th lt sid o th hotomicogah is th hi t o o th th blad, wh il th gio on th ight is th cast cast on ha dl o th dagg dagg h igl a sti btwn th two two gios is dost c o st ing om om coosi on o th bon. hi s is th s lt o th coosi on o th tctoi has in th high ti cotnt aloy o th ha ndl  90

e

Frgment of  Thi bronze coniner is fragent fragent is part f a irar  ntainer ntaine r wit a plised te r srfae srfae and a rgh inner sr fae Als, the al is rrded n te srfae, ri, and art f te te bd The diaeter diaeter is appriate .4  and the tikness f te te etal etal abt abt 1  5  e bet is ne f a grp f etal nds fr Ban Dn a Pet, a ilage in te pe distrit f Phan an Kananabri Pr ine s twest twest aiand he date  f the site is tght t e abt 0000 e psi tin f the al was deterined b indtiel indtiel pled pasa spetrsp spetrsp as  70% 



Sn 1 %, Pb 0.% As 00%, Sb 0.0%  e 0.0% 0.0% Ag 1 .%. Eainatin f the ntainer reeals a well deeped deeped dendriti strte wit an inling f a atrix that appears s erial t be srathed Hweer, this strtre is de t te deepent f a artensiti strtre in te brnze as a reslt f qenhing te brnze al flwing flwing asting e qenhing predre  reents reents the rnze all (whih is ightin) fr desing int the sal alha deta etetid strtre. Th is was arried t as a deiberate press in the an fatre f te ntainer with the reslt that te

+

Appendix F 

Figr 1 1 4 top ight ight Cast diti  strtur o ord alpa gai s wit a ii l o bta-phas ls Th s  to b two typs typs o ds prst   atsit ds ad tikr tua ds th: FCl x62 gu  I 1 5 botto botto right right largd largd iw o o t sa ara i wi wi  t bta bta artsiti stutur is  arly isibl T llik artsiti pas s dsigat � a th ddrti oppr-i  pas s t apha. Miohadss as s wr ad a ga sts o 1 88 H or t dditi pas ad 2 27 H o th th bta pas. t FCl x20



deapae an an i ppreed and inead a beaphae aenie grw grw de  he eenin  he high eperae bea pae Te irre ake ake i pib e  renr he anaring anaring pre  he nainer. The be wa  a in a ld. Aer Aer aing i wa biey anneaed and hen enhed The eper are a wh he en hing wa aried  i  eiaed  have have been 58 68 The needleike aenii phae i deignaed a bea and he dendii pperrih phae i  he alpa. Mrhardne eareen wee ade and gav gav rel  1 88  r r he dendi phae and 22  r r e bea phae

cc 

Clmn cst S e nment

gur I 1 6. Pat o a a orat ro th Si zo i ort wstr wstr Colobia 42  

Ti ype  ne ligree ear naen wa rigi naly g  be ade by he lderng geher  a nber  wie wie wever, wever, eall graph exainain a prven a hey were were ade by he wax pre. The ein  ranverely hrg he ear rnaen hw he a nare  he gldp per ay. Te p r peni n i lighy neven a he p a i n in any her ear na en r r hi area, hwing ha he prb able ang pii n wa wh he nne and hannel iaed abve he penin lp aahed  i a he pper pin. The pihed ein hw an ndred a dendri re in whih niderabe rin ha aken plae. An eiain  he dendrii ar paing gave a vale  33 irn averag averaged ed ver ver nine ar (S 1 86) . Analyi Analyi yielde yielded: d: A  6.  1 .2 Ag Ag 1 . Pb 0. 0 e nd Ni nd Sb nd A nd (nd  n deeed.

Figur I 1 7 T ortatio o t t oodd oppr rh gio  o t or d rits rals t orgial ast strtr o o t gold-oppr alloy. Strtur s lk tis a diiul diiul t to t satisa satisat tori ori y wit it r K CN (NHS or N HCI FCI alo will oly t t oppr-r gold all oys wit p to about 30% god by wigt. Utd x36

Appendix F 96

igue igue  1 8 top ight. ight. Oveall view view showing the lage gaphite lakes with ini ling o peaite and the white unetched tenay tenay phosphi de eutectic, which cannot be eadily esolved at this magni icaton. Etch nital 70 gue gue I 1 9, iddl e ight. g ht. ine pealte wt h vaiations in the sze o the the gaphte plates. Etch nital  x. Figue 1 20 bottom bottom ight. ight. The pealite is clealy visible. Some peali te egions have vey ne spacng and appea gey. he whte phase on he let s the phosphde eutectic steadite steadite while cabon  in the om ogaphte o gaphte laes appeas as dak lines. Etch nital 390.

Cast on cannonall fom Sandal Castle This pished fragen is a sein fr a an nnb a sed in he siege f Sanda Sanda Case in 1 645 beween beween J and Sepeber  f ha ear. ear. One f he reasns fr fr exaining hese annn bas is  see i f here her e are an di fferenes beween b eween he h e 64 pnd bals brgh fr H speia fr he prpse and he 32pnd an nnbals sed earier in he apaign. The srre f bh pes in fa fa prved  be he sae (rhe r deais neing he hisr and he annnbals he seves an an be fnd fnd in Maes and Ber 1  .) Exainain Exainain f he sape shws shws he annn annn ba  be ade  f a fair fair pia gre as irn. The srre nsiss f raher raher variabesized b qi e arge graphie akes akes se in a arix ha is prinipa pearie. Se  f he pearie ee id is ver ne spaed and is bare resvable a x 000 agniai n. Mh pearie an ear ear be seen hwever and here are a few areas ha k ferrii. n se paes a whie phase an be seen ha has a pah appearane appearane wih sa gbar hes. This is a ernar phsphide ee i beween ferrie (sal wih a ie phsphide nen) eenie and irn phsphide eP This ernar eei aled seadie has a e ing pin fab f ab 60 60 C (Ras (Rasnn 1 73) and s i is h e as ns ien  fr as he as irn ls ls dwn.  is a ver brie phase b is sa n presen in sa ans saered as is aed aed isands (see (see Pae Pae 1 3).

 "  -" . \

nx 7

Bne Age Age cppe c ppe ingt

Figure 1 2   abov above e Copper ngo ngott ound in assocation with ronze Age matera matera in Hampshire, ngland. 27 mm Figure 1 22 right right Overal Overal view view showing the large gran bou ndaries and the scatter scatter o cuprite globules at the the grain boundari es and wthn the grains N ote ote also the presence o some porosiy in the ingot and the absence o any twin i nes or stran stran lines i n the copper grains. grains. tch: FeC I   I 05

The sall plannvex ing i lsraed ere was seined  is pia f he nvenien prds sed fr fr rading ra ding as ppe r. The  fae fae shws a nar appearane whih sggess direina slidiain XR analsis deeed a sall an f nikel nikel as an ip ri in hewise pre pper. he irsrre shws a rearkable rearkable saer f prs xide inlsins Grains are arge (AS (ASM M 1 2)  wih n annealing win win r slip lines presen, indiaing ha he pper was as The pri f he pper explains he absene f ring and visible dendries. The large and and ners glblar xide inlsins r bh wihin he grains and as sligh lenilar shaped diss ha rn alng he grain bndaries. There is se prsi preen Wih his paril ar as as ing

he pper prded wld need rening r reeling and alling befre being sed  pr de sall ar ifas ifas bease f he nsall n sall high prie nen, herwise herwise he grain bndaries f he aerial wld be ver weak.

Rman a cin

Figure 1 23. Ths oman bras brasss coin is rom the period o Augustus who regned d uring the irst century A.D. 48 mm

Man Ran ins were ade fr brass raer han brnze he irsrre  f his i n ehed wih ferri ferri hlr ide shws a pial resallized grain sr re wih exensive evidene f defrain prded in he press f sriking he in B h win lines and slip lines an be seen in he seins. Man ne ne ses f parallel slip (r srain) ines an an be seen bh a x66 and x1 32 agniain. agniain. Se f he win win lines are re difl difl  bserve and here is se variain in heir appearane Man f he twin lines see qie sraigh while hers see rved indiaing eiher hwrking  r se ldwrking afer he nal sage f rersalizain Sine he sal anfaring anfaring ehnlg invlved sriking heaed in blanks here a be a dal har aer  hese pe f srres.

Figure 1 24 top oman oman brass ch: ch: FeCI ; 66. Figure 1 25, bottom bottom Same Same as Figure Figure 1 20. tch tch FeC  32

F

Anx F 8

Tha onze contane fagment Thi i i  a fragent fragent fr fr the ri f a Thai Thai brnze b rnze cntainer fr fr the ite f Ban Dn Ta Phet with an aciated radicarbn date f 1 8 1 0 2 1 0 The ally ally ii . 22% cpper 2 2.% t in with trace f irn an d lead Exainatin f the ectin revea apha phae cpperrich cpperrich iland which are etie jagged and ccr in area with pecic rienta tin a well a rand catter. The backgrnd backgrnd atrix f thee alphaphae cpp er iland i d i ct t etabih etabih It c ld be et her gaa phae phae r a hgene beta phae. Banded artenite i preent and thi dicatin i etie caled beta . he aciclar arente i ften ften labeled labeled a beta beta   dging by the icrtrctre and cp i tin ne can ay that the bject wa prbably cat initialy and then alwed t t cl It wa then heated t between 520 and 586 ° which crre pnd t the alpha gaa regin f the phae iagra After annealing the cntainer wa qenched qenched preerving e f the hightepera tre beta phae Micrhardne reading fr fr the tw pr inci pal phae gave the fllwing fllwing relt  alpha phae  257 H gaa r beta grain 25 H



BP

+

Figure 1 26, top. -phase islans, some clearly outinng grain bouna ry regions regions tch eCI  40 Figue Figue 1 27 bottom. bottom. he vey vey ine ne � nee les appear to be stain li nes , but are not Note th that at the orie ntation o the  precpitates is not ranom bt occurs as grain bon ary an as nragranla nragranla  orms orms his orm orm o martensite martensite is cal le bane martenste tch eCI; 280.

nx F 

ay as the sheet itse t has been wrked rather re heaviy as the grain size is sa er and here are se aw ines ines re sting r r ainatin  the strctre dring wrking.

M cohadess Weighr

1



2

4 

5

5 0g 5 0g 5 0g 5 0g 5 0g

Dagonal avag 15.5 6.5  50 1 9 0 165

 56 49



60 49

Rests Rests 1 2 and 3 were btained r r the nai  with the highest reading  60 btained bta ined r r the nai tip. Rests 4 and 5 were aken aken r r he gd sheet and sh w ha the hardness hardness vaes are qite w. Hwever Hwever it sees n ikey tha the the nai wd be abe t penetrate the sheet eec tivey and the evidence sggess that the sheets were pierced ater psitining the and bere the nais were appied. Anaysis A 83.  1 .5 Ag 1 2.8 e nd Pt nd Sb nd nd Ni nd As nd Pb nd Si 50 pp

igu 1 34 top right ght Tang and blad ro a lat d ival sit at Ardngly Suss igur 1 35 botto botto right This is th transtion zon btwn artnsit at th right sid  through a Wid anstttn anstttn stuctur to th th bginnn bgi nnngg o so rrt t grains tch ni ta   40.

Blad sctn The sectin thrgh the bade reveas hat a stee strip was weded t a principay erritic strip. Therere Therere the variatins in strctre are de t the change in the rae  cing and in carbn cntent between errite grains and epered ar tensite. The angar hes evident in the icrstrctre crrespnd t the psit in  sag incsins any which  which have aen aen  t dring grinding and pishing. A bade rged rged r r a strip str ip   stee and a strip  wrght irn w as a airy airy cn ethd   anactre Vickers DPN hardness easreents n di  erent cnstitent areas  the bade gave the  wing rests erritic area in the center 83 H tepered artensite twards twards the the edge edge  8 5 24 H

gur  32 abov Sction Sction though a nai l showing th th oldd gold sht and th oval shap o th nail 60 gur  33 botto Gold sht tchd tchd in aqua rgia rgia with arg winnd gains and bnt twns showing so doration doration at at ina annal ng  1 60.

nx F 10 1

Ion knfe The plihed and eched ecin hw ha he enire blade wa ade fr carbn eel qenched qenched  prdce arenie hrgh . Marenie eched in nial i a dark raw clr ward ward he edge. Slag cnen i  derael lw wih gla fragen laened  alng he lengh fhe f he ecin. The arenie near he w rf r face f he blade appear epered wih cca inal inal  ggein f rie. The fac fac ha he arenie eche darker cld be d e  a change in he carbn cnen near he rface r  e pering pering afer qenching.   weld line are eviden in hi ecin. The carbn cnen near he id dle regin f he blade hw hw e banding  h erwie i appear  be ver even.

Figur e 1 36 to. Bae setio o from from a late late meieval site at Aringley ussex Figure 1 37 bottom hows hows transitio betwe betwee e light ethig an ark ething temere artesite artesite towars towars a uttig ege of the bla e Eth ir al x280

Figure  38 Coin o the Emeror Doitian whih ates ro A.D. 8 1  It is from from the the it of Rome CO.YI DEII (Roma meria Coinage Coinage 237 ). he srition on the obverse obverse s  P CAE. DII EP. F DOIAN AUG. P.  with a hea l aureate. he reverse reverse is R P COY I DEYI PP PP  nerva avaig bran ishi ng a javeli javeli a a hoi ng a rou shiel iew o the ethe wnne an rerystallize rerystallize grains wi th art of the mi setion rak through the oi showig as a blak lie Note that the the struture aears singl e hase. hase. Eth: FeC x39

Ron copper lloy con The rcre hw a wellfred recralized grain arix wih raigh win line and ver li le pri preen. The inclin preen are n aacked aacked b feric chlride dri ng eching ggeing ha he a be lde inclin raher han cprie inclin which are exen ivel dilved dilved b ferric ferric chlride  lin . The inclin are aened  alng he lengh f he cin and are allale allalerr han h e grain ize which i ab  ASTM ASTM 6. There i n evi dence f an ecnd phae Xra recence recence anali carried  n he cin ielf hwed ha nl inr alling cnien ccr wih cp per being he nl ajr cnien in zinc and anin were deeced deeced in all an. Thi evidence  he eallgraphic evidence evidence ha he all i inglephaed.

A deep crack penerae penerae he idecin  f he cin Thi crack de n appear  have been fred a a rel  f crrin f he cin b raher a a anfacring anfacring fal fal Midecin cracking i fen fen aciaed wih verwrking a e age dring anfacre. Thi can pr dce crack in he wrked all all which alhgh he grain are recrallized pn annealing are n reved b beqen wrking and annealing.

Appendx F 1 0

Fure 1 39. Roman on on ail from from te te o o nhtuthil Pethe, ota 1 40 m. ure  40. Part Part of the nai hank howi mall ferrite ferrite ai with eonate la tre ain alon the lenth of the hak The la tiner i ti nail are two two hae (lay (lay atix an wtite FeO). Thi i a tyial wrout wrout on truture. Et nita x90.

Rom o  A he Ran Agrilan frre frre b i a Inh il in Pehhi e an enr nd f irn nail wa nveed. Te e   f he nail had rded and preed he inei  f e nd fr fr exenive rrin . The ahe f nail n bering hndred f hand daed daed he abandnen f he eleen b he Ran Ran a   00 80  The ein aken fr fr  he nail i a lngidi nal  hrgh he head f he nail hank. The hank and head appear  have been ade ade in ne piee  frging fr ble irn. A few lag ringer an be flwed flwed f f he ein hgh he head a  he rve dwn ang he lengh f he nail. Thee lag inin d n rerallize when he irn bl i heaed b he blakih  fge he nail and a a rel e bee elngaed in inger pn eavy wking. Thi an be een in evera area in he plihed ein. Tward Tward e ene f he nail ank hee i a large, elngaed lag inlin whi a a agnia in f x 1 00 an be een  be ped f w pae There i a gla darkgre darkgre phae wih a ne di perin f glbar dendrii wie preipiae (eO ) . Thi kind f wphae ag inli n i a n feare f anien ber in alhgh higqali prd a hw ve lie evidene f lag nen. The veined ge aea aea inrding in he nail rfae are ae and rrin prd ha

AD

±

an be een nde parized ig h  e redrwn and ae pia feare feare f ligh  rrded i n wrk. There i a li ghl rrded area nar he ead f e nail whee whee irn ide  line e  e par f he grain bndaie f he wrgh irn.  fr fr her feare are viie in e need ndiin. Te nail wa ehed in nial fr 5  0 nd and hi reveaed a piaril ferii ferii grain r re wi n indiain f abn nen. The raw aerial varie ewha in arn nen beae anher nai fr he ae  ie wed e pearlii egin. The grain ize in e ank f he he nai i lighl lager (ASTM 56)  paed  he h e heavier wked aea f he nai head (ASTM 6)

Ntve coppe

Fire Fire  4 1 . Native oer from from the Great ake ake eion in N ort Amera 42 .

Thi aple i  fr fr a dendi i a f naive pper. In i  plihed ndii n here are few few inin pre en in he pper a a whih appear  be brken p in a nber farge egen. The rak beween he differen eg en are led wih prie and greened pper in prd . The er rfae rfae f he  aple a w e ingre f rrin wih pah nverin  pie.

In he ehed ndiin (eh in ahli eC) , arge grain an be een wi e ve lng win ine a are qie learl rved. In  e pa f h e peien rain in e ae vi den b hee are e feare be een a well. Lngzned line appear  ark e pi in f ipriie r grwh pia wihin he r ein f he dendrii ar.

t

Aenx F 10

Figure 1 42 top top ight. Cro Cro etio throgh the enrite ar ethe i FeC , x20 howig large grain ize a  nuua l trtural eature eature within the grain. Figre  43 top ar ight A loer view o o igure 1 38 at x 1 65 howig unuu al eature eature withi the grain an well-eine grai bounare Figre  44 lower ight ight.. A high agiiato agiiato view o Figure 1 38 at x500 howing a ne ne tran o ma prepitate prepitate ourin g within bae regio o the enrte am that may be epoito a eatue eatue ourring a a eult o growth growth phenome phen ome a n the native oper.

Hed of  togge pn

Fgure 1 45 above. above. Togge Togge in hea rom ran 20 mm Figue 1 46 top right right Eth: Eth: eC x50 Figre  47 bottom right Eth: Eth: eCI  x I 00

This fragen is he head f a gge pin prba bly daing f he Lae Brn ze Age  he Early Irn Age perid. The icrsrcure f he he gge pin head can b e clealy seen afer afer eching in i n ferc ferc chlrde fr fr 35 secnds  The icrgraph a x50 agnican (g. 146) shws ha he srcure is   cred dendries wh cnsiderable inerden driic rsy, which appears in he phicr gaph as black znes beween he dendre ars. The srcure s heavily cred as can be seen fr fr he phicrgrap phicrgraphh a x  00. The euecid inl ha als ccupes he spaces beween he dende ams has a dfferen charace frm ha which can be seen, fr example, in igures igures  56 Because Because f he ange f f cpsi n and  f he diff diffeen raes f cing he exen f cring and  he appeaance f he euecid in in brnes can be quie vaable.

nx

F

 

Jvns on ld Tis l frgn fr fr v is  gh   fr  1 01 2 cny I is pnilly f inrs sinc sin c vry fw fw Jvns j cs  f is  v n xin. xin. I is g h nickl ccs in s f hs prcs s n iinl llying cnsin in iin  cn. A scin kn g  cpl lngh f  l frgn frgn vls q i  cplx c plx scr s cr. . Tr T r r  nr f iff iffrn f f rs  sl  scri. Ovll  fg s  pil src  fr  nr f iff iffn cnns c nns frg gr.  gr. A rw ing f s f  fs fs is ill sr in igr i gr 14. Ps f  f  srcr sr cr sw n frri  gins wic is rr ncn. Tis y v risn f f clwki ng f  irn  s sg ring n fc. fc. Tr is s pri  psn  h fri fri grin nr is s wll s  fw s sg inclsins incls ins  Tis rgin s isplys  n sc r T ns  fr fr fr rli n v ny ccsin grin nry pr cipis cssing  ns prpnicr  h lng Tis y f ning is gnrlly ssci  wi wi h yin g cnsins sis c n sc s nickl rsnic r psphs Tw Tw h  si  f  l r r s

D

Figur e  48 Fagment Fagment of avanese iro blae. blae. I  0 mm Figue 1 49 I llustation llustation of oss oss setion of  o b ae

some loss through fattee  ferrte grais orroson

oroe ti abure areas near su rfae rfae

stri angua slag inlusio s

grins grins h sw sgrin srcr. T grins svs svs r qi lrg ASTM 4) n y c  lig srw srw clr in nil. T sgrins pp s ccsinly qix sl rs  lin y n rk lins  y  in s css css n prcipis (n slv  x000). A igh gnicin s pcipis cn  sn   grin nris in is rgin. T crn cnn is grr in n  f   pil srips n  n  f prli is grr n  grin siz sllr ASTM ASTM 8 ). Twrs   n f  l  irn srip s clrly n n fl fl vr. T is  i pic ls wic ccrs clrly in h iscin rgin f is spl spl n  i ns wi n f  r vr pics wr   cing g. T r  cnin s  lrg scr sc r fnglr f nglr slg inclsins psss lng h lng f  scin. T slg is  glssyps ril wic r pprs gns gns n i  hs n rkn rkn  p in sll nglr rnns pn wrking. Tr is n inicin  is l ws qnc. T crn cnn is wl lw  ci cpsiin, n in s rs wl n v n scinly ig  prc c cng in ppris pn qncing. T cing s vl vl i n s grins  vining ssrcr  riss wn  nil cks sgrin  nris s wll s grin nris nris (Sls (Sls 1 80 ). I is g  is vlps s  rsl f c pii ng   wlls f  iscins iscins   sgrin nris. B   vlpn f sgrin sr cr n  s wih wic  c pis vlp is pn n n  pysicl n rl i sry f  swr. I cn ris fr wrking r fr qncging ffcs    rgnc f cri grw n  c pii ng in frris    ing  lw lw pr prrs rs (.g 5 01 50 °C will sfc).

"e

Appendix 105

F

Figure 1 50 right Part of the tructure with carburize u rface rface angu ar lag region an ferrite grain Etch: nital  x70. igre 1 5   far right right Angul Angular ar ncl uio n with ome earlite earlite an ubgrain ubgrain tructure that can be een a veine lne aing through the ferrite grain. Very ark region are angular lag fragment which are moty glay ingle-hae lag incluion inclui on Etc h nita; x280

Bronze e fragment

Figure 1 52 Bronze axe fragment from Iran 90 mm

Figure 1 54. Well-eveloe hexagonal hexagonal grain tructure u ually outlin e with a reciitation of uhae (the coerrich whiter material material ) howing variation in color a a reu lt of ifferent ifferent grain orentation in the bra 60 Cu 40 Zn u bra. bra. Etch Etch FeC x3 1 

+

P

Ths fragmnt s thought to b a part of a Lurstansyl crmonal bronz ax datng to about 8 th cntury cntury BC., from Iran, composd of 87 1 % coppr and 72% tn wth no othr l l mnts dtctd by Xray uorscnc analyss Th sampl  s takn from from th cu t nd of th tran gular n whch was probaby ntgra wth th blad Th trangular plat s carfully mad and has smooh surfacs wth a ang ang  around th cr cumfrnc cumfrnc on both sds o f h h plat h samp rmovd for xamnaton s a ransvrs scton through part o f th brokn nd of on of th projctons o f th th plat

Laboratory cast 60:40 brass Ths 6% coppr  % znc alloy s tchd wth FC n whch cas th phas phas rgon appars darkr or black Not th wllformd wllformd Wdman stttn st ttn prcptaton of wthn wthn th grans grans pro ducng prcptats prcptats only o n crtan crysta crysta pans S pag 2 for a brf dscusson of th th Wdmanstttn Wdmanstttn prcptaton

� a � a

gure gure  53 above Slight' Slight' coring vi ible together with oroity oroity an recrytallize recrytallize grain grain with well-eveloe twinne  crytal. Note that the twin li ne are traght. traght. Thi evence ugget ugget that the axe wa roughly ca t to hae an lightly fin  he by working an anneal ing with annealing being the inal abrication roce Etch eC  x62 (ee (ee Plate Plate 1 9).

Appendix F 10

+ 

Fiure 1 55 60 Cu 40 Zn brass brass Twophase � brass showin etail of the Wiman sttten sttten formaton of plates within the � rystals. rystals. Eth FeCI  x  00

Nte tat te t e undamental d  erene beween te Wdmanttten and martent tranrmatn  tat te Wdmanttten nvlve te demptn  ld pae nt pae we te marent tranrma tn nvlve te rapd lng  ne pae pr dung metatable metatable pae n lng

n

w n

Gded Gde d se eang eang Te mplete mplete earng earng drawn drawn n Fgure 1 6  ne  a par rm rm te te  ell ara n Jrdan and  dated t te Mdde rnze Age rt al  te end mllennum Tey were bt made rm glded lver te end eample beng n a ragmentary ndt n rm w a ampe uld be taken ar te brken end by areul awng wt a ne jeweller aw t bet were derated wt granulated gld pere attaed t te glded urae Te termnal  te earrng end n lp w are eured eured wt twted gld we ere ere nevatn b t bet were vered n dark grey rrn  a way way nteny n teny Xray d dratn analy wed wed tat te man nttuent   t rr n wa lver lrde Cnervatn wrk wa arred ut bt emally and meanally ung 1 % ammnum t ulate ulate and and and tl Te rrn prdut ad erupted trug te gldng n everal plae plae and ad red te g ldng utward  utward Caratert ea ea ture  lea gldng were berved n partular te verlappng and rrugatng  te tk gld l e metallgrap ample revealed revealed a par tally rrded lver ubtrate vered wt a tk layer  gld e gldng ad beme detaed rm rm everal rrded area but n me area a gd nt erae erae between te gldng an d te lver uld be een T nterae  everal mrn tk and ugget tat a del berate d d u u n bnd wa reated between te appled lea gldng and te lver re Analy wt te ele

trn prbe yelded 2.% lver 2.% lrne, 1 4% pper pper and 07% gld

..

iure 1 56 above above Drawin ofile silver earrin from from Joran 22 mm ure  57 top riht Part of the ol foi overin with ovelappe join  n the outer ol foil foil  The foi foi l has been ifusionifusion- bone to the silver beneath Note that the silver ro s he aviy orroe with few remainin soun meta meta reions. Uneth Unethe e x2 x2 1  Fiure 1 58 mil e riht riht exaona exaonall rain bounaries i n the slver ro The ark areas are orrosion, an the rain boun aries that an be seen are not strai straiht  ht lines This is a onse quene of the ae of the the silve r Over the past 3,50 0 years oper has prei pitate from the silver ro an the ran bounaries have move as a result Eth aiifie aiifie potassium  ih romate romate x200. Fiure 1 59, bottom bottom riht. "Wiy rain bounaries as a result of isont inuous prei pitation on of opper from from the silver al loy Eth aiifie potassium i hromate hromate x500

'

•

mx

F

17

Fgur e  60 o righ. righ. Fage of a brass brass e ali o fro he La Perouse w hih hi h sa of of he he oas of Ausralia Ausralia i  726 Uehe x20. Figre  6 1  boo boo  rig Eh FeCl x75

Fagment of a ass medallon Ths brass brass has ajr cns iuns  f cppr and inc wih nr auns f in, ad, in and chriu. Th rs icrgraph unchd a x20 agnicain shws h rakabl dph f crrsiv pnain in h brass. Crrsin has ulind h dndric frs f h cas bass dallin which has bn lighl chd wih fr ric chrid hug h lss f bh cp p and inc has ccurrd h, i sh uld b nd ha h dndriic ars hav bn prfrnial crdd whil h nrdndiic aras a in s gns prfrnial prfrnial prsrvd This is vidn in h sc nd phicrgraph a x75 agnican and suggss ha h dndriic ars a rich n inc cpard wih wih h inrdndri ic l, sinc nra nc is ls prfrn prfrniall in sawar buria such as his shipwck s (s Pla 4)

Fagment Fagment of a small S S  ea onament Ths a rnans wr cas as pairs b h ls  wax wax prcss and rpsn v skilful falslig g wir wr. Th wh rn an s dld n wax in n  prain and hn cas Fgure 1 62. S ear oae frage frage Pe-His a Colob a

Figue 1 63 Ue he low agifiaio agifiaio view a a x20 showig exesive orrosio o he gol-oe  alloy wire seio he eve e shows ha ha e ora e has bee as by los-wax wihou ay worig The erii  sruure of e alloy i s learly eve.

Figure  64 E arge arge view a x I 00 showig he igh erihe i  gol a he surfaes surfaes as wel as he selei ve eeio of soe areas of he e ries as a resu of orig of he gooer alloy o asig. he grey grey arix is iia ly uie

ppdx

F

 

Figue 1 65 Seton of a Roan  o agent agent at x agni ation ethe ethe i n alohol  fe hoe showing the the ei itaton on of age lea globu les at the botto of the ast i o (on the eft-han sie of the itue) he gain bounaies an ust be seen as a esult of the ieent ething of the suae suae with with fei  hloi e It is a vey ine tutue fo a ast bonze showin g that that esite the goss segegaton segegaton of the lea g ob ules the oolng of the alloy was fast enough to event the usu al eniti  stutue fo eveloing

D D 

Figue 1 66 next next age age Roan bonze figuine of Roa 468 igue 1 67 ight ight Roa bone bone i ostutue. ostutue. he oe su fae of the Roa asting is to the left left han si e of this hotoio gah whih shows the anneale ast stutue of the bone The gain sze is lage with sall in u sions of ea an oe oxies o sufies Eth eC ; x90

Roman mo fagmen The ealy exape  Ran i ade in upe in a peiaized peiaized pdin ene in Ge any wee fen fen ade in a leaded highin bnze whih i paially paially quenhed  fagen he eueid ei d phae. The i  dae  he ealy enuie and hi exaple i f Ran anebuy and dae  he 4h enuy I i ade in an ay f8% ead 9% in and 3% ppe (ee ae 5)

+ 0

AD

AD

Roman onze gune hi all all guine abu 3 3  in heigh i f he J ulilaudian peid f 4068 and he i hwn weaing a h Aaznian uni The  an d head wee wee hllw a in ne piee wih he lef leg ju abve he knee. The igh a wa aahed by aingn  de. The leg and fee wee hen an. he Ra wa a a in a leaded bnze bnze f 89. 8% ppe, 7. 1 %  in . % lead wih a ae e f zin, in nikel and ilve.

AD

nx F 10

Thee i n unuul feue n he bk f hi R :  eie  exgnl exgnl newklike uue e in he e A e le w ken in hi e n he bk  y  eve he uein neing neing he nue f he gin u ue in hi  e The iuue i hwn hee in igue 16 The uue i ehed in lhi fei hlide wih he  ufe f he R   e lef lef f he hig h The uue f he bne i eenily eenily h  n n nneed ing The gin e hexgn in he i n ny e e f he ein ein wih he uid fenilly uing  he gin bundie bundie nd ui ning e f he hexgnl hexgnl gin Sll xide  ulde inuin n be een eed hugh he ein lng wih e l led inuin nd iy The bene f  yil dendii uue ugge h he y be  iuul exnin  he newk  hexgn be vble n he ue f he bne ine e hexgn nneled ene f he ein i unuu f   bne The iue hw h he gin e n i bu e euixed Th lene lene f hee hexgnl gin duing lidiin uld be enible  he ufe n f h bne

e

8

e

e

Fige  68 enaissae sve asn om Genoa ate o about A.D 1 625. 755 755 m

Renassance slve asn Thi bin i n elbe eu wk wih ny   ddiin nd ldeed nen  I h been nihed by hing engving nd he ddiin  f ny nen  he wked hee f he bin iel ef efe e he le  6h en ury fk fk wee wee unn in ue nd eing w ied u uin g he nge Thi bwl w bby b by nly f f hw nd ny wee b bly eled dwn when hey wen u  f fhi hi n nd uned in  ilve knive nd fk The le i de f n lly f 99% ilve ilve 3 % e e ll un f led led eni in in nd niny niny e l een een (S 1 99 1 )

nx

F lIO

Figue 1 69. Pat o a ole blob fo fo a eai to te oute aial ane e o le ow a cat oology o ology o te coe ic an ilve-ic  ae wc ae ot eu i bu  ae o o te lve coe bi nay yte bt ave nvual ae cooition cooition eove o tei ei cte vaue   tcte o altenat altenatee ei tc ooogy i tyica o any cat cat ilvecoe ole  aoy. e oveall cooito of te oe ue ee  abot 50% ilve 50% coe. coe. Etc FeC  x0

Th spls f s udy w vd vd wh  dndppd   dll 1  5  nnl d    vng s f h pnns  f h slv bsn, s    n dg dg ws vsbl  h n  h b wn  ps  ssbld.  ws sy n h Rnssn  s pn ps by ppng  dd wx  gss dl, usuly fullsl fullsl T slvs  hn fully pd h dl n slv, s wng h ps  ndd ndd  b sd T hs pss wng ws d d  u  n bl h ls  d l h ln   s dd ns Th s pnns w dd n wx, s pbbly n h bsn slf nd hn vd nd ppd f f sng s ng Whn s n d sldd n p ll h sufs sufs w nshd by hsng nd ngvng xly s f  n bsn hd bn d n n p. Fgue 1 70 to gt. gt. Potocoga Potocoga o a of of te te ecto tog te ban etce wit aciiie otai otai u i coate une atialy olaize ligt to eveal te conti uato of te gain tuctue of te ilve c ytal aco te bounay ito a u face face atee zone. zone. i ic oga oga  ll tate tate te te cotiu ity of te oveal ic otuctue wtin two aaently vey ifeent ifeent tctual egion of te ilve bain. x155. gue 1 7    e gt gt Oveal view of a coe-ile coe-ile ace of te bain ug o te i ve ba n. e to  ace i e ot n ti otoga otoga an ow te extent a nat e of te uface-atee one of te il ve bai An uuu al featue featue i te  ace ace cac a coeoning coeoning onig one o oxiize eta. eta. e uf u face ace alteation one  ee ae ue to te aggoeation aggoeation of coe atice atice a tei oxiato to cute ice ive i vey ucetble to ox oxyge ygenn abotio uig annealng.   oxyge ca ca te cobne wit te coe to ae cite. Etc: aciife otai otai   coate x50

Figue 1 72 botto above above Vew of at of of te ilve eet etce i aciife otaiu otaiu icoate e gai tuctue of te lve can be een e gain boaie ae not taigt a ave a "jigaw aeaace i lace bt te eciitatio of coe een ee occu a coti uou  oe at te te gai bounae uggetig uggetig tat te bain a been eate beq et to it aufactue aufactue obably fo fo eai  a  fo te catig catig of te all aitio x40 x40

Appendx F III

igue  7, to ght ght Oveall the the stutue is tyal of a ast aloy; the baelet has bee ast itegally a joie ea the ete ete egio Lage aeas of extesive oosty oos ty ae lealy leal y eviet togethe togethe with salle oes, soetes flle with oosio a, teestigy, a ath of astig astig oe ateial   the hollow betwee the two egios of the baelet The astig oe has bee eae as a fie ix a aeas i eete eete light li ght as a gey ieal as seb age age he astg oe aeas aeas to be ii al y i ea ea  i oositio with o ogai ogai ebis aaet aaet Oe o  tw twoo s all aeas that that ae of ae o lo ay be eats of the eutetoi, ow athe athe ooe he e is also a thi ust of oosio suoug the su faes faes of the baelet seto The e iti stutue of the baelet has obably bee oifie by heatig uig a ufatue ufatue sie it is ot vey ooue, a the oig that that eais is subtle Uethe x40

e (

Ccula acelet fom haland Ths is a ransvrs sin u arss a irular bral fr fr Thaiand.  s fr h si  f Ban Ciang and is dad  abu 5 n p siin h bral bral s a in brnz wih 8 . % ppr ppr 5 .4% i n and 6% zin Th inusins inusins prsn in h a ar ppr suds and whn analyz analyzdd n was fnd fnd  nain  6. 5% ppr . 5%  in and 1   1 % slfur slfur wih silvr silvr lad and zin undd. Th snd snd inlusin sudid naind 1.8% ppr 5.% lad and 83% sulfur sulfur wih i n zin an d silvr ndd. Cupr nlusins als  and and h in nn an vay p  abu  . %. xainain in h nhd ndiin rvas rvas a nubr nu br f diff diffrn faurs. aurs . Tward s f h shapd dgs f h bal n rsshahing uin d in rrsin an b sn whih indias ha hr has bn s wrking f h bral flwing asing prbably  n ish h surfa rahr han  pdu a gra hang n shap.



Figue  74 i le ight Stutue afte afte ethig i alohol fei hloie Soe oig a be see i the stutue togethe togethe with eviee fo sli sl i laes (soe (so e eviet as seuoohi eats eats i the iial ly uite oosio us t ajaet ajaet to the eaiig etal  Soe of the i us os a e ot afete afete by ethig i ths way a ay be oe sufie iu sios ; othe athe a gey gey egios ae a to be ooe etali egos, whih aga suggest suggestss eats of the eutetoi hase A othe iteestig featue featue of this sale is the ay oe-oloe aeas eset  the eutetoi eutetoi egos o as sa  sattee sattee blobs  his oe u aloye wth t, ay be eset as a esult of su iie t eltig  the ogia ast ast o as a seu o oh i elaeet of the oigial etetoi egos It is o e li ey to to be eset as a esult of oosoeeositio eh aiss that that have esute i the oosio of the tiih  hase efeetialy x70

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Figue 1 7, botto botto ight High-agifiato High-agifiato view showig a sall gob ule (l ight i olo of eeoste oe i a ooe egio, togethe wth oe sulfe il usio s (l ight gey a boze etal etal showig stai lies fo woig Eth FeI; x 1 70

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Anx F 1 1

Romn one owl The saple was exained carefully in he uneched condiion. Exensive inergranular cor rosion has occurred ou inin g os of he he grain boundaries wih cuprie very clearly Soe sraigh lines of cuprie corrosion can be seen passing occasionally occasionally ino a grain in erior suggesing ha he eal us have been sressed a soe sage during anufacure o produce soe slip, alhough no win lines are apparen in he secion before before eching. Soe of he inclusions presen in he eal are of cuprie, ofen ofen conin uous now wih he nework of corrosion hrough he grain boundaries. There are oher regions where he ypica variegaed s urface urface appearance of ead incusions o ccur and hese are ore concenraed raed i n he hicker region of he secion where hey appear have segregaed. Noe also ha here is considerabe porosiy as well as soe areas areas where lead globules ay have fallen fallen ou  as a resul of grinding and po lishing. Tha he alloy in ques ion here is a leaded in brone, can alos cerainly be deduced fro fro he occasional pres ence of soe regions regions o f he euecoid. Where he euecoid phase occurs, i  is usually surrounded by islands o f corrosion where he copperr ich grains have been aacked. In his exaple hen he priary corrosion process i s he aack of he grains surrounding he euecoid region he wiin he euec oid is also aacked. If he corrosion crus is carefully carefully exained, soe areas of reaining euecoid can be clearly seen wihin he corrosion surroun ded by copper oxides This is an i neresing exaple of he pre erenial reenion of he he copperrich phase Careful Careful exainaion exaina ion of he corrosion layers under polarized ligh is also useful useful i n he sudy o f his aerial since he crus can be resolved resolved in o d if if feren layers

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igue  76 Seton o te ase of a oan oe ow. he owl as a opos itio of 87.0% ope 1 1 .% ti an 0.9% 0.9% asei asei wit wit sive lea zn zn slfu a io unetete unetete I 00



The secion has has o be eched eched for for abou 1 0 2 seconds in alcoholic ferric chloride o br ing ou he grain conras. The grains are no winned winned which shows ha his saple is essenialy an annealed casing. Soe of he grains show coring where he disribuion of copper and in in s olid soluio n is sil unequilibraed Noe ha he hin srip ha appears o be ben back o produce a unifor unifor edge has uliple s rain lines apparen in he crysas A sall island of eal eal grains in  his region ou ined by corrosion is also heavily srained The euecoid euec oid is uch easier o see in his secion in he eched condiion, and he grains have color conras as a resul of diering orienaion in he poished secion. The overal overal srucure is a cas one ha has been annealed and hen pary worked worked in soe areas o produce he srain lines visible in soe regions. The casing has resuled in soe segrega segrega ion of he ead coponen while while annea ing has no been exensive enough o eliinae al of he euecoid.

e+ 8

nx

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1 1

igure 1 77, to right. right. Brass sheet ethe ethe in aoholi ferri hlori e a the otassum otassum  ih romae romae Heavily ethe setion reveas the ore e rti strture o the brass Small ea gobue s a be see i intere rti regions x. x. Figure 1 78, bottom bottom right right erys erys talize an heavily woe ga ga  strute of the stu rob ably hamme re at this oint to attah attah to the the brass shee . The grais are heavily strane strane  an eforme robaby by aitional hammein g afer afer worng an an eaing yles to shae the the stu. Corrosio has outline some of the str strain ain  ines by ar ar ooe regios assig through the gains Eth potassium ih oate   40

Ealy Medeval ass sheet This fragent fragent f  f a brken brnze sheet has three studs pushed thrugh the plate. The sheet is English fr the Early Medieval erid and has 836% cpper, cpper,  5% zinc. efre efre etching  the saple was eained i n the plished state whi ch reveals reveals th e feature featuress f crrsin crrsin t be seen in the sectin. Crrsin f the brnze stud head can b e cleary cleary seen utining the wrked and recrystallized recrystallized grain structure in thi s part  f the artifact. artifact. Crrsin h as selectivey selectivey reved part f the grains  f the etal, advanc ing alng twin bundaries r slip planes. After After etching in alchlic alch lic ferric ferric chlride chl ride fr fr a few secnds fllwed by etching in ptassiu dichrate, the icrstructure can be eained. It i s iediately clear clear that the sheet brass has been cast t shape, as is apparent fr the undis trted dendritic structure which is cred. There are se depressed depres sed areas n the surf su rface ace f the cast sheet that shw the presence f strain ines fr se su rface rface wrking wrking f the casting. The st ud n the ther han d, has b een etensively wrked wrked t shap e and has a cpletely recrystallized recrystallized grain structure i n which st f the twinned crystals crystals have straight win lines indicating that a nal annealing peratin verall was the last stage in anufacture. anufacture. Hwever Hwever u st past the area f the the cast etal sheet, there i s a zne f the stud that shws a cncentratin f slip lines that culd nly have resulted fr fr severe strain str ain f the brnze stud in this particular regin. This is perhaps due t

haering t attach the cast pate t a backing. The stud appears slighty be nt when eained by eye and this ay have been caused by haering int place althugh the cast pate wuld prbaby have had the hles fr the studs cast in situ. Haering thrugh such a thickness f etal etal culd nt have been accplished with this stud and there is n indicatin f defra defra tin t the cast structure in the vicinity f the he which wuld have ccurred had the hle been drilled fr the insertin f the stud.

Anx F l f4

ige 1 79 Pa of of he he aowheas ic osucue showing a ypcal wough ion wih slag siges (a in his phooicogaph) passing alog he l engh of he he aow The gain siz e of he feie feie is vaiae a   is ypical fo a piece of looey ion o fin his n of vaiaion in appaenly hoogeneous aeial Ech: nial; x75

ige 1 80 op op igh nusal nusal coosio  pae pae hogh he onze lae esulig in he gaual isolaon of sa l gai enans in a aix o cupe he ngess of coosion coosion is a so sevee an oh sufaces sufaces of he lae ae eane eane in a hic  coosion cs Uneche; x70 Figue  8 1 , oo oo  igh igh Heavily Heavily eche view, in which soe suface suface scaches ae visile as we ll as he one gains an coosion cus, showng wine gais wih soe san lies s eve The shaing in he eallc aea s ue o coig fo he oiga cas ingo, sill no eniely eniely eove y woing an annealig, a he gais coninu e acoss aeas aeas o slighly feen coposii o Ech: Ech: FeC; x  60

RomnoGeek on owhed Ths sall irn arrwhad is sqar in crss sc in and aprs aprs  a pin I s RanGr  ab h 2nd cnry and s ad  wrgh irn In h pishd sa h wrgh wrgh irn shws shws a scar  slag incls ins s  which which ar lngad acrss h widh  hs scin whil hrs ar rndd and gblar Al lk i wsi in a gassy arix Th ngrss  s rn xids as crrsn prdcs can als b sn sn n h s racs racs  h scin Ar ching in nial r ab 015 sc nds h rric rric grain srcr can b sn Th rri wld chnicaly b dscrbd as assd rri grains and i  prpry chd h s bgran bgra n srcr can b sn wihin s  h h rri rri Th grain siz in any aras  h h arrwhad arrwhad apprxias  ab ATM 8 Tward n srac  h arrwhad h carbn cnn

AD

Bntne efshped lde Th scin r hi s sall Byzanin lashapd lashapd blad is akn acrss p ar  h dg  h blad  is ad in a lwin brnz wh wh ab  2% cppr % in Thr is vry vry i l a raining n hs sapl, whch has sly bn cnvd cnvd  cpri Th al ha ds rain shws rahr n dissinain  crsin a h srac srac sggsing ha h gran srcr s qi n Ar ching wh alchic rric chrid h grain srcr can b  sn in a  b vry vry sall sggsing ha h ally sd  ad h bad has bn wlwrkd and annald in a nbr  cycls  shap h blad Many winnd cysas ar vsibl as wll as xnsv srain lins hr gh h grains Thr ar ar s blgry nclsins in h a ha ay ay b sal sld inclsins hard  ang h lngh lngh  h sci n

riss als  crany d  dbra carbriza in hr sinc hr is n carbn cnn  b sn swhr in h sin h rri rri bgns ass idansn characrisics and parl i as up h inll shwing ha a sl dg has bn prdcd hr Th dph  pnra n  carbn is qi l id as gh b xpcd r a cascarbrid s

t

nx

F

1

Figue 1 82,  igh igh.. Oveall view view  he e b ae hw ig ae ehig egi wa wa ug i whee he ab e i geae Oue aea ae i u, my i xie h: ial x0 Fgue 1 8 m le igh. View View  a we whee iee iee  i have bee i e gehe. he ab e i he ue a lwe ze i geae while he ee iagula egi  u wugh  wh me ag ige h: al x70 Fige 1 84 bm igh igh w ab eel aea  he bla e wih aia Wima e uu e  eie a eaie. h: al x120

Medeva on  on knfe knfe Thi rn knif blad i fr Mdival riain and i ly wrugh rn rahr han l Th apl akn i acr h cu ing dg n h plih pl ihdd a h havily ngad ngad lag ringr can b n paing alng h ngh f h cin Crrin f h urfac urfac i al apparn: h rucur f h crrin hr d d n rva any pudrph ic prvain prvai n f h rucur f h irn Afr Afr ching i n na h cparaivy cparaivy larg z f h rigina au nic grain grain can b n ward bh ng urfac urfac  f h c n whr dcpiin f h aun ha ccurrd upn cing ruling in grain bu nday nday frri frri wih an inl  ffrr ffrr and parli In  ara h bginning f a idann idann rucur can b n in  h frr, frr, bu hi i n  vry vry pr nuncd which an ha h blad ha bn cld farly lwly fr fr h auniic aunii c rgin and ha n bn qunchd a la n in h par f h ru cur. Th lwcarbn l dg dg gradually grad n a frric grain rucur nhr l rgin wih lw carn cnn appar abu idway idway hrugh  hi cin which ugg ha  wlding f diffrn carbn cnn pic ay hav bn ud  fabrica h bad

Set of panppes hi i a fragn f tumbaga ally fr a  f panpip fr h Dparn fNari, Cbia daing  abu h 81 0h cnury und in h uncipi fP upial. upial. Th analy analy  f hi apl apl gav 25 % gld 62.4 % cppr, cppr, 4. 0% lvr and 00 1 % planu. Th rucur ha bc qui crrdd crrdd a a rul f burial and h fac ha   a tumbaga ally a Su h Arican gldcppr ally) ally) ha  qui dbad Thr ar ar  dark riain



paing alng h lngh  f h curvd cin whch ar ara f l du   grgain pang vr fr h ca ing in h wrkd h f h panpip panpi p Thi grgain fr ca ing ha ruld n unqua diribuin f h gld and cppr f h ally wih h cn qunc ha h cpprrich cpprrich gn  f h wrkd h ar prfrniay crrdd Apar fr hi gr rval hr  al crrin ang win band lp in grain bundari

Appendix F

 

igure igure 1 8 his setin setin is ethe ethe i yanie/ersulfate yanie/ersulfate The eleti gil e s urfae urfae aears at the t f the htmi rgrah rgrah The lamel lar struture in the gl er ally interir i s reate reate by ieretial ieretial rrs i f the wre wre an aeal e sheet Sme twi ystals an be seen i  the gl ally shwing that that anealig was the final stage stage i man ufature 6

and hrough oe of he grain heelve iola ing all pache of reidual eal. Noe ha in oe area here i very good peudoorphic replaceen of he original grain rucure wih cuprie, epecially along oe win line. Corroion ha already ouined o o f he feaure feaure of hi goldcopper alloy, and here i lile poin in aeping o ech he aple The grain rucure can be een o be worked and annealed wih recryall recryallied ied grain and predoinanly raigh win line Careful exainaion of he urface cuprie layer revea a hin line ebedded in he corroion which i ore golden in color han he alloy ielf and which i, in fac, he renan of he depleion gilded layer layer on hi tumbaga alloy The depleion gilded layer here i decepively hin and could eaily be iaken for oe oher for o f gilding if he alloy ielf did no co nain gold, and he echnology of he region wa no underood.

Figure  86 htmi htmi rgrah rgrah f art f the blae ege shwing a lw-arbn steel wth wth Wiman Wi man statten statten sie  lates an sawteeth in a ferrite te a ea rlite steel f abut 04% arb Eth Vil leas reaget reaget 

Bantne dagger lade Thi i a fragen of a Byzanine iron dagger blade, wih he ecion aken acro he cuing edge of he blade n he uneched condiion , he aple ecion i qui e corroded wi h hick cru o f iron oxide eviden There Th ere i a ne cae r of glay lag inclu ion, lighly elongaed, oward he cener of he blade ecion and oe ner lag ringer ore heavily heavily elongaed along par of he lengh o f he blade Afer Afer eching in ni al for for abou 1 0 econd, very lile relief could be een and inead, Ville la reagen wa ued for for abou eigh econd. hi revealed ha he blad e ha been ade fro a eel of variable carbon conen. One ide i predoinanly rich in carbon wih Widanen ide plae and aweeh aweeh viible The carbon conen in hi region u be of he order order of % n o oher region he rucure i ha of blocky blocky fer fer riic grain wih oe fairly unifor pearlie inll

The edge of he blade he deail of which which i ill preerved in corroion, can be een o have he ae ucure a he cabonrich zone in which he Widanen ferrie and pearlie appear appear o con inue down ino he edge, howing ha he blade had no been quenched, bu  had been ade fro a owcarbon ee

enx F 11

Figue  87 botto botto left left Oveall view of the oi, sowig a ast stutue with suei ose eyst eystal al ie gain stutue i ati g that the flan was ast to to a sutable siz e an the stu. Et Et FeCI x0 Figue 1 88 botto botto ight he gan stutue of of the oin s  eay show in thi s hotoogah. The ysals ae lightly twinne showing that soe woig an aealing (i this ase hotwoin hotwoing) g) has been ae out The light atiles eset betwee the gas ae silve-ih atiles. Vaiation in shai g is ue to ong n the oigial as stutue Eth: FeCI 14



Romn con of Vcto Vctoen en

s

Ti s is a dbasd silvr coin of t  Roan ror Victornus fro 680 In coosition coosition t coin is about 96. 1 % cor cor .5% sivr T corrosion roducts wr xaind xaind undr rct rctdd olarizd ligt Bow t id iat surf su rfac ac a vry crystall crystallin in ass of grn corrosion corr osion roducts ar to b sn and tr ar so blu crystals crystals also and adacnt to tat so br igt rd curit ayrs togtr wit corrosion roducts assing into corrodd tal Tr ar d blu azurit crystals on t surfac surfac of tis co in wil in t icrostructur tr ar tin zons of gry corrosion wic aar to b ford around so o f t grain boundaris Aftr tcing in acooic frric corid for about 1 0 sconds t grain structur can b sn Parts of t t structur of t coin btray btray an alost cast structur towards towards on nd o f t coin an wr i t as n ot bn ff ffctivly dford dford o n working: t unc as not toucd toucd tis rgion



Hr tr ar so rcrystallid and twinnd grains suriosd on t ascast structur structur wr so liitd working of t coin as occurrd Tis ty ofartially ofartially rcrystallizd rcrystallizd structur  is vry suggstiv suggstiv of otworking o f t cast coi n an Tr is so silvr contnt to t aloy aloy but t aount o f t silvrric as wic can b sn longatd along t lngt lngt of t coin is not vry grat assing along t sction on ss t avily workd grain st ructur; ructur ; again t for for o f t d d initio n o f ts ts grains against t sligtly cord background suggsts otworking to sa Not t ow in t grain structur of t coin towards arts of t dsign wic ar lss avily workd by t di Strain lins also occur in tis rgion Passing along to t or nd o f t sction tr is a vry unifor unifor dgr of o f grain siz aar nt wit twinnd crystals in wic t twin ins ar straigt

Appndx F 1 18

gue  89, to ight ght Oveall view of the at ion miotutue, howing itibuti on of gahite flae ight aea ae motly feite feite th nital   igue  90 bottom bottom ight Vew Vew of the gahite flae an eal iti nfill . he white aea aoiate with the gahite ae feite he ealite  motly a gey hee ue to the fine  aing of the feite feite an ementite ementite Eth nital 10.

igue 1 9   to ight g ht The a att tutue of thi ionabon alloy an be een  n ome eniti aea aea eveale by ething ething n nital an ial. Gey aea ae fine ealite 40 igue 1 92 bottom bottom ight ight G ahite ahite flae in a feite feite mati with an infil l of ealite ontaining ome teaite teaite athe. Eth nital an  ial ial   0.

ey

st on

This gry cas ir f h arly 20h cury c ais abu 4% carb ad a il psprus. Bfr Bfr chig h ui s f s f h hick grapi aks ca b s a w pwr whil a highr pwr h cars aur f h srucur is appar Afr cig i ial fr abu  scds h high carb c  f his cas ir ca b s  sic h wl f h ill surru dig h graphi  aks aks is ad up f parli  f diff diffr spacigs S w i uchd rgis i his cas ir ar f h h r ary ucic sadi. h is is a c csi u  f ay ay cas irs bcaus bcaus f  phsphrus c

ey

st on

This is a gry gry cas cas ir circa 1 920  wi abu 3% carb carb ad 0 2% phsphrus. I h plisd sa h  graphi aks ca b s i his fairy ypical gry cas ir gh r wih sall iclus is ha ar praby sulds. I s aras, car rslik rslik rgis f grwh fh f h graphi laks laks ca b s ghr wih s s i  which hickr aks av  dpsid Afr Afr chig i ial fr fr abu 1 0 scds h srucur ca b s  csis f sall graphi aks i a frriic surrud wih  parli accuig fr   raidr f h srucur. Ths ar ar h ypica csius f ay dr dr ad isrical cas irs.

Anx F  1

Fige 1 9 to ight ght Oveal stte of white ast ion showing long e entite laths an sal gl ola egions of ealte. Eth ial x40 Fgue  94 otto otto ight. Cast Cast ion ethe n M uakais eagen eagentt an ial. The soli white aeas aeas ae eentite ak gey ones ae eaite wth oasional non etali etali inlsions an the finely sttue white aeas wth ak sots ae feite feite in a whte atix of ion ae an on  hoshe. x160.

Wte cast on This white cast in dates t the ealy ealy 20th centuy and has abut 4% cabn and 2% phsphus. Befe etching, se stuctual detail can be seen in t he f f  f sighty white and hade needlelike gwths in a e ceacled atix. te that thee ae seveal integanua cacks that aff affect this saple as well as a egin  f psity psity n  ne side f the ingt. Afte Afte etching i n pical, the stuctue can be seen t cnsist  f ceentite ceentite laths with a n e inll f peaite se f which can be eslved unde the icscpe. The eaining ateial beween the ceentite aths and the pealite is the tenay eutectic, eutectic, steadite. Hee it tends t be pesent pesent as ne paticles f feite, seties shwing a he ing bne effect effect set i n a white atix f in ca bide and in phsphide. Using alkaline sdiu picate etch  pical wil daken the cabide, cabide, athugh i t shuld be used ht while Muakai's eagent can can be used f exainatin  f the in phsphide i n these cast ins.

Tn ngot fom Conwal

gue gue 1 9 aove Tn ingot fo Conwal Conwal 8  . Fige 1 96 ght ght Heavly veine an o oe fagent fagent fo the tn ingot n whih no etal eans no s thee any lea seuo oh etention etention of the oigina ast sttue of the ngot. he shae of the ingot s ese ve etely n ooson outs Unethe; x 

Many tin ingts have been ecveed f aine excavatins excavatins ff ff the cast f Cnwall ngland This sal tin ing t is heavily cded and fag fag entay with little etallic stuctue eaining The cpnents ae nw stly the tin xides cassiteite achite and hydachite. The st fthese f these is Sn while the the ineals ae SnO and hydated SnO espectively

AENDIX G

PHAE IAGA

Th fw fwing ing phs digrms hv bn sctd s bing th mst usfu fr invstigtins int ncint mts  ny f th gurs drwn rir in th txt r schmtic rprsnttins f th th cmpt phs digrms incudd hr n mst css th d iff iffrnt rgin r ginss f  f ch digrm hv bn bd with th pprprit Grk ttr by which th phs rgin cncrnd is usuy knwn m trnry digrms r givn thugh discussin  f thir ppictin hs nt bn dt with in th txt Thy hv  dirct rtinship t sm f th binry phss nd

trnry mixturs tht my ccur in ncint mts nd r givn hr bcus f thir us funss s rfrnc rfrnc mtri r furthr dtis cncrning phs digrms th rdr is rfrrd rfrrd t th th bks by Cttr Cttr   97 ) , Lrd   949) Ws Wstt   98) nd Bi Biy y  960) inc th phs in ncint brns is nt prsnt bw but 8% in tin sm diffrnt vr sins f th cpprtin digrm r r incudd t rprsnt th vrib vrib imits  f  sid s utin in prctic trms, such s undr nrm cst ing cnditins r if w nnd

£

igue  97 Teile oetie oetie ima value a hane of woght oe-i alloy



  u

 









 

4

 





o







Ti n



25

s·s·  

nx G



Figue

98 Coetin syse

°

C

1 000 L 900 900

(a)

600

I 8 s

500 400

E+ L a   '

300

E+

T L

aE

 E + 

u

0

0

30

40

50

'

S

60

W n Tin

70

80

90

 S

Appendix G 1

gue 99. Par of he o e n i agra uer ifferen ifferen oios

1100

I  00

1000

L

L

00 00

798

I

000

L

700

 



00 400

600

 £  8 £ 8 8£ 350'

8

300

£

200 10

20 Full lbru

8

£ 30

%

10

20 Anl

: l

I      8 .�: 400 c: I �

300

1 00

1 00

00

 L

700 600

I

30

1 00 n%

0

 £

I

I I 10

20

30

ul  in

%

Appendx G 124

igue

. Coppea seni sste. sste.

° 1 L

9

n

8 7 6

8

L

1.

677

+



0



 5 0. 1



4

X 39

3

As S a 03C

5°

+ o _ 5°

7. 8

X





(As)

£+0 1



30

4



6

 P 

7

8

9

_ 

Appendx G 125

igure 20   Coerlea Coerlea nary syste

  

Cu +  3 6.

)  + 

9

95 5 "



Cu +  ) )

7





4

26" 

99. 9

_ Cu) Cu) 

Cu + b 





4

Pb) 



Wh r r

7



9

 P

Append G 

Figure 202 202 Coer- ron na y syste



 48

L



 4



liquid

 39 39

,

 Y

Y-

s li 

e



08     

40 

solid



E + old Y

9  2

\



83 6  

solid 







4

E + olid a 

-

,









 P n

7



Appendix G 127

Figue 20. Coppe-god bny systems.



4S L



+L 



7

 



 4 0

4

 

'





u







4





 Pn Gl

7





u

Anx G 128

gure 0. Coer-anmony bnary sysems.

°

0

 \ \ \



L



7 6 

e



  0 0

315

\ f

I " II  I 

 00 

4

6 

 ,  y

(Sb)

_



I



 u





 

4





Wg Prn nmny

7







Appndx G 129

Fgure 0 Copper-slver bnary system.

° 





96193

+

OO

79 7



 5

4

u







4

5



Wgh Pn vr

7





g

Appendix Ap pendix G 130

Fgure 206. Copper-nickel bary system.

° L 4





--

  4









 s. 







4

5



h Pn Nk

7





N

Append G 11

Fgure 207. Copper-znc bary sysem.

°

84



e

9





L

+L

835 83 5  



e

7

y +y





558 5

468 '

I  

4



88

250









4

5

    

  

�' + y 

Wgh Pr 

973

7



(Z)



  

Appendix G 12

Fgure 208 Io-arbo system. system. 1 55 0

°C

lqud

400

u  r: E

austete

&

450

qud

(y)



�

emette

soldus

90

austete

&

o

1400

02

0.4

06

eretage of Carbo

emette

Te 8-Rego of te ro-Carbo Dagram

695

eutetod orzotal

ferrte

earlte

& i

&

emette

earte

% arbo

20

43 4 3 e Comlete  ro-Carbo Dagram Dagram

Y

000



austete

  r: E

u  : E 0

o

austete

&

ferrte

ferrte earlte

&

austete

ferrte

earlte

&

&

004%

10

600

400

emette

y

  Fe3C

200 emette

0

0006% 0

005

0 1

015

eretage of Carbo

% arbo

08

Te Steel orto of te roCarbo Dagram

1 .4

Costtutoa Dagam Dagam I datg Solub lty of Carbo  ro

ppend G 1

Fgure 209a e lead-tn system (pewters).

5 5 

 Lqud

5



�+L 

61.9

9.2

97.5 97.5

 O

 

o o

o







4

O



7





 

W %  

Fgure 20b e gold-slver system

   

1 000 000

950

900

o



  A u







O



7





 

ppendix G 14

Fg 2  0  Copp-silv-gold ay lqds.













  



7







Appendi G 1

Figure 2  I  opper-lve-gol ernary ol











4

W % 



7







Apped G 136

Fgure 2  2  Coppert-Iead terar sstem.



hm f P 

4





LOARY

Accula

Amalgam

ssessing an elngated r needleshaped needleshaped struture

 utdated ter r an alpha brass in whih se zin is replaed replaed b tin usuall nl abut 2% tin is added.

An interetali pund r iture  erur with ther etals Merur a r r an aalga with gld silver tin zin lead pper and ther etals. The irstruture  these aagas aagas a be  pe

Agehadenng

Amalgam gldng

The The press  hardening sp ntaneusl ver ver tie at a bient nditins Se steels age harden as d ther alls. The press was rst studied in aluiniupper where where herent regins  dierent struture r as the rst stage  the press.

The press used r the gild ing  an pper als in anient and histri ties. Gld bees pas when ied with eru and a be applied as a paste ver a surae. This Th is an be llwed b heating t drive   st  the erur erur r the erur  an an be applied applie d t the lean su rae rae  the bet t be gilded llwed lwed b t he attahent  gld lea r il

Admalty Admalty ass as s

Alloy A iture  tw r re etals. The ter alling suggests suggests the iture was deliberate

Antmony Alpha ass An all  pper and in with n re than 38% in n antiqui the eentatin press r the anu ature  brass brass eant that n up t 28% in ight be absrbed in the pper when the zin  re was redued redued in situ Mst anient brasses d nt ntain ver 28% zin.

Eleent with with ati nu ber 5   ati ati wei weigh ghtt 1 2  .75 p 630 C spei spei gravi gravi 6.6 2. A lustrus etal etal with with a bluis h silverwhite appearane. The etal des nt tarnish readil n epsure t air and an be used as a derative ating. Antin is und und in se pper alls alls  antiqui and in the regi n  3% has a n siderable hardening eet.

Alumnum Ati weight 268 ati nuber 13 p 660.3 C spei spei gravi gravi  26 . t is the st abundant  the the etalli eleents but bu t is ver diult diult t etrat and was nt prperl knwn until 1827

Annealng A press  heattreatent arried ut n a etal  r al usuall t sten the aterial t allw urther urther deratin . Stritl speaking i  an all is invlved invlved annealing sh uld be

urther desribed desri bed b suh ters as stressrelie anneal s lid slutin annea nralizing et

B

n CC etals a press  rerstallizatin ten  wrked wrked an d annealed etals) in whih a irrr plane in the rstal grwth results in tw parallel straight lines appearing arss the grain when the etal is ethed ethed

Bdentered ubi A unit e in whih ats are sit uated at eah rner   a ube with ne at in the enter  the ube Eah at at the rners is shared b eah neighbr. Beause  the lse paking BCC etals suh as bariu hriu irn bdenu tantalu vanadiu and tung sten annt be heavil wrked wrked but the have a gd bin a tin   dutiit and strength

Anode

Bd

Cpnent  a sste that is usuall rrded n an eletrheial reatin the eletrde at whih idatin urs.

Nae r an ndian pper zinlead al  nished b sur ae treatent t lr it blak and ten inlaid with siver

Asenc

Bloom

Eleent with ati nuber 33 ati ati weight weight 2 1  spei gravi gre r 573 The usual variet is gre arseni whih subliates at 6 1 0 C Arseni Arseni is a steelg steelgre re lr with a etalli luster and was the rst alling eleent  iprtane. Arsenial pper alls preede the use  tin brnes in st areas  bth the Old and New Wrlds Arseni ntents usuall var r abut 1 t 8%.

A rughl nished etali prdut speiall the spng ass  irn prdued in a bler bl er urnae urnae in whih the irn is redued in situ and is nt lten during redutin The rude rude irn bl  ust be etensivel wrked at red heat t nslidate the irn and reve eess slag and har al.

Annealng twn

Bante A ter re nl applied in the past t the depsitin   artensite in steels b tepering at abut 200350 200350 C. C.

Bass An all  pper and zin usuall with pper as the ajr alling eleent and zin up t 0% b weight weight Earl brasses were binar als ntaining 070% pper and 1 030% zin. The lr  brass hanges with inreasing in ntent r a rih p perred thrugh pale ellw t white as the zin inreases.

Ga 138

Gilding mal mal cnaining 1 0 1 5% zinc is suiabl fr fr cld wrk wrkiing ng  is usd usd fr rna rna mnal wrk and wlry wlry Rd brass cnains 0% zinc and 70% cppr and has gd wrking prpris Th cm mn frm frm  f brass is 60% cp pr 40% zinc and is knwn as yllw brass r Munz mal s als alpha brass brass 

Bng ini ng f mas mas ghr wih an ally f cppr and inc Mdrn brazing allys allys may cnain cppr inc and silvr and ar fn calld silvr sl drs n ancin ims silvr gld cpprsilvr and sivr gldcppr alys wr usd fr brazing r sldring pr ains n prcius mals in paricular

Bone

mhd is bcming lss cm mn bu ds allw sm cmpa mpari ris snn wi wihh r rsul suls frm h Vickrs Scal r hr scals usd mr fr indusrial purpss such as h Rckwl Rckwl Scal

C A rm usd  prss h dgr f pur iy r nnss f gld Pur gld is 4 cara r 1 000 n Th nnss nnss f allyd gld can b prssd in h numbr f par f gld ha ar cnaind in 4 pars f h ally r ampl 1 8 cara cara gd cnains 1 8/4 par f gld and is 5 % gld r  50 n

Cuon Th prcss  f incrasing h carbn cn n f h surfac surfac layrs f a mal fn wrugh wrugh  ir n by haing hai ng h mal bw is mling pin wih carbnacus mar such as wd charcal

n aniquiy and hisrical usag usag an ally  f cppr and in sually wih up   4% in bu many amps f ancin allys ar knwn wih highr in cnns cnns 14%  in is  limi fsid f sid suin  f in in wll annald brnzs n mdrn usag h rm brn is assciad wih a num br f cppr allys ha may cnain n in a al and h cmpsi in  f h ally mus b spci d

A prcss cnsising f n r mr haramns fr pr ducing a hard surfac layr n mals as in carburizain n h cas fsl f sl h carbn cn n f h surfac surfac can b incrasd incrasd by haing i n a mdium cnaining carbn fl lwd by ha ramn

Bnell

Csng

Th Brinl Hardnss Scal in which h hardnss is masurd masurd by h rsisanc  indnain f a small sl ball This

Th prain fpuring fpuring mal in sand plasr r hr mlds and allwing i  sid i Mr  gnrally gnrally a mallic



Csehdenng

bjc ha has b n mad by casing h mal in a shap Th simpl s frms frms ar pn mlds ha ar uncvrd a h im  f casing This frm was fn usd fr fr simpl si mpl arly Brnz Ag as as Pic mds ar mad fw f w r mr ing pics in sn brnz r rfracry rfracry clay Hllwcas bcs bc s ar usually pic mlds wih fals crs A gur was mdld in clay and a pic mld was buil up arund h md Th mdl was rmvd and cud b shavd dwn i n siz  prvid h cr arund which h mld pics an d mhr mlds wuld wuld b assmbld Many variains ar pssibl s als lswa lswa cas ing

Csngon Th prcss f making a cas par aachd  an alrady ising bjc r cmpnn n an iquiy a lswa addi addi in mad by craing a small mld arund p ar f an an bc and casing n ma ma dircly  i Ofn Ofn us d fr fr daggr han ds r rpair r cnsrucin f arg brnz gurs

Cs on An irncarbn aly ha usu ally ally cnains % carbn Gnrally Gnrally dividd in hr grups ( 1 ) Gry cas cas irn irn in which fr carbn ccurs as aks f graphi  has cl ln casing prpris and can b machind () hi cas irn i n which all f h carbn is akn up as cmni C

and as parli Ths irns ar usually hard and bril () Malabl cas irns ar usually baind by haramn f whi cas irns by cnvring h cmbind carbn in fr carbn r mpr carbn n h whihar prcss fr ampl a crain amun f carbn i s rmvd frm frm h surfac by idain

Chode n an lcrchmica cll h cmpnn n which rduc in aks plac n many crr sin prcsss h cahdic rgins ar prcd prcd dur ing crrsin w hi aack aks plac a andic rgins

Cemenon Th rm has svra manings Cmnain f gld alys wih sal i n a cupl may rmv rmv silvr laving pur gld bhind Carbnacus maria may b usd  cvr h wrugh irn which is hn had Carbn can diffus in h srucur srucur craing a lwcarbn sl sur fac by cmnain

Cemene Th hard bril bril cmpnn f irncarbn allys cnaining abu 66% carbn crr spnding  h phas C and crysallizing crysallizing in h rh rhmbic sysm  is subl in mln irn bu h slubiliy dcrass dcrass in ausni  ab u 0.9% a h ucid mpra ur Parli h ucid f frri and cmni is h ms cmmn cmpnn

9

cnanng cemene n ancen an d hsrc seels ancen

Cengal casng Casng by he lsax rcess (usually lled by rad ran  he casng mld  rce he mlen meal n he casng saces. Oen used n mdern denal casng echnques and mre asscaed asscaed h mdern casngs han h ancen racce

men usually cnss s  rllng hammerng  r drang a rm emeraures hen he hardness and ensle srengh are ncreased h he amun  cldrk b u he ducly and mac srengh are reduced.

Columna

CPH

Lng clumnlke grans ha can rm hen a ure meal s cas n a mld.

Clseacked hexagnal. A hexagnal ne n hch he ams are arranged n a reea ng sequence sequence ABABABA. ABABABA. . . . . One un lace has a hexag nal rsm h ne am a each crner ne n he cener  he bm and  aces and hree n he cener  he he rsm. CPH meals end  be brle brle e g cadmu cadmu cbal cbal anum and znc.

Connuous pecpaon

Small egs res r her maerals used  hld a hll lsax casng n sn n he mld by securng he nvesmen nvesmen r casng cre  he mld s ha  ll n mve hen he ax s mlen u

he rman  a recae r nclusn dsrbun un rmy hrugh he grans hemselves.

Dslacemen  meal by use  a chasng l  en en  brass r brnze r rugh n. Unlke engravng meal s ds red arund he chased desgn and s n remved remved..

Ce pedue erm meanng lsa lsaxx casng

Coheen pecpaon An amc rearrangemen  srucure ha s merceble by cal mcrscy.

Coppe An elemen h amc number 2 amc egh egh 63 54, m 1083 secc gravy 8.6 Pure cer s reddsh n clr and malleable and ducle.  ccurs n nave cer n dendrc masses and has been knn r husands  years Many cer mnerals ere used  exrac cer mea n r mve urnaces urnaces n he rm   cer rlls and lae r as cakes cakes and ngs  cer. here are abu 20 cerbearng mnerals and bh c er xdes and su ldes des ere smeled  ban he meal.

0c0c,,

Cong Coldwokng he lasc derman  a meal a a emeraure l enugh  cause ermanen sran hardenng The rea

Cupellaon Oen aled  he remva  basc meals rm slver r gld by use  a cuel and eher x dan  base meallc cnsuens r che cal cal cmbnan h sal

Cuponckel

Chaples

Chasng

changes n cmsn ccurs as he dendre dendr e arm s rmed. rmed. secaly cmmn n ancen cas brnzes and cas slvercer allys Crng s accenuaed n allys  h a de se aran beeen qudus and sdus curves.

The segregan  an aly n successve reezng  he sld. Znes are rmed rmed esecally n dendrc casngs n hch a cnnu us seres  small

Cmpng Mechancal jn beeen  eces  meal n hch hey are dermed  shae an ver la r aachmen

Cupel A rus ceramc en made rm bneash r her reracry cmnens The cuel s used  mel smal amuns  meal usually slver r he exracn exrac n  lead lead  r he assay  gld. n he exracn exracn  lead rm rm slver he xdzed lead s absrbed n he cuel leavng a bun  slver The cuel can hen be brken and smeed  recver he lead.

Alys cnanng cer and ncke usually rm 1 5%  70% nckel bu n ancen ays en h less nckel han hs. Allys h abu 25% nckel are n used r r cnage meals. ary exames  cerncke alys are as knn he ms amus beng b eng he Bacran cnage.

Damascenng An ancen rcess  rna menng a meal sur sur ace h a aern n he eary Mddle Ages srds h hs aern ere sad  be r r Damascus made by reeaedly edng drang u and dubng u a bar cmsed  a mxure  rn and seel. The surace as laer reaed h acd  darken he seel areas. erre remans brgh  n he as he rcess  nlayng meal n meal s cmmn arcularly n ars  raq and nda here  s knn as Ku rk.

Dendc Shaed lke he branches  a ree. Dendres are cmmn n cas allys and may lk ke an nersecng snake aern

Ga 140

Depleton gldng

Dslocaton

Gidi ng b reoa reoa of one or ore baser oonents Co on used in anient South Aeria for for the giding of baga or godsieroer aos b reoing oer fro the outer o uter s urfaes urfaes b ik ing

Defets in the rsta struture ofa of a eta that ao w oeent of anes or atos within the attie dge and srew disoa tions are two oon tes tes

Depleton slveng Sieroer aos aos usua deeo a sae when worked and anneaed eoing oide sae enrihes the surfae in si er reat ing a deeted deeted oer zone and aking the ao sier in oor

Dson he igration of one ao or eta into another nterdiffusion aso ours with the se ondar eta eta igrating in o the rst Usua heat is required for for this roess to our

Dson bondng onding or oining of two two et et as b heating the together ah wi diffuse diffuse into the other other  at different rates reating a strong and eranent etaurgia bond

Dscontnuous pecptaton reiitates aid down at grain boundaries often often b a roess of aging aging or of esoutio esoutionn of etastabe hases An eae is the reiitat ion of oer fro sier oer aos

Dslocaton entanglement The densit o f disoations inreases on working the eta unti  disoation entangeent entangeent is reahed At this oint the eta is britte sine no further oeent an our Annea ing wi restore working roerties

Dawng The at of u ing a wire usu a of sier or god through a drawate of hard ateria Drawing is not thought to hae ourred bef b efore ore the 6th entu r

thin god surfae Used in anient eru as a giding tehnque

Electum Natura ourring aos of god and sier us ua white or sier sier in oo r and ontaining u to about 40 % sier

Engavng Use of an engraer us ua of hardened stee to reoe eta fro a surfae

EPNS etroated nike sier An ao of oer  nike and and in tia tia with with 60% o er 22% nike 18% zin, eetro ated with sier

Equlbum dagam



Ductlt

Equlbum stuctues

he abiit of a eta to be drawn or defored defored D utie etas are usua CC tes tes suh suh as sier or god

Mirostrutures that reresent fu e quiibriu hases re dited fro ase diagras  n anient etas the struure a be far fro equiibriu

Electocemcal coOOn

Equ-axed

Electocemcal eplacement patng Ceaned oer wi ehange with god soutions to for a

Deoosition fro a soid hase into wo ne disersed soid hases reates reates a struture aed a euteoid The eute oid oint is ed in b inar aos and in orhoog a resebe the euteti

Faalte

A snon for for a hase dia gra

Corrosion of a eta in whih whih anodi and athodi reations resut in etai dissoution he ost oon for of orrosion orrosion o f buried o r arine etas

Eutectod

e ost ost oon oon ent of anien sags often often our ring as sag stringers in wrough t iron aaie is an iron iron si iate 2eO  Si whih whih ets at abou 8 °C rstai rstaies es in the orhorhobi sste, and usu a takes he for o f broken eongated gre ahs i n s iiate based sags

Flng eoa of eta with a e iing is unoon in anient etawork sine hard see es were not aaiabe

F

Of equa equa diensions o r roer ties in a diretions quiaed quiaed grains are heagona in for

aeentered aeentered ubi  n his at tie sste tere is an ato at eah orner o f a ube and an ato at eah enter o f the ube faes aeentered ubi et as end to be soft and easi worked suh as sier auin iu god oer, ead and atinu

Eutectc

Fuson gldng

n binar aos the oosi ion with the owest eing eing oint The euei is a ed oosition i n binar aos aos and is often a ne interiture of two two hases tia and �

A roess roess used in anien Sou h Aeria, eseia uador for the gid ing o f oer oer aos b diing or fusion fusion of oten oten god aos to the surfae resuting in thik god ao oaings Ma aso be used to



Ga 14 1

reae reae silver alloy alloy oaings oain gs over opper.

Gaa-hada Japanese deoraive deoraive ehnique aking use of iisibe e as suh as silver or silver opper alloy droples on ir on.

Gean slve Aloys Aloys of opper opper nikel and zin usually oprising abou 528% opper 535% nikel nikel and 1 35% zin This alloy was forerly used for any deoraive purposes as a heap heap subs iue for silver, s ine i does no readily arnish and is of silvery silvery hu e.

Glded Covered wih god.

Gold Eleen wih aoi nuber 7 aoi weigh weigh 1 6.6 p 63 spei spei gravi graviyy 1 8. 88 . Naive gold usually onains soe opper and siver Typial Typial gold onenraions are are 8 5 5 % wih wih he reainder reainder being osly silver Gold is brigh yelow yelow bu  wih inreasing sil ver onen he olor is whie while opper provides red ins o he olor P ainu fro fro 2 o 2 5% an d nikel ake ake he alloy wih gold whie.

dcdc 

God eaf Leaf in anien ehnoogy is rare. The er is reserved for gold less han 1 iron hik

Gold fol

Gunetal

ntaglo

Any gold shee greaer han 1 iron hik.

May have differen differen oposiopo siions bu usually an aloy of opper in and zin.

The proess of engraving or reoving eal o reae a design. The depression so fored ay be lled lled wih niello or enael.

Gan n rysalline rysalline eas he grain is an area or zone o f rysal rysal growh in a unifor unifor and hoogeneous for. for. Mos eals onsis of grains and he grain boun daries are he iner fae beween a suession of grains in he solid ass of rysas.

Gan bounday segegaton The preipiaion of a phase or inlusion a he grain bound aries o f a polyrysalline polyrysalline so lid.

Ganulaton Usuay refers o sall god grains aahed o an obe wih solder, eiher ade in siu by reduion of a opper sal wih glue or by use of diffu diffusion sion bonding o f he gold grains. Coon in Erusan gold work

Gaphte An aloropi for of arbon ourring in he rigonal sys e as grey, sof lusrous paes  is he for of arbon found in seels and as irons and usualy ours in grey as irons as hin akes or nodules.

Gey cast on on Cas iron wih a grey fraure. The fraure olor is indiaive ha he as iron onains free arbon as graphie.

Had soldeng An alernaive er for he use of a brazing alloy alloy or a opper silver alloy for for oini ng, as opposed o  he use of leadin alloys.

Hot-wokng Deforaion of he eal or alloy above he eperaure neessary for for plasi plasi  defora defora ion o f he eal.

ntesttal A sal eeen ha ay oupy laie spaes wihou ausing oo grea a disorion of he original laie sruure. An exaple isis arbon in iron. Carbon is a sal eleen and an inser ino he ubi iron laie.

on H ardness on he Vikers or Diaond Pyraid Nuber DPN sale. sale.

Hypeeutectod Conain ing a greaer greaer aoun ofen ofen of arbon seels  han ha required o for a opleely eueoid sruure. n seels his would require ore han .8 % arbon he aoun aoun needed o reae a opleely pearlii sruure

Hypoeutectod Conainin g a lesser lesser aoun ofen ofen o f arbon s eels han ha required requi red o for for he h e eue oid suure suure o f 8% arbon. arbon. Mos anien seels are hypoeueoid, eo id, exep for Wooz seels ade in a ruible o r laer his orial produs, suh as u seel beads fro rane

An eleen wih aoi nu ber 26, aoi aoi weigh weigh 55 .85  p 1528 spei graviy . 8  A heavy heavy whiish eal and one of he os abundan and widely disribued.  ron was known early as eeori iron whih usually onains soe nikel. Exraion by he blooery proess was oon by he eary enuries and his oninued unil he inven ion of he blas furnae. furnae. Laer ehods of exraion exraion in he Wesern world were able o el iron and and by he 1 3h en ury ake as iron. n China, iron wih arbon ould aready be oen during he ie of Chris and as iron was produed uh earlier han in he Wes

0c

B.C

.

Latten Copperzinin alloy soe ies wih lead as well used in he edieval period for heap

Ga 1 2

decraive and funcinal e awrk

liuidus is a surface surface n a lin e

st-w castng ad

c

Aic nuber nuber 82  aic weigh weigh 207.1  p 327. speci specic c gravi gravi 1 1 .35 . ure lead lead rec recr rsa salllliz izes es a a r r e e peraure when defred The eal can readil be exruded in pipes r rd bu lacks he enaci  be drawn in wire ead was was cnl cn l exraced fr galena ead sulde and was fen a bprduc f he exracin fsilver fsilver fr galena since an f hese hese lead res are argeniferus argeniferus L ead is a use  fu addiin  brnzes and brasses especiall fr aking casings and is used as an al wih in as a sf slder

Casing fr fr a wax del The bjec  be ade is shaped in wax (eiher slid r hllw and is cvered in a cla ld When When he he wax is le lenn u u he space can be lled led wih len eal usuall brnze r brass

Matnst Ofen used nl fr he hard needelike cpnen f uenched seels bu re gen erall, an needlelike hard ransfrain ransfrain prduc f a uenched al The s cn in ancien aerias is arensie arensie i n lwcarbn seels r arensie in beauenched brnzes

dbut ae applied  he ceenieausenie euecic a .3% carbn which freezes a ° 1  3 0 C During cling he ausenie in he euecic a ransfr in a ixure f ceenie and ausenie

qudus The line n a b inar phase dia gra ha shws he epera ure a which which slidica in begins upn cling fr he el In a ernar diagra diagra he

Mtc n Irn fr uer space Usuall an all f irn and nickel nickel  Sall aun s f cbal and anganese are pical Se earl irn expliain ade use f eeric eeric irn 

Ptctd An isheral reacin in which w slid phases in a binar sse reac  fr a new slid slid phase A periecid reacin ccurs in he brnze sse fr exaple i n which a 65% cpper a reacin ccurs beween CSn and he slid sluin gaa prduc ing a new phase phase CS n a abu 580

c

Pwt

A priiive fr fcasing f casing in an penshaped depressin in sne seies cvered par iall  preven excessive xi dain

cien pewer pewer i s an al f lead and in uch used in Ran ies The pisnus naure f lead has resuled in he repaceen f lead lead wih anin, alhugh anin is als inadvisable in high auns fr fr uensils  Cn pewer in ani ui a a cnsis f 6080%  in 020% lead whie dern pewer a be 1 530% cpper 5 5 10% ani n and 87% in

Palt

Phas A hgeneus cheical c psiin and uni fr aerial describing ne cpnen in a eallic sse

Twinned crsals prduced b echanical echanical srain alne  as in zinc

The ne ixure f  f ferrie and an d ceenie fund fund in seels The euecid pearie will will be c plee when when he carbn cnen reache reachess 08 %. In s ancien seels a ixure f ferrie ferrie and pearlie is cn

Mcu

Ptctc

af gldng Cvering wih gld b he appicain f gld leaf r fil  Seies held echani call b rugheni ng he surf sur face r b a diffusin bnd  he subsrae eal

uid a r eperaure The earlies exracins were carried u b rasing cinnabar er er cur I sude in an xidizing xidizing asphere and cllecing he ercur b disillain

Matnstc tansfmatn A prduc fred b rapid cling cl ing f an all Se alls a be speciall frulaed  allw arensiic evens  ccur n cling

Mchancal twnnng

0c,

Aic nuber 80, aic weigh wei gh 2005 p 38. 8 specic specic gra gravi vi  1 3. 55 . Mercur has been fund fund in Egpian bs bs f 1 500 and was widel knwn in he cenuies in China and India A sil ver ver whie eal which is li

BC

B.C.

Ntdng In seels he hardening due  nirgen cnen ha ha a resul in nirides being fred in he all all

pn mld

Reacin f a phase ha has fred wih wi h a liuid f a diff differ en cpsi in  fr a new slid phase The new phase a cnsue all f he liuid  fr fr a al  new slid, p icall bea phase in he brnze sse

Phas dagam A diagra wih axes f eper aure and and cpsi in describ ing he d iff ifferen phases p hases ha  ha a ccur in an all wih change change in eiher cps iin r eperaure A b inar phase diagra cnsiss f w eal lic cpne ns A ernar ss ss e e which is usuall re cplex cplex cnsiss f hree hree eals

Gl 1

Pecemol A ld aken fr a de a ay be assebled in a nuber f piees befre befre bei ng used fr slusing wax ver e ld inerir fr lswax p ies f a aser del Su eniques were were n in e Renaissane.

Platnum Meall eleen ai nu ber 7, ai weig 150 p 772 spei graviy 2 1 5 irs irs dis disver vered ed in Su Aeria by Ulla in 1 735, bu used used by e ndians f Euadr Euadr and Cl bia w snered e eal w gld inds are knwn pariularly fr La lia daing  e early early enur ies  an be presen in e naive sae usu aly allyed wi se irn Te eal is alleable and duile  is used in early sien i insruens sine is ef en f expansn is very siar  sdalie gass

0c,

BC.

Jin ing f eal eal see by sall ea pegs passing rug and aered dwn

Pseuomohc

Sau

Te replaeen in e rr sin press f a aerial wi aner a i is e fr f  e replaed prdu Pseudrpi replaeen replaeen  f rgan aerials is n n irn arif ari fas and an ur n p per alys and siver pper allys as well

sai er fr ig n brne s fen fen wie in lr

Quenchng Te a  f quikly ling a eal r ally by plunging in ld waer r il

Quenche stuctues

Manysded. S e grain sapes ay be plygnal

Usally nnequlbriu sru ures r pases a ave been ade easable in an ally by quening n waer r il. Te s n quened prd us are arensie aren sie in seels and arensie in igin brnzes Quening Quening ay als be used  suppress rdering reains, espeially in gld allys and se anien exs refer refer  is praie  avd ebrile en 

Pll

Reouss

n e exrain f pper fr priiive ses e eal is prdued as sall drpes r pariles n a slaggy arx. Tese sall eali

Wrkng fr e bak f a eal fen fen n e slg  reief f a ased design n e frn. frn. Te eal is en dsplaed by aering fen n a sf suppr su as pi s as 

Polcstallne Cnsisi ng f any any individual rysalline rysalline grains Ms eals are pyrysalline pyrysalline sli ds

Polgonal

reae reae raised designs n e frn

pariles are alled alled prills and were  fen exraed by brea ing up e seled prdu and srng e ea. n ruible presses prils are sal drp les f eal adering  e ruibe ruibe lning 

Rvetng

Segegaton n allys usally f ree frs: r s: nra segregain segregain (2 dendri segregain segregain  and (3 inverse segregan. segregan. n nral segregan segregan e lwer eling pin eal is nenraed nenraed wards wards e  e inner inne r regin f e as. n dendri segregain fernlie grw urs fr la psinal gradiens. n inverse segregan, segregan,  e lwer elng pin nsiu ens, su as  n r arsen in brnzes is nenraed ward e er as srfaes.

)

Shakuo Japanese er fr e deiberae deibera e use and anfaure f gld pper alys

Shuch apanese er fr derave siverpper alys fen wred and annealed  reae deraive surf su rfaes aes wen l red by eia eng r sanin g.

Slve An eleen f ai nber 7, 7, ai weg weg 1 077 p 60 C spei spei gravi graviyy 1 05 0

One f e nbe eals a is n xidized by eaing in air  is wie in r and very duie and aeabe. S lver lver was usualy bained by upel ain f lead lead res alug i ay als be exraed direly fr silver sude depsis Pure slver is fen saed  be 1 000 ne and alys are based based n is nenlaue r exape, serlng siver (qv is 25 ne.

Snkng A eniqe w w a vessel an be prdued by aer ng f e inside. Te see eal is aered eier n e a surfae f an avi r re nly aered n a sallw nave depres sn n e anvl. As alled bling r lwng.

Slag A glassy pase r ixe f pases sually  be fnd n anen anen  r isr wrg rn r seel. Te sag s an pran byprdu f e seing f eas. eas.  ay be nrpraed in pper r irn allys allys as a resul  f inplee separan r nplee el ing during exrain exrain as in e bery press.

Slag stnges Sa pees f slag a ave bee inrpraed inrpraed n  e ea and are en srung  as sal engaed rbbns as a resl f wrking e ea sape .

t

Ga 144

Slp plaes

Speculum

CC tals a show sli lans a n sris of lins in wo intrsctin dirctions on hav dforat dforat ion of th tal.

A na sotis alid to Roan or bronz irrors con tainin a hih rcnta rcnta of tin. Historic scl a contain abot 7% cor 33% tin. Ancint irrors ad s of siilar allos sall of bta bronz coosition and  to abot 2% tin.

Slush castg A thod of castin castin in wich tal is ofn sn or aitatd aitatd in th old so that a thin shl is ford ford Mor coon in ancint and hist oric talwor is sl sh wax wor in which wax is sls h cast ovr a ic old int rior bfor bfor invstnt.

Spg Trnin Tr nin on o n a lath folowd folowd b drssion of tal whil in otion.

Stampg So soldes A tr alid to ladtin allos sd in soldrin sall not of rcios tals Th r lii t of th th ltin ran ran is abot abot 300 C and and an an alo alos s lt lt at abo abott 1 30 30 1 8 0 C

Soldus Th lin in th has diara that sarats th ast sta of th allo sall a ixtr of soid and liq id fro th co ltl sold allo blow th tratr tratr of th th solds lin. Th solids tratr a a b diffrnt at diffrnt allo coositi ons dndin on th t o f has diara.

Dislacnt of tal b a hard di oftn for for assa r  r oss

Steel A allabl allo of ron and carb carbon on that that conta contains ins abot abot 0. 1  1 % carbon carbon.. Th carbo carbonn is rsnt as cntit sall as a coonnt of arlit. Lowcarbon stls contain fro 0.0 % carbon to 0.% and ar soft Mdi carbon stls contain 0. 0% carbon and hih carbon stls or than 0%

Stkg A thod of an coins and dals. Th irsson s ct in nativ in a vr hard at rial and this di is thn lacd lacd ovr th coin blan and ivn a snl  hav hav blow ths co rssin th ta of th blan nto th rcsss of t di Bfor Bfor th introdct intro dcton on of stl bronz coins cold onl hav bn strc sin ston or bronz dis. Strin a cas strssrlatd fatrs in th strc tal sch as srfac cracin or intrnal dfcts. dfcts.

empeg Usall alid to stls n which so o f th hardnss is rovd b hatin at odr at tratrs fro 50 to 5 0 C dndin dndin on t t t of trin trin rqrd In ancnt tals trn or slftri slftrin n of artnsit wold hav bn carrid ot to rdc th br ittlnss of th fl qnchd st cttn ds of swords

Stelg slve



A coo n coina bnar allo allo of 5% silvr silvr 5 % cor.

An nt of atoc nbr 50 atoic atoic wih wihtt 1 1 8.  2318 scic sci c ravit (r) 5. 5 (whit (whit))  .3  . A soft soft whit whit lstros tal tal obtaind alost ntirl fro th inral cas sitrit Sn Tin s not aff affctd on xos  xosr r to air ai r at ordinary tratrs At t ratrs ratrs abov 1 3  C th whit ttraonal aotroic

Sote A dcoosition rodct of artnsit artnsit fond in stls t consists of n articls of cntit i n a atrix of frrit frrit Sorbitic strctrs a b rondd cntit not ncs saril drivd fro fro artnsit.

worin worin  d to sli of lans of atos ast ach othr.

Sta hadeg A snon for wor hardnin.

Sta les Sa as sl lans. Oftn sn in CC tals t als aftr aftr hav

dc

for is stabl stabl and blow this th r cbic for a xist . Abov Abov 1 70 C tin is rhobic rhobic in crsta strctr. Th tal has low tnsil strnth and hardnss bt ood dctilit

g Th oration of coatin a bas tal tal ( sall) with tin. Th coatin a b obtaind b hot din into oltn tn or b own th oltn tin ovr th srf s rfac ac of th obct. obc t.

ooste A vr n xtr of arlit not rsolvab b otical icrosco odlar troosit is fond in stls not coold qicl noh to for ar tnsit On tchin in low carbon stls troosit aars as a bl tchin coonnt in nital. nital .

umaga Th na ivn in ancint Soth Sot h Arica to th allos of cor and  old of wid ran of coosition coosition and coor.

uteag Corzncncl allo of silvr silvr color col or iortd fro China to Ero Ero in 1 8 th cntr

..

 dagams Titratrtransfora ton diaras. Most sf sf i n consdrn th natr of th qnchd icrostrctr to b fond in stls and hih tn bronzs. Th qnchin rat rat and coostion rslts in a

Ga 145

dff dfferng ere ere f TTT dagram that are cmmnly ued t nvetgate tranfrmatn eff effect n cmpnen cmp nen t fun fundd durng quench ng f ally ally

Vce A hardne cale that ue a damnd havng havng an angle f 13 6 degree between the face. The ladng can be ued ealy fr mcrhardne meaurement. t  ne f the mt ueful ueful hardne tetng cale.

Weld A term ued t decrbe a  nt made between tw metal made by the heatng heatng and  n ng the eparate part wth n lder apped Ancent wed were ften made n precu metal, uch a gld a nd lver and n the jnng f rn cmpnent epecally n the fabrfabrcatn  f wrught rn.

Wte cat on Cat Cat rn  rn wth wt h a whte fracture fracture due t the preence f the car bn n the cat rn a a cementte rather than free graphte.

Wdmanttten A type f tructure tructu re that frm when a new ld phae  prduced frm frm a parent ld phae a plate r lath alng certan cytallgraphc plane f the rgnal crytal. The tructure  acated wth many meterc rn, and wth change upn clng n wrked wrked rn and cpper ally ally Mt cm mnly fund fund a an ncdental

feature f  f wrught lwcarbn teel

Wootz Wtz  a knd f teel, made n mall crucble n ancent nda and ften f hypereutectd teel wth a very lw lag cntent Th cat teel wa wdely ued fr the manufacture f wrd blade and ther qualty prduct

Wought The prce f hammerng r defrmng a metal r ally, a pped t catng.

Wought on rn that ha been prduced frm the blmery bl mery prce and ha been cnldated by hammerng and annealng nt a wrught prduct. Wrught rn uualy cntan lag trnger that have been elngated and attened ttened n the prce  f wrkng frm t he blm.

Znc Element f amc number 30, atmc weght weght 653 8, mp 4 1 95 8 C pecc pecc grav gravty ty 7. 1 33 Znc re re were were ued ued fr fr makng bra by cementatn lng bef b efre re the metal wa ue d n t pure frm. The lmt f znc that can enter nt ld lutn n cpper by th prce  8% The Rman made extenve extenve ue f bra and n nd a, znc wa wa beng made by dtllatn n retrt durng the 1 3th century century The metal

.

wa nt knwn n Eurpe untl redcvered n 1746. Znc  a bluhwhte lutru metal, brttle at rdnary temperature temperature but malleable at 100150

0c

BLOGHY

Amrican Soci for Mas

19721973 Ala f Micucue Micucue f Iduial l I Metals Handbook Vl  8h ed Meal Meal Pak Oh i: Aeica Scie f Meal An  M.  Brion and H H. oghan

970 Metaugical Repots on Bitish and ish BonzeAge Bonze Age mplements mplements and Weapons in the Pitt Rives Museum Pi Rie Mueu Occaa Pape   T eclg N 1 0 Oxfd: Oxfd: Oxfd Oxfd Uiei Pe

Aaed Aaed Mealgaphic Specie 92 e ole ofmicostuctue in metals Becw Sue: Aaed Mealgaphc Specie Braha E

97 Colo Metaogaphy. Metaogaphy. Meal Pak Oh: Aeca Sce f Meal M eal

Bachmann Hans-Gr

982 e dentcation of Slags om Achaeological Sites Iiue f Acaelg: Occaal Pub icai N 6 Ld: Ld: Ii ue u e f Achaelg Bai A R

960 A Textbook extb ook ofMetalu ofMetalu L d Macilla Macilla 1967 The stuctu st uctue e and a nd stenth of of metals Bechwh Sue:

92 Pble i e uecece Aal f CuAg CuAg Bzaie Tachea Tachea ad Mealugical I fai f f Seci I Methods Methods ofChemical Chemic al and a nd Metal lugical lugical Investi In vestigation gation ofA ncient nci ent Coinage. E T Hall ad D M Mecalf (ed)  Ral Ral Nui aic Scie Special Publca i N 8 Ld: Ra Rall Nuiac Scie ogh l an, H . H . C oghl

Brandon  G.

1 975

966 Moden Moden Techniqu echn iques es in Metalog Metalog aphy Ld: Buew

Notes on the Pehistoic Metal lu of of Cop Coppe pe  and a nd Bon B one e in ed Pi  the Old Wold. 2d ed Rie Rie Mue u Occaia Pape Pape  Techlg Techlg N 4 Oxfd: Oxfd Uie Pe

Andrson E A.

959 ic: e ciece ad ecl g f e eal  al ad cpud I The Physical Physical Metallu Metallu  ofinc in c  H  Mahew (ed) New Yk: Reihld Publig Ld: Capa ad Hall

har hars s ] A  and  A  Lak Lak

Brown B F H  Burn Goodwa ] W  has M Goodwa Kugr and M Pourbaix (ds) 1 97

Coosion and metal atcts a dialogue between consevatos and achaeolo acha eologi gists sts and coosion c oosion scientists. NBS Special Publica i 479 Waig Waig D : U S Depae Depae f C ece Bushn G H S

195 e  e A chaeolo chaeo lo  ofthe ofthe Santa Elena Penins Pen insula ula in South West Ecuado. Cabidge: Cabidge Uie Pe hars ]. A.

1968 The i Shefeld Plae Antiqui 42:28285

oghan H H and R F co

198 Mediaeal I I  Aefac Aefac f he Newbu Aea Aea f Bekhie: Meallugica Exaia Exaia i Jouna ou nall ofthe ofthe Histoical Metalu Socie 12:2329 ook R B S an d S Aschn Aschn brnnr

195 The ccuece f eallic i i acie cppe Jouna ou nall of Field Field Achaeo A chaeolo lo  2:251266

orrosion and a nd mtal articts: a dlogu dlogu btwn consrvators consrvato rs and archaologts archaologts and corro corro  sion scintts 1979

B d Bw Ha Ha  Bu e W Tha Cae, Ma ha dwa ee Kuge ad Macel Pubaix (ed) NBS Special Special Publicai 49 Waig Waig, , D : US Depae  f Cece or A

1975 An ntoduction to Metau Ld: Edwad Edwad Ald Fink

C

G and A H Kopp

1933 Acie Egpa Ai Plaig  Cppe Objec Metopo Metopollitan Museums Muse ums Studies Studies 4:163167

C

Fink G and E P. Poushkn

936 Miccpic Miccpic Sud f Acie Acie Bze ad Cppe Tansac tions ofthe Ameican Am eican nstitute of Mining and an d Metau Metaugical Engi nees Meal Diii 122:901 122:901 17 Ghandour 

1981 Elemen Elemental tal and an d Metalo Metalog gaphic aphic Anasis ofObects om om Tel Aul Palestine MA Deai (upublihed) Uiei f Ld Ld Ii ue f Achae Achae lg Goodwa M and H onkin

C

198 Queced higi bze f e Philippie Achaeo mateials 2: 27

Bbogpy  8

Ha E. T. and D. M. Mcaf ds

cman cman H N.  A Erj Erj and E J Barr

7 Methods of ofChemical Chemi cal ad a d Metal lugical lugical Ivestig Ives tigati atio o ofA cie c iett Ral Nua  Coiage Ral S Spial Pubia in . 8. Lndn: Ral Nuiai Si

18 w ppiv ppiv n Mh allug allug hniu  f gldglding pp a La ga Nhn Pu. Ameica Atiqui 7330. ord ord J. O

Hndrckson R C

167 Alicatios of Metallugical Micoscopy w k: Bauh b.



Hong G and

H

Jumng

183 Ra Rahh n Han   phi dalgaphi a in. Sud Tad Tadee Joual Jou al Iteati Ite atioal oal 58.

 A oy oy System ystemss Nw k: Pi an. Maron H.

17 Metalwok Metalwok ad a d Eameli Eam eli  Nw k: Dv Publa n. Rpubihd f  5 , h din. Lndn: Chapan and Hall Mawson C. H.

Kssing R. and N ang

1636 Nnali inluin in . Io ad Steel Istitute Special pecia l Repot No 90.

115 A Mallgaphi Mallgaphi Dp in f S Anin Puvan Bnz f Mahu Pihu. Ameica Am eica Joual ofSciece (0)0:55616.

cman H. 

7 Anin Mhd f Glding Silv: Eapl f f h O d and Nw ld. ld. In Sciece ad A chaeolo. chaeolo. R. H. Bil (d) Cabidg Ma: Ma: MIT P. 30. 73 Th Gldng f Ma n P Cban Pu In Applica tio ofSciece i the Examia tio of Woks of At . ] ung ung (d.) Bn: Muu f in A. 385 

Mas P. and  Bur

77 Ecavatio Ecavatioss at a t Sadal Castle 191973 akd Hi a S McCron  C. and J. G D

7 VlThe Paticle Atlas nd d. Vlu IIV. Mihigan: Ann Ab Sn Publiain

 xpinal and aha gial nidain Achae omet 8: 13316 Ndam Ndam Sr J.

15 Sciece a d Civili Civilisatio satio i Ca Chia Vl. 5, Pa II Ca bidg: Cabidg Unvi P. son J. A.

185 Mallgaph Mallgaph and Mi uu. uu. Ca in. I n Metals Metals Ha Hadboo dbook k Vl.  h d Ma Pak Ohi: Ai an Si f Mal.

186 Tinh ufa n bnz

H

E Exnr

175 Rn Dvlpn Dvlpn in M allgaphi Ppaain Th niu. Micostuctual Sciece. 3:6306 Pps V A.

171 Mode Metallogaphic Tech iques ad thei Ap Applicatios. plicatios. Nw Nw k: k: ]. i i Sn



Pousckn E P

16 Stuctual Chaacteistics of Metals. Ada: Elvi Rapiak  and  J S

Odd Andw W

177 Th pduin f gd gd wi i n aniqui hand aking h d bf bf h induin f h daw pla. old Bulleti 10787.

17 Th Bnz Bwl f Ban Dn T a Ph Thaiand: an niga  f phii phii a a lug. Wold Achae A chaeolo olo  1 1 :63. Rapak 

 8 8 Ann  wll wll a a u f hnlgial hnlgial n fan : a ud f hniqu f aking w. In Fouth Iteatioal Iteatio al Restoe Semia Veszpem 15. Budap: Nainal Cn f Muu

183 The developmet of coppe aoy metallu i Thailad i the peBuddhistpeio peBuddhistpeio with special eece to highti bozes PhD hi (unpublihd).  vl. Univi f Lndn ni u f Ahal Ahalg. g.

O'Ni

Rns N   E. Bond and R A Rumm

H

13 The Hadess ofMetals a a  d its Measuemet Lndn: Chap an and Hal Pow G

Mks N. D.

Pow G. and

176 Metallog Metalloga aphi phicc Etchig. Mal Pak, Ohi : Aian Si f Mal.



155 Cniuin fding f ding all all f h  gdpp. Tasactio Tasactios s ofthe ofthe Ameica Am eica Socie Soc ie  ofMetals 7:57857

Bbgraph 14

Rolason, E C 1973 Metaur Metaurr Engn Engneers. eers. Lon

don Edward Edward Arnold.

H

Samans, Cal 1963 Metac Materas n Enneer n ew York Macillan. Samuels,  E 980 Optca pt ca Mcroscop Mcr oscopy y of arbon rb on Stee Metal Park Oio

Aerican Society or Metal. Schweizer, 1978



and P Meyes

Autenticity o ancient ilver object: a new approac. Masca Joua:9-0. Scott, D A 980

Te conervation conervation and analyi analyi o oe ancient copper alloy bead ro ro Co lobia. Studes n ons onser erva vat ton on 2 5 1 57 1 64. 983 Depletion g ilding an d urace urace treatent o o  gold alloy ro te ario area o ancient ancient Colobia Journa Journa  ofthe ofthe Hs torca Metaur Soce 17:99-115. 1986 Gol d and ilver alloy coating over copper an exaination o oe ateact ateact ro ro Co lob ia and Ecuador Archaeomet 28:3355.

1991 Tecnological analytica and icrotructural tudie o  a Renaiance Renaiance ilver bain . A rche rcheomate omater ra ass 5:  1 -45  Slunder, Slunder, C J and W K Boyd Boyd 1971 Znc ts corroson resstance.

London: Zinc Developent Aociation. Smth, C S 1960 A Hsto Hsto ofMetaogr Meta ography aphy

Cicago: Univerity o Ci cago Pre. 191 Te Tecnique o te Luritan Si S i t n Scence and an d Archaeo Archaeo ed) CaCao R H. rill ed) bridge Ma MT Pre. 3-54. 1981 A Searchr Structure S tructure Seected Seected Essays on Scence Art and Hs to. Cabridge, Ma: MT Pre. Thompson, S C and A K Chatterjee 1954

Te ageebrittleent o ilver coin. Studes n onserva ton ton 1 : 1 1 5  1 6 6 .



Tylecote, R 1968 The Sod hase hase Weng ofMet Edward Arnold a London: Edward

1976 A Hsto ofMetaur Lon don: Te Metal Society.

1986 The rehsto ofMetaur n the Brtsh Ises London Te ntitute o Metal. Metal. 1987 The Ear Hsto of Metaur n Europe. London: Longan Tylecote, R E and B   Glmour 1986 The Metaogra Meta ography phy ofEa ofEar r Fer rous ro us Edge Edge Too Too  and an d Ed Edged Weapons AR riti Serie nuber 1 5 5 . Oxord Oxord riti

Acaeologica Report. Untracht, Oppi 1975 Meta Technues echn ues r s Dou bleday. men. New York: Doubleday.



West, R E 1982 Tema Eubrum u brum Dagr Dagrams. ams.

nd ed London: Capan Capan and Hall

N

H

Wnchell, A and Winchell 1964 The Mcrosco M croscop p ca haracters of Artca Inorganc Sod Sub stances Optical ropertie o

Articial Minera 3r d ed. ew York: Acadeic Pre Yakowtz, 1970

H

Soe ue o color i n etalograpy Appcatons of Modern Metaographc Technues. ASTM STP 48050-65 Metal Park Oio: Aerican Soci ety or Teting and Material

NDEX

 acd acded passu dchrae 72

acd acded selec acd  3 acded sulfae/chrc xde 73

acded hsulfae/aceae 3 acded ed hiurea 3 aggregae aggregae carb 4 1 alchlc ferrc chlrde xv  alkale sdu pcrae 0 allys aealg  phase 4 alpha 14 1 5 alpha bea brass 1 9 alpha bea euec euecc c 1  1 4 alpha dela euecid 5 alpha epsl phase regi 5 alph alphaa brass brass 1 9 0 alpha dedres 1 3 apha sld slui 1  alua 64 i plshg 66 aa/hydrge aa/hydrge perxde  3 au persulfae/ passu cyade  ace ace seel seel 1 6 asrpc asrpc 39 49 aealed aealed casg 9 3 ae aeal al gg 3 6 1 4 eperaures eperaures  s 5 aqua dag 63 aqua aqua reg rega a  1  99 1 00 aqueus aiu persulfae  aqueus ferrc chlrde  Aralde XD5 59 archae archaeg gca call aer aerals als 1 1  1 4 5 arrhead 88, 114 ASTM uber 5 ac packg facr 1 aus ause e ee 38 39 41

++ ++

sld slu 16 ause ausec gra budares budares 3   35 ause ausec c gras gras  1   1 5 auseic auseic reg reg 1  Ausrala 106 axe ax e 92 frage 1 05 azure azure crysa crysals ls 1 1

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Bacha Bacha 5 0 baded srucure 3 Bauas pr slu 0 bead rech cuseel 36 gld ecklace 99 Beaujard's reage 0 bell 6  93 bedg bedg 1 0 Beraha's reage 0 bea 14 18 brass 19 bze 6 8 eedles 8 beaphase brass 0 beaphase aresie 95 beaqueched brze 8 blle 89 bary  brzes 6 blackhear blackhear 3 9 blade frage 1 1 4 blas furace 3 bl 89 bl ble ery ry r r 1 0 1 14 bdyce bdyceere eredd cubc 1  49 bl 94 98, 112 Ra 1 12 bracele 1 1 1 brass 19 6 ally 3 gra sze 53 jg 63 edal xv brgheld ld uparzed llua 49

Brell hardess hardess esg    br brze ze 5  5 ally 3 aealed 6 bell 93 beaqueched 8 cldrked 6 dagger dagger h l xv exa exaa a f 5 gra sze 53 hgh 5 gs 8 l 5 rrr 8 sculpure xv syse 6 Brze Age 88, 97 srd x Buehler epxde res 54 Maserex clh 55 aferg ache 63 Bushell 9 Byzae 114, 116 C

caball 4 96 carbde 3 carb 3 ally 3 equvale value 3 8 seel seel 1 5 carb ce 3 f ace bjecs bjecs 1 6 f cas cas r 3 cas 87 88 92 93, 95 9 9 99, 103 103 105 105, 107 107 108 108 11 118, 119 cas ad rked 111 112 cas brze  cas cas brze cese bu rer  cas cas r 1 6 caball xv xx 4 96 echas 69 erferece echa 3

crsrucure 40 scales xv xv 4  spherdal graphie 3 hehear 3 4 cas eals 6 cas queched rked 94, 98 casg 5 defecs  4 cahdc graphe akes xv ceea 19 ceee ceee xv xv xx xx 3  3  3  free 38 gra gra budary 3 1 lahs xvi xvi 4  eed eedle less xx xx 13 35 36 erks 0 cees 50 cerea axe cpper 4 Charles ad eake  chasg 109 cheepiaxy 43 chll casgs casgs 6 Cha Cha 19  3 38 4  cas r 39 Chese cas r  xv chrc acd/sulfae echa 4 chru (V) xde  clsepacked hexagal c 8 9 101 117 zc zc x cldrk degree f9 99 Clba 3 46 90, 95 99 10 115 clr echg cpper allys 4 clr eallgraphy 3 cuar grh 6 cpuds  ereallc  ccera cceraed ed HC  1 Cke ad Aschebreer 4 c cg g 1 1 5 clig clig rae 1 4 1  3 4 5 3 1  3 39 5 1



ndex 152

pp pper er  1  47 10 pper all all 3  90 9 101 ethant 7 interferene ethant 73 pper and tin all all   pper rrin prdut xvi pper glbule 47 pper xide  8 pper ulde inluin xvi pper ul ulde  0 pperareni all 92 ppergld all 95, 95, 115 1 15 pperlead all 3 pperilver all 1,  ethant ethant 7  ppertin all all   88 88 93 94, 98, 98, 103, 103, 105, 105, 1 1 1, 1 12 ppertin phae phae diagram diagram 1 8 ppertin ppertin tem tem 1 6, 6 ppertinareni all  ppertinead ppertinead al 93, 108 ppertininlead all  ppertinin tem xviii pperin all all 9 105, 107 1 13 pperin pperin tem 1  red brne  ring xvi   1 ,  ,     7   Crnwall 120 rr rr i inn 1 07 1 13 lr 4 f gldpper all 46 rrin rut 7 rrin p ree ree 43 metalli fragment 43 rrin prdut 43, 44, 7 ditributin 4 examinatin 6 mrphlg f 4 rabtpe graphite 41 rtal fault  uprite 43 44 46 1 07 uprite lamellae 0 uring 63

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



dagger 4 blade 1 1  handle 94 damage due t ampling 8 damping apait 37 debaed ilver  1 all 7 in in  17 defrmatin perentage perentage f  defrmed defrmed grain g rain 8 degree degree  f ldwrk  delta delta 1  dendri dendrite te arm arm 13  native native pper 1 03 dendri dendrite te   40 alpha alpha 1 3 ght  grwth   nnntinuu 86 egregatin  ilverrih 86 truture 6 3 4 dendriti arm paing  meaurmen meaurmentt  1 depletin f euteti phae  4 f the euteti phae 1 4 depletingilding 46 diamnd plihing 44 Diamnd ramid Number  77 dimethlglxime nikel tet 71 di derative 90 dintinuu dintinuu preipitatin preipitatin   dilatin entanglement 3 dilatin  diperin flead 7 drawing 6 Dub Dub  1 dutilit 3

ear rnament 46, 95, 107 ear pl 99 earl earl 0t h entur 1 1 , 119 Earl Medieval 1 13 earring 1 0 Eatern Han dnat 38 Euadr Euadr 47 0  edge dilatin , 3 edge retentin 64 64 7  edged tl 1 6 eletrhemia replaement plating tehnique 47 eletrlti eletrlti plihing 66 eletrmehania eletrmehania plihing 66 elngatin 41 embedding mall ample 6 emulin 3 England England 3, 4  medieval 100-102 1 13 13, 1 15 15 engravin engravingg 1 0 epitaxia grwth 43 Epxide 7 epx 63 epx rein 7  epiln phae 1, , 6 epilnarbide 3 equiaxed grain xvi equilibrium  3 1 dened  diagr diagram am 1 1   truture 6 eta and tin tin 1  eta phae 1  4 6 eth pitting 04 ething 67 plihed metal 6 ething lutin fr arhaegial material 6 euteti 14 euteti phae phae diagram diagram 1  euteti pint 1, 14 euteti truture 1 

eutetid interdendriti  pearlite 13 phae phae 1  pint 17 truture  tranfrmatin 16 tpe tpe tranfrmatin tranfrmatin 1 



faeen eentere teredd ubi 1  7, 4 faeligree 1 07 faalite faalite  0 ferri hlride xvi  ferrit erritee xvii xvii xix, xix,  1  4 3 1  3 41,4 grainbundar grainbundar  1 grain truture  grain grain 3 1 04 maed maed  1 gurine 1 08 ligree  ink and Kpp 6 ake ake graphite 38 4 1 rane 36 free ementite 38 free ferrite 38 free graphite 37 40 renh utteel bead 36 G

gamma irn 4 gamma phae 6 gamma gamma lid lutin lutin 1 6 handur 88 gilded ilver 106 gildin gildingg 1 16 glerl glerl ethant 7 1 gld gld   all all 1 1 gld al ethant ethant 7 gld fil 7 gdppe gdpperr all , 3 46 90, 95, 10 gldpper tem 3

ndx 153

goldsilver allo 99 goldsilver goldsilver sst sste e   grai grai boudaries boudaries 20 2   26 2 8 8 3 2 2  6   9 austetiti austetiti 3  grai boudar eetite eetite 3 gra sze easureet 5 grai struture equiaal 6 heagoa 6 grai boudar ferrite ferrite 2  gras austeiti austeiti 2 graphte graphte vii, 37 0 akes akes 38 2 free 0 atri 38 uleatio 39 polgoal 39 spheroidal 39 gravi segregatio 27 Greek Greek Her  viii viii ,  gre gre ast ast iro vii, vii, 37 38  96  8 grdig 2 2 26  5 6 5 growth spirals 02



haksaw 6 haerig haeri g 6 Ha Wei period 37 hardess 2 heat treatet 39 Hegistbur Hegistbur Head   Hes reaget reaget 70 highti allo 26 highti highti broze broze 25 26 irror i, i, 2 8 highti leaded leaded broze vii,  9  28 Hilliard's irular iterept ethod 52 hoogeeous hoogeeous brozes 2 5 hoogee hoogeeous ous soid solutio solutio  5 Hog Hogee ad Jueig Jueig 37 38 2

hotworkig 7 H 2 Hdroge peroide/iro () hloride hloride 7  hpereuteti hpereuteti 3 8 hpereutetoid hpereutetoid steel 2  hpoeuteti 38 hpoeutetoid steel 2 

v



iisible strutures 23 iese burer vii, 93 ast broze 27 ilusios 0 uprite 90 uprous oide 90 i aiet etals 7 oetalli 9 sulde sulde 7  di diaa i i, 9 26 35 36 dia Wootz igot i i dia zi oi 9 doGreek 86 105 1 19 igot 9 105 ikwell 8 iterept ethod 5  iterdedriti haels 5 iterdedriti poros 7 iterdiffusio 26 iterf it erferee eree  etalograp 73 iteretalli opouds 22 iteral oidatio 7 iterstitia aterials 2 iverse segregatio 5 iverted stage etallurgial irosope 56 ra viii,  27  8 94 105 raia  ro Age dagger dagger hil t



lll

iro 9 23 89 115 ethats 69 iterferee ethat 73 iro allo 23 100 101, 102 1 14 iro arbid arbidee 38  39

iro ode 38 rust iro phosphide 37 iroarbo allo 9 104 11 118 iroarbo phase diagra diagra  6 7 iroarbophosphorus allo 1 19 iroiro arbide diagra diagra 0 slai 26 8 slai i kwell kwell viii viii , 8 isotropi isotropi 2  9



J apaese sword 29 apaese swordblade i ava i, 26 28 1 04 eweller's saw saw 6  orda 1 06

K

kish graphite graphite 38 2 Kle  s reaget 70 kife 101 115 grai size size 3  Koop 77 Korea 26 kris 36



Late Broze Age 88 103 lath artesite 29 35 lattie struture  lead 9 2 lead alo ethat ethatss 7  lead lead globul globules es 23 2 87  2 lead ilusios 2 leadopper euteti euteti 2 3 leaded opper 23 leaded highti broze  08 leaded zi brass vi leaded ti broze 27 leadiro allo 23 leadti allos allos  5

leaf leaf gildig  06 Lehta 22 7 ledeburite ledeburite 0   euteti 38 of ast ast iro 38 trasfored 38 iqudus 2 liquidus liquidus ie ie   lost wa wa 93 95  07 lowarbo lowarbo steel steel 3  lowti brozes 25 27 Lurista 94 Lurista ereoial ae  7 Lurista dagger hadle vi



M

agesiu oide i polishg 66 agetite 50 agaese 37 aufaturig proesses 57 arte artesi site te 20 23 32 35 98 0 artesite eedles 35 artesiti 26 trasforatio 20 06 Maro 6 assed ferri te 2  atte 50 MCroe et al 50 MCroe owlevel irohardess tester tester 77 edallio 1 0 edieval 1 15 dia zi oi kife blade 35 Meeks 27 elt eltss   etalli bods  etalli etalli zi   9 etallographi etallographi eaiatio eaiatio 6  etallograph etallograph 57 etals deforatio  etastable phase 28 etastable state 2 

x

ne  4

irr irrrr xvii xvii  8 9 26 1 08 hihtin brnze 28 Javanese 28 R Ran 9 26 2 dern 1 05 lbdate/biuride lbdate/biuride  nteti 23 ttled ast irn 3 2 ttled ttled irn 3 8 untin resins 5

N

nail 1 02 native er 1 02 Near East 26 nekae bead 99 Nelsn 39 nikel silver rain size 53 nital 39 69  ndular rahite  nrah nrah 5  nral sereatin 5 Nrth eria Great akes 1 02 nse rnaent 90 nserin 91



berhffer s reaent 0 tial irs 35 rdered rdered reins 2 2 xide laers laers n ir n ethants 2 xide sale 26

p

x,

Palestine 88 Palertns reaent  anies 1 15 Paralid B 59 ear earlilite te xvii xvii xix xix  2   29 3   3 2  3 5 5 3 6  3 8  96 laellae 0 erentae f defrat defrat in 9

eriteti rea reati tin n 8  22 2 strutures  transfratin 9 26 eritetid 22 Petzw Petzw and Exn er 3 hase 5 dened 5 diara diara   Phillis 3 hshrus 3 iklin 86 iral iral 39 69   i irn 3 ients exainatin 56 lasters 50 lasti defratin  Plastiine 58 late 1 1 0 late artensite artensit e 36 36   lehris lr hane 9 larized illuinatin 9 larized liht 3 lishin 2 38  66 eletrheial 63 eletrlti 63 unted sale 55 lrstalline  lester 63 5 lnal lnal rains 2  r rsi si 6 2 2 6 6   8 8  2 f ast etals 6 tassiu ferrianide 2 Pratt ailtn xvi reethin  ress anneal  reutetid eentite 2 reutetid ferrite ferrite 2  seudrhi 3 seudr hi relaeent relaeent b rrsin rdus 5 seudrhi retentin 6

Q uasiake uasiake rahite   uenh aein 0 uenhin uenhin 20 26 26 3  with water 23

R

raisin 6 raid raid lin lin  3 rerstallizatin teeratures 9 rerstallized rains 8 redesited er  reeted liht irs 5 reeted larized liht 39 reetin reetin lehris 39 2 Renaissane 109 110 Rhines nd and Ruel 22 Rkwell  Rllasn 96 Ran xvii  89 9 101 1 02 108 1 12 12 11 7 erid 9 in 97 117 urine 1 08 irrr xvii 2 28  108 10 8 wruht irn 89 RanGreek 1 1



sadru 26 sale riteria t be et 6 ebeddin 63 untin 63 rearatin 58 63 reval reval 6  sall 6 strae 55 Sandal Castle xix 96 saturated saturated thisulfate thisulfate slut in 3 salel 62 Sandilast 63 5 Shweizer Shweizer and Meers Meers  2  slerse slerse 

Stt 22 50 90 srew dislatins 2 sereatin 9 2 inverse 5 nral 5 seleni aid aid slut in  sheet fraent 1 13 silin 3 3 3 8 0 silin arbide 65 silv silver er 2 2  8 1 09 all alls s   iure iure 2  silver all ethants 2 silver and ld all 1 06 silver bjets bjets 5  silv silver er  e err all all 2 3   5 5  1 09 euteti hase diara diara  2 silverer silverer hase diara diara 2  Sin 1 07 Skandauta 86 sla sla  36 lbules  inlus inlusin inss  6 striners   29 02  5 sli 3 bands 9 lanes 3 slw lin 3 f ast ast irn   Sith  sft sft slders  5 slid slub slubilit ilit   slid slutin anneal  slidu sliduss   srbite srbite 3  seulu 8 26 seiss 50 sheridal sheridal rah rahite ite 39    2 ast irn 3 slat lin lin  stanni xide 50 steadite steadite xvi 3 3 8 2 96 euteti 2

ndex 155

 ll 1 6, 0 ancnt 16 blad 1 00 tchant 6 ntrrnc tchant 3 prl 35 tran tran n ,  5 tr actr  trrl annal  trtran dagram 1 tructur bandd 3 Strur Autpl machn 66 ubgran tructur 31 ud ud nclun xv , 7 1 uur 3 Sumatra 8 uprattc uprattc   urac dtal  ancnt mtallc artact  wrd 88 wrd blad 1 3,  1 04

x



tapr ctn 65 tmpr tmpr carbn  1 ndul 3 tmprd tmprd martnt martnt 3 1 tmp tmpr rn ngg , 35, 1 0 1 trnary utctc  tadt xv trnary tn brnz 6 txturd ct  ha hghtn brnz vl xv 94 98 98 1 1 1 haland 6, 93 94 thrmal thrmal htry 5 7 thul thul at/actat tchant 7 thulatactat thulatactat xv, xv hmpn and Chattrj Chattrj  1 tn ,  ,  6 ally 1 19 brnz brnz 1 5 5 tchant 71 tnnd urac 6

x

tntng cppr ally 7 tggl pn 1 03 cat  Twr  Lndn  trt   3311 , 3, 10 1 umbaga , 0 turnng 6 wn ln 8, 10 twn plan 10 n znc znc 1 0 twnnd crytal xv gran 8, 7, 0 nnrru nnrru ally ally 5 1 twnnng n CPH mtal  pha ally 1 twphad ld 1

U

ultranc clanng  untmprd martnt martnt 3 5 Untracht 6

V

Vckr 77 Vckr tt  Vllla Vllla rag ragn ntt 6, 7  , 1 1 6

W

warng warng blad 6 1 Warrng Warrng Stat prd 3 7 watr watr qunchng  3 Wtrn Wtrn Han 3 7 wht wht brnz  6 wht wht cat cat rn 37, 38  3,  0, , 1 1  whthart 3 cat rn 37,  Whtly mthd 71 Wdman Wdmantt tttn tn 0, 1 06 parlt  d d plat plat 1 1 6 tru truct ctur ur xv, xv, 7, 31 , 1 1 5 tranrmatn tranrmatn 0

Wnchll 50 wr ngtudnal ampl 58 amplng amplng 5 8 ranvr ampl 58 Wtz crucbl 3 5 Wtz tz t tll 1 3 wrkd 8 88 88 89, 90, 91 97, 97, 99, 100, 101 102, 104, 105, 1 0 0 109 109 113, 1 13, 114 1 15 wrkd and cat 94 wrkhardnng 3, 6 wrkng 5, 6, 1 wru wrugh ghtt rn rn  1, 1 1 wtt tt 8, 1 0, 1 1

X

Xray urcnc analyzr analyzr 5 

y

Yakwtz 73 Yung Mdulu 1

Z

znc , 1 ally ancnt  crrn prduct xv crytal  tchant tchant 7 1 znclad ally 3

B -9236-195-6 Prnd n Sngar