Kaolin 101 A Unique Mineral for Value Added Applications
Doug Carter, Ph.D. Vice President Technology and Business Development
Doug Carter • Dr. Carter has served as KaMin's Vice President of Technology and Business Development since 2008, but has over 20 years of experience working for Kamin/J.M. Huber in a variety of roles including Marketing, Business Development and Technology, new product development, and new business development. With a Bachelor of Science in Chemistry from Berry College and a Ph.D. in Bio-Physical Chemistry from Clemson University, Dr. Carter leads the innovation efforts for KaMin. Dr. Carter currently serves as the Board Chair of Centre International Couchage, as the Chair of the China Clay Producers Association Environmental Committee, and also serves on the board of local charitable and educational organizations. •
Kaolin 101 • Origin and Unique Properties – KaMin’s Unique Position
• Mining, Processing and Finishing • Some Product Uses • Regulatory Aspects – Approvals – GHS
What is Kaolin?
Al2O3 2SiO2 2H2O
How is it formed? Hydrothermally or Weathered Granite TYPICAL CROSS SECTION THROUGH A PIT
Typical Cross-Section Through a Deposit Sparta, Georgia
Cornwall, England S AND WASTE TI P Orig inal l and surface
Land surface
CHINA CLAY PIT
Deeply Weathered Granite Altered in-situ to Kaolin
Hydrothermally Altered Granite
0
Casserite-tourmaline granite Hydrothermal Solutions
CHINA CLAY AVAILABLE FOR FUTURE WORKING
200m
Unweathered Low-Iron Biotite-Muscovite Granite 0
? CHINA CLAY THAN CANNOT BE WORKED
3m
UNALTERED GRANITE Slide from Ian Wilson Consultancy Cornwall, England -modified MAL 2003
Soil
KAOLIN TO BE MINED
UNALTERED GRANITE
KAOLIN GEOLOGY IN MIDDLE GEORGIA
Formation Between 50 and 100 million years ago, during the geological periods known as Cretaceous*, Paleocene* and Tertiary*, the Atlantic Ocean covered much of Georgia south of an imaginary line drawn from Columbus to Augusta, which is where the Piedmont Plateau meets the coastal plain.
* Chemical Composition is very similar but subtle differences do exist
In Georgia From
To
East Georgia Kaolin Mine
KaMin Reserves Span the Range of Crude Types
Western Crudes
Coarsest Clays in Ga.
Eastern Reserves
High Quality Fine Clays
Modifications Possible • Physical • Size and Shape • Surface Chemistry • Charge, Hydrophillic/Hydrophobic Balance • Structurally • Can Manipulate Crystal Structure
Products in Wide Variety of Ranges can be Produced
And Pigment Can be Physically Modified From Blocky to Individual Plates
Goal is Individual Plates
Hydrous Clays are Inert Particles but Edges can be Reacted Charge Characteristics of Kaolin Particles
Silica Edges
Aluminum Edges
Vishal Gupta, Ph.D Dissertation 2011
And those Sites Can be Treated with Various Chemistries No Dispersant (Acid Dried) No Dispersant (Neutral pH)
Clay - OH
Inorganic Dispersant (Na-silicate, Na-phosphate …) Organic Dispersant (Hydrophillic) Organic Dispersant (Hydrophobic)
Or a Complete Reaction with Surface Clay - OH
+
Et-O-Si - R
Clay – O – Si - R Where R = Alkyl, Vinyl, Acids, Amine, etc.
Can Modify Structural Characteristics Through Calcination Hydroxyls converted to Oxides, Material becomes more Hydrophobic Good Lewis Acid
• Hydrous
Calcined @ 1000 C
Process Converts Kaolin Physically, Chemically and Structurally!
Can also Change Surface Area and Pore Size to Provide Structure to Application
KaMin
KaMin
Internal pore size and pore volume of calcined products can be manipulated.
Kaolin Process
All Kaolin Processes: Remove Contaminants and Modify Particle Size…
Air Float – focused on separation of silica
Water wash– Focuses on separation of silica and iron based minerals (illmenite)
Can remove silica down below 1%. Little impact on other impurities
Silica Levels below 0.1%
Kaolin Process – Distinct Processes to Generate Value First step is getting crude ready for the processing….conditioning Overburden must be removed so the targeted clay can be reached.
First separation step remove sand
Crude blend is made into a slurry to enhance physical separation
Clay is stockpiled based on Quality parameters
Kaolin Processing: 4 Distinct Steps Classification Physically separates larger particles from small particles
Physical Separation of Impurities Floatation, Selective Separation, Magnetic Separation, Ozone, Dithionate Bleach Removes Organic (Humus) and iron based materials
Process focuses on removal of Fe2O3(rust), FeTiO4 and Residual Organic Material Process does not affect the level of trace elements Bagging
Converting a Crude Kaolin into a Customer Product
Kaolin Efficiency
100
62.5
% Silica
4-12
< 0.1
Brightness
75-85
85-91
Size
Broad
Specific
Kaolin Processing: Continued Dewatering Process Filtration Evaporation Drying
Packaging and Shipping Spray Dried Bead or Milled Product
Calcination Process
Laching/Filtration
Bagging
Calcination Process : Changes in Physical Properties of the Kaolin Crude/Crude Chemistry + Process Chemistry + Process Variables = Final Product
Milling
Brightness Oil Absorption Particle Size Pore size
Today Kaolin Used to Deliver Value in a Variety of Applications
GREENLAND
ALASKA (USA)
SWEDEN
ICELAND
RUSSIAN FEDERATION
FINLAND NORWAY
CANADA
ESTONIA
LATVIA DENMARK LITHUANIA
REPULIC OF IRELAND
BELARUS
UNITED KINGDOM
NETHERLANDS
GERMANY
POLAND
BELGIUM CZECH REPUBLIC
UKRAINE SLOVAKIA
KAZAKHSTAN
AUSTRIA
MONGOLIA
HUNGARY
FRANCE
SWITZ.
ROMANIA ITALY UZBEKISTAN
BULGARIA
PORTUGAL
GEORGIA
UNITED STATES of AMERICA
KYRGYZSTAN
SPAIN
NORTH KOREA GREECE
TURKEY
TURKMENISTAN
SYRIA
SOUTH KOREA
CHINA
AFGHANISTAN
JAPAN
IRAN
IRAQ
TUNISIA
MOROCCO
TAHKISTAN
PAKISTAN
ALGERIA
NEPAL
LIBYA
EGYPT
WESTERN SAHARA
SAUDI ARABIA
MEXICO
TAIWAN
UAE OMAN
INDIA VIETNAM
CUBA
MYANMAR
MAURITANIA
LAOS
MALI NIGER GUATEMALA
CHAD SUDAN
HONDURAS
THAILAND
YEMEN
SENEGAL
NICARAGUA
PHILIPPINES
CAMBODIA
BURKINA GUINEA NIGERIA
COSTA RICA PANAMA
ETHIOPIA
GHANA
VENEZUELA LIBERIA
GUYANA
COLOMBIA
SURINAME
FRENCH GUIANA
COTE D’IVOIRE
SRI LANKA
CENTRAL AFRICAN REPUBLIC CAMEROON
MALAYSIA SOMALIA UGANDA
KENYA GABON CONGO
ECUADOR
DEMOCRATIC REPUBLIC OF CONGO TANZANIA
PAPUA NEW GUINEA
INDONESIA
BRAZIL PERU
ANGOLA ZAMBIA
BOLIVIA MADAGASCAR
ZIMBABWE NAMIBIA PARAGUAY
BOTSWANA
AUSTRALIA REPUBLIC OF SOUTH AFRICA URUGUAY
CHILE
ARGENTINA
NEW ZEALAND
Markets: Story of New Opportunities and shifting needs In 2005, 6%
In 2005, 45%
In 2005, 20%
Source: Roskill 2013
Growing Ceramics Market
Kaolin As a Resin Extender for Clear Coatings
Resin Extender Comparision (Polyurethane Resin Application) 125
Gloss, 60 degree
115 105 95 85 75 65 55
Polygloss® 90
45
Ultrafine Ground Calcium Carbonate (0.4 µm)
35
Standard No. 1 Fine Particle Size Kaolin
25 4
6
8
10
12
14
16
Pigment Loading (%)
Polyurethane Coating extended with 15% Kaolin .
Designing Clay to Disappear Allows Significantly Higher Extension Levels
And Technology to Allows Us to Take it to the Next Level
3.0 231.0 100.6 43.85 19.11 8.325 3.627 1.580 0.6885 0.3000
2.8
refractive index of coating
2.6 2.4 2.2 2.0 1.8 1.6 1.4 10
20
30
40
50
60
70
80
thickness of coating, nm
Why? Enhance Barrier Properties without Impacting Optical Performance
Improved Barrier Properties Drives Economic Savings and Longer Life of End Products Use of Fine Kaolin allows Maximum Loading
% Kaolin Loading = % Reduction in Gas Permeability
Product Formally Launching in June
Or Kaolin for Foam Applications •
Traditional Fine Kaolins Increase the Compression Set and Reduce Shrinkage
– But they Increase Density •
Solution:
– Patented treatment maintains density of product allowing additional performance to be leveraged.
Material None Fine Coarse Fine Treated
Density 3.29 16.7 3.39 3.24
Foam Volume 30.4 6.6 32.4 34
psi @ 50% % Deflection Compression 0.05 29.5 --0.65 21.1 0.62 6.2
Calcined Clay for Reinforced Nylon: Nylok 171
2000 C
US Patent 5,571,851 in Nylon 6,6
But Maybe the Best Thing about Kaolin Is it is Green Natural Product that is REACH Exempt Listed by EPA as Green Chemical for Use in Household Goods Qualifies for Ecolabeling in Europe
Kaolin Regulatory Approvals Exempt from Registration under European REACH.
US FDA 176.170 Components of paper and paperboard in contact with aqueous and fatty food (dated 1 April 2014) US FDA 176.180 Components of paper and paperboard in contact with dry food (dated 1 April 2013) US FDA 175.300 Resinous and Polymeric Coatings (dated 1 April 2014) US FDA 175.105 Adhesives and Components of Coatings, Subpart B (dated 1 April 2043) US FDA 186.1256 Packaging Additive Used in Indirect Contact with Food (dated 1 April 2014) US FDA 178.3297 Colorants for Polymers (dated 1 April 2014). US FDA 177.2600 Rubber Articles Intended for Repeated Use (dated 1 April 2014) BFR XXXVI, XXXVI/2, LII. COE’s Paper Resolution Version 2 EU 10/2011 GB 9685-2008 Hygenic Standards for Use of Additives in Food Containers and Packaging. (listed) Meets all Requirements for US and European Cosmetics Acts Meets all Requirements for EU Toy Safety Standard US EPA as inert ingredients for food use under 40 CFR 180.910 & 930 US EPA Safer Ingredients List US EPA listed for direct crop application Meets standards for Eco labeling in Europe
Kaolin
General Information • • • • •
MSDS goes to SDS SDS will have 16 section format Use of Standard Pictograms All Products Labeled with Hazard or Danger (unless non-hazardous) GHS Labels Required for all Materials (unless Non-Hazardous)
• Deadlines for compliance – December 2013 – employees have to be trained in new SDS format – June 2015 – All manufacturers must have new SDS – June 2016 – New Labels in place on all materials
General Information • Global is not truly Global (Harmonized but not the same). • Other regions have own rules that are similar but not the same. • Rules have gone in effect in Asia prior to US • Europe has REACH which is compatible with GHS but not the same. – Threshold for some contaminants is higher in Europe (silica ) • Trigger level for silica in US and ROW is > 0.1% • Trigger level for silica in Europe is > 1%
KaMin Information • KaMin’s Kaolin Products exempt from GHS Rules
– Non-Hazardous Materials exempt! • We have provided updated SDS as a courtesy to our customers. – They are found at bottom of our website: www.kaminllc.com
• Non-Hazardous and do not require any symbol or labeling – KaMin Letter our exempt status with regard to Classification, Labeling and Packaging (CLP) Regulations is available on our web site.
• Not all kaolins are considered non-hazardous.
GHS Labeling Example
Some Kaolin Products will be Labeled on each bag.
Product Name Hazard Statement: May cause cancer. May cause damage to organs (Lung) through prolonged exposure. Precautionary Statement: Details provided on best handling practices Storage: Technically required to be locked
Danger Manufacture name Address Contact Number
This product is a “Hazardous Chemical as defined by OSHA Hazard Communication Standard, 29 CFR 1910.1200
The CAS# 1332-58-7 is the same for labeled and unlabeled kaolin products. Difference is in the presence or absence of contaminant
KaMin has Airfloat Alternative that does not require hazard labeling
•
Target customers are those that do not want to deal with new GHS issue. (Likely smaller customers without air handling systems in their factories)
•
Price Point above airfloat but below other hydrous clays
•
See your sales/tech service person for more details.
Thank you for your time and attention
Certificate of Completion Kaolin 101 April 13, 2015
Questions?
