ACC Europe Training Dec 06 v3
ACC Europe Training Dec 06 v3
ACC Europe Training Dec 06 v3
Btgenbach Belgium
December 2006 An Introduction To Australian China Clays
Company Profile
ACC Europe
Paper Andrew Pleeth Polymers James Marsh Ceramics Neil Mifflin Paint Philip Sambells China William Wang Europe Alain Heck
Garry Donaldson Technical Manager Dr Sanjib Banerjee Cairns Office Financial Controller David Hockey Group Geology Exploration & Environment Sue Border (Consultant)
Locations
Other Locations :
Key; Fully Operational Plant Pilot Plant Exploration Interests Business Investments
Skardon River
World class high-grade resource over 100 years mine life
fluvial deposit has the finest particle size of premium quality kaolin known worldwide overburden stripping ratio initially less than 3:1, compared to Georgia current ratios of over 9:1
Fully commissioned hi-tech stainless steel plant 175k tpa capacity Focus on global sale to paint, ceramics, rubber and paper industries
CHINA
KOREA
JAPAN
TAIWAN
THAILAND MALAYSIA
CANADA
West Coast
USA
INDONESIA
EUROPE AND MIDDLE EAST
AUSTRALIA
PROJECT
LOCATION
TASMANIA
NEW ZEALAND
China
China Calcined Kaolin Agency agreement Commenced 2004 100% owned Exclusive 5 yr export agency agreement Strategic extension to product range Increasing importance of PR China market JV agreement reached
K3
Fluvial
K3
Rolling Downs
Claystone Stockpile
Blunger
Degritting Centrifuge Sand Decanter Centrifuge Disc-nozzle Centrifuge Tailings Dam High Gradient Magnet Separator Membrane Filter Pipeline to Dry Plant
Windows Based Control System. This Automation Allows For An Efficient And Controlled Processing Environment
Loading up the front end of the wet plant with kaolin ore
Blunger
Screens
Degritting Centrifuges
Decanter Centrifuge
Superconducting Magnet
Pulveriser
Rotary Kiln
3.4 The Pilot Plant at Skardon River Kaolin contains scaled down versions of all the unit processes
Mobile Tanks
Feed Hopper
Carpco Magnet
The Pilot Plant at Skardon River Kaolin contains scaled down versions of all the unit processes
Rotary Kiln
Loose Bulk
Shipping By Road
Packaging
Hydrous Grades Bulk Shredded Typically for Ceramic applications Blends available Big Bags 500 1000Kg 25Kg paper bags Calcined Grades Big Bags 500Kg to 1000Kg 20Kg & 25kg paper bags Silane Treated Grades Big bags 500Kg to 1000Kg 25Kg paper bags Melt processable bags and special weights available
Wide range of industrial applications Represents the bulk of world supply Targeting paint, polymers, ceramics, paper and ink markets.
Higher performance Better brightness, opacity Extends TiO2 Premium price Limited number of producers Targeting paint, polymers, paper, inks.
Skardon Hydrous Grades First Letter = ore body origin (C=Claystone, F=Fluvial, R=Rolling Downs) Second Letter = product type (H=Hydrous, C=Calcined, M= Metakaolin, R=Raw Ore) Number = weight percent less than 2um (80 = 80wt% < 2um)
Hydrous Grades Microbrite CH80 Microbrite CH98 Microbrite FH95 Microbrite FH100 Microbrite FH100BP Microbrite CH40SR*
Kerabrite CH35 Kerabrite CH80 Kerabrite CH98 Kerabrite RH Kerabrite CR, FR, RR
Kaolin
Naturally Occurring Hydrous Aluminium Silicate Also known as China Clay
Al2O3.2SiO2.2H2O.
Plate like hexagonal flat shape. Specific Gravity 2.6. Refractive Index 1.56. Based on the crystalline mineral Kaolinite. Inert and insoluble in water. Skardon River Kaolins are amongst the finest in the world. In particle size In quality
HO OH OH
OH
OH
Surface Chemistry: Edges - Positive; Faces - Negative : Covered with SiOH monolayer, OH groups, Al3+ Si4+ Lewis Acid Sites pH: 4 - 5; Inert to Acids and Alkalis
Micrograph of Kaolin
Micrograph of Kaolin
An example of primary kaolins is found in Cornwall, England. For every tonne of kaolin mined there are 8 9 tonnes of waste causing significant environmental problems.
Secondary kaolins Formed in the same way as Primary Kaolins Washed and deposited away from where they were formed Low impurities - typically 90% of the deposit is saleable Very fine particle size Lower brightness
The continuous weathering washed the kaolin from the granite along with other minerals from the upland regions.
Reactivation of prehistoric fault lines led the ground to sink in places forming basins and shallow inland seas.
Streams from the uplands emptied into the basins and seas forming short lived lakes and river systems. Heavier sands and gravels settled from the water first forming the layers over marine shales, eventually forming what would become todays kaolin deposits. The fine clay particles remained in suspension in the water until a chemical reaction, making the water acidic causing the clay particles to clump together and form sedimentary layers.
Movement of the plates of the Earths crust cause the rock far below ground to melt. This molten rock bubles up and forms granite domes (called plutons) which are still below the ground surface.
Over several million years the rocks overlying the hard plutons were weathered away exposing the granite. In the sub tropical climate some of the feldspathic minerals in the granite were naturally altered to kaolinite.
The upland areas were heavily forested by prehistoric specimens. When they died these were washed downstream and became part of the mass of vegetation and other material forming what would eventually become todays coal deposits.
Calcined kaolin is formed when kaolin is heated to above 980C It has an amorphous structure with some hydroxyl (-OH) groups at the surface If heated above 1200C hard, abrasive mullite is formed
Hydrous Kaolin
Calcined Kaolin
Exotherm
Endotherm
High price must be justified by significant performance improvements Essential where stress and moisture resistance at high temperatures is required
e.g. High voltage electric cables
Ceramics (Pottery)
What Is Paint ?
Traditionally the term paint described a pigmented liquid coating and was used to distinguish it from a clear varnish. Today the word applies to a wide variety of materials used for coating purposes and the terms paint & surface coatings have become almost synonymous. A pigmented liquid coating, which when applied to a substrate and allowed to dry forms a surface coating which provides a desired function..
The exact composition will be dependant upon many factors, eg : The Substrate.
The method of application.
Price
Paint Types
Production
Decorative Paints (Architectural Coatings) 50%
Industrial Paints
50%
Decorative Paints
% of extender used
Water Based
Gloss. Semi Gloss. Matt (Flat) Interior. Matt (Flat) Exterior 05 5 15 15 50 5 15 05 5 15 5 15 15 50
Solvent Based
Gloss Semi Gloss Primers Undercoats
Auto OEM
ED Primer Surfacer Colour Coat Clear Coat
Auto Refinish
Primer Colour Coat Clear Coat
General Industrial
Wood Metal
Coil Coatings
White Goods Cladding
Powder Coatings
Indicates potentials for SRK Materials
Calcined Kaolin.
Calcium Carbonate.
Talc.
Mica.
Barium sulphate.
Silica
This presentation concentrates on the use of Kaolins & Calcined Kaolins as extenders in paints Specifically kaolins from Australian China Clays
What is an extender ?
Minerals. Which are : Usually supplied as a powder.
Hydrous and Calcined Kaolins From Australian China Clays can help to enhance
Opacity, (Hiding Power). The Mechanical properties of the dry paint film. Improve mudcrack resistance Improve scrub resistance The Weathering resistance. Improve corrosion resistance Improve resistance to chalking They can also help to Modify the rheology of the liquid paint.
Extenders
Hydrous & Calcined Kaolins Colour from Grey to White Refractive index 1.56
The greater the difference in refractive index between two substances the greater the degree of refraction. eg. The different refractive indicies between air & water is illustrated when a straight object which is partly immersed in water and viewed at an angle appears to be bent.
The effect on Opacity by TiO2 & Extender Particles below the Critical Pigment Volume Concentration (CPVC)
Light meter
Light meter
substrate
Because the refractive index of the resin (1.5) and the extender (1.5 1.7) are similar, the light easily passes through the paint film to the substrate and back out giving this paint low opacity.
The difference in the refractive index between the resin and TiO2 (2.7) is however greater and this difference gives the paint its opacity.
TiO2
Dry Hiding
Gloss region
% PVC
100
Property Increases
Scrub Resistance
% PVC
CPVC Region
100
Microbrite FH95
Is an ultrafine hydrous kaolin from Skardon River Kaolin with high brightness.
It can be used in water based emulsions as an excellent extender, with the ability to partially replace TiO2 in gloss & semi gloss emulsion paints. Supplied as a spray dried powder for convenient handling it is also very easily dispersed.
Finer & well dispersed extender particles offer improved utilization of expensive pigments & hence can reduce formulation costs by partial replacement of these pigments. With coarse extenders the expensive pigment tends to form together in pockets leaving large areas (windows) where no pigment is employed and hence gives poor opacity.
Light meter
Light meter
Latex / binder
Coarse extender
TiO2 Particles
substrate
Hydrous Kaolin
Air Voids
Microbrite C70/90 C2
Is a high quality Calcined Kaolin from Australian China Clays. With 70% passing 2 microns and a 90 ISO brightness. It is an excellent extender for Matt Emulsion Paints giving good opacity and excellent mechanical properties.
Microbrite C80/95 C1
Is a high quality ultrafine Calcined Kaolin from Australian China Clays. With 80% passing 2 microns and a 95 ISO brightness. Used in formulations where opacity is the main requirement.
In a paint above the CPVC the calcined kaolin offers improved opacity (hiding power) over coarse blocky extenders due to the trapped air increasing the changes in refractive indecies.
Light meter
Light meter
substrate
It also offers improved scrub resistance as the calcined kaolin is harder and its irregular shape means it is stuck firmly into the paint surface. The Calcium Carbonate is easily removed (Chalking).
substrate
Calcium Carbonate is easily dissolved in acid conditions making the paint defective. One form of calcium carbonate is chalk, hence the term chalking. This is where white powder is easily rubbed off and is commonly seen in cheap poor quality paints where a high level of calcium carbonate has been used. Calcined kaolins are inert and unaffected by harsh chemicals.
substrate
Mudcracking is another factor which blocky extenders are prone to. Propagation of cracks where a platey extenders are employed is more tortuous and therefore thicker paint films can be applied before cracking happens.
Latex / binder
Coarse extender
TiO2 Particles
substrate
At Skardon River Kaolin we have the ability to carry out a range of paint testing.
ACC sell 2000 tonnes of Microbrite FH95 into China per year for printing ink applications.
Filler ATH Asbestos Ground Calcium Carbonate Precipitated Calcium Carbonate Calcined Kaolin Hydrous Kaolin Synthetic Silica Crystalline Silica Talc
1998 160.0 Small 1075 100 25.0 96.0 53.0 3.0 19.0
Particle Size
Particle Shape
Surface Chemistry
Particle Size
Particle size directly effects reinforcement in polymers: Fine particle size = bigger surface area = higher reinforcement When used at the optimum level For example the finest kaolin from Australian China Clays is: Microbrite CH40SR This gives excellent reinforcement elastomers and can
partially replace expensive synthetic silica
80 70 60 50 40 30 20 10 0
Physical Properties
Characteristic plate-like shape gives unique properties in polymer compounds High aspect ratio gives excellent impermeability to gas and liquid Used in stoppers, hose, tube, chemical liners and membranes Particles align themselves isotropically under stress improving compound flowability and extrusion performance, whilst reducing dieswell and melt fracture
Calcined Kaolin
Interfacial fusion during calcination decreases the aspect ratio and gives them an inert surface Excellent electrical insulation performance and low dielectric loss due to amorphous structure Widely used in the pharmaceutical, power cable insulation, extruded profile and film industries
Maximum stress resistance is critical Maximum moisture resistance is critical Performance at elevated temperature is critical
Amino silane - Mainly used in polyamides (nylon) with some small use in rubber applications Vinyl silane - Mainly used in the rubber EPR/EPDM cable industry
Calcined Kaolin Calcined Kaolin+silane Calcined Kaolin Pretreated Calcined Kaolin Pretreated+silane
Strong far infrared absorption for thermal barrier effect High stability to resist ageing and degradation Excellent processability low moisture and good flow characteristics
Higher calcined kaolin loadings are claimed in mulch and silage wrap applications
Calcined kaolins improve electrical properties of pPVC cable Works at low concentrations (up to 20phr) replacing CaCO Used where good electrical properties are required at high temperatures,
3
Improves the electrical performance of flame retardant and smoke suppressant For example, replacing 14 phr of CaCO
volume resistivity
pPVC compounds
Calcined kaolin also improves all other dielectric properties of pPVC insulation Calcined kaolin is also sometimes used in EVA cable compound
phr PVC-PVA Copolymer D.A.P. Plasticiser Stabiliser/lubricants Epoxidised Soya bean Oil Coarse Limestone Kaolin 150 450 100 33 10 7
Kaloin 15%
Definition of a Filler
A filler is a particulate material added to rubber for one or more of the following reasons: Modification of physical properties Modification of processing performance Reduction in cost
Filler Definitions
Classified into three broad groups according to the influence on a high quality natural rubber gumstock
1. Reinforcing Filler
Fine particle size carbon blacks and precipitated silica
2. Semi-reinforcing Filler
Coarse carbon blacks, fine particle size clays (Hard Clays) and precipitated calcium
carbonates
3. Non-reinforcing Filler
Mainly natural products - coarse clays (Soft Clays), calcium carbonate, talcs etc.
PolymerFiller Adhesion
Very High Very High Very High Very High Low Very High Low Low Very Low Low Low Low Low Very Low Very Low Very Low Very Low
Particle Shape
Highly Reinforcing
Fumed Silicas Precipitated Silicas Carbon Blacks Silane Treated Fine Kaolin Fine Kaolin
Structured Structured Structured Platey Platey Platey/Structured Spherical Spherical Platey Particulate Platey/Structured Platey Semi-Platey Platey Particulate Particulate Particulate
Reinforcing
Silane Treated Calcined Kaolin Zinc Oxide Precipitated Calcium Carbonate Micronised Talcs Synthetic ATH
Semi-reinforcing
Calcined Kaolin Coarse Kaolin Neuburger Chalk Coarse Talcs Ultrafine Chalks
Non-reinforcing
Packaging adhesives
Woodworking adhesives Glazing Sealants
Automotive Adhesives/Sealants
Construction Sealants
PVA/PVOH
Fine kaolins Medium fineness kaolins Starch/Dextrin Medium fineness kaolins
Woodworking adhesives
PVA Medium fineness kaolins
Automotive Adhesives/Sealants
PU assembly adhesives - Calcined kaolin
Construction Sealants
Polysulphide 1K - Calcined kaolins Acrylic - Fine kaolins Solvented Rubber - Fine kaolins
Functionally variable
Pharmaceutical rubber Profile extrusion Thermoplastic vulcanisates (TPVs) Rubber cable High quality rubber flooring Hose Polyurethane sealants Thermal barrier film Antiblock film Seals & Gaskets Plasticised PVC cable
Plasticised PVC Cable Low voltage rubber cable Extrusion profile Hose
Can be used as lower cost alternative to fully
Microbrite FH95
Extension of coarse/medium carbon black Technical mouldings Cable sheathing Shoe soles Rubber flooring High strength adhesives
Microbrite CH40SR
Extension of carbon black Replacement of precipitated silica Tyres Shoe soles Flooring
Technical advantages
Increased strength Reduced water absorption Reduced chloride penetration Increased sulphate resistance Increased acid resistance Elimination of ASR Efflorescence control
Waxes and polish calcined kaolin Carriers calcined kaolin Cosmetics hydrous kaolin Soaps/detergents hydrous kaolin Animal feed hydrous kaolin Pigment/dye hydrous & calcined kaolin Pharmaceuticals hydrous kaolin
Imerys
Polwhite B, C Polsperse 10/20 Speswhite Light Kaolin BP NeoGen EFP NeoGen 2000 NeoGen JDF PoleStar 200R Glomax LL PoleStar 501 MetaStar 400 PoleStar 450
Engelhard
NE ASP-170/602
Burgess
NE No.17/20
Huber
NE Polyfil S Huber 80B
NE Polyfil 70 Polyfil 40
Microbrite C75/95 C1 Opacilite Microbrite C80/95 C1 (Depends on particle size) Microbrite C80/95 C1 PoleStar 400 Microbrite C80/92 C2 Neogen 2000 (Depends on colour) Silane Treated Calcined Kaolin Multibrite 1AS Multibrite 2AS Multibrite 3AS* Multibrite 1VS Multibrite 2VS Multibrite 3VS (NE = No Equivalent) Polarite 102A Polarite 402A Polarite 103A Polarite 503S NE
NE Satintone 5 Ultrex 98
NE
Polyfil 90
N.B sometimes direct equivalents are not required and other kaolins can be substituted depending on formulation and application specifications.
Quality Control
Brightness
Particle Size
Viscosity
Dispersion
Moisture
Quality Control
The two Chinese calcined kaolin factories have ISO9001 certification
Skardon River has Quality Control laboratories at the Wet Plant and at the Dry Plant where hourly production samples are analysed
Skardon River Pilot Plant also has a laboratory for product development
Environmental
At Skardon River Kaolin we take the responsibility for our activities very seriously
Website: www.skardon.com.au
Thank You