Filler Basics for Vinyl Plastisols

Joann C. Foster
Patrick C. Wernett

Specialty Minerals Inc.

SPE 2005, Vinyl Formulators Division

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Objectives:
• Provide a basic understanding of the
nature of mineral fillers used in
vinyl plastisols

• Provide a working knowledge of the

critical physical properties of
mineral fillers and how they relate
to end-use applications
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Critical Filler Functions:

Reduce
Cost

Opacify
t Modify
en
m Rheology
r ce
o
i nf Chemical
e
R
Resistance

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Primary Fillers for Vinyl Plastisols

• Calcium Carbonate
• Kaolin Clay
• Barium Sulfate
• Talc

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 Definition of a Mineral

• Any naturally occurring, homogeneous

inorganic substance having a definite
chemical composition and crystalline
structure, color and hardness.

• Synthetic minerals meet the above

criteria, except they are not naturally
occurring.
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Important Filler Properties
Chemical Composition

Color

Morphology

Hardness

Particle Size

Specific Gravity

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Chemical Composition/Crystal Structure

• Crystal structure is controlled

by the regular arrangement of
atoms in the mineral.

• Determines the outward

appearance of a mineral.

• Determines the cleavage plane

and thus particle shape.

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Color and Refractive Index
• The first thing noticed
• Whiteness = quality
• Dry powder color can
differ from color in
matrix (dry vs wet)
• Refractive Index (RI)
governs opacity

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 Morphology (shape)
• Determined by the arrangement of
atoms which make-up mineral

• There are four basic shapes

Cube Sphere Rod Plate

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 Aspect Ratio
Length

Thickness

Length
= Aspect Ratio
Thickness

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Consequences of Aspect Ratio
• Non-reinforcing fillers have no
or low aspect ratio. They are
Cube Sphere used to extend resin and reduce
cost.

• Reinforcing fillers have a high

aspect ratio. They contribute to
Rod Plate
stiffness and strength of a
composite.
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 Consequences of High Aspect Ratio

• High aspect ratio fillers tend to have poor flow

properties

• Liquid and melt viscosity can be very high

• May lead to roughness or dull surface effects

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 Mineral Hardness

• Determined by atomic structure

• Effects some composite properties, like surface

wear

• Directly effects process equipment wear

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 The Moh’s Scale of Hardness

CORUNDUM
TOPAZ

TITANIUM DIOXIDE

WOLLASTONITE
QUARTZ

FLUORITE

CALCITE

KAOLIN

TALC
9 8 7 6 5 4 3 2 1
MOHS HARDNESS

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Ferrigno, T. H. Principles of Filler Selection and Use, From: Handbook of Fillers, Eds. Katz, H. S.;
Milewski, J. V., Van Norstrand Reinhold Co., Inc.: New York (1987), p. 28. MINERALS
Particle Size & Distribution
• Has the most significant impact on
physical and performance properties

• Determined by processing method

• Agglomerates vs. Discrete particles

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Properties Impacted by PSD
• Surface area
• Oil Absorption
• Viscosity
• Bulk Density
• Particle packing
• Reinforcement
• Cost
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 Surface Area
Function of particle size and particle shape

Sphere Cube Rod Plate

Surface Area

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 Particle Packing Efficiency

Void Volume
Particle packing is more
efficient with a broad PSD
PP

Narrow PSD Broad PSD

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Particle Shape vs. Viscosity
atio
r
e ct
asp
low
ooth
Sm a tio
r
e ct
at e sp
r ig ha
w h
fl o ug
ho
r
R o

at e
w r
fl o

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Particle Size vs. Viscosity

flow rate

flow rate

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Fillers for Review

• Calcium Carbonate
• Kaolin Clay
• Barium sulfate
• Talc

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CALCIUM CARBONATE

100 nm

CaCO3

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Geological Terms for Calcium Carbonate
• Chalk:
• Soft accumulation of sediment
• Composed of microscopic skeletal remains
• Limestone:
• Compacted chalk beds
• Harder & more dense than chalk
• Marble:
• Metamorphosed chalk or limestone
• Very dense, hard & crystalline

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Basic Limestone Processing

Quarry Crusher Sizer

Classifier Grinding Screens

Surface Coated

QC/QA Packaging/Shipping
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 Precipitated CaCO3 Chemistry
CaCO3 + Heat CaO + CO2

CaO + H2O Ca(OH)2 + Heat

Ca(OH)2 + CO2 CaCO3 + H2O

Why? Enhance Purity Morphology Control
Particle Size Control Narrow PSD
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Types of Precipitated Calcium Carbonate

• Aragonite

Most common
• Calcite
and abundant

• Vaterite

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Crystal Habits of Calcite

Scalenohedral

Prismatic

Rhombic
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 Calcite
ALBACAR® PCC ALBAFIL® PCC

Clustered Scalenohedral Prismatic

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 Calcite and Aragonite
ViCality® Heavy STURCAL® F PCC

Rhombic Clustered, Acicular

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Characteristics of Calcium Carbonate

• Hydrophilic
• Low oil absorption
• White color
• High brightness
• Alkaline
• 9 - 9.5 pH typical
• Low Aspect Ratio
• Moh’s Hardness 3.0
• Specific Gravity 2.7

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 Calcium Carbonate Physical Properties
Properties Ground Limestone Precipitated CaCO3
(GCC) (PCC)
Coarse Medium Fine Ultrafine Rosette Fine Ultrafine

Median Particle 14 - 20 7-9 2-7 0.8 - 2 2 0.80 0.07

Size, micron

Top Size, micron 45 - 50 30 - 45 15 - 25 5 -10 --- --- ---

Surface Area, 1 1-2 3-4 8 9 20 - 22 20 - 22

2
m /g

Oil Absorption 12 - 15 11 - 14 11 - 18 22 - 30 50 30 30
g/100 g

Dry Brightness 85 - 90 86 - 93 88 - 95 92 - 96 96 98 98

Examples of Marblewhite 325 Vicron 31-6 Vicron 15-15 Omya-Carb Albacar 5970 Albafil Multifex
Trade Names Omyacarb 18 Omyacarb 6 Camel-White UFT Superflex Socal
Hubercarb Q-200 Hubercarb Q-60 Duramite Camel-Cal Winnofil
No. 9 White Atomite Hubercarb Q-1 Ultra-Pflex
Thixo-Carb

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 PSD of GCC vs PCC

The PSD Curve

100
PCC has narrow PSD
GCC has broad PSD
% finer than

50

0
100 10 1.0 0.1
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 GCC vs. PCC

Viscosity Increase PCC >> GCC

Thixotropy PCC >> GCC
Loading Level GCC >> PCC
Whiteness PCC >> GCC
Reinforcement PCC >> GCC
Cost Efficiency GCC >> PCC

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 CaCO3 SURFACE TREATMENT

• Produce hydrophobic surface

• Improve dispersion

• Improve shelf stability

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Function of Calcium Carbonate in Vinyl Plastisols

• Rheology Control
– Viscosity build
– Thixotropy
• Resin extension
• Increase hardness and tensile strength
• Opacity & Whiteness
• Reduce plasticizer mobility

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CaCO3 IN PVC PLASTISOL APPLICATION
GROUND LIMESTONE VS. COATED PCC

FORMULATION A B C
PHTHALATE PLASTICIZER 180 180 180
PVC DISPERSION RESIN 100 100 100
GROUND LIMESTONE - 216 76
COATED PRECIPITATED CaCO3 - - 140
CALCIUM OXIDE 12 12 12
ADHESION PROMOTER 3 3 3

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FLOW CURVE OF PVC PLASTISOL FORMULATIONS
FILLER EFFECTS/GROUND LIMESTONE VS. PCC

A B
C
Shear Rate

A
A == NON-FILLED
NON-FILLED
B
B = GROUND LIMESTONE
= GROUND LIMESTONE
C
C = ULTRAFINE ++ GLS
= ULTRAFINE GLS

Shear Stress

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 Coated PCC in PVC Plastisol Sealant

Effect of Particle Size/Surface Area on Rheology

Viscosity Sag Resistance

1600 Bead Sag, mm
60
Apparent Viscosity, cps

1400
50

1200 40

30
1000
20
800
10

600 0
0 0.2 0.4 0.6 0.8 0.06 0.07 0.15 0.7

Particle Size, um Particle Size, um

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 KAOLIN CLAY
Aluminum Silicate

Al2Si2O5(OH)4

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 Types of Kaolin Clay

• Air-Floated

• Water-Washed Hydrous

• Delaminated

• Calcined

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Characteristics of Kaolin Clay
• Hydrophilic
• Platy Morphology
• High Oil Absorption
• Fine Particle Size
• Low to Moderate Brightness
• 2-3 Moh’s Hardness (4 -6 calcined)
• Specify Gravity 2.6
• Acidic - Neutral

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Typical Properties of Kaolins
Property Hydrous Delaminated Calcined

Median Particle Size, 0.3 - 4.8 0.4 – 1.0 0.8 – 2.0

microns

Oil Absorption, g/100g 31 – 46 38 - 46 50 – 95

Brightness, GE 85 – 92 86 - 92 86 - 95

Refractive Index 1.56 1.56 1.62

Specific Gravity 2.58 2.58 2.50 – 2.63

Free Moisture (% Max.) 1.0 1.0 0.5

pH 3.5 – 8.0 6.0 – 8.0 5.0 – 6.0

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Advantages of Hydrous Kaolin

• Particle Size Control

• Brightness Control

• Low Residue

• Low Soluble Salts

• Good Consistency

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Function of Kaolin Clay in Vinyl Plastisols

• Rheology control
– Thixotropy
• Decrease plasticizer mobility
• Low abrasivity (hydrous)
• Improve electrical resistance (calcined)

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 BARITE
BARIUM SULFATE

BaSO4

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 Types of Barium Sulfate

• Barite (or Barytes)

– Natural mineral with origin from sedimentary rock or
gangue mineral in hydrothermal metalliferous veins
– associated with fluorite and calcite
– Most common barium mineral
• Blanc fixe
– Precipitated grade
– Ultrafine particle size

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 Characteristics of Barite

• Fine white powder

• Blocky (Tabular) morphology
• Acid and alkali resistant
• Water insoluble
• Specific gravity 4.25 - 4.5
• Moh’s Hardness 3 - 3.5
• pH 7.0
• Low oil absorption
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 Function of Barite in Vinyl Plastisols

• Increase density

• Improve chemical resistance

• Impart X-ray opaqueness

• High load bearing properties

• Increase frictional resistance MINERALS

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 TALC
Magnesium Silicate

3MgO 4SiO2 H2O

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Origins of Talc
• Dolomitic or Magnesite Ores

• Serpentine Ore

• Siliceous/Alumino Ore

• Sedimentary Magnesium Containing

Ores

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General Characteristics of Talc

• High Aspect Ratio

• High Oil Absorption

• 1 Moh’s Hardness

• Naturally Hydrophobic

• Platy Morphology

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 Commercial Grades of Talc
SUPPLIER TALC MEDIUM PARTICLE BRIGHTNESS TRADE NAMES
ORIGIN SIZE RANGE

Specialty Montana 0.9 - 14 High Microtalc 

Minerals Inc. TalcronTM
China 
Ultra-talc

Luzenac America Montana 1.8 - 13 High to Low Mistron

Vermont Nicron
TM
Silverline

R. T. Vanderbilt New York 1.8 - 13 Medium Nytal

I.T.

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Talc’s Function in Vinyl Plastisols:

• Viscosity Build

• Water Resistance

• Chemical Resistance

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 Summary
• Mineral filler particle shape and size are critical to
their function.

• Mineral fillers serve a greater purpose than cost

reduction. They are multifunctional.

• Different fillers serve different functions based on their

specific attributes. Specialty
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