Mineral Fillers for Rubber

KAOLIN CLAY

R.T. Vanderbilt Company, Inc.

Before viewing this presentation, please be sure to read the usage

statement.

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 Mineral Fillers For Rubber: KAOLIN CLAY

FILLER BASICS

A rubber compound contains, on average, less than 5 lbs. of chemical

additives per 100 lbs. of elastomer, while filler loading is typically 10-15
times higher. Of the ingredients used to modify the properties of rubber
products, the filler often plays a dominant role. The term “filler” is
misleading, implying, a material intended primarily to occupy space and
act as a cheap diluent of the more costly elastomer. Most of the rubber
fillers used today offer some functional benefit that contributes to the
processability or utility of the rubber product. Styrene-butadiene rubber,
for example, has virtually no commercial use as an unfilled compound.

Kaolin clay is the primary non-black filler in rubber, accounting for more
than 50% of all non-black filler used. Of this, about 80% is airfloat hard
clay, with calcined clay, delaminated clay and water-washed clay
making up the balance.

A review of kaolin clay and its performance in rubber compounds is best

undertaken within the context of certain general considerations
regarding the ways that fillers and elastomers interact.

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 Effects of Mineral Fillers Depend On

Particle Size
Particle Shape
Particle Surface Area
Particle Surface Activity
(Compatibility With/Adhesion To Matrix)

The characteristics which determine the properties a filler will impart to

a rubber compound are particle size, particle shape, surface area and
surface activity. Surface activity relates to the compatability of the filler
with a specific elastomer and the ability of the elastomer to adhere to
the filler.

Functional fillers transfer applied stress from the elastomer matrix to the
strong and stiff mineral. It seems reasonable then that this stress
transfer will be better effected if the mineral particles are smaller,
because greater surface is thereby exposed for a given mineral
concentration. If these particles are needle-like, fibrous or platy in
shape, they will better intercept the stress propagation through the
matrix. Likewise, intimate adhesion of the matrix onto mineral particles
is essential, since air gaps represent points of zero strength. Thus,
compound strength can be further enhanced if the matrix is adhered to
the mineral surface via chemical bonding.

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 Particle Size
Smaller is Better
µ m): Degradants
>10,000 nm (10µ
µ m): Diluents
1000-10,000 nm (1-10µ
µ m): Semi-reinforcing
10-1000 nm (0.1-1µ
µ m): Reinforcing
10-100 nm (0.01- 0.1µ

If the size of the filler particle greatly exceeds the polymer interchain
distance, it introduces an area of localized stress. This can contribute to
elastomer chain rupture on flexing or stretching. Fillers with particle size
greater than 10,000 nm (10 µm) are therefore generally avoided
because they can reduce performance rather than extend or reinforce.
Fillers with particle sizes between 1,000 and 10,000 nm (1 to 10 µm)
are used primarily as diluents and usually have no significant affect,
positive or negative, on rubber properties. Semi-reinforcing fillers range
from 100 to 1000 nm (0.1 to 1µm). The truly reinforcing fillers, which
range from 10 nm to 100 nm (0.01 to 01 µm) significantly improve
rubber properties.

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 Particle Size Distribution

ESD!!!

Median Particle Size = Half the particles are larger, half are smaller

Size (top and bottom) Counts

The particle size of a mineral filler is often reported in terms of median

or average size and in most cases is actually measured as equivalent
spherical diameter rather than actual size or dimensions. For round or
block-shaped, such as natural calcium carbonate, there is no significant
difference. For platy minerals, such as clay, talc and mica, or needle-
like minerals, such as wollastonite, most automated particle sizing
instrumentation will match the behavior of a particle to that of an
idealized round particle of specific diameter. For example, a clay plate
that is reported as 200 nm eqivalent spherical diameter might be 1 nm
thick by 600 nm across. Comparing the particle size of two fillers by
comparing their respective median esd can therefore be very
misleading if differences in particle shape are not accounted for. Further
complicating the issue is the fact that median (or average) particle size
can poorly represent particle size distribution, as suggested here. Both
distributions have the same median size, but the lower one may have
particles large enough to compromise compound properties.

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 Basic Particle Shapes

Shape Sphere Cube Needle

Aspect 1 1 5-20+
Ratio

Shape Block Plate/Flake Fiber

Aspect 2-4 20-200 20-200+
Ratio

A particle’s shape plays a significant role in its ability to intercept stress

applied to the elastomer composite. In general, anisometric particles -
those having a significant difference in length vs width - are more
effective as reinforcements than isometric particles - those similar in
length and width. The basic particle shapes characteristic of mineral
fillers are shown here along with their typical aspect ratios, the measure
of their anisometry.

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 Aspect Ratio

Needle/Fiber Aspect Ratio:

Ratio of mean length to mean diameter
D
L
Plate Aspect Ratio:
Ratio of mean diameter of a circle of the same
area as the face of the plate to the mean
thickness of the plate

D T

For needle and fiber shaped fillers, aspect ratio is the ratio of length to
diameter. For kaolin clay and other platy minerals, it is the ratio of the
diameter of a circle with the same are as the face of the plate to the
thickness of the plate.

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 Particle Shape
Broader (and Longer) is Better
Isometric: calcium carbonate
Platy: kaolin, talc, mica
Acicular: wollastonite
Fiber: glass fiber
Chain: carbon black, ppt silica

Isometric fillers that are approximately round, cubic or blocky in shape,

are considered low aspect ratio. Low, in this context, means less than
about 5:1 aspect ratio. Platy, acicular (needle-shaped) and fibrous fillers
are considered high aspect ratio.

Aspect ratio is not applied to carbon black and precipitated silica. The
primary particles of these fillers are essentially spherical, but these
spheres aggregate in such a way that the functional carbon black and
precipitated silica filler “particles” are chains or bundles with various
degrees of branching. The anisometry of these fillers is described in
terms of “structure”, which incorporates aggregate shape, density and
size. The higher the structure, the greater the reinforcement potential.

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 Particle Surface Area
Bigger Is Better
From smaller particle size
From higher aspect ratio

A filler must make intimate contact with the elastomer chains if it is

going to contribute to reinforcement of the rubber-filler composite.
Fillers that have a high surface area have more contact area available,
and therefore have a higher potential to reinforce the rubber chains.
The shape of the particle is also important. Particles with a planar
shape have more surface available for contacting the rubber than
spherical particles with an equivalent average particle diameter. Clays
have planar-shaped particles that align with the rubber chains during
mixing and processing, and thus contribute more reinforcement than
spherical-shaped calcium carbonate particles of similar average particle
size. Carbon black and precipitated silica chains and bundles are
considerably smaller than the particles of clay. They thus have more
surface area per unit weight available to make contact with the polymer.
Rubber grade carbon blacks vary from 6 to 250 m2/g. Most reinforcing
precipitated silicas range from 125 to 200 m2 /g; a typical hard clay
ranges from 20 to 25 m2 /g.

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 Particle Surface Activity
More is Better
Active sites on filler surface
Reactive surface treatments

A filler can offer high surface area, high aspect ratio and small paricle
size, but still provide relatively poor reinforcement if it has low specific
surface activity. The specific activity of the filler surface per cm2 of filler-
elastomer interface is determined by the physical and chemical nature
of the filler surface in relation to that of the elastomer. Nonpolar fillers
are best suited to nonpolar elastomers; polar fillers work best in polar
elastomers. Beyond this general chemical compatibility is the potential
for reaction between the elastomer and active sites on the filler
surfaces. Carbon black particles, for example, have carboxyl, lactone
quinone, and other organic functional groups which promote a high
affinity of rubber to filler. This, together with the high surface area of the
black, means that there will be intimate elastomer-black contact. The
black also has a limited number of chemically active sites (less than 5%
of total surface) which arise from broken carbon-carbon bonds as a
consequence of the methods used to manufacture the black. The close
contact of elastomer and carbon black will allow these active sites to
chemically react with elastomer chains. The carbon black particle
effectively becomes a crosslink. The non-black fillers generally offer
less affinity and less surface activity toward the common elastomers.
This can be compensated to a greater or lesser extent by certain
surface treatments.

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 Clays, silicas, silicates have
chemically active surface silanols

OH OH
Si Si OH
OH OH O-H+
OH Si =
OH OH Si Si
Si Si
Si Si Silanol

Kaolin clay and all of the non-black, non-carbonate reinforcing or semi-

reinforcing fillers have one feature in common. The clays, silicas, and
silicates all have surface silica (SiO2) groups which have hydrolyzed to
silanols (-SiOH). These silanol groups behave as acids (-SiO-H+) and
are chemically active. The higher surface area fillers have more silanols
available and are thus more reactive.

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 Silanols will interfere with sulfur cures,
Zn
TEA
O O DEG iva tor
+ -act
Si Si PEG O- N
O- OH Si
O- OH
Si Si
Si Si

but their activity can be controlled.

Silanols show similarities to carboxylic acid groups in their reactions

with amines, alcohols, and metal ions. While water adsorbed on th e
surface of filler particles will reduce silanol reactivity, hot compounding
volatilizes some of this, leaving a reactive surface. Some of the
reactions with silanols can have a significant effect on the properties of
the rubber compound, especially where the chemical involved is an
important part of the cure system. Most of the accelerators used in
sulfur cure systems contain an amine group. Strong adsorption or
reaction with filler particles can decrease the amount of accelerator
available for vulcanization reactions. This can give slower cure rates
and a reduced state of cure. Similar effects can result from the reaction
of zinc ions with filler particles.

The adsorption or reaction of accelerators by hard clay usually requires

about 15-25% increase in acceleration. These negative effects on the
cure system can be reduced or completely avoided, however,by adding
other chemicals that will tie up the silanol groups and reduce their
activity. Triethanolamine (TEA), diethylene glycol (DEG) and high
molecular weight polyethylene glycol (PEG) typically serve this function.
These are mixed into the compound prior to the addition of the
accelerators.

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 Silanes = Rubber
Polymer Reactivity
Si CH2 CH 2 CH2 S
O O
Si Si OH
OH OH Si
OH OH
Si Si
Si Si
Modulus
Tensile Strength
Abrasion Resistance

One effective means of modifying the surface chemistry of non-black

fillers is by the addition of silane coupling agents. These react with the
silanols on the filler surface to give a strong bond, and also contain a
functional group that will bond to the rubber during vulcanization. The
result is filler-polymer bonding (crosslinking) that increases modulus
and tensile strength and improves other compound properties.
Modification of the filler surface also improves dispersion.

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 SILANES
Sulfur Cure
Mercapto
Tetrasulfide
Thiocyanate
Non-Sulfur Cure
Amino
Epoxy

There are three silane coupling agents commonly used in sulfur-cured

compounds filled with kaolin clay and other non-black fillers. These
have mercapto, tetrasulfide and thiocyanate functionalities, respectively.
The sulfur-containing group of each reacts during vulcanization to bond
to the polymer. For non-sulfur cures, amino silane and epoxy silane are
typically used.

Clay pretreated with silane is available, but in situ treatment of clay and
other non-black fillers is common. In this case, the silane is added
during compounding so that it can react with the filler. The addition
sequence is very important when adding silane coupling agents,
particularly with sulfur cures. The polymer, filler, and silane coupling
agent should be mixed for 1 to 2 minutes before adding any other
ingredients that will interfere with the reaction between the filler and the
silane.

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 Fillers Effects
Increasing Surface Area (Decreasing Particle Size)
Higher Mooney viscosity, tensile strength, abrasion
resistance, tear resistance, and hysteresis .
Lower resilience

Increasing Surface Activity

Higher abrasion resistance, chemical adsorption or
reaction, modulus (at elongation >300%), and hysteresis
(except silated clay).
Increasing Aspect Ratio
Higher Mooney viscosity, modulus (at elongation
<300%) and hysteresis .
Lower resilience and extrusion shrinkage; longer
incorporation time.

The principal characteristics of rubber fillers – particle size, shape,

surface area and surface activity – are interdependent in improving
rubber properties. In considering fillers of adequately small particle size
to provide some level of reinforcement, the general influence of each of
the other three filler characteristics on rubber properties can be
generalized as follows:

1) Increasing surface area (decreasing particle size) gives: higher

Mooney viscosity, tensile strength, abrasion resistance, tear resistance,
and hysteresis; lower resilience.

2) Increasing surface activity (including surface treatment) gives: higher

abrasion resistance, chemical adsorption or reaction, modulus (at
elongation >300%), and hysteresis (except for silane treated clay, as
we’ll see).

3) Increasing aspect ratio gives: higher Mooney viscosity, modulus (at

elongation <300%), and hysteresis; lower resilience and extrusion
shrinkage; longer incorporation time.

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 Stretching Force

Movable
Grip
Tensile Properties
Test
Strain Gauge Specimen

Fixed
Grip

The primary filler effects in rubber can be related to tensile properties: in

simplest terms, the ability of the filler-rubber composite to respond to
stretching forces.

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 Modulus: Resistance to stretching

Stretching
Resistance to Stretching
Force

300% Elongation

Uncompouded elastomer: disentangle polymer chains,

break weak inter-chain bonds
Vulcanized, unfilled elastomer: break sulfur crosslinks

The force required to stretch a defined specimen of rubber to a given

percent elongation is measured as modulus. Most often, modulus is
reported at 300% elongation (four times original length). This can be
alternatively viewed as the resistance to a given elongating force. For
an uncompounded elastomer, elongation is primarily a function of
stretching and disentangling the randomly oriented polymer chains and
breaking the weak chain-chain attractions. Vulcanized, but unfilled,
elastomers, for example, more strongly resist elongation because the
sulfur crosslinks must be stretched and broken to allow chain extension
and separation.

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 Tensile Strength:
Resistance to stretching rupture

Break

Elongation at Break

If stretching continues, rupture ultimately results.

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 Viscous Drag

Coupling

The introduction of a filler into the vulcanizate provides additional

resistance to elongation. A filler with low surface activity will increase
resistance to elongation by the viscous drag its surface provides to the
polymer trying to stretch and slide around it. Higher surface area,
greater aspect ratio, and higher loading (the latter two effectively
increasing the surface area exposed to the elastomer) will all increase
the modulus. Fillers with strong chain attachments, via active sites or
coupling agents, provide the most resistance to the chain extension and
separation required for elongation and ultimate rupture.

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 A1 A3
A2 A4

(1) B1 B4
B2
B5
B3 B6

A1 A3
A2 A4

(2) B1
B4
B2
B5
B3 B6

A1
A4
A2 A3

(3)
B2 B1 B4 B5

B3 B6

The effect of filler particles on the ability of the compound to stretch can
be pictured as shown here. Before stretching, as in step 1, the polymer
chains are in random configuration. Chains A and B have multiple
points of attachment to the filler particles, corresponding to the particle’s
active sites. On elongation, resistance is supplied as the energy
required to detach the chain segments from these active sites, as in
steps 2 and 3.

The amount of energy required to attain maximum elongation, and then

required to cleave chain-chain and chain-filler attachments, accounts for
the tensile strength of a filled system of this type.

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 A1
A4
A2 A3

(3)
B2 B1 B4 B5

B3 B6

A1
A4

(4)

B3 B6

After the elongating force has been removed, the elastomer chains
return to their preferred random orientation, as in step 4, except that
now they have the minimum number of points of attachment to the filler
as a consequence of having been extended in Step 3. Less force would
now be required to return these chains to ultimate extension, because
the intermediate points of attachment that existed in Steps 1 and 2 have
been eliminated. This explains the phenomenon known as stress
softening. With repeated stress-relaxation cycling, a decrease in
modulus from the initial maximum is obtained. Stress softening is a
temporary effect. After a period without strain, the rubber will recover to
near its original modulus, as the active filler sites again attach to
polymer segments. A percentage of the original modulus is permanently
lost, however, due to irrecoverable chain and bond cleavage.

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 Resilience / Hysteresis

Reinforcement Resilience

Resilience Hysteresis

Resilience is essentially a measure of rubber elasticity – the

characteristic ability to quickly return to original shape following
deformation. Unfilled elastomers are at their peak resilience because
there is no obstacle to elastomer chain extension and contraction
(return to randomness). The introduction of a filler creates such an
obstacle in proportion to the strength of the particle-polymer interaction.
Resilience is therefore generally in inverse proportion to filler loading
and reinforcement.

If resilience is considered the ratio of energy release on recovery to the

energy impressed on deformation, hysteresis can be viewed as a
measure of the amount of impressed energy that is absorbed. An
unfilled (elastic) elastomer will convert most of the energy of
deformation into the mechanical energy used in returning to the original
shape. The degree to which input energy is converted to heat, due to
friction from polymer chains sliding past each other, is a function of
polymer chain morphology. All fillers tend to increase the hysteresis of
rubbers, the most reinforcing fillers generally producing the largest
increases. This is due to the energy consumed in polymer-filler friction
and in dislodging polymer segments from active filler surfaces. This is
heat energy which would otherwise have a mechanical manifestation as
elastic rebound. In short, hysteresis is inversely related to resilience.

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 Related to Tensile Properties

Abrasion Resistance
Impact Strength
Tear Strength
Flex Resistance

Soft Edge of Depression

Filler size, shape and matrix adhesion are also reflected in abrasion
resistance, impact strength, tear strength and flex resistance.
Loss of large or poorly bound filler particles by abrasion exposes the
relatively soft surrounding elastomer matrix to wear. The effect is acute
on the edge of the depression left by the dislodged particle. This is the
area most susceptable to elongation, crack initiation and ultimate loss.

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 Abrasion Resistance
Impact Strength
Tear Strength
Flex Resistance

Impact strength is the measure of a hard rubber’s resistance to fracture

under sudden impact or force. The impact force is one of compression
on one side of the rubber and tension on the other, so that fracture is a
result of failure similar to that occuring when a tensile sample is
elongated to break.

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 Abrasion Resistance
Impact Strength
Tear Strength
Flex Resistance
Compression

Tension
Tear

Tear strength and flex resistance are essentially a measure of

resistance to crack or slit propagation. Both typically measure the
growth of a crack under tension. Large or poorly bound fillers will act as
flaws and initiate or propagate cracks under test conditions. Small
particles size, high surface area, high surface activity and high aspect
ratio allow the filler particles to increase flexural modulus (i.e.,
resistance to bending), act as barriers to the propagation of
microcracks, and provide the higher tensile strength required to resist
failure.

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 Mineral Fillers For Rubber: KAOLIN CLAY

CLAY BASICS

9 million tons of 225k tons of

US kaolin clay: rubber clay:
90% from GA 30% from GA
5% from SC 70% from SC

The United States is the leading supplier of kaolin filler clay. At 9 million
tons per year, it provides about 40% of world production. Nearly all US
filler kaolins are produced in the world’s major kaolin belt, the 250 miles
between Aiken, SC and Eufala, AL, which has estimated reserves o f up
to 10 billion tons. Nearly 90% of the kaolin produced in this country,
comes from Georgia, and about 5% from South Carolina. However, of
the approximately 225,000 tons of kaolin clay sold to the US Rubber
Industry annually, 70% comes from South Carolina.

An additional 34,000 tons of kaolin clays for rubber are exported.

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 OH
OH OH

OH OH
OH

=O = Si = Al or Mg
Silica tetrahedron Al, Mg Octahedron

Kaolin clay and related platy silicates (talc, mica, pyrophyllite) can be
considered inorganic polymers based on two basic “monomer”
structures - the silica tetrahedron and the alumina or magnesia
octahedron. These minerals contain a continuous octahedral layer with
the joined octahedra tilted on a triangular side. This layer is bound on
one side (as in kaolin) or both sides (as in talc, mica and pyrophyllite)
by a continuous silica layer.

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 Linked Silica

Rings

=O = Si

The continuous silica layer is composed of tetrahedra with three shared

oxygens and every fourth (apical) oxygen pointed in the same direction.
This forms a layer of linked rings with hexagonal openings, as illustrated
here.

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 OH

~0.72nm

OH OH OH
OH OH

=O = Shared O = Si = Al
Kaolinite

The prototypical clay mineral is the aluminum silicate, kaolinite. Its

structure, as illustrated here, is composed of an octahedral alumina
layer joined to a tetrahedral silica layer via shared apical oxygens.

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 Kaolin “Books”

The continuous sheet structure produces thin particles which are often
found in nature as overlapping flakes. These are informally called
“books” because of their resemblance under magnification to stacks of
paper. Kaolin books are bound via hydrogen bonding of the octahedral
layer hydroxyl face of one flake to the tetrahedral layer oxygen face of
the adjacent flake. Separation of books into individual clay flakes is
therefore difficult.

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 Kaolin Types

Kaolin clays are classified in various ways, with terminology specific to

certain industries. We’ll preface the descriptions of the clays commonly
used in the Rubber Industry, with a brief review of several clay aliases.

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 Geologically
Primary kaolin: The clay occurs in the deposit
where it formed.
Sedimentary kaolin: The clay has been eroded and
transported from its site of formation. The GA/SC
clays are all sedimentary.

Primary or residual kaolin clay occurs in the deposit where it formed.

The world’s major source of primary kaolin is Cornwall, England.
Sedimentary or secondary kaolin clay has been eroded and transported
from its site of formation and deposited at a distant location. The
eastern US kaolin belt consists of sedimentary kaolin.

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 In the Ceramics Industry
China clay: Pure white or near white, usually well
crystallized kaolin with low plasticity and low green
strength. (Soft clay)
Ball clay: Fine-grained sedimentary clay containing
natural organic matter that confers high plasticity
and high green strength.
Fire clay: A heat resistant kaolin used to raise the
vitrification temperature of ceramics.
Flint clay: A highly refractory hard rock composed
mainly of well ordered kaolinte.

The Ceramics Industry differentiates four types of kaolin:

China clay is pure white or near white, usually well crystallized kaolin
with low plasticity and low green strength. China clay generally
corresponds to what is called soft clay in the Rubber Industry.
Ball clay is fine-grained sedimentary clay containing at least 70%
kaolinite and also natural organic matter. The organics give ball clay
high plasticity and high green strength, which means that, when mixed
with water, it has the properties associated with modeling clay.
Fire clay is a refractory (heat resistant) kaolin used to raise the
vitrification temperature of ceramics.
Flint clay is a highly refractory hard rock composed mainly of well
ordered kaolinte.

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 Multi (Paint, Paper, Rubber) Industry
Water-washed clay: Kaolin slurried in water and
centrifuged or hydrocycloned to remove impurities
and produce specific particle size fractions. Water-
washed clays are often treated to improve
brightness.

Water-washed kaolin has been slurried in water and centrifuged or

hydrocycloned to remove impurities and produce specific particle size
fractions. The refined slurry is either dewatered (to reduce soluble
impurities) and dried, or concentrated to 70% solids and sold in slurry
form to the Paint and Paper Industries. Water-washed clays are often
treated to improve brightness. This includes chemical bleaching and/or
high-intensity magnetic separation to remove iron and titanium
impurities. Although most of the clay used in rubber is airfloat, some
water-washed clay is used because its lower level of impurities provides
better color and less die wear with rubber extrusions.

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 Rubber Clays
Hard clay: Very fine-grained, relatively poorly
crystallized. Provides good tensile properties,
stiffness and abrasion resistance. Improves
properties of GCC compounds. Low cost substitute
for portion of carbon black or ppt silica without loss
of properties.
Soft clay: Better crystallized, low reinforcing effect.
Higher loadings, quicker extrusions.

Rubber filler clays are classified as either “hard” or “soft” in relation to

their particle size and stiffening affect in rubber. A hard clay will have a
median particle size of approximately 250 to 500 nm, and will impart
high modulus, high tensile strength, stiffness, and good abrasion
resistance to rubber compounds. Soft clay has a median particle size of
approximately 1000 to 2000 nm and is used where high loadings (for
economy) and faster extrusion rates are more important than strength.

More hard clay than soft is used in rubber because of its semi-
reinforcing effect and its utility as a low cost complement to other fillers.
It is used to improve the tensile and modulus of ground calcium
carbonate compounds and will substitute for a portion of the more
expensive carbon black or precipitated silica in certain compounds
without sacrificing physical properties.

35
 Airfloat clay: Dry-ground
kaolin that has been air
separated to minimize
impurities and control
particle size distribution.

Airfloat clay is dry-ground kaolin that has been air separated to

minimize impurities, such as quartz, mica and bentonite, and control the
particle size distribution. About 80% of the kaolin used in the Rubber
Industry is airfloat hard clay.

36
 Comparison of Clay and Calcium Carbonate in SBR
SBR 1006 100 AGERITE® STALITE® S 1.5
VANFRE® AP2 2 Sulfur 2
Zinc Oxide 5 METHYL CUMATE® 0.1
Stearic Acid 2 ALTAX® 1.5

Filler 300% Tensile Elong. Hardness Tear1 Comp. Mooney

phr MPa (psi) MPa (psi) % Shore A kN/m (pli) Set2, % T5/ML3
Hard ClayA
50 1.7 (250) 9.0 (1310) 770 50 13.2 (75) 46 2725
100 3.2 (460) 12.8 (1860) 810 61 24.6 (140 50 25/32
150 4.8 (700) 10.1 (1470) 700 67 37.0 (210) 51 19/47
Soft ClayB
50 1.8 (260) 3.3 (480) 540 50 11.4 (65) 43 27/23
100 2.8 (410) 8.8 (1270) 740 62 20.2 (115) 50 24/32
150 3.3 (480) 7.6 (1100) 730 67 22.9 (130) 54 23/40
Calcium CarbonateC
50 1.4 (200) 1.7 (250) 390 49 6.2 (35) 40 24/21
100 1.2 (170) 1.6 (230 410 53 5.3 (30) 45 24/23
150 1.1 (160) 1.4 (200) 420 59 7.0 (40) 50 24/25
1Die 222
A hours, 70oC 3132oC AAirfloat, DIXIE CLAY BAirfloat, McNamee CLAY CAtomite

This table compares calcium carbonate, hard clay and soft clay in an
SBR compound. The effects of particle size and shape are evident. The
calcium carbonate represents large (approximately 2500 nm average)
isometric particles providing little improvement in compound properties
compared to the clays. The hard clay provides greater tensile and tear
strength than the soft clay.

37
 Silica Plus Lower Cost Fillers in Shoe Sole Compound
SBR 1502 100 ALTAX® 0.7
Diethylene Glycol 3 CAPTAX® 0.4
Stearic Acid 1 UNADS® 0.3
Zinc Carbonate 1 VANAX® DPG 0.1
Sulfur 2

HI-SIL® 233 (ppt silica), phr 45 30 30

Hard Clay, phr -- 23 --
Calcium Carbonate (dry-ground), phr -- -- 23

t90% Cure, 150 oC 12 7 3

Cure Time, 150oC 15 11 10
Hardness 66 65 65
300% Modulus, MPa 3.6 3.1 3.1
Tensile Strength, MPa 20.5 20.9 20.4
Elongation, % 735 770 720
Trouser Tear, kN/m 27 25 8
Pico Abrasion Index 68 67 48
Rebound, 23oC 48 43 49
Rebound, 100oC 54 50 60

This compound compares the ability of a hard clay and a dry-ground

calcium carbonate to reduce the cost of a 65 Durometer shoe sole
compound reinforced with precipitated silica. All three compounds show
equivalent modulus and tensile strength. The compound with calcium
carbonate, however, has significantly reduced tear strength and
abrasion resistance while the clay maintains these properties.

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 Delaminated clay: Coarse clay fraction from water
washing is milled to reduce the kaolinite stacks into
thin, wide individual plates. This improves brightness
and opacity.

To produce delaminated clay, the coarse clay fraction from water

washing is attrition milled to break down the kaolinite stacks into thin,
wide individual plates. This improves brightness and opacity.

39
 Comparison of Delaminated Clay to Hard Clay
Narural Rubber 100 Stearic Acid 4
(Smoked Sheets) Cumar® MH 2½ 7.5
Clay 156 Sulfur 3
Zinc Oxide 5 CAPTAX® 1

Delaminated ClayA Hard ClayB

Hardness, Shore A 74 70
300% Modulus, psi 2400 2200
Tensile Strength, psi 3080 3000
Elongation, % 360 390
NBS Abrasion Index, % 53 28
Olsen Stiffness 27 17
(2” span, in-lbs)
Die Swell 100 150
(% comparison)
APolyfil® BSuprex ®
DL

Delaminated clay is the highest aspect ratio form of clay available, and
it is used for high stiffness and low die swell, as demonstrated in this
natural rubber compound.

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 Calcined clay: The
kaolin, usually water-
washed soft clay, is
calcined to partially
remove surface
hydroxyls. Used in wire
and cable coverings for
excellent dielectric and
water resistance
properties.

To produce calcined clay for filler uses, the kaolin, usually water-
washed soft clay, is calcined to partially remove surface hydroxyl
groups. Calcining increases brightness and opacity, both useful in the
Paint Industry, as well as oil absorption and hardness (i.e., abrasivity or
abrasion resistence). The partial or complete removal of surface
hydroxyls provides a corresponding decrease in surface activity, and
thus reinforcement. Calcined clay is commonly used in wire and cable
coverings because it provides excellent dielectric and water resistance
properties.

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 Flexible Cord Insulation
Royalene® X3751 100 Parafin Wax 5
(EPDM) Vinyl Silane A-172 2
Whitex® Clay 180 Kadox® 911C 5
(Calcined Kaolin) SR-350 2
Naugard® Q 1 VAROX® DCP-40KE 7.5
Sunpar® 2280 55

SIC, PF @ 75oC Water SIC @ 80 v/mil PF @ 80 v/mil PF @ 40 v/mil

1 Day 3.23 1.6 1.6
7 Days 3.21 1.7 1.6
14 Days 3.22 1.5 1.5
Capacitance Change
7-14 Days, % 0.3
1-14 Days, % -0.3
Stability Factor
1 Day/14 Days/Change, 1-14 Days 0.00.00.0

This EPDM insulation compound illustrates how calcined clay is used

to maintain electrical properties.

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 Surface-treated clay: Processed kaolin that has
been surface modified (e.g., with silanes) to
improve compatibility with and performance in
elastomer matrices.

High Modulus
and
Low Hysteresis

Silane treated hard clays provide better reinforcement than untreated

clay, and in some applications can rival furnace blacks. The
combination of platy shape and chemical reactivity enable the silane-
treated kaolins to impart a unique blend of properties to elastomers.
These include high modulus, low hysteresis, good abrasion resistance,
low viscosity, low set, and resistance to heat and oxidative aging. The
unusual combination of high modulus and low hysteresis, in particular,
have earned them a place alone or as a partial carbon black
replacement in products requiring good dynamic properties, such as
transmission and V belts, and non-tread tire components.

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 Comparison of Treated to Untreated Hard Clay
NATSYN® 400 100 AGERITE® White 1
Hard Clay 75 Sulfur 2.75
Zinc Oxide 5 AMAX® 1.25
Stearic Acid 5 METHYL TUADS® 0.2

Clay Treatment Aminosilane A Mercaptosilane B None C

Harness, Shore A 62 65 60
300% Modulus, psi 1630 1770 770
Tensile Strength, psi 2960 3240 3080
Elongation, % 480 480 580
Die C Tear, ppi 245 235 155
Compression Set B 12.4 14.0 29.6
o
(22 hours, 70 C)
Mooneyo Scorch, min. 19 23 18
(MS-3/121 C)
Mooneyo Viscosity 58 42 33
(ML-4/100 C)

ANulok ® BNucap® CSuprex ®

321 200

Aminosilane and mercaptosilane treated clay are compared here to an

untreated hard clay in a synthetic polyisoprene compound. The
improvements in modulus, tear strength, compression set and the
reduction in elongation with the treated clays are all indicative of the
improved elastomer-clay bonding. The ultimate tensile strength is not
significantly affected since the rupture strength of the polymer-polymer
linkages remains unchanged.

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 Comparison of Treated Hard Clay to Carbon Black
Narural Rubber 100 Cumar® MH 2½ 7.5
(Smoked Sheets) Sulfur 3
Zinc Oxide 5 CAPTAX® 1
Stearic Acid 4

Clay Treatment Aminosilane A Mercaptosilane B

Carbon Black -- -- N330
Level, phr 75 75 45
Harness, Shore A 56 55 57
300% Modulus, psi 1630 1360 1400
Tensile Strength, psi 3320 3320 3880
Elongation, % 520 560 590
Die C Tear, ppi 235 215 660
NBS Abrasion Index, % 83 79 204
Heat Buildup, oF 183 142 219
(Firestone)
Mooneyo Scorch, min. 12 9 10
(MS-3/121 C)
Mooneyo Viscosity 46 45 61
(ML-4/100 C)
ANulok ® 321 BNucap® 200

The high modulus with low hysteresis of the treated clays vs. carbon
black in this natural rubber compound suggests that the silane mediated
polymer-clay bond is stronger than the polymer-black bonds at the
carbon black active sites. Deformation results in loss of fewer polymer-
filler bonds with the treated clays, so that energy loss as heat is less
compared to the carbon black. This stronger polymer-clay bond is also
consistent with the higher modulus and abrasion resistance.

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 Mineral Fillers for Rubber

KAOLIN CLAY

R.T. Vanderbilt Company, Inc.

For all the functionality it provides in rubber, kaolin clay, and airfloat
hard clay in particular, can convincingly claim to be the biggest bargain
in rubber additives.

46
 Mineral Fillers for Rubber

KAOLIN CLAY

R.T. Vanderbilt Company, Inc.

Use of Information
The information presented herein, while not guaranteed, was prepared by technical
personnel and, to the best of our knowledge and belief, is true and accurate as of the
date hereof. No warranty, representation or guarantee, express or implied, is made
regarding accuracy, performance, stability, reliability or use. This information is not
intended to be all-inclusive, because the manner and conditions of use, handling,
storage and other factors may involve other or additional safety or performance
considerations. The user is responsible for determining the suitability of any material
for a specific purpose and for adopting such safety precautions as may be required. R.
T. Vanderbilt Company does not warrant the results to be obtained in using any
material, and disclaims all liability with respect to the use, handling or further
processing of any such material. No suggestion for use is intended as, and nothing
herein shall be construed as, a recommendation to infringe any existing patent or to
violate any federal, state or local law or regulation.
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