Effect of filler on rubber

compound properties
Muhammad Farooq
Effect of Filler Properties on Elastomer
Performance
• The influence of the filler physical properties on reinforcement and
other important properties is a very complex subject as they interact
with one another. The general trends are summarized in very simple
form in Table 1 below. This shows that the best reinforcement is
achieved by small particle size, high structure, strong filler/polymer
interaction, and good dispersion. Only a few filler types are able to
achieve this, notably carbon blacks, synthetic silicas when used with
coupling agents such as organosilanes, and precipitated calcium
carbonates with unsaturated carboxylated polymer coupling agents.
Some Effects of Particle Size
• Table 2 exemplifies how tensile strength and abrasion resistance vary
with carbon black primary particle size. This is a based on data in a
sulfur cured SBR compound.
 Some Effects of Filler Dispersion
• Table 3 shows how various filled elastomer properties develop as a function
of dispersion. This study was achieved by measuring dispersion and property
profile of a compound as a function of mixing time.
• This study did not consider the effect of the actual size or nature of the poorly
dispersed material. This was investigated in detail in the classic studies by
Boonstra and Medalia who found that particles become detrimental at a size
of about 1 μm. They found little further effect of size above this critical value,
but did find that properties deteriorated as the hardness of the particles
increased. The most sensitive property to poor dispersion in both studies was
found to be abrasion resistance. Even trace amounts of grit (a few 100 ppm)
was found to cause a detectable loss in performance in fatigue tests and are
thus important in some critical applications, notably tires
The Effects of Filler to Elastomer Adhesion
• The effects of filler to elastomer adhesion can be illustrated by
comparing the effect of a typical reinforcing carbon black before and
after a process known as graphitization.
• There is a strong natural adhesion between elastomers and the
surface of conventional carbon blacks, but this can be removed by the
graphitization process, which involves treating the carbon black at
high temperature under an inert atmosphere. The results of such a
comparison are presented in Table 4.
continued
• The graphitization procedure used had only a minor effect on the physical
properties of the carbon black (specific surface area and oil absorption) and
no significant effect on dispersion in the elastomer.
• As shown in the table, the main effect was an almost complete removal of
bound rubber. Bound rubber is a test carried out on compounded but
uncured elastomer and measures the amount of polymer “insolubilized” in a
good solvent for the elastomer, after mixing with the filler. This is used as a
measure of filler/elastomer interaction and indicates that graphitization has
destroyed this. All of the reported compound properties have been changed
by the graphitization, but by differing amounts. The biggest effects are seen
to be on high extension modulus, abrasion loss, and hysteresis.
The Effects of Filler Structure
• The main effects associated with filler permanent structure are
illustrated in Table 5. The carbon blacks used here are of similar
specific surface area (and particle size), but differ significantly in oil
absorption and hence structure. They both dispersed equally well in
the elastomer. Some properties are little affected by the changes in
structure, notably tensile strength and abrasion loss, but others show
significant effects. Compound viscosity increases while extrusion
shrinkage decreases; both of these effects are consistent with the
concept of occluded rubber mentioned earlier. High extension
modulus increases while elongation decreases with increasing
structure, again consistent with occluded rubber.
Dynamic Properties of Filled Elastomers
• This subject deserves special treatment as it plays a vital role in many applications, especially
in vehicle tires, which account for the majority of elastomer, and hence filled elastomer,
applications.
• Here, we are dealing with repeated deformations with limited recovery times between them
and this can have a marked effect on performance. This is a complex topic and only the
simplest treatment will be attempted here. The key feature is the amount of energy lost in
the deformation/recovery process, which largely manifests itself as heat and noise.
• In tire applications, this lost energy is of considerable significance for the fuel efficiency of a
vehicle (through a property known as rolling resistance) and also for road grip and has
received considerable attention in the drive to improve efficiency and reduce fuel usage and
the associated emissions.
• A number of methods of measuring this energy loss are used: ranging from resilience and
heat buildup tests to complex dynamic mechanical tests. The former are the easier to
understand. Resilience is usually measured by some form of rebound test and low resilience
means more energy loss on deformation. Heat build-up is measured during repeated cyclic
deformation and a high heat build-up corresponds to higher energy losses.
continued
• The dynamic mechanical tests are more informative and the most difficult to
understand, but have a prominence in the important tire applications. Essentially,
these tests are carried out using an oscillating sinusoidal stress and allow the
sample response to be separated into an elastic and viscous component (storage
and loss moduli).
• From this, one can derive a loss factor, which is commonly referred to as tan delta;
the higher this value, the higher the energy losses and heat generation. The loss
factor is dependent on energy dissipating processes and is temperature dependent.
• It is also frequency and rate dependent, with higher frequencies bringing about
the same change as reducing temperature. Thus, the change of tan delta with
temperature can be used as a guide to how it will change with frequency or rate of
deformation.
Tire Applications
• Tires are the main user of elastomers and also of the reinforcing fillers such as carbon
blacks, which have always played a key role in them. Indeed, it is very unlikely that a
useful tire could be made without them. As a result of this, and with the dominance
of this market, these fillers have evolved in parallel with tire developments and
continue to do so.
• Tires are very complex items with the elastomeric components being required to
fulfill a number of demanding roles. As a result, one has to consider a number of
properties not well known outside of this technology. In the early days, the main
concern was with tire life and the use of fillers to reduce tread wear and for some tire
(truck and especially off-road ones) to also reduce cutting and chunking. Heat buildup
in use was another important consideration and is still a significant factor in failure of
truck tires. Grip (also known as traction) is a further important criterion which has to
be maintained under a wide range of road, driving, and climatic conditions.
continued
• Over time, the contribution of the filler to grip began to be understood and developed.
Precipitated silica, in particular, was noted for good grip, especially in the wet and under cold,
winter conditions. More recently, attention has shifted to minimizing fuel consumption by
reducing rolling resistance, while maintaining adequate tire life and grip. This has led to the
emergence of what is known as the green or energy tire. Again the filler choice has proved to be a
key factor in optimizing this type of tire.
• The service conditions and hence requirements of a tire also vary according to the type of vehicle,
automotive, van, truck, off-road, etc. Tires are made up of several parts in order to maximize
performance, each optimized for the role that it has to play. The main parts of the tire that can be
recognized are tread, side wall, beading, and inner liner. These use different types of elastomer
and impose different requirements on the filler. Most interest today is focused on the tread, which
is responsible for the grip and for most of the wear issues and requires the highest filler
performance. In automotive tires, it is also responsible for most of the rolling resistance. While
carbon black has been, and remains, the principal filler used, different grades have evolved to suit
the different tire parts
Tire Treads, Green Tire, Precipitated Silica Versus
Carbon Black ,Payne Effect, Rolling Resistance, etc.
• While all the elastomeric components of a tire use fillers, the tread is especially
important and has the highest performance requirements. Quite complex
properties are involved when one comes to consider the use of reinforcing fillers in
tire treads. Notable among these are abrasion resistance, hysteresis and the related
properties of heat build-up, grip (traction), noise, and rolling resistance.
• Of particular interest is the relationship between rolling resistance, grip, and
abrasion resistance. This is commonly referred to as the magic triangle (Fig. 6), with
improvements in one of these usually being offset by deterioration in another.
• As a result, compromises usually have to be made. Many of the published studies
use dynamical mechanical analysis to predict the rolling resistance and grip of filled
elastomer compounds. This is done by measuring the energy losses (tan delta) at
two temperatures, usually 0 C and 60 C or 70 C.
continued
• This uses the temperature, strain rate equivalence referred to above, with
the lower temperature being considered equivalent to high strain rates
(grip), and the high temperature to low strain rates (rolling resistance).
• While a good approximation in most cases, this analysis is not infallible and
must be treated with caution.
• One of the major advances in recent years has been the development of
effective passenger tire tread compounds based predominately on the use
of precipitated silica as the filler rather than carbon black. As will now be
explained, this change of filler, together with the use of specialized
coupling agents, allows an expansion of the “magic triangle” referred to
above and a better balance to be achieved between tread wear, grip, and
rolling resistance (fuel consumption) than was achieved with carbon blacks.
Silica Versus Carbon Black in Tire Treads
• The results in Table 7 give a comparison of a carbon black and silica of similar
specific surface area in a typical low rolling resistance tread formulation (Solution
SBR/BR blend) and provide a good illustration of the effects discussed in the
previous section. It is seen that, even without coupling agent, the silica gives lower
tan delta at the higher temperature, but markedly worse abrasion resistance.
• The use of silane coupling agent brings the abrasion resistance close to that of the
carbon black, without any loss in the tan delta properties. (NB the laboratory
abrasion and tan delta tests are only a guide to actual rolling resistance, grip, and
road-wear, which themselves vary according to the severity of the test conditions.
It is generally accepted that silica plus silane, while about equal to carbon blacks
under modest road-wear conditions, are still inferior at the highest severity).
continued
• As expected, the use of TESPT markedly improves tread wear due to the strong
coupling and better dispersion. Fortunately, the destruction of the filler network doe
not have any negative effect on the dynamic properties discussed above, and the
rolling resistance and wet grip advantages are retained.
• Despite the better balance of properties obtainable, the precipitated silica/silane
technology has some significant issues. These are partly around raw material costs,
but mostly around processing. Reaction of the coupling agent with the filler is most
commonly achieved during the compounding process and as a result it is necessary
to control mixing conditions very carefully, if the silane is to react efficiently with the
filler surface without the sulfide group entering into premature reaction with the
polymer (a process known as scorch). Prereacted fillers are now becoming available,
but have made little impact so far. The increased hardness of silica also leads to
faster machine wear.