Nielsen 1979

Dynamic Mechanical Properties of Polymers Filled
with Agglomerated Particles
LAWRENCE E. NIELSEN, 3208 N . W. Lynch Way, Redmond, Oregon 97756
Synopsis
The filler particles in most filled polymers are not perfectly dispersed but are more or less ag-
glomerated. The degree of agglomeration and the strength of the agglomerates, which can be
modified by surface treatments, have a very great effect on the dynamic mechanical properties. Filler
agglomerates which are wetted by the polymer matrix produce higher elastic moduli than similar
agglomerates which are not wetted. The relative damping in most filled polymers is very temper-
ature-dependent. A qualitative explanation is given for this temperature dependence. The degree
of’ agglomeration and the strength of the agglomerates are important factors in determining the
damping.
INTRODUCTION
Nearly all theories of the elastic modulus and other mechanical properties of
filled polymers assume perfect dispersion of the filler particles. However, in
actual practice, the filler particles are more or less agglomerated. Agglomeration
can have a very great effect on mechanical properties, so it is not surprising that
there often are large differences between theoretical predictions and experimental
data. In this paper, some of the effects of agglomeration on the dynamic me-
chanical properties will be discussed.
Three characteristics of the filler phase in the polymer matrix are important
in determining the dynamic mechanical properties of the composite: (i) a gen-
eralized Einstein coefficient, which is determined by the shape and the state of
agglomeration of the filler; (ii) the maximum packing fraction of the filler, which
also is determined by the particle shape and the state of agglomeration as well
as by the filler-polymer interactions; and (iii) the mechanical strength of the
agglomerates.
In this paper, an agglomerate will be defined as a particle made up of a number
of primary particles in contact with one another. The agglomerate particles will
be assumed to behave as a rigid unit under the action of small stresses, but above
some critical stress, relative motion of the particles within the agglomerate can
occur.
The beneficial effects of surface treatments of filler particles, including silane
treatments, are generally attributed to improved adhesion of the polymer to the
filler surface. However, it should be realized that in many cases, the changes
in the degree of agglomeration brought about by the surface treatments are
equally, or more, important.
Thomas G Fox Memorial Issue

Journal of Polymer Science: Polymer Physics Edition. Vol. 17, 1897-1901 (1979)
cc) 1979 John Wiley & Sons, Inc. 0098-1273/79/0017-1897$01.00
1898 NIELSEN
ELASTIC MODULI OF FILLED POLYMERS

The elastic moduli and the mechanical damping are the two properties making
up the dynamic mechanical properties. The most versatile equations for esti-
mating the elastic moduli of filled polymers are1P2
M/Mi = ( 1 + AB42)/(1 - B#42) (1)
where
A=kE-1
# 1 + [ ( I - 4m)/4m2142 (4)
where M is the elastic modulus of the composite (shear, Young’s, or bulk); MI
is the modulus of the polymer matrix; M2 is the modulus of the filler particles;
A is a constant determined by the generalized Einstein coefficient k E (values
are tabulated in refs. 1 and 3); II/ is a reduced concentration term dependent upon
the maximum packing fraction 4 m of the filler in the polymer (values of 4m are
tabulated in refs. 1and 3); 42 is the volume fraction filler; and B is a constant near
1.0 in many cases. The generalized Einstein coefficient, which is analogous to
the intrinsic viscosity of polymer solutions, is defined by
Agglomeration greatly increases the modulus of a filled polymer, if the

agglomerates are rigid, by increasing k E and decreasing 4m.4 For example, for
dispersed spheres with cubic packing, k E = 2.5 and +m = 0.524, while for rigid
spherical agglomerates made up of many primary particles, k E = 4.77 and @m
= 0.5242 = 0.275.
Agglomerates, which are not wetted by the polymer, remain filled with air
instead of polymer. Such agglomerates have a smaller apparent volume fraction
of solid than do ones which are wetted and filled with polymer. This is
proved by the following analysis:
Wetted case:
where Vi is the volume inside the agglomerate which is not occupied by the filler
material: V; = V2(1/& - 1); V1 is the volume of polymer; and V2 is the volume
of filler.
Nonwetted case:
In this case., V; is the volume of air inside the agglomerates. As an illustration,

in the case where V1 = V2 and 4m = 0.64, &a = 0.78 for the wetted case, and
DYNAMIC MECHANICAL PROPERTIES 1899
= 0.61 for the nonwetted case. The apparent concentration is higher for the
wetted case since part of the matrix material is entrapped inside the filler
agglomerates, and thus, it is not available for taking part in deformation pro-
cesses. On the other hand, all the matrix can take part in any deformation
process if the agglomerates are not wetted by the matrix polymer. For rigid
agglomerates,
Thus, for the above example, kE is 3.9 for the wetted case and 3.1 for the non-
+
wetted case. In eq. (9), $2 is defined as Vz/( V1 V2).
MECHANICAL DAMPING OF POLYMERS FILLED WITH

AGGLOMERATES
The temperature dependence of the relative moduli MIM1 of polymers filled
with agglomerated particles has been discussed using a modified version of eqs.
(1)through (4).5 A few authors have discussed the effect of particle agglomer-
ation or aggregation of dynamic mechanical proper tie^.^^ However, very little
has been written on the temperature dependence of the relative damping AIA1
of such systems. Damping A here is defined by such terms as M"IMf or tans.
Unless there is a change in the mechanism of damping, the relative damping AlA1
should be a value which is nearly independent of temperature. The expected
value of AIA, when all the damping comes from the polymer is roughly equal
to the volume fraction $1 of the polymer.lJOJ1 That is,
A
damping of filled polymer - _
damping of unfilled polymer A1
= 41
However, experimental data show that, in general, AIA1 varies greatly with
temperat~re.~J~ Figure
J ~ 1 shows typical behavior of a filled amorphous
polymer. The minimum value of A/A1 in Figure 1often is roughly what would
be predicted by eq. (10). This minimum occurs near Tgor a t a slightly higher
temperature. Above Tg, the damping even may be higher than that of the un-
filled polymer. How can one explain this behavior?
The damping can be explained qualitatively by the same mechanisms used
to explain the dynamic modulus b e h a ~ i o r . Below
~ the glass-transition tem-
perature, part of the decrease in relative damping as the temperature is raised
may be due to the frozen-in stresses caused by the mismatch in the coefficients
of thermal expansion of the two materials.l* Polymers under high stress gen-
erally have a higher damping than the material a t low stress levels. However,
part of the temperature dependence below Tg also can be due to a decrease in
motion of particles within agglomerates as the polymer softens. As the modulus
of the polymer decreases on raising the temperature, the polymer exerts less force
on the agglomerate particles, so there is a smaller probability that one primary
particle will move with respect to another one within agglomerates. Frictional
heat generated by the movement of one particle against another adds to the total
damping of the system. In the neighborhood of Tgor somewhat above it, the
modulus of the polymer has decreased to such a small value that deformation
1900 NIELSEN
TEMPERATURE
Fig. 1. Typical behavior of a filled amorphous polymer.
of the material no longer produces forces great enough to deform agglomerate

particles, so they appear to be rigid. A t this point, the relative damping is small
since most of the damping may come only from the polymer.
What causes the relative damping to increase again a t higher temperatures?
The increase appears to be due to a combination of two effects. Since the coef-
ficient of thermal expansion of the polymer is much greater than that of the filler,
the polymer exerts less “squeezing” force on the agglomerate particles as the
temperature increases above Tg.As the force between the polymer and the filler
particles decreases, it becomes easier for either polymer-filler or for filler-filler
motion to occur at the interfaces. This frictional motion a t interfaces generates
heat which produces an increase in the relative damping as the temperature in-
creases.
The qualitative explanation given here for the temperature dependence of
the relative damping is supported by the more quantitative explanation of the
temperature dependence of the relative m o d ~ l u s . ~ The J ~ above explanation
makes it easy to see why there can be great changes in the dynamic mechanical
properties of a given polymer-filler system just by treating the surface of the filler.
Filler treatments can change the polymer-filler adhesion, change the state of
agglomeration, and change the coefficient of friction between filler particles.
References
1. L. E. Nielsen, Mechanical Properties of Polymers and Composites, Vol. 2, Marcel Dekker,
New York, 1974.
2 . L. E. Nielsen, J . Appl. Phys., 41,4626 (1970).
3 . L. E. Nielsen, Predicting The Properties of Mixtures, Marcel Dekker, New York, 1978.
4. T. B. Lewis and L. E. Nielsen, Trans. SOC.Rheol., 12,421 (1968).
5. B-L. Lee and L. E. Nielsen, J . Polym. Sci. Polym. Phys. Ed., 15,683 (1977).
6. G. Kraus, Angew. Makromol. Chem., 60/61,215 (1977).
DYNAMIC MECHANICAL PROPERTIES 1901
7. A. R. Payne, J . Appl. Polym. Sci., 7,873 (1963).

8. A. I. Medalia, Rubber Chem. Technol., 47,411 (1974).
9. M. Takano and H. Kambe, Bull. Chem. SOC.Jpn., 36,24,1418 (1963); 37,78,89 (1964).
10. R. A. Dickie, J . Appl. Polym. Sci., 17,45 (1973).
11. J. Kolarik, J. Janacek, and L. Nicolais, J . Appl. Polym. Sci. 20,841 (1976).
12. F. R. Schwarzl, H. W. Bree, C. J. Nederveen, G. A. Schwippert, L. C. E. Struik, and C. W. Van
der Wal, Rheol. Acta, 5,270 (1966).
13. L. Aras, R. P. Sheldon, and H. M. Lai, J . Polym. Sci. Polym. Lett. Ed., 16,27 (1978).
14. L. E. Nielsen and T. B. Lewis, J. Polym. Sci., A-2, 7,1705 (1969).
Received August 25,1978

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Dynamic Mechanical Properties of Polymers Filled

with Agglomerated Particles

LAWRENCE E. NIELSEN, 3208 N . W. Lynch Way, Redmond, Oregon 97756

Thomas G Fox Memorial Issue

ELASTIC MODULI OF FILLED POLYMERS

Agglomeration greatly increases the modulus of a filled polymer, if the

In this case., V; is the volume of air inside the agglomerates. As an illustration,

MECHANICAL DAMPING OF POLYMERS FILLED WITH

Fig. 1. Typical behavior of a filled amorphous polymer.

of the material no longer produces forces great enough to deform agglomerate

7. A. R. Payne, J . Appl. Polym. Sci., 7,873 (1963).

Received August 25,1978

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