MECHANICAL PROPERTIES AND BEHAVIOR OF POLYMERIC MATERIALS
SIMULATED BY MOLECULAR DYNAMICS
Witold Brostow (1), António M. Cunha (2), Ricardo Simões (1,2) and Júlio C. Viana (2)
(1)
Laboratory of Advanced Polymers and Optimized Materials (LAPOM), Dept. Materials Sci & Eng,
University of North Texas, Denton, TX 76203-5310, USA; brostow@unt.edu
(2)
Department of Polymer Engineering, University of Minho, 4800 Guimarães, Portugal;
amcunha@dep.uminho.pt ; rsimoes@dep.uminho.pt ; jcv@dep.uminho.pt
Abstract
We have used computer simulations to investigate
the behavior of polymeric materials under a uniaxial tensile
force. The simulations allow us to follow the behavior of
individual macromolecular chains at the molecular level
during deformation and thus study the deformation
mechanisms developing up to fracture under different
loading conditions.
The influence of micro-structural features on the
mechanical properties has also been investigated. For this
we simulate materials with varying skin-core ratio and
orientation of the chains. Although we use simplified
models for the structure of the skin and core regions, the
behavior of the simulated materials is akin to that observed
in real materials.
From the simulations we have gained a better
understanding of the structure-properties relationships in
polymeric materials. This knowledge can be used to create
materials with improved properties.
1. Introduction
The molecular phenomena taking place during the
deformation of polymeric materials are not yet completely
understood. The structure-properties relationships are
difficult to characterize due to several factors, among
which are the complex molecular and supramolecular
structures developing in some polymers.
However, being able to understand the
deformation mechanisms and behavior of a polymer under
tension is not only of interest from the academic point of
view but also from the industrial standpoint. Much of the
process optimization in injection molding is still being
achieved based on empirical data. These methods create
problems when something as simple as a change of
material batch occurs. Moreover, understanding the
behavior of polymers is of interest to the society in general,
since ultimately we all depend on the reliability and
performance of plastic parts [1, 2].
Many of the phenomena taking place at the
molecular level are extremely difficult to characterize
because there are no adequate apparatus capable of
following such dynamic processes taking place inside a
material. In order to tackle this problem and obtain
information about these molecular-level phenomena, we
resort to computer simulations of polymeric materials.
By using the molecular dynamics method, one can
study the individual mesoscale elements of a polymeric
structure as they respond to external conditions, such as an
applied force. The dynamic behavior of the elements along
time can also be investigated in this way. Computer
simulations have been used for many years to study such
problems and their use will continue to grow [3],
particularly since current computer hardware is becoming
powerful enough to allow realistic materials to be
simulated using non-trivial models.
In earlier papers we have reported on the use of
computer simulations to study the phenomena of crack
formation and propagation in two-phase polymer liquid
crystals (PLCs) [4, 5] and the deformation mechanisms
occurring in two-dimensional and three-dimensional
computer-generated materials (CGMs) [6]. More recently
[7] we reported on the true stress measurement and
viscoelastic recovery during the simulation of polymeric
materials under a tensile force, and the effect of the tensile
force increase rate on the mechanical properties of the
material.
In the present paper we shall show how a
simplified model of the skin-core morphology can provide
important structure-properties relationships information. In
our simulations, we start by creating a polymeric structure
of either highly oriented or randomly oriented chains using
the procedures described in Sections 2 and 3, and then we
apply external loading conditions and observe the material
response.
It is important to point out that the purpose of our
simulations is not to replace experimental testing, but to
complement it. We believe that the concomitant use of
experiments and simulations can yield a synergistic effect.
To achieve this, we try to reproduce experimentally the
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CGMs and the conditions of the simulations performed on
them.
2. Single-phase material generation
In order to create a realistic polymeric system on
the computer, we follow the approach developed by Mom
[8] and later modified to better meet our needs [9]. As
advocated by Flory [10], we use a united atom model so
that each segment in the CGM corresponds to a statistical
segment representing a small part of a polymeric chain.
Initially, all segments are positioned in equidistant
lattice points, each segment representing a chain of size 1.
We have chosen the triangular lattice for reasons stated
before [9, 11]. Chains grow by bonding neighboring
segments together. The system is repeatedly searched for
two neighboring end-of-chain segments which can be
bonded. When that happens, the two chains become one
and the search continues.
Often, particularly at the early growth stages,
there are many neighboring segments that can be equally
bonded. In that case, the choice is made randomly; this
gives rise to systems of coiled chains, with absolutely no
preferential orientation of chain growth direction.
Conversely, systems of oriented chains can also be created,
with the chain growth direction aligned with the force
application direction.
This relatively simple generation method allows
for several realistic features to develop, such as a
molecular weight distribution and presence of physical
entanglements in the 3D polymeric CGMs. A detailed
description of the chain generation procedures and the
realistic features of the resulting CGMs has been provided
elsewhere [9].
3. Two-phase material generation
We have also studied two-phase polymeric
systems, with a rigid liquid-crystalline (LC) second phase
dispersed in a flexible matrix. The LC phase was found
experimentally [12, 13] to form quasi-spherical
agglomerates, which we call islands.
We introduce the second phase in the flexible
matrix by random sequential addition. Each island is
represented by a polygon, which is as close as we can get
to a sphere using a discrete number of segments [5, 9]. In
order to study the influence of the second phase on the
properties and behavior, we create materials with varying
LC concentration. A detailed description of the second-
phase addition procedure has been provided in a previous
paper [9].
Since the islands are randomly positioned in the
material, regions of high and low local concentration are
often found. The distribution of the LC phase has been
shown before to significantly influence the mechanical
properties and the behavior during deformation. Moreover,
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they substantially influence the crack initiation loci and the
crack propagation paths [5].
Previous simulations have also shown that
although the presence of the islands influences the
properties of the material, their size does not [7]. However,
the island size does influence the mechanisms of crack
initiation and propagation. In order to isolate other
variables, in the present work we have kept a constant
island diameter of 3 segments. In fact, the ability to study
different variables independently of one another is one of
the main advantages of computer simulations.
4. Simulation model and parameters
As mentioned before, we perform simulations
using the molecular dynamics (MD) method. The
preference over the Monte Carlo or Brownian dynamics
methods has been previous discussed [4, 5].
The MD method was initially developed by Alder
and Wainwright [14]; in this method, the system is
comprised of individual segments positioned in three-
dimensional space. Each segment is characterized by three
Cartesian coordinates and three momentum components
along the main axes. During the simulation these six
variables are repeatedly calculated, and by monitoring their
values we can investigate the time-dependent behavior of
each individual segment.
The interaction between the segments is
determined by a series of potentials as a function of the
inter-segmental distance [4]. Different potentials describe
the behavior of flexible and rigid LC segments. Distinct
potentials are also employed to describe primary (intra-
chain) and secondary (inter-chain) interactions.
For the intra-chain bonds between rigid LC
segments, we have incorporated a narrow Morse-like
potential. For the intra-chain bonds between flexible
segments, we have incorporated spliced double-well
potential, which allows for conformation transitions as in
real polymer chains. A Morse-like potential with a
relatively broad well describes the weak inter-chain van
der Walls interactions.
The external force is applied to the edges of the
material along one direction. In the case of systems of
chains oriented with the force application direction, the
force is thus applied to both ends of each chain. In systems
of randomly oriented chains, the force can be applied to
any segment of any chain, depending on the particular
arrangement of the structure.
After the material is created, the segments are
perturbed from their original ideal lattice positions by
applying a random but small displacement to each
segment. Then, the first simulation step is run with an
external force of zero, to allow the system to reach quasi-
equilibrium. After that, the external force increases by a
constant value at each simulation step until the material
fractures.
 From the simulation we obtain information for
each time step, such as the strain, engineering stress, true
stress, free volume, etc. From these we can plot the stress
vs strain curve and calculate the elastic modulus and tensile
strength, among other properties.
5. Effect of the skin-core ratio
In order to simulate the skin-core structure
typically resulting from the injection molding process, we
have adopted Tadmor’s three-region model [15]. The
model has been adapted to consider the two types of chain
structures described in Section 2. The skin region is
represented by highly oriented chains aligned with the
direction of force application. The core region is
represented by randomly oriented chains.
The effect of the skin-core ratio has been studied
by simulating single-phase CGMs of the same dimensions
but containing varying ratios of these two regions –
between 0 and 1 in equal intervals of 0.2. Naturally, single
skin region and single core region materials have also been
simulated to establish the limiting behavior of both types.
The chain structure of the single skin region and single
core region materials is shown in Figure 1.
The simulations clearly show a distinct behavior
for the skin and core regions; see Figure 2. The core region
is ductile and exhibits high strain at break and a relatively
homogeneous deformation along time. The skin region, on
the other hand, allows for some deformation due to
conformation changes of the flexible bonds, but for higher
deformations becomes very brittle and fails
catastrophically.
Interestingly, both skin and core regions fail at
approximately the same true stress level; see again Figure
2. This would be expected, since both simulations were
performed on the same type of material, only with different
chain orientations. However, they fail at very different
values of the engineering stress, which implies that the
deformation mechanisms and the changes in the cross-
sectional area of the simulated materials are quite different
for each case.
The behavior and properties of the 3-region skin-
core CGMs varies between those of the single-region
materials, as one might have expected at first. The
modulus, as shown in Figure 3, increases with the increase
of the skin-core ratio Sr. Note that both the secant modulus
(calculated at a fixed strain value) and the apparent
modulus (calculated from the slope of the initial linear
region of the stress-strain curve) are shown in this Figure.
Inversely, the strain at break tends to decrease
with increasing skin-core ratio; see Figure 4. This effect is
directly connected with what was observed for the
modulus, or rigidity, of the material. Thus, the increase of
the highly oriented skin region makes the material stronger
but simultaneously more brittle. Note that Figure 4a
corresponds to the strain at break while Figure 4b
corresponds to the strain at a fixed time in the simulation.
This alternative representation is useful since the exact
moment of fracture is often difficult to define in the
simulations.
6. Effect of the LC concentration
As previously stated, the concentration and
distribution of the LC phase in the material influence the
mechanical properties and behavior. In order to confirm
this statement we have also performed simulations of
CGMs with varying amount of the LC phase as well as
varying skin-core ratio. For each skin-core ratio discussed
in Section 5, CGMs were created with 20 % and 30 % of
the LC phase, in addition to the purely flexible material.
The results obtained from these simulations are in
accordance with those previously reported for single region
PLCs [5]. As discussed in Section 5 for purely flexible
materials, the modulus also increases with the skin-core
ratio for the 20 % and 30 % materials; see Figure 5a. In
this Figure we can also observe how the concentration of
the LC phase increases the modulus. The noticeably higher
increase for the case of 30 % LC is due to the combined
effect of Sr and the rigid second phase.
As we had seen in Section 5 for the single-phase
material, the increase of the modulus with Sr is
accompanied by a decrease of the strain levels also in the
cases of 20 % and 30 % of the LC phase; see Figure 5b.
7. Concluding remarks
We have used computer simulations to study a
variety of issues concerning the behavior and properties of
polymeric materials under tension. From the simulations
we begin to understand the physical phenomena occurring
at the molecular level in these materials.
Although the three-region model used for
simulation is a clear simplification of the real structure
developing in injection molding parts, it provides useful
information. Individually, the skin and core regions behave
very differently, and multi-region CGMs exhibit properties
and behavior that depend, among other variables, on the
skin-core ratio.
The influence of a rigid LC second phase on the
flexible matrix has also been evaluated for multi-region
materials. The LC phase increases the modulus of the
material, while simultaneously making it more brittle.
Further work with more complex chain structures
is required in order to understand the plethora of
phenomena developing in real polymeric materials.
Acknowledgements
Parts of this project have been supported by the
Robert A. Welch Foundation, Houston, TX (Grant # B-
1203) and by the Fundação para a Ciência e a Tecnologia,
3° Quadro Comunitário de Apoio, Lisbon.
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Figure 1 – CGMs of randomly oriented chains (on the left) and chains aligned with the direction of force application (on the
right). These correspond respectively to core and skin regions in our three-region model.

Figure 2 – Stress vs strain curves for the single core (on the left) and single skin region materials (on the right).

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 Figure 3 – Effect of the skin-core ratio on the modulus.

Figure 4 – Effect of the skin-core ratio on the strain behavior. On the left: strain at break; on the right: strain at a fixed time.

Figure 5 – Effect of the LC concentration on the modulus (on the left) and the strain (on the right).

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