Molecular Simulation

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Molecular dynamics simulation of diffusion

of small atmospheric penetratesin
polydimethylsiloxane

Alexander Sudibjo & Douglas E. Spearot

To cite this article: Alexander Sudibjo & Douglas E. Spearot (2011) Molecular dynamics simulation
of diffusion of small atmospheric penetratesin polydimethylsiloxane, Molecular Simulation, 37:2,
115-122, DOI: 10.1080/08927022.2010.524646

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Molecular Simulation
Vol. 37, No. 2, February 2011, 115–122

Molecular dynamics simulation of diffusion of small atmospheric penetrates

in polydimethylsiloxane
Alexander Sudibjo and Douglas E. Spearot*
Department of Mechanical Engineering, University of Arkansas, Fayetteville, AR 72701, USA
(Received 18 June 2010; final version received 28 August 2010)

Motivated by the development of a microelectromechanical (MEMS) corrosion sensor which utilises a thin polydimethylsiloxane
(PDMS) membrane as a permeable medium, molecular dynamics (MD) simulation is used to study the diffusion of CH4, N2 and O2
penetrates in uncrosslinked PDMS. Both PDMS and penetrates are modelled within the MD framework using a hybrid coarse-
grained interatomic potential; the accuracy of this model and its ability to capture structural aspects of PDMS, including bulk
densities and radius of gyration, is evaluated. Diffusion constants and activation energies are computed after reaching steady state
using simulation models with ‘long’ and ‘short’ PDMS chains (above and below the entanglement molecular weight of PDMS,
respectively). Diffusion coefficients computed using short-chain models are higher than those with long-chain models, due to the
presence of molecular entanglements in the long-chain PDMS systems. A linear correlation is found between the natural logarithm
of the diffusion constant and the activation energy for diffusion in agreement with experimentally determined phenomenological
relationships.
Keywords: molecular dynamics; diffusion; polydimethylsiloxane

1. Introduction model. The role of metallic nanoparticles on the diffusion

A microelectromechanical (MEMS) corrosion sensor is
currently under development by Pan and Huang [1] to
provide an inexpensive and reliable means to detect
damage caused by corrosion on civil infrastructure. This
sensor is both novel and timely as damage due to corrosion
has been estimated to cost over $650 billion annually in
the USA [2,3]. This expense is attributed primarily to the
maintenance of civil infrastructure, replacing parts after
component failure (corrective) or prior to component
failure on a conservative maintenance schedule (pre-
ventative). The proposed sensor by Pan and Huang utilises
a composite film with metallic nanoparticles embedded
within a polydimethylsiloxane (PDMS) matrix. Small
corrosive agents, such as O2 in the atmosphere or corrosive
ions if the structure is immersed in fluid, will diffuse
through the PDMS membrane and interact with the
metallic inclusions. This interaction will induce a change
in the properties of the nanocomposite film, such as
electrical resistivity. Calibration is then necessary to
correlate changes in electrical resistivity and the level of
corrosion of the metallic nanoparticles. As a first step
towards calibration, it is necessary to develop a detailed
understanding of the diffusion rate of small atmospheric
penetrates through bulk PDMS and the mechanisms by
which diffusion occurs. This understanding will be
achieved in this work using molecular dynamics (MD)
simulations with an uncrosslinked PDMS simulation
of small atmospheric molecules will be addressed in a
subsequent work.
It has been previously established that MD simulations
are capable of computing accurate diffusion-related data in
polymers (cf. [4 –12]). For example, Sok et al. [4] analysed
the effect of penetrate size on the diffusion coefficient in
PDMS using a hybrid coarse-grained interatomic potential
and reported very good agreement with experimental
results. Tamai et al. [5] used the same force field as Sok
et al. to evaluate the effect of free volume distribution of
various polymers on the diffusion coefficient. More recent
studies have examined other aspects of diffusion, such as
motion of penetrate molecules in silicone polymers with
different side groups [7], a wider range of molecular
weights of diffusing species [6] and have provided
correlations between diffusion coefficients and the kinetic
molecular diameters of the penetrate species [12].
Typically, an acceptable agreement is found between the
diffusion coefficients calculated using MD and exper-
imental data. This work extends beyond the above
simulation efforts to examine the role of PDMS chain
length (molecular weight) on diffusion and computes the
pre-exponential factors (diffusion constants) and acti-
vation energies explicitly from the diffusion data extracted
from the MD simulation. A linear relationship is observed
between the activation energy and the natural logarithm of
the diffusion constant, in good agreement with exper-
imental observations [13].

*Corresponding author. Email: dspearot@uark.edu

ISSN 0892-7022 print/ISSN 1029-0435 online
q 2011 Taylor & Francis
DOI: 10.1080/08927022.2010.524646
http://www.informaworld.com
116 A. Sudibjo and D.E. Spearot
2. Molecular dynamics
MD is a method of modelling atoms as interacting point
masses in a defined space [14]. The movement of an atom
or united atom is governed by an augmented version of
Newton’s second law of motion. Augmentation is
necessary to align the system with a desired temperature
and pressure, which in this work is achieved using a
Nosé – Hoover style thermostat and barostat, so that the
calculations are performed in the NPT ensemble [15]. The
resolved force on each atom, F k i , is derived from the
potential energy of the system, which is defined via an
interatomic potential,
›UðkrN Þ
ki ¼ 2
F :
›kri
In Equation (1), kri represents the position vector of
atom i while krN represents the positions of all N atoms in
the simulation. For molecular systems, the interatomic
potential, U, is commonly separated into two contri-
butions,
UðkrN Þ ¼ U bonded þ U non-bonded
¼ U bond þ U angle þ U torsion þ U LJ þ U coulombic :
The first contribution is the intramolecular bonded
term, which typically include bond stretch, angle bending
and dihedral angle torsion effects within a polymer chain.
The second contribution is the intramolecular or
intermolecular non-bonded term, which account for van
der Waals and coulombic interactions. Combined, these
two contributions to the potential energy govern the
behaviour of the polymer chains in the system. The total
potential energy is taken as the non-weighted sum of
bonded and non-bonded terms for use in Equation (1).
For computational reasons, a simplifying approach is
commonly employed by combining multiple atoms into a
single point mass. This method of modelling is known as
the united atom model or coarse-grained model. For
PDMS, the most common use of this method is to simplify
the methyl (CH3) side groups while the Si and O atoms are
modelled explicitly, representing a hybrid approach. For
example, both Sok et al. [4] and Frischknecht and Curro
[16] have proposed hybrid coarse-grained interatomic
potentials for PDMS with explicit modelling of Si and O.
The PDMS interatomic potential developed by Sok
et al. was used by several authors to study small molecule
diffusion [4,5]. Sok et al. [4] showed the validity of
measuring diffusion properties using this type of united-
atom model; their results were within an acceptable error
range from the experimental data. They calculated a
diffusion coefficient of 2.1 £ 1025 cm2/s at 300 K, which
is 5% lower than the experimental value [17,18]. In their
model, non-bonded interactions are computed via a
Lennard-Jones (LJ) 12-6 potential. In this work, the
interatomic potential developed by Frischknecht and
Curro [16] is used to model PDMS. This model combines
an explicit atom class II potential for Si and O interactions
while keeping the LJ 12-6 potential for other non-bonded
interactions. The class II potential allows for weaker non-
bonded interactions by employing a 9-6 term rather than
the LJ 12-6 term. A cut-off distance of 12 Å is used for
both 12-6 and 9-6 non-bonded interactions. Both
interatomic potentials include coulombic contributions.
The model by Frischknecht and Curro [16] is used in this
work because it provides a better representation of PDMS
when pressure is considered. The set of equations for the
Frischknecht and Curro PDMS interatomic potential is
ð1Þ
presented in Equations (3) – (8). These equations, in
combination with Equations (1) and (2), are used to
calculate the forces on each atom or united atom in the
simulation. Model parameters are provided in Ref. [16].
U bond ðlÞ ¼ kb ðl 2 l0 Þ2 ; ð3Þ
U angle ðuÞ ¼ ka ðu 2 u0 Þ2 ; ð4Þ
U torsion ðfÞ ¼ kt ½1 þ cosðnfÞ
; ð5Þ
ð2Þ 

sab 12
sab 6
U LJ ðrÞ ¼ 41ab 2 ;
r r ð6Þ
when a or b ¼ CH3 ;


sab 9
sab 6
U II ðrÞ ¼ 1ab 2 23 ;
r r ð7Þ
when a and b ¼ Si and O;
qa qb
U coulombic ðrÞ ¼ : ð8Þ
4p 10 r
A harmonic form is used for bond length and bending
angle interactions, with bond spring stiffness kb and angle
spring stiffness ka . The equilibrium bond length between
two atoms and angle between a set of three atoms is l0 and
u0 , respectively. Torsional interactions are accounted for
using a periodically repeating cosine function with
stiffness kt and period n, respectively. Pair interactions
within the siloxane backbone use a soft 9-6 form to better
capture the flexibility of the PDMS chain while all other
pair interactions use a more standard LJ 12-6 form to
model non-bonded effects. The parameters sab and 1ab
define, respectively, the shape and strength of the non-
bonded interaction in each case. Penetrates in this work
(N2, O2 and CH4) are also modelled using a coarse-grained
approach [4]. van der Waals interactions between the
penetrates and atoms within the PDMS chain are modelled
using the LJ 12-6 form using the Berthelot mixing rules for
cross-interactions.

3. Simulation methodology
3.1 Model construction
The repeating unit of PDMS includes an Si – O segment of
the chain backbone with two CH3 groups attached to each
Si atom, CH3 ½SiðCH3 Þ2 O
n SiðCH3 Þ3 . Experimentally,
chain lengths vary within a given sample; however, for
simplicity in this work, the construction of PDMS will
consider only chains of uniform length. To study the effect
of chain entanglement, two different sets of chain lengths
will be considered. The short-chain systems will consist of
chains with mass well below the entanglement molecular
weight of 24,500 g/mol [19], while the long-chain systems
will consist of chains with mass above the entanglement
molecular weight. The short-chain systems are composed
of n ¼ 10 repeating units with system sizes of 50, 100 and
150 chains. The long-chain system are composed of
n ¼ 339 repeating units each with system sizes of 10 and
20 chains. Cross-linking between molecular chains is not
considered in this work. For each diffusing species (N2, O2
and CH4), 100 united atoms are used as the penetrate. By
keeping the number of penetrates constant, changing
system size (number and/or length of PDMS chains)
allows for the analysis of penetrate concentration on
diffusion. Finally, for each system size, three independent
simulations are performed with different initial random
constructions of the molecular chains. Data presented are
averages of three simulation runs, unless otherwise stated
in the discussion.
To create the initial configuration for the PDMS
chains, a self-avoiding random walk algorithm is used.
First, a simulation cell much larger than that necessary for
the number of chains to be created is divided into a 3D grid
with 1 Å spacing. A point is randomly selected on the grid
for the initial Si atom in the chain backbone. Adjacent
points to the initial point are stored in an array and one of
those points is chosen randomly. The chosen point is
checked for occupancy and if it is empty, that point is
added as the next point in the chain with appropriate
chemical distinction. If the point is occupied, then another
point is chosen randomly from the array. This process
continues until the entire backbone of the chain is
constructed and is then repeated to add CH3 united-atom
side groups on the Si atoms within the chain backbone.
The entire process is repeated for each chain to be placed
in the simulation cell. The resulting initial configuration
will start in a very high-energy state due to an incorrect
conformational structure with 908 bond angles. Equili-
bration procedures are performed to allow the chains to
move into a more appropriate conformational state.
After an initial random distribution of molecular
chains is created, the system, undergoes an NPT
equilibration run at 300 K for 1 ns. During this run and
all subsequent runs, the system pressure is maintained at
1 atm using a Nosé –Hoover style barostat as described by
Molecular Simulation 117
Melchionna et al. [15]. This equilibration step allows the
chains to relax into a more appropriate conformation while
the entire system contracts to its equilibrium density. After
this initial run, the temperature of the system is gradually
changed to the desired temperature for the diffusion
simulation over 100 ps; simulations of diffusion are
performed at temperatures between 225 and 400 K in
this work. Once the system reaches the desired
temperature, an additional NPT run is done for 100 ps to
allow the system to reach equilibrium density at the new
temperature. Penetrates are then introduced at random in
the system at the current system temperature. Since
penetrates are distributed randomly, another NPT run is
done for 500 ps to allow the penetrates to diffuse evenly
throughout the system, before diffusion-related data are
extracted. Finally, an NPT production run is done for
100 ps and data are recorded during this simulation.
3.2 Model validation
Two methods are used to validate the initial conformation
of the PDMS chains prior to computing diffusion-related
data. First, density is computed using the classical
definition of mass per unit volume and compared with
experimental measurements (0.97 g/cm3 [20]). Second, the
radius of gyration of the PDMS chains is computed using
the root mean-squared distance from each atom to the
centre of mass of the system,
D E
1X
R2g ¼ mi ðkri 2 krcm Þ2 : ð9Þ
M i
In Equation (9), M is the total molecular weight of the
system, mi is the mass of an individual atom or united atom
and krcm is the position of the centre of mass of the system.
This value is used to determine the size of the molecular
chains, normalised by the molecular mass. A high value of
radius of gyration indicates linear or ‘stretched-out’
chains, while a low value indicates chains that are
‘bunched-up’ in a localised mass. The experimental value
for the normalised radius of gyration of PDMS is reported
to be (7.7 ^ 0.3) £ 1022 Å2·mol/g [21,22].
The densities of each size model considered in this
work with different initial constructions are evaluated to
ascertain the statistical error range of the equilibration
method; results are shown in Figure 1. The statistical error
margin of this equilibration method is found to be around
2%, with respect to the experimental density [20], which is
an acceptable range. Radius of gyration values are also
evaluated and compared to experimental results as shown
in Figure 2. The radius of gyration is clearly dependent on
the number of chains included in the simulation (system
size). Regardless, it is found that the calculation of
the diffusion coefficient for each material system is not
118 A. Sudibjo and D.E. Spearot

1.6 penetrates (diffusing species) [4],

50 short chains
1.4 100 short chains
150 short chains 1 d 2 1d
10 long chains D¼ kr ðtÞl ¼ k½rðtÞ 2 rð0Þ
2 l: ð11Þ
1.2 20 long chains 2y dt 6 dt
Experiment
Density (g/cm3)

1.0
0.8
0.6
0.4
0.2
0.0
0 200 400
Time (ps)
Figure 1. Density evolution during equilibration at 300 K with
comparison to experimental data from [20].
influenced appreciably by variations in the radius of
gyration within the range presented in Figure 2.
3.3 Computing diffusion coefficients
The classical definition of steady-state diffusion is
provided by Fick’s first law,
kj ¼ 2D7c;
where kj, the flux of the diffusing species, is proportional
to the negative gradient of the concentration of that species,
c. The constant of proportionality, D, is known as
the diffusion coefficient. The diffusion coefficient describes
the rate of motion of particles in the concentration of that
species. Within MD simulations, the diffusion coefficient
can be computed using several methods. The most common
method is to compute the mean-squared displacement of the
Equation (11) is derived by combining Equation (10)
with a statement of conservation of mass of the diffusing
species in the system. In Equation (11), kr 2(t)l is the mean-
squared displacement of the diffusing species and y is the
dimensionality of the system. With the assumption that
the examined temperature range is sufficiently narrow,
the temperature dependence of the diffusion coefficient
600 800 1000
can be captured via an Arrhenius relation,
 
Q
D ¼ D0 exp 2 ; ð12Þ
RT
where D0 is the diffusion constant, Q is the activation energy,
R is the gas constant and T is the temperature. As discussed
above, MD simulations in the work are performed three times
at different temperatures ranging from 225 to 400 K and thus
multiple values of D are computed. By fitting an exponential
curve to the data (in appropriate format), the values of D0 and
Q can be extracted.
4. Results and discussion
ð10Þ 4.1 Short-chain models
Mean-squared displacement data are plotted along with
least-squared linear fits for every combination of diffusing
species, system size and temperature; an example of such
data is shown in Figure 3 for the case of 100 PDMS chains
with 100 CH4 penetrates. As expected, the observed
diffusion flux increases as temperature increases, for each
species studied. Diffusion coefficients are calculated from
MD using Equation (11) and are listed in Table 1 for all
short-chain simulation models for each penetrate type at

1000
2.0 225K
250K
50 short chains
275K
100 short chains 800 300K
150 short chains 325K
10 long chains 350K
1.5
<[r(t) - r(0)]2> (Å2)

20 long chains 375K

<Rg2> / M (Å -mol / g)

Experiment 600 400K

Least-square fits
2

1.0
400

0.5 200

0
0.0 0 20 40 60 80 100
0 200 400 600 800 1000 Time (ps)
Time (ps)
Figure 3. Mean-squared displacement vs. time for one
Figure 2. Radius of gyration evolution during equilibration at configuration of 100 short PDMS chains with 100 CH4
300 K with comparison to experimental data from [21,22]. penetrates at varying temperatures with least-squared fits.
 Molecular Simulation 119

Table 1. Calculated diffusion coefficients at 300 K with the standard deviation obtained from different initial conformations compared
with experimental results at 308 K.

Number of chains (penetrate weight %) Diffusing species Dcalc Standard deviation Dexp [17,18]
50 (3.83%) CH4 5.127 ^0.1986
100 (1.95%) CH4 3.960 ^0.4881 2.2 ^ 0.2
150 (1.31%) CH4 3.509 ^0.2046
50 (6.50%) N2 5.725 ^0.1629
100 (3.36%) N2 5.008 ^0.3675
150 (2.27%) N2 3.507 ^0.3116 3.9
10a (1.13%) N2 2.257 ^0.2424
20a (0.57%) N2 2.187 ^0.2271
50 (7.36%) O2 5.632 ^0.0878
100 (3.82%) O2 4.340 ^0.7604
150 (2.58%) O2 3.689 ^0.3764 4.1
10a (1.29%) O2 2.115 ^0.2815
20a (0.65%) O2 2.337 ^0.2362
a
Units for all diffusion coefficients are 1025 cm2/s. Long-chain systems.

300 K. In Figure 4, the computed diffusion coefficients for
100 PDMS chains with 100 CH4 penetrates are plotted as a
function of inverse temperature; data from all three
simulations are shown at each temperature (labelled as
1 –3) to illustrate the spread in the data due to statistical
variation in the initial PDMS chain and penetrate
distributions. Equation (12) is fitted to the calculated
diffusion coefficients at each temperature to extract values
for D0 and Q. Note that the gas constant R is included in
the calculation of D0 and Q, even though data are not
plotted as a function of 1/RT in Figure 4.
4.2 Long-chain models
The long-chain system is composed of chains with
individual length greater than the entanglement molecular
weight. At this length, the system exhibits significantly
increased viscosity due to the presence of entanglements
and reduced chain self-diffusion. Understanding the
behaviour in this highly viscous phase provides a stepping
2.1e-4
1.8e-4
1.5e-4
stone to understanding the behaviour of PDMS in a
rubbery solid state after cross-linking is introduced. For
the long-chain simulations, system sizes of 10 and 20
chains are tested. An example of diffusion in a long-chain
system can be seen in Figure 5 for a case of 10 long PDMS
chains with 100 N2 penetrates. Figure 6 shows the
temperature dependence of the diffusion coefficient with
Arrhenius fits for all three initial distributions; data at
300 K are presented in Table 1. In comparison to Figures 3
and 4, it is clear that the calculated diffusion coefficients
for the long-chain simulation models are lower than that of
the short-chain models for all temperatures studied. This
difference can be attributed to the chains in the system
being entangled due to their length, thereby confining the
movement of penetrates and restricting potential diffusion
jumps in the system. A direct comparison between short-
chain and long-chain systems is presented in Figures 7 and
8 for N2 and O2 penetrates for each simulation model.
600
225K
100 short CH41 250K
100 short CH42 500 275K
100 short CH43 300K
325K
100 short CH4fit 1
400 350K
<[r(t) - r(0)]2> (Å2)

100 short CH4fit 2 375K

100 short CH4fit 3 400K
D (cm2/s)

1.2e-4 Least-square fits

300
9.0e-5

200
6.0e-5

3.0e-5 100

0.0 0
0.0020 0.0025 0.0030 0.0035 0.0040 0.0045 0.0050 0 20 40 60 80 100
–1
1/T (K ) Time (ps)

Figure 4. Diffusion coefficient as a function of temperature Figure 5. Mean-squared displacement vs. time for one
with Arrhenius fits for three different initial configurations of 100 configuration of 10 long PDMS chains with 100 N2 penetrates
short PDMS chains and 100 CH4 penetrates. at varying temperatures with least-squared fits.
120 A. Sudibjo and D.E. Spearot

1.2e-4 5. Discussion
10 long N21
10 long N22 In comparison with prior MD simulation efforts which
1.0e-4 10 long N23
10 long N2 avg
employed PDMS models with chain lengths below the
8.0e-5
10 long N2 avg fit entanglement molecular weight [4 – 11], the diffusion
coefficients computed at 300 K in this work are slightly
D (cm2/s)

6.0e-5 higher than those previously reported. Discrepancies

between diffusion coefficients can be attributed to
4.0e-5 differences in the molecular weight of the simulation
models, differences in concentration of the penetrate
2.0e-5
species and differences in the way that pressure is (or is not
0.0
in the case of NVT) controlled during the MD simulation.
0.0020 0.0025 0.0030 0.0035 0.0040 0.0045 0.0050 Previous MD studies of diffusion of CH4 in PDMS
–1
1/T (K ) have yielded a diffusion coefficient of 0.57 £ 1025 cm2/s
by Tamai et al. [5] and 2.1(^ 0.8) £ 1025 cm2/s by Sok
Figure 6. Diffusion coefficient as a function of temperature
with Arrhenius fits for three different initial configurations of 10 et al. [4]. Both Sok et al. and Tamai et al. used a system
long PDMS chains and 100 N2 penetrates. size of five PDMS chains with n ¼ 30 and one penetrate
molecule. The longer chain length (than the short-chain
models in this work) reduces the ability of the penetrate
molecule to diffuse through the system, because the local
mobility of the PDMS chains is constrained [13]. Previous
3.0e-4
50 short N2 avg
MD studies of N2 diffusion through PDMS have reported a
2.5e-4
100 short N2 avg diffusion coefficient of 3.74 £ 1025 cm2/s by Jawalkar and
150 short N2 avg
10 long N2 avg
Aminabhavi [9] and 1.2 £ 1025 cm2/s by Charati and Stern
2.0e-4 20 long N2 avg [7]. The studies by Jawalkar and Aminabhavi, and Charati
50 short N2 avg fit
and Stern also reported diffusion coefficient values for O2
D (cm2/s)

100 short N2 avg fit

1.5e-4 150 short N2 avg fit of 3.7 £ 1025 and 1.8 £ 1025 cm2/s, respectively. Here,
10 long N2 avg fit
20 long N2 avg fit discrepancies can be attributed to the system size and
1.0e-4 penetrate concentration. Jawalkar and Aminabhavi used a
unit cell of 15 Å width and Charati and Stern used a unit
5.0e-5
cell of 22 Å width with eight PDMS chains and four
0.0
penetrate molecules. The higher penetrate concentration
0.0020 0.0025 0.0030 0.0035 0.0040 0.0045 0.0050 used in this work may provide a higher driving force for
1/T (K–1) diffusion leading to increased diffusion rates [23]; this is
Figure 7. Comparison between short-chain and long-chain
evident in this work from data presented in Table 1.
systems with 100 N2 penetrates. Finally, most of the previous studies of MD diffusion have
used the canonical NVT ensemble, with the exception of
Sok et al. [4] who used the NPT ensemble. In the NVT
ensemble, the volume and temperature of the system are
held constant and thus there is no guarantee that the system
3.0e-4
pressure is consistent between this work and previous
50 short O2 avg
2.5e-4
100 short O2 avg efforts, making direct quantitative comparison
150 short O2 avg challenging.
10 long O2 avg
2.0e-4 20 long O2 avg In agreement with the experiment, the MD simulation
50 short O2 avg fit
results in this study show that CH4, N2 and O2 exhibit only
D (cm2/s)

100 short O2 avg fit

1.5e-4 150 short O2 avg fit minor differences in diffusion characteristics, as shown in
10 long O2 avg fit
20 long O2 avg fit Table 1. This is true for the diffusion of comparatively
1.0e-4
sized small molecules in highly permeable polymers
5.0e-5
[13,17]. To quantitatively illustrate the accuracy of the MD
simulations in this work in comparison with experiment,
0.0 activation energies and diffusion constants are computed
0.0020 0.0025 0.0030 0.0035 0.0040 0.0045 0.0050
–1
for every combination of system size and diffusing species
1/T (K )
using Equation (12). For amorphous rubbery polymers,
Figure 8. Comparison between short-chain and long-chain a linear relationship has been observed experimentally
systems with 100 O2 penetrates. between the natural logarithm of the diffusion constant and

–4
N2 penetrates
–6
O2 penetrates
CH4 penetrates
–8
Stem et al. [24]
Zheng et al. [13]
–10 Current work
In(Do) (m2/s)
–12
–14
–16
–18
–20
5000 10000 15000 20000
Q (J/mol)
Figure 9. Correlation between the natural logarithm of the
diffusion constant and the activation energy for diffusion
showing good agreement with experimentally observed linear
relationship [13] and experimental data [24].
the activation energy, known as the ‘compensation effect’
[13]. This relationship has been used historically to relate
experimental data for the diffusion of different penetrates
in the same polymer or for the same penetrate with
different polymers (with the same rubbery or glassy
characteristics), implying a universal relationship between
the diffusion constant and the activation energy. Figure 9
shows that the MD simulations in this work capture
this linear trend and provide the relationship,
ln D0 ¼ 219:0428 þ 0:3821 £ 1023 Q. By comparison,
for small molecule diffusion (which includes O2, N2 and
CH4) through PDMS Zheng et al. [13] proposed, ln D0 ¼
218:2673 þ 0:2740 £ 1023 Q to describe a range of
amorphous rubbery polymers; this linear relationship
is shown for comparison in Figure 9. Also included in
Figure 9 are experimental data for diffusion of CO2, CH4
and C3H8 through PDMS from Stern et al. [24].
6. Conclusions
In this work, MD simulations are used to compute the
diffusion coefficient, diffusion constant and activation
energy for CH4, N2 and O2 penetrates in uncrosslinked
PDMS. The chain length of PDMS is varied to study the
effect of chain entanglements on diffusion. Diffusion
coefficients are calculated using the mean-squared
displacement method. Diffusion coefficients computed in
this work for short-chain models are higher than previous
MD diffusion studies. The differences are attributed to the
molecular weight of the chains, the physical size of the
system which impacts the concentration of the diffusing
species and differences in equilibration procedures.
Comparison of diffusion coefficients between short-chain
and long-chain systems shows a decrease in the diffusion
coefficients as the chain length is increased. This trend is
due to entanglements in the long-chain system which
Molecular Simulation 121
confine the local motion of the PDMS chains and reduce
the number of available diffusion jumps for the penetrates.
In a unique contribution in this work, activation
energies and diffusion constants are calculated from MD
using an Arrhenius relation to characterise the relationship
between the diffusion coefficient and temperature. A linear
trend is identified between the natural logarithm of the
diffusion constant and the activation energy, in good
agreement with the proposed phenomenological relation-
ship of Zheng et al. [13]. This provides quantitative
indication of the accuracy of the MD simulations
presented in this work. Future studies will analyse
25000 diffusion characteristics in a nanocomposite system
composed of a PDMS matrix and metallic nanoparticle
inclusions to align the simulations with experiments aimed
at corrosion sensor development. Cross-linking agents will
also be considered in future studies to evaluate their effect
on diffusion. It is also recognised that thin film properties
of polymers will vary from bulk properties [25 – 28]. As
such, future studies will also consider surface reconstruc-
tion and segregation to advance the development of the
corrosion sensor.
Acknowledgements
This work was supported by the National Science Foundation
under Grant No. CMMI#0800718 with additional support
provided by the University of Arkansas. MD simulations were
performed on the Star of Arkansas provided in part by the
National Science Foundation under Grant No. MRI#072265.
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