Proceedings of the ASME 2015 International Mechanical Engineering Congress and Exposition

IMECE2015
November 13-19, 2015, Houston, Texas

IMECE2015-53602

MECHANICAL PROPERTIES OF SILANE TREATED GLASS NANOFIBER-EPOXY

RESIN INTERPHASE USING MOLECULAR DYNAMICS SIMULATION

Vinod B. Suryawanshi Mahdi Ghazizadeh

Research Scholar, Joint School of Nanoscience Research Scholar, Joint School of Nanoscience
and Nanoengineering, and Nanoengineering,
Greensboro, North Carolina, USA Greensboro, North Carolina, USA
vbsuryaw@aggies.ncat.edu mgaziza@aggies.ncat.edu

Ajit D. Kelkar
Professor and Chairman, Nanoengineering,
Joint School of Nanoscience and Nanoengineering,
Greensboro, North Carolina, USA
kelkar@ncat.edu

ABSTRACT
Fiber/matrix interphase in composite materials plays an
important role on its structural performance. However, structure
and properties of this region are not completely known, due to
lack of understanding of the processes occurring at
atomic/molecular level during formation of interphase and
comprehensive experimental methods for characterization of
interphase. In addition, most of the currently used experimental
techniques are available for micron size fibers and are not
sufficient to characterize the nanofiber/matrix interphase.
Recently, molecular dynamics simulations have shown
promising results in obtaining the mechanical properties of
fiber reinforced polymer composites. The objective of this
study is to determine the mechanical properties of silane treated
glass nanofibers and epoxy resin interphase using molecular
dynamics simulations. To simulate the interphase (blend of
sizing/coupling agent and matrix), atomistic models of blend of
silane coupling agent (3-aminopropyl) triethoxysilane (APTES)
and cross linked epoxy 862 resin system are developed.
Mechanical properties of the interphase are predicted for
different weight fractions of silane using molecular dynamics
simulation.
Keywords: Composite, Interphase, Molecular Dynamics,
Mechanical Properties
INTRODUCTION
In the past decade, the use of fiber reinforced composites
(FRCs) as structural materials in variety of applications such as
aerospace, automotive, sport goods and wind turbine has
increased significantly mainly due to their superior properties
such as light weight, high strength and flexibility in design [1-
5]. FRCs consists of two major components: fibers such as
carbon, glass and aramid, and polymeric matrix. In typical FRC
structure, fiber acts as primary component for carrying the load
while matrix is responsible for protecting the fibers from
surrounding environment and more importantly, transferring the
load to the fibers. In order to achieve effective load transfer,
fiber and matrix interphase must possess very good
compatibility and bonding at atomic scale. Lack of bridging
between matrix molecules and fiber can result in premature
failure of the structural composites under various loading
conditions.
While, different techniques can be used to improve the
adhesion between fiber and matrix, introducing coupling agents
compatible with both fiber and matrix is considered one of the
most effective approaches [6-9]. Commercially, other
components such as film formers and surfactants are added to
coupling agents leading to the mixture popularly known as
‘sizing’. The interaction of coupling agents/sizing with
surrounding matrix during manufacture of composite material
leads to formation of a distinct region between fiber and matrix,
popularly known as ‘interphase’. Although, many researchers
have studied the effect of interphase on bulk performance of
FRCs, little work has been done on understanding the structure
and properties of interphase [16].
Among different theories proposed to explain the
formation of interphase, chemical bonding and inter diffusion
are considered to be most agreed upon [10]. The structure of
interphase based on these two mechanisms is modeled as two
distinct regions namely chemically bonded interface and

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 diffused interface or interpenetrating network (IPN) [11].
Figure 1 shows the structure of interphase for silane treated
glass fiber reinforced composite. Chemically bonded interface
is formed due to covalent bonding between the fiber and
coupling agent (functional group), while physisorbed interphase
(or IPN) is formed due to diffusion of sizing/coupling agent in
matrix.
Fig. 1: Structure of interphase [11]
Conventional experimental techniques for characterization
of interphase include micromechanical tests (fiber pull out,
fiber fragmentation test, fiber fragmentation test etc.) [12],
indentation tests (micro and nano) [13] and ‘model interphase’
method [14-16]. Among these techniques, micromechanical
tests and indentations tests are more accurate however not
suited for nanofiber interphase. ‘Model interphase’ approach
can be used for nanoscale fiber. This approach involves
synthesis of interphase material which has similar composition
as that of the material found at the interphase. The mechanical
characterization of this laboratory synthesized material is then
carried out to obtain its properties. A brief review of literature
for this approach is presented.
Al-Moussawi et al. [14] synthesized model interphase as
blends of sizing or silane coupling agents, and matrix. Three
different silanes and a commercial glass fiber sizing, and two
epoxy resins were separately blended. The results indicated that
mechanical properties of these blends were substantially
different than those of bulk matrix. Tangolu et al. [15] used
nuclear magnetic resonance (NMR) technique to obtain the
composition of the sizing bound to the glass fibers. The sizing
material was then synthesized in laboratory based on this
composition information. The laboratory synthesized sizing
was blended with epoxy/amine resins to make the test coupons
for dynamic mechanical analysis (DMA). In another study,
epoxy-silane IPN was synthesized by diffusion of epoxy resin
and curing agent into particles of condensed and cross-linked
silane [16]. This IPN composition was chosen to simulate the
typical properties of a silane modified interphase found in glass
reinforced composites.
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Although experimental methods for measuring properties
of interphase have been successful to some extent, challenges
and lack of a comprehensively accepted approach motivates
researches to explore new options [13]. Additionally, while
much of the research work involving the development of new
sizing and treatments has relied on experimental methods, it is
clear that numerical modeling has a potentially large role to
play in guiding the development of these sizing and treatments
[17].
During recent years, molecular dynamics (MD) has been
successfully used to predict the properties of material
interfaces. Lau et al. [18] predicted intrinsic strength of epoxy
silica interface at molecular level. The predicted strength was
then used to study the global interface behavior by
incorporating MD results into finite element model. Zhang et
al. [19] performed parametric study of interfacial behavior of
carbon nanotube polyethelene interface. In another study,
Mohan et al. [20] used MD simulations to study the interface
behavior of functionalized and non-functionalized alumina, it
was observed that silane-alumina and epoxy interface possesses
higher interfacial adhesion as compared to alumina-epoxy
interface. These findings helped them to explain improved
fracture toughness (due to improved interfacial adhesion)
during experiments in silane treated alumina reinforced
composite specimen compared to non-functionalized specimen.
This paper presents the results of computational
experiments which are performed using MD simulations to
predict the interphase properties. Objective of MD simulations
is to build atomistic model of physically absorbed interphase or
IPN to predict the properties of silane treated glass nanofiber
and epoxy interphase.
SIMULATION DETAILS
To obtain the properties of IPN or diffused interphase
region, atomistic model of silane diffused in epoxy resin is
developed using Materials Studio package commercially
offered by Accelrys Inc. The IPN model consists of different
weight fractions of (3-Aminopropyl) triethoxy silane (APTES)
molecules and cross linked epoxy 862 resin system (which is a
two part thermoset composed of Epon 862 and hardener
DETDA). During experimental work, most researchers [15, 16]
have used silane in condensed form to synthesize model
interphase, while, few researchers [14] have used its non-
condensed form. Since, silane undergoes hydrolysis and
condensation during surface treatment of glass fibers,
condensed silane is more accurate representation of
physiabsorbed silane. However, synthesis of model interphase
material with noncondensed silane is easier which can expedite
experimental validation of MD simulation results. In the
present work, IPN atomistic models are created using both,
condensed and non-condensed silane.
In the first step, atomistic models of (3-aminopropyl)
triethoxy silane (APTES), condensed APTES, bisphenol-F
epoxy resin (Epon 862) and diethyltoluenediamine (DETDA)
curing agent are created. The structure of condensed form of
silane, is the structure of silane after hydrolysis and
 condensation [21]. The condensed silane used in this study is
nothing but a silane oligomer formed from polymerization of
eight silane monomers. Atomistic models of silane and silane
oligomer are shown in Fig. 1 and Fig. 2 respectively. To build
the cross linked epoxy model, eight molecules of Epon 862 and
four molecules of curing agent DETDA were bonded to
represent cross linked thermoset structure, which is called unit
cell (Fig. 3). The ratio used (8 Epon and 4 DETDA molecules)
is based on manufacturer’s recommendation in order to obtain
cured polymer with optimal performance. Finally, interphase
models are created by assembling six epoxy unit cells and
varying numbers of silane or silane oligomer molecules in the
periodic box.
Fig. 1: Atomistic model of silane
Fig.2: Atomistic model of condensed silane oligomer
Three atomistic models for each case namely non-
condensed (hereafter will be called as silane models) and
condensed silane (hereafter will be called silane oligomer
models) are prepared. The silane models has silane weight
fractions of 0.12, 0.15 and 0.21 corresponding to the 12,16 and
24 number of silane molecules respectively. While the silane
oligomer models has weight fractions of 0.11 (2 oligomers),
0.16 (3 oligomer), 0.2 (4 oligomer) and 0.24 (5 oligomer)
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weight fractions corresponding to 2, 3 and 4 number of silane
oligomers. The range of weight fractions of silane/silane
oligomers selected in the present study has been reported as
possible weight fractions of sizing in the interphase [14].
Additionally, a model with just epoxy resin with hardener was
created as the reference model for comparison purpose.
Fig.3: Epoxy unit cell
To perform the simulations, COMPASS (Condensed-phase
Optimized Molecular Potentials for Atomistic Simulation
Studies) force field is chosen due to its ability in providing
reliable predicting behavior of Epoxy 862 resin system [22-23].
All the atomistic models are subjected to energy minimization
for 50,000 steps followed by NPT simulation at 600 K and
target pressure of 1.025x105 pa for 100 ps with time step of 1
fs. Elevated temperature of 600K is chosen to achieve two
goals; first, increasing the molecular mobility of the structures
in order to reduce the computational time required for reaching
to experimental density. Second, the curing process of resin
requires heating at relatively high temperature resulting better
imitation of experimental process. Therefore, the structures
were subjected to NPT simulation at 600 K to allow the
formation of a stable IPN (by continuing the simulation until
the system has reached its equilibrium). After that, NPT
simulation at 298 K and target pressure of 1.025x105 pa was
performed with time step of 1 fs for 100 ps which is twice more
that the time required for the system to reach its equilibrium
state. The equilibrated system was then used to obtain
mechanical properties. In Material Studio software, elastic
constants are calculated using equation (1)
1 𝜕2 𝑈
𝐶𝑖𝑗 = (1)
𝑉 𝜕𝜀𝑖 𝜕𝜀𝑗
where,
Cij is elastic stiffness matrix, εi, εj are lattice strain components,
U is potential energy, and V is simulation cell volume.
 Using, stiffness matrix, compliance matrix, Sij (Inverse of Cij) is resin interphase is stiffer than matrix [13]. Also, they found that
obtained. The three elastic constants Ex, Ey, and Ez are obtained stiffness of the interphase increases with silane concentration
from compliance matrix using equation (2) and the shear during the treatment. Additionally, upcoming techniques such
modulus is obtained using Reuss, Voigt and Hill Method [24]. as ‘phase imaging’ have also reported the interphase of silane
treated e-glass fiber and epoxy resin to be stiffer than the matrix
[26]. To conclude, since nanoindentation and ‘phase imaging’
−1 −1 −1
𝐸𝑥 = 𝑆11 , 𝐸𝑦 = 𝑆22 , 𝐸𝑧 = 𝑆33 (2) are in-situ techniques, the results from these methods can be
considered more accurate as compared to ex-situ technique
such as ‘model interphase’.
RESULTS AND DISCUSSION
Computational experiments were performed as per the
steps mentioned in earlier section. In order to make sure that all
structures after NPT at 298 K are at equilibrium state, for test
purpose additional NPT run at 298 K was performed. It is
observed that after first 50 ps, during the first NPT run the
density starts to fluctuate around a specific number. The
average density at last 50 ps of first run is 1.034 g/cc while the
average density for the second NPT run at 298 K is 1.035 g/cc.
This result demonstrates that the first 100 ps of NPT at 298 K
is, both efficient and reliable, therefore all other models were
subjected only to 100 ps of NPT at room temperature. Figure 4
shows the density changes in Epoxy 862 model during NPT
simulation at 298 K for first 100 ps. Once the density of model
was reached to its steady state, mechanical properties Fig. 5: Young’s Modulus for silane models
calculations were performed. The results of the mechanical
properties namely Young’s modulus and shear modulus for
silane models are presented in Fig. 6 and Fig. 7 respectively.
While, the results for silane oligomer models are shown in Fig.
8 and Fig. 9. Since, macroscopic silane epoxy IPN can be
considered as an isotropic system, a small variation in three
Young’s modulii Ex, Ey, and Ez observed in simulation results
was neglected and simulation cell was assumed as isotropic.

Fig. 6: Shear Modulus for silane models

Fig 4: Density variation during NPT simulation at 298K for Epoxy

862 model

In the literature, contrasting results have been reported for

stiffness of interphase in comparison with matrix; and whether
the interphase is stiffer than the surrounding matrix material is
not known [13]. Researchers using ‘model interphase’ Fig. 7: Young’s Modulus for silane oligomer models
technique in most cases have reported softer interphase [15-16,
25]. However, interphase characterized using nanoindentation
have observed that silane treated glass fiber and vinyl ester

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 Fig. 8: Shear Modulus for silane oligomer models

Simulation results for Young’s modulus in Fig. 5 and Fig.

7 show that the interphase is predicted for silane model is softer
while one with silane oligomer model as stiffer than the matrix.
This can be explained with atomistic models in Fig. 9 and Fig.
10. Fig. 9 shows that epoxy and silane (shown by blue color)
are phase separated. Here, lack of synergy between the two
constituents may be attributed to softer interphase. Whereas, in
Fig. 10, silane oligomers (blue color) are interpenetrating the Fig. 9: Final structure for 24 silane molecules model
epoxy matrix and causing the entanglement with epoxy chain
causing increase in stiffness. It may be noted that, entanglement
of silane and matrix polymer has been reported as one of the
mechanism responsible for formation of interphase [11]. Higher
stiffness of IPN in oligomer models similar to experimental
results by nanoindentation [13] and mechanism of polymer
chains entanglement observed during simulation suggests that
condensed silane gives better approximation of the material at
the fiber surface responsible for formation of IPN. Finally, the
results of shear modulus for silane model are similar to Young’s
modulus and similar explanation may be valid, while for the
silane oligomer models there is a mix trend and hence difficult
to draw any conclusions and need further investigation.

CONCLUSION
Moecular Dynamics simulation for silane-epoxy IPN has
been carried out to predict the mechancal properties at different
weight fractions of silane in epoxy resin. It is observed that,
MD simulations can help to understand molecular level
mechanisms such as polymer chain entanglement occuring
during formation of interphase. In addition, computational
experiments can help to tailor the interphases to achieve the
optimal performance of the composite materials
Fig. 10: Final structure for 5 silane oligomer model

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