Journal of the Mechanical Behavior of Biomedical Materials 75 (2017) 529–537

Contents lists available at ScienceDirect

Journal of the Mechanical Behavior of

Biomedical Materials
journal homepage: www.elsevier.com/locate/jmbbm

Investigating the properties and interaction mechanism of nano-silica in T

polyvinyl alcohol/polyacrylamide blends at an atomic level
⁎ ⁎
Qinghua Weia,b, Yanen Wanga, , Shuzhi Wanga, Yingfeng Zhanga, Xiongbiao Chenb,
a
Department of Industry Engineering, College of Mechanical Engineering, Northwestern Polytechnical University, Xi'an 710072, PR China
b
Department of Mechanical Engineering, College of Engineering, University of Saskatchewan, Saskatoon, Canada, S7N5A9

A R T I C L E I N F O A B S T R A C T

Keywords: The nano-silica can be incorporated into polymers for improved mechanical properties. Notably, the interaction
Nano-silica between nano-silica and polymer is of a microscopic phenomenon and thus, hard to observe and study by using
PVA/PAM blends experimental methods. Based on molecular dynamics, this paper presents a study on the properties and the
Nanocomposite interaction mechanism of nano-silica in the polyvinyl alcohol (PVA)/polyacrylamide (PAM) blends at an atomic
Molecular dynamics simulation
level. Specifically, six blends of PVA/PAM with varying concentrations of nano-silica (0–13 wt%) and two in-
Interaction mechanism
terfacial interaction models of polymers on the silica surface were designed and analyzed at an atomic level in
terms of concentration profile, mechanical properties, fractional free volume (FFV), dynamic properties of
polymers and X-ray diffraction patterns. The concentration profile results and micromorphologies of equilibrium
models suggest PAM molecular chains are easier to be adsorbed on the silica surface than PVA molecular chains
in blends. The incorporation of nano-silica into the PVA/PAM blends can increase the blend mechanical prop-
erties, densities, and semicrystalline character. Meanwhile, the FFV and the mobility of polymer chain decrease
with the silica concentration, which agrees with the results of mechanical properties, densities, and semi-
crystalline character. Our results also illustrate that an analysis of binding energies and pair correlation functions
(PCF) allows for the discovery of the interaction mechanism of nano-silica in PVA/PAM blends; and that hy-
drogen bond interactions between polar functional groups of polymer molecular chains and the hydroxyl groups
of the silica surface are involved in adsorption of the polymers on the silica surface, thus affecting the interaction
mechanism of nano-silica in PVA/PAM blend systems.

1. Introduction Sureshkumar, 2014; Wei et al., 2017a) so as to obtain the combined

Polyvinyl alcohol (PVA) is a water-soluble synthetic polymer, which
is commercially available in a form of partial or complete hydrolysis of
poly(vinyl acetate). Due to its hydrophilicity, biodegradability, bio-
compatibility, and high mechanical strength, PVA has been widely used
in potential drug delivery systems and scaffolds for various tissue en-
gineering applications (Anastasia et al., 2016; Morales-Hurtado et al.,
2015; Jiang et al., 2011) PVA, however, has some demerits, such as lack
of biological activity, inability to withstand complex loads, and un-
favorable properties for cell adhesion and growth (Choi et al., 2012),
thus limiting its application to tissue engineering. Polyacrylamide
(PAM) is a type of water-soluble polymer formed from acryl amide
monomers; and its hydrogel possesses favorable characteristics for
tissue engineering, such as three-dimensional network structure, non-
toxic side effects, good biocompatibility and biological activity (Leng
et al., 2011; Suriano et al., 2014; Labarre et al., 2002). Therefore, PAM
has been always used for the modification of PVA (Patel and
advantages of PVA and PAM. Meanwhile, it is noted that due to the
brittleness and poor mechanical properties of PAM, the addition of PAM
can weaken the original mechanical properties of PVA hydrogel (Wei
et al., 2017a; El-Zawawy et al., 2012), which limits the application of
PVA/PAM blends in some tissue engineering application, such as bone
and cartilage repair, where the mechanical property is a critical issue
(Olubamiji et al., 2016; Chen, 2014; Little et al., 2011).
A large number of studies show that adding the nanoparticles into
polymers can significantly improve the mechanical properties (e. g.,
strength, stiffness, elastic modulus) of polymers (Qiao et al., 2016;
Gomez et al., 2016; Zhao et al., 2016). Due to its properties of non-
toxicity, nano-silica has been widely used as an inorganic nanomaterial
to improve the mechanical properties as well as thermodynamic prop-
erties, chemical stability and water resistance (Dil et al., 2016; Zhou
et al., 2016; Griffin et al., 2016). Taheri-Behrooz et al. (Taheri-Behrooz
et al., 2015) investigated the addition of nano-silica in phenolic resin,
with the results illustrating that the resultant Young's modulus and

⁎
Corresponding authors.
E-mail addresses: wangyanen@126.com (Y. Wang), xbc719@mail.usask.ca (X. Chen).

http://dx.doi.org/10.1016/j.jmbbm.2017.08.027
Received 19 July 2017; Received in revised form 18 August 2017; Accepted 22 August 2017
Available online 24 August 2017
1751-6161/ © 2017 Elsevier Ltd. All rights reserved.
Q. Wei et al. Journal of the Mechanical Behavior of Biomedical Materials 75 (2017) 529–537

hardness steadily increased as the weight percent of silica synthesizing nano-silica/polymers composites for various applications.
nanoparticles. Malaki et al. (2016) studied the erosion resistance, ad-
hesive strength, micro-hardness and weathering stability of the acrylic- 2. Materials models and simulation methods
based polyurethane nano-composites and found that they could be re-
inforced with the addition of nano-silica particles. Sowjanya et al. 2.1. Polymer model
(2013) fabricated biocomposite scaffolds from the blends of chitosan,
alginate and nano-silica by using a freeze drying method; and they An appropriate molecular chain length in polymers is critically
found the scaffolds possessed a well-defined porous architecture with important to the model development, thus contributing the accuracy of
pore sizes varying from 20 to 100 µm suitable for cell infiltration and the simulation results. A short molecular chain length may not re-
that the presence of nano-silica in the scaffolds increased the protein present the real polymers appropriately, while a long molecular chain
adsorption and reduced the swelling occurred. Besides, the silica pro- length may lead to difficulties for computer simulations. In the present
cessed in this scaffold also assisted with osteoblast cell proliferation, study, each polymer molecular chain with the same molecular weight
and the collagen fiber network interconnecting the ß-TCP/silica gran- was constructed, so that the results of models in simulations can com-
ules yielded a rigid, fleece-like mold (Wilmowsky et al., 2008; Ghanaati pare with each other. In this study a PVA molecular chain with 50 re-
et al., 2010). peat units and a PAM molecular chain with 31 repeat units were con-
As discussed above, adding nano-silica particles into PVA/PAM structed according to the molecular structural formula (Fig. S1) as per
blend composite can not only improve mechanical properties, but also our previous study (Wei et al., 2016b, 2016c). The all simulation
promote proliferation of cells in blend. These advantages make PVA/ models were constructed by using the Materials Studio software
PAM/nano-silica composite suitable for bone tissue engineering. To this (Accelrys Inc., 2010).
end, the knowledge on the micro properties and interaction mechanism
of nano-silica in PVA/PAM blend is of importance to prepare the PVA/
2.2. Nano-silica model
PAM/nano-silica composites. Notably, the interaction between nano-
silica and polymer is of a microscopic phenomenon and thus, is hard to
The crystal structure of a-quartz (silica, space group P3321) was
observe and study by using experimental methods. As a result, the in-
adopted from the Cambridge Structural Database with the lattice
teraction mechanism of nano-silica in PVA/PAM blend has been rarely
parameters as follows: a = b = 0.491 nm, c = 0.5402 nm, α = β =
investigated and elucidated.
90°, γ = 120°, and its density is 2.648 g/cm3 (Fig. S2a). Considering the
Molecular dynamics (MD) simulations has been illustrated pro-
computer efficiency and the specific surface area, a spherical silica
mising for investigating material properties and interfacial interactions nanoparticle with a radius of 6 Å was constructed, without considera-
of inorganic fillers and polymer matrix in an atomic scale (Lammers tion of surface functionalization or covalent grafting (Fig. S2b). The
et al., 2017; Roussou and Karatasos, 2016; Hagita et al., 2016), thus unsaturated boundary effect was avoided by adding hydrogen atoms to
providing the microscopic information or details of molecular interac- the unsaturated oxygen atoms and hydroxyl groups to the unsaturated
tions inside materials. Base on MD simulations, Lai et al. (2014) in- silicon atoms of the silica particle surface (Fig. S2c).
vestigated the mechanical characteristics of the interfaces between os-
teopontin and hydroxyapatite and they found that the interfacial
2.3. PVA/PAM/silica blend models
mechanical behavior was governed by the electrostatic attraction be-
tween acidic amino acid residues in OPN and calcium in HA. Boulet and
Before constructing the blend models, the PVA chain, PAM chain
Coveney (2004) and Gardebien et al. (2005) also employed the ex-
and the spherical silica nanoparticle were all optimized by using the
perimental and MD methods to study the properties of the montmor-
geometry optimization method (as detailed below), to ensure the en-
illonite polymer nanocomposite, which helped understand different
ergies of the models built were minimized and following the stable
aspects of structures and properties of polymer nanocomposite. Sahu
configurations of PVA, PAM and silica nanoparticle were obtained. To
and Anup (2016) applied MD simulations to investigate the effect of the
eliminate the effects of polymer composition ratio on calculation re-
structural arrangement of reinforcements on the mechanical properties
sults, the amount ratio of PVA and PAM chains in each model was 1:1.
of a nano-composite under transverse loading. In this regard, we have
Furthermore, to purely study the interaction mechanism of nano-silica
also successfully employed MD simulations to investigate the properties
and polymers and prevent any finite size effect of nanocomposites and
of biopolymer blends (Wei et al., 2016a, 2016b, 2017a; Wang et al.,
account for any particle effect at the bulk level, only one silica nano-
2017) and interfacial interaction (Wei et al., 2016c, 2017b).
particle was embedded at the center of the blend unit cell and the
Inspired by the above studies, we employed the MD simulation
periodic boundary condition was used. Thus, all the simulation models
method to investigate into the micro structures and properties of PVA/
used here were constructed under an ideal condition without con-
PAM/nano-silica blend composites, as presented in this paper. We also
sidering the agglomeration of nano-silica, and the blends with different
present the discovery of interaction mechanism between nano-silica
silica contents were constructed by changing the number of polymer
and polymers in blend system from the perspective of molecular in-
chains in the models. In our research, six blend models with different
teraction. This work not only elucidates the reinforcing mechanism of
compositions of PVA/PAM/silica were constructed, and the ratios of
nano-silica in polymeric matrix, but also provides theoretical basis for
molecular number in models were 7/7/0, 7/7/1, 6/6/1, 5/5/1, 4/4/1,

Table 1
Parameters of simulated blend models.

Cell component Weight fraction (wt%) Cell after refinement

PVA PAM Silica Cell length (nm) Density (g/cm3) 2θ (°) d-spacing (nm)

7PVA/7PAM/0silica 50.0 50.0 0.0 3.412 1.295 18.65 0.476

7PVA/7PAM/1silica 47.0 47.0 6.0 3.459 1.317 18.95 0.468
6PVA/6PAM/1silica 46.5 46.5 7.0 3.288 1.329 19.15 0.463
5PVA/5PAM/1silica 45.9 45.9 8.2 3.091 1.350 19.35 0.459
4PVA/4PAM/1silica 45.0 45.0 10.0 2.876 1.368 19.45 0.456
3PVA/3PAM/1silica 43.5 43.5 13.0 2.624 1.397 19.65 0.452

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Q. Wei et al.
Fig. 1. Final equilibrium structures of PVA/PAM blend models with different silica contents. (a) 7PVA/7PAM (0.0 wt% silica content); (b) 7PVA/7PAM/1silica (6.0 wt% silica content);
(c) 6PVA/6PAM/1silica (6.9 wt% silica content); (d) 5PVA/5PAM/1silica (8.2 wt% silica content); (e) 4PVA/4PAM/1silica (10.0 wt% silica content); (f) 3PVA/3PAM/1silica (13.0 wt%
silica content).
3/3/1. To ensure the molecular chains have sufficient space for re-
laxation and to avoid chain winding and overlapping, the initial den-
sities of the blends were all set to 0.3 g/cm3. Table 1 lists the detailed
parameters of all simulated blend amorphous cells at the temperature of
298 K.
2.4. MD simulations
The geometry optimization was conducted on all the initial models
of polymer chain, silica nanoparticle, and blend models prior to their
use in simulations. Geometry optimizations were performed by utilizing
the smart minimization method, the convergence tolerance was applied
using customized quality with an energy convergence of 4.186 ×
10−4 kJ/mol and displacement of 5 × 10−6 nm. The number of
iterations was set as 5000 and the non-bonded van der Waals and
electrostatic interactions were truncated using atom-based at the fine
level of quality were applied for simulations. The energies of the
amorphous cells were minimized by using the smart minimization al-
gorithm to remove unfavorable interactions and attain the lowest en-
ergy state.
All the MD simulations were performed after geometry optimization
and under the COMPASS (Condensed-Phase Optimized Molecular
Potentials for Atomistic Simulation Studies) force field. This force field
is the first ab initio force field based on the Polymer Consistent Force
Field (PCFF) (Sun, 1998), its parameterization and validation have been
done using condensed-phase properties and various ab initio and em-
pirical data of various molecules. Thus this force field can accurately
predict the various properties for a wide range of materials especially
for polymer molecules (Wescott et al., 2006). The MD simulations of
blend amorphous cells involve the following three steps. First, MD si-
mulation was conducted under the NVT ensemble for 100 ps to release
any possible tension; secondly, the MD simulation was performed on
531
Journal of the Mechanical Behavior of Biomedical Materials 75 (2017) 529–537
the equilibrium systems under the NPT ensemble (P = 1 bar) until the
density and energy of the system no longer changed (Fig. S3 shows the
time evolution density profiles during MD simulation under the NPT
ensemble of 6PVA/6PAM/1silica blend model); and last an additional
MD simulation under the NVE ensemble was carried out on the above
systems for 40 ps, and the trajectory frames of the last 30 ps were used
for results analysis. For the single polymer molecular chains and nano-
silica, only the first step of MD simulation above needs to be performed.
All the parameters used of MD simulations were selected as follows.
The Verlet velocity integration method was used with a time step of
1 fs, the Anderson thermostat and barostat (Andersen, 1980) were used
to maintain the temperature and pressure for all NVT and NPT simu-
lations. The non-bonded van der Waals and electrostatic interactions
were truncated using a group based cut off distance of 1.25 nm. The
spline width was 0.1 nm, and the buffer width was 0.05 nm. The co-
ordinates of the system were collected every 500 time steps. Trajectory
frames were captured during the production run, and the data from the
final 30 ps was used for analysis.
2.5. System balance
For a molecular dynamics simulation, an equilibrium calculation
model is of vital importance, which determines the accuracy and re-
liability of the simulation results. Generally, there are mainly two
methods to determine the equilibrium: (1) the temperature equilibrium,
at which the standard deviation is less than 10%; (2) the energy equi-
librium, at which the energy is constant or fluctuates up and down
along the constant value (Gupta et al., 2011). In the present study, all
the results were calculated under the condition of system equilibrium.
As showed in Fig. S4, the temperature and energy of the system (6PVA/
6PAM/1silica) met the above equilibrium standard, indicating that the
system reached equilibrium after the MD simulation.
Q. Wei et al. Journal of the Mechanical Behavior of Biomedical Materials 75 (2017) 529–537

After the MD simulation, the final equilibrium models of PVA/PAM

blends with different silica contents at a temperature of 298 K were
obtained, as shown in Fig. 1 and their final densities were present in
Table 1. To better distinguish the components in blend models, the PVA
molecular chains were represented in green, and the PAM molecular
chains were represented in purple.

2.6. Model development and simulations of the interfacial interaction

To further investigate into the interaction mechanisms of polymer

molecular chains and silica in PVA/PAM/silica blend, here two inter-
facial interaction models of PVA and PAM molecular chains on silica
crystal surface were constructed and simulated. The most re-
presentative silica (110) surface was selected to build the super cell,
whose dimensional parameters were 2.161 × 3.402 × 1.436 nm, α =
β = γ = 90°. Besides, the unsaturated atoms on the surface of silica
super cell were treated by adding hydrogen atoms to the unsaturated
oxygen atoms and hydroxyl groups to the unsaturated silicon atoms. In
each interaction model of polymer/silica, only one molecular chain
built above was contained. A vacuum slab with a thickness of 3 nm was
added to the polymer layer to ensure the polymer chain only interacts
with one side of the silica surface. Geometry optimizations and MD
simulations were conducted on the interaction models once con-
structed. In this section, MD simulation involved two steps: (1) MD
simulation under NVT ensemble for 60 ps at 298 K to obtain the equi-
librium models (Fig. S5). (2) An additional 30 ps MD simulation under
NVE ensemble at 298 K was performed.

3. Results and discussion

Fig. 3. Relative concentration distributions of different components in (a) 7PVA/7PAM
(0.0 wt% silica content) and (b) 7PVA/7PAM/1silica (6.0 wt% silica content) blend
3.1. Concentration distributions of compositions models along Z axis direction.

After reaching equilibrium, an interesting phenomenon can be ob-

served from each equilibrium blend model in Fig. 1. The polymer chains
tend to gather around the nano-silica particle, and relative to the PVA
molecular chains (the green), the probability of PAM molecular chains
(the purple) appearing around the silica nanoparticle is higher. From
the distribution of PVA and PAM molecular chains in blend models
(Fig. 1), the nano-silica particle was almost wrapped by the PAM mo-
lecular chains, and the larger number of polymer chains in blend
system, the more obvious of this phenomenon. To further investigate
density distributions of different components in blends, the blends of
7PVA/7PAM and 7PVA/7PAM/1silica were chosen to analyze the
concentration profile. Fig. 2 shows the concentration profile maps of (a)
the whole nanocomposite, (b) PAM molecules and (c) PVA molecules in
7PVA/7PAM/1silica blend model. And Fig. Fig. 3 show the con-
centration profiles of different components in blend models of (a)
7PVA/7PAM (0.0 wt% silica content) and (b) 7PVA/7PAM/1silica
(6.0 wt% silica content) along Z axis direction.
In Fig. 2a, the blue in the center represents the silica particle and the
density decreases outward therefrom. The polymer density in the area
around the spherical silica particle is significantly higher than further
away from the silica nanoparticle. Moreover, the concentration profile
map of PAM (Fig. 2b) also shows the density decreases outward
therefrom, and the greatest density appears near the surface of nano-
silica particle, while the opposite pattern appears in the concentration
profile map of PVA (Fig. 2c). This result is consistent with the adsorp-
tion behavior of polymer molecular chains on the surface of the sphe-
rical nano-silica particle in the final equilibrium models of PVA/PAM
blends (Fig. 1). Additionally, the comparison of the relative con-
centration distributions among polymers in 7PVA/7PAM and 7PVA/
7PAM/1silica blend models illustrates that the addition of nano-silica
has a great influence on the distribution of the polymers. The relative
concentration distributions of PVA and PAM in PVA/PAM blend model
(Fig. 3a) indicate the polymers in this system are distributed evenly,
which shows a agreement with their good miscibility. But after adding
the nano-silica into the PVA/PAM blend, the relative concentration

Fig. 2. Concentration profile maps of different components in 7PVA/7PAM/1silica blend system, and each color band corresponds to a range of field values. (a) The whole nanocomposite
which contains all components in system; (b) PAM component without PVA and nano-silica; (c) PVA component without PAM and nano-silica.

532
Q. Wei et al. Journal of the Mechanical Behavior of Biomedical Materials 75 (2017) 529–537

distributions of polymers in system (Fig. 3b) changed greatly. Closed to
the surface of the nano-silica particle, the relative concentration of PAM
is greater than that of PVA. This means a stronger interaction force
exists between the PAM molecules versus PVA molecules and the nano-
silica, which is the primary reason affecting their distribution.
3.2. Mechanical properties
It is noted that the mechanical properties mentioned here refers to
the micro mechanical properties, which are obtained by analyzing the
trajectories of atoms. Besides, they are different from the macro ex-
perimental mechanical properties. Here, the micro mechanical prop-
erties were calculated by means of the static model, in which the fol-
lowing equation was used to evaluate the internal stress tensor (σ ) at
the atomic level (Swenson, 1983).
N
1 ⎡
σ=− ∑ mi (Vi , ViT ) ⎤⎥
V0 ⎢ i = 1
⎣ ⎦
where mi and Vi represent the quality and speed of atoms, respectively,
and V0 is volume without distortion.
The elastic coefficient matrix is obtained by solving the first deri-
vative of the corresponding stress and strain. The blend systems used in
the present study are assumed to be the isotropic material, for which
the static elastic properties, i.e., tensile (Young's) modulus (E), bulk
modulus (K), and shear modulus (G), and Poisson's ratio (γ ) were cal-
culated as follows:
μ (3λ + 2μ) 2 λ
E= , K = λ + μ, G = μ, γ =
λ+μ 3 2(λ + μ)
where μ and λ are the Lamé coefficients, which are calculated from the
elastic coefficients according to the statistical mechanics of elasticity
(Watt et al., 1976).
1 2
λ= (C11 + C22 + C33) − (C44 + C55 + C66)
3 3
1
μ= (C44 + C55 + C66)
3 (4)
According to the principles of static mechanics, the mechanical
properties of PVA/PAM blends with different silica contents were ob-
tained by calculating the trajectories of the equilibrium models at the
temperature of 298 K. The elastic stiffness constants and the en-
gineering modulus are listed in Table 2.
The elastic modulus of a material is a measurement of its rigidity.
Generally, the hardness of a material is closely related to E and G; and
larger values of E and G suggests a stronger rigidity and hardness. The
Table 2
Mechanical properties of PAM/PVA blends with different compositions at 298 K (GPa).
fracture toughness of a material is determined by K, with a higher value
indicating greater fracture resistance (Jin et al., 2000). Cauchy pressure
(C12-C44) is often used to evaluate the ductility of a material, a more
positive Cauchy pressure corresponds to a better ductility (Weiner,
2002).
The previous study (Sakineh et al., 2015) illustrates that the addi-
tion of nano-silica can improve the mechanical properties of polymer
blends. As inspired by this, the present study the nano-silica was used to
improve the mechanical properties defect of PVA/PAM blends. Notably,
the calculated Poisson's ratios of blends here consistently fluctuate be-
tween 0.29 and 0.32, this is within the range of Poisson's ratio of plastic
(0.2–0.4), suggesting that the blends possess the properties similar to
plastics. However, the Cauchy pressure value of the blends decreases
with the increase of silica content, but it is always positive, suggesting
that the blends with nano-silica generally have a good ductility al-
though less than that of pure PVA/PAM blend and that the addition of
nano-silica weakens the ductility of blends. Finally, comparing the two
(1) group elastic coefficient values of C11, C22, C33 and C44, C55, C66 shows
that the addition of nano-silica can change the properties of isotropy,
with the anisotropy of the system becoming correspondingly more ob-
vious.
To verify the reliability of the computed results here, PVA (17–99,
MW 80,000), PAM (Analytical reagent, MW 200,000) and spherical
nano-silica (diameter 10–15 nm) were used to prepare the PVA/PAM
blend membranes with different nano-silica contents by the method of
vacuum evaporation, then their tensile strength were obtained by the
electronic universal testing machine. Fig. 4 shows the results of ex-
perimental tensile strength and simulation tensile modulus, from which
(2) we can know both the experimental tensile strength and simulation
tensile modulus increase with the silica content, the different tendency
was mainly caused by the small scale effect and the aggregation be-
havior of nano-silica. Anyway, this conclusion can verify the reliability
of simulation results to some extent.
(3)
3.3. Fractional free volume
The void space within the molecules is termed as the free volume,
which can be measured by fractional free volume (FFV). In our simu-
lations, atoms were represented by the hard spheres with van der Waals
radius as per the previous study (Pan et al., 2008), and the method of
Connolly surface was adopted for use. The FFV is evaluated by the
following equation (Peng et al., 2011).
Vf
FFV = × 100%
Vf + Vo (5)
where Vf is the free volume and Vo is the volume occupied by the

Systems 7/7/0 7/7/1 6/6/1 5/5/1 4/4/1 3/3/1

C11 10.60 12.38 13.41 14.09 15.39 16.22

C22 11.65 12.64 14.28 16.50 13.23 19.91
C33 10.26 11.88 12.47 13.55 17.19 14.78
C44 2.42 2.59 3.07 3.27 3.90 5.23
C55 3.41 3.74 3.84 3.98 4.26 4.11
C66 3.66 3.90 4.15 4.26 4.02 4.94
C12 5.25 5.20 5.19 5.25 5.76 6.44
C13 5.20 5.33 6.91 7.67 6.16 5.98
C23 5.39 5.70 6.21 7.11 10.25 9.65
C15 0.27 0.32 −0.14 −1.65 −0.27 −1.42
C25 0.13 −0.48 0.62 0.20 −0.62 0.42
C35 −0.16 0.36 −0.71 −1.14 0.12 0.36

Tensile modulus 8.16 8.92 9.67 10.12 10.71 12.42

Bulk modulus 6.56 7.75 8.46 9.27 9.86 10.62
Shear Modulus 3.16 3.41 3.69 3.84 4.06 4.76
Poisson ratio 0.29 0.31 0.31 0.32 0.32 0.31
Fig. 4. Results of experimental tensile strength and simulation tensile modulus for PVA/
C12-C44 2.83 2.61 2.12 1.98 1.86 1.21
PAM/silica with different silica contents.

533
Q. Wei et al.
Fig. 5. FFVs of PVA/PAM blends at different probe radii.
polymeric material. Fig. 5 shows the distributions of the FFVs for the
different blends, in which the value of probe radius, r, varies from 0.00
to 0.30 nm and Δr is set as 0.02 nm.
It is seen from Fig. 5 that the FFVs in blends with different silica
contents are all decreased with the increase of probe radius. In other
words, the bigger the solvent molecule causes the smaller FFV. It is also
seen that for the probe radius, the FFVs decrease with the addition of
silica content, suggesting that the addition of silica can enhance the
intermolecular interaction, thus decreasing the value of FFV. In other
words, the addition of silica makes the system denser, which is con-
sistent with the observation from both the calculated density results in
Table 1 and the mechanical property results in Table 2. The main
reason behind this is that with the enhanced interaction between silica
and polymers, the distance between molecules is reduced, thus making
the system denser.
3.4. Dynamic properties of polymer chains
The mean square displacement (MSD), which is associated with the
temperature and pressure, is one of the critical parameters to determine
the mobility of the polymer chains. Therefore, the MSD can used to
characterize the effect of silica particle on the mobility of the polymer
chains in blends, as per the previous study (Luo and Jiang, 2010).
MSD = < (ri (t ) − ri (0))2>
where ri(t) and ri(0) are the positions of Atom i at time t and 0, re-
spectively. The bracket denotes the ensemble average, which was ob-
tained from averaging over all molecules and all time origins t = 0.
Here, all the atoms of a PAM chain were selected to study the mobility
of the PAM chains in different blends at 298 K, and the MSDs of PAM
molecular chains are presented in Fig. 6.
Fig. 6. MSDs of PAM molecular chains in different blends at 298 K.
Journal of the Mechanical Behavior of Biomedical Materials 75 (2017) 529–537
As seen from Fig. 6, the MSD-t curves exhibit linear as expected, and
the slopes of the MSD-t curves decrease with the addition of silica
content, which indicates the mobility of the PAM polymer chains be-
come worse. This probably attributes to the interaction force between
polymer and the nano-silica particle increasing with the addition of
silica content. This result is also in agreement with the FFV results.
To further examine the effect of nano-silica on the flexibility of the
polymer chains, the PAM chain radii of gyration (Rg) in 7PVA/7PAM
and 7PVA/7PAM/1silica blends were analyzed and compared to each
other. The radius of gyration is a parameter commonly used to describe
the size of a flexible molecular chain by the following equation (Wang
et al., 2015).
∑i mi ri2
Rg =
∑i mi (7)
where mi is the mass of Atom i, and ri is the position of Atom i with
respect to the center of mass of the molecule. In general, the more
flexible of the polymer chain, the smaller Rg of the polymer chain is.
Fig. S6 shows the radii of gyration for PAM and PVA chains in the pure
PVA/PAM and PVA/PAM/silica blends, in which there were seven PAM
and seven PVA molecular chains, respectively. It is noted that the radii
of gyration for the most of PAM chains in PVA/PAM/silica blend (Fig.
S6b) are much bigger than those in PVA/PAM blend (Fig. S6a) at the
same temperature. This indicates that nano-silica particle can sig-
nificantly weakened the flexibility of PAM molecular chains, which can
also be found in the radius of gyration results of PVA molecular chains.
This result is also in agreement with the analytical results of MSD and
FFV. Therefore, the interaction between nano-silica particle and poly-
mers plays a fundamental role in the structural morphology of polymer
systems.
3.5. Simulated X-ray diffraction patterns
X-ray diffraction (XRD) is a method to investigate material micro-
structure, and is usually used to evaluate the crystal characteristics of
systems. The simulated scattering intensity curve, I(Q), for each system
is related to the radial distribution function through a Fourier transform
operation by (Jawalkar and Aminabhavi, 2007)
f j fk (sin Qr jk ) 4π sin θ
I (Q) = ∑∑ , Q=
j k
Qr jk λ (8)
(6)
where λ is the wavelength, θ is the scattering angle, rjk is the distance
between two adjacent atoms, and f is the atomic diffraction factor. In
general, the maximum peak in the diffraction pattern is noteworthy
because it is associated with the Bragg equation and is represented by
λ
d=
2 sin θ (9)
The d-spacing value is representative of inter-chain distances be-
tween polymer backbones. The XRD pattern was obtained by employing
the Forcite module. The wavelength was set to 0.15418 nm and the
angle of diffraction was varied from 0 to 45° using a step size of 0.05°.
The XRD patterns of the blends are shown in Fig. 7.
By comparing the integrated intensity of the background pattern to
that of the sharp peaks, the crystallinity of the system can be de-
termined. In contrast to a crystalline pattern consisting of a series of
sharp peaks, amorphous materials produce a broad background signal
(Shariatinia et al., 2016). For polymers, an ordered crystallite can be
formed by folding the molecule, possesses a semicrystalline character.
The XRD patterns in Fig. 7 display some relatively sharp peaks with
moderate intensity below 20° for all of the blends, and a very sharp
peak is observed near 2θ = 3° and 2θ = 7° in the XRD patterns of all the
blends, which demonstrates that all of the blends are of a semicrystal-
line structure. The intensity of peaks around 2θ=3° and 2θ=7° also
increase markedly with increasing silica content, which indicates the
534
Q. Wei et al.
Fig. 7. Calculated X-ray intensity versus 2θ of PVA/PAM blends with different silica
content.
addition of silica can enhance the semicrystalline character of the
blends. A pure PVA/PAM blend exhibits a semicrystalline structure
with three sharp peaks at 2θ = 16.8°, 18.5° and 21.5°. Therefore, the
peak near 2θ = 16–22° present in the XRD patterns of all of our systems
was used to calculate the inter-chain distance with Eq. (9). If there
existed more than one peak, the average of the peaks was used. The
calculated results of d-spacing (Table 1) show that the distance between
polymer molecular chains decreases with the addition of silica. The
decrease in d-spacing can be attributed to the enhanced intermolecular
interactions between the nano-silica and the polymers, which has the
same pattern with the FFV and mechanical property analyses.
3.6. Interfacial analysis
3.6.1. Interfacial binding energy
The size of binding energies between polymers and silica crystal-
lographic surfaces can reflect their interaction strength. Generally, the
larger the binding energy, the stronger the interaction force between
polymers and silica is. Therefore, comparing the binding energies be-
tween different compositions will help us understand the interaction
mechanism and better explain the density distribution on the silica
surface. The average binding energies of each polymer repeat unit for
PVA/silica and PAM/silica interaction models can be calculated by:
Etotal − EPolymer − Esilica
Ebind = −Eint er = −
N (10)
where Etotal is the energy of the polymer/silica, Epolymer is the energy of
polymer, and Esilica is the energy of the silica surface, N is the number of
repeat units for a polymer chain. All the energies in this research were
calculated by using the Dreiding force field, and by this force field the
hydrogen bond energies of each part can be obtained. The average
binding energies and hydrogen bond energies between each PVA and
PAM repeat units and the silica surface are given in Table 3.
It is seen that the average binding energy of each PVA repeat unit is
smaller than that of PAM repeat unit, which suggests the interfacial
interaction force between a PVA repeat unit and silica is smaller than
that between a PAM repeat unit and silica. This conclusion can also be
reflected by observing their equilibrium interfacial interaction models
(Fig. S5). The PAM molecular chain in Fig. S5b spreads out on the silica
surface and they fully interact with each other, while the PVA
Table 3
Binding energies and hydrogen bond energies for each PVA and PAM repeat unit on silica surface (kJ/mol).
System Etotal Epolymer
PVA/silica − 206,872.08 −3388.73
PAM/silica − 207,789.48 −4219.15
Journal of the Mechanical Behavior of Biomedical Materials 75 (2017) 529–537
molecular chain in Fig. S5a folds on the silica surface and cannot fully
interact with each other. This result can well explain why the prob-
ability of PAM molecular chains appearing around the silica nano-
particle is higher than PVA. Additionally, the hydrogen bond energy
and interaction energy of two polymer repeat units are nearly equal,
which indicates the interactions between polymers and silica mainly
attribute to hydrogen bonds.
3.6.2. Interfacial interaction mechanism
The binding energy results suggest the polymers interact with silica
in blends mainly by hydrogen bonds and that the hydrogen bonds may
exist between functional groups or polar atoms in polymers and atoms
on the silica surface. Therefore, to further discover the interaction
mechanism between PVA, PAM, and the silica surface, the pair corre-
lation functions (PCF) of PVA/silica and PAM/silica interaction models
were studied by analyzing their balancing trajectory files. For PCF, the
probability of finding another particle at a distance r from a specific
particle characterizes the microstructure and the interaction between
non-bonding atoms. This probability, denoted by g(r), is given by
nB N
gA − B (r ) = ⎛ ⎞/⎛ B ⎞
⎝ 4πr 2dr ⎠ ⎝ v ⎠ (11)
where nB is the number of B atoms that surround A atoms at a distance
r, NB is the total number of B atoms, and V is the volume of the entire
system.
Figs. 8 and 9 show the PCF g(r) values of functional groups and
polar atoms that exert stronger interaction forces in PVA/silica and
PAM/silica interfacial models, respectively. In these PCFs, OH(PVA)
denotes the hydroxyl groups (-OH) of the PVA molecular chain and H
(PVA) represents the hydrogen atoms connecting with the carbon
backbone. Similarly, in a PAM molecular chain, the oxygen of the
carbonyl groups (-C˭O), amino groups (-NH2), and hydrogen atoms
directly connecting with the carbon atoms were marked as O (PAM),
NH2(PAM), and H(PAM), respectively. For the silica model, OH(SiO2),
O(SiO2), and Si(SiO2) represent the hydroxyl groups (-OH) on the SiO2
surface and the oxygen atoms and silicon atoms of the SiO2 cell, re-
spectively.
Generally, intermolecular interactions involve chemical bonding,
hydrogen bonding, and van der Waals forces. A peak value below
0.35 nm indicates chemical bonds and hydrogen bonds, and values
higher than 0.35 nm indicate van der Waals interactions (Yang et al.,
2015).
Fig. 8 shows the PCFs for the PVA/silica interfacial interaction.
There are two peak values of g(r) for OH(PVA)~OH(SiO2) appearing at
r = 0.2 nm and r = 0.3 nm, which predict that the hydroxyl groups
(-OH) in PVA interact with the hydroxyl groups on the silica surface
mainly by the strong hydrogen bonding. Two peak values of g(r) for OH
(PVA)~Si(SiO2) occur at r = 0.4 nm and r = 0.65 nm, which are
within the effective range of van der Waals forces. Similarly, the g(r) for
H(PVA)~OH(SiO2) features two peak values at r = 0.25 nm and r =
0.48 nm; the value at r = 0.25 nm is the smaller of the two, which
indicates only a small portion of the H(PVA) atoms can interact with the
hydroxyl groups on the silica surface by hydrogen bonding, and most of
them form van der Waals interactions. The other interactions of func-
tional groups and atoms in the PVA/silica interfacial model are all weak
van der Waals interactions because their peak g(r) values are > 0.5 nm.
These results above are consistent with the FTIR measurement results
obtained by Chrissafis et al. (2008).
Esilica Einter Ebind Ehydrogen bond
− 202,731.62 −15.03 15.03 −14.55
− 202,706.59 −27.86 27.86 −26.80
535
Q. Wei et al.
Fig. 8. PCFs of the PVA/silica interfacial interaction.
Fig. 9. PCFs of PAM/silica interfacial interaction.
As Fig. 9 indicates, the PFC g(r) values for O(PAM)~OH(SiO2)
contain two obvious peaks at r = 0.19 nm and r = 0.28 nm, which
means stronger hydrogen bonds form between the oxygen from the
carbonyl groups in PAM and the hydroxyl groups on the silica surface.
Moreover, the g(r) for O(PAM)~Si(SiO2) reaches two peak values at r =
0.36 nm and r = 0.48 nm, which is within the range of van der Waals
interactions. This demonstrates a strong van der Waals interaction can
form between the oxygen of the carbonyl groups of the PAM and the
silicon atoms on the silica surface. The value of g(r) for NH2(PAM)~OH
(SiO2) reaches a significant peak value close to r = 0.29–0.32 nm,
which means the amino groups of the PAM interact with the hydroxyl
groups of the silica surface mainly by hydrogen bonds. Two peak values
of g(r) for NH2(PAM)~Si(SiO2) occur at r = 0.45 nm and r = 0.65 nm,
which are within the effective range of van der Waals forces. Similarly,
The PCF g(r) for H(PAM)~OH(SiO2) reaches peak values at r =
0.28 nm and r = 0.58 nm, and the peak value at r = 0.58 nm is larger
than that at r = 0.28 nm. This means a small portion of the H(PAM)
atoms can interact with the hydroxyl groups on the silica surface by
hydrogen bonding, and the remainder participate in van der Waals
interactions. Finally, other peak values of g(r) between functional
groups and atoms in the PVA/silica interfacial model are not particu-
larly evident, indicating they only interact with each other by weak van
der Waals interactions.
In brief, analyzing the PCFs of PVA and PAM at the interface of silica
revealed the interaction mechanism of nano-silica in PVA/PAM blends.
Hydrogen bond interactions between polar functional groups of the
polymer molecular chains and the hydroxyl groups on the silica surface
explain how the polymer adsorbs on the silica surface. Moreover, by
analyzing the peak values size of PCFs, the strength of hydrogen bond
formation can be compared, the larger the peak value, the stronger the
hydrogen bonds are to be formed. Thus, from the peak values of the
536
Journal of the Mechanical Behavior of Biomedical Materials 75 (2017) 529–537
PCFs above, we can determine the strength of each type of the hydrogen
bonds has the order of O(PAM)…OH(SiO2) > NH2(PAM)…OH
(SiO2) > OH(PVA)…OH(SiO2) > H(PAM)…OH(SiO2) > H(PVA)…OH
(SiO2). This conclusion shows a good agreement with the analysis re-
sults of binding energies between polymers and silica interface and
hence is why PAM molecular chains more easily absorb on the silica
surface.
4. Conclusions
In this research, six models of PVA/PAM/nano-silica blends of
varying concentrations were constructed and used to investigate into
the effects of nano-silica on the properties of, and the interaction in-
volved in, the blends. At each concentration, the mechanical properties,
FFVs, dynamic properties of polymers and XRD patterns were system-
atically examined. The results of micromorphologies from the equili-
brium models showed PAM molecular chains are easier to be adsorbed
on the silica surface than PVA molecular chains in blends. The ex-
amination of mechanical properties suggested that the addition of silica
into the polymer blend can significantly improve the stiffness of
polymer blend, meanwhile affecting the properties of ductility and
anisotropy. Due to the interaction between the polymers and nano-si-
lica, the FFV and the mobility of polymer chain decreased as the con-
centration of silica increased, suggesting that the systems became
denser. Also, the results of XRD patterns illustrated that the addition of
nano-silica enhanced the semicrystalline character of the blends and
decreased the distance between polymer molecular chains, which
concurred with the results of FFV and mechanical property. Finally, two
interfacial interaction models featuring PVA/silica and PAM/silica were
designed to explore the interaction mechanisms and explain how nano-
silica particles influence the properties of PVA/PAM blends. The results
of binding energies and PCFs indicated hydrogen bond interactions
between polar functional groups of polymer molecular chains and the
hydroxyl groups of silica surface are implicated in polymer adsorption
onto the nano-silica surface. The interaction between PAM and the si-
lica surface is stronger than that between PVA and the silica surface,
which agrees with the observed concentration profiles of different
compositions in blend systems. The results of this research not only aid
in understanding the microscopic structure and interaction mechanism
of nano-silica in PVA/PAM blends, but also provide theoretical gui-
dance for the in-depth study and design of PVA/PAM/silica blend na-
nocomposites.
Acknowledgements
This project was sponsored by the China Scholarship Council (CSC,
201606290095), the National Natural Science Foundation of China,
(Grant No. 51175432), the Innovation Platform of Biofabrication
(Grant No. 17SF0002), the Key Industrial Science and technology pro-
jects of Shaanxi (Grant No. 2015GY047), and Natural Sciences and
Engineering Research Council of Canada (NSERC RGPIN-2014-05648).
Appendix A. Supplementary material
Supplementary data associated with this article can be found in the
online version at http://dx.doi.org/10.1016/j.jmbbm.2017.08.027.
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