J Polym Res (2015) 22: 1
DOI 10.1007/s10965-014-0642-x
ORIGINAL PAPER
Strain-induced crystallization of natural rubber/zinc
dimethacrylate composites studied using synchrotron X-ray
diffraction and molecular simulation
Yijing Nie
Received: 20 August 2014 / Accepted: 10 December 2014 / Published online: 20 January 2015
# Springer Science+Business Media Dordrecht 2015
Abstract Natural rubber (NR) reinforced by in situ polymer-
ization of zinc dimethacrylate (ZDMA) exhibits excellent
mechanical properties. However, the corresponding reinforce-
ment mechanism is still unclear. Using synchrotron wide-
angle X-ray diffraction (WAXD) measurements, we observed
that strain-induced crystallization of NR/ZDMA composites
had a direct affect on the ultimate mechanical properties. An
increase in ZDMA fraction resulted in a lower strain at the
onset of crystallization. Further analysis revealed that three
factors contributed to the reduction in onset strain, including
higher whole cross-linking density due to the emergence of
ionic cross-linking clusters, strain amplification of
nanodispersion of poly-ZDMA (PZDMA), and the confine-
ment effect of the filler network. The results of dynamic
Monte Carlo simulation showed that the confinement effect
of the filler network on chain segments favored segmental
orientation in regions near the polymer–filler interface, thus
inducing a decline in onset strain.
Keywords Strain-induced crystallization . Molecular
simulation . Rubber . Filler network
Introduction
The principal reason for the outstanding tensile properties and
good crack growth resistance of natural rubber (NR) can be
attributed to strain-induced crystallization [1–8]. During de-
formation, highly stretched chain segments form fringed-
micelle nuclei, which then induce the initiation of crystal
growth with chain-folding in the surrounding, less-stretched
Y. Nie (*)
School of Materials Science and Engineering, Jiangsu University,
301 Xuefu Road, Zhenjiang 212013, China
e-mail: nieyijing18@126.com
segments [9–12]. To further enhance the mechanical and
fatigue properties of NR to meet industry needs, conventional
fine particulates such as carbon black are usually introduced,
which change the network structure and local deformation of
the rubber portion [13, 14]. Rubber chains are overstrained
around particles, resulting in acceleration and improvement in
strain-induced crystallization [6, 15].
For peroxide-cured elastomers, metal salts of methacrylic
acids, particularly zinc dimethacrylate (ZDMA), are normally
used as co-agents to cure rubber chains, leading to higher
cross-linking density and producing a complex network struc-
ture [16–18]. During peroxide curing, ZDMA undergoes po-
lymerization, which is initiated by peroxide radicals, to form
poly-ZDMA (PZDMA) [19, 20]. In addition, PZDMA radi-
cals can also react with NR radicals, resulting in the formation
of NR-graft-PZDMA [17, 20]. The PZDMA chains are as-
sembled to form local nano-phases dispersed in the rubber
matrix, as has been confirmed by transmission electron mi-
croscopy (TEM) [17, 21] and small-angle X-ray scattering
measurements (SAXS) [22, 23]. In addition, due to the strong
electrostatic interactions between the large numbers of ion
pairs in PZDMA chains, clusters consisting of several pairs
can be formed [17, 24, 25]. These ion clusters dramatically
depress the mobility of chain segments in PZDMA [26]. Due
to the presence of NR-graft-PZDMA, the motion of the cor-
responding rubber chain segments near the grafted PZDMA
or ion clusters is also inhibited. Thus, these clusters can be
considered as new kinds of cross-linking points, i.e., ionic
cross-linking points [27].
Rubbers reinforced by ZDMA exhibit excellent mechani-
cal properties and even much higher modulus at low strains
compared with those filled with carbon black [28]. Because of
the complexity of the network structure of NR/ZDMA com-
posites, and despite numerous studies that have been carried
out [24, 26, 27, 29], the reinforcement mechanism is still
unclear. Strain-induced crystallization plays a major role in
1 Page 2 of 10
the reinforcement of NR, and thus an in-depth understanding
of its mechanism is of great importance. Unfortunately, to
date, there has been little research with regard to the structural
evolution of NR/ZDMA composites during stretching, and
additional investigation is warranted. Because of the morpho-
logical differences between NR/ZDMA composites and rub-
bers filled with conventional fillers [17, 21], the correspond-
ing strain-induced crystallization behaviors may exhibit dif-
ferent molecular mechanisms.
The aim of the present work was to determine the influence
of PZDMA nano-phases on the strain-induced crystallization
of NR using a combination of synchrotron wide-angle X-ray
diffraction (WAXD) measurements and dynamic Monte Carlo
(MC) simulation. Synchrotron WAXD measurements enable
us to monitor changes in crystalline structure induced by
deformation in real time [2, 4, 30]. In addition, molecular
simulation, which can probe the structural changes at the
molecular level, has proven to be an effective method for
studying the mechanism of polymer crystallization [31–35].
The authors have successfully applied MC simulation for the
study of strain-induced crystallization of polymer networks
[11, 12]. Based on experimental and simulation results, we
have proposed a reasonable molecular mechanism with regard
to strain-induced crystallization of the NR/ZDMA
composites.
Experimental
Materials
NR (ribbed smoked sheet [RSS] grade 1) was purchased from
Indonesia. ZDMA was purchased from the Xian Organic
Chemical Technology Plant, China. Dicumyl peroxide
(DCP) was manufactured at the Chengdu Kelong Chemical
Technology Plant in China. The formulations of rubber com-
posites are listed in Table 1.
Measurements
Synchrotron WAXD experiments were performed to detect
structural development of NR during uniaxial stretching under
room temperature conditions at U7B beam-line in the Nation-
al Synchrotron Radiation Laboratory (NSRL), University of
Science and Technology of China, Hefei. The wavelength was
Table 1 Formulations
of NR composites Ingredient Content (phr)a
NR 100
DCP 2
a
Parts by weight per ZDMA 0, 10, 20, 40
hundred parts of rubber
J Polym Res (2015) 22: 1
0.154 nm. Two-dimensional (2D) WAXD patterns were re-
corded every 180 s using the MarCCD 165 X-ray detector
system, and a custom-made stretching machine with symmet-
ric extension was used for deformation at strain rate of 35 %/
min in order to record the time-resolved WAXD patterns
continuously. The crystallinity (Xc) was calculated from dif-
fraction intensity data as follows
X c ¼ Ac =ðAc þ Aa Þ; ð1Þ
where Ac and Aa represent the areas of the crystalline and
amorphous regions, respectively.
The stress–strain curves were tested on an Instron 5567
material testing machine at room temperature according to
GB/T1040-92 standards.
The Payne effect of samples was measured using dynamic
mechanical analysis in tension mode at room temperature, at a
frequency of 1 Hz, in a dynamic strain range of 0–7500 μm
using a Q800 dynamic mechanical spectrum device (TA In-
struments, New Castle, DE, USA).
Cross-linking density was determined on the basis of the
equilibrium swelling measurements by application of the
Flory–Rehner equation [36]

 h i
– lnð1 – Φr Þ þ Φr þ χΦr 2 ¼ V 0 n Φr 1=3 – Φr =2 ð2Þ
where Φr is the volume fraction of polymer in the swollen
mass, V0 is the molar volume of the solvent (106.2 cm3 for
toluene), n is the number of active network chain segments per
unit of volume (cross-linking density), χ is the Flory–Huggins
polymer–solvent interaction term, taken as 0.427+0.112Φr2
for cross-linked NR and toluene pair at 25 °C [37]. The value
of Φr is calculated according to the correction method as
reported by Valentín [38]
 
w2 −f ins w0 w2 − f ins w0 w1 −w2
Φr ¼ = þ ð3Þ
ρ2 ρ2 ρ1
where w0 represents the weight of the dry sample before
swelling, w1 and w2 are the weights of the swollen and de-
swollen samples, respectively, ρ1 and ρ2 are the densities of
the solvent and polymer, respectively, and fins is the weight
fraction of insoluble components, namely (insoluble compo-
nents weight)/(recipe weight). In our case, PZDMA nano-
phase is taken as a non-swellable component due to its strong
polarity, and thus fins is equal to the fraction of PZDMA. Note
that the covalent and ionic cross-linking densities can be
separated using solvents with different polarities [27]. The
detailed measurement process can be found in [26].
A dynamic lattice Monte Carlo simulation is employed to
study the effect of filler network confinement on strain-
J Polym Res (2015) 22: 1
induced crystallization. A schematic model of the filled rubber
network is shown in Fig. 1a. In order to improve simulation
efficiency, we introduce only a section of the filled rubber
network into simulation rather than the whole network, as
indicated with the red dashed circle in Fig. 1a. In the cubic
lattice model, each monomer of a polymer chain is assigned to
one lattice site. In the rectangular box (sides denoted as XYZ),
we put 1,920 network chains, each containing 128 monomers,
with each chain end separately restricted on two YZ boundary
planes. The occupation density is set at 0.9375 to mimic a bulk
polymer phase, and a small number of vacancy sites act as free
volume for chain motion. These restricted chain ends repre-
sent cross-linking points. All of the surfaces of the simulation
box are set as hard-wall boundaries to mimic the confinement
of the filler network. In other words, these hard-wall bound-
aries can be considered a polymer–filler interface. For NR
with greater fraction of ZDMA, rubber chains are confined to
a smaller space, i.e., they are exposed to a stronger confine-
ment effect. To reflect the different confinement effects on
chains, the lateral dimensions of the simulation box along the
Y and Z axes are varied in lengths of 128, 64, 32, and 16. The
stretching direction is set along the X axis, and the initial size
of the simulation box along the X axis is 16. Here, as we are
only studying the confinement effect of the filler network on
strain-induced crystallization, the chain length in our simula-
tion is kept constant. Polymer chains can move in the lattice
space via a micro-relaxation model [31], which allows a
monomer jumping from an occupied site to a neighboring
vacancy site, occasionally with partial sliding diffusion along
the chain. The bonds are oriented either along lattice axes or
along diagonals, and therefore the coordination number of
each monomer can be as high as 26 (summed over 6 axes, 8
body diagonals, and 12 face diagonals). Each bond contains a
maximum of 13 possible orientations. Both double occupation
Fig. 1 (a) Sketch of a typical filled polymer network structure. Curves
represent the network chains, squares denote the covalent cross-linking
points, and spheres denote the nanofillers. The red nanofillers and the
blue network chains belong to the network section that we introduce into
simulation. (b) Snapshots demonstrating affine deformation of the bulk
polymer network. Blue cylinders in the box represent polymer bonds, and
red dots denote the chain ends that are restricted in the YZ boundary
Page 3 of 10 1
of monomers on lattice sites or bond-crossing are prevented
due to the volume exclusion of polymer chains. The preset
fully ordered network chains are relaxed for 106 MC cycles to
reach a random-coil state under athermal conditions (each MC
cycle is defined as a step during which all monomers moved
once on average. In thermodynamics, the athermal condition
corresponds to an infinitely high temperature).
We successfully produced homogeneous stretching of the
bulk lattice polymer network in our MC simulations [11]. As
demonstrated in Fig. 1b, polymer chains with two restricted
ends mimic network chains under affine deformation. Here,
we tentatively avoid any entanglement in the initial state. The
athermal random coils are then quenched to a temperature in
order to observe strain-induced isothermal crystallization.
Network chains, prepared as referenced above, are stretched
by moving the right YZ boundary step-by-step along the X
axis. We first randomly select one X site, and cut all of the
chains passing through its corresponding cross-sectional YZ
plane into two parts. We then shift the right part for one more
X site, and reconnect all of the broken bonds at the YZ plane
via local sliding diffusion to open the first kink in the left part
of the chains. If the sliding diffusion demands that the left
chain end moves away from its YZ boundary plane, this trial
stretching event will be rejected, and we will immediate
proceed to the next trial event at another randomly selected
X site. The probabilities of breaking the bonds along the
chains are almost equal, the exception occurring for those
near two chain ends, mimicking a homogeneous stretching
of the bulk polymer network. After each successful stretching
event, the system relaxes for 4,000 MC cycles, defined as a
strain rate of 6.25 %/4,000 MC cycles. New vacancy sites are
introduced into the bulk sample with volume expansion dur-
ing the stepwise shifting of the right YZ boundary, which
should be expelled as soon as possible under normal stress
planes, i.e., cross-linking points. The left snapshot was obtained after the
relaxation of polymer chains for 10 6 MC cycles under athermal
conditions, and the right snapshot was obtained when polymer chains
in the simulation box with an initial size of 16×32×32 (XYZ) were
stretched to 100 % strain at T*=4.5 with a strain rate of 6.25 %/4,000
MC cycles
1 Page 4 of 10 J Polym Res (2015) 22: 1

upon stretching polymers. Therefore, a strongly centrifugal a 25 10

energy Ea, driving the newly added vacancy sites away from
the central X axis of bulk polymers, is introduced to ensure
20 8

Tensile strength (MPa)

constant volumes upon affine deformation in the bulk polymer

Initial modulus (MPa)

sample, as demonstrated in Fig. 1b. The conventional Metrop-
15 6
olis sampling algorithm is employed at each step of micro-
relaxation, with a potential energy penalty
10 4
E ¼ cE c þ pE p þ aE a ð4Þ
5 2

where Ec is the potential energy change for non-collinear 0 0

0 10 20 30 40
connection of consecutive bonds along the chain, reflecting
ZDMA content (phr)
the chain flexibility; Ep is the potential energy change for each
pair of nonparallel packed bonds, reflecting the molecular
b
driving force for polymer crystallization [31]; c is the net 600
change of non-collinear connection pairs of bonds along the
chain; p is the net change of nonparallel packed pairs of bonds; 500

Elongation at break (%)

and a is the net change of pair contacts between monomers
and newly added vacancy sites. In practice, Ep/Ec is fixed at 1 400
to allow for a proper flexibility of chains at crystallization
temperatures, Ea/Ec is set at 1,000 to expel the newly added 300
vacancy sites from the bulk phase during stretching, and kT/
Ec =4.5 represents a reduced system temperature (k is the
200
Boltzmann constant and T the temperature; the reduced tem-
perature is simplified below as T*).
100
0 10 20 30 40
ZDMA content (phr)
Fig. 2 (a) Tensile strength and initial modulus of NR/ZDMA composites
as a function of ZDMA content. (b) Extension of the break of NR/ZDMA
Results and discussion composites as a function of ZDMA content

Morphology and mechanical properties
The tensile strength and initial modulus of rubber are dramat-
ically improved with the addition of ZDMA (see Fig. 2a),
while the extension at break is gradually reduced as the
content of ZDMA increases (see Fig. 2b). The remarkable
reinforcement properties appear to originate from the particu-
lar microstructure of NR/ZDMA composites. During vulcani-
zation, the simultaneous polymerization of ZDMA monomers
results in the formation of separated nano-phases of PZDMA
dispersed in the rubber matrix [16–20]. In addition, the strong
electrostatic interactions between ion pairs in PZDMA chains
result in the freezing of the PZDMA chain segments (the glass
transition temperature of PZDMA is above 300 °C [24]), and
these glassy nanodispersions of PZDMA can thus act as
nanofillers for NR [24, 26]. Due to the presence of NR-
graft-PZDMA, the ion clusters containing several ion pairs
can also restrict the motion of rubber segments near the
grafted PZDMA, and therefore act as ionic cross-linking
points. A typical ionic cross-linking cluster scheme is illus-
trated in the inset of Fig. 3.
As shown in Fig. 3, both whole and ionic cross-linking
densities increase with an increase in ZDMA content, while
covalent cross-linking density remains almost unchanged. In
other words, the marked increase in whole cross-linking den-
sity is primarily derived from the higher ionic cross-linking
density.
Strain-induced crystallization
With an understanding of the network structure of NR/ZDMA
composites at the static state, we then go further to determine
the structural evolution during stretching that directly deter-
mines the mechanical property of rubbers. The stress–strain
curves for the neat NR and composites filled with different
fractions of ZDMA are shown in Fig. 4. For the filled NR, the
upturn in stress shifts to lower strain values compared with the
neat, signifying that the structural changes in NR/ZDMA
composites occur earlier during stretching.
With the use of synchrotron WAXD measurements, the
strain-induced crystallization of rubber composites can be
directly observed. Figure 5a displays selected representative
J Polym Res (2015) 22: 1 Page 5 of 10 1

8
Whole cross-linking density a
Covalent cross-linking density
Ionic cross-linking density
6
Cross-linking density

Rubber chains

2+
Zn2+ Zn
Zn2+
4 Zn2+ Zn
2+

2+
Zn
Grafted PZDMA

0 10 20 30 40
ZDMA content (phr)
Fig. 3 Three types of cross-linking density (whole cross-linking density, b
ionic cross-linking density, and covalent cross-linking density) as a 50
function of ZDMA content. The inset illustrates a microstructure model NR
of an ionic cross-linking cluster NR/10phrZDMA
40
NR/20phrZDMA

Crystallinity (%)
NR/40phrZDMA
30
2D WAXD patterns during the drawing of NR with 10 phr
ZDMA. At relatively large strains, we see that the correspond-
ing images exhibit highly oriented crystalline reflection peaks, 20

indexed as the 200, 120, and 201 reflections, indicating the

emergence of rubber crystallites with high anisotropy [2–5]. 10
The intensity of these reflections increases with increased
strain, suggesting the development of strain-induced crystal- 0
lization. We the use the Fit2D software package to analyze the
2D WAXD patterns in order to obtain more detailed informa- 0 1 2 3 4 5

tion. After the subtraction of the air scattering, the corrected
WAXD patterns are integrated along an azimuthal line from 0°
to 360°. The resultant profiles are subsequently deconvoluted
into corresponding crystal diffractions (the 200, 120, and 201
reflections) and amorphous peaks [2–4]. All crystalline and
amorphous peaks are described using Gaussian functions. The
25
NR/40phrZDMA
20
NR/20phrZDMA
Stress (MPa)
Strain
Fig. 5 (a) Selected synchrotron 2D WAXD patterns during stretching for
NR with 10 phr ZDMA. ε in the figure represents the strain of rubber
samples. (b) Variations in crystallinity as a function of strain for various
NR samples. Dashed lines represent the linear fits
crystallinity can be calculated from the diffraction intensity
data using Eq. 1. Accordingly, the variations in crystallinity
for the different rubber samples during stretching are calculat-
ed, as depicted in Fig. 5b. During stretching, the crystallinity
of all samples increases monotonically, but the rubbers with
higher ZDMA content exhibit lower onset strains and higher
rates of crystallization, indicating the enhanced ability of

15 strain-induced crystallization for the filled rubbers. Due to

the low intensity of the crystalline area at the onset strain of
NR/10phrZDMA
crystallization, the precise time of onset is difficult to deter-
10
mine simply from the 2D WAXD patterns. As such, the onset
strain is calculated as the intercept position of the regression
5 NR line (solid line in Fig. 5b) in the plot of crystallinity against the
strain [14]. As illustrated in Fig. 6a, an increase in ZDMA
content leads to a reduction in onset strain. The mechanism of
0
0 1 2 3 4 5 6 decline in onset strain in sulfur-cross-linked rubbers filled
Strain with conventional fillers such as carbon black was revealed
Fig. 4 Stress–strain curves of pure NR and NR/ZDMA composites in a previous work [14]. Due to the presence of the un-
1 Page 6 of 10 J Polym Res (2015) 22: 1

a phenomenon has been attributed to the relatively homogenous

4
network structure of peroxide-cross-linked NR [41, 43]. Thus,
for filled peroxide-cross-linked NR, there are at least two key
Experimental onset strain

factors determining the onset strain: the whole cross-linking

3
density and the strain amplification effect. We then further
explore the contributions of these two factors in reducing
onset strain.
2
Under the hypothesis of affine deformation of Gaussian
chains and the condition of uniaxial stretching, the reduction
in entropy induced by stretching (ΔSd) can be calculated on
1 the basis of the classical theory of rubber elasticity [41]
h i
ΔS d ¼ –ð1=2Þvk ðε þ 1Þ2 þ 2=ðε þ 1Þ – 3 ð5Þ
0
0 10 20 30 40
ZDMA content (phr)
where v denotes the whole cross-linking density of rubber
b 3
samples and ε is the strain of stretched rubber samples. Ac-
cording to the findings of Ikeda et al., the reduction in entropy
Experimental onset strain
required for onset of crystallization in peroxide-cross-linked
Modified onset strain
Theoretical onset strain NR is independent of cross-linking density [41, 42]. Equa-
tion 5 shows that cross-linking density and onset strain are co-
2
Onset strain

determinants of the entropy reduction required for the onset of

1
0 taking the values of the whole cross-linking densities of the
1 2 3 4
Whole cross-linking density
Fig. 6 (a) Experimental onset strain of crystallization as a function of
ZDMA content. (b) Different onset strains (experimental, modified, and
theoretical) of crystallization as a function of whole cross-linking density
deformable filler particles, the local effective strain of the
rubber portion in filled rubber is higher than the nominal
macroscopic value during deformation, a phenomenon that
is described as "strain amplification effect". Recent studies
have verified that this effect is largely caused by the inhomo-
geneous dispersion of the fillers [39, 40]. Poompradub et al.
found that the onset strain of sulfur-cured NR filled with
carbon black after modification by strain amplification was
nearly equal to that of neat NR [14].
The situation for peroxide-cured rubber, however, is differ-
ent from that for sulfur-cured rubbers [41]. Ikeda et al. report-
ed that strain-induced crystallization occurred at the point
when a specific reduction in entropy was reached for
peroxide-cross-linked NR samples by stretching [42]. In other
words, the onset strain to produce the required reduction in
entropy for crystallization of peroxide-cross-linked NR upon
stretching is dependent upon cross-linking density. This
crystallization. In other words, peroxide-cross-linked rubbers
with different cross-linking densities have different onset
strains. Since we have obtained the value of onset strain for
neat peroxide-cross-linked NR and its cross-linking density,
the decrease in entropy required for onset of crystallization
can be calculated directly. Here, we assume that the required
reduction is the same in both unfilled and filled NR. Then, by
NR/ZDMA composites in Eq. 5, the corresponding theoretical
onset strains can be evaluated, as plotted versus the whole
cross-linking density in Fig. 6b.
Interestingly, as shown in Fig. 6b, the theoretical onset
strains are higher than the experimental results, and we should
further confirm whether this difference is caused by the strain
amplification effect of the hard PZDMA nano-phases. The
strain amplification effect describing the relationship between
the macroscopic imposed strain and the local effective strain
in the rubber matrix is expressed as follows [13]
αm ¼ ðα–φÞ=ð1–φÞ ð6Þ
where φ is the volume fraction of filler, αm is the modified
extension ratio, and α is the macroscopic imposed extension
ratio (α=ε+1). The density of PZDMA as measured by a
pycnometer is 1.5376 g cm−3 [20]. The local effective onset
strain can then be modified according to Eq. 6, as also shown
in Fig. 6b. The modified local onset strains are still smaller
than the theoretical values for filled rubbers, indicating that
there are other factors involved in onset strain reduction.
As confirmed by TEM measurements [17, 20, 21], nano-
granular dispersions of PZDMA exist in the cured rubber
J Polym Res (2015) 22: 1 Page 7 of 10 1

matrix. Nanocomposites exhibit extensive interfacial area per
volume of nanodispersions, and thus a low percolation thresh-
old [44, 45]. Consequently, a filler network of PZDMA can
percolate though the entire rubber at a low volume fraction. It
appears that the presence of this percolated filler network
exerts an influence on the crystallization process upon
stretching. The Payne effect in filled rubbers usually refers
to the reduction in dynamic storage modulus with increasing
strain amplitude, which can be attributed to the de-
agglomeration of the filler network [45, 46]. In other words,
the amplitude of the Payne effect (E0 –E∞ ) can be used to
reflect the intensity of the filler–filler interactions; i.e., the
strength of filler network (E0 denotes the initial elastic mod-
ulus in the linear plateau and E∞ the modulus at the highest
strain) [45]. As depicted in Fig. 7, higher ZDMA content
results in a larger amplitude of the Payne effect, indicating
the formation of a stronger filler network [45, 47] (the mod-
ulus plateau was not reached at a high dynamic strain
a 8
NR
NR/10phrZDMA
Storage modulus (MPa)
amplitude due to the strain limitation of the device). It appears
that as the filler network becomes stronger, more rubber chain
segments will be confined.
From a thermodynamic perspective, the filler network con-
fines the motion of chain segments, decreases the number of
network chain conformations, and consequently leads to a
reduction in conformational entropy, accompanied by an in-
crease in melting point and degree of supercooling, which is
beneficial for strain-induced crystallization. Thus, we believe
that the presence of a filler network can also contribute to a
reduction in onset strain. The effect of filler networks on
strain-induced crystallization is difficult to directly probe
using experimental measurements, however, and therefore
molecular simulation was further applied to explore the effect.
Molecular simulation
We used dynamic Monte Carlo simulation to investigate
strain-induced polymer crystallization under confinement
conditions. Figure 8a summarizes the strain evolution curves
of crystallinity for polymer chains under different confine-
ment during stretching. Crystallinity has been found to in-
crease suddenly at a certain strain level, which can be defined

NR/20phrZDMA as the onset strain of crystallization. This is consistent with the

6
NR/40phrZDMA above experimental results, as depicted in Fig. 5b. A method
similar to that used in experiments was applied to evaluate the
4 value of onset strain in simulation. The resultant onset strains
under different confinement effects are plotted in Fig. 8b. The
enhancement of the confinement effect on chains through the
2 reduction in the lateral dimension of the simulation box results
in reduced onset strain. In other words, the ability of strain-
induced crystallization is improved by confinement. From the
0
perspective of thermodynamics, the onset strain is determined
0.1 1 10 by the reduction of conformational entropy [1, 41, 42], which
Strain amplitude (%) is caused by the extension or orientation of polymer chains.
As such, it appears that stretching can cause an exten-
b 4
sion or orientation of polymer chains, a reduction in
conformational entropy, and an increase in the melting
point and degree of supercooling, thus inducing the
3 onset of crystallization.
E 0 E (MPa)

There are factors other than stretching, however, that may

also cause the orientation of chains. Since the chains are
2 confined in a local space surrounded by a nanofiller network,
the lateral fluctuations in chains near the polymer–filler inter-
1
face will be limited. Moreover, the confinement of lateral
fluctuations will force the chain segments to orient along the
direction of stretching. To support our explanation, we calcu-
0 late the orientational-order parameter of amorphous bonds
distributed in different locations at different distances from
0 10 20 30 40 50 the center of the simulation box before the onset of crystalli-
ZDMA content (phr) zation, as shown in Fig. 9 (we take the system with a lateral
Fig. 7 (a) Storage modulus versus dynamic strain amplitude for different dimension of 64 as a typical example, and the definition of
rubbers. (b) Magnitude of the Payne effect versus ZDMA content these locations is explained in the inset of Fig. 9). The
1 Page 8 of 10 J Polym Res (2015) 22: 1

a 0.10
0.8

Distance
Orientational-order parameter
Lateral size 128 Location

Lateral size 64 0.08 Distance

0.6 Lateral size 32
Lateral size 16 Z Center point
Crystallinity

Y
0.06
0.4

0.04
0.2

0.02
0.0 0 5 10 15 20 25
0 1 2 3 4
Distance
Strain
Fig. 9 Orientational-order parameter of polymer bonds distributed in
different locations at different distances from the center of the
b 2.0 simulation box for the system with a lateral dimension of 64 at a strain
of 1.125 (before the onset of crystallization). The inset illustrates the
definition of the locations. During stretching, the distance between the
box center and polymer–filler interface decreases gradually due to the
1.5
affine deformation, and thus the maximum distance in the figure is
smaller than 32
Onset strain

1.0 orientational order. In a word, the confinement effect of the

filler network increases the segmental orientation in the re-
gions near the interface, and thus brings about a reduction in
0.5
conformational entropy, which induces a further rise in the
melting point and degree of supercooling, and a decline in the
onset strain of crystallization.
0.0
0 25 50 75 100 125 150 Figure 11 depicts the strain dependence in orientational-
Lateral size of simulation box order parameters of the amorphous bonds under different
Fig. 8 (a) Strain evolution of crystallinity for polymers under different confinement conditions. Orientational orders show an in-
confinement effects (simulation boxes with different lateral dimensions). crease, decrease, and re-increase tendency with increasing
Crystallinity is defined as the fraction of monomer bonds containing more strain. The first increase stage is attributable to the effect of
than five parallel neighbors of other monomer bonds. Using this criterion,
the small values of crystallinity at low strains are caused by thermal
fluctuations before crystallization. (b) Onset strain of crystallization as a
function of lateral dimension of simulation box

orientational-order parameter of the amorphous bonds is de-

fined as
 
P ¼ 3 < cos2 θ > – 1 =2 ð7Þ

\where θ refers to is the angle of the bond orientations in the

stretching direction, and < > refers to an average across all of
the amorphous bonds.
Figure 9 clearly shows that the bonds near the interface
have larger orientational-order parameters along the direction
of stretching. The improvement in segmental orientation near
the interface is favorable for strain-induced crystallization.
Figure 10 describes the spatial distribution of strain-induced Fig. 10 Snapshot of strain-induced nuclei (red cylinders) for a system
with a lateral dimension of 64 at the onset strain of crystallization. The
nuclei at the onset strain for a system with a lateral size of 64. observation direction of this snapshot is along the stretching direction,
It is clear that most of the nuclei appear in the regions near the and thus we are only able to see the circular end surface of the highly
polymer–filler interface, where the segments have a higher oriented nuclei. The black lines denote the polymer-filler interface
J Polym Res (2015) 22: 1
0.10
Lateral size 128
Orientational-order parameter
0.08 Lateral size 64
Lateral size 32
Lateral size 16
0.06
0.04
0.02
0.00
-0.02
0 1 2 3
Strain
Fig. 11 Strain evolution of orientational-order parameters for polymers
under different confinement effects
stretching. After the onset of crystallization, however, the
priority for these highly stretched amorphous segments is to
join the crystalline phase, thus resulting in the decrease in
orientational orders. Subsequently, the orientational orders
increase again, indicating that more highly stretched segments
are generated in the amorphous phase due to the pulling of the
crystalline segments from the crystalline domains. When the
confinement effect becomes stronger (in the simulation, the
enhancement of confinement effect is achieved by a decrease
in the lateral dimension of the simulation box), the fraction of
chain segments that suffer the confinement effect and have
relatively higher orientational orders will increase. As such,
the system with stronger confinement has a higher orienta-
tional order of bonds at low strains before the onset of crys-
tallization, as demonstrated in Fig. 11. This is the microscopic
mechanism of the improvement of strain-induced polymer
crystallization under the confinement of a filler network.
In addition to the confinement effect, the surface of filler
networks may induce the heterogeneous nucleation of poly-
mers, depressing the nucleation potential barrier, accelerating
the crystallization process, and thus reducing the onset strain
of crystallization. Similarly, Chen et al. found that the addition
of ZDMA promoted the nucleation process of polypropylene,
leading to an increase in crystallization rate and temperature
[48].
Conclusions
The polymerization of ZDMA during peroxide vulcanization
of NR results in the emergence of certain microstructures,
including ionic cross-linking clusters and nanodispersion of
PZDMA, that result in an improvement in strain-induced
rubber crystallization. With the use of in situ synchrotron
WAXD measurements, we observe that the addition of
Page 9 of 10 1
ZDMA effectively decreases the onset strain of crystallization.
Detailed analysis reveals that, apart from the increase in cross-
linking density and strain amplification of PZDMA
nanodispersion, there is another factor (the confinement effect
of the nanofiller network) contributing to reduced onset strain.
We further solidify the analysis through the use of dynamic
MC simulation. Simulation results demonstrate that the con-
finement of the nanofiller network on chain segments favors
segmental orientation in regions near the polymer–filler inter-
face, and thus causes a reduction in onset strain. The combi-
nation of two very different technical approaches—WAXD
measurements and molecular simulations—provides us a new
4 microscopic mechanism of strain-induced crystallization of
NR/ZDMA composites, the comprehension of which is help-
ful for the design of new high-performance rubber materials.
Acknowledgments The authors gratefully acknowledge the financial
support of the Research Foundation of Jiangsu University (NO.
14JDG059), the National Natural Science Foundation of China (No.
21404050), and the Jiangsu Planned Projects for Postdoctoral Research
Funds (No. 1402019A). We also wish to thank Professors Liangbin Li
and Guoqiang Pan for their invaluable assistance in the Synchrotron
WAXD experiments.
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