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Stress-Strain Behaviors and Crosslinked

Networks Studies of Natural Rubber-Zinc
Dimethacrylate Composites
a b
Yukun Chen & Chuanhui Xu
a
School of Mechanical and Automotive Engineering , South China
University of Technology , Guangzhou , China
b
College of Material Science and Engineering , South China
University of Technology , Guangzhou , China
Accepted author version posted online: 18 Oct 2011.Published
online: 15 May 2012.

To cite this article: Yukun Chen & Chuanhui Xu (2012) Stress-Strain Behaviors and Crosslinked
Networks Studies of Natural Rubber-Zinc Dimethacrylate Composites, Journal of Macromolecular
Science, Part B: Physics, 51:7, 1384-1400, DOI: 10.1080/00222348.2011.629904

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 Journal of Macromolecular Science

R
, Part B: Physics, 51:1384–1400, 2012
Copyright © Taylor & Francis Group, LLC
ISSN: 0022-2348 print / 1525-609X online
DOI: 10.1080/00222348.2011.629904

Stress-Strain Behaviors and Crosslinked

Networks Studies of Natural Rubber-Zinc
Dimethacrylate Composites

YUKUN CHEN1 AND CHUANHUI XU2

1
School of Mechanical and Automotive Engineering, South China University
of Technology, Guangzhou, China
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2
College of Material Science and Engineering, South China University
of Technology, Guangzhou, China

The stress-strain behaviors of natural rubber (NR)-zinc methacrylate (ZDMA) composite

have been studied by uniaxial tension. The results indicated that there was a large
reinforcement by ZDMA and the NR/ZDMA composites exhibited a high stress-softening
effect. Meanwhile, the recovery stretch curve was close to the second stretch curve; thus
a weak stress recovery of the composites was shown. The analysis of crosslink density
indicated that the damage to the crosslink network was mainly due to the breakage of
ionic crosslinks at low strain (100%). A more developed ionic crosslink network was
formed at a higher content of ZDMA. When the vulcanizate is subjected to loading in
tension, the ionic crosslink network will suffer the force first. Next, the slippage of ionic
bonds will take place under the stress. A new ionic crosslink network might be formed
rapidly after the ionic bonds were broken during the stretching. Therefore, it could not
return to the initial state. The analysis of crosslink density and stress recovery indicated
that the rubber chains could be adsorbed to the ZDMA aggregates due to the formation
of poly-zinc methacrylate (PZDMA). A molecular analysis of NR/ZDMA composites is
proposed in the last part of this article.

Keywords crosslink density, natural rubber, networks, stress-softening, stress-strain

behavior, zinc methacrylate

Introduction
Metal salts of unsaturated carboxylic acids have usually been used as coagents in peroxide-
cured rubbers due to the enhancement of both the crosslinking reaction in the vulcanization
process and the crosslink density.[1] Recently, some of these metal salts of unsaturated
carboxylic acids, such as zinc methacrylate (ZDMA), have been used as new reinforcing
agents for rubbers. Rubbers reinforced with this kind of reinforcing agent have high tensile
strength, tear strength, and modulus, while still retaining a high elongation at break. Metal
salts of unsaturated carboxylic acids can be added into rubbers directly or prepared in situ
through the neutralization of metal oxides and acids.[2,3] It has been reported that many
kinds of rubbers can be reinforced by metal salts of methacrylic acids (MAA), such as

Received 16 June 2011; accepted 8 September 2011.

Address correspondence to Yukun Chen, School of Mechanical and Automotive Engineering,
South China University of Technology, Guangzhou, 510640, China. E-mail: cyk@scut.edu.cn

1384
 Stress-Strain and Networks Studies of NR/ZDMA 1385

natural rubber (NR), butadiene rubber (BR), ethylene-propylene-diene rubber (EPDM),

nitrile-butadiene rubber (NBR), and poly (α-octylene-co-ethylene) elastomer (POE).[4–11]
When a peroxide is used as a curing agent, the metal salts of unsaturated carboxylic
acids will be polymerized simultaneously during rubber vulcanization no matter whether
in homo-polymerization or graft-polymerization. Ionic bond crosslinks are formed due
to the graft-polymerization of metal salts onto the rubber chains, while the poly-(metal
salt) chains separate from the rubber matrix and aggregate into nano-scaled fine particles,
forming salt crosslinks.[12–14] The fine particles, with diameters of 20–40 nm, were found
to disperse in the rubber matrix.[2,11,14] This structure, originating from the polymerization
of metal salts in rubber, is the reason for the reinforcement.[12] However, there has not been
a clear and well-accepted explanation of the mechanism and microstructure model for the
reinforcement of rubbers filled with metal salts of unsaturated carboxylic acids to date.
Tensile stress-strain measurements have been one of the useful methods for charac-
terizing rubber vulcanizates.[15] The tensile stress at a certain strain is usually used for
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characterizing the properties of the vulcanizates and interpreting the network structure
and reinforcement mechanisms.[16] Numerous constitutive models have been developed to
describe the mechanical behavior of stretched rubber. Possible sources of damage under
stress included debonding and recreation of crosslinks, chain residual stretch, and chain
breakage.[17–29] However, these descriptions cannot determine the network deformation of
rubber reinforced by metal salts of unsaturated carboxylic acids when it is stretched, and
this indetermination limits further research on the reinforcing mechanism and the rela-
tionship between structure and properties of the vulcanizates. It is necessary to study the
network deformation of rubber reinforced by metal salts of unsaturated carboxylic acids
during uniaxial tension on the microstructure level.
In this article, we focus on an NR/ZDMA system and analyze the deformation and
breakage of networks (containing covalent crosslinks and ionic crosslinks) in different
stretching cycles at different strains by using equilibrium swelling. In this system, the exis-
tence of the two types of crosslinks results in a complex microstructure of the composite. It
is considered that the reinforcement of the ZDMA–rubber is affected by various structural
factors, that is, unsaturation, polarity, formation of a nano-dispersion, ionic crosslinked
network, etc. One of the most important factors among them is the crosslinked network.
Thus, this article mainly deals with the crosslinked network of the vulcanizate during uni-
axial stretching at room temperature. Investigations of the evolution of the network during
vulcanization of the NR/ZDMA system and other influencing factors for reinforcement are
in progress.

Experiments and Methods

Materials and Sample Preparation

NR (Malaysia 1#) was provided by Guangzhou Rubber Industry Research Institute (China).
MAA, purchased from Guangzhou Xin’gang Chemical Factory (China), was purified by
distillation under nitrogen at reduced pressure. Zinc oxide (ZnO) was purchased from
Tianji Yaohua Chem. Co., Ltd. (Guangzhou, China). Dicumyl peroxide (DCP), purchased
from Sinopharm Chemical Reagent Co. Ltd. (Shanghai, China), was purified by anhydrous
alcohol recrystallization before use.
In this article, NR was reinforced by in-situ prepared ZDMA. Rubber compounds were
prepared in a two-roller mill. ZnO and MAA were added into the NR and mixed for several
minutes, then DCP was added. Theoretically 1 mol ZnO and 2 moles MAA will react to
 1386 Y. Chen and C. Xu

form ZDMA and water completely. Equivalent amounts of ZnO and MAA (ZnO/MAA
molar ratio 0.5) were used to react in the NR matrix during mixing. A high degree of
conversion to ZDMA from the in-situ reaction of ZnO and MAA had been verified by
many articles (e.g., refs. 11, 13). Here, the neutralization was assumed to have occurred
completely to form ZDMA. The compounds containing 100 weight parts of NR, 1.5 phr
(parts per 100 parts of rubber) DCP, and 0–40 phr ZDMA were sheeted on a two-roll mill
and then press cured to 2-mm-thick sheets at 155◦ C.

Tensile Stress-Strain Characteristics

Stress-strain characteristics were obtained by uniaxial tension. Samples for the tensile
tests were cut from the pressed films with a thickness of about 2 mm in a dumbbell
shape (6-mm-wide cross section). Tensile tests were carried out at room temperature using
a Computerized Tensile Strength Tester (UT-2080) produced by U-CAN Dynatex Inc.
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(Nantou, Taiwan) with a crosshead speed of 500 mm/min.

The stretching force (F) value was converted to engineering stress (σ ) using the relation
σ = F(λ)/A0 . A0 is the cross section of the sample before stretching, λ defines the principal
stretch ratio by λ = L/L0 where L0 and L are the sample lengths before and after stretching,
respectively. Therefore, the strain ε is defined as ε = (L − L0 )/L0.
The specimen was stretched to a fixed strain and then the stress was retraced to zero,
then the operation was repeated again. Because the third and fourth stretch curve almost
overlapped each other, the third stretch curve is defined as the equilibrium stretch curve.
The recovery stretch curve is defined as the stress-strain curve obtained after the specimen
had rested after the equilibrium stretch for 24 h at room temperature to ensure full recovery.

Crosslink Density Measurement

The apparent crosslink density was determined by equilibrium swelling experiments. To
determine the crosslink density at different elongations, the dumbbell-shaped specimens
were stretched to 100%, 200%, 300%, and failure elongation. Then, the middle section of
the stretched samples was chosen for the equilibrium swelling experiment. To determine the
crosslink density for different stretch cycles, the dumbbell-shaped specimens were stretched
several times to a fixed strain in the same way as described before. Then, again, the middle
section of the stretched samples was chosen for the equilibrium swelling experiments.
To calculate the crosslink density of the rubber, five weighed test pieces of rubber were
immersed in toluene at about 23◦ C for a period of 72 h. Then, the samples were blotted with
tissue paper to remove excess solvent and immediately weighed on an analytical balance.
Finally, the samples were dried in a vacuum oven for 48 h at 60◦ C until constant weight.
The volume fraction of swollen rubber in the gel, V r , which was used to represent the
crosslink density of the samples, was determined by the following equation:

m0 ϕ(1 − α)ρr−1
Vr = (1)
m0 ϕ(1 − α)ρr−1 + (m1 − m2 )ρs−1

where m0 is the sample mass before swelling; m1 and m2 are the swelled sample masses
before and after drying, respectively; ϕ is the mass fraction of NR rubber in the unswollen
vulcanizates; α is the mass loss of the vulcanizates after swelling; and ρ r and ρ s are the
rubber and toluene density (ρ s = 0.865 g/cm3), respectively.
To distinguish ionic crosslinks from covalent crosslinks, the above samples were
swollen in a mixture of toluene and chloroacetic acid once again for 120 h to destroy the
 Stress-Strain and Networks Studies of NR/ZDMA 1387

ionic crosslinks, followed by swelling in toluene for 72 h and weighed, then vacuum dried
and reweighed. Finally, V r1 was calculated from Eq. (1), which represents the covalent
crosslink density. V r2 , which is calculated by subtracting V r1 from V r , was used to represent
the ionic crosslink density.[14,20–23] In the discussion, the crosslink density of a rubber with
a given ZDMA content was the average over five test pieces from one sample.

Results and Discussion

Stress-Strain Behavior
Stress-strain curves of NR reinforced by different amounts of ZDMA stretched to rupture
were obtained with standard dumbbell-shaped samples. Maximum elongation and strength
at rupture can be evaluated from these curves. In addition, the samples had sufficient pieces
after stretching to be studied by the equilibrium swelling experiments. NR gum processed
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similarly but without the ZDMA, which was used as a reference sample. In Fig. 1, the stress-
strain curves with low ZDMA concentration (see 10 and 20 phr) display low tensile stress
at small deformations of the rubbers, followed by an abrupt increase at high deformations.
The tensile strength of the NR gum was surprisingly high, with the stress at rupture, σ max ,
of 7–8 MPa. In the presence of ZDMA, the magnitude of the stress increased rapidly with
ZDMA concentration, which we attribute to a great reinforcement by the in-situ ZDMA.
The maximum failure stress occurred for the highest loading of ZDMA (40 phr) used,
about 26 MPa. However, the strain at break decreased as the loading of ZDMA increased.
Regardless, the elongations were maintained at relatively large values.

Stress-Softening Behavior
Figure 2 shows the various stress-strain curves to 100% strain of the ZDMA-reinforced
NR. The most important information which can be obtained from Fig. 2 is the presence of
three main regimes for 100% strain:

Figure 1. Stress-strain curves to the breaking strain of the ZDMA-reinforced NR.

 1388 Y. Chen and C. Xu
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Figure 2. Stress-strain curves at 100% strain of the ZDMA-reinforced NR (color figure available
online).

• With ZDMA content in the range from 0 to 10 phr, the samples showed very weak
stress-softening behavior in which all four curves essentially superimposed. The
stress-strain behavior of the 10 phr ZDMA sample was similar to the NR gum
sample.
• With 20 phr ZDMA, stress-softening behavior was able to be distinguished. However,
the second stretch, the equilibrium stretch, and the recovery stretch curves seemed
to overlap each other.
 Stress-Strain and Networks Studies of NR/ZDMA 1389
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Figure 3. Stress-strain curves at 200% strain of the ZDMA-reinforced NR (color figure available
online).

• With 30 and 40 phr ZDMA, the different curves can be distinguished clearly. The
recovery stretch curve is close to the second stretch curve rather than the initial
stretch curve, showing a weak recovery.

From Fig. 3, two main regimes can be seen with 200% strain imposed:

• For the NR gum, the stress-softening behavior was very weak. The stress-strain
curves seem to overlap with each other.
 1390 Y. Chen and C. Xu
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Figure 4. Stress-strain curves at 300% strain of the ZDMA-reinforced NR (color figure available
online).

• With ZDMA content from 10 to 40 phr, the different stretch curves can be distin-
guished clearly. The recovery stretch curve was again much close to the second
stretch curve than the first, showing a weak recovery.

At 300% strain imposed, additional important information can be obtained, as shown

in Fig. 4:
 Stress-Strain and Networks Studies of NR/ZDMA 1391

• For the NR gum, the second stretch and equilibrium stretch curves can be distin-
guished to a small degree, but the recovery stretch curve and the initial stretch curve
were superimposed, showing a good recovery.
• From 10 to 40 phr ZDMA, the different curves can again be distinguished clearly.
In these cases, the second stretch, equilibrium stretch, and recovery stretch curves
were very close to each other when the strain did not exceed 200%. However, they
separated from each other when the strain was between 200% and 300%, and the
stress of the recovery stretch curve showed a more abrupt increase in this strain
range than the second and equilibrium stretch curves.

The stress-softening effect, often discussed in connection with filler reinforcement and
reflecting a kind of viscous loss, can be used to characterize the rubber–filler and filler–filler
interactions.[24] Figures 2–4 show stress-softening behaviors of the vulcanizates at 100%
strain, 200% strain, and 300% strain, respectively. It can be seen from these figures that the
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NR gum exhibits a weak stress-softening effect, even at 300% strain. The stretch curves of
NR gum almost overlap for both 100% strain (see Fig. 2[a]) and 200% strain (see Fig. 3[a]),
and the stretch curves for 300% strain were also very close to each other (see Fig. 4[a]).
These results indicate that the uniaxial tension had little influence on the crosslink network
of the NR gum. The stress increased quickly with increasing content of ZDMA for any
fixed strain, and the composites showed a high stress-softening effect with high content of
ZDMA. From the stress-strain characteristics of the filled samples for 100%, 200%, and
300% maximum strain, similar behaviors were observed in that the stress for any fixed strain
in the second stretch decreased in comparison to the first stretch, and the equilibrium stretch
was slightly lower than the second stretch. Here, a special behavior should be pointed out,
that is, the recovery stretch curves (recovery for 24 h at room temperature) were close to
the second stretch curves rather than the first, which shows a poor recovery of the filled
samples. This behavior is different from that of the NR filled with conventional reinforcing
fillers, such as carbon black, silica, or clay.[30] A general stress-softening recovery behavior,
which can be observed in rubber/conventional-filler systems, is that the recovery stretch
curve is close to the first stretch curve, showing very good stress recovery.[26,27]
The stress-softening effect is related to the destruction and reconstruction of crosslink-
ing bonds, local orientation of rubber molecular chains, and interactions between filler and
rubber chains.[24] In the case of a conventional reinforcing filler, such as carbon black, a
set of NR chains between two aggregates will be bound to their active sites through the
adsorption effect. These NR chains generally represent parts of longer NR chains. In the
course of stretching, the NR chains slide on or debond from the aggregates’ surface. This
debonding starts with the shortest interconnecting chain and gradually involves longer and
longer chains. The strength of monomer bonds within the NR chains is far higher than
that of NR–filler bonds. Thus, at a fixed strain, the NR chains would not break but rather
debond from their bonding sites on the aggregate surface.[28,29] Such interactions could be
rebuilt after a rest period at room temperature. The recovery of stress-softening has also
been observed through the recovery of the permanent set, the return to initial values of the
stress at a fixed strain, or of the complete stress-strain response at a high temperature. For
instance, Mullins[30] studied the stress recovery of a filled NR. He measured the stress at
an elongation of 200% after recovery at 100◦ C and compared it to the stress measured on
the material stretched to the same elongation for the first time. The material recovered 80%
of the softening after only 2 days. Similarly, Laraba-Abbes et al.[31] showed a complete
recovery of the softening of a carbon-black filled NR exposed to 95◦ C for 48 h. These
studies indicate that the physical adsorption of rubber chains on reinforcing filler particles
 1392 Y. Chen and C. Xu

is dynamic and can be rebuilt after a long time of relaxation or upon heat treatment. Fol-
lowing unloading, the debonded chains reattached back to the aggregates surface to rebuild
a new network similar to the original. Therefore, in the recovery stretch experiments, the
tension stress increased and was close to the first tension stress, showing a good recovery.
However, in the situation of ZDMA as fillers, as indicated above, the peroxides ini-
tiated the polymerization of ZDMA (both homo-polymerization and graft-polymerization
on the NR).[12,13] As a result, there were three types of ZDMA components in the vulcan-
izate: homo-PZDMA (poly-zinc methacrylate), P(NR-g-ZDMA), and residual monomeric
ZDMA. Thus, the vulcanizates contained both covalent crosslinks and ionic crosslinks,
and the slippage of ionic bonds occurred under the effect of stress. As a result, the stress-
softening mechanism of ZDMA differs from that of conventional reinforcing filler such as
carbon black. The deformation mechanism of the crosslinked network of NR vulcanizate
reinforced by ZDMA in the uniaxial tension will be discussed in the crosslink density
section below.
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Deformation of Crosslinked Network During Stretching

The stress-strain behavior indicates a remarkable reinforcing effect of in-situ formed ZDMA
in NR and a particular stress-softening behavior. The reinforcing mechanism of ZDMA is
also different from that of conventional fillers. It is thus essential to analyze the deformation
of the crosslinked network of the samples in the range of elongation investigated.
Figure 5 shows the crosslink density of the vulcanizates with different amounts of
ZDMA. The gross crosslink density (V r ) and the ionic crosslink density (V r2 ) increase
with increasing ZDMA content. On the contrary, the covalent crosslink density (V r1 ) shows
a decrease. As shown in Figs. 1–3, the stress for any given strain increased rapidly with
ZDMA concentration, which is attributed to the increasing ionic crosslink density. The ionic
crosslinks are also considered as a main reason for the reinforcement of the composites.[32]
As shown in Fig. 6, the V r , V r1 , and V r2 curves decreased with increasing strain.
All three types of crosslink densities reached a minimum at the failure elongation. The
significant variation in the crosslink density indicates that damage of the micro-structure

Figure 5. Effect of ZDMA content on crosslink density of NR/ZDMA vulcanizates.

 Stress-Strain and Networks Studies of NR/ZDMA 1393
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Figure 6. Crosslink density of vulcanizates at different strains (color figure available online).

occurred when the samples were stretched. As shown in Fig. 6(a), the V r values for 100%
strain were close to the un-stretched one when the ZDMA content did not exceeded 20
phr, whereas the V r values for larger strains were lower than that of the un-stretched one
(10 and 20 phr). This indicated that the effects of low strain (100%) on the damage of the
networks of low content ZDMA composites (10 and 20 phr) were limited, but the higher
strains (>100%) did destroy the networks of the composites. As seen from Fig. 6(b), the
V r1 values for 100% strain were also close to the un-stretched one when the ZDMA content
exceeded 20 phr, whereas the V r curve for 100% strain was lower than the un-stretched
curve in Fig. 6(a). Thus the changes of V r (30 and 40 phr) for 100% strain were attributed
to the decreases of the V r2 which was shown in Fig. 6(c). This indicates that the damage of
the crosslink network of high content ZDMA composites at low strain (100%) was mainly
due to the breakage of the ionic crosslink network. This could be explained that the high
content of ZDMA could form a more developed ionic network which was more sensitive
to the strains.
As shown in Fig. 6(c), the values of V r2 at a low concentration of ZDMA (10 phr) were
almost superimposed. Thus the changes of V r (see Fig. 6[a], strain>100%) were attributed
to the V r1 (see Fig. 6[b]). The no changes of V r2 could be explained that the low content of
ZDMA (10 phr) could only form a small quantity of ionic crosslinks (see Fig. 5) rather than
a developed ionic crosslinked network. Thus, the strains had hardly any influence on the
V r2 of 10 phr ZDMA/NR composite. We have mentioned in the introduction that the in-situ
polymerization of ZDMA results in the formation of a nano-dispersion during peroxide
curing.[7] It is also well known that the strength of the covalent bonds of NR chains is far
higher than that of ionic bonds. Thus, we suggest that an adsorption effect, as with carbon
 1394 Y. Chen and C. Xu

black, existed in the peroxide-cured ZDMA/NR composite. In Figs. 2(b) and 3(b), the
stress-strain behaviors for 10 phr ZDMA were similar to the NR gum, which is evidence
of the adsorption effect to some extent. Therefore, the observed V r1 is not a pure covalent
crosslink density but a multiple type crosslink density containing covalent crosslinks and
physical adsorption crosslinks (there might also be some other type of physical crosslinks
than adsorption on the PZDMA which will be further studied, e.g., rubber entanglement).

Crosslink Density of Different Stretching Stages

To investigate the dependence of the changes of crosslink densities on the strain amplitude,
and to see whether the ionic crosslink densities recovered after 24 h, crosslink densities for
different stretching stages were evaluated, with the initial crosslink densities being used as
a standard reference.
Figure 7 shows the (a) gross crosslink density, (b) covalent crosslink density, and
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(c) ionic crosslink density of different stretching cycles at 100% strains depending on the
ZDMA content. The decreases of V r after different stretching cycles (see Fig. 7[a]) are
mainly attributed to the damage of V r1 at low content of ZDMA (see Fig. 7[b], such as
10 and 20 phr). As long as the content of ZDMA was in excess of 20 phr, V r1 remained
nearly constant and was not affected much by different numbers of stretching cycles. For
high ZDMA content, V r2 played the main role in the network breakage (see Fig. 7[c]).
Considering Fig. 5, V r2 grew quickly, while the V r1 maintained a slow decline with increas-
ing ZDMA. And as seen in Figs. 2(d) and (e), the second stretch curve was far below the
first curve when the content of ZDMA was in excess of 20 phr. All these results indicate that

Figure 7. Crosslink density for different stretch cycles at 100% strain (color figure available online).
 Stress-Strain and Networks Studies of NR/ZDMA 1395
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Figure 8. Crosslink density for different stretch cycles at 200% strain (color figure available online).

a more developed ionic crosslink network may be formed at a higher content of ZDMA.
When the vulcanizate is subjected to a loading in tension, the ionic crosslink network will
suffer the force first, resulting in slippage of the ionic bonds under the stress.
A similar trend as in Fig. 7 can be found in Fig. 8 with 200% strains. Compared with
100% strain in Fig. 7, the crosslink network was stretched to a larger degree, to 200% strain
here. In this case, ionic crosslinks were also deformed even at low content of ZDMA (see
Fig. 8[c]). The covalent crosslinks were also inevitably destroyed. But at higher contents of
ZDMA, the effects on the covalent crosslinks became smaller and smaller (see Fig. 8[b]).
What should be mentioned here is that, after recovery for 24 h at room temperature, V r
showed a recovery to a certain degree which was mainly attributed to the recovery of V r1
(V r2 recovered to a very limited extent, see Figs. 8[b] and [c]). This result is consistent
with the tensile stress-strain behavior. As seen in Fig. 3, different stretch curves can be
distinguished clearly even at 10 phr ZDMA, and the recovery stretch showed a weak
recovery, being close to the second stretch.
As shown in Fig. 9 with a large strain of 300%, the covalent crosslinks and ionic
crosslinks were both destroyed by stretching, and the breakage of the ionic crosslinks was
very significant at high content of ZDMA. Comparing Fig. 7 to Fig. 9 and using the curves
before stretch as a reference curve, the greater the content of ZDMA or the higher the
strain, the larger the degree of reduction of V r and V r2 that results. The crosslink densities
of the second stretch and the equilibrium stretch are consistent with the tensile stress-strain
behaviors. The recovery of V r after 24 h is mainly attributed to the recovery of V r1 , V r2
maintains at a relatively stable state after being stretched. When a sample was stretched,
some bonds (such as physical adsorption) debonded, as in the case of carbon black as
 1396 Y. Chen and C. Xu
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Figure 9. Crosslink density for different stretch cycles at 300% strain (color figure available online).

mentioned before, but lots of ionic bonds slipped and broke, especially at a high content of
ZDMA. At the same time, a new ionic crosslink network was formed. Once the stress was
relieved, the slippage of ionic bonds ceased, and thus the stress recovery was very low.[33]

Crosslink Density at Different Strains

Figure 10 shows the effect of strain on the crosslink density of the NR/ZDMA vulcanizates.
This gives more intuitive information of the internal network of the vulcanizate following
stretching. The NR gum vulcanizate only has covalent crosslink density and it is almost a
horizontal line (see Fig. 10[b]). This means that there is almost no damage to the crosslink
network of NR gum in the stretching. Note that in Figs. 1(a), 2(a), and 3(a), the stress-strain
behaviors also showed no damage to the crosslink network of NR gum. V r1 decreased
significantly with the addition of ZDMA and drops with increasing strain, and reached its
lowest value at the breaking strain (see Fig. 10[b]). As shown in Fig. 10(c), V r2 exhibits
a weak declining trend for 10–30 phr ZDMA with increasing strain; however, the 40 phr
ZDMA, the highest content in this particular experiment, shows an apparent decrease. This
can be interpreted that the slippage of the ionic bonds in stretching of the low content
ZDMA rubbers led to a rapid destruction–reconstruction of the ionic crosslink networks,
resulting in a relatively stable ionic crosslink network. A more developed ionic crosslink
network was formed initially at a high loading of ZDMA (40 phr), showing more sensitivity
to strain.
Even considering the possible uncertainties in these measurements, it is clear that the
formation of the ionic crosslink network in a filled rubber with high content of ZDMA can
 Stress-Strain and Networks Studies of NR/ZDMA 1397
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Figure 10. Effect of strain on crosslink density of NR/ZDMA vulcanizates.

be considered as one of the main reasons for the remarkable reinforcement, which is also
supported by the stress-strain behaviors.

Micro-Structural Model for ZDMA/NR Composites

In our studies, poly-ZDMA was assumed to form the aggregates of diameter 20–40 nm,
which have been observed by others in rubber matrices.[2,7,11,34] At the micro-level, multi-
plet clusters were formed by the aggregates consisting of ion pairs because of the strong
electrostatic interaction between ion pairs in poly-ZDMA molecules.[35] Therefore, these

Figure 11. Microstructure model of vulcanizates: left, before stretching; right, after stretching.
 1398 Y. Chen and C. Xu

Figure 12. Microstructure of the change of ionic crosslink: left, before stretching; right, after
Downloaded by [Akdeniz Universitesi] at 02:03 25 December 2014

stretching.

multiplet clusters restrict the mobility of adjacent polymer chains (NR and poly-ZDMA),
and some of the NR chains near poly-ZDMA (mainly the NR-g-PZDMA) can also be
restricted by the adjacent multiplet clusters. The multiplet clusters formed by the grafted
polymer and homopolymer will act as a new kind of crosslink—ionic crosslinks. Simul-
taneously, some NR chains are adsorbed to the aggregates to form adsorption bonds by
Van Der Waals force, which contribute to the crosslinking. Thus, comparing the crosslink
density of the stretched networks and the stress-strain behaviors, stress-softening can be
attributed to both the adsorption bonds’ rupture or slippage along the aggregates’ surface
and ionic bonds’ slippage when the chains reached their limit of extensibility.
On the basis of our study of stress-strain behaviors and crosslink densities, we propose
a microstructure model of NR/ZDMA composites and the PZDMA phase. Figure 11 shows
schematics of the network of NR/ZDMA vulcanizates containing covalent crosslinks and
ionic crosslinks (before and after stretching). The adsorption before stretching and de-
adsorption (loss of adsorption points) by stretching are used to explain the recovery of
stress-strain behavior and the recovery of V r1 . Figure 12 shows the change of ionic crosslink
after stretching. The ionic crosslinks after stretching does not decrease so much, but it also
does not recover to the initial arrangement, and thus does not contribute so much to the
stress-strain properties.

Conclusions
The stress-strain behaviors of NR reinforced by ZDMA were studied in uniaxial stretching.
Stress-strain curves of the composites stretched to rupture showed a large reinforcement
by in-situ formed ZDMA. The composites showed a high stress-softening effect at high
content of ZDMA and large strain. In addition, after the equilibrium stretch and consequent
24-h rest at room temperature, the composites exhibited a poor stress recovery. This unique
property was different from that of conventional reinforcing fillers, such as carbon black.
The crosslink densities indicated that the ionic crosslinks contributed greatly to the
mechanical properties. The present study showed that the so-called “V r1 ,” calculated from
the swollen equilibrium, was not the pure covalent crosslink density but a multiple crosslink
density containing NR matrix covalent crosslinks and physical adsorption crosslinks. After
rest for 24 h at room temperature, the recovery of V r to a certain degree was mainly
due to the recovery of “V r1 .” The slippage of the ionic bonds in stretching led to a rapid
 Stress-Strain and Networks Studies of NR/ZDMA 1399

destruction–reconstruction of the ionic crosslink networks. Thus, the ionic crosslinks after
stretching did not decrease so much, but also did not recover to the initial state and did not
contribute so much to the stress-strain properties. It is suggested that the stress-softening
of NR/ZDMA composite is mainly due to the breaking of the adsorption bonds and the
slippage of the ionic bonds in those chains reaching their limit of extensibility.

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