Received: 26 December 2022 Revised: 8 March 2023 Accepted: 10 March 2023

DOI: 10.1002/app.53909

RESEARCH ARTICLE

Effects of polyamide elastomer on the morphology,

crosslink density, mechanical, and oil-resistant properties
of acrylonitrile-butadiene rubber/polyamide elastomer
vulcanizates

Huiyu Wang 1 | Xianggong Zhang 2 | Guangyong Liu 1

1
Ministry of Education/Shandong
Provincial Key Laboratory of Rubber- Abstract
Plastics, Qingdao University of Science & Polyamide elastomer (PAE) is a novel material which may improve the perfor-
Technology, Qingdao, Shandong, China
mances of acrylonitrile-butadiene rubber (NBR). This work uses equilibrium
2
Wuhan Institute of Marine Electric
swelling and rheological apparatus to study the effects of the PAE content on
Propulsion, China State Shipbuilding
Corporation Limited, Wuhan, Hubei, the overall crosslink densities of NBR/PAE vulcanizate. The presence of PAE
China significantly increased the overall crosslink density. During the aging stage,
Correspondence
the overall crosslink density first increased and then decreased with increasing
Guangyong Liu, Ministry of Education/ aging temperature from 25 to 150
C. There was a linear relationship between
Shandong Provincial Key Laboratory of the tensile strength with the overall crosslink density of the NBR/PAE vulcani-
Rubber-Plastics, Qingdao University of
Science & Technology, Qingdao, zate. Oil resistance of the NBR/PAE vulcanizate was improved with increasing
Shandong 266042, China. PAE content.
Email: liuguangyong@qust.edu.cn
KEYWORDS
Funding information
acrylonitrile-butadiene rubber, aging, crosslink density, mechanical properties, oil-resistant
Natural Science Foundation of Shandong
properties, polyamide elastomer
Province, Grant/Award Number:
ZR2020QE079

1 | INTRODUCTION use at high temperatures, up to 175
C, and can be used

Acrylonitrile-butadiene rubber (NBR) is a copolymer of
butadiene and acrylonitrile, which has many advantages
in excellent resistance to oil and corrosive media over
other commonly used rubbers such as butadiene rubber
and styrene-butadiene rubber.1,2 Therefore, NBR has
been extensively used in automotive profiles, such as oil
pipes, oil tanks, and oil seals3–5 and it has become one of
the largest consumptions of synthetic rubber except used
in tire products.6,7 By contrast, polyamide elastomer
(PAE) is a class of thermoplastic block copolymers made
from nylon molecular chain segments as hard segments
and polyether amine, polyether ester chain segments as
soft segments.8–10 It has the advantages of sufficient elas-
ticity, toughness, oil resistance, and high temperature
resistance. PAE is a class of nylon elastomers suitable for
for long periods at 150
C.8 Thus, PAE is frequently
applied in multiple fields, such as automotive industry,
machinery, electronic appliances, electrical precision
instruments, sporting goods, medical treatment, and
telecommunications.10,11
Crosslink density is an important parameter that dic-
tates the physical properties of vulcanizates. The type and
degree of crosslinking network of the vulcanizates deter-
mines the physical properties, such as modulus, hard-
ness, and tensile strength.12–14 Three main vulcanization
systems, namely phenolic resin vulcanization, sulfur vul-
canization, and peroxide vulcanization systems, are
widely used for the vulcanization of NBR. Phenolic vulca-
nization gives rubber good mechanical properties and
heat resistance, and it is the predominant vulcanization
system used in industry to produce thermoplastic

J Appl Polym Sci. 2023;e53909. wileyonlinelibrary.com/journal/app © 2023 Wiley Periodicals LLC. 1 of 12

https://doi.org/10.1002/app.53909

2 of 12
elastomers (TPE). Compared with sulfur vulcanization,
the peroxide curing system endows the NBR rubber prod-
ucts with high modulus, low compression permanent
deformation and thermal aging properties. On the other
hand, peroxide crosslink has many disadvantages, such
as low tensile and tear strengths and flexural resistance,
which limit its application in diene rubber. The crosslink
density of NBR composites all change with increasing
amounts of phenolic resin, sulfur, and peroxide. The
aging temperature exerts an important influence on the
crosslink density. The tensile strength of NBR composites
is improved by slightly increasing the crosslink density in
the early stages of thermo-oxidative aging.15 As the aging
temperature increases, the formation of surface defects
and inhomogeneities lead to significant changes in the
crosslink structure under the thermo-oxidative environ-
ment, which accelerates the microcrack sprouting in the
NBR composites during deformation. The microcracks
expand rapidly with stretching, leading to a decrease in
tensile properties.16
Attempts to improve the mechanical properties and oil
resistance of NBR were made. Setua et al.17 developed dif-
ferent grades of oil resistant TPE based on blends of NBR
and high density polyethylene to replace NBR/polyvinyl
chloride blends. Yu et al.18 blended an epoxy resin modi-
fied NBR with lignin to enhance the oil resistance and
mechanical properties of NBR. Ning et al. developed a
unique microstructure to improve the oil resistance of
NBR/polypropylene vulcanizate19 which was similar to
ethylene-vinyl acetate rubber/poly(vinylidene fluoride)
vulcanizate.20 In the manufacturing process of Geolast by
Monsanto Company, the technology of full dynamic vulca-
nization was used, and the technology of compatibilizers
was used fully. The reactive compatibilizer NBR with ter-
minal carboxyl group and maleic anhydride grafted with
polypropylene were used as compatibilizers in the NBR/PP
blending system, and TPEs with good properties were
obtained.21,22 However, research on the mechanical prop-
erties and oil resistance of NBR/PAE blends has rarely
been reported. Thus, the motivation of this study is to
develop and characterize NBR/PAE blends.
In this work, NBR/PAE blends with various ratios
were prepared and then vulcanized to investigate the cur-
ing characteristics, mechanical properties and oil resis-
tance. Equilibrium swelling and rheological testing
methods were used to characterize the overall crosslink
density. It is expected to quantify the effect of aging tem-
perature on the overall crosslink density of the NBR/PAE
vulcanizates and that of the overall crosslink density on
their tensile strength. Changes in mechanical properties
and overall crosslink density of the NBR/PAE blends
under different aging conditions were further analyzed to
provide some references for the practical applications of
NBR/PAE based rubber products.
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WANG ET AL.
FIGURE 1 The chemical structure of PAE.
TABLE 1 Designations for the formulation of NBR/PAE
blends.
Ingredients/phr 1 2 3 4 5
NBR 100 100 100 100 100
PAE 0 10 20 30 40
Note: The other ingredients (phr): sulfur 1.5, TMTD 0.5, DM 2, antioxidant
4020 1, antioxidant RD 0.5, zinc oxide 5, stearic acid 1.
Abbreviation: phr, parts per hundreds of rubber.
2 | MATERIALS AND
EX P ERI MEN TS
2.1 | Materials
Nitrile rubber (34% acrylonitrile content, Mooney viscosity
(ML1 + 4100
C), 45). Nylon elastomer (Arkema 35R53)
used in this work was provided by Arkema France, and its
chemical structure is shown in Figure 1. Vulcanization sys-
tems consisting of sulfur and 2,20 -dithiobis(benzothiazole)
and tetramethylthiuram disulfide as well as zinc oxide and
stearic acid were purchased from Shanghai Rheinland,
China, and antioxidant systems consisting of antioxidant
poly(1,2-dihydro-2,2,4-trimethylquinoline) and antioxidant
N-1,3-dimethylbutyl-N0 -phenyl-p-phenylenediamine (4020)
were commercially available industrial products.
The formula of NBR/PAE blends is listed in Table 1.
2.2 | Preparation of NBR/PAE blends
NBR was first mixed in internal mixer (XSM-500; Shanghai
KCCK Co., Ltd., Shanghai, China) at 200
C for half a
minute with a rotation speed of 70 rpm. Then PAE as well
as antioxidant was added and mixed for 3 min. The total
mixing time was 3.5 min. The mixing curves of NBR/PAE
blends in internal mixing process were shown in Figure 2.
Then, the mixtures were removed from the internal mixer
and processed into sheets at 50
C with crosslink agents on
a laboratory two-roll mill (Farrel, GX-2003-GLT, America)
with a roller speed ratio of 1:1.2 and then kept at room tem-
perature for 24 h before curing. It should be noted that mix-
ing characterized by stress and (residence) time is always a
crucial operation for any multiphase materials such as
polymer blends.23–26 In this work, it was not optimized.
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WANG ET AL. 3 of 12

F I G U R E 2 Mixing curves of 210

25 (a) (b)
NBR/PAE blends in internal 200
mixing process: (a) Torque–time
20 190 Add NBR

Torque, dNm
curves, (b) temperature–time

Temperature,
Add PAE and antioxidant
180
curves. [Color figure can be 15
viewed at 170
Add PAE and antioxidant
wileyonlinelibrary.com] 10
160

5 150
NBR NBR
NBR/PAE=100/10 NBR/PAE=100/10
Add NBR NBR/PAE=100/20 140 NBR/PAE=100/20
NBR/PAE=100/30
0 NBR/PAE=100/30
NBR/PAE=100/40 NBR/PAE=100/40
130
0 50 100 150 200 0 50 100 150 200
Time, s Time, s

The curing time was determined by a Moving Die Rheome-
ter 2000 (MDR2000) from Alpha Technologies. The pre-
pared NBR/PAE blends were vulcanized at 150
C for
t90 + 5 min to obtain 2 mm rubber sheets.
2.3 | Experiments
2.3.1 | Thermal aging
Oil aging test was performed in an aging oven in the tem-
perature range of 150
C for 24 and 48 h as per ASTM
D471-98. We used 10# Hydraulic oil. When the specified
time was reached, the test specimens were removed from
the oil and wiped with tissue paper to remove the excess
oil from the sample surface. Finally, tensile properties of
the specimens after aging were measured to estimate oil
resistance according to ASTM D471-98. Equation (1) was
used for calculating the change in volume. Hot air aging
was carried out in a temperature-controlled aging cham-
ber. In this work, NBR/PAE blends were aged at
100, 120, and 150
C for 24 h according to GB/T 3512-200.
wafter  wbefore
Change in volume ð%Þ ¼  10:
wbefore
2.3.2 | Vulcanization characteristics
The vulcanization characteristics of samples were ana-
lyzed with the MDR2000 at 150
C for 20 min according
to ASTM D2084-95.
temperatures were set to 100, 120, and 150
C to investi-
gate the tensile strength at different aging temperatures.
2.3.4 | Overall crosslink density by
equilibrium swelling method
The overall crosslink density of the NBR/PAE vulca-
nized rubber was studied by equilibrium swelling
method by using the modified Flory–Rehner
Equation (2). Circular specimens (ca. 1.0 g, 2 mm thick-
ness) were punched by using a circular die and swollen
in cyclohexanone (200 mL) at room temperature (25
C)
for 96 h until arriving at the equilibrium swelling state.
After the equilibrium, the swollen weight and
de-swollen weight were measured and used to calculate
the vr as per Equation (3). From the swollen and
de-swollen weight, the overall crosslink density was
calculated relative to the NBR and PAE phases as
expressed by (ν + PAE)27 by Equation (2). The swelling
ratio q was calculated by Equation (6).
1 Lnð1  vr Þ þ vr þ χvr 2
ðν þ PAE Þ ¼  1 , ð2Þ
ð1Þ vs vr 3  0:5vr
vR
vr ¼ , ð3Þ
vR þ vsol
Mf  Mi
vsol ¼ , ð4Þ
ρs
MR
vR ¼ , ð5Þ
ρR

2.3.3 | Tensile strength  

M f M i
ρs
q¼ , ð6Þ
The tensile strength of the NBR/PAE vulcanized rubber Mi
was characterized using a universal testing machine where (ν + PAE) = number of moles of effectively elastic
(Zwick/Roell Z005, Germany) at a crosshead speed of chains per unit volume of NBR [mol/mL] (crosslink den-
500 mm/min according to ASTM 412. The aging sity) in presence of PAE.
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4 of 12 WANG ET AL.

Mi is the initial mass of the vulcanizate before swell-
ing, Mf is the final mass of the vulcanizate after swelling,
ρs is the density of cyclohexanone, ρR is the density of
unfilled NBR/PAE, and MR is the mass of NBR/PAE. χ is
the Flory–Huggins interaction parameter between rubber
and solvent which can be calculated using three-
dimensional solubility parameters as described in our
previous work,28–30 and the calculated χ values are:
0.0598 for NBR-cyclohexanone, 0.05938 for NBR/PAE
(100/10)-cyclohexanone, 0.06058 for NBR/PAE (100/20)-
cyclohexanone, 0.06279 for NBR/PAE (100/30)-
cyclohexanone and 0.06279 for NBR/PAE (100/40)-cyclo-
hexanone, vs is the molar volume of solvent (103 cm3/
mol for cyclohexanone).
2.3.5 | SEM analysis
The samples were placed in liquid nitrogen for 3 min and
then brittle fractured to form a new surface, followed by
gold spraying of the low-temperature fractured surfaces.
Scanning electron microscope can directly observe size,
distribution, and agglomeration of nanomaterials. It is
also possible to directly observe the microscopic morphol-
ogy of polymers, such as the dispersion of the reinforcing
value, in the order of pure NBR (0.49 N*m) < PAE
(10 phr) (0.68 N*m) < PAE (20 phr) (0.85 N*m) < PAE
(30 phr) (1.07 N*m) < PAE (40 phr) (1.31 N*m). Pure
NBR has a lower torque value due to the absence of PAE.
It shows that the maximum torque rises with the increas-
ing PAE content. The increase in maximum and mini-
mum torque is probably due to the interaction between
the PAE and NBR molecules forming physical crosslink-
ing points, which increases the overall crosslink density.
As shown in Figure 3b, the torque difference (MH  ML)
reflecting the crosslinking level of the vulcanizates
decreases as the amount of PAE decreases except for the
pure NBR.
The optimum curing time refers to the time when the
torque value continues to rise (MH  ML) * 90% after the
rubber compound reaches the minimum torque ML in
the mold cavity, which characterizes the vulcanization
rate of the rubber. It is shown in Figure 4 that with the
5
4.69
4
T90, min

material within the matrix.31–33 The dispersion and cross- 3

sectional structure of the PAE phase in NBR were evalu- 2.29 2.21 2.15 2.08
ated by scanning electron microscopy (JSM-6360LV;
2
JEOL, Tokyo, Japan) at an accelerating voltage of 10 kV.

1
3 | R ES U L T S A N D D I S C U S S I O N
0
3.1 | Curing characteristics of NBR/PAE 0 10 20 30 40
vulcanizates PAE content, phr
Curing behaviors of NBR/PAE blends are shown in F I G U R E 4 Effect of PAE on the optimum curing time (T90) of
Figure 3a, it can be seen that the minimum torque indi- NBR/PAE vulcanizates. [Color figure can be viewed at
cating the flow ability of the compound shows a high wileyonlinelibrary.com]

16 16
(a) (b)

12 14
(MH-ML), dNm
Torque, dNm

8 12
F I G U R E 3 The effect of
PAE content on the
10 vulcanization characteristics of
4 NBR
NBR/PAE=100/10 NBR/PAE vulcanizates:
NBR/PAE=100/20
NBR/PAE=100/30 8 (a) vulcanization curves,
0 NBR/PAE=100/40
(b) MH  ML curve. [Color
0 2 4 6 8 10 12 0 10 20 30 40
figure can be viewed at
Time, min PAE content, phr wileyonlinelibrary.com]

WANG ET AL.
NBR 10phr PAE
PAE
30phr PAE
PAE
F I G U R E 5 Scanning electron microscopy images of brittle fracture of NBR filled with 0, 10, 20, 30, and 40 phr PAE. [Color figure can
be viewed at wileyonlinelibrary.com]
addition of PAE, the optimum curing time (T90) of
NBR/PAE vulcanizates shows a downward trend, and it
decreases from 4.69 to 2.29 min after adding 10 phr of
PAE. It indicates that PAE added to NBR matrix can
greatly improve the vulcanization rate and production
efficiency, which may be attributed to the possibility of
the generation of amines from the degradation of PAE at
the curing temperature. These amines can be used as
activation accelerators during vulcanization reaction
process.
3.2 | SEM analysis of NBR/PAE
vulcanizates
Phase morphology is an important factor for multiphase
materials.34–36 The morphology of an immiscible polymer
blend depends mainly on its composition,37,38
compatibilization,39,40 and the processing conditions.41,42
PAE and NBR are polar polymers and interact with each
other to a certain extent.
The typical matrix-dispersed droplet morphology
can be seen in Figure 5, where PAE is dispersed in the
NBR matrix. It can be seen in Figure 5 that the number
of black holes produced on the low-temperature brittle
fracture surface gradually decreases with the gradual
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5 of 12
20phr PAE
PAE
40phr PAE
PAE
increase of PAE, which are produced due to the poor
bonding between the PAE phase and the interface of
the NBR matrix. The number of black holes decreases
with the increase of PAE, which can be explained that
the interaction between the polar groups on the surface
of PAE and the polar groups on the surface of NBR is
gradually enhanced and the interfacial bonding
becomes better. With the increase of PAE, it is obvious
from Figure 5 that the particle size of PAE phase gradu-
ally increases.
3.3 | Effect of PAE on overall crosslink
density
Crosslinking refers to the formation of a stable three-
dimensional network structure between chain segments,
which can be formed by various vulcanizing agents such
as (sulfur, peroxide, and so forth) or by physical means.
A number of factors influence the overall crosslink den-
sity of filled vulcanizates, such as filler–rubber interac-
tion, chemical crosslinking, and physical crosslinking.
Strong intermolecular forces occur when PAE blends
with NBR. The oriented arrangement of the amide
groups of PAE results in a regular arrangement of the
macromolecular chains, and the formation of hydrogen
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6 of 12 WANG ET AL.

bonds between the –NH– and –CO– groups results in ment, crystallization, and physical crosslinking points.44
more stable connections.43 Therefore, speculation is made that the tensile strength
The equilibrium swelling measurement was adopted of NBR should also increase gradually with the gradual
to calculate the overall crosslink density of NBR/PAE increase of PAE, so the plot between the tensile strength
vulcanizates. The effect of PAE on the overall crosslink and the overall crosslink density is finished as shown in
density of NBR blends is shown in Figure 6a. With the Figure 13. It can be seen from Figure 6a that the overall
dosage gradually increasing of PAE, the overall crosslink crosslink density shows a linear increase with the
density of NBR/PAE vulcanizates increases from increase of PAE.
3.21  104 to 6.98  104 mol/cm3, and the increasing The linear relationship between the overall crosslink
trend in overall crosslink density is clearly observed. This density and the PAE content is given by Equation (7).
increase in overall crosslink density may be due to the
increase in the crosslinking network between NBR and Overall crosslink density ¼ 0:091  ½C PAEðphrÞ


PAE. The abundant crosslinking network is mostly attrib- þ 3:29 R2 ¼ 0:9937 : ð7Þ
uted to NBR chains crosslinking and the creation of the
bound NBR/PAE structure via chemical bonding and
physical entanglement points of the molecular chains. The coefficient of determination R2 is more than 0.99,
With the content of polar groups such as amide groups indicating that the linear regression fits the data well.
increased, the intermolecular chain interaction may It can be seen from Figure 6a,b that with increasing
increase because the hydrogen bond can be produced PAE content, (MH  ML) and the overall crosslink den-
between the cyano groups of NBR and amide groups of sity show the same trend. Thus attempt has been made to
PAE. Moreover, this agglomeration increases the physical correlate (MH  ML) with the overall crosslink density,
crosslink density of vulcanized rubber. As the PAE con- and a linear dependency of (MH  ML) as a function of
tent increases, the intermolecular chain interactions may the overall crosslink density has been quantitatively
make the molecules locally generate regular arrange- obtained, as Equation (8).
Overall crosslink density, 10-4mol/cm3

7.2 (a) Unaged 15.0 (b)

y=0.091x+3.29 y=7.13+0.90x
6.4 R2=0.9937 13.5 R2=0.9864
(MH-ML), dNm

F I G U R E 6 (a) The overall

5.6 12.0
crosslink density measured by
4.8 10.5 the equilibrium swelling method
9.0
13.5
of NBR/PAE vulcanizates,
(MH-ML), dNm

4.0
12.0 (b) Relationship of MH  ML
7.5 with the overall crosslink
3.2 10.5

6.0
4.5 6.0
Overall crosslink density, 10-4mol/cm3
density. [Color figure can be
0 10 20 30 40 0.0 1.5 3.0 4.5 6.0 7.5 viewed at
PAE content, phr Overall crosslink density, 10-4mol/cm3
wileyonlinelibrary.com]

3.2 3.2
(a) (b)
3.0 y=2.92-0.027x 3.0 y=3.90-0.298x
2.8
R2=0.9547 2.8
R2=0.9657
q, ml/cm3
q, ml/cm3

2.6 2.6

2.4 2.4
F I G U R E 7 Correlations of
2.2 2.2
swelling ratio (q) with PAE
2.0 2.0 content (a) and the overall
1.8 1.8
crosslink density (b). [Color
0 10 20 30 40 3 4 5 6 7 figure can be viewed at
PAE content, phr Overall crosslink density, 10-4mol/cm3 wileyonlinelibrary.com]

WANG ET AL.
F I G U R E 8 Swelling
mechanism diagram of the
NBR/PAE vulcanizates. [Color
figure can be viewed at
wileyonlinelibrary.com]
½M H  M L  ¼ 7:13 þ 0:90
to less swelling response of vulcanizates. It can be
 Overall crosslink density R2 ¼ 0:9864 :
ð8Þ
In order to investigate the effect of PAE on the swell-
ing ratio (q), the plot of q and PAE is achieved in
Figure 7a. It can be seen that the swelling ratio of the
NBR/PAE vulcanizates gradually decreases with the
increasing PAE content, and a linear correlation trend is
obtained by mathematical fitting in Equation (9). The
increased number of crosslinking points introduced by
excess PAE content led to the polymer network acting as
a barrier against cyclohexanone diffusion. On the other
hand, the enlargement of the elastic force in the chain
caused by the increased crosslinking points restricts the
stretching of the network structure, thus generates a
decline in the swelling ratio.


q ¼ 2:92  0:027  ½C PAE R2 ¼ 0:9547 : ð9Þ
Swelling ratio is affected significantly by the overall
crosslink density, and thus the relationship between
swelling ratio and overall crosslink density is attempted
to be established. It can be seen from Figure 7b that the
swelling ratio decreases with the increase of overall cross-
link density, and a linear result is obtained by mathemat-
ical fitting. Therefore, it is now easier to explain the
phenomenon that higher overall crosslink density leads
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7 of 12
inferred from the mathematical fit that the swelling reac-
tion tends to disappear at this very high crosslinking level
when the overall crosslink density is greater than
13  104 mol/cm3.
The cyclohexanone transport behavior of NBR/PAE
vulcanizates can be explained with the morphology of
the blends. Figure 5 shows the scanning electron micro-
graphs of the fractured surface of NBR/PAE blends with
NBR/PAE ratios 100/0, 100/10, 100/20, 100/30, and
100/40. Figure 5 represents PAE is dispersed in the con-
tinuous NBR matrix. The continuity of the NBR phase
facilitates the smooth passage of small cyclohexanone
molecules, even in the presence of a heterogeneous dis-
persion morphology.45,46 A small amount of cyclohexa-
none molecules will also enter the PAE phase. The
schematic diagram of cyclohexanone swollen the
NBR/PAE vulcanizates can be deduced as shown in
Figure 8.
3.4 | The effect of temperature on the
overall crosslink density of NBR/PAE
vulcanizates
The variation of overall crosslink density with tempera-
ture is mainly due to postvulcanization, oxidative
crosslinking, and the degradation of chain at high tem-
perature.47 Figures 9 and 10 clearly demonstrate that
the overall crosslink density of NBR/PAE vulcanizates

8 of 12
(a)
(c)
F I G U R E 1 0 Effect of aging temperature and PAE content on
overall crosslink density of NBR/PAE vulcanizates. [Color figure
can be viewed at wileyonlinelibrary.com]
increases and then decreases with the increasing aging
temperature. With the gradual increase in aging tem-
perature, the residues of the vulcanizing agent are
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WANG ET AL.
F I G U R E 9 Effect of PAE
(b)
content on overall crosslink
density of NBR/PAE
vulcanizates at different aging
temperatures. (a) Unaged.
(b) Aging at 100
C for 24 h.
(c) Aging at 120
C for 24 h.
(d) Aging at 150
C for 24 h.
[Color figure can be viewed at
wileyonlinelibrary.com]
(d)
evenly distributed in the NBR/PAE vulcanizates, pro-
moting the continued crosslinking of the molecular
chains in the high aging temperature environment.
The NBR/PAE vulcanizates may form a more compact
three-dimensional crosslinking network structure,
which restricts the movement of the molecular chains
and gradually increases overall crosslink density. When
the temperature exceeds the vulcanization temperature
of 150
C, the postvulcanization effect is basically com-
pleted. The high temperature leads to molecular chain
cleavage, which may destroy the vulcanization cross-
linking network structure of polymer molecular chains,
decreasing the overall crosslink density and showing
poor performance retention. The predicted changes in
the crosslinking network during aging are simulated in
Figure 11.
From Figure 9, it can be clearly noticed that the over-
all crosslink density shows a correlation trend with the
PAE. The linear dependencies of the overall crosslink
density and PAE are performed via mathematical fittings
to further study the effect of PAE on the overall crosslink
density of NBR at different aging temperatures as given
in Table 2.
As can be seen from Table 2, the slope of the change
in overall crosslink density with PAE is basically around
0.09 at different aging temperatures for 24 h, respectively,
almost showing the same trend of change.
 10974628, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.53909 by Indian Institute Of Technology, Kharagpur Central Library, Wiley Online Library on [04/04/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
WANG ET AL. 9 of 12

T A B L E 2 Relationship between the

Aging temperature Fitted curve R2
overall crosslink density and PAE
components at different aging Unaged Overall crosslink density = 0.091*[C]PAE(phr) + 3.29 0.9937


temperatures. Aging at 100 C for 24 h Overall crosslink density = 0.092*[C]PAE(phr) + 4.21 0.9451


Aging at 120 C for 24 h Overall crosslink density = 0.091*[C]PAE(phr) + 4.38 0.9836
Aging at 150
C for 24 h Overall crosslink density = 0.090*[C]PAE(phr) + 3.64 0.9931

F I G U R E 1 1 Predicted
changes in the crosslinking
network during aging of
NBR/PAE vulcanizates. [Color
figure can be viewed at
wileyonlinelibrary.com]

3.5 | Effect of PAE on the mechanical
properties and oil resistance of NBR
It can be seen from Table 3 and Figure 12 that the 100%
modulus, 300% modulus, hardness, and tensile strength
of the NBR/PAE vulcanizates increase significantly with
increasing PAE content. It is obvious that the modulus of
the mixture will be higher than that of the matrix if the
high modulus component reinforces the low elastic mod-
ulus matrix, mainly due to the reduction in the volume
content of the matrix material. However, there are many
other factors to make the component truly reinforced in
nature, the most important of which is the mutual bond-
ing between the matrix and the component. The increase
in modulus and tensile strength of NBR/PAE is due to
the fact that PAE contains a large number of polar
groups, such as amide bonds, which can generate van der
Waals forces and hydrogen bonds with the cyanide of the
NBR molecule. These interactions can allow the transfer
of stress to the reinforcing phase, which in turn increases
 10974628, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.53909 by Indian Institute Of Technology, Kharagpur Central Library, Wiley Online Library on [04/04/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
10 of 12 WANG ET AL.

TABLE 3 Effects of different fractions of PAE on mechanical properties of NBR blends.

PAE content, phr 0 10 20 30 40

100% Modulus, MPa 1.3 1.4 1.7 2.1 2.8
300% Modulus, MPa 2.0 3.1 4.5 5.0 6.5
Tensile strength, MPa 2.8 5.2 7.7 8.7 10.1
Elongation, % 435 427 456 457 468
Hardness, Shore A 52 54 58 62 64

10.5

Tensile strength, MPa

9.0

7.5

6.0

4.5
y=-3.2225+1.9829x
3.0 R2=0.9481
2.8 3.5 4.2 4.9 5.6 6.3 7.0
Overall crosslink density, 10 mol/cm3 -4

F I G U R E 1 3 Relationship between overall crosslink density

F I G U R E 1 2 Stress–strain curves of NBR blends with different and tensile strength of NBR/PAE vulcanizates. [Color figure can be
fractions of PAE. [Color figure can be viewed at viewed at wileyonlinelibrary.com]
wileyonlinelibrary.com]

load during deformation of NBR/PAE vulcanized rub-

the modulus and tensile strength of the NBR/PAE vulca-
nizates. However, the effect of PAE on the elongation at
break was not significant, which indicates that the free
space between the chains of the NBR/PAE vulcanizates
does not change significantly after the addition of PAE.
And with the increase of PAE, the hardness of the
NBR/PAE vulcanizates also gradually increases, which is
because the degree of crosslinking network of NBR/PAE
vulcanized rubber keeps getting bigger.
As discussed above, PAE similarly impacts the ten-
sile strength and overall crosslink density. Therefore,
attempts are made to correlate the tensile strength and
overall crosslink density to deeply understand the
effect of crosslinking structure on the mechanical prop-
erty. As shown in Figure 13, it can be seen that the ten-
sile strength increases with the increase of overall
crosslink density, and there is a certain linear trend of
the overall crosslink density and tensile strength. This
is because with the overall crosslink density increases,
the number of effective molecular chains that bear the
ber increases.
Different ratios of NBR/PAE vulcanizates were tested
for high temperature oil resistance, as shown in
Figure 14 below.
It can be seen from Figure 14 that the oil resistance of
the NBR/PAE vulcanized rubber gradually improves with
increasing PAE content. In particular, the tensile strength
and elongation at break show only slight changes com-
pared with the other blends when the PAE content is
40 phr. This may be because the overall crosslink density
of NBR/PAE vulcanized rubber keeps increasing with the
addition of PAE. Meanwhile PAE molecules contain a
large number of polar groups, which can greatly resist
the entry of oil small molecules. When the PAE content
is less than 20 phr, the tensile strength and elongation at
the break of the vulcanized rubber show a significant
decrease compared with the unaged sample. This is prob-
ably due to the entry of small oil molecules into the vul-
canized rubber, resulting in the fracture of the molecular
chain when subjected to stress. As the aging time
 10974628, 0, Downloaded from https://onlinelibrary.wiley.com/doi/10.1002/app.53909 by Indian Institute Of Technology, Kharagpur Central Library, Wiley Online Library on [04/04/2023]. See the Terms and Conditions (https://onlinelibrary.wiley.com/terms-and-conditions) on Wiley Online Library for rules of use; OA articles are governed by the applicable Creative Commons License
WANG ET AL. 11 of 12

F I G U R E 1 4 Stress–strain 14
10 (a) 10.1 468 (b) 12.0(402)
curves of NBR/PAE under 12
8.7 457
different aging conditions: 8 NBR/PAE=100/0 NBR/PAE=100/0
7.7 456 10 NBR/PAE=100/10
NBR/PAE=100/10

Stress, MPa

Stress, MPa
(a) Unaged; (b) Aging in 10# NBR/PAE=100/20 NBR/PAE=100/20 8.3(345)
Hydraulic oil for 24 h at 150
C; 6 NBR/PAE=100/30
5.2 427
8 NBR/PAE=100/30
NBR/PAE=100/40
NBR/PAE=100/40
(c) Aging in 10# Hydraulic oil 6 5.9(310)
4
for 48 h at 150
C, and
4 3.9 256
2.8 435
(d) Volume change of vulcanized 2
2 1.9 182
rubber with different PAE ratios
immersed in 10# Hydraulic oil 0 0
at 150
C for 48 h. [Color figure 0 100 200 300 400 500 0 100 200 300 400
can be viewed at Strain, % Strain, %
wileyonlinelibrary.com]

2.0

%
12 (c) 12.3 389 (d)
1.8

Change in volume
10 NBR/PAE=100/0
NBR/PAE=100/10 1.6
8.5 294
Stress, MPa

NBR/PAE=100/20
8 1.4
NBR/PAE=100/30
NBR/PAE=100/40
6 6.3 275 1.2

4 4.1 262 1.0

0.8
2 2.0 215
0.6
0
0.4
0 50 100 150 200 250 300 350 400 NBR N/P=100/10 N/P=100/20 N/P=100/30 N/P=100/40

Strain, %

increases, the molecular chains continue to be cross-
linked, resulting in improved performance.
Figure 14d shows the percentage of volume swell
after immersion of NBR and NBR/PAE in 10# Hydraulic
oil at 150
C. It can be seen that as the PAE content
increases, the volume change decreases, and the oil resis-
tance improves. Specifically, the NBR compounding with
40 phr PAE shows approximately three times the resis-
tance to 10# Hydraulic oil. The improvement in oil resis-
tance is mainly due to the increased polarity in PAE. In
addition to this, the additional crosslinking network for-
mation in the NBR/PAE vulcanized rubber transforms
the vulcanized rubber into a harder and less oil-
permeable material. The higher the overall crosslink den-
sity of the vulcanized rubber, the more difficult it is for
oil to enter the vulcanized rubber.
4 | C ON C L U S I ON S
This work revealed the effects of the PAE content on
the curing characteristics, overall crosslink density,
mechanical properties, and oil resistance of NBR/PAE
vulcanizates as well as that of the aging temperature on
their overall crosslink density. The addition of the PAE
not only accelerated the vulcanization process but also
increased the overall crosslink density of the NBR/PAE
vulcanizates. The overall crosslink density of NBR/PAE
vulcanizates increased first and then decreased with
increasing aging temperature from 25 to 150
C, the
change of the crosslink density with the temperature
from 25 to 150
C might be attributed to the crosslinking
network formation and the molecular chain degrada-
tion. Below 120
C, the formation of new crosslinking
bonds prevailed. Above 120
C, the degradation of the
crosslinking network dominated. The mechanical prop-
erties, such as tensile strength, hardness, and modulus,
all improved with increasing PAE content. The tensile
strength of NBR/PAE vulcanizates increased linearly
with the overall crosslink density. The oil resistance of
NBR increased with the addition of PAE. Interesting
conclusions were obtained for better understanding the
effects of PAE content on the curing characteristics,
overall crosslink density, mechanical properties and oil
resistance of NBR/PAE vulcanizates and for providing
effective experimental and theoretical support for prac-
tical application.
AUTHOR CONTRIBUTIONS
Huiyu Wang: Data curation (lead); formal analysis
(lead); software (lead); supervision (lead);
writing – original draft (lead); writing – review and edit-
ing (lead). Xianggong Zhang: Investigation (support-
ing); resources (supporting); software (supporting);

12 of 12
validation (supporting). GuangYong Liu: Funding
acquisition (equal); investigation (equal).
A C K N O WL E D G M E N T S
We thank Qingdao University of Science and Technology
and Wuhan Institute of Marine Electric Propulsion for
permission to publish this article.
DATA AVAILABILITY STATEMENT
The authors declare that the main data supporting the
findings and conclusions of this study are available
within the article. Original and additional data is avail-
able from the corresponding author upon request.
D E C LA R A T I O N O F CO M P E T I N G I N T E R E S T
The authors declare that they have no known competing
financial interests or personal relationships that could have
appeared to influence the work reported in this article.
ORCID
Guangyong Liu https://orcid.org/0000-0002-8193-1215
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How to cite this article: H. Wang, X. Zhang,
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