Received: 9 December 2022 Revised: 13 February 2023 Accepted: 27 February 2023

DOI: 10.1002/app.53860

RESEARCH ARTICLE

Systematic investigation on the effect of processing

procedures on the performance of oil-resistant
thermoplastic vulcanizates based on HNBR/TPEE

Ziwen Cui | Liping Wei | Yingjun Liu | Aihua Du

Key Laboratory of Rubber-Plastics,

Ministry of Education/Shandong
Provincial Key Laboratory of Rubber-
Plastics, School of Polymer Science and
Engineering, Qingdao University of
Science and Technology, Qingdao, China
Correspondence
Aihua Du and Yingjun Liu, Key
Laboratory of Rubber-Plastics, Ministry of
Education/Shandong Provincial Key
Laboratory of Rubber-Plastics, School of
Polymer Science and Engineering,
Qingdao University of Science and
Technology, Qingdao, 266042, China.
Email: aihuadu@qust.edu.cn and yjliu@
qust.edu.cn
Funding information
National Natural Science Foundation of
China, Grant/Award Number: 52103058;
Natural Science Foundation of Shandong
Province, Grant/Award Number:
ZR2021QE104
Abstract
The unique “sea-island” phase of thermoplastic vulcanizates (TPVs) dictates
an inseparable correlation between micro-morphology and properties, the
studies on the processing procedures in dynamic vulcanization are of great sig-
nificance for the preparation of TPVs with desirable performance. Herein, a
new type of oil-resistant TPV with superior stretchability, low hardness, and
high elasticity has been successfully fabricated based on hydrogenated acrylo-
nitrile butadiene rubber (HNBR) and thermoplastic polyester elastomer
(TPEE). The effect of processing procedures on the phase morphology, rubber
network strength, mechanical properties, rheological performance, thermal
stability, and oil resistance of HNBR/TPEE TPV was systematically investi-
gated. In the masterbatch procedure, the homogeneous dispersion of the cross-
linking agent in the rubber phase contributes to stronger rubber networks and
effectively reduces HNBR particle size. TPV prepared by masterbatch proce-
dure exhibits a more comprehensive performance with improved mechanical
properties, better rheological performance, enhanced thermal stability and oil
resistance. In contrast, excessive dispersion of peroxide in the plastic phase
during the pre-compound procedure is demonstrated to the degradation of
TPEE, resulting in large-sized defective domains, while the deterioration of the
rubber network leads to the inferior performance of TPV. This study provides
new insights into the selection of the optimal procedure for preparing oil-
resistant TPVs.

KEYWORDS
dynamic vulcanization technology, hydrogenated acrylonitrile butadiene rubber (HNBR),
masterbatch procedure, peroxide cross-linking, thermoplastic vulcanizates (TPVs)

1 | INTRODUCTION the unique morphology of TPVs, which typically consists

Thermoplastic vulcanizates (TPVs), as a special kind of
thermoplastic elastomers (TPEs), combine the excellent
elasticity of vulcanizates at room temperature with the
superior melt processability of thermoplastics under pro-
cessing conditions.1–3 This characteristic is attributable to
of two different polymer phases, with the high content of
the cross-linked rubber phase (50–80 wt%) dispersed as
particles in the low content of the continuous phase ther-
moplastic matrix (20–50 wt%).4,5 Dynamic vulcanization
technology (DV) is the classic method for the preparation
of TPVs, as a special polymer reaction compounding

J Appl Polym Sci. 2023;e53860. wileyonlinelibrary.com/journal/app © 2023 Wiley Periodicals LLC. 1 of 12

https://doi.org/10.1002/app.53860

2 of 12
technique, first proposed by Gessler and Haslett.6,7 DV
can be implemented using a variety of equipment, includ-
ing open mills, screw extruders, and internal mixers.1
Under the DV conditions, specifically in the presence of a
temperature field above the melting temperature of the
plastic and a strong shear field, it is important to achieve
the mixing of rubber with thermoplastic melt and the
selective cross-linking process of the rubber phase with
the curing agent.8–10 After the in-situ cross-linking reac-
tion, the cross-linked rubber phase is broken up under
continuous strong shear and dispersed as particles in a
continuous resin matrix, creating a “sea-island” resem-
bling phase structure in TPVs.1,11,12 Thus, TPV materials
have been widely explored and applied in academia and
industry respectively for the superior performance, excel-
lent processability, capability of being reprocessed, and
versatility in molding methods.13–15 Notably, the tradi-
tional generally-used TPVs based on ethylene-propylene-
diene monomer rubber (EPDM)/polypropylene (PP),
natural rubber (NR)/PP, etc., were found to have signifi-
cant limitations in some extreme conditions where tem-
peratures above 135
C were consistently used and good
oil resistance was required, for example in the oil pipe-
line and automotive sectors.16 To address this challenge,
academics have developed a new category of TPVs with
excellent heat and oil resistance based on special rubbers,
which are commonly referred to as high-performance
TPVs on special purpose, also known as “Super TPVs” by
some scholars, particularly suited to industrial applica-
tions such as under-the-hood of automotive and
seals.17–20 TPVs prepared based on hydrogenated acrylo-
nitrile butadiene rubber (HNBR) are one of the most rep-
resentative categories.21
The unique phase morphology of TPVs determines a
strong correlation between the microstructure and proper-
ties. Significantly, the morphology and properties of TPVs
are affected by various factors, which include the composi-
tion ratio of rubber/plastic, the crosslinking degree and dis-
persion state of the rubber phase, the type of curing system
selected, the preparation methods and process conditions
in DV technology, and compatibility of blending compo-
nents, etc.1,22 To achieve a high-performance product, the
exploration of processing procedures is essential for a given
blending components TPV. The processing technologies of
dynamic vulcanization have been demonstrated to have a
significant effect on the cross-linking degree and size of the
rubber phase, the extent of degradation of the plastic phase,
the final phase morphology, and the overall performance
of TPVs.1 Naskar et al.23,24 reported that the performance
of peroxide-cured polypropylene (PP)/ethylene octene
copolymer (EOC) TPVs was strongly influenced by the pro-
cessing procedures. PP/EOC TPVs exhibited better
mechanical properties and thermal stability due to the
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CUI ET AL.
smallest size of rubber particles prepared by adding EOC
masterbatch to the molten PP (phase-mixed method). Fur-
thermore, their work indicated that the decrease in
mechanical properties of TPV in the conventional pre-
blending method may be attributed to the severe degrada-
tion of the PP matrix. The results of previous studies by
Yang et al.25 also suggested that the size of the cross-linked
rubber domains of the prepared conductive TPVs were sig-
nificantly affected by processing procedures, where the
average diameter of rubber particles was 550 nm for TPV
prepared by one-step method (pre-compound procedure)
and 230 μm for TPV prepared by two-step method (master-
batch procedure). For the two-step method, the rubber par-
ticles were broken down to a smaller size during the same
processing time because of a faster DV rate caused by a bet-
ter mixing state between the rubber and curing agent com-
pared with the case for the one-step TPV. As a further
demonstrated by Duan's group26 who developed a 3D
printable TPV product based on brominated butyl-rubber
(BIIR) and PP with good rheological and mechanical per-
formance via masterbatch procedure. In comparison with
the pre-compound procedure, they found that a more even
dispersion of the cross-linking agent and prolonged scorch-
ing time during the masterbatch procedure facilitated the
homogeneous cross-linking of BIIR and the effective for-
mation of small-sized rubber particles, resulting in
improved rheological properties and mechanical strength
of BIIR/PP TPV. In general, the investigations into the
preparation procedures of dynamic vulcanization can pro-
vide some novel information and insights into the relation-
ship between the morphology and properties of TPVs,
leading to crucial theoretical guidance for the exploitation
of TPV materials with desirable properties.
In this study, we have developed a new system of oil-
resistant TPV based on HNBR and thermoplastic polyester
elastomer (TPEE) with four different preparation proce-
dures by implementing the compounding and dynamic
vulcanization processes in a torque rheometer, which
promises to be an alternative material to conventional ther-
mosetting rubbers in the automotive and oil pipeline sec-
tors. Due to the highly saturated structure of the molecular
chains (selectively hydrogenated by the molecular chains
of nitrile rubber) and the presence of strong polar groups,
HNBR exhibits a comprehensive performance with high
tensile strength, outstanding oil resistance, and miraculous
aging resistance.27,28 As a block copolymer, TPEE com-
bines rubber's excellent elasticity with thermoplastic's melt
processability, with adjustable hardness, excellent mechan-
ical properties, and heat resistance, making it ideal as the
plastic phase of TPV.29 Notably, HNBR with a higher con-
tent of polar acrylonitrile groups (43 wt%) and fully satu-
rated molecular chains were chosen to work with the
peroxide cross-linking system to achieve better oil

CUI ET AL.
resistance of HNBR/TPEE TPV at high temperatures. The
development of the appropriate and highly efficient proces-
sing procedure for HNBR/TPEE TPV is the main concern
in the present work. Aiming to achieve this objective, four
different preparation methods1 were adopted, to systemati-
cally investigate the effects of the processing procedures on
the mechanical properties, rheological characteristics, ther-
mal stability, and oil resistance of HNBR/TPEE TPV. The
morphology of TPV was investigated by scanning electron
microscope (SEM), and differences in the cross-linking
degree and rubber network in TPV were studied using the
combination of equilibrium swelling experiments and a
rubber processing analyzer (RPA). Finally, the relationship
between the processing procedures and TPV performance
was obtained, shedding some new light on the preparation
of high-performance HNBR-based TPVs.
2 | EXPERIMENTAL
2.1 | Materials
HNBR (tradename THERBAN® 4307, acrylonitrile con-
tent: 42.5 wt%, residual double bonds: less than 0.9%,
mooney viscosity ML (1 + 4)100
C: 63), was kindly pro-
vided by ARLANXEO (Germany). TPEE (tradename
Bexloy® GPV36C2 NC010) with a melt flow rate of
7 g/10 min (220
C /2.16 kg), was purchased from
Dupont. 2,5-Dimethyl-2,5-di (tert-butyl peroxy) hexane
(DBPH, TRIGONOX101) with a “half-life” time of 1 h at
134
C and 0.1 h at 156
C, was obtained from Akzo Nobel
N.V (the Netherland). Pentaerythritol tetrakys
3-(3,5-ditert-butyl-4-hydroxyphenyl)-propionate (antioxi-
dant 1010) and Tns-(2.4-di-tert-butyl)-phosphite (antioxi-
dant 168) were all commercial products obtained from
Shanghai Macklin Biochemical Co., Ltd (China).
2.2 | Sample preparation
According to our previous work, the TPV with a rubber/
plastic composition ratio of 60/40 showed the best overall
balance of thermoplastic elastomeric properties and pro-
cessability.30 Therefore, the 60 wt% rubber/40 wt% plastic
was chosen for the preparation of HNBR/TPEE TPVs in
this work. In addition, DBPH was selected as the cross-
linking agent for HNBR at the dosage of 1.5 phr (parts
per hundred of rubber). And antioxidants 1010&168 were
added to the TPV system to reduce the degradation reac-
tion of the plastic phase during the DV process, at a dos-
age of 0.5 wt% of TPEE for each antioxidant. In the
present work, HNBR and TPEE were subjected to melt
mixing and dynamic vulcanization processes using a
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3 of 12
HAAKE torque rheometer (HAAKE PolyLab OS and
Rheomix OS, Thermo Fisher Scientific). Unless otherwise
stated, the mixing temperature for the TPV preparation
was 205
C with a rotating speed of 80 rmin1, and the
DV time for all TPVs was 6 min. TPEE was dried in an
oven at 80 to remove moisture before preparation.
HNBR/TPEE-TPVs were prepared by four different
methods, and the detailed processing procedures were sys-
temically presented in Figure 1. Method 1 and Method
2 both carried out the premixing process of HNBR and
TPEE by simple melt blending first at 205
C and high shear
stress, where TPEE and antioxidants were melted in the
internal mixer for 3 min, followed by simple mixing of
HNBR to the melt for 2 min. In Method 1 (named as pre-
compound procedure, also known as the pre-blending
method23,24 or one-step method25), DBPH was subsequently
added into the molten HNBR/TPEE premixed blends for
the DV of 6 min under the same processing conditions. The
HNBR/TPEE TPV prepared by Method 1 was named
M1-TPV. Method 2 (named as cooling mixing with cross-
linker procedure) differed from Method 1 in that DBPH
was added to the cooled-down HNBR/TPEE premix and
mixed at room temperature to obtain a better dispersion of
DBPH in HNBR of the premix, as the plastic phase TPEE
was in a solid state in the premix. The blends with the
cross-linking agent were then dynamically vulcanized to
obtain M2-TPV. Method 3 was the masterbatch procedure,
also known as the phase mixing method23,24 or two-step
method25 in some studies, and comprised two steps. As a
first step, HNBR and DBPH were mixed in the internal
mixer at room temperature for 5 min to obtain the HNBR
masterbatch. For the second step, TPEE and antioxidants
were compounded for 3 min. Subsequently, HNBR master-
batch was added to the melt to carry out the DV for 6 min.
As a comparison, we also proposed the most facile Method
4, where all components were added to the HAAKE torque
rheometer simultaneously for the mixing and DV for 6 min.
The HNBR/TPEE TPVs prepared via Method 3 and Method
4 were named M3-TPV and M4-TPV. As soon as the com-
pounds were discharged from the HAAKE, TPVs were
immediately sheeted at room temperature by a two-roller
mill, followed by hot- and cold-compression molding under
a pressure of 10 MPa at 215
C and ambient, respectively.
2.3 | Characterization
2.3.1 | Volume swell ratio measurements
To understand the formation of the network structure of
the rubber phase during dynamic vulcanization, the
swelling behavior of TPVs prepared from different proce-
dures was investigated by the equilibrium volume

4 of 12
F I G U R E 1 Schematic illustration of the preparation procedures of HNBR/TPEE TPV. [Color figure can be viewed at
wileyonlinelibrary.com]
swelling method.31 The volumetric swelling ratio (Q) was
used to qualitatively indicate the cross-linking degree
(CD) of the rubber phase, with a small Q value denoting
a high CD.5 Circular samples were first cut from the
sheets and immersed in cyclohexanone for diffusion
experiments. After reaching the equilibrium swelling
state within 48 h, the test samples were removed from
the liquid container and the excess solvent was quickly
wiped from the surface. Then the samples were weighed
immediately (Ws). Subsequently, the samples were dried
in a vacuum oven at 80
C for 12 h, then weighed (Wd)
and measured the density of the dried samples by drain-
age method. The experiments were performed at room
temperature (25
C) and three samples were selected for
each test to minimize the weighting error. The volume
swell ratio Q of TPV samples was calculated by the fol-
lowing Equation (1)32:
W s  W d ρd
Q¼1þ  ð1Þ
Wd ρs
where ρs is the density of the solvent and ρd is the density
of TPV sample after dissolution and drying.
2.3.2 | Rubber network analysis
The rubber networks of HNBR/TPEE-TPVs were also mea-
sured by a rubber processing analyzer (RPA 2000, Alpha
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CUI ET AL.
Technologies, USA) in strain scanning mode.5,33 The test
conditions were as follows: test temperature 190
C, fre-
quency 0.2 Hz, the strain scanning range of 1%–1200%, and
the specimen preheated for 5 min before testing.
2.3.3 | Mechanical properties measurements
The tensile tests of TPVs were measured at room tempera-
ture using a tensile machine (Zwick/Roell Z005, Germany)
according to ISO 37:2011. The hardness of TPVs was tested
at room temperature according to ISO 7619-1:2010 on a
Shore A hardness tester (GT-GS-MB, GOTECH testing
machines Inc, China). The elasticity of TPVs was studied
by strain recovery test at room temperature using the ten-
sile machine, with a tensile rate of 100 mm/min.34,35 TPV
samples were first extended to the strain of 50%, and then
the tensile force was relaxed to zero; the residual strain was
defined as the permanent set. The hysteresis loss of TPVs
at 50% deformation was calculated by the ratio of the inte-
gral area of the loading-unloading loop to the integral area
under the loading curve.36 All results were taken from the
middle value of at least five measurements.
2.3.4 | Rheological behavior measurements
The rheological characterization of TPVs was investi-
gated using a rotational rheometer (ARES-G2, TA

CUI ET AL.
Instruments, USA) with a parallel plate of 2 mm gap
and 8 mm diameter. The strain scanning mode was
first performed in the range of 0.1%–10% to deter-
mine the linear viscoelastic range at 200
C for each
TPV. A strain value within the linear viscoelastic
region (typically 0.1%) was then selected and the
TPVs were measured in oscillatory shear mode at
200
C with a frequency scan range of 0.1–100 rad/s.
Every specimen was preheated for 5 min before
testing.
2.3.5 | Melt flow rate
The melt flow rate (MFR) of TPVs was measured at
220
C with a 5 kg load using a melt indexer (GT-
7100-MI, GOTECH testing machines Inc, China), accord-
ing to ISO 1133-1:2011.
2.3.6 | Morphological analysis
The morphological study of HNBR/TPEE-TPVs was
investigated using a scanning electron microscope, SEM
(JSM-7500F, JEOL Co., Japan). The specimens were first
fractured after being frozen in liquid nitrogen, and the
fractured surface of the specimens was then etched in N,
N-dimethylformamide (DMF) for 60 min. Subsequently,
the samples were fully dried in a vacuum-drying oven.
All the samples were gold-coated before SEM
observation.
2.3.7 | Thermal gravimetric analysis
The thermal stability of TPVs was determined using a
thermogravimetric analyzer (TG209F1, NETZSCH,
Germany), and the test temperature ranged from 30 to
600
C at the heating rate was 10
C/min under an N2
atmosphere.
2.3.8 | Oil resistance measurements
The oil aging study of the TPVs was measured by
immersing the rectangular test specimens in IRM903 oil
at the temperature of 150
C for 72 h, according to ISO
1817:2011. After the specified time, the samples were
removed from the oil, and then removed the excess oil
from the surface. The change of samples in weight (ΔW)
and volume (ΔV) were measured to assess the oil resis-
tance at high temperatures.
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5 of 12
3 | RESULTS A ND DISCUSSIONS
3.1 | Effect of processing procedures on
rubber network strength of HNBR/
TPEE TPV
The different processing procedures have a significant
effect on the cross-linking degree of the rubber phase and
the rubber network strength formed in TPV, and the
cross-linking condition of the rubber phase is strongly
related to the phase morphology and various properties
of TPV.1 Firstly, it was reported that the cross-linked rub-
ber particles can be considered as fillers dispersed in the
continuous phase of the thermoplastic by the unique
phase morphology of TPVs.5,34,35 As a result, the varia-
tion in rubber network strength of HNBR/TPEE TPV
with different preparation procedures can be investigated
by RPA. Specifically, the difference between the maxi-
mum and minimum values of the storage modulus (ΔG´)
represents the rubber network strength in TPV, with a
higher ΔG´ indicating a stronger rubber network.37,38
Furthermore, considering the poor resistance of HNBR to
ketone solvents, equilibrium swelling tests were carried
out on HNBR/TPEE TPV in the presence of cyclohexa-
none, of which there was no effect on TPEE. Therefore,
the volume swelling ratio Q of TPV indicates the CD of
HNBR, with a smaller Q value representing a higher
CD. To investigate the variation in the CD and network
strength of the rubber phase in HNBR/TPEE TPV under
different preparation procedures, the combination of the
RPA test and volume swell ratio was used in this work,
and the results are shown in Figure 2a and b,
respectively.
It can be seen that the ΔG´ of four kinds of TPV have
the order in M3-TPV>M4-TPV>M2-TPV>M1-TPV, while
the volume swell ratio Q follows in the opposite order:
M3-TPV<M4-TPV<M2-TPV<M1-TPV. The results of
both ΔG´ and Q indicate that M3-TPV prepared by the
masterbatch procedure shows the highest CD of HNBR
and forms the strongest rubber network in HNBR/TPEE
TPV system. In contrast, the M1-TPV prepared by the
pre-compound procedure shows a significant decrease in
the CD of HNBR and the deterioration of the rubber net-
work. M2-TPV, on the other hand, shows a slightly
increased ΔG´ and a smaller Q based on M1-TPV, indicat-
ing that the method of blending the cross-linking agent
with the HNBR/TPEE premix at room temperature is
effective in improving the rubber network strength and
the CD. The discrepancies in the CD and rubber network
are mainly attributed to the processing procedure deter-
mining the dispersion of the cross-linking agent (DBPH)
in the rubber phase. Only a sufficient dispersion of DBPH

6 of 12
in HNBR can improve the CD and rubber network
strength, simultaneously reducing the impact on the plas-
tic phase. As the masterbatch procedure involves mixing
the DBPH with HNBR uniformly in advance, a more suf-
ficient cross-linking reaction can be carried out in the
rubber phase of the TPV after the start of DV and an opti-
mal rubber network is formed.
3.2 | Effect of processing procedures on
morphology of HNBR/TPEE TPV
The phase morphology of TPVs plays a decisive role in
aspects such as tensile properties, elasticity, and rheologi-
cal behavior.1,39,40 The phase morphology of HNBR/
TPEE TPV prepared by different processing procedures
was observed in this work by SEM, as shown in Figure 3.
The high magnification images (a-d) are used to show the
approximate size and shape of HNBR, with the represen-
tative rubber domains being labeled, while the low mag-
nification images (a’-d’) show the overall uniformity of
the two-phase distribution in the TPV system. Notably,
the brittle fracture surfaces of all TPV specimens were
etched using the polar solvent DMF before SEM observa-
tion. Consequently, part of the TPEE on the surface was
dissolved, allowing the cross-linked HNBR particles to be
exposed.
As can be observed in Figure 3, the variation in the
micro-morphologies of HNBR/TPEE TPV with different
processing procedures is evident. Among all TPVs,
M3-TPV and M4-TPV show a more refined phase struc-
ture, with smaller rubber domain sizes (1–3 μm) and a
more homogeneous dispersion in the TPV system, fur-
thermore, the etched samples show a flatter surface with
no obvious defects as observed in low magnification
images. In contrast, a significant increase in rubber size
is found in M2-TPV, with the diameter of the cross-linked
rubber domains increasing to around 5 μm. As for
M1-TPV prepared from pre-compound procedure, a more
disordered phase morphology is shown, where the
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CUI ET AL.
F I G U R E 2 (a) Storage modulus
versus shear strain and (b) volume swell
ratio of HNBR/TPEE TPV with different
processing procedures. [Color figure can
be viewed at wileyonlinelibrary.com]
dispersed HNBR particles are irregular in shape and span
a wide range of size distributions (1–10 μm). In particu-
lar, the M1-TPV shows large-sized striated domain
defects (see low multiplicity Figure 3a’) and therefore the
overall homogeneity of the two phases of the TPV is low.
It can be assumed that in the pre-compound procedure,
the plastic phase TPEE underwent degradation due to
the influence of the cross-linking agent, resulting in a
chaotic morphology. To verify this speculation, we have
separately conducted an important validation experiment
to clarify the negative effect that peroxide DBPH has on
TPEE under DV conditions, which is placed in the sup-
plementary material. The rheological results from
Figure S1 confirm that, in addition to the cross-linking
effect of HNBR during DV, the excessive dispersion of
peroxide in the plastic phase can aggravate the degrada-
tion of TPEE. Therefore, a rational processing procedure
is significant for the preparation of HNBR/TPEE TPV
with a well-defined phase morphology (small-sized rub-
ber domains and good dispersion).
The special micro-morphology of TPV and the “sea-
island” phase structure determine an inextricable link
between the performance and morphology. Specifically,
the differences in the morphology of the rubber phase,
rubber network strength, and degradation degree of the
plastic phase of HNBR/TPEE TPV with different prepara-
tion procedures inevitably have a significant impact on
the properties of TPV, including mechanical properties,
elasticity, rheological properties, thermal stability and oil
resistance of HNBR/TPEE TPV, which are systematically
investigated in the following sections.
3.3 | Effect of processing procedures on
mechanical properties of HNBR/TPEE TPV
The stress–strain behavior of HNBR/TPEE TPV with dif-
ferent preparation procedures is shown in Figure 4a, and
the specific mechanical properties data are presented in
Figure 4b, including the tensile strength (TS), elongation

CUI ET AL.
F I G U R E 3 Micromorphology of
HNBR/TPEE TPV with different
processing procedures. [Color figure can
be viewed at wileyonlinelibrary.com]
at break (EB) and shore A hardness of TPV. The TPV for
all preparation procedures in Figure 4a exhibited the
stress–strain behavior of a typical elastomer. At low
strains (<50%), the stress of TPV increased significantly
with increasing strain, when the elastic modulus was
analogous to that of thermoplastics. While at high strains,
the stress of TPV increased relatively slowly without
yielding, which was similar to the deformation behavior
of vulcanized rubber.
From the mechanical property data in Figure 4b, it
was observed that preparation procedures had a
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7 of 12
significant effect on the tensile properties of HNBR/TPEE
TPV. The lowest TS (7.6 MPa) and EB (739%) were
observed in M1-TPV and M4-TPV, respectively. While
M2-TPV and M3-TPV showed better tensile properties,
with the TS both around 10.2 MPa, the EB of M2-TPV
achieved the maximum value (1059%) in all TPVs. The
improved stretchability of M2-TPV demonstrated
the effectiveness of Method 2. The procedure of adding
the curing agent to the cooled-down HNBR/TPEE premix
ensured that DBPH was mostly dispersed in HNBR and
that TPEE was subjected to less degradation than in

8 of 12
Method 1. The elastic properties of TPEE were main-
tained after the DV, providing better ductility for the TPV
system. As shown by the stress–strain curves, however,
the modulus of M3-TPV prepared by the masterbatch
procedure showed a significant increase at high strains
(>300%) with a small margin of error in the tensile prop-
erties, indicating a more homogeneous blending system.
The hardness of HNBR/TPEE TPV did not fluctuate sig-
nificantly with the change in processing procedures, with
the shore A hardness of all TPVs remaining stable at
around 65, which is in the category of low hardness
elastomers.
Elasticity is an important index to evaluate the
mechanical properties of elastomers, and the tensile
recovery tests were adopted in this work to investigate
the elasticity of TPV with different preparation proce-
dures, as shown in Figure 5a. The two important parame-
ters (the permanent set and hysteresis loss) derived from
tensile recovery curves are summarized in Figure 5b. The
smaller values shown for both parameters indicate the
higher elasticity of TPV.34,35 Notably, the deformation at
50%, the permanent set was less than 14% for all TPVs,
indicating the good elasticity of HNBR/TPEE TPV. In
addition to the high CD of HNBR, it was attributed to the
plastic phase TPEE which also provided excellent elastic-
ity to the TPV system. In contrast, M3-TPV prepared by
the masterbatch procedure demonstrated the best elastic-
ity by simultaneously showing the lowest permanent set
(11.7%) and hysteresis loss (56.8%) among all TPVs, while
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CUI ET AL.
F I G U R E 4 (a) Stress–strain
curves; (b) Tensile strength,
elongation at break and shore A
hardness of HNBR/TPEE TPV with
different processing procedures.
[Color figure can be viewed at
wileyonlinelibrary.com]
F I G U R E 5 (a) Tensile recovery
curves; (b) Permanent set and
hysteresis loss of HNBR/TPEE TPV
with different processing
procedures. [Color figure can be
viewed at wileyonlinelibrary.com]
M4-TPV showed a slight decrease in elasticity. The better
elasticity is provided by the higher CD of the rubber
phase and rubber network strength of M3-TPV, as dem-
onstrated in Section 3.1. Moreover, the more homoge-
neous phase structure and smaller rubber domain sizes
formed in the TPV system have been proven to be condu-
cive to improving elasticity. M1-TPV exhibits a significant
decrease in elasticity (higher permanent deformation and
hysteresis loss) attributed to the combination of deterio-
ration of the rubber network and degradation of the plas-
tic phase TPEE.
The preparation of HNBR/TPEE TPV by Method
3 (masterbatch procedure) ensures that the peroxide
cross-linker can be almost completely dispersed in the
rubber phase, allowing for a higher CD of HNBR during
DV. More importantly, the good dispersion of peroxide in
HNBR reduces the degradation of the plastic phase
TPEE, so that M3-TPV exhibits more comprehensive and
improved mechanical properties. Furthermore, Method
3 is much easier in processing than Method 2, which is
important for improving preparation efficiency.
3.4 | Effect of processing procedures on
rheological properties of HNBR/TPEE TPV
DV technology is the compounding process in which the
plastic phase is in the molten state. One of the major
advantages of TPV materials is that a wide range of

CUI ET AL.
F I G U R E 6 (a) Storage modulus (G´)
and (b) complex viscosity (η*) versus
angular frequency (ω) of HNBR/TPEE
TPV with different processing
procedures. [Color figure can be viewed
at wileyonlinelibrary.com]
F I G U R E 7 Melt flow rate of HNBR/TPEE TPV with different
processing procedures. [Color figure can be viewed at
wileyonlinelibrary.com]
molding methods is available, including compression,
extrusion, and injection. Smooth and stable melt flow of
the compounds under the DV and molding conditions
are essential to obtain TPV products with excellent prop-
erties. Therefore, the rheological properties are of great
importance in guiding the processing of TPV. The rheo-
logical properties of HNBR/TPEE TPV prepared by differ-
ent procedures were systematically investigated in this
work with a rotational rheometer and melt flow rate
(MFR) test, and the results are shown in Figures 6 and 7,
respectively. The low storage modulus (G´), low complex
viscosity (η*) and high MFR values of TPV in the molten
state have been reported to indicate better rheological
properties, which lead to better melt processability, easy
recyclability, and high preparation efficiency of TPV
materials.17,30
As shown in Figure 6b, the complex viscosity (η*) of
all TPVs decreased linearly with the increasing angular
frequency (ω), exhibiting the typical characteristics of
pseudoplastic fluids with shear thinning behavior. The
TPVs exhibit the rheological behavior that resembles that
of a pure plastic melt at high frequencies (HF), caused by
the collapse and deformation of the strong rubber net-
work at HF, demonstrating that all HNBR/TPEE TPVs
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9 of 12
prepared in this work showed rheological characteristics
of an elastomer in the molten state, with fully melt pro-
cessing properties under the temperature and shear fields
of dynamic vulcanization.1,39 Combining the data from
Figures 6 and 7, it can be obtained that M3-TPV and
M4-TPV show similar rheological behavior with lower G´
and η* at higher frequencies, whereas M3-TPV has a
slightly higher MFR value, indicating the better rheologi-
cal property. This is attributed to the fact that the master-
batch procedure achieves a homogeneous dispersion of
the cross-linked rubber particles in the continuous phase
TPEE and reduces the size of the rubber domains and the
probability of coalescence. In contrast, the significant
increase in G´ and η* and the decrease in MFR for
M2-TPV indicate a deterioration in rheological proper-
ties, which is related to the increase in density and size of
the HNBR phase, as demonstrated in Section 3.2. The
excessive size of the rubber phase domains leads to poor
processing flow performance for TPV in the molten state
and a difficult molding process. A pronounced improve-
ment in the rheological properties (decrease in G´ and η*
and increase in MFR) was found for M1-TPV as com-
pared to M2-TPV, attributed to the excessive degradation
of TPEE in the pre-compound procedure, which resulted
in a slightly lower viscosity of TPV in the molten state.
3.5 | Effect of processing procedures on
thermal stability of HNBR/TPEE TPV
The effect of the processing procedures on the thermal
stability of TPV can be investigated by comparing the
thermogravimetric (TG) curves, as shown in Figure S2. It
was observed that the gaps between each curve were
slight because all TPVs had the same formulation. Hence
two parameters were derived from the TG curves to fur-
ther characterize the thermal stability of TPV, namely
the initial decomposition temperature (temperature at 5%
mass loss, Ti) and maximum decomposition temperature
(temperature at maximum mass loss, Tmax), all of which
are summarized in Table 1.

10 of 12
T A B L E 1 Thermogravimetric data of HNBR/TPEE TPV with
different processing procedures
Thermogravimetric analysis data
Initial
decomposition Maximum
temperature decomposition
Samples (Ti) /
C temperature (Tmax) /
C
M1-TPV 361.9 453.7
M2-TPV 363.9 454.6
M3-TPV 364.9 455.6
M4-TPV 364.0 453.7
It can be demonstrated from the TG data in Table 1
that Ti and Tmax of M3-TPV achieved the highest values
among all TPVs, indicating a pronounced improvement
in thermal stability. M3-TPV prepared by the master-
batch procedure showed better thermal stability. In con-
trast, M1-TPV prepared by the pre-compound procedure
showed the lowest thermal stability. The higher thermal
stability of M3-TPV achieved by the masterbatch proce-
dure is due to two factors, one being the higher CD of
HNBR achieved in the M3-TPV specimen, which is the
main factor. The other reason is that the masterbatch
method reduces the degradation of the plastic phase,
allowing TPEE to maintain high thermal stability in the
blending system as well.
3.6 | Effect of processing procedures on
oil resistance of HNBR/TPEE TPV
The preparation procedures have already been demon-
strated to have a significant influence on the CD of the
rubber phase in HNBR/TPEE TPV, and HNBR with its
high content of polar acrylonitrile groups takes on more
responsibility for the oil resistance of TPV system.
HNBR-based TPVs have the potential for applications in
hydraulic pipes and seals, and therefore a proper and effi-
cient preparation procedure must be chosen to ensure
that the best possible high-temperature oil resistance of
TPV is achieved. The oil resistance was investigated by
immersing HNBR/TPEE TPV with different preparation
procedures in IRM903 oil. The change in weight (ΔW)
and volume (ΔV) of the samples were measured after
72 h, as shown in Figure 8, with smaller values for both
parameters indicating better oil resistance. Notably, to
amplify the differences in oil resistance between the dif-
ferent preparation methods of TPV, we selected more
severe conditions for the oil aging test, with the aging
temperature raised to 150
C.
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CUI ET AL.
F I G U R E 8 Mass and volume change rates of HNBR/TPEE
TPV after being immersed in IRM903 oil at 150
C for 72 h. [Color
figure can be viewed at wileyonlinelibrary.com]
The data in Figure 8 clearly showed that the oil aging
study at high temperatures obtained similar results to the
TG analysis, where M3-TPV prepared from the master-
batch procedure exhibited the optimal oil resistance. Spe-
cifically, after the oil aging at 150
C, the ΔW and ΔV of
M3-TPV were reduced by 4.2% and 5.2%, respectively, rel-
ative to M1-TPV. Combining the results of previous sub-
sections, it can be concluded that the reduced size of the
HNBR phase in the M3-TPV sample prepared by the
masterbatch procedure leads to a higher phase density of
the dispersed HNBR and a strengthening in the rubber
network. Consequently, the formation of a higher cross-
linking degree in the rubber phase of the TPV system
facilitates the improvement of the thermal stability and
the oil resistance of TPV in extreme environments.
4 | CONCLUSIONS
In this work, we have successfully fabricated oil-resistant
TPV based on HNBR and TPEE with fine morphology,
superior stretchability, low hardness and high elasticity,
by four different processing procedures of dynamic vulca-
nization technology. It has been demonstrated by the sys-
tematic investigation that the processing procedures have
a significant effect on the phase morphology, rubber net-
work, and multifaceted properties of HNBR/TPEE TPV.
In the masterbatch procedure, the homogeneous disper-
sion of the cross-linking agent in the rubber phase con-
tributes to the formation of a highly cross-linked HNBR
and a stronger rubber network in the TPV system, with
effective reduction of the HNBR particles size and better

CUI ET AL.
dispersion in M3-TPV observed by phase morphology
analysis. As a result, M3-TPV exhibits more comprehen-
sive performance with improved mechanical properties,
better rheological properties, enhanced thermal stability,
and high-temperature oil resistance. While in the pre-
compound procedure, excessive dispersion of peroxide in
the plastic phase is demonstrated to result in degradation
of TPEE, which consequently causes an increase in
HNBR particle size and the presence of large size defect
domains, and the lower CD of HNBR and deterioration
of rubber network leads to the inferior performance of
M1-TPV. Method 2, with the addition of a cooling blend
cross-linking agent, based on method 1, has proved to be
effective in improving the tensile properties of HNBR/
TPEE TPV, but has the disadvantage of being a cumber-
some process with low processing efficiency. This study
provides information and insight into exploring the rela-
tionship between processing procedures in dynamic vul-
canization and the performance of TPVs, providing
theoretical guidance and production guidelines for the
preparation of HNBR-based TPVs with desirable proper-
ties to facilitate further applications in automotive and
other heat- and oil-resistant applications.
CONFLICT OF INTEREST STATEMENT
The authors declare that they have no conflict of interest
or personal relationships that could affect the work in
this paper.
A U T H O R C ON T R I B U T I O NS
Ziwen Cui: Data curation (lead); formal analysis (lead);
software (lead); visualization (lead); writing – original
draft (lead). Liping Wei: Formal analysis (supporting);
methodology (supporting); software (supporting); writing
– original draft (supporting). Yingjun Liu: Funding
acquisition (equal); investigation (equal); writing –
review and editing (supporting). Aihua Du: Funding
acquisition (lead); project administration (lead); valida-
tion (lead); writing – review and editing (lead).
A C K N O WL E D G M E N T S
This work was funded by the National Natural Science
Foundation of China (52103058) and the Natural Science
Foundation of Shandong Province of China
(ZR2021QE104).
DATA AVAILABILITY STATEMENT
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
ORCID
Ziwen Cui https://orcid.org/0000-0002-2120-5609
Aihua Du https://orcid.org/0000-0002-8098-6759
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11 of 12
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