Polymer Bulletin (2024) 81:2179–2196

https://doi.org/10.1007/s00289-023-04808-3

ORIGINAL PAPER

Fabrication of EPDM/LDPE shape memory composites:

the effect of vulcanization and crystals

Qiangqiang Han1 · Wei Liu1 · Yunwang Xu2 · Ziwu Cao2 · Yukun Chen1,3

Received: 4 January 2023 / Revised: 13 April 2023 / Accepted: 17 April 2023 /

Published online: 2 May 2023
© The Author(s), under exclusive licence to Springer-Verlag GmbH Germany, part of Springer Nature 2023

Abstract
In this paper, a series of ethylene propylene diene monomer/low density polyeth-
ylene (EPDM/LDPE) composites with the shape memory effect (SME) are pre-
pared by polymer blending method. The cross-link structure and crystallization are
regulated by the impact of thermodynamic factor and content of peroxide, and the
influence on SME is also investigated. The results demonstrate that the interfacial
adhesion originates from the good interfacial compatibility and interfacial graft-
ing reaction between the phases, and the cross-linked chemical structure improves
interfacial adhesion and forms abundant tiny LDPE crystals, which plays a crucial
role in exploring the SME and improving the mechanical performance of EPDM/
LDPE composites. A balanced state between the mechanical properties and SME is
achieved when dicumyl peroxide content is 1 wt.%; the tensile strength and elonga-
tion at break reach 19.2 MPa and 1499%, respectively, while the shape fixation ratio
(Rf) and shape recovery ratio (Rr) are ~ 99% and ~ 85%, respectively.
Graphical abstract

Extended author information available on the last page of the article

13
Vol.:(0123456789)

Content courtesy of Springer Nature, terms of use apply. Rights reserved.

 2180 Polymer Bulletin (2024) 81:2179–2196

Keywords Ethylene propylene diene monomer · Covalent cross-links ·

Crystallization · Shape memory behavior

Introduction

Recently, stimuli-responsive materials that can respond to external stimuli (e.g.,

heat, light, magnetism, and electricity) have attracted increasingly attention from
researchers in academia and industry [1–3]. As polymeric stimuli-responsive mate-
rials, shape memory polymers (SMPs) have achieved fruitful results. Due to the fas-
cinating and practical capabilities, SMPs have a wide range of applications in many
fields covering smart devices [4–6], packaging [7], biomedicine [8–10], and aero-
space [11, 12].
The most classical way to trigger the shape memory effect (SME) is driven by
heat, or the respond of heat shape memory polymers (HSMPs) to temperature [3].
For HSMPs, the melting temperature (Tm) [13, 14] or glass transition temperature
(Tg) [15–17] is the switching temperature (Ttrans). To achieve SME, two phrases
should exist, one of which is the reversible phase, responsible for restoring the
deformed shape to its original state and holding, where the presence of chain entan-
glement, physical cross-link, and chemical cross-link facilitates recovery process.
Another is the permanent phase, which is used for freezing the temporary shape in
response to different stimuli, and is charged by crystals or hard segments. SME has
been found in a variety of polymers including semicrystalline polymers [18, 19],
amorphous polymers [20], and liquid crystalline elastomers [21].
Over the past few decades, a large number of SMPs with excellent performance
have been designed based on thermomechanical theory and phase transition theory.
Initially, many researchers worked on the synthesis of various complicated block
polymers, which combine the phase separation with excellent compatibility [22–24].
However, the synthesis process and fabrication of polymer are relatively distressing,
resulting in limited applications. Due to the availability, convenience, and efficiency
in preparation, a lot of attention had been diverted into SMPs prepared by polymer
blending method [25–27]. The SMPs based on polymer blending method combine
the desired properties of individual components directly and effectively, and tremen-
dous reports have demonstrated the feasibility of this strategy [28]. For example, Liu
et al. [29] designed SMPs based on carboxylic styrene butadiene rubber (XSBR)/
ferriferrous oxide (­Fe3O4)/zinc dimethacrylate (ZDMA) composites, ­ Fe3O4 was
incorporated to endow XSBR with a magnetic property to achieve SME, ZDMA
was employed as a compatibilizer for ­Fe3O4 and XSBR. They also confirmed that
the interfacial adhesion between the phase played a critical role in transferring
stress process and effectively improved the SME. Fan et al. [13] designed heat-trig-
gered shape memory (HSM) fluorosilicon thermoplastic vulcanizates (TPVs) via
core–shell dynamic vulcanization, in which the appropriate interfacial compatibility
facilitated the increasing of interface area and promoted abundant tiny crystals in the
composites.
In the work, we designed a SMP based on ethylene propylene diene monomer
(EPDM) and low-density polyethylene (LDPE) via polymer blending method.

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 Polymer Bulletin (2024) 81:2179–2196 2181

The crystallization of LDPE is regarded as permanent phase to retain the tempo-

rary shape, while the energy is stored in the chemically cross-linked EPDM phase.
LDPE with a low degree of cross-linking promotes tiny crystals, which enables it
to obtain better SME [30]. The cross-linked structure and crystallinity of different
EPDM/LDPE composites were investigated in detail by regulating their DCP con-
tent. Meanwhile, the effects of crystallinity and cross-linking structure on SME and
mechanical properties were examined. The results indicate that excellent SME was
benefited from interfacial adhesion and abundant tiny crystals. Considering the mass
production and a substantial cost advantage of EPDM and LDPE, the prepared mate-
rials have good potential applications in pipe connection and packaging materials.

Experimental section

Materials

EPDM was purchased from Jilin Chemical Co. Ltd. (China) with 56% ethylene
and 7.5% 5-ethylidene-2-norbor-nene, its density was 0.87 g/cm3, and ML (1 + 4,
100 °C) was 40; LDPE was purchased from Prime polymer Co. Ltd., density was
0.90 g/cm3, and MFI was 3.8 g/10 min (190 °C, 2.16 kg); dicumyl peroxide (DCP)
was purchased from Sinopharm Chemical Reagent Co. Ltd; ZnO (analytical pure)
was purchased from Xi Long Chemical Company (Guangzhou, China).

Preparation of EPDM/LDPE composites

EPDM and LDPE were compounded in torque rheometer (H RTOI-55/20, POTOP,

China) to prepare EPDM/LDPE compounds at 110 °C with a rotation rate of 60 rpm.
It should be noted that the volume of the torque rheometer chamber is 200 ­cm3 and
the filling ratio is about 67.8%. To realize the homogeneous blend, mix for 4 min
after torque stabilization. Subsequently, the compounds were removed from the
chamber to a two-roll mill, and DCP and ZnO were added and masticated for 7–10
times to mix homogeneously. Finally, the EPDM/LDPE compounds were pressed
into sheets by hot cured at 180 °C for 5 min.
The formulations of investigated EPDM/LDPE composites are listed in Table 1. For
all composites, the weight ratio of EPDM/LDPE was fixed at 50/50, and the loading
amount of ZnO was fixed at 5% weight of EPDM and LDPE, DCP was 0%, 0.5%, 1%,

Table 1  Formulations of Sample EPDM LDPE ZnO DCP

EPDM/LDPE composites
E50L50-D0 50 50 5 0
E50L50-D0.5 50 50 5 0.5
E50L50-D1 50 50 5 1
E50L50-D1.5 50 50 5 1.5
E50L50-D2 50 50 5 2

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 2182 Polymer Bulletin (2024) 81:2179–2196

1.5%, 2% weight of EPDM and LDPE. And the composites with various DCP content
were named briefly as ExLy-Dz, where x, y represent EPDM and LDPE, respectively,
z represents the content of DCP in the composites. For example, E50L50-D0.5 repre-
sented the composite with the weight ratio of 50/50/0.5(EPDM/LDPE/DCP).

Mechanical property measurements

Stress–strain behaviors at room temperature were carried out in a computerized ten-

sile strength tester (UT-2080, U-CAN Dynatex Inc., Taiwan) using dumbbell-shaped
specimens (gauge length was about 25 mm) and tests were proceeded at 500 mm/min.
Cyclic tensile tests was evaluated at room temperature as well, with a stretching speed
at 500 mm/min and the strain of specimens at 100%. To evaluate stress relaxation, the
samples were stretched to a strain of 100% at a strain rate of 500 mm/min. Then, the
samples were held at that strain for 30 min and the change of stress with time was
recorded. Five specimens were performed to ensure repeatability in the experiments
described above.

Contact angle measurement

Contact angles were carried out on an optical contact angle measuring device (manu-
factured by German dataphysics company, OCA40 Micro), and the interface tension
was deduced by the contact angles. The contact angles given were the average of the
five measurements.

Curing characteristics of EPDM/LDPE composites

The curing characteristics of EPDM/LDPE composites were measured by a UR2010SD

Rotorless Rheometer (U-CAN Dynatex Inc.) at 180 °C, and the optimum cure time,
scorch time, the maximum torque and the minimum torque were determined from the
graphs.

Gel weight fraction (f𝐰

𝐠
) measurements

The fgw represents the weight fraction of cross-linked polymer components in the
composites and is measured using the follow method. EPDM/LDPE composites was
extracted in boiling xylene (~ 150 °C) for 48 h to selectively extract the un-cross-linked
linear polymer component until the samples reached a constant weight, then, the resi-
dues were dried in a vacuum oven at room temperature for 12 h to remove the residual
solvent. Finally, the weight fraction was determined according to the following equa-
tion [14]:
wf
fgw = wg
× 100% (1)

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 Polymer Bulletin (2024) 81:2179–2196 2183

wg and wf were referred to the weight of sample before the solvent extraction and
after dried, and the reported values were the average of three samples with the same
processing conditions for the reproducibility.

Fourier transform infrared (FT‑IR)

The EPDM/LDPE composites were extracted in boiling xylene to remove the free
chains completely for FT-IR observation under attenuated total reflectance (ATR).
FT-IR spectra were recorded using a Bruker Tensor 27 Spectrometer with a resolu-
tion of 4 ­cm−1 and an accumulation of 32 scans.

Scanning electron microscope (SEM)

The morphology of EPDM/LDPE composites was characterized by Merlin field-

emission scanning electron microscopy (FE-SEM, Carl Zeiss). To improve the con-
ductivity of EPDM/LDPE composites, all the cross sections of samples were sputter
coated with a thin layer of gold, and the accelerating voltage was set to be 5.0 kV in
the present study.

Different scanning calorimetry (DSC)

Crystallinity of LDPE phase was investigated by DSC (240 F1, NETZSCH, Ger-
many) in nitrogen atmosphere. About 5–10 mg sample was first heating from 25 to
200 °C at a rate of 20 °C/min and hold for 5 min at 200 °C to erase previous thermal
history. Then, the sample cooling down to 30 °C at a rate of 20 °C/min and reheat-
ing to 200 °C at a rate of 20 °C/min. The date utilized for thermal analysis is the first
cooling and the second heating scan. Relative crystalline degree (Xc, %) was deter-
mined according to equation as follows:
ΔH m
Xc = 𝜔×ΔH ∗m
× 100% (2)

where ΔH m was caculated from the area of the melting enthalpy, ΔH ∗m corresponded
to the perfect polymer crystals of LDPE, which is ca. 277.1 J/g [31], and 𝜔 refers to
the weight percentage of the portion of LDPE.

Polarized optical microscopy (POM)

To observe the crystallization morphology of LDPE during the isothermal crystal-

lization process, an Axioskop 40 polarized optical microscopy (POM) (ZEISS, Ger-
many) was used, and a hot stage was used to control the temperature. The samples
were first melted at 150 °C for 5 min and then slowly cooled to room temperature
(~ 0.2 K/min). Due to the specificity of the observation conditions, the unique obser-
vation conferred an opportunity to analysis crystallization.

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 2184 Polymer Bulletin (2024) 81:2179–2196

Shape memory effect

Shape memory effect was evaluated by a fold-deploy test [32] using rectangular spec-
imens (thickness = 1 mm, length = 70 mm, width = 5 mm), the samples were bended
into a temporary “U” shape in a water bath at 100 °C firstly and then fixed the tempo-
rary by immersing the sample in ice water for 10 s and maintained “U” for 24 h at room
temperature, and the shape recovery was conducted in the 100 °C water bath.
The shape fixing angle (𝜃f ) and shape recovery angle (𝜃r) were evaluated by picture,
and the shape fixing (Rf ) and shape recovery (Rr) ratios were calculated using the fol-
lowing equations.
𝜃f 𝜃f −𝜃r
Rf = 180
× 100% ; Rr = 𝜃f
× 100% (3)

where 𝜃f is the recovery angle fixed at room temperature and 𝜃r is the recovery angle
under thermal stimulation.

Results and discussion

Compatibility between EPDM and LDPE

According to our previous reports [13, 29, 33–35], the rubber-plastic SMP prepared
by polymer blending method consists of two phases, and the excellent interfacial com-
patibility between the rubber and plastic phases plays a crucial role in the transfer of
stress between the phase in both shape fixing and shape recovering process. Most of
the compounds of rubber–plastic have typical phase separation structure in morphol-
ogy. The solubility parameter (𝛿) is often used to forecast the compatibility of polymer
blend systems; fortunately, the inquired 𝛿 values of EPDM [36] and LDPE [37] are 16.9
(J/cm3)1/2 and 17.72 (J/cm3)1/2, respectively, which means that similar intermolecular
chain force of EPDM and LDPE.
Since the phase structure is primarily determined by interfacial tension [38], the sur-
face tension in dispersion and polar components were calculated by Eqs. (4), (5), and
(6), and the contact angles with water and diiodomethane are shown in Fig. 1.
( d d p
)
𝛾H O 𝛾 𝛾H O 𝛾 p
(4)
( )
1 + cos 𝜃H2 O 𝛾H2 O = 4 𝛾 d 2 +𝛾 d + 𝛾 p 2 +𝛾 p
H2 O H2 O

( d p
)
𝛾CH 𝛾d 𝛾CH 𝛾p
(5)
( ) 2 I2 2 I2
1 + cos 𝜃CH2 I2 𝛾CH2 I2 = 4 d
𝛾CH +𝛾 d
+ 𝛾CH
p
+𝛾 p
2 I2 2 I2

𝛾 = 𝛾d + 𝛾p (6)

p p
𝛾Ad 𝛾Bd
( 𝛾A 𝛾B
)
𝛾AB = 𝛾A + 𝛾B − 4 𝛾Ad +𝛾Bd
+ p p
𝛾A +𝛾B (7)

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 Polymer Bulletin (2024) 81:2179–2196 2185

Fig. 1  Contact angles on neat EPDM and neat LDPE

where 𝛾 is surface tension, 𝜃H2 O and 𝜃CH2 I2 are contact angles of the polymer with
water ­(H2O) and methylene iodide ­(CH2I2), d is dispersion component, p is polar
component, respectively, and 𝛾H2 O = 𝛾Hd O + 𝛾H O, 𝛾CH2 I2 = 𝛾CH + 𝛾CH I . The sur-
p d p
2 2 2 I2 2 2
face tension calculated was 𝛾EPDM=30.04 mN/m and 𝛾LDPE=36.75 mN/m, and the
interfacial tension calculated by Eq. 7 [13] was 𝛾EPDM−LDPE=0.719 mN/m. The
requirement of minimizing the surface free energy drives interface contact, infiltra-
tion and diffusion of polymer chains to enhance the interface combination between
EPDM and LDPE during the polymer blending process. The potential interfacial
compatibility plays an essential role in the SME of EPDM/LDPE composites, which
will be discussed in the subsequent parts.

Construction and influence of covalent cross‑linking networks

Interfacial compatibility and adhesion will be enhanced by interfacial grafting,

which contributed to the stress transfer between EPDM and LDPE in shape recov-
ery and deformation process. The curing properties and curing curves are shown in
Table2 and Fig. 2a. With the increase of DCP content, ­MH and ­(MH-ML) showed an
increasing trend. ­(MH-ML) was always considered to represent the degree of cross-
link network, suggesting that DCP impressed an effective promotion on cross-link,
which was further evidenced by the gel weight fraction (Fig. 2b). Besides, ­ML was
almost unaffected by DCP content.
As shown in Fig. 2b, the gel weight fraction ( fgw) increased gradually with the
increase of DCP content. As seen, fgw of all the samples exceeded 50%, showing that
the LDPE molecular chains were vulcanized and grafted with EPDM molecular
chains by cross-linking. Meanwhile, the appearance of the extracted specimens was
observed by digital photographs. As the DCP content was over 1 wt.%, the speci-
mens which were extracted retained relatively intact shape and remained flat,

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 2186 Polymer Bulletin (2024) 81:2179–2196

Table 2  Curing characteristics of EPDM/LDPE composites

Properties E50L50-D0.5 E50L50-D1 E50L50-D1.5 E50L50-D2

MH (dN.m) 1.18 2.05 3.84 5.71

ML (dN.m) 0.11 0.11 0.15 0.13
MH-ML (dN.m) 1.07 1.94 3.69 5.58
T10(min) 0.80 0.77 0.72 0.68
T90(min) 6.22 5.53 3.40 3.35

Fig. 2  a Curing curves of EPDM/LDPE composites. b The gel weight fraction of EPDM/LDPE compos-
ites, c, d FT-IR spectra of the xylene-extracted residues of E50L50-D1, neat EPDM and neat LDPE

suggesting that LDPE molecular chains involved in the composition of the covalent
cross-linking network. Therefore, the co-polymerization of LDPE and EPDM was
confirmed here by FT-IR analysis, and the spectra are shown in Fig. 2c, d. The
absorption bands at about 2855 ­cm−1 and 2920 ­cm−1 represented the aliphatic
stretching of –C–H, and 1462 ­cm−1 and 1380 ­cm−1 represented the rocking of -CH2
and the symmetric bending of –CH3, respectively. The bands mentioned above were
observed in EPDM, LDPE and the xylene-extracted residues of E50L50-D1, which
can be attributed to the structural similarity of EPDM and LDPE [39]. As expected,

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 Polymer Bulletin (2024) 81:2179–2196 2187

from the spectra of the xylene-extracted residues of E50L50-D1, an absorption band

was observed at 719 ­cm−1 representing the –(CH2)n wagging of LDPE, which sug-
gested that LDPE chains had been grafted onto EPDM chains during DCP-induced
vulcanization and improved the interfacial adhesion between the phases.
The formation of cross-linked networks in the EPDM/LDPE composites is shown
in Fig. 3. Homolytic reaction of DCP was promoted under the presence of heat to
generate free radicals. The macromolecular chains of EPDM formed macromolecu-
lar radicals via free-radical addition reaction ­(E1∙) and capturing α-hydrogen atoms
­(E2∙). LDPE formed macromolecular radicals via capturing α-hydrogen atoms (L∙).
Since the efficiency of cross-linking is generally determined by macromolecular
structures of polymers, the active sequence of macromolecular radicals is E ­ 1∙ > ­E2∙≈
L∙, suggesting that the cross-link of EPDM happened prior to polymerization of
LDPE at the same condition. According to the above results, the cross-linking of
composites can be controlled by the DCP content to achieve excellent interfacial
cross-linking under the condition that EPDM was cross-linked basically.
The characteristics and formation process of the cross-linking network had been
confirmed by the curing properties and the gel weight fraction; the FT-IR spectra
demonstrated interfacial cross-linking and co-polymerization between EPDM and
LDPE. Further investigation of the interfacial microstructure was required. Figure 4
shows the morphological changes of the cryogenically fractured surface microscopic
morphology of EPDM/LDPE composites with the increasing DCP content. The
SEM image of E50L50-D0 is shown in Fig. 4a. Obviously, the interface debond-
ing between the two phases does not exist, and the co-continuous structure with
faint phase boundary on the surface had been formed by polymer blending method,
which demonstrated there is an acceptable interface interaction between the two
components. Compared with E50L50-D0 (Fig. 4a), the phase interface between
the two phases at the fracture of the composites became blurred with the increase
of DCP, and the LDPE phase gradually became smaller and dispersed, showing a
net-like dispersion structure (Fig. 4b, c), which indicated that the bonding strength

Fig. 3  Schematic diagram of cross-linked network structure in EPDM/LDPE composites

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 2188 Polymer Bulletin (2024) 81:2179–2196

Fig. 4  SEM images of the EPDM/LDPE composites. a E50L50-D0, b E50L50-D0.5, c E50L50-D1, d

E50L50-D1.5, e E50L50-D2

improved and interfacial compatibility enhanced owing to the addition of DCP. The
covalent cross-linking formed at high temperature includes intra-phase cross-link-
ing and inter-phase cross-linking. The cross-linked LDPE molecular chains cannot
be arranged in a regular crystalline manner, resulting in a decrease in crystallinity
(Table 3), and the inter-phase grafting promoted the adhesion between the inter-
faces, making it difficult to distinguish the two phases.

Crystallization behavior of EPDM/LDPE composites

As a semicrystalline polymer, shape fixing effect is closely related to the crystalliza-

tion behavior [14]. Therefore, the heat changes during crystallization and melting
process were characterized by DSC measurements (all DSC samples were heated
before use to erase previous thermal history), and Fig. 5 shows the DSC curves of
EPDM/LDPE composites, respectively, in the presence of different content of DCP.
As can be seen from Fig. 5, the melting transitions of LDPE occur during the
heating scan of the DSC curve; it is obvious that there are double melting peaks
for EPDM/LDPE blends. With the increase of DCP content, the temperature of
peak 1 increased firstly and decreased after E50L50-D1, and peak 2 at about

Table 3  The maximum Sample Tmax (°C) Xc(%)

crystallization temperature and
crystalline degree of LDPE E50L50-D0 91.1 110.7 19.3
component in the composites
E50L50-D0.5 91.6 – 17.7
E50L50-D1 91.7 – 17.6
E50L50-D1.5 91.1 – 13.8
E50L50-D2 89.7 – 13.5

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 Polymer Bulletin (2024) 81:2179–2196 2189

Fig. 5  DSC curves of EPDM/LDPE composites (Heating scan)

110 °C became smaller to disappear, which indicated that vulcanization abate

crystallization of LDPE molecules. The strong restriction force was mainly orig-
inated from chemical cross-link inside LDPE crystal and the interface; the graft-
ing in the interface and the internal cross-linking of LDPE led to the breaking of
the orderly chain segments and poor capacity of changing their conformations.
The arrangement process of molecular chains was hindered; a relatively com-
plete crystal cannot be formed.
The melting enthalpy of composites was substituted into Eq. 2 to calculate the
crystallinity, and the melting temperature (Tm) and relative crystalline degree
( Xc ) are shown in Table 3. With increasing DCP content, Xc of LDPE showed
a decrease trend, higher cross-link density led to less crystalline. The reduced
peak temperature and degree of crystallization indicated that there were few
crystalline regions within the material; a large amount of space was filled with
complex chemical cross-linking, which damaged the elasticity of the rubber.
Composites with tiny crystals show high Rf and excellent Rr due to their abil-
ity to increase the contact area between the crystalline region and the rubber
chain. To further study the crystallization behavior, samples were characterized
by polarizing microscopy (POM), and the images of this are shown in Fig. 6. As
seen, since the DCP content was gradually improved to 1 wt.%, the black cross
extinction size decreased, indicating that the spherulite diameter of LDPE was
effectively reduced. When the DCP content was increased from 1 to 2 wt.%, size
of the black cross extinction kept falling; besides, numbers of spherical crystals
in unit area tended to decrease. This phenomenon can be attributed to cross-link,
which improved the interfacial adhesion of EPDM/LDPE and cross-link inside
“LDPE crystal”. Therefore, the DCP content, which is directly associated with
the interfacial adhesion and crystallization of LDPE, was identified as the prior-
ity factor for SME of EPDM/LDPE composites.

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 2190 Polymer Bulletin (2024) 81:2179–2196

Fig. 6  POM images of EPDM/LDPE composites. a E5L5-D0, b E50L50-D0.5, c E50L50-D1, d

E50L50-D1.5, e E50L50-D2

Mechanical properties

The tensile behavior and mechanical properties of EPDM/LDPE composites

are shown in Fig. 7. From the stress–strain curves in Fig. 7a, all the composites
showed an increase in stress with increasing strain and no significant yielding
occurred, exhibiting a typical rubber stretching characteristics. It is worth clarify-
ing that E50L50-D0 has a surprising performance in terms of mechanical proper-
ties, tensile strength (~ 7 MPa) and elongation at break (~ 1450%), which is due
to the fact that EPDM and LDPE possess similar solubility parameters and good
interfacial compatibility between the two phases.
The strength and elasticity of the composites are strong associated with cross-
link density and SME, as shown in Fig. 7b, The tensile strength and elongation
at break of the composites increased and then decreased with the increase of
DCP content, reaching the optimum value at E50L50-D1; meanwhile, tension at
100%/200%/300% of elongation showed an increase trend. This phenomenon can
be explained by the fact that the higher the cross-linking density with increasing
DCP content, the more pronounced the restriction of the macromolecular chains.

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 Polymer Bulletin (2024) 81:2179–2196 2191

Fig. 7  a Tensile behaviors of EPDM/LDPE composites. b Mechanical properties of EPDM/LDPE com-
posites. c The 1st cycle curves of the composites. d Stress relaxation curves of the composites

Due to the incorporation of DCP, the dense cross-linked network led to the inabil-
ity to cope with deformation by chain stretching and slipping; thus, tension at
100%/200%/300% of elongation of the composite increased and the elongation
at break decreased, which in turn led to a significant decrease in tensile strength.
The network was not easy to be damaged and a good flexibility of composites
underpinned the mechanical and SME performance.
The essence of SME was the deformed molecular chains return to the natural curl
state under the action of entropic elasticity [1]. Therefore, the rearrangement phe-
nomenon of molecular chains during deformation was investigated by cyclic stretch-
ing experiments, and the shape memory behavior of EPDM/LDPE composites was
analyzed. Cyclic stress–strain curves were shown in Figure S1, and samples were
stretched to 100% strain in every cycle under the same condition. During the stretch-
ing process, the previous thermodynamically stable state was broken, the slip and
breakage of macromolecular chains lead to changes in internal conformation and
aggregation state of molecular chains, consuming the external forces and resulting
in macroscopic change in shape, and the specimens could not return to the origi-
nal shape. Therefore, E50L50-D0 showed typical stress softening (Mullin’s effect)
[40]. The formation of chemical cross-linking bonds induced by peroxide had a
strong restriction on macromolecular chains, leading to a weakening of the Mullin’s
effect. To characterize the effect quantitatively, the work lost in the stretch-reversion

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 2192 Polymer Bulletin (2024) 81:2179–2196

cycle was measured by calculating the area of the loop, and the results are shown in
Fig. 7c. With the increase in addition of DCP content, the area of the loop decreased
first, which meant that the rubber chains responded quickly after release and the Rr
improved significantly. Later, the increase in the area of the loop was due to the
over-perfection of the internal cross-linked network of the composites and the break-
age of the macromolecular chain segments caused by 100% stretching, which can
also be observed in stress relaxation (Fig. 7d, Table S1). Hence, the improved shape
recovery ratio of E50L50-D1 was attributed to the large amount of internal stress
storing in the composites.

Shape memory behaviors

The excellent interfacial compatibility and the interfacial cross-linking between the
two phases further enhanced the interfacial adhesion under the action of peroxide,
which served as the recovery driving force. On the other hand, the tiny-crystalline
LDPE controlled by cross-link served as the fixing phase. On the basis of the above,
a strong interface with effective stress delivery and excellent crystal morphologies
were formed. In contrast, E50L50-D0 showed a weak SME, which was difficult
to delivery stress to LDPE crystals effectively. Therefore, excellent shape mem-
ory effect can be observed in the EPDM/LDPE composites with appropriate DCP
content.
Before conducting the shape memory experiments, the approximate melting tem-
perature was determined by DSC; as can be seen in Fig. 5, the maximum crystalliza-
tion temperature of composites was about 90 °C, and due to the intrinsic character-
istic of polymers, each sample exhibited broad crystallization and melting transition.
Therefore, the shape memory effect was measured at a series of ­Ttrans (60, 70, 80,
90, and 100 °C) in order to achieve high performance of SME. SME were charac-
terized by fold-deploy test and the results were shown in Table S2. All of the com-
posites exhibited lower ­Rf and ­Rr at 60, 70, and 80 °C; this result can be attributed
to the slight melting of the plastic phase was not sufficient to provide fixation effi-
ciently. As the T­ trans increased, more of the crystalline LDPE melted, improving the
fixed ability of the composites. However, when the temperature increased to 110 °C,
almost all the LDPE crystals in the sample melted and could not maintain the shape.
Therefore, 100 °C was chosen as the ­Ttrans to conduct shape memory tests; as
shown in Fig. 8a and b, all the samples had an amazing shape memory behavior. It is
clear that all samples possessed excellent shape fixation (about 98%) due to the fact
that the compound contains 50% LDPE, which was in the crystalline state at room
temperature, and the complete freezing of the LDPE chain ends limited the elastic-
ity of the rubber molecular chains. However, the worst shape recovery was reaching
only 56.25% (E50L50-D0), while other compounds achieved about 95% recovery to
the original shape. The reason for this situation was that the composites without per-
oxide did not form an effective cross-linked network, and the energy applied from
outside during deformation could not be stored by the rubber chains, while the stress
could not be transferred effectively through the interfacial compatibility between the
two phases. Therefore, with the increase of the DCP content, the recovery effect and

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 Polymer Bulletin (2024) 81:2179–2196 2193

Fig. 8  a Shape fixity and shape recovery percentage of EPDM/LDPE composites. b Digital photographs
of shape memory effect, c shape memory behavior of the composites

the recovery rate increased due to the perfection of the cross-linked network which
provided sufficient recovery force for the composites.
In light of the analyses above, Fig. 8c illuminates an action mechanism of cross-
link and crystals in shape memory behavior of composites; it is clear that appropri-
ate cross-link improved SME by improving interface adhesion and forming abun-
dant tiny crystals. Thus, the potential interfacial compatibility was advantageous to
polymer blending, interfacial adhesion and abundant tiny crystals played an essen-
tial role in SME. On the one hand, the interfacial adhesion effectively transferred the
elasticity to LDPE for complete recovery, and increased interfacial contact area pro-
vided increased points of elasticity force. On the other hand, the grafting at the inter-
face with EPDM or the internal cross-linking of LDPE contributed to tiny crystals,
the orientation of LDPE chains which was originated from concentration fluctuation
in the interface accelerated the crystallization of LDPE, and crystals tend to form

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 2194 Polymer Bulletin (2024) 81:2179–2196

near by the interface. Finally, the interfacial adhesion and tiny crystals improved by
cross-link contributed to the stress transfer and shape fix, which plays a significant
role for shape fixation and recovery.

Conclusions

In this work, we successfully prepared shape memory EPDM/LDPE composites

with excellent mechanical properties through an appropriate vulcanization pro-
cess. The chemical cross-linking improved cross-link density and interfacial adhe-
sion, contributed to abundant tiny LDPE crystals. This special structure effectively
facilitates the storage of response forces in the rubber chain and the efficiency of
stress transfer at the interface, resulting in an excellent shape memory effect (SME).
The proper mechanical properties and SME were achieved at the E50L50-D1, with
tensile strength and elongation at break of 19.2 MPa and 1499%, respectively, and
shape fixity ratio and shape recovery ratio were 99% and 85%, respectively. We
envision that the prepared materials might have good potential applications in pipe
connection and packaging materials.
Supplementary Information The online version contains supplementary material available at https://​doi.​
org/​10.​1007/​s00289-​023-​04808-3.

Acknowledgements This work was supported by 2019YFE0110700, the Key Projects of Basic Research
and Applied Basic Research in Colleges and Universities in Guangdong Province (Grant Number:
2018KZDXM004) and Special project for innovation of high-end scientific research institutions in
Zhongshan City (Grant Number: 2019AG013).

References
1. Zende R, Ghase V, Jamdar V (2022) A review on shape memory polymers. Polym-Plast Technol
Mater 64(2):467–485
2. Huang JR, Fan JF, Yin SH, Chen YK (2019) Design of remotely, locally triggered shape-memory
materials based on bicontinuous polylactide/epoxidized natural rubber thermoplastic vulcanizates
via regulating the distribution of ferroferric oxide. Compos Sci Technol 182:107732
3. Dayyoub T, Maksimkin AV, Filippova OV, Tcherdyntsev VV, Telyshev DV (2022) Shape memory
polymers as smart materials: a review. Polymers-Basel 14(17):3511
4. Xia Y, He Y, Zhang F, Liu Y, Leng J (2021) A review of shape memory polymers and composites:
mechanisms, materials, and applications. Adv Mater 33:2000713
5. Cui R, Ding J, Chen Y (2019) Magnesium acrylate induced interfacial compatibilization of EPDM/
PP thermoplastic vulcanizate and shape memory behavior. Compos A Appl Sci Manuf 122:27–35
6. Zhang R, Yang Q, Liu M, Chen X, Xue P (2022) Thermal actuation shape memory of ultra-high-
molecular-weight polyethylene (UHMWPE) with molecular orientation. Mater Lett 325:132813
7. Salehi S, Mirjalili G, Amrollahi J (2004) Effects of high-energy electron beam on low-density poly-
ethylene materials containing EVA. J Appl Polym Sci 92:1049–1052
8. Sun LY, Gao X, Wu DC, Guo QY (2021) Advances in physiologically relevant actuation of shape
memory polymers for biomedical applications. Polym Rev 61:280–318
9. Lendlein A, Langer R (2002) Biodegradable, elastic shape-memory polymers for potential biomedi-
cal applications. Science 296:1673–1676
10. Garle A, Kong S, Ojha U, Budhlall BM (2012) Thermoresponsive semicrystalline poly(epsilon-
caprolactone) networks: exploiting cross-linking with cinnamoyl moieties to design polymers with
tunable shape memory. Acs Appl Mater Inter 4:645–657

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 Polymer Bulletin (2024) 81:2179–2196 2195

11. Zhao HX, Lan X, Liu YJ, Bhattacharyya D, Leng JS (2022) Flexural and shape memory proper-
ties of unidirectional glass and carbon fibers reinforced hybrid shape memory polymer composites.
Smart Mater Struct 31(11):115024
12. Guo WS, Kang HL, Chen YW, Guo BC, Zhang LQ (2012) Stronger and faster degradable biobased
poly(propylene sebacate) as shape memory polymer by incorporating boehmite nanoplatelets. Acs
Appl Mater Inter 4:4006–4014
13. Fan J, Yan M, Huang J, Cao L, Chen Y (2019) Fabrication of smart shape memory fluorosilicon
thermoplastic vulcanizates: the effect of interfacial compatibility and tiny crystals. Ind Eng Chem
Res 58:15199–15208
14. Zhao J, Chen M, Wang X, Zhao X, Wang Z, Dang Z, Ma L, Hu G, Chen F (2013) Triple shape
memory effects of cross-linked polyethylene/polypropylene blends with cocontinuous architecture.
Acs Appl Mater Inter 5:5550–5556
15. Liu YT, Huang JR, Zhou JD, Wang YP, Cao LM, Chen YK (2020) Influence of selective distri-
bution of SiO2 nanoparticles on shape memory behavior of co-continuous PLA/NR/SiO2 TPVs.
Mater Chem Phys 242:122538
16. Wang YP, Zhang CH, Ren YR, Ding T, Yuan DS, Chen YK (2018) Shape memory properties of
dynamically vulcanized poly(lactic acid)/nitrile butadiene rubber (PLA/NBR) thermoplastic vul-
canizates: the effect of ACN content in NBR. Polym Advan Technol 29:2336–2343
17. Jing X, Mi HY, Peng XF, Turng LS (2015) The morphology, properties, and shape memory behav-
ior of polylactic acid/thermoplastic polyurethane blends. Polym Eng Sci 55:70–80
18. Yan MW, Cao LM, Xu CH, Chen YK (2019) Fabrication of “Zn2+ salt-bondings” cross-linked
SBS-g-COOH/ZnO composites: thiol-ene reaction modification of sbs, structure, high modulus, and
shape memory properties. Macromolecules 52:4329–4340
19. Sattar R, Kausar A, Siddiq M (2016) Shape memory and physical properties of composites of
polyethylene oxide/poly(propylene glycol)-block-poly(ethylene glycol)-block-poly(propylene
glycol)/2,4-toluene diisocyanate, polypyrrole, and modified MWCNT. Polym-Plast Technol Eng
55:1099–1114
20. Qiu XY, Guo QQ, Wang YY, Huang X, Cao J, Zheng Z, Zhang XX (2020) Self-healing and recon-
figurable actuators based on synergistically cross-linked supramolecular elastomer. Acs Appl Mater
Inter 12:41981–41990
21. Marotta A, Lama GC, Ambrogi V, Cerruti P, Giamberini M, Gentile G (2018) Shape memory
behavior of liquid-crystalline elastomer/graphene oxide nanocomposites. Compos Sci Technol
159:251–258
22. Wang GQ, Jiang M, Zhang Q, Wang R, Qu XL, Zhou GY (2018) Biobased multiblock copolymers:
synthesis, properties and shape memory behavior of poly(hexamethylene 2,5-furandicarboxylate)-b-
poly(ethylene glycol). Polym Degrad Stabil 153:292–297
23. Wang GQ, Jiang M, Zhang Q, Wang R, Zhou GY (2017) Biobased multiblock copolymers: syn-
thesis, properties and shape memory performance of poly(ethylene 2,5-furandicarboxylate)-b-
ly(ethylene glycol). Polym Degrad Stabil 144:121–127
24. Koosomsuan W, Yamaguchi M, Phinyocheep P, Sirisinha K (2019) High-strain shape memory
behavior of PLA-PEG multiblock copolymers and its microstructural origin. J Polym Sci Pol Phys
57:241–256
25. Wang Y, Pei X, Xia L, Xin Z (2022) Covalent crosslinks turn naturalEucommia ulmoides gum/poly-
butene-1 composites into multiple shape memory materials. Polym Compos 43:1371–1382
26. Liu C, Huang JR, Yuan DS, Chen YK (2018) Design of a high-strength XSBR/Fe3O4/ZDMA
shape-memory composite with dual responses. Ind Eng Chem Res 57:14527–14534
27. Chatterjee T, Dey P, Nando GB, Naskar K (2015) Thermo-responsive shape memory polymer
blends based on alpha olefin and ethylene propylene diene rubber. Polymer 78:180–192
28. Xu CH, Wu WC, Zheng ZJ, Wang ZW, Nie JD (2018) Design of shape-memory materials based on
sea-island structured EPDM/PP TPVs via in-situ compatibilization of methacrylic acid and excess
zinc oxide nanoparticles. Compos Sci Technol 167:431–439
29. Liu C, Huang J, Yuan D, Chen Y (2018) Design of a high-strength XSBR/Fe3 O4 /ZDMA shape-
memory composite with dual responses. Ind Eng Chem Res 57:14527–14534
30. Khonakdar HA, Jafari SH, Rasouli S, Morshedian J, Abedini H (2007) Investigation and modeling
of temperature dependence recovery behavior of shape-memory crosslinked polyethylene. Macro-
mol Theor Simul 16:43–52
31. Handbook of Polymers. Elsevier Inc., 2022

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
 2196 Polymer Bulletin (2024) 81:2179–2196

32. Chan B, Heng S, Liow SS, Zhang KY, Loh XJ (2017) Dual-responsive hybrid thermoplastic shape
memory polyurethane. Mater Chem Front 1:767–779
33. Xiong J, Huang J, Wang W, Mou W, Chen Y (2021) Study on shape memory behavior of ternary
poly(lactic acid)/poly(methyl methacrylate)-grafted natural rubber/natural rubber thermoplastic vul-
canizates. Polym-Plast Technol Mater 60:550–561
34. Xu CH, Huang XH, Li CH, Chen YK, Lin BF, Liang XQ (2016) Design of “Zn2+ salt-bondings”
cross-linked carboxylated styrene butadiene rubber with reprocessing and recycling ability via rear-
rangements of ionic cross-linkings. Acs Sustain Chem Eng 4:6981–6990
35. Liu W, Ding JP, Chen YK (2022) Thermoplastic vulcanizates dynamically cross-linked by a tailored
small molecule. Polym Adv Technol 33:3418–3429
36. Jiang X, Yuan X, Guo X, Zeng F, Wang H, Liu G (2022) Study on the application of Flory-Huggins
interaction parameters in swelling behavior and crosslink density of HNBR/EPDM blend. Fluid
Phase Equilibr 563:113589
37. Narses S, Sadaka F, Brachais C, Couvercelle J (2013) Polymer stain resistance: prediction versus
experiment. J Appl Polym Sci 129:2891–2904
38. Reignier J, Favis BD (2000) Control of the subinclusion microstructure in HDPE/PS/PMMA ter-
nary blends. Macromolecules 33:6998–7008
39. Radosavljević J, Nikolić L (2018) Interplay between key variables of peroxide cured EPDM and
evaluation of electromechanical efficiency for MV cables. J Appl Polym Sci 135:46139
40. Sasikumar K, Jayesh P, Manoj NR, Mukundan T, Khastgir D (2018) Effect of pristine multiwalled
carbon nanotubes on tensile hysteresis in carboxylated nitrile rubber composites. Polym Composite
39:E1269–E1279

Publisher’s Note Springer Nature remains neutral with regard to jurisdictional claims in published maps
and institutional affiliations.

Springer Nature or its licensor (e.g. a society or other partner) holds exclusive rights to this article under
a publishing agreement with the author(s) or other rightsholder(s); author self-archiving of the accepted
manuscript version of this article is solely governed by the terms of such publishing agreement and
applicable law.

Authors and Affiliations

Qiangqiang Han1 · Wei Liu1 · Yunwang Xu2 · Ziwu Cao2 · Yukun Chen1,3

* Yunwang Xu
[email protected]
* Ziwu Cao
[email protected]
* Yukun Chen
[email protected]
1
School of Mechanical and Automative Engineering, South China University of Technology, 381
Wushan Road, Tianhe District, Guangzhou 510640, China
2
Guangdong Meirun New Material Technology Co., LTD, Foshan 528000, China
3
Zhongshan Institute of Modern Industrial Technology, South China University of Technology,
Zhongshan 528437, China

13
Content courtesy of Springer Nature, terms of use apply. Rights reserved.
Terms and Conditions
Springer Nature journal content, brought to you courtesy of Springer Nature Customer Service Center
GmbH (“Springer Nature”).
Springer Nature supports a reasonable amount of sharing of research papers by authors, subscribers
and authorised users (“Users”), for small-scale personal, non-commercial use provided that all
copyright, trade and service marks and other proprietary notices are maintained. By accessing,
sharing, receiving or otherwise using the Springer Nature journal content you agree to these terms of
use (“Terms”). For these purposes, Springer Nature considers academic use (by researchers and
students) to be non-commercial.
These Terms are supplementary and will apply in addition to any applicable website terms and
conditions, a relevant site licence or a personal subscription. These Terms will prevail over any
conflict or ambiguity with regards to the relevant terms, a site licence or a personal subscription (to
the extent of the conflict or ambiguity only). For Creative Commons-licensed articles, the terms of
the Creative Commons license used will apply.
We collect and use personal data to provide access to the Springer Nature journal content. We may
also use these personal data internally within ResearchGate and Springer Nature and as agreed share
it, in an anonymised way, for purposes of tracking, analysis and reporting. We will not otherwise
disclose your personal data outside the ResearchGate or the Springer Nature group of companies
unless we have your permission as detailed in the Privacy Policy.
While Users may use the Springer Nature journal content for small scale, personal non-commercial
use, it is important to note that Users may not:

1. use such content for the purpose of providing other users with access on a regular or large scale
basis or as a means to circumvent access control;
2. use such content where to do so would be considered a criminal or statutory offence in any
jurisdiction, or gives rise to civil liability, or is otherwise unlawful;
3. falsely or misleadingly imply or suggest endorsement, approval , sponsorship, or association
unless explicitly agreed to by Springer Nature in writing;
4. use bots or other automated methods to access the content or redirect messages
5. override any security feature or exclusionary protocol; or
6. share the content in order to create substitute for Springer Nature products or services or a
systematic database of Springer Nature journal content.
In line with the restriction against commercial use, Springer Nature does not permit the creation of a
product or service that creates revenue, royalties, rent or income from our content or its inclusion as
part of a paid for service or for other commercial gain. Springer Nature journal content cannot be
used for inter-library loans and librarians may not upload Springer Nature journal content on a large
scale into their, or any other, institutional repository.
These terms of use are reviewed regularly and may be amended at any time. Springer Nature is not
obligated to publish any information or content on this website and may remove it or features or
functionality at our sole discretion, at any time with or without notice. Springer Nature may revoke
this licence to you at any time and remove access to any copies of the Springer Nature journal content
which have been saved.
To the fullest extent permitted by law, Springer Nature makes no warranties, representations or
guarantees to Users, either express or implied with respect to the Springer nature journal content and
all parties disclaim and waive any implied warranties or warranties imposed by law, including
merchantability or fitness for any particular purpose.
Please note that these rights do not automatically extend to content, data or other material published
by Springer Nature that may be licensed from third parties.
If you would like to use or distribute our Springer Nature journal content to a wider audience or on a
regular basis or in any other manner not expressly permitted by these Terms, please contact Springer
Nature at

[email protected]