European Polymer Journal 117 (2019) 280–303

Contents lists available at ScienceDirect

European Polymer Journal

journal homepage: www.elsevier.com/locate/europolj

Deep focusing on the role of microstructures in shape memory properties of T

polymer composites: A critical review
Mahyar Panahi-Sarmada,b, Mahbod Abrishamc, Mina Noroozib, Arian Amirkiaic,
Parham Dehghanc, Vahabodin Goodarzia, , Beniamin Zahirid,
⁎ ⁎

a
Applied Biotechnology Research Center, Baqiyatallah University of Medical Science, P.O. Box 19945-546, Tehran, Iran
b
Polymer Engineering Department, Faculty of Chemical Engineering, Tarbiat Modares University, P.O. Box 14115-114, Tehran, Iran
c
Department of Polymer Engineering and Color Technology, Amirkabir University of Technology, P.O. Box 15875-4413, Tehran, Iran
d
Clean Energy Research Centre, The University of British Columbia, 6250 Applied Science Lane, Vancouver, BC V6T 1Z4, Canada

ARTICLE INFO ABSTRACT

Keywords: In the last two decades, shape memory polymers (SMPs) find promising applications in various fields such as
Shape memory micro-actuators, medicine, basic sciences, anti-counterfeit technology, sensor, and automobile. This class of
Polymer composite active polymers can switch between an original shape and one or more temporary shapes. Although SMPs have
Microstructure been extensively admitted as smart materials, due to low density, excellent biocompatibility, and facile pro-
Carbon- & silicate-based fillers
cessing, but still exposes numerous weaknesses and limitations based on engineering aspects, analogous: mul-
tiple approaches to improvement of driving methods, reinforcement of mechanical properties, the creation of
specific deformations and the formation of multifunctional materials. For this purpose, SMP composites (SMPCs)
is introduced to eliminating the mentioned disadvantages. This review is intensely focused on the most recent
research on microstructure-property of SMPCs filled by different carbon and silicate-based nano/micro-particles
as well as hybrid particles. Silicate fillers in SMPCs divided base on natural shapes (1, 2 and 0 D) and the
necessary information for tailoring an appropriate SMPCs is deliberated. On the other hand, the embedded
carbonic fillers (carbon black, CNT and graphene) in polymeric matrixes for improving shape memory behavior
are separately deliberated. In addition, the current review offers a comprehensive discussion on micro- and
macro-morphology of polymer composites in order to design proper shape memory properties. A systematic
approach has been undertaken to highlight the advancements and challenges of SMPCs and the critical research
areas that need immediate attention.

1. Introduction or multi temporary shapes by imposing an external stimulus. After

Modern material sciences have dramatic developments in the last
decades that lead to ameliorations in their performance and applica-
tions. Smart materials have become vastly popular in scientific society
because of having variability functionality depend on diverse environ-
mental conditions [1–3]. Shape-memory materials have been in-
troduced at the ~ 1940s for the first time, and it converts to one of the
most critical classes of smart materials [2]. The programmable behavior
of shape-memory materials is a beneficial advantage that of other smart
material groups because of the ability to memorize one (dual shape
memory effect) or more (multi-shape memory effect) temporary shapes
[1,4–6]. Shape-memory materials are variable programmable material
and also have significant features to recover their initial form. In other
words, shape-memory materials will be generally programmed in one
programming, shape-memory materials have capable of returning to
permanent (original) shape under the external stimuli fields, such as
heat, light, radiation, microwaves, pressure, moisture, magnetism,
electric, or chemicals [7–10]. Noteworthy, changing temperature is
used as a decisive external stimulus in the most shape-memory material
systems. However, the approach of controlling temperature is not the
same in different systems [11,12]. For example, the temperature can be
increased locally by applying an electric or magnetic field. As a sub-
stitute definition, altering temperature is the dominant mechanism in
shape memory systems, directly and indirectly. The shape-memory
materials can divide into three groups: alloys, ceramics, and polymers
[13].
The polymers groups have been investigated in this paper because
of some privileges that of other groups such as low weight, good

⁎
Corresponding authors.
E-mail addresses: v.goodarzi@bmsu.ac.ir (V. Goodarzi), beniamin.zahiri@gmail.com (B. Zahiri).

https://doi.org/10.1016/j.eurpolymj.2019.05.013
Received 24 March 2019; Received in revised form 2 May 2019; Accepted 9 May 2019
Available online 10 May 2019
0014-3057/ © 2019 Elsevier Ltd. All rights reserved.
M. Panahi-Sarmad, et al.
compatibility with the human body, facile widespread processing
methods, high-stress endurance, the ability to tolerate large deforma-
tions, a plentiful selection of stimulating methods, etc. [5,14,15]. The
shape memory polymers (SMPs) frequently possess a chemical cross-
linking structure, crystalline/amorphous hard phase, or physical cross-
linking structure and a low-temperature transition of crystalline,
amorphous or liquid–crystal phase as a switch. Owing to their unique
properties, the shape-memory polymers are applied in many applica-
tions such as aerospace [16], automobile, actuation, biomedical [17-
19], packaging, self-healing [20,21] and textile [14,22,23]. Besides,
shape-memory polymers not only appear in the bulk material state but
also use as a shape-memory surface [24], shape-memory microparticles,
shape-memory hydrogels [22,25] and porous shape-memory [14,26].
Overall, the polymers that are used for designing shape-memories are
divided into thermoset and thermoplastic polymers. Although thermo-
sets can store more energy and endure more cycles (shape-changing)
than thermoplastics due to the cross-linked bonds but thermoplastic
materials have a facile processing method [27–29]. Thus, the final
application dictates the type of materials that will have been used [30].
The shape changing procedure of SMPs can separate in two steps: I)
Shape fixing: stability in temporary shape and II) Recovery: a capability
to return to permanent state. When the polymer temperature reached
up (from the permanent state) to transition temperature (Ttrans), a SMP
has capable of programming. In upper than the Ttrans, shape program-
ming has occurred owing to the augmentation movement of polymer
chains with imposing external force. It noteworthy that the SMP is
locked in temporary shape (shape fixity) because of the entropy of the
system have declined under the quenching process. Thus, the shape
fixity behavior leads to stabilizing SMPs in their temporary state.
Whereas, the polymer chains can unlock when the stimulation field is
applied. While the system temperature rises to above of Ttrans, the re-
covery process happens due to reducing the free energy of the system
(increasing entropy), so, the SMP can be coming back to the permanent
state (shape recovery). According to the types of polymers, Ttrans in
amorphous, crystalline and semi-crystalline polymers is glass transition
(Tg), melting temperature (Tm) and liquid-crystal isotropic transition
temperature (Ti), respectively [2,14,31,32].
Shape fixity and recovery parameters determine the shape memory
performance of polymers. Thus, fixing ratio (Rf) and recovery ratio
(Rrec) is calculable via equations (1) and (2), sequentially. In these two
equations, ε is corresponded to fixed strain after removing the external
force at the temperature below Ttrans. It is worth mention, the viscoe-
lastic behavior of polymers leads to strain recover immediately after
removing the external force, especially elastic parts. εload and εrec relate
to temporary strain under the external force (at permanent state) and
permanent recovery strain after heating the system (above Ttrans), re-
spectively [5,33].
Rf = × 100
(1)
load
rec
Rrec = × 100
(2)
The widespread model is containing net-points and switch-units
introduced by Chen et al. [23] that can describe the mechanisms of
SMPs. Fig. 1 demonstrates the SMPs molecular mechanism that consists
of net-points and switch-units. Net-points determine the permanent
shape of SMPs and include chemical and physical interactions [1,5].
Switch-units can capable of defining shape fixity and recovery behavior
[1]. In one hand the most momentous switch-units (in phase level) for
crystalline, semi-crystalline and amorphous polymers are Tm, Ti, and Tg,
respectively [1,5,34].
On the other hand, switch-units in molecular level can be in-
tramolecular interactions or reversible chemistry reactions such as su-
pramolecular, mercapto and photosensitive units [1,35]. For instance,
an amorph polymer (with certain Tg) has the chain entanglements in
281
European Polymer Journal 117 (2019) 280–303
coil (or random) state. Thus Tg and physical chain entanglements re-
cognize respectively as a switch-unit and net-points in shape memory
system. It is worth mentioning that the decrement in entropic energy of
the system will be observed when the system temperature rises to above
of Tg while the polymeric chains are stretching. In the flowing, the
energy is stored because of changing the chain conformations when
quenching the system to the below of Tg. It can lead to recuperate the
shape recovery properties. Furthermore, the physical chain entangle-
ment/net-points (that endure stretching) can help to shape recovery
behavior above of Tg [8,10]. Consequently, the switch-unit and net-
points correlate with the type of materials and structural bonding in
diverse shape-memory systems. For example; Poly-olefins, poly-ethers,
and poly-esters (as SMPs) are usually designed based on Tm in one
hand, and on the other hand, the broad range of polymers, such as
epoxy and low crosslink density polyimide, are fabricated based on Tg
[3].
One of the classifications of SMPs is based on shape-memory effects
(SMEs) that refer to the ability to memorize two or more temporary
shapes and shifting between the temporary shapes. The both one-way
and two-way SMEs can be capable of programming into dual, triple and
multiple temporary shapes [1,5,14,36]. The difference between the two
groups is hidden in reversibility [11]. In one-way SMEs, the temporary
shape can recover with stimulation and cannot reverse. While the two
distinct temporary shapes can inversely change by applying two dif-
ferent external stimuli in two-way SMEs [3,11]. Fig. 2 displays (a) one-
way SME with dual shape and (b) two-way SME with the triple shape.
Triple shape SMEs can recover to dual temporary shapes. Therefore, the
shape temporary A and the temporary shape B have been occurred by
imposing the external force, and then recovered with stimulation, re-
spectively [1,5,14]. Multiphase polymers have two or more detached
domains that regularly produced the triple shape SMEs. Multiple shapes
SMEs can memorize more than one temporary shape and one perma-
nent shape. The SMEs comprising multi-shape memory properties are
desired for many applications that require complex adjustable shapes,
such as deployable 3-D structures, precisely smart medical devices,
smart valves, and assembly systems [37–41]. The polymers with the
broad range of Tg can make multiple SMEs because several temperature
spans can be considered, so, the shape of the material is changed in
every span by imposing the diverse external forces and recovered re-
spectively [1]. However changing the shape in one-way SMEs occur in
one direction, they are very flexible, adaptable and applicable [1].
Polyurethanes, polyurethane-urea, and polyurethane ionomers are
more common SMPs in one-way SMEs [1]. Besides in two-way SMEs,
the most important materials that behave as similar to them are liquid
crystal elastomers [1,5].
The combination of SMPs with divers fillers generate shape-memory
polymer composites (SMPCs) because of overcoming some drawbacks
such as low elastic modulus, stiffness, strength, recovery stress, low
thermal/electrical conductivity, etc. [3,42–44]. Furthermore, in-
corporation some conductive fillers to SMPs leads to create stimulating
ability under the electric or magnetic field instead of direct heating
[45]. The purpose of producing SMPCs is the improvement of ther-
momechanical properties and the discovery of new external stimulus
that leads to applied them in more advanced applications [3,14]. For
example, SMPCs containing active filler can be employed in biomedical
applications for increasing the specific temperature in the local pointe
of the human body (indirect heating) alternative to increasing the en-
vironment temperature/direct heating [5,14,46].
The present work discusses the effects of silicate- and carbon- base
filler on the shape memory behavior of polymeric composites at mi-
crostructure perspective (e.g., crystallization, filler dispersion, filler-
polymer interaction, etc.). As already defined in the previous section,
the most common and convenient way to trigger the SMP materials is a
direct increase in the surrounding temperature. Nevertheless, this
exogenous heating is not always appropriate for some applications.
Thus an alternative way to prevail this problem is to generate direct
M. Panahi-Sarmad, et al.
Fig. 1. The molecular mechanism of SMPs (two-way SME). Blue lines: molecular chains with low mobility below Ttrans; red lines: molecular chains with high mobility
above Ttrans. Adopted from Refs. [1,5]. (For interpretation of the references to colour in this figure legend, the reader is referred to the web version of this article.)
heat from inside the material. For this purpose, we can embed the
micro/nano-fillers into the polymer matrix to convert chemical energy,
optical, magnetic, acoustic or electrical to heat. Furthermore, the
manufacture of the shape memory polymer composites is a facile route
for combining the advantages of polymers and the functional properties
of nanofillers. Base on this regards, diverse tactics are deliberated base
on content, type, and functionalization of filler. Also, the possibility to
locally produce temperature into the bulk of shape memory composites
and also converting exogenous fields, such as electric or magnetic field
and even heat, to local temperature is studied. In each section, a special
resolution is considered that clarified the influence of composite mi-
crostructure in shape memory properties.
2. Silicate-based shape memory composites
Silica nanomaterials, including silica sphere, halloysite (tube shape/
1-dimension), and clay platelets, are particularly promising fillers for
various applications due to their unique structure, mechanical proper-
ties, and chemical stability [47–49]. Resembling other polymer com-
posites, silica-based filler faces a colossal challenge called uniform
dispersion in the polymer matrix [50–52]. Therefore, two main routes
of treatment have been generated for ameliorating dispersion of the
silica-based fillers; (I) chemical modifications, for example grafting
functional polymers or functional groups on to the filler surface. The
improvements in the interaction force between filler-polymer and also
physicomechanical and thermal properties of the nanocomposites will
be observed via controlling and tuning the modifier properties. (II) The
second one is physical adsorption. On the contrary with the first route,
structure of the silica-based filler remains virgin and just thermo-
dynamic affinity between filler and polymer has been altered in the
Fig. 2. (a) One-way SME with dual-shape (b) two-way SME with triple-shape (reversible SME). Adopted from Ref. [1,11].
282
European Polymer Journal 117 (2019) 280–303
physical modification. Likewise, the weak polymer-filler interaction
force is observable in the physical adsorption method that of chemical
modifications [53,54].
SMPCs containing silica-based fillers are one of the promising ca-
tegories at the last decades [55,56]. Embedding silica-based filler can
capable of improving shape memory properties, especially mechanical
properties and shape recovery stress as well as shape recovery rate [56].
In addition, the elastic stiffness and proper shape memory behavior are
guaranteed via incorporating silicate-based because a vital weakness of
neat polymers is low modulus in shape memory applications [55]. It is
worth mentioning that nano-scale (with high surface area) fillers have
some advantages over micro-scale fillers; for instance, better stiffness
and tensile strength, higher modulus and flexural strength were ob-
served in the nano-composites that of composites [55].
Among all the silicate-based nano-fillers, clays are in the center of
attention due to granting superior mechanical properties than metal
particles when adding to the polymer nanocomposites. Clays platelet
generally refers to the specific division of materials made of layered
silicates (or clay minerals) which trace of metal oxides and organic
material can found inside their structure. The change in the interlayer
spacing of clay by intercalating long chains or by grafting with different
functional groups results in a change from hydrophilic to hydrophobic
nature, and it can design a wide range of new attractive properties.
Hence, the modification of clay is now of immense interest in the pre-
paration of polymer-clay nanocomposites. As mentioned, the mod-
ification of clay may also lead to improving dispersion of these mate-
rials in a polymer matrix via intercalation process.
The state of clay dispersion/distribution and the quality of the
polymer-filler interfacial interaction are classified as the principal fac-
tors in discovering the microstructure and the essential properties of the
M. Panahi-Sarmad, et al.
Fig. 3. The different dispersion state of clay platelets.
resulting polymer composites [50]. The characteristics of the polymer
and filler, the extent of surface functionalization/modification and the
fabrication method of the polymer composite intensely influence the
degree of dispersion and intercalation of the clay platelets [57]. It is
worth mentioning that both of filler-polymer and filler-filler interaction
can be changed capable of dictating the intercalation phenomenon.
Thus, clay-polymer composites maybe have four morphologies, which it
depends on declared thermodynamic and kinetic parameters; (I) phased
separated (especially in conventional micro-composite), (II) inter-
calated, (III) flocculated and (IV) exfoliated composite (Fig. 3). A phase-
separated morphology will be achieved if polymer chains cannot pe-
netrate and intercalate into the interlayer distance of silicates platelets.
This morphology is assigned to the weak clay-polymer interaction
owing to resulting from the incompatibility between these two phases.
Accordingly, there is an odd distance between clay platelets and the
taken stacking composition in the polymeric matrix results in the ag-
glomeration of clay tactoid. Consequently, it operates only similar to a
traditional composite (in micro-scale), expecting an abundant clay
filling to accomplish notable augmentation in their mechanical prop-
erties [58,59]. Alternatively, the intercalated nanocomposite is pro-
duced when polymer chains favorably relocate and enter to the inter-
layer spacing of layered silicate, contributing positively to the
augmentation of interlayer spacing. It is noted that the structure of
layered silicate remains in a regular stacking of alternating clay layer
and polymeric chain in a well-ordered manner. In this structure, se-
paration of distance between the clay layer is approximately about in-
dependent of the clay to polymer ratio [60,61]. Clearly, this structure
displayed better properties than a phase-separated composite when the
same amount of clay was added. Adversely, nanocomposite, somewhat
similar to an intercalated structure, only differs from intercalated na-
nocomposite in the sense that appeared due to the hydroxyl interaction
between clay layers. Meanwhile, when the clay platelets are entirely
separated from each other so that the regular periodicity of the clay
platelets has been completely disoriented, such morphology is termed
as a delaminated or exfoliated state of clay platelets in a clay-containing
polymer nanocomposite. The resulting microstructure is attributed to
the inclusion of the polymer chains that have successfully overcome the
electrostatic interaction between adjoining lamellar of some clay pla-
telets. Hence, the interlayer distance between clay layers falls in the
range of or more. Attributed to the high aspect ratio and the strong
interfacial interaction of the filler phase with the continuous matrix,
this structure imparts the most pleasant improvement to the resulting
polymer properties compared to an intercalated structure. Besides, each
283
European Polymer Journal 117 (2019) 280–303
clay particle in the delaminated nanocomposite peels off into multiple
layers of platelets, indicating an increase in the number of reinforcing
particles in the continuous organic phase, facilitating maximization and
optimization of nanocomposite’s properties even at low clay loading
[62–64]. However, a thoroughly exfoliated structure is not often hardly
attained in usual practice.
These Structures are hydrous aluminum phyllosilicates and usually
crystalline which traces of iron, magnesium, alkali metals, alkaline
earths and other cations; each unit can be found in various amounts
inside unique structure [65]. Nano-scale layers have a great tendency to
re-stack when intercalated or fully exfoliated and form the agglomer-
ated tactoids when possible (absence of dispersing and/or distributing
force). On the other hand, intrinsic and robust incompatibility between
hydrophilic clay layers and hydrophobic polymers is another task at
hand, which may lead the monolayers into the reformation phase of the
agglomerated tactoids in the polymer matrix [65–71]. In this work, clay
platelets are categorized into two major types: natural and synthetic.
Natural clays composed of alternating sheets of SiO2 and Al2 O6 units in
ratios of 1:1 (Kaolinite), 2:1 (Montmorillonite and Vermiculite) and 2:2
(Chlorite), Although Chlorites is not generally considered as clay, which
is sometimes categorized as a discrete member of the phyllosilicate
family [65,72].
Smectite Clays: The natural Smectite family is perhaps the largest
family of clay fillers from the applicability and property-granting point
of view, which belongs to the family of 2:1 phyllosilicate. The crystal-
line structure of this group consists of stacked layered made of two
silica tetrahedrons fused to an edge shared octahedral sheet of alumina.
Abundance in the world, > 1000 in aspect ratio, 1 nm in layer thickness
and > 300 Å to several microns in lateral dimension has made this
particular family of nano-fillers capable of higher cation exchange ca-
pacity. Montmorillonite, hectorite, saponite, vermiculite, laponite, se-
piolite and bentonite are the common smectite clays [65]. Fig. 4(a)
displays two layers of stacked sheets in a smectite clay.
Kaolinite Clays: Kaolinite is another member of the clay family
which belongs to the 1:1 layer silicates. The structure of the kaolinite
group is composed of silicate sheets bonded to gibbsite layers (alu-
minum oxide/hydroxide), which are firmly bonded. Presence of dif-
ferent cations such as K+ , Ca2+ and Mg2+ in the kaolinite structure can
compel the negative charges ineffective. Apart from this, water mole-
cules are present between the sheets and are held together by hydrogen
bonding. Unlike smectites, kaolinite has a low cation exchange capacity
[65]. Fig. 4(b) demonstrates the general structure of a chlorite clay.
Chlorite Clays: The structure of chlorite is as follows: -tetrahedral-
M. Panahi-Sarmad, et al.
Fig. 4. The structure of (a) smectite clays, (b) kaolinite clays, (c) chlorite clays, and (d) Halloysite nanotube. Reproduced by permission from Refs. [65,74].
octahedral-tetrahedral-(Mg2 +, Fe3+)(OH)6 along with a crystalline unit
which contains two tetrahedral silica sheets and two magnesium-
dominated trioctahedral sheets which can result in a 2:1:1 or 2:2
structure. Fewer studies have been executed on nanocomposites con-
taining chlorite clays due to confined sources of this clay [65]. Fig. 4(c)
demonstrates the general structure of a chlorite clay.
Halloysite nanotube: Halloysite (HNT) is an essential member of
the kaolinite family with the structure of nanotubes and the chemistry
of kaolinite. This nanotube has a similar composition to kaolinite except
that additional water molecules are present between the layers. The
outer surface is generally consisting of a tetrahedral sheet which com-
posed of siloxane groups whereas the inner surface is inhabited by
octahedral sheets of alumino groups (Fig. 4(d)). One of the most sig-
nificant advantages of HNT is the dispersion simplicity in a polymer
matrix due to weak secondary interaction among the nanotubes [65].
Attapulgite nanorods: A naturally hydrated magnesium-aluminum
silicate clay containing the vast amount of hydroxyl group on the sur-
face in the shape of nanorods, which can form hydrogen bonds with
several proton acceptor groups, leading to the considerable ameliora-
tion of mechanical properties [73].
Several SMPCs containing each one of silica-based filler will be re-
viewed in the following:
2.1. Influence of silica spheres on shape memory properties
Yan et al. [75] investigated the thermal, mechanical and shape
memory properties of polylactide- co-polyester (PLAE) nanocomposites
incorporating nano-SiO2 in range of 1–7 wt% filler loading. Prepolymer
was first synthesized from L-lactide and then reacted with poly-tetra-
methylene ether (PTMEG), as illustrated the molecular structure of the
polylactide-based polyurethane in Fig. 5(a). The yield strength and
tensile modulus of samples at room temperature and 40 °C is summar-
ized in Fig. 5(b) and (c) that retrieved from stress-strain curves. The
yield strength of composites has decreased at room temperature due to
284
European Polymer Journal 117 (2019) 280–303
decrement ductility with increasing filler content. On the other hand,
when the temperature was increasing to upper Tg of soft segments
(40 °C), the ascending trend is observed in yield strength behavior by
increasing filler content. Therefore, the incorporation of SiO2 leads to
the decreasing and enhancing of yielding strength as presented in
Fig. 5(b). Shape fixity (SF) and recovery ratios (RR) of the pristine PLAE
and its nanocomposites is demonstrated in Fig. 5(e) at 40 °C. In the
indicated filler loading range, high values of SF (above 95%) is de-
tected. By increasing the filler loading, alteration of SF from 97.7% for
pristine PLAE to 95.7% for 7 wt% nanocomposite is observed. The
variation of SF is an ascending change up to the 3 wt% nanocomposite
and thereupon, a descending change for the 5 wt% and 7 wt% nano-
composites. This alteration can be elucidated through relying to the
provided DSC data for the crystallinity evolution, which is the fusion
heat of pristine PLAE is much higher than the nanocomposite samples.
Higher crystallinity results in higher stiffness of the samples, which can
eventuate in the convenient retainment of stretched length after the
releasing of tensile load. This results is in coordination with Jana et al.
[76] findings. Noteworthy, by the augmentation of modulus in 1 wt%
and 3 wt% nanocomposites at low temperatures, higher reinforcing
features is observed in Fig. 5(c), which can be attributed to the higher
SF of 1 wt% and 3 wt% nanocomposites compared to the pristine PLAE.
The static and dynamic elastic modus results have a good agreement
that reposted in Fig. 5(d). Since the crystals of PLA, chain segments and
SiO2 are acting as the fixed phase in 1 wt% and 3 wt% nanocomposites,
higher elastic modulus can be observed at lower temperatures, which
results in more RR compared to the pristine PLAE. The nanocomposites
containing 5 and 7 wt% filler demonstrate lower elastic modulus
comparing to the lower loadings due to the poor dispersion and ag-
glomeration as well as its can be disordering parameter in the crystal-
line state. Consequently, lower values of RR are believed to be observed
from the nanocomposites with higher loadings of SiO2 . Pristine PLAE
and the lower-filled nanocomposites displayed higher SF in all the cy-
cles, which corresponds with previous interpretations. In addition,
M. Panahi-Sarmad, et al.
Fig. 5. (a) chemical structure of polylactide-based polyurethane, (b) yield strength, (c) tensile modulus, (d) dynamic-mechanical-thermal analysis (DMTA) and (e)
shape fixity and shape recovery ratio (at 40 °C) of neat polymer and composite containing varied silica content [75].
lower-filled nanocomposites demonstrate higher recovery speed, which
might be due to the increase in shape recovery stress. In the other as-
pects, the dissipation factor (tanδ) can approve that the 5 and 7 wt%
silica composites have lower crystallinity and improper dispersion be-
cause the tanδ of these composites is inferior than neat polymer
(Fig. 12(c)) [77,78]. As it is clear, the recovery ratio has been no sa-
tisfied even in 1 wt% composite.
Odent et al. [79] systematically investigated the recovery ratio (RR)
effect in blend nanocomposites system, including imidazolium termi-
nated poly(lactide acid) (im-PLA) and rubbery poly[ε-caprolactone-co-
D,L-lactide] (im-P[CL-co-LA], neat PLA and ionic-modified silica nano-
particles. Pristine PLA demonstrates poor recovery properties (10%)
and then blending 50/25/25 of PLA/im-P[CL-co-LA]/im-PLA can
ameliorate RR to 17%. Blend composites containing ionic silica nano-
particles shows better RR properties than that of the filler-free blend,
owing to nature of the ionic bonding between the imidazolium-termi-
nated polymers and the sulfonated silica nanoparticles leading to better
nanoparticle dispersion with separate morphologies and enhance in the
gel-like plateau behavior and storage modulus. The ionic hybrids
system is also plentiful deformable that of the neat PLA. Best shape
285
European Polymer Journal 117 (2019) 280–303
memory properties were observed for 25 wt% im-PLA and 25 wt% im-P
[CL-co-LA] including 5 wt% ionic-modified silica nanoparticles. Which
the RR of this system is equal to 79%.
2.2. Influence of halloysite nanotube, attapulgite nanorod and sepiolite
nanorod on shape memory properties
A nanocomposite system based on PU and containing Halloysite
nanotube (HNT) was fabricated through the melt mixing by Bouaziz
et al. [80]. The remarkable enhancement in the mechanical properties
(such as strength and the modulus) of PU/HNT nanocomposite was
observed without losing significant ductility that of neat PU. Interest-
ingly, the crystallization volume in samples has been grown with in-
creasing filler content. Howsoever, the HNT content has no significantly
affected the shape fixity ratio but the shape recovery speed of nano-
composite increases as the HNT content enhance. In this work, The
Cauchy stress fluctuations versus temperature are considered as an in-
dication of nanocomposite shape recovery stress. Thus, the Cauchy
stress has deterioration behavior with reducing the temperature. It is
worth mentioning that the phase Transition above the shape recovery
M. Panahi-Sarmad, et al.
temperature will result in the development of residual stresses, which
slightly increased the degree of crystallization.
Xu et al. [81] studied the shape memory behavior of a nano-
composite system based on polyurethane/attapulgite nanorods. The
application of mechanical mixing in order to produce the mentioned
nanocomposite lead to fine dispersion of the nanorods in the polymer
matrix. Based on the analysis results, the mechanical and thermal be-
havior of the nanocomposites strongly depends on the treatment of the
attapulgite nano-clay as the presence of moisture in the untreated at-
tapulgite cause plasticization in the PU matrix, which leads to the de-
crease in glass transition temperature (Tg ) and hardness of the fabri-
cated nanocomposites. Based on the TEM results, after the heat
treatment of attapulgite, the formation of the crystallized and bundled
structure is inevitable which lead to the improvement of mechanical
properties due to the enhancement of interfacial properties of atta-
pulgite. The shape recovery of the 30 wt% filled nanocomposites ren-
dered the same values as pristine PU, although the recovery speed was
slightly slower. In a similar study, Xu et al. [82] studied the influence of
pre-treatment of attapulgite clay on the shape memory properties of
PU-based nanocomposites. Bundled structures of attapulgite were ob-
served after heat treatment, which can be attributed to the expunction
of inter-fibrillar water in the presence of elevated temperature treat-
ment. Good shape recovery ratio was observed after 2 shape memory
cycles, which implies the effect of heat treatment of attapulgite clay on
shape memory properties of PU.
Xu and Chen [73] investigated the self-healing and shape memory
properties of attapulgite-filled PU nanocomposites. The proper disper-
sion was achieved while the filling content was at the lowest. Tensile
properties demonstrated increasing procedure with increasing filler
content until 3 wt%, which can be attributed to the strong filler-
polymer interactions. The tensile stress and elongation at break drop in
5 wt%. nanocomposite implies the adverse effect of large agglomerates
on the mechanical properties of the nanocomposite. The analysis of
displacement data indicated that the introduction of attapulgite on the
shape recovery is limited. However good shape memory effect has been
achieved upon heating.
Yu et al. [83] studied the influence of sepiolite on shape memory
properties of PCL-based Polyurethane nanocomposites. Strong adhesion
between sepiolite and polyurethane was observed from the SEM
images, which resulted in the uniform filler dispersion. The influence of
sepiolite on the mechanical properties was clarified by DMTA and the
results storage modulus and tanδ versus temperature of composites are
presented in Fig. 6(a) and (b) respectively. According to Fig. 6(a), the
storage modulus has been augmented as filler content increase; because
the available surrounding interface of sepiolite increases with an in-
crease in content. The tanδ results of PU composites evidenced that the
high quality of filler-polymer interaction presented; due to integral of
dissipation peak (at Tg) of samples have monotonically declined with
increasing filler content. When the Sepiolite existence as filler, the
crystallinity of soft segments in the polyurethane nanocomposites are
much higher than that of pristine polyurethane. Furthermore, the
crystallinity of soft segments increased with increasing in sepiolite
content until 3 wt%. On the contrary, the decreasing trend of crystal-
linity was observed in the highly filled nanocomposite containing 5 wt
% sepiolite. The shape fixity ratio and recovery of the pristine poly-
urethane and its nanocomposites is perceived in Fig. 6(c) and (d), re-
spectively. Fig. 6(c) indicating that the shape fixity ratio of composites
first shown an increasing and then decreasing behavior with increasing
sepiolite content in the first cycle. Furthermore, a slight amplification in
shape fixity ratio was observed with increase in shape memory cycles.
Likewise, the shape fixity ratios of nanocomposites are higher than that
of pristine polyurethane. This indicates that the shape fixity ratio is
affected by the soft segment phase structure and reversible melt-solid
transition. As illustrated in Fig. 6(d), a slight decrease in shape recovery
ratio was observed with increasing in sepiolite content in the first cycle.
Increasing the shape memory cycles caused increasing the shape
286
European Polymer Journal 117 (2019) 280–303
recovery ratios of pristine polyurethane and its nanocomposites until
100%, which indicates the shape recovery ratio is affected by the
structure of hard segments. Albeit the organization of hard segments is
rarely impressed by the presence of sepiolite, the polymer chain mo-
tions are dominantly immobilized by filler. The changing micro-
structure of described composites under the shape memory process is
summarized in Fig. 6(e).
In a similar study, Zhan et al. [84] fabricated a shape memory poly
(p-dioxanone)-poly(ε-caprolactone) (PPDO-PCL/OSEP) nanocomposite
comprising 0.8, 2.4 and 8 wt% absolute sepiolite nanorods (OSEP). The
schematic of PPDO-PCL/OSEP composite preparations as well as the
technique of PCL grafting to OSEP surface is shown in Fig. 7(a). Grafted
PCL segments on the surface of OSEP revels that the fillers were uni-
formly distributed in 0.8% and 2.4 wt% nanocomposites, while ag-
gregation was observed in 5 wt% specimen. Noteworthy, the crystal-
lization behavior of samples has a vital role in both shape fixity and
recovery behavior, as ascribed in Fig. 7(b). The both of soft segment
(PPDO) and hard segment (PCL) obviously shows ascending trend in
crystalline degree with loading higher filler content. The shape memory
performance of samples is evaluated via cyclic thermo-mechanical test,
the result for filler free specimen and composite containing 3 wt% OSEP
is reposted in Fig. 7(c) and (d), respectively. With the comparison of the
cyclic thermal mechanical properties of mentioned samples, the stress
value in various cycles has progressed in 3 wt% composite that of the
filler-free sample, which leads to improving shape fixity behavior. The
3 wt% nanocomposite demonstrates fine excellent shape fixity and re-
covery ability with values higher than 99%, approximately. In the basis
of improper dispersion, a negligible decrease was observed in shape
recovery ratio in 5 wt% nanocomposite. It is worth mentioning that the
grafted PCL on the particle surface for creating brilliant interfacial in-
teraction has a dominant impact on these superior shape memory
properties of composites.
2.3. Influence of clay platelets on shape memory properties
Ali et al. [85] designed a hyperbranched Polyurethane/reactive
nano-clay system by using a hybrid polyol system based on Poly-
caprolactone-diol (PCL-diol) and Palm oil polyol with a specified molar
ratio. As expected, incorporating the nano-clay leads to the decrement
in soft segment crystallization and also the nano-clay platelets have an
interdiction effect on phase separation of soft and hard segments.
Subsequently, existing the strong interfacial bonding (between the
matrix and nano-clay) in 1 and 3 wt% PU nanocomposites reveals to
improve the breakpoint in the stress-strain curves. On the other hand,
the absence of hydrogen bonding and dipole-dipole interactions in 5 wt
%. nanocomposite can lead to obtaining a noteworthy decrease in
strength and strain at break owing to filler agglomeration and reducing
interfacial zone. Consequently, well shape fixity and shape recovery
ratio were observed in 1 and 3 wt%. nanocomposites. In the other as-
pect, a slight decrease in shape fixity and a significant deterioration in
the shape recovery ratio was detected in 5 wt% nanocomposite due to
the weak filler-polymer interaction.
Zubir et al. [86] have investigated the shape memory properties of
poly(urethane) PU/nano-clay nanocomposite system. The XRD patterns
show an inverse relationship between the nano-clay content and peak
height, which it is pertaining to the decrease in PCL-diol crystallinity
caused by interdiction effect of nano-clay on polymer chain mobility.
Shape fixity ratio is principally depending on the soft segment crys-
tallinity; the excessive nano-clay content (5 wt%) can prevent adequate
crystallinity degree of the soft segments that lead to decrease shape
fixity ratio of 5%w nanocomposite. Decrementing behavior of shape
recovery ratio in 5 wt% is detected. The reason for this phenomenon
relates to the deterioration of physical crosslinks between the polymer
matrix and nano-clay. The composites containing 1 and 3 wt% have the
best shape fixity and shape recovery ratio (100%) owing to presenting
the optimum value of soft segment crystallinity. On the other work, the
M. Panahi-Sarmad, et al. European Polymer Journal 117 (2019) 280–303

Fig. 6. the temperature dependence of (a) storage modulus- temperature and (b) tanδ- temperature, (c) shape fixity ratio and (d) shape recovery ratio for pristine
Polyurethane and its nanocomposites. (e) Schematic diagram of the structural changes of SMPU-0 and SMPU-3 in the shape memory process. With permission from
Ref. [83].

mechanical and shape memory properties of a nanocomposite system
based on epoxy foam containing various weight contents of MMT-based
nanoclay was studied by Quadrini et al. [87], utilizing a novel solid-
state foaming process. Shape recovery tests were conducted on the
appropriated composites containing lower 5 wt% nano-clay. When high
filler content (10 wt%) was embedding in the matrix, the rigidity of
nanocomposite is disorientated. Thus, acceptable recovery ratios are
attributed to mentioned nanocomposites, which were above 97%.
Cao and Jana [76] prepared a tethered shape memory Polyurethane
(PU)/nano-clay nanocomposite. Based on the microscopic results, lower
contents of nano-clay platelets have been well exfoliated in the PU
matrix. As shown in Fig. 8(a), wide-angle x-ray diffraction (WAXD)
patterns of nano-composite consist of various clay content have no
shown observable peaks except 5 wt%, which it is relevant to the good
exfoliation of nano-clay in the polymer matrix. The observable peak at
2θ = 6.5° and a distinctive shoulder at 2θ = 3.4° are presented in the

287
M. Panahi-Sarmad, et al.
Fig. 7. (a) Schematic fabrication of PPDO-PCL/OSEP nanocomposites, (b) Schematic illustration of the molecular mechanism of polymer chains under shape memory
process, and cyclic thermal mechanical properties of (c) filler free PPDO-PCL and (d) PPDO-PCL/OSEP 3 wt% nanocomposites [84].
WAXD pattern of PU containing 5 wt% (Fig. 8(a)). Noteworthy; clay
platelet expresses the presence of multiple clay sheets in this nano-
composite. On the other hand, TEM micrograph of 3 wt%. PU nano-
composite clarifies the simultaneous existence of exfoliated and stacked
platelets of nano-clay, which summarized in Fig. 8(b). The in-
corporating of nano-clay can convince the intense phase mixing of the
soft and hard segment of the nanocomposite followed by the crystal-
lization of both soft and hard segment. The presence of clay platelets
leads to reduce the crystalline state in the soft segment. Although,
significant phase separation is observed between soft and hard segment
in pure PU, but the phase separation has been decreased in PU com-
posites due to prevent crystalline formation. The reduction of nano-
composite crystallization has a negligible destructive effect on shape
memory behavior; because of the improvement in the shape fixity and
shape recovery ratio are observed in PU/Clay composites. For instance,
shape recovery force of PU composite containing 1 wt% nano-clay has
1.2 times augmentation that of neat PU. Moreover, shape fixity de-
creased from 96% to 93% for the pristine PU by incorporating the 5 wt
% of clay platelets. Firstly, the shape fixity has been decreased by
adding nano-clay to the system owing to the disruption in crystal-
lization order, while the shape fixity of 5 wt% composite is more than
other composites. According to Fig. 8(c), a little increment in 5 wt% PU
composite elucidated that filler-filler interaction has a positive impact
on shape fixity behavior. Consequently, the best exfoliation degree of
nano-clay is observed in the 1 wt% nanocomposite, which leads to
achieving the minimum rate of relaxation and the maximum shape
recovery stress (Fig. 8(d)).
Sun et al. [88] prepared a nanocomposite system based on PLA/TPU
blend and Montmorillonite (MMT) nano-filler. SEM images have in-
dicated the inclination of TPU in forming droplets in PLA media, which
288
European Polymer Journal 117 (2019) 280–303
is due to the lack of tendency of TPU in establishing strong bonds to
PLA macromolecules. Introducing MMT by only 1 wt% in the matrix
enhances the compatibility of TPU and PLA by extenuating the TPU
droplets by 100–200 nm. Incorporation of 3 wt% MMT in the polymer
matrix caused the PLA media approximately surround the TPU droplets.
DSC results are indicated that the incorporation of MMT has behaved as
defects, which intercept the crystallization process. On the other hand,
the temperature increment directly influences the chain mobility,
which is caused by the decay of nano-filler incorporation on crystal-
linity. The introduction of 1 wt% MMT increased the storage modulus.
On the contrary, increasing the nano-filler content above 1 wt% sig-
nificantly decreased the storage modulus; This is due to the major value
of crystals in the 1%w nanocomposite. The application of the annealing
process reduced the tanδ from 1.35 to 0.35 which is due to the dete-
rioration of viscoelastic properties of the crystalline phase. Using DMA,
Shape Memory behavior of the neat PLA/TPU and its nanocomposites
were observed. Fig. 9 demonstrates the Shape Recovery Ratio (Rr) and
Shape Fixity Ratio (Rf) of the mentioned specimen. According to the
data, an increase of about 10% in Shape Recovery Ratio can be ob-
served in 1 wt% nanocomposite due to the enhancement of PLA/TPU
compatibility and significant augmentation in polymer-polymer inter-
action. Increasing the nano-filler content acts as defect points and
prevents Shape Recovery. However, Rf has almost a constant value in
all nanocomposites, which is attributed to the process of deformation
under room temperature. This causes the specimens to undergo sig-
nificant plastic deformation.
Dong et al. [89] prepared a novel triple shape memory nano-
composite consists of electrospun PCL microfiber membranes/epoxy
(EP) blend. To achieve suitable SF, 3%, 5% and 7 wt% of MMT were
added to the PCL/EP blend. Enthalpy decrease occurs when the
M. Panahi-Sarmad, et al.
Fig. 8. (a) WAXD Patterns of TPUs and its Cloisite 30B nanocomposites, (b) mechanism of clay dispersion, (c) shape fixity and (d) relaxation behavior of shape
memory TPU composites [76]. Reproduced with permission from Elsevier Ltd.
Fig. 9. Shape Memory Properties of different wt% of MMT in PLA/TPU nano-
composites. With permission from Ref. [88].
nanocomposites are highly filled (5 and 7 wt%), which led to the filler
aggregation and increasing the free space and easier chain movements.
These events have a direct effect on crystallinity behavior of the na-
nocomposites, which can lead to the fluctuations of shape memory
properties. Triple shape memory cycles of epoxy blend composites are
reported in Fig. 10. The impact of blend mixing method in shape
memory properties is evaluated via incorporating 6 wt% of PCL to EP,
as shown Fig. 10(a) for blending method and Fig. 10(b) for electro-
spinning method. For this porpoise, all samples are firstly heated to
289
European Polymer Journal 117 (2019) 280–303
75 °C, deformed to the first temporary shape (shape b), and then cooled
to 40 °C, the first temporary shape then fixed. The second fixing tem-
porary shape (shape c) is deformed at 40 °C, followed by cooling to 0 °C
and fixing the second temporary shape. The first and final recovery
shapes are observed after heating to 40 and 75 °C, respectively. The
recovery ratio at both C and B states have obviously improved (from
73% to 100% at C state) that clarified in strain curves. Indeed, the
electrospuned specimen shows better fixation ration that of the blended
sample, which it increased from 48% to 61.2 (at B state). Finally, the
MMT was appended to the electrodspuned system to compensate for the
shortcoming of shape memory behavior of filler-free blends. According
to Fig. 10(c), the Samples incorporating 3 wt% of MMT showed ex-
cellent shape recovery and moderate shape fixity which can be related
to the reduced fusion of heat in the 3 wt% nanocomposite led to re-
duced crystallinity and easier recovery to the orginal shape. As results,
we realized that the clay platelets could tune in crystalline order for
improving shape memory properties even in polymeric blends.
Liu et al. [90] prepared and studied the mechanical, structure and
shape memory properties of a series of OMMT/epoxy nanocomposites.
Incorporation of OMMT increased toughness, which is measured by
elongation at break and tensile strength of the nanocomposite com-
paring to the pristine epoxy. However, 3 wt% nanocomposite displayed
better mechanical results among other nanocomposites. Restrained
crack propagation has been happened due to the formation of micro-
cracks around the OMMT layers. Meanwhile, slipping characteristic of
OMMT is a key reason in increasing the toughness of epoxy nano-
composites, which can be attributed to the ability of OMMT in ab-
sorbing the fracture energy. Intercalated structure of OMMT is the
reason for the total increase in tensile strength of nanocomposites,
M. Panahi-Sarmad, et al.
Fig. 10. Triple shape memory cycles of epoxy blend composites containing (a) 6 wt% of PCL via blending (b) 6 wt% of PCL via electrospinning and (c) 6 wt% of PCL
and 3 wt% of MMT via electrospinning method. With permission from Ref. [89].
Fig. 11. Full recovery time of the fabricated nanocomposites and pristine epoxy
in two different temperatures. With permission from Ref. [90].
which can be attributed to the necessity of matrix failure prior to the
tensile failure. Aggregation and poor dispersion of OMMT in nano-
composites containing higher filling ratio than 3%wt. resulted in the
decrement of toughness and tensile strength. Furthermore, shape re-
covery speed results demonstrate that the nanocomposite samples can
recover their original shape in less time than the pristine epoxy sample.
3 wt% nanocomposite demonstrates faster shape recovery than other
samples, which can be attributed to the enhancing of molecular inter-
actions and stiffness and thus, increasing the recovery speed. Ag-
gregation of the higher-filled nanocomposites leads to the generation of
structural irregularities and lower molecular interactions, and is the
290
European Polymer Journal 117 (2019) 280–303
reason for increased recovery time. Elevation of the recovery tem-
perature does not influence the recovery behavior and its influence can
solely be observed on the decrement of recovery time in higher tem-
peratures, which can be seen in Fig. 11.
Li et al. [91] synthesized a nanocomposite system based on Poly-
urethane/montmorillonite-polymethyl methacrylate (PU/MMT-PMMA)
and systematically studied the influence of grafting ratio of PMMA on
shape memory properties of the mentioned nanocomposite, which is
directly related to the hydrogen bonding between hard-hard segments
and hard segments/PMMA. The formation of PMMA between the
layered structures due to the atom-transfer radical polymerization leads
to the exfoliation of Organophilic MMT (OMMT) which was concluded
to the absence of diffraction peak in XRD patterns. The crystallinity
values of PU/MMT is smaller than pristine PU. Shape fixity ratio and
Shape recovery ratio were elucidated that the 1:5 MMT:MMA (weight
ratio) is optimum grafting value (3%), and also all of the nanocompo-
sites demonstrated better results than pristine PU.
The literature results obtained from SMPCs containing the silica-
based particles are summarized in Table 1. The shape fixity and re-
covery, filler content, filler shape, and stimulus field of composites is
determined and compared in the table.
3. Carbon-based shape memory composites
Carbon-based nanoparticles have latterly excited a numerous op-
portunity of attention due to their naturally high mechanical perfor-
mance and exceptional transport features, especially in polymeric
composites [99–103]. Due to their sp2 structure-dependent conductivity
[104–109], their addition into polymers could solve some transport
properties-related issues of composite materials at low or even ex-
tremely low concentrations for several applications, such as dielectric
elastomer composites [110,111], electromagnetic shielding
[99,112,113], and shape memory composites [42]. According to their
 M. Panahi-Sarmad, et al.

Table 1
Effect of silica-based filler on the shape memory properties of polymer composites.
Matrix Nanoparticle Content Treatment Stimulus Field Rf Rr Ref.

Hyperbranched PU (HPU) MMT (Cloisite30B) 1 and 3 Organic quaternary ammonium ions (*) Thermal ≈100 ≈100 [85]
PU MMT (Cloisite30B) 1 and 3 Organic quaternary ammonium ions (*) Thermal ≈100 ≈100 [86]
Epoxy foam MMT 1–5 – Thermal Above 97% N/A [87]
TPU MMT (Cloisite 30B) 1 and 5 Organic quaternary ammonium ions (*) Thermal (1%) ≈90 (5%) ≈93 [76]
PLA/TPU Blend MMT (Cloisite 15A) 1 Ammonium salt Modified (*) Thermal 95 97 [88]
PCL-PCL/Epoxy Blends MMT 3 – Thermal 90.8 98.93 [89]
Epoxy MMT 2–5 Cetyltrimethylammonium Thermal 100 N/A [90]
PU MMT 1:5 (MMT: PMMA Thermal 99 100 [91]
MMA)
PU HNT 2–6 – Thermal 100 N/A [80]
PLA Nano-SiO2 1 and 3 Silane coupling agent surface modified Thermal (1%) 90.6 (3%) 98.5 [75]
PLA/PCL Nano-SiO2 5 Sulfonate-modified Thermal 79 100 [79]
PU Attapulgite 30 Heat-Treated Thermal Same as pristine PU N/A [81]

291
PU Attapulgite 30 Heat-Treated Thermal 99.2 N/A [82]
PU Attapulgite 1 – Thermal N/A N/A [73]
PU Sepiolite 3 Silane-treated Thermal ≈92 ≈87 [83]
PPDO/PCL Sepiolite 1–5 Organic-modified Thermal ≈99 ≈99 [84]
PLA Bentonite 15 Citric Acid modified Thermal Shape Upwards: ≈90 100 [92]
Shape Downwards:
80
Thermoplastic Starch/EVA Blend Bentonite 1 Na+ modified (*) Humidity 84 80 [93]
t-butylacrylate-copoly(ethyleneglycol) Bentonite 1 quaternary benzyl hydrogenated tallow dimethylammonium ions modified Thermal 100 100 [94]
dimethacrylate (tBA-co-PEGDMA)
Segmented Polyurethane (SPU) Cloisite 10A/Cloisite 3 Dimethyl, benzyl, hydrogenated tallow, quaternary ammonium chloride/N- Thermal ≈100 ≈100 [95]
30B methyl tallow bishydroxyethyl quaternary ammonium
PU MMT (Cloisite 30B) 0.25/0.5/0.75 Organically-modified (*) Thermal ≈82 ≈30 [96]
Thermoplastic Starch MMT 1–10 – Thermal 100 N/A [97]
PU Nano-SiO2 1 Vinyltrimethoxysilane (VTMS)-modified Thermal ≈99 ≈99 [78]
PU Nano-SiO2 2 triethyl amine (TEA)-modified Thermal 99 99 [77]
Epoxy Nano-SiO2 5.4 – Thermal 99.7 100 [98]
European Polymer Journal 117 (2019) 280–303
M. Panahi-Sarmad, et al.
Fig. 12. Types of carbon-based nanoparticles: amorphous nanometric-sized carbon black (CB), single-wall carbon nanotubes (SWNT), multi-wall carbon nanotubes
(MWNT) and graphene. With permission from Ref. [117].
reduced density, the use of polymer-based composite materials with
added functionalities resulting from carbon-based particles has received
a great deal of interest for tailoring composites [102,114,115]. Carbon-
based nanoparticles can arrange according to their structure and di-
mensions. As shown in Fig. 12, the most common particles are carbon
nanotubes (CNT) and more recently graphene, alongside nanometric-
sized carbon black (CB). CNTs, graphene and their derivatives are low-
density materials in the nanoscale, making them suitable candidates to
be used in the fabrication of high-performance polymer composites.
Their geometric characteristics provide the possibility of high surface
interaction with polymers, which could result in significant mechanical
and/or shape memory properties enhancements [8,14,30,116].
As mentioned, shape memory polymers (SMPs) have several re-
strictions. When proper fillers incorporated to the polymeric matrix,
these limitations have vanished. Although, the influence of these na-
noparticles in shape memory behavior depends on various factors that
including; polymer-filler affinity, polymer-filler interaction, filler-filler
interaction as well as intrinsic properties of filler (such as conductivity,
aspect ratio and shape) and polymer (such as semi-crystalline or
amorphous nature) [118–120]. Shape memory performance of SMPCs
has been ameliorated by adding various conductive carbonic fillers
(e.g., carbon black (CB), carbon nanotube (CNT), Graphene nanopla-
telet (GNP), etc. Embedding carbon particles in polymer matrix caused
that decreasing the electrical resistance and force the polymer to stimuli
with joule heating [121]. Fillers which are chemically bonded to the
polymer chains (performing the function of cross-linking agents) are
more efficient in enhancing the shape memory performance and the
mechanical properties of SMPs. Therefore, shape memory behavior of
polymers can be positively affected by incorporating carbon-based fil-
lers through the improvement of SMPs thermal conductivity.
One of the useful conductive filler is carbon black (CB). Electro
response of shape memory composites comprising CB can obtain when
it was homogeneously dispersed. Even though CB is not as useful as
high aspect ratio fillers to improve the mechanical strength, shape re-
covery stress and electrical conductivity, but amorph carbonic filler has
292
European Polymer Journal 117 (2019) 280–303
lower cost that of CNT and graphene [122]. One of the critical factors in
dispersing CB is the mixing duration; as the mixing time optimizes, the
electroactive properties of composites can be drastically improved
[123]. Generally, incorporating CB in polymer matrix causes to de-
crease the amount of crystallinity of these SMPCs and also will be
wholly discussed about shape memory properties.
CNT is another of the best nanoparticles for achieving thermally and
electrically conductive SMPCs. In other words, the carbonic tube-shape
fillers can capable of improving mechanical, thermal, chemical and
electrical properties as well as shape memory properties of the SMPCs
[124–127]. Anisotropic nature of CNT (or MWCNT) caused that
reaching to percolation threshold at low volume fractions [128]. On the
other hand, graphene has a plate-like geometry and this nanoparticle is
two-dimensional structure. The availability of graphene is good due to
easy procedures that make graphene from graphite [129]. These na-
noparticles showed excellent thermal conductivity due to the sp2 net-
works in the graphene structure [130]. Graphene nanoparticles have
high mechanical strength, flexibility and surface area [131]. Notable,
the most challenge of composites is uniformly dispersion of these na-
noparticles in the polymeric matrix, especially in SMPCs. Dispersion
and distribution of nanoparticles can be improved via mechanical and/
or chemical methods such as melt mixing, in-situ polymerization, so-
lution mixing followed by casting or assisted with ultrasonic distribu-
tion and chemical functionalization. Howbeit, the electrical con-
ductivity of SMPCs decreases by the surface modification of the CNT
and graphene due to the increment defects and disorder SP2 structure
during functionalization [104,109]. Several SMPCs containing each one
of carbon-based filler will be reviewed in the following:
3.1. Influence of carbon black nanoparticles on shape memory properties
Ma et al. [123] investigated the effects of carbon black (CB) nano-
particles on two-way, reversible shape memory, cycles in crosslinked
polyethylene (PE). The CB has been used in this study for improving
shape memory response. All samples showed good elongation during
M. Panahi-Sarmad, et al.
cooling process except for PE composite containing 20 vol%, which
have decreased in elongation value that of pristine PE. This decrement
in elongation at break indicated that an excess amount of CB content
could be deteriorated for shape memory behavior. Indeed, increasing
CB nanoparticle content in PE composites caused the amount of crys-
tallization has been decreased. The pristine PE showed 94% fixity ratio
and 97% recovery ratio. On the other hand, shape fixity and recovery
ratio have been improved by constructing CB/PE composites, but the
shape recovery and fixity reduced in PE composite comprising 20 vol%
CB nanoparticles. The decrement in fixity ratio in happening due to the
crystallinity state decreased in PE composite comprising 20 vol% CB.
Thus, this composite has slightly missed the ability to remain in tem-
porary shape after removing tension. The recovery ratio of the highly
filled composite is declined, owing to an enhancing the creep after in-
corporating 20 vol% CB nanoparticles.
Recently, Arun et al. [132] designed polyurethane (PU) resin
polymer containing 2–40 wt% CB (as conductive filler) based on cyclic
and aliphatic polyisocyanates to prepare shape memory polymer with a
high glass transition temperature (85 °C). The shape memory polymer
made by these polyether-based polyols that high Tg of these composites
has the ability to tailoring for various applications. Interestingly, the PU
composites are of exceptional ability to auction under the thermal and
electrical field. The electrical field can convert to heat through the
composites with existing interfacial polarization or electrical dissipa-
tion. The intensity of electrical dissipation has grown upper the per-
colation threshold; so, the highly filled composite is a proper candidate
to shape memory actuator. Hence, the percolation threshold of the
composite was detected at 6 wt% filler content, as shown in Fig. 13(a).
In addition, the dispersed morphology was observed in the PU com-
posite containing 10 and 25 wt%, but the aggregate size is obviously
more prominent in 25 wt% composite than that of 10 wt% composite
(see Fig. 13(a)). Fig. 13(b) illustrates an empirical relationship between
time and temperature to achieve Tg + 20 °C with various voltages in
25 wt% PU/CB composite. This relationship transferred from parabolic
to linear as the voltage increased. This phenomenon indicated the
tunneling effect of electrons through the nonconductor matrix was ac-
complished due to the closeness of CB particles in the highly filled
composite. Noteworthy, the tunneling generated some parallel electron
path in the system and these paths affect the rate of increasing tem-
perature. For instance, in this study, time to reach the Tg + 20 °C
temperature decreased from 5000 s (for 10 V) to 26 s (for 60 V) due to
increasing in the number of parallel electron paths by applying higher
voltages. Another attractive result in this work is irregular changes of
Fig. 13. (a) electrical resistivity versus filler loading, (b) variation in time to reach Tg + 20 °C with change in applied voltage, (c) variation of Tg against filler
loading, and shape fixity and recovery of PU composites under (d) thermal stimulation and (e) electrical stimulation. With permission from Ref. [132].
293
European Polymer Journal 117 (2019) 280–303
Tg in composites. According to Fig. 13(c), the Tg value shows a de-
crement trend from neat PU to 10 wt% composite owing to a gradual
increase in thermal conductivity and thus heat absorption by CB par-
ticles. Then the Tg increased beyond 10% as the increased particle
content affected chain mobility and thus adds to the hard domain ri-
gidity. Hence it can be elucidated that beyond 10 wt% CB content, the
rigidity of the composite matrix governs the transition and thus the
temperature to achieve transition increased resulting in higher Tg. The
efficiency of electric simulation was higher than thermal simulation for
all cycles on the basis of Fig. 13(d) and (e). The amount of shape re-
covery was 94% for thermally stimulated samples and 98% for elec-
trically stimulated samples due to the tunneling phenomenon for
electron paths.
Liu [133] et al. designed a series of novel laser-triggered shape
memory composites which prepared by using hydro-epoxy resin (HEP)
as the matrix with non-filled, 0.5, 1.0, 1.5 and 2.0 wt% CB. The laser as
an external trigger is a controllable remote, capable to focus with high
accuracy and rapid switching source. Laser-trigged shape memory be-
havior is based on the ability of photothermal conversion of fillers
which used on these SMPCs to generating heat. As mentioned, shape
memory behavior has responded to heat. When laser irradiated on
HEP/CB composite, CB free electron started to vibrate at very high
frequency and then the kinetic energy of these electrons converted into
heat energy. Based on this phenomenon, the shape memory behavior
started to appear when the bulk temperature reached above Tg, and it is
based on the relaxation process between electrons and lattices. Shape
recovery ratio increased with increasing of CB content and this trend
remained constant (97% at 3 min). The CB nanoparticles agglomerate
easily due to these nanoparticles have considerable surface energy, and
thus it is difficult to achieve homogeneous distribution in HEP resin
matrix. So, increasing of CB content in HEP/CB composites made these
composites more easily crack. In another word, these composites were
more prone to ductile fracture due to increasing defects in HEP/CB
composite during a laser-trigged shape recovery process. The growth
trend of shape recovery ratio increased with increasing in the amount of
power density and decreasing material thickness. This phenomenon
occurred due to the number of photons irradiated on per unit area of
the composite surface has been increased and thereupon more heat
released from CB particles during absorption. The 1.064 μm laser irra-
diating used for comparing shape recovery ratio of HEP/CB (0.5 wt%,
1.0 wt%, 1.5 wt% and 2.0 wt%) because the 10.64 μm could vibrate
both electrons and molecules during the shape recovery process. Based
on results, the rate of recovery ratio is of acceptable in 1 and 1.5 wt%
M. Panahi-Sarmad, et al. European Polymer Journal 117 (2019) 280–303

Fig. 14. (a) Stress relaxation curves of the pristine PU and its nanocomposites at 25 °C and (b) DMA curves of the pristine PU and its nanocomposites. With permission
from Ref. [134].

Fig. 15. (a) Rheological Storage modulus properties, (b) tensile properties, and Dynamic mechanical thermal analysis (c) storage modulus and (d) loss factor (Tanδ)
of pure TPU and TPU/CNT composites. With permission from Ref. [137].

composite that of other samples.
3.2. Influence of carbon nanotube on shape memory properties
Due to the low recovery stress in polymers, there is always a pe-
culiar assiduity from researches on this field of study. For this purpose,
the nanocomposites consist of ester-based amorphous PU and 1 wt%
oxidized carbon nanotubes (Ox-CNT) or neat CNT were fabricated
through the melt mixing process, by Gu [134] et al. The stress-relaxa-
tion test performed in a constant strain of 50% at a temperature above
the trigger temperature (25 °C) and it can be observed that the amount
of recovery force, and thereupon the shape recovery of composite
containing Ox-CNT was more suitable than neat PU and CNT/PU
composites due to the more stored stress and rapid relaxation
(Fig. 14(a)). A Dynamic mechanical thermal analyzer (DMTA) is a
beneficial instrument for measuring the composite viscoelastic response
and chains mobility in the solid state. The DMTA results (Fig. 14(b))
show the slight increase in storage modulus (E′) for nanocomposites at
low temperature (below Tg). In other words, the incorporation of the
CNTs may enhance the E′ of nanocomposites in the glassy state because
of filler stiffness effect, and also better dispersion of the ox-CNTs has
inevitably contributed to more stiffness effect at low temperature. On
the other hand, E′ values (above Tg) can interestingly capable, illus-
trating that the rubbery modulus of the nanocomposites is lower than

294
M. Panahi-Sarmad, et al.
the pristine PU. The rubbery modulus of the neat PU is 10 times more
than modulus of the CNT/PU and ox-CNT/PU nanocomposites at room
temperature, which is in the classification of the characteristic value of
the SMPs rubbery modulus (< 10–15 MPa). The decrease of rubbery
modulus can be attributed to the disorder of hard segments (diisocya-
nate segments) owing to the addition of the CNTs; and also, better
dispersion of the ox-CNTs will cause more reduction of the rubbery
modulus. On the contrary, the dissipation factor (Tanδ) has been in-
creased at the transition region when the filler dispersion improves. It
has clarified that the interfacial zone between filler and polymer have a
vital role in viscoelastic behavior and other application [135,136],
especially shape memory actuator. Consequently, these nanocomposites
demonstrate an appropriate shape recovery value, approximately 98%.
Noteworthy, these nanocomposites illustrated the shape fixity ratio
about 98% due to the entity of hard domains, hydrogen bonding be-
tween ester groups of polyols and OH/COOH groups of CNTs.
Chen [137] et al. prepared a nanocomposite based on thermoplastic
polyurethane (TPU) containing carbon nanotube (CNT) introduced in
0.5, 1, 2, and 5 wt% through melt mixing processing method. The
rheological evaluation clarified that the rheological percolation
threshold in created at CNT content above 2 wt%. on the other hand,
the electrical assessment of CNT/PU composites exposed that the
electrical percolation of CNTs formed in 0.39 wt% filler content. They
measured the network structure of CNT through rheological measure-
ment and morphological characteristics (Fig. 15(a)). Rheological tests
showed a plateau modulus in weight fractions upper than 2 wt% na-
nocomposite, which illustrated the percolation threshold. Transporta-
tion from liquid-like to solid-like in lower frequencies demonstrated
that the mobility of polymer chains reduced due to the formation of the
CNT network even upper Tg. As shown in Fig. 15(b), tensile properties
measurement shows that the percolated CNT network structure exhibits
apparent reinforcement effect for TPU matrix and the composites still
exhibit excellent rubbery elasticity at CNT content of 2 and 5 wt%.
According to Fig. 15(c), the storage modulus under Tg has mono-
tonically increased via enhancing filler content. It can be demonstrated
that TPU composite containing 5 wt% CNT has a weak shape recovery
compared to 2 wt% CNT/TPU composite because of the immobilization
effect of filler networks in 5 wt% nanocomposite. In one hand, heat
induces properties have increased by 5 wt% of CNT. On the other
hands, the shape recovery of 5 wt% composite decreases owing to the
mobility of matrix chains compared to neat TPU. Fig. 15(d) illustrated
that the amount of Tg remained constant and also the integral area
below the tanδ peaks was reduced with increasing CNT content. In fact,
energy dissipation decreased as the amount of CNT contents increased
due to the formation of the CNT network that intercepted TPU mole-
cular chains from showing viscous behaviors. This energy dissipation
reduction caused the more amount of energy stored in polymer and
thereupon shape recovery increased. Finally, thermal and electrical
actuation has been conducted which is used for triggering these nano-
composites. At first, using thermal actuation demonstrated that in-
creasing the amount of CNT caused the reduction in shape recovery
ratio comparing to pristine TPU due to the formation network structure
of CNT. This network restricted the motions of polymer chains, but the
final amount of shape recovery in all samples was approximately equal.
It means that the shape recovery behavior of polymers depends on
unlocked oriented chains and modulus in room temperature. Then,
exerting electrical actuation showed that in 5 wt% nanocomposite, the
amount of shape recovery increased comparing to pristine TPU. Actu-
ally, electrical actuation caused a larger quantity of heat in system
comparing thermal actuation due to forming conductive CNT network.
Consequently, using electrical actuation reveals that higher shape re-
covery ratio and shape recovery rate compared to pristine polyurethane
at 5 wt% of CNT.
Cho et al. [138] synthesized an electroactive shape memory com-
posite based on conducting polyurethane (PU) and multi-walled carbon
nanotubes (MWCNTs). The pristine MWCNTs were treated by acid in
295
European Polymer Journal 117 (2019) 280–303
two different temperatures (90 and 140 °C). The mechanical assessment
demonstrates that modulus and stress (at 100% elongation) have been
increased with the incorporation of modified MWCNT content. The
mechanical properties of composites containing modified MWCNTs at
140 °C were weaker than the composites filled by treated MWCNTs at
90 °C. An improvement in mechanical properties was accomplished
with filler modification, because of surpassing interfacial bonding
strength between the nanoparticles and the polymer matrix. Typically,
the electrical conductivity of MWCNTs has been dropped when con-
ducting surface modification. This phenomenon occurred because acid
treatment increases defects in the carbonic nanotube lattice structure.
Nevertheless, the composites having lower conductivity but the elec-
trical conductivity of composites containing 5 wt% modified-MWCNT
was attained to 10−3 S/cm. The composite triggered electrically under
40 V and also recovered from its temporary shape to its original shape
in 10 s. Therefore, it can be concluded that the rate of shape recovery is
strongly depended on the magnitude of the applied voltage surface,
modification and the content of MWCNT.
Xu [139] et al. fabricated a self-healing shape memory blend based
on PU/ Polycaprolactone (PCL) with different mixture content (%PU:
25, 50, 67, and 75 wt%). Due to the higher melting temperature (Tm) of
PU than PCL, so PCL and PU play roles as a switching segment and a net
point, respectively. As a result, by increasing the temperature above
−60 °C, the shape memory effect can be observed when the crystalline
phase of PCL has been broken down above −60 °C. As resulted, with
increasing the amount of TPU content, the shape recovery ratio has
improved due to the elastomeric nature of TPU and the shape fixity
ratio have augmented when increasing the PCL content due to the
crystallized nature of PCL. By incorporating MWCNTs in PU/PCL blend,
the local temperatures (at the interface) in blend composites have been
increased using near IR irradiation (NIR); thus, this system has accu-
rately employed as a remote-control and self-healing material.
Moghim et al. [140] prepared a nanocomposite based on poly-
urethane incorporating CNTs through a solution casting method. Flex-
ural tests (Fig. 16(a)) showed an improvement of about 130% for
strength in PU-1% CNT sample compared to pure polyurethane. In fact,
an increment in the amount of flexural strength demonstrated a good
stress transition between CNT and TPU because of interaction between
COOH groups of CNT and CONH groups of TPU. At higher contents of
CNT, SEM micrographs (Fig. 16(b)) showed the presence of agglomer-
ates which leads to a decrease in flexural strength after the maximum
value. Incorporation of carbon nanotubes enhanced thermal degrada-
tion of samples and shifted the diagrams to the higher temperatures.
This behavior is because of the thermal stability of CNTs and good in-
terfacial interactions between the matrix and nanoparticles. By in-
vestigation of dynamic mechanical tests, it can be observed that storage
modulus improved because of the reinforcing effect of CNTs on poly-
urethane. An increment in Tg was also observed in Fig. 16(c) and this
mainly attributed to the excellent thermal properties of CNTs and the
effect of these nanoparticles on the mobility of polyurethane chains.
Shape memory behavior showed about 100% improvement in recovery
stress (Fig. 16(d)). It demonstrated that CNTs have significantly positive
effects on shape memory behavior, especially PU-1 wt% CNT in shape
recovery stress.
3.3. Influence of graphene nanoparticles on shape memory properties
Abbasi et al. [141] prepared polyurethane based on crystalline PCL
by incorporation of graphene nanoplatelets (0.5, 1, 1.5 wt%), which
demonstrating shape fixity ratio at about 91–96% and shape recovery
ratio at about 95–99%. In this study, the effect of graphene nanopla-
telets (GNP) on the melting and crystallization behavior of samples has
been investigated prior to shape memory studies of the mentioned na-
nocomposites. The ester groups of PCL diol in soft segments were able
to gather and to increase the amount of crystallization. X-ray diffraction
(XRD) analysis clarified that with increasing GNP content, the PCL peak
M. Panahi-Sarmad, et al.
Fig. 16. (a) Effect of CNTs on flexural strength of polyurethane, (b) SEM micrographs taken from the fracture surfaces, (c) dissipation factor (Tanδ) and (d) recovery
stress of PU and PU‐%CNTs. With permission from Ref. [140].
remained at the same position through its intensity has been enhanced.
This peak intensity relates to the amount of crystalline state which
means that the crystalline state in nanocomposite increased as GNP
content enhance. This phenomenon indicated that GNP acted as a
crystallization nucleation agent in the soft segment as well as it caused
a phase separation. Howbeit the castor oil used in these samples to
increase the amount of crystallinity but these samples were not fully
crystallized. Thus, the un-crystallized polymer chains generate a rapid
retractive force that results in a fast strain recovery. Unfortunately, this
rapid recovery has a contradictory effect on the shape fixity value.
Choi et al. [142] prepared a PU/graphene nanocomposite through
in-situ polymerization. Graphene nanoparticles were functionalized
with hydroxyl groups through oxidation with H2O2. These oxygen
groups can graft to polyurethane chains during the situ polymerization.
However, the electrical conductivity of nanocomposites was reduced
with filler oxidation process, but the mechanical properties of compo-
sites have improved due to increase adhesion between graphene oxide
(GO) and PU. Morphology evaluation shows that polyurethane covers
most of the pulled-out graphene sheets; it indicated the excellent ad-
hesion between the nanoparticles and the polymeric matrix. Tensile
results (in cyclic mode) elucidated that 1 phr (low content) of GO-
graphed PU have a decisive role in improving shape memory behaviors,
especially fixing the structure. As expected, the recoverable stress was
reduced at high filler content. Nevertheless, the intermediate
296
European Polymer Journal 117 (2019) 280–303
conductivity value (about 10−2 S/cm) was observed for the 2 phr na-
nocomposites, shape recovery for large deformation, about 20%, needs
resistive heating by the implementation of a high voltage, about 100 V.
Rana et al. [143] designed a nanocomposite containing graphene-
crosslinked and CNT-crosslinked polyurethane based on PCL soft seg-
ments by solution casting. In most cases, reduction in elongation at
break of the composites is observed incorporating conductive nano-
fillers into PU. On the contrary, incorporation of functionalized gra-
phene into PU increased the tensile strength and modulus without
significant reduction in the elongation at break due to the both covalent
and non-covalent (π-π interaction) bonding between the PU chains and
the graphene. Its noticed that the crystallinity significantly decreased
via incorporation of filler (graphene or CNT) due to crosslinking effect.
Thermal and electrical conductivities of graphene-based composites
were higher than CNT-based composites; this could be related to mo-
lecular level interaction of polyurethane chains with graphene sheets.
The electroactive shape recovery ratio of graphene-crosslinked was
compared to CNT-crosslinked composites by measuring the time de-
pendence of their surface temperature during constant voltage applied
to the samples. Graphene-based samples reached to a temperature
above Tg (around 45 °C) in 6–7 s under 60 V electric field, but CNT-
based samples need 10–12 s to reach the transition temperature. This
observation elucidated that the electroactive shape recovery rate and
thermal conductivity of graphene-crosslinked composites are
 M. Panahi-Sarmad, et al.

Table 2
Effect of carbon-based filler on the shape memory properties of polymer composites.
Matrix Nanoparticle Content Treatment Stimulus Field Rf Rr Ref.

Cross-linked Polyethylene Carbon Black 0.5 vol% – Thermal 95.6% ± 2.4 92.7% ± 0.2 [123]
polyurethane resin polymer based on cyclic and Carbon Black 25 wt% – Electrical 94% for thermal 98% for thermal [132]
aliphatic polyisocyanates Thermal 98% for electrical 99% for electrical
Hydro-epoxy resin Carbon Black 2.0 wt% – Laser trigged Above 97% N/A [133]
(Thermal)
ester-based amorphous PU Carbon Nanotube 1.0 wt% Oxidized Thermal Above 98% Above 98% [134]
TPU Carbon Nanotube 5.0 wt% – Electrical 87.8% N/A [137]
Polyurethane Carbon Nanotube 5.0 wt% Acid treatment Electrical N/A N/A [138]
Polyurethane/PCL Carbon Nanotube 3.0 wt% – Thermal (NIR 96.8% 63.9% [139]
radiation)
Polyurethane Carbon Nanotube 1.0 wt% Functionalized with COOH Thermal 99% 81–90% [140]
PLA(70)/TPU(30) CB/CNT Hybrid 1 phr Carbon – Electrical 85% Above 88% [147]
Nanotube
3 phr Carbon
Black
Waterborne Carbon Nanotube 1 wt% – Thermal 99.81% 99.26% [148]

297
Epoxy
TPU/ABS Blend Carbon Nanotube 2 wt% – Thermal 98% 98% [149]
Epoxy Resin Carbon Nanotube 0.25 wt% – Thermal‘ 98.1% 92.1% [150]
Polyurethane Graphene nanoplatelets 1.5 wt% Functional groups, such as ethers, carboxyl, Thermal 96.6% ± 1.4 99.8% ± 1.2 [141]
hydroxyls (Totally containing 8 wt% of oxygen)
Polyurethane Graphene 1.0 phr functionalized with hydroxyl groups through Electrical 98.6% 98.4% [151]
oxidation with H2O2
Polyurethane Graphene nanoplatelets 4 wt% Functionalized Electrical 97% 95% [143]
Hyperbranched Aliphatic hydroxyl group 2.0 wt% Grafting aliphatic carboxyl groups on GO surface Thermal 93% 98% [144]
Polyurethane functionalized graphene sheets
Polyurethane Graphene Nanosheet 2.0 wt% – Electrical 95% 93% [145]
Castor Oil based-Hyperbranched Polyurethane Graphene Oxide 2.0 wt% Functionalized with H2SO4 and KMnO4 Thermal 99.5% ± 0.2 90.1% ± 1.8 [146]
Waterborne Epoxy Graphene Oxide 6.0 wt% Modified Hummer's Method Thermal 99.1% 92.4% [152]
Ionic Polyurethane Graphene Oxide 25.0 wt% the modified Hummers' method Electrical 82% 99% [128]
Epoxy Resin Graphene Oxide 0.5 wt% Modified Hummer’s Method Electrical 98% ± 3 95% ± 3 [153]
Liquid Crystalline Polyurethane Graphene Oxide 20 wt% Hummer’s Method Thermal 100% 92% [154]
Thermoplastic Polyurethane Graphene Nanoplatelets 2 phr – Microwave 100% N/A [155]
Irradiation
Polylactic Acid (PLA) Graphene Nanoplatelets 3 wt% Surface Modified 91% 94% [156]
Thermoplastic Polyurethane Graphene Oxide 3 wt% Modified with H2SO4, H3PO4 and KMnO4 Thermal 99.2% 69.7% [157]
European Polymer Journal 117 (2019) 280–303
M. Panahi-Sarmad, et al.
Fig. 17. (a) Thermal response speeds of waterborne epoxy, (b) relationship of
storage modulus, thermal conductivity and thermal response speeds of the GO/
CNT/WEP composites. With permission from Ref. [166].
considerably faster than that of CNT- crosslinked composites.
Mahapatra et al. [144] fabricated a hyperbranched polyurethane in
the presence of different content (0.5, 1, and 2 wt%) of functionalized
graphene through in-situ polymerization. Note that the solubility of
hyperbranched polymers is more than linear polymers; thus these
polymers have proper processability that of the linear polymer. In ad-
dition, the surface of graphene platelets is decorated via aliphatic car-
boxyl groups because the polymer chains have many terminal groups
which can easily create hydrogen-bonding with graphene. The crys-
talline state shows ascending trend in the presence of graphene sheets
owing to the fillers have fine dispersion in soft segment of PU. The
graphene sheets are actually acting as a nucleating agent, so the trigger
temperature will be controlled with changing the PU crystalline state.
In this work, the thermo-mechanical properties of the composites are
studied; All the PU/graphene composite illustrated more than 95%
shape recovery and shape fixity. This can be attributed to good dis-
persion and higher filler-polymer compatibility, which helps to obtain
further recovery due to the release of stored elastic strain energy. A lot
of stored elastic strain energy is produced owing to the high surface
area of filler, which in turn admitted the nanocomposites to gain more
recovery stress. With enhancing the graphene content in PU composites,
the composite shape recovery has improved; for instance, 98% shape
recovery and 93% shape fixity is detected in PU composite comprising
2 wt% graphene.
Jiu et al. [145] fabricated a two-way reversible shape memory
polyurethane nanocomposite by in situ synthesized method containing
graphene nanosheet contents varying from 1.0 to 8.0 wt%. The gra-
phene crosslinked polyurethane (PU) composites demonstrated better
thermostability comparing to pure polyurethane. Indeed, the in-
corporation of graphene nanosheet (GNS) increased the amount of
crystallization temperature (Tc) of soft segments significantly owing to
the fine dispersion of GNS in the polymer matrix and its role as a nu-
cleation agent. According to shape memory results, the shape fixity was
about 93%, and shape recovery reached 95% by incorporating 2 wt%
GNS. Increasing the GNS content resulted in the increment the
298
European Polymer Journal 117 (2019) 280–303
conductivity of PU composites. As expected, the maximum conductivity
was observed in 8 wt% composite. Noteworthy, the shape fixity ratio
and shape recovery ratio were not well enough in PU composite con-
taining 8 wt%. The PU matrix consists of the soft and hard segment and
its hard segments was not separated in the pure PU (when absenting
filler). So only physical chain entanglements had the role of memor-
izing the original shape and therefore the fixed structure cannot strong
enough for demonstrating shape memory effect. Consequently, the GNS
incorporation to PU significantly improved the shape fixity ratio and
recovery ratio that of pure PU. The optimized shape memory behavior
(shape fixity = 93% and shape recovery = 95%) corresponded to 2 wt
% composite. The recoverable strain has reduced in 8 wt% composite
due to poor dispersion and formation of agglomerates of GNS in the PU
matrix.
The thermo-mechanical properties of hyperbranched polyurethane
(HPU)/graphene oxide (GO) composite (composed of 0.5, 1, and 2 wt
%) is studied by Thakur et al. [146]. Noteworthy, the direct linkage of
the HPU chain with the oxygen group on the surface of GO may en-
hance the filler-polymer compatibility. According to the strain-stress
curve, augmentation in the fracture strength, tensile modulus, elonga-
tion at break and toughness are obtained by increasing GO content.
Hence, the mechanical properties have been improved because of pre-
senting strength interfacial interaction between polymer and filler (due
to the unique branched architecture of HPU), as well as the uniform
dispersion of GO in the matrix. The surrounding polymer chains of GO
platelets can slip or partially immobilized on the surface of GO, but here
the dominant mechanism is the immobilized HPU chains on GO surface
owing to the unique interaction between GO-HPU, so elongation at
break, Tm and Tg of composites is higher than that of pristine HPU.
Besides, the GO platelets can play as a nucleating agent role; thus the
crystallinity of system enhances with increasing the GO content. Like-
wise, the thermal stability of HPU-GO composites has improved that of
pure HPU as another consequence of the immobilized polymeric chains.
Where the HPU chains have high elastic entropy as well as close to
melting temperature (switching temperature: 50 °C), the specimens are
programmable. Owing to existing the interaction between GO and HPU,
the strong net points are begotten which make them able to gain stored
elastic strain energy. In another hand, the high stored elastic strain
energy can aid in having a suitable shape recovery up to 99% and also
the enhancement in the crystalline state (in the presence of filler) may
generate unlocked chains. Alternatively, the elastic energy causes the
shape fixity of pure HPU (93%) more than that of HPU-2%GO (90%).
The literature results obtained from SMPCs containing the carbon-
based particles are summarized in Table 2. The shape fixity and re-
covery, filler content, filler shape, and stimulus field of composites is
determined and compared in the table.
4. Shape memory composites containing hybrid filler
According to reviewed researches, each one of carbon- and silica-
based materials have some disadvantage that it can be jeopardizing the
shape memory performance of polymeric composites. Hence, various
functionalization methods including covalent, noncovalent modifica-
tions and branched polymer structures on the surface on filler were
employed to improve the properties of polymer composites [158,159].
The use of hybrid filler structures as an alternative method for enhan-
cing dispersion of particles with no surface modification. It is worth
mentioning that hybrid filler in meaning when using two filler in one
composite, simultaneously. These hybrid particles can also significantly
affect the mechanical and electrical properties of the polymer compo-
sites. The hybrid fillers are divided into three groups; including (1)
different shape and constant matter, (2) constant shape and different
matter, and (3) different shape and matter. Examples of such polymer
composites include polypropylene/RGO/MWNTs [160], polyaniline/
graphene nanosheet/CNTs [161], poly(vinyl alcohol)/MWNT/GO
[162], and polypropylene/CNT/MMT [163], polypropylene/MWCNT/
M. Panahi-Sarmad, et al.
Fig. 18. (a) Frequency dependence of storage modulus, (b) loss factor (tanδ), (c) shape memory mechanism, and (d) shape fixity and recovery ratio of PLA/PU/CB/
CNT blend composites. With permission from Ref. [147].
CB [164], epoxy/clay/CNT [165].
Wang et al. [166] prepared a waterborne epoxy (WEP) in-
corporating carbon nanotube and graphene oxide (GO). SMPs have
lower mechanical strengths and thermal conductivities comparing to
SMPCs, which have significantly restricted their broad applications.
Albeit, mixing a low content of reinforcing fillers can significantly im-
prove the mechanical strengths and thermal conductivity as well as the
thermal response speed as another important shape memory properties.
The thermal response speed is the time between storing the stress due to
reducing the temperature and releasing the stress due to the increment
in the amount of stress in a constant strain. As shown in Fig. 17(a). As
illustrated in Fig. 17(b), thermal response speed decreased after 2 wt%
299
European Polymer Journal 117 (2019) 280–303
CNT/GO content. Indeed, Incorporating hybrid carbon nanoparticles
lead to observe the synergic effect in thermomechanical properties that
of GO/WEP and CNT/WEP composites. The mechanical strength of the
hybrid composites augmented 13% and 28% compared to the CNT/
WEP composites and GO/WEP composites, respectively, when em-
ploying same filler content (1 wt%). The observation resulted from the
homogenous dispersion of hybrid GO/CNT filler in WEP matrix that of
single GO and CNT. In other words, graphene oxide overcomes the
substantial van der waals forces and the addition of GO had a synergic
effect with CNT and reduced the agglomeration in the system. Besides,
the filler polymer interaction has improved and 3D network provided
when incorporating CNT and GO simultaneously. According to
M. Panahi-Sarmad, et al.
Fig. 17(b), the storage modulus of GO/CNT/WEP composites increases
until 4 wt% and after that shows dropped behavior (at 6 wt%). The
decrement in storage modulus straightly relates to composite micro-
structure because of existing numerous agglomerates in the highly filled
composite (due to filler-filler interaction). On the contrary, the thermal
conductivity of hybrid composites was continuously enhanced via in-
creasing filler content. As declared, the thermal response speed shows
optimum value at 2 wt% CNT/GO, which it is clarified that the shape
memory and mechanical properties strongly depend on the micro-
structure of composites.
In another work, the Polylactide (PLA)/Poly(ether)urethane (TPU)/
CB/CNT blend composites were fabricated by Wei et al. [152]. It is
worth noting that the fraction of blend was constant (70 PLA/30 TPU)
and just filler content has changed. The hybrid filler and CB particle
were localized at TPU phase owing to nearing thermodynamic affinity
and it helps to observe a more continuous TPU phase in blend mor-
phology. According to rheology assessment of hybrid composite in
Fig. 18(a), the filler network is formed at 3 Phr CB; thus storage mod-
ulus of PLA70/TPU30/CB3 blend composites becomes independent of
the shear-frequency, particularly in low frequency. Notable, demon-
strating a plateau in low-frequency region elucidated a transition from a
liquid-like to a solid-like viscoelastic performance and also indicated 3
phr CB have formed a percolated filler network. With increasing CNT
content in percolated composite, the storage modulus gradually en-
hances at all frequency range. The dynamic mechanical analysis proved
that two immiscible phases existed in all samples owing to presenting
one peak at −35 °C for TPU and another one at 65 °C for PLA, as shown
in Fig. 18(b). The filler compatibilization impact between TPU and PLA
leads to dropping the Tanδ intensity peak at the transition region. The
schematic of the shape memory mechanism for TPU/PLA/CB and hy-
brid TPU/PLA/CB/CNT is presented in Fig. 18(c). Interestingly, the
hybrid filler can tune the morphology of TPU/PLA blend from the ty-
pical sea-island structure to a unique co-continuous phase. In the basis
of microstructure, the shape recovery (Rr) ratio of PLA/TPU blend was
lower than the other blend composites (see Fig. 18(d)). The continuous
TPU phase stronger generated strong resilience and caused absorbing
more energy during deformation, thus the blended composite con-
taining 3 Phr CB displays higher Rr than neat blend. Indeed, the in-
corporating hybrid filler can result in stronger filler network, which
leads to further enhance in Rr. In the other hand, the filler structure has
no significant influence on Shape fixity ratio.
5. Conclusion
The natural behavior of polymers displays good potential for the
development of smart materials, especially shape memory materials.
Although the neat polymers have shortcomings such as low mechanical
properties and slow actuation rate but the solution to the problems is
not so complicated, which one of the most effective strategies is the use
of composites. The composites containing silica-based filler provide
large tunable switching segment while upper the percolation threshold
of filler. Strictly to say, the carbonic-based filler is a highly conjugated
conductive material and especially very appropriate as a filler for shape
memory polymer composites (SMPCs). The inconvenient dispersion/
distribution of silica- and carbon-based filler in polymer and poor filler-
polymer interfacial interaction between in the absence of modification
or tuning surface chemistry of fillers were caused to discovery several
tricks for solving these problems, resembling hybrid fillers. These tricks
must be having unique features for using in SMPCs application, such as
control the reduction of composite shape recovery rate, optimize the
dispersion, the electrical and thermal conductivity of filler, maintain
the elastic modulus and crystalline state of the composite at acceptable
value and maximize the shape recovery and fixity ratio of the compo-
site. Notwithstanding occurred developments adequately in SMPCs in
recent years ago but some issues still need to be addressed; being their
major disadvantage the controlled microstructure required to obtain a
300
European Polymer Journal 117 (2019) 280–303
proper shape memory behavior. This review has comprehensively
presented the progress on the different traced routes to reach the high
performance of the SMPCs containing silica- and carbon-based filler as
well as hybrid fillers to solve this central issue. Further progresses on
the composite microstructure will absolutely result in the widespread
application of in everyday SMPCs applications.
Acknowledgement
The authors wish to thank Mr. Ahad Rabani-Doost and Mr. Shahrad
Panahi-Sarmad for their helpful cooperation.
References
[1] J. Hu, Y. Zhu, H. Huang, J. Lu, Progress in polymer science recent advances in
shape – memory polymers: structure, mechanism, functionality, modeling and
applications, Prog. Polym. Sci. 37 (2012) 1720–1763, https://doi.org/10.1016/j.
progpolymsci.2012.06.001.
[2] C. Liu, H. Qin, P.T. Mather, Review of progress in shape-memory polymers, J.
Mater. Chem. (2007) 1543–1558, https://doi.org/10.1039/b615954k.
[3] F. Pilate, A. Toncheva, P. Dubois, J.M. Raquez, Shape-memory polymers for
multiple applications in the materials world, Eur. Polym. J. 80 (2016) 268–294,
https://doi.org/10.1016/j.eurpolymj.2016.05.004.
[4] M.D. Hager, S. Bode, C. Weber, U.S. Schubert, Shape memory polymers: past,
present and future developments, Prog. Polym. Sci. 49–50 (2015) 3–33, https://
doi.org/10.1016/j.progpolymsci.2015.04.002.
[5] Q. Zhao, H.J. Qi, T. Xie, Recent progress in shape memory polymer: new behavior,
enabling materials, and mechanistic understanding, Prog. Polym. Sci. (2015),
https://doi.org/10.1016/j.progpolymsci.2015.04.001.
[6] W. Li, Y. Liu, J. Leng, Light-actuated reversible shape memory effect of a polymer
composite, Compos. Part A Appl. Sci. Manuf. 110 (2018) 70–75, https://doi.org/
10.1016/j.compositesa.2018.04.019.
[7] A. Lendlein, S. Kelch, Shape-Memory Effect From shape ... ... to permanent shape,
n.d.
[8] T. Liu, T. Zhou, Y. Yao, F. Zhang, L. Liu, Y. Liu, J. Leng, Stimulus methods of multi-
functional shape memory polymer nanocomposites: a review, Compos. Part A
Appl. Sci. Manuf. 100 (2017) 20–30, https://doi.org/10.1016/j.compositesa.
2017.04.022.
[9] J. Leng, X. Lan, Y. Liu, S. Du, Shape-memory polymers and their composites: sti-
mulus methods and applications, Prog. Mater. Sci. 56 (2011) 1077–1135, https://
doi.org/10.1016/j.pmatsci.2011.03.001.
[10] X. Zhang, H. Tan, Z. Li, Biodegradable polyester shape memory polymers: Recent
advances in design, material properties and applications, Mater. Sci. Eng. C.
(2017), https://doi.org/10.1016/j.msec.2017.11.008.
[11] K. Wang, S. Strandman, X.X. Zhu, A mini review: shape memory polymers for
biomedical applications, Front. Chem. Sci. Eng. 1 (2017) 1–11, https://doi.org/10.
1007/s11705-017-1632-4.
[12] H. Meng, J. Hu, A brief review of stimulus-active polymers responsive to thermal,
light, magnetic, electric, and water/solvent stimuli, J. Intell. Mater. Syst. Struct.
21 (2010) 859–885, https://doi.org/10.1177/1045389X10369718.
[13] L. Sun, W.M. Huang, Z. Ding, Y. Zhao, C.C. Wang, H. Purnawali, C. Tang, Stimulus-
responsive shape memory materials: a review, Mater. Des. 33 (2012) 577–640,
https://doi.org/10.1016/j.matdes.2011.04.065.
[14] T. Mu, L. Liu, X. Lan, Y. Liu, J. Leng, Shape memory polymers for composites,
Compos. Sci. Technol. 160 (2018) 169–198, https://doi.org/10.1016/j.
compscitech.2018.03.018.
[15] E. Hornbogen, Comparison of shape memory metals and polymers, Adv. Eng.
Mater. 8 (2006) 101–106, https://doi.org/10.1002/adem.200500193.
[16] L. Santo, Progress in aerospace sciences shape memory polymer foams, Prog.
Aerosp. Sci. (2016) 1–6, https://doi.org/10.1016/j.paerosci.2015.12.003.
[17] W. Zhao, L. Liu, F. Zhang, J. Leng, Y. Liu, PT NU SC, Mater. Sci. Eng. C, 2018
#pagerange#. https://doi.org/10.1016/j.msec.2018.12.054.
[18] B.Q.Y. Chan, Z.W.K. Low, S.J.W. Heng, S.Y. Chan, C. Owh, X.J. Loh, Recent ad-
vances in shape memory soft materials for biomedical applications, ACS Appl.
Mater. Interfaces 8 (2016) 10070–10087, https://doi.org/10.1021/acsami.
6b01295.
[19] A. Lendlein, R. Langer, Biodegradable, elastic shape-memory polymers for po-
tential biomedical applications, Science (80-.) (2002), https://doi.org/10.1126/
science.1066102.
[20] X. Kuang, K. Chen, C.K. Dunn, J. Wu, V.C.F. Li, H.J. Qi, 3D printing of highly
stretchable, shape-memory, and self-healing elastomer toward novel 4D printing,
ACS Appl. Mater. Interfaces 10 (2018) 7381–7388, https://doi.org/10.1021/
acsami.7b18265.
[21] V.K. Thakur, M.R. Kessler, Self-healing polymer nanocomposite materials: a re-
view, Polymer (Guildf) 69 (2015) 369–383, https://doi.org/10.1016/j.polymer.
2015.04.086.
[22] M. Mahinroosta, Z. Jomeh, A. Allahverdi, Z. Shakoori, Hydrogels as intelligent
materials: a brief review of synthesis, properties and applications, Mater. Today
Chem. 8 (2018) 42–55, https://doi.org/10.1016/j.mtchem.2018.02.004.
[23] J. Hu, S. Chen, A review of actively moving polymers in textile applications, J.
Mater. Chem. 20 (2010) 3346–3355, https://doi.org/10.1039/b922872a.
M. Panahi-Sarmad, et al.
[24] J. Wang, J. Li, N. Li, X. Guo, L. He, X. Cao, W. Zhang, R. He, Z. Qian, Y. Cao,
Y. Chen, A bottom-up approach to dual shape-memory effects, Chem. Mater. 27
(2015) 2439–2448, https://doi.org/10.1021/cm504527w.
[25] B. Gyarmati, B.Á. Szilágyi, A. Szilágyi, Reversible interactions in self-healing and
shape memory hydrogels, Eur. Polym. J. 93 (2017) 642–669, https://doi.org/10.
1016/j.eurpolymj.2017.05.020.
[26] K. Hearon, P. Singhal, J. Horn, W. Small, C. Olsovsky, K.C. Maitland, T.S. Wilson,
D.J. Maitland, Porous shape-memory polymers, Polym. Rev. 53 (2013) 41–75,
https://doi.org/10.1080/15583724.2012.751399.
[27] Z. Fang, N. Zheng, Q. Zhao, T. Xie, Healable, reconfigurable, reprocessable ther-
moset shape memory polymer with highly tunable topological rearrangement ki-
netics, ACS Appl. Mater. Interfaces 9 (2017) 22077–22082, https://doi.org/10.
1021/acsami.7b05713.
[28] Y. Gao, W. Liu, S. Zhu, Polyolefin thermoplastics for multiple shape and reversible
shape memory, ACS Appl. Mater. Interfaces 9 (2017) 4882–4889, https://doi.org/
10.1021/acsami.6b14728.
[29] F. Xie, L. Huang, J. Leng, Y. Liu, Thermoset shape memory polymers and their
composites, J. Intelligent Mater. Syst. Struct. (2016), https://doi.org/10.1177/
1045389X16634211.
[30] W. Wang, Y. Liu, J. Leng, Recent developments in shape memory polymer nano-
composites: actuation methods and mechanisms, Coord. Chem. Rev. 320–321
(2016) 38–52, https://doi.org/10.1016/j.ccr.2016.03.007.
[31] Y. Liu, K. Gall, M.L. Dunn, P. Mccluskey, Thermomechanics of shape memory
polymer nanocomposites, Mech. Mater. 36 (2004) 929–940, https://doi.org/10.
1016/j.mechmat.2003.08.012.
[32] T. Xie, Recent advances in polymer shape memory, Polymer (Guildf). 52 (2011)
4985–5000, https://doi.org/10.1016/j.polymer.2011.08.003.
[33] A. Anis, S. Faiz, M. Luqman, A.M. Poulose, S.K.H. Gulrez, H. Shaikh, S.M. Al-
Zahrani, Developments in shape memory polymeric materials, Polym. - Plast.
Technol. Eng. 52 (2013) 1574–1589, https://doi.org/10.1080/03602559.2013.
824466.
[34] J. Karger-Kocsis, S. Kéki, Review of progress in shape memory epoxies and their
composites, Polymers (Basel) 10 (2017) 34, https://doi.org/10.3390/
polym10010034.
[35] Z. Jiang, Y. Xiao, Y. Kang, M. Pan, B. Li, S. Zhang, J. Accepted, Shape memory
polymers based on supramolecular interactions, 2017.
[36] Y. Zhou, W.M. Huang, Shape memory effect in polymeric materials: mechanisms
and optimization, Procedia IUTAM 12 (2015) 83–92, https://doi.org/10.1016/j.
piutam.2014.12.010.
[37] S. Chatani, C. Wang, M. Podgórski, C.N. Bowman, Triple shape memory materials
incorporating two distinct polymer networks formed by selective thiol-Michael
addition reactions, Macromolecules (2014), https://doi.org/10.1021/ma501028a.
[38] Y. Bai, Y. Chen, Q. Wang, T. Wang, Poly(vinyl butyral) based polymer networks
with dual-responsive shape memory and self-healing properties, J. Mater. Chem. A
(2014), https://doi.org/10.1039/c4ta00856a.
[39] Y.-N.N. Chen, L. Peng, T. Liu, Y. Wang, S. Shi, H. Wang, Poly(vinyl alcohol)–tannic
acid hydrogels with excellent mechanical properties and shape memory behaviors,
ACS Appl. Mater. Interfaces (2016), https://doi.org/10.1021/acsami.6b08374.
[40] M.Q. Li, F. Song, L. Chen, X.L. Wang, Y.Z. Wang, Flexible material based on poly
(lactic acid) and liquid crystal with multishape memory effects, ACS Sustain.
Chem. Eng. (2016), https://doi.org/10.1021/acssuschemeng.6b00582.
[41] M. Sabzi, M. Babaahmadi, M. Rahnama, Thermally and electrically triggered
triple-shape memory behavior of poly(vinyl acetate)/poly(lactic acid) due to
graphene-induced phase separation, ACS Appl. Mater. Interfaces (2017), https://
doi.org/10.1021/acsami.7b02259.
[42] H. Meng, G. Li, A review of stimuli-responsive shape memory polymer composites,
Polymer (Guildf). 54 (2013) 2199–2221, https://doi.org/10.1016/j.polymer.
2013.02.023.
[43] Y. Liu, H. Du, L. Liu, J. Leng, Shape memory polymers and their composites in
aerospace applications: a review, Smart Mater. Struct. 23 (2014), https://doi.org/
10.1088/0964-1726/23/2/023001.
[44] T. Mu, L. Liu, P. Smp, 6,16 Shape Memory Polymer and Its Composite : Function
and Application, Elsevier Ltd., 2018 https://doi.org/10.1016/B978-0-12-803581-
8.10027-X.
[45] S.A. Madbouly, A. Lendlein, Shape-Memory Polymer Composites, 2010, pp.
41–95. https://doi./org/10.1007/12.
[46] H. Luo, Z. Li, G. Yi, Y. Wang, X. Zu, H. Wang, H. Huang, Z. Liang, Temperature
sensing of conductive shape memory polymer composites, Mater. Lett. 140 (2015)
71–74, https://doi.org/10.1016/j.matlet.2014.11.010.
[47] A.I. Alateyah, H.N. Dhakal, Z.Y. Zhang, Processing, properties, and applications of
polymer nanocomposites based on layer silicates: a review, Adv. Polym. Technol.
32 (2013), https://doi.org/10.1002/adv.21368.
[48] S. Sinharay, M. Bousmina, Biodegradable polymers and their layered silicate na-
nocomposites: in greening the 21st century materials world, Prog. Mater. Sci. 50
(2005) 962–1079, https://doi.org/10.1016/j.pmatsci.2005.05.002.
[49] S. Sinha Ray, M. Okamoto, Polymer/layered silicate nanocomposites: a review
from preparation to processing, Prog. Polym. Sci. 28 (2003) 1539–1641, https://
doi.org/10.1016/j.progpolymsci.2003.08.002.
[50] S.-L. Bee, M.A.A. Abdullah, S.-T. Bee, L.T. Sin, A.R. Rahmat, Polymer nano-
composites based on silylated-montmorillonite: a review, Prog. Polym. Sci. 85
(2018) 57–82, https://doi.org/10.1016/j.progpolymsci.2018.07.003.
[51] Y. Cui, S. Kumar, B. Rao Kona, D. van Houcke, Gas barrier properties of polymer/
clay nanocomposites, RSC Adv. 5 (2015) 63669–63690, https://doi.org/10.1039/
C5RA10333A.
[52] J.W. Gilman, W.H. Awad, R.D. Davis, J. Shields, R.H. Harris, C. Davis,
A.B. Morgan, T.E. Sutto, J. Callahan, P.C. Trulove, H.C. DeLong, Polymer/layered
301
European Polymer Journal 117 (2019) 280–303
silicate nanocomposites from thermally stable trialkylimidazolium-treated mon-
tmorillonite, Chem. Mater. 14 (2002) 3776–3785, https://doi.org/10.1021/
cm011532x.
[53] Q.T. Nguyen, D.G. Baird, An improved technique for exfoliating and dispersing
nanoclay particles into polymer matrices using supercritical carbon dioxide,
Polymer (Guildf) (2007), https://doi.org/10.1016/j.polymer.2007.09.015.
[54] S.L. Bee, M.A.A. Abdullah, M. Mamat, S.T. Bee, L.T. Sin, D. Hui, A.R. Rahmat,
Characterization of silylated modified clay nanoparticles and its functionality in
PMMA, Compos. Part B Eng. (2017), https://doi.org/10.1016/j.compositesb.
2016.10.084.
[55] B. Yang, B. Yang, Porous Polyurethane Shape Memory Polymers, in: Polyurethane
Shape Mem. Polym., first ed., CRC Press, 2011, pp. 185–240. https://doi.org/10.
1201/b11209-9.
[56] D.K. Tripathy, B.P. Sahoo, C.B. Polymer, Properties and Applications of Polymer
Nanocomposites, Springer-Verlag GmbH, Germany, 2017https://doi.org/10.
1007/978-3-662-53517-2.
[57] S. Sinha Ray, Clay-containing Polymer Nanocomposites: From Fundamentals to
Real Applications, 2013. https://doi.org/10.1016/C2011-0-07134-X.
[58] K. Khederlou, R. Bagheri, A. Shojaei, A mathematical method for XRD pattern
interpretation in clay containing nano composites, Appl. Surf. Sci. 318 (2014)
90–94, https://doi.org/10.1016/j.apsusc.2014.01.044.
[59] J.-H. Lin, Y.-J. Pan, C.-T. Hsieh, C.-H. Huang, Z.-I. Lin, Y.-S. Chen, K.-H. Su, C.-
W. Lou, Using multiple melt blending to improve the dispersion of montmor-
illonite in polyamide 6 nanocomposites, Polym. Test. 56 (2016) 74–82, https://
doi.org/10.1016/j.polymertesting.2016.09.016.
[60] R. Sengupta, S. Chakraborty, S. Bandyopadhyay, S. Dasgupta, R. Mukhopadhyay,
K. Auddy, A.S. Deuri, A short review on rubber/clay nanocomposites with em-
phasis on mechanical properties, Polym. Eng. Sci. 47 (2007) 1956–1974, https://
doi.org/10.1002/pen.20921.
[61] D.R. Paul, L.M. Robeson, Polymer nanotechnology: Nanocomposites, Polymer
(Guildf) 49 (2008) 3187–3204, https://doi.org/10.1016/j.polymer.2008.04.017.
[62] P. Kiliaris, C.D. Papaspyrides, Polymer/layered silicate (clay) nanocomposites: an
overview of flame retardancy, Prog. Polym. Sci. 35 (2010) 902–958, https://doi.
org/10.1016/j.progpolymsci.2010.03.001.
[63] D. Ratna, N. Manoj, R. Varley, R. Singh Raman, G. Simon, Clay-reinforced epoxy
nanocomposites, Polym. Int. 52 (2003) 1403–1407, https://doi.org/10.1002/pi.
1166.
[64] A. Okada, A. Usuki, Twenty years of polymer-clay nanocomposites, Macromol.
Mater. Eng. 291 (2006) 1449–1476, https://doi.org/10.1002/mame.200600260.
[65] M. Kotal, A.K. Bhowmick, Progress in polymer science polymer nanocomposites
from modified clays: recent advances and challenges, Prog. Polym. Sci. 51 (2015)
127–187, https://doi.org/10.1016/j.progpolymsci.2015.10.001.
[66] M. Okamoto, Recent advances in polymer/layered silicate nanocomposites: an
overview from science to technology, Mater. Sci. Technol. 22 (2006) 756–779,
https://doi.org/10.1179/174328406X101319.
[67] I. Scarlatescu, M. Spunei, A. Chis, S. Negru, M. Bunoiu, N. Avram, Experimental
dosimetric checkup under positioning errors according to gamma criterion, UPB
Sci. Bull. Ser. A Appl. Math. Phys. 80 (2018) 271–280, https://doi.org/10.1002/
polb.
[68] A. Choudhury, A.K. Bhowmick, C. Ong, Novel role of polymer-solvent and clay-
solvent interaction parameters on the thermal, mechanical and optical properties
of polymer nanocomposites, Polymer (Guildf) 50 (2009) 201–210, https://doi.
org/10.1016/j.polymer.2008.10.044.
[69] T. Xie, Y.L. He, Z.X. Tong, W.X. Yan, X.Q. Xie, Transient heat transfer character-
istic of silica aerogel insulating material considering its endothermic reaction, Int.
J. Heat Mass Transf. 68 (2014) 633–640, https://doi.org/10.1016/j.
ijheatmasstransfer.2013.09.074.
[70] M. Alexandre, P. Dubois, 5 Nano C 10.1016@S0927-796X(00)00012-7, 28, 2000,
pp. 1–63. https://doi.org/10.1016/S0927-796X(00)00012-7.
[71] F. Xie, E. Pollet, P.J. Halley, L. Avérous, Starch-based nano-biocomposites, Prog.
Polym. Sci. 38 (2013) 1590–1628, https://doi.org/10.1016/j.progpolymsci.2013.
05.002.
[72] H.H. Murray, Overview - clay mineral applications, Clays Clay Miner. 5 (1991)
379–395.
[73] Y. Xu, D. Chen, Self-healing polyurethane/attapulgite nanocomposites based on
disul fi de bonds and shape memory effect, Mater. Chem. Phys. 195 (2017) 40–48,
https://doi.org/10.1016/j.matchemphys.2017.04.007.
[74] R.S. Hebbar, A.M. Isloor, K. Ananda, A.F. Ismail, Fabrication of polydopamine
functionalized halloysite nanotube/polyetherimide membranes for heavy metal
removal, J. Mater. Chem. A 4 (2016) 764–774, https://doi.org/10.1039/
C5TA09281G.
[75] B. Yan, S. Gu, Y. Zhang, Polylactide-based thermoplastic shape memory polymer
nanocomposites, Eur. Polym. J. 49 (2013) 366–378, https://doi.org/10.1016/j.
eurpolymj.2012.09.026.
[76] F. Cao, S.C. Jana, Nanoclay-tethered shape memory polyurethane nanocompo-
sites, Polymer (Guildf) 48 (2007) 3790–3800, https://doi.org/10.1016/j.polymer.
2007.04.027.
[77] M.K. Jang, A. Hartwig, B.K. Kim, Shape memory polyurethanes cross-linked by
surface modified silica particles, J. Mater. Chem. 19 (2009) 1166, https://doi.org/
10.1039/b816691a.
[78] D.H. Jung, H.M. Jeong, B.K. Kim, Organic–inorganic chemical hybrids having
shape memory effect, J. Mater. Chem. 20 (2010) 3458, https://doi.org/10.1039/
b922775j.
[79] J. Odent, J.M. Raquez, C. Samuel, S. Barrau, A. Enotiadis, P. Dubois,
E.P. Giannelis, Shape-memory behavior of polylactide/silica ionic hybrids,
Macromolecules 50 (2017) 2896–2905, https://doi.org/10.1021/acs.macromol.
M. Panahi-Sarmad, et al.
7b00195.
[80] R. Bouaziz, K. Prashantha, F. Roger, Thermomechanical modeling of halloysite
nanotube-filled shape memory polymer nanocomposites, Mech. Adv. Mater.
Struct. 6494 (2018) 1–9, https://doi.org/10.1080/15376494.2018.1432793.
[81] B. Xu, W.M. Huang, Y.T. Pei, Z.G. Chen, A. Kraft, R. Reuben, J.T.M. De Hosson,
Y.Q. Fu, Mechanical properties of attapulgite clay reinforced polyurethane shape-
memory nanocomposites, Eur. Polym. J. 45 (2009) 1904–1911, https://doi.org/
10.1016/j.eurpolymj.2009.04.004.
[82] B. Xu, Y.Q. Fu, W.M. Huang, Y.T. Pei, Z.G. Chen, J.T.M. De Hosson, A. Kraft,
R.L. Reuben, Thermal-mechanical properties of polyurethane-clay shape memory
polymer nanocomposites, Polymers (Basel) 2 (2010) 31–39, https://doi.org/10.
3390/polym2020031.
[83] G. Yu, H. Chen, W. Wang, Y. Zhou, J. Zhang, Y. Li, Influence of sepiolite on
crystallinity of soft segments and shape memory properties of polyurethane na-
nocomposites, Polym. Compos. 39 (2018) 1674–1681, https://doi.org/10.1002/
pc.24115.
[84] M.Q. Zhan, K.K. Yang, Y.Z. Wang, Shape-memory poly(p-dioxanone)-poly(ε-ca-
prolactone)/sepiolite nanocomposites with enhanced recovery stress, Chinese
Chem. Lett. 26 (2015) 1221–1224, https://doi.org/10.1016/j.cclet.2015.07.019.
[85] E.S. Ali, S.A. Zubir, S. Ahmad, Clay reinforced hyperbranched polyurethane na-
nocomposites based on palm oil polyol as shape memory materials, Adv. Mater.
Res. 548 (2012) 115–118, https://doi.org/10.4028/www.scientific.net/AMR.548.
115.
[86] S. Ahmad Zubir, S. Ahmad, E.S. Ali, Palm oil polyol/polyurethane shape memory
nanocomposites, Appl. Mech. Mater. 291–294 (2013) 2666–2669, https://doi.org/
10.3892/mmr.2013.1266.
[87] F. Quadrini, L. Santo, E.A. Squeo, Solid-state foaming of nano-clay-filled thermoset
foams with shape memory properties, Polym. - Plast. Technol. Eng. 51 (2012)
560–567, https://doi.org/10.1080/03602559.2012.654579.
[88] Y.C. Sun, S. Cai, J. Ren, H.E. Naguib, Room temperature deformable shape
memory composite with fine-tuned crystallization induced via nanoclay particles,
J. Polym. Sci. Part B Polym. Phys. 55 (2017) 1197–1206, https://doi.org/10.
1002/polb.24370.
[89] Y. Dong, C. Qian, J. Lu, Y. Fu, Clay montmorillonite-poly(ε-caprolactone) elec-
trospun microfiber/epoxy composites with triple shape memory effect, Pigment
Resin Technol. 47 (2017) 29–37.
[90] Y. Liu, C. Han, H. Tan, X. Du, Organic-montmorillonite modified shape memory
epoxy composite, Polym. Adv. Technol. 22 (2011) 2017–2021, https://doi.org/10.
1002/pat.1712.
[91] W. Li, X. Jiang, R. Wu, W. Wang, Fast shape recovery by changing the grafting
ratio in polyurethane/montmorillonite-poly(methyl methacrylate) composites,
Polym. J. 49 (2017) 263–271, https://doi.org/10.1038/pj.2016.98.
[92] L. Fu, F. Wu, C. Xu, T. Cao, R. Wang, S. Guo, Anisotropic shape memory behaviors
of polylactic Acid/Citric Acid−bentonite composite with a gradient filler con-
centration in thickness direction, Ind. Eng. Chem. Res. 57 (2018) 6265–6274,
https://doi.org/10.1021/acs.iecr.8b00602.
[93] V. Sessini, J.M. Raquez, D. Lourdin, J.E. Maigret, J.M. Kenny, P. Dubois, L. Peponi,
Humidity-activated shape memory effects on thermoplastic starch/EVA blends
and their compatibilized nanocomposites, Macromol. Chem. Phys. 218 (2017)
1–12, https://doi.org/10.1002/macp.201700388.
[94] M.J. Barwood, C. Breen, F. Clegg, C.L. Hammond, The effect of organoclay addi-
tion on the properties of an acrylate based, thermally activated shape memory
polymer, Appl. Clay Sci. 102 (2014) 41–50, https://doi.org/10.1016/j.clay.2014.
10.010.
[95] Y.N. Gupta, T. Bhave, S.M. Abbas, R.B. Sharma, D.K. Setua, Low temperature
shape memory characteristics of segmented polyurethane-nanoclay composites, J.
Therm. Anal. Calorim. 124 (2016) 1449–1461, https://doi.org/10.1007/s10973-
016-5248-6.
[96] S.J. Hong, W.R. Yu, J.H. Youk, Mechanical behavior of shape memory fibers spun
from nanoclay-tethered polyurethanes, Macromol. Res. 16 (2008) 644–650,
https://doi.org/10.1007/BF03218574.
[97] G. Coativy, N. Gautier, B. Pontoire, A. Buléon, D. Lourdin, E. Leroy, Shape memory
starch-clay bionanocomposites, Carbohydr. Polym. 116 (2015) 307–313, https://
doi.org/10.1016/j.carbpol.2013.12.024.
[98] S. Ponyrko, R.K. Donato, L. Matějka, Erratum: Tailored high performance shape
memory epoxy-silica nanocomposites. Struct. Des. (Polym. Chem. (2016) 7
(560–572)), Polym. Chem. 7 (2016) 3200. https://doi.org/10.1039/c6py90066f.
[99] R. Sengupta, M. Bhattacharya, S. Bandyopadhyay, A.K. Bhowmick, A review on
the mechanical and electrical properties of graphite and modified graphite re-
inforced polymer composites, Prog. Polym. Sci. 36 (2011) 638–670, https://doi.
org/10.1016/j.progpolymsci.2010.11.003.
[100] H. Qian, E.S. Greenhalgh, M.S.P. Shaffer, A. Bismarck, Carbon nanotube-based
hierarchical composites: a review, J. Mater. Chem. 20 (2010) 4751, https://doi.
org/10.1039/c000041h.
[101] J.R. Potts, D.R. Dreyer, C.W. Bielawski, R.S. Ruoff, Graphene-based polymer na-
nocomposites, Polymer (Guildf) 52 (2011) 5–25, https://doi.org/10.1016/j.
polymer.2010.11.042.
[102] N.G. Sahoo, S. Rana, J.W. Cho, L. Li, S.H. Chan, Polymer nanocomposites based on
functionalized carbon nanotubes, Prog. Polym. Sci. 35 (2010) 837–867, https://
doi.org/10.1016/j.progpolymsci.2010.03.002.
[103] T. Kuilla, S. Bhadra, D. Yao, N.H. Kim, S. Bose, J.H. Lee, Recent advances in
graphene based polymer composites, Prog. Polym. Sci. 35 (2010) 1350–1375,
https://doi.org/10.1016/j.progpolymsci.2010.07.005.
[104] T.S. Sreeprasad, V. Berry, How do the electrical properties of graphene change
with its functionalization? Small 9 (2013) 341–350, https://doi.org/10.1002/
smll.201202196.
302
European Polymer Journal 117 (2019) 280–303
[105] Z. Tang, L. Zhang, W. Feng, B. Guo, F. Liu, D. Jia, Rational design of graphene
surface chemistry for high-performance rubber/graphene composites,
Macromolecules 47 (2014) 8663–8673, https://doi.org/10.1021/ma502201e.
[106] W. Gao, The chemistry of graphene oxide, in: Graphene Oxide, Springer
International Publishing, Cham, 2015, pp. 61–95. https://doi.org/10.1007/978-3-
319-15500-5_3.
[107] M. Acik, G. Lee, C. Mattevi, A. Pirkle, R.M. Wallace, M. Chhowalla, K. Cho,
Y. Chabal, The role of oxygen during thermal reduction of graphene oxide studied
by infrared absorption spectroscopy, J. Phys. Chem. C 115 (2011) 19761–19781,
https://doi.org/10.1021/jp2052618.
[108] R.E. Reduction, G. Oxide, Reversible Electrical Reduction and Oxidation of
Graphene Oxide, 2011, pp. 2475–2482.
[109] Z. Dang, M. Zheng, J. Zha, 1D/2D carbon nanomaterial-polymer dielectric com-
posites with high permittivity for power energy storage applications, Small 12
(2016) 1688–1701, https://doi.org/10.1002/smll.201503193.
[110] M. Panahi-Sarmad, E. Chehrazi, M. Noroozi, M. Raef, M. Razzaghi-Kashani,
M.A. Haghighat Baian, Tuning the surface chemistry of graphene oxide for en-
hanced dielectric and actuated performance of silicone rubber composites, ACS
Appl. Electron. Mater. 1 (2019) 198–209, https://doi.org/10.1021/acsaelm.
8b00042.
[111] M. Panahi-Sarmad, M. Razzaghi-Kashani, Actuation behavior of PDMS dielectric
elastomer composites containing optimized graphene oxide, Smart Mater. Struct.
27 (2018) 085021, https://doi.org/10.1088/1361-665X/aacfe6.
[112] S. Sankaran, K. Deshmukh, M.B. Ahamed, S.K. Khadheer Pasha, Recent advances
in electromagnetic interference shielding properties of metal and carbon filler
reinforced flexible polymer composites: a review, Compos. Part A Appl. Sci.
Manuf. 114 (2018) 49–71, https://doi.org/10.1016/j.compositesa.2018.08.006.
[113] C. Wang, V. Murugadoss, J. Kong, Z. He, X. Mai, Q. Shao, Y. Chen, L. Guo, C. Liu,
S. Angaiah, Z. Guo, Overview of carbon nanostructures and nanocomposites for
electromagnetic wave shielding, Carbon N.Y. 140 (2018) 696–733, https://doi.
org/10.1016/j.carbon.2018.09.006.
[114] H. Pang, L. Xu, D.-X. Yan, Z.-M. Li, Conductive polymer composites with segre-
gated structures, Prog. Polym. Sci. 39 (2014) 1908–1933, https://doi.org/10.
1016/j.progpolymsci.2014.07.007.
[115] B. Guo, Z. Tang, L. Zhang, Transport performance in novel elastomer nano-
composites: mechanism, design and control, Prog. Polym. Sci. 61 (2016) 29–66,
https://doi.org/10.1016/j.progpolymsci.2016.06.001.
[116] A. Kirillova, L. Ionov, Shape-changing polymers for biomedical applications, J.
Mater. Chem. B 7 (2019) 1597–1624, https://doi.org/10.1039/C8TB02579G.
[117] H. Abbasi, M. Antunes, J.I. Velasco, Recent advances in carbon-based polymer
nanocomposites for electromagnetic interference shielding, Prog. Mater. Sci. 103
(2019) 319–373, https://doi.org/10.1016/j.pmatsci.2019.02.003.
[118] C.A. Garcia Rosales, M.F. Garcia Duarte, H. Kim, L. Chavez, D. Hodges, P. Mandal,
Y. Lin, T.-L. (Bill) Tseng, 3D printing of shape memory polymer (SMP)/carbon
black (CB) nanocomposites with electro-responsive toughness enhancement,
Mater. Res. Exp. 5 (2018) 065704. https://doi.org/10.1088/2053-1591/aacd53.
[119] M. Babaahmadi, M. Sabzi, G.R. Mahdavinia, M. Keramati, Preparation of amor-
phous nanocomposites with quick heat triggered shape memory behavior,
Polymer (Guildf) 112 (2017) 26–34, https://doi.org/10.1016/j.polymer.2017.01.
074.
[120] D.A. Nguyen, Y.R. Lee, A.V. Raghu, H.M. Jeong, C.M. Shin, B.K. Kim,
Morphological and physical properties of a thermoplastic polyurethane reinforced
with functionalized graphene sheet, Polym. Int. 58 (2009) 412–417, https://doi.
org/10.1002/pi.2549.
[121] J.H. Park, T.D. Dao, H. Il Lee, H.M. Jeong, B.K. Kim, Properties of graphene/shape
memory thermoplastic polyurethane composites actuating by various methods,
Materials (Basel) 7 (2014) 1520–1538, https://doi.org/10.3390/ma7031520.
[122] Z. Tong, X. Pei, Z. Shen, S. Wei, Y. Gao, P. Huang, B. Shi, F. Sun, T. Fu, An en-
hanced thermo-actuated shape memory polymer composite coupled with elas-
tomer, Pet. Explor. Dev. 43 (2016) 1097–1106, https://doi.org/10.1016/S1876-
3804(16)30128-8.
[123] L. Ma, J. Zhao, X. Wang, M. Chen, Y. Liang, Z. Wang, Z. Yu, R.C. Hedden, Effects of
carbon black nanoparticles on two-way reversible shape memory in crosslinked
polyethylene, Polymer (Guildf) 56 (2015) 490–497, https://doi.org/10.1016/j.
polymer.2014.11.036.
[124] K. Yu, Z. Zhang, Y. Liu, J. Leng, Carbon nanotube chains in a shape memory
polymer/carbon black composite: to significantly reduce the electrical resistivity,
Appl. Phys. Lett. 98 (2011) 074102, https://doi.org/10.1063/1.3556621.
[125] Y.C. Jung, H.J. Yoo, Y.A. Kim, J.W. Cho, M. Endo, Electroactive shape memory
performance of polyurethane composite having homogeneously dispersed and
covalently crosslinked carbon nanotubes, Carbon N.Y. 48 (2010) 1598–1603,
https://doi.org/10.1016/j.carbon.2009.12.058.
[126] M. Raja, S.H. Ryu, A.M. Shanmugharaj, Thermal, mechanical and electroactive
shape memory properties of polyurethane (PU)/poly (lactic acid) (PLA)/CNT na-
nocomposites, Eur. Polym. J. 49 (2013) 3492–3500, https://doi.org/10.1016/j.
eurpolymj.2013.08.009.
[127] H. Deka, N. Karak, R.D. Kalita, A.K. Buragohain, Biocompatible hyperbranched
polyurethane/multi-walled carbon nanotube composites as shape memory mate-
rials, Carbon N.Y. 48 (2010) 2013–2022, https://doi.org/10.1016/j.carbon.2010.
02.009.
[128] H. Lian, W. Chang, Q. Liang, C. Hu, R. Wang, L. Zu, Y. Liu, A shape memory
polyurethane based ionic polymer–carbon nanotube composite, RSC Adv. 7 (2017)
46221–46228, https://doi.org/10.1039/C7RA07476J.
[129] M.-S. Cao, X.-X. Wang, W.-Q. Cao, J. Yuan, Ultrathin graphene: electrical prop-
erties and highly efficient electromagnetic interference shielding, J. Mater. Chem.
C 3 (2015) 6589–6599, https://doi.org/10.1039/C5TC01354B.
M. Panahi-Sarmad, et al.
[130] C.K. Chua, M. Pumera, Chemical reduction of graphene oxide: a synthetic chem-
istry viewpoint, Chem. Soc. Rev. 43 (2014) 291–312, https://doi.org/10.1039/
C3CS60303B.
[131] P.V. Kumar, N.M. Bardhan, G. Chen, Z. Li, A.M. Belcher, J.C. Grossman, New in-
sights into the thermal reduction of graphene oxide: impact of oxygen clustering,
Carbon N.Y. 100 (2016) 90–98, https://doi.org/10.1016/j.carbon.2015.12.087.
[132] D.I. Arun, K.S. Santhosh Kumar, B. Satheesh Kumar, P. Chakravarthy, M. Dona,
B. Santhosh, High glass-transition polyurethane-carbon black electro-active shape
memory nanocomposite for aerospace systems, Mater. Sci. Technol. (United
Kingdom) (2019) 1–10, https://doi.org/10.1080/02670836.2019.1575054.
[133] Y. Huo, Y. Liu, H. Liu, G. Zhu, X. Hou, W. Liu, T. Ren, An investigation on laser-
triggered shape memory behaviors of hydro-epoxy/carbon black composites,
Smart Mater. Struct. 27 (2018) 095008, https://doi.org/10.1088/1361-665x/
aad254.
[134] S. Gu, B. Yan, L. Liu, J. Ren, Carbon nanotube-polyurethane shape memory na-
nocomposites with low trigger temperature, Eur. Polym. J. 49 (2013) 3867–3877,
https://doi.org/10.1016/j.eurpolymj.2013.10.007.
[135] S. Javadi, M. Panahi-Sarmad, M. Razzaghi-Kashani, Interfacial and dielectric be-
havior of polymer nano-composites: effects of chain stiffness and cohesive energy
density, Polymer (Guildf). 145 (2018) 31–40, https://doi.org/10.1016/j.polymer.
2018.04.061.
[136] E. Chehrazi, M. Raef, M. Noroozi, M. Panahi-Sarmad, A theoretical model for the
gas permeation prediction of nanotube-mixed matrix membranes: unveiling the
effect of interfacial layer, J. Memb. Sci. 570–571 (2019) 168–175, https://doi.org/
10.1016/j.memsci.2018.10.038.
[137] J. Chen, Z. Xing Zhang, W. Bin Huang, J. Le Li, J. Hui Yang, Y. Wang, Z. Wan Zhou,
J. Hong Zhang, Carbon nanotube network structure induced strain sensitivity and
shape memory behavior changes of thermoplastic polyurethane, Mater. Des. 69
(2015) 105–113, https://doi.org/10.1016/j.matdes.2014.12.054.
[138] J.W. Cho, J.W. Kim, Y.C. Jung, N.S. Goo, Electroactive shape-memory poly-
urethane composites incorporating carbon nanotubes, Macromol. Rapid Commun.
26 (2005) 412–416, https://doi.org/10.1002/marc.200400492.
[139] X. Xu, P. Fan, J. Ren, Y. Cheng, J. Ren, J. Zhao, R. Song, Self-healing thermoplastic
polyurethane (TPU)/polycaprolactone (PCL) /multi-wall carbon nanotubes
(MWCNTs) blend as shape-memory composites, Compos. Sci. Technol. 168 (2018)
255–262, https://doi.org/10.1016/j.compscitech.2018.10.003.
[140] M.H. Moghim, S.M. Zebarjad, R. Eqra, Experimental and modeling investigation of
shape memory behavior of polyurethane/carbon nanotube nanocomposite, Polym.
Adv. Technol. 29 (2018) 2496–2504, https://doi.org/10.1002/pat.4361.
[141] A. Abbasi, G. Mir Mohamad Sadeghi, I. Ghasemi, M. Shahrousvand, Shape
memory performance of green in situ polymerized nanocomposites based on
polyurethane/graphene nanoplatelets: synthesis, properties, and cell behavior,
Polym. Compos. 39 (2018) 4020–4033, https://doi.org/10.1002/pc.24456.
[142] J.T. Choi, T.D. Dao, K.M. Oh, H. Lee, H.M. Jeong, B.K. Kim, Shape memory
polyurethane nanocomposites with functionalized graphene, Smart Mater. Struct.
21 (2012) 075017, https://doi.org/10.1088/0964-1726/21/7/075017.
[143] S. Rana, J.W. Cho, L.P. Tan, Graphene-crosslinked polyurethane block copolymer
nanocomposites with enhanced mechanical, electrical, and shape memory prop-
erties, RSC Adv. 3 (2013) 13796–13803, https://doi.org/10.1039/c3ra40711j.
[144] S.S. Mahapatra, M.S. Ramasamy, H.J. Yoo, J.W. Cho, A reactive graphene sheet in
situ functionalized hyperbranched polyurethane for high performance shape
memory material, RSC Adv. 4 (2014) 15146, https://doi.org/10.1039/
c4ra01095g.
[145] H. Jiu, H. Jiao, L. Zhang, S. Zhang, Y. Zhao, Graphene-crosslinked two-way re-
versible shape memory polyurethane nanocomposites with enhanced mechanical
and electrical properties, J. Mater. Sci. Mater. Electron. 27 (2016) 10720–10728,
https://doi.org/10.1007/s10854-016-5173-2.
[146] S. Thakur, N. Karak, Bio-based tough hyperbranched polyurethane-graphene oxide
nanocomposites as advanced shape memory materials, RSC Adv. 3 (2013)
9476–9482, https://doi.org/10.1039/c3ra40801a.
[147] Y. Wei, R. Huang, P. Dong, X. Qi, Q. Fu, Preparation of polylactide/poly(ether)
urethane blends with excellent electro-actuated shape memory via incorporating
carbon black and carbon nanotubes hybrids fillers, Chinese J. Polym. Sci. 36
(2018) 1175–1186, https://doi.org/10.1007/s10118-018-2138-3.
[148] J. Lu, A. Arsalan, Y. Dong, Y. Zhu, C. Qian, R. Wang, C. Cuilan, Y. Fu, Q.Q. Ni,
K.N. Ali, Shape memory effect and recovery stress property of carbon nanotube/
waterborne epoxy nanocomposites investigated via TMA, Polym. Test. 59 (2017)
462–469, https://doi.org/10.1016/j.polymertesting.2017.03.001.
303
European Polymer Journal 117 (2019) 280–303
[149] F. Memarian, A. Fereidoon, M. Ghorbanzadeh Ahangari, The shape memory, and
the mechanical and thermal properties of TPU/ABS/CNT: a ternary polymer
composite, RSC Adv. (2016), https://doi.org/10.1039/c6ra23087c.
[150] Y. Liu, J. Zhao, L. Zhao, W. Li, H. Zhang, X. Yu, Z. Zhang, High performance shape
memory epoxy/carbon nanotube nanocomposites, ACS Appl. Mater. Interfaces. 8
(2016) 311–320, https://doi.org/10.1021/acsami.5b08766.
[151] G. Erdenedelger, J.H. Kim, J.T. Choi, T.D. Dao, K.M. Oh, H. Lee Il, H.M. Jeong,
Shape memory polyurethane nanocomposites with a functionalized graphene, in:
8th Int. Forum Strateg. Technol, 2013, IFOST 2013 - Proc. 1, 2013, pp. 124–127.
https://doi.org/10.1109/IFOST.2013.6616958.
[152] E. Wang, Y. Dong, M.Z. Islam, L. Yu, F. Liu, S. Chen, X. Qi, Y. Zhu, Y. Fu, Z. Xu,
N. Hu, Effect of graphene oxide-carbon nanotube hybrid filler on the mechanical
property and thermal response speed of shape memory epoxy composites,
Compos. Sci. Technol. 169 (2019) 209–216, https://doi.org/10.1016/j.
compscitech.2018.11.022.
[153] E. D’Elia, H.S. Ahmed, E. Feilden, E. Saiz, Electrically-responsive graphene-based
shape-memory composites, Appl. Mater. Today 15 (2019) 185–191, https://doi.
org/10.1016/j.apmt.2018.12.018.
[154] Y. Li, H. Lian, Y. Hu, W. Chang, X. Cui, Y. Liu, Enhancement in mechanical and
shape memory properties for liquid crystalline polyurethane strengthened by
graphene oxide, Polymers (Basel) (2016), https://doi.org/10.3390/
polym8070236.
[155] K. Kumar Patel, R. Purohit, Improved shape memory and mechanical properties of
microwave-induced thermoplastic polyurethane/graphene nanoplatelets compo-
sites, Sensors Actuat. A Phys. 285 (2019) 17–24, https://doi.org/10.1016/j.sna.
2018.10.049.
[156] M. Keramati, I. Ghasemi, M. Karrabi, H. Azizi, M. Sabzi, Incorporation of surface
modified graphene nanoplatelets for development of shape memory PLA nano-
composite, Fibers Polym. (2016), https://doi.org/10.1007/s12221-016-6329-7.
[157] D. Ponnamma, K.K. Sadasivuni, M. Strankowski, P. Moldenaers, S. Thomas,
Y. Grohens, Interrelated shape memory and Payne effect in polyurethane/gra-
phene oxide nanocomposites, RSC Adv. 3 (2013) 16068–16079, https://doi.org/
10.1039/c3ra41395k.
[158] P.-C. Ma, N.A. Siddiqui, G. Marom, J.-K. Kim, Dispersion and functionalization of
carbon nanotubes for polymer-based nanocomposites: a review, Compos. Part A
Appl. Sci. Manuf. 41 (2010) 1345–1367, https://doi.org/10.1016/j.compositesa.
2010.07.003.
[159] V. Georgakilas, M. Otyepka, A.B. Bourlinos, V. Chandra, N. Kim, K.C. Kemp,
P. Hobza, R. Zboril, K.S. Kim, Functionalization of graphene: covalent and non-
covalent approaches, derivatives and applications, Chem. Rev. 112 (2012)
6156–6214, https://doi.org/10.1021/cr3000412.
[160] P. Song, L. Liu, S. Fu, Y. Yu, C. Jin, Q. Wu, Y. Zhang, Q. Li, Striking multiple
synergies created by combining reduced graphene oxides and carbon nanotubes
for polymer nanocomposites, Nanotechnology. 24 (2013) 125704, https://doi.
org/10.1088/0957-4484/24/12/125704.
[161] J. Yan, T. Wei, Z. Fan, W. Qian, M. Zhang, X. Shen, F. Wei, Preparation of gra-
phene nanosheet/carbon nanotube/polyaniline composite as electrode material
for supercapacitors, J. Power Sources 195 (2010) 3041–3045, https://doi.org/10.
1016/j.jpowsour.2009.11.028.
[162] Y. Li, T. Yang, T. Yu, L. Zheng, K. Liao, Synergistic effect of hybrid carbon nan-
tube–graphene oxide as a nanofiller in enhancing the mechanical properties of
PVA composites, J. Mater. Chem. 21 (2011) 10844, https://doi.org/10.1039/
c1jm11359c.
[163] S.P. Bao, G.D. Liang, S.C. Tjong, Positive temperature coefficient effect of poly-
propylene/carbon nanotube/montmorillonite hybrid nanocomposites, IEEE Trans.
Nanotechnol. (2009), https://doi.org/10.1109/TNANO.2009.2023650.
[164] Q. Li, S. Basavarajaiah, N.H. Kim, S.B. Heo, J.H. Lee, Synergy effect of hybrid
fillers on the positive temperature coefficient behavior of polypropylene/ultra-
high molecular weight polyethylene composites, J. Appl. Polym. Sci. (2010),
https://doi.org/10.1002/app.31478.
[165] L. Liu, J.C. Grunlan, Clay assisted dispersion of carbon nanotubes in conductive
epoxy nanocomposites, Adv. Funct. Mater. (2007), https://doi.org/10.1002/adfm.
200600785.
[166] E. Wang, Y. Dong, Z. Islam, L. Yu, F. Liu, S. Chen, X. Qi, Y. Zhu, Y. Fu, Z. Xu, N. Hu,
E ff ect of graphene oxide-carbon nanotube hybrid fi ller on the mechanical
property and thermal response speed of shape memory epoxy composites,
Compos. Sci. Technol. 169 (2018) 209–216, https://doi.org/10.1016/j.
compscitech.2018.11.022.