Thermal Stability of Shape Memory

Polymers, Polymer Blends,

and Composites

Sunan Tiptipakorn and Sarawut Rimdusit

Abstract This chapter will focus on the thermal analysis and interesting related
properties of high performance shape memory polymers (SMPs), shape memory
polymer blends (SMPBs), and shape memory polymer composites (SMPCs) in dif-
ferent length scales. In general, thermal behaviors of shape memory materials are very
relevant to the potential uses in many demanding applications. In order to develop
durable industrial products, it is necessary to investigate the thermal stability of these
polymers. The polybenzoxazine (PBZ)-based shape memory materials are mainly
mentioned in this chapter due to the outstanding properties and high thermal stability
of the novel phenolic polymers. This kind of thermoset can be alloyed with other
polymers such as epoxy and polyurethane suitable to be used to produce SMPCs in
high temperature applications with synergistic behaviors. Therefore, the PBZ/epoxy
alloy-based systems and PBZ/polyurethane alloys-based systems are mentioned as
well.

Keywords Shape memory polymer · Thermal stability · Blends · Composites ·

Benzoxazine

1 Introduction

Shape memory materials (SMMs) have been well known for a long time as stimuli-
responsive materials having recoverability of their original shape. Generally, various
kinds of external stimulus such as temperature change [1–4], light induction [5],

S. Tiptipakorn
Department of Chemistry, Faculty of Liberal Arts and Science, Kasetsart University, Malaiman
Road, 73140 Nakhon Pathom, Thailand
e-mail: faassntk@ku.ac.th
S. Rimdusit (B)
Department of Chemical Engineering, Faculty of Engineering, Chulalongkorn University, 10330
Bangkok, Thailand
e-mail: sarawut.r@chula.ac.th

© Springer Nature Singapore Pte Ltd. 2020 167

J. Parameswaranpillai et al. (eds.), Shape Memory Polymers,
Blends and Composites, Advanced Structured Materials 115,
https://doi.org/10.1007/978-981-13-8574-2_8
168 S. Tiptipakorn and S. Rimdusit

Table 1 Comparison on characteristics between typical SMAs and SMPs [1, 14]
Characteristic SMAs SMPs
Density (g/cm3 ) Approximately Approximately 0.9–1.1
6.5
Transformation strain (%) 8% at max. Up to 800%
Thermal conductivity (W m−1 K−1 ) As high as 20 0.15–0.30
for NiTi
Processing condition Over 1000 Lower than 200 °C/low pressure
°C/high pressure
Cost High Low

electrical current [6], solvents [7], ions [8], magnetic field [9], pH variation [10]
or even irradiation [11] are applicable. The temperature is typically the most com-
mon stimuli [12–15]. Recently, shape memory polymers (SMPs) and shape memory
metallic alloys (SMAs) as two main types of SMMs that are widely used in many
applications such as smart medical devices, smart actuators and sensors, deployable
structure, smart fabrics etc. [16–19]. The characteristics of typical SMPs and SMAs
are compared in Table 1.
It could be seen that SMPs provided comparatively greater advantages than shape
memory alloys (SMAs) in aspects of lower density, higher elastic deformation,
greater processability, and lower cost [19–22]. Moreover, the strain of SMP was
reported to be up to 800% (for some polymers) [11]. That is higher than the max-
imum values of SMA, shape memory ceramics, shape memory glasses (10, 1, and
0.1%, respectively) [23, 24]. The shape memory behaviors of SMP could be demon-
strated as shown in Fig. 1. It could be seen that the shape of SMP can be deformed
when applying external force and heating above switching temperature or transition
temperature (Ttrans ) of the polymer component, i.e., melting temperature (Tm ) or glass
transition temperature (Tg ) [19, 25]. The deformed shape can be kept after cooling
to temporary shape. At this state, the energy was stored. When further heated, the
kept energy is released. The shape can automatically recover to its original shape.
Typically, SMPs are categorized into two types, i.e., thermoset-shape memory
polymers (TS-SMPs) and thermoplastic-shape memory polymers (TP-SMPs). The
TS-SMPs are more preferable for some severe applications such as light weight
deployable spacecraft structures, and smart actuators [26, 27]. Although both TS-
SMPs and TP-SMPs possess more interesting intrinsic advantages than SMA, some
major shortcomings of SMP are their lower modulus [28–35] and longer response
time [36, 37]. Recently, most researches relevant to SMP have been mainly focused
on some areas, e.g., searching for the new applications, modification of molecular
structure to meet the usage requirement, and exploration of the new shape memory
effects [19]. In order to develop the thermomechanical properties of the SMPs to meet
the requirement of applications, there are many approaches, i.e., blending or alloying
with other polymeric components as shape-memory polymer blends (SMPBs) and
Thermal Stability of Shape Memory Polymers … 169

Fig. 1 SMP behaviors upon heating and applying force [25]

Table 2 Selected analytical techniques for decomposition investigation of polymers [42]

Scale of decomposition Observed aspect Analytical technique
Macroscopic scale Reduction of mechanical properties Mechanical test
Microscopic scale Progress of Micro-cracking Optical microscope
Supramolecular scale Morphology change TEM, DSC
Macromolecular scale Molecular weight distribution change GPC
Chemical structure scale Generated degradation products FTIR, Raman, NMR

the addition of functional fillers as shape memory polymer composites (SMPCs)

[38–41].
The thermal stability of the SMPs, SMPBs, and SMPCs is a key parameter, indi-
cating the limitation for the usage of the materials. In general, many methodologies
for decomposition investigation of polymers in various scales have been proposed
as shown in Table 2.
Although many techniques have been developed as previously mentioned, the
most commonly used methodology to determine the thermal stability of shape mem-
ory materials are carried out via thermogravimetric analysis (TGA) [43], which could
provide the information in terms of thermal decomposition temperature, and char
yield. In the degradation process, the change in thermal decomposition of the poly-
mers is from the chemical reaction by means of chain scission of the macromolecules.
Many steps are composed in the thermal degradation pathway, i.e., (a) initiation, (b)
propagation, and (c) termination steps. In the composite system, the thermal stability
of the multicomponent materials not only rely on the individual thermal stability of
the polymeric matrix and the functional filler, but also the degree of filler dispersion
170 S. Tiptipakorn and S. Rimdusit

in the matrix, and interfacial adhesion [42, 44, 45]. In aspects of char formation,
the residual solid remained upon the decomposition process generally occurs from
crosslink reactions. The char residues are able to act as a physical barrier for heat
and oxygen diffusion, and prevent the component from further decomposition [42].
Though some reviews on SMPs, SMPBs, and SMPCs have been reported. A
review focusing on the thermal stability and related thermal properties has been
rarely mentioned. This chapter focuses on the shape memory polymer and associated
systems derived from high temperature polymers such as polybenzoxazine-based
SMPs and other polymeric materials with high stability SMP systems.

2 SMPs and SMPBs and Their Thermal Characteristics

2.1 A Brief Overview of SMPs and SMPBs

In general, SMPs and SMPBs are composed of two portions, i.e., (i) hard portion
having a function to keep the structure stable, (ii) soft portion having a function
to recover the shape of the materials [17]. The hard portion can be derived from
the stable network segment from chemical or physical linkage; while the soft por-
tion is acted as a reversible switching transition segment. In the soft portion, the
melting/crystallization transition and glassy/rubbery transition exhibit a reversible
phase transition at Tm and Tg , of the polymeric domain, respectively [46, 47]. The
SMPs and SMPBs can be categorized into four classes based on types of polymeric
components and type of linkage in the materials as presented below [48].
(a) Chemically linkaged thermoset polymers (Class I)
The elasticity of Class I SMPBs is attributed to the covalent bonds. The advan-
tage of this class is its high shape recovery (as close as 100%) from strong
chemical bonds. This class possesses the difficulty to recover the original shape
more than one time. The examples of the materials in this class are polynor-
bonene (Ttrans = 40 °C) [29], and dehydrochorinated crosslinked PVC (Ttrans =
80 °C) [49].
(b) Chemically linkaged semi-crystalline polymers (Class II)
The deformed shape of the materials in this class can be recovered when heating
beyond the melting temperature of the crystalline domain. The shape recovery
is in the range of 30–95% [50]. The examples of the materials in this class are
gamma radiated polycaprolactone (Ttrans = ca. 55 °C) [51], and ethylene vinyl
acetate (EVA) blended with nitrile rubber (Ttrans = 85 °C) [52].
(c) Physically linkaged amorphous thermoplastics (Class III)
In this class, physical bonds (such as Van der Waals forces and hydrogen bonds)
exist in a blend of two thermoplastic components. The Tg value of hard portion
in this material is higher than that of the soft one. The modulus of the material
in this class is greater than that of two former classes [53, 54]. The examples of
the materials in this class are polypropylene (PP)—poly(1-hexadecene) (PHD)
Thermal Stability of Shape Memory Polymers … 171

Fig. 2 Triple-shape memory polymers [23]

(Ttrans = ca. 65 °C) [53], and polyhedral oligomeric silsesquioxane (POSS)-

poly(ethylene glycol) (PEG) (Ttrans = 55 °C) [54].
(d) Physically linkaged semi-crystalline block copolymers (Class IV)
This class is similar to Class III; but, the melting temperature (Tm ) of the
soft portion exhibits as Ttrans.. The examples of the materials in this class are
polyurethane (PU)- poly(tetramethylene glycol) (PTMG) with 1,4 butanediol
(Ttrans = 0–46 °C) [55], and polyurethane (PU)-PCL diol with 1,4 butanediol
(Ttrans = ca. 60 °C) [56].
Based on the number of temporary shape of the materials, shape memory poly-
meric materials can be categorized into two main types. In case of dual shape memory
polymers as shown in Fig. 1, only one temporary shape is presented; the triple-shape
and multi-shape memory polymers have more than one temporary shape as shown
in Fig. 2 [57–59].

2.2 Benzoxazine-Based Shape Memory Polymers/Blends

Benzoxazine resins (BA-a) has been well known as a novel kind of thermosetting phe-
nolic resin. The monomer of BA-a can polymerize by heating without any need of cat-
alyst or curing agent. Polybenzoxazine (PBZ) exhibits many outstanding characteris-
tics such as high thermal stability and high mechanical properties with good process-
ability from low viscosity before curing; this noble polymer with high glass transition
temperature (Tg ) provides great potential for many usage areas [60]. Polybenzox-
azine can be used as shape memory materials due to its chemical crosslink structure
related to permanent shape for SMPs [61]. Recently, two siloxane-containing PBZ
172 S. Tiptipakorn and S. Rimdusit

types (i.e., poly(TMDSBPDP-a) and poly(TMDSBPDP-m)) were synthesized from

the reaction between a siloxane-containing ortho-substituted diphenol, formalde-
hyde, and either aniline or methylamine [62]. Both of them show one-way dual
shape memory behavior with excellent shape fixity ratios (ca. 100%) in tensile and
bending modes. The Tg values of poly(TMDSBPDP-a) and poly(TMDSBPDP-m)
are 53 and 39 °C, respectively. In the recent year, shape memory polybenzoxazines
were developed from polyetheramine (PEA), formaldehyde and one of five different
compounds, i.e., phenol, o-allylphenol, o-cresol, p-cresol, and m-cresol [61]. All
five PBZ-based materials exhibit one-way dual shape memory behaviors. From the
dynamic mechanical analysis, the glassy moduli of PBZ synthesized from p-cresol
and o-cresol are close and lower than the other three types of PBZ. The Tg values
are ranged from 40 to 97 °C. The difference in the chemical structure affects shape
memory behaviors. From the three thermomechanical cycles in a tensile mode, the
two PBZ based on the ortho-substituted phenols could exhibit better shape mem-
ory effect than those based on para- and meta-substituted phenol and unsubstituted
phenol. The PBZ based on o-cresol provides the greatest values of shape fixity ratio.

2.2.1 Polybenzoxazine/Epoxy Alloy-Based SMP

One of the intriguing characteristics of polybenzoxazine is its wide molecular

design flexibility and ability to be alloyed with other polymers such as epoxy and
polyurethane. Moreover, the novel phenolic thermoset has been reported to act as a
curing agent with epoxy [63]. That could be attributed to the fact that the phenolic
products generated from the thermal polymerization of benzoxazine monomer could
have a function as a hardener of the curing process of epoxy [64]. Also, the synergistic
behaviors for some properties of copolymers between benzoxazine and epoxy were
reported [65, 66]. Epoxy resins are thermosetting polymers containing more than
one epoxide functional groups per molecule [67]. Typically, the epoxy resins pos-
sess preferable characteristics, such as low viscosity, low shrinkage, good chemical
resistance, high adhesive strengths, great mechanical properties, and high electrically
insulative properties. In a pioneering work, Rimdusit and Ishida [64] reported the
synergistic behaviors of the Tg of ternary systems based on benzoxazine, epoxy, and
phenolic resins. The maximum of Tg was presented at approximately 180 °C in the
mass ratio of benzoxazine/epoxy/phenolic at 5/4/1. The Tg of neat polybenzoxazine
was reported at ca. 160–170 °C, and that of phenolic Novolac was at ca. 170 °C.
The Tg of EPON825 epoxy resin was in the range of 100–170 °C. Because syner-
gistic behavior was observed in both the binary of benzoxazine and epoxy resins
[68]. The effects of benzoxazine resin and Jeffamine D230 mol ratios on thermal
stability, mechanical and shape memory properties were investigated later by Rim-
dusit et al. [69]. From Table 3, the notation of E, N, D, and B stands for EPON 826
(aromatic epoxy), NGDE (alphatic epoxy), Jeffamine D230 (curing agent) and BA-a,
respectively. The researchers reported that the increase of BA-a content leads to the
increase in storage modulus, crosslink density, and Tg . They also reported that the
recovery time was shortened with increasing epoxy contents. At high temperature,
Thermal Stability of Shape Memory Polymers … 173

Table 3 Storage modulus, crosslink density, and glass transition temperature (Tg ) of benzoxazine-
modified epoxy SMP [69]
Molar ratio of Storage modulus at Crosslink density Tg from DMA
E:N:D:B 35 °C (GPa) (mol/cm3 ) analysis (°C)
1:1:0:1 4.70 4.29 × 10−3 120
1:1:0.2:0.8 4.62 3.81 × 10−3 92
1:1:0.4:0.6 4.44 3.79 × 10−3 85
1:1:0.6:0.4 4.34 3.62 × 10−3 80
1:1:0.8:0.2 3.90 3.25 × 10−3 72
1:1:1:0 3.18 2.90 × 10−3 47

the movement of chain segments was accelerated with heat, leading to increase the
recovery force on the samples [69].
In general, the aromatic epoxy was used in the epoxy-based SMPs. How-
ever, Tanpitaksit et al. [70] recently fabricated SMP derived from polybenzoxazine
(PBZ)/NGDE epoxy alloys without the use of aromatic epoxy. Benzoxazine resin
(BA-a) was used as the curing agent and a stable network segment in the system [67].
From FTIR spectra, the network formation between BA-a and NGDE aliphatic epoxy
after thermal cure were observed [70]. The breakage of a C–O bond in the oxazine
ring of BA-a resin was observed, and then a network structure generated. The epoxide
functional group could form ether linkage with phenolic hydroxyl group. The chem-
ical structure rings of both benzoxazine resin and aliphatic epoxy can be opened, and
the curing process was conducted without other curing agents [71, 72]. These results
were corresponding to the previous works of Rimdusit et al. [64] and Kimura et al.
[73] using the different epoxy types. The polymerization of BA-a monomers and
the chemical reaction between benzoxazine monomer (BA-a) and aliphatic epoxy
(NGDE) were proposed in Fig. 3, respectively.
For the DMA thermogram [67], the storage moduli at room temperature (at glassy
region) were observed ranging from approximately 2.8 to 4.5 GPa at BA-a contents
ranging from 30 to 50 mol%. The values tended to increase with increasing BA-a
content in the alloys because of the addition of the more rigid molecular segment
of PBZ in the alloy SMPs [74]. The addition of BA-a resin from 30 to 50 mol%
could also systematically increase the modulus in rubbery plateau region in the
range from 40 to 172 MPa due to significant improvement of crosslink density of
the alloy. The crosslink density can be predicted from the storage modulus curve
at high rubbery plateau over 107 Pa according to the equation proposed by Nielsen
[75]. From the calculation, the crossslink density of the alloys was increased with
increasing BA-a content ranging from 3.8 × 10−3 to 6.0 × 10−3 mol/cm3 . The
enhancement of crosslink density could lead to an increase in char formation upon
thermal decomposition [44, 45]. Furthermore, the great value of crosslink density
leads to the high values of storage modulus and Tg . That is attributed to higher rigidity
in the molecular structure of PBZ component [76]. Moreover, the increase in Tg value
directly reflected that the segmental mobility of polymer chains was decreased, and
174 S. Tiptipakorn and S. Rimdusit

Fig. 3 Proposed synthesis reaction of BA-a/epoxy copolymer [73]

the stiffness of the alloys was increased with increasing crosslinked density upon
increasing benzoxazine component in the alloy. Additionally, the peak height of
the loss tangent curve was reported to decrease with increasing the benzoxazine
content, indicating that the elastic behavior of the alloys was increased with the
benzoxazine component. It could be noticed that the width at half height of the
curves was increased, when increasing the amount of benzoxazine. That implied
more network heterogeneity was observed when benzoxazine was added in the resin
mixtures. The single broad switching transition region in some ratios when alloying
epoxy with benzoxazine could have some benefits to provide multiple-shape memory
Thermal Stability of Shape Memory Polymers … 175

effects [77], which are highly beneficial for various applications, e.g., packaging
and robotic uses. For the SMPBs derived from the NGDE/PBZ alloys, the shape
recovery time of the SMPs was ranged from 75 s at Tg (of 51 °C for 30 mol% BA-
a) to 145 s at Tg, (of 140 °C for 50 mol% BA-a), and ranged from 64 to 120 s at
Tg + 20 °C [70]. That means shape recovery time was shortened with increasing
the active temperature. That was attributed to the fact that the activated molecular
chain segments intensely moved with increasing temperature. In addition, the shape
recovery time was increased with increasing BA-a content because the molecular
chain segment of the alloys could be impeded with increasing crosslink density.
Comparatively, the recovery times of the SMPBs derived from benzoxazine alloyed
with aliphatic epoxy were less than that of the SMPs of neat epoxy resin E-51 (WSR
618) cured by aromatic amine as reported by Liu et al. [78]. In the alloy system,
the addition of BA-a component into SMP was able to adjust the shape recovery
time, and broaden the applications of the resulting alloy SMPs. The shape fixity of
NGDE/PBZ alloys-based SMPBs was reported to be almost 100%. Moreover, their
flexural strength and flexural modulus were increased with the increase of BA-a
content. From the study, the NGDE/PBZ SMPs possess flexural strength ranging
from 52 MPa (for 30 mol% BA-a) to 132 MPa (for 50 mol% BA-a), and flexural
modulus ranging from 1.6 GPa (for 30 mol% BA-a) to 4.0 GPa (for 50 mol% BA-a).
That was attributed to the fact that flexural strength and flexural modulus of pure
PBZ are as high as approximately 126–139 MPa and 4.5–5.8 GPa, respectively. In
addition, it was due to an enhanced crosslink density of the obtained polymer network
as previously described.

2.2.2 Shape Memory Epoxy Polymers

For many years ago, Wu et al. [79] prepared shape memory epoxy polymers by
mixing epoxy resin at varied hardeners contents, i.e., 27–41 wt%. The Tg values of
the fabricated SMP sheet were in the range of 75–114 °C and increased with the
hardener content. The decomposition temperature at 10% weight loss from TGA
thermograms were reported to be over 300 °C for all SMPs. The obtained epoxy
SMP possesses a high thermal stability possibly due to the component of the network
structure. Later, Lu et al. [80] prepared the epoxy SMPs based on diglycidyl ether
of bisphenol A (DGEBA) and tricarballylic acid. The SMP system obtained the
modulus of 1.3 GPa at room temperature and was thermally stable up to 380 °C.
From the thermomechanical cycle test for the epoxy SMPs, the compressive stress
was 2.3 MPa when the strain was 10% at elevated temperature. Recently, Kuang et al.
[81] prepared a series of tripe-shape memory epoxy materials through the reaction
of a conventional epoxy oligomer, an aliphatic diamine and a diamine Dielse–Alder
(DA) adduct cross-linker via a one-pot approach with varying the molar ratio of the
diamine adduct cross-linker from 33 to 67. The thermal resistance of epoxy polymers
was reported as the degradation temperature at 2% weight loss (Td2 ). The values for all
epoxy-based SMPs were greater than 280 °C. The char yield at 600 °C was increased
with increasing the DA adduct content. One stage of weight loss was found in the
176 S. Tiptipakorn and S. Rimdusit

Maximum decomposition temperature ( C)

Fig. 4 Initial decomposition 400 400

Initial decomposition temperature ( C)

temperature and maximum

o
decomposition temperature
at various triblock
copolymer contents [84] 350 350

300 300

250 250

o
200 200
0 10 20 30 40 50
Triblock Copolymer Content (wt%)

range of 393–411 °C. The service temperature of this system could be less than 160
°C [81, 82]. In the recent year, Parameswaranpillai et al. [81] prepared the SMPB
system of poly(propylene glycol)-block poly(ethylene glycol)-block-poly(propylene
glycol) (PPO-PEO-PPO) triblock copolymer blended with DGEBA epoxy. They
reported that the blends possessed UV resistance and high thermal stability. The
glass transition temperature of the blends could be tunable as the composition ratio
of the components. In addition, the parameters from TGA analysis were reported
as shown in Fig. 4. It could be observed that the initial decomposition temperatures
of the SMPBs was decreased with the addition of the triblock copolymer. However,
it was reported that there was no significant difference between the temperatures at
maximum decomposition rate of the blends at all triblock copolymer contents [81].
In the recent time, Wei et al. [83] reported that the hydrogenated bisphenol A epoxy
resin with different curing agents provided better shape memory properties than
bisphenol A epoxy resin. The hydrogenated bisphenol A possesses lower Tg , greater
toughness, and much higher shape recovery rate because of its rigidity cyclohexane
rings in the chemical structure.

2.2.3 SMPBs from Bio-Based Polybenzoxazine/Bio-Based Epoxy

Copolymer

As previously mentioned, Tanpitaksit et al. [70] fabricated SMPs from aliphatic

epoxy modified with benzoxazine resin. They reported that benzoxazine resin was
acted as a curing agent and a stable network segment which has the ability to enhance
the properties of SMPBs, such as outstanding shape fixity, and short recovery time.
However, these kinds of rendered products are petroleum-based materials. Due to
environmental concern, there has been an idea to develop renewable natural mate-
rials as an alternative choice to reduce the consumption of petroleum-based prod-
Thermal Stability of Shape Memory Polymers … 177

ucts. These bio-based resins have attracted increasing attention due to low cost and
biodegradability of the products [82] In the recent time, bio-based polybenzoxazine
was synthesized by using natural compounds such as cardanol [85, 86], vanillin [87,
88], furfurylamine [89], stearylamine [89], and eugenol [89], Recently, Sini et al.
[87] prepared monofunctional benzoxazine based on vanillin and furfurylamine. The
obtained bio-based benzoxazine with highly crosslinked structure showed a lower
curing temperature, extremely higher Tg and higher char yield than petroleum-based
benzoxazines. Thirukumaran et al. [89] synthesized and investigated the proper-
ties of bio-based benzoxazine monomer systems based on eugenol, furfurylamine
and stearylamine.They successfully synthesized bio-based benzoxazine monomers
(F-BZ and S-BZ) via a solventless method. Both the F-BZ based polybenzoxazine
(PF-BZ) and the S-BZ based polymer (PS-BZ) exhibited excellent flame retardant
properties. However, PF-BZ possessed much higher thermal stability than PS-BZ.
Not long ago, Hombunma et al. [90] prepared two bio-based alloys, i.e., the
eugenol and furfurylamine-based polybenzoxazine/NGDE epoxy. The related char-
acteristics of bio-based shape memory polymer such as shape fixity, shape recovery,
thermal and mechanical were determined. Eugenol-based benzoxazine resin (E-fa)
was synthesized from eugenol, furfurylamine and formaldehyde at the mole ratio of

Fig. 5 Synthesis reaction of E-fa monomer [90]

178 S. Tiptipakorn and S. Rimdusit

Fig. 6 Proposed chemical reaction between E-fa monomer and NGDE epoxy resin [90]

1:1:2 as shown in Fig. 5. Then, the mixture was heated and stirred until a homo-
geneous mixture was obtained. The chemical reaction between E-fa monomer and
NGDE epoxy resin are presented in Fig. 6. The obtained E-fa monomer was pale
yellow. The copolymers were prepared by mixing E-fa monomer with NGDE.The
thermally cured films of the mixture were obtained. The IR spectra of E-fa based
benzoxazine monomer displayed the peak at 1226 cm−1 from the aromatic ether
C–O–C stretching mode of an oxazine ring. The peak at 919 cm−1 confirmed the
presence of a benzene ring attached with an oxazine ring. The spectrum showed a
peak at 1151 cm−1 from the C−N−C symmetric stretching vibrations. The peaks
observed at 1001 and 738 cm−1 might be attributed to the vibrations of the furan ring
[89].
From the analysis of the thermomechanical properties of E-fa based polybenzox-
azine alloyed with NGDE, the modulus of the alloys was increased with increasing
E-fa content because of the high rigidity of E-fa. The glass transition temperature
(Tg ) observed from the peak of loss tangent as exhibit in Fig. 7. It could be noticed
that the Tg values were added from 26 to 51 °C when E-fa was increased from 30
to 50 wt%. That was because the greater rigidity segment of E-fa hindered chain
mobility of the polymer [91]. The thermal degradation, char yield and shape fixity of
the E-fa based polybenzoxazine (poly(E-fa)) alloyed with NGDE was summarized
in Table 4. It could be noticed that the increase of E-fa content led to the increase of
thermal stability, while the shape fixity of the obtained alloys was ca. 98–99%.
Thermal Stability of Shape Memory Polymers … 179

Fig. 7 Loss tangent of

NGDE alloys at various E-fa 0.8
contents: (▲) 30 wt%, (▼)
40 wt%, and () 50 wt%
[91]
0.6

Loss tangent
0.4

0.2

0
-50 0 50 100
o
Temperature ( C)

Table 4 thermal stability and E-fa Td,5 (°C) Residual weight Shape fixity (%)
shape fixity properties of content (%)
poly(E-fa/NGDE) alloys [91]
0 196 5 –
30 269 18 98.0
40 271 22 98.7
50 279 28 98.7
100 310 43 –

In the recent year, Rimdusit et al. [92] successfully prepared the shape memory
polymer from vanillin-based polybenzoxazine alloyed with castor oil-based epoxy
copolymer. Vanillin-based benzoxazine resin (V-fa) was synthesized from vanillin,
furfurylamine and formaldehyde at a mole ratio of 1:1:2 according to the patented
solventless method as shown in Fig. 8. The copolymer was prepared by mixing V-fa
monomer with epoxidized castor oil (ECO) at various contents ranging from 30 to
50 wt%. The thermal curing was conducted without other chemicals needed. The
reaction between two polymeric components was proposed as shown in Fig. 9. The
thermal stability of the V-fa/ECO copolymer can be exhibited as shown in Table 5. It
could be noticed that the thermal degradation at 5% weight loss (Td5 ) was decreased
from 318 to 314 °C at the ECO content ranging from 30 to 50 wt%. In addition, the
char yield at 800 °C was decreased with increasing ECO. In this system, the shape
fixity at 25 °C decreased with increasing ECO content ranging from 93 to 86%.
While the shape recovery at Tg + 20 °C was increased ranging from 87 to 96%.
180 S. Tiptipakorn and S. Rimdusit

Fig. 8 Proposed synthesis reaction of E-fa monomer [92]

Table 5 Thermal properties ECO content (wt%) Td,5 (°C) Char yield (%)
of V-fa/ECO copolymer at
various ECO contents [92] 30 318 48
40 317 35
50 314 34

2.2.4 Polybenzoxazine/PU Alloy-Based SMP

In the recent year, Erden and Jana prepared the SMP from polybenzoxazine (BA-a)
compounded with polyurethane. They reported the ability of polybenzoxazine to act
as an additional hard portion of SMP because of its high glass transition temper-
ature and much higher storage modulus than the soft portion of SMP [93]. It has
been reported that the alloys between bifunctional BA-a monomer and urethane pre-
polymer exhibited only one glass transition temperature (Tg ), indicating no phase
segregation between two components. Moreover, only small amount of added ben-
zoxazine could enhance the thermal stability of the polyurethane [76]. The hydroxyl
group of benzoxazine resin generates ether linkage with the isocyanate group of
urethane prepolymer as demonstrated in Fig. 10. In the alloy system, the synergistic
behaviors of Tg value was observed. For instance, the alloy at PU content of 30 wt%
showed the Tg at ca. 220 °C, which was greater than −70°C of neat PU and 165 °C
of pure polybenzoxazine [94, 95].
Thermal Stability of Shape Memory Polymers … 181

OH
O O
O N
O

H3CO O
O

+ O OH

O OH
O
CHO
O

V-fa Epoxidized
CHO

OCH3

O N O OH
CHH
3 2C O
O
CHO
O
OCH3

O N O OH
CHH
3 2C O

O
CHO
O
OCH3

O N O OH
CHH
3 2C O
O

V-fa benzoxazine/Epoxidized castor oil

Fig. 9 Proposed chemical reactions between V-fa and epoxidized castor oil [92]

The properties of shape memory polymer from polyurethane (PU) has been inves-
tigated and reported for a long period of time. Lee et al. [55] studied the thermome-
chanical properties of shape memory polyurethane (PU) block copolymers composed
of 4,4-methylenebis-(phenylisocyanate), and poly(tetramethylene glycol). The 1,4-
butanediol was used as a chain extender. The maximum stress, tensile modulus,
elongation at break, and highest loss tangent was observed at 30 wt% of hard seg-
ment content. It has been reported that the type of chain extender has an effect
on the properties of SMP. In some studies, the pyridine rings in the chemicals
such as 2,6-pyridinedicaroxamide was used as a chain extender to synthesize lin-
ear and crosslinked polyurethane. The thermal stability from TGA analysis was
significantly enhanced [96]. Recently, Weng et al. [97] prepared 2,6-diaminoyridine
and 4-hydroxybenaldehyde to provide the pyridine-containing chain extender N,
N’-bis(4-hydroxybenylidene)-2,6-diaminopyridine (BHBP). The hydrogen bonding
was generated between nitrogen atoms of pyridyl and imine functional groups and
N-H functional group of polyurethane. This could improve the thermal stability and
mechanical properties of the obtained polymers. In their system, polytetramethy-
lene glycol (PTMG) and 4,4 -diphenylmethane diisocyanate (MDI) were used as
reactants to synthesize PU prepolymer. Then, the reaction between BHBP and the
prepolymer was proceeded as shown in Fig. 11. In the study, the greater content of
182 S. Tiptipakorn and S. Rimdusit

O
CH3
O C N (CH2)8 N C O + R' N
C
Urethane Prepolymer N R'
CH3
O
Bifunctional
BA-a monomer

O O
H H
C N (CH2)8 N C
O O

N N
R' N
R
R
H3C C CH3 3HC C CH3

R'
R
N
N

O O
C NH (CH2)8 NH C
O O

Poly(benzoxazine-urethane) Alloy

Fig. 10 Proposed chemical reaction between BA-a monomer and urethane prepolymer [76]

Table 6 Thermal decomposition onset temperature, temperature at maximum decomposition rate,

and char yield at various amounts of chain extender [97]
MDI (mol) PTMG BHBP (mol) Td , onset (°C) Td , max (°C) Char Yield at
(mol) 700 °C (%)
4 3.50 0.50 334 403 3.5
4 3.25 0.75 338 408 8.5
4 3.00 1.00 342 413 9.2

BHBP could provide higher value of molecular weight and the greater percentage of
hard segment in the obtained polymer. From TGA analysis, the thermal properties
of the polyurethane at different BHBP contents were presented in Table 6.
Thermal Stability of Shape Memory Polymers … 183

Fig. 11 Proposed chemical reaction between BHBP and PU prepolymer [97]

2.2.5 Multiple-Shape Memory Polymers

As previously mentioned, multiple-SMPs possess more than one temporary states.

Two procedures are proposed for the design of multiple-SMPs, i.e., (i) a very wide
range of thermal transition temperature, and (ii) multiphase design which each of
them provides independent transition and correspond to shape memory effect [98].
Recently, many multiple-SMP systems have been studied. Xie [99] presented that the
perfluorosulphonic acid ionomer (PFSA), possessing only one wide glass transition
temperature region starting from 55 to 130 °C, revealed multi-shape memory effects
without any adjustment of the material composition. Hoeher et al. [100] prepared the
crosslinked polyethylene blends composed of ethylene-1-octene copolymers (EOC),
low density polyethylene (LDPE), and high density polyethylene (HDPE). The mass
ratio of EOC: LDPE: HDPE in the blends was 80:15:5. The results reveal that the
programmed material exhibits an excellent recovery ratio of 99.7 ± 0.3%. In addition,
a wide transition temperature region of triple-shape memory starting from 35 to 150
°C. In the recent year, Samuel et al. [101] prepared SMPs from the miscible polymer
blends between poly-L-lactic Acid (PLLA) and poly(methyl methacrylate) (PMMA).
The mass blending ratio of PLLA: PMMA at 50:50 could provide the broadest region
of glass transitions temperature starting from 60 to 100 °C. Lee et al. [55] synthesized
shape memory polyurethane (PU) block copolymers composed of 4,4-methylenebis-
(phenylisocyanate), and poly(tetramethylene glycol) via a two-step process. The
1,4-butanediol was used as a chain extender. The obtained SMPs exhibited multiple-
184 S. Tiptipakorn and S. Rimdusit

Table 7 Glass transition BA-a:PU mass Tg (°C) Tg range (°C) Tg (o C)

temperature of BA-a/PU ratio
copolymers at various
contents [94] 55:45 130 120–220 100
60:40 135 100–214 114
70:30 157 90–180 90
80:20 180 80–180 100
100:0 170 130–190 60

shape memory effect. When the hard segment of PU was increased from 30 to
45%, the Tg and shape fixity were reported to be increased in the range of −3.6 to
0.3 °C and 89 to 92%, respectively. Moreover, the shape recovery of 80–95% was
obtained. Erden and Jana [93] examined the properties of SMPs from polyurethane-
polybenzoxazine copolymer synthesized form 4,4 -methylenebis phenyl isocyanate
(MDI), polytetramethylene glycol (PTMG), and benzoxazine (BA-a) monomer. The
1,4-butanediol was applied as a chain extender. When MDI and PTMG were kept at 5
and 1 mol, respectively, it was reported that the hard segment of SMPs was increased
with BA-a contents. A single peak of loss tangent from the dynamic mechanical
analysis (DMA) revealed an increase in Tg (51, 65, and 91 °C) with increasing BA-a
content (at 0, 0.5, and 1 mol, respectively).
From the work of Rimdusit et al. [94], not only the synergism of glass transi-
tion temperature was observed in the benzoxazine-urethane copolymers, the broad
region of glass transition temperature was shown in the range of 90–110 °C at PU
content of 0 to 40 wt%. This characteristic was important for the determination of
the number of temporary shapes for the multiple-shape memory system. Recently,
Prathumrat et al. [102] determined the feasibility of benzoxazine-urethane copoly-
mers as multiple-shape memory polymers. The thermal stability of the copolymers
was shown as Fig. 12. It could be noticed that the addition of BA-a content could
lead to an increase in both degradation temperature at 5% weight loss (Td5 ) and char
yield at 800 °C of the alloys. For instance, the Td5 value and char yield of the alloy at
BA-a/PU weight ratio of 55:45 were reported to be 268 °C and 16.2%, respectively.
While those of the alloy at 80:20 were presented at 333 °C and 24.6%, respectively.
They reported that the suitable curing conversion of the alloy mixture could affect the
shape memory behaviors. From the testing result of the flexural strength and flexural
modulus at various temperature of the alloys, the mechanical properties are increased
with increasing BA-a content. The glass transition temperature range observed from
loss tangent of DMA for pure polybenzoxazine and BA-a/PU copolymers are pre-
sented in Table 7. The broadest range of glass transition temperature was reported at
suitable composition.
Recently, Zhuo et al. [103] prepared the novel multiple-SMPs from the copoly-
mer of 2-methoxyethyl acrylate and N-methylol acrylamide with different molar
fractions of acrylate component. The physical crosslinks generated by entanglement
and hydrogen boding between the polymeric chains. With increasing acrylamide con-
Thermal Stability of Shape Memory Polymers … 185

Fig. 12 Thermal 400

degradation temperature at 48
5% weight loss (Td5 ) and
char yield at 800 °C of 360
40
benzoxazine-urethane

Char yield (%)

multiple-SMPs at various PU 320

( C)
contents [102] 32

o
d5
T
280
24

240
16

200
0 10 20 30 40 50
PU content (wt%)

tent, the Tg values were increased in the range of 7.5–55.2 °C, and the tensile strength
enhanced from 10.7 to 71.5 MPa. They also reported that the obtained multiple-SMPs
presented superior multiple-shape memory effect in a broad range of temperature.
The recovery ratio was reported at greater than 93%, and the fixing efficiencies was
closed to 100%. The obtained multiple-SMPs could be a good candidate for the
uses in potential deployable structure. At a recent time, Zheng et al. [104] prepared
the multiple-SMPs by means of the multilayer between thermoplastic polyurethane
(TPU) and co-continuous poly(bytylene succinate) (PBS)/polycaprolactone (PCL)
blends. The shape fixity and recovery ratio of obtained dual- and triple-SMPs were
increased with increasing the number of layers, and reported at 95% and 85%, respec-
tively at the number of layers of 128. They also reported that the multilayer systems
could have greater shape fixity and recovery ratio than those of the blending system
at the same components.

2.2.6 Polyimide-Based SMP

Polyimide is a kind of engineering polymers possessing high thermal stability and

mechanical properties. In the recent years, Xiao et al. [105] synthesized shape
memory polymer based on polyimide with tunable glass transition temperature in
the range of 299–322 °C. In their study, the thermoplastic polyimide-based SMPs
were prepared by polycondensation reaction between 4,4 -(hexafluorisoproylidene)
diphthalic anhydride (6FDA) and 4,4 -diaminodiphenyl ether (ODA). Other sys-
tems of the polyimide-based SMPS from bisphenol A dianhydride (BPADA) and
4,4 -diaminodiphenyl ether (ODA) were also prepared [106]. The ether bonds
within the backbone were acted as recovery phase of shape memory effect, while
the high molecular weight of polyimide could generate physical crosslinking as
fixed phase. They also prepared the thermoset polyimide-based SMPs by using
tris(4-aminophenyl)amine (TAP) cross-linker. From their report, the thermosetting
186 S. Tiptipakorn and S. Rimdusit

Table 8 Glass transition temperature and degradation temperature of SMPs based on ODA/6FDA
polyimide and ODA/BPADA polyimide [105, 106]
ODA/6FDA Shape memory polyimide
Molar ratio of ODA/6FDA 0.9250 0.9400 0.9625 0.9825
Thermoplastic ODA/6FDA Tg (°C) 299 304 311 304
Td5 (°C) 510 510 515 522
Thermoset ODA/6FDA Tg (°C) 322 323 322 321
Td5 (°C) 519 520 517 518
ODA/BPADA shape memory polyimide
Molar ratio of ODA/BPADA 0.9100 0.9250 0.9550 0.9850
Thermoplastic ODA/BPADA Tg (°C) 229 231 234 236
Td5 (°C) 486 488 490 491
Thermoset ODA/BPADA Tg (°C) 240 241 243 242
Td5 (°C) 495 497 501 499

polyimide-based SMP rendered higher storage modulus and greater shape memory
effect than the thermoplastic polyimide-based SMP because of its chemical crosslink-
ing and high crosslink density. As shown in Table 8, the degradation temperatures
at 5 wt% loss (Td5 ) for all polyimide-based SMPs were over 500 °C. Compara-
tively, the glass transition temperature values of thermoset polyimide-based SMPs
were over 320 °C, being higher than those of thermoplastic ones. Moreover, it was
reported that the residual weights for both polyimide systems were over 50% due
to the remained aromatic group. Another interesting polyimide-based SMPB system
was prepared from 4,4 -(1,1’-biphenyl-4,4 -diyldioxy)-dianiline (BAPB)/bisphenol
A dianhydride (BPADA) in dimehtylformide (DMF) by Kong and Xiao [107]. The
researchers reported that the obtained polyimide could keep high shape fixity and
shape recovery after over 1000 thermomechanical bending cycles. In an aspect of
thermal stability, the degradation temperature at 5 wt% loss was reported at 505 °C,
and the temperature at maximum weight loss was found at ca. 536 °C. That confirmed
that the obtained polyimide-based SMPB possessed greater thermal stability.

3 Shape Memory Polymer Composites and Their Thermal

Characteristics

3.1 A Brief Overview of SMPCs

As previously mentioned, shape memory polymers generally had some shortcomings

on their low recovery stress and low mechanical performance. These drawbacks are
able to limit the applications of smart materials. The addition of reinforcing fillers in
Thermal Stability of Shape Memory Polymers … 187

the polymeric matrix to form shape memory polymer composite (SMPC) is able to
enhance recovery stress and mechanical characteristics [74]. Currently, SMPCs have
been developed to gain potentials for a broad range of usage areas such as deployable
components in aerospace, smart textiles, automobiles, actuators, and medical devices
[2]. Moreover, many patents related to the uses of SMPCs (such as intravascular
delivery system, hood/seat assembly, and tunable automotive brackets in vehicles)
have been issued [108, 109]. Generally, two main types of SMPC can be categorized
as particle-filled SMPC and fiber-filled SMPC [2].

3.1.1 Particle-Filled SMPCs

The particle-filled SMPC are developed with many types of reinforcing elements
in forms of particulate matter, such as carbon black, carbon nanotubes, carbon
nanofibers, silicon carbide, nickel powder, ferromagnetic (Fe3 O4 ), and clay in order
to meet various requirements for practical applications [30, 110–112]. The particle-
filled SMPCs typically are developed for certain specific functions, e.g., great elec-
trically conductive characteristic, magneto-responsive properties, etc. Therefore, the
smart materials with multifunctional properties have been developed with particle-
filled SMPCs [2]. Generally, this type of SMPCs is not applied for structural mate-
rials, but it is for some specific characteristics. The examples of the particle fillers
possessing particular functions for SMPCs are electrically conductive carbon black,
carbon nanotubes, and nickel powders, which are incorporated for fabricating elec-
troactive SMPs. While Fe3 O4 filler is added to generate magnetism induced SMPs
[2]. Additionally, silicon carbide (SiC) with dielectric properties is composited with
SMPs to develop microwave-induced SMPs [113].

3.1.2 Fiber-Filled SMPCs

As mentioned above, SMPCs embedded with particles or short fibers are not suitable
for using as structural materials. On the other hand, significant improvement in
stiffness, strength, and resistance against relaxation and creep can be obtained in the
SMPCs reinforced with continuous fiber. The fiber-filled SMPCs have high potential
for many advanced applications such as the use in deployable structures including
antennas and solar arrays [2].

3.2 Epoxy-Based SMPCs

Epoxy resin is thermoset polymers used in many industrial fields, e.g., adhesive, coat-
ing, and sealant due to its high adhesive properties, good thermal and mechanical
properties [114]. The recent researches had focused on the properties modification of
SMP. Nowadays, shape memory epoxies have gained much attention from industrial
188 S. Tiptipakorn and S. Rimdusit

researches. This kind of SMP provides higher properties than other shape memory
polymers (such as polyurethane, and styrene rubber systems) due to great thermal,
thermo-physical and mechanical characteristics with its easiness for fabrication. For
instance, the systems of SMP based on aromatic epoxy, aliphatic epoxy and curing
agent (Jeffamine D230) have been reported to exhibit good shape fixity and, the com-
plete shape recovery [115]. Although many types of epoxy resins have been known,
diglycidyl ether of bisphenol A (DGEBA) is the most common type for fabrication
of SMPs [116].The systems of thermoset epoxy filled with functional filler have been
studied for a long period of time. Gall et al. [117] successfully prepared the epoxy-
based SMPs nanocomposites filled with silicon carbide nano-filler. They reported
that the increase in SiC content led to the improvement of elastic modulus and
bending recovery force in the composites. In the later year, Athimoolam and Moor-
thy [116] successfully prepared the SMPCs from epoxy blended with polyurethane
filled with amine treated nanoclay. They reported that the thermal stability of the
composite was improved with the addition of nanoclay filler. Recently, Liu et al.
[118] prepared a series of SMPC based on polymeric mixture between DGEBA
and metylhexahydrophthalic anhydride (MHHPA) filled with multi-walled carbon
nanotube (MWCNT). The molar ratios of DGEBA/MHHPA were varied from 0.5
to 1.2, while the MWCNT nano-filler contents were in the range of 0.25 to 0.75
wt%, respectively. The Tg values of the obtained nanocomposite SMPCs were in the
broad range from approximately 65 to 140 °C. From the thermogravimetric analysis,
the starting degradation temperature (at approximately 2 wt% loss) of the blends
at the DGEBA/MHHPA ratio of 0.5 (ca. 243 °C), which was less than that of the
blends at the ratio of 1.0 (ca. 335 °C). This could be due to the amount of uncured
epoxy providing less thermal stability. The temperature at the high decomposition
rate for all studied samples was found at ca. 412 °C. Furthermore, the increase of
nano-filler content in the studied range could lead to a slight improvement in decom-
position temperature [118]. Later, Chen et al. [119] prepared the nanocomposites
of shape memory polymer based on epoxy filled with thermally reduced graphite
oxide (TGO). They reported that added TGO nano-filler could provide the 41–71%
enhancement of the modulus and 44–64% improvement of tensile strength with 1–3
wt% TGO. The thermal stability of the obtained SMPCs was significantly improved
when applying 1–2 wt% of TGO. This could be due to barrier effects of TGO filler
[120]. The nano-filler, which possesses high surface area, could act as a barrier to
prevent the displacement of broken polymeric chains, and impede the diffusion of
volatile products and generate the char [121]. However, the amount of 3wt% TGO
could lower the thermal stability of the SMPCs. The possible reasons could be due to
the partial aggregation of the nano-filler. Furthermore, the high loading of TGO filler
could provide higher thermal conductivity than polymeric matrix. That could sup-
port the thermal degradation of the SMPCs [122]. In the recent year, the electroactive
shape memory polymers composites from epoxy/cyanate ester nanocomposites filled
with graphene were prepared by Wang et al. [123]. The graphene was dispersed in
N,N- dimethylformamide and then the mixture was fed into the polymeric mixture
to fabricate the SMPC. They reported that the incorporation of graphene could lead
to the enhancement of the shape memory behavior. In addition, the degradation tem-
Thermal Stability of Shape Memory Polymers … 189

perature of the nanocomposite-based SMP was improved with the nano-filler. The
reason for the improvement of thermal stability was related to the tortuous path effect
of the nano-filler, which could be able to form the char and impede the diffusion of
volatile degradation products [123, 124].
Not long ago, Biju and Nair [125] fabricated the SMPCs from the reaction
between DGEBA epoxy and pyromellitic dianhydride (PMDA). Carboxyl telechelic
poly(tetramethylene oxide) (PTAC) was used as the polymer precursor. They reported
that the SMPCs for all composition was stable at least 300 °C. In the later year,
the polycaprolactone (PCL)/epoxy-based SMPC microfiber has been developed by
Zhang et al. [126]. In this system, the core layer of epoxy and the shell layer of
PCL were fabricated via coaxial electrospinning. They reported that the entire shape
memory was recovered by only approximately 6 s at 70 °C. From the TGA analysis,
two decomposition steps were observed, i.e., at the range of 300–350 °C exhibiting
the decomposition range of epoxy, and the range of 350–450 °C relating to the PCL
degradation range.

3.2.1 Benzoxazine-Epoxy Alloy-Based SMPCs

As previously mentioned, Tanpitaksit et al. [70] developed SMPs from the alloys
between BA-a and aliphatic epoxy (neopentyl glycol diglycidyl ether, NGDE). In the
system, BA-a was acted as a latent curing agent for epoxy resin. The rendered SMPs
provided high thermo-mechanical characteristic and great shape memory properties.
Recently, Likitaporn et al. [124] studied the characteristics of slicon-carbide whisker
(SiCw )-filled in benzoxazine-epoxy SMPC. The reported that the Tg value from loss
tangent was increased with SiCw contents, i.e., 154 °C (at 0 wt%) to 170 °C (at 20
wt%). Moreover, at Tg + 20 °C and room temperature, the increase in SiCw contents
could lead to an increase of flexural strength and flexural modulus. In addition,
the degradation temperature at 5 wt% loss (Td5 ) and char yield of the SMPC from
benzoxazine-epoxy alloys were increased with increasing SiCw content as shown in
Fig. 13. The degradation temperature at 5 wt% (Td5 ) was systematically increased
from 293 to 303 °C when SiCw filler was increased from 0 to 20 wt%. This is
attributed to the physical barrier effect of SiCw , which could prevent the thermal
transmission, and reduce the escaping rate of pyrolysis products. Moreover, it could
impede the further degradation of the polymeric matrix [42]. For the amount of char
residue at 800 °C, the value was found to increase with increasing SiCw contents, i.e.,
ranging from 28.1 to 43.0% when the filler content varying from 0 to 20wt%. This
phenomenon well corresponded to the rule of mixture. Interestingly, in this system,
the increase of SiCw contents led to shorten the recovery time, i.e., the recovery time
when microwave-induction and conventional heating induction were in the range
of approximately 3.5 to 5 min and ca. 8.5 to 18 min, respectively. Moreover, the
addition of SiCw could drastically enhance the recovery stress from 3.4 MPa (for
neat benzoxazine/epoxy alloy) to 11.2 MPa (at 20 wt% SiCw ). That was attributed to
the intrinsically great elastic modulus of the filler. In addition, the outstanding shape
fixity of approximately 99% was reported in the system.
190 S. Tiptipakorn and S. Rimdusit

Fig. 13 TGA results of 50

SMPCs at various filler 340
contents: (●) Degradation
temperature at 5% weight 40
loss, and () Char Yield 320

Char Yield (%)

[124] 30

T , C
o
300

d5
20
280
10
260
0
0 5 10 15 20
SiC content (%)
w

Table 9 Thermal stability of the BA-a/epoxy alloys reinforced with woven carbon fiber at various
filler contents [127]
Woven carbon fiber content Degradation temperature at 5 Char Yield at 800 °C (%)
(vol.%) wt% loss (°C)
0 306 24.6
23 289 45.6
47 314 63.5
57 323 73.7
100 850 95.4

In recent times, benzoxazine-epoxy alloys filled with carbon fiber has been pre-
pared by Plylaharn et al. [127]. They revealed that the BA-a/epoxy systems could
be reinforced with woven carbon fiber. The shape recovery was reported to be close
to 100%. In their work, the recovery stress of the SMPCs has been enhanced from
3.4 MPa (without reinforcing fiber) to 28.9 MPa (at the filler content of 47 vol.%).
The thermogravimetric analysis of the SMPCs was presented in Table 9. It could be
noticed that the values of Td5 and char yield were increased with the woven carbon
fiber content. This could be due to the thermal properties of carbon fiber.

3.2.2 Polyurethane-Based SMPCs

Polyurethane (PU) is one of the polymeric materials commonly used for fabrication
of SMPCs because of its high strain recovery and good physical properties. More-
over, its versatility can be extended through compositing with other functional fillers.
In recent time, Deka et al. [128] prepared hyperbranched polyurethane (HPU) rein-
forced with multi-walled carbon nanotube (MWCNT). The tensile strength of the
SMPC was 300% higher than that of neat HPU. The notable improvement of thermal
Thermal Stability of Shape Memory Polymers … 191

Table 10 Decomposition temperature of TPU/ABS/MWCNT composites at various compositions

[130]
TPU (wt%) ABS (wt%) MWCNT Td max (°C) Td offset (°C) Char Yield
(wt%) (%)
80 20 0 407 515 4.5
79 20 1 412 544 6.5
77 20 3 413 555 7.4
75 20 5 410 573 10.0

stability, i.e., onset Td of 275 °C for 1 wt% of MWCNT higher than that of 215 °C
for neat HPU. They reported that one degradation step was observed for all SMPC
samples, exhibiting great interactions between nano-filler and HPU matrix. Later,
Mahapatra et al. [129] prepared SMPCs from functionalized HPU reinforced with
graphene oxide (GO) sheet. The GO sheet was functionalized by adding aliphatic
hydroxyl groups on its surface. In general, the reduction of GO could lead to high
thermal stability because of the elimination of the oxygen-containing functional
groups. The addition of GO into the HPU matrix led to the increase of initial decom-
position temperature. The given reason for the enhancement of thermal stability is
the barrier effect that could prevent the permeation of oxygen and the emission of
volatile decomposition products. Moreover, the surface of nano-filler could serve as
a radical remover, leading to the delay of onset Td . In the recent year, Memarian
et al. [130] SMPCs derived from thermoplastic polyurethane (TPU) compositing
with acrylonitrile-butadiene-styrene (ABS) and MWCNT by melt blending process.
The addition of MWCNT into SMPCs could increase the tensile strength and mod-
ulus but decrease the elongation at break. The TGA analysis revealed the thermal
stability as shown in Table 10. It could be noticed that the improvement of the thermal
decomposition temperature was observed because of great thermal stability and high
thermal conductivity of MWCNT.

4 Conclusions

The thermal stability is one of the crucial parameters that can indicate the limitation
for the usage of the shape memory materials (i.e., SMPs, SMPBs, and SMPCs). In
general, the thermal stability could be identified in terms of thermal degradation tem-
peratures, and char yield. For SMP and SMPB system, the chemical structures of the
materials have an effect on the thermal stability, i.e., the aromatic structures and/or
the network structure could provide high thermal degradation and char yield to the
materials. The degradation process is composed of many steps such as initiation,
propagation, and termination steps. For SMPC systems, the thermal stability does
not depend on the individual thermal stability of each component. Some of the phe-
nomena are relevant, e.g., the barrier effect to prevent the oxygen emission, and the
192 S. Tiptipakorn and S. Rimdusit

char formation. This chapter provides the information related to the thermal stability
of high-temperature shape memory materials, i.e., shape memory materials based on
polybenzoxazine, epoxy, polyurethane, and polyimide. Polybenzoxazine is an inter-
esting novel thermosetting resin that could be alloyed with other polymeric such as
epoxy and urethane. Its alloy systems provide high degradation temperature and char
yield. For example, the SMPS based on V-fa/ECO copolymer, the degradation was
over ca. 300 °C with high char yield over 30%. Furthermore, the synergistic behaviors
of Tg for the systems of benzoxazine/epoxy alloys and benzoxazine/urethane alloys
were reported. The SMPs based on polyimide are generally fabricated in forms of
films. It could provide a high decomposition temperature over 400 °C and char yield
over 50%.

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