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 Smart Materials and Structures

Smart Mater. Struct. 32 (2023) 085016 (12pp) https://doi.org/10.1088/1361-665X/ace226

Influence of crystallization on the shape

memory effect of poly (lactic acid)
Rafael Braga da Cunha1,∗, Filipe Rodrigues Pê1, Pankaj Agrawal1,
Gustavo de Figueiredo Brito1,2 and Tomás Jeferson Alves de Mélo1
1
Department of Materials Engineering, Federal University of Campina Grande, Campina Grande,
Paraiba, Brazil
2
Department of Design, Paraiba Federal University, Rio Tinto, Paraiba, Brazil

E-mail: rafaelbragadacunha@gmail.com

Received 5 April 2023, revised 25 June 2023

Accepted for publication 27 June 2023
Published 5 July 2023

Abstract
The objective of this study is to investigate the influence of crystallization on the shape memory
effect (SME) of poly (lactic acid) (PLA). Different thermal treatment times were applied to the
PLA to obtain different degrees of crystallinity. Additionally, a PLA sample was cooled rapidly
to obtain an amorphous PLA. The characterization techniques used in this study were Fourier
transform infrared spectroscopy, x-ray diffraction, Dynamic Mechanical Analysis, the
differential scanning calorimetry, optical microscopy, and the SME was evaluated by
fold-deploy and torsion modes. Results show that crystallization positively affected the SME,
both in shape fixity and shape recovery. Different crystallization times provided different
degrees of crystallinity, and the SME gradually increased with increasing crystallinity.
Additionally, it was found that the SME of PLA is higher in water. The study concludes that the
crystallization process plays a crucial role in the SME of PLA, and this work contributes to the
understanding of the relationship between crystallization and the SME of PLA, which can
contribute to the development of new technologies and applications for shape memory polymers.
Keywords: poly (lactic acid), shape memory, crystallization, thermal treatment, biopolymers

(Some figures may appear in colour only in the online journal)

1. Introduction is known to affect the thermal, mechanical and morphological

Shape memory polymers (SMPs) have been the subject of
increasing research interest in recent years due to their ability
to recover their original shape by applying a particular external
stimulus, such as heat [1], light [2], pH changes, electric [3]
or magnetic field, and others [4–6]. The shape memory effect
(SME) is a promising technology that can be applied in vari-
ous fields such as biomedical, aerospace and automotive. Poly
(lactic acid) (PLA) is one of the most popular SMPs due to
its biocompatibility and biodegradability [7–11]. However, the
SME of PLA is affected by the crystallization process, which
∗
Author to whom any correspondence should be addressed.
properties of the polymer [4, 7–15].
The crystallization of polymers is a complex process that
depends on various factors such as temperature, time, and
cooling rate [16, 17]. The degree of crystallinity of the poly-
mer directly influences the shape memory properties of the
material, and the understanding of this relationship is essen-
tial to improve the performance of SMPs [16, 18–20]. Despite
the increasing interest in the subject, the influence of crys-
tallization on the SME of PLA is still not fully understood.
The crystallization process of polymers plays a crucial role in
the SME by creating ordered structures, that act as a spring-
like mechanism that interconnects the polymer chains [21].
These ordered structures, also known as crystallites, consist
of a highly organized arrangement of polymer chains. The

1361-665X/23/085016+12$33.00 Printed in the UK 1 © 2023 IOP Publishing Ltd

Smart Mater. Struct. 32 (2023) 085016
crystallites act as a spring that allows the polymer to recover
its original shape upon heating [21–24]. The behavior of shape
memory in amorphous polymers arises from the tremendous
change in molecular mobility of the polymeric chains through
the glass transition. Generally, SMPs consist of two phases:
the frozen phase (glassy state) and the active phase (rubbery
state). The frozen phase is characterized by limited molecular
mobility, where the polymer is in a rigid state and deforma-
tion is hindered. On the other hand, the active phase exhibits
high molecular mobility, allowing for stretching and folding
of the chains, which is a characteristic property of the rub-
bery phase. Another way to understand the SME in polymers
is through the thermo-viscoelastic theory. Generally, polymers
are in a tangled state at room temperature due to the fact that
monomers, when connected, form large and highly entangled
molecules. Entanglement increases as the polymer’s molecu-
lar weight also increases, resulting in greater resistance to
chain mobility at room temperature. As the temperature rises,
molecular agitation increases, favoring chain mobility. At this
point, when chain mobility is facilitated with the temperature
increase, the polymer can be easily deformed and elongated,
leading to a decrease in randomness and entropy of the system
[25–27]. The degree of crystallinity of the polymer directly
influences the shape recovery behavior, and the understand-
ing of this relationship is essential to improve the performance
of SMPs.
In the case of PLA, the process of crystallization results in a
high degree of crystallinity, which leads to a high thermal sta-
bility and mechanical properties of the polymer [16, 28, 29].
This high degree of crystallinity is one of the reasons why
PLA has a high shape fixity, that is, the ability to maintain the
shape after programming. The high rigidity of the polymer,
due to the presence of crystallites, leads to a high shape fixity
and a high recovery ratio upon heating [19, 30–32]. According
to literature [26], achieving high shape fixity ratio and shape
recovery ratio depends on several factors such as the weight
fraction of the transition component, programming temper-
ature, maximum programming strain, and residual strain. To
achieve high shape fixity ratio, it is recommended to program
the material at low temperatures where the strong interaction
between the elastic and transition components can reduce the
shape fixity ratio. Additionally, it is noted that the shape fixity
ratio is actually higher at a smaller maximum programming
strain in all samples. To achieve high shape recovery ratio,
the programming temperature should be within the transition
temperature range. If the programming temperature is within
this range, a large portion of shape recovery occurs upon heat-
ing to around the previous programming temperature. It is also
recommended to program the parts, which are expected to drop
out at lower temperatures, to lower strain only to ensure well
controllable recovery in a more gradual manner.
The goal of this study is to investigate the influence of crys-
tallization on the SME of PLA. The study aims to analyze
the relationship between the degree of crystallinity and the
thermal and the shape recovery behavior. By understanding
the relationship between crystallization and the SME of PLA,
2
R B D Cunha et al
it is possible to improve the performance of the polymer and
expand the range of applications for this material. In this con-
text, we intend to propose an innovative approach to under-
stand the relationship between crystallization and the SME of
PLA, through the use of methods like FTIR, DSC, DMA, OM
and XRD, to evaluate the thermal, mechanical and morpholo-
gical properties of the polymer, and to understand the beha-
vior of the shape recovery. Through this research, we hope to
contribute to the development of new technologies and applic-
ations for SMPs.
2. Experimental
2.1. Materials
PLA—PLA Ingeo™ 4043D, from Nature Works,
MFI = 6 g/10 min (210 ◦ C/ 2.16 kg).
2.2. Samples preparation
PLA pellets were dried at 80 ◦ C for 12 h in a vacuum oven.
The test specimens with dimensions of 54.0 × 13.0 × 3.2 mm
were prepared by compression molding using a Solab SL-11
hydraulic press. The specimens were molded under 25 MPa,
at a temperature of 180 ◦ C for 5 min. After compression, the
samples were cooled in two different ways. To obtain amorph-
ous samples, the samples were quenched in iced water right
after compression. For the four different crystallized samples,
the samples were cooled to room temperature (26 ◦ C) and then
thermally treated at a temperature of 115 ◦ C for 15, 30, 60 and
120 min.
2.3. Characterizations
Fourier transform infrared spectroscopy (FTIR) spectra were
recorded using a Bruker Alpha II spectrometer, in attenuated
total reflectance mode, sweeping from 4000 to 500 cm−1 , with
a resolution of 4 cm−1 and 32 scans. Dynamic Mechanical
Analysis (DMA) was performed in an Anton Paar Physica
MCR 301 rheometer, in torsion mode. The samples, with
dimensions of 54.0 × 13.0 × 3.2 mm, were heated from room
temperature to 150 ◦ C at a heating rate of 5 ◦ C min−1 , a fre-
quency of 1 Hz, and a strain of 0.1%. The DRX essays were
performed on a Shimadzu XRD 6000 x-ray diffractometer (Cu
Kα radiation) operating in the 2θ range of 2◦ –30◦ at a rate
of 2◦ min−1 . The analyses were done on impact test speci-
mens. The differential scanning calorimetry (DSC) analyses
were conducted on a TA Instruments SDT Q20 equipment,
operating at a heating rate of 10 ◦ C min−1 , with temperature
ranging from ambient to 200 ◦ C in a nitrogen atmosphere. The
mass of the samples was approximately 7 mg. Optical micro-
scopy (OM) of polarized light was used to observe the spher-
ulites in the samples. A microscope equipped with a polarizer
was used for the observation of the samples. The samples were
melted at 200 ◦ C between two glass plates, later the samples
Smart Mater. Struct. 32 (2023) 085016 R B D Cunha et al

Figure 1. Two different characterization methods of shape memory effect and programming cycle. (a) Fold-deploy, (b) torsion mode and (c)
shape memory cycle.

were subjected to heat treatment at 115 ◦ C in an oven, for 15, the specimen with the temporary shape was immersed again
30, 60 and 120 min. in hot water to restore its initial shape (θr ). The shape fixity
(Rf1 ) and recovery ratios (Rr1 ) were calculated according to
equations (1) and (2), respectively
2.4. Evaluation of SME

The SME was evaluated by two different characterization θi − θf

Rf1 = × 100% (1)
methods, fold-deploy and torsion. First, it was evaluated by θi
fold-deploy tests in a water bath (figure 1(a)), following pro-
cedures adapted from the literature [13, 33]. The specific pro- θ r − θf
cedure was as follows: initially, a flat specimen (θi = 180◦ ) Rr1 = × 100%. (2)
θi − θ f
with dimensions of 50 × 10.0 × 1.5 mm was put into the water
at 80 ◦ C for 1 min. Subsequently, the specimen was folded into Furthermore, the SME of the samples was characterized in
a U-shaped structure (θ0 = 0◦ ). Afterward, it was cooled down torsion mode using an Anton Paar Physica MCR 301 rheo-
to room temperature to fix the temporary shape (θf ). Finally, meter, working in a ‘strain-controlled’ mode, equipped with a

3
Smart Mater. Struct. 32 (2023) 085016
convectional temperature device, which allowed control of the
sample temperature.
To evaluate the SME in torsion mode a solid rectangu-
lar bar fixture (SRF) device was used (figure 1(b)) [31, 34].
Initially, a sample with dimensions of 54 × 13.0 × 3.2 mm was
fixed on the SRF device. The temperature was set to 80 ◦ C.
Then the specimen was twisted to a strain of 25%, equival-
ent to a deflection angle of 90◦ and the strain was denoted as
(ε1 ). The strain was maintained constant while the temperature
was reduced to room temperature. Afterward, the constraint
was released from the sample while keeping the room tem-
perature (ε2 ). Finally, the sample was heated again to the ini-
tial temperature of 80 ◦ C and maintained at this temperature
for 15 min (ε3 ). Shape fixing ratio (Rf2 ) and shape recovery
ratio (Rr2 ) were calculated according to equations (3) and (4),
respectively
ε2
Rf2 = × 100% (3)
ε1
ε2 − ε3
Rr2 = × 100%. (4)
ε2
3. Results and discussion
3.1. Fourier transform infrared (FTIR)
The objective of conducting FTIR analysis of amorphous and
crystallized PLA (poly lactic acid) samples was to investigate
the differences in the vibrational modes associated with the
C=O bond between the two samples and to provide insights
into the chemical structure and bonding environment of the
polymer in its amorphous and crystalline states.
Characteristic peaks observed for PLA were CH3 asymmet-
ric stretching at 3000 cm−1 , CH2 asymmetric and symmetric
stretching at 2915 and 2850 cm−1 , respectively, symmetric
stretching of the C=O carbonyl at 1750 cm−1 , CH3 bending at
1357 cm−1 , and ester bonds stretching at 1180 to1043 cm−1
[35, 36]. PLA crystallinity can be qualitatively evaluated from
the FTIR spectrum. According to literature [37] when PLA has
high crystallinity, absorption bands are observed at 920 and
1207 cm−1 . Crystallinity in polymers refers to the degree to
which the polymer chains are organized in a crystalline struc-
ture, as opposed to an amorphous structure. In the case of
PLA, these absorption bands are associated with the stretch-
ing vibrations of the C=O bond in the crystalline regions of the
polymer [29, 37, 38]. As the degree of crystallinity increases,
the intensity of these absorption bands also increases. From
the detail of the PLA spectrum in the range of 800–1500 cm−1
(figure 2), the presence of bands at 920 and 1207 cm−1 can be
observed for PLA with treatment, and it can be concluded that
PLA presents high crystallinity after being subjected to heat
treatment, whereas for PLA without treatment, the absence of
bands at 920 and 1207 cm−1 can be observed, and it can be
concluded that PLA presents low crystallinity after being sub-
jected to sudden cooling.
4
R B D Cunha et al
Figure 2. FTIR Spectra of amorphous PLA and PLA with heating
treatment.
3.2. X-ray diffraction (XRD)
X-ray diffraction (XRD) analysis of PLA (poly lactic acid)
(figure 3) samples was conducted to investigate the degree
of crystallinity in each sample. The analysis showed that the
amorphous sample did not exhibit any characteristic peaks,
but rather showed noise. This is because amorphous samples
lack any long-range order and do not possess a specific crystal-
line structure that would produce diffraction peaks [39, 40]. In
contrast, the samples that were subjected to various heat treat-
ment times exhibited characteristic peaks at different angles,
which correspond to different planes in the crystal lattice of
PLA [35, 39–41]. The intensity of these peaks is proportional
to the degree of crystallinity of the sample.
The sample with 15 min of heat treatment exhibited 14.1%
crystallinity, which is relatively low. The sample with 30 min
of heat treatment exhibited a higher degree of crystallinity,
with 31.15%. As the heat treatment time increased, the degree
of crystallinity also increased, with the sample treated for
60 min exhibiting 37.7% crystallinity and the sample treated
for 120 min exhibiting the highest degree of crystallinity at
42.2% (table 1). These results indicate that the degree of crys-
tallinity of PLA can be controlled by adjusting the heat treat-
ment time. The degree of crystallinity affects the physical
and mechanical properties of the material, such as stiffness,
strength, and thermal stability. Therefore, it is important to
carefully control the heat treatment time to obtain the desired
properties of the material [36, 42].
The characteristic crystal planes of PLA are (200), (110),
(010), (203), and (015) [39, 40]. These planes are detected
through XRD after thermal treatment, with the most intense
peak occurring at the (200) and/or (110) plane. These peaks
correspond to the repeating units of the crystalline structure of
PLA and are used to determine the degree of crystallinity of the
material [28, 29, 36, 39, 40]. As mentioned earlier, the intens-
ity of these peaks is proportional to the degree of crystallinity
Smart Mater. Struct. 32 (2023) 085016
Figure 3. X-ray diffraction (XRD) analysis of PLA (polylactic
acid).
Table 1. Crystallinity values from XRD for amorphous PLA and
with different annealing times.
Samples Crystallinity (%)
Amorphous PLA 0%
PLA 15 min 14,10
PLA 30 min 31,15
PLA 60 min 37,70
PLA 120 min 42,20
of the material. PLA exhibits polymorphism with three main
crystalline forms that depend on the conditions of crystalliz-
ation. The α phase, with an orthorhombic crystal structure
and crystal cell parameters a= 1.066 nm, b= 0.616 nm, and
c= 2.888 nm, originates from melt, cold crystallization, and
solution. Disorder in the α phase, known as α′ phase, has
also been detected in PLA at different crystallization temper-
atures. The β phase is observed in fiber manufacturing under
high stretching conditions, and the γ phase is observed under
crystallization conditions on a hexamethylbenzene substrate
[28, 29, 36, 39, 40]. Upon thermal treatment, a well-defined
peak at 2θ = 16.04◦ is observed for pure PLA due to dif-
fraction from (200) and/or (110) planes, along with smaller
peaks at 2θ = 14.38◦ from (010) plane, 2θ = 18.08◦ from
5
R B D Cunha et al
Figure 4. Dynamic mechanical characterization of PLA: storage
modulus (a), and loss modulus (b).
(203) plane, and 2θ = 21.86◦ from (015) plane. These are the
characteristic peaks of the α phase [43].
3.3. Dynamic mechanical characterization
The storage modulus curve of PLA, as depicted in figure 4(a),
demonstrates a clear transition step at around 60 ◦ C. This
transition coincides with the glass transition temperature (T g )
of PLA. At room temperature (25 ◦ C), PLA is a rigid plastic,
which hinders the movement of the molecular chain, result-
ing in a higher modulus. However, at 60 ◦ C, the restriction
on the movement of the molecular chain is lifted, leading to
a decrease in the modulus value [44]. Crystallinity in poly-
mers is a measure of the degree of structural organization of
monomers in a crystalline polymer. The greater the crystallin-
ity, the greater the structural organization of the monomers
and, therefore, the greater the intermolecular force between
them. As the storage modulus (or modulus of elasticity) is a
measure of a material’s resistance to deformation, it is expec-
ted that polymers with greater crystallinity have higher val-
ues of storage modulus, a result shown in figure 4(a). From
110 ◦ C it can be seen that amorphous PLA and PLA with heat
treatment for 15 and 30 min show an increase in modulus (as
Smart Mater. Struct. 32 (2023) 085016
shown in figure 4(a)), which is attributed to the cold crys-
tallization of PLA. While for PLA with thermal treatment
of 60 and 120 min, the curves from 110 ◦ C show a decay,
showing that the polymers reached a sufficient crystalliza-
tion, not needing to crystallize even more. Crystallized poly-
mers already have chains organized in an orderly manner,
so there is no need for additional crystallization, that is, the
mechanical behavior would already be stabilized, and this
transition would have already occurred in the previous crystal-
lization process [40, 44]. The temperature at which the trans-
ition occurs, determined through experimentation, is used as
the trigger point to deform and recover the SMP system [45].
The material can be easily manipulated at temperatures above
the transition temperature (T > T g ) allowing its programming,
its shape is maintained at temperatures below the transition
temperature (T < T g ) and quickly returns to its original shape
at the transition temperature (T g ) [45].
Figure 4(b) shows the loss modulus of PLA with different
heat treatment times. The loss modulus was used to determine
the T g of PLA [17, 46]. The value found for the T g of PLA was
around 62.5, which is in good agreement with the literature
[17, 18, 28, 39, 40, 46]. However, the glass transition temper-
ature (T g ) varied according to the degree of polymer crystalliz-
ation because crystallization increases the structural order of
the polymer and this affects the thermal stability of the poly-
mer. Loss modulus is a measure of the energy dissipated by a
material when subjected to cyclic deformation. The loss modu-
lus depends on the frequency and temperature of deformation,
and is used to evaluate the viscoelastic behavior of materials.
PLA presents a typical behavior of a semicrystalline polymer,
with a glass transition (T g ) around 60 ◦ C and a melting (T m )
around 180 ◦ C. It is observed that the loss modulus increases
with temperature until it reaches a peak in the glass transition
region, where the material changes from a glassy state to a
rubbery state. In this region, the material has a greater capa-
city to dissipate energy, as the molecular chains gain mobility
and can rearrange themselves under deformation. The damp-
ing factor also shows a peak in the glass transition, indicat-
ing that the material has greater damping in this temperature
range. After the glass transition, the loss modulus decreases
with temperature until it reaches a minimum in the melting
region, where the material changes from a solid state to a liquid
state. In this region, the material loses its rigidity and its abil-
ity to store elastic energy, as the molecular chains are disor-
ganized and move freely. Crystallization is a process where
polymeric chains are organized in an orderly manner, forming
crystals. The crystalline structure is more rigid and resistant to
thermal changes than the amorphous structure. The greater the
degree of crystallization, the greater the thermal stability of the
polymer, and the greater the glass transition temperature.
In the DMA results reported for PLA, temperature-induced
and stress-induced phase transformations can exhibit distinct
characteristics [47]. Let us discuss the differences between
these two types of phase transformations: Temperature-
induced phase transformations in PLA occur when the mater-
ial is subjected to changing temperature conditions dur-
ing the DMA analysis. PLA typically exhibits two primary
temperature-induced transitions: Glass transition and melting
6
R B D Cunha et al
transition. The glass transition is a reversible transition that
occurs below the melting temperature of the polymer. It is
characterized by a change in the molecular mobility and the
transition from a rigid, glassy state to a rubbery state. In DMA,
the glass transition is observed as a significant change in the
storage modulus (E′ ) and the loss modulus (E′ ). PLA has a
distinct melting point where it undergoes a transition from the
solid state to the molten state [28]. This transition is observed
as a sharp decrease in the storage modulus and is reflected as
a peak in the loss modulus in the DMA results. However, the
melting temperature of PLA is around 180 ◦ C, and the DMTA
test was only programmed to go up to 150 ◦ C, preventing the
material from melting and damaging the equipment.
Stress-induced phase transformations occur when the
material is subjected to mechanical stress or strain during
DMA analysis. PLA can exhibit stress-induced transitions,
such as: Under the influence of stress or strain, PLA can
undergo crystallization. This process involves the alignment
and organization of polymer chains, resulting in the forma-
tion of crystalline regions within the material. Crystallization
is typically seen as an increase in the storage modulus in the
DMA results. It is important to note that temperature-induced
phase transformations are primarily driven by changes in tem-
perature, while stress-induced phase transformations occur
due to the application of mechanical stress or strain. Both
types of phase transformations can significantly influence the
mechanical properties of PLA and are essential to understand
its behavior in different temperature and stress conditions.
However, it is important to point out that in this specific case,
the phase transformations are being induced mainly by tem-
perature. The peak displacement observed in the loss modulus
curves (E′ ) is attributed to the effect of crystallization in these
samples, crystallization induced before the DMTA assay and
not generated by stress [28, 34, 40].
3.4. DSC
DSC analysis is a useful technique to investigate the crystalline
structure of polymers, and the results obtained for amorphous
PLA and PLA annealed at different times are interesting.
The PLA curve shows an endothermic peak, 60 ◦ C, which
is attributed to the enthalpy of relaxation, ∆H rel , of the mater-
ial. According to [48] such a peak is related to physical aging
and the fragility of PLA, and increases with decreasing molar
mass, in addition, the peak corresponds to the glass trans-
ition temperature (T g ) of this polymer, which is around 60◦
C for all samples. An exothermic event with a maximum at
around 124 ◦ C is attributed to cold crystallization (T cc ) of
PLA, and only appears in amorphous samples, with 15 and
30 min of thermal treatment. After prolonged heat treatment
(60 and 120 min), the T cc of PLA disappeared in the thermo-
grams of the blends, these results are in line with [49], the T g
and the double melting peak were shifted to the right, in addi-
tion to the melting peaks becoming more intense. This must
have occurred due to PLA crystallization during heat treat-
ment. It is also observed for pure PLA an endothermic event
characterized by a peak with a maximum at 151 ◦ C referring
to the crystalline melting temperature (T m ) of the α phase of
Smart Mater. Struct. 32 (2023) 085016
Table 2. Differential scanning calorimetry DSC analysis of PLA samples.
Samples Tg (◦ C) Tc (◦ C)
Amorphous PLA 60,33 127,98
PLA 15 min 60,35 124,94
PLA 30 min 60,39 124,88
PLA 60 min 61,14 — 148,79
PLA 120 min 61,23 — 150,68
Figure 5. Differential scanning calorimetry of PLA with different
annealing times.
the PLA crystalline structure. In table 2, it can be observed
that the sample with 120 min of annealing showed a higher
degree of crystallinity compared to the other samples, indic-
ating that a longer annealing time is necessary to increase the
PLA crystallinity. Furthermore, the glass transition temperat-
ures (T g ) obtained by DSC were close to 60 ◦ C for all samples,
which is consistent with the results obtained by DMTA. It is
important to emphasize that the determination of T g by DSC
can be influenced by the heating rate, while the determination
by DMTA is less sensitive to these experimental variations.
Notably, the samples with 60 and 120 min of annealing did
not show a cold crystallization temperature (T cc ) (figure 5),
indicating that the annealing time was sufficient to crystallize
the PLA. This is because, during annealing, the PLA polymer
chains rearrange into a more ordered structure, which leads to
crystallization [16, 17, 28, 40, 50, 51]. However, samples with
shorter annealing times (15 and 30 min) showed a cold crystal-
lization temperature, indicating that there was not enough time
for complete crystallization to occur. This result is consist-
ent with the literature and with the results obtained by DMTA
[16, 17, 28, 40, 50, 51].
The degree of crystallinity was determined by both XRD
and DSC. Although both methods provide information about
the crystalline structure of the material, they differ in terms
of the depth of penetration in the sample and the sensitivity
for detecting small crystallites. While DRX is able to provide
information about the crystalline structure of the surface of
R B D Cunha et al
Tm (◦ C) ∆Hc (J g−1 ) ∆Hm (J g−1 ) Xc (%)
145,50 8,21 9,67 1,57
146,32 7,87 23,25 16,53
146,54 5,73 35,17 31,65
0 40,12 43,13
0 44,35 47,68
the sample, the DSC evaluates the crystallinity in the entire
volume of the sample [16, 17, 28, 40].
In the case of PLA, the DSC and XRD results indicated
that the annealing time significantly affects the degree of crys-
tallinity, with the 120-minutes sample showing the highest
value of about 48% from the DSC, while from the XRD
42%. The result of the degree of crystallinity obtained by
DSC may have been slightly higher than the value obtained
by XRD due to the sensitivity of the DSC to detect small
crystallites. However, both techniques indicated a significant
increase in the degree of crystallinity with increasing anneal-
ing time, which is consistent with the literature. Regarding
the glass transition temperatures (T g ), it was observed that the
PLA samples showed similar values by DSC and DMTA, both
close to 60 ◦ C. However, it is important to note that the exper-
imental conditions used in each method can influence the val-
ues obtained, mainly the heating rate and sample geometry.
DMTA, for example, can provide more accurate information
about the T g in materials with complex structures, such as
PLA, since the technique evaluates the mechanical proper-
ties of the material at different frequencies and amplitudes of
deformation [16, 17, 28, 40].
3.5. Polarized light microscopy (POM)
The OM analysis of PLA samples reveals an increase in the
amount of spherulites with longer annealing or crystallization
times. The samples were crystallized at 115 ◦ C for 15, 30,
60, and 120 min. In figure 6 spherulites can be observed start-
ing at 30 min of annealing, and their quantity increases with
longer times. The presence of spherulites in the PLA struc-
ture is important for its SME [18, 20, 29]. Spherulites are
regions of highly ordered crystalline structure that form dur-
ing the crystallization of the polymer. The SME of polymers
is a unique property that allows them to return to their original
shape after being deformed, due to the rearrangement of the
polymer chains within the spherulites [18, 20, 32].
The crystallization process is crucial in creating the neces-
sary spherulite structure for the SME to occur. The increase
in spherulite quantity with longer annealing times indicates a
greater degree of crystallinity in the PLA, which can lead to
enhanced shape memory behavior. Understanding the form-
ation of spherulites in PLA is essential for designing mater-
ials with specific shape memory properties [4–6]. By con-
trolling the crystallization process, it is possible to adjust the
size, distribution, and orientation of the spherulites, which can
have a significant impact on the shape memory behavior of
7
Smart Mater. Struct. 32 (2023) 085016 R B D Cunha et al

Figure 6. Polarized optical micrographs of PLA spherulites isothermally melt crystallized at 115 ◦C for (a) 15 min, (b) 30 min, (c) 60 min,
(d), (e) and (f) 120 min.

Figure 7. Fold-deploy programming example for amorphous and crystallized PLA samples.

the polymer. Moreover, the formation of spherulites in PLA
also affects other physical and mechanical properties, such as
thermal and mechanical stability, tensile strength, and stiffness
[28]. Thus, it is important to carefully tune the crystallization
process to achieve the desired properties in the material.
3.6. SME
The shape memory properties of PLA were examined using
two distinct methods. Initially, fold-deploy (figure 7) tests
were conducted in a water bath, followed by a torsion mode
analysis using a rheometer set to ‘strain-controlled’ mode.
The shape fixity (Rf ) and recovery ratio (Rr ) are essential
indicators for assessing the SME. The shape fixity measures
the material’s ability to maintain the mechanical deformation
applied during the programming process, while the recovery
ratio quantifies the ability of the material to return to its per-
manent shape [19, 20, 28, 31, 33]. The results of these tests
for the compositions studied, in both fold-deploy and torsion
modes, are presented in table 3.
SMPs typically have two components: shape-fixing and
shape-switching parts. The shape-fixing parts are respons-
ible for maintaining dimensional stability during program-
ming and recovery, and can include structural domains or
fixed points. The shape-switching parts are long polymeric
chains that stretch during programming to store elastic energy.

8
Smart Mater. Struct. 32 (2023) 085016
Table 3. PLA without and with heat treatment, comparison of their shape memory properties measured in different modes (fold-deploy and
torsion), at a switching temperature of 80 ◦ C.
Fold-deploy
Samples Rf (%)
Amorphous PLA 98,30
PLA 15 min 99,10
PLA 30 min 99,50
PLA 60 min 100,0
PLA 120 min 100,0
Figure 8. Shape fixity and recovery ratio of PLA obtained from
fold-deploy tests in a water bath at 80 ◦ C. (Rf —fixed ratio;
Rr —recovery ratio).
Theoretically, all high-molecular-weight PLA should have
shape memory ability due to physical entanglement and the
crystallization of PLA, however, the observation of this effect
in PLA is often limited in practice [18, 19].
Figure 8 displays the shape fixity (Rf ) and recovery ratio
(Rr ) of PLA as obtained from fold-deploy tests performed in a
water bath. All samples had an Rf value of more than 90% at
every time heating examined. Despite having moderate shape
memory capabilities, literature suggests possible explanations
for these results. The use of a water bath during the fold-deploy
tests likely contributed to the high Rr values of the PLA. The
material’s hydrophilic nature allows for some water to enter its
structure and act as a plasticizer, increasing the flexibility of its
macromolecular chains and lowering its T g for shape recovery
to occur [52]. Additionally, the absorbed water in PLA weak-
ens the hydrogen bonding between O–H and C=O groups, fur-
ther lowering its T g [53, 54]. As shown in figure 8, all meas-
ured Rr values were above 90% for all samples analyzed.
The SME of PLA was analyzed using torsion mode in
this study, as shown in the 3D diagram of figure 9. The pro-
cess was carried out using a rheometer operating in a strain-
controlled mode, with an SRF device. The shape memory
cycle includes four main steps: heating the polymer above
its switch temperature to create a pre-defined strain, cooling
the material to room temperature while maintaining the strain,
9
R B D Cunha et al
Torsion
Rr (%) Rf (%) Rr (%)
93,40 91,10 43,10
95,30 93,60 50,20
97,10 95,50 51,30
98,30 96,20 52,80
99,10 97,60 54,40
Figure 9. 3D diagram of the shape memory cycle for PLA with and
without heating treatment, obtained in torsion mode using a
rheometer operating in a strain-controlled mode.
releasing the strain while the material maintains its pro-
grammed shape, and raising the temperature again to release
stored energy and return the material to its original shape
[13, 14, 18, 20, 31, 34, 44, 54]. The switch temperature and
strain applied in torsion mode were 80 ◦ C and 25% respect-
ively. It was found that the SME of PLA was affected by the
degree of crystallinity, with higher crystallinity resulting in
better shape fixity and recovery. Additionally, it was observed
that the SME of PLA was higher in water.
Comparing the torsion mode test with the fold-deploy test
and water immersion, it can be seen that the recovery ratio
(Rr ) of PLA in torsion mode was lower, approximately 43%–
54%, compared to the fold-deploy test. It was observed that
the water acted as a favorable factor for the recovery of PLA,
this is why the results are different between the two tests. It
is important to note that while the fold-deploy test is simple
and inexpensive, the torsion test using the SRF device is more
precise and provides graphical results that aid in understand-
ing the SME. However, it is important to keep in mind that the
precision of the measurements in fold-deploy test are obtained
by a person and not by the equipment and the duration of the
Smart Mater. Struct. 32 (2023) 085016
experiment is considerably lower than that using a rheometer
or DMA equipment. It is also important to note that the heat
transfer in the fold-deploy test occurs by conduction, while in
torsion test it occurs by convection. Therefore, both methods
are suitable for the analysis of the SME, but different factors
must be considered depending on the desired outcome and
resources available. In this study, the torsion mode test was
used to further understand the SME of PLA and its relation-
ship with crystallinity. Additionally, the use of water immer-
sion was included as a factor to analyze its impact on the SME.
Through the analysis of the results, it was determined that the
degree of crystallinity plays a significant role in the SME of
PLA, and that water immersion can be used to improve the
recovery ratio.
4. Conclusion
In conclusion, this study provides valuable insights into the
influence of crystallization on the SME of PLA, shedding light
on the fundamental understanding of this important material
property. This comprehensive study elucidated the signific-
ant influence of crystallization on the SME of PLA, a widely
used biodegradable polymer. By varying the thermal treat-
ment times, different degrees of crystallinity were achieved,
and it was observed that crystallization positively impacted
the SME of PLA. The shape fixity and shape recovery of
PLA were found to be progressively enhanced with increas-
ing crystallinity, highlighting the critical role of the crystal-
lization process in optimizing the shape memory properties.
The use of characterization techniques such as FTIR, XRD,
DMA, DSC, and OM provided valuable insights into the struc-
tural and mechanical changes occurring during the crystalliza-
tion process. Moreover, this study demonstrated that the SME
of PLA was particularly pronounced in water, indicating its
potential for water-responsive applications in fields such as
biomedical engineering and environmental science. The find-
ings of this research significantly contribute to the understand-
ing of the relationship between crystallization and the SME
of PLA, providing a foundation for further advancements in
the field of SMPs. The knowledge gained from this study
can be leveraged to design and fabricate PLA-based materials
with tailored shape memory properties, leading to the develop-
ment of innovative technologies and applications. The ability
to control the crystallinity of PLA opens up new avenues for
designing smart materials that can respond to specific stim-
uli and recover their original shapes, thereby enabling novel
applications in areas such as tissue engineering, drug deliv-
ery, and flexible electronics. This research lays the ground-
work for future investigations on optimizing the crystalliza-
tion process of PLA and exploring its potential synergies with
other additives or processing techniques to further enhance
the SME. Ultimately, the advancements made in understand-
ing the relationship between crystallization and the SME of
PLA hold great promise for the development of sustainable
and intelligent materials that can revolutionize various indus-
tries and contribute to a more environmentally friendly and
technologically advanced future.
10
R B D Cunha et al
Data availability statement
All data that support the findings of this study are included
within the article (and any supplementary files).
Acknowledgments
The authors would like to thank the Brazilian research fund-
ing agencies National Council for Science and Technology
(CNPq), (PA Grant Number 442128/20142/UNIVERSAL, T
J A M Grant Numbers 426191/20161 and 577061/20089) and
the Coordination for the Improvement of Higher Education
Personnel (CAPES) (RBC: Scholarship).
ORCID iDs
Rafael Braga da Cunha  https://orcid.org/0000-0003-0304-
4220
Pankaj Agrawal  https://orcid.org/0000-0002-5078-8321
Gustavo de Figueiredo Brito  https://orcid.org/0000-0002-
4114-9552
Tomás Jeferson Alves de Mélo  https://orcid.org/0000-
0002-5879-6764
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