polymers

Article
Thermal Insulation and Mechanical Properties of
Polylactic Acid (PLA) at Different
Processing Conditions
Mohamed Saeed Barkhad 1 , Basim Abu-Jdayil 1, * , Abdel Hamid I. Mourad 2 and
Muhammad Z. Iqbal 1
1 Chemical and Petroleum Engineering Department, United Arab Emirates University,
Al Ain 15551, Abu Dhabi, UAE; 200935051@uaeu.ac.ae (M.S.B.); mziqbal@uaeu.ac.ae (M.Z.I.)
2 Mechanical Engineering Department, United Arab Emirates University, Al Ain 15551, Abu Dhabi, UAE;
ahmourad@uaeu.ac.ae
* Correspondence: babujdayil@uaeu.ac.ae; Tel.: +971-3-7135317; Fax: +971-3-7624262




Received: 15 August 2020; Accepted: 3 September 2020; Published: 14 September 2020


Abstract: This work aims to provide an extensive evaluation on the use of polylactic acid (PLA)
as a green, biodegradable thermal insulation material. The PLA was processed by melt extrusion
followed by compression molding and then subjected to different annealing conditions. Afterwards,
the thermal insulation properties and structural capacity of the PLA were characterized. Increasing
the annealing time of PLA in the range of 0–24 h led to a considerable increase in the degree of
crystallization, which had a direct impact on the thermal conductivity, density, and glass transition
temperature. The thermal conductivity of PLA increased from 0.0643 W/(m·K) for quickly-cooled
samples to 0.0904 W/(m·K) for the samples annealed for 24 h, while the glass transition temperature
increased by approximately 11.33% to reach 59.0 ◦ C. Moreover, the annealing process substantially
improved the compressive strength and rigidity of the PLA and reduced its ductility. The results
revealed that annealing PLA for 1–3 h at 90 ◦ C produces an optimum thermal insulation material.
The low thermal conductivity (0.0798–0.0865 W/(m·K)), low density (~1233 kg/m3 ), very low water
retention (<0.19%) and high compressive strength (97.2–98.7 MPa) in this annealing time range are
very promising to introduce PLA as a green insulation material.

Keywords: polylactic acid; biopolymer; green thermal insulator; thermal properties; water retention;
mechanical properties

1. Introduction
Biodegradable materials have attracted much attention from researchers due to the pressing
need to reduce enduring waste worldwide. Among the biodegradable materials, biodegradable
polymers have received the most attention [1]. They are classified into three groups based on their
sources: natural, semi-synthetic, and synthetic. Most biodegradable polymers are obtained from
renewable sources such as starch. Aliphatic and mixed aliphatic/aromatic polyesters or polysaccharides
(cellulose and its derivatives) are the most widely studied biodegradable polymers [2]. With depleting
fossil-based raw materials for conventional polymers, biodegradable polymers provide an alternative
with improved functional properties [3]. In addition, the biodegradability feature offers a real solution
of municipal waste management issue.
Polylactic acid (PLA) is a natural biodegradable polymer derived from renewable raw materials
such as corn, starch, and sugarcane [4,5]. PLA is an enantiomeric polyester, which includes poly
(L-lactic acid) and poly (D-lactic acid), as shown in Figure 1 [6]. Comparatively high D content (>20%)

Polymers 2020, 12, 2091; doi:10.3390/polym12092091 www.mdpi.com/journal/polymers

Polymers 2020, 12, 2091 2 of 16
Polymers 2020, 12, x FOR PEER REVIEW 2 of 16

can
can yield
yield an
an entirely
entirely amorphous
amorphous polymer,
polymer, whereas
whereas lower
lower D
D content
content (<2%)
(<2%) leads
leads to
to highly
highly crystalline
crystalline
material [7].
material [7].

(a) (b)

Figure 1. Chemical structure of (a) L-lactic acid and (b) D-lactic acid.

Furthermore,
Furthermore,PLA PLAis aisthermoplastic,
a thermoplastic, high-modulus,
high-modulus,high-strength polymer with
high-strength polymerlarge with
production
large
rates and various
production rates and applications. PLA is easily
various applications. PLAprocessable on standard
is easily processable onplastic
standard equipment into films,
plastic equipment
fibers or molded
into films, fibers parts [5]. However,
or molded parts [5]. despite
However,numerous
despite positive
numerousfeatures, PLA features,
positive is brittle and PLArigid with
is brittle
low
and plastic
rigid withdeformation
low plastic (~3%) [8]. The inherent
deformation (~3%) [8]. brittleness
The inherentshortens PLA useshortens
brittleness in implementations
PLA use in
which require plastic deformation at higher levels of stress (e.g.,
implementations which require plastic deformation at higher levels of stress (e.g., fracture fracture fixation plates and screws) [9].
fixation
plates PLA
andexhibits
screws)a[9]. slow degradation rate which is critical in biomedical applications [10] as well as in
the disposal
PLA exhibitsprocess of consumer
a slow degradationcommodities.
rate which The degradation
is critical of PLA isapplications
in biomedical a function of[10] its molecular
as well as
weight
in the disposal process of consumer commodities. The degradation of PLA is a functionrate
and its distribution, crystallinity, morphology, stereoisomeric content and diffusion of
of its
water
molecular [11]. Nevertheless,
weight and its PLA is relatively crystallinity,
distribution, hydrophobic morphology,
and lacks reactive side-chain groups
stereoisomeric contentonand its
surface
diffusion [5,9].
rate of water [11]. Nevertheless, PLA is relatively hydrophobic and lacks reactive side-chain
groups Theon mechanical
its surfaceproperties
[5,9]. of a polymer are a complex function of a microstructure, such as chain
relaxation, degree ofproperties
The mechanical crystallization and orientation
of a polymer are a complex[12]. Heat treatment
function (annealing) improves
of a microstructure, such as chainthe
mechanical characteristics of a polymer. Annealing improves heat
relaxation, degree of crystallization and orientation [12]. Heat treatment (annealing) improves the and chemical resistance, glass
transition
mechanicaland tensile strength
characteristics of a in polymers
polymer. [7,13]. Most
Annealing improves likely,
heatannealing
and chemical improves a material’s
resistance, glass
performance
transition andbytensile refining its crystallinity
strength in polymers [7]. However,
[7,13]. Most annealing may not alter
likely, annealing improvesmelting and glass
a material’s
transition
performance temperatures
by refiningwhen the molecular
its crystallinity [7].weight
However, is high enough [5,14].
annealing may not alter melting and glass
The microstructural
transition temperatures when orientation and annealing
the molecular weightare considered
is high enougheffective
[5,14]. techniques for enhancing
the mechanical performance
The microstructural of PLA. and
orientation The annealing
orientationare improves
considered andeffective
increasestechniques
toughnessfor and strength
enhancing
whereas annealing improves the chain unwinding and crystallinity
the mechanical performance of PLA. The orientation improves and increases toughness and strength in PLA [12]. Temperature, shearing,
stretching,
whereas annealingand other processing
improves the conditions
chain influence
unwinding theandresulting formation
crystallinity inofPLA
the crystal structure [15].
[12]. Temperature,
PLA
shearing, stretching, and other processing conditions influence the resulting formation ofdenoted
exhibits three crystalline forms: α, β, and γ, and a new crystal modification of α as
the crystal
0 -form (disorder [15,16]. three 0
The αcrystalline
-form appears byα,annealing ◦
α
structure [15]. PLAα)exhibits forms: β, and γ,PLA and below
a new 120 crystal C [16].
modification of α
denoted Takayama
as α′-form et al. [17] examined
(disorder α) [15,16]. theThe
mechanical
α′-form appearsproperties of PLA/poly-epsilon-caprolactone
by annealing PLA below 120 °C [16].
(PLA/PCL)
Takayama and et PLA/poly-epsilon-caprolactone/Lysine
al. [17] examined the mechanical properties triisocyanate (PLA/PCL/LTI) blends. These
of PLA/poly-epsilon-caprolactone
blends
(PLA/PCL) face annealing processes. The annealing impact on
and PLA/poly-epsilon-caprolactone/Lysine the PLA/PCL
triisocyanate blend led to an
(PLA/PCL/LTI) increase
blends. Thesein
the
blendsflexural
face strength
annealingand modulusThe
processes. of itannealing
because of the crystallization
impact on the PLA/PCL of the PLAled
blend phase
to anbyincrease
annealing in
as
thewell as the
flexural PLA/PCL/LTI
strength blend which
and modulus experienced
of it because of the polymerization
crystallization ofbesides
the PLA annealing.
phase byIn general,
annealing
the annealing
as well process leads to
as the PLA/PCL/LTI strengthening
blend the microstructure,
which experienced polymerization which consequently
besides annealing. improves the
In general,
mechanical
the annealing properties.
process leads to strengthening the microstructure, which consequently improves the
Tabi et al.
mechanical [18] reported effects of annealing PLA on crystallinity induced in neat, processed, and
properties.
injection
Tabimolded
et al. [18] resins. Theyeffects
reported reported that annealing
of annealing PLA injection molding
on crystallinity grade PLA
induced in neat,in the temperature
processed, and
range of 100–140 ◦ C for 10 min resulting in high crystallinity (up to 40%). Annealing PLA for 10 min in
injection molded resins. They reported that annealing injection molding grade PLA in the
the 100–140 ◦ C
temperature temperature
range of 100–140 range°C achieved
for 10 min very high crystallinity
resulting (40%) in an(up
in high crystallinity injection-molded
to 40%). Annealing grade
PLA.
PLA for Moreover,
10 min complete
in the 100–140annealing disappeared range
°C temperature the cold crystallization
achieved very high exotherm in PLA.
crystallinity (40%) in an
injection-molded grade PLA. Moreover, complete annealing disappeared the cold crystallization
exotherm in PLA.
Polymers 2020, 12, 2091 3 of 16

Weir et al. [19] investigated the effects of the annealing, molecular weight and morphology of
poly-L-lactide (PLLA) on its degradability. The annealing increased crystallinity to 43% and 40% in
compression-molded and extruded PLLA, respectively. Consequently, increased crystallinity decreased
extension at the break and tensile strength whereas the Young’s modulus was improved.
Hassan et al. [20] added PLA to starch/cellulose composite foams to enhance their water barrier
property and other properties. Different proportions of PLA were added to the mixture, and their
thermo-mechanical and water absorption properties were analyzed. They found that PLA has a
considerable impact in water barrier properties, flexural strength, and stiffness. Furthermore, the
addition of PLA to the mixture increased the peak thermal degradation temperature resulting in the
formation of a more stable structure.
PLA is the most extensively researched and utilized biodegradable aliphatic polyester in human
history [5]. Due to its merits, PLA is a leading biomaterial for numerous applications in industry
replacing conventional petrochemical-based polymers. Owing to its low thermal conductivity and
hydrophobic nature, PLA can work as a potential thermal-insulating material to replace conventional
fossil-based insulating materials. However, there is a scarcity of data on PLA as insulation material in
the published literature to date. This work primarily focuses on the effects of processing conditions
on the thermal insulation behavior of melt-processed PLA and its construction capacity. The impact
of annealing conditions is reported on various thermal and mechanical properties as well as the
morphology of PLA.

2. Materials and Methods

2.1. Materials
Poly(lactic acid) (PLA) (commercial grade 4032D; weight-average molar weight = 1 × 105 g/mol;
specific gravity = 1.24, and Tm = 155–170 ◦ C) was supplied by Zhejiang Zhongfu Industrial Ltd. and
imported from Nature Works LLC (Hangzhou, China) in granule form with a ratio of L-lactide
to D-lactide from 24:1 to 32:1 (manufacturer data). PLA was used in this study without any
further modifications.

2.2. PLA Samples Preparation and Thermal Treatment

PLA was dried for two hours under vacuum at 90 ◦ C followed by drying in a desiccator for one
hour prior to processing due its hydrolytic susceptibility at higher temperatures. After that, an internal
mixer mini-twin conical screw extruder (MiniLab Haake Rheomex CTW5, Dreieich, Germany) was
used to melt the PLA pellets. PLA (5 g) was melt blended in a twin screw microcompounder (MiniLab
Haake Rheomex CTW5, Dreieich, Germany) at 190 ◦ C and 140 rpm for 3 min. The extruded PLA
compression molded in hot press (Carver, AUTOFOUR/3015) in three heating-pressure cycles: (1) a
force of 0.5 tons at 180 ◦ C for 16 min, (2) a 0.52 ton force at 185 ◦ C for 10 min, and (3) 3 tons of force at
100 ◦ C for 3:30 min. The molded samples were thermally annealed in a convection oven (explained
later). Figure 2 shows the molded sample for the thermal conductivity (a) and cylindrical sample (b)
used for additional tests.
2.4. Thermal Conductivity
The thermal conductivity was measured using the Lasercomp FOX-200 thermal conductivity
tester. Samples were shaped in specially designed molds with dimensions of 110 × 110 × 3 mm3
(Figure2020,
Polymers 2a) 12,
and thermal conductivity was measured using ASTM C1045-07 [23]. The results
2091 4 ofare
16
reported as the average of three measurements.

(a) (b)
Figure 2. Dimensions
Dimensions of
of prepared
prepared specimens: (a)
(a) the
the thermal
thermal conductivity
conductivity specimen; and (b) the water
retention and compression strength
strength specimen.
specimen.

Thermal annealing
2.5. Differential Scanningwas conducted in a convection oven at 95 ◦ C. Since annealing between melting
Calorimetry
(Tm ) and the glass transition temperature (T g ) is more effective [21,22], annealing was performed at
Thermal properties of PLA were studied using a differential scanning calorimeter (DSC 25—TA
95 ◦ C (PLA Tm = 155–170 ◦ C and T g ~ 60 ◦ C). The annealing was conducted for a range of annealing
Instruments, TA Instruments, New Castle, DE, USA). An approximately 5–7 mg sample was heated
times of 0.5, 1, 3, 10, 17, and 24 h. One sample was annealed “Fast” by cooling from hot press
under a 50 mL/min nitrogen flow rate. The DSC results are reported as two cases: Case A simulates
temperature to room temperature by flowing air over the samples in a fume-hood. Sample codes as a
the oven-based annealing of PLA whereas in Case B, the effects of the fast cooling rate on PLA thermal
function of annealing time interval are provided in Table 1.
properties are reported. The temperature protocols followed in these two cases are detailed below:
Case A: Samples were quickly heatedTable 1.toSamples
200 °C abbreviation.
at 40 °C/min and kept isothermally at 200 °C for
5 min to eliminate the thermal history. Subsequently, the molten samples were cooled to 95 °C at 5
°C/min and isothermally annealed for the Annealing following Processing Interval
time intervals: 0 min (fast cooling/without
stopping at 95 °C), 30 min, 0-PLA
and 1, 3, 10, 17, and 24 h. This step
Fast is a simulation of the external annealing
process. Following complete 0.5-PLAannealing, the samples 0.5 h cooled to 20 °C at 5 °C/min and
were
1-PLA 1h
subsequently heated from 20 °C to 200 °C at 2 °C/min to evaluate the thermal characteristics (glass
3-PLA 3h
transition temperature and10-PLA
degree of crystallinity) as a function
10 h of annealing time interval (see Figure
3a). 17-PLA 17 h
Case B: Samples were24-PLA
quickly heated to 200 °C at 40 24 h
°C/min and kept isothermally at 200 °C for
5 min to eliminate thermal history (Figure 3b). The samples were rapidly cooled to 95 °C at 80 °C/min
to
2.3.avoid the Electron
Scanning development of premature
Microscopy (SEM) crystallinity before reaching 95 °C. The samples were
annealed at 95 °C for 0, 5, 10, 20, 30, 40, 50, or 60 min. Followed by annealing, the samples were cooled
A JEOL-JCM 5000 NeoScope SEM (JEOL, Tokyo, Japan) was used to investigate the microstructure
in processed PLA. The samples were sputter coated with gold for 3 min to remove the electrostatic
charges in order to attain the maximum magnification of textural and morphological features. The
SEM images are reported at various magnifications.

2.4. Thermal Conductivity

The thermal conductivity was measured using the Lasercomp FOX-200 thermal conductivity tester.
Samples were shaped in specially designed molds with dimensions of 110 × 110 × 3 mm3 (Figure 2a)
and thermal conductivity was measured using ASTM C1045-07 [23]. The results are reported as the
average of three measurements.

2.5. Differential Scanning Calorimetry

Thermal properties of PLA were studied using a differential scanning calorimeter (DSC 25—TA
Instruments, TA Instruments, New Castle, DE, USA). An approximately 5–7 mg sample was heated
under a 50 mL/min nitrogen flow rate. The DSC results are reported as two cases: Case A simulates
Polymers 2020, 12, 2091 5 of 16

the oven-based annealing of PLA whereas in Case B, the effects of the fast cooling rate on PLA thermal
properties are reported. The temperature protocols followed in these two cases are detailed below:
Case A: Samples were quickly heated to 200 ◦ C at 40 ◦ C/min and kept isothermally at 200 ◦ C
for 5 min to eliminate the thermal history. Subsequently, the molten samples were cooled to 95 ◦ C
at 5 ◦ C/min and isothermally annealed for the following time intervals: 0 min (fast cooling/without
stopping at 95 ◦ C), 30 min, and 1, 3, 10, 17, and 24 h. This step is a simulation of the external annealing
Polymers 2020, 12, x FOR PEER REVIEW 5 of 16
process. Following complete annealing, the samples were cooled to 20 ◦ C at 5 ◦ C/min and subsequently
heated from 20 ◦ C to 200 ◦ C at 2 ◦ C/min to evaluate the thermal characteristics (glass transition
to 20 °C at 80 °C/min and subsequently heated from 20 °C to 200 °C at 10 °C/min to evaluate the
temperature and degree of crystallinity) as a function of annealing time interval (see Figure 3a).
thermal properties.

(a)

(b)
Figure 3. Differential scanning calorimeter (DSC) heating–cooling
heating–cooling cycle for (a) Case A and (b) Case B.

Case B: Samples ◦ ◦ ◦
2.6. Compression Test were quickly heated to 200 C at 40 C/min and kept isothermally at 200 C
for 5 min to eliminate thermal history (Figure 3b). The samples were rapidly cooled to 95 ◦ C at
The compression test was conducted following ASTM D695-15 using a universal testing
80 ◦ C/min to avoid the development of premature crystallinity before reaching 95 ◦ C. The samples
instrument (MTS model MH/20) with 100 kN load cell and with an overhead speed of 1.3 mm/min at
were annealed at 95 ◦ C for 0, 5, 10, 20, 30, 40, 50, or 60 min. Followed by annealing, the samples were
room temperature. The compressive modulus, compressive strength, and elongation at break were
reported. Cylindrical specimens of a length of 25.7 mm and diameter of 12.3 mm (Figure 2b) were
compressed between the fixed (lower) and movable (upper) plates. The loading was continued until
either the value of the load decreased by 10% of the maximum value or the specimen fracture
occurred; otherwise, the experiment was interrupted manually when a specific contraction value was
reached. Figure 4 shows the specimen after compression: the left image represents a buckled sample
Polymers 2020, 12, 2091 6 of 16

cooled to 20 ◦ C at 80 ◦ C/min and subsequently heated from 20 ◦ C to 200 ◦ C at 10 ◦ C/min to evaluate

the thermal properties.

2.6. Compression Test

The compression test was conducted following ASTM D695-15 using a universal testing instrument
(MTS model MH/20) with 100 kN load cell and with an overhead speed of 1.3 mm/min at room
temperature. The compressive modulus, compressive strength, and elongation at break were reported.
Cylindrical specimens of a length of 25.7 mm and diameter of 12.3 mm (Figure 2b) were compressed
between the fixed (lower) and movable (upper) plates. The loading was continued until either the
value of the load decreased by 10% of the maximum value or the specimen fracture occurred; otherwise,
the experiment was interrupted manually when a specific contraction value was reached. Figure 4
shows the specimen after compression: the left image represents a buckled sample while the right one
shows a fractured sample.
Polymers 2020, 12, x FOR PEER REVIEW 6 of 16

Figure 4.
Figure 4. Samples after
Samples thethe
after compression test.test.
compression On the
Onleft:
thebuckled sample.sample.
left: buckled On the right: fractured
On the right:
sample.
fractured sample.

2.7. Water Retention

For the
the water
waterretention
retentiontest
testfollowing
following ASTMASTM D570-98
D570-98[24], twotwo
[24], cylindrical specimens
cylindrical (L: 12.3
specimens (L: mm
12.3
and D: 25.7 mm) (Figure 2b) were prepared for 0-PLA, 3-PLA, and 24-PLA.
mm and D: 25.7 mm) (Figure 2b) were prepared for 0-PLA, 3-PLA, and 24-PLA. The samples were The samples were dried
in an oven
dried in an at 80 ◦at
oven C 80for°Cfour
forhours followed
four hours by drying
followed in a desiccator
by drying until until
in a desiccator a constant weight
a constant was
weight
attained (called initial weight (W )). The samples were immersed in distilled water at 25 ◦ C. The
was attained (called initial weightinitial ( )). The samples were immersed in distilled water at 25 °C.
specimens werewere
The specimens removed within
removed the first
within the24 h, pressed
first dry with
24 h, pressed dry awith
clotha and
clothweighed up to seven
and weighed times
up to seven
(Intervals: 3, 3, 3, 3,
times (Intervals: 3, 3,
4, 4,
3, and
3, 4,44,h).
andWithin
4 h). the second
Within the24 h, each24specimen
second was weighed
h, each specimen was up to five times
weighed up to
(Intervals:
five times (Intervals: 5, 5, 5, 5, and 4 h). Afterwards, the specimens were weighed once every Total
5, 5, 5, 5, and 4 h). Afterwards, the specimens were weighed once every three days. three
water absorbed
days. Total water was calculated
absorbed wasusing Equation
calculated using(1):Equation (1):

W f inal −
− Winitial × 100
WR((%) =
%) = × 100 (1)
(1)
Winitial
where WR(%) is the total water absorbed, and represents the weight after immersing in
where WR(%) is the total water absorbed, and W f inal represents the weight after immersing in distilled
distilled water for a specific time. Three samples were tested for each type and averaged results were
water for a specific time. Three samples were tested for each type and averaged results were reported.
reported.
2.8. Density
2.8. Density
The volume and the mass as a function of annealing intervals were measured up to four significant
digitsThe volume the
to calculate andsample
the mass as aThe
density. function of values
reported annealing intervals of
are averages were
threemeasured up to four
repetitions.
significant digits to calculate the sample density. The reported values are averages of three
repetitions.

3. Results and Discussion

Polymers 2020, 12, 2091 7 of 16

3. Results
Polymers 2020,and
12, xDiscussion
FOR PEER REVIEW 7 of 16

3.1. Thermal Properties of Processed PLA

depends on D-lactate contents and the molecular weight. Accordingly, PLAs exhibit lower (up to
60 °C)Case
3.1.1. compared
A to petroleum-based polyesters, with as high as 80 °C [14,25]. In addition, a cold
crystallization exotherm was observed in the 0-PLA sample (Figure 5) at = 89.9 °C and ∆ = 19.2
Thedisappearance
J/g. The effect of the annealing time
of the cold on the thermal
crystallization peakbehavior of processed
from annealed PLA is (0.5-PLA–24-PLA)
PLA samples shown in Figure 5.
The DSC that
indicates probes several
no more properties
crystalline of PLA including
structures the glass
are generated during transition temperature
the heating (T gis
cycle. There ), amelting
strong
temperature (T
relationship betweenm ), crystallization temperature (T ), enthalpy of crystallization
the annealing time and ∆ ,c as when the annealing time increases, (∆H c ), degree
the ∆ of
crystallinity
decreases. In(X c ), and melting
addition, almost enthalpy (∆H
there is no m ). Table 2peak
exothermic lists that
the thermal
could beproperties
identifiedextracted
at PLAs’ from the
samples
DSC profiles
that have of the processed
~ 40% [18,26]. PLA.

Figure 5. Effect
Effect of
of the
the annealing time on the DSC profile of processed polylactic acid (PLA).

Table 2. Effect of annealing time on the DSC profile of the processed PLA.
The annealing time showed no significant effect on the melting temperature as reported
elsewhere [27].
Interval (h)The peak melting Ttemperature
Tg (◦ C) ◦
c ( C) Tslightly
◦
m ( C)
increased
∆Hc (J/g)as a ∆H
function
m (J/g)
of annealing
Xc (%) time
interval from 168.4
Fast (0)
for 0-PLA
53
to 169.7
89.9
°C for 24-PLA.
168.4
However,
19.2
increasing
50.6
the annealing
33.8
interval
increased ∆0.5 , which was 57.6 calculated as 50.6 J/g,168.7
50.3 J/g, 54.5 J/g, and 60.348.8
J/g for 0-PLA, 3-PLA, 10-
52.5
PLA, and 117-PLA, respectively
56 . The increased168.6∆ further indicates47.7a change in 51.3degree of
3 with annealing.
crystallization 56.4 168.5
The degree of crystallization 50.3 by Equation
(%) was calculated 54.1 (2):
10 57.6 168.8 54.5 58.6
17 56.6 168.3 ∆ −∆ 60.3 64.8
%Crystallinity = = (2)
24 59 169.7 ∆ 54.3 58.4

where ∆ is the experimental enthalpy of melting, ∆ is the enthalpy of cold crystallization if

Generally,
observed, and ∆increasing
is thethe annealingmelting
theoretical time of enthalpy
PLA increases T g . crystalline
of 100% The fast cooling sample
PLA (93 exhibited
J/g [28]). The
T g =
degree 53 ◦ C whereas T = 59 ◦ C was observed in 24 PLA samples. The values of T measured for
of crystallizationg for all samples is reported in Table 2. The degree of crystallization g improved
neat PLA in this
substantially withstudy were within
the increasing the range
annealing reported
time. in the literature
The calculated [5,6].
values wereIn 33.8, 51.3,T54.1,
general, g in PLA
58.6
depends on D-lactate contents and the molecular weight. Accordingly, PLAs exhibit
and 64.8% for 0-PLA, 1-PLA, 3-PLA, 10-PLA, and 17-PLA, respectively. The 24-PLA exhibited a lower lower T g (up to
60 ◦ C) compared to petroleum-based polyesters, with T as high as 80 ◦ C [14,25]. In addition, a cold
crystallization percentage indicating that PLA might have g reached crystallization saturation between
annealing.was observed in the 0-PLA sample (Figure 5) at Tc = 89.9 C and ∆Hc = 19.2 J/g.
crystallization ◦
17 and 24 h of exotherm
The disappearance of the cold crystallization peak from annealed PLA samples (0.5-PLA–24-PLA)
indicates that no Table
more 2.crystalline structures
Effect of annealing areongenerated
time during
the DSC profile of the
the heating
processedcycle.
PLA. There is a strong

Interval (h) (°C) (°C) (°C) ∆ (J/g) ∆ (J/g) (%)

Fast (0) 53 89.9 168.4 19.2 50.6 33.8
0.5 57.6 168.7 48.8 52.5
Polymers 2020, 12, 2091 8 of 16

relationship between the annealing time and ∆Hc , as when the annealing time increases, the ∆Hc
decreases. In addition, almost there is no exothermic peak that could be identified at PLAs’ samples
that have Xc ~ 40% [18,26].
The annealing time showed no significant effect on the melting temperature as reported
elsewhere [27]. The peak melting temperature slightly increased as a function of annealing time interval
from 168.4 for 0-PLA to 169.7 ◦ C for 24-PLA. However, increasing the annealing interval increased
∆Hm , which was calculated as 50.6 J/g, 50.3 J/g, 54.5 J/g, and 60.3 J/g for 0-PLA, 3-PLA, 10-PLA, and
17-PLA, respectively. The increased ∆Hm further indicates a change in degree of crystallization with
annealing. The degree of crystallization (%) was calculated by Equation (2):

∆Hm − ∆Hc
%Crystallinity = Xc = (2)
∆Hm∞

Polymers ∆H
where 2020, is xthe
m 12, PEER REVIEW enthalpy of melting, ∆Hc is the enthalpy of cold crystallization
FORexperimental if
8 of 16
observed, and ∆Hm is the theoretical melting enthalpy of 100% crystalline PLA (93 J/g [28]). The
∞

1
degree of crystallization 56samples is reported
for all 168.6
in Table 2. The degree47.7 51.3
of crystallization improved
substantially with3 the increasing
56.4 annealing time.168.5 50.3
The calculated Xc values 54.1 51.3%, 54.1%,
were 33.8%,
58.6% and 64.8% 10 57.6
for 0-PLA, 1-PLA, 168.8
3-PLA, 10-PLA, 54.5 The 24-PLA
and 17-PLA, respectively. 58.6 exhibited a
lower crystallization17 percentage
56.6 indicating that168.3
PLA might have reached 60.3crystallization
64.8 saturation
24
between 17 and 24 h of annealing. 59 169.7 54.3 58.4
Figure 6 shows the degree of crystallization of the processed PLA and its measured density. With
Figure 6 shows the degree of crystallization of the processed PLA and its measured density.
an increasing annealing time interval, the density increase was attributed to the structural compactness
With an increasing annealing time interval, the density increase was attributed to the structural
which consequently increased the degree of crystallization. It is noteworthy, however, that the density
compactness which consequently increased the degree of crystallization. It is noteworthy, however,
difference in 0-PLA and 17-PLA was not significant. The fast cooling in 0-PLA might not have resulted
that the density difference in 0-PLA and 17-PLA was not significant. The fast cooling in 0-PLA might
in a completely amorphous structure.
not have resulted in a completely amorphous structure.

80

70
Crystallinity (%)

60

50

40

30

20

10
1228 1230 1232 1234 1236 1238 1240
Density (kg/m3)

Figure
Figure 6.
6. Degree
Degree of
of crystallinity
crystallinity versus
versus samples
samples density.
density.

3.1.2. Case B
Case B involves the effects of fast fast cooling
cooling on
on the
the degree
degree of
of crystallization
crystallization (X
( c ) and the thermal
properties of PLA before reaching the annealing temperature (95 ◦ C). A cooling rate of 80 ◦ C/min was
properties of PLA before reaching the annealing temperature (95 °C). A cooling °C/min
applied
applied toto avoid
avoidany
anypremature
prematurecrystallinity
crystallinitybefore
beforethe
theannealing
annealing temperature
temperature (Figure
(Figure3b). The
3b). effect
The of
effect
annealing
of annealing time (0, 5,
time (0,10, 20, 30,
5, 10, 20, 40,
30, 50
40,and 60 min)
50 and on the
60 min) onPLA’s thermal
the PLA’s profile
thermal is shown
profile in Figure
is shown 7 and
in Figure
7 and the thermal parameters are enlisted in Table 3. The decreased slightly with the increasing
annealing interval contradicting the behavior observed in Case A. In general, the observed was
in the range of 49.1–55.1 °C [14,25]. Comparing with the annealing time, the fast cooling in Case
B reduced . Unlike in Case A, Figure 7 shows three peaks of crystallization at 101, 99, and 94.3 °C
for a 0, 5, and 10 min annealing time, respectively. The appearance of these peaks indicated that these
Polymers 2020, 12, 2091 9 of 16

the thermal parameters are enlisted in Table 3. The T g decreased slightly with the increasing annealing
interval contradicting the behavior observed in Case A. In general, the observed T g was in the range of
49.1–55.1 ◦ C [14,25]. Comparing T g with the annealing time, the fast cooling in Case B reduced T g .
Unlike in Case A, Figure 7 shows three peaks of crystallization at 101, 99, and 94.3 ◦ C for a 0, 5, and
10 min annealing time, respectively. The appearance of these peaks indicated that these samples still
have the
Polymers capacity
2020, toPEER
12, x FOR produce crystalline structures during the heating cycle of the DSC.
REVIEW 9 of 16

Figure
Figure7.
7. Effect
Effectof
ofannealing
annealingtime
timeon
onthe
theDSC
DSCprofile
profile of
of the
the processed
processed PLA
PLA (Case
(Case B).

Table 3. DSC results for the PLA in one hour of the annealing process at 95 ◦ C (Case B).
Table 3. DSC results for the PLA in one hour of the annealing process at 95 °C (Case B).
Tg Tc Tm1 Tm2 ∆Hm1 ∆Hm2 Xc
Interval (min) ∆Hc (J/g)
Interval (min) (◦ C) (◦ C) (◦ C) (◦∆
C) (J/g) ∆ (J/g)
(J/g) (J/g)
∆ (%)
(J/g)
Fast (0) (°C)55.1 (°C) 101 (°C) 168.6 (°C) 32.5 36 38.7
(%)
Fast (0)5 55.154.3 101 99 168.6 167.6 32.5 30.4 36
41.4 44.5 38.7
10 54 94.3 152 167 3.5 2.5 43.6 49.6
5 20 54.355 99 167.6 152.5 165.8
30.4 41.4
3.8 40.9 48.1
44.5
10 30 5454.1 94.3 152 152.8167 165 3.5 2.5
5.3 36.3 43.6 44.7 49.6
20 40 55 52.1
152.5 153.1
165.8 164.2 54.7
3.8 40.9 58.8
48.1
50 50.8 153.2 163.1 55.4 59.6
30 60 54.149.1 152.8 153.3
165 162.1 5.3
55 36.3 59.1 44.7
40 52.1 153.1 164.2 54.7 58.8
50
Moreover, 50.8
a shoulder to the 153.2
melting 163.1
point was observed for annealing 55.4 over 5 min (Figure 59.67)
60 49.1 153.3 162.1 55
attributed to the presence of two crystalline structures with annealing [15,16]. With increasing 59.1
annealing time, atwo
Moreover, meltingtopeaks
shoulder (Tm1 and
the melting Tm2 )was
point appeared closer
observed fortoannealing
each otherover
(Table 3). The
5 min degree
(Figure 7)
of crystallization increased with increasing annealing time following the Case
attributed to the presence of two crystalline structures with annealing [15,16]. With increasing A trend and similar
to that previously
annealing time, tworeported
melting by Angela
peaks ( et al. [29].) appeared
and However,closer
fast cooling
to eachin Case
other B produced
(Table a more
3). The degree
crystalline
of PLA atincreased
crystallization the samewith
annealing time.annealing time following the Case A trend and similar to
increasing
that previously reported by Angela et al. [29]. However, fast cooling in Case B produced a more
3.2. Thermal Conductivity
crystalline PLA at the same annealing time.
Figures 8 and 9 show the effect of the annealing time on the thermal conductivity of processed PLA
3.2. Thermal range of 5–50 ◦ C. A significant impact of the annealing process was observed on the
Conductivity
in the temperature
thermal conductivity of PLA. For example, the thermal conductivity increased from 0.06426 W/(m·K)
Figures 8 and 9 show the effect of the annealing time on the thermal conductivity of processed
PLA in fast
for the cooled PLA to
the temperature 0.09044
range W/(°C.
of 5–50 m·KA)significant
for the 24 h-annealed samples.
impact of the Increasing
annealing processannealing time
was observed
on the thermal conductivity of PLA. For example, the thermal conductivity increased from 0.06426
W⁄(m ∙ K) for the fast cooled PLA to 0.09044 W⁄(m ∙ K) for the 24 h-annealed samples. Increasing
annealing time interval increased the thermal conductivity. Increasing annealing time might have
allowed spherulites to form comfortably and crystallites to grow in a more orderly fashion, which
helped the fast heat transfer due to compact structure [22]. Additionally, the increasing degree of
Polymers 2020, 12, 2091 10 of 16

interval increased the thermal conductivity. Increasing annealing time might have allowed spherulites
Polymers 2020, 2020,
12, x 12,
FOR PEER REVIEW 10 of 16
to form comfortably
Polymers and
x FOR crystallites
PEER REVIEW to grow in a more orderly fashion, which helped the 10 fast
of 16 heat

transfer due to compact structure [22]. Additionally, the increasing degree of crystallization of PLA
the samples
the samples annealed
annealed forfor
oneonehour
hourshowed
showed promising lowthermal
promising low thermal conductivities
conductivities (0.074–0.086
(0.074–0.086
might have reduced gaps between the chains and air voids resulting in increased thermal conductivity.
W⁄(m W∙⁄K (m
)),∙ K )), indicating
indicating that they
that can
they canact
actas
asthermal insulators.
thermal insulators.

0.110.11
Thermal conductivity (𝑊∕(𝑚 . 𝐾))

0.10
. ))

0.10
0.09
0.09
Thermal conductivity ( ∕(

0.08
0.08
0.07
0.07
0.06
0.06
0.05

0.05
0.04
5 10 15 20 25 30 35 40 45 50
0.04 Temperature (oC)
5 10 15 20 25 30 35 40 45 50
24 hr 3 hrTemperature
1 hr (oC) Fast cooling

248.hr
Figure 3 hr for PLA1athr
Thermal conductivity Fast times.
different annealing cooling

Figure 8.
Figure 8. Thermal
Thermal conductivity
conductivity for
for PLA
PLA at
at different annealing times.
different annealing times.

0.05
0.06
0.10
0.07
0.08
/m.K )

0.09
0.05
0.09 0.10
conductivity (W

0.06
0.10
0.07
0.08
0.08
0.09
0.09 0.10
0.07
Thermal

0.08
0.06 20
)

15
hr
e(

0.07 0.05
10
m
Ti

310
g

5
lin

300
0.06 20
ea

Temp 290
eratu 0
n

280
)

re (K
hr
An

15
r e hT

)
e(

0.05
m

10
lam

Ti

Figure 9.
FigureDependence of of
9. Dependence thethe
PLA
PLAthermal
thermalconductivity onthe
conductivity on thetemperature
temperature
andand annealing
annealing time.time.
310
g

5
lin

300
( yti vi t c udnoc

ea

Temp 290
0
n

eratu 280
An

re (K
)

Figure 9. Dependence of the PLA thermal conductivity on the temperature and annealing time.
W
Polymers 2020, 12, 2091 11 of 16
Polymers 2020, 12, x FOR PEER REVIEW 11 of 16

The blue
3.3. Water code in Figure 9 indicates the low thermal conductivity region where thermal conductivity
Retention
is comparable to conventional insulators [30]. Since less thermal conductivity is desired, the samples
In the selection of thermal insulation materials, water retention is a pertinent physical property
annealed for one hour showed promising low thermal conductivities (0.074–0.086 W/(m·K)), indicating
dictating the performance of thermal insulation materials. Figure 10 presents the effect of annealing
that they can act as thermal insulators.
time on the water retention (WR%) of processed PLA as a function of immersion time (hours). The
WR%
3.3. increased
Water with increasing time without reaching an equilibrium value within 8 days of the
Retention
immersion period. Furthermore, the 𝑊𝑅(%) calculated from Eq. 1 increased with the annealing time
In the selection of thermal insulation materials, water retention is a pertinent physical property
(24 h > 3 h > fast cooling).
dictating the performance of thermal insulation materials. Figure 10 presents the effect of annealing
It is difficult to compare the water retention results from this study with the published literature
time on the water retention (WR%) of processed PLA as a function of immersion time (hours). The
due to the scarcity of published data. The processed PLA exhibited a very low WR% (<0.35%), which
WR% increased with increasing time without reaching an equilibrium value within 8 days of the
is less than polyesters and polyester-based composites [31], and various types of polyurethane (1–6%
immersion period. Furthermore, the WR(%) calculated from Equation (1) increased with the annealing
after 24 h) [32] proposed for thermal insulation applications. The low WR% of PLA is attributed to its
time (24 h > 3 h > fast cooling).
hydrophobic characteristics [33] which make it a potential candidate for thermal insulation.

0.4

0.35
Water retention (WR%)

0.3

0.25

0.2

0.15

0.1

0.05

0
0 50 100 150 200
Time (hrs)

Fast cooling 3 hrs 24 hrs

Figure
Figure 10.
10. Water
Water retention results for
retention results for the
the processed
processed PLA
PLA samples.
samples.

3.4. Mechanical andtoMorphological

It is difficult Characteristics
compare the water retention results from this study with the published literature
due to the scarcity of published data. The processed PLA exhibited a very low WR% (<0.35%), which
The mechanical performance of semi-crystalline polymers depends on multiple factors
is less than polyesters and polyester-based composites [31], and various types of polyurethane (1–6%
including the degree of crystallinity. The stress–strain behavior of processed PLA is shown in Figure
after 24 h) [32] proposed for thermal insulation applications. The low WR% of PLA is attributed to its
11a. The effect of the annealing process on the compression properties of PLA is presented in Figure
hydrophobic characteristics [33] which make it a potential candidate for thermal insulation.
11a–d.
3.4. Mechanical and Morphological Characteristics
The mechanical performance of semi-crystalline polymers depends on multiple factors including
the degree of crystallinity. The stress–strain behavior of processed PLA is shown in Figure 11a. The
effect of the annealing process on the compression properties of PLA is presented in Figure 11a–d.
Polymers 2020, 12, 2091 12 of 16
Polymers 2020, 12, x FOR PEER REVIEW 12 of 16

(a) (b)

140

Stress (MPa)
120
100
80
60
40
20
0

Annealing time

Compression strength Yield Point

(c) (d)
3.5 0.6
3.0 0.5
Modulus (GPa)

2.5
0.4
Strain (mm/mm)

2.0
0.3
1.5
0.2
1.0
0.5 0.1
0.0 0

Annealing time Annealing time

Figure
Figure 11.
11. Effect
Effect of
ofthe
thePLA
PLAannealing
annealingtime
timeon
on(a)
(a)the
thestress–strain
stress–straincurve,
curve,(b)
(b)the
thecompressive
compressivestrength,
strength,
and yield point, (c) the compressive modulus and (d) the compressive strain.
and yield point, (c) the compressive modulus and (d) the compressive strain.

Increasing the annealing time improved the compressive strength, compressive yield point, and
the compression
compression modulus
modulusofofthe theprocessed
processed PLA.
PLA. The The compressive
compressive strength
strength of the
of the fast-cooled
fast-cooled PLAPLA was
was 58 MPa, which increased by 70% and 84% to reach 98.7 MPa and 108
58 MPa, which increased by 70% and 84% to reach 98.7 MPa and 108 MPa upon annealing for 3 and MPa upon annealing for 3
and
24 h,24 h, respectively.
respectively. This behavior
This behavior can becan be attributed
attributed to the to the shaping
shaping of the spherulites
of the spherulites and crystals
and crystals during
during the annealing
the annealing period. period.
Therefore,Therefore,
increasingincreasing 𝑋 is
Xc is likely to likely to strengthen
strengthen the structure
the structure of the
of the polymer,
polymer, resulting in the increase in the compressive strength and compressive
resulting in the increase in the compressive strength and compressive modulus [17]. The compressive modulus [17]. The
compressive
modulus increasedmodulus withincreased with time
the annealing the annealing time interval,
interval, reaching reaching
a maximum a maximum
for 24-PLA (Figurefor11c).
24-PLAThe
(Figure 11c). The 24 h-annealed PLA exhibited a 73% increment compared to
24 h-annealed PLA exhibited a 73% increment compared to the neat PLA, from 1700 MPa to ~3000 MPa. the neat PLA, from 1700
MPa Figure
to ~300011d MPa.
shows that the maximum strain decreased with the annealing time interval. A
Figurestrain
maximum 11d shows
decrease that
wasthe maximum
noticed for thestrain
24-PLA decreased
where the with the annealing
maximum time interval.
strain reduced from 0.58 A
maximum strain decrease was noticed for the 24-PLA where the maximum
for 0-PLA to ~0.095 for 24-PLA. The annealed PLA samples gradually lost their ability to absorb strain reduced from 0.58
for 0-PLA
energy to ~0.095
to fracture withforthe
24-PLA. Theannealing
increasing annealed timePLAinterval.
samplesMoreover,
graduallythe lostdecreased
their ability to absorb
fracture strain
energy to fracture
also indicates with the of
the formation increasing annealing
a more compact time interval.
structure Moreover,
with annealing, in the decreased
agreement with fracture
above
strain
results.also
Theindicates
length of the
the formation of a more
annealing process compact
plays a pivotalstructure with annealing,
role in rearranging in agreement
the PLA’s with
microstructure
above results.
as reflected by The length of the
the mechanical annealingThe
properties. process plays process
annealing a pivotal role inthe
reduces rearranging
degree of the PLA’s
molecular
microstructure as reflected by the mechanical properties. The annealing process
randomization and hence, improves the mechanical modulus and overall strength [22]. Overall, the reduces the degree
of
PLAmolecular
annealed randomization
from 1 to 3 h and hence,high
produces improves the mechanical
compressive strengthmodulus and overall
PLA (97.2–98.6 MPa)strength
with a high[22].
Overall,
degree ofthe PLA annealed
ductility from 1 to 3 hThe
(strain ~ 0.37–0.18%). produces high compressive
compressive strength andstrength
modulusPLA were(97.2–98.6 MPa)
high compared
with a high degree of ductility (strain ~ 0.37–0.18%). The compressive strength and modulus were
Polymers 2020, 12, x FOR PEER REVIEW 13 of 16
Polymers 2020, 12, 2091 13 of 16
high compared to the polyester and its composites (strength: 19–103 MPa and modulus: 264–1370
MPa) [34] used for insulation applications.
to the polyester and its composites (strength: 19–103 MPa and modulus: 264–1370 MPa) [34] used for
The SEM micrographs of the annealed PLA shown in Figure 12 support the observed mechanical
insulation applications.
and thermal behavior. Figure 12A1 and Figure 12A2 show the morphology of 0-PLA at 10 μm and 2
The SEM micrographs of the annealed PLA shown in Figure 12 support the observed mechanical
μm, respectively. However, it can be described as ductile, while Figure 12B1 and Figure 12B2 exhibit
and thermal behavior. Figure 12A1,A2 show the morphology of 0-PLA at 10 µm and 2 µm, respectively.
the morphology of 24-PLA at 10 μm and 2 μm, respectively, which can be recognized as brittle. The
However, it can be described as ductile, while Figure 12B1,B2 exhibit the morphology of 24-PLA at
comparison between the 0-PLA and the 24-PLA samples revealed that the ductile deformation of the
10 µm and 2 µm, respectively, which can be recognized as brittle. The comparison between the 0-PLA
0-PLA is suppressed by the annealing and the microstructure of 24-PLA is more rigid than that of 0-
and the 24-PLA samples revealed that the ductile deformation of the 0-PLA is suppressed by the
PLA. The voids and cavities between the polymer segments were reduced significantly upon
annealing and the microstructure of 24-PLA is more rigid than that of 0-PLA. The voids and cavities
annealing for 24 h.
between the polymer segments were reduced significantly upon annealing for 24 h.

(a1) (a2)

(b1) (b2)

Figure 12. SEM micrograph for the PLA specimens at different resolutions: (a1)
Figure 12. (a1) 0-PLA
0-PLA (low
(low zoom),
zoom),
(a2) 0-PLA (high zoom), (b1) 24-PLA (low zoom), and (b2) 24-PLA (high zoom).
(a2) 0-PLA (high zoom), (b1) 24-PLA (low zoom), and (b2) 24-PLA (high zoom).

4. Conclusions
4. Conclusions
In this study, the effect of the annealing conditions on the thermal insulation and mechanical
In this study, the effect of the annealing conditions on the thermal insulation and mechanical
properties of the biopolymer PLA processed with a melt extruder and shaped in a compression molding
properties of the biopolymer PLA processed with a melt extruder and shaped in a compression
system was reported. Increasing the annealing time in the range of 0–24 h led to a significant increase
molding system was reported. Increasing the annealing time in the range of 0–24 h led to a significant
in the degree of crystallization, which had a direct effect on the thermal conductivity, density, and glass
increase in the degree of crystallization, which had a direct effect on the thermal conductivity,
transition temperature. The thermal conductivity of PLA at 25 ◦ C increased from 0.06426 W/(m·K))
density, and glass transition temperature. The thermal conductivity of PLA at 25 °C increased from
for the fast-cooled samples (0-PLA) to 0.09044 W/(m·K)) for the samples annealed for 24 h (24-PLA).
0.06426 W⁄(m · K) ) for the fast-cooled samples (0-PLA) to 0.09044 W⁄(m · K) ) for the samples
The glass transition temperature increased approximately by 11.33% between the 0-PLA and the
annealed for 24 h (24-PLA). The glass transition temperature increased approximately by 11.33%
24-PLA samples to 59 ◦ C. Moreover, the annealing process improved the compressive strength and
between the 0-PLA and the 24-PLA samples to 59 °C. Moreover, the annealing process improved the
Polymers 2020,
Polymers 12, x12,
2020, FOR2091PEER REVIEW 14 of
1416
of 16

compressive strength and rigidity of PLA substantially, by more than 80%, and reduced its ductility.
rigidity
From of PLA insulation
a thermal substantially, by more than
perspective, the80%,
low and reduced
thermal its ductility.low
conductivity, Fromdensity,
a thermal andinsulation
high
compressive strength are required. A brief comparison between the aforementioned properties is A
perspective, the low thermal conductivity, low density, and high compressive strength are required.
brief comparison
presented between
in Figure 13 the aforementioned
and shows that the annealingproperties
process of is PLA
presented
for 1–3inhFigure
produces13 and shows that
an optimum
thermal insulation material. The PLA thermal conductivity values (0.0798–0.0865 W⁄(m · K)The
the annealing process of PLA for 1–3 h produces an optimum thermal insulation material. PLA
), and
3 ) in this annealing
density (~1233 kg⁄m ) in this annealing time range are very promising and comparable with
thermal conductivity values (0.0798–0.0865 W/ ( m·K ) ), and density (~1233 kg/m
time range
traditional andare very promising
commercial and comparable
heat insulators, while with traditional andcompressive
the corresponding commercial strength
heat insulators, while
(97.2–98.7
the corresponding compressive strength (97.2–98.7 MPa) is much higher than that
MPa) is much higher than that of traditional thermal insulators and comparable with construction of traditional thermal
insulators and comparable with construction materials.
materials.

0.000813 110
105

Compressive strength (MPa)

Specific volume (m3/kg)

0.000812
100
95
0.000811
90
0.00081 85
80
0.000809
75
70
0.000808
65
0.000807 60
0 4 8 12 16 20 24
Annealing time (hr)
Specific volume Thermal resistance Compressive strength

Figure
Figure 13. 13. Thermal
Thermal resistance,
resistance, specific
specific volume,
volume, andand
the the compressive
compressive strength
strength of PLA.
of PLA.

Author
Author Contributions:
Contributions:M.S.B.: Data curation;
M.S.B.: Data curation; Formal
Formal analysis;
analysis; Investigation;
Investigation; Writing—original
Writing—original draft
draft preparation.
preparation. B.A.-J.: Conceptualization;
B.A.-J.: Conceptualization; Funding
Funding acquisition; acquisition;
Investigation; Investigation;
Methodology; Project Methodology; Project
administration; Resources;
Supervision; Writing—review
administration; & editing.Writing—review
Resources; Supervision; A.H.I.M.: Investigation; Resources;
& editing. Supervision;
A.H.I.M.: Writing—review
Investigation; Resources; &
editing. M.Z.I.:
Supervision; Investigation;
Writing—review & Methodology;
editing. M.Z.I.:Resources; Writing—review
Investigation; Methodology; & editing. All Writing—review
Resources; authors have read&and
agreed to the published version of the manuscript.
editing. All authors have read and agreed to the published version of the manuscript.
Funding: This research was funded by The Emirates Center for Energy and Environment Research—UAE
Funding: This(Project
University research was funded by The Emirates Center for Energy and Environment Research—UAE
# 31R163).
University (Project # 31R163).
Conflicts of Interest: The authors declare no conflict of interest.
Conflicts of Interest: The authors declare no conflict of interest.
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