polymers

Article
Bio-Based PLA/PBS/PBAT Ternary Blends with Added
Nanohydroxyapatite: A Thermal, Physical,
and Mechanical Study
Pei-Hua Chen 1,2 , Chin-Wen Chen 3, * , Hsu-I Mao 3 , Chi-An Dai 4 , Chie-Shaan Su 5 , Jung-Chin Tsai 6
and Feng-Huei Lin 1, *

1 Department of Biomedical Engineering, National Taiwan University, Taipei 106319, Taiwan;

[email protected]
2 Department of Orthopedics, Shuang Ho Hospital, Taipei Medical University, New Taipei City 235041, Taiwan
3 Department of Molecular Science and Engineering, Institute of Organic and Polymeric Materials,
Research and Development Center of Smart Textile Technology, National Taipei University of Technology,
Taipei 106344, Taiwan; [email protected]
4 Department of Chemical Engineering, Institute of Polymer Science and Engineering,
National Taiwan University, Taipei 106319, Taiwan; [email protected]
5 Department of Chemical Engineering and Biotechnology, National Taipei University of Technology,
Taipei 106344, Taiwan; [email protected]
6 Department of Chemical Engineering, Ming Chi University of Technology, New Taipei City 243303, Taiwan;
[email protected]
* Correspondence: [email protected] (C.-W.C.); [email protected] (F.-H.L.)

Abstract: The physical and mechanical properties of novel bio-based polymer blends of polylactic
acid (PLA), poly(butylene succinate) (PBS), and poly (butylene adipate-co-terephthalate) (PBAT)
with various added amounts of nanohydroxyapatite (nHA) were investigated in this study. The
formulations of PLA/PBS/PBAT/nHA blends were divided into two series, A and B, containing 70
or 80 wt% PLA, respectively. Samples of four specimens per series were prepared using a twin-screw
extruder, and different amounts of nHA were added to meet the regeneration needs of bone graft
Citation: Chen, P.-H.; Chen, C.-W.; materials. FTIR and XRD analyses were employed to identify the presence of each polymer and nHA
Mao, H.-I.; Dai, C.-A.; Su, C.-S.; Tsai, in the various blends. The crystallization behavior of these blends was examined using DSC. Tensile
J.-C.; Lin, F.-H. Bio-Based and impact strength tests were performed on all samples to screen feasible formulations of polymer
PLA/PBS/PBAT Ternary Blends with blends for bone graft material applications. Surface morphology analyses were conducted using SEM,
Added Nanohydroxyapatite: A and the dispersion of nHA particles in the blends was further tested using TEM. The added nHA also
Thermal, Physical, and Mechanical
served as a nucleating agent aimed at improving the crystallinity and mechanical properties of the
Study. Polymers 2023, 15, 4585.
blends. Through the above analyses, the physical and mechanical properties of the polymer blends
https://doi.org/10.3390/
are reported and the most promising bone graft material formulations are suggested. All blends were
polym15234585
tested for thermal degradation analysis using TGA and thermal stability was confirmed. The water
Academic Editor: Roberto Pantani absorption experiments carried out in this study showed that the addition of nHA could improve the
Received: 22 September 2023
hydrophilicity of the blends.
Revised: 22 November 2023
Accepted: 28 November 2023 Keywords: PLA; PBS; PBAT; nHA; polymer blends; mechanical strength; physical properties
Published: 30 November 2023

1. Introduction
Copyright: © 2023 by the authors.
In recent years, the research and development of biomaterials have developed rapidly
Licensee MDPI, Basel, Switzerland.
to meet the needs of tissue engineering to improve human life. The interface between syn-
This article is an open access article
distributed under the terms and
thetic biology and biomaterial design creates promising challenges in health, biotechnology,
conditions of the Creative Commons
and sustainability [1]. Proper design of biomaterials must cover both their mechanical
Attribution (CC BY) license (https://
properties and biological activity. Future biomaterials can maintain organ transport and
creativecommons.org/licenses/by/ self-healing functions, biocompatibility, biodegradability, bioactivity, and tissue regenera-
4.0/). tion activity [1,2]. Biomaterials are generally classified as natural, metal and alloy-based,

Polymers 2023, 15, 4585. https://doi.org/10.3390/polym15234585 https://www.mdpi.com/journal/polymers

Polymers 2023, 15, 4585 2 of 21

ceramic-based, polymer-based, or composite materials for tissue engineering scaffolds,

each of which has a variety of applications [3,4]. It has been reported that surgeries to treat
bone defects in orthopedics has a growing rate [5], and the development of biomaterials for
orthopedic implants has received much attention [6–10]. The design and fabrication tech-
niques for bone tissue engineering have been reported in the review literature, addressing
engineering processes and functional properties [11–14]. Although most bone implants are
metal-based, polymers and their composites are projected to become more suitable in the
future [15]. In recent reviews, next-generation bone tissue bio-based materials, especially
biodegradable polymers and nanotechnology, have received much attention [16–18].
Polylactic acid (PLA) is the most commonly used semi-crystalline bio-based polymer
approved by the U.S. Food and Drug Administration (FDA) for its desired biocompati-
bility and biodegradability [19]. In order to improve some of its limitations in terms of
mechanical properties, toughness, hydrophilicity, and cell affinity, composites of PLA with
other polymers or inorganic additives have been studied in the literature. For example,
hydroxyapatite (HA) has been added to PLA to study the in vitro osteogenic differentiation
of human mesenchymal stem cells [20]. According to previous reports [21,22], the current
improvement of tough PLA was achieved through polymer blending, copolymerization,
plasticization, or composite modifications. Blending PLA with other elastomeric poly-
mers is relatively easy and often considered to be the most effective method. PLA with
biodegradable polymers such as polycaprolactone (PCL), poly(butylene succinate) (PBS),
poly(butylene succinate-co-adipate) (PBSA), and poly(butylene adipate-co-terephthalate)
(PBAT) have been discussed. Recent literature has reported the mechanical and physical
properties of blends of PBS and PBAT with various compositions, including behavior after
supercritical CO2 foaming [23,24]. The mechanical and physical properties of PLA/PBS
or PLA/PBAT blends with proper compositions have been investigated in previous re-
ports, demonstrating their morphology, mechanical properties, and potential applications
as scaffolds in tissue engineering [25–31]. Biomaterials for tissue engineering preferably
contained bioactive components such as chitosan (a natural polysaccharide) or HA (the
main component of human bone tissue) in structured scaffolds to facilitate the regenerative
process. The fabrications of PLA-based scaffolds with other biodegradable polymers and
bioactive materials have been shown in the literature [32–38]. It has been reported that
loaded nano-HA (nHA) particles could promote cell proliferation and mimic the structure
of the bone extracellular matrix [20,35–39].
To the best of our knowledge, most literature reports have presented the properties
and applications of biodegradable binary polymer blends (for example, PLA/PBS or
PLA/PBAT) [28,29,31] or a single polymer with nHA particles added [36,40,41]. Although
some studies on ternary systems have been carried out [38,40–42], more experimental
measurements are still needed. The aim of this study was to explore the properties of
novel polymer blends containing three biodegradable polymers (PLA, PBS and PBAT) with
inorganic nHA added. The main component of the blends was PLA, which is suitable for
bone graft applications due to its good mechanical strength. The elongation and toughness
limits of PLA can be improved by blending with ductile PBS and PBAT. Biodegradable PBS
also showed good cell viability [38]. PBAT has a strong but underexploited potential for
bone growth in vivo, and the studies on including nHA in PBAT are still limited [35,36].
Therefore, this study proposes a novel bone graft biomaterial, a PLA/PBS/PBAT/nHA
composite, produced using a twin-screw extruder. No organic solvent was used in this
study to avoid any safety concerns as implant biomaterials. The mechanical and physical
properties of various formulations of this blend were measured and promising blends for
further bone graft applications are illustrated.

2. Materials and Methods

2.1. Materials
Polylactic acid (PLA, Ingeo 4032D) was purchased from NaturalWorks LLC, Min-
netonka, MN, USA. It is semi-crystalline, with an average D-lactide content of 1.4 wt%.
Polymers 2023, 15, 4585 3 of 21

Poly(butylene succinate) (Bio PBS, FZ 91), a semi-crystalline polyester, was purchased from
PTT MCC Biochem Co. Ltd., Bangkok, Thailand. Poly(butylene adipate-co-terephthalate)
(PBAT, ecoflex F blend C1200) was purchased from BASF SE, Ludwigshafen, Deutsch-
land. The physical and mechanical properties of these polymers are listed in Table 1.
Nano-hydroxyapatite (nHA, CAS registry number 12167-74-7) was purchased from Sigma-
Aldrich, UNI-ONWARD Corp., Taiwan, with purity greater than 97 wt%, mean particle
size of 72–80 nm, molecular weight of 502.3, and melting temperature of about 1100 ◦ C.

Table 1. Physical and mechanical properties of polymers used in this study a .

Physical Properties PLA PBS PBAT

Density (g/cm3 ) 1.24 1.26 1.25–1.27
Melt flow index (g/10 min, at 190 ◦ C, 2.16 kg) 7 5 2.7–4.9
Melting temperature, Tm (◦ C) 155–170 115 110–120
Tensile yield strength (MPa) 60 39 36
Tensile modulus (GPa) 3.5 0.58 –
Tensile elongation (%) 6.0 350 560
a: according to the suppliers.

2.2. Preparation of Composite Blends

PLA, PBS, and PBAT polymers were first dried in a vacuum oven at 80 ◦ C for 6 h
before compounding. These blends were prepared using a twin-screw extruder (Process 11,
Thermo Fisher Scientific, Waltham, MA, USA). The extruder was equipped with a volu-
metric feeder and a strand pelletizer for blending the polymers. The diameter of the screw
extruder is 11 mm, with an L/D ratio of 40. Polymers were fed into the hopper of the
extruder for the compounding process. The extruder has six zones, from feed to die, where
the extrusion temperatures were controlled independently. The feed rate of the polymer
pellets was 1 kg h−1 , and the screw speed was 50 rpm. The temperature settings for the
feed and mixing zones were adjusted to be 200–210–220–225–225–220 ◦ C. After blending, a
water bath was used to cool the extruded products. These products were then granulated
and dried for a sufficient time before mechanical property testing. Plate specimens with a
thickness of 1.2 ± 0.2 mm were made by compression molding at 200 ◦ C for 5 min, followed
by cooling to room temperature. The specimens were packed in plastic bags and stored in
cool surroundings before tests. The extruded products for polymers with added nHA were
prepared with the same procedure. Samples with various formulations were also used for
thermal, chemical composition, morphology, and water absorption analyses.
Table 2 lists the formulations of PLA-based polymer blends in this study. The specimen
code PLA60 represented a polymer blend containing 60 wt% PLA and two other polymers
(25 wt% PBS and 15 wt% PBAT), without the addition of nHA. Sample series A and B listed
in Table 2 included specimen codes with various amounts of nHA added. For example,
specimen A0 listed in Table 2 represented a blend containing 70 wt% PLA, 20 wt% PBS,
10 wt% PBAT, and no added nHA. Specimens A3, A5, and A7 in sample series A had the
same PLA/PBS/PBAT composition as specimen A0, but with the addition of 3, 5, and
7 wt% nHA, respectively. Sample series B contained 80 wt% PLA, 15 wt% PBS, 5 wt% PBAT,
with 0, 3, 5, and 7 wt% nHA added to specimens B0, B3, B5, and B7, respectively. It has
been pointed out that nanocomposites comprising nHA favored the biocompatibility of
bone formation [10,36–39,43,44]. The average particle size of nHA used in this study was
within the range of nHA particle sizes reported in the literature [44].
Polymers 2023, 15, 4585 4 of 21

Table 2. Formulations of PLA/PBS/PBAT/nHA blends in this study.

Specimen Code PLA (wt%) PBS (wt%) PBAT (wt%) nHA (wt%)
Sample with 60 wt% PLA
PLA60 60 25 15 0
Sample series A
A0 70 20 10 0
A3 70 20 10 3
A5 70 20 10 5
A7 70 20 10 7
Sample series B
B0 80 15 5 0
B3 80 15 5 3
B5 80 15 5 5
B7 80 15 5 7

2.3. Analysis and Testing

2.3.1. Fourier-Transform Infrared Spectroscopy (FTIR)
Fourier-transform infrared spectroscopy (FTIR, Thermo Fisher Scientific Summit LITE
Spectrometer, Madison, WI, USA) using the ATR technique was employed for analyzing
the chemical structures of the polymer blends. The wavenumber in the tests ranged from
4000 to 500 cm−1 . The resolution was 4 cm−1 , and the number of scans was 32.

2.3.2. X-ray Diffraction Analysis

The intensity of crystallinity of the polymer blends was analyzed using an X-ray
diffractometer (XRD, Rigaku, Tokyo, Japan) with Cu-Kα radiation (λ = 1.54 Å) operated at
40 kV and 15 mA. The XRD data were collected in the 2θ angle range from 5 to 40◦ , with a
scanning rate at 10◦ min−1 .

2.3.3. Differential Scanning Calorimeter Measurements

The thermal and crystallization behavior of various polymer blends was analyzed
using differential scanning calorimetry (DSC, Hitachi High-Tech Science DSC-7000, Tokyo,
Japan) under a nitrogen atmosphere. Each sample of 4–6 mg was heated at a rate of
10 ◦ C min−1 from 30 to 200 ◦ C and held at 200 ◦ C for 5 min in the first heating process to
remove any thermal history. The sample was cooled to −50 ◦ C at a rate of 10 ◦ C min−1 and
kept at −50 ◦ C for 5 min. In the second heating process, the sample was heated from −50
to 200 ◦ C at a rate of 10 ◦ C min−1 . The glass transition temperature, cold crystallization
temperature, melting temperature, enthalpy of cold crystallization, and enthalpy of melting
were recorded for each sample.
DSC (Hitachi High-Tech Science DSC-7000, Tokyo, Japan) was also employed to evalu-
ate the nonisothermal crystallization behavior of various polymer blends. The prepared
samples were kept in aluminum pans under nitrogen atmosphere. The samples were first
heated from 30 to 200 ◦ C at 10 ◦ C min−1 and then maintained at 200 ◦ C for 5 min to remove
any thermal history. Next, the samples were cooled to 50 ◦ C at various rates of 2.5, 5, 7.5,
and 10 ◦ C min−1 . Finally, heat flow traces were recorded for analysis.

2.3.4. Mechanical Testing

The tensile and impact strength for various polymer blends were measured in this
study. A universal material testing machine (Cometech QC-508M2F equipment, Taichung,
Taiwan) was used. The tensile tests were conducted at a tensile rate of 50 mm min−1
using dumbbell specimens (ASTM D638 Type IV, length: 33 mm, width: 6 mm, thickness:
3 mm, the gauge length being 50 mm). The impact tests (ASTM D412; the degree between
pendulum and sample was set at 150◦ ) were performed using a Ceast pendulum impact
tester (Model Resil 50B) and a Ceast notch cutting machine. The Izod method was employed.
A 2.75 J hammer was sufficient to break all specimens tested for impact strength. At least
Polymers 2023, 15, 4585 5 of 21

five repeated tests were conducted for tensile and impact strength measurements. The
averaged values and standard deviations for these mechanical properties were recorded.

2.3.5. Surface Morphology

A scanning electron microscope (SEM, TESCAN VEGA 3 SBH, Brno, Czech Republic)
was used to observe the surface morphology and the dispersion of nHA in the PLA/PBS/
PBAT/nHA blends. The SEM was operated at an acceleration voltage of 20 kV and a
magnification of 3000×. All samples were dried under vacuum and sputter-coated with
gold before SEM experiments. The chemical composition of the blends was studied using
an energy-dispersive X-ray spectroscope (EDX) attached to the SEM (Nova NanoSEM 230,
currently supported by Thermo Fisher, Waltham, MA, USA).

2.3.6. TEM Measurements

A transmission electron microscope (TEM, Hitachi H-7650, Tokyo, Japan) was used
to investigate the distribution of nHA in the PLA/PBS/PBAT/nHA blends. Ultrathin
sections of sample were prepared using a cryomicrotome with a diamond knife in a dry N2
atmosphere at −100 ◦ C. The thin film pieces were placed on a copper grid and the TEM
analyses were conducted at a low voltage of 70 kV to prevent electron beam damage.

2.3.7. Thermogravimetric Analysis (TGA)

The thermogravimetric analyses for the polymer blends were performed using a ther-
mogravimetric analyzer (TGA, Pyris 6, Perkin Elmer, New Castle, DE, USA) to investigate
the thermal stability of the blended samples. Approximately 8 mg of each polymer blend
sample was heated from 40 to 600 ◦ C under a nitrogen atmosphere at a heating rate of
10 ◦ C min−1 . TGA thermograms were recorded during the heating process and differential
thermogravimetric analyses (DTGAs) were also performed.

2.3.8. Water Absorption Measurements

The water absorption for various polymer blends was investigated in this study. The
specimens with 20 mm × 10 mm × 2 mm were dried in a vacuum oven at 50 ◦ C for 48 h.
The specimens were weighed after the drying process using a balance (Precisa ES 225
SM-DR, Dietikon, Switzerland, readability 0.01 mg). The specimens were then completely
immersed in distilled water at 25 ◦ C for 24 h and longer, up to 8 days. After immersing the
specimens in distilled water for t days (t = 1, 2, 5, and 8), they were taken out and wiped
with filter paper before weighing for water absorption. The water absorption percentages
for various samples were determined from weight gain after the water immersion process.

3. Results and Discussion

3.1. Tensile Strength Test Results for PLA/PBS/PBAT Blends
The mechanical strength of polymer blends without the addition of nHA was first
tested to screen for acceptable formulations. The tensile strength test results for these
polymer blends without nHA are presented in Table 3. It is observed that specimen PLA60
had a maximum tensile stress (tensile strength) of 37.6 ± 1.8 MPa, while specimens A0
and B0 both had maximum tensile stress greater than 45 MPa. The tensile strength of
human cortical and cancellous bone, although age-dependent, is 50–150 and 10–100 MPa,
respectively [10,45,46]. According to the literature [42], tensile strength higher than 40 MPa
meets the need for bone tissue engineering material. It is observed from Table 3 that
specimens A0 and B0 almost reached the lower limit of the tensile strength of human
cortical bone. The elongations at maximum tensile stress were about 8%. The tensile
modulus results for specimens A0 and B0 were also better than that of human cancellous
bone [8]. Therefore, PLA-based polymer blends containing 70 or 80 wt% PLA in this study
were considered acceptable biomaterials for bone grafts. Specimens in series A and B listed
in Table 2 were used for further physical and mechanical property analyses.
 B listed in Table 2 were used for further physical and mechanical property analyses.

Table 3. Tensile test results of PLA/PBS/PBAT blends.

Polymers 2023, 15, 4585 Elongation at Max- 6 of 21

Sample of Maximum Tensile Tensile Modulus
imum Tensile Stress
PLA/PBS/PBAT Blends Stress (MPa) (MPa)
(%)
Table 3. Tensile test results of PLA/PBS/PBAT blends.
PLA60 37.6 ± 1.8 7.0 ± 0.5 584.8 ± 71.9
Sample of PLA/PBS/PBAT
A0 Maximum Tensile Stress
47.1 ± 2.9 Elongation at Maximum
7.9 ± 0.4 Tensile Modulus
642.0 ± 109.1
Blends (MPa) Tensile Stress (%) (MPa)
B0 49.6 ± 1.6 8.0 ± 0.6 686.1 ± 91.3
PLA60 37.6 ± 1.8 7.0 ± 0.5 584.8 ± 71.9
A0 47.1 ± 2.9 7.9 ± 0.4 642.0 ± 109.1
B0FTIR
3.2. Measurement 49.6 ± 1.6
Results for 8.0 ± 0.6Blends
PLA/PBS/PBAT/nHA 686.1 ± 91.3

The chemical structures for various PLA/PBS/PBAT/nHA blends were characterized

3.2. FTIR Measurement Results for PLA/PBS/PBAT/nHA Blends
using FTIR spectroscopy. The results for all specimens are presented in Figure 1. The
The chemical structures for various PLA/PBS/PBAT/nHA blends were characterized
band around the wavenumber
using of 3000
FTIR spectroscopy. Thecm
−1 represented the symmetric and asymmetric
results for all specimens are presented in Figure 1. The
stretching vibration
band around 3 in
of CHthe PLA. The ofpeak
wavenumber 3000 at
cm1750 cm−1 showed
−1 represented the stretching
the symmetric of the
and asymmetric
stretching vibration of CH in −1 showed
C=O group of PLA as well as PBS and 3 PBAT. The bands at 1181 cm and 1082 cmof−1 the
PLA. The peak at 1750 cm −1 the stretching be-
C=O group of PLA as well as PBS and PBAT. The bands at 1181 cm−1 and 1082 cm−1
longed to the peaks of C-O-C. The peak at 1040 cm is attributed−1 to C-CH3 [42,47–50]. The
belonged to the peaks of C-O-C. The peak at 1040 cm−1 is attributed to C-CH3 [42,47–50].
characteristic peaks at 602 cm peaks
The characteristic
−1 andat570
602 cm
cm−1 represented
−1 the characteristic
and 570 cm−1 represented peaks peaks
the characteristic of POof3−4
in nHA [42,48,50].
PO3 −4 in nHA [42,48,50].

(a)
Figure 1. Cont.
, x FOR PEER REVIEW 7 of 24
Polymers 2023, 15, 4585 7 of 21

(b)
Figure 1. FTIR measurement results for polymer
Figure 1. FTIR measurement blends:blends:
results for polymer (a) sample series
(a) sample A Aand
series and(b) sample
(b) sample series
series B,
B, with various amounts of amounts
with various nHA added.
of nHA added.

It was observed that no nHA peaks were present in specimens A0 and B0, to which no
It was observed that no nHA peaks were present in specimens A0 and B0, to which
nHA particles were added during the preparation of the polymer blends. The characteristic
no nHA particlespeakswere added
of nHA in theduring the preparation
FTIR spectra of the
for other specimens polymer
in Figure blends.
1a,b clearly The char-
indicated the
acteristic peaksexistence
of nHAofinnHAtheinFTIR spectra for other specimens in Figure 1a,b clearly in-
the blends.
dicated the existence of nHA in the blends.
3.3. XRD Measurement Results for PLA/PBS/PBAT/nHA Blends
XRD analysis was performed to further confirm the presence of nHA in the PLA/PBS/
3.3. XRD Measurement Results
PBAT/nHA for blends
polymer PLA/PBS/PBAT/nHA
and to identify the Blends
crystalline species in the polymer blends.
The results
XRD analysis was are presented into
performed Figure 2a,b for
further sample series
confirm the A and B withof
presence various
nHAamounts
in the
of nHA added. The diffraction peaks between 2 θ at 15◦ and 20◦ were owing to the
PLA/PBS/PBAT/nHA polymer blends and to identify the crystalline species in the
characteristic pattern of PLA. The diffraction peaks of PBS were observed at 22.5◦ . The
poly-
mer blends. Thediffraction
results arepeakspresented in◦ ,Figure
at 25.9◦ , 28 and 32–352a,b for sampletoseries
◦ contributed A and B with
the characteristic peaksvar-
of
ious amounts ofnHA
nHA added.There
[42,49,50]. Thewere
diffraction peaksforbetween
no nHA peaks specimens2 A0
θ at
and15° and 20°added
B0 without werenHA
ow-
in the PLA/PBS/PBAT
ing to the characteristic pattern ofblends.
PLA. ItThe is also shown thatpeaks
diffraction the characteristic
of PBS were peaks observed
of nHA wereat
observed for specimens A3 to A7 and B3 to B7.
22.5°. The diffraction peaks at 25.9°, 28°, and 32–35° contributed to the characteristic
peaks of nHA [42,49,50]. There were no nHA peaks for specimens A0 and B0 without
added nHA in the PLA/PBS/PBAT blends. It is also shown that the characteristic peaks of
nHA were observed for specimens A3 to A7 and B3 to B7.
 Polymers2023,
Polymers 2023,15,
15, 4585
x FOR PEER REVIEW 8 of 24 8 of 21

(a)

(b)
Figure 2. XRD measurement results for polymer blends: (a) sample series A and (b) sample series
Figure 2. XRD measurement results for polymer blends: (a) sample series A and (b) sample series B,
B, with various amounts of nHA added.
with various amounts of nHA added.
3.4. DSC and Crystallization Analysis Results for PLA/PBS/PBAT/nHA Blends
3.4. DSC and Crystallization Analysis Results for PLA/PBS/PBAT/nHA Blends
DSC analyses were used to measure the reliable thermal history and crystallization
DSC analyses
of semi-crystalline wereThe
polymers. used to measure
second the reliable
heating curves thermal
of the DSC history and
measurements for crystallization
of semi-crystalline polymers. The second heating curves of the DSC measurements for
sample series A and B with various amounts of nHA added are shown in Figure 3a,b. The
glass transition temperature of PLA (Tg,PLA ), cold crystallization temperature (Tcc ), melting
temperature of PLA (Tm,PLA ), enthalpy changes of cold crystallization (∆Hcc ), and enthalpy
changes of melting of blends (∆Hm ), as listed in Table 4, were retrieved from the DSC
thermogram. Addition of nHA affected the crystallization behavior of the PLA/PBS/PBAT
 Polymers 2023, 15, x FOR PEER REVIEW 9 of 24

Polymers 2023, 15, 4585 9 of 21

sample series A and B with various amounts of nHA added are shown in Figure 3a,b. The
glass transition temperature of PLA (Tg,PLA), cold crystallization temperature (Tcc), melt-
ing temperature of PLA (Tm,PLA), enthalpy changes of cold crystallization (ΔHcc), and en-
thalpy changes
blends and,of therefore,
melting of blends
their (ΔH m), as listed in Table 4, were retrieved from the
physical properties [42,51]. The relative crystallinity Xc of
DSC thermogram. Addition of nHA affected the crystallization behavior of the
blends with various formulations was calculated by:
PLA/PBS/PBAT blends and, therefore, their physical properties [42,51]. The relative
crystallinity Xc of blends with various formulations was calculated by:
∆Hm − ∆Hcc
Xc = ∆𝐻 − ∆𝐻 × 100% (1)
𝑋 = ω PLA ∆H o,PLA + ω PBS ∆H 0, PBS + ω PBAT ∆H 0,PBAT
× 100% (1)
𝜔 ∆𝐻 , + 𝜔 ∆𝐻 , +𝜔 ∆𝐻 ,
where
where 𝜔 ω PLA ,, and
,𝜔 𝜔 , andrepresented
ω PBS ω PBAT represented the weight
the weight fractions fractions
of PLA, of PBAT
PBS, and PLA,inPBS, and PBAT in
the the polymer
polymer blends,
blends, respectively. ΔH0,PLA, ∆H
respectively. ΔH0,PLA , ∆HΔH
0,PBS, and 0,PBS ,
0,PBAT and ∆H
denoted the denoted
enthalpy
0,PBAT of the enthalpy of
fusion values
fusion for 100%
values for crystalline polymers.polymers.
100% crystalline The theoreticalThevalues ΔH0 of values
theoretical ∆Hand
PLA, PBS, 0 of PLA, PBS, and
PBAT are 93.1,
PBAT 200, and
are 93.1, 200,114and
J g−1114 J g−1 , respectively
, respectively [42,51–54]. [42,51–54].

Polymers 2023, 15, x FOR PEER REVIEW 10 of 24

(a)

(b)
Figure 3. DSC curves (second heating) for polymer blends: (a) sample series A and (b) sample se-
Figure 3. DSC curves (second heating) for polymer blends: (a) sample series A and (b) sample series
ries B, with various amounts of nHA added.
B, with various amounts of nHA added.
Table 4. DSC test results and the calculated degree of crystallinity for various polymer blends.

Tg,PLA Tcc Tm,PLA ΔHcc ΔHm Xc

Specimen Code
(°C) (°C) (°C) (J g−1) (J g−1) (%)
A0 62 103 169 12.0 36.3 20.1
A3 63 100 169 13.0 41.9 24.8
A5 63 99 168 14.9 45.2 26.0
A7 61 99 168 13.5 45.0 27.0
B0 62 103 169 15.7 37.9 20.1
Polymers 2023, 15, 4585 10 of 21

Table 4. DSC test results and the calculated degree of crystallinity for various polymer blends.

Specimen Tg,PLA Tcc Tm,PLA ∆Hcc ∆Hm Xc

Code (◦ C) (◦ C) (◦ C) (J g−1 ) (J g−1 ) (%)
A0 62 103 169 12.0 36.3 20.1
A3 63 100 169 13.0 41.9 24.8
A5 63 99 168 14.9 45.2 26.0
A7 61 99 168 13.5 45.0 27.0
B0 62 103 169 15.7 37.9 20.1
B3 63 101 169 18.6 41.3 20.6
B5 63 102 169 15.6 40.2 22.3
B7 63 102 169 14.8 38.5 21.5

As discussed in the literature, the thermodynamic compatibility between PLA and PBS
or PLA and PBAT was poor [26,51,55–57]. Nanoparticles were used as a nucleating agent
in the crystallization process to increase crystal growth [55–58]. As shown in Table 4, the
relative crystallinity Xc in the PLA/PBS/PBAT blend (specimen A0) was 20.1%. The relative
crystallinity Xc in polymer blends with the addition of various amounts of nHA (specimens
A3, A5, and A7) increased from 24.8 to 27.0%. Increased crystallinity of polymer blends
would lead to better mechanical properties. It is observed from Table 4 that sample series B
(specimens B0, B3, B5, and B7) also had a similar slight increase in relative crystallinity Xc
as the added amount of nHA increased.

3.5. Nonisothermal Crystallization Behavior of PLA/PBS/PBAT/nHA Blends

Heterogeneous nucleation effects in nonisothermal crystallized polymer nanocompos-
ites characterized by DSC have been discussed in the literature [59,60]. Figure 4 shows the
heat flow curves of the prepared specimens in this study during cooling from 200 ◦ C to
50 ◦ C at rates of 2.5, 5, 7.5, and 10 ◦ C min−1 .
The cooling traces showed that no obvious peak was observed in specimen A0, and its
melt crystallization ability was poor. When the nHA content in the specimen increased from
0 to 3 wt%, the appearance of crystallization behavior was observed during the cooling
process at 2.5 ◦ C min−1 , which exhibited an increase in the crystallization enthalpy value
∆Hhc from 0 to 7.8 J g−1 . This result can be attributed to the introduced nHA, which may
play a role as a nucleating agent and lead to heterogeneous nucleation behavior. As the nHA
content further increased, the ∆Hhc values increased slightly. Compared with specimen A0,
specimen B0 showed a relatively high melt crystallization ability, exhibiting a ∆Hhc value
of 10.1 J g−1 at a cooling rate of 2.5 ◦ C min−1 in the absence of nHA. However, similar
∆Hhc values were observed in B3, B5, and B7 specimens, indicating that no significant
crystallinity change was obtained upon the addition of nHA.
All nonisothermal DSC-measured data are listed in Table 5. The different tendencies
of the sample series A and B may result in the basic crystallization ability of PLA in
different compositions. The PLA content in specimen A0 was lower, resulting in limited
melt crystallization during the cooling process. When nHA was added, a nucleation effect
occurred, making crystal formation less difficult. Therefore, as the nHA content increased,
the ∆Hhc increased significantly. On the other hand, specimen B0 had a relatively higher
PLA content and had advantages in crystallization. The addition of nHA in sample series
B may not have produced significant improvements in crystallization compared to neat
specimen B0 without nHA.
Polymers 2023, 15, x FOR PEER REVIEW 11 of 24
Polymers 2023, 15, 4585 11 of 21

4. DSC curves of prepared specimens in cooling

the cooling process at 2.5, 5, 7.5, ◦ C min −1
Figure
Figure 4. DSC curves of prepared specimens in the process at 2.5, 5, 7.5, andand 10 min
10 °C −1 (a)

(a) A3,
A0, (b) A0, (c)
(b)A5,
A3, (d)
(c) A5,
A7, (d)
(e) A7, (e) B3,
B0, (f) B0, (g)
(f) B3,
B5, (g)
andB5,
(h)and
B7.(h) B7.

The cooling traces showed that no obvious peak was observed in specimen A0, and
its melt crystallization ability was poor. When the nHA content in the specimen increased
from 0 to 3 wt%, the appearance of crystallization behavior was observed during the
cooling process at 2.5 °C min−1, which exhibited an increase in the crystallization enthalpy
Polymers 2023, 15, 4585 12 of 21

Table 5. Crystallization enthalpy values of sample series A and B under various cooling rates.

Cooling Rate (◦ C min−1 )

Specimen
2.5 5 7.5 10
Code
∆Hhc (J g−1 )
A0 0 0 0 0
A3 7.80 1.08 0.63 0.37
A5 9.88 1.70 0.45 0.41
A7 10.90 2.72 0.91 0.50
B0 10.12 3.46 0.74 0.55
B3 11.96 3.31 0.94 0.46
B5 10.09 2.56 0.84 0.36
B7 10.91 2.71 0.94 0.48

3.6. Tensile and Impact Strength Test Results for PLA/PBS/PBAT/nHA Blends
Tensile and impact strength tests were conducted in this study to examine the me-
chanical properties of various polymer blends. Typical tensile stress measurement results
of sample series A and B with various amounts of nHA added are graphically shown in
Figure 5. The maximum tensile stress (tensile strength), elongation at maximum tensile
stress, tensile modulus, and impact strength data obtained from repeated tests in this
study are listed in Table 6. It was observed that sample series B containing 80 wt% PLA
exhibited higher tensile strength, up to 57.9 ± 1.0 MPa, while the tensile strength of sample
series A with 70 wt% PLA was about 47 to 50 MPa. The elongation of sample series A and
B both ranged from 7 to 8%, better than neat PLA (6%, as shown in Table 1) or human
bone (1–3% for cortical bone and 3–7% for cancellous bone) [8]. The tensile modulus for
sample series A with various nHA contents ranged from 642 to 905 MPa, while that of
sample series B could reach 1.0 GPa. Tensile strength and tensile modulus increased with
increasing nHA addition, reaching the highest values for polymer blends containing 5 wt%
nHA (specimens A5 and B5). Polymer blends with a higher 7 wt% nHA (specimens A7 and
B7) showed a slight decrease in tensile strength, suggesting that there might be an optimal
nHA addition. Impact strength measurements indicated the toughness of the polymer
blend. The impact strength of neat PLA was about 2.5 kJ m−2 [21]. All polymer blends
yielded better toughness by blending PLA with ductile PBS and PBAT. It can be seen from
Table 6 that the additional amount of nHA in this study had no significant effect on the
impact strength results for a specific sample series. Examination of these comparisons
indicated that specimens B3 or B5 could be the formulations with acceptable mechanical
strength for composite bone graft materials. It was deduced from the mechanical prop-
erty measurements that the added nHA nanoparticles acted as nucleating agents during
the crystallization process of the polymer blends, thereby increasing the crystallinity and
tensile strength.

Table 6. Tensile and impact test results of polymer blends with various compositions of nHA.

Specimen Maximum Tensile Elongation at Maximum Tensile Modulus Impact Strength

Code Stress (MPa) Tensile Stress (%) (MPa) (kJ m−2 )
A0 47.1 ± 2.9 7.9 ± 0.4 642.0 ± 109.1 4.83 ± 0.19
A3 47.5 ± 0.7 7.5 ± 0.3 887.8 ± 57.2 4.32 ± 0.17
A5 50.2 ± 1.0 7.4 ± 0.4 905.5 ± 64.1 4.64 ± 0.21
A7 47.4 ± 0.3 6.7 ± 0.3 707.5 ± 15.0 4.20 ± 0.07
B0 49.6 ± 1.6 8.0 ± 0.6 686.1 ± 91.3 3.36 ± 0.20
B3 57.8 ± 0.7 7.1 ± 0.2 1039.4 ± 37.5 3.21 ± 0.16
B5 57.9 ± 1.0 7.3 ± 0.2 1062.2 ± 97.8 3.42 ± 0.17
B7 56.7 ± 1.0 7.3 ± 0.1 962.6 ± 17.4 3.19 ± 0.25
 Polymers 2023, 15, x FOR PEER REVIEW 13 of 24

mechanical strength for composite bone graft materials. It was deduced from the me-
chanical property measurements that the added nHA nanoparticles acted as nucleating
Polymers 2023, 15, 4585 13 of 21
agents during the crystallization process of the polymer blends, thereby increasing the
crystallinity and tensile strength.

Figure Typicaltensile
5. Typical
Figure 5. tensile stress
stress measurement
measurement results
results for polymer
for polymer blends:
blends: (a) sample
(a) sample series A series
and (b)A and
sample
(b) series
sample B, with
series various
B, with amounts
various of nHA
amounts of added.
nHA added.

3.7.
TableSEM Analysis
6. Tensile Resultstest
and impact forresults
PLA/PBS/PBAT/nHA
of polymer blends Blends
with various compositions of nHA.
SEM analyses of fractured surfaces have been
Elongation at demonstrated in the literature discussing
polymer Specimen
compositeMaximum
morphologyTen- and additive distribution
Tensile Modulus Impactmatrix
in the polymer Strength [61–63].
Maximum Ten-
Code from
The transition sile Stressto(MPa)
ductile brittle in polymer composites(MPa)
and the (kJ m−2)
morphology–mechanical
sile Stress (%)
properties relationship can be examined using SEM analyses. SEM images of the impact-
A0 47.1 ± 2.9 7.9 ± 0.4 642.0 ± 109.1 4.83 ± 0.19
Polymers 2023,fractured surfaces for sample series A and B of polymer blends in this study 14
15, x FOR PEER areof shown in
A3 REVIEW 47.5 ± 0.7 7.5 ± 0.3 887.8 ± 57.2 4.32 ± 0.17 24
Figures 6 and 7, respectively.
A5 50.2 ± 1.0 7.4 ± 0.4 905.5 ± 64.1 4.64 ± 0.21
A7 47.4 ± 0.3 6.7 ± 0.3 707.5 ± 15.0 4.20 ± 0.07
B0 49.6 ± 1.6 8.0 ± 0.6 686.1 ± 91.3 3.36 ± 0.20
B3 57.8 ± 0.7 7.1 ± 0.2 1039.4 ± 37.5 3.21 ± 0.16
B5 57.9 ± 1.0 7.3 ± 0.2 1062.2 ± 97.8 3.42 ± 0.17
B7 56.7 ± 1.0 7.3 ± 0.1 962.6 ± 17.4 3.19 ± 0.25

3.7. SEM Analysis Results for PLA/PBS/PBAT/nHA Blends

SEM analyses of fractured surfaces have been demonstrated in the literature dis-
cussing polymer composite morphology and additive distribution in the polymer matrix
[61–63]. The transition from ductile to brittle in polymer composites and the morpholo-
gy–mechanical properties relationship can be examined using SEM analyses. SEM im-
ages of the impact-fractured surfaces for sample series A and B of polymer blends in this
study are shown in Figures 6 and 7, respectively.

Figure 6. Comparison of the SEM images for polymer blend sample series A with various amounts
Figure 6. Comparison of the SEM images for polymer blend sample series A with various amounts
of nHA added in (a) Specimen A0, (b) Specimen A3, (c) Specimen A5, and (d) Specimen A7.
of nHA added in (a) Specimen A0, (b) Specimen A3, (c) Specimen A5, and (d) Specimen A7.

Figure 6a shows the SEM image of specimen A0. Figure 6b–d show the SEM images
of specimens A3, A5, and A7, respectively. Figure 6a indicates that specimen A0 without
nHA presented a relatively rough and tough fractured surface. For specimen A3 with
3 wt% nHA added, well-dispersed nHA particles can be observed as small white dots in
Figure 6b. With the higher amount of added nHA, a brittle fractured morphology with
cracks appeared, as shown in Figure 6c,d. A transition in fractured surface morphology
from relatively rough and ductile to hard and brittle was observed. These SEM results
Polymers 2023, 15, 4585 14 of 21

are also supported by the TEM results discussed in the next section, showing that the
nanoparticles were uniformly distributed. The effect of nHA addition on tensile and impact
strength was consistent with the SEM results, where the polymer blends became harder
Polymers 2023,and brittle
15, x FOR with increasing nHA addition. As the amount of nHA added increased,
PEER REVIEW 15 of 24 the
mechanical tensile strength showed an increasing trend.

Figure 7. Comparison of the SEM images for polymer blend sample series B with various amounts
Figure 7. Comparison of theinSEM
of nHA added images
(a) Specimen B0,for
(b) polymer blend
Specimen B3, sample
(c) Specimen B5,series
and (d)BSpecimen
with various
B7. amounts of
nHA added in (a) Specimen B0, (b) Specimen B3, (c) Specimen B5, and (d) Specimen B7.
Figure 6a shows the SEM image of specimen A0. Figure 6b–d show the SEM images
of specimens A3, A5, and A7, respectively. Figure 6a indicates that specimen A0 without
Figure 7 shows similar SEM images for sample series B, containing 80 wt% PLA.
nHA presented a relatively rough and tough fractured surface. For specimen A3 with 3
An impact-fractured
wt% nHAsurface morphology
added, well-dispersed nHAconsistent with
particles can be Figure
observed 6 was
as small whiteobserved.
dots in No
nHA particlesFigure
were6b.detected in Figure
With the higher amount7a, which
of added presented
nHA, a relatively
a brittle fractured morphologyrough
with surface.
cracks appeared,
When nHA particles as shownto
were added in the
Figure 6c,d. A transition
polymer blends,inthey
fractured surface morphology
produced sharp fractured
from relatively rough and ductile to hard and brittle was observed. These SEM results are
surface morphologies, as shown in Figure 7b–d. The nHA particles were
also supported by the TEM results discussed in the next section, showing that the nano-
well dispersed
in the polymerparticles
matrix and became aggregated at higher nHA contents.
were uniformly distributed. The effect of nHA addition on tensile and impact As the amount
strength was consistent with the SEM results, where the polymer
of nHA added increased, the fracture morphology once again exhibited hard and brittle blends became harder
characteristics.and
Tobrittle with increasing nHA addition. As the amount of nHA added increased, the
confirm the chemical compositions of nanoparticles shown in the SEM
mechanical tensile strength showed an increasing trend.
images, the EDX spectrum for similar
Figure 7 shows a typical
SEMpolymer
images for blend of specimen
sample series B780
B, containing iswt%
shownPLA.in
AnFigure 8.
The
Polymers 2023, 15, x FOR PEER REVIEW
characteristic peaks of
impact-fractured Ca and
surface P elements
morphology shown
consistent in Figure
with Figure86indicated the
was observed. No
16 of 24
nHA
nHAparticles
in specimens. particles were detected in Figure 7a, which presented a relatively rough surface. When
nHA particles were added to the polymer blends, they produced sharp fractured surface
morphologies, as shown in Figure 7b–d. The nHA particles were well dispersed in the
polymer matrix and became aggregated at higher nHA contents. As the amount of nHA
added increased, the fracture morphology once again exhibited hard and brittle charac-
teristics. To confirm the chemical compositions of nanoparticles shown in the SEM im-
ages, the EDX spectrum for a typical polymer blend of specimen B7 is shown in Figure 8.
The characteristic peaks of Ca and P elements shown in Figure 8 indicated the nHA par-
ticles in specimens.

Figure 8. Typical results of the EDX spectra of a polymer blend (specimen B7, with the addition of 7
Figure 8. Typical results of the EDX spectra of a polymer blend (specimen B7, with the addition of
wt% nHA).
7 wt% nHA).
3.8. TEM Measurement Results for PLA/PBS/PBAT/nHA Blends
TEM images of sample series A are shown in Figure 9 at 20,000× magnification. No
nHA particle images were detected in specimen A0. In addition, phase separation mor-
phology in the blend can be observed in Figure 9a, with a continuous region (or lighter
region) as the major component PLA matrix and a darker region as the minor PBS/PBAT
Polymers 2023, 15, 4585 15 of 21

3.8. TEM Measurement Results for PLA/PBS/PBAT/nHA Blends

TEM images of sample series A are shown in Figure 9 at 20,000× magnification.
No nHA particle images were detected in specimen A0. In addition, phase separation
morphology in the blend can be observed in Figure 9a, with a continuous region (or lighter
region) as the major component PLA matrix and a darker region as the minor PBS/PBAT
dispersed phase. With the addition of 3 wt% nHA, the TEM image shown in Figure 9b
exhibits the presence of small black dots of nHA, with a particle size in the range of
70–100 nm. Furthermore, the PBS/PBAT dispersed phase became smaller in size with the
addition of nHA particles, indicating that the addition of nHA particles helped to disperse
polymer phases during the twin-screw mixing process. With a further increased amount of
nHA addition from 5 to 7 wt%, the degree of uniform dispersion of the polymer phases
also increased, and PBS/PBAT phases became even smaller, as seen in the images shown
in Figure 9c,d. However, it is noted that with a higher amount of nHA addition, nHA
particles became larger due to aggregation during mixing. For 7 wt% of nHA addition,
a near-micrometer size of nHA particles was observed, as seen in the image shown in
Figure 9d. Similar results for TEM images of sample series B are presented in Figure 10.
For specimen B0, no nHA particle images were detected, as seen in Figure 10a. When the
addition of nHA increased from 3 to 7 wt% as shown in Figure 10b–d, an increased number
Polymers 2023, 15, x FOR PEER REVIEW 17 of 24
of fine black dots of nHA particles was displayed. TEM images also showed nHA-induced
morphological refinement, indicating that nHA helped disperse polymer domains.

Figure
Figure9.9.TEM
TEMimages
imagesforfor
polymer
polymerblends of sample
blends series
of sample A with
series various
A with amounts
various of nHA
amounts of added
nHA added
(magnification
(magnification20,000×).
20,000×(a) Specimen
). (a) A0, A0,
Specimen (b) Specimen A3, (c)
(b) Specimen Specimen
A3, A5, and
(c) Specimen A5,(d)and
Specimen A7.
(d) Specimen A7.
Polymers 2023,15,
2023,
Polymers 15,4585
x FOR PEER REVIEW 18 of 2416 of 21

Figure 10.
Figure 10.TEM
TEMimages
imagesforforpolymer
polymerblends
blendsof sample series
of sample B with
series various
B with amounts
various of nHA
amounts addedadded
of nHA
(magnification 20,000×). (a) Specimen B0, (b) Specimen B3, (c) Specimen B5, and (d) Specimen
(magnification 20,000×). (a) Specimen B0, (b) Specimen B3, (c) Specimen B5, and (d) Specimen B7. B7.

3.9. TGA
TGAfor
forPLA/PBS/PBAT/nHA
PLA/PBS/PBAT/nHABlends
Blends
This
This study
studyexamined
examinedthe thethermal
thermalstability
stability of of
polymer
polymer blends
blendswith different
with differentformu-
formula-
lationsusing
tions usingthermogravimetric
thermogravimetric analysis
analysis(TGA).
(TGA). TheTheresults for for
results sample series
sample A and
series A Band
are B are
shown with
shown withTGA
TGAand andDTGA
DTGA thermograms
thermograms in Figures
in Figures11 and 12, respectively.
11 and TableTable
12, respectively. 7 lists7 lists
the decomposition
the decompositiontemperatures
temperaturesfor for5%
5%andand50%50%weight
weightloss (T5%
loss andand
(T5% T50%T), the), temper-
50% the tempera-
ature of maximum decomposition rate (T max), and residual weight percent at 600 °C (W
ture of maximum decomposition rate (Tmax ), and residual weight percent at 600 ◦ C R)
(WR )
for all specimens measured in this study. For sample series A, the TGA
for all specimens measured in this study. For sample series A, the TGA thermograms in thermograms in
Figure 11a
Figure show that
11a show that the main decomposition
the main decomposition temperature
temperatureof ofeach
eachspecimen
specimen(A0 (A0totoA7) A7) was
was between 300 and ◦400 °C. The DTGA thermograms shown in Figure 11b depict the
between 300 and 400 C. The DTGA thermograms shown in Figure 11b depict the two-step
two-step decomposition of each specimen. The first peak indicated the maximum de-
decomposition of each specimen. The first peak indicated the maximum decomposition
composition rate of PLA [64], and the second peak was owing to the maximum decom-
rate of PLA [64], and the second peak was owing to the maximum decomposition rate of
position rate of PBS/PBAT. As shown in Figure 11 and Table 7, adding nHA did not seem
PBS/PBAT. As shown in Figure 11 and Table 7, adding nHA did not seem to significantly
to significantly affect the Tmax of the polymer blends. The residual weight percent in the
affect the Tmax of the polymer blends. The residual weight percent in the temperature range
temperature range of 500 to 600 °C increased reasonably well with increasing thermally
of
stable to 600 ◦ C nHA
500 inorganic increased reasonably
content, as shownwell with increasing
in Figure 11a and Tablethermally stable inorganic
7. The similar TGA and nHA
content,
DTGA thermograms of sample series B are shown in Figure 12, with data alsothermograms
as shown in Figure 11a and Table 7. The similar TGA and DTGA listed in
of sample
Table 7. Theseries
main B are shown intemperature
decomposition Figure 12, withrangedata
was also listed in 300
also between Table
and7.400The °C,main
as de-
composition temperature range was also between 300 and 400 ◦ C, as shown in Figure 12a.
shown in Figure 12a. The increase in residual weight percent for four specimens of sam-
The increase
ple series in residual
B was weight percent
again consistent with thefor four specimens
increasing amount of of nHA
sample series
added. FromB wastheagain
consistent with the increasing amount of nHA added. From the TGA results, polymer
blends in this study all had good thermal stability for bone graft material applications.
 Polymers 2023, 15, x FOR PEER REVIEW 19 of 24

Polymers 2023, 15, 4585 17 of 21

TGA results, polymer blends in this study all had good thermal stability for bone graft
material applications.

Figure 11.
Figure Thermogravimetric
11.Thermogravimetric analysis
analysis results
results of (a)ofTG
(a)and
TG(b)
and (b)thermograms
DTG DTG thermograms forse-
for sample sample
series
ries A, A, with
with various
various amounts
amounts of nHA
of nHA added.
added.

Figure 12.
Figure Thermogravimetric
12.Thermogravimetric analysis
analysis results
results of (a)ofTG
(a)and
TG(b)
and (b)thermograms
DTG DTG thermograms forse-
for sample sample
ries B, B,
series with various
with amounts
various of nHA
amounts added.
of nHA added.

Table
Table 7.
7. Thermogravimetric
Thermogravimetricmeasurement
measurementresults forfor
results PLA/PBS/PBAT/nHA blends.blends.
PLA/PBS/PBAT/nHA
WR (%)
Specimen Code T5% (°C) T50% (°C)◦ Tmax (°C) ◦ WR (%)
Specimen Code T5% (◦ C) T50% ( C) Tmax ( C) at 600at°C
600 ◦ C
A0 325 361 361 1.6
A0 325 361 361 1.6
A3 318 360 360 4.5
A3 318 360 360 4.5
A5
A5 306
306 354354 355 355 5.7 5.7
A7
A7 319
319 367367 366 366 7.6 7.6
B0
B0 317
317 355355 371 371 0.7 0.7
B3
B3 310
310 353353 369 369 2.3 2.3
B5
B5 302
302 348348 362 362 4.5 4.5
B7 295 343 352 6.3
B7 295 343 352 6.3

3.10. Water
3.10. WaterAbsorption
AbsorptionMeasurement
Measurement Results
Results for for PLA/PBS/PBAT/nHA
PLA/PBS/PBAT/nHA Blends
Blends
Thewater
The waterabsorption
absorptionpercentage
percentage gain
gain (WA)
(WA) waswas calculated
calculated by: by:
𝑊 −𝑊
WA (% Wt − W×d 100%
WA %)== 𝑊 × 100% (2) (2)
Wd

where Wd was the weight of the sample after drying (dried at 50 ◦ C for 2 days before the
water absorption test) and Wt was the weight of the sample measured after immersion in
distilled water for t days (t = 1, 2, 5, and 8). The water absorption results for all specimens
after immersion in distilled water for 24 h are shown in Figure 13. For sample series A, due
to the hydrophilicity of nHA, the water absorption tended to increase with the increase in
nHA addition. Sample series B also exhibited a similar water absorption trend. Compared
15, x FOR PEER REVIEW where
where W Wdd was
was the the weight
weight of of the
the sample
sample after after drying
drying (dried
(dried at
20 50
at 50 °C
of 24 for 2 days before the
°C for 2 days before the
water absorption test) and W t was the weight of the sample measured after immersion in
water absorption test) and Wt was the weight of the sample measured after immersion in
Polymers 2023, 15, x FOR PEER REVIEW
distilled 20 of 24
distilled waterwater for for tt days
days (t (t == 1,
1, 2, 2, 5,
5, and
and 8).8). The
The water
water absorption
absorption results results forfor all
all specimens
specimens
where after
afterofimmersion
Wd was the weight the samplein
immersion distilled
inafter drying
distilled water
water (dried for
forat24
2450h
h °Care
areforshown
2 days
shown in Figure
inbefore
Figurethe 13.
13. For
For sample
sample seriesseries A, A,18 of 21
Polymers 2023, 15, 4585
due
water absorption test) dueand toto
Wtthethe hydrophilicity
washydrophilicity
the weight of the of nHA,
of nHA, sample the water
themeasured absorption
after immersion
water absorption tended
tended in to
to increase with the
increase with the in-
in-
crease
distilled water for t days where
(t = 1,
crease in
W2,nHA
in d was
5, and
nHA addition.
addition.The Sample
the8).weight of the
water
Sample series
sample
absorption
series B also
B after exhibited
drying
results
also exhibited aaspecimens
(dried
for all similar
at 50water
similar °C forabsorption
water 2 days before
absorption trend.
the
trend.
Compared
water
after immersion in distilled
Compared to
absorption
watertofor sample test)
24 h are
sample series
andshown
series WA, sample
was
A, sample
t the
in Figure series
weight Bof
13. BFor
series displayed
the sample
sample series
displayed lower
measured
lower A, water
water absorption due to
absorption
after immersion due in
to
due to the hydrophilicity to
its sample
higher
distilled
of nHA, series
PLA
water forA,t
thecontent.sample
content.
days For
(t
water absorption =series
the
1, 2,24 B
5, hdisplayed
andtest,
8).the
The lower
water
water water
absorption
absorption absorption
of due
specimens
results for to
all B5its higher
and
specimens B7 PLA
its higher PLA For the 24 tended h test, theto increase with the in-
water absorption of specimens B5 and B7
crease in nHA addition. content.
was
after
was about For
15%
immersion
Sample
about series the
15% better 24
better
in h test,
than
distilled
B alsothan the
that
exhibitedwater ofwater
specimen
that ofaspecimenfor absorption
24 h
similar water B0.
are The
shown
B0. The of specimens
waterin
absorption trend. results for a longer 15%
absorption
Figure
water absorption B5
13. and
results
For B7
sample was
for a about
longer
series A,
Compared to sample series better
time
due
time areare
to than
the that
depicted ofinspecimen
hydrophilicity
A, depicted
sample series Figure
in Figure 14
of
B displayedB0.for
nHA, The
all
14 for alllower the water
specimens.
water absorption
It is
absorption
water It
specimens. absorption results
demonstrated duefor
tended
is demonstrated aincrease
longer
totothat
that aftertime
after five
withdays
five are
thedepicted
days of
in-
of
its higher PLA content. in
waterFigure
crease in 14
immersion,
nHA
For immersion,
water for all specimens.
the
addition.
the 24 h test,the degree
Sample
thedegree
water of of It is
water
series
absorption demonstrated
absorption
B also of
exhibited
of specimens
water absorption that
each
of each a after
similar
B5 specimen five
specimen days
water of
increased water
absorption
and B7 increased by about by immersion,
about
trend.
was about 15% better than40%
the
40% to
degree
Compared
that
to 50%
50% compared
of of
to water
specimen
compared to
to the
sampleabsorption
series
B0. TheA,
the degree
degree of each
sample
water of
of water
series
absorption
water absorption
specimen increased
B results
displayed
absorption for on the
onalower byfirst
longer
the day.
about
water
first 40%Afterto absorbing
day.absorption
After 50%due compared
absorbing to
water
to
time are depicted in Figureitsthe for
higher
water14 eight
degree
forfor PLA of days,
water
content.
all specimens.
eight the degree
absorption
For
days, the degree the of
24
It is demonstratedwater
on
h the
test,absorption
first
the
of water absorption day.
water increased
After absorbing
absorption
that afterincreased
five daysby by ofabout 70
specimens to
for 80%
of about 70 to 80% com- the
water eight
B5 andcom-
days,
B7
pared
water immersion, the pared was
degree
degreewith with
about one-day
15%
water
of water
one-daybetter water
than
absorption
absorption absorption
that of
ofincreased
water absorption specimen
each specimen results.
B0.
by about
results. These
The waterincreased
70 toincreased
increased
These 80% absorption
by aboutcomparedwater
water absorption
results
withfor
absorption per-
a longer
one-day per-water
centages
time are
absorption
40% to 50% comparedcentagesto the degreewere
depicted
were consistent
results.
of in
water
consistent Figure
These with 14 those
for
increased
absorption
with thoseon shown
all water
the
shown in
specimens.
first the literature
It is
absorption
day.
in the for
demonstrated composites
percentages
After absorbing
literature for composites that involving
after
were five PLA
days
consistent
involving PLA of with
water for eight days, the[65,66].
water
those
[65,66]. The
shown
degree results
immersion, in theof
Theofresults
water of
the water
degree
literature
absorption absorption
of
water absorption water
for composites
increased indicated
absorption
by about
indicated that
of
involving the
each
70 tothe
that 80% addition
specimen
PLA com-
addition of
[65,66]. hydrophilic
increased
The results
of hydrophilic by nHA
about
of water
nHA
pared with one-day water enhanced
absorption
enhanced the
40% toabsorption
50%the water
compared
indicated
water absorption
results. to the
that thedegree
These
absorption rate, ofwhich
increased
addition
rate, water
which is
water beneficial
isabsorption
of hydrophilic absorption
beneficial nHAto
on
to thethe
per- application
first
enhanced
the day.the
application After of
water polymer
ofabsorbing
absorption
polymer
centages were consistent blends
water
with
rate,
blends in
for
which bone
eight
those
in bone tissue
isshowndays,in
beneficial
tissue engineering.
the degree
theto literature
engineering. of water
the application absorption
for composites
of polymer increased
involving blends PLA by abouttissue
in bone 70 to 80% com-
engineering.
pared with one-day water absorption
[65,66]. The results of water absorption indicated that the addition of hydrophilic nHA results. These increased water absorption per-
centages were consistent with those
enhanced the water absorption rate, which is beneficial to the application of polymer shown in the literature for composites involving PLA
[65,66]. The results of water absorption indicated that the addition of hydrophilic nHA
blends in bone tissue engineering.
enhanced the water absorption rate, which is beneficial to the application of polymer
blends in bone tissue engineering.

Comparison of
Figure 13. Comparison
Figure water absorption percentage gain (WA) at 24 h forspecimens
all specimens with
Figure 13.
13. Comparison of
of water
water absorption
absorption percentage
percentage gain
gain (WA)
(WA) at
at 24
24 h
h for
for all
all specimens with
with
various amounts
variousamounts
various of nHA
amountsofofnHA added.
nHAadded.
added.( : sample
( ( : sample series
: sample A;
series
series A; A; : sample series
: sample
: sample B).
series
series B). B).

Figure 13. Comparison of water absorption percentage gain (WA) at 24 h for all specimens
with various amounts of nHA added. : sample series A; : sample series B).
Figure 13. Comparison of water absorption percentage gain (WA) at 24 h for all specimens
with various amounts of nHA added. : sample series A; : sample series B).

Figure
Figure14.
Figure 14.Water
14. Waterabsorption
Water absorption
absorption profiles
profiles for
profiles (a)
forfor sample
(a)(a) series
sample
sample A
A and
series
series (b)
(b) sample
A and
and series
(b) sample
sample B.
seriesseries
B. B.

4. Conclusions
The physical
Figure 14. Water absorption profiles and series
for (a) sample mechanical properties
A and (b) of B.
sample series novel bio-based polymer blends of PLA/
PBS/PBAT/nHA were investigated in this study. The aim was to screen promising for-
Figure 14. Water
mulations absorption
of polymer profileswith
blends for (a)biocompatible
sample series A and
and(b) sample series B. nHA to provide
osteoconductive
options for bone graft materials. Various analytical results for physical and mechanical
property tests were reported. The conclusions are as follows: (1) Polymer blend formula-
tions containing 70 or 80 wt% PLA content with the addition of 3 to 5 wt% nHA exhibited
tensile strengths ranging from 47 to 57 MPa, suitable for bone graft applications. The
elongation and impact strength of these formulations were also satisfactory. (2) The thermal
degradation temperatures of various PLA/PBS/PBAT/nHA blends ranged from 300 to
400 ◦ C, suggesting that the polymer blends had satisfactory thermal stability. (3) The
Polymers 2023, 15, 4585 19 of 21

addition of nHA in the polymer blends increased water absorption due to its hydrophilicity.
Addition of 5 wt% nHA resulted in about a 15% increase in water absorption in the 24 h
water immersion test compared to polymer blends without nHA.

Author Contributions: Conceptualization, P.-H.C. and C.-W.C.; data curation, P.-H.C., H.-I.M. and
C.-A.D.; formal analysis, P.-H.C., C.-S.S. and J.-C.T.; funding acquisition, C.-W.C.; investigation,
C.-W.C. and F.-H.L.; methodology, P.-H.C., C.-W.C., H.-I.M., C.-A.D., C.-S.S. and J.-C.T.; supervision,
C.-W.C. and F.-H.L.; writing—original draft, P.-H.C.; writing—review and editing, C.-W.C. All authors
have read and agreed to the published version of the manuscript.
Funding: The authors gratefully acknowledge the financial support from the National Science and
Technology Council of Taiwan (NSTC 111-2222-E-027-005).
Institutional Review Board Statement: Not applicable.
Data Availability Statement: Data are contained within the article.
Acknowledgments: The authors are grateful to the National Taiwan University, the National Taipei
University of Technology, and Ming Chi University of Technology for supporting the experimental
equipment. Valuable comments and assistance from Chun-Ta Chen, Ming-You Chen, Jui-Yang Chou,
and Yu-Lin Wang are highly appreciated.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Liu, A.P.; Appel, E.A.; Ashby, P.D.; Baker, B.M.; Franco, E.; Gu, L.; Haynes, K.; Joshi, N.S.; Kloxin, A.M.; Kouwer, P.H.J.; et al. The
living interface between synthetic biology and biomaterial design. Nat. Mater. 2022, 21, 390–397. [CrossRef] [PubMed]
2. Eldeeb, A.E.; Salah, S.; Elkasabgy, N.A. Biomaterials for tissue engineering applications and current updates in the field: A
comprehensive review. AAPS PharmSciTech 2022, 23, 267. [CrossRef] [PubMed]
3. Ajmal, S.; Hashmi, F.A.; Imran, I. Recent progress in development and applications of biomaterials. Mater. Today Proc. 2022, 62,
385–391. [CrossRef]
4. Williams, D.F. Challenges with the development of biomaterials for sustainable tissue engineering. Front. Bioeng. Biotechnol. 2019,
7, 127. [CrossRef] [PubMed]
5. Pollock, J.R.; Moore, M.L.; Hogan, J.S.; Haglin, J.M.; Brinkman, J.C.; Doan, M.K.; Chhabra, A. Orthopaedic group practice size is
increasing. Sports Med. Arthrosc. Rehabil. Ther. Technol. 2021, 3, e1937–e1944. [CrossRef] [PubMed]
6. Szpalski, C.; Wetterau, M.; Barr, J.; Warren, S.M. Bone tissue engineering: Current strategies and techniques—Part I: Scaffolds.
Tissue Eng. Part B Rev. 2012, 18, 246–257. [CrossRef] [PubMed]
7. Polo-Corrales, L.; Latorre-Esteves, M.; Ramirez-Vick, J.E. Scaffold design for bone regeneration. J. Nanosci. Nanotechnol. 2014, 14,
15–56. [CrossRef]
8. Lee, S.S.; Du, X.; Kim, I.; Ferguson, S.J. Scaffolds for bone-tissue engineering. Matter 2022, 5, 2722–2759. [CrossRef]
9. Haugen, H.J.; Lyngstadaas, S.P.; Rossi, F.; Perale, G. Bone grafts: Which is the ideal biomaterial? J. Clin. Periodontol. 2019, 46
(Suppl. S21), 92–102. [CrossRef]
10. Qu, H.; Fu, H.; Han, Z.; Sun, Y. Biomaterials for bone tissue engineering scaffolds: A review. RSC Adv. 2019, 9, 26252–26262.
[CrossRef]
11. Koons, G.L.; Diba, M.; Mikos, A.G. Materials design for bone—Tissue engineering. Nat. Rev. Mater. 2020, 5, 584–603. [CrossRef]
12. Ravoor, J.; Thangavel, M.; Elsen, R.S. Comprehensive review on design and manufacturing of bioscaffolds for bone reconstruction.
ACS Appl. Bio Mater. 2021, 4, 8129–8158. [CrossRef] [PubMed]
13. Bahraminasab, M.; Janmohammadi, M.; Arab, S.; Talebi, A.; Nooshabadi, V.T.; Koohsarian, P.; Nourbakhsh, M.S. Bone scaffolds:
An incorporation of biomaterials, cells, and biofactors. ACS Biomater. Sci. Eng. 2021, 7, 5397–5431. [CrossRef] [PubMed]
14. Collins, M.N.; Ren, G.; Young, K.; Pina, S.; Reis, R.L.; Oliveira, J.M. Scaffold fabrication technologies and structure/function
properties in bone tissue engineering. Adv. Funct. Mater. 2021, 31, 2010609. [CrossRef]
15. Szczesny, G.; Kopec, M.; Politis, D.J.; Kowalewski, Z.L.; Łazarski, A.; Szolc, T. A review on biomaterials for orthopaedic surgery
and traumatology: From past to present. Materials 2022, 15, 3622. [CrossRef] [PubMed]
16. Sheikh, Z.; Najeeb, S.; Khurshid, Z.; Verma, V.; Rashid, H.; Glogauer, M. Biodegradable materials for bone repair and tissue
engineering applications. Materials 2015, 8, 5744–5794. [CrossRef] [PubMed]
17. Wei, S.; Ma, J.-X.; Xu, L.; Gu, X.-S.; Ma, X.-L. Biodegradable materials for bone defect repair. Mil. Med. Res. 2020, 7, 54. [CrossRef]
18. Modrák, M.; Trebunová, M.; Balogová, A.F.; Hudák, R.; Živcák, J. Biodegradable materials for tissue engineering: Development,
classification and current applications. J. Funct. Biomater. 2023, 14, 159. [CrossRef]
19. Yu, H.; Liu, H.; Shen, Y.; Ao, Q. Synthetic biodegradable polymer materials in the repair of tumor-associated bone defects. Front.
Bioeng. Biotechnol. 2023, 11, 1096525. [CrossRef]
Polymers 2023, 15, 4585 20 of 21

20. Bernardo, M.P.; da Silva, B.C.R.; Hamouda, A.E.I.; de Toledo, M.A.S.; Schalla, C.; Rütten, S.; Goetzke, R.; Mattoso, L.H.C.;
Zenke, M.; Sechi, A. PLA/Hydroxyapatite scaffolds exhibit in vitro immunological inertness and promote robust osteogenic
differentiation of human mesenchymal stem cells without osteogenic stimuli. Sci. Rep. 2022, 12, 2333. [CrossRef]
21. Zhao, X.; Hu, H.; Wang, X.; Yu, X.; Zhou, W.; Peng, S. Super tough poly(lactic acid) blends: A comprehensive review. RSC Adv.
2020, 10, 13316–13368. [CrossRef]
22. Nofar, M.; Sacligil, D.; Carreau, P.J.; Kamal, M.R.; Heuzey, M.-C. Poly(lactic acid) blends: Processing, properties and applications.
Int. J. Biol. Macromol. 2019, 125, 307–360. [CrossRef] [PubMed]
23. De Matos Costa, A.R.; Crocitti, A.; de Carvalho, L.H.; Carroccio, S.C.; Cerruti, P.; Santagata, G. Properties of biodegradable films
based on poly(butylene Succinate) (PBS) and poly(butylene Adipate-co-Terephthalate) (PBAT) blends. Polymers 2020, 12, 2317.
[CrossRef] [PubMed]
24. Hu, D.; Xue, K.; Liu, Z.; Xu, Z.; Zhao, L. The essential role of PBS on PBAT foaming under supercritical CO2 toward green
engineering. J. CO2 Util. 2022, 60, 101965. [CrossRef]
25. Sun, Z.; Wang, L.; Zhou, J.; Fan, X.; Xie, H.; Zhang, H.; Zhang, G.; Shi, X. Influence of polylactide (PLA) stereocomplexation on
the microstructure of PLA/PBS blends and the cell morphology of their microcellular foams. Polymers 2020, 12, 2362. [CrossRef]
[PubMed]
26. Su, S.; Kopitzky, R.; Tolga, S.; Kabasci, S. Polylactide (PLA) and its blends with poly(butylene succinate) (PBS): A brief review.
Polymers 2019, 11, 1193. [CrossRef] [PubMed]
27. Zhang, X.; Liu, Q.; Shi, J.; Ye, H.; Zhou, Q. Distinctive tensile properties of the blends of poly(l-lactic acid) (PLLA) and
poly(butylene succinate) (PBS). J. Polym. Environ. 2018, 26, 1737–1744. [CrossRef]
28. Ou-Yang, Q.; Guo, B.; Xu, J. Preparation and characterization of poly(butylene succinate)/polylactide blends for fused deposition
modeling 3D printing. ACS Omega 2018, 3, 14309–14317. [CrossRef]
29. Yu, P.; Mi, H.-Y.; Huang, A.; Geng, L.-H.; Chen, B.-Y.; Kuang, T.-R.; Mou, W.-J.; Peng, X.-F. Effect of Poly(butylenes succinate) on
poly(lactic acid) foaming behavior: Formation of open cell structure. Ind. Eng. Chem. Res. 2015, 54, 6199–6207. [CrossRef]
30. Zhao, H.; Liu, H.; Liu, Y.; Yang, Y. Blends of poly(butylene adipate-co-terephthalate) (PBAT) and stereocomplex polylactide with
improved rheological and mechanical properties. RSC Adv. 2020, 10, 10482–10490. [CrossRef]
31. Kang, Y.; Chen, P.; Shi, X.; Zhang, G.; Wang, C. Preparation of open-porous stereocomplex PLA/PBAT scaffolds and correlation
between their morphology, mechanical behavior, and cell compatibility. RSC Adv. 2018, 8, 12933–12943. [CrossRef] [PubMed]
32. Canales, D.A.; Pinones, N.; Saavedra, M.; Loyo, C.; Palza, H.; Peponi, L.; Leones, A.; Baier, R.V.; Boccaccini, A.R.; Grünelwald, A.;
et al. Fabrication and assessment of bifunctional electrospun poly(L-lactic acid) scaffolds with bioglass and zinc oxide nanoparti-
cles for bone tissue engineering. Int. J. Biol. Macromol. 2023, 228, 78–88. [CrossRef] [PubMed]
33. Kaliva, M.; Georgopoulou, A.; Dragatogiannis, D.A.; Charitidis, C.A.; Chatzinikolaidou, M.; Vamvakaki, M. Biodegradable
chitosan-graft-poly(l-lactide) copolymers for bone tissue engineering. Polymers 2020, 12, 316. [CrossRef] [PubMed]
34. Yao, Q.; Song, Z.; Li, J.; Zhang, L. Micromorphology, mechanical, crystallization and permeability properties analysis of
HA/PBAT/PLA (HA, hydroxyapatite; PBAT, poly(butylene adipate-co-butylene terephthalate); PLA, polylactide) degradability
packaging films. Polym. Int. 2020, 69, 301–307. [CrossRef]
35. Dos Santos Silva, A.; Rodrigues, B.V.M.; Oliveira, F.C.; Carvalho, J.O.; de Vasconcellos, L.M.R.; de Araújo, J.C.R.; Marciano, F.R.;
Lobo, A.O. Characterization and in vitro and in vivo assessment of poly(butylene adipate-co-terephthalate)/nano-hydroxyapatite
composites as scaffolds for bone tissue engineering. J. Polym. Res. 2019, 26, 53. [CrossRef]
36. Santana-Melo, G.F.; Rodrigues, B.V.M.; da Silva, E.; Ricci, R.; Marciano, F.R.; Webster, T.J.; Vasconcellosa, L.M.R.; Lobo, A.O.
Electrospun ultrathin PBAT/nHAp fibers influenced the in vitro and in vivo osteogenesis and improved the mechanical properties
of neoformed bone. Colloids Surf. B 2017, 155, 544–552. [CrossRef] [PubMed]
37. Zhang, J.; Li, J.; Jia, G.; Jiang, Y.; Liu, Q.; Yang, X.; Pan, S. Improving osteogenesis of PLGA/HA porous scaffolds based on dual
delivery of BMP-2 and IGF-1 via a polydopamine coating. RSC Adv. 2017, 7, 56732–56742. [CrossRef]
38. Khan, M.A.; Hussain, Z.; Liaqat, U.; Liaqat, M.A.; Zahoor, M. Preparation of PBS/PLLA/HAP composites by the solution casting
method: Mechanical properties and biocompatibility. Nanomaterials 2020, 10, 1778. [CrossRef]
39. Gui, X.; Peng, W.; Xu, X.; Su, Z.; Liu, G.; Zhou, Z.; Liu, M.; Li, Z.; Song, G.; Zhou, C.; et al. Synthesis and application of nanometer
hydroxyapatite in biomedicine. Nanotechnol. Rev. 2022, 11, 2154–2168. [CrossRef]
40. Wang, W.; Zhang, B.; Li, M.; Li, J.; Zhang, C.; Han, Y.; Wang, L.; Wang, K.; Zhou, C.; Liu, L.; et al. 3D printing of PLA/n-HA
composite scaffolds with customized mechanical properties and biological functions for bone tissue engineering. Compos. B Eng.
2021, 224, 109192. [CrossRef]
41. Mou, Z.-L.; Zhao, L.-J.; Zhang, Q.-A.; Zhang, J.; Zhang, Z.-Q. Preparation of porous PLGA/HA/collagen scaffolds with
supercritical CO2 and application in osteoblast cell culture. J. Supercrit. Fluids 2011, 58, 398–406. [CrossRef]
42. Yan, D.; Wang, Z.; Guo, Z.; Ma, Y.; Wang, C.; Tan, H.; Zhang, Y. Study on the properties of PLA/PBAT composite modified by
nanohydroxyapatite. J. Mater. Res. Technol. 2020, 9, 11895–11904. [CrossRef]
43. Park, J.-W.; Hwang, J.-U.; Back, J.-H.; Jang, S.-W.; Kim, H.-J.; Kim, P.-S.; Shin, S.; Kim, T. High strength PLGA/Hydroxyapatite
composites with tunable surface structure using PLGA direct grafting method for orthopedic implants. Compos. B Eng. 2019, 178,
107449. [CrossRef]
44. Lowe, B.; Hardy, J.G.; Walsh, L.J. Optimizing nanohydroxyapatite nanocomposites for bone tissue engineering. ACS Omega 2020,
5, 1–9. [CrossRef] [PubMed]
Polymers 2023, 15, 4585 21 of 21

45. Velasco, M.A.; Narváez-Tovar, C.A.; Garzón-Alvarado, D.A. Design, materials, and mechanobiology of biodegradable scaffolds
for bone tissue engineering. BioMed Res. Int. 2015, 2015, 729076. [CrossRef] [PubMed]
46. Shelton, T.J.; Delman, C.; McNary, S.; Taylor, J.R.; Marder, R.A. Aging decreases the ultimate tensile strength of bone-partellar
tendon-bone allografts. Arthroscopy 2021, 37, 2173–2180. [CrossRef] [PubMed]
47. Rodrigues, S.C.S.; de Mesquita, F.A.S.; de Carvalho, L.H.; Alves, T.S.; Folkersma, R.; Araújo, R.S.d.R.M.; Oliveira, A.D.; Barbosa, R.
Preparation and characterization of polymeric films based on PLA, PBAT and corn starch and babassu mesocarp starch by flat
extrusion. Mater. Res. Express 2021, 8, 035305. [CrossRef]
48. Gheisari, H.; Karamian, E.; Abdellahi, M. A novel hydroxyapatite–Hardystonite nanocomposite ceramic. Ceram. Int. 2015, 41,
5967–5975. [CrossRef]
49. Rasheed, M.; Jawaid, M.; Parveez, B.; Bhat, A.H.; Alamery, S. Morphology, structural, thermal, and tensile properties of bamboo
microcrystalline cellulose/poly(Lactic Acid)/poly(Butylene Succinate) Composites. Polymers 2021, 13, 465. [CrossRef]
50. Solechan, S.; Suprihanto, A.; Widyanto, S.A.; Triyono, J.; Fitriyana, D.F.; Siregar, J.P.; Cionita, T. Characterization of
PLA/PCL/Nano-Hydroxyapatite (nHA) biocomposites prepared via cold isostatic pressing. Polymers 2023, 15, 559. [CrossRef]
51. Qiu, T.Y.; Song, M.; Zhao, L.G. Testing, characterization and modelling of mechanical behaviour of poly (lactic-acid) and poly
(butylene succinate) blends. Mech. Adv. Mater. Mod. Process. 2016, 2, 7. [CrossRef]
52. Qahtani, M.; Wu, F.; Misra, M.; Gregori, S.; Mielewski, D.F.; Mohanty, A.K. Experimental design of sustainable 3D-printed
poly(Lactic acid)/biobased poly(butylene succinate) blends via fused deposition modeling. ACS Sustain. Chem. Eng. 2019, 7,
14460–14470. [CrossRef]
53. Righetti, M.C.; Di Lorenzo, M.L.; Cinelli, P.; Gazzano, M. Temperature dependence of the rigid amorphous fraction of
poly(butylene succinate). RSC Adv. 2021, 11, 25731–25737. [CrossRef] [PubMed]
54. Bai, J.; Pei, H.; Zhou, X.; Xie, X. Reactive compatibilization and properties of low-cost and high-performance PBAT/thermoplastic
starch blends. Eur. Polym. J. 2021, 143, 110198. [CrossRef]
55. Zhao, X.; Zhang, D.; Yu, S.; Zhou, H.; Peng, S. Recent advances in compatibility and toughness of poly(lactic acid)/poly(butylene
succinate) blends. e-Polymers 2021, 21, 793–810. [CrossRef]
56. Wang, B.; Jin, Y.; Kang, K.; Yang, N.; Weng, Y.; Huang, Z.; Men, S. Investigation on compatibility of PLA/PBAT blends modified
by epoxy-terminated branched polymers through chemical micro-crosslinking. e-Polymers 2020, 20, 39–54. [CrossRef]
57. Zhou, Y.; Qiu, S.; Waterhouse, G.I.N.; Zhang, K.; Xu, J. Enhancing the properties of PBAT/PLA composites with novel phosphorus-
based ionic liquid compatibilizers. Mater. Today Commun. 2021, 27, 102407. [CrossRef]
58. De Luna, M.S.; Filippone, G. Effects of nanoparticles on the morphology of immiscible polymer blends—Challenges and
opportunities. Eur. Polym. J. 2016, 79, 198–218. [CrossRef]
59. Zhao, Q.; Wang, B.; Qin, C.; Li, Q.; Liu, C.; Shen, C.; Wang, Y. Nonisothermal melt and cold crystallization behaviors of
biodegradable poly(lactic acid)/Ti3C2Tx MXene nanocomposites. J. Therm. Anal. Calorim. 2022, 147, 2239–2251. [CrossRef]
60. Mata-Padilla, J.M.; Avila-Orta, C.A.; Almendarez-Camarillo, A.; Martinez-Colunga, J.G.; Hernandez-Hernandez, E.; Cruz-
Delgado, V.J.; Gonzalez-Morones, P.; Solis-Rosales, S.G.; Gonzalez-Calderon, J.A. Non-isothermal crystallization behavior of
isotactic polypropylene/copper nanocomposites. J. Therm. Anal. Calorim. 2021, 143, 2919–2932. [CrossRef]
61. Gao, H.; Qiang, T. Fracture surface morphology and impact strength of cellulose/PLA composites. Materials 2017, 10, 624.
[CrossRef]
62. Pivsa-Art, W.; Pivsa-Art, S. Effect of talc on mechanical characteristics and fracture toughness of poly(lactic acid)/poly(butylene
succinate) blend. J. Polym. Environ. 2019, 27, 1821–1827. [CrossRef]
63. Mao, H.-I.; Hsu, T.-S.; Chen, C.-W.; Huang, K.-W.; Rwei, S.-P. Sunthesis and characteristics of poly(ethylene terephthalate) with
EO-PO-EO triblock copolymers: A thermal and mechanical property study. J. Appl. Polym. Sci. 2022, 139, e51065. [CrossRef]
64. Zhao, T.; Yu, J.; Zhang, X.; Han, W.; Zhang, S.; Pan, H.; Zhang, Q.; Yu, X.; Bian, J.; Zhang, H. Thermal, crystallization, and
mechanical properties of polylactic acid (PLA)/poly(butylene succinate) (PBS) blends. Polym. Bull. 2023, 1–24. [CrossRef]
65. Ecker, J.V.; Haider, A.; Burzic, I.; Huber, A.; Eder, G.; Hild, S. Mechanical properties and water absorption behaviour of PLA and
PLA/wood composites prepared by 3D printing and injection moulding. Rapid Prototyp. J. 2019, 25, 672–678. [CrossRef]
66. Avci, A.; Eker, A.A.; Bodur, M.S.; Candan, Z. Water absorption characterization of boron compounds-reinforced PLA/flax fiber
sustainable composite. Int. J. Biol. Macromol. 2023, 233, 123546. [CrossRef] [PubMed]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.