journal of the mechanical behavior of biomedical materials 141 (2023) 105813

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Journal of the Mechanical Behavior of Biomedical Materials

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

Effect of poly (ethylene glycol) on 3D printed PLA/PEG blend: A study of

physical, mechanical characterization and printability assessment
Ritesh Kumar a, c, *, Y. Alex a, Biswabaibhaba Nayak b, Smita Mohanty a
a
School for Advanced Research in Petrochemicals: Laboratory for Advanced Research in Polymeric Materials (LARPM), Central Institute of Petrochemicals Engineering
and Technology (CIPET), Bhubaneswar, 751024, Odisha, India
b
Institute of Petrochemical Technology (IPT), Central Institute of Petrochemicals Engineering and Technology (CIPET), Bhubaneswar, 751024, Odisha, India
c
Department of Packaging and Logistics, Yonsei University, 1 Yonseidae-gil, Wonju-si, Gangwon-do, 26493, South Korea

A R T I C L E I N F O A B S T R A C T

Keywords: The growing popularity of additive manufacturing in the science, industry is associated with high-quality
Polylactic acid products for futuristic applications. This study presents an in-depth characterization and analysis of the effect
Poly (ethylene glycol) of poly (ethylene glycol) (PEG) having molecular weight 6000 g/mol used with various concentrations
Injection moulding
(1%,3%,5%) to modify the 3D printed Polylactide (PLA) part. The influence of PEG on the morphology, structure,
Finite element analysis (FEA)
thermal, wettability and mechanical properties of the 3D-printed PLA/PEG part was investigated. Herein, the
mechanical property of injection moulding, 3D printed specimens, and finite element analysis (FEA) simulation
results were also compared. The structure and properties of PLA/PEG blends were different from those of virgin
PLA. By DSC analysis, it was found that the glass transition temperature (Tg) and cold crystallization temperature
decreased in the case of the PLA/PEG blend. From TGA it was observed that PLA/PEG blend was thermally
stable. It was shown that with the addition of PEG into PLA the tensile strength and young’s modulus decrease,
whereas elongation percentage and impact strength increase predominantly. The contact angle results indicate
that the addition of PEG lowers the contact angle value of the PLA/PEG blend (from 69.32 ± 1.4◦ to 45.67 ±
1.2◦ ) and increases surface wettability. With 5% PEG loading, PLA/PEG blend showed optimum structural and
mechanical properties together with simple processibility.

1. Introduction 2019). These high-end technologies use thermoplastic-based polymer as

the raw material. The widely used polymer for 3D printing is polylactic
In recent years, additive manufacturing (AM), also known as three- acid (PLA)(Sharifabad et al., 2021), polyamide (PA)(Zhang et al., 2020),
dimensional 3D printing (3DP) technology has been widely used in in­ acrylonitrile butadiene styrene (ABS)(Gonçalves et al., 2020), and
dustry and science. Initially, additive manufacturing was mainly limited thermoplastic elastomer (TPE)(Chen et al., 2022). In recent years, with
to rapid prototyping (RP) but with the technology advancement, it is the excessive use of petrochemical polymers for 3D prototyping the huge
being used in the production of finished products and also known as waste product generated may result in environmental pollution.
rapid manufacturing (RM)(Backes et al., 2020; Eshraghi and Das, 2012; Therefore, more and more attention is required for the development of
Myers et al., 2022).Nowadays, additive manufacturing is employed in a filament for 3D printing, which is based on materials that are biode­
variety of industries, including product design, wearable technology gradable and/or obtained from renewable resources(Sanchez-Rexach
(WT), assistive technology (AT), and physical human-machine interac­ et al., 2020). Polylactic acid (PLA) is a biodegradable thermoplastic
tion (HMI)(Brooks et al., 2022; Ikeuchi et al., 2012; Takkalkar et al., polymer obtained from natural resources that have been extensively

Abbreviations: AM, Additive manufacturing; PLA, Polylactic acid; PEG, Polyethylene glycol; FEA, Finite element analysis; RP, Rapid prototyping; RM, Rapid
manufacturing; WT, Wearable technology; AT, Assistive technology; HMI, Human machine interaction; PA, Polyamide; ABS, Acrylonitrile butadiene styrene; TPE,
Thermoplastic elastomer; STL, Stereolithography; MFR, Melt flow rate; FTIR, Fourier transform infrared spectroscopy; XRD, X-ray diffraction; TGA, Thermogravi­
metric analyzer; DSC, Dynamic scanning calorimetry; DMA, Dynamic mechanical analyzer; UTM, Universal testing machine.
* Corresponding author. School for Advanced Research in Petrochemicals: Laboratory for Advanced Research in Polymeric Materials (LARPM), Central Institute of
Petrochemicals Engineering and Technology (CIPET), Bhubaneswar, 751024, Odisha, India.
E-mail address: [email protected] (R. Kumar).

https://doi.org/10.1016/j.jmbbm.2023.105813
Received 3 February 2023; Received in revised form 23 March 2023; Accepted 26 March 2023
Available online 30 March 2023
1751-6161/© 2023 Elsevier Ltd. All rights reserved.
R. Kumar et al. Journal of the Mechanical Behavior of Biomedical Materials 141 (2023) 105813

Fig. 1. Schematic representation of fabrication of PLA/PEG 3D printed specimen.

Fig. 2. Dimensions of tested samples. (a) Dumbbell shaped tensile specimen (ASTM D638), (b) Charpy impact specimen (ASTMD256).

Fig. 4. X-ray diffraction patterns of 3D printed virgin PLA, and PLA/PEG blend.
Fig. 3. Melt flow rate of VPLA, PLA/PEG1%, PLA/PEG3%, and PLA/PEG5%.

(Bernardo et al., 2021; Gao et al., 2020) Different non-biodegradable

used in the biomedical field such as drug delivery systems, absorbable
and biodegradable plasticizer has been employed to improve process­
sutures, bone fixation part, and for the development of 3D scaffold
ability, and flexibility to lower the glass transition temperature, and
(Gregor et al., 2017; Serra et al., 2014). However, the application of PLA
increase ductility. Blending PLA with various plasticizers such as poly­
is somewhat restricted because of its brittleness, low melt strength,
ethylene glycol (PEG), polypropylene glycol, and citrate esters is a
hydrophobicity, poor heat resistance, slow degradation rate, and crys­
simple and efficient method to overcome the disadvantages of PLA and
tallization kinetics of PLA. For 3D printing of PLA filament, keeping the
extend its application(Mohapatra et al., 2014). Polyethylene glycol
right solution viscosity during the entire printing process is a big chal­
(PEG) is one of the most efficient plasticizers for PLA because of its
lenging task. To maintain the viscosity of PLA, the selection of the right
excellent biocompatibility, dispersibility, high mobility, non-toxicity,
plasticizer and optimized processing temperature for 3D printing play a
and hydrophilicity(Ucpinar Durmaz and Aytac, 2021). The addition of
crucial role without causing thermal degradation to the polymer
PEG in PLA solution facilitates the printing process and introduced a

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R. Kumar et al. Journal of the Mechanical Behavior of Biomedical Materials 141 (2023) 105813

Table 1
Value of TGA/DTG measurements for the virgin PLA, and PLA/PEG loading with
1%,3% and 5% polyethylene glycol.
Sample Ti (◦ C) Tm(◦ C) Tf Char residue at 500 ◦ C

VPLA 327 370 388 1%

PLA/PEG1% 324 372 386 1%
PLA/PEG3% 324 373 386 1%
PLA/PEG5% 324 372 388 1%

Fig. 5. FTIR spectra of VPLA, PLA/PEG1%, PLA/PEG3%, and PLA/

PEG5% blend.

structural and physico-chemical change to the resultant scaffolds.

Meanwhile, the addition of PEG still maintains biodegradability, and
biocompatibility and can significantly enhance the mobility of the PLA
molecular chain(Li et al., 2015; Mohapatra et al., 2014; Whulanza et al.,
2022).
Recently various studies on PLA/PEG blends have been reported on
analyzing the effect of PEG on the structural, thermal, and mechanical
Fig. 7. DSC curve of VPLA, PLA/PEG1%, PLA/PEG3%, and PLA/PEG5%.
properties of PLA.Nedaipour et al. (2020) fabricated polylactic
acid-polyethylene glycol-hydroxyapatite composite for interference
screws used for the treatment of ruptured ligaments. They observed that They found that the PEG (8000 g/mol) shows the best enhancement
the addition of PEG to the mixture resulted in increasing hydrophilicity, effect on the interlayer bond strength and exerts a very minor effect on
elongation, and reduction in tensile strength. Gao et al. (2020) studied the crystallization of the 3D printed PLA part.Serra et al. (2014) studied
the effect of PEG with three different molecular weights 4000,8000, and the relevance of PEG (4000 g/mol) concentrations (0,5,10, 20% w/w)
20000 g/mol on crystallization, interlayer bond, and mechanical per­ on PLA based blend used for the fabrication of 3D printed scaffold for
formance of polylactide part fabricated by fused filament fabrication. tissue engineering applications. They found that the 5% PEG lead to

Fig. 6. TGA and DTG curve of VPLA, PLA/PEG1%, PLA/PEG3%, and PLA/PEG5%.

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R. Kumar et al. Journal of the Mechanical Behavior of Biomedical Materials 141 (2023) 105813

Table 2 study has compared the mechanical study of injection moulding speci­
Characteristics temperature and percentage of crystallinity of Virgin PLA, and mens, 3D printed specimens, and simulation results. The effect of
PLA/PEG blend loaded with 1,3,5% polyethylene glycol. different weight percentages of polyethylene glycol on the crystalliza­
Sample Tg (◦ C) Tcc(◦ C) Tm(◦ C) ΔHm(J/g) Xc(%) tion behavior, crystal structure, thermal stability, wettability, and me­
VPLA 67.11 100.63 178.04 32.69 19.76
chanical properties of the blend is investigated in detail by fourier
PLA/PEG1% 63.83 91.65 176.56 29.48 17.62 transform infrared spectroscopy, x-ray diffraction, thermogravimetric
PLA/PEG3% 63.08 90.31 176.31 15.76 9.7 analysis, dynamic scanning calorimetry, dynamic mechanical analysis,
PLA/PEG5% 61.62 89.50 177.02 51.86 33.80 contact angle and tensile test.

2. Materials and methods

improve the PLA processing with fair balance between structure and
mechanical properties. However, the addition of 10 and 20% PEG led to 2.1. Reagents
less uniform 3D structure with lower mechanical properties.
In this work, we evaluated the potential of different weight per­ PLA granules (TX0175, Skyi Biopolymers), Poly (ethylene glycol)
centages (1%,3%,5%) of polyethylene glycol (6000 g/mol) on com­ MW 6000, was purchased from Himedia. Chemicals were used without
mercial PLA to modify its properties to obtain a new kind of PLA further purification.
filament for biomedical applications. To the best of our knowledge, no

Fig. 8. (a,b) Storage modulus, and Tanδ of VPLA, PLA/PEG1%, PLA/PEG3%, and PLA/PEG5%.

Fig. 9. Tensile strength, elongation at break, and Young’s modulus results of VPLA, PLA/PEG1%, PLA/PEG3%, and PLA/PEG5%. (a, b) Injection moulded specimen
(c, d) 3D printed specimen.

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R. Kumar et al. Journal of the Mechanical Behavior of Biomedical Materials 141 (2023) 105813

Table 3 2.4. Finite element analysis (FEA) simulation

Mechanical properties of virgin PLA and PLA/PEG blend (injection moulding,
3D printed, and Simulation results (Young’s modulus values taken from injec­ Finite element simulation of tensile testing of PLA/PEG blend was
tion moulding results)). carried out using (Ansys Workbench 21). Fig. 2 shows the schematic of
Sample Specimen Youngs Maximum Elongation at the specimen used in the simulation study of virgin PLA and PLA/PEG
Modulus Stress break blend. In tensile testing simulations, the left-hand side of the specimen
Virgin (MPa) (MPa) (mm/mm) was kept fixed, limiting the movement of nodes in all three directions,
PLA Injection 2669.39 ± 5 55.02 ± 0.5 5.62 ± 0.05 whereas, the right-hand side of the specimen could move in the x-di­
Moulded rection (upwards), with respective loads. The overall length, thickness,
3D Printed 2044.60 ± 5 32.146 ± 1 2.33 ± 0.2
Simulation 2669.39 ± 5 54.36 ± 0.5 1.09 ± 0.05
and width of the specimen were 165, 3, and 19 mm, respectively. The
PLA/PEG Injection 2658.69 ± 9 52.85 ± 0.9 9.91 ± 0.05 material data used in the simulation were achieved from tensile testing
1% Moulded of the PLA/PEG blend. The tensile specimen for virgin PLA and blends
3D Printed 2014.105 ± 31.19 ± 1.2 2.45 ± 0.5 was discretized to 398690 of total elements and 581549 nodes. To
10
perform the simulation, 0.5 mm element size and 0.025 mm tolerance
Simulation 2658.69 ± 9 51.12 ± 0.9 1.319 ± 0.09
PLA/PEG Injection 2497.70 ± 9 46.43 ± 0.9 11.25 ± 0.05 with high-quality mesh was used. The data obtained from the machine
3% Moulded was in the form of force (N) vs elongation (mm), which was converted
3D Printed 2098.45 ± 31.79 ± 1.5 2.41 ± 0.6 into stress (MPa) vs strain (%) at the end to perform the simulation.
12
Simulation 2497.70 ± 9 50.52 ± 0.9 1.405 ± 0.09
PLA/PEG Injection 2526.51 ± 9 47.23 ± 0.9 12.62 ± 0.05
2.5. Characterization techniques
5% Moulded
3D Printed 2068.074 ± 32.056 ± 1.8 2.29 ± 0.7 The melt flow rate (12g/10 min) of the PLA/PEG blend granules
14 were investigated by a melt flow tester (Melt flow modular 7027, Ceast,
Simulation 2526.51 ± 9 49.14 ± 0.9 1.511 ± 0.09
Italy) by applying a standard weight of 2.16 kg at melting temperature of
180◦ . The x-ray diffraction pattern of 3D printed specimens were
2.2. Preparation of PLA/PEG filament recorded by an x-ray diffractometer (XRD-7000L, M/s Shimadzu, Japan)
with CuKα radiation (λ = 0.15418 nm) at 40 kV and 40 mA. The scan­
PLA/PEG blends were prepared using a twin screw extrusion process ning angle range varied between 5◦ and 60◦ with a scanning speed of 5◦ /
(See Fig. 1). Firstly PLA/PEG blends were prepared by placing them into min. The FTIR spectra of PLA/PEG 3D printed specimens were recorded
a co-rotating twin screw extruder (HAAKE™ Rheomex 100 OS, M/s on a fourier transform infrared spectrometer (Nicolet 6700, M/s Ther­
Thermo fisher Scientific, Germany). The temperature was in the range of mofisher, USA) in the spectral range of 4000 to 500 cm− 1during 64
150-170 ◦ C in six heating zones. The screw speed was between 100 and scans, with 4 cm− 1 resolution. The thermal stability of PLA/PEG 3D
150 rpm. The extruded PLA/PEG blends were granulated after drying. printed specimen was investigated using a thermogravimetric analyzer
Then to obtain filament (Ø = 1.75 mm) for 3D printing PLA/PEG blend (TGA Q 50 (M/s TA instrument, USA) from room temperature to 600 ◦ C
was passed through a twin screw extruder (Parallel twin-screw filament at 10 ◦ C/min rise in temperature under continuous nitrogen flow ac­
extruding machine - Process 11, M/s. Thermo Fisher Scientific, USA) cording to ASTM E 1868 standard. The thermal transition of the PLA/
with a barrel length of 40:1(L/D), six heating zone and two head zone, PEG 3D printed specimen was analyzed using a differential scanning (15
one cooling tube filled with water (22 ◦ C), a laser diameter measurement DSC Q 20 (M/s TA instrument, USA) by heating in the temperature range
system (laser sensor accuracy 0.01 mm), the puller (pulling velocity of 25–300 ◦ C at 10 ◦ C/min rise in temperature under continuous ni­
~5.2 m/min), and a spool winding system. The temperature profile of trogen flow. Universal testing machine (UTM) (M/s Instron-3382, UK)
barrels zone was I-100 ◦ C, II-100 ◦ C, III-165 ◦ C, IV-165 ◦ C, V-165 ◦ C, VI- equipped with a load cell of 10 kN was used to analyze the mechanical
170 ◦ C and head zones, VII-170 ◦ C, VIII-170 ◦ C. The temperature of the property of injection moulded(IM) and 3D printed at a constant ramp
melt was 170 ◦ C, the head pressure was 36 ± 2 bar and the extrusion speed of 10 mm/min in accordance with ASTM D822-18 standard. Three
velocity were set at 255 rpm. samples of each blend were measured. The charpy impact strength of the
injection moulded(IM) and 3D printed specimen was analyzed using a
2.3. Fabrication of 3D printed specimen pendulum impact tester (Tinius Olsen, USA) with a 2.75J hammer ac­
cording to the ASTM D256 standard.Dynamic mechanical analysis of 3D
Mechanical properties of the prepared filaments (3D Printing sam­ printed specimen was carried out using DMA Q 800 (M/s TA instrument,
ples – PLA + PEG), were designed using computer aided (3D) design USA) under the dual cantilever mode with 1.0Hz frequency. The sample
software (Unigraphics NX) – the 3D models for the tensile (dog-shaped), dimension is 63 × 12.7 × 3.2 mm3 and the test was performed from
Impact (rectangular), samples were designed, as per the ASTM standards room temperature to 200 ◦ C at a heating rate of 4◦ /min− 1 in accordance
(see Fig. 2). These designed samples were then sliced using MakerBot with ASTM D-5026 standards. The micro morphology of the fractured
slicing software and converted to stereolithography (STL) format. The surface of the PLA/PEG 3D printed specimen was investigated using
specimens were printed on a Makerbot Method-X FDM printer, equipped scanning electron microscopy (EVO MA 15, Carl Zeiss SMT, UK), oper­
with a double extruder, one with main material and the other with ated at an accelerating voltage of 20 kV. A wettability study of the 3D
supporting material, with a nozzle diameter of 0.4 mm, and maintained printed specimen was performed by a contact angle tester (M/s APEX
print bed temperature of 40 ◦ C. The printer nozzle temperature will vary instrument PVT.LTD, Germany). Five different measurements were
with the type of material used. For virgin PLA and (PLA + PEG) com­ performed for each specimen.
bination filament, the temperature was set to 210 ◦ C, and 220 ◦ C,
respectively. 3. Result and discussion
For comparison, all kinds of PLA/PEG filaments were pelletized
using a granulator. Tensile specimens were prepared using injection 3.1. Melt flow rate (MFR)
moulding (x Plore,15 ml, DSM, Netherland) at the temperature of
180 ◦ C. The specimens were held for 5s at a holding pressure of 6 bar. MFR is an important parameter that allows for a quick and easy way
to estimate the appropriate printing temperature for the tested filament
which shortens the time and reduces the cost of production.The effect of
PEG on melt flow rate of PLA/PEG blend was examined. From Fig. 3 it

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R. Kumar et al. Journal of the Mechanical Behavior of Biomedical Materials 141 (2023) 105813

Fig. 10. (a,b) Finite element analysis (stress and strain distribution in the tensile specimen of Virgin PLA and PLA/PEG blends).

was observed that the melt flow rate of all specimens was higher than 3.3. Fourier transform infrared spectroscopy
that of virgin PLA (11.50 g/10min.), which is primarily due to the
plasticizing effect of polyethylene glycol.PEG molecules can enter in The functional group and interaction between blend components of
between PLA macromolecules and can considerably affect the mobility PLA/PEG blends were investigated by ATR-FTIR analysis as presented in
of polymeric chain (Gao et al., 2020; Nedaipour et al., 2020). Fig. 5. For virgin PLA, peak observed at 2994 cm− 1 and 2949 cm− 1
corresponds to the asymmetric and symmetric stretching of CH3 group,
3.2. X-ray diffraction (XRD) respectively. Similarly, the peak appeared at 1745 cm− 1 and 1085 cm− 1
indicated the characteristics C– – O stretching vibration and C–O–C
XRD patterns collected from 3D printed virgin PLA, and PLA/PEG stretching vibration of the PLA ester group, respectively (Haryńska
blend is shown in Fig. 4. The diffraction pattern for the 3D printed virgin et al., 2021; Li et al., 2015).Chieng et al. (2014) reported the charac­
PLA showed a broad hump in the range of 2θ equal to 10–25◦ , which is teristic peak at 3446 cm− 1, which is related to the terminal hydroxyl
characteristic of amorphous-based PLA (Chieng et al., 2014). The peak group of PEG. Although the concentration of PEG in the blend varied
intensity of PLA increases with the increase in PEG content. However, from 1% to 5%, however, the characteristic peaks of all blend spec­
PLA/PEG blend showed a similar diffraction pattern like virgin PLA (Yu imensshow almost same absorption peaks as virgin PLA. This result in­
et al., 2015). dicates that there was no new bond formation took place or strong
chemical interaction occurred within the blend.

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R. Kumar et al. Journal of the Mechanical Behavior of Biomedical Materials 141 (2023) 105813

showed the DSC heating curve of virgin PLA, and PLA/PEG blend with
the loading of 1%,3%, and 5% polyethylene glycol and Table 2 sum­
marizes the DSC results. The figure shows glass transition temperature
(Tg), cold crystallization peak (Tcc), and melting point (Tm). The addi­
tion of PEG did not show any significant change in the glass transition
temperature (Tg) and melting temperature (Tm) of the PLA/PEG blend.
With the increase in the concentration of PEG slight change in glass
transition temperature from 67.11 ◦ C to 61.62 ◦ C appeared, while in the
case of melting point, only a marginal drop from 178 ◦ C to 176 ◦ C is
observed. The cold crystalline temperature of the PLA/PEG5% blend
(89.50 ◦ C) appeared at a lower temperature than the virgin PLA
(100.63 ◦ C). These results indicate that the presence of PEG molecule
between PLA chain converted PLA-PLA strong homogeneous bonds into
heterogeneous PLA-PEG bonds, and cause easier movement of PLA
molecule, thus lowering Tg, Tm, and TCC (Nedaipour et al., 2020; Sheth
et al., 1997). The result is in accordance with what is reported in the
literature. Moreover, a single Tg peak confirmed the miscibility of both
PLA and PEG material(Mohapatra et al., 2014). It also observed that
Fig. 11. Impact strength results of Injection moulded and 3D printed virgin PLA/PEG blend with 5% PEG concentration showed higher crystallinity
PLA and PLA/PEG blend. (33.80%) as compared to virgin PLA (19.76%), which is in agreement
with the XRD data. This might be possible due to the crystalline nature of
3.4. Thermogravimetric analysis (TGA/DTG) PEG that enhanced nucleation points and mobility of the PLA chain(Yu
et al., 2015).
Fig. 6 (a, b, c, d) shows the TGA/DTG thermogram of virgin PLA, and
PLA/PEG blend with different concentrations of PEG, respectively, and
3.6. Dynamic mechanical analysis (DMA)
the detailed data is also listed in Table 1. Fig. 6(a) showed that the virgin
PLA exhibits one step of degradation in the range of 320–390 ◦ C.In PLA/
Fig. 8 (a,b) show the storage modulus and dissipation factor (tanδ) of
PEG blend, a slight shift in initial decomposition temperature (Ti) and
virgin PLA, and PLA/PEG blend with the loading of 1%,3%, and 5%
final decomposition temperature (Tf) from 327 ◦ C to 324 ◦ C and from
PEG. Fig. 8(a) show that with the increase in PEG content in the polymer
388 ◦ C to 386 ◦ C was observed, respectively. In fact, PLA/PEG blend
matrix resulted in a decrease in storage modulus that indicates the
showed quiet similar behavior to virgin PLA. It appears that the incor­
reduction in elastic properties of PLA. Fig. 8(b) showed that the virgin
poration of PEG part (1,3,5%) in PLA/PEG blend did not influence
PLA has a glass transition temperature (Tg) around 77 ◦ C, while with the
thermal stability of PLA(Chieng et al., 2014; Serra et al., 2014).
increase in PEG content, it decreases to 66.53 ◦ C which is because of the
enhanced segmental mobility with the addition of PEG, which is in
3.5. Dynamic scanning calorimetry (DSC) agreement with the DSC data. Moreover, a single glass transition (Tg)
observed for all the PLA/PEG blends indicate the complete miscibility
DSC test indicates the thermal transition properties of blends. Fig. 7 for both polymers because phase separated blends will exhibit two

Fig. 12. Scanning electron micrographs of fractured surface of 3D printed (a) virgin PLA (b)PLA/PEG1%,(c) PLA/PEG3% and (d) PLA/PEG5%.

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R. Kumar et al. Journal of the Mechanical Behavior of Biomedical Materials 141 (2023) 105813

0◦ specimen showed a similar trend to injection moulded specimen. This

trend may be due to the plasticizing effect of PEG with a virgin PLA
matrix. Small PEG molecules formed strong heterogeneous PLA-PEG
bonds as compared to homogeneous PLA-PLA bonds increasing the
mobility of the PLA chain(Bijarimi et al., 2016; Li et al., 2015). As a
result, the addition of PEG increased the flexibility and plasticity of the
blend but decrease its tensile strength. Fig. 10 (a, b) showed the
graphical representation of simulated specimen tensile stress and strain
distribution. The finite element analysis simulation of tensile specimens
of virgin PLA and PLA/PEG blend clearly depicts the simulated specimen
values were relatively close to the values of injection moulded
specimens.
At the node of 4534, the virgin PLA and PLA/PEG blend showed the
maximum tensile stress value of 54.36, 51.12, 49.14, and 50.55 MPa,
respectively. At each node, the stress concentration values are varying
with respect to the load/force applied. This could be helpful while
designing or selecting a material for study. Similarly, here at the node of
27902, the PLA and PLA/PEG blend showed the maximum tensile strain
value of 1.09, 1.32, 1.40, and 12.512 mm, respectively.

3.9. Impact strength

Fig. 13. Wettability result of VPLA, PLA/PEG1%, PLA/PEG3%, and
PLA/PEG5%. Fig. 11 depicts the effect of plasticizer on the impact strength of in­
jection moulded and 3D printed virgin PLA and PLA/PEG blend. Virgin
distinct glass transition(Gao et al., 2020). PLA of injection moulded, and 3D printed specimens showed an impact
strength of 3.4 kJ/m2, and 1.6 kJ/m2, respectively. With the addition of
3.7. Printability assessment PEG into PLA the impact strength of injection moulded, and 3D printed
specimens increase up to 13.64 kJ/m2, and 1.97 kJ/m2, respectively. It
Virgin PLA and PLA/PEG blend filament having diameter 1.70–1.75 was clearly observed that the PEG effectively served as a plasticizing
mm was used to prepare 3D printed samples (tensile and impact) using effect by amplifying the impact strength of the PLA/PEG blend. PEG
FDM 3D printer as per ASTM standards. Several hit and trial runs were weakens the intermolecular force of attraction of the PLA chain thus
conducted for achieving the appropriate condition for 3D printing. allowing the PLA molecules to move readily, which increases the flexi­
Hence, the hit and trial run starts with the virgin PLA. The temperature bility of the polymer(Gao et al., 2020; Li et al., 2018).
was initially set to 180 ◦ C, and the printer starts purging. However, the
rate of flow was lower than it would be for commercial PLA, so the 3.9.1. Scanning electron microscopy (SEM)
temperature was increased to 185 ◦ C, and purging continues.Finally, at Fig. 12 displays the scanning electron micrographs of the tensile
210 ◦ C, the expected flow range had been achieved. Similarly, PLA/PEG fractured surface of 3D printed virgin PLA, and PLA/PEG blends. As seen
blend filament achieved a better flow rate between 210 ◦ C and 220 ◦ C. in the Fig. 12(a), virgin PLA showed a smooth surface while with the
An appropriate diameter of filament (1.70–1.75 mm) and flow rate was increase in loading of PEG content surface roughness increases. How­
required for continuous printing of 3D printed specimen. After ever, longer fibrils were observed for higher loading of PEG into the
completion of each process, the extruder of the printer was purged with PLA/PEG blend. PLA/PEG blend with surface roughness and more fibrils
virgin PLA, at 220 ◦ C. This process has been done to avoid the sticking of indicate complete miscibility of PEG with PLA matrix and characteristics
filament into the extruder tube, which creates coagulation and finally of enhanced ductility(Mohapatra et al., 2014; Nedaipour et al., 2020).
tends to severe problems for the next printing. After the completion of
each printing set, the printed specimens will be kept in the chamber for 3.10. Wettability study
30min, as a part of the post-processing. This improves the strength of the
specimens. Fig. 13 showed the wettability of virgin PLA and PLA/PEG blend
with loading of 1,3 and 5% polyethylene glycol. The water contact angle
3.8. Mechanical study of the 5% PEG loaded blend (45.67 ± 1.2◦ ) was lower than that of virgin
PLA (69.32 ± 1.4◦ ) indicating that PLA/PEG5% blend had higher hy­
The tensile stress-strain curve, elongation at break and young’s drophilicity than the virgin PLA. The contact angle was gradually
modulus of virgin PLA, and PLA/PEG blend (IM and 3D printed spec­ reduced by increasing the concentration of PEG in the PLA/PEG blend.
imen) with different loading of polyethylene glycol are shown in Fig. 9, This decrease in the contact angle of the blend was happening due to the
and the specific data are also listed in Table 3. The tensile strength, high hydrophilicity of the PEG fraction because of the presence of many
elongation at break, and young’s modulus of (IM) virgin PLA are 55.02 hydrophilic hydroxyl groups(Jia et al., 2017; Srisuwan and Baimark,
MPa, 5.62%, and 2669.39 MPa, respectively. The addition of 1–5% PEG 2022).Nedaipour et al. reported a similar trend in the contact angle by
concentration into the PLA/PEG blend resulted in a significant decrease adding PEG to PLA(Nedaipour et al., 2020). Contact angle results indi­
in tensile strength and young’s modulus and an increase in elongation at cate that the PEG is beneficial to enhance the compatibility of PLA with
break; these results are in accordance with previously reported results other polymers in the melt compounding process.
(Nedaipour et al., 2020; Srisuwan and Baimark, 2022). In the case of 3D
printed specimen tensile strength is low as compared to the injection 4. Conclusion
moulded specimen because of weak interlayer bond zones and a large
amount of inter-filaments voids, while injection moulded specimens are In this work, we have successfully fabricated 3D printed PLA/PEG
dense because of enough external pressure and build time on polymer specimen by fused filament fabrication technique.The addition of PEG to
melt(Levenhagen and Dadmun, 2018; Spoerk et al., 2017). However, the PLA matrix is an effective method for improving the processing, and
tensile strength, young’s modulus, and elongation at break of 3D printed tailoring the both surface and structural property. Morphological

8
R. Kumar et al. Journal of the Mechanical Behavior of Biomedical Materials 141 (2023) 105813

observation confirms the complete miscibility of both the PLA and hydroxyapatite composite scaffolds prepared by selective laser sintering for bone
tissue engineering. Acta Biomater. 8, 3138–3143. https://doi.org/10.1016/j.
plasticizer PEG which was being evident from the XRD and FTIR results.
actbio.2012.04.022.
DMA results showed the decrease in storage modulus of PLA/PEG blend Gao, X., Qi, S., Zhang, D., Su, Y., Wang, D., 2020. The role of poly (ethylene glycol) on
compared to virgin PLA. In addition, DSC results revealed that with the crystallization, interlayer bond and mechanical performance of polylactide parts
addition of PEG into PLA matrix reduces the glass transition temperature fabricated by fused filament fabrication. Addit. Manuf. 35, 101414 https://doi.org/
10.1016/j.addma.2020.101414.
because of the plasticizing effect of PEG. Moreover, it was shown that Gonçalves, N.I., Münchow, E.A., Santos, J.D., Sato, T.P., de Oliveira, L.R., de Arruda
the incorporation of different percentage of PEG leads to significantly Paes-Junior, T.J., Bottino, M.C., Borges, A.L.S., 2020. The role of polymeric
increase in wettability and decrease mechanical property of 3D printed nanofibers on the mechanical behavior of polymethyl methacrylate resin. J. Mech.
Behav. Biomed. Mater. 112 https://doi.org/10.1016/j.jmbbm.2020.104072.
and injection moulded PLA/PEG blend. To conclude, it appears that the Gregor, A., Filová, E., Novák, M., Kronek, J., Chlup, H., Buzgo, M., Blahnová, V.,
addition of 5% of PEG in PLA matrix allow the fabrication of 3D printed Lukášová, V., Bartoš, M., Nečas, A., Hošek, J., 2017. Designing of PLA scaffolds for
PLA/PEG blend with the fair balance between structural and mechanical bone tissue replacement fabricated by ordinary commercial 3D printer. J. Biol. Eng.
11, 1–21. https://doi.org/10.1186/s13036-017-0074-3.
property. Haryńska, A., Janik, H., Sienkiewicz, M., Mikolaszek, B., Kucińska-Lipka, J., 2021. PLA-
potato thermoplastic starch filament as a sustainable alternative to the conventional
Funding PLA filament: processing, characterization, and FFF 3D printing. ACS Sustain. Chem.
Eng. 9, 6923–6938. https://doi.org/10.1021/acssuschemeng.0c09413.
Ikeuchi, M., Tane, R., Ikuta, K., 2012. Electrospray deposition and direct patterning of
This research was funded by the Department of chemicals and pet­ polylactic acid nanofibrous microcapsules for tissue engineering. Biomed.
rochemicals, ministry of chemicals and fertilizers (DCPC), Government Microdevices 14, 35–43. https://doi.org/10.1007/s10544-011-9583-x.
Jia, S., Yu, D., Zhu, Y., Wang, Z., Chen, L., Fu, L., 2017. Morphology, crystallization and
of India (F: No 25012/01/2020-PC-II (FTS:16020).
thermal behaviors of PLA-based composites: wonderful effects of hybrid GO/PEG via
dynamic impregnating. Polymers 9. https://doi.org/10.3390/polym9100528.
CRediT authorship contribution statement Levenhagen, N.P., Dadmun, M.D., 2018. Interlayer diffusion of surface segregating
additives to improve the isotropy of fused deposition modeling products. Polymer
(Guildf). 152, 35–41. https://doi.org/10.1016/j.polymer.2018.01.031.
Ritesh Kumar: Writing – original draft, Methodology, Formal Li, D., Jiang, Y., Lv, S., Liu, X., Gu, J., Chen, Q., Zhang, Y., 2018. Preparation of
analysis, Conceptualization. Y. Alex: Visualization, Validation, Investi­ plasticized poly (lactic acid) and its influence on the properties of composite
gation. Biswabaibhaba Nayak: Resources, Data curation. Smita materials. PLoS One 13, 1–15. https://doi.org/10.1371/journal.pone.0193520.
Li, F.J., Liang, J.Z., Zhang, S.D., Zhu, B., 2015. Tensile properties of polylactide/poly
Mohanty: Writing – review & editing, Supervision, Project (ethylene glycol) blends. J. Polym. Environ. 23, 407–415. https://doi.org/10.1007/
administration. s10924-015-0718-7.
Mohapatra, A.K., Mohanty, S., Nayak, S.K., 2014. Effect of PEG on PLA/PEG blend and
its nanocomposites: a study of thermo-mechanical and morphological
Declaration of competing interest characterization. Polym. Compos. 35, 283–293. https://doi.org/10.1002/pc.22660.
Myers, D., Abdel-Wahab, A., Hafeez, F., Kovacev, N., Essa, K., 2022. Optimisation of the
The authors declare that they have no known competing financial additive manufacturing parameters of polylactic acid (PLA) cellular structures for
biomedical applications. J. Mech. Behav. Biomed. Mater. 136, 105447 https://doi.
interests or personal relationships that could have appeared to influence org/10.1016/j.jmbbm.2022.105447.
the work reported in this paper. Nedaipour, F., Bagheri, H., Mohammadi, S., 2020. Polylactic acid-polyethylene glycol-
hydroxyapatite composite” an efficient composition for interference screws.
Nanocomposites 0, 99–110. https://doi.org/10.1080/20550324.2020.1794688.
Data availability
Sanchez-Rexach, E., Johnston, T.G., Jehanno, C., Sardon, H., Nelson, A., 2020.
Sustainable materials and chemical processes for additive manufacturing. Chem.
No data was used for the research described in the article. Mater. 32, 7105–7119. https://doi.org/10.1021/acs.chemmater.0c02008.
Serra, T., Ortiz-Hernandez, M., Engel, E., Planell, J.A., Navarro, M., 2014. Relevance of
PEG in PLA-based blends for tissue engineering 3D-printed scaffolds. Mater. Sci. Eng.
Acknowledgments C 38, 55–62. https://doi.org/10.1016/j.msec.2014.01.003.
Sharifabad, S.S., Derazkola, H.A., Esfandyar, M., Elyasi, M., Khodabakhshi, F., 2021.
The authors are grateful to the Department of chemicals and petro­ Mechanical properties of HA@Ag/PLA nanocomposite structures prepared by
extrusion-based additive manufacturing. J. Mech. Behav. Biomed. Mater. 118,
chemicals, ministry of chemicals and fertilizers (DCPC), Government of 104455 https://doi.org/10.1016/j.jmbbm.2021.104455.
India for sponsoring of “Centre of Excellence” in the field of Sheth, M., Kumar, R.A., Dave, V., Gross, R.A., McCarthy, S.P., 1997. Biodegradable
Petrochemicals. polymer blends of poly(lactic acid) and poly(ethylene glycol). J. Appl. Polym. Sci.
66, 1495–1505. https://doi.org/10.1002/(SICI)1097-4628(19971121)66:8<1495::
AID-APP10>3.0.CO;2-3.
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