pubs.acs.

org/journal/ascecg Research Article

PLA−Potato Thermoplastic Starch Filament as a Sustainable

Alternative to the Conventional PLA Filament: Processing,
Characterization, and FFF 3D Printing
Agnieszka Haryńska,* Helena Janik, Maciej Sienkiewicz, Barbara Mikolaszek, and Justyna Kucińska-Lipka
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ABSTRACT: The growing popularity of the fused filament

fabrication (FFF) 3D printing technology in science, industry,
and in-home use is associated with an increased demand for high-
Downloaded via 132.157.128.124 on March 3, 2024 at 05:06:18 (UTC).

quality polymer filaments. This study presents an in-depth

characterization and analysis of a self-made bio-based polylactide
(PLA)/thermoplastic potato starch (TPS) filament dedicated for
the FFF 3D printing technology. The obtained results were
compared with the commercial PLA filament (FF). The series of
conducted studies (i.e., Fourier-transform infrared spectroscopy,
Raman spectroscopy, differential scanning calorimetry, thermogra-
vimetric analysis, and dynamic mechanical analysis) revealed that
both of the investigated filaments are stable under FFF 3D printing
conditions. The mechanical test showed a correlation between the
print orientation and raster angle on the strength features. The most favorable strengths values were recorded for the ZX_0°
configuration, which were ∼18/22 MPa of tensile strength and ∼9/18 kJ m−2 of Charpy impact strength for the PLA/TPS filament
and FF, respectively. Also, it was observed that the developed bio-filament has a more hydrophilic surface and is more susceptible to
hydrolytic degradation in the phosphate-buffered saline solution than the FF. The composting study (according to the EN ISO
20200 standard) revealed that the commercial PLA printouts remain intact, while the PLA/TPS samples showed a mass loss of 19%.
Finally, the remarkable printability of PLA/TPS was successfully demonstrated by FFF 3D printing of personalized anatomical
models and complex porous structures.
KEYWORDS: fused filament fabrication, 3D printing, potato thermoplastic starch, polylactide, material characterization,
bio-based filaments

■ INTRODUCTION
The use of additive manufacturing (AM) technologies in
on fossil fuels-based filament substitutes with less negative
environmental impact are being sought.2
industry and science has become widespread nowadays. These More and more attention is being paid to the development of
methods are irreplaceable in rapid prototyping as well as more bio-filaments for FFF 3DP, which are based on materials that are
and more often used in the production of finished products. The biodegradable and/or obtained from renewable resources. The
example of the AM technologies that is particularly popular in most recent literature reports regarding this topic are presented
the industry, medicine, and home use is the fused filament in Table 1. The developed materials are, in most cases, PLA-
fabrication (FFF). This highly available technology primarily based composites modified with natural powders (walnut shell
uses thermoplastic-based polymers as the raw material. The powder4) or managed eco-wastes (spend coffee grounds5 and
most popular materials (filaments) for FFF 3D printing (3DP) spruce pulp fibers3). Other studies focus on the use of recyclates
are acrylonitrile butadiene styrene (ABS), polylactide (PLA), as efficient feedstocks for FFF 3D printers. Idrees et al.6
polyamide (PA), and thermoplastic elastomer (TPE).1 Never- proposed a filament based on waste polyethylene terephthalate
theless, along with the growing interest in this molding method,
the amount of petrochemical polymers used is constantly
increasing. As prototyping involves the formation of disposable Received: January 2, 2021
products, the amount of FFF 3D-printed waste reaches a very Revised: March 29, 2021
alarming level. While the recycling of unmodified thermoplastics Published: May 10, 2021
is not regarded as a problem, the effective recovery of raw
materials from modified 3D printout waste (blends and
composites) is much more difficult. Therefore, new solutions
© 2021 The Authors. Published by
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6923 ACS Sustainable Chem. Eng. 2021, 9, 6923−6938
ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Table 1. Latest Literature Reports on Bio-Filaments for 3D Printing in the FFF Technology
bio-filaments
type of filament composition short description material propertiesb suggested application refs
fiber-based PLA/TMP a
development of biocomposite filaments of PLA tensile strength = 10−23 MPa, water contact antibacterial 3D-printed 3
composites with modified spruce thermomechanical pulp angle of selected samples up to 100° (highly devices
fibres (TMP) (10 and 20 wt %) hydrophobic properties)

particle-based PLA/WSPa studies of bio-based composite filaments based melt flow index (MFI, 160 °C, 3.8 kg) = trabecular bone tissue 4
composites on the PLA matrix with a walnut shell powder 8−18 g 10 min−1, compressive strength = scaffolds
(WSP) modifier (5 wt %) 212−276 MPa, Young modulus =
2.5−3.0 GPa, tensile strength = 48−52 MPa
PLA/Ox-SSGa fabrication and characterization of bio-based toughness = 5−25 MJ m−3 personalized prosthesis 5
PLA filaments loaded with oil-extracted spent
coffee grounds (Ox-SCG) (5−20 wt %)
PET/Biochar development of sustainable filaments from Young modulus = 0.7−09. GPa, tensile a sustainable, recycle-based 6
recycled PET bottles enhanced with biochar strength = ∼50 MPa alternative for automotive
derived from packaging waste (0.5−5 wt %) and engineering applica-
tion

nanocomposite PA-11/sepiolite development of fully biorenewable filaments Young modulus = 0.7−1.15 GPa, tensile biorenewable alternative to 7
nanoclaya based on a PA-11 monomer (11-amino- strength = 27−47 MPa, strain at break = PLA filaments with higher
undecanoic, castor beans origin) modified 5−38% printing temperature for
with natural clay (1, 3, and 7 wt %) engineering application
PHBH/CNCa studies of bio-based PHBH filaments modified disintegration ratio in a laboratory-scale external medical devices, 8
with functionalized cellulose nanocrystals composting test (60th day of the test) = surgical implants, tissue
(CNC) (5−20 wt %) 55−80% scaffolds

polymer blends TPS/ABS development of partly bio-based filaments impact strength (Izod, notched) = 8−18 J m−1, household gadgets, inductrial 9
composed of 30 wt % debranched-with- flexuralmodulus = 2.1−2.5 GPa, tensiles- design, architecture
α-isoamylase thermoplastic starch (TPS) and trength = 34−48 MPa
acrylonitrile butadiene styrene (ABS)
PBS/PLA fabrication and characterization of biodegrad- tensile strength = 16−21 MPa architectural design 10
able filaments consisting of the mixture of
PBS with PLA (20−60 wt %)
PLA/PBAT formulation of biofilaments with increased Impact strength (Izod, notched) = not specified 11
impact strength from PLA-based blends 30−719 J m−1, Young modulus =
containing 10, 20, and 30% of poly(butylene 2.2−3.0 GPa, tensile strength = 40−63 MPa,
adipate-co-terephthalate (PBAT) elongation at break = 7.6−84%
a
Fully bio-based. bThe given mechanical properties refer to FFF 3D printouts made using developed filaments.

(PET) bottles with the addition of biochar (derived from direct comparison of the formed PLA/TPS filament with
packaging waste) as a sustainable alternative to conventional commercially available products, all of the presented studies
filaments. Another interesting solution seems to be a were also carried out for the FlashForge PLA filament. The
modification of poly(3-hydroxybutyrate-co-3-hydroxyhexa- schematic flowchart showing the steps of the work is presented
noate) (PHBH) with cellulose nanocrystals (CNC), proposed in Figure 1. Structural, thermal, and mechanical properties, as
by Giubilini et al.8 As a result, a printable FFF filament with well as wettability, susceptibility to hydrolysis, and disintegra-
enhanced thermal and mechanical properties as well as tion in composting conditions, were evaluated. Furthermore,
improved compostability was obtained. This product combines
spectroscopic and thermal studies were carried out for both
both compostability and fully renewable origin; therefore, it can
be considered as “double green”. However, the relatively high
production costs of PHBH and CNC may hamper the
introduction of this product at an industrial scale. Thus,
nowadays, it seems reasonable to follow the “double-ECO”
approach proposed by Tanabe12 which takes into consideration
not only the environmental and ecological issues but also an
economical aspect of the production.
In our previous research, we developed a biodegradable and
compostable polymer composition based on renewable and
natural-origin ingredients.13 The composition consists of PLA
and thermoplastic potato starch (TPS) modified with
epoxidized soybean oil (ESO). As a result, we improved PLA’s
ductility as well as reduced the costs of the granulate without
compromising biodegradability and compostability. In the next
step, we started research on the use of the developed
composition as a sustainable material for FFF 3DP. Therefore,
in this study, we present the full characteristics of self-made
PLA/TPS filament which can be a sustainable alternative to the
commonly used petrochemical filaments. Moreover, to facilitate Figure 1. Schematic flowchart representing the steps of the work.

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Figure 2. Scheme of the PLA/TPS filament composition: (a) PLA, (b) potato starch, (c) glycerin, and (d) ESO and (e) SEM image of the PLA/TPS
filament (in cross-section view).

filaments and the formed printouts to assess the stability of the Table 2. Symbols and Description of Materials Used in the
material under FFF 3DP conditions. Finally, the FFF printability Study
of the proposed novel bio-filament was evaluated and compared
composition (wt %)
with that of commercial PLA printouts. For this purpose, we
printed (FFF 3DP) personalized anatomical models (cervical TPS
and lumbar vertebrae) and complex-shaped porous structures symbol description PLA potato starch plant glycerin ESO
(gyroid and cancellous bone-like structure). To our best PLA/TPS_F filament 60 26.3 13.3 0.4
knowledge, we have not found so far any literature reports on PLA/TPS_P printout
PLA-based filaments modified with TPS for FFF 3DP. Thus, the symbol description PLA thermoplastic elastomer mineral oils
presented research may be an interesting offer for other
FF_F filament 95 4 1
scientists or industries looking for bio-based filaments with
FF_P printout
increased compostability and adequate printability.

■ EXPERIMENTAL SECTION
Materials. The PLA/TPS granulate used to obtain the PLA/TPS_F
°C, II160 °C, and III168 °C and for head zones IV170 °C and
V172 °C. The temperature of the melt was 176 °C, the head pressure
filament was previously developed and described in detail in our earlier was 21 ± 2 bar, and the extrusion velocity was set at 35 rpm. The
article.13 The composition selected for this work contained fully plant- scheme and detailed description of the applied filament-forming system
based-origin biodegradable raw materials, that is, 60 wt % PLA (7032D are presented in our previous article.14
transparent injection grade, NatureWorks, USA, MFR = 7 g 10 min−1 at 3D Printer, Test Samples, Anatomical Model Design, and 3D
210 °C and 2.16 kg) and 40 wt % TPS (Figure 2). TPS was obtained by Printing Settings. Prusa i3 MK3S (Prusa Research, Prague, Czech),
melt extrusion of the following mixture: native potato starch (ZetPezet, an FFF-based 3D printer, with PrusaSlicer software (2.20 version) was
Poland, humidity 16%), plant pharmaceutical-grade glycerin, used as a used to print the studied details. Autodesk Inventor software
plasticizer (TechlandLab, Poland, ρ = 1.26 g cm3), and ESO (Brenntag, (Autodesk, Warszawa, Poland) was used to prepare SLT files of test
Germany), which served as a reactive modifier. The wt % ratio of the specimens (for tensile, compression, and impact tests). The 3D printing
TPS components was as follows: potato starch 65.7%; glycerin 33.3%; settings of all test samples used for characterization are listed in Table
and ESO 1%. S1, and dimensions of samples for strength tests are presented in Figure
A wildly available commercial PLA filament produced by FlashForge S1 (the Supporting Information). The L3 and C1 vertebrae were
(Zhejiang, China) was selected as the reference material. The selected as exemplary anatomical models, while the gyroid and
FlashForge PLA filament (FF) (blue colour, Ø = 1.75 mm) is cancellous bone were selected as porous structures. Vertebrae models
characterized by the producer in terms of printing conditions (printing L3 and C1 were prepared by the segmentation of the CT scan of the
temperature: 190−220 °C and bed temperature: 50−60 °C) and basic spine of a healthy woman. The segmentation process was conducted via
material properties (density: 1.24 g cm−1, yield strength: 62 MPa, 3D Slicer software (https://www.slicer.org/, 4.10.2 version). 3D Slicer
tensile break: 15%, and impact strength: 4.2 kJ m−2). It is also described is an open-source software platform for visualization and medical image
as environmentally friendly and biodegradable. According to the computing. 15 The scheme of the segmentation procedure of
material safety data sheet, the FF contains 95% of PLA, 4% of TPE, and personalized anatomical models is presented in Figure S2. In turn,
1% of additives in the form of mineral oils. Symbols and description of the description of porous models (the gyroid and cancellous bone) and
studied materials are presented in Table 2. detailed 3D printing settings are shown in Tables S2 and S3 (the
Filament (PLA/TPS_F) Formation. The filament-forming system Supporting Information).
used to obtain the PLA/TPS filament (Ø = 1.75 mm) consisted of a Characterization of the Filaments and Printouts. A series of
granulator dryer (50 °C/5 h), a single-screw extruder (L/D = 32, with studies including spectroscopy [Fourier-transform infrared (FTIR) and
three heating barrel zones and two head zones), two cooling tubes filled Raman], X-ray diffraction (XRD), thermal studies [differential
with water (40 °C/22 °C) and equipped with calibrators (Ø = 2 and 1.8 scanning calorimetry (DSC) and thermogravimetric analysis (TGA)],
mm), a laser diameter measurement system (laser sensor accuracy 0.01 dynamical mechanical analysis (DMA), melt flow rate (MFR)
mm), the puller (pulling velocity ∼70 rpm), and a spool winding measurements, mechanical properties tests (tensile, Charpy impact,
system. The extrusion temperature profile of barrels zones was I140 and compression tests), and water contact angle (wCA) measurements

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Figure 3. View of the build orientation and raster angle of test specimens.

were conducted on both materials to characterize and compare the FF carried out on flat surfaces of the printouts (infill density = 100% and
with the self-made PLA/TPS one. raster angles of 0 and 90°).
Spectroscopic Studies. The infrared spectra of the samples were Mechanical Properties. The hardness of the printed samples was
collected via an attenuated total reflectance FTIR Nicolet 8700 measured using the Shore D-type durometer (Zwick/Roell, Germany)
spectrometer (Thermo Fisher Scientific, Waltham, USA). The spectral according to the ISO 868 standard. Fifteen repetitions per sample were
range was 4000−500 cm−1, resolution 4 cm−1, and 64 scans per made, and the results were averaged. The tensile tests were performed
measurement. The study was carried out at room temperature. The on printed dumbbell-shaped specimens using a Zwick/Roell Z020
Raman spectra were obtained using a confocal micro-Raman system universal tensile machine equipped with an adapter for determining the
(inVia, Renishaw, UK) equipped with a red laser (785 nm) operating at Young modulus. The measurements were carried out according to the
50% of the total power (50 mW). ISO 527 standard at room temperature. The cross-head speed was 5
XRD Analysis. XRD analysis was conducted via the Rigaku mm min−1, and the initial force was 1 N. At least six samples were tested,
Intelligent X-ray diffraction system SmartLab (Rigaku Corporation, and results were averaged. The Charpy impact strength was determined
Tokyo, Japan) equipped with a sealed tube X-ray generator (a copper using a pendulum impact tester (Zwick/Roell HIT5.5P) with a 5 J
target; operated at 40 kV and 30 mA). Data were collected in the 2θ hammer according to the ISO 179 standard (unnotched). The uniaxial
range of 5−50° with a scan speed of 2° min−1 and a scan step of 0.01°. compression test was carried out on cubic specimens via a Zwick/Roell
Thermal Properties. Thermal characteristic was studied by DSC Z020 machine. Samples were compressed until 25% strain was reached
and TGA. DSC measurements were collected using a Netzsch 204F1 at a rate of 5 mm min−1 (five samples per series). The brittleness (B) of
Phoenix apparatus (Netzsch, Germany) under a nitrogen atmosphere samples was calculated based on eq 2 formulated by Brostow et al.17
(20 ml min−1) at the temperature range of 25−220 °C and a heating/ 1
cooling rate of 5 °C min−1. The sample weight was ∼6 mg. In turn, a B=
Netzsch TG 209 instrument (Netzsch, Germany) was used to collect εb × E′ (2)
TGA data. The temperature range was 35−600 °C with a heating rate of where εb (%) is the tensile elongation at break and E′ (Pa) represents
10 °C min−1 under a nitrogen atmosphere (sample weight ∼7 mg). The the value of the storage modulus (at a temperature of 25 °C) which was
degree of PLA crystallinity (Χc PLA) was calculated based on the determined by DMA. To facilitate the presentation of the obtained
following formula 1 values, the brittleness is expressed as (% Pa 10−10).

ji ΔHm − ΔHcc zyz

Χc PLA (%) = jjjj zz ×
Detailed information on test specimen design and dimensions are

z
1
k {
× 100% shown in Figure S1. The tensile and impact tests, as well as brittleness,
0 were rated depending on the infill raster angle (0, 45, and 90°) and the
ΔHm wPLA (1)
orientation of the printout in relation to the plane of the printer’s build
where ΔHcc, ΔHm, and ΔH0m represent the heat of cold crystallization, table (flat XY and aside ZX) (Figure 3).
heat of melting, and melting of 100% crystalline PLA (93 J g−116), Degradation Studies. Filaments (FF_F and PLA/TPS_F) were
respectively. The 1/wPLA factor takes into account the actual content of incubated in 0.1 M phosphate-buffered saline (PBS, Sigma-Aldrich)
PLA in the tested samples. and food-grade canola oil for 30 days at 37 °C. The filaments were cut
Dynamic Mechanical Analysis. The dynamical mechanical test into pieces (∼3 mm length) and then dried and weighed (m0) in a
was performed via a DMA Q800 analyzer (TA Instruments, USA) thermobalance (Radwag MAX50/SX, Radom, Poland) at 60 °C. Thus,
under the single cantilever bending mode with 1.0 Hz frequency of an the prepared samples were placed in 50 mL polypropylene Falcon tubes
oscillatory deformation (sample dimension 40 × 10 × 2 mm3). The and immersed with 35 mL of the appropriate medium. Three samples
temperature range was −100 to 130 °C (heating rate 4 °C min−1). per series were tested, and results were averaged. At each respective
Rheological Properties. The MFR and melt volume rate (MVR) time point (1 h, 5 h, 1, 3, 7, 14, and 30 days), samples were carefully
of the samples were measured by a Zwick/Roell load plastometer (M- removed. In the case of PBS incubation, samples were further rinsed
Flow, BFN-001, Zwick, Poland) in accordance with the ISO 1133:2005 with DI water and dried in a laboratory oven at 50 °C for 48 h.
standard. The measurement was conducted at four different temper- Subsequently, the pH of PBS residues was also monitored (pH-100
atures (180, 190, 200, and 210 °C) under a load of 2.16 kg. Five ATC, Voltcraft, Germany). Mass loss (Ms) was calculated as follows 3
repetitions were made for each sample, and the result was presented as m − mx
an average (n = 5). Ms (%) = 0 × 100%
m0 (3)
Water Contact Angle. The wCAs of the samples were determined
with a ramé-hart 90-U3 goniometer and DROPimage Pro software where (m0) is the initial mass of the sample and (mx) is the residual
(ramé-hart, USA). Before measurements, the sample surface was mass.
degreased and a 2 μL droplet of deionized (DI) water was deposited. Furthermore, incubation in 0.1 M PBS was monitored by FTIR
Then, the images were collected. Six repetitions were made for each measurements and a scanning electron microscope (Phenom Pro
sample, and the result was calculated as an average (n = 6). The test was Generation 5, Thermo Fisher, Eindhoven, Netherlands, AV = 5 kV).

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Figure 4. FTIR spectra of (a) FF and (b) PLA/TPS filaments and printouts.

Figure 5. Raman spectra of (a) FF and (b) PLA/TPS filaments and printouts.

In the case of incubation in canola oil, in addition to the mass loss, the m0 − my
D (%) = × 100%
degree of swelling (Sw %) was also determined. For this purpose, after m0 (5)
removing the sample from the medium, excess oil was gently removed

■
from the surface with a paper towel, and then, the sample was weighed.
The Sw % was calculated based on the following formula 4
RESULTS AND DISCUSSION
mx − m0
Sw (%) = × 100% Structural Characterization (FTIR Spectroscopy,
mx (4)
Raman Spectroscopy, and XRD). The results of the FTIR
Laboratory-Simulated Composting. Evaluation of the degree of studies are shown in Figure 4. Spectroscopic studies were
disintegration of the printouts (FF_P and PLA/TPS_P) under a conducted on both filaments (FF_F and PLA/TPS_F) and
laboratory-scale composting environment was carried out according to printouts (FF_P and PLA/TPS_P) to evaluate the structural
the EN ISO 20200 standard. The composition of the composting
mixture is given in Table S4. The initial pH of the compost was 5.95 and
stability during the FFF 3D printing (3DP) process.
relative humidity over 90% (water was added periodically to the Analyzing the spectrum of the commercial filament (FF_F),
containers during the test according to the procedure given in the ISO the presence of functional group characteristics for PLA was
standard to ensure constant humidity). Printed samples with the noted (Figure 4a). The absorption band visible in the range of
dimensions of 1.5 cm length, 1 cm width, and 2 mm thickness were 2380−3010 cm−1 corresponds to the symmetric and asymmetric
tested (three samples for each material). The samples were dried (60 stretching of the CH3 group. The CO stretching vibration
°C, 48 h) and weighed before testing. Then, the samples were put in
polypropylene reactors filled with compost and placed in a bioreactor
occurred at 1748 cm−1. The band at 1452 cm−1 is attributed to
(48 °C for up to 60 days). To ensure aerobic conditions, the containers the CH3 asymmetric bending vibration. The band at 1264 cm−1
were opened and flipped each week. At each time interval (7, 14, 30, 50, is associated with the CO bending vibration, whereas the
and 60 days), samples were carefully removed, rinsed with DI water, bands at 1179, 1083, and 1043 cm−1 correspond to the C−O−C
dried, and weighed. The degree of disintegration (D %) was calculated stretching vibration of PLA-ester groups. In turn, the spectrum
based on mass loss measurements (eq 5), where (m0) is the initial mass of the PLA/TPS filament shows additional bands derived from
of the sample and (my) is the dry mass of the tested sample at different
composting periods. The composting process was monitored via mass
TPS, that is, a broad signal at 3310 cm−1 (O−H stretching
measurements, optical photos of the sample’s surface (magnification vibration), a band at 1020 cm−1 (deformation of C−O, glucose
×20, Delta Optical Generic, Pro, Mińsk Mazowiecki, Poland), scanning ring), and signals in the region of 1080−1100 cm−1 (C−O
electron microscopy (SEM), and FTIR spectroscopy. stretching of the C−O−H group).18
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Since the FFF 3DP is a high-temperature process, some For further structural analysis, both materials were studied by
changes in the polymer structure could be expected. However, means of XRD (Figure 6).
no visible changes between FF_F and FF_P spectra were noted.
According to Jia,19 the bands in the region of 921 and 955 cm−1
can be responsible for crystalline and amorphous phases of the
PLA, respectively. In the case of FF_F, the intensity of the band
at 955 cm−1 (amorphous) matches well with the literature
data.19 This suggests the larger share of the amorphous state of
PLA and indicates that the crystallization process as a result of
the 3DP did not occur. The PLA/TPS filament showed a small
“crystalline” band at 925 cm−1, which slightly decreased after the
printing process (Figure 4b). This might suggest that due to the
fast cooling rate during FFF 3DP, the degree of the crystalline
phase decreased slightly. There was also a slight decrease in the
intensity of the −OH-derived signal in the PLA/TPS printout,
which may be related to the reduction of hydrogen bonds as a
result of the 3DP process. It is also worth noting that in the PLA/
TPS_P spectrum, the band at ∼1652 cm−1 appeared. This range
corresponds to the presence of water molecules or CC bond Figure 6. XRD spectra of FF_P and PLA/TPS_P.
vibrations resulting from the decomposition of the material.20
However, no changes in the intensity or positions of the main The XRD analysis of FF_P showed a broad hump in the range
bands were noted; thus, it can be observed that the materials of 2θ equal to 10−25°, which is characteristic for amorphous-
during the 3DP process were stable. Therefore, the signal at based PLA.21,25 This confirms the previous spectroscopic
∼1652 cm−1 probably comes from the dampness of the material. considerations that confirmed the amorphous nature of the
To expand chemical structure analysis of the filaments, the studied FF. PLA/TPS_P showed a similar course with a slight
complementary technique, that is, Raman spectroscopy, was peak at 2θ = 19°. According to Bulatović et al.,26 TPS is formed
performed (Figure 5). by the process of plastification and destruction of the native
The obtained spectrum for the FF_F sample was generally in starch crystalline structure; hence, the TPS shows a semi-
line with the FTIR results. Characteristic signals derived from crystalline-to-amorphous behavior. Thus, a slight peak at 2θ =
PLA were noted: symmetric and asymmetric vibrations of −CH 19° can correspond to residues of the A-type crystals present in
(2951 and 2887 cm−1, respectively); the CO carbonyl group the native starch.27 Nevertheless, the mild course of the XRD
(1774 cm−1); CH3 asymmetric modes (1453 cm−1); C−O plot and the lack of clear peaks corresponding to the crystal
stretching (1045 cm−1); C−COO vibration (874 cm−1), and structure indicate a high proportion of the amorphous phase in
CO stretching at 749 cm−1.19,21 Moreover, the presence of both tested materials.
additional strong signals in regions characteristic for aromatic Thermal and Thermomechanical Properties of the FF
structures was also noted at 1532 and 690 cm−1. Those and PLA/TPS Filament and Printout. Thermal character-
istics of both materials before and after the printing process are
additional signals come from the −CH stretching vibration of
presented in Figure 7. First, DSC measurements were
the aromatic ring (1532 cm−1) and the bending vibration of the
performed. The results are shown in Figure 7a,b, and the
Ar ring (690 cm−1), as Raman spectroscopy is relatively sensitive
corresponding numerical values are listed in Table 3. Based on
to these structures.22,23 According to the information from the
the thermograms, the glass transition temperature region (Tg),
manufacturer, the FF, apart from PLA, contains additional cold crystallization (Tcc), crystalline phase transition (Tct),
substances, that is, TPE (4%) and mineral oils (up to 1%). Both melting temperature (Tm), heat of cold crystallization (ΔHcc),
additives contain aromatic carbons in their structure, which heat of melting (ΔHm), and degree of crystallinity (Χc) were
correspond to the additional signals located on the Raman determined.
spectrum. In turn, the Raman spectrum of PLA/TPS_F (Figure The glass transition of polymers is a gradual phenomenon that
5b) significantly complemented the characteristics of the takes place in a certain temperature range.28,29 Although the so-
composition. In addition to the PLA-derived bands, that is, called glass transition temperature (within the meaning of a
C−H stretching (2954 and 2889 cm−1); CO stretching (1775 single temperature value) is an incorrect concept, to facilitate
cm−1); C−H bending (1458 cm−1); C−O stretching (1042 comparison and analysis, Table 3 summarizes the single Tg
cm−1), and C−COO vibrations (878 cm−1), the TPS-derived values corresponding to the midpoint of the heat capacity
bands were noted. They corresponded to the peaks at 3010 cm−1 change recorded in DSC scans. The commercial FF_F PLA
(−OH stretching) and 1309 cm−1 (C−O−H bending) as well as filament showed a Tg at 67.4 °C, a Tcc at 96.6 °C, a Tct at 156.3
to the range of deformation modes in the glycoside bond present °C, and a melting point at 171.9 °C. The calculated degree of
in the TPS structure (C−O, C−C, and C−O−C deformative crystallinity was 12.2%. The characteristic exothermic peak (Tct)
vibrations in the range of 1088−1129 cm−1).18,24 However, is associated with PLA polymorphism. These values are typical
when analyzing the spectroscopic results of both of the studied for PLA filaments and do not significantly differ from the
materials, no significant changes in the spectra of filaments and literature data.30 As a result of the FFF 3DP process (FF_P
printouts were observed. There was no carbonyl peak splitting, sample), a shift of the Tg value (∼3 °C) toward lower
which would indicate re-crystallization as a result of the printing temperatures was noted. This suggests a very slight increase in
process. Further, there were no visible bands shifts or changes in the mobility of the polymer chains in the amorphous state.
their intensity; hence, the structural stability of both studied The glass transition, melting point, and degree of crystallinity
materials under given printing conditions can be pre-confirmed. for the PLA/TPS filament were found to be 70.8 °C, 165.2 °C,
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Figure 7. Thermal and thermomechanical characteristics of the FF and PLA/TPS filament and printout; (a,b) DSC curves (first heating run), (c,d)
thermogravimetric curves TG and DTG, and (e,f) DMA results.

Table 3. Values of DSC Measurements for the FF and PLA/TPS Filament and Printout (First Heating Run)
sample Tga (°C) Tcc (°C) ΔHcc (J g−1) Tct (°C) Tm (°C) ΔHm (J g−1) Χc PLA (%)
FF_F 67.4 96.6 22.3 156.3 171.9 33.1 12.2
FF_P 64.7 100 19.8 157.3 172.9 30.9 12.6
PLA/TPS_F 70.8 146.5 165.2 25.9 46.3
PLA/TPS_P 63.1 100 12.6 151.9 166.1 22.3 17.4
a
The value provided in the table corresponds to the midpoint of the heat capacity change recorded in DSC scans.

and 46.3%, respectively. No cold crystallization process was process significantly affects the degree of crystallization of the
found in the thermogram of the formed PLA/TPS filament PLA/TPS filament. Therefore, when planning a 3DP process
(Figure 7b). This indicates sufficient cooling time during the with this filament as a feedstock, the above considerations
filament-formation process to achieve a very high degree of should be taken into account. Moreover, the manufacturer can
crystallinity of the sample (Χc PLA = 46.3%). The printed sample manipulate with a cooling rate or annealing after printing to
(PLA/TPS_P) showed a cold crystallization transformation at achieve various values of crystallinity and thus different
100 °C during DSC analysis, which indicates that the cooling properties of the material. In this manner, by post-treatment
rate for the printout process was higher than the one for filament (annealing), it is possible to obtain details with a relatively
making. What is more, a significant reduction in the degree of higher thermal resistance, hardness, or increased resistance to
crystallinity to 17.4% was observed. It follows that the 3DP solvents.31 Furthermore, a decrease of the Tg by 7 °C relative to
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Figure 8. MFR (a) and MVR (b) results for the FF and PLA/TPS filament. The load was 2.16 kg. * At 210 °C, the melt fluidity of PLA/TPS_F was too
high, and it was not possible to receive the data.

that of the PLA/TPS filament was also noted. Such a decrease in property. The loss factor curve of PLA/TPS_P (Figure 7f)
the glass transition temperature of the printed sample may be revealed the presence of an additional transition peak at −34 °C.
related to the destruction of hydrogen bonds occurring in the It is most likely related to the α-relaxation of the TPS
PLA/TPS structure and thus the increase in the mobility of the molecules.34,35 It can also be seen that FF_P is characterized
polymer chains. It is consistent with the FTIR results, which by significantly higher values of the E′ over the entire
showed a clear decrease in the intensity of the −OH band of the temperature range than those for PLA/TPS_P and thereby
PLA/TPS_P sample compared to that of PLA/TPS_F. exhibits greater stiffness.
Subsequently, the thermal stability of both filaments and Conducted thermal and thermo-mechanical studies showed a
printouts was determined based on the TGA measurements. similar trend in thermal characteristics of both filaments.
The curves show the amount and rate of change in the mass of a Moreover, the tests revealed that the 3DP process does not
sample as a function of temperature. Obtained curves and their significantly affect the properties of the commercial filament. On
derivatives (DTG) are shown in Figure 7c,d. The thermograms the other hand, the printing process slightly changes the degree
of the commercial filament and printout indicated a single-stage of crystallinity of the PLA/TPS_P sample, which results in a
degradation course, and their curves overlap to a large extent. slight deterioration of the thermal stability of the PLA/TPS
The thermal stability (Toffset) of FF_F and FF_P was around 320 printouts. The two-phase nature of the prepared PLA/TPS
°C, while the complete decomposition takes place above 500 °C. composition was also confirmed. It has also been observed that
There was no effect of the 3DP process on the course of the FF due to the addition of TPS into PLA, the Tm of the composition
thermograms. is lowered; thus, effectively, the temperature of 3D printing is
In turn, the thermal stability of PLA/TPS_F was ∼200 °C. reduced.
The PLA/TPS material as a two-component composition MFR and MVR Results. The MFR and MVR characterize
showed a two-stage degradation course with distinctly separated the flow velocity of thermoplastics under thermal processing.
DTG peaks (Figure 7d), thus confirming the polymer phase These values express the number of grams or volumes of
separation.32 The first DGT peak (Tmax I) for the PLA/TPS_F material pressed during 10 min through a die of a specific
sample corresponds to the decomposition of TPS at 309 °C, diameter under specific load and temperature. The MFR/MVR
while destruction of the PLA takes place at 357 °C (Tmax II). The values are also inversely proportional to the dynamic viscosity of
Toffset for the PLA/TPS_P sample dropped by 19 °C, while the the melt as well as allow for a quick and easy way to estimate the
Tmax I and Tmax II dropped by 4 °C. The decrease in thermal appropriate printing temperature for the tested filament.
stability was probably related to the dropped crystallinity degree Furthermore, according to Wang et al.,36 the MFR/MVR is
of PLA/TPS_P observed after the 3DP process. Thus, unlike the related to the inter-layer adhesion of details formed by FFF 3DP.
FF_F, the thermal stability of the PLA/TPS filament is slightly Thus, it is worth paying attention to this study. The MFR/MVR
changed due to the 3DP process. Moreover, the 3D printing results of commercial PLA (FF_F) and self-made PLA/TPS_F
temperature of PLA/TPS_F should not exceed ∼190 °C to are presented in Figure 8.
avoid possible degradation and release of glycerin vapors The FF_F showed an MFR ranging from ∼8−30 g 10 min−1
originally contained in TPS (T5% = 201 °C). at 180 and 210 °C, respectively. The proportional increase in the
DMA results are presented in Figure 7e,f. The curves show the index (by about 7 g 10 min−1 per 10 °C) with the increasing
temperature dependence of storage modulus (E′) and loss factor measurement temperature was noted. This proves the high
(damping factor). As a standardized sample size is required for stability of the material and a wide range of effective plasticizing
DMA measurements, the test was performed only for printed temperature and thus a comparatively wide range of possible
samples (FF_P and PLA/TPS_P). The maximum of the loss 3DP temperatures. When compared to other commercial PLA
factor curves indicates the relaxation processes occurring near filaments, the MFR value of the FF_F sample was relatively high.
the glass transition temperature region of polymers33 and was The PLA filament from Prusa (Prusament PLA) indicates that
observed at 73.5 °C for FF_P and 71.7 °C for PLA/TPS_P. The MFR = 10.4 g 10 min−1 and that of Ultimaker PLA and Fiberlogy
value of E′ in the glassy state region of FF_P was above 2550 R-PLA around 6 g 10 min−1 (at 210 °C, 2.16 kg). These values
MPa and decreased rapidly after exceeding 65 °C (700 MPa). were over 3 times lower than those recorded for FF_F (MFR =
The maximum amplitude of the damping factor for FF_P 30 g 10 min−1). This may be due to the lower molecular weight
reached 1.55 which corresponds to an impeccable damping of FF PLA or the presence of additives (TPE and mineral oils)
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Table 4. Summarized Result of Mechanical Studies of FF_P and PLA/TPS_P

Young
print raster angle modulus ultimate tensile elongation at Charpy impact strength hardness brittleness
sample orientation (deg) (GPa) strength (MPa) break (%) eUa (kJ m−2) (Sh D) (% Pa 10−10)
FF_P XY 0 1.62 ± 0.25 15.81 ± 5.19 2.97 ± 1.26 13.31 ± 1.47 79 ± 2 1.611
45 1.69 ± 0.31 15.21 ± 4.58 2.67 ± 0.46 9.00 ± 1.01 78 ± 3 1.792
90 1.597 ± 0.08 15.36 ± 3.05 1.83 ± 0.29 7.59 ± 1.33 78 ± 1 2.615
ZX 0 2.03 ± 0.13 21.81 ± 3.36 4.28 ± 0.75 18.48 ± 1.63 1.118
45 1.53 ± 0.22 5.83 ± 2.29 5.28 ± 0.55 15.84 ± 1.87 0.906
90 2.19 ± 0.64 11.83 ± 3.06 3.68 ± 0.73 12.98 ± 0.88 1.300
PLA/TPS_P XY 0 1.47 ± 0.36 24.72 ± 1.21 3.83 ± 0.31 7.65 ± 0.94 60 ± 2 1.355
45 1.45 ± 0.37 9.35 ± 1.78 1.25 ± 0.12 4.97 ± 1.11 62 ± 2 4.152
90 1.93 ± 0.47 14.86 ± 1.42 3.11 ± 1.19 3.88 ± 1.31 61 ± 3 1.669
ZX 0 1.51 ± 0.38 17.85 ± 1.31 4.61 ± 0.11 9.73 ± 1.04 1.126
45 1.53 ± 0.35 17.28 ± 1.41 3.78 ± 0.52 5.91 ± 0.64 1.373
90 1.74 ± 0.41 16.87 ± 2.15 2.57 ± 0.78 4.44 ± 0.91 2.019
a
eUunnotched Charpy specimen.

Figure 9. Average tensile stress−strain curves of FF_P (a) and PLA/TPS_P (b) depending on the build orientation and raster angle.

that act as PLA plasticizers, thus increasing MFRs under test Effect of the Print Orientation and Raster Angle on
conditions. Mechanical Properties (Tensile and Impact Strength and
The MFR value of self-made PLA/TPS_F was in the range of Brittleness). Since there are no specific standards for testing the
11 g 10 min−1 at 180 °C to 47 g 10 min−1 (200 °C). The rising mechanical properties of FFF 3DP filaments so far, the tensile
trend of the index with the test temperature was much larger and and impact strength tests were performed taking into account
more irregular compared to that of commercial FF_F. At 210 two types of print orientation (XY and ZX) and three values of
°C, the melt viscosity of PLA/TPS_F was too low to collect raster angle (0, 45, and 90°). The results are summarized in
measurement data. In the temperature range of 200−210 °C, the Table 4.
initial material decomposition was recorded (color change and The results of the tensile test of the FF_P samples in the XY
gas formation). Therefore, the 3DP temperature of the PLA/ configuration showed no visible dependence on the raster angle.
TPS filament should not exceed 200 °C. Due to the lack of The Young modulus was in the range of 1.6−1.7 GPa, the tensile
research on the PLA filament modified with TPS in the strength was around 15−16 MPa, and the elongation at break
literature, the discussion on PLA/TPS_F MFR values is difficult. was at 1.8−3.0%. It was noticed that in the ZX orientation, the
However, considering the MFR threshold value for PLA FF_P samples showed higher strength parameters than that in
filaments reported by Wang et al.36 (∼10 g min−1, at 2.16 kg), XY, in particular, the Young modulus and elongation at break
it can be concluded that the printing temperature for PLA/ (∼22 GPa and 4.5%, respectively). Furthermore, the Charpy
TPS_F at ∼180 °C is proper. impact strength of FF_P_ZX samples was significantly higher
As the MFR increases, the melt fluidity becomes higher. Thus, than that of FF_P_XY. In turn, considering the raster angle, it
it can be assumed that it is easier for the 3DP extruder to push was observed that the FF_P_0° system showed the highest
the molten plastic through the die, and therefore, the printing overall strength parameters, while the FF_P_90° system
speed can be higher. Nevertheless, it should be remembered that exhibited the lowest impact strength (∼7.6 kJ m−2) and the
the high MFR may be also related to the low molecular weight of FF_P_45° system had the lower tensile strength.
the polymer or its partial degradation under the measurement For the PLA/TPS system, again the samples printed at a raster
conditions, which can significantly deteriorate the print quality. angle of 90° showed the lowest impact strength; in turn, ZX_0°
Therefore, when analyzing the MFR of filaments for 3DP, one had the highest values of elongation at break (4.6%) as well as
should also simultaneously consider the data derived from DSC tensile (17.8 MPa) and impact strengths (9.7 kJ m−2). However,
and TGA. the Young modulus in both print orientations (XY and ZX) was
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the highest for the 90° raster angle. In the case of PLA/TPS Samples with three different infill densities were studied (25, 50,
material, it is difficult to clearly determine which orientation of and 100%), and the results are displayed in Table 5.
the printout (XY and ZX) shows the most favorable values.
As FFF printouts cannot be treated as a continuous material Table 5. Results of the Compression Test for FF_P and PLA/
(isotropic material),37 the assessment of the mechanical TPS_P Samples
properties of such products is difficult. The stress−strain curves
of FF_P and PLA/TPS_P are presented in Figure 9. It should be infill density 25% 50% 100%
noted that the course of the FF_P curves more closely resembles yield strength (MPa)
those of ductile materials than that of PLA/TPS_P. Here,13 we FF_P 20.44 ± 0.63 34.64 ± 4.77 82.49 ± 8.32
noticed that the addition of the TPS composition to pure PLA compression strength (MPa)
increases the elongation at break while lowering the tensile PLA/TPS_P 9.44 ± 2.53 19.65 ± 3.83 30.13 ± 0.91
strength. However, these studies were carried out on injected-
molded (continuous) test samples. Thus, it can be assumed that
due to insufficient interlayer adhesion of FFF 3D-printed The compressive strength of the printouts increases with the
specimens, the effect of increased ductility of PLA/TPS_P increase in the degree of infill.42 This effect is more visible for the
samples was not observed.37 FF_P samples where a more than 4-fold increase in the yield
Summarizing, for both studied filaments, the ZX_0° strength was noted. For PLA/TPS_P, the increase in
configuration showed the most favorable strength parameters. compressive strength was proportional to the increase in the
Similar observations were reported by Chacón et al.38 In the infill density, reaching a value of ∼30 MPa (100% infill).
article, the influence of a number of FFF 3DP parameters on the The course of the compression curves is presented in Figure
mechanical properties of PLA was investigated. It was found that 10. The stress−strain curves of the FF_P samples showed a clear
the on-edge (ZX) print orientation exhibits the most optimal yield point (*), while for PLA/TPS_P, the course is mild and
mechanical properties in terms of strength, stiffness, and characteristic for elastic polymers (Figure 10b). Therefore, for
ductility. However, studies conducted by Dave et al.39 have PLA/TPS_P samples, the inflection point of the curves (marked
shown that the flat orientation (XY) of PLA printouts possesses as #) was adopted as the compressive strength.
the highest tensile strength. The presented discrepancies Water Contact Angle. During the measurement of the
indicate the need to take into account additional printing contact angle, significant changes in the wettability values were
conditions (layer height, flow rate, print speed, temperature noticed depending on the direction of the sample arrangement
conditions, etc.) when comparing the mechanical properties of on the measuring table and thus the sample’s raster angle.
resulting printouts.40 Thus, it is highly desirable to standardize Changing the raster angle to 90° significantly increased the
methods of assessing the mechanical properties of details hydrophobicity of both samples. The wCA of FF_P was ∼75 for
obtained with FFF 3DP in order to be able to effectively test and 0° raster angle and around 111 for 90° raster angle, which
compare new filaments.37 correspond to the moderately hydrophilic to hydrophobic
Generally, the concept of material brittleness is recognized surface nature (Table 6). PLA/TPS_P showed a more
indirectlynot quantitatively, for example, by evaluation of the hydrophilic surface with the wCA ranging from 63 to 81°. The
results of the tensile test. It is related to the analysis of the difference in wettability between FF_P and PLA/TPS_P is
related to the presence of TPS, which, being a highly hydrophilic
fracture surface type or the character of the stress−strain curve.
material, lowers the contact angle of PLA.43 However, such large
However, these methods constitute a qualitative analysisthey
differences in the wCA depending on the raster angle should be
only provide information on whether the material is brittle- or
considered in terms of surface morphology and not of the
ductile-type. Recently, Brostow et al.17 proposed an equation
material properties.
that allows for quantitative validation of the material’s According to the literature, PLA shows poor hydrophilicity in
brittleness. According to this definition, the brittleness (B) is the range 70−95° of the static wCA.44 However, these values
inversely proportional to the product of tensile elongation at refer to a solid PLA surface (continuous material, most
break (εb) and storage modulus (E′). Thus, when these values commonly obtained by plastic molding) and not to FFF 3DP
increase, the value of B decreases. In our considerations, the printouts, which are characterized by many defects (voids) and
storage modulus value is constant for each of the tested materials discontinuities in the structure.45
and equal to 2090 MPa for FF and 1927 MPa for PLA/TPS The surface of the FFF 3DP samples consists of connected
(data were taken from Figure 7e,f at 25 °C), while the εb layers of polymer fibers of a given thickness and height. As a
parameter is variable and depends on the printout configuration result, the printed surface (on a micro-scale) is wavy. Thus, due
(as shown in Table 4). Thus, the samples with the highest εb to the unevenness of the surface, the applied drop of water wets
trend are predicted to be the least brittle (B = 0.906 for the material depending on the direction of the fibers on which it
FF_ZX_45° and B = 1.126 for PLA/TPS_ZX_0°). However, is placed, which radically changes the contact angle. The above
comparing these materials to others tested by41 the obtained considerations are confirmed by the Modi and Prakash46 study,
value of B, which is in the range of around 1.0−4.0 (see Table 4), in which they proved that the orientation and raster angle of the
suggests rather high brittle properties. For comparison, Hytrel FFF 3D-printed parts significantly affect the wettability of PLA.
(TPE which represents ductile-type materials with a very high They found huge differences in the values of the PLA wCA,
elongation at break) exhibits a brittleness (B) of less than 0.1, ranging from 40 to 75° for 0 and 90° raster angles, respectively.
whereas unmodified polystyrene (known as a brittle-type Therefore, we believe that the standard method of contact
polymer) has a value of around 9.0.41 angle measurement does not provide reliable data. The influence
Effect of Infill Density on Compression Strength. The of the surface shape on the wCA should be minimized by
uniaxial compression test was another study aimed at character- significantly reducing the measuring droplet. Otherwise, the
izing the mechanical properties of FF_P and PLA/TPS_P. sample’s data regarding the printing parameters and printout
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Figure 10. Averaged compressive stress−strain curves of FF_P (a) and PLA/TPS_P (b) depending on the infill density. * Yield strength; #
compression strength.

Table 6. CAs of FF_P and PLA/TPS_P with Different Raster Angles (0 and 90°)

design should be precisely specified to allow the reliable The mean mass loss after the first hour was 1.3%, and after 3
comparison of the printout surface properties. days, it increased sharply to 13%. At the end of the study, a mass
Incubation of the Filaments in 0.1 PBS Solution and loss of 14.5% was noted. At the same time, a drop in pH was
Canola Oil (Mass Loss, Swelling, and pH Measurements). observed, down to 7.38 after 3 days and 7.27 after 30 days of
PLA, as a representative of biodegradable polymers, undergoes incubation. The acidification of the electrolyte could be related
hydrolytic degradation in the PBS environment, which might to material hydrolysis which results in oligomer and monomer
proceed through the surface or bulk erosion mechanism.47 formation.50 The resulting PLA-carboxyl end groups,51 as well as
However, in the case of solid PLA with a relatively high TPS-origin glucose, glycerin, or ESO, could lower the pH due to
molecular weight (so-called injection or extrusion grades), the the dissociation in the PBS solution. The SEM images (Figure
PBS degradation might proceed up to 5 years.48 Therefore, PLA S3) of the PLA-TPS_F surface after 30 days of incubation show
belongs to the long-term degrading biopolymers. Besides numerous cracks and discontinuities in the structure (red
temperature, pH, and molecular weight, the ability of water to arrows), while the cross-view shows the formation of a fibrous-
diffuse into the PLA matrix is the main factor that controls the like structure that may have arisen as a result of washing out of
degradation process.47 Consequently, to estimate the degrad- the TPS particles from the PLA matrix. The resulting surface
ability of both filaments, the incubation in 0.1 M PBS solution at
defects of the PLA/TPS structure may additionally facilitate the
37 °C for 30 days was performed. During the PBS incubation,
diffusion of water in the inner part of the filament, and thus
the weight change, the pH of the solution, and SEM images were
increase the susceptibility to degradation of PLA itself.52 Such an
recorded. Figure 11a,b represents the mass loss of the samples
and the pH change of the PBS buffer with respect to the effect is highly desirable as we consider the developed filament to
immersion time for FF_F and PLA/TPS_F, respectively. be biodegradable.
The recorded change in the weight of the FF filament during To confirm the above considerations, the FTIR spectra of the
30 days of PBS incubation not exceeding 0.1%, as well as the filament samples before (0 d) and after 30 days (PBS_30d) of
relatively constant pH (7.50−7.48), indicates the stability of the PBS incubation were compared (Figure 11e,f). In the case of
material under given conditions. This is confirmed by SEM FF_PBS_30d, the spectrum did not change significantly. There
photos, which show no changes in the morphology of the surface was a slight decrease in the intensity of the band derived from the
or the cross-section of FF_F (Figure S3). This is in line with CO group (1748 cm−1), while the rest of the spectrum
other studies of PLA degradation in the PBS medium, in which remained intact. The degradation of PLA/TPS_F proceeded
no mass changes or drops in pH were recorded during the 56 mostly through the destruction of bonds originating from TPS
days of study.49 (−OH 3310 cm−1, −C−O 1020 cm−1, and −COH 1080 cm−1).
In turn, during the incubation of the PLA/TPS filament in The PLA-origin aliphatic CH2 and ester groups (CO 1747
PBS, significant changes in both mass and pH were noted. cm−1) were also broken. Thus, it can be assumed that the
Thermoplastic starch, as a material sensitive to water, enhances erosion of TPS and the resulting surface roughness, cracks, and
significantly the degradation process of the PLA/TPS filament. voids promote hydration and thus facilitate degradation of PLA.
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Figure 11. Results of degradation studies in 0.1 M PBS solution of (a) FF_F and (b) PLA/TPS_F. SEM images showing the process of PBS incubation
are presented in the Supporting Information (Figure S3). The results of incubation in canola oil of (c) FF_F and (d) PLA/TPS_F. FTIR spectra of (e)
FF_F and (f) PLA/TPS_F after 30 days of incubation in PBS and 60 days of composting.

For further characterization of studied filaments, the mass loss sieve with 2 mm of the mesh) over 90 days at 58 °C in the
and swelling in contact with food-grade canola oil was simulated compost.
investigated (Figure 11c,d). As expected, the FF filament Figure 12 shows the results of the composting test of FF and
showed high resistance to oil. Both the weight loss and the PLA/TPS 3D printouts. FF_P samples exhibited high
swelling ratio of the samples were unnoticeable, whereas the composting resistance. There was no change in the weight
PLA/TPS_F swelling was ∼3% and the weight loss was 1.2% during the test (Figure 12a), and the morphology of the samples
was not intact. The discoloration of the samples was observed
after 30 days of testing. Thus, PLA/TPS_F shows moderate
from about the 30th day of composting (Figure 12b). The
resistance to oil contact.
surface of the sample remained homogeneous and smooth
Results of Laboratory-Scale Composting. The labo-
(Figure 12c) up to the 50th day of the study. Single surface
ratory composting study was conducted to assess the filament’s cracks were recorded only after 60 days (Figure S4). However,
susceptibility to disintegration in composting conditions. It the recorded FTIR spectrum of the sample after 60 days of the
should be noted that this study cannot be regarded as an test (Figure 11e, FF_compost_60d) showed a noticeable
assessment of the biodegradability of the bioplastic.53 According decrease in the intensity of the bands, resulting from the
to the EN 13432 standard, bioplastics marked as compostable vibration of the CO (stretching at 1748 cm−1 and bending at
should show a disintegration of 90% (into pieces smaller than a 1264 cm−1) and C−O (stretching at 1043 cm−1) bonds was
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Figure 12. Results of a laboratory-scale composting test of FF_P and PLA/TPS_P: (a) disintegration degree over composting time, (b) optical
microscopy images of samples before (0 d) and after 7, 14, 30, 50, and 60 days of composting (red arrows indicate progressive cracks and
discontinuities of the PLA/TPS sample surface), and (c) representative SEM micrographs of the sample surface before (0 d) and after 50 days of
composting (more SEM images are presented in the Supporting Information; Figures S4 and S5).

Figure 13. FFF 3D-printed FF and PLA/TPS complex structures: (a) personalized anatomical models of vertebrae C1 (atlas) and L3, (b) porous
gyroid, and cancellous bone-like structure printouts. Detailed information on models and the 3DP process is presented in the Supporting Information
(Figure S2 and Tables S2 and S3). More optical photos of the printouts can be found in Figure S6.

observed, which may indicate the initial destruction of the into the structure, thereby destroying the sample in its entire
surface layer of the FF_P printouts. Nevertheless, overall, the volume. The FTIR spectrum confirms the above considerations
FF_P was left practically intact under the 60 days of simulated (Figure 11f). There was a clear degradation of bonds originating
composting. In turn, PLA/TPS_P showed an evident trend of an mainly from TPS. Signals from vibrations of −OH (3310 cm−1)
increased degree of disintegration during the composting time. and C−O groups (a glucose ring at 1020 cm−1) were flattened,
Already after 7 days of incubation, a disintegration degree of 7% and the intensity of the whole spectrum significantly decreased.
was noted, and at the end of the study, it reached over 18% Therefore, the addition of TPS contributed to an increase in the
(Figure 12a). Optical microscopy images showed the formation susceptibility to the disintegration of PLA under composting
of cracks and defects on the sample’s surface from the 14th day conditions. This is most likely related to the facilitated
of testing. SEM micrographs revealed a high roughness and penetration of moisture into the material and the presence of
heterogeneity of the PLA/TPS_P surface compared to that of glucose (as a result of TPS degradation), which acts as a nutrient
FF_P. At the beginning of composting, the TPS cavities were medium for the microorganisms present in the compost.52
observed (14th day), where pinholes in the PLA/TPS_P The results of laboratory composting presented by Arrieta et
structures were formed (Figure S5). The initially changed al.54,55 shows a disintegration rate of PLA of over 90% within 35
surface started to erode, and the destruction proceeded deeper days. In turn, the study by Quiles-Carrillo et al.56 conducted at
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the same conditions (ISO 20200) reveals a disintegration of the available FFF filament. Our approach, namely, replacing up to
PLA/TPS (40 wt % TPS) blend of over 90% after 57 days of 40% of PLA with TPS, resulted in considerable improvement of
composting. However, it should be noted that the above data hydrophilicity, susceptibility to hydrolytic degradation, and thus
refer to samples in the form of thin films with thicknesses of 0.1 enhancement of compostability in contrast to that of
and 1 mm, respectively. Therefore, it is difficult to compare these commercial PLA printouts. Furthermore, we demonstrated
results with the values obtained for solid FF and PLA/TPS that the PLA/TPS filament shows a comparable printability to
printouts. However, the findings of our earlier studies on the its commercial counterpart and is suitable for FFF 3DP of both
PLA/TPS/ESO composition (which was used to form the PLA/ personalized anatomical models as well as complex porous
TPS filament) revealed that this material was completely structures. We also believe that the developed filament might
disintegrated after 57 days of simulated composting13 (the challenge traditional petroleum-based filaments as a more
study was carried out on thin sheets with 2 mm thickness). environmentally friendly alternative.
Printability AssessmentFFF 3D Printing of Anatom- Furthermore, our results challenge/question commercial
ical Models and Porous Structures. Finally, to illustrate the terms of marking filaments (e.g., PLA) as “biodegradable/eco-
usefulness of the developed PLA/TPS filament, complex-shaped friendly”. The use of a biopolymer as a base material cannot
details were printed and compared with those obtained from the determine its final “bio-properties”. The addition of printability-
commercial filament. The resulting printouts are presented in improving agents (oils and plasticizers) or fillers and pigments,
Figure 13. To allow a fair comparison of the printability of both at the stage of filament formation, may cause numerous changes
filaments, they were printed with the same 3D printing settings. in the pristine properties of the biopolymer (including a
The only difference was the printing temperature, which was 215 decrease in biodegradability). Due to that, the final product
°C for the FF_F and 185 °C for the PLA/TPS filament. cannot be recognized as “eco-friendly”, although it is based on
First, the personalized STL files of two types of vertebrae were biodegradable polymers. Therefore, to verify the filament’s “eco-
converted from an abdominal CT scan. The scheme illustrating friendly” character, additional research should be carried out to
the process of segmentation and conversion is illustrated in establish whether a final product is truly biodegradable or it is
Figure S2 (the Supporting Information). Thus, obtained only partly bio-based.

■
projects required the use of support structures to ensure a
good quality of printouts; hence, detachable-type supports were ASSOCIATED CONTENT
introduced. The printing process in both cases ran smoothly,
and the printing times were ∼5.5 and 2 h for L3 and C1 *
sı Supporting Information

vertebrae, respectively. As a result, personalized anatomical The Supporting Information is available free of charge at
models with high surface mapping and quality and good https://pubs.acs.org/doi/10.1021/acssuschemeng.0c09413.
dimensional stability were obtained. No shrinkage effect was
Test sample preparation; preparation and description of
noticed. Printouts with the PLA/TPS filament did not differ in
the virtual models; SEM images of the degradation study
quality in any way from those obtained from FF_F. Similar
in 0.1 M PBS; laboratory compostingcompost
observations were made in the case of 3D printing porous
composition and SEM images; images of printed
structures (which were printed without the use of support
anatomical models and porous structures; and description
structures). The gyroid project was very well mapped. No
of challenges faced during 3D printing with the PLA/TPS
defects or discontinuities in the structure were observed for both
filament (PDF)
the FF and PLA/TPS gyroid printouts (Figure 13b). Never-

■
theless, some issues were encountered in cancellous bone-like
printouts. As this sponge-like structure possesses many over- AUTHOR INFORMATION
hangs and very thin walls, it is highly demanding for FFF 3D
printing. The printout from the FF filament turned out to be Corresponding Author
defectless. In turn, in the case of PLA/TPS, some defects of the Agnieszka Haryńska − Department of Polymers Technology,
printout surface were noted. Pores of the cancellous bone-like Faculty of Chemistry, Gdansk University of Technology
structure were partially blocked by the so-called stringing, that is, (GUT), 80-233 Gdansk, Poland; orcid.org/0000-0001-
thin threads made of the material leaking out of the printing 8017-6070; Email: [email protected]
nozzle (hotend) in an uncontrolled manner. However, this
phenomenon can be minimized by changing the printing Authors
parameters such as speed, temperature, or the retraction Helena Janik − Department of Polymers Technology, Faculty of
distance. More challenges faced during 3DP with the PLA/ Chemistry, Gdansk University of Technology (GUT), 80-233
TPS filament are described in Table S5 (the Supporting Gdansk, Poland
Information). Maciej Sienkiewicz − Department of Polymers Technology,
Summarizing, we can state that our developed bio-filament is Faculty of Chemistry, Gdansk University of Technology
suitable for effective FFF 3DP, and the printouts thus formed do (GUT), 80-233 Gdansk, Poland
not differ in quality from those obtained using available Barbara Mikolaszek − Department of Pharmaceutical
commercial filaments. Technology, Faculty of Pharmacy, Medical University of

■ CONCLUSIONS
In this work, we presented an extensive characteristic of a self-
Gdansk, 80-416 Gdansk, Poland; orcid.org/0000-0001-
5894-7705
Justyna Kucińska-Lipka − Department of Polymers
made bio-filament for FFF 3DP, consisting of PLA modified Technology, Faculty of Chemistry, Gdansk University of
with TPS. For comparative purposes, the properties and Technology (GUT), 80-233 Gdansk, Poland
printability of the PLA/TPS filament were confronted with Complete contact information is available at:
those of the FlashForge PLA filamentthe commercially https://pubs.acs.org/10.1021/acssuschemeng.0c09413
6936 https://doi.org/10.1021/acssuschemeng.0c09413
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ACS Sustainable Chemistry & Engineering pubs.acs.org/journal/ascecg Research Article

Author Contributions Poly(Butylene Adipate- Co-Terephthalate) for 3D Printing Applica-

A.H. conceptualization, methodology, software, validation, tions: Compatibilization Methods and Material Performance Evalua-
investigation, writingoriginal draft, writingreview and tion. ACS Sustainable Chem. Eng. 2020, 8, 6576−6589.
editing, visualization, project administration. H.J. conceptualiza- (12) Tanabe, I. Double-ECO Model Technologies for an Environ-
mentally-Friendly Manufacturing. Procedia CIRP 2016, 48, 495−501.
tion, resources, writingreview and editing. M.S. material
(13) Przybytek, A.; Sienkiewicz, M.; Kucińska-Lipka, J.; Janik, H.
conceptualization, writingreview and editing. B.M. inves- Preparation and Characterization of Biodegradable and Compostable
tigation (SEM), writingreview and editing. J.K.-L. resources, PLA/TPS/ESO Compositions. Ind. Crops Prod. 2018, 122, 375.
writingreview and editing. (14) Haryńska, A.; Carayon, I.; Kosmela, P.; Brillowska-Dąbrowska,
Funding A.; Łapiński, M.; Kucińska-Lipka, J.; Janik, H. Processing of Polyester-
Part of the research realized at the Gdansk University of Urethane Filament and Characterization of FFF 3D Printed Elastic
Technology (GUT) was financed by the Ministry of National Porous Structures with Potential in Cancellous Bone Tissue Engineer-
Education via the Knowledge & Technology Transfer Center at ing. Materials 2020, 13, 4457.
(15) Kikinis, R.; Pieper, S. D.; Vosburgh, K. G. 3D Slicer: A Platform
the GUT under the program Innovation Incubator Plus.
for Subject-Specific Image Analysis, Visualization, and Clinical Support.
Notes In Intraoperative Imaging and Image-Guided Therapy; Jolesz, F. A., Ed.;
The authors declare no competing financial interest. Springer New York: New York, NY, 2014; pp 277−289.
The raw data required to reproduce these findings cannot be (16) Pyda, M.; Bopp, R. C.; Wunderlich, B. Heat Capacity of
shared at this time due to technical or time limitations. Poly(Lactic Acid). J. Chem. Thermodyn. 2004, 36, 731−742.
Nevertheless, they can be made available on request. (17) Brostow, W.; Hagg Lobland, H. E.; Narkis, M. Sliding Wear,

■
Viscoelasticity, and Brittleness of Polymers. J. Mater. Res. 2006, 21,
ACKNOWLEDGMENTS 2422−2428.
(18) Nobrega, M. M.; Olivato, J. B.; Müller, C. M. O.; Yamashita, F.
We acknowledge Paulina Kosmela for technical help in Biodegradable Starch-Based Films Containing Saturated Fatty Acids:
conducting DSC, TGA, and DMA studies. Thermal, Infrared and Raman Spectroscopic Characterization.

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