coatings

Review
Extrusion-Based 3D Printing Applications of PLA Composites:
A Review
Eda Hazal Tümer and Husnu Yildirim Erbil *

Department of Chemical Engineering, Gebze Technical University, 41400 Gebze, Kocaeli, Turkey;
edabaran@gtu.edu.tr
* Correspondence: yerbil@gtu.edu.tr; Tel.: +90-0262-605-2117

Abstract: Polylactic acid (PLA) is the most widely used raw material in extrusion-based three-
dimensional (3D) printing (fused deposition modeling, FDM approach) in many areas since it is
biodegradable and environmentally friendly, however its utilization is limited due to some of its
disadvantages such as mechanical weakness, water solubility rate, etc. FDM is a simple and more
cost-effective fabrication process compared to other 3D printing techniques. Unfortunately, there
are deficiencies of the FDM approach, such as mechanical weakness of the FDM parts compared to
the parts produced by the conventional injection and compression molding methods. Preparation of
PLA composites with suitable additives is the most useful technique to improve the properties of
the 3D-printed PLA parts obtained by the FDM method. In the last decade, newly developed PLA
composites find large usage areas both in academic and industrial circles. This review focuses on
the chemistry and properties of pure PLA and also the preparation methods of the PLA composites
which will be used as a raw material in 3D printers. The main drawbacks of the pure PLA filaments



and the necessity for the preparation of PLA composites which will be employed in the FDM-based


3D printing applications is also discussed in the first part. The current methods to obtain PLA
Citation: Tümer, E.H.; Erbil, H.Y. composites as raw materials to be used as filaments in the extrusion-based 3D printing are given
Extrusion-Based 3D Printing in the second part. The applications of the novel PLA composites by utilizing the FDM-based 3D
Applications of PLA Composites:
printing technology in the fields of biomedical, tissue engineering, human bone repair, antibacterial,
A Review. Coatings 2021, 11, 390.
bioprinting, electrical conductivity, electromagnetic, sensor, battery, automotive, aviation, four-
https://doi.org/10.3390/
dimensional (4D) printing, smart textile, environmental, and luminescence applications are presented
coatings11040390
and critically discussed in the third part of this review.
Academic Editor:
Fengwei (David) Xie
Keywords: polylactic acid; PLA; composite; 3D printing; fused deposition modeling; additive manu-
facturing
Received: 1 March 2021
Accepted: 24 March 2021
Published: 29 March 2021
1. Introduction
Publisher’s Note: MDPI stays neutral Fused deposition modeling (FDM) is one of the additive manufacturing (AM) pro-
with regard to jurisdictional claims in cesses to fabricate objects from three-dimensional (3D) models. The use of FDM has been
published maps and institutional affil- increasing rapidly in the last decade and it was proposed that this technology can revo-
iations.
lutionize the manufacturing practices in many sectors [1–5]. Polylactic acid (PLA) is the
most widely used raw material in the FDM-based 3D printing process due to its biodegrad-
ability and environmentally friendly properties, however the use of pure PLA polymer is
limited in the FDM approach due to its disadvantages such as mechanical weakness, water
Copyright: © 2021 by the authors. solubility rate, etc. [6–8]. Thus, the preparation of PLA composites with suitable additives
Licensee MDPI, Basel, Switzerland. is suggested to be a feasible method to improve the properties of the 3D-printed PLA parts
This article is an open access article which are obtained by the FDM method.
distributed under the terms and Many good review articles were published on the applications of the FDM approach
conditions of the Creative Commons
and also on the use of pure PLA polymer in 3D printing [1–8]. However, there is lack
Attribution (CC BY) license (https://
of a review article on the use of novel PLA composite filaments in the FDM-based 3D
creativecommons.org/licenses/by/
printing technology and also on the main preparation methods to obtain the PLA composite
4.0/).

Coatings 2021, 11, 390. https://doi.org/10.3390/coatings11040390 https://www.mdpi.com/journal/coatings

Coatings 2021, 11, 390 2 of 42

filaments which will specifically be used as a raw material in 3D printers. Moreover, the
improvements of the properties of the 3D-printed objects by using the novel PLA com-
posites in the fields of biomedical, tissue engineering, bioprinting, electrical conductivity,
automotive, aviation, sensor, battery, robotic, and smart textile industries have not been
reviewed before and this review will also fill this gap.
We will focus on the chemistry, physical properties, and drawbacks of homopolymer
PLA in the second section of this review. The main preparation methods of the PLA
composites which can be utilized as a raw material in the FDM-based 3D printers will be
presented in the third section. Finally, the main applications of the novel PLA composites
by using the extrusion-based 3D printing technology will be reviewed in the fields of
biomedical, tissue engineering, antibacterial, bioprinting, electrical conductivity, electro-
magnetic, sensor, battery, automotive, aviation, four-dimensional (4D) printing, smart
textile, environmental, luminescence, and fluorescence in the fourth section.

2. Chemistry of PLA and its Use and Limitations in FDM-Based 3D Printing

2.1. Outline of the Chemistry of Lactic Acid and PLA
Lactic acid (2-hydroxypropanoic acid)-based polymers are called either poly (lactic
acid) or polylactide and they are both abbreviated as PLA. In the last two decades, pure
PLA polymer filaments which are used in the FDM approach became the most important
thermoplastic source in the three-dimensional (3D) printing field [1–8]. The production of
PLA polymer is environmentally preferred since it is generally obtained from renewable
sources (e.g., corn, sugar cane, wheat, and rice) and also large amounts of carbon dioxide
gas is consumed during its production [9–15]. PLA has many advantages, such as it is
biodegradable, recyclable, and can easily be processed thermally, as schematically shown
in Figure 1.

Figure 1. Environmentally friendly polylactic acid (PLA) cycle.

Coatings 2021, 11, 390 3 of 42

The use of PLA polymers in the injection molding, blow molding, thermoform-
ing, fiber spinning, film forming, and biomedical industries is expanded in the last
decade [9–12].
Lactic acid (LA) is the monomer of PLA polymer and chemically synthesized LA
gives the racemic mixture (50% D and 50% L). LA is generally manufactured by bacterial
fermentation mainly from corn starch by using a strain of Lactobacillus giving essentially
one major stereoisomer, i.e., LA consists of about 99.5% of L-isomer and 0.5% of D-isomer
and the presence of 99.5% of L-isomer introduces the high mechanical strength into the
PLA polymer after polymerization [15–17].
Lactic acid exists in two enantiomeric forms, L- and D-isomer, differing in their effect
on polarized light, where the L-isomer rotates the plane of polarized light clockwise, and
the D-isomer rotates it counterclockwise, as seen in Figure 2. LA has a hydroxyl and an acid
functional group in it and can give both intermolecular and intramolecular esterification
reactions. The cyclic dimer (lactide) can be formed by intramolecular esterification of lactoyl,
lactic acid or alternatively by the breakdown of higher oligomers. The dehydrated, cyclic
dimer of LA is called “lactide” (3,6-dimethyl-1,4-dioxane- 2,5-dione) and exists in three
different forms due to the two asymmetric carbon atoms in the molecule: D,D-lactide (called
D-lactide), L,L lactide (called L-lactide), and L,D- or D,L-lactide racemate (called meso-
lactide), which is optically inactive [9,11–15]. Apart from its use as a monomer in the PLA
polymerization, LA is generally used in cosmetics, food and beverages, pharmaceutical,
chemical, and medical industries as a pH regulator, flavoring agent, and an inhibitor of
residual bacteria in the food and beverages sectors [15,17].

Figure 2. Lactic acid stereoisomers [7].

PLA is industrially produced via the polymerization of LA or by the ring opening

polymerization of lactide (the cyclic dimer of lactic acid, as an intermediate). In the first
one, the direct polycondensation of LA using organic solvents under high vacuum is
applied, where only low to intermediate molecular weight PLA can be produced. In the
second method, the formation and later the ring-opening polymerization of lactide is
carried out, where no solvent is used [9–15]. The second method is usually preferred
since the catalytic ring-opening polymerization of the purified lactide gives high molecular
weight (>100,000 Daltons) PLA [18,19]. In the first step of the lactide production process
by the ring-opening polymerization, the produced water is distilled out in a continuous
condensation reaction giving low molecular weight oligomers or prepolymers. Later, the
produced prepolymer is catalytically converted through an internal transesterification
reaction to the cyclic lactide and then purified by distillation under vacuum. Then, the
catalytic ring-opening polymerization of the purified lactide is carried out by using a
stannous octoate-based catalyst, or other organo-tin catalysts. After polymerization, the
residual lactide monomer is removed and recycled within the process. The selection of the
type and concentration of the catalysts and the residence time and temperature during the
polymerization enables to control the molecular weight, and also the ratio of D- and L-lactic
Coatings 2021, 11, 390 4 of 42

acid units in the final PLA polymer [9,15,18,19]. If PLA consists entirely of L-LA acid
monomer, then it is called PLLA, and if it is composed of D-LA monomer, it is called PDLA.
Many PLA types having different isomer ratios can be formed and the thermal,
mechanical, and biodegradation characteristics of PLA are dependent on the choice and
distribution of stereoisomers within the polymer chains. For example, when D-content
is larger than 20%, then a fully amorphous polymer can be obtained, whereas highly
crystalline PLA can only be obtained when the L-content is larger than 90% [9,15,17]. PLA
has a slow crystallization rate. Commercial PLA is mostly a blend of PLLA and PDLA
or copolymer PDLLA, which is obtained by the polymerization of L-LA and DL-LA. The
melting temperature (Tm ), glass transition temperature (Tg ), and crystallinity % of PLA
decrease with the decrease of L- and increase of the D-isomer content. PLA granules have
a certain degree of crystallinity which was introduced during the production stage. In
general, commercially available PLA polymer has a glass transition temperature in the
range 60–65 ◦ C and melting temperature of 160–180 ◦ C [15]. Antioxidants, heat stabilizers,
light stabilizers, impact modifiers, and several other additives are used to improve the
properties of commercial PLA [10].
PLA polymer is biodegradable and recyclable since it degrades by the hydrolysis of
the backbone ester groups and sometimes by microbial attack. The rate of PLA degradation
depends on its properties such as crystallinity, molecular weight, morphology, water
diffusion rate, and stereoisomeric content. In general, PLA has a slow degradation rate,
which is useful in some biomedical applications but is a problem with the disposal of the
consumer commodities such as packaging films [9–15,20]. PLA is biocompatible with the
body fluids and thus can be used in biomedical applications. It does not produce toxic
or carcinogenic effects in local tissues. PLA hydrolyzes to its constituent hydroxyl acid
when used in the interior of a human body. The resultant metabolites are incorporated
into the tricarboxylic acid cycle after hydrolysis, and excreted from the body [16,20,21].
The use of PLA as a suture material is confirmed by the Food and Drug Administration
(FDA) in cases of direct contact with biological fluids [22]. However, PLA is a relatively
hydrophobic polymer with an apparent water contact angle of 75◦ –85◦ and its cell affinity
is low, and sometimes an inflammatory response happens from the contacting surrounding
tissue [23,24].

2.2. Use of PLA Filaments in 3D Printers

3D printing (also known as “additive manufacturing” (AM) and “rapid prototyping”
(RP)) is a process to create objects from 3D model data drawn with the aid of computer-
aided design (CAD) or a similar program. There are many 3D printing methods with
different working principles. FDM, selective laser sintering, inkjet 3D printing, stere-
olithography, and 3D printing are the main AM methods. At present, FDM is the most
budget-friendly and popular 3D printing method due to its easy use and available cheap
raw materials [6–8,25–33].
A 3D printer working with the FDM method extrudes thermoplastic filaments, while
the temperature and the rate of polymer flow are precisely controlled, as shown in Figure 3.
There is one (or sometimes two) small extruder head nozzle in a printer. Polymeric filaments
melt into a semi-liquid state at the nozzle to create successive object layers. The fused
filaments are extruded onto a build platform layer by layer, where the extruded filament
cools, solidifies, and adheres with the adjoining material which was previously deposited.
The print nozzle or the base plate moves along the horizontal xy plane and the molten
material is placed on the build surface during this motion. The base plate moves down
(or the nozzle moves up) in the vertical z-direction by an increment which is equal to the
height of the filament during the deposition process. After a whole layer is placed, another
layer is deposited again until all the layers solidify into a final 3D object whose shape and
dimensions are previously determined. In the FDM approach, the mechanical strength and
surface finish quality of the printed parts can be controlled by altering the type (properties)
of the polymeric filaments and also the printing parameters of the 3D printer by varying
Coatings 2021, 11, 390 5 of 42

the temperature of the nozzle, polymer flow, layer thickness, orientation, raster width, and
raster angle, etc. [33]. The temperature history of the interfaces plays an important role
in determining the adhesion quality between the deposited layers. In fact, the adhesion
between these extruded filaments depends on the molecular diffusion and randomization
of the PLA polymer chains across the interfaces of the filaments [2,3,8,25–27].

Figure 3. Three-dimensional (3D) printer using PLA filaments in the fused deposition modeling (FDM) approach.

The popular polymers used in FDM-type printers are as follows: PLA, acrylonitrile
butadiene styrene (ABS), polyamide (PA), polypropylene (PP), polyethylene (PE), and
polycarbonate (PC) [1–8,26]. At present, PLA filaments are going to be the most used
material with an annual growth rate of around 20% [7]. The ease of printing, glossiness,
and multicolor appearance are the reasons for the choice of PLA. The accuracy for the
dimensional parts of the PLA objects is high since it poses less warp behavior than the
ABS filaments.
3D printers which are used in the FDM process are small in size and PLA or composites
of PLA flow through single or multiple nozzles (sometimes through multi-channels). PLA
has a melting point of 150–160 ◦ C, which is low when compared with other polymers
which are used in the FDM printing industry and requires less energy consumption during
printing [34]. PLA has high tensile, flexural strength, and Young’s modulus when compared
with other feedstock polymers such as PS, PP, and PE [35].

2.3. Main Drawbacks of the PLA Filaments and the Necessity for the PLA Composite Preparation
to Be Used in the Extrusion-Based 3D Printing Applications
Unfortunately, PLA polymer has some disadvantages, such as low toughness, high
brittleness (with less than 10% elongation at break), low melt strength, poor heat bending
temperature, poor thermal stability, narrow processing window, and non-conductivity,
which limit its use in many industrial applications [6–8,25–32,36]. The mechanical strength
of PLA is low in comparison with ABS and PC polymers, since PLA has a more linear molec-
ular chain structure preventing chain entanglement and imparting mechanical strength.
Moreover, the dimensional stability of PLA objects after printing is not good due to the
volume changes occurring and stress forming during 3D printing, which is caused by the
variation of PLA crystallinity.
Coatings 2021, 11, 390 6 of 42

The adhesion between two fused PLA filaments during 3D printing occurs via a three-
step process, as seen schematically in Figure 4. Initially, the surfaces of two independent
PLA filaments contact with each other, and later a neck grows between them, and finally,
the molecular diffusion of the PLA chains occurs at the interphase region between two
adjacent filaments in order to remove the presence of the solid surface meniscus [37]. In
general, the weak interfacial adhesion between the fused filaments is the mean cause for
the poor mechanical properties of the 3D-printed PLA objects. It was proposed that the
reason for the weak interfacial adhesion is due to the short contact time of the extruded
PLA filaments which are kept around their melting points, since the temperature of the
filaments decreases rapidly to the PLA melting point (or sometimes lower) in a short
time due to the rapid heat transfer towards the environment (usually around the room
temperature) [37–39]. When this happens, the linear PLA macromolecules which are
present in the interfacial region of two neighboring filaments cannot be diffused into each
other completely, and usually some cavities occur in the interphase and the presence of
these cavities decreases the mechanical strength of the printed object.

Figure 4. Reasons for the problems of the 3D-printed PLA objects due to the printing direction of the fused filaments.

When the cooling speed of the injected filaments is slow, then some disordered parts
and poor surface quality occur on the object. Conversely, when the cooling speed of
injected filaments is rapid, then poor PLA macromolecular diffusivity happens in the
interface between adjacent filaments, resulting in the consequent weak interfacial bonding,
which is the main reason for the poor mechanical properties of the final 3D-printed object.
Thus, the selection of the nozzle temperature, polymer flow rate, and also the local printing
temperature is important to control the state of PLA macromolecules and the corresponding
mechanical properties of the final object [40,41].
Another problem is the mechanical strength variation of the 3D-printed PLA objects
according to the printing direction of the fused filaments, as seen schematically in Figure
4. The direction of the filaments should be the same with the direction of main stretching
load and this property was investigated and reported in many articles [25–30,33,42,43].
Coatings 2021, 11, 390 7 of 42

There are limitations of improving the mechanical and other properties of homopoly-
mer PLA printed objects using the FDM approach. The use of PLA composites instead of
pure PLA polymer was proposed to increase the mechanical strength of PLA homopolymer.
PLA composites were formed by the incorporation of metal, ceramic, organic, inorganic,
and nanomaterials into the PLA matrix. The objective is to obtain better-performing fila-
ments which will be used as feedstock in FDM-based 3D printers instead of homopolymer
PLA filaments. It was suggested that the development of such successful PLA composite
filaments as raw materials would expand the use of the 3D printing technology [25–27].

3. Methods to Synthesize Pla Composites as Raw Materials to Be Used in the

Extrusion-Based 3d Printing
There are many techniques to prepare the PLA composites, such as melt mixing,
injection molding, thermoforming, compression molding, etc. However, a continuous
PLA composite filament is needed as a raw material for the FDM-based 3D printing
applications and the most appropriate method to prepare such a PLA composite is the
extrusion melt compounding by using single (or preferably) twin screw extruders [15,25].
Apart from obtaining better mechanical properties, the incorporation of various optical,
thermal, and electrical functionalities that cannot be attained by the pure PLA polymer is
another objective of the PLA composite preparation [44,45]. A composite consists of two
general parts, the matrix and the reinforcing agent. Mainly, micro- or nano-particles of
inorganic, carbon, and organic origin, short or long continuous fibers, and some specific
metal particles are used to obtain the reinforced PLA composites [8,26,27,46–52]. Another
method is the incorporation of continuous fibers into PLA by using special FDM-based 3D
printers to obtain mechanically strong printed parts. The schematic description of the co-
and dual-extrusion 3D printing of the PLA with continuous fibers is given in Figure 5.

Figure 5. (a) Co- and (b) dual-extrusion 3D printing of PLA with continuous fibers (adapted from Reference [8], copyright
2020, MDPI Publishing).

The nature of dispersed phases, blend composition, and processing conditions (shear,
temperatures, mixing time, etc.) in the melt compounding in an extruder are all important.
However, the absence of water in the produced PLA composite is the most important
requirement. The content of water in the PLA composite filament should be less than
50–250 ppm, otherwise the presence of larger amounts of water can cause swelling and also
the hydrolytic degradation. Moreover, if a water-swollen filament is fed into a 3D printer,
Coatings 2021, 11, 390 8 of 42

then it will block the hot nozzle. The moisture trapped in the PLA filament can convert into
steam if the printer heats it rapidly and the tiny pockets of steam will interfere with the flow
of the printing filament while passing through the hot nozzle. Thus, all precautions should
be applied to prevent the presence of water in a PLA composite filament [10,15]. On the
other hand, the morphology of the blend and the interactions between polymer—polymer
and polymer—nanoparticles also affect the final properties of the 3D-printed product and
should be considered [53].
In the present literature, there are many articles reporting the addition of cellulose
based natural fibers such as wood, hemp, kenaf, bamboo, sugarcane bagasse and flax
to PLA using extrusion blending to form PLA composites. It was determined that the
application of fiber chemical treatments improved the stiffness and mechanical strength
of the resultant PLA composites depending on the ratio of the filler and also processing
conditions during compounding [54–67]. However, it is known that cellulose based fibers
are highly hygroscopic and must be dried before or after compounding with PLA polymer.
Moreover, these PLA composites should be kept in a dry store in order to prevent water
vapor take-up. The effect of the incorporation of suitable plasticizers to cellulose based
additives [68–70] and also to the toughening agents [71,72] was also investigated.

4. 3D Printing Applications of the PLA Composites

In this section, 3D printing applications of the PLA composites will be presented
in nine separate parts to enable the readers to find their selections easily. Biomedical,
tissue engineering, biodegradability, and bio-printing applications are related to the health
industry. Electrical, microelectronic, electromagnetic, sensor, battery, and photocatalytic cell
applications are related to the electromechanical system industries. Automotive, aviation,
and space applications are related mostly with the mechanical engineering industries.
Finally, the recently developed 4D printing applications were also discussed in this section.

4.1. Biomedical, Tissue Engineering, and Antibacterial Applications

3D-printed PLA composites were used to produce artificial tissues, bones, some organs,
and cellular structures [30,73–75]. These composites were applied for the reconstruction
of skeletal defects and damaged bone structures to renew their functions. Micro- or nano-
bioactive ceramic powders like hydroxyapatite (HA) were incorporated to increase the
mechanical strength and osseointegration properties of the printed PLA composites [76].
HA is a source of minerals for bone cells and similar to the bone tissue, and thus is suitable
for the bone regeneration. HA powders having the average particle size between 90 nm and
1 micron were generally used for this purpose. In a study, mixing of PLA and 15% weight
HA powder was carried out in a screw extruder to obtain the composite filaments, and
then PLA-HA porous scaffolds with porosity of 30 vol.% for bone implants were prepared
using a 3D printer, where the architecture of porous scaffolds was similar to the structure
of a trabecular bone [76]. Compression and three-point bending tests were conducted to
examine the mechanical properties of the synthetic scaffolds, and it was found that the
use of PLA-HA composite improved the mechanical strength of the scaffolds, which can
withstand up to 10 MPa pressure without deformation and loss of mechanical strength.
The mechanical properties of these 3D-printed biocompatible, biodegradable scaffolds
were in the range of targeted properties of the bone tissue and thus they could be used for
the treatment of small bone defects [76].
PLA-chitosan-hydroxyapatite load-bearing porous hydrogel scaffolds were obtained
by applying 3D printing in order to increase the compressive strength of the synthetic
bone tissue. The large pores which were present in the structure of the 3D-printed scaf-
fold provided enough free space to form a composite hydrogel and a higher human
stem cell osteogenesis occurred in 3 weeks [77]. In another study, a PLA composite with
poly-ε-caprolactone and small amounts of titanium oxide were prepared and then bone
replacement objects were 3D-printed using these composite filaments [78]. It was found
that the addition of titanium oxide increased the tensile strength and the fracture strain,
Coatings 2021, 11, 390 9 of 42

resulting in values of approximately 45 MPa and 5.5% elongation. Moreover, these 3D-
printed composites showed good in vitro biocompatibility, including cell proliferation and
adhesion [78].
In another study, composites of PLA and hydroxyapatite (HA) were obtained by
extrusion mixing and then porous scaffolds which would be used in the replacement
of the trabecular bone defect were obtained by 3D printing [79]. Long-term creep and
Charpy impact tests of the samples have shown that PLA-HA scaffolds could be operated
under a load of up to 10 MPa, at 119 N impact without deformation and weakening of the
mechanical strength. In vivo tests have been performed to investigate the biocompatibility
of scaffolds and it was found that these scaffolds can be used as implants for the unloaded
small bone-defect replacements [79]. The same group investigated the effect of the cultural
environment on the properties of the scaffolds which were obtained by using PLA and
micro- and nano-particulate HA composites after extrusion mixing [80]. Compression
tests were conducted on the samples and a decrease in the mechanical properties was
observed after incubation. These PLA-HA scaffolds were found to support the growth of
mesenchymal stromal cells and also stimulated their active proliferation [80].
Homogenous PLA/HA starting composite materials were pre-mixed using a roto-
molding machine which produced a PLA composite in the form of pellets, and then these
pellets were processed to obtain a continuous wire which was suitable to feed a 3D printer
in another investigation [81]. It was found in the composite filament that the HA content
was homogeneously distributed within the PLA matrix, as confirmed by SEM and EDX
analyses. Despite adding a small amount of HA content, the flexural modulus increased
slightly when compared with the pure PLA. This filament was successfully used to fabri-
cate a 3D-printed osteogenic hydroxyapatite PLA bone graft using the clinical images of a
maxillary sinus which were obtained by tomography [81].
The production of bone screws is an important objective of the 3D printing approach.
For example, PLA bone screws containing iron oxide (Fe3 O4 ) nanoparticles were fabricated
by loading 20% Fe3 O4 [82]. The mechanical properties of the PLA-Fe3 O4 composite screws
were evaluated by applying anti-bending and anti-torque strength tests. Histologic and
computer tomographic (CT) imaging studies using an animal model were applied to assess
the tissue response and radiopacity of these composite screws. It was found that the
addition of Fe3 O4 increased the crystallization and thermal stability of the 3D-printed
composite bone screws, which provided very good local tissue response [82].
An interesting study was the production of 3D-printed porous PLA-HA composite
scaffolds which have shape memory effect, to be used for self-fitting implants [83]. The
incorporation of HA nanoparticles to the PLA matrix affected the alignment of polymer
molecular chains, which resulted in a consequent change in the friction between molec-
ular chains and served as a stationary phase center to govern the shape memory effects.
It was found that the 3D-printed porous PLA-HA skeletons supported the survival of
mesenchymal stromal cells and stimulated the active proliferation of these cells to help
vascularization of the implant, which was essential for the successful bone prosthesis [83].
PLA-HA composite scaffolds were also used to repair large bone defects having
complex geometries [84]. Rabbit bone was used as a model and the fabrication of a
vascularized tissue-engineered bone was carried out with the aid of an in vivo bioreactor.
A tibial periosteum capsule was seeded with the bone marrow stromal cells and filled with
3D-printed PLA-HA composite scaffolds which crossed with a vascular bundle. The tissue-
engineered bone was found to be medically successful after four and eight weeks [84].
PLA-HA scaffolds having three different pore sizes were produced and it was found
that the 3D printing decreased both PLA molecular weight and degradation temperatures,
but there was no change in the crystallinity. No effect of the pore size was seen on the
mechanical properties of the scaffolds. The scaffold samples did not show any cytotoxicity
towards human bone marrow stromal cells after the sterilization by γ irradiation, indi-
cating that they can be used for the tissue engineering [85]. Later, one-step fabrication of
high loaded PLA/HA composite filament for 3D printing was carried out to increase the
Coatings 2021, 11, 390 10 of 42

bioactivity of the scaffold material. The properties of the filaments remained the same after
the 3D printing process and HA was found to be well-distributed in the polymer matrix
for the viscosity range around the melting point [86].
In general, fixing of multiple fragmented bony fractures is difficult using internal
fixation devices, and to drill in the bone to install such devices may result in secondary
fractures. 3D-printed PLA–HA–silk composite bone clip internal fixation devices were
produced based on the CT scan of a femur in a rat [87]. The novel PLA–HA–silk composite
bone clip exhibited similar mechanical stability and better biocompatibility in comparison
with the performance of the original PLA–HA clips. PLA–HA–silk clip was found to be
relatively noninvasive since there is no requirement to drill holes in the bone [87].
Composites which were formed by mixing PLA, thermoplastic polyurethane (TPU),
and graphene oxide (GO) were found to be suitable to construct tissue engineering scaf-
folds [88]. PLA-TPU-GO composites were prepared using a solvent-based method, where
dichloromethane and dimethylformamide solvents were used to dissolve the above poly-
mers, and later, the mixed polymer solutions were co-precipitated in alcohol and finally
dried. Next, the composite filaments were prepared by the melt extrusion of the dried com-
posite. The use of TPU polymer improved the elasticity and toughness of the composite.
FTIR and SEM images indicated a good dispersion of GO nanoparticles in the polymer
matrix. The addition of GO enhanced the thermal stability, and the novel composites can
be easily printed into complex shapes. It was found that the addition of GO improved the
mechanical properties of the TPU-PLA-GO composite by 167% in compression modulus
and 75.5% in tensile modulus after 3D printing, as seen in Figure 6. Degradation tempera-
ture increased (90 ◦ C) and better crystallinity was obtained. These composites showed very
good cell viability with the NIH3T3 cells, indicating that the addition of GO had no toxicity
to the cell growth in the used ratios and PLA-TPU-GO scaffolds could be successfully used
in tissue engineering applications [88].

Figure 6. (a) SEM image of cross-section of S specimen (0.5 wt.%) (inset shows image of specimen
after S compression testing). (b) SEM image of cross-section of L specimen (0.5 wt.%) (inset shows
image of specimen after L compression testing). (c) 3D-printed micro-lattice under bending (5 wt.%
of graphene oxide (GO)). (d) 3D-printed Ultimaker robot (0 wt.% of GO). (e) 3D-printed micro-
lattice (5 wt.% of GO) (Reproduced with permission from Reference [88], copyright 2017, American
Chemical Society).

In vivo and in vitro analysis of two-layer 3D-printed scaffolds containing PLA and
a biphasic PLA-bioglass (G5) layer were carried out in another study [89]. It was found
that PLA-G5 scaffolds had a higher-pressure modulus than the untreated PLA scaffolds,
however, a decrease in other mechanical properties was also observed. The structural
integrity of the scaffold was preserved with some changes in morphology. The addition of
G5 reduced the weight loss of the PLA scaffold. The use of a two-layer scaffold resulted
Coatings 2021, 11, 390 11 of 42

in a different in vivo response even though the PLA and PLA-G5 layers were physically
close. [89].
PLA-Nano-b-tricalcium phosphate (b-TCP) composites were manufactured as a raw
material to be used for the consecutive 3D printing of a cervical fusion cage structure.
In vitro biomechanical studies and biocompatibility tests have shown better mechanical
properties in comparison with the traditional fusion cages based on endplate matching [90].
In a similar study, a biodegradable 3D-printed PLGA (poly (D,L)-lactide-co-glycolide) cage
was produced as a mechanical support and it was combined with nanofibrous membranes,
while the nanofibrous membrane was embedded in antibiotics during the treatment for
the sustainable release of antimicrobial agents in order to treat the femoral metaphyseal
comminuted fracture [91]. It was found that ceftazidime and vancomycin were sustainably
detected above the effective levels in the local tissue fluid around the fracture site after
3 weeks. Moreover, animal studies have shown that the rabbits which were implanted
with the synthetic 3D cages have better cortical integrity, leg-to-length ratio, and maximum
bending strength. It was finally concluded that the developed 3D composite cage could be
used in fracture fixations [91].
Hierarchical biocomposite scaffolds containing PLA micro-protrusions and nanocom-
posite gelatin-forsterite fibrous layers were produced using the combined extrusion-based
3D printing and electrospinning approaches [92]. It was determined that the elastic modu-
lus of the composite scaffolds was significantly higher than the non-composite ones after
performing SEM, FTIR, and uniaxial compression tests. SEM images showed that the
calcium phosphate-like deposits were present on the surface of the scaffolds. The enhanced
bioactivity of the scaffolds was confirmed due to the presence of a nanocomposite fibrous
layer. It was proposed that the produced biocomposite scaffolds can be used for the bone
tissue regeneration [92].
Thermoplastic PLA was used as an encapsulable matrix in combination with the
photocurable gelatin hydrogels to produce a novel functionalized hybrid hydrogel after
the addition of bioactive gold nanoparticles to be applied in bone tissue regeneration [93].
In general, hydrogels have insufficient mechanical properties to be used in musculoskeletal
tissue repair. Thus, hybrid hydrogels having higher mechanical strengths should be
developed for this purpose. The mechanical properties of the hybrid gelatin hydrogel-PLA
composites were determined, and human adipose-derived stem cells were used for the
viability tests. It was found that stem cells could live in the composite hydrogel and spread
well on the 3D-printed PLA microstructures, as seen in Figure 7. This hybrid hydrogel-
PLA composite was found to be suitable for the bone tissue regeneration and stem cell
differentiation control studies [93].

Figure 7. Patient-specific bone tissue regeneration using 3D-printed PLA incorporated with a hybrid
gelatin hydrogel composed of gold nanoparticles and human adipose-derived stem cells (Reproduced
with permission from Reference [93], copyright 2017, The Royal Society of Chemistry).
Coatings 2021, 11, 390 12 of 42

PLA-cellulose derivative composites were also tried in biomedical 3D printing appli-

cations. Six biocomposites were prepared using PLA and six different lignocellulosic fibers
with widely varying particle characteristics. The interfacial bonding between PLA and
these fibers was found to be strong after applying the quantitative estimation of adhesion
strength, acoustic emission measurements, and SEM. The mechanical tests indicated that
the dominating micromechanical deformation process was the fracture of the fibers [94].
PLA-wood fiber biocomposites were synthesized and the effects of print orientation and
print width on the mechanical properties of 3D-printed samples were studied [95]. It was
found that the mechanical strengths of the samples were dependent on printing orientation
(0 or 90◦ ) due to fiber anisotropy and also on printing width (overlapping of filaments),
with a lower Young’s modulus than in the compressed samples. It was suggested that
this might be associated with highly porous (around 20%) microstructures of printed
biocomposites, resulting in water absorption and swelling [95].
The morphology, mechanical properties, and in vitro biocompatibility of strips which
were obtained by 3D printing of composite materials containing PLA-Camellia oleifera fruit
peel powder (COFHP) were also investigated [96]. Acrylic acid was also grafted to PLA
composite and showed better mechanical strength. PLA-g-AA-COFHP composites were
easier to process due to formation of ester. In vitro biocompatibility trials indicated that
both materials were non-toxic, and the antibacterial activity of the composites increased
with the use of COFHP [96]. PLA-microcrystalline cellulose (MCC) composites were
synthesized using solvent casting and twin-screw extrusion approaches, while the cellulose
concentrations were varied between 1 and 5 wt.% in order to obtain a fully degradable
biocomposite [97]. MCC was surface-modified with a titanate coupling agent to increase
its compatibility with PLA polymer. The incorporation of MCC resulted in an increase in
crystallinity and storage modulus of the printed parts, with 3 wt.% surface-modified MCC
showing the highest value [97].
Spruce wood hemicellulose (galacto-glucomannan) was used to try to partially replace
the PLA as a matrix polymer in 3D printing in another study [98]. The solvent blending
method was used to obtain homogeneous biocomposite feedstock. Mixtures of hemicellu-
lose and PLA in certain proportions were extruded into filaments and then these filaments
were used in a 3D printer. Tissue engineering and drug washing scaffold applications
were reported to be successful with these PLA composites since they were biocompatible
and biodegradable [98]. 3D-printed PLA-carbohydrate hybrid material was used in the
bone implants [99]. For this purpose, different proportions of carbohydrate particles were
added to the PLA matrix while preparing the scaffold samples. Bioactivity and surface
tests and mechanical analysis of the frames were examined, and it was found that the
surface roughness was proportional with the added carbohydrate powder content and the
mechanical properties were affected by the reduced interactions between the PLA matrix
and carbohydrate particles [99].
A fully biodegradable PLA composite which can be used in 3D printers was produced
using a novel tetramethylpiperidin-1-yloxyl (TEMPO)-mediated oxidation reaction with
bacterial cellulose (TOBC) and also Pickering emulsions [100]. PLA composite microspheres
were found uniformly coated by TOBC, via the Pickering emulsion approach, and later
melt extrusion was applied to prepare the PLA-TOBC composite filaments. Mechanical
properties, crystallinity, fluidity, and thermal stability of PLA-TOBC nanocomposites were
studied and it was found that when a TOBC content of up to 1.5 wt.% was added, the
mechanical and crystallization properties of the resultant composites were improved [100].
A novel chemical precipitation method was applied to prepare a biodegradable 3D
scaffold containing PLA and polyethylene glycol (PEG) as the polymer matrix, nano-
hydroxyapatite (nHA) as the ceramic additive, and dexamethasone as the organic addi-
tive [101]. The results of water contact angle measurements, DSC, and mechanical tests
showed that the addition of dexamethasone resulted in a substantial increase in wetta-
bility and crystallinity. In the in vitro experiments, mouse MC3T3-E1 cells were used
and the release of dexamethasone from the PLA-PEG-nHA-dexamethasone scaffolds im-
Coatings 2021, 11, 390 13 of 42

proved the late mineralization and also the alkaline phosphatase secretion. Moreover,
the increase in osteo-induction was noticed in the other in vivo experiments on the rat
calvarial defects [101]. In another study on the repair of bone defects, 3D-printed porous
PLA-nHA composite scaffolds were applied to give enhanced osteogenesis and osteo-
conductivity [102,103]. The morphological, composition, and structural analysis indicated
that nHA was distributed homogeneously in the scaffold. Based on in vitro antibacterial
test results, PLA-nHA scaffolds were found to be highly efficient in loading and releasing
levofloxacin and vancomycin. Moreover, cytocompatibility assessment using MG-63 cells
was carried out. Positive results were obtained for the osteogenesis and osteo-conductivity
of the scaffolds by using the rabbit model [28,102].
3D-printed PLA-microsphere-HA scaffolds were also applied to increase the bone
regeneration capacity, biomimicry, and bioactivity [103]. In order to do this, microscale
HA spheres were synthesized by spray-drying and were dispersed into the PLA matrix
by melt extrusion. Later, the novel composite filaments were used in a 3D printer to
produce the macroporous scaffolds. Pure PLA scaffolds were also 3D-printed and used
as the reference samples for comparison. It was observed that the crystallinity and Tg
of PLA did not change with the addition of microsphere-HA. However, a rough surface
was obtained when microsphere-HA was added to the composite in comparison with the
smooth surfaces of the 3D-printed pure PLA samples. Composites scaffolds were stiffer,
having values similar to a natural bone tissue [103]. On the other hand, template-oriented
synthesis of the PLA-HA composites for the 3D bone printing was also carried out [104].
A simple hard template was fabricated to synthesize single-crystal nanoplates of HA. HA
sol-gel was prepared using graphitic nitride (g-C3N4) under hydrothermal conditions and
HA nanostructure was formed by the calcination and removal of g-C3N4 from the template
at high temperatures. Then, PLA-HA composites were prepared in different HA weight
ratios for artificial 3D bone samples, which were found to be mechanically stable and had a
very good in vitro viability in biological tests [104]. Novel apatite-wollastonite (AW-PLA)
composite structures were produced that could match the cortical and cancellous bone
characteristics after 3D printing. In vitro cell assays indicated that the AW-PLA structure
showed good osseointegration and proliferation of rat bone marrow stromal cells [105].
3D-printed PLA-Ti composite scaffolds were produced after applying melt extru-
sion [106]. The thermal stability, crystallization temperature, and crystallinity percentage
of PLA-Ti composite scaffolds decreased with the increasing Ti content, while the Tg and
Tm values of the composite increased. The compressive, tensile, and impact strengths of
PLA-Ti composites exceeded the results obtained by the pure PLA. The addition of Ti
was found to increase the in vitro biocompatibility [106]. PLA-silver nano-wired (Ag-NW)
nanocomposites were produced by dispersing the Ag-NW in the PLA matrix using a
solution mixing method [107]. The morphological, thermal, and antimicrobial properties
were examined, and it was found that PLA-Ag-NW nanocomposites had good antibacterial
effect against both Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). When
the amount of Ag-NW was increased, better antibacterial results were obtained, and a
cost/performance optimization study was also carried out in the same study [107].
The incorporation of inorganic additives into PLA to obtain 3D-printed composite
scaffolds was reported in some articles. For example, PLA composite scaffolds containing
calcium carbonate and beta-tricalcium phosphate (β-TCP) were produced and their mor-
phological, mechanical, and biological tests were carried out in order to evaluate the effect
of each additive [108]. According to the results, both inorganic additives increased the
porosity, surface roughness, and hydrophilicity of the PLA composite scaffolds, which led
to the improvement in the metabolic activity of human osteoblastic osteosarcoma SaOS-2
cells. In terms of cell attachment after 1 week, the best results were obtained when both
additives were used, and also an increase in micro-porosity and osteo-conductivity was
observed to promote the cell adhesion [108].
3D-printed PLA composites were sometimes used in the drug industry. The objective
was the preparation of tablets with defined drug release profiles. For this purpose, pharma-
Coatings 2021, 11, 390 14 of 42

ceutical PLA-polyvinyl alcohol multi-component composite tablets were 3D-printed, where

the thickness of the PVA filler was varied to achieve different drug release delay times [109].
Wound dressings were also prepared using 3D-printed PLA-lignin powder composites,
where the compatibility of the 3D-printed samples was increased by the addition of castor
oil. Melt extrusion was applied to obtain the feedstock filaments which can be successfully
printed in a 3D printer. These wound dressings had low resistance to breakage, were more
wettable, and also showed good antioxidant properties [110].

4.2. Bioprinting Applications

Bioprinting is a special technology where cells, growth factors, and the nutrients
keeping the cells alive are incorporated with suitable biocompatible polymers to form
“bio-inks”. These bio-inks are then used as feedstocks for FDM-based 3D printers, where
specific tissue-like structures are formed by applying the layer-by-layer method. These 3D-
printed parts can be converted into tissues or organs by various post-treatment approaches.
For example, a bioprinted pre-tissue is transferred to an incubator and kept in a specific
solution where it matures to a tissue. Generally, computed tomography (CT) or magnetic
resonance imaging (MRI) are used to obtain the model of a specific organ or tissue which
will be used in transplantation in the second stage. In some studies, cells are encapsulated
in cellular spheroids having 500 µm in diameter and used in the preparation of the 3D
printer feedstock. The post-bioprinting treatment should be carefully applied to obtain a
stable tissue or organ structure, but the mechanical integrity and function of the synthetic
object is usually risky. Both mechanical and chemical stimulations are needed to send
signals to cells to control the growth of the tissues.
In brief, bioprinting is a novel technology and the production of successfully used
artificial organs such as livers and kidneys is very difficult at present, since the growth of
billions of cells is necessary to fabricate these organs during the post-treatment. Moreover,
there is a lack of some elements such as working blood vessels, tubules for collecting urine,
and enough oxygen in the interiors in most of the final 3D-printed tissues and organs.
PLA biopolymer is sometimes used in bio-inks as the matrix polymer, as shown below in
some reports.
The combination of bioprinting with the cell-laden microcarrier technology was ap-
plied to generate an osteochondral tissue which caused the extensive expansion of cells,
while forming multi-cellular aggregates [111]. Gelatin methacrylamide-gellan gum bio-inks
were used to encapsulate the mesenchymal stromal cell-laden polylactic acid micro-carriers
which were produced via static culture or spinner flask expansion methods. Hydrogel
constructs having high cell concentration and viability were fabricated via 3D printing,
as seen in Figure 8. The use of microcarrier encapsulation enhanced the compressive
modulus of the constructs, facilitated the cell adhesion, and also supported the osteogenic
differentiation and bone matrix deposition of the mesenchymal stromal cells [111].
In another study, a fibrous bio-ink which was composed of alginate hydrogel, PLA
nanofibers, and human adipose-derived stem cells was used for 3D bioprinting of mus-
culoskeletal soft tissue constructs [112]. Initially, human adipose-derived stem cell prolif-
eration and viability were assessed in 3D-bioplotted strands over 16 days in vitro. Later,
a human medial knee meniscus was bioprinted and evaluated over 8 weeks in vitro. It
was found that the cell metabolic activity on day 7 was 28.5% higher in this bio-ink when
compared with the neat bio-ink, as seen in Figure 9. Cell density was high, and collagen
and proteoglycans were present in areas surrounding the cells [112].
Coatings 2021, 11, 390 15 of 42

Figure 8. Bi-layered GelMA-GG cylindrical osteochondral graft model (16 mm diameter, 1 cm height).
(A) MC-laden layer top view, (B) GelMA-GG layer top view, (C) perspective, (D) cross-section. Scale
bars are (A,B) 400 µm and (C,D) 4 mm (Reproduced with permission from Reference [111], copyright
2014, IOP Science Publishing).

Figure 9. Overview of the procedures in the bioprinting of a PLA nanofiber-alginate hydrogel bio-ink with encapsulated
human adipose-derived stem cells (hASC) (Reproduced with permission from Reference [112], copyright 2016, American
Chemical Society).

The mechanical strength of the 3D-printed hydrogel structures which will be used as
cartilage tissue was studied by 3D bioprinting of composite bio-inks containing alginate and
submicron PLA fibers [113]. It was found that when PLA short fibers were incorporated,
the Young’s modulus of alginate products can be increased three-fold. The prepared
bio-inks were loaded with human chondrocytes and later the obtained structures were
cultured in vitro for up to 2 weeks. It was determined that 80% viable human chondrocytes
were trapped in the obtained hydrogel filaments [113]. In another study, PLA was mixed
Coatings 2021, 11, 390 16 of 42

with gellan gum-poly (ethylene glycol) diacrylate to form double network hydrogel and
to improve the mechanical strength of the hydrogels which would be used to repair the
intervertebral disc [114]. The mechanical and degradation properties of the dual 3D-printed
cell-laden hydrogel constructs were controlled by varying the infill patterns and density
of the PLA frameworks. It was found that the bone marrow stromal cells which were
co-printed into these scaffolds retained high viability and showed a good distribution
in the composite hydrogels [114]. Hyaluronic acid (HA) was used as a raw material to
produce a new bio-ink to obtain a synthetic hydrogel cartilage tissue after 3D bioprinting.
HA-based bio-ink was co-printed with PLA as a composite and the cell functionality was
enhanced by an increase in the expression of chondrogenic gene markers, resulting in
tissue formation [115].
The majority of the bioprinting methods giving tissue constructs with open vasculature
lack the ability to be directly perfused and the fabrication of the thick and densely populated
tissue constructs with controlled vasculature and microenvironment. In a novel study, thick
(around 1 cm) and densely populated (10 million cells/mL) 3D tissue constructs having a
stiffness of soft tissues such as the liver were obtained by using water-soluble polyvinyl
alcohol as the main constituent and PLA as the support structure [116]. PLA support
structure was removed, and the water-soluble PVA structure was used to obtain a 3D
vascular network within a customized extracellular matrix, giving the stiffness of the liver
and with encapsulated hepatocellular carcinoma (HepG2) cells. These tissue constructs
could be directly perfused for long periods (>14 days) with the medium inducing the
proliferation of the HepG2 cells and the formation of spheroids. It was proposed that
the new method could enable the design of the tissue-engineered constructs for tumor
modeling and for regenerative medicine [116].
In order to repair the endothelial cells, different types of biocompatible and biodegrad-
able macroporous scaffolds having a diameter of 10 mm with interconnected pores of
~500 µm diameter were formed by 3D bioprinting [117]. Different compositions of PLA,
polyethylene glycol, and pluronic F127 were used to obtain semi-solid viscous bio-inks
giving a texture where the macropores were homogeneously distributed throughout the
surface. Dimethyloxalylglycine and erythroprotein were used as the model drugs and the
release of dimethyloxalylglycine from scaffolds into phosphate buffer saline solution was
found to continue longer than 48 h [117].
A review article on the overview of 3D-printed constructs with a proper selection
of biomaterials and compatible bioprinting methods was published and the challenges
were reported to remain for the improved printing resolution (possibly at the nanometer
level) and biomaterial compatibilities [118]. It was proposed that the hybrid 3D bioprinting
technologies which combined the additive and conventional manufacturing processes
have shown promising improvements, introducing higher mechanical strength, native-like
biological microenvironments, and cell-related activities [118].

4.3. Electrical Conductivity Applications

The cost-effective fabrication of highly conductive micro- or nano-flexible circuits is
an important objective in the electronics industry. Polymer-graphene and polymer-other
carbonaceous material composites were used for this purpose. PLA was occasionally used
as the matrix polymer in 3D printing. For example, conductive 3D microstructures were
obtained by using PLA-multi-walled carbon nanotube (MWCNT) dispersion composites
as raw material [119]. Electrical conductivity and rheological measurements were made
on these nanocomposites to find the optimum processing conditions and printability by
varying the MWCNT and PLA concentrations. Many nanofillers were also tried to obtain
better properties [119]. 3D-printed PLA-graphene flexible circuits were produced using
reduced graphene oxide (r-GO), which was pre-synthesized in the laboratory [120]. After
melt blending PLA and r-GO, the obtained filaments were used as raw material in 3D
printing. Both two-dimensional (2D) and 3D flexible circuits were printed having smooth
surface and superior mechanical properties. The electrical conductivity of the PLA-r-
Coatings 2021, 11, 390 17 of 42

GO composite filaments reached up to 4.76 S/cm when r-GO was used as 6 wt.% in the
composite. The mechanical properties of these filaments were also good [120]. Graphene-
doped PLA (G-PLA) and pure PLA were blended and used as feedstock for 3D printing of
conductive filaments. The effects of extrusion rates, applied voltage, and heat dissipation
of G-PLA and PLA were investigated, and samples were tested at temperatures between
20 and 90◦ C depending on the electronic current and voltage applied. The resistance of
the filament products was controlled by the extrusion rate in the 3D printer [121].
PLA was melt-mixed with carbon nanotubes (CNT) and natural graphite (G) powder
to obtain polymer composites with high electric and thermal conductivity after 3D printing.
Volume resistance of PLA-CNT composites and the thermal conductivity of PLA-G com-
posites could be varied by changing additive concentration, and the minimum increase
in thermal conductivity was 40% with the addition of a small amount of CNT to PLA-G
composites [122].
In another study, PLA-MWCNT composites were prepared using different MWCNT
ratios to obtain electrically conductive products after 3D printing. The highest conductivity
was obtained when 5% MWCNT was used, as seen in Figure 10. The feedstock had a good
flow rate and thermal properties [123].

Figure 10. The fabrication process of poly lactic acid (PLA)/multi-walled carbon nanotubes (MWCNTS) composite materials
by three-dimensional (3D) printing (Reproduced with permission from Reference [123], copyright 2018, MDPI Publishing).

PLA was blended with industrial graphene nanoplates (GNP) and MWCNT to pro-
duce electrically conductive filaments made of PLA-GNP-MWCNT hybrid composites.
Nanoparticles are uniformly distributed in the polymer matrix according to SEM, TEM,
and Raman spectroscopy results. Both electrical and heat conductivities were measured.
Nanocomposites formed smaller and more homogeneous aggregates. Thermal conductiv-
ity increased with higher filler content. A more effective network was created due to the
interactions between GNP and CNT which limits bridging the adjacent graphene platelets
and GNP aggregation [124]. The mechanical and dielectric properties of neat PLA and
PLA-G nanocomposites were studied to observe the effect of the fillers. Considerable
increase in the dielectric values was observed with the addition of graphene [125]. Mechan-
ically strong PLA-GNP composites having good electrical conductivity were obtained by
dispersing the liquid exfoliated GNP powder in surfactant-free isopropyl alcohol. PLA
was dissolved in chloroform and then both solutions were mixed and dried, as seen in
Figure 11. After 3D printing, PLA-GNP composites demonstrated improved mechanical
properties and good conductivity (1 mS/cm) even at low GNP concentrations (>1.2% by
weight) [126].
Coatings 2021, 11, 390 18 of 42

Figure 11. (a) Schematic process flow of the GNP−PLA composite fabrication, extrusion, and 3D printing: (i) GNP
dispersion in IPA and dissolution of PLA in chloroform, (ii) mixing and drying of two dispersions, (iii) extrusion of the
GNP−PLA filaments, and (iv) 3D printing of the GNP−PLA object. (b) Optical micrograph of graphene flakes spray-coated
on a SiO2 substrate. AFM image of a representative graphene flake in the inset, with a height profile to measure the flake
thickness. (c) Optical image and magnified SEM image of the cross-section of the GNP−PLA filament (Reproduced with
permission from Reference [126], copyright 2019, American Chemical Society).

PLA composites with reduced graphene oxide nanoplatelets (rGO) or MWCNTs were
prepared by masterbatch melting to improve the distribution of the nanofillers in PLA
matrix. The apparent viscosity, interface compatibility, and the thermal stability of the
composites were good. The volumetric electrical resistance of the composites reached to a
minimum of 103 Wm with the addition of 9% rGO by weight. When modified rGO, which
was functionalized with sodium dodecylbenzene sulphonate, was used as the additive,
then the electrical conductivity increased more than the previous composites [127]. In
another study, PLA was solution-blended with mesoporous nanocarbon (mNC) to produce
electrical wires to be used in 3D-printed prostheses, robots, drones, orthoses, and others
having high mechanical strength. Melt extrusion was used to make feedstock filaments.
NC was seen to be uniformly distributed in the PLA matrix in SEM images and there was
no important change in Tg for all composites, as found from DSC analysis. The electrical
conductivity and yield strength properties were improved for most of the composites [128].
The shelf-life of 3D-printed PLA-GNP and PLA-MWCNT filaments were examined after 2
years of storage in a laboratory environment. Normal annealing and pre-melting annealing
were applied at specific times and temperatures to enhance crystallinity, thermal, electrical,
and tensile properties of aged PLA-based filaments. Annealing was found to be useful in
improving the mechanical, thermal, and electrical properties of composite filaments, but
the annealing temperature must be changed according to the carbon nanofiles’ type and
the target properties [129].
The shape recovery properties of SiC- and carbon-filled PLA filaments which were
prepared by extrusion were examined by bending and tensile tests after 3D printing.
The shape recovery time was related to the thermal conductivity of the material [130].
Heterophase composites which were prepared from PLA, polystyrene (PS), and ABS were
produced by mixing them with copper powder (as the conductive material) to obtain
electrically conductive composite filaments. Such filaments had Ohmic characteristics at
low-voltage regime and the electrical power consumed in the composites caused a rapid
increase in temperature in the high-voltage regime. It was proposed that the polymer
matrix affected the value of the maximum electrical power to be dissipated in the filament
Coatings 2021, 11, 390 19 of 42

before it lost its electrical conductivity [131]. Titanium oxide-based PLA photocatalytic
filters were produced by the immobilization of photoactive TiO2 nanoparticles in PLA.
PLA-TiO2 scaffolds were formed by 3D printing after the composite filament formation
and it was found that the distribution of nano-charges was improved in comparison with
the samples obtained by thermos-pressing. The thermal degradation of the composites
was also investigated [132].

4.4. Electromagnetic Applications

3D PLA parts can be coated with conductive paints to give composite low-cost anten-
nas. For example, in one study, the conical shape of an antenna was mainly made of PLA
and coated with a carbon-based conductive paint, HSF55, to form the antenna element
enabling an impedance bandwidth of 20:1. The measured normalized directivity patterns
correlate with simulations and the antenna is more than 90% efficient up to 5 GHz [133].
In another study, a lightweight, X-band waveguide horn antenna was fabricated by 3D
printing and conductive spray coating [134]. Initially, the antenna CAD model was split
into four pieces to metalize the inside of the horn antenna. Later, the four assembly parts
were 3D-printed with PLA in an FDM-based 3D printer. After printing, each part was
metalized using a commercial conductive spray (Kontakt Chemie, EMI 35). Finally, the
sprayed parts were assembled using polycarbonate bolts and nuts. Experimental results
showed that the new antenna weight was only 19.3% of the commercial metallic antenna,
with good antenna performance [134].
Highly conductive polymer nanocomposites can be used in electromagnetic inter-
ference (EMI) shielding, microwave absorption, and antenna applications. For example,
PLA-ABS composite structures were produced by 3D printing to construct microwave
metamaterials [135]. Metamaterials are artificial structures in which periodic unit cells can
be infinitely arranged. The reducing activity of the 3D-printed PLA surface was provided
by the chemical modification with a Tin coating by a wet process, and a highly conductive
Ag-plated membrane was formed on the PLA surface. The metamaterial, which was a com-
position of Ag-plated PLA and non-plated ABS parts, was characterized experimentally
and also numerically, and the numerical simulation reproduced the experimental results
both qualitatively and quantitatively, revealing the bi-anisotropic responses arising from
the fabricated metal-dielectric metamaterial structures [135]. In another metamaterial study,
a frequency-diverse computational imaging system was produced using 3D-printed PLA
frequency diverse meta-surface antennas [136]. A composite of PLA with a conductive poly-
mer material (Electrifi) removed the need for expensive conventional fabrication methods
such as machine milling, photolithography, and laser-etching. The new 3D-printed meta-
surface antennas could be used to image in the K-band frequency regime (17.5–26.5 GHz)
by means of a simple frequency-sweep in an all-electronic manner, avoiding active circuit
components at the diffraction limit. It was found that the conductivity of the Electrifi
polymer material significantly affected the performance of the 3D-printed antennas [136].
Metamaterial absorbers have the disadvantage of a narrow bandwidth, due to their
use of electromagnetic resonance, and a frequency-tunable metamaterial absorber would
be a solution for this deficiency. This property was achieved by changing the substrate
thickness, which would result in the varying absorption frequency of the metamaterial
absorber [137]. 3D-printed PLA layers with air space were used in order to mechanically
control the substrate thickness. The proposed structure consists of two layers and one
frame: the FR4 board substrate, which was made of glass fiber cloth, as the base material,
epoxy resin as the adhesive, and copper foil coated on one or both sides, PLA frame, and
air substrate, as seen in Figure 12. The thicknesses of FR4 and PLA were kept constant and
only the air thickness was varied using the PLA frame to control the effective dielectric
constant of the overall substrate. The performance of the proposed tunable absorber was
determined by using full-wave simulation and measurements and it was found that the
absorption frequency was changed between 8.0 to 8.9 GHz [137].
Coatings 2021, 11, 390 20 of 42

Figure 12. Pictures of the 3D-printed frame for the fixed air thickness. (a) Fabricated 3D PLA frame. (b) The fabricated
absorber. (c) 3D PLA frame with an absorber printing (Reproduced with permission from Reference [137], copyright 2018,
Hindawi Publishing).

3D-printed microwave absorbers could be produced by adding suitable salts to PLA.

Li0.44 Zn0.2 Fe2.36 O4 (LZFO) particles were mixed with the PLA matrix for the preparation of
3D-printed composites to be used as a microwave absorber. The mechanical, thermal, and
microwave absorption properties of PLA-LZFO composites with various LZFO content
were determined and the composite with 5% LZFO content by weight was found to be the
best in the thermal stability tests [138]. In a similar study, the electromagnetic absorption
properties of PLA-graphite nanoplatelet (GNP) composites in microwave and terahertz
frequency ranges were reported after obtaining the 3D-printed parts. The complex dielectric
permeability of PLA-GNP composites was modeled using Maxwell-Garnett theory. It was
found that the combination of conductive and geometric parameters of GNP which were
embedded in the PLA matrix allowed the composite to absorb THz frequency below the
perforation threshold [139].
An all-fiberized and low-cost 3D-printed PLA-graphene composite saturable absorber
was produced for the ultra-fast mode locking of a fiber laser operating in the 1.9 µm
wavelength region [140]. PLA-graphene composite was 3D-printed onto a side-polished
fiber and this fiber absorber was placed within a thulium (Tm)-Holmium co-doped fiber-
based ring cavity, and it was shown that mode-locked pulses with a temporal width of
~924 fs could be obtainable, as seen in Figure 13 [140].
Coatings 2021, 11, 390 21 of 42

Figure 13. (a) Schematic diagram of FDM-based 3D printer. (b) Four steps to prepare a side polished fiber suitable for 3D
printing. Step 1: Fixing optical fiber onto a V-grooved slide glass. Step 2: masking the target polished fiber section with
tape and dropping epoxy on the left-hand and right-hand sides of the taped section to form thick epoxy layers. Step 3:
dropping a small amount of epoxy onto the target polished fiber section after removing the masking tape. Step 4: polishing
the cladding of the fiber (Reproduced with permission from Reference [140], copyright 2019, IOP Science Publishing).

The electrical, electromagnetic, and thermal properties of the 3D-printed PLA-MWCNT-

GNP nanocomposites having different weight percentages were investigated and all of
the above properties were found to be well-workable at concentrations above the leakage
threshold. Shielding efficiency in the 26–37 GHz sample ranges was found to be higher
than the unfilled PLA. It was determined that the thermal conductivity of PLA loaded
with 12% GNP by weight was much higher than that of unfilled PLA. However, lower
improvements were found for MWCNTs and the PLA matrix loaded with both fillers [141].
The electromagnetic, morphological, and mechanical properties of the 3D-printed
PLA-carbonyl iron powder composites were investigated using SEM, vibrating sample
magnetometer, broadband dielectric spectrometer, and universal testing machine. It was
determined that the saturation magnetization of the iron powders of composites per unit
mass did not have a linear relationship with the filler content, and the resulting composite
materials have slightly better tensile strength and total elongation than those produced
by the conventional methods [142]. SiC-coated PLA filaments were used to improve the
mechanical performance of the microwave-heated PLA composites. Temperature increase
characteristics and temperature distribution of the interface in the microwave field were
reported. For this purpose, 3D-printed PLA-SiC composites were heated in a microwave. It
was found that PLA-SiC composites had better temperature rise properties and temperature
distribution after microwave heating, due to the re-melting at the interface of the 3D-printed
samples and strengthening the interface bonding, showing an increase in tensile strength,
tensile modulus, and interlayer rupture stress when compared to neat PLA [143].
Complex geometries of wideband phased array and metamaterial designs were stud-
ied for 3D-printed PLA composites with conductive inks at room temperature [144]. The
dielectric constant and loss tangent of PLA were found to be stable up to 18 GHz. 3D-
printed microstrip line samples were produced giving simulated and measured insertion
loss data, which validated the high conductivity through millimeter wave frequencies.
Later, a 3D-printed monopole Wi-Fi antenna was built and successfully tested [144].
After 3D printing PLA via FDM, nickel and silver conductive-based paints were used
and the realization of a Ku-band feed system for reflector antenna in satellite communica-
tion systems was achieved [145]. A corrugated conical horn antenna which was designed
to operate at 10.5 to 18.5 GHz and an H-plane waveguide diplexer were fabricated. It
was reported that this low-cost 3D-printed system could be successfully used in compar-
ison with a high-cost CNC-based metallic system, especially to manufacture prototype
structures or proof-of-concept-type studies of Ku-band systems [145].
Conductive scaffold microstructures of PLA-CNT nanocomposites were obtained by
3D printing and the effect of parameters such as spacing between fibers, number of layers,
and printing patterns on the transparency and EMI shielding efficiencies were investi-
gated [146]. It was found that 3D-printed PLA-CNT nanocomposites were significantly
better in the EMI shielding efficacy in comparison with the hot-pressed PLA-CNT samples.
Coatings 2021, 11, 390 22 of 42

It was suggested that the 3D-printed composites would be used as EMI shields for portable
electronic devices, aviation, and space systems [146].
3D-printed PLA-CNT composites having strong mechanical properties were demon-
strated to achieve good EMI performance [147]. CNTs were coated on a 3D-printed PLA
scaffold to give an interconnected conductive network after compression. EMI SE (Elec-
tromagnetic Interference Shielding Efficiency) of the composite was found to be 67.0 dB
when 5.0 wt.% CNTs were loaded. The bending strength (87.8 MPa) and Young’s modulus
(4.43 GPa) were found, which were 101% and 43% higher than 43.7 MPa and 3.08 GPa for
the conventional CNT/PLA composite. It was proposed that 3D printing technology is an
effective approach to develop the good structures having high EMI properties [147].
3D-printed PLA-rGO composites with different amounts of rGO were used as an
ultra-broadband EM absorber [148]. Multilayer absorbers were designed with a gradient
index of characteristic impedance by manipulating the rGO content and the geometric
parameters of the unit cell to enable good impedance matching and wave attenuation. The
obtained results indicated that effective ultra-broadband absorbers could be produced,
and the seven-layer absorber achieved an absorption above 90% in a broad bandwidth of
4.5–40 GHz [148].

4.5. Sensor Applications

3D-printed PLA composites were used in many sensor applications, which can be
used in soft robotics, biomedical, analytical devices, and other high-tech areas. For example,
PLA-MWCNT nanocomposite actuators were manufactured to obtain free-form spiral-
shaped multifunctional 3D liquid sensors, as seen in Figure 14 [149]. The solvent casting
approach was used to synthesize the PLA nanocomposite. After 3D printing, the resultant
sensor had a relatively high electrical conductivity and also liquid capture functionality,
good sensitivity, and selectivity due to its coiled helical structure, and worked successfully
even when immersed in solvents for a short time [149].

Figure 14. (a) Schematic representation of the solvent-cast 3D printing of nanocomposite microstruc-
tures. Schematic circuits of the liquid sensing test for (b) the straight-line sensor and (c) the 3D
helical sensor. (d) Process-related apparent viscosity of PLA nanocomposite solutions (typical pro-
cessing window used in this work is shown by the dashed box) (Reproduced with permission from
Reference [149], copyright 2015, The Royal Society of Chemistry).

Hygromorphic biocomposite sensors were produced by using wood fiber-reinforced

and 3D-printed PLA-polyhydroxyalkanoate (PHA) as self-spinning devices which can act
on a moisture gradient [95]. These devices took advantage of the hygro-elastic behavior of
natural fibers by mimicking the natural actuators. The differences in mechanical properties
were dependent largely on the printing direction (0◦ or 90◦ ) due to the fiber anisotropy. It
was found that the mechanical properties were related to the print width. The Young’s
modulus of the 3D-printed products was lower than the compressed samples. The relatively
high-porosity microstructure of printed biocomposites lead to damage mechanisms as well
as water absorption and swelling [95].
3D-printed PLA-MWCNT nanocomposites were also used to create flexible photothermal-
sensitive strain actuators on paper substrates. It was observed that the PLA-MWCNT
Coatings 2021, 11, 390 23 of 42

nanocomposite exhibited excellent photothermal effect and sensitivity under the irradia-
tion of near-infrared light. The temperature of the composites increased up to the Tg of
PLA after 1 s irradiation and approached to the Tm of PLA after 15 s of irradiation. These
nanocomposite strain actuators were deformed under near-infrared light and regained
their original state when the light was turned off [150].
A linear resistive temperature sensor was formed using 3D-printed PLA-graphene
nanowires (GNR) nanocomposite, which was able to measure the temperature changes
due to the variation in the resistance of the printed pattern [151]. This sensor could be used
both in air and underwater up to 70 ◦ C, without the need for any encapsulation process.
PLA acted as a binding matrix and GNR to impart conductivity. Microscopic physical
expansion of the polymer matrix occurred when the temperature increased, reducing the
contact between conductive GNR. When cooled, physical properties were preserved in
the sensor and its electrical resistance decreased. However, when the temperature was
above 70 ◦ C, then the deformation in the PLA polymer matrix became permanent [151].
In another study, 3D-printed PLA-commercial graphene nanocomposites were used as
composite sensors and also as electrochemical flow cells, as seen in Figure 15. These sensors
were modified with Au electroplating to be used to determine the catechol under flowing
conditions [152].

Figure 15. Schematic of the experimental setup and devices. (a) Schematic of dual-extrusion 3D
printing setup with two materials, (b) schematic representation of the channel flow geometry and the
positions of the two electrodes. This schematic is not to scale. (c) CAD drawing of a channel flow
cell with a 1.5 mm × 1.0 mm channel and two band electrodes (Reproduced with permission from
Reference [152], copyright 2019, Elsevier).

An electrochemical sensing platform was formed by using 3D-printed PLA-carbon

black composite [153]. A non-conductive, chemically inert electrochemical cell was also
3D-printed. These 3D-printed components were partially coated with silver ink in order to
behave similarly to the conventional Ag/AgCl reference electrodes, as seen in Figure 16.
Coatings 2021, 11, 390 24 of 42

Figure 16. Schematic diagrams of the AM electrochemical platform and the 3D printing working electrode preparation
procedure: (a) complete AM electrochemical platform, (b) transversal cut view of the AM electrochemical platform (total
volume = 5 mL), (c) polishing procedure of the hollow printed cube (3.0 × 3.0 × 1.5 cm3 and thickness of 0.75 mm), (d)
rectangular printed base after polishing (3.0 × 1.5 cm2 and thickness of 0.70 mm). Other information: (R) 3D-printed
pseudo-reference electrode, (C) 3D-printed counter electrode, (W) 3D-printed working electrode. SEM images of the
polishing 3D-printed working electrode before and after electrochemical activation are also shown (Reproduced with
permission from Reference [153], copyright 2019, American Chemical Society).

A very good electrochemical behavior (current intensity and voltammetric profile)

could be obtained for model analytes, such as dopamine, hexaammineruthenium (III)
chloride, ferricyanide/ferrocyanide, uric acid, and ascorbic acid, after the electrochemical
activation step was carried out. It was reported that similar or better performance was
obtained than those obtained using commercial glassy carbon and screen-printed carbon
electrodes [153].
A review article was published on the 3D-printed electrochemical sensors which could
be used to monitor different biomolecules [154]. It was reported that the limitations in the
sensor geometry have restricted the scope of currently used electrochemical sensors and
3D printing was a promising manufacturing approach to fabricate such electrochemical
sensors, which can work successfully in biological environments. The applications of the
3D-printed PLA-carbon composite electrodes as biosensors in several media were reported
in recent studies [154–158].

4.6. Battery Applications

3D-printed PLA-graphene composite filaments were used to fabricate a range of 3D
disc electrodes using the FDM approach and characterized both electrochemically and
physicochemically within Li-ion batteries and as solid-state supercapacitors. No current
collector was required in the battery and these disc electrodes showed a very high catalytic
activity [159]. The same group reported the production and application of Li-ion anodes for
Li-ion batteries, using 3D-printed PLA-graphene composite filaments, where the graphene
content varied in the range of 1–40 wt.% [160]. It was found that a graphene content of
20 wt.% exhibited appropriate electrical conductivity and avoided the need for a copper
current collector. The specific capacity was very poor in Li-ion batteries but could be
significantly improved through the use of a chemical pre-treatment increasing the electrode
porosity, which results in a 200-fold increase in specific capacity [160].
In a similar study, 3D-printed PLA-graphite nanocomposites were prepared to be
used as negative electrodes in Li-ion batteries to prevent the interpenetration problems in
electrodes, as seen in Figure 17 [161]. The graphite loading in the PLA matrix was increased
as much as possible to obtain better electrochemical performances and also the addition
of poly (ethylene glycol) dimethyl ether, propylene carbonate (PC), and some plasticizers
such as acetyl tributyl citrate were carried out to adjust the filament flexibility. It was
Coatings 2021, 11, 390 25 of 42

reported that 40% by weight of poly (ethylene glycol) dimethyl ether was found to be the
optimum proportion of plasticizer to be added to the PLA matrix to increase its ductility
and decrease its hardness [161].

Figure 17. Main steps of the 3D-printed negative electrode disc elaboration process (Reproduced
with permission from Reference [161], copyright 2018, American Chemical Society).

In general, the most important problem is the poor ionic conductivity of the materials
used in 3D printing. The same research group prepared and characterized 3D-printed
anodes using PLA-lithium iron phosphate (LFP) and PLA-SiO2 separators to be utilized
in lithium-ion batteries [162]. Carbon black was used as the conductive additive at the
anode. The thermal, electrical, and electrochemical effects were investigated as well as the
analysis of determining the electrolyte uptake of the ceramic additives which were used in
the separator in order to increase the liquid electrolyte impregnation and to avoid short
circuits [162].
In another study in the battery field, PLA was infused with a mixture of propylene
carbonate, ethyl methyl carbonate, and LiClO4 , and mixed with electrically conductive
materials such as Super P, graphene, MWCNT, and active (lithium titanate, lithium man-
ganese oxide) raw materials in order to determine the effect of their presence and also
concentration on the conductivity and charge storage capacity of the battery, as seen in
Figure 18 [163]. A target conductivity value of 0.085 mS-cm−1 was chosen and it was
reported that up to 30% (v/v) of solids were still miscible into PLA to suit printing, and the
80:20 (conductivity:active material) ratio maximized the charge storage capacity, while the
best capacity was achieved when lithium titanate and graphene nanoplatelets were used at
the anode, and Li-Mn oxide and MWCNT at the cathode [163].
Coatings 2021, 11, 390 26 of 42

Figure 18. (A) Individual components of the 3D-printed coin cell. (B) Assembled 3D-printed coin cell (Reproduced with
permission from Reference [163], copyright 2018, American Chemical Society).

4.7. Automotive and Aviation Applications

It was suggested that the time required for tooling and the cost of manufacturing
prototypes will be reduced sharply by using 3D printing methods in the automotive
and aviation industries. The most popular polymer which is used in the 3D printing in
these industries is polyamide 12 due to the suitability of its crystallinity to achieve better
functional properties such as mold shrinkage, and also its chemical, wear, and thermal
resistances [8]. However, there are many studies where the PLA composites were used
for this purpose. For example, PLA-flax fiber composites were produced with the help
of a twin screw extruder, having 30% and 40% flax fiber content by weight. It was found
that the mechanical properties of PLA-flax fiber composites were appropriate to be used
in automotive panels, however the addition of the plasticizers did not have a positive
effect on the impact strength of the samples [54]. 3D-printed PLA composites which were
reinforced by short carbon fibers, graphene, and silicon carbide nanowires (SiC) were
also used for 3D printing, and the effects of added materials, printing layer thickness,
and compression properties were studied. It was observed that both the strength and the
elastic modulus of the printed specimens increased with the decrease in the thickness of
the several printing layers, as seen in Figure 19. The highest elastic modulus was found to
be 1.69 GPa, containing a high ratio of carbon fiber modulus [164].

Figure 19. Specimens printed by PLA with one layer of SiCnw, two layers, three layers, four layers, and five layers with
dimensions in millimeter (Reproduced with permission from Reference [164], copyright 2019, Wiley).

The indentation creep resistance and strain rate sensitivities of neat PLA and PLA-
graphene composites were studied and the increased creep resistance in PLA-graphene was
Coatings 2021, 11, 390 27 of 42

attributed to the restriction of polymeric chains by graphene particles. It was determined

that the wear resistance of the PLA-graphene composite was larger than to PLA alone [165].
The prototypes used in the automotive sector should reproduce textural effects
(sparkle or graininess) or metallic or gonio-appearance to increase their attractive appeal.
In a related study, grey metallic PLA was mixed with diffractive pigments and statistically
designed experiments were carried out to find the best printing parameters which would
affect the final gonio-appearance of the 3D-printed samples, as seen in Figure 20. Printing
speeds, layer heights, and sample thicknesses were varied, and it was found that the layer
height was the most significant parameter to maximize the flop or sparkle effects [166].

Figure 20. Printing factors schematic with the controlled and changed parameters and the possible disposition of the
metallic/diffractive pigments across the printed sample (Reproduced with permission from Reference [166], copyright
2019, MDPI).

In another study, open hole tensile strength testing of the 3D-printed parts which will
be used in automotive and aerospace industries were carried out by applying in-house
fabricated neat PLA filaments. Three process parameters, raster angle, raster width, and
layer thickness, were varied and the tensile strengths of the samples were measured. It was
determined that the raster angle had a significant effect on the tensile strength of open-hole
tensile specimen. The maximum tensile strength was obtained when the specimens built
with 0◦ raster angle, 200 micrometer layer thickness, and 500 micrometer raster width were
used [167]. 3D-printed PLA-hemp fiber honeycomb sandwich structures were fabricated
in order to be used in small-scale automotive and aerospace prototype fields and their
mechanical behavior in flatwise and edgewise 3D printing directions were analyzed [168].
On the other hand, the aviation and space industries also benefitted from the 3D
printing methods in order to replace the conventional structures with lightweight, flexible,
and improved geometrical structures to reduce fuel consumption and material waste.
Cellulose-based PLA composites have been used in extrusion-based 3D printing for the
aviation industries [10,11,51,52]. More recently, novel PLA composites were developed
for this purpose, for example, continuous carbon fibers were incorporated into the PLA
matrix and also simultaneously fed during the 3D printing process. The performance of
printed samples was studied by monitoring the influence of the applied process parameters
Coatings 2021, 11, 390 28 of 42

on the temperature and pressure during the process. A flexural strength of 335 MPa was
measured when the continuous carbon fiber content of the samples reached to 27% [169].
A torsion box fragment, which is a thin-walled load-bearing structure which is used
in the aviation technology, was 3D-printed using PLA composites. The samples were
subjected to twisting and underwent post-critical deformation tests in order to determine
the influence of the printing direction of the individual layers on the system stiffness.
Nonlinear numerical analyses of the models were also carried out to check the usefulness
of the adopted novel method for 3D modeling [170].
Carbon-infused PLA has good tensile strength and can find applications in various
industries such as automotive, aeronautical, and aerospace [171]. Two different post-
treatment techniques were applied to these 3D-printed PLA-carbon composite objects:
chemical treatment and heat treatment. It was reported that chemical post-treatment was
giving a much better result than the heat post-treatment approach [171].

4.8. 4D Printing Applications

3D expression which is used in 3D printing contains dimensional (length, width, and
height) parameters, however “time” is the other parameter in 4D printing. It is well-known
that an object which is made by 3D printing can change its shape or properties over time as
a reaction to the applied external stimulants. For example, 4D-printed biomedical scaffolds
stretch over time after implantation in the body, and this process reduces the surgical
incision, which is beneficial to a patient’s recovery [28]. Thus, 3D printing technology is
combined with the stimulating responsive materials in 4D printing. External effects such
as heat, light, and electric current, etc., are effective for the shape changes of 3D objects by
time. It was proposed that 4D printers will be used in industries such as medicine, robotics,
textiles, construction, etc., in the future.
4D-printed PLA-thermochromic pigment composites were used to fabricate shape-
color dual-sensitive objects. The effects of the process parameters and stimulating methods
were examined on 4D deformation and discoloration properties and it was found that
stimulus conditions, strain rate, and color transition can be controlled simultaneously by
changing or optimizing many process parameters [172]. 4D-printed PLA-polyethylene
glycol (PEG) composites were developed to maintain the shape memory effect [173]. PEG
was incorporated to the PLA matrix in the composite to give a plasticizing effect which will
cause the movement change of the polymer chains, resulting in different shape memory
behaviors. Initially, commercial PLA pellets were dried and mixed with 10% to 30% PEG
to obtain 3D-printable PLA-PEG composite filaments. Then, these filaments were 3D-
printed to give specific arcs, as seen in Figure 21. It was reported that a 4D object was
produced which would provide a localized thermal recovery according to PEG content in
the composite [173].

Figure 21. (a) Four-dimensional (4D)-printed PLA arc and (b) flattened temporary shape (Reproduced with permission
from Reference [173], copyright 2019, Nature).
Coatings 2021, 11, 390 29 of 42

4D-printed carbon nanotube (CNT)-reinforced PLA was fabricated, which could be de-
formed by the application of DC electric current [174]. The temperature-dependent volume
resistance, electroactive shape memory properties of the 4D object were investigated. It
was found that the change in temperature and volume resistance of PLA-CNT composites
was due to the CNT contact resistance variation and PLA matrix shrinkage. In addition,
the 0◦ /90◦ sample had a higher degree of homogeneity and faster recovery in comparison
with the 0◦ sample [174].
The shape memory behavior and recovery power of PLA-silicone elastomer matrix
composite was studied by using 3D-printed PLA circular knitted preforms and silicone
elastomer matrix composites, as seen in Figure 22. The effects of mesh angle, tube wall
thickness, and shape recovery temperature on the shape memory behavior were inves-
tigated. The shape recovery temperature and braided microstructural parameters were
found to have significant effects on preform shape memory behavior. The incorporation of
the silicone elastomer matrix to the composite increased the radial compression load and
also the shape recovery strength [175].

Figure 22. Shape memory behavior of an open 4D-printed braided tube preform/silicone elastomer matrix composite with
the braiding angle of 30◦ and three braiding layers at the shape recovery temperature of 70 ◦ C (Reproduced with permission
from Reference [175], copyright 2018, Elsevier).

4.9. Other Applications

4.9.1. Smart Textile Applications
The integrated or tailored production of smart and functional textiles is important to
refrain from the unnecessary use of water, energy, chemicals, and also to minimize the waste
to improve ecological footprint and productivity. Some PLA composites were fabricated
for this purpose. For example, the adhesion performances of 3D-printed PLA, PLA-carbon
black composite, and PLA-carbon nanotube composite onto various textile fabrics were
investigated in order to develop smart and functional textiles. The adhesion forces were
quantified using an innovative sample preparation method combining with the standard
method of peeling, as seen in Figure 23. The parameters such as 3D printing process
parameters, fabric, and filler type added to the PLA polymer were examined and the
results indicated that various 3D printing process variables such as extruder and platform
temperature and printing speed could have a substantial effect on the adhesion strength of
polymers to fabrics. In addition, it has been observed that PLA and its composites have
high adhesion strength to fabrics made of PLA itself [176].
Coatings 2021, 11, 390 30 of 42

Figure 23. Adhesive and cohesive forces, with deposition of polymer as an adhesive to fabric as an adherent (Reproduced
with permission from Reference [176], copyright 2017, Elsevier).

When the direct deposition of polymeric materials onto textiles through 3D printing
was applied, the maintenance of equal or better mechanical resistance, durability, and
comfort than those of the plain textile substrates is a great challenge. In a study, non-
conductive PLA and conductive PLA-carbon composite filaments were deposited onto
polyethylene terephthalate (PET) white woven fabrics through 3D printing process, as seen
in Figure 24 [177]. It was found that the deposition process affects the tensile properties
of the printed textile due to the lower flexibility and diffusion of the printed polymer
track through the PET fabric, leading to a weak adhesion at the polymer/textile interface.
Moreover, the printing platform temperature and fabric properties affected the tensile
and deformation properties of the 3D-printed PLA on PET textiles. It was found that the
incorporation of conductive fillers into the PLA did not affect the tensile properties of the
extruded polymeric materials [177].
In another study, the same group tried to optimize the adhesion of 3D-printed PLA
onto PET-woven fabrics through modelling using textile properties [178]. The thermal
conductivity, surface roughness, and mean pore size properties of the uncoated PET-woven
fabrics were determined using the “hot disk”, profilometer, and capillary flow porosimetry
methods. The same properties were also determined after the 3D printing process. It
was observed that the higher roughness coefficient, mean pore size, and lower thermal
conductivity of the PET-woven textiles improved the polymer/fabric adhesion properties.
However, the adhesion strength decreased by half after the washing. The rougher and
more porous textile structures demonstrated better durability. These results were explained
by the surface topography properties of the PET fabrics, which determined the anchorage
areas between the printed PLA layer and the PET fabrics [178].

Figure 24. Fused deposition modeling process onto textiles (Reproduced with permission from Reference [179], copyright
2020, MDPI).

The wear resistance of 3D-printed conductive PLA composite monofilaments onto PET
fabrics was also studied by the same group [179]. It was found that the type of pattern and
Coatings 2021, 11, 390 31 of 42

the printing bed temperature significantly affected the abrasion resistance of the 3D-printed
final product. Conductive PLA-printed PET had a higher abrasion resistance and lower
weight loss after abrasion compared to the original PET fabrics due to the higher capacity
of the surface structure and stronger fiber-to-fiber cohesion. The mean pore size which was
localized at the surface of the 3D-printed PLA onto PET was five to eight times smaller
than the PET textile. Moreover, the abrasion process had a considerable impact on the
electrical conductivity of 3D-printed conductive PLA onto PET textile [179].

4.9.2. Environmental Applications

Membranes, coated meshes, and porous fabrics having super-hydrophilic, super-
hydrophobic, and super-oleophilic properties are used for the separation of oil/water
mixtures, and the production of such porous webs are the subject of 3D printing with PLA
composites. In a study, the surface polymerization using Fe (II)-mediated redox reaction
was applied to obtain PLA-Fe hydrogel composite, as seen in Figure 25, in order to be used
to separate oil-in-water mixtures with an efficiency of approximately 85% [180]. In another
study, a 3D-printed hybrid PLA-graphene oxide (GO)-chitosan (CS) composite sponge
filter was prepared to remove dyestuff from water as seen in Figure 26. The performance of
this sponge on the dye-removal mechanism such as water adsorption, temperature, contact
time, and pH was investigated, and it was found that good extraction of “Crystal Violet”
dye was possible with this novel sponge from solutions [181].

Figure 25. (a) Typical schematic illustration of the fused deposition modeling (FDM) 3D printing
process. (b) Design of 3D printing orthogonal mesh with parameter of diameter, layers, and spacing.
(c,d) Optical and SEM photographs of Fe/PLA composites mesh with through-hole (Reproduced
with permission from Reference [180], copyright 2019, MDPI).

Similarly, a PLA-metal-organic-frameworks (MOFs) layer was fabricated to remove

malachite green (MG) in wastewater [182]. In situ step-by-step growth of Cu-MOFs on
the surface of the 3D-printed parts was carried out. PLA skeleton and the prepared
Cu-MOFs/PLA layers were characterized by SEM and XRD. The adsorption capacity of
Cu-MOFs/PLA films towards MG was high, and more than 90% removal efficiency was
determined in 10 min. Moreover, used Cu-MOFs/PLA films were found to be recyclable
over more than five times after washing with acetone [183].
Coatings 2021, 11, 390 32 of 42

Figure 26. Schematic description of the fabrication process of the PLA-GO-CS composite (a) GO
aqueous solution. (b) The mixture of CS and GO solution. (c) PLA scaffold was put into the mixture
along with the first lyophilization. (d) PLA-GO-CS immersed in the sodium hydroxide solution
(10%). (e) PLA-GO-CS after the second lyophilization. (f) The digital photo of the real PLA-GO-CS
scaffold (Reproduced with permission from Reference [181], copyright 2018, Elsevier).

3D-printed PLA composites were used in a water-filtration system to remove arsenic

contamination which was a threat to the public [182]. Iron (III) oxide was used as an
adsorbent for arsenite located in the internal surface areas of filters. The effects of the
controlled surface area on the flow rate and the deposition of the adsorbent properties were
examined and isotherm studies were carried out to quantify the adsorption of arsenic on
the 3D-printed filtration system [182].
A 3D-printed PLA-carbon black composite with controlled internal porosity was
used to remove model VOC contaminants (benzene, toluene, and ethyl benzene) from
water [184]. The pseudo-second-order rate constants for the VOC sorption were found to
increase with a decrease of internal pore size of this 3D-printed sorbent [185].
When Chlorella vulgaris is immobilized in alginate beads, it is useful for the reduction
of several chemical and microbial contaminants present in the highly polluted waters.
However, alginate beads had a short shelf-life in the natural environment and a 3D-printed
PLA composite device was used for the same purpose [184]. The growth kinetics param-
eters and the bioremediation capacity of immobilized microalgal cells were determined,
and it was found that the successful bioremediation of the target water was possible using
the novel device, where all inorganic nitrogen forms and total phosphorus were reduced at
least by 90% after 5 days of bioprocess in an agitated bioreactor. Standardized cytotoxi-
city tests using “Allium cepa” seeds have shown the effectiveness of the bioremediation
process [184].

4.9.3. Luminescence and Fluorescence Applications

Cadmium sulfide selenide-grade alloy quantum dots (CdSSe-QD) were embedded
into the PLA matrix and PLA-CdSSe-QD composite was 3D-printed to give a fluorescent
object. The photoluminescence, absorbance, mechanical tests, and thermal analysis were
performed on the 3D-printed objects and it was found that the Tg of composite decreased
in comparison with the pure PLA, as well as the ultimate tensile strength for the highest
CdSSe-QD concentrations used in the composite [186].
Luminescent bioplastic composite filaments which will be used for 3D printing
were produced using PLA and samarium-doped magnesium aluminate phosphorus
(MgAl2 04 :Sm3+ ) after modifying the inorganic powder with 3-aminopropyl triethoxysilane
Coatings 2021, 11, 390 33 of 42

to improve its compatibility with PLA. Later, PLA-MgAl2 O4 :Sm3+ composite filaments
containing different amounts of phosphorus were produced by melt extrusion process.
The incorporation of the phosphorus fillers reduced the melting, glass transition, and
crystallization temperatures of pure PLA and increased the mechanical strength of the
composite. After 3D printing, it was observed that the luminescent density increased as
the phosphorus ratio increased [187].
Green luminescence properties were introduced to 3D-printed PLA composite by
incorporating SrAl2 O4 :Eu2+ , Dy3+ powders into the PLA matrix together with SiO2 . PLA-
powder composite filaments were prepared by melt extrusion, as seen in Figure 27. It was
determined that the modified salt particles were evenly distributed in the PLA matrix and
the mechanical properties were also improved. Moreover, the modified composite showed
both hydrophobic and antibacterial properties [188].

Figure 27. The microscopic image of the composite filament of 1 wt.% modified phosphors and spline with 1 wt.%
unmodified phosphors (a) and different content modified phosphors (b–d) under UV light (b: 1 wt.%, c: 2 wt.%, d: 3 wt.%)
scaffold (Reproduced with permission from Reference [188], copyright 2020, Wiley).

4.9.4. PLA Composite Modifications

In some studies, post-treatments were especially applied to 3D-printed PLA compos-
ites. For example, surfaces of anti-bacterial scaffolds made of PLA filled with copper, bronze,
and silver particles was treated with acetic acid to create a thin porous network [189]. The
thermal, mechanical, and biological characteristics including bioactivity and bactericidal
properties of these scaffolds were evaluated, and it was found that a significant increase
(~20–25%) occurred in the antibacterial properties and bioactivity (~18–100%). It was
suggested that there was a synergetic effect of reinforcement of metallic/metallic alloy
particles and acid treatment [189].
In the bone engineering field, 3D-printed scaffolds made of PLA-halloysite nanotubes
(HNT) loaded with zinc nanoparticles (PLA + HNT + Zn) had a hydrophobic surface and
was coated with two layers of fetal bovine serum (FBS) on the sides and one layer of NaOH
in the middle [190]. A layer of gentamicin was also coated on the outermost layer against
bacterial infection. Surfaces became hydrophilic afterwards and enhanced cell adhesion.
These scaffolds had high mechanical strength and showed an osteo-inductive potential.
The external coating of antibiotics preserved the previous osteogenic properties of the
scaffold but also resulted in reduced bacterial growth [190].
A coating or gluing of the 3D-printed PLA-wood composite parts is required and
dielectric barrier discharge (DBD) plasma treatment was applied to activate the object
surface and improve its coating capabilities in a study [191]. The formation of carbonyl and
carboxyl groups was detected by XPS measurements. Laser scanning microscopy showed
a surface roughening after the treatment. Contact angles of water and diiodomethane
decreased and corresponding surface free energy increased significantly after the plasma
treatment. An improvement was seen for the adhesion tests to the plasma-treated 3D
Coatings 2021, 11, 390 34 of 42

object after applying the acrylic dispersion, where the pull-off strength increased consider-
ably [191].

5. Conclusions
In this review, the chemistry and properties of the pure PLA and its main disad-
vantages as a feedstock for FDM-based 3D printing were initially given. The need and
requirements for the preparation of the PLA composites which will be used in 3D printing
applications in several industries as well as the production methods of the PLA composites
were discussed. In general, 3D-printed PLA composite production is a two-step process,
where the selected additives for a specific application are incorporated with the PLA matrix
polymer, mostly using the melt extrusion (or sometimes solvent precipitation) process to
obtain the PLA composite feedstock filaments in the first step. These filaments are then
used in a FDM-based 3D printer under controlled conditions, where raster angle, raster
width, layer thickness, polymer flow rate, the temperature of the nozzle, and the medium
are kept in predefined conditions in order to obtain the targeted 3D object in the second
step. 3D printing is a sensitive process since the printing orientation and temperature
history of the interfaces are important to determine the adhesion strength between the
deposited layers, which will later define the total mechanical strength of the object.
It was realized that tissue engineering and bone repair applications in the biomedical
industry are very important fields for the use of the 3D-printed PLA composites since
biodegradable specific body parts for personal usage which will not harm the body can be
produced easily and accurately by 3D printing. The utility of 3D-printed PLA composites
in the medical field is constantly expanding and many useful implants and restorations
were developed in the last decade. It is possible that 3D-printed PLA composite scaffolds
will replace the traditional titanium alloy scaffolds and bioactive ceramic scaffolds in the
near future. Moreover, 3D-printed PLA composite prototypes play an important role in the
training of surgeons and medical students. The use of PLA in bioprinting is an original and
important research area. However, there are many problems that remain unresolved in the
medical field, for example, ensuring the required mechanical strength for the 3D-printed
PLA objects in the body is always a challenging issue. Other problems are to control the
rate of degradation (dissolution of PLA composite in the body) and the effective pore size
of the scaffolds, especially for bone applications.
The second important field for the applications of the novel FDM-based 3D-printed
PLA composites are electrical conductivity, electromagnetic, sensor, and battery industries.
The incorporation of many types of carbon-based and also other conductive additives
to PLA resulted in improved properties but controlling the porosity and conductivity
between particles and increasing the mechanical strength is still a challenge. The use of the
3D-printed PLA composites in automotive, aviation, and space industries are expanding
in order to decrease the weights of the vehicles, but maintaining the mechanical strength,
high abrasion resistance, and smoothness of the surface of the 3D-printed part still needs
development.
The popularity of 4D printing has been increasing in the last years, where 3D-printed
PLA polymer composites having shape memory properties are used and time is the other
dimension. 4D-printed objects change their shapes with the external stimulus effects such
as heat, light, electricity, etc., and return to their original state after the effect disappears.
The use of PLA composites in 4D printing applications is a promising research area for the
future. Smart textiles and environmental separation applications of the 3D-printed PLA
composites are two important industrial fields for the development of novel 3D-printed
PLA composite products.

Funding: This research received no external funding.

Institutional Review Board Statement: This study did not involve humans or animals.
Informed Consent Statement: This study did not involve humans or animals.
Coatings 2021, 11, 390 35 of 42

Data Availability Statement: Data sharing not available.

Acknowledgments: This research did not receive any specific grant from funding agencies in the
public, commercial, or not-for-profit sectors.
Conflicts of Interest: Authors declare no conflict of interest.

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