Progress in Polymer Science 98 (2019) 101162

Contents lists available at ScienceDirect

Progress in Polymer Science

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

Advances in 3D printing of thermoplastic polymer composites and

nanocomposites
Arnaldo D. Valino a,b , John Ryan C. Dizon a,c , Alejandro H. Espera Jr. a,d , Qiyi Chen a ,
Jamie Messman e , Rigoberto C. Advincula a,∗
a
Case Western Reserve University, Department of Macromolecular Science and Engineering, 2100 Adelbert Road, Kent Hale Smith Bldg, Cleveland, OH
44106, United States
b
Mechanical Engineering Department, College of Engineering, Adamson University, Manila City 1000, Metro Manila, Philippines
c
Additive Manufacturing Research Laboratory, Industrial Engineering Department, College of Engineering and Architecture, Bataan Peninsula State
University, City of Balanga, Bataan, 2100, Philippines
d
Electronics Engineering Department, School of Engineering and Architecture, Ateneo de Davao University, Davao City, 8016, Philippines
e
Department of Energy, Kansas City National Security Campus – Honeywell FM&T, Kansas City, MO 64147

a r t i c l e i n f o a b s t r a c t

Article history: Commodity thermoplastics and thermoplastic composites are staples in Additive Manufacturing (AM).
Accepted 11 September 2019 Their use is widespread and accounts for the largest volume of 3D printed materials. Accessible prop-
Available online 17 September 2019 erty ranges of current material formulations are limited, and thus there is high interest in extending AM
to high-performance engineering polymers and nanocomposites that have yet to gain wide commer-
Keywords: cial acceptance in AM. Current applications of high-performance thermoplastic polymers are limited to
Additive manufacturing
adaptations from conventional plastics processing such as injection molding, thermoforming, extrusion,
Thermoplastic composites
and others. Thermoplastic composites can be categorized into particle-, fiber-, and nanomaterial-based
Polymer blends
Processing techniques
composites as well as polymer blends. The importance of these different composite systems to AM is
3D printing discussed in this review. Also reviewed are trends in instrument development such as in-nozzle impreg-
nation, dual print heads, and higher temperature FDM that improve printing of thermoplastic composites.
An overview of newer types of AM techniques allowing higher filler loading for thermoplastic compos-
ites like liquid deposition modeling (LDM) sometimes known as direct ink writing (DIW) are discussed.
Finally, a perspective is given on the important parameters and standards needed to make AM printed
objects from polymer composites more effective in cost/performance ratio.
© 2019 Elsevier B.V. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 2
2. Processing techniques of thermoplastic and thermoplastic composites . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
2.1. Comparison of injection molding over additive manufacturing . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

Abbreviations: 1D, One-Dimensional; 2D, Two-Dimensional; 3D, Three-Dimensional; ABS, acrylonitrile butadiene styrene; Al2 O3 , Alumina; AM, Additive Manufacturing;
C-30B, Cloisite 30B; CAD, Computer-Aided Design; CB, Carbon Black; CF, Carbon Fiber; CFRP, carbon-fiber reinforced thermoplastic; CNC, Computer Numerical Control;
CNT, carbon nanotubes; Cu, Copper; DCM, dichloromechane; DIW, Direct Ink Writing; DPS, Dual Particle Size; FDM, Fused Deposition Modeling; Fe, Iron; G, Graphene;
G-PLA, Graphene doped polylactic acid; G’, storage modulus; GO, Graphene Oxide; GPa, Gigapascal; HA, Hydroxyapatite; HA-PE, Hydroxyapatite-reinforced polyethylene;
HDPE, high-density polyethylene; HPP, High Performance Polymers; JFRTP, jute fiber reinforced thermoplastic composites; L/D, Length over Diameter Ratio; LBM, laser beam
melting; LDM, Liquid Deposition Modeling; mm, millimeter; MPa, Megapascal; MPP, melamine polyphosphate; MWCNT, Multi-walled carbon nanotubes; Nylon, Polyamide;
PBF, Powder Bed Fusion; PBT, polybutylene terephthalate; PCL, polycaprolactone; PDMS, Polydimethylsiloxane; PEEK, polyether ether ketone; PEG, polyethylene glycol;
PEI, Polyetherimide; PLA, polylactic acid; POE-g-MAH, maleic anhydride grafted poly (ethylene 1-octene); PP, polypropylene; PS, Polystyrene; PVA, polyvinyl alcohol; SCG,
homopolypropylene; SEBS-g-MA, styrene ethylene butylene styrene with maleic anhydride graft; SEM, scanning electron microscope; SLA, Stereolithography; SLBM, selective
laser beam melting; SLM, Selective Laser Melting; SLS, Selective Laser Sintering; SPS, Single Particle Size; SrTiO3 , Strontium Titanate; .stl, Surface Tessellation Language; TCP,
tricalcium phosphate; TiO2 , titanium dioxide; TPS, Triple Particle Size; TPU, polyurethane; UTM, universal testing machine; UV, ultraviolet; xGnP, Functionalized graphene
nanoplatelets; ZnO, Zinc Oxide; ␮m, micrometer; ␶, yield stress; %vol, percent volume.
∗ Corresponding author.
E-mail address: rca41@case.edu (R.C. Advincula).

https://doi.org/10.1016/j.progpolymsci.2019.101162
0079-6700/© 2019 Elsevier B.V. All rights reserved.
2 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162

3. Additive manufacturing processing techniques and materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

3.1. Additive manufacturing process flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
3.2. Fused Deposition Modeling (FDM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2.1. Recent materials used for Fused Deposition Modeling (FDM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
3.2.2. Advanced thermoplastic composites and nanocomposites used in FDM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5
3.3. Selective laser sintering (SLS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3.1. Materials used for selective laser sintering (SLS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.3.2. Advanced thermoplastic composites and nanocomposites used in SLS . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
3.4. Selective laser melting (SLM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.5. Materials used for SLM and LBM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10
3.6. Liquid deposition modeling (LDM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.6.1. Materials used for liquid deposition modeling (LDM) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11
3.6.2. Advanced thermoplastic composites and nanocomposites used in LDM nanomaterial reinforced composites . . . . . . . . . . . . . . . . . . . . 11
4. Comparison of different processing techniques applicable to AM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
5. Comparison of FDM, SLS, and LDM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
6. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
6.1. Aerospace . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
6.2. Medical parts and devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
6.3. Rapid tooling and rapid molding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16
7. Challenges with the use of thermoplastic composites in AM . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
7.1. Defects due to fillers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
7.2. 3D printer design limitations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
8. Summary and conclusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Disclaimer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18

1. Introduction Table 1
AM Abbreviations and their definition.

Polymer materials are of central importance to Additive manu- Abbreviations AM Type Definition Ref.
facturing (AM) and eventually for fabrication of original equipment FDM Fused Deposition FDM involves deposition of [7]
manufacturer (OEM) parts. The majority of materials currently Modeling melt extruded layers of
in use, can be divided into two classes, thermoplastics and ther- material through a nozzle
using a feedstock filament
moplastic composites. The methods for employing high volume
SLA Stereolithography SLA used a liquid resin [4]
polymer thermoset and elastomer materials for AM are just Apparatus photocuring processes
recently emerging. The aim of this review paper is to provide SLS Selective Laser SLS involves sintering of [5]
an overview of recent advances of thermoplastic and composite Sintering layer-by-layer powdered
materials in 3D printing, including the need to improve their per- materials.
SLM Selective Laser SLM involves polymer [6]
formance and properties which is key to growing the technological
Melting powder and laser
impact and marketability of polymer-based AM. beam-based
Additive manufacturing or 3D-printing is characterized as a pro- manufacturing process
cess of joining layers of materials to create 3D objects from a Surface LDM Liquid Deposition LDM deposits polymer [8–10]
Modeling using a solvent or a UV
Tessellation Language (.stl) file designed from a computer-aided
photocurable resin
design (CAD) [1] program or digitized images. Objects or parts are – Material jetting It involves droplets of bulk [1]
sequentially built up one layer at a time on an X–Y substrate plane material
surface [2] and added to the preceding layer (i.e. in the Z-direction). – Binder jetting It involves powder [1]
AM was first demonstrated by Charles Hull in 1986 who created an material that was joined by
a liquid bonding agent
apparatus capable of generating 3D objects [3]. Since then, various
technologies have been introduced in additive manufacturing, as
shown in Table 1.
The advantage of AM is its ability to create complex object Finite element methods and computer-aided engineering tech-
geometries composed of multiple material constituents – two char- nologies can be used to create design that enables lightweight and
acteristics that are not easily achieved with traditional subtractive high strength structures [13].
manufacturing (such as CNC milling) that are limited due to the An important challenge in the field of AM is the lack of advanced
difficulty of material subtraction from bulk monoliths [4]. Addi- polymer materials and available nanocomposites to match the
tive Manufacturing opens new possibilities to apply geometrical performance and fabrication requirements. Thus, research efforts
design (rather than only intrinsic material properties) to engineer on academic, government and industrial institutions have been
properties of manufactured devices [6]. By reducing the design- focused on developing new high-performance materials, improv-
manufacturing cycle, AM also provides the possibility of reducing ing the efficiency and speed of the process, and widening the
production cost and increasing the effectiveness of the manufactur- range of its properties and application [14]. The introduction and
ing process [11] in an on-demand production process. AM reduces development of novel polymers, additives, and other thermoplastic
material waste by approximately 90% as compared to subtractive composites for AM, aims to extend the impact of AM on the fabrica-
manufacturing [2]. It also has potential to create lightweight but tion of end-product components [15] and real parts replacement.
high strength structures, for example, for the aerospace or automo- A common issue in using commodity thermoplastic products in
tive industries, military supply chain and logistics, art replication AM is their lack of strength and functionality as high load-bearing
or education or structural models in the area of architecture [12]. parts. The use of engineering plastics and high-performance poly-
 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
mers (HPP) is desirable, but the cost and the requirement for
more demanding processing conditions (such as higher temper-
atures) present a challenge, especially if high build volumes are
desired. Common matrix materials used in AM are thermoplastic
materials, to which filler components such as fiber-, particle- or
nanoparticle-based materials can be added for new material for-
mulations. Traditional polymer blending has been used to combine
the strength of two polymers or reinforce the weaker polymer with
a high-performance polymer. It can also be done with the use of
compatibilizers, telechelic copolymers, plasticizers, and other syn-
ergistic additives [16]. In a review by Dizon et al., it was emphasized
that mechanical properties of 3D printed parts are indeed affected
by the intrinsic material properties (before printing), the chosen
manufacturing method, and build orientation among many other
factors. Thus it is essential to constantly focus on improving the
intrinsic properties of polymer materials from molecular to the
macroscopic level [17].
In this review, we present, analyze and summarize trends
related to advances in thermoplastic composites used in AM
methods. The different types of 3D printing methods that uti-
lize commodity polymers and thermoplastic composites are first
discussed. Next, an analysis and summary of the preparation,
processing, and properties of improved thermoplastic compos-
ites based on the filler types such as particle-based, fiber-based,
nanomaterial-based, and polymer blends with high-performance
polymers is presented. The emphasis is on outlining progress in
the development of materials used in AM through recent litera-
ture. The limitations of current technologies and a perspective on
materials preparation, performance requirements and applications
are also discussed.
2. Processing techniques of thermoplastic and
thermoplastic composites
In this section, a brief background on conventional process-
ing techniques of thermoplastic and thermoplastic composites is
provided to help the reader better understand the particular differ-
ences and features of AM methodologies.
Extrusion is the most common method of melt-blending ther-
moplastic and thermoplastic composites through mixing, melting,
and reaction of polymer materials through a cylinder with rotating
screw at higher temperature [18–20]. Injection molding allowed
the thermoplastic and thermoplastic composites material to flow
at elevated temperatures and pressure inside a cylindrical chamber,
exiting unto a mold [19]. Tape laying or tow placement utilizes the
principle of fusion joining in which interface between two layers
were bonded through heat and pressure treatment. Pultrusion is a
thermoplastic composite manufacturing technique in which fiber
reinforcement is impregnated in a thermoplastic resin bath [19]. By
pultrusion, many lightweight, corrosion-resistant, and low electri-
cally conducting thermoplastic and thermoplastic composites can
be made [24]
Filament winding is a continuous fiber reinforcement in the
form of roves or monofilament around a rotating core or man-
drel [19]. Hoop winding, helical winding, and longitudinal winding
are within the winding capability of specially designed machines
with the synchronized speed of the mandrel, winding angles, and
fiber-reinforced placement [24]. By contrast, in-nozzle impregna-
tion utilizes modified FDM print heads in order to impregnate
molten filaments with fibers inside the nozzle before printing using
separate print heads [25,26]. The dual print head design utilizes two
stages of printing using two separate heads. The first head prints
the thermoplastic matrix, while the second head prints the fiber
reinforcement [27].
3
Mechanical fastening requires designers to cut a hole on parts in
order to facilitate a fastening mechanism between components. The
induced hole into components is susceptible to stress concentration
which is an initial concern to creep resistance of the material [19].
Melt fusion is a fusion bonding process that utilizes heat and pres-
sure application with new surface chemistry for reprocessing and
promoting good adhesion properties with the thermoplastic. Melt
fusion becomes more important than mechanical fastening when
high loads and high reliability are needed in joining components
[19].
Solvent casting is a polymer processing technique where a poly-
mer is dissolved in an organic solvent and deposited layer by layer
[8].
Powder processing and mixing can be categorized into three,
such as separate grains, composite grains, and coated grains. In
separate grains, polymer powder acts as a binder while the struc-
tural grains can either be metal or ceramic [28]. In order to obtain
composite grains, a grain binder and a structural material are incor-
porated into the same composite grain, which can either be done
by melt blending, dissolution-precipitation or solvent evaporation
[28,31]. In melt blending, both binder and structural grains are fed
into an extruder to produce pellets. The pellets are then ground to
form a fine powder of composite material. Coated grains are the
combination of binder and a structural material; the term coated
grains are usually applied in nanomaterial-based composites [28].
2.1. Comparison of injection molding over additive
manufacturing
Research undertaken by Krishna and Gundeti focused on the
comparison of components fabricated by Fused Deposition Mod-
eling (FDM) and injection molding using the parameters such as
dimensional accuracy, surface roughness manufacturing time, and
manufacturing cost.
Table 2 provides a summary of the comparative analysis of com-
ponents fabricated by injection molding and 3D printing. In terms
of dimensional accuracy, 3D printed PLA was better than with ABS
injection molded parts, and 3D printed ABS parts. In terms of sur-
face roughness, electronic parts and starter box that was fabricated
using injection molding has a smooth surface as compared to PLA,
and ABS printed parts. Rough surface of 3D printed parts is due
to layer-by-layer addition in 3D printing that results in a staircase
effect on the surface parts.
Fabrication time with 3D printing includes loading time, melting
time and printing time while fabrication time for injection mold-
ing includes mold open time, mold closing time, injection time,
cooling time and ejection time [23]. Injection molding manufac-
tured parts much faster as compared with 3D printing. However,
the design of mold and mold making takes days to months. With
the use of filled polymer composite materials in injection molding,
sometimes the high viscosity and inhomogeneous distribution of
the filler materials may prevent the fabrication of higher quality
parts.
3. Additive manufacturing processing techniques and
materials
This section provides an overview of the different AM processes
that currently use thermoplastic materials. Recently developed
thermoplastic composites for each AM process are also highlighted
in this section.
3.1. Additive manufacturing process flow
The general AM process starts with design conceptualization
via preparation of a 3D model using computer-aided design (CAD)
4 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162

Table 2
Comparison of Components Fabricated by Injection Molding and Additive Manufacturing [23].

3D Printing
Specifications Injection Molding
PLA ABS

Dimensional Accuracy for Electronic Casing (average variations) 0.068mm 0.066mm 0.13mm
Dimensional Accuracy for Starter Box (average variations) 0.165mm – 0.198mm
Surface Roughness Value 0.45 microns 2.34 microns 3.53 microns
Manufacturing Time
Electronic Casing (4 pieces) 68 seconds 42 minutes
Starter Box 76 seconds 6 hours and 15 minutes

Fig. 1. Additive manufacturing (AM) process flow.

modeling software. Parts can be built from the CAD model by con-
verting to an. STL file format. In the. STL format, triangular facets can
be used to simulate the shape of the objects [1]. Fig. 1 portrays the
overall additive manufacturing process flow regardless of the AM
system used [34]. Slicing software is used to prepare the model for
printing based on a specific AM system. The slicing software pro-
vides the interface platform between the specific AM system and
computer to produce quality parts by optimizing various process
parameters in the AM system [35]. The slicing software converts
the. STL file into an appropriate file type that applies to specific 3D
printers and parameters (G-code) [14]. The universality of the CAD
file format for the various AM methods (despite their use of dis-
tinct layer-by-layer deposition or printing methods) is a significant
advantage of AM.
From here on, AM techniques will be divided into sections based
on the most common methods, as well as examples of particles,
fibers, polymers, nanoparticles fillers that have been used to make Fig. 2. Schematic representation of a typical FDM set up. [11], copyright 2015.
composites. The improvement in properties and potential pitfalls Reproduced with permission from from Elsevier Ltd.
are also discussed. It should be noted that anisotropic thermo-
mechanical properties are obtained based on the print direction. first layer deposition, the build platform moves along the negative
However, other unique properties may be observed based on their Z-axis to facilitate deposition of the succeeding layer. Each process
respective chemical, thermal, and post-processing properties that is performed repeatedly until the 3D printed part is completed [11].
change with the particular AM method as highlighted. The poten-
tial of using nanofiller materials and their systematic use in the 3.2.1. Recent materials used for Fused Deposition Modeling (FDM)
methods above will be specially noted. The most common commercially available thermoplastic mate-
rials for FDM filaments include acrylonitrile butadiene styrene
3.2. Fused Deposition Modeling (FDM) (ABS) and polylactic acid (PLA), polyvinyl alcohol (PVA), poly-
caprolactone (PCL) and polyamide (Nylon) [26]. High-performance
In the late 1980s, this deposition method was first developed engineering thermoplastic such as polyether ether ketone (PEEK)
and subsequently commercialized by Stratasys in 1990. FDM has and Polyetherimide (PEI) are also commercially available [14]. The
been used to make 3D printed parts through an extrusion and layer- PEEK and PEI filaments are commercially available in 3D4Makers
by-layer deposition of thermoplastic materials [1]. As shown in [36a] and 3DXTech [36b], respectively. These high-performance
Fig. 2, similar to extrusion, filaments are heated until a viscous semi- engineering polymers offer superior mechanical and thermal prop-
liquid state is reached at the extrusion nozzle. The nozzle extrudes erties but at a relatively high cost. Also, not all commercially
the thermoplastic material layer by layer onto the print bed where available 3D printers can handle the high-temperature demand of
layers are fused and allowed to solidify (quenched) to produce the these high-performance engineering polymers.
final part [12]. The heated head moves through the print bed (X–Y Table 3 summarizes some commercially available thermoplas-
axis) to generate the tool path for the first layer of material. After the tic composite filaments. Particles, fiber, and nanomaterials are
 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
Table 3
Commercially Available Thermoplastic Composite Filaments.
Company Product
3DXNanoTM ESD ABS + Carbon
Nanotube Filament
3DXTech [36b]
3DXNanoTM ESD PETG + Carbon
Nanotube Filament
CarbonXTM Carbon Fiber Ultem 3D
printing Filament
Carbon Fiber Based Filament (Matrix:
Ultem, PC, Nylon, PLA, PETG, ABS)
Functionalize F-Electric [36c] Functionalize F-Electric filament (PLA
& Carbon Nanotube)
MWCNT1 Multi-Walled Carbon
Filabot [36c]
Nanotube Pellets
Graphite Infused Filament—ABS Matrix
Based Filament
Conductive Graphene Filament (Matrix
Black Magic 3D [36d] used: HIPS, Nylon, PLA)
Ferro-Magnetic PLA
G6-Impact HIPS-Carbon
Fiber-Graphene Filament
usually used as reinforcement for FDM thermoplastic filaments.
During the layer-by-layer deposition, it is important to limit the
size of the fillers based on nozzle size in order to avoid nozzle
clogging. Also, aggregation of fillers can cause clogging at the noz-
zle. Therefore, research has often focused on the determination
of percolation percentage composition of fillers that will avoid
aggregation. There is the possibility of using more nanofillers to
overcome such difficulties by using a different approach such as
liquid deposition modeling or dispersing the nanofillers in the poly-
mer matrix through solvent dissolution. However, higher costs and
any non-mitigating effects based on the aversion of some end users
on using nanomaterials have to be addressed. Recently, it has also
been reported that aggregation of fillers in carbon nanotubes (CNT)
have caused nozzle clogging and flux instability. Graphene also has
some limitations such as non-uniform particle size and tempera-
ture deflection due to poor filler distribution within the polymer
matrix [36c].
3.2.2. Advanced thermoplastic composites and nanocomposites
used in FDM
3.2.2.1. Particle reinforced composites. There have been advantages
reported for using particle filler materials in terms of tensile
strength, Young’s modulus, and elongation. The addition of par-
ticle filler materials is common and has been applied to more
isotropically and conventionally-fabricated polymer composite
parts. With 3D printing, the flow properties, quenching proper-
ties, size of voxelization, layer thickness, can cause problems with
using particle-based thermoplastic composites. In FDM 3D printing,
this includes a variety of filament diameter, nozzle clogging, layer
delamination and overfilling of materials. The examples below
exemplify particle filler materials considered to be in the conven-
tional range (10 s–100 s of microns in size and aspect ratio). The
potential of using nanofiller materials and their systematic use in
FDM will be covered in the latter part of this review.
3.2.2.1.1. Iron/nylon composites. Metal-polymer composites
using nylon as the matrix with iron (coarse: 50–80 ␮m and fine:
<30 ␮m) as metal fillers have been reported [37]. The melt blend-
ing of iron and nylon were performed using a single screw extruder.
Metal-polymer composites with a particle size of 50–80 ␮m exhib-
ited superior tensile modulus and stress as compared to particle
sizes of <30 ␮m at the same volume fraction. Consistency in terms
of particle size greatly affected the properties of the composites.
Metal-polymer composites with a large polydispersity in parti-
cle size resulted in a lower tensile modulus, tensile strength, and
percentage elongation. The highest tensile modulus and tensile
5
strength were observed with 30:70%vol iron/nylon composites.
Tensile strength and modulus of the iron/nylon composites were
3.87 MPa and 54.52 MPa, respectively [37].
3.2.2.1.2. Iron/acrylonitrile butadiene styrene (ABS) composites.
Highly metallic iron-filled composites for FDM filament were pre-
pared by using ABS plastic as matrix and iron as metallic fillers. The
maximum tensile strength of 12.8 MPa was achieved with 24%vol
Iron/ABS composites. In terms of binder selection, paraffin wax was
used as a more suitable surfactant/compatibilizer for Iron/ABS com-
posites compared to palm stearin. The use of highly metallic-filled
composites offers the possibility of developing a suitable material
of molds for injection molding and wire filament for FDM [38]. This
research focuses on material preparation and explores the use of
surfactant/compatibilizer in order to control the melt flow behavior
during the extrusion process.
3.2.2.1.3. Copper/acrylonitrile butadiene styrene and
iron/acrylonitrile butadiene styrene composites. Nikzad et al.
also investigated the effect of copper/ABS composites for FDM
filament. Their research study was focused on determining the
effect of filler size, filler loading type of metal fillers in metallic
filament composites. The thermal conductivity of both ABS/Cu
and ABS/Fe composites improved with increasing metal content.
However, the mechanical properties of metallic filled composites
decreased significantly at 10 vol% of iron powder due to the weak
adhesion between metal fillers and the polymer matrix [7].
3.2.2.1.4. Carbon black /Polypropylene/Homopolypropylene com-
posites. Kwok et al. demonstrated the possibility of using
conductive thermoplastic composites in FDM printing. An electri-
cally conductive filament was prepared through melt blending of
polypropylene (PP), homopolypropylene (SCG), and carbon black
(CB) in a single screw extruder. Results showed that at weight per-
centages greater than 30%, an electrical resistivity of 10−2 ohms
was achieved making it suitable for printing electrical circuits for
a 2D or 3D printed circuits and sensors. The advantage of using
CB as a particle filler is in enabling higher thermal stability and
higher electrical conductivity. The potential application of the elec-
trically conductive thermoplastic composites is for electromagnetic
shielding, sensors, 2D circuit printing, and 3D circuit printing. Low
adhesion between polymer-polymer blends in 2D and 3D circuit
printing can be overcome by partial encapsulation or anchoring in
the electrical circuit [39].
3.2.2.1.5. Strontium titanate (SrTiO3 )/acrylonitrile butadiene
styrene composites. Torrado et al. investigated the effect of 5 wt%
strontium titanate (SrTiO3 ) as ceramic fillers on ABS polymer
matrix. Melt blending of SrTiO3 and ABS was performed in a
twin-screw extruder. The ultimate tensile strength of pure ABS
and ABS/SrTiO3 were 33.96 ± 1.74 MPa and 21.60 ± 0.63 MPa,
respectively. Poor mechanical properties of ABS/SrTiO3 was due to
its brittleness and presence of micro-voids [40].
3.2.2.1.6. Alumina (Al2 O3 )/ acrylonitrile butadiene styrene com-
posites. Aside from strontium nitrate, Torrado et al. used alumina
(Al2 O3 ) as fillers for ABS composite filaments. The ultimate
tensile strength of pure ABS and ABS/Al2 O3 composites were
33.96 ± 1.74 MPa and 28.8 ± 2.62 MPa, respectively. The same
observation with SrTiO3 /ABS composite printed parts was seen in
that the presence of microvoids served as crack nucleation that
probably weakens the tensile properties of ABS/Al2 O3 composites
[40].
3.2.2.1.7. Tricalcium phosphate/polypropylene composites. Jyoti
et al. utilized FDM printing to form scaffolds with controlled
porosity. In their work, thermoplastic composite filaments were
prepared with polypropylene (PP) as matrix and tricalcium phos-
phate (TCP) as the ceramic fillers. The melt mixing of PP and TCP to
form the filament was made with a single screw extruder (HAAKE
torque rheometer). The researchers optimized the CAD model and
FDM printing parameters to prepare complex porous structures.
6 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
Fig. 3. “Self-healing of porous PLA/HA scaffold by narrowing the cracks after heating over Tg . [43], copyright 2016. Reproduced with permission from Elsevier Ltd.
The PP/TCP composites showed an ultimate tensile and highest
compressive strength of 19.8 MPa and 12.7 MPa, respectively [41].
The 3D interconnectivity of polymer-ceramic composite scaffolds
promotes the richer supply of blood, oxygen, and nutrients for
healthy in-growth of bone cells [41].
3.2.2.1.8. Alumina (Al2 O3 )/nylon6 composites. Singh et al.
investigated the effect of variation in particle size used in thermo-
plastic composites for FDM feedstock filament. They investigated
the effect of single particle size (SPS), dual particle size (DPS),
and triple particle size (TPS) of alumina (Al2 O3 ) to Polyamide-6
(Nylon6) in thermoplastic composites. The SPS composites pro-
vided an optimum result for percentage elongation. However, the
DPS composites showed superior mechanical properties in terms
of tensile strength (44.52 MPa), yield strength (31.19 MPa) and
Young’s modulus (871.81 MPa). Empirical relations to tailor-made
mechanical properties of FDM feedstock filaments were developed
in order to expand its industrial application [42].
3.2.2.1.9. Hydroxyapatite /polylactic acid (PLA) composites. Sen-
atov et al. prepared a 3D printed porous scaffold using PLA as a
polymer matrix and hydroxyapatite as ceramic fillers. Extrusion
and 3D printing did not affect the amorphous structure of PLA.
Self-healing by crack narrowing leads to a shape memory effect
on the printed PLA/HA scaffolds [43]. Fig. 3 shows the self-healing
mechanism of porous PLA/HA scaffold by narrowing cracks after
heating over the glass transition (Tg ) temperature. The 3D printed
PLA/HA scaffolds can be used as a self-fitting implant for small bone
replacement due to its shape memory effect [43].
3.2.2.1.10. Graphite/PA6/PS/POE-g-MAH composites. Jia et al.
fabricated a polymer/graphite composite with the good thermally
conductive property that was applicable as a heat sink. Using Haake
twin screw extruder, maleic anhydride grafted poly (ethylene 1-
octene) (POE-g-MAH), polystyrene (PS), polyamide 6 (PA6) and
graphite flakes were melted and mixed. Heat conductive pathways
were generated with the melt blended thermoplastic composites.
Due to the presence of voids in FDM printing, conductive heat path-
ways were suspended [44].
3.2.2.2. Natural fiber-reinforced composites.
3.2.2.2.1. Jute fiber /acrylonitrile butadiene styrene composites.
Torrado et al. demonstrated the applicability of jute fiber as rein-
forcement for thermoplastic composite filaments for FDM 3D
printing. High-temperature applications during melt blending in
a twin-screw extruder and filament extrusion in nozzle lead to
thermal degradation of jute fiber in filament composites. Therefore,
the thermal degradation of jute fibers also leads to the formation
of voids that ultimately weakened the material [40]. The ultimate
tensile strength of ABS/Jute fiber composite was 8.63 ± 3.59 MPa
which is much lower to ABS printed of 17.73 ± 2.52 MPa.
3.2.2.2.2. Jute fiber/polylactic acid composites. Matsuzaki et al.
prepared 3D printed jute fiber reinforced thermoplastic compos-
ites (JFRTP). Thermoplastic composites consisted of jute fiber as
reinforcement and PLA as the polymer matrix. The tensile strength
and modulus of JFRTP were 57.1 ± 5.33 MPa and 5.11 ± 0.410 GPa,
respectively. Twisted yarn during in-nozzle impregnation affects
the fiber orientation of the polymer matrix during material extru-
sion. Mechanical properties of JFRTP tend to vary and decline due
to fiber misalignment, poor adhesion between fiber and polymer
matrix, and the formation of voids [25]. Research revealed that a
fiber volume fraction of 40–50%, which was difficult to achieve with
traditional thermoplastic composites processing.
3.2.2.3. Synthetic fiber-reinforced composites.
3.2.2.3.1. Carbon fiber/polylactic acid composites. Improvement
in terms of stiffness was observed with carbon fiber (CF) reinforced
PLA composites (PLA/CF composites). PLA/CF composite materials
display a lower strain as compared to pure PLA, leading to brit-
tle 3D printed structures. Based on morphological analysis using
scanning electron microscope (SEM), carbon fibers tend to align
with the printing direction during material extrusion using FDM
printers. Fig. 4 shows a highly oriented carbon fiber dispersed in
the PLA matrix. It can be seen that short fibers were aligned with
the printing direction [45].
3.2.2.3.2. Carbon fiber/acrylonitrile butadiene styrene composites.
Ning et al. prepared a carbon-fiber-reinforced thermoplastic (CFRP)
composite as a filament for FDM material extrusion. The thermo-
plastic composites undergo the second extrusion using a single
screw extruder to produce high bulk density [11].Single screw
extrusion leads to uniform flow rates and better adhesion between
layers during printing. The carbon fiber (150 and 100 ␮m lengths)
into ABS improved the mechanical properties of the FDM printed
part. Superior tensile strength was observed in CFRP compos-
ites with 5 wt% carbon fiber. While CFRP composites with 7.5 wt%
exhibited the largest mean value for the modulus of elasticity.
Beyond 10 wt% carbon fiber, an increase in porosity lead to poor ten-
sile strength, toughness, yield strength and ductility of 3D printed
CFRP composites. The ruptured part as shown in the SEM image in
 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
Fig. 4. Specimen of PLA/CF at 90◦ magnified 1000x showing fiber alignment with the
printing direction. [45], copyright 2017. Reproduced with permission from Elsevier
Ltd.
Fig. 5 indicates a successful load transfer from polymer matrix to
carbon fiber reinforcement.
3.2.2.3.3. Carbon fiber/acrylonitrile butadiene styrene composites.
Tekinalp et al. investigated the effect of highly oriented printed
parts of carbon fiber thermoplastic composites. The acrylonitrile
butadiene styrene and carbon fibers were compounded using
Brabender Intelli-Torque Plasti-Corder prep-mixer at 220 ◦ C and
60 rpm. A cylindrical die was used to extrude the filament that was
later on used into a commercial FDM unit. The FDM dog-bones
were prepared and tested in UTM to obtain its mechanical prop-
erties. It was found that the tensile strength increased by 115%
while the modulus of elasticity increased by 700% for the highly ori-
ented composites. Even if the mechanical properties of the highly
oriented fiber composites improved, certain challenges with mate-
rial processing and FDM printing still exist such as fiber breakage
during melt mixing and formation of voids due to weak adhesion
between fiber and polymer matrix [46].
3.2.2.3.4. Continuous glass, carbon, and kevlar fibers/nylon com-
posites. Continuous glass, carbon and Kevlar fibers reinforced
nylon composites enhanced the tensile properties by 6.3 times for
tensile strength and five times for flexural strength from nylon
printed specimen. Fiber-reinforced thermoplastic composites were
prepared using the dual print head mechanism of a Mark One Com-
posite 3D printer. Still, there were some limitations with the use
of continuous fiber as reinforcement to thermoplastic composites.
Increase in fiber content resulted in the formation of voids due
to weak adhesion between the surface of the fiber and matrix as
Fig. 5. The pulled-out carbon fibers in the fracture interface of CFRP composites (carbon fiber content is 10 wt%; carbon fiber length is 150 ␮m). [11], copyright 2015.
Reproduced with permission from Elsevier Ltd.
7
shown in Fig. 6 [27]. The same behavior of fiber-reinforced com-
posites can be observed with traditional thermoplastic processing
[27].
3.2.2.3.5. Continuous carbon fiber/polylactic acid composites.
Using an in-nozzle impregnation method, a continuous CFRP com-
posite was fabricated. Integration of this innovated set-up for print
headresulted in tensile strength and modulus of 185.2 ± 24.6 MPa
and 19.5 ± 2.08 MPa, respectively. The use of the in-nozzle impreg-
nation technique in FDM printing resulted in enhanced mechanical
properties as compared to typical melt blending of short fibers
in a polymer matrix. In fiber-reinforced thermoplastic compos-
ites, fiber orientation and fiber content were critical parameters to
obtain optimum properties. The development of in-nozzle impreg-
nation techniques offers the possibility of using printed parts in
load-bearing application [25]. Tian et al. (2016) modified the FDM
printhead by using the in-nozzle impregnation set up in order to
incorporate continuous carbon fiber into the PLA matrix. It can be
concluded that parameters such as layer thickness, hatch spacing,
and feed rate affected the interface and properties of the printed
part [26]. At 27% carbon fiber content in thermoplastic composites,
the optimum flexural strength (335 MPa) and modulus (30 GPa)
was observed.
3.2.2.4. Nanomaterial reinforced composites.
3.2.2.4.1. Polyurethane /poly(lactic acid)/graphene oxide
nanocomposites (TPU/PLA/GO). Chen et al. prepared TPU/PLA/GO
nanocomposites by a solvent-based mixing process. The resulting
nanocomposites are extruded into a filament that is applicable
to FDM printing. The inclusion of GO nanofillers to TPU and PLA
nanocomposites improved its mechanical property and thermal
stability. Also, the mechanical behavior of TPU/PLA/GO nanocom-
posites is highly dependent on its printing orientation. The
nanocomposites can be used as a potential biomaterials scaffold
for tissue engineering application due to its compatibility with
NIH3T3 mammalian cells [47].
3.2.2.4.2. Carbon nanotubes and graphene fillers/ Polybutylene
terephthalate (PBT) composites. Gnanasekaran et al. demonstrated
FDM printing of nanomaterial reinforced polybutylene terephtha-
late (PBT) using multi-walled carbon nanotubes and graphene as
fillers. Results showed that PBT/CNT 3D printed composites gave
superior elastic behavior, conductive properties, and printability
as compared to PBT/G printed composites. In terms of printability,
the formation of voids lead to surface roughness, and brittleness
of the PBT/G 3D printed composites. Voids were formed probably
due to vaporization of moisture in graphene in high-temperature
applications. Due to the difference in nanomaterials structures (1D
in CNT and 2D in graphene), agglomeration of nanoparticles is pos-
8 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
Fig. 6. SEM Images of protruding carbon fibers (A) and Kevlar fibers (B) following tensile tests. This examination indicated that carbon fibers fractured cohesively, with Kevlar
fibers pulling free due to inter-laminar failure. [27], copyright 2017. Reproduced with permission from Elsevier Ltd.
Fig. 7. Optical micrographs showing the surface of a 3D printing nozzle before and
after printing. (a) Unused nozzle. (b) Nozzle after printing ∼10 cm of PBT/G. (c) Noz-
zle after printing ∼1.5 m of PBT/CNT. (d) SEM image of PBT/G composite printed
with an abraded nozzle. [32], Open Access from Elsevier Ltd.
sible resulting in increased electrical resistance [32]. Commercially
available FDM printers have certain limitations in using thermo-
plastic composites. For instances like 3D printing nanomaterials
reinforced based composites, nozzle wear is common due to abra-
sive materials in contact with its surface. In Fig. 7, SEM analysis
showed nozzle wear due to FDM printing of PBT/CNT and PBT/G.
3.2.2.4.3. Zinc oxide nanorod/acrylonitrile butadiene styrene com-
posites. Torrado et al. utilized 2 wt% zinc oxide nano-rods in ABS
composites. Using a twin-screw extruder, zinc-oxide nanorods and
ABS were melt blended to produce a thermoplastic composite.
Results showed that the ABS/ZnO composites exhibited crack prop-
agation in fractured specimen similar to brittle materials [40].
Ultimate tensile strength of 20.70 ± 0.55 MPa was observed with
ABS/ZnO which was much lower compared to the ultimate strength
of pure ABS of 33.96 ± 1.74 MPa. The poor performance of ABS/ZnO
composites was attributed to the presence of micro-voids when
ZnO nano-rod fillers were added [40].
3.2.2.4.4. Graphene nanoplatelets/acrylonitrile butadiene styrene
composites. An optimized nanofiller content of 4 wt% of graphene
nanoplatelets was introduced to ABS matrix by melt blending. The
inclusion of graphene nanoplatelets enhanced the elastic modu-
lus of pure ABS by almost 30%. Tensile strength and modulus of
38.8 ± 0.8 MPa and 1866 ± 118 MPa were obtained, respectively.
Other than enhancing tensile properties, the inclusion of graphene
nanoplatelets improved thermal stability by improving the coeffi-
cient of thermal expansion and creep compliance [48].
3.2.2.4.5. Cloisite/polylactic acid composites. Guo et al. devel-
oped a biodegradable flame retardant thermoplastic composite
by using a nano clay filler Cloisite 30B (C-30B) and PLA with
melamine polyphosphate (MPP) as a matrix. The nanocomposites
were prepared by melt blending and later processed as a fila-
ment using a single screw extruder. The PLA/MPP polymer blends
exhibited poor conduction of heat resulting in flame resistivity but
significantly decreased its mechanical properties [49]. With the
addition of C-30B nano clay fillers, the thermoplastic nanocompos-
ites yielded improved mechanical properties. The tensile strength
and modulus of the 3D printed PLA/MPP/C-30B nanocomposites
were 70.0 ± 3.8 MPa and 3.91 ± 0.22 GPa, respectively. In terms of
the mechanical properties of 3D printed and molded PLA/MPP/C-
30B nanocomposites, there was no significant difference observed.
3.2.2.4.6. Titanium oxide/acrylonitrile butadiene styrene compos-
ites. Torrado et al. investigated the effect of compounding 5 wt%
titanium dioxide (TiO2 ) nanoparticles with ABS. There was no sig-
nificant difference observed with the ultimate tensile strength of
pure ABS printed parts (16.23 ± 3.07 MPa) and ABS/TiO2 printed
part (16.22 ± 3.53 MPa) [40]. Addition of TiO2 nanoparticles typi-
cally results in improvement of tensile strength, but the variation
in filler size of TiO2 somewhat affected its properties. Functional-
ization of TiO2 before melt blending reduced agglomeration and
improved particle distribution in the polymer matrix [40].
3.2.2.4.7. Graphene doped polylactic acid/polylactic acid (G-
PLA/PLA). Zhuang et al.utilized the dual-head printing mechanism
with pure PLA and graphene doped polylactic acid (G-PLA) as fil-
ament materials. Controlling the printing parameters allows the
researchers to vary the ratio between PLA and G-PLA. Higher con-
tent of G-PLA reduced the electrical resistance of the thermoplastic
composites [50].
3.2.2.5. Polymer blends.
3.2.2.5.1. ABS/SEBS/UHMWPE polymer blends. Torrado
et al.prepared polymer blends of ABS, styrene ethylene butadiene
styrene (SEBS) and ultra-high molecular weight polyethylene
(UHMWPE) by melt blending in a twin-screw extruder. The
ratio of ABS/SEBS polymer blends used in this research was 95:5
and 80:20 wt percentages. An increase in SEBS content showed
no significant differences in terms of ultimate tensile strength.
However, a higher level of plastic deformation was observed with
increasing SEBS content due to high plastic flow at the fractured
region [40]. With the addition of UHMWPE in the polymer blends,
polymer/polymer composites were formed where ABS/SEBS serves
as the matrix. The three polymer blends exhibit ductile fracture
mechanism with the presence of fibrils and spheroids at the
fractured region. These spheroids at the fractured region were
believed to be UHMWPE that did not blend with ABS/SEBS matrix
[40]. The ultimate tensile strength diminished with an increasing
 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
Fig. 8. SLS setup. [85], Open Access from Elsevier Ltd.
weight content of ABS/SEBS/UHMWPE in the polymer blends as
compared with pure ABS printed part.
3.2.2.5.2. UHMWPE/HDPE/PEG polymer blends. Ramli et al.
demonstrated that polymer blending of ultra-high molecular
weight polyethylene (UHMWPE) with high-density polyethylene
(HDPE) improved its applicability in extrusion within the 60 wt%
HDPE composition. Polymer blends of UHMWPE and HDPE solved
the problem of ultra-high viscosity of UHMWPE. Thus, making
it possible for UHMWPE/HDPE polymer blends to be used as
3D-printed artificial implants due to UHMWPE biocompatibility
characteristics. It was also found that polyethylene glycol (PEG)
was not useful with UHMWPE in polymer blends. The PEG offset the
heat transfer mechanism and lessen the kinetic effect in the poly-
mer blends that leads to a reduction in degradation temperature
and thermal stability [51].
3.2.2.5.3. PC/SEBS-g-MA polymer blends. A novel polycarbon-
ate/ styrene ethylene butylene styrene with maleic anhydride graft
(SEBS-g-MA) was prepared as a new rubberized filament for FDM
printing. A decrease in ultimate tensile strength was observed
when the weight percentage of SEBS-g-MA was increased. How-
ever, the percentage elongation of the PC/SEBS-g-MA polymer
blends increased with SEBS-g-MA composition. The ultimate ten-
sile strength of 23.82 MPa was observed in polymer blends that
have 25 wt% SEBS-g-MA. Polymer blends with 75 wt% SEBS-g-MA
exhibit superior rubberized characteristics with 784.48% elonga-
tion [52].
The issue of surface adhesion between printed layers, especially
with FDM-printed parts needs to be addressed in any 3D printing
protocol since this can be one of the failure modes for the object
as various polymers have different quenching characteristics once
extruded from the nozzle head unto to the previously deposited
layer. The temperature and humidity in the printer oven can have
a dramatic effect on the failure modes and void space formation
during the extrusion of individual layers. A decrease in mechanical
properties of 3D-printed parts were observed at exposure to 0.16%
moisture or greater due to increase in porosity content that comes
from entrapped volatis during layer-by-layer addition [53].
3.3. Selective laser sintering (SLS)
Selective Laser Sintering (SLS) or Selective Laser Beam Melting
(SLBM) is a Powder Bed Fusion (PBF) technique through directed
heating [54]. It has become the most popular PBF process since it
was the first technique to be commercialized under this category of
AM [55]. In this method, a power-based heating source such as CO2
or Nd-YAG laser is selectively aimed at a bed of powder metal, ther-
moset or thermoplastic that created a solid object made of fused
powder [12]. A hybrid additive manufacturing technique for SLS has
been introduced in the research of Wudy and Drummer in which
9
combined reactive liquids of thermoset resin and thermoplastics
were used [56]. Thermoplastics, such as polyamide 12, polyamide
11, polypropylene and thermoplastic elastomers, are the conven-
tional materials being used in a typical SLS setup [56]. The typical
SLS setup is shown in Fig. 8. The chamber is usually heated just
below the melting point of the powder material before the sinter-
ing process is applied. A high-power beam of laser moving in the
X–Y axis is directed on the printing area with the preheated powder
to melt the powder materials partially. Partially molten materials
bind together and form a layer of an object [57]. The piston (vertical)
of the printing area moves down while the powder reservoir pis-
ton moves up to allow the application of a new layer of powder on
the printing surface via the leveling drum. The printing is complete
when the entire object is formed inside the printing chamber. To
get the final shape, the excess powder is shaken off [58]. The print
quality of SLS depends on the power and the scan speed of the laser,
the particle size of the powder material and the layer thickness [59].
3D models with overhanging layers (features greater than 45◦ from
vertical) are usually held in place by support structures printed. In
SLS, structural support is not needed since the powder holds the
printed object in place. Selective laser sintering allows the printing
of objects with more complex geometries and interlocked designs
free from overhangs, which needs to be removed on the final print.
3.3.1. Materials used for selective laser sintering (SLS)
The most common materials used in SLS are thermoplastic
polymers such as polyurethane (TPU), polycaprolactone (PCL) and
polyamide (PA). These thermoplastics can be filled with glass,
aluminum, or fibrous materials to cater to certain applications.
Industry-grade SLS machines also use ceramics and metals. A draw-
back is that the surface porosity is high in SLS-printed products
since the sintering process of SLS creates a porous mass of these
materials without reaching the point of liquefaction (melting). Oth-
erwise, it will be called Selective Laser Melting (SLM). SLS machines
are more expensive than other 3D printing machines due to the high
cost entailed by using a high-power laser [60].
3.3.2. Advanced thermoplastic composites and nanocomposites
used in SLS
3.3.2.1. Particle-reinforced composites.
3.3.2.1.1. Hydroxyapatite-reinforced polyethylene/polyamide
composites (HA-PE/PA). Zhang et al., (2008) prepared compos-
ite mixtures of hydroxyapatite-reinforced polyethylene and
polyamide by using a twin-screw extruder to melt and blend
the polymer/filler. The composites were processed to produce a
powder suitable for SLS printing. The use of smaller particle sizes
produced a higher density and stiffness in the printed part [30].
3.3.2.1.2. Carbon black/polyamide 12 (CB/PA12). Espera et al.,
(2019) prepared a facile approach of combining CB and PA12 pow-
10 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
Fig. 9. SEM Micrographs of the fractured surfaces of the 30% CF/PA SLS parts at the magnification of (a) 500x and (b) 4000 × . [5], copyright 2011. Reproduced with permission
from Elsevier Ltd.
ders using SLS printer. An increasing concentration of 0, 1.5, 3, 5,
and 10 wt% of CB were added with PA12 powders. The CB/PA12
sintered parts exhibit enhanced mechanical, thermal and electri-
cal properties. However, for concentration greater than 3 wt%, the
mechanical properties weaken due to increasing concentration of
CB results in low adhesion of carbon black in PA12 matrix [61].
3.3.2.2. Synthetic fiber-reinforced composites.
3.3.2.2.1. Carbon fiber/polyamide 12 composites. A composite
powder made of carbon fiber and polyamide 12 (Nylon 12) was pre-
pared using a dissolution-precipitation process. Carbon fiber was
initially treated by an oxidation method. The dissolution process
and oxidation method allow good interfacial adhesion and uni-
form distribution of carbon fiber within the polyamide matrices in
powder form. The 50 wt% carbon fibers exhibit an improvement in
flexural strength by 114% and flexural modulus by 243.4%. As shown
in Fig. 9, the fractured surface indicates that the carbon fibers were
encapsulated and bonded well with polyamide 12 [5].
3.3.2.3. Nanomaterial reinforced composites.
3.3.2.3.1. Nanosilica/polyamide 12 composites. Chunze et al.
(2008) used nano silica as nanofillers for polyamide 12 (PA12 or
Nylon-12) in SLS. A 3 wt% nano silica was dispersed in polyamide
12 using the dissolution-precipitation process. A composite pow-
der was produced after the dissolution-precipitation process. An
increase in tensile strength, tensile modulus, and impact strength
of SLS printed specimens were observed by 20.9%, 39.4% and 9.54%
as compared with tensile strength, tensile modulus and impact
strength of unfilled polyamide 12 [62].
3.3.2.3.2. Nanosilica/polyamide 11 composites. Chung and Das
prepared a functionally graded Nylon 11/silica nanocomposites by
SLS. Using a rotary tumbler, powder mixtures of Nylon 11 and silica
nanoparticles (0–10%vol) were prepared. The mechanical proper-
ties of Nylon 11/silica nanocomposites exhibit nonlinear variations
in terms of its filler volume fraction [29].
3.3.2.3.3. Nanoclay/polyamide 6 composites. Kim and Creasy
prepared a polyamide 6/clay reinforced composites for SLS printing.
Samples were reduced into powder at liquid nitrogen temperature.
Due to clay-polymer chain interactions, an increase in values of
melt of fusion and heat of crystallization was observed. Increasing
clay composition leads to a viscous polymer composite. The crystal-
lization temperature of nanocomposites was reduced by 3 ◦ C due
to the constraint in polymer molecules mobility [63].
3.3.2.3.4. Functionalized graphite nanoplatelets/polyamide 12
composites. A nanocomposite powder of PA12 and functionalized
graphite nanoplatelets were prepared in an effort to achieve supe-
rior mechanical properties in SLS printing. The functionalization of
graphite nanoplatelets improves its interfacial bonding force with
polyamide 12 matrices. A few nanofillers increased the mechanical
properties of SLS printed parts without compromising the thermal
and rheological behavior of the nanocomposites [64].
3.3.2.3.5. Carbon nanotube/polyamide 12 composites. Bai et al.
(2014) investigated the effect of carbon nanotubes (CNT) on the
rheology and dynamic mechanical properties of polyamide 12
for SLS printing. The presence of CNT in polyamide 12 increased
the storage modulus, loss modulus and viscosity of nanocompos-
ites [33]. The interaction between nanofillers and polymer matrix
interfered with the chain mobility of polymer molecules. The laser-
sintered part of PA12-CNT nanocomposites had an increase in
elastic modulus as compared with unfilled PA12.
3.4. Selective laser melting (SLM)
Selective laser melting (SLM) uses a high-power-density fiber
laser (ytterbium fiber laser) to melt and fuse metallic powders to
form a 3-dimensional part [65]. This process is similar to Selective
Laser Sintering (SLS); the only difference being that the material
is melted while in SLS it is heated to a temperature just enough
to allow fusion of the powder. First, the CAD model is sliced into
2-dimensional layers and transferred to the SLM machine [66].
Moreover, then, an even layer of powder material is distributed
using a coater. Under a tightly-controlled inert atmosphere, the
laser then scans and fuses the layer following the geometric infor-
mation of the sliced model. The substrate is then lowered by one
layer thickness. These scanning/fusing and layering processes are
repeated until the final part are complete. The finished part is
removed from the powder bed and undergoes post-processing
steps such as heat treatment, etc.
Laser beam melting (LBM) is another additive manufacturing
technology that allows layer-based production of geometrically
complex parts from metal powder [67]. The CAD drawing is
sliced into 2D + 1D representation. A thin powder layer of 20 ␮m
is deposited on top of the platform and melted using the two-
dimensional geometry. After the process is done, the platform is
lowered and allow another layer of powder to be deposited on top.
The process is repeated until the whole 3D objects if finished.
3.5. Materials used for SLM and LBM
Polystyrene has been used to produce spherical micron-sized
particles having adequate flowability for LBM and SLM printing.
The process included wet grinding, rounding, and dry coating [6].
 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
Fig. 10. Schematic of LDM printing process. [75], copyright 2017. Reproduced with
permission from the Royal Society of Chemistry.
Drummer et al. investigated the density and flowability of new
and used PA12 powders for SLM printing. Other than the particle
parameters, they found out that the density of laser-molten parts
depends on the heating rate and applied coating parameters and
mechanisms [68]. The authors also used polyamide 12 to investi-
gate the influence of different ways of energy input on the resulting
melt pool for SLM printing. Also, time-dependent effects during
exposure have been studied [69]. Lastly, they reported on the
morphological structure of PA12 blended with PEG and polyvinyl
alcohol [70]. Laumer et al. [71] reported on several requirements for
compatibility between different polymeric materials for LBM print-
ing of polymers. They also provide a matrix of possible material
combinations for composite structures. Schmidt et al. developed a
process chain to produce spherical polymeric particles made out of
poly(butylene terephthalate) (PBT) [72]. Their process included wet
grinding of polymer microparticles, and then the particle is rounded
in a heated downer reactor, and lastly, the particle is dry-coated
with fumed silica [73].
3.6. Liquid deposition modeling (LDM)
Liquid deposition modeling (LDM), also called direct ink writ-
ing, has been garnering more attention in recent years [74][75].
Similar to FDM, this technique fabricates 3D structures by con-
secutive addition of layers of extrudates into computer-designed
geometries; however, LDM involves the extrusion of viscous liq-
uids rather than melted filaments (Fig. 10) [76]. The preparation of
viscous liquids even at room temperature offers LDM the highest
versatility among all the 3D printing techniques. The disadvantage
of LDM is the selection of solvent and polymer concentration to
achieve appropriate flow parameters without compromising rapid
evaporation of the solvent in the solution [77]. Printing parameters
must be optimized to achieve the desired material extrusion of the
dissolved polymer.
3.6.1. Materials used for liquid deposition modeling (LDM)
A wide range of materials, including ceramics, metals, hydro-
gels, carbon-based materials, polymers, and biomaterials can be
3D printed using LDM, once it is successfully formulated into
a viscous liquid. Very porous structures can be fabricated using
this method. For example, Zhu et al. 3D-printed micro-lattice of
11
graphene aerogel that possesses a porous structure [78]. Minas
et al. demonstrated the fabrication of hierarchical porous ceramic
foams with LDM, in which viscous liquid ink is prepared by emul-
sified ceramic powders and PVA binders [79]. Shah has reported
3D printing of various metal materials into complex architectures
where metal powders were suspended in a solvent mixture to form
viscous liquid inks [80]. A PDMS elastomer was filled with silica
nanoparticles to form viscous inks which were 3D printed into
different lattice structures to exhibit designed mechanical proper-
ties [81]. In order to successfully 3D print by LDM the highly filled
materials described above (vide supra), materials with thixotropic
rheological properties are required. When extruded from the noz-
zle, inks are under high shear stress; thus, shear thinning behavior
is required so that the flowing of ink is consistent and controllable.
The deposited ink should be able to retain its shape, and also be
mechanically strong to support the weight of subsequent layers
without deforming its original shape. Thus most materials need to
be thixotropic and curing (or thermosetting). Therefore, sufficient
storage modulus (G’) and yield stress () is necessary, normally G’ >
1000 Pa and  > 200 Pa [81]. To satisfy these rheological properties, a
mixture of organic solutions and powder fillers are normally used,
where the solution acts as a liquid matrix to provide the flowa-
bility while powder fillers serve as rheology modifiers. Owing to
the high versatility of materials processed in LDM, the curing pro-
cedures are very diversified and determined by the nature of the
ink materials. Liquid deposition modeling includes the selection of
solvent and polymer to be combined in a solution. Setup for LDM
must be optimized in order to ensure flowability of the solution
during the extrusion and rapid evaporation of the solvent after the
extrusion.
3.6.2. Advanced thermoplastic composites and nanocomposites
used in LDM nanomaterial reinforced composites
3.6.2.1. Carbon nanotubes/polylactic acid composites (CNT/PLA).
Recently, thermoplastic polymer materials have been processed
by LDM. The ink material was prepared by dissolving PLA in
dichloromethane (DCM) with a high content of CNT. In this case,
the ink material is not thixotropic, it cannot retain its geometri-
cal shape or support subsequent layers, but its “curing” process is
conducted by the fast evaporation of DCM upon being extruded
from the nozzle, during which the PLA simultaneously solidifies
[76]. This process allows for the inclusion of higher concentration
of nanofillers in thermoplastic polymers which cannot be pro-
cessed by FDM due to nozzle clogging caused by a higher content
of nanofillers.
3.6.2.2. Multi-walled carbon nanotube/polylactic acid composites
(MWCNT/PLA). Postiglione et al. fabricated a nanocomposite using
MWCNT as fillers and poly(lactic acid) (PLA) as the matrix [8].
Using a new 3D printing method based on LDM, conductive
3D microstructures were formed. Fig. 11a shows a substantial
increase in volume electrical conductivity with increasing con-
tent of MWCNT in the solvent-cast nanocomposite. A key factor
in achieving a conductive nanocomposite is the uniform disper-
sion of conductive fillers in the PLA matrix [8]. The fracture surface,
as shown in Fig. 11b, exhibited a good level of dispersion of
MWCNT (white dots in the image) in a PLA matrix. It means that
even at high concentration of MWCNT no noticeable traces of
MWCNT agglomeration were observed. The potential application
of MWCNT/PLA is the 3D printing of fully-functional conductive
microstructured systems in the field of microelectronics [8]. Strong
interfacial interaction between the polymer and nanoparticle com-
posites is important to achieve a good mechanical properties
[22].
As shown in the optical microscopy image in Fig. 12a, the liq-
uid deposition of MWCNT/PLA nanocomposite generated planar
12 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162

Fig. 11. (a) Volume electrical conductivity as a function of MWCNT concentration. The inset shows the log-log plot of the electrical conductivity versus the volume fraction
of MWCNTs; (b) SEM micrograph of cryo-fractured 3D-printed MWCNT/PLA nanocomposites (10 wt%MWCNT in PLA). [8], copyright 2015. Reproduced with permission from
Elsevier Ltd.

Fig. 12. (a) Top-view optical microscopy image of an LDM-based3D printed two-layer woven-like microstructure; SEM (b) top and (c) side view images of a representative
ten- layer scaffold; (d) optical photograph of a LDM-based 3D printed filament deposited in a freeform manner (a 1 cent euro coin is reported in the image for dimensional
reference); (e) 3D printed MWCNT-based nanocomposite woven structure used as a conductive element in a simple electrical circuit. [8], copyright 2015. Reproduced with
permission from Elsevier Ltd.

solid features with an average width of 100 ␮m. SEM images of 3D
printed MWCNT/PLA scaffold are shown in Fig. 12(b and c). Also,
the LDM technique can be utilized to 3D print conductive elec-
tronic components at microscale with the flexible woven structure
as shown in Fig. 12(d and e) [8].
4. Comparison of different processing techniques
applicable to AM
This section discusses different processing techniques used in
the fabrication of thermoplastic composites and polymer blends
for AM. Table 4 summarizes the advantages and disadvantages of
each processing techniques to materials used in AM.
Table 4 shows that the most common way to prepare ther-
moplastic composites for AM is an extrusion. In terms of
material preparation, extrusion is a solvent-free, robust, quick,
and economy-favored manufacturing process. Research articles
gathered showed that the extrusion process applies to the par-
ticle, short fiber and nanomaterial reinforced composites. Short
fiber-reinforced to allow a highly oriented and aligned fiber rein-
forcement to composites while particle reinforced composites
improved the mechanical properties especially for metal fillers
[37,38,42]. The percolation threshold of particle reinforced and
short fiber reinforced composites are 10 vol% and 10 wt%, respec-
tively [7,11]. A common problem with the particle, short fiber, and
nanomaterial reinforced composites is the low adhesion between
fillers and polymer matrix that leads to the formation of voids. The
presence of microvoids served as crack nucleation that results in
weak mechanical properties. Pore volume increases with increas-
ing amount of fillers in the polymer matrix [37,40,41]. Thermal
degradation with natural fibers also leads to the formation of voids
[40]. Nanomaterials in polymer matrix tend to form aggregates that
weaken its mechanical properties [32,49]. However, the complex
porous structure of 3D printed parts can also be an advantage in
biomedical applications such as bone replacement and growth of
bone cells. Preparation of complex porous structure or scaffolds
results to a shape recovery effect to 3D printed parts up to 98%
[41,43].
Table 4
Advantages and Disadvantages of Thermoplastic Processing Techniques Applied to AM.

Processing Filler Types Composites AM Types Advantages Disadvantages

Techniques

Extrusion Particle Reinforced Iron/Nylon FDM At same filler volume content, large particle No strong bond between filler particles and [37]
Composites size exhibit greater tensile strength and the polymer matrix.
modulus compared with smaller particle size.
Mechanical Properties of polymer-metal Beyond 10vol% mechanical properties [7]
composites increased with more metal fillers decreased significantly.
Copper/ABS FDM Good thermal conductivity with increasing [38]
metal content that can be used for rapid
tooling.
Iron/ABS Addition of CB results in higher thermal Low adhesion between polymer-polymer
stability and electrical conductivity. blends.

A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
CB/PP/SCG FDM No improvement with the composites. [39]
SrTiO3 /ABS FDM No improvement with the composites. Poor mechanical properties due to its [40]
brittleness and presence of micro-voids.
Al2 O3 /ABS FDM Prepare complex porous structures (scaffolds) Presence of micro-voids served as crack [40]
that can be used for biomedical applications nucleation that weakens the mechanical
such as in the growth of bone cells. properties
PP/TCP FDM SPS provide optimum result for percentage Compressive strength decreases as pore [41]
elongation and DPS provide superior volume increases.
mechanical properties.
3D Print a scaffold with a shape memory effect Triple size particle exhibit lower [42]
that can be used for bone replacement. mechanical properties as compared with
SPS and DPS.
Al2 O3 /Nylon6 FDM Heat conductive pathways were generated The activation temperature for the shape 43]
that can be applied as a heat sink. memory effect is higher than the body
temperature of 37o C.
PLA/HA FDM Smaller particle size improves the
thermo-mechanical properties of the SLS
printed part.
Graphite/PA6/ FDM Presence of voids suspended the heat [44]
PS/POE-g-MAH conductive pathways.
Rough surface and porous structure of 3D [30]
printed parts.
HA-PE/PA SLS
Fiber Reinforced ABS/Jute Fiber FDM No improvement with the composites. Thermal degradation of jute fiber during [40]
Composites melt blending leads to the formation of
voids. This results in a lower ultimate
tensile strength of ABS/Jute fiber
composites compares to pure ABS printed.
Proto-Pasta FDM A highly oriented and aligned CF were Addition of CF leads to lower strain as
PLA/CF dispersed in the PLA matrix. compared to pure PLA that leads to its
(commercially brittle structure.
available)
Poor adhesion between PLA and carbon [45]
fibers.
Beyond 10wt%, an increase in porosity was
observed that lead to poor mechanical
properties.
ABS/CF FDM The second cycle of extrusion produces high Repeated use can damage the lower end [11]
bulk density that leads to uniform flow rates type of nozzle due to clogging.
and better adhesion during layer-by-layer
adhesion. Improvement in mechanical
properties was observed.
ABS/CF [46] FDM Highly oriented printed parts increased the TS Fiber breakage during melt mixing. Void [46]
and E by 115% and 700%, respectively. formation due to weak adhesion between
fiber and polymers.

13
 14
Table 4 (Continued)

Processing Filler Types Composites AM Types Advantages Disadvantages

Techniques

PBT/CNT FDM In terms of elastic behavior, conductive Agglomeration of nanoparticles resulted in [32]
properties, and printability an increase in electrical resistance.
Nanomaterial PBT/G PBT/CNT > PBT/G Surface roughness and brittleness due to
Reinforced void formation brought by vaporization of
Composites moisture in G at higher temperatures.
ZnO/ABS FDM 3D printed parts exhibit a mechanical Nozzle wear due to abrasive characteristics
performance similar to the brittle material of Graphene and CNT [32].
The optimized performance was at 4wt% UTS lower compared to pure ABS. Crack [40]
nanofiller content. propagation similar to brittle materials.
Presence of micro voids.

A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
The decrease in stress and strain at the
break with xGnP.
xGnP/ABS FDM The inclusion of xGnP improved elastic [48]
modulus and dynamic storage moduli.
Improvement in thermal stability such as C-30B aggregates in MPP leads to
reduction in the coefficient of thermal ineffective char formation.
expansion and creep resistance.
PLA/MPP/C- FDM PLA/MPP exhibited poor conduction of heat [49]
30B leading to flame resistivity. The inclusion of
C-30B improved mechanical properties. No
significant difference between 3D printed and
molded parts in terms of mechanical
properties. [49]
Functionalization of TiO2 prior to melt
blending in extruder reduced agglomeration
and improved particle distribution.
TiO2 /ABS FDM Increase in the values of melt of fusion and the
heat of crystallization due to clay-polymer
chain interactions. Increase in clay content
results to increase in viscosity.
No significant difference with UTS of ABS [40]
printed and TiO2 /ABS printed.
Nanoclay/PA6 SLS Laser sintering of the composites requires [63]
higher holding temperature and laser
power. Low final density on sintered parts
Polymer Blends PLA/MPP [49 FDM PLA/MPP exhibited poor conduction of heat Low mechanical properties [49] [49]
leading to flame resistivity.
ABS/SEBS/UHMWPE FDM A higher level of plastic deformation at No significant difference in UTS with [40]
increasing SEBS content due to high plastic increasing SEBS content.
flow at the fractured region.
Ductile fracture mechanism due to the [51]
presence of fibrils and spheroids.
UTS decreased with an increasing weight [82]
content of the mixture.
UHMWPE/HDPE FDM Address the problem of ultra-high viscosity of
UHMWPE with 60wt% of HDPE. Provide
adequate thermal stability.
UHMWPE/PEG FDM Provide adequate mechanical properties in PEG is not suitable to blend with UHMWPE
terms of elastic and flexural properties for despite its internal lubrication
biomedical applications with improvement in characteristics due decrease in tensile,
flowability flexural and impact strength.
PC/SEBS-g-MA FDM A new rubberized filament was developed due The decrease in ultimate tensile strength
to an increase in percent elongation up to with increasing SEBS-g-MA composition.
784.48%.
In-Nozzle Fiber Reinforced PLA/Jute Fiber FDM A small increase in tensile properties as Failures such as fiber misalignment, fiber [25]
Impregnation Composites compared to pure PLA printing. pullout, poor adhesion between fiber and
PLA, and formation of voids were observed
No tension was applied during the printing
that results in the non-uniform
configuration of the jute fibers.
PLA/CF FDM Exhibits superior mechanical properties as
compared to pure PLA
PLA/CF>PLA/Jute Fiber>Pure PLA
Dual-Print Head Fiber Reinforced Continuous FDM Enhanced mechanical properties by 6.3 times Higher fiber contents of more than 33% [27]
Composites for TS and 5 times for FS. yield a minor increase in strength.
CF/Nylon Maximum efficiency in TS can be achieved as

A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
fiber content approaches 18%
GF/Nylon Carbon fiber>Glass Fiber>Kevlar Fiber
Kevlar/Nylon
Nanomaterial G-PLA/PLA FDM Higher content of G-PLA reduced the electrical Formation of anisotropic materials.
Reinforced resistance of the thermoplastics.
Composites
Formation of printed objects with anisotropic [50]
heat distribution via distribution of amorphous
materials.
Solvent Nanomaterial TPU/PLA/GO FDM Addition of GO nanofillers improved the Presence of small voids within the layers [47]
Casting/Solvent Reinforced mechanical properties and thermal stability of and large voids between layers [47].
Based Mixing Composites TPU and PLA.
Process
Nanosilica/PA12 SLS An improvement in tensile strength, tensile As the nanosilica volume fraction [62]
modulus, impact strength, and thermal increases, the SLS printed parts become
stability were observed. Uniform dispersion of more brittle.
nanosilica in SLS parts composite powder.
CNT/PLA LDM Higher concentration of nanofillers in the PLA The nanosilica has a heterogeneous effect
matrix is possible. Highly conductive nucleation effect on PA12.
composites. Scaffold-shaped liquid sensors are
demonstrated
A substantial increase in volume electrical Fast evaporation of solvent upon extrusion [76]
conductivity with increasing MWCNT content.
Uniform dispersion of MWCNT in the polymer
matrix.
MWCNT/PLA LDM Rapid solvent evaporation. [8]
Powder Processing Fiber Reinforced CF/PA12 SLS (coated Allow good interfacial adhesion and uniform Need for surface treatment of CF prior to [5]
and Mixing Composites powders) distribution of CF in powder form. dissolution-precipitation process of
Improvement in mechanical properties and CF/PLA.
thermal stability. Low part bed temperature is
needed during printing.
Nanomaterial Nanosilica/PA11 SLS (separate Produce 3D components with spatially varying The tensile and compressive properties [29]
Reinforced powders) mechanical properties. exhibit nonlinear variation in terms of
Composites volume fraction of silica.
Particle Reinforced CB/PA12 SLS (separate Sintered parts exhibit enhanced mechanical Decrease in mechanical properties above [61]
Composites powders) and thermal stability. 3wt% CB. Increasing content of CB results to
low adhesion between CB and PA12 matrix.
Intercalation in an Nanomaterial PA12/Functionalized SLS (composite Improve the mechanical properties without No improvement with the thermal [64]
autoclave Reinforced GNP powder) compromising the thermal and rheological properties.
Composites behavior of the SLS printed parts.
Functionalization of GNP improved the
interfacial bonding force.

15
16 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
Table 5
Comparison between FDM, SLS, and LDM in terms of Material Used.
AM Types Particle Reinforced Composites Fiber Reinforced Composites
FDM X X
SLS X X
LDM
Compared with extrusion, the use of solvent casting and
solvent-based mixing reduced the amount of void formation and
agglomeration in the particle and nanomaterial reinforced compos-
ites [47,62,8]. Also, the inclusion of a higher concentration of fillers
is possible with solvent-based mixing for thermoplastic composites
[76]. However, the disadvantage of using a solvent is its toxicity and
rapid evaporation during the mixing and extrusion process [8,76].
The dual print head used separate heads while in-nozzle
impregnation impregnates molten filaments with fibers within the
print head. In-nozzle impregnation is limited to fiber-reinforced
composites while dual-print head can be utilized for fiber and nano-
material reinforced composites. In-nozzle impregnation is prone
to fiber misalignment, pull out, poor adhesion between fiber and
polymer and fiber breakage during printing. Dual-print head has
a percolation threshold of 33% for fiber-reinforced composites as
compared to 10 wt% using extrusion [27,7]. Also, the use of dual
print head in 3D printed parts lead to formation of anisotropic
materials [50]. However, the distribution of amorphous materials
using dual-head 3D printing allow an anisotropic heat distribution
with the 3D printed parts [50].
5. Comparison of FDM, SLS, and LDM
Tables 4 and 5 show the comparison of thermoplastic compos-
ites used in FDM, SLS, and LDM. FDM has been used in extrusion
and layer-by-layer deposition of thermoplastic materials [1]. The
process of mixing fillers with polymers at its molten state is much
easier as compared using the dissolution-precipitation method.
Therefore, a wide range of fillers are available for FDM such as
particle, fiber, nanomaterial and polymer blends except for nat-
ural fibers. Natural fibers tend to degrade at elevated temperatures
[40]. SLS creates a solid object by fusing powder materials through
directed heating and partial melting [12]. An SLS printer has a
required particle size of powder to be used in printing objects [61].
This is the reason why the applicable fillers for SLS are limited to
the particle, short fiber, and nanomaterial. Powder materials used
in SLS can be categorized into separate grains, composite grains,
and coated grains. Liquid deposition modeling (LDM) extrudes vis-
cous liquid instead of melted filaments [76]. Preparation of viscous
liquids with LDM is the challenging part since it involves proper
selection of solvents applicable to polymers and its fillers without
compromising the rheological requirements for printing such as
storage modulus (G’ > 1000 Pa) and yield stress ( > 200 Pa) [81].
6. Applications
There are many possible applications for AM using thermoplas-
tic materials and composites. They are for aerospace, automotive,
marine, tooling, gauges, molds, and other industries where high-
value adding allows for limited production and more complex
designs using AM. However, it is not yet able to compete with tra-
ditional formative and subtractive manufacturing in high volume
parts production for OEM in performance/cost ratio. The following
are some applications of 3d-printed thermoplastic materials and
composites.
Nanomaterial Reinforced Composites Polymer Blends
X X
X
X
6.1. Aerospace
Enhanced mechanical properties of the thermoplastic compos-
ite enable the application of AM in the areas of aviation and
aerospace (including military) [26]. The advantage of using AM
especially in the area of aerospace are as follows: reduce time
to market; complex-design tools; flexibility to design iterations;
tooling at lower costs; waste reduction; improved functional-
ity with embedded electronics; part simplification and intricate
geometries; ease of product customization; production at or near
point of use; collaboration with suppliers to create new prod-
ucts with AM, and; acquisition of niche AM providers to build
in-house AM capabilities [34]. Despite the benefits provided by
AM, several obstacles are preventing it from being applicable in
the aerospace sector. These include size and scalability limitations;
narrow range of materials and high material cost; limited multi-
material printing capability, and; quality consistency [34]. Recent
advances in the development of thermoplastic composites for AM
technologies will, however, provide new opportunities for research
organizations to address the challenges currently associated with
AM. Another opportunity is to explore different engineering prop-
erties from new polymers that are suitable for lightweight and
fire-resistant properties.
6.2. Medical parts and devices
Recent studies in the field of AM focused on biocompatibility
and cellular viability [83]. Porous scaffolds can be designed and
fabricated using AM and can be used as bone grafts through 3D
interconnectivity that can promote the richer supply of blood, oxy-
gen, and nutrients for healthy in-growth of bone cells. In order to
fabricate high-quality medical parts, the physical, mechanical, and
biological properties of the materials used are critical [41]. Porous
scaffolds with a shape memory effect can be fabricated by additive
manufacturing and used as self-fitting implants for bone replace-
ment [43]. Other possible medical and biomedical applications are
in orthopedic devices, prosthesis, medical instrument fabrication.
Dental applications have been gaining ground in terms of commer-
cial success for AM.
6.3. Rapid tooling and rapid molding
Rapid tooling and rapid molding refer to direct fabrication of
molds with different types of rapid prototyping techniques such
as AM. Important characteristics of the mold should be consid-
ered, such as the benchmark mechanical properties, dimensional
accuracy and surface quality through post-processing [84]. Additive
manufacturing is applicable for direct rapid tooling applications
since it reduces the lead time needed to produce molds using
traditional subtractive manufacturing techniques such as milling.
Further research is needed for design optimization, selection of
materials with good thermal stability and heat dissipation, and an
increase in tool life [37] to enable high production capacities. A
major challenge that researchers will have to overcome is poor
thermo-mechanical properties based on deformation and expan-
sion (heat capacity and coefficient of thermal expansion), that
result in poor reproduction or loss of design integrity over usage
and time. In order to compete with metals and milled shapes (tools,
 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
molds, and casts), these properties for polymers and composites
need to be improved.
7. Challenges with the use of thermoplastic composites in
AM
7.1. Defects due to fillers
The formation of voids and microvoids is a common problem
when fillers are introduced into a thermoplastic. Poor adhesion
and vaporization of volatile compounds with fillers themselves
during melt blending and material extrusion causes the forma-
tion of voids and microvoids. The quality of the finished product
depends on the quality of mixing process [21]. Under stress load-
ing, defects propagate crack nucleation and can cause inconsistent
quality and properties in printed parts [40]. For particle-based and
nanomaterial-based composites, agglomeration and non-uniform
dispersion is a common problem. Further increase in filler loading
in composites with agglomoreation and non-uniform dispersion
may not be cost-effective especially with higher cost fillers and
nanofillers. Also, a variety of particle size within the thermoplastic
composites can cause inconsistent thermo-mechanical properties
of the thermoplastic composites [37].
For fiber-reinforced based composites, commercially avail-
able 3D printers are limited to printing short fiber reinforced
thermoplastic composites. The use of continuous fiber reinforce-
ment in a printed part requires complex print head designs and
computer programming. Also, poor adhesion between fiber and
thermoplastic can cause inconsistent quality and properties of the
thermoplastic composites. Preprocessing is needed to ensure good
fiber-matrix adhesion [25,46]. Natural fibers can thermally degrade
at an elevated temperature that caused the formation of voids [40].
7.2. 3D printer design limitations
Commercially available printers are not designed to handle ther-
moplastic composites with different filler types and loadings. For
SLS printing, thermoplastic composites should be prepared into a
fine powder in order to ensure good flowability during printing
[30]. For FDM, it is difficult to introduced fibers in 3D printing due
to limited types of the commercially-available nozzle. The use of
more anisotropic and larger fillers can cause nozzle clogging and
abrasion [32]. In LDM, the use of a highly volatile solvent is needed
to allow the material to flow through the nozzle. Further research
is needed in order to explore the applicability of other solvents in
LDM. It is important to consider the type of solvents that are being
used since it is highly dependent on the polymer solubility.
8. Summary and conclusion
In this review, an overview and discussion of the different types
of processing techniques and materials for 3D printed thermo-
plastic composites are provided. The most common method used
in the preparation of thermoplastic composite materials is melt
blending and extrusion due to its simple approach and ease of
preparation. Preparation of composite powders or coated powders
can be performed either by melt blending/milling or dissolution-
precipitation. Composite or coated powders improve the adhesion
between fillers and matrix. Current efforts focus on the improve-
ment of the print-head design of FDM printers through in-nozzle
impregnation and dual print heads. In the future, this should allow
for the 3D printing of a larger variety of thermoplastic composites
without the need for preprocessing or mixing. Also, new variants
of AM techniques (such as LDM) are developed that allow for with
higher filler loading in thermoplastic composites. Because of the
17
need for solvents, the application of LDM in 3D printing thermo-
plastic composites remains limited, and further research is needed.
While thermoplastics and thermoplastic composites have been
successfully applied in AM (including particle, fiber-, nanomaterial,
and polymer-polymer composites) the application of AM in filled
systems still needs to be optimized for each new type of printer
head that is being developed. Even with the addition of fillers,
there is no assurance that the thermo-mechanical properties of the
printed material are bound to improve. As noted, filler addition
can result in the unpredictable formation of defects. To control and
reduce defect formation, it is important to understand the nature
of compatibilization, miscibility, and surface migration to improve
the properties. Aggregation and agglomeration of fillers is a fre-
quent problem in filled systems. Also, understanding the quenching
properties and their effect on the semi-crystalline nature of the
extruded material and adhesion between deposited layers is a pri-
mary concern.
Highly oriented and continuous fiber reinforcements increase
the properties of printed parts as compared to unfilled thermoplas-
tics. The use of synthetic fibers in thermoplastics leads to improved
properties during preparation and printing. The use of natural fibers
such as jute fiber is not recommended since these materials tend
to degrade at higher extrusion temperatures. Also, at high temper-
atures, gas compounds can evolve that leads to micro-voids within
the filament, and 3D printed part.
With thermoplastic composites, the use of nanomaterials
improves mechanical properties without compromising thermal
stability at the right percolation threshold. Also, nanocompos-
ites enable 3D printed parts with low electrical resistance and
biodegradable flame retardant properties. However, the use of
nanomaterials in AM has certain limitations. First of all, the filler
loading is limited to the nozzle size in order to avoid nozzle
clogging. Besides, agglomeration of fillers in the thermoplastic
matrix is an unpredictable problem with nanomaterials and can
be addressed by surface treatment of nanomaterial fillers. More-
over, the inclusion of these fillers could result in micro defects such
as voids. Lastly, commercially available printers that use nanoma-
terials can abrade the nozzle surface opening which would make
nozzle replacement more frequent.
While not thoroughly discussed in this review, the issue of sur-
face adhesion between printed layers, especially with FDM, needs
to be addressed since this can be the main reasons for part fail-
ure as various polymers have different quenching characteristics
once extruded from the nozzle head. The temperature and humid-
ity in the printer oven can have dramatic effects on the failure
modes and void space formation during the extrusion of individual
layers.
In summary, the extension of AM to filled polymers holds the
promise of novel applications and improved properties of AM
fabricated parts. However, the required optimization of process
parameters depending on materials system and AM techniques
presents a challenge for the AM of filled polymers and defines
the need for future research. It is hoped that this article will help
advance the general applicability of thermoplastic composites and
nanocomposites in AM.
A portion of this work is funded by the Department of Energy’s
Kansas City National Security Campus, operated by Honeywell Fed-
eral Manufacturing & Technologies, LLC under contract number
DE-NA0002839.
Disclaimer
The Department of Energy’s Kansas City National Security Cam-
pus is operated and managed by Honeywell Federal Manufacturing
& Technologies, LLC under contract number DE-NA0002839.
18 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
Acknowledgment
The work at the Advincula Research Group has been supported
by Department of Science and Technology-Philippine Council for
Industry, Energy, and Emerging Technology Research and Devel-
opment (DOST-PCIEERD), Honeywell- National Security Campus
(KCNSC), and PETROCase at Case Western Reserve University. A
portion of this work (RCA) is funded by the Department of Energy’s
Kansas City National Security Campus, operated by Honeywell Fed-
eral Manufacturing & Technologies, LLC under contract number
DE-NA0002839.
References
[1] Anonymous, ASTM international, ASTM F2792. Standard terminology for
additive manufacturing technologies (No. F2792-12a). ASTM Int; 2013, 3.
[2] Lim CWJ, Le KQ, Lu Q, Wong CH. An overview of 3-D printing in the
manufacturing, aerospace, and automotive industries. Smart Manuf IEEE
Potentials 2016;35:18–22.
[3] Hull CW. Apparatus for production of three-dimensional objects by
stereolithography; 1986. US4575330A 16 pp.
[4] Manapat JZ, Chen Q, Ye P, Advincula RC. 3D Printing of Polymer
Nanocomposites via Stereolithography. Macromol Mater Eng 2017;302,
1600553/1–13.
[5] Yan C, Hao L, Xu L, Shi Y. Preparation, characterisation and processing of
carbon fibre / polyamide-12 composites for selective laser sintering. Compos
Sci Technol 2014;71:1834–41.
[6] Schmidt J, Sachs M, Blümel C, Winzer B, Toni F, Wirth K, et al. A novel process
route for the production of spherical LBM polymer powders with small size
and good flowability. Powder Technol 2014;261:78–86.
[7] Nikzad M, Masood SH, Sbarski I. Thermo-mechanical properties of a highly
filled polymeric composites for Fused Deposition Modeling. Mater Des
2011;32:3448–56.
[8] Postiglione G, Natale G, Griffini G, Levi M, Turri S. Conductive 3D
microstructures by direct 3D printing of polymer / carbon nanotube
nanocomposites via liquid deposition modeling. Compos Part A Appl Sci
Manuf 2015;76:110–4.
[9] Dizon JRC, Chen Q, Valino AD, Advincula RC. Thermo-mechanical and swelling
properties of three-dimensional-printed poly (ethylene glycol)
diacrylate/silica nanocomposites. MRS Commun 2018;9:209–17.
[10] Postiglione G, Natale G, Griffini G, Levi M, Turri S. UV-assisted
three-dimensional printing of polymer nanocomposites based on inorganic
fillers. Polym Compos 2017;38:1662–70.
[11] Ning F, Cong W, Qiu J, Wei J, Wang S. Additive manufacturing of carbon fiber
reinforced thermoplastic composites using fused deposition modeling.
Compos Part B Eng 2015;80:369–78.
[12] Wang X, Jiang M, Zhou Z, Gou J, Hui D. 3D printing of polymer matrix
composites : a review and prospective. Compos Part B Eng 2017;110:442–58.
[13] Zhu L, Li N, Childs PRN. Light-weighting in aerospace component and system
design. Propuls Power Res 2018;7:103–19.
[14] De Leon AC, Chen Q, Palaganas NB, Palaganas JO, Manapat J, Advincula RC.
High performance polymer nanocomposites for additive manufacturing
applications. React Funct Polym 2016;103:141–55.
[15] Frketic J, Dickens T, Ramakrishnan S. Automated manufacturing and
processing of fiber-reinforced polymer (FRP) composites : An additive review
of contemporary and modern techniques for advanced materials
manufacturing. Addit Manuf 2017;14:69–86.
[16] Ching YC, Chuah CH, Ching KY, Abdullah LC, Rahman A. 5 - applications of
thermoplastic-based blends. In: Visakh PM, Markovic G, Pasquini D, editors.
Recent developments in polymer macro, micro and nano blends. Cambridge:
Woodhead Publishing; 2017. p. 111–29.
[17] Dizon JRC, Espera AH, Chen Q, Advincula RC. Mechanical characterization of
3D-Printed polymers. Addit. Manuf 2017;20:44–67.
[18] Patel A, Sahu D, Dashora A, Garg R, Agraval P, Patel P, et al. A review of hot
melt extrusion technique. Int J Innov Res Sci Eng Technol 2013;2:2194–8.
[19] Allen KA. Processing of thermoplastic composites. In: Kessler M, editor.
Polymer and composites processing. Online-Iowa State Univ; 2012. Chapt
1/1-10 https://polycomp.mse.iastate.edu/files/2012/01/Whole-Class-Book-
Project-Chapter-1-14.pdf/.
[20] Morris BA, Chapter 6 Polymer blending for packaging applications. Sci.
Technol. Flex. Packag 2017:149–77.
[21] Wolcott MP, Englund K. A technology review of Wood-plastic composites.
33rd Int. Part. Mater. Symp 1999:103–11.
[22] Yang J, Chen Q, Chen F, Zhang Q, Wang K, Fu Q. Realizing the full nanofiller
enhancement in melt-spun fibers of poly (vinylidene fluoride)/carbon
nanotube composites. Nanotechnol 2011;22, 355707/1-10.
[23] Krisna LSR, Gundeti A. A Comparative study on the components fabricated by
injection moulding and FDM 3D printing process. Int J Mech Prod Eng Res Dev
2017;5:116–21.
[24] Hoa SV. Principles of the manufacturing of composite materials. Lancaster:
DEStech Publications Inc.; 2009, 343pp.
[25] Matsuzaki R, Ueda M, Namiki M, Jeong T-K, Asahara H, Horiguchi K, et al.
Three-dimensional printing of continuous-fiber composites by in-nozzle
impregnation. Sci Rep 2016, 6/1-7.
[26] Tian X, Liu T, Yang C, Wang Q, Li D. Interface and performance of 3D printed
continuous carbon fiber reinforced PLA composites. Compos Part A Appl Sci
Manuf 2016;88:198–205.
[27] Dickson AN, Barry JN, Mcdonnell KA, Dowling DP. Fabrication of continuous
carbon, glass and Kevlar fibre reinforced polymer composites using additive
manufacturing. Addit Manuf 2017;16:146–52.
[28] PIJP Kruth, Mercelis IP, Van Vaerenbergh J, Froyen PIL, Rombouts IM. Binding
mechanisms in selective laser sintering and selective laser melting. Rapid
Prototyp J 2005;11:26–36.
[29] Chung H, Das S. Functionally graded Nylon-11 / silica nanocomposites
produced by selective laser sintering. Mater Sci Eng A 2008;487:251–7.
[30] Zhang Y, Hao L, Savalani MM, Harris RA, Tanner KE. Characterization and
dynamic mechanical analysis of selective laser sintered hydroxyapatite-filled
polymeric composites. J Biomed Mater Res Part B Appl Biomater
2008;86A:607–16.
[31] Cheng S, Grest GS. Dispersing nanoparticles in a polymer film via solvent
evaporation. ACS Macro Lett 2016;5:694–8.
[32] Gnanasekaran K, Heijmans T, Bennekom SVan, Woldhuis H, Wijnia S. 3D
printing of CNT- and graphene-based conductive polymer nanocomposites by
fused deposition modeling. Appl Mater Today 2017;9:21–8.
[33] Bai J, Goodridge RD, Hague RJM, Song M. Influence of carbon nanotubes on the
rheology and dynamic mechanical properties of polyamide-12 for laser
sintering. Polym Test 2014;36:95–100.
[34] Coykendall J, Cotteleer M, Holdowsky J, Mahto M. 3D opportunity in a
erospace and defense: additive Manufacturing takes flight. New York:
Deloitte University Press; 2014, 28pp.
[35] Chen Q, Zhao J, Ren J, Rong L, Cao PF, Advincula RC. 3D Printed
Multifunctional, Hyperelastic Silicone Rubber Foam. Advincula, R. C., Adv.
Funct. Mater 2019;30, 1900469/1-9.
[36] a Anonymous. High quality filament PEEK, PEEKQ, PEI, PPSU, PCL, PETG, ABS,
PLA, C8; 2019, accessed March2019 https://www.3d4makers.com/;
b Anonymous. Ultra-performance 3D printing filament; 2019, accessed
March2019 https://www.3dxtech.com;
c Acquah SFA, Leonhardt BE, Nowotarski MS, Magi JM, Chambliss KA, Venzel
TES, et al. Carbon nanotubes and graphene as additives in 3D printing. In:
Berber M, Hafez IH, editors. Carbon nanotubes - current progress of their
polymer composites. London: IntechOpen; 2016. p. 227–51;
d Anonymous. Blackmagic3d; 2019, accessed March2019 http://www.
blackmagic3d.com/.
[37] Masood SH, Song WQ. Development of new metal / polymer materials for
rapid tooling using Fused deposition modelling. Mater Des 2004;25:587–94.
[38] Sa’ude N, Ibrahim M, Ibrahim MHI. Mechanical properties of highly filled
lron-ABS composites in injection molding for FDM wire filament. Mater Sci
Forum 2014;773–774:456–61.
[39] Kwok SW, Hin K, Goh H, Tan ZD, Ting S, Tan M, et al. Electrically conductive
filament for 3D-printed circuits and sensors. Appl Mater Today
2017;9:167–75.
[40] Torrado AR, Shemelya CM, English JD, Lin Y, Wicker RB, Roberson DA.
Characterizing the effect of additives to ABS on the mechanical property
anisotropy of specimens fabricated by material extrusion 3D printing. Addit
Manuf 2015;6:16–29.
[41] Jyoti S, Bose S, Hosick HL, Bandyopadhyay A. Development of controlled
porosity polymer-ceramic composite scaffolds via fused deposition modeling.
Mater Sci Eng 2003;C23:611–20.
[42] Singh R, Bedi P, Fraternali F, Ahuja IPS. Effect of single particle size, double
particle size and triple particle size Al2O3 in Nylon-6 matrix on mechanical
properties of feed stock filament for FDM. Compos Part B Eng 2016;106:20–7.
[43] Senatov FS, Niaza KV, Zadorozhnyy MY, Maksimkin AV, Kaloshkin SD, Estrin
YZ. Mechanical properties and shape memory effect of 3D-printed PLA-based
porous scaffolds. J Mech Behav Biomed Mater 2016;57:139–48.
[44] Jia Y, He H, Geng Y, Huang B, Peng X. High through-plane thermal
conductivity of polymer based product with vertical alignment of graphite fl
akes achieved via 3D printing. Compos Sci Technol 2017;145:55–61.
[45] Thiago R, Ferreira L, Cardoso I, Assis T, Bürger D. Experimental
characterization and micrography of 3D printed PLA and PLA reinforced with
short carbon fibers. Compos Part B Eng 2017;124:88–100.
[46] Tekinalp HL, Kunc V, Velez-garcia GM, Duty CE, Love LJ, Naskar AK, et al.
Highly oriented carbon fiber – polymer composites via additive
manufacturing. Compos Sci Technol 2014;105:144–50.
[47] Chen Q, Mangadlao JD, Wallat J, De Leon A, Pokorski JK, Advincula RC. 3D
printing biocompatible polyurethane/poly(lactic acid)/graphene oxide
nanocomposites: anisotropic properties. ACS Appl Mater Interfaces
2017;9:4015–23.
[48] Dul S, Fambri L, Pegoretti A. Fused deposition modelling with ABS – graphene
nanocomposites. Compos Part A Appl Sci Manuf 2016;85:181–91.
[49] Guo Y, Chang C, Halada G, Cuiffo MA, Xue Y, Zuo X, et al. Engineering flame
retardant biodegradable polymer nanocomposites and their application in 3D
printing. Polym Degrad Stab 2017;137:205–15.
[50] Zhuang Y, Song W, Ning G, Sun X, Sun Z, Xu G, et al. Materials & Design 3D –
printing of materials with anisotropic heat distribution using conductive
polylactic acid composites. Mater Des 2017;126:135–40.
[51] Ramli MS, Wahab MS, Ahmad M, Bala AS. FDM preparation of bio-compatible
uhmwpe polymer for artificial implant. ARPN J Eng Appl Sci 2016;11:5474–80.
 A.D. Valino, J.R.C. Dizon, A.H. Espera Jr. et al. / Progress in Polymer Science 98 (2019) 101162
[52] Roberson DA, Siqueiros JG. Novel polycarbonate / SEBS-g-MA blend for
FDM-Type 3D printing. Soc. Plast. Eng. ANTECTM Indianap 2016;2016:10–4.
[53] Zaldivar RJ, Mclouth TD, Ferrelli GL, Patel DN, Hopkins AR, Witkin D. Effect of
initial filament moisture content on the microstructure and mechanical
performance of ULTEM® 9085 3D printed parts. Addit Manuf 2018;24:457–66.
[54] Espera AH, Dizon JRC, Chen Q, Advincula RC. 3D-printing and advanced
manufacturing for electronics. Prog Addit Manuf 2019:23 pp, http://dx.doi.
org/10.1007/s40964-019-00077-7.
[55] Attar E. Simulation of selective Electron beam melting processes. Erlangen
Germany: University of Erlangen-Nuremberg; 2011, 150pp.
[56] Wudy K, Drummer D. Infiltration behavior of thermosets for use in a
combined selective laser sintering process of polymers. JOM 2019;71:920–7.
[57] Cima M, Cornie J. Three-dimensional printing: rapid tooling and prototypes
directly from a CAD model. Ann CIRP 1990;39:201–4.
[58] Kerns J. What’s the difference between stereolithography and selective laser
sintering?; 2015, accessed July 2019 https://www.machinedesign.com/3d-
printing/what-s-difference-between-stereolithography-and-selective-laser-
sintering/.
[59] Gibson I, Shi D. Material properties and fabrication parameters in selective
laser sintering process. Rapid Prototyp J 1997;3:129–36.
[60] Kim GD, Oh YT. A benchmark study on rapid prototyping processes and
machines: quantitative comparisons of mechanical properties, accuracy,
roughness, speed, and material cost. Proc Inst Mech Eng B J Eng Manuf
2008;222:201–15.
[61] Espera Jr AH, Valino AD, Palaganas JO, Souza L, Chen Q, Advincula RC. 3D
printing of a robust Polyamide-12-Carbon black composite via selective laser
sintering: thermal and electrical conductivity. Macromol Mater Eng
2019;182, 1800718./1-8.
[62] Chunze Y, Yusheng S, Jinsong Y, Jinhui L. A Nanosilica/Nylon-12 Composite
Powder for Selective Laser Sintering. J Reinf Plast Compos 2008;28:2889–902.
[63] Kim JÃ, Creasy TS. Selective laser sintering characteristics of nylon 6 /
clay-reinforced nanocomposite. Polym Test 2004;23:629–36.
[64] Kim HC, Hahn HT, Yang YS. Synthesis of PA12/functionalized GNP
nanocomposite powders for the selective laser sintering process. J Compos
Mater 2012;47:501–9.
[65] Udroiu R. Powder bed additive manufacturing systems and its applications.
Acad J Manuf Eng 2015;10:122–9.
[66] Bremen S, Meiners W, Diatlov A. Selective Laser Melting. Laser Tech J
2012;9:33–8.
[67] Jacobsmühlen Jzur, Kleszczynski S, Witt G, Merhof D. Compound quality
assessment in laser beam melting processes using layer images. 2017 IEEE Int
Instrum Meas Technol Conf 2017:1–6.
[68] Drummer D, Drexler M, Wudy K. Density of laser molten polymer parts as
function of powder coating process during additive manufacturing. Procedia
Eng 2015;102:1908–17.
[69] Drummer D, Drexler M, Wudy K. Derivation of heating rate dependent
exposure strategies for the selective laser melting of thermoplastic polymers.
Am Inst Phys Conf Proceeding 2015;1664, 160006/1–5.
19
[70] Drummer D, Medina-hernández M, Drexler M, Wudy K. Polymer powder
production for laser melting through immiscible blends. Procedia Eng
2015;102:1918–25.
[71] Laumer T, Karg M, Schmidt M. Laser beam melting of multi-material
components. Phys Procedia 2012;39:518–25.
[72] Schmidt J, Sachs M, Fanselow S, Zhao M, Romeis S, Drummer D, et al.
Optimized polybutylene terephthalate powders for selective laser beam
melting. Chem Eng Sci 2016;156:1–10.
[73] Schmidt J, Sachs M, Blumel C, Winzer B, Toni F, Wirth K-E, et al. A novel
process route for the production of spherical SLS polymer powders. Powder
Technol 2015;102:550–6.
[74] Chen Q, Cao PF, Advincula RC. Mechanically robust, ultraelastic hierarchical
foam with tunable properties via 3d printing. Adv Funct Mater 2018;28,
1800631/1-9.
[75] Hurt C, Brandt M, Priya SS, Bhatelia T, Patel J, Selvakannan PR, et al.
Combining additive manufacturing and catalysis: a review. Catal Sci Technol
2017;7:3421–39.
[76] Chizari K, Daoud MA, Ravindran AR, Therriault D. 3D printing of highly
conductive nanocomposites for the functional optimization of liquid sensors.
Small 2016;12:6076–82.
[77] Wei P, Leng H, Chen Q, Advincula R, Pentzer EB. Reprocessable 3D-printed
conductive elastomeric composite foams for strain and gas sensing. ACS Appl
Polym Mater 2019;1:885–92.
[78] Zhu C, TY-J Han, Duoss EB, Golobic AM, Kuntz JD, Spadaccini CM, et al. Highly
compressible 3D periodic graphene aerogel microlattices. Nat Commun
2015;6, 6962/1-8.
[79] Minas C, Carnelli D, Tervoort E, Studart AR. 3D printing of emulsions and
foams into hierarchical porous ceramics. Adv Mater 2016;28:9993–9.
[80] Jakus AE, Taylor SL, Geisendorfer NR, Dunand DC, Shah RN. Metallic
architectures from 3D-Printed powder-based liquid inks. Adv Funct Mater
2015;25:6985–95.
[81] Duoss EB, Weisgraber TH, Hearon K, Zhu C, Small W, Metz TR, et al.
Three-dimensional printing of elastomeric, cellular architectures with
negative stiffness. Adv Funct Mater 2014;24:4905–13.
[82] Ahmad M, Wahit MU, Rafiq M, Zaman K, Jawaid M. Thermal and mechanical
properties of ultrahigh molecular weight polyethylene/high-density
polyethylene/polyethylene glycol blends. J Polym Eng 2013;33:599–614.
[83] Palaganas NB, Mangadlao JD, de Leon ACC, Palaganas JO, Pangilinan KD, Lee YJ,
et al. 3D Printing of photocurable cellulose nanocrystal composite for
fabrication of complex architectures via stereolithography. ACS Appl Mater
Interfaces 2017;9:34314–24.
[84] Yan Y, Li S, Zhang R, Lin F, Wu R, Lu Q. Rapid prototyping and manufacturing
technology : principle, representative technics, applications, and
development trends *. Tsinghua Sci Technol 2009;14(Suppl. 1):1–12.
[85] Patil H, Tiwari RV, Repka MA. Hot-melt extrusion: from theory to application
in pharmaceutical formulation. AAPS PharmSciTech 2016;17:20–42.