Direct Ink Writing Technology (3D Printing) of Graphene-Based Ceramic Nanocomposites: A Review

nanomaterials
Review
Direct Ink Writing Technology (3D Printing) of
Graphene-Based Ceramic Nanocomposites: A Review
Nestor Washington Solís Pinargote * , Anton Smirnov * , Nikita Peretyagin, Anton Seleznev
and Pavel Peretyagin
Spark Plasma Sintering Research Laboratory, Moscow State University of Technology “STANKIN”,
Vadkovsky per. 1, Moscow 127055, Russia; [email protected] (N.P.); [email protected] (A.S.);
[email protected] (P.P.)
* Correspondence: [email protected] (N.W.S.P.); [email protected] (A.S.);
Tel.: +7-4999-7323-70 (N.W.S.P. & A.S.)

Received: 2 June 2020; Accepted: 27 June 2020; Published: 2 July 2020
Abstract: In the present work, the state of the art of the most common additive manufacturing
(AM) technologies used for the manufacturing of complex shape structures of graphene-based
ceramic nanocomposites, ceramic and graphene-based parts is explained. A brief overview of the AM
processes for ceramic, which are grouped by the type of feedstock used in each technology, is presented.
The main technical factors that affect the quality of the final product were reviewed. The AM processes
used for 3D printing of graphene-based materials are described in more detail; moreover, some studies
in a wide range of applications related to these AM techniques are cited. Furthermore, different
feedstock formulations and their corresponding rheological behavior were explained. Additionally,
the most important works about the fabrication of composites using graphene-based ceramic pastes
by Direct Ink Writing (DIW) are disclosed in detail and illustrated with representative examples.
Various examples of the most relevant approaches for the manufacturing of graphene-based ceramic
nanocomposites by DIW are provided.
Keywords: additive manufacturing; graphene oxide; graphene-based paste; direct ink writing;
ceramic nanocomposites
1. Introduction
A ceramic is a nonmetallic, inorganic solid [1], which has exceptional and diverse physical
and chemical properties that characterize it as a multipurpose material. Typical properties that can
be found in ceramics materials are ultra-high-temperature ability, excellent wear resistance, great
hardness and mechanical strength, high melting points, good thermal stability, and chemical inertness,
low density, and low electrical and thermal conductivity. Thanks to these properties, ceramics are
used in multifunctional applications such as biomedical engineering, electronics, aerospace, chemical
industry, and machinery [2]. Note that the advantage of ceramics over other materials is the ability to
obtain predetermined characteristics by changing the raw materials composition and the production
technology [3–8]. Commonly, raw materials are composed by mixtures of ceramic powders with or
without binders and additives, and these mixtures are used to form green bodies with desired simple
shape by different forming methods as dry pressing, slip casting, injection molding, gel casting, tape
casting, extrusion and others [9,10]. After forming, the green parts are very soft; therefore, it is necessary
to apply heat upon them to get a dense product by sintering. Sintering can be defined as a thermal
process at higher temperatures with or without pressure for compacting and forming a solid structure
via mass transport events that often occur on the diffusional processes [10]. Although traditional
methods of ceramic forming are well-studied and widespread, they have several drawbacks such as
Nanomaterials 2020, 10, 1300; doi:10.3390/nano10071300 www.mdpi.com/journal/nanomaterials

Nanomaterials 2020, 10, 1300 2 of 48
high cost, long processing times and the impossibility of producing pieces with interconnected holes or
with highly complex shapes. In addition, for obtaining a sintered ceramic part with high surface quality
and accuracy, mechanical post-processing work is necessary. This post-process work is expensive and
time-consuming due to the natural high hardness and brittleness of ceramics materials [2,11].
Over the past 30 years, new technologies for processing materials called additive manufacturing
(AM) have been developed rapidly and they are being introduced more and more every day in a
wide range of fields thanks to their ability to produce, in a very fast and cheap way, complex 3d parts
by adding material instead of cutting it away. AM, also known as three-dimensional (3D) printing
technologies [12], can be explained as a technique of blending materials by either fusion, binding,
or solidifying materials such as liquid resin and different powders materials. These technologies
build a part in a precisely adding material layer-by-layer fashion using 3D computer-aided design
(CAD) modeling [13], and their advantages include design freedom, low-quantity economy, material
efficiency, reduced assembly and predictable production.
AM involves a group of advanced manufacturing technologies that allow the flexible production
of precise structures with highly complex shapes, which are complicated to manufacture using
conventional methods like machining or casting [14].
In 2015, the International Organization for Standardization Technical Committee (ISO/TC 261)
on AM together with the American Society for Testing Materials (ASTM) Committee F42 released a
new International Standard ISO/ASTM 52900:2015 in which the terms used in AM are established
and defined [15]. In this standard, the AM technologies have been classified into groups taking into
consideration the feedstock type, the deposition technique, and the fusing or solidification way of
material. Table 1 categorizes the most popular AM technologies in the industry today into the following
groups: vat photopolymerization, material jetting, binder jetting, powder bed fusion, direct energy
deposition, sheet lamination, and material extrusion.
Table 1. Groups of additive manufacturing technologies by the International Organization for

Standardization (ISO)/American Society for Testing Materials (ASTM) 52900:2015.
Additive Manufacturing
Category Abbreviation Feedstock
Technology Type
Stereolithography SLA Liquid photopolymers, hybrid
Digital Light Processing DLP polymer-ceramic, hybrid
Vat photopolymerization
Two-Photon Polymerization TPP polymer-graphene
Continuous Liquid Interface
CLIP Liquid photopolymers
Production
Multi Jet Fusion MJF Thermoplastic polymers
Selective Laser Sintering SLS Plastics, composites
Powder bed fusion
Selective Laser Melting SLM Metals
Electron Beam Melting EBM Metals
Material Jetting MJ Photopolymers
Material jetting NanoParticle Jetting NPJ Metals, ceramics
Drop On Demand DOD Wax, ceramic-, graphene-inks
Thermoplastic polymers, metal-,
Fused Deposition Modeling FDM ceramic-, graphene-reinforced
Material Extrusion
polymers
Direct Ink Writing DIW Ceramics
Electron Beam Additive
EBAM Metals and alloys in the form of
Direct Energy Deposition Manufacturing
powder or wire
Laser Engineering Net Shape LENS
Binder jetting Binder Jetting BJ Ceramic, metal, gypsum, sand
Ceramic, metal-filled tapes, paper,
Sheet Lamination Laminated Object Manufacturing LOM
polymer composites.
The main differences between each of the categories mentioned above can be summarized as
follows [16]:
• In vat photopolymerization the 3D object is created layer by layer thanks to the curing of a liquid
photopolymer resin under the influence of an ultraviolet (UV) light. The liquid photopolymer
is held in a vat with a built support submerged near the surface of the resin. Then the UV
light is directed to the resin surface following a determined path thus allowing a selective local
polymerization of the liquid photopolymer. After that, the built support is re-submerged into the
resin and the process is repeated until the 3D object is fully obtained;
• The material jetting principle is used to create a solid 3D object layer by layer from droplets,
which are mainly composed of liquid photopolymer resin, that are selectively sprayed by an
inkjet-style printhead and immediately cured thanks to the expose of a UV light. Commonly,
technologies that work under this principle are compared to the two-dimensional (2D) inkjet
printing, which deposits only a single layer of ink droplets;
• In the technologies that operate under the principles of binder jetting a liquid binder, which is
selectively deposited by drops onto a powder-based material using an inkjet-style print head,
is utilized in order to produce a solid 3D object layer by layer. During the process, alternate layers
of powder material and binding material are depositing as follow: powder particles are spread
over a built support using a roller while the print head deposits the liquid binder, which acts as a
glue between powder particles and layers, on top of the powder bed; after that, the built support
is lowered by the model’s layer thickness and then the process is repeated until the 3D object
is formed;
• The powder bed fusion category utilizes an energy source that allows the local sintering or melting
between the particles of a powder material for the forming of a solid 3D object layer by layer.
The energy sources can be lasers or electron beams depending on the using material powder.
The electron beam is necessary for metals, while lasers are required for polymers. The forming
part process is very similar to binder jetting: powder particles are spread over a built support
using a roller while the energy source fuses the first layer; after that, the built support is lowered
by the model’s layer thickness and a new layer of powder is spread across the previous layer
repeating the process until the 3D object is formed;
• In direct energy deposition the 3D object is created layer by layer thanks to the directly melting of
build-material and deposing them on the workpiece using a focused thermal energy source such
as laser, electron beam or plasma arc. This principle can be applied for a wide kind of materials
such as polymers, ceramics, and metal framework composites; however, it is predominantly used
for wire and powder metals, which explains why this technology is often called metal deposition.
Direct energy deposition utilizes a nozzle mounted on a multi-axis arm can move freely in any
direction of the x, y and z-axes that deposits melted material onto the predetermined workpiece
surface, where it is automatically solidified;
• In sheet lamination a 3D part is created by bonding together, layer-by-layer, thin sheets of material
(usually supplied via a system of feed rollers), which is then cutting into a final 3D object. In the
process, the sheet material is positioned on the cutting bed and then it is bonded over the previous
layer using any suitable sticky method; after that, the required shape is cut by laser or knife and
the process is repeated until the 3D object is formed. Laminated object manufacturing (LOM) and
ultrasonic consolidation (UC) are both examples of sheet lamination techniques;
• Material extrusion is a category of AM, in which the 3D object is formed by a layer by layer
selective deposition of the extruded build-material through a nozzle in a continuous stream.
In material extrusion, the layers are built when the nozzle deposits a viscoelastic material where it
is required. The following layers are added on top of previous layers and bonded upon deposition
as the material shows viscoelastic behavior. In the last past years, this technology became popular
in the world for its use in 3D printers. Direct Ink Writing (DIW) and Fused deposition modeling
(FDM) are the two common technologies that operate under the principles of material extrusion.
However, in the last past years, a new AM technique named Pyro-EHD Tethered Electrospinning
(TPES) that is based on electrohydrodynamic processes and can be related to material extrusion
category became more and more popular [17–19].
The introduction of AM into the ceramic forming process proposes a powerful way of producing
complex 3D parts. However, despite the wide variety of AM technologies, only a few of them can be
implemented for printing ceramic parts. Among such technologies, the so-called Direct Ink Writing
(DIW) offer greater versatility and particular suitability for the fabrication of ceramic parts [20]. DIW,
also referred to as Robocasting [21], is an extrusion-based technique used in 3D printing in which new
materials can be implemented most economically and flexibly [22,23]. The main requirement of this
technology is the use of pastes with controlled rheological behavior that allows them to be able to be
extruded into filaments capable of maintaining their shape and not collapsing during the 3D object
forming process [24]. The required rheological characteristics can be achieved through the correct
selection of the number of components, solid-phase parameters and the additives used [25].
In the industrial manufacture of ceramic parts, it is very common the use of slurry that contains
various additives, such as plasticizers, dispersants, surfactants, binders, defoamers, lubricants, etc.,
which in many occasions produce the formation of defects during sintering [26]. These defects can
be related to the evaporation of the aforementioned additives that leads to volumetric shrinkage and
crack formation, which considerably reduces the mechanical properties of the part [27].
Some years ago, the use of chemically modified graphene (in other words, graphene oxide (GO))
has been proposed with aim of prepare an aqueous paste without any additive for the 3D printing
of graphene-based heaters [28]. Later, García-Tunñoón et al. formulated free additives pastes of
diverse materials, based only on the use of GO as a dispersant, rheological modifier, and binder [29].
It was possible, because GO has a great similarity to clay, including its viscoelastic behavior. Clay has
exceptional chemistry and structure that permit the design of water-based suspensions for shaping with
excellent viscoelastic behavior in a procedure that cannot be done with any other natural material [30].
The special combination of surface chemistry and the structure of GO sheets in contact with water
under special conditions allow the preparation of a very stable GO suspension with viscoelastic
behavior comparable to clay [29,31]. In addition, GO as an oxide can be homogeneously dispersed
in water, and, consequently, mixtures of graphene oxide with any ceramic oxide can be processed
following conventional ceramic processing routes [32–35]. Therefore, the implementation of GO to
obtain ceramic pastes without additives for their use in AM opens up new possibilities for obtaining
complex parts with the help of robocasting technology.
The aim of the present work is to explain the state of the art of the most common AM technologies
used for the manufacturing of complex shape structures of both ceramic and graphene-based parts;
and, disclose the most important works about the fabrication of composites using graphene-based
ceramic pastes by DIW. Where it was necessary, an explanation of important aspects of AM techniques
for ceramic or graphene-based materials will be presented. Moreover, overviews of diverse examples
of graphene-based pastes for DIW are given. In where it was possible, historical facts of diverse AM
techniques were explained.
Our article is structured as follows: Section 2 explains a short review of the AM processes for
ceramic, which are grouped by the type of feedstock used in each technology; besides, we tried to
summarize their principles and applications, and to provide their most important historical facts.
Section 3 describes in more detail the AM processes used for 3D printing of graphene-based materials
and cites some studies in a wide range of applications related to these AM techniques. Different
feedstock formulations and their corresponding rheological behavior were explained. Section 4
is focused on the more actual developments on direct ink writing by the use of graphene-based
ceramic pastes. We provide some examples of the most relevant approaches for the manufacturing of
graphene-based ceramic composites by DIW. Finally, in Section 5, a summary of this work is described.
2. Additive Manufacturing Processes for Ceramic and Their Principles

The beginning of AM technologies dates back to July 16, 1984, when André J.C., Le Mehauté A.
and De Witte O. filed a patent at Cilas Alcatel [36], in which the stereolithography process was proposed.
Three weeks 2020,
Nanomaterials later,10,on
x August 8, 1984, Charles W. Hull filed his patent at UVP, Inc. and coined 5 of 48the
term “stereolithography” (SLA) [37]. After that, the development of AM was followed by technologies
as technologies
powder bed as powder
fusion, fusedbeddeposition
fusion, fused deposition
modelling modelling
(FDM), inkjet (FDM),
printinginkjet printing
and others andHowever,
[38]. others
[38]. However, it was only in the 1990s when the first reports of 3D printing of ceramic materials
it was only in the 1990s when the first reports of 3D printing of ceramic materials appeared [39].
appeared [39].
Today, there is a wide variety of AM technologies used for different types of materials. Table 1
Today, there is a wide variety of AM technologies used for different types of materials. Table 1
lists the most popular manufacturing additive technologies in the industry, and the possible types of
lists the most popular manufacturing additive technologies in the industry, and the possible types of
feedstock that can be used in each technology [17]. From this, it is easy to appreciate that not all AM
feedstock that can be used in each technology [17]. From this, it is easy to appreciate that not all AM
technologies
technologies areare
suitable
suitableforforthe
theprocessing
processingof ofceramic
ceramic materials.
materials.
In In
1991,
1991, Professor J.P. Kruth first organized the AMAM
Professor J.P. Kruth first organized the processes
processes according
according to theto theofform
form of the
the used
used material before printing [40], and his classifications were: powder, solid and
material before printing [40], and his classifications were: powder, solid and liquid-based techniques. liquid-based
techniques.
Using thisUsing this principle,
principle, it istopossible
it is possible to group
group the the AM technologies
AM technologies for ceramicfor ceramicinto
materials materials
powder- into
powder-based, bulk solid-based,
based, bulk solid-based, and slurry-based,
and slurry-based, as shown asinshown
Figurein1.Figure 1.
Figure 1. Classification of AM technologies for ceramics by the type of feedstock used: SLS – Selective
Figure 1. Classification of AM technologies for ceramics by the type of feedstock used: SLS–Selective
Laser Sintering; BJ – Binder Jetting; SLM – Selective Laser Melting; SLA – Stereolithography; DLP –
Laser Sintering; BJ–Binder Jetting; SLM–Selective Laser Melting; SLA–Stereolithography; DLP–Digital
Digital Light Processing; TPP – Two-Photon Polymerization; IJP – Ink Jet printing; LOM – Laminated
Light Processing; TPP–Two-Photon Polymerization; IJP–Ink Jet printing; LOM–Laminated Object
Object Manufacturing; FDM – Fused Deposition Modeling and DIW – Direct Ink Writing.
Manufacturing; FDM–Fused Deposition Modeling and DIW–Direct Ink Writing.
In addition, it should be noted that the traditional ceramic forming technology such as dry and
In addition, it should be noted that the traditional ceramic forming technology such as dry and
isostatic pressing, sliding and tape casting, etc. have some limitations. They cannot be used for parts
isostatic pressing, sliding and tape casting, etc. have some limitations. They cannot be used for
with complex shapes (with inner holes, sharp corners, etc.), and which require high precision.
parts with complex shapes (with inner holes, sharp corners, etc.), and which require high precision.
Moreover, these forming methods need the manufacture of molds and post-processing, which is
Moreover, these forming methods need the manufacture of molds and post-processing, which is
time-consuming and costly [41,42]. Meanwhile, AM technologies such as powder-, slurry- and bulk
time-consuming and costly
solid-based techniques are[41,42]. Meanwhile,
promising methodsAMfor technologies
producing nearsuch netascomplex
powder-, slurry-
shape andand
parts bulk
solid-based
consequently techniques are saving
allows for promisingtimemethods for producing
and reducing productionnear net of
costs complex
requiredshape parts in
products and
consequently allows for saving time and
comparison with traditional forming methods. reducing production costs of required products in comparison
with traditional forming methods.
2.1. Powder-Based Technologies
2.1. Powder-Based Technologies
In this group of AM technologies for ceramic materials, powder beds are used. During the
In this group
additive of AM
process, technologies
the ceramic powderfor ceramic
can be materials,
bonded by powder beds
melting, are used.orDuring
sintering, the agent,
a binder additive
process,
depending on the type of technology used. Among the AM technologies that utilize powder beds,on
the ceramic powder can be bonded by melting, sintering, or a binder agent, depending forthe
ceramic materials three of them are the most important in the industry: selective laser sintering (SLS),
selective laser melting (SLM) and binder jetting (BJ).
type of technology used. Among the AM technologies that utilize powder beds, for ceramic materials
three of them are the most important in the industry: selective laser sintering (SLS), selective laser
melting (SLM) and binder jetting (BJ).
Nanomaterials 2020, 10, x 6 of 48
2.1.1. Selective Laser Sintering (SLS)

2.1.1. Selective Laser Sintering (SLS)
This method was first reported by Deckard when he filed a patent in 1986 at the University of
This method was first reported by Deckard when he filed a patent in 1986 at the University of
Texas, and the main goal of this technology was to fabricate wax objects for their use in investment
Texas, and the main goal of this technology was to fabricate wax objects for their use in investment
casting in order to obtain metallic prototypes [43]. The SLS process belongs to the category “powder
casting in order to obtain metallic prototypes [43]. The SLS process belongs to the category “powder
bed fusion”, and utilizes a high power laser beam as a thermal source for the local sintering of a thin
bed fusion”, and utilizes a high power laser beam as a thermal source for the local sintering of a thin
layer in
layer in the
the powder
powder material
material surface.
surface.When
Whenthe thepowder
powderisisheated
heatedenough
enoughby byaalaser
laserbeam
beama adiffusion
diffusion
process takes place between particles in the powder, which leads to the densification
process takes place between particles in the powder, which leads to the densification of the material. of the material.
The part
The part forming
forming is is aa layer
layer by
by layer
layer process.
process. InInthis
thisway,
way,when
whenaalayer
layerisissintered,
sintered,the
thepowder
powderbed bed
moves down by an elevator system, a new powder layer is distributed onto
moves down by an elevator system, a new powder layer is distributed onto the previous surface the previous surface using
a spreading
using system,
a spreading and then
system, a new
and then cyclecycle
a new of sintering, descent,
of sintering, andand
descent, spreading is repeated
spreading until
is repeated the
until
finalfinal
the partpart
is formed.
is formed.Figure 2a, 2a,
Figure [44], shows
[44], showsa schematic
a schematicdiagram
diagramof the SLSSLS
of the process.
process.
Figure 2. Schematic diagrams of powder-based additive manufacturing (AM) technologies main

Figure 2. (a)
methods: Schematic
SLS anddiagrams of Adapted
SLM; (b) BJ. powder-based additive
from [44], manufacturing
with permission from(AM) technologies
Wiley-VCH main
Verlag GmbH
methods: (a) SLS and SLM;
and Co. KGaA, Weinheim, 2018.(b) BJ. Adapted from [44], with permission from Wiley-VCH Verlag
GmbH and Co. KGaA, Weinheim, 2018.
The powder bed can be a single material with a low melting point, or a mixture of a high
The point
melting powder bed cantogether
material be a single
with material withor
inorganic a low melting
organic point,which
binders or a mixture
may need of a high melting
debinding by
point material together
high-temperature with inorganic
heat treatment or organic
to get the final partbinders
[45–47]. which mayprocess
The SLS need debinding by high-
must be carried out
temperature
in vacuum orheat treatment
inert atmospheresto getsuchthe final part and
as argon [45–47]. The SLS
nitrogen process
to avoid the must be carried
oxidation of theout in
binder
vacuum or inert atmospheres such as argon and nitrogen to avoid the oxidation
during sintering. An advantage of this method is that it does not need the creation of additional of the binder during
sintering.
supports, An advantage
since of this method
the low sintering is that itdo
temperatures does
notnot need the
produce creation
internal of additional
stresses supports,
that can deform the
since the low
fabricated part. sintering temperatures do not produce internal stresses that can deform the fabricated
part. Although the laser beam can generate a high local temperature, it is not enough for the sintering of
Although
the ceramic the laserThus,
materials. beamitcanalsogenerate
requiresaahigh
longlocal
dwelltemperature, it is not
time of the laser beamenough for the
exposition forsintering
ceramics.
of the ceramic materials. Thus, it also requires a long dwell time of the
A solution can be to use a binder material with a lower melting point to coat or mix the ceramics laser beam exposition for
ceramics. A solution can be to use a binder material with a lower melting
particles with it. This approach was used by Lakshminarayan et al. in 1990, when they reported the point to coat or mix the
ceramics particles
first complex shapewith it. This
3D part approach
obtained by SLSwas used by Lakshminarayan et al. in 1990, when they
[48].
reported
Moreover, the high porosity remaining in theby
the first complex shape 3D part obtained SLSparts
final [48]. and the high shrinkage are two major
Moreover, the high porosity remaining in
problems related to SLS of ceramics [49]. On the other hand, the final parts and
thethe high shrinkage
benefit are two
of this method major
is that no
problems related tohave
support structures SLS toof be
ceramics [49]. On
deliberately the other
fabricated forhand, the benefit
overhanging of this
regions methodthe
because is parts
that noare
support
among the structures have toinbethe
loose powder deliberately fabricated
bed at all times. Thus,fortheoverhanging
propertiesregions because
of the parts the parts
produced by are
SLS
among the loose powder in the bed at all times. Thus, the properties of the parts produced by SLS are
are affected by several factors involved primarily with the feedstock materials and laser–material
affected by several factors involved primarily with the feedstock materials and laser–material
interactions should be taken into account during the fabrication process.
interactions should be taken into account during the fabrication process.
2.1.2. Binder Jetting (BJ)

Binder jetting is a process invented 1989 by Sachs et al. when they filed a patent for it at
Massachusetts Institute of Technology [50], and thanks to its main characteristics, it belongs to the
category “Binder jetting”. The principal objective of this technology was to rapidly-produce of parts
2.1.2. Binder Jetting (BJ)

Binder jetting is a process invented 1989 by Sachs et al. when they filed a patent for it at
Massachusetts Institute of Technology [50], and thanks to its main characteristics, it belongs to the
category “Binder jetting”. The principal objective of this technology was to rapidly-produce of parts
from a larger variety of materials as plastics, metals and ceramics [14]. The BJ process utilizes an
organic binder solution that is dropped into a powder bed for the gluing of particles in the surface by a
printhead in determined paths. The scheme of the BJ process is shown in Figure 2b [44].
The first report about the application of the BJ process on ceramic materials was made by
Sachs et al., in 1992, when they used a matrix of alumina and silicon carbide with colloidal silica as
a binder [51]. Any ceramic powders, can be used to prepare ceramic preforms, and color printing
all of these provide the benefit of BJ with regards to other fabrication methods. However, it must be
mentioned that the binder agent, powder material, equipment, printing parameters, and post-treatment
influence on the strength of ceramic parts and their accuracy. In BJ, like SLS, the part forming is one
layer at a time. When a layer is consolidated, a new powder layer is distributed onto the previous
surface using a spreading system, and then a new cycle of gluing and spreading is repeated until
the final 3D part is formed. After the part was fabricated, the organic binder must be removed by
sintering to obtain the desired mechanical properties. The debinding generally produces shrinkage
and porous in the part that depends on the binder percentage in it. The mechanical properties are
negatively affected by the amount of porosity in the model. Despite this, BJ is a good method used
in biomedical fields for the ceramic scaffold production, thanks to porosities that facilitates the cell
cultivation purposes.
In the coming years, BJ must become a widespread technique for making 3D ceramic printed
parts if the difficulties with their strength and accuracy can be solved producing a preform of any
complex form that does not shrink after post-treatment.
2.1.3. Selective Laser Melting (SLM)

The SLM method was first reported in Germany by Wilhelm Meiners et al. when they filed the
patent DE 19649865 in 1996 [52]. This process belongs to the category “powder bed fusion” because it
is considered a variant of SLS that uses a laser beam with much higher energy densities for the local
sintering of material [16]. The presence of a more power thermal source allows the sintering process to
be carried out in a single step (without any postprocessing) and not using second phases with low
melting temperatures as binders. Figure 2a [44], shows the schematic of the SLM conceptual principle,
which is the same as SLS.
Throughout time, this technique remains very popular among AM technologies for metals thanks
to the ability to manufacture parts quickly and efficiently [53]. Moreover, SLM allows the formation
of dense parts since the powder particle is completely melted into the liquid phase ensuring rapid
densification without the need for a debinding process.
This technique can be included in the manufacture of ceramic parts, but it implies the need to
achieve the complete melt of ceramic powder [54]. Since ceramic materials have very high melting
points their complete melt in SLM represents a serious technological problem that limits the application
of this technology in ceramic production [55]. Despite this, when the laser sweeps across the powder
bed, different areas of the parts will experience high-temperature fluctuation, creating high thermal
stresses. Combined with the low ductility of ceramic materials, cracks can form [56]. The correct control
and management of the energy applied to the powder are of great importance since the application of
low energy levels leads to the incomplete melting of the material, and on the other hand, under the
action of a high energy level, the powder material is spattered around it [57].
However, ceramic parts with a 100% density were produced by SLM with complete melting of the
material and without any post-processing [58]. In this work, the authors utilized a eutectic mixture of
Al2 O3 ± ZrO2 to lower the melting point of the material, which was ultrahigh preheated above 1600 ◦ C
in order to prevent the possible crack formation during the build-up process. This approach made the
process very complicated, but it demonstrates that SLM is the only perspective method that promises
to get ceramic parts with full density directly after its use.
As in other methods, the SLM-produced ceramic part quality is affected by several factors,
like fabrication parameters, raw material properties, post-processing and the interaction of the energy
source and the materials.
2.2. Slurry-Based Technologies

This group of AM technologies for ceramic materials involves the methods that use feedstock, in the
form 2.2. Slurry-Based
of inks. Technologies
These inks are liquid systems dispersed with fine ceramic particles. During the additive
process, the ceramic
This group ofparts
AMcan be printedforbyceramic
technologies photopolymerization
materials involves orthe
material
methods jetting, depending
that use feedstock,on the
type of technology
in the used.
form of inks. Among
These the liquid
inks are AM technologies that utilize
systems dispersed inks,
with fine for ceramic
ceramic materials
particles. During thefour of
themadditive process,
are the most the ceramic
important parts
in the can be [13]:
industry printed by photopolymerization
stereolithography or material
(SLA), digital light jetting,
processing
depending on the type of technology used. Among the AM technologies that
(DLP), two-photon polymerization (TPP) and inkjet printing (IJP). Note that slurry-based utilize inks, for technologies
ceramic
materials
utilize four ofare
inks, which them are the of
mixtures most important
polymer in ceramics
with the industry [13]: stereolithography
particles, (SLA), digitalin the
that have low-viscosities
light processing (DLP), two-photon polymerization (TPP) and inkjet printing (IJP). Note that slurry-
range of mPa·s and with a low ceramic loading (up to 30 vol%).
based technologies utilize inks, which are mixtures of polymer with ceramics particles, that have low-
viscosities in the range of mPa·s and with a low ceramic loading (up to 30 vol%).
2.2.1. Stereolithography (SLA)
2.2.1. Stereolithography
Stereolithography (SLA) the start of the additive manufacturing era in the mid-1980s when
imposed
a patent about this method
Stereolithography was filed
imposed [37].ofThe
the start the SLA process
additive utilizes aera
manufacturing light source
in the for the
mid-1980s curing
when a of
a liquid
patent about this method was filed [37]. The SLA process utilizes a light source for the curing of a with
photopolymer tiny layer in a vat consisting mainly of photopolymerizable monomer
otherliquid
additives in very small
photopolymer amounts
tiny layer in a vat[59].consisting
For this mainly
reason,ofthis process is included
photopolymerizable in the with
monomer category
other additives in very small
“Vat photopolymerization”. amounts [59].
Commonly, in For
thisthis reason, an
method, thisultraviolet
process is included
(UV) light in the category
source is used.
“Vatlight
This UV photopolymerization”.
scans the surface Commonly, in this method,
of the photopolymer, an ultraviolet
following (UV) light
a controlled source
path, thanks is used. This
to the help of
UV light scans the surface of the photopolymer, following a controlled path,
motorized mirrors. A schematic diagram of the SLA is shown in Figure 3a [44]. When a photopolymer thanks to the help of
motorized mirrors. A schematic diagram of the SLA is shown in Figure 3a [44]. When a photopolymer
interacts with the UV beam, the light activates a series of reactions that are known as polymerization.
interacts with the UV beam, the light activates a series of reactions that are known as polymerization.
Polymerization is a process in which monomers crosslink to form polymers, that lead to a phase change
Polymerization is a process in which monomers crosslink to form polymers, that lead to a phase
from change
liquid to solid
from resin
liquid [60]. resin
to solid In SLA[60].the
In part
SLA theforming is a layer
part forming is aby layer
layer process.
by layer In this
process. way,
In this when a
way,
part layer
when a part layer is polymerized its support is lowered a distance equal to the thickness of the newby an
is polymerized its support is lowered a distance equal to the thickness of the new layer
elevator system.
layer After that,
by an elevator a new
system. cycle
After that,ofa polymerization and lowering
new cycle of polymerization andislowering
repeated is until
repeatedthe until
final part
is formed. Figure
the final part is3a, [44], shows
formed. Figure a3a,scheme of the
[44], shows SLA process.
a scheme of the SLA process.
Figure 3. Cont.
Nanomaterials 10, 1300
2020,2020,
Nanomaterials 10, x 9 of 489 of 48
Figure 3. Schematic
Figure diagrams
3. Schematic diagrams of
of slurry-based
slurry-based AM AM technologies
technologies mainmain methods:
methods: (a)(b)SLA;
(a) SLA; DLP;(b)
(c) DLP;
(c) two-photon
two-photonpolymerization
polymerization (TPP).
(TPP). Figure
Figures 3a,b
3 (a)adapted from [44],
and (b) adapted with
from permission
[44], from Wiley-VCH
with permission from
Verlag GmbH &Verlag
Wiley-VCH Co. KGaA,
GmbHWeinheim,
& Co. KGaA, 2018.
Weinheim, 2018.
The first study

The first of SLA
study of SLA with ceramic
with ceramicparticles was reported
particles was reportedinin19941994 [61].
[61]. In that
In that work,
work, the authors
the authors
used slurry with a very high concentration of particles, about 65 vol%.
used slurry with a very high concentration of particles, about 65 vol%. Commonly, the SLA Commonly, the SLA of of
ceramics uses fine ceramic particles that are dispersed in the liquid photopolymer
ceramics uses fine ceramic particles that are dispersed in the liquid photopolymer [62,63]. In this [62,63]. In this case,
case, the
thephotopolymer
photopolymer is cured by light irradiation creating a solid resin with a uniform distribution of
is cured by light irradiation creating a solid resin with a uniform distribution
ceramic particles. After the fabrication of a 3D part, this green body must be processed at high
of ceramic particles. After the fabrication of a 3D part, this green body must be processed at high
temperatures to eliminate the organic compounds and to rich a higher density.
temperatures to eliminate the organic compounds and to rich a higher density.
As a slurry-based AM technology, the feedstock must have certain essential requirements to
As a slurry-based AM technology,
obtain a good result during the feedstock
the polymerization. First of must have
all, there certain
is the essential
need for requirements
a suspension with a to
obtain a good
high result duringdistribution
and homogeneous the polymerization. Firstparticles.
of the ceramic of all, there
This is the need must
suspension for a have
suspension
a good with
a high and homogeneous
rheological behavior thatdistribution of the ceramic
includes an optimum viscosityparticles. Thisofsuspension
in each case material andmustgood have a good
stability
of the suspension over time [16].
rheological behavior that includes an optimum viscosity in each case of material and good stability of
The advantages
the suspension over timeof[16].
this method are the ability to build intricate geometries, accommodate large
build areas, smooth surface,
The advantages of this method accuracy, andability
are the high resolution [64]. However,
to build intricate this technique
geometries, accommodate is still large
limited to ceramic materials, which are no able to absorb UV radiation. Indeed, the introduction of
build areas, smooth surface, accuracy, and high resolution [64]. However, this technique is still limited
small (<1 µm) ceramic particles in a curable monomer increase a level of complexity in comparison
to ceramic materials, which are no able to absorb UV radiation. Indeed, the introduction of small
to the classical fabrication of pure polymeric materials. The main difficulty is related to the scattering
(<1 µm) ceramic particles in a curable monomer increase a level of complexity in comparison to
phenomena, which decrease the cure depth and then increase rise the processing time. Besides, this
the classical
phenomenonfabrication
decreases of the
pure polymericresolution
dimensional materials. Theprinted
of the main part.
difficulty is related to the scattering
phenomena, which decrease the cure depth and then increase rise the processing time. Besides,
2.2.2. Digital Light
this phenomenon Processing
decreases (DLP)
the dimensional resolution of the printed part.
The DLP process is an improved version of SLA, in which a UV light source is not used for the
2.2.2. Digital Light Processing (DLP)
solidification of the photopolymer. In this process, a white light source is used to project the cross-
sections
The DLP of process
the 3D part, oneimproved
is an projection at a time,of
version with the in
SLA, help of a digital
which a UVmask
light[65]. The idea
source of used
is not this for
process was invented by Nakamoto and Yamaguchi in 1996 when they used a physical mask
the solidification of the photopolymer. In this process, a white light source is used to project the instead
cross-sections of the 3D part, one projection at a time, with the help of a digital mask [65]. The idea
of this process was invented by Nakamoto and Yamaguchi in 1996 when they used a physical mask
instead of a digital projector [66]. This process, as well as the SLA, also belongs to the category
“vat photopolymerization”.
During the DLP process, the liquid photopolymer is exposed to the direct projection of the
sectioned figure of the model for its polymerization with the help of the digital mask [67]. Then,
the solid surface changes its vertical position, thanks to the help of an elevation system, changing the
planar focus for the projection and formation of the new layers with the required sectioned shape of
the 3D model. This process is repeated until the part is completely fabricated. Figure 3b, [44], shows a
scheme of the DLP process.
DLP, as opposed to to SLA, is a much faster and cheaper process that has a very high-resolution
thanks to the easy choice of the optimal size of the projected pixel [68]. These advantages make it
a very attractive process for the ceramic industry [69]. The use of this method in the production of
ceramic pieces has acquired a great impact, and to this day it is one of the most used techniques thanks
to the possibility of obtaining pieces with high densities and hardness including a high quality of the
surface [70]. The DLP technology used exclusively for ceramic materials is generally marketed under
the name of lithography-based ceramic manufacturing (LCM) [71]. Generally, this method is used to
fabricate heat exchangers [72], meta-material structures and cellular ceramic structures with very small
feature sizes [73,74].
At the same time, the main disadvantages of this technology compared to SLA are: parts cannot
be left out in the sun or they will degrade; parts overall have worse mechanical properties—they break
or crack more easily and are at risk of deteriorating over time; resins are expensive, and the regular
replacements of resin tanks and occasionally print platforms also adds up.
2.2.3. Two-Photon Polymerization (TPP)

Two-photon polymerization (TPP) is an AM technology related to the “vat photopolymerization”
group in which a multiphoton polymerization-based process is used. The principal purpose of this
method is to utilize the nanoscale fabrication of parts for their application in different areas such as
nanoelectronics, nanomechanics, and nanobiomedicine. The first work-related with the TPP field
was carried out by Wu et al. in 1992 to get high-aspect-ratio trenches of simple shapes [75]. Later,
this process was improved and applied to fabricate complex forms, as was shown in the work of
Maruo et al. in 1997 [76].
The polymerization process in TPP is based on the interaction of two or more photons from a
laser with a specific wavelength when it focuses on a specific point within a liquid photopolymer.
A schematic diagram of the TPP is shown in Figure 3c. After polymerization of a certain volume of
material, the focus point of the laser is moved for the formation of the following layers. The final
resolution and the quality of the surface obtained depend directly on the precise positioning and
control of the size of the focal point [77].
The advantages of TPP are mainly related to the possibility of polymerizing tiny volumes at
high speed within the photopolymer which gives the possibility of manufacturing microstructures
with lateral feature sizes in the order of nanometers [78,79]. The use of a technology with this type of
characteristics for the ceramic part production with complex shapes opens up new and interesting
possibilities for this industry.
The first work on TPP for the obtaining of ceramic parts was published by Pham et al. [80]. In that
work, a SiCN woodpile nano- and micro-ceramic microstructures of submicron resolution was created.
This technology has a series of restrictions that limit its use and among these, we can define:
very expensive, time-consuming, and challenging for complex structures. Furthermore, the working
principle of TPP allows only the use of transparent polymers; this means that the opaque polymers that
were usually used for SLA and DLP processes are not applicable for TPP. It should be noted that this
process can produce only very small parts on the order of a few microns and due to the high precision
of the process; it also takes a longer amount of time to completely manufacture a part.
2.2.4.
2.2.4. Inkjet
Inkjet Printing
Printing (IJP)
(IJP)
Inkjet
Inkjet printing,
printing, sometimes
sometimes known
known as as material
material jetting,
jetting, isis aa non-contact
non-contact method
method of of AM
AM mainly
mainly
created to obtain two-dimensional patterns inspired by a technology developed
created to obtain two-dimensional patterns inspired by a technology developed in the 1950s [81].in the 1950s [81]. TheTheIJP
process is based
IJP process on the
is based oncontrollable dispensing
the controllable of liquid-phase
dispensing of liquid-phasematerials by thebyuse
materials theofuse
micrometer-sized
of micrometer-
printhead
sized printhead nozzles [82], which is the reason why this technology is related to thematerial
nozzles [82], which is the reason why this technology is related to the materialjetting
jetting
category.
category. The
The liquid-phase
liquid-phase material,
material, also
also known
known as as Ink,
Ink, isis dispensed
dispensed ontoonto aa surface
surface by by droplets
droplets in in aa
specified
specified pattern
pattern in in which
which the
the ink
ink drying
drying occurs
occurs forming
forming aa thinthin layer
layer of
of the
the ink
ink residue.
residue. After
After that,
that,
new layers can be placed on top of each other to form a multilayer 3D object.
new layers can be placed on top of each other to form a multilayer 3D object. The IJP processesThe IJP processes can use
can
one
use of
onetheofmain two methods
the main of ink of
two methods dispensing: continuous
ink dispensing: inkjet (CIJ),
continuous inkjetor(CIJ),
drop-on-demand (DOD)
or drop-on-demand
printing [83]. Figure
(DOD) printing [83].4Figure
shows4the printing
shows methodsmethods
the printing used in used
IJP. in IJP.
Figure 4. Schematic diagrams of printing methods used in Inkjet printing: (a) continuous inkjet (CIJ);
Figure 4. Schematic diagrams of printing methods used in Inkjet printing: (a) continuous inkjet (CIJ);
(b) drop-on-demand (DOD).
(b) drop-on-demand (DOD).
The CIJ method involves the production of a stream of drops jetting out through a controllable
The CIJ method involves the production of a stream of drops jetting out through a controllable
micronozzle [65]. Then, the formed droplets pass through an electrostatic field that influences them
micronozzle [65]. Then, the formed droplets pass through an electrostatic field that influences them
and deflects their trajectories to print on a substrate or allows them to follow their movement towards
and deflects their trajectories to print on a substrate or allows them to follow their movement towards
a collector for reuse. In this way, only small quantities of droplets are used for printing, and the
a collector for reuse. In this way, only small quantities of droplets are used for printing, and the
largest number of drops is recycled, i.e., CIJ is a non-economical material process. The DOD method
largest number of drops is recycled, i.e., CIJ is a non-economical material process. The DOD method
produces ink droplets when and where it is required, thus this method is more economical than CIJ.
produces ink droplets when and where it is required, thus this method is more economical than CIJ.
Moreover, the small size of droplets and the high positioning accuracy make it more ideal for 3D
Moreover, the small size of droplets and the high positioning accuracy make it more ideal for 3D
printing [84]. In DOD the droplets can be formed by the piezoelectric effect, thermal excitation or
printing [84]. In DOD the droplets can be formed by the piezoelectric effect, thermal excitation or
pyro-electric effect in the printing nozzle head [84–86]. Piezoelectric DOD utilizes a piezoelectric
pyro-electric effect in the printing nozzle head [84–86]. Piezoelectric DOD utilizes a piezoelectric
element located in the fluid chamber near the nozzle head for the droplet formation [87]. In this case,
element located in the fluid chamber near the nozzle head for the droplet formation [87]. In this case,
the droplet is created and ejected by a generating pressure pulse that forces the ink to leave the nozzle
the droplet is created and ejected by a generating pressure pulse that forces the ink to leave the nozzle
head [84]. The pressure pulse is formed thanks to the piezoelectric element deformation under the
head [84]. The pressure pulse is formed thanks to the piezoelectric element deformation under the
application of a voltage. When a droplet is ejected, it falls by gravity, and then it is impregnated in
application of a voltage. When a droplet is ejected, it falls by gravity, and then it is impregnated in
the subtracted thanks to the momentum obtained during its movement [14]. After that, occurs the
the subtracted thanks to the momentum obtained during its movement [14]. After that, occurs the
solvent evaporation from the impregnated droplet creating a small layer made up of the ink residue.
solvent evaporation from the impregnated droplet creating a small layer made up of the ink residue.
In thermal DOD process, sometimes named as bubble jet printing [14], a thermal excitation for the
In thermal DOD process, sometimes named as bubble jet printing [14], a thermal excitation for the
formation and ejecting of the droplets is used [15]. The thermal excitation is generated when a current
formation and ejecting of the droplets is used [15]. The thermal excitation is generated when a current
cross through a resistive element located in the fluid chamber near the nozzle head and that directly
cross through a resistive element located in the fluid chamber near the nozzle head and that directly
contacts with the ink. When the heater element temperature reaches the ink’s boiling point, rapid ink
contacts with the ink. When the heater element temperature reaches the ink’s boiling point, rapid ink
vaporization is occurred creating a bubble that expands in the fluid chamber, forcing a droplet out of
vaporization is occurred creating a bubble that expands in the fluid chamber, forcing a droplet out of
the nozzle. The bubble formation is followed by a very fast collapse when the pulse current source is
the nozzle. The bubble formation is followed by a very fast collapse when the pulse current source is
“switched off”.
“switched off”.
Different types of materials, such as metals or polymers for electronic patterning [88], paste for
Different types of materials, such as metals or polymers for electronic patterning [88], paste for
electronics soldering and cells for restoration in tissue engineering [89,90], were used in IJP. However,
electronics soldering and cells for restoration in tissue engineering [89,90], were used in IJP. However,
the IJP method is limited only to the production of miniaturized parts due to the low ink volume used
the IJP method is limited only to the production of miniaturized parts due to the low ink volume
used in each droplet. The obtaining of a solid ceramic part after an IJP process involves the drying
and sintering post-processing of the printed part.
in each droplet. The obtaining of a solid ceramic part after an IJP process involves the drying and
sintering post-processing of the printed part.
Thanks to the development of computational technologies, the increase in positioning precision
and advances in the 3D printing field, the use of the IJP method has been achieved for ceramic materials
dispersed in liquid solvents. The first report of IJP with ceramic materials dates back to 1995 when
Blazdell et al. used ceramic inks (ZrO2 and TiO2 ) with a volumetric fraction of 5% [91]. After that,
different researches groups improved the IJP and the feedstock preparation for obtaining materials
with ceramic loading until 20% [92].
2.3. Bulk Solid-Based

This group of AM technologies for ceramic materials involves the methods that use material sheets,
semi-molten or semi-liquid systems in which fine ceramic particles are well dispersed as feedstock.
Note that semi-molten and semi-liquid systems, commonly of ceramic/polymer mixtures, have a
high-viscosity in the range of some Pa·s like pastes that have a higher content of ceramic (up to 60 vol%).
In this group, some AM technologies that belong to different categories such as Sheet lamination or
Material Extrusion will be considered. Among the AM technologies that utilize solid feedstock for
ceramic materials are laminated object manufacturing (LOM), Fused Deposition Modeling (FDM),
and direct ink writing (DIW) that are the most important in the industry [13].
2.3.1. Laminated Object Manufacturing (LOM)

Laminated object manufacturing is a process related to the Sheet lamination group and it was
mainly developed for the fabrication of metal, paper or plastic parts. The first report of this method was
in 1984 when Kunieda published his work “Manufacturing of High Cycle and High Precision Injection
Molds by Diffusion Bonding of Laminated Thin Metal Sheets” in which molds for injection molding
of plastics were obtained by laminating metal sheets cut by laser [93]. As said before, the concept of
this method is to utilize, generally obtained by laser cutting, tiny pre-patterned material sheets that
are superposed on top of each other and attached by either using a heat source or adhesives to form
3D parts [94]. The type of the used joining process is depending on the raw material. For instance,
sheets of metal materials are bonding by the use of ultrasonic processes that produce local heating of
the sheets creating a very strong bond [95]. For paper sheets, an adhesive material, as glue, is used.
In the case of polymer materials, the use of heat and pressure is necessary [96]. Generally, this method
needs a machining post-process to reach the final shape, surface quality and accuracy of the part.
Figure 5a, [44], depicts the process scheme for LOM.
Laminated object manufacturing exhibit several advantages such as low process and machine cost,
high volumetric build rate, low material requirement, high surface finish and the ability to obtaining
parts of combination material and composites [97]. However, this technology has some disadvantages
such as the necessary use of tiny sheets of material, different bonding processes for different types of
materials and a non-high resolution of complex parts.
Only after 10 years that Kunieda published his work, the first report about LOM with ceramic
materials appeared [98]. The authors of this work, Griffin et al., used sheets of alumina and zirconia
for the manufacturing of solid parts with a high density after removing the binder and sintering at
high temperatures.
After Griffin’s investigation, a large number of materials such as Al2 O3 and SiC [99,100], binary
composites like ZrO2 /Al2 O3 , Si/SiC, TiC/Ni [101–103], or more complex systems, for example,
LiO2 –ZrO2 –SiO2 –Al2 O3 (LZSA) glass–ceramic composite have been investigated for they use
in LOM [104].
Despite the great effort made in the study of ceramics for LOM, in recent years no progress has
been observed in this field. Thus, the application of this technique is restricted only for the manufacture
of ceramic parts with simple geometry, and large sizes, which create a problem for its application in
the production of advanced ceramic components that, are generally characterized by their complex
geometry and much times for its miniature sizes.
Figure 5. Schematic diagrams of bulk solid-based AM technology main methods: (a) LOM; (b) FDM;
Figure 5. Schematic diagrams of bulk solid-based AM technology main methods: (a) LOM; (b) FDM;
(c) direct ink writing (DIW). Figure 5a,b adapted from [44], with permission from Wiley-VCH Verlag
(c) direct ink writing (DIW). Figures 5 (a and b) adapted from [44], with permission from Wiley-VCH
GmbH & Co. KGaA, Weinheim, 2018.
Verlag GmbH & Co. KGaA, Weinheim, 2018.
2.3.2. Fused Deposition Modeling (FDM)
2.3.2. Fused Deposition Modeling (FDM)
FDM, also called fused deposition of ceramics (FDC), was first reported by Crump when he
filed his also
FDM, owncalled
patentfused deposition
US 5121329 of ceramics
“Apparatus and(FDC), wasfor
method first reported
creating by Crump whenobjects”
three-dimensional he filed in
his1989
own[105].
patent US 5121329 “Apparatus and method for creating three-dimensional
Nowadays, this process is considered as the most usual AM technology in the world objects” in 1989
thanks
[105]. Nowadays,
to its thiseasy
accessibility, process
in useis considered
and low cost as the most
[106]. usual AM
Different typestechnology
of materialsin the
canworld thanksintothe
be utilized
its FDM
accessibility,
process,easy
suchin asuse and lowmetals,
polymers, cost [106].
and Different
ceramic-ortypes of materials
metal-filled can beThe
polymers. utilized
main in the FDM
concept of the
process, such as polymers, metals, and ceramic-or metal-filled polymers.
FDM process is to create a part layer by layer by supplying a filament of semi-molten materials The main concept of the
[107].
FDM process is to create a part layer by layer by supplying a filament of semi-molten
The feedstock is a thermoplastic polymer filament such as acrylonitrile butadiene styrene copolymers materials [107].
The(ABS),
feedstock is a thermoplastic
polycarbonate polymer(PA)
(PC), Polyamide filament such as acrylonitrile
and polylactic acid (PLA)butadiene styrene copolymers
that is permanently providing to
(ABS),
a nozzle which is heated at a temperature just above the filament melting point [108]. Theproviding
polycarbonate (PC), Polyamide (PA) and polylactic acid (PLA) that is permanently semi-molted
to amaterial
nozzle is
which is heated at a temperature just above the filament melting
extruded through the moving controlled nozzle to form the desired pattern [13]. After point [108]. The semi-the
molted material is extruded through the moving controlled nozzle to form
extrusion, the filament adheres to previously deposited layers and immediately cools allowing the desired pattern [13]. its
After the extrusion,
solidification. When the filament
a layer adhereswith
is solidified to previously deposited
the desired pattern the layers and immediately
part support cools
is lowered a distance
allowing its solidification. When a layer is solidified with the desired pattern the
equal to the thickness of the new layer by an elevator system and a new cycle of extrusion and lowering part support is
lowered a distance equal to the thickness of the new layer by an elevator system and a new cycle of
extrusion and lowering is repeated until the final part is formed [14]. The schematic diagram of the
FDM process is shown in Figure 5b [44]. Generally, FDM technology is widely used to manufacture
parts with poor surface finish, low resolution, and mechanical properties. These low characteristics
is repeated until the final part is formed [14]. The schematic diagram of the FDM process is shown
in Figure 5b [44]. Generally, FDM technology is widely used to manufacture parts with poor surface
finish, low resolution, and mechanical properties. These low characteristics are commonly related to
the influence of many factors such as material properties, air gap, printing orientation, raster angle,
layer thickness, and raster width [109]. For this reason, the polymer parts obtained by FDM are often
used as conceptual prototypes.
For the application of FDM in ceramic production, it is necessary to prepare filaments composed
of binder thermoplastic polymers and tiny ceramic particles with a loading of about 60 vol%. In order
to achieve a constant and stable flow of melt material, the ceramic particles should be well dispersed
in the filaments, moreover, the viscosities of the melt filaments should be above 10 to 100 Pa·s [12].
Once the green body is obtained by FDM, the elimination of the binder polymer and the sintering are
necessary to get the ceramic part. As Danforth reported in the first work about ceramic part fabrication
by FDM in 1995 [110], the debinding step leads to the formation of pores that directly influence on the
formation of defects and obtaining low densities. Despite this, thanks to the successful development
of this technology and material science, the mechanical properties of parts obtained by FDM are
now comparable with other processing routes [111]. This is why the application of FDM for ceramic
production is successfully expanding into various fields as electronic components [112], biological
parts [113], sensors [114], bioceramic scaffolds [115], and others [116,117].
2.3.3. Direct Ink Writing (DIW)

Direct ink writing is a process related to the material extrusion group and it is also known as
Robocasting [118], Direct Write Fabrication or Robot-Assisted Shape Deposition [119,120]. DIW was
first reported by Cesarano and Calvert when they filed a patent at Sandia National Laboratories
on October 28, 1997 [121]. DIW is an uncomplicated, responsive, and cheap process, appropriate
for various materials, as follows: ceramics, metal alloys, polymers, and even edible materials [122].
Moreover, this is the most universal technique to produce the 3D prototypes [123], whose main goal is
to make parts by extrusion of concentrated suspensions formulated of main material together with
additives to get appropriate viscoelastic behavior [13]. The concept of this technique is very close
to de FDM with the difference that the DIW process depends on the feedstock rheology behavior
to maintain the shape of the printed part in the time [118]. The high viscosity (103 –106 mPa s)
pseudoplacticity performance of the feedstock are indispensable for this technique [123]. In this
way, the pseudo-plastic feedstock is extruded through a moving controlled nozzle to form a desired
two-dimensional pattern [13]. In DIW, the possibility of nozzle clogging is much lower than IJP.
When a layer was printed the part support is lowered a distance equal to the thickness of the new layer.
After that, a new layer is deposited on top of previously deposited forming a part thanks to a layer by
layer procedure. As other technologies of ceramic production debinding and sintering post-processes
are necessary to obtain a ceramic part without organics. Figure 5c demonstrates a schematic diagram
of the DIW process.
This technology for ceramic materials, compared to SLA, is much faster and cheaper. The exclusive
use of ceramic pastes with required viscoelastic behavior allows printing figures that can maintain
their original form regardless of the loads generated by the newly deposited layers on them. Generally,
the used pastes have a high loading of ceramic particles and the optimal content of additives. Thanks to
this, it is possible to build parts with different configurations from complex porous scaffolds [25],
to composite materials and solid monolithic parts [124,125]. Moreover, some researchers could prepare
and use for printing filaments with different cross-sectional forms [126,127].
Thanks to the flexibility and simplicity of DIW, other scientists have been able to implement this
technology for the fabrication of parts with periodic structures [128], for electrodes for lithium-ion
(Li-ion) batteries [129] and, in recent years, the manufacture of bioceramic implants [130]. The last is
the prominent application thanks to/as a result of the porosities that appear in the part after sintering.
These porous structures are preferred in the manufacture of ceramic implants because they promote
the growth of human body tissue in them [131]. Therefore, DIW fits very well for the manufacture of
porous ceramic structures with periodic features, and when a little surface resolution is needed.
The aforementioned results show that DIW is a prominent technique for obtaining ceramic pieces
with complex geometry, but with the great disadvantage that it is not possible to obtain highly dense
pieces, which limits their application in the industry.
3. Additive Manufacturing for Graphene-Based Materials

As previously stated, in the last few years AM technologies have become so popular throughout
the world that they have come to be applied in different fields of science and industry using different
types of materials such as polymers, metals, ceramics, and composites. At the same time, in the last
20 years the development of materials science, specifically in the area of nanotechnology, has allowed
the appearance, study, and development of interesting and perspective new materials, which are
known as nanomaterials, for their application in the industry [32]. Micro- and nanomaterials of the
same compound differ in that the latter can have exceptional and never-before-seen optical, electronic,
and mechanical properties in comparison with the first. The great interest in nanomaterials is also
because the properties of macro materials drastically change when nanomaterials are added to their
structure [132]. Thanks to this, many ceramic-based composites that have a certain percentage of
nanomaterials are converted into materials with improved mechanical properties. One of these
promising nanomaterials is graphene [133,134]. Graphene is a revolutionary material that opens wide
perspectives with its use, as an example, for increasing the flexural strength and fracture toughness
of ceramic materials [135]. In the following sections, the characteristics and possible applications of
graphene-based material, as well as the most popular additive technologies for them will be explained
in more detail.
3.1. Graphene and Its Derivatives Materials

Graphene is a two-dimensional carbon allotropic form consisting of a single layer of sp2
hybridized atoms that are organized in a honeycomb lattice structure [136]. Graphene was
discovered in 2004 by Andre Geim and Konstantin Novoselov, who worked at the University of
Manchester [137]. This material demonstrates unique properties such as very high thermal conductivity
(above 5000 W mK−1 ), high modulus of elasticity (1 TPa), large surface area (2630 m2 /g), high electron
mobility in room temperature (250.000 cm2 /V s) and high tensile strength of 130 GPa [138]. Moreover,
graphene shows high light transmittance, very high electrical conductivity, and complete impermeability
to any gases, that make it a very promising material for a large number of multifunctional applications
such as medicine [139], composite materials, electronics, light processing, supercapacitors, energy,
strain sensors and others [138].
Different methods of obtaining graphene have been investigated, but the most used are chemical
vapor deposition, epitaxial growth, the mechanical, oxidation–reduction method, and liquid phase
and electrochemical exfoliation [138]. It should be noted that the widespread use of pristine graphene
is limited mainly because it is hydrophobic [140]. The solution to this problem is the surface
functionalization of graphene that is carried out by chemical modification [141]. Generally, chemical
modification of graphene can be done in two ways: covalent, or non-covalent functionalization.
Functionalization via non-covalent interactions creates a weak interaction of a π–π, van der Waals
or electrostatic type between graphene and the target matter, while the covalent modification use
the covalent bonding of oxygen-containing functional groups on the surface of graphene, forming
carboxylic acid groups at the edges and epoxy and hydroxyl groups at the basal plane [142,143].
Usually, researchers around the world use processes based on the Hummers method, which are
known as the modified Hummers method [144], for the covalent modification. The main idea of
the Hummers method is the use of very strong oxidizing agents, such as concentrated sulfuric acid,
nitric acid, and potassium permanganate, for the formation of oxygenated functional groups on the
graphite, which is then mechanically exfoliated to obtain fine sheets of graphene with functional
groups also on its surface. This material is called graphene oxide and it is hydrophilic that disperses
easily in water [145].
The oxidation of graphene creates a large number of defects in its lattice structure that degrade
the material properties, moreover, the functional groups in the GO surface make it electrically
insulating [145]. Fortunately, a partial restore of graphene properties is possible thanks to a reduction
process of GO that can be carried out mainly by chemical or thermal ways, although other less popular
routes have also been used [146]. The idea of the reduction process is to eliminate the hydrophilic
functional groups on GO surface to produce reduced graphene oxide (rGO) by the application of heat
treatment or reducing agents in the thermal or in chemical way, respectively.
Graphene and rGO differ from each other primarily by the presence of defects and some functional
groups that remained in their structure after the reduction process. This fact turns rGO into a material
with properties close to graphene and, at the same time, soluble in different media that allows it
to be used in industry [147]. For instance, a large number of graphene-based composites have
been created to improve the mechanical [148], thermal and electrical properties of polymer matrices
used with applications in aerospace [149], electronics [150], and energy storage [145]. Furthermore,
graphene-based composites with inorganic matrices, such as metals, ceramics, and composites have
been developed [151,152].
3.2. Additive Technologies for Graphene-Based Materials

Like ceramic materials, graphene and its derivatives materials are also being studied to define
their role and use in AM [153]. Since graphene oxide is hydrophilic, it is the most suitable material to
be used as a precursor of graphene in additive technologies since this material can be easily dispersed
in different solvents, and especially in water. Thus, the appropriate AM techniques to be used with
graphene-based materials should belong to the categories vat photopolymerization, material jetting
and material extrusion. In this review, only the AM techniques that are more typical for the production
of graphene-based composites, in particular SLA, IJP, FDM, and DIW, are analyzed. Some of these
methods are based on the use of polymers; and the introduction of graphene-based material into
them allows the obtaining of polymer nanocomposites with improved properties, for example, barrier
properties [154], optical properties [155], thermal properties [156], electrical properties [157,158] and
mechanical properties [159,160].
The final properties of polymer nanocomposites crucially depend on the effectiveness of the
nanoparticle dispersion process [161]. Thus, good nanofiller dispersion in the polymer will produce
a maximum increase in the properties of the composite [162,163]. In many studies, the process of
preparing composites has been taken into account to obtain a high homogeneity and dispersion
of graphene-based materials within a polymer matrix [164]. The tactics implemented in different
works can be summarized in three strategies [161]: 1–in situ intercalative polymerization. According
to this technique, graphene oxide or graphene is first expanded in the liquid monomer, then an
appropriate initiator is diffused and polymerization response use as the means of heat or radiation;
2–solution intercalation. In this case, the technology consists of three stages: dispersion of graphene
or GO in a relevant solvent by sonication, the addition of polymer and removal of the solvent. Then,
the graphene-based-solution is mixed with the polymer matrix, which is adsorbed onto the carbon
sheets. Next, the carbon sheets sandwich the polymer to create a nanocomposite by removing the
solvent, which is essential for the nanocomposites characteristics. The primary benefit of this technique
is introducing low or even no polarity through the synthesis process; 3–melt intercalation. Graphene
or GO and thermoplastic polymer mixing by mechanical means at high temperatures by extrusion or
injection molding. This method is solvent-free.
Of these three strategies the last two are the most widely used, while, as far as is known, data on
the fabrication of graphene composites with the addition of polymer by in situ polymerization before
being extruded into filaments for fused deposition modeling are scarce [165].
3.2.1. Stereolithography (SLA)

In Section 2.2.1, the historical facts, basic principles, advantages and disadvantages of this technique
were considered. It is necessary to take into consideration two essential issues for SLA-based composites:
(1) rapid solidification of by light initiated polymerization, which requests a fast light-responsive
composite resin system; (2) the reached low viscosity that enables for the dipping of the resin17layer,
Nanomaterials 2020, 10, x of 48
and which defines a low graphene concentration and uniform filler distribution [166].
Over time,
Over time, the
the SLA
SLAevolved
evolvedand andimproved
improved versions
versionsof this technique
of this suchsuch
technique as DLP, continuous
as DLP, liquid
continuous
interface production (CLIP), projection microstereolithography (PµSL) and
liquid interface production (CLIP), projection microstereolithography (PµSL) and TPP [64,167–169] TPP [64,167–169] appeared.
These modifications
appeared. allow manufacturing
These modifications parts with a higher
allow manufacturing partsresolution, shorter resolution,
with a higher manufacturing time
shorter
and low post-process
manufacturing time and requirements
low post-process [170]. requirements [170].
In 2015, Lin et al. reported
In 2015, Lin et al. reported the first the firstmanufacturing
manufacturingof ofGOGOreinforced
reinforcedcomplex
complexarchitectures
architecturesby by
maskprojection-based
mask projection-basedStereolithography
Stereolithography(MPSL), (MPSL),alsoalsocalled
calleddigital
digitallight
lightprocessing
processing(DLP),(DLP),with
withaa
good combination of strength and ductility [161]. First of all, the expected
good combination of strength and ductility [161]. First of all, the expected weight amount of weight amount of GO
GO
nanosheets was sonicated in acetone and then they were dispersed in the polymer
nanosheets was sonicated in acetone and then they were dispersed in the polymer resin. This research resin. This research
demonstratedthat
demonstrated thattensile
tensilestrength
strengthand andelongation
elongationof ofprinted
printedcomposite
compositeparts partswith
withonly
only0.20.2wt%
wt%GO GO
increased by 62.2% and 12.8%, respectively. Moreover, this research
increased by 62.2% and 12.8%, respectively. Moreover, this research group noticed a new fracturegroup noticed a new fracture
behavior of
behavior of 3D
3D printed
printed truss
trussarchitecture
architectureduringduringcompression
compression testing. Later,
testing. in 2017
Later, in 2017 an experiment
an experiment was
carried
was out by
carried outManapat
by Manapat et al.eton
al.the
on manufacture
the manufacture of high-strength
of high-strength nanocomposites
nanocomposites by aby typical SLA
a typical
process. In this work, the authors used the GO metastable structure to
SLA process. In this work, the authors used the GO metastable structure to improve the thermo-improve the thermo-mechanical
properties of
mechanical a printed of
properties parta that was part
printed then that
annealed at lowannealed
was then temperatures.
at lowFor this, composites
temperatures. with
For this,
different GO contents (between 0 and 1 wt%) were prepared by dispersing
composites with different GO contents (between 0 and 1 wt%) were prepared by dispersing the GO the GO in acetone and
then mixing the as prepared dispersion with a resin. The viscosities of the
in acetone and then mixing the as prepared dispersion with a resin. The viscosities of the prepared prepared GO resin varied
between
GO resin0.6 and 1.6
varied Pa·s depending
between 0.6 and 1.6 on the
Pa.sconcentration
depending on of GO. Before, the as-obtained
the concentration GO resins
of GO. Before, thewere
as-
used to manufacture the 3D parts with an axial resolution of 50 microns,
obtained GO resins were used to manufacture the 3D parts with an axial resolution of 50 microns, which were then annealed
at lowwere
which temperatures
then annealed(50 ◦ Catandlow100
◦ C for 12 h). The best results were obtained after annealing at
temperatures (50 °C and 100 °C for 12 h). The best results were
100 ◦ C for the 1 wt% GO nanocomposite that showed a very high increase of 673.6% on tensile strength
obtained after annealing at 100 °C for the 1 wt% GO nanocomposite that showed a very high increase
compared with the casted material (Figure 6) [171].
of 673.6% on tensile strength compared with the casted material (Figure 6) [171].
6. (A)
Figure 6.
Figure Tensile strength
(a) Tensile strengthcomparison
comparison of of
casted andand
casted 3D-printed parts;parts;
3D-printed SLA-printed complex-shaped
SLA-printed complex-
graphene oxide (GO) nanocomposites: (B) nested dodecahedron and (C) diagrid
shaped graphene oxide (GO) nanocomposites: (b) nested dodecahedron and (c) diagrid ring.ring. Reproduced
from [171], with
Reproduced frompermission
[171], withfrom American
permission fromChemical Society,
American 2017.Society, 2017.
Chemical
The previous work result shows that SLA is a good candidate to be used in the rapid manufacturing
The previous work result shows that SLA is a good candidate to be used in the rapid
of parts based on graphene reinforced composites that can be used in different applications, such as in
manufacturing of parts based on graphene reinforced composites that can be used in different
the biomedicine field. For example, in the work published in 2018, a graphene-reinforced composite for
applications, such as in the biomedicine field. For example, in the work published in 2018, a
bone structure scaffolds was reported. Here, Feng et al. invented a biodegradable UV-cured resin by
graphene-reinforced composite for bone structure scaffolds was reported. Here, Feng et al. invented
SLA to create the personalized complex structure for bone tissue scaffolds, which have been reinforced
a biodegradable UV-cured resin by SLA to create the personalized complex structure for bone tissue
by the filling of graphene layers [172]. The composite consists of an easily accessible polyurethane resin,
scaffolds, which have been reinforced by the filling of graphene layers [172]. The composite consists
trimethylolpropane trimethacrylate (TEGDMA) and phenylbis (2, 4, 6-trimethylbenzoyl)-phosphine
of an easily accessible polyurethane resin, trimethylolpropane trimethacrylate (TEGDMA) and
oxide (Irgacure 819) as an oligomer, a reactive diluent and a photoinitiator, respectively. The obtained
phenylbis (2, 4, 6-trimethylbenzoyl)-phosphine oxide (Irgacure 819) as an oligomer, a reactive diluent
and a photoinitiator, respectively. The obtained resin had suitable viscosities for SLA in the order of
847 Pa.s (at 25 °C) and 500 Pa.s (at 30 °C). Thanks to the inclusion and the good dispersion of graphene
fillers, the manufactured parts by SLA had improved their mechanical performance compared with
traditional direct casting techniques. Thus, the tensile strength of the printed part rose to 68MPa from
42MPa that is the value for the same material but produced by direct casting. Other improvements
resin had suitable viscosities for SLA in the order of 847 Pa·s (at 25 ◦ C) and 500 Pa·s (at 30 ◦ C).
Thanks to the inclusion and the good dispersion of graphene fillers, the manufactured parts by SLA
had improved their mechanical performance compared with traditional direct casting techniques.
Thus, the tensile strength of the printed part rose to 68 MPa from 42 MPa that is the value for the
same material but produced by direct casting. Other improvements are also been registered in the
flexural strength (115 MPa) and flexural modulus (5.8 GPa). Consequently, these results show that
this graphene-reinforced resin has a great ability to produce biotissue compared to the conventional
mold-based step by step techniques that have a considerably low cost. Figure 7 shows the images
of jawbones,
low cost. Figureand7 gyroid scaffolds
shows the imagesofofpure UV-cured
jawbones, andresin and
gyroid graphene-reinforced
scaffolds nanocomposite
of pure UV-cured resin and
manufactured in this work.
graphene-reinforced nanocomposite manufactured in this work.
Figure
Figure 7.
7. Pictures
Picturesof of(a,c)
(a,c)monolithic
monolithicUV-cured
UV-curedresin
resinand
and(b,d)
(b,d)graphene-reinforced
graphene-reinforcednanocomposite
nanocomposite
jawbone
jawbone with
with aa square
squarearchitecture
architectureand
andgyroid
gyroidscaffold
scaffoldfor
forbone
bonetissue engineering,
tissue engineering,respectively.
respectively.
Reproduced
Reproduced from
from[172],
[172],with
withpermission
permissionfrom
fromZuying
ZuyingFeng
Fengetetal.,
al.,2019.
2019.
A short
A short time
timeago,
ago,Hensleigh
Hensleighetetal. al.investigated
investigatedthethemanufacturing
manufacturing ofof complex
complex micro-architected
micro-architected
graphene aerogels by using an “XGO” resin. In this study was demonstrated that
aerogels by using an “XGO” resin. In this study was demonstrated that graphene graphene containing
resin couldresin
containing be could
precisely designed
be precisely to any to
designed complex shapeshape
any complex withwith
3D 3D
spatial characteristic
spatial characteristicsizes
sizes of
~10 microns
of ~10 microns(Figure 8G,8g,
(Figure [173]) by by
[173]) light, which
light, is aismuch
which higher
a much resolution
higher compared
resolution withwith
compared otherother
works
works
where where the obtained
the obtained featurefeature sizeson
sizes were were
theon the order
order of 100of 100 µm.
µm.
In the current state of the art, other graphene-based 3D parts obtained by SLA improved versions
as DLP [174], TPP and others can be found [170,175].
Figure 8.
Figure (A)Four
8. (a) Four“Green”
“Green”MAGMAGpartspartsofofdiffering
differing unit-cell
unit-cell structures
structures before
before pyrolysis
pyrolysis from
from leftleft
to to
right: octet-truss, gyroid, cubo-octahedron, and Kelvin foam; (B) optical image
right: octet-truss, gyroid, cubo-octahedron, and Kelvin foam; (b) optical image of pyrolyzed gyroid; of pyrolyzed gyroid;
(C)SEM
(c) SEMimage
imageofofpyrolyzed
pyrolyzedgyroid
gyroidwith
withintricate
intricate overhang
overhang structures
structures (d)(D) zoomed
zoomed image
image of pyrolyzed
of pyrolyzed
gyroidin
gyroid in(c);
(C);(e)
(E)optical
opticalimage
imageofofpyrolyzed
pyrolyzed MAG
MAG octet-truss,
octet-truss, ofof a different
a different design
design than
than shown
shown in in
(a)(A)
supportedby
supported byaasingle
singlestrawberry
strawberryblossom
blossomfilament;
filament;(f)(F) SEM
SEM image
image ofof pyrolyzed
pyrolyzed octet-truss
octet-truss MAG
MAG in in
(E);(g)
(e); (G)zoomed
zoomedimage imageofofoctet-truss
octet-trussinin(e)(E) showing
showing thethe very
very high
high 1010 micron
micron resolution
resolution achievable
achievable in in
ourprocess.
our process.Reproduced
Reproducedfrom from[173],
[173],with
withpermission
permissionfrom fromthe
theRoyal
Royal Society
Society ofof Chemistry,
Chemistry, 2018.
2018.
3.2.2. In the current

Inkjet Printingstate
(IJP)of the art, other graphene-based 3D parts obtained by SLA improved versions
as DLP [174], TPP and others can be found [170,175].
This technology was considered in Section 2.2.4 of this paper. For the accurate fabrication in this
technique,
3.2.2. Inkjetit Printing
is necessary
(IJP) to make spherical droplets that can be obtained by an optimal choice of
jetting characteristics, as follows: voltage, frequency, and viscosity waveform [123]. Besides, the used
This technology was considered in Section 2.2.4 of this paper. For the accurate fabrication in
feedstocks commonly are low-viscosity suspensions with the desired flow behavior, which is
this technique, it is necessary to make spherical droplets that can be obtained by an optimal choice
determined by their viscosity, shear elastic and yield stress points and surface forces that form a layer
of jetting characteristics, as follows: voltage, frequency, and viscosity waveform [123]. Besides,
on the surface of suspension [176]. Moreover, the nozzle diameter α (µm) and density ρ (g/cm3),
the used feedstocks commonly are low-viscosity suspensions with the desired flow behavior, which is
surface tension γ (mN/m), viscosity η (mPa s) of the ink directly influence on the drop formation
determined
[176]; and theseby their
inkviscosity, shear elastic
characteristics must and yield stress
be taken points and
into account surface
during theforces that form
preparation ofathe
layer
on the surface of suspension [176]. Moreover, the nozzle diameter α
graphene-based feedstock [177–179]. One of the methods for ink preparation is the liquid phase ),
(µm) and density ρ (g/cm 3
exfoliation [180],γ in
surface tension (mN/m),
which graphite η (mPa·s)
viscosity is of the ink
first dispersed in adirectly
solventinfluence
and thenon the dropby
exfoliated formation [176];
sonication.
and these ink characteristics
Unfortunately, must be
solvents that could taken
give into account
a better during
exfoliation theespecially
result, preparation of the graphene-based
N-methyl pyrrolidone
(NMP) and dimethylformamide (DMF), are highly toxic. For this reason, studies exfoliation
feedstock [177–179]. One of the methods for ink preparation is the liquid phase [180],
are constantly
in which graphite is first dispersed in a solvent and then exfoliated by sonication.
carried out to find a replacement for these toxic materials [180–182]. Despite the efforts that were Unfortunately,
solvents
made that could
to obtain suchgive a better
materials, theexfoliation
dispersityresult, especially
of graphene N-methylremained
suspensions pyrrolidone (NMP)
poor. A veryand
practical way to stabilize the inks is to use GO or rGO together with surfactants that improve the
dimethylformamide (DMF), are highly toxic. For this reason, studies are constantly carried out to find
a replacement for these toxic materials [180–182]. Despite the efforts that were made to obtain such
materials, the dispersity of graphene suspensions remained poor. A very practical way to stabilize the
inks is to use GO or rGO together with surfactants that improve the dispersity of sheets [180,183,184],
thereby it reduces the probability of agglomerate formation in graphene-based inks.
Different studies on IJP with graphene-based inks have been carried out, mainly for applications
in electronic, bioelectronic, and energy storage [185–190]. For example, Li et al. reported an easy
IJP method for the fabrication of micro-supercapacitors (MSCs) based on graphene and printed
on various substrates. The authors prepared an ink based on high-performance graphene with
dimethylformamide (DMF) that had a level of 2.3 mg/mL of graphene sheets and a sustained trend of
more than half a year. This suspension was used for the fabrication of very thin films (with a depth up
to ~0.7 µm) which are used as electrodes and current collectors. The fully printed graphene-based
MSCs demonstrated an extremely high capacitance of about 0.7 mF/cm2 , which considerably exceeds
the maximum value reached (~0.1 mF/cm2 ) in printed graphene-based MSCs [191,192] before this
study. Moreover, the authors demonstrated that this approach enabled the multi-scaled production of
MSCs and outstanding connection in parallel and/or in series [165], for instance, over 100 devices were
connected to create large-scale MSC arrays as power banks on Kapton and silicon wafers. Free from
extra protection or encapsulation, the MSC arrays can save their efficiency, for a 12 V charging,
even eight months after fabrication.
Karim et al. first reported a pre-treatment of a textile surface for inkjet printing using organic
nanoparticle-based ink [193]. This treatment permits the printing by IJP of any wearable e-textiles
based on graphene. In this study, the authors developed the printing process on porous and rough
textile material of a conductive path, because it is the main problem related to inkjet printing of
conductive inks on textiles. Figure 9 displays a diagram of the IJP process of graphene-based inks for
e-textile manufacturing. The textile surfaces were pre-treated with hydroxyl functionalized cross-linked
styrene/divinylbenzene nanoparticles (NP1); on the other hand, the aqueous ink of reduced GO was
obtained utilizing L-ascorbic acid in polyvinyl alcohol (PVA), which act as a non-toxic reducing agent.
Later, a continuous conductive electrical path of water-based rGO inks onto the pre-treated coating
was printed by inkjet printing. The results of this study show that this approach reduces the sheet
resistance of graphene-based printed e-textiles by three orders of magnitude from 1.09 × 106 Ω/sq to
2.14 × 103 Ω/sq compared with untreated textiles. Here, the pre-treated surface acts as a receptor of
the aqueous ink of reduced GO, which is after that dried at 100 ◦ C; thus the chance of harm to the
heat-sensitive fabrics is reduced. In this way, the IJP process of aqueous ink of bio-compatible reduced
GO provides opportunities for the fabrication of next-generation e-textiles for military, healthcare,
and sports applications. In Figure 10 are shown the different conductive paths, which were IJP on the
untreated and treated areas of the fabric with NP1. Figure 10a is an SEM image (×2000) of the untreated
cotton fabric coated with 6 layers of IJP silver ink. In Figure 10b are appreciated thee different areas of
the cotton fabric: (1) area printed with 12 layers of NP1; (2) 6 layers of IJP silver conductive path onto
NP1; and (3) untreated cotton fabric coated with 6 layers of IJP silver ink. Moreover, in Figure 10c is
possible to see an SEM image (×1000) of the IJP silver conductive path (six layers) onto treated cotton
fabric with 12 layers of NP1. On the other hand, Figure 10d–f show the image of the untreated cotton
fabric coated with 6 layers of IJP rGO ink (×1000), the IJP conductive rGO paths on the untreated and
treated areas of the fabric with NP1, and SEM image (×500) of IJP rGO conductive path (six layers)
onto treated cotton fabric with 12 layers of NP1.
Figure 9.
Figure 9. Diagram
Diagram of
of the
the IJP
IJP process
process of
of graphene-based
graphene-based inks
inks for
for e-textile manufacturing. Reproduced
e-textile manufacturing. Reproduced
from [193], with
from [193], with permission
with permission from
permission from the
from the Royal
the Royal Society
Royal Society of
Society of Chemistry,
of Chemistry, 2017.
Chemistry,2017.
2017.
Figure
Figure 10.10.
10. The
The different conductive
conductive paths,
different conductive paths, which
which were
were IJP
IJP on the
on the untreated
the untreated and
untreated and treated
and treated areas
treated areas of
areas of the
of the
the
Figure The different paths, which were IJP on
cotton fabric
cotton fabric with
fabric with NP1.
with NP1. (a)
NP1. (a,c) and
(a) and (c) show
(c) the
show the SEM
theimages images
SEM images of the untreated
of the untreated cotton fabric coated with 6
cotton show SEM of the untreated cotton cotton fabric coated
fabric coated with 6 with
layers6
layers
layers of
of IJP silver
IJP ink
silver ink
ink (×2000),
(×2000), and
and the IJP
IJP silver conductive path (6
(6 layers) onto
onto treated cotton fabric
of IJP silver (×2000), and the IJPthe
silver silver conductive
conductive path (6path
layers) layers)
onto treated treated
cottoncotton
fabricfabric
with
with 12 layers of NP1 (×1000), respectively. (b) and (e) show 3 different areas of the cotton fabric for
12 layers of NP1 (×1000), respectively. (b,e) show 3 different areas of the cotton fabric for silverfabric
with 12 layers of NP1 (×1000), respectively. (b) and (e) show 3 different areas of the cotton and rGOfor
silver
silver and
and rGO
rGO ink,
ink, respectively:
respectively: (1)
(1) area
area printed
printed with
with 12
12 layers
layers of
of NP1;
NP1; (2)
(2) 66 layers
layers of
of IJP
IJP silver
silver (or
(or
ink, respectively: (1) area printed with 12 layers of NP1; (2) 6 layers of IJP silver (or rGO) conductive
rGO) conductive
rGO)onto
conductive path
path onto NP1; and
onto NP1;cotton
and (3)(3) untreated
untreated cotton fabric coated with 6 layers of IJP silver (or
path NP1; and (3) untreated fabric coatedcotton
with 6fabric
layerscoated with (or
of IJP silver 6 layers
rGO)of IJP(d,f)
ink. silver (or
show
rGO)
rGO) ink.
ink. (d)
(d) and
and (f)
(f) show
show the
the SEM
SEM images
images of
of the
the untreated
untreated cotton
cotton fabric
fabric coated
coated with
with 66 layers
layers of
of IJP
IJP
the SEM images of the untreated cotton fabric coated with 6 layers of IJP rGO ink (×1000), and the IJP
rGO
rGO ink
ink (×1000), and
and the
(×1000), path the IJP
IJP rGO
rGO conductive
conductive path
path (6 layers)
(6fabric
layers) onto
onto treated cotton fabric with 12
12 layers
rGO conductive (6 layers) onto treated cotton with 12treated cotton
layers of NP1 fabric
(×500), with layers
respectively.
of
of NP1
NP1 (×500),
(×500), respectively.
respectively. Reproduced
Reproduced from
from [193],
[193], with
with permission
permission from
from the
the Royal
Royal Society
Society of
of
Reproduced from [193], with permission from the Royal Society of Chemistry, 2017.
Chemistry,
Chemistry, 2017. 2017.
Recently, Asli et al. proposed a method for high-efficiency preparation of graphene-based aqueous
Recently,
Recently, Asli
Asli etet al.
al. proposed
proposed DOD aa method
method for high-efficiency
for of
high-efficiency preparation
preparation of
of graphene-based
graphene-based
suspension for electrohydrodynamic printing conductive patterns [187]. Here, an exfoliation
aqueous
aqueous suspension
suspension for
for electrohydrodynamic
electrohydrodynamic DOD
DOD printing
printing of
of conductive
conductive patterns
patterns [187].
[187]. Here,
Here, an
an
process of graphite in water that is easy and scalable to high yield was suggested for the first time.
exfoliation
exfoliation process
process of graphite in water that is easy and scalable to high yield was suggested for the
This approach can of graphite
prepare in water that
high-quality is easy thanks
graphene and scalable
to thetocombination
high yield was suggested
of the for the
sheer force of
first
first time.
time. This
This approach
approach can prepare
canball
prepare high-quality
high-quality graphene
graphene thanks
thanks to the
the combination
to Serumcombination of the
the sheer
continuous low-speed wet milling process together with Bovine Albomineof(BSA) sheer
that
force
forceasof continuous
ofan
continuous low-speed
low-speed wet ball milling process
process together with Bovine
Bovine Serum Albomine (BSA)
acts exfoliating agent. Inwetthisball
way,milling
the exfoliation together withparticles
of graphite Serum
to 2–3 Albomine (BSA)
layers graphene
that acts as an exfoliating agent. In this way, the exfoliation of graphite particles
that acts as an exfoliating agent. In this way, the exfoliation of graphite particles to 2–3 layers to 2–3 layers
graphene
graphene sheets
sheets on
on average
average can
can bebe achieved.
achieved. TheThe as-obtained
as-obtained graphene
graphene suspensions
suspensions possessed
possessed aa
concentration
concentration of 5.1 mg/mL and it remained stable for weeks. This stable graphene dispersion is
of 5.1 mg/mL and it remained stable for weeks. This stable graphene dispersion is
sheets on average can be achieved. The as-obtained graphene suspensions possessed a concentration
of 5.1 mg/mL and it remained stable for weeks. This stable graphene dispersion is preferred for the
printing
preferred process, as it dramatically
for the printing process, asreduces the probability
it dramatically reduces of thenozzle clogging.
probability Then,
of nozzle the prepared
clogging. Then,
ink was printed on a flexible substrate (Polyimide) with the controlled resolution
the prepared ink was printed on a flexible substrate (Polyimide) with the controlled resolution by the usebyofthe
an
electrostatic field in the drop-on-demand printer. After printing, thermal annealing
use of an electrostatic field in the drop-on-demand printer. After printing, thermal annealing is is essential for the
improvement
essential for theof improvement
the conductivity of the
of the printed few-layer
conductivity graphene.
of the printed On the
few-layer one hand,
graphene. On itthe
is one
necessary
hand,
for the BSA combustion, which is fundamental for the pattern stability
it is necessary for the BSA combustion, which is fundamental for the pattern stability when theywhen they are in contact
are
with water; with
in contact and on the other
water; and onhand,
the itother
diminishes
hand, itthe defects between
diminishes graphene
the defects betweenand graphene
substrate andand
graphene
substrate sheets that improve
and graphene sheetsthe
thatorder of thethe
improve surface
ordermorphology.
of the surfaceThus, the post-processing
morphology. Thus, the post-was
carried out in different durations (from 10 to 120 min), and temperatures (from 50 ◦ C to 280 ◦ C).
processing was carried out in different durations (from 10 to 120 min), and temperatures (from 50 °C
The results
to 280 demonstrated
°C). The that no-annealed
results demonstrated layer had alayer
that no-annealed sheethadresistance of 133 Ω/sq,
a sheet resistance while
of 133 annealed
Ω/sq, while
samples reduced the sheet resistance to 36.75 Ω/sq in a standard oven at
annealed samples reduced the sheet resistance to 36.75 Ω/sq in a standard oven at 280 °C with a280 ◦ C with a duration of
30 min. After
duration of 30annealing,
min. Afterthe conductive
annealing, thelayers did not
conductive lose their
layers did notadhesion to Polyimide
lose their adhesion to they were in
Polyimide
contact withinwater.
they were contactThis approach
with water. Thiscan approach
be used forcaninnovative
be used for biosensor
innovativeapplications, as well as other
biosensor applications, as
applications in printable and flexible electronics. Figure 11, [187], displays SEM
well as other applications in printable and flexible electronics. Figure 11, [187], displays SEM and and optical analysis of
printed
optical patterns.
analysis of printed patterns.
Figure11.
Figure 11.(A)
(a) DOD printer for the printing of graphene suspension; (b) (B) SEM
SEM image of printed
printed pattern
cross-sectionalview;
cross-sectional view;(C)
(c) image
image of printed graphene suspension a contour in which the average height
wasmeasured
was measuredthrough
throughthe thewhite
whiteline.
line.(D)
(d) Sample
Sample print
print section
section (20×
(20× magnification).
magnification). (e)
(E) height
height vs.
vs.
distanceof
distance ofthe
thesample
sampleline
lineinin(C).
(c). (F)
(f) SEM image of the printed
printed graphene suspension top view after
annealing.Reproduced
annealing. Reproducedfromfrom[187],
[187],with
withpermission
permission from
from the
the authors,
authors, 2020.
2020.
3.2.3.
3.2.3.Fused
FusedDeposition
Deposition Modeling
Modeling (FDM)
(FDM)
Thanks
Thanksto to the
the facility to add
facility to adddifferent
differentphases
phasesininthe
thethermoplastic
thermoplastic matrix,
matrix, this
this technology
technology cancan
be
be used for the production of parts with a wide type of composite materials [194].
used for the production of parts with a wide type of composite materials [194]. As an example, the As an example,
the inclusion
inclusion of of electrically
electrically conductivecarbon
conductive carbonallotropic
allotropicforms
forms likelike graphene,
graphene, graphite,
graphite, carbon
carbon
nanotubes, and carbon black into the filament of the printed parts can demonstrate
nanotubes, and carbon black into the filament of the printed parts can demonstrate an improvement an improvement in
electrical properties and, as in the case of graphene and CNT, in mechanical
in electrical properties and, as in the case of graphene and CNT, in mechanical properties properties [153,195,196].
The first study about the possibility of using graphene-based compounds in FDM to manufacture
[153,195,196].
parts The
was reported
first studyby about
Wei et theal. [197]. In thisofwork,
possibility usingthegraphene-based
solution intercalation strategy
compounds in was
FDM used.
to
The authors utilized N-Methylpyrolidone (NMP) as a solvent, to get good dispersion
manufacture parts was reported by Wei et al. [197]. In this work, the solution intercalation strategy of ABS and GO.
After the GOThe
was used. wasauthors
reduced some quantities
utilized of rGO/ABS (NMP)
N-Methylpyrolidone powderas formed and precipitated
a solvent, to get good from solution.
dispersion of
Next, this powder was used for the preparation by extrusion of a filament
ABS and GO. After the GO was reduced some quantities of rGO/ABS powder formed and that would later be used for
the manufacture
precipitated fromofsolution.
parts by Next,
FDM.this Thepowder
maximum wascontent
used forofthe
graphene in thebymanufactured
preparation extrusion of afilaments
filament
was
that7.4 wt%.later be used for the manufacture of parts by FDM. The maximum content of graphene in
would
the manufactured filaments was 7.4 wt%.
Nanomaterials 2020,
Nanomaterials 2020, 10,
10, 1300
x of 48
23 of 48
In recent years, different studies have been carried out on the application of graphene-based
In recentinyears,
composites FDMdifferent studies have
to be applied been carried
in different areas,outas on
wellthe as
application
biomaterialof graphene-based
scaffolds [198],
composites in FDM to be applied in different areas, as well as biomaterial
electrochemical energy storage architectures [199,200], and flexible circuits [201]. scaffolds [198], electrochemical
energy
Forstorage architectures
example, [199,200],
in 2017 Chen et al.and flexiblescaffolds
fabricated circuits [201].
for tissue engineering by application of
For example, in 2017 Chen et al. fabricated
thermoplastic polyurethane (TPU)/PLA/GO nanocomposites and scaffolds for tissue engineering
explored their by application of
biocompatibility.
thermoplastic polyurethane (TPU)/PLA/GO nanocomposites and explored
These nanocomposites were obtained by a solution intercalation strategy and then the as obtained their biocompatibility.
These nanocomposites
mixtures wereinobtained
were precipitated alcohol toby a solution
obtain intercalation
the precipitates. strategy
Next, and then the
the precipitates wereasdried
obtained
and
mixtures were precipitated in alcohol to obtain the precipitates. Next, the precipitates
extruded for the fabrication of nanocomposite filament. Diverse amounts of GO (0.5, 2, and 5 wt%) were dried and
extruded
were mixed for with
the fabrication
polymer withof nanocomposite
a fixed ratio offilament.
TPU/PLADiverse
equal to amounts of GOa(0.5,
7:3. Thereby, 2, and 5 of
monolayer wt%)
the
were mixed with polymer with a fixed ratio of TPU/PLA equal to 7:3. Thereby,
as-prepared composite was printed on a glass substrate; then the live/dead viability/cytotoxicity a monolayer of the
as-prepared
assay using composite was printed
NIH3T3 mouse embryonicon a glass substrate;
fibroblast cells then
was the
carrylive/dead viability/cytotoxicity
on. According to research, in assay
the
using NIH3T3
structure mouse
of the embryonic
obtained fibroblast
3D printed cells wasonly
composites carrylive
on. cells
According to research,i.e.,
were observed, in the
all structure
scaffolds
of the obtained
provided 3D printed
cell growth. compositesdensity
The maximum only live cells was
of cells werereached
observed, i.e., scaffold
in the all scaffolds
withprovided
0.5 wt% GO,cell
growth. The maximum
Figure 12b [198]. density of cells was reached in the scaffold with 0.5 wt% GO, Figure 12b [198].
Figure 12.96
Figure 12. 96h hcell culture
cell cultureresults of NIH3T3
results cells on
of NIH3T3 3Don
cells printed TPU/PLA
3D printed with different
TPU/PLA GO loadings:
with different GO
(a) 0 wt% GO,
loadings: (a) 0(b)
wt0.5% wt%
GO, GO, (c) wt
(b) 0.5 2 wt% GO,(c)
% GO, (d)25wt
wt%% GO.
GO,Green color
(d) 5 wt % indicates
GO. Greenlivecolor
cells,indicates
whereas live
red
color
cells, indicates
whereas dead cells. indicates
red color Adapted dead
from [198],
cells. with permission
Adapted from American
from [198], Chemical
with permission fromSociety, 2017.
American
Chemical Society, 2017.
Foo et al. developed a method for producing 3D printed electrode (3DEs) and its novel applications
in electronic
Foo et al. devices.
developed Here,a the 3Des for
method were created by
producing 3Demploying a commercial
printed electrode (3DEs) graphene-based
and its novel
conductive filament that was purchased from Black Magic. Besides,
applications in electronic devices. Here, the 3Des were created by employing a commercial a coat of gold was deposited
graphene-
on the surface of the 3DEs for the complete fabrication of the
based conductive filament that was purchased from Black Magic. Besides, a coat of gold electrode, which was named 3DE/Au,
was
Figure 13 [202]. The 3DE/Au was used as the current collector and working
deposited on the surface of the 3DEs for the complete fabrication of the electrode, which was named electrode for a solid-state
supercapacitor
3DE/Au, Figurewith a multilayered
13 [202]. The 3DE/Au structure.
was usedBeforeas thethe assembly
current of the
collector andsupercapacitor,
working electrode a layer
forofa
polypyrrole/reduced graphene oxide (Ppy/rGO) nanocomposites were deposited
solid-state supercapacitor with a multilayered structure. Before the assembly of the supercapacitor, on the 3DE/Au face
in-situ by means of electrochemical polymerization technique. The
a layer of polypyrrole/reduced graphene oxide (Ppy/rGO) nanocomposites were deposited on the assembled supercapacitor showed
appropriate
3DE/Au face capacitance
in-situ by behavior
meanswith of aelectrochemical
specific capacitance of 98.37 F/g. technique.
polymerization These 3DEs The were assembled
fabricated
into a photoelectrochemical sensing platform that had a photocurrent
supercapacitor showed appropriate capacitance behavior with a specific capacitance of 98.37 response at ~724.1 µA and a
F/g.
lower detection limit (0.05 µM) compared to the indium (ITO)-or fluorine-doped
These 3DEs were fabricated into a photoelectrochemical sensing platform that had a photocurrent tin oxide (FTO) glass
electrode.
response atZhang ~724.1et µAal. manufacture
and a lower by FDM highly
detection conductive
limit (0.05 graphene to
µM) compared flexible circuits.(ITO)-or
the indium In this
study, the authors prepared high conductive graphene with a conductivity
fluorine-doped tin oxide (FTO) glass electrode. Zhang et al. manufacture by FDM highly conductive above 600 S/cm by a
two-step
graphenein-situ
flexible reduced method.
circuits. In thisThe first the
study, stepauthors
was a chemical
prepared reduction by 4-iodoaniline,
high conductive graphene while
withthea
next stage included a thermal reduction in the Ar atmosphere at 1050 ◦ C for 1 h. The conductive
conductivity above 600 S/cm by a two-step in-situ reduced method. The first step was a chemical
(4.76 S/cm)by
reduction filaments of PLA-rGO
4-iodoaniline, composite
while the next stage were finally fabricated
included by homogenously
a thermal reduction in the Armixing
atmosphererGO
(6
at wt%)
1050 °C using
for 1melt
h. The intercalation.
conductive SEM imagesfilaments
(4.76 S/cm) showed of that graphene
PLA-rGO was wellwere
composite dispersed
finallyinfabricated
the PLA
substrate. The authors demonstrated that the orientation of r-GO fillers
by homogenously mixing rGO (6 wt%) using melt intercalation. SEM images showed that graphene takes place during the extrusion
process,
was welland this effect
dispersed contributes
in the to theThe
PLA substrate. increase
authors indemonstrated
the conductivity thatof
thethe filaments.ofIn
orientation r-GOaddition,
fillers
the 3D flexible circuits exhibit good bonding force between layers, indicating
takes place during the extrusion process, and this effect contributes to the increase in the conductivity that the 3D structure
can maintain
of the filaments.the same good mechanical
In addition, property
the 3D flexible in both
circuits the axial
exhibit good direction
bonding andforce
transverse
between direction.
layers,
Besides,
indicating thethat
manufactured 2D flexible
the 3D structure circuits on
can maintain thepaper
sameand good polyimide
mechanical(PI) property
substratesinshowed
both the a great
axial
bonding force between the composite circuits and both substrates, Figure
direction and transverse direction. Besides, the manufactured 2D flexible circuits on paper and 14 [201].
polyimide (PI) substrates showed a great bonding force between the composite circuits and both
substrates, Figure 14 [201].
Figure 13. Physiochemical characterization. (a) Optical image of the 3D printing process, (b) 3D
Figure13.
Figure 13.Physiochemical
Physiochemical characterization.
characterization. (a)(a) Optical
Optical image
image of 3D
ofimage
the theprinting
3D printing process,
process, (b)
(b) 3Dand 3D
printed
printed electrode used throughout the study. (c) FESEM of 3DE/Au electrode, (d)
printed electrode used
electrode used magnified
throughout throughout the study.
the study. (c) area.
FESEM (c) FESEM image
image of 3DE/Au of 3DE/Au
electrode, electrode, and
and (d) corresponding(d)
corresponding cross-sectional Reproduced from [202], with permission from Springer
corresponding
magnified magnifiedarea.
cross-sectional cross-sectional
Reproduced area. Reproduced
from from
[202], with [202], with
permission permission
from Springerfrom Springer
Nature, 2018.
Nature, 2018.
Nature, 2018.
Figure
Figure14.
Figure 14.(a)
14. (a)Simplified
(a) Simplifiedschematics
Simplified schematicsdepicting
schematics depicting
depicting the
the
theprocess
process of graphene-based
of of
process graphene-based
graphene-based 3D3D
3D printing
printing byFDM;
by
printing FDM; (b)
(b)
by FDM;
two
two
(b) units
units
two of
units 3D
of of printed
3D3Dprinted paper-based
printedpaper-based
paper-based flexible
flexible circuits pattern; (c) LED
flexible circuits pattern; (c)LED circuit
LEDcircuit with
circuitwith a bunch
witha abunch of
bunchofof3D3D
3D
printed filaments;
printedfilaments;
printed (d)
filaments; (d) 3D
(d) 3D printed
3Dprinted flexible
printed flexible circuits.
circuits. Reproduced
flexible circuits. Reproduced fromfrom [201],
from [201], with
[201], with permission from
with permission
permission from
from
Elsevier,
Elsevier,2016.
2016.
Elsevier, 2016.
3.2.4.
3.2.4. Direct
3.2.4.Direct Ink
DirectInk Writing
Writing(DIW)
InkWriting (DIW)
(DIW)
Direct
Directink
Direct inkwriting
ink writingis
writing an
isisan AM
anAM technique
AMtechnique based
technique based
based on on the
the extrusion
extrusion and and deposition
and depositionof
deposition ofaaapseudo-plastic
of pseudo-plastic
pseudo-plastic
material (paste),
material(paste),
material which
(paste),which
whichcan can maintain
canmaintain
maintain the the shape
the shape
shape of of the
the extruded
extruded filament
filament and
filament and the
and the printed
the printedpart
printed partin
part inthe
in the
the
time after
timeafter
time extrusion.
afterextrusion. Previously,
extrusion.Previously,
Previously, we we had
we had already
had already considered this
already considered this technique technique
technique at at the
at the Section
the Section 2.3.3
Section2.3.3 of
2.3.3of the
ofthe
the
present work.
presentwork.
present work.
Among
Amongthe
Among the all
all AM
the all AMAM technologies,
technologies, direct
technologies, direct ink
ink writing
writing is is one
one of of the
the most
the most broadly
most broadly
broadly usedused
used forfor the
for the
the
manufacturing
manufacturing of
of 3D
3D parts
parts from
from
manufacturing of 3D parts from a graphene-based a
a graphene-based
graphene-based feedstock
feedstock tanks
tanks to
to the
the combination
combination of
of
to the combination of the great the
the great
great
possibilities
possibilitiesof
possibilities of
ofDIW
DIWwith
DIW with the
with the unique
the unique properties
unique properties of
properties of graphene
graphene that that has shown
has shown noteworthy
shown noteworthy printing
noteworthy printing
printing
capabilities
capabilities and
and unique
unique viscoelastic
viscoelastic
capabilities and unique viscoelastic properties properties
properties [203].
[203].
Naficy
Naficyet
Naficy etetal. reported
al. reported
al. reported that that graphene-based
graphene-based
graphene-based pastes pastes with
pastes with concentration
with concentrationup
concentration upto
up to 13.3
to 13.3mg/mL
13.3 mg/mLare
mg/mL are
are
suitable
suitable for
suitablefor DIW.
DIW.In
forDIW. InFigure
In Figure15
Figure 15the
15 storage
thestorage
the (filled
storage (filled squares) and
(filled squares) and loss moduli (open
loss moduli
moduli (opensquares)
(open squares)of
squares) ofgraphene
of graphene
graphene
oxide
oxide suspensions
suspensions and
and the
the schematic
schematic illustrations
illustrations of the liquid
oxide suspensions and the schematic illustrations of the liquid crystal (LC) phase changes uponcrystal
crystal (LC)
(LC) phase
phase changes
changes uponthe
upon the
the
increasing
increasing concentration
concentration ofof the
the graphene
graphene oxide
oxide suspensions
suspensions are
are showed.
showed.
increasing concentration of the graphene oxide suspensions are showed. In this work, the GO ability InIn this
this work,
work, the
the GO GO ability
ability to
totodissipate
dissipate
dissipate stressstress
stress through
through
through heat
heatheat at 13.3
at 13.3
at 13.3
mg/mL mg/mL
mg/mLwas waswas measured
measured
measured and
and itsand its
its value
value was
was found
was found
value to be to
found tobe
in bein
the the
range
in the
range of 350 to 490 Pa. These values considerably exceed the calculated elastic modulus value (~60
ofrange
350 toof 350
490 to
Pa. 490
These Pa. These
values values considerably
considerably exceed exceed
the the
calculatedcalculated
elastic elastic
modulus modulus
value value
(~60 (~
Pa) of
60a
Pa) of
single-walla single-wall
nanotube nanotube
(SWNT) (SWNT)
suspension suspension
with the same with the same
concentration.
Pa) of a single-wall nanotube (SWNT) suspension with the same concentration. The rheological concentration.
The rheological The rheological
behavior of LC
GObehavior ofofLC
dispersions
behavior LCGO GOdispersions
are isdispersions
shown in Figure are is
are is shown
shown
16 [204].in Figure
in Figure 16
16 [204].
[204].
Nanomaterials 2020,
Nanomaterials 2020, 10,
10, 1300
x 25 of
25 of 48
48
Figure 15. Storage (filled squares) and loss moduli (open squares) of graphene oxide suspensions and
Figure
Figure15.15.Storage
Storage (filled
(filled squares)
squares) andand loss
loss moduli
moduli (open squares) of graphene oxide suspensions and
the schematic illustrations of the liquid crystal (LC) phase changes upon the increasing concentration
the
theschematic
schematicillustrations
illustrationsof ofthe
theliquid
liquidcrystal
crystal (LC)
(LC) phase
phase changes
changes upon the increasing concentration
of the graphene oxide suspensions. (a) At extremely low concentration. (b) and (c) Some nematic
ofofthe
thegraphene
grapheneoxide
oxidesuspensions.
suspensions.(a)(a)AtAtextremely
extremely low concentration.
low concentration.(b,c)
(b)Some nematic
and (c) Some ordering
nematic
ordering begins to appear when the concentration increases to 0.25 mg/mL. (d) In the dispersion
begins to appear when the concentration increases to 0.25 mg/mL. (d) In the dispersion
ordering begins to appear when the concentration increases to 0.25 mg/mL. (d) In the dispersion single-phase
single-phase nematic LC starts to form. (e) The increase of the nematic phase packing is higher with
nematic LC starts
single-phase to form.
nematic (e) The
LC starts to increase
form. (e)ofThe
theincrease
nematic ofphase packing phase
the nematic is higher with the
packing increase
is higher of
with
the increase of the GO concentration. (f) Some regions of GO exhibit orientation in the nematic phase.
the
theGO concentration.
increase of the GO (f) Some regions
concentration. (f)of GO exhibit
Some regions orientation in the
of GO exhibit nematicin
orientation phase. (g,h) Smaller
the nematic phase.
(g) and (h) Smaller monodomains are formed associated with an exceptional increase in elastic
monodomains are formed
(g) and (h) Smaller associated
monodomains arewith an exceptional
formed associated increase in elastic modulus.
with an exceptional increase inAdapted
elastic
modulus.
from [204],Adapted
with from [204],
permission fromwith
The permission
Royal fromofThe
Society Royal Society
Chemistry, 2014. of Chemistry, 2014.
modulus. Adapted from [204], with permission from The Royal Society of Chemistry, 2014.
Figure 16. Fingerprints of the rheological characteristic of LC GO dispersions. (a) Yied stress (σY)
Figure 16. Fingerprints of the rheological characteristic of LC GO dispersions. (a) Yied stress (σY) and
Figure
and yield16.strain
Fingerprints of theGO
(γY) versus rheological
volume characteristic
fraction. (b) of LC GOand
Storage dispersions. (a) Yied
loss moduli of GOstress (σY) and
suspensions
yield strain (γY) versus GO volume fraction. (b) Storage and loss moduli of GO suspensions versus
yield strain
versus strains(γY) versus GO
(frequency volume
of 0.01 Hz). fraction. (b) Storage
(c) No aging and fluidization
after shear loss moduli can
of GO suspensions
be observed. versus
Adapted
strains
strains (frequency
(frequency of
of 0.01
0.01 Hz).
Hz). (c)
(c) No
No aging
aging after
after shear
shear fluidization
fluidization can
can be observed.
be observed. Adapted
Adapted from
from
from [204], with permission from The Royal Society of Chemistry, 2014.
[204], with permission from The Royal Society of Chemistry,
[204], with permission from The Royal Society of Chemistry, 2014. 2014.
In other work, Yao et al. fabricated by DIW high-temperature and high rate heaters by using an
In
aqueousInother
pastework,
other with Yao
work, aYao et
et al.
high al. fabricated
fabricated by
concentration of DIW
by DIW
GO (80high-temperature
high-temperature
mg/mL) [28]. The and
and high rate
high rateviscosity
apparent heaters by
heaters bythe
of using
using an
an
paste
aqueous
aqueous
falls paste
pastewith
in a range with
of 10a2aand
high concentration
high10 of
of GO
3 Pa·s (at a shear
concentration GO (80
(80ofmg/mL)
rate mg/mL) [28].
[28]. The
1 s−1 ), while The apparentmodulus
apparent
the storage viscosity(G
viscosity of0 )the
of the paste
paste
shows a
falls in a range of 10 2 and 103 Pa·s (at a shear rate of 1 s−1), while the storage modulus (G′) shows a
falls in a range of 10 and 10 Pa·s (at a shear rate of 1 s ), while the storage modulus (G′) shows a
2 3 −1
1300
constant value at 104 Pa, while the shear stress was in the order of 10−1 Pa and 102 Pa. These values
constant value at 10 4 −1 Pa and 102 Pa. These values are
are appropriate for Pa,
thewhile the shear
printing by stress
DIW was
wherein the order
parts areof 10
formed by layer-by-layer stacked
appropriate for
architectures inthe printing
order by DIW
to have goodwhere
shapeparts are formed
retention. by experiments,
In the layer-by-layerthestacked architectures
prepared heaters
in order to have good shape retention. In the experiments, the prepared heaters
generated high temperatures up to 3000 K in a monitored form, while the temperature ramping generated high
temperatures up to 3000 K in a monitored form, while the temperature ramping response
response was fast and the heating rate was up to ~20,000 K/s. Moreover, 3D heaters also exhibited was fast and
the heating rate was up to ~20,000 K/s. Moreover, 3D heaters also exhibited high
high working stability at high temperatures including a gradual change in temperature in the working stability at
high temperatures
ambient temperature including a gradual
range and 2000 K change in temperature
over 2000 cycles. Figurein17the ambient
shows temperature
schematic range and
illustrations and
2000 K over 2000 cycles. Figure
pictures of the 3D printable heater.17 shows schematic illustrations and pictures of the 3D printable heater.
17. Schematic
Figure 17.
Figure Schematicdemonstration
demonstrationofofthe the3D3Dprintable heater.
printable (a) (a)
heater. 3D 3Dprinting of RGO
printing heater.
of RGO The inset
heater. The
has 4 has
inset heaters shown
4 heaters with awith
shown sizeaofsize
1.5 of
mm.1.5 (b)
mm. The
(b)image of theof
The image as-printed 3D heater.
the as-printed (c) The
3D heater. (c)RGO
The
heaterheater
RGO achieves temperatures
achieves above above
temperatures 3000 K3000
whenKawhen
driving currentcurrent
a driving is applied. (d) image
is applied. (d)ofimage
3D printed
of 3D
heater atheater
printed high temperature. Adapted from
at high temperature. [28], with
Adapted frompermission
[28], with from American
permission from Chemical
AmericanSociety, 2016.
Chemical
Society, 2016.
In 2014, were first reported 3D-printed nanostructures composed entirely of graphene by
Kim In et al.
2014,[205].
wereItfirst wasreported
stated that a meniscus-guided
3D-printed nanostructures growth
composed technique
entirelywasof adopted
grapheneto bywrite
Kim
et al. [205]. It was stated that a meniscus-guided growth technique was adopted to write free-standinga
free-standing reduced graphene oxide (rGO) nanowires without any supporting materials by
micropipette.
reduced graphene Dueoxide to the(rGO)
very small open without
nanowires diameterany (1–2 µm) of the
supporting micropipette,
materials the water would
by a micropipette. Due
evaporate very fast which led to the solidifying of the GO
to the very small open diameter (1–2 µm) of the micropipette, the water would evaporate suspension by pulling the micropipette.
very fast
Thanksled
which to the high
to the control of of
solidifying moving
the GO various freestanding
suspension by pullinggraphene structures could
the micropipette. Thanks be printed with
to the high
100 nm resolution, ranging from straight wires, bridges, suspended
control of moving various freestanding graphene structures could be printed with 100 nm resolution,junctions to woven structures [166].
rangingDiverse
from studies
straight about
wires, DIWbridges, of suspended
graphene-based junctionsmaterials
to woven with diverse [166].
structures applications, like as
scaffold [203], Li-ion battery [122], and supercapacitor had
Diverse studies about DIW of graphene-based materials with diverse applications, been reported too [206]. For example, like as
scaffold [203], Li-ion battery [122], and supercapacitor had been reported too [206]. composite
Jakus et al. fabricated multifunctional microsystems by 3D printable graphene (3DG) For example, for
electronic
Jakus et al.and biomedical
fabricated applications
multifunctional [207]. In thisbystudy,
microsystems graphene
3D printable powder(3DG)
graphene and polylactide-co-
composite for
glycolide (PLG) were mixed in dichloromethane (DCM).
electronic and biomedical applications [207]. In this study, graphene powder and During extrusion, the fast polylactide-co-
evaporation of
DCM provided
glycolide (PLG)awere self-supporting filament that would
mixed in dichloromethane not beDuring
(DCM). changed after deposition.
extrusion, the fast The composites
evaporation of
had a maximum graphene loading of 60 vol%. Additionally,
DCM provided a self-supporting filament that would not be changed after deposition. The the authors demonstrated that during
the extrusion
composites hada flakes orientation
a maximum occursloading
graphene along withof 60the filament
vol%. microstructure.
Additionally, the authorsGraphene particles
demonstrated
stacked
that within
during thetheextrusion
filament but aligned
a flakes in the exterior
orientation occursof the filament.
along with the filament microstructure.
Fu et al. produced Li Ti O (LTO)/GO and
Graphene particles stacked within the filament but aligned in the exterior
4 5 12 LiFePO 4 (LFP)/GO composites
of the for the AM of Li-ion
filament.
battery
Fu et al. produced Li4Ti5O12 (LTO)/GO and LiFePO4 (LFP)/GO composites for the AMannealing
by DIW [122]. The composites showed a high electrical conductivity after the thermal of Li-ion
of GO. Composite pastes were obtained by adding an LFP or LTO
battery by DIW [122]. The composites showed a high electrical conductivity after the thermal to GO suspension (80 mg/mL) with
a mass ratio of 7:3, in which only water was de solvent. The storage modulus (G 0 ) of both pastes was
annealing of GO. Composite pastes were obtained by adding an LFP or LTO to GO suspension (80
in the region 4 to 105 Pa during the plateau region, which indicated a stiffer ink with a solid-like
mg/mL) withofa 10 mass ratio of 7:3, in which only water was de solvent. The storage modulus (G′) of
response. On the other
both pastes was in the region hand, elastic
of 104 tolimit
105values for the
Pa during thetwo composite
plateau region,pastes
whichwere 103 Pa.a These
indicated stiffer two
ink
high values are necessary for the paste application in DIW. After
with a solid-like response. On the other hand, elastic limit values for the two composite pastes werethe obtaining of electrodes were
freeze-dried
10 3 Pa. Theseand twothenhighthermally
values are annealed
necessary in Ar/H
for the2 gas.
pasteThe initial charge
application and discharge
in DIW. capacities of
After the obtaining of
LFP/rGO electrode, at a specific current of 10 mA/g, were 168 and
electrodes were freeze-dried and then thermally annealed in Ar/H2 gas. The initial charge and 164 mAh/g, respectively, that are very
close values
discharge to the theoretical
capacities of LFP/rGO capacity of LFP
electrode, at a(170 mAh/g);
specific while
current LTO/rGO
of 10 electrode
mA/g, were 168 and showed values
164 mAh/g,
of 184 and 185
respectively, mAh/g,
that are very respectively,
close values that
to are
the higher thancapacity
theoretical the theoretical capacity
of LFP (170 mAh/g);of LTO while(175 mAh/g).
LTO/rGO
On the other hand, the fabricated battery demonstrated initial charge
electrode showed values of 184 and 185 mAh/g, respectively, that are higher than the theoretical and discharge capacities of 117
and 91 mAh/g at a specific current of 50 mA/g.
capacity of LTO (175 mAh/g). On the other hand, the fabricated battery demonstrated initial charge
Liu et al. capacities
and discharge studied the of preparation
117 and 91 mAh/g of graphene oxide/polyaniline
at a specific current of 50(PANi)mA/g. feedstock for flexible
micro-supercapacitors (fMSCs) [206]. The authors
Liu et al. studied the preparation of graphene oxide/polyaniline (PANi) made composites with aligned
feedstockPANifor nanorods,
flexible
which were vertically grown
micro-supercapacitors (fMSCs) on[206].
the two
Thesurfaces
authors of the GO
made sheets. For
composites withthis, the vertical
aligned nanorods
PANi nanorods,
which were vertically grown on the two surfaces of the GO sheets. For this, the vertical nanorods
were fixed on the graphene oxide surfaces by an interfacial polymerization approach; and then,
a clearly defined nanostructure of GO/PANi composite was obtained. Next, the conductive poly(3,4-
ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS) was utilized as a dispersing agent to
achieve highly dispersed aqueous GO/PANi-PEDOT:PSS (GO/PA-PE) feedstock with the appropriate
rheological behavior for printing by extrusion. Here, PANi nanorods were wrapped by PEDOT:PSS
changing their morphology giving them a much smoother surface than the started sharp protrusions.
The PEDOT:PSS application provides the formation of a material with high electrical conductivity and
permits the complete utilization of inner surface capacitance, in addition to improving its printability
properties. The printed flexible micro-supercapacitors from GO/PA-PE showed high volumetric
capacitance (19.2 F/cm3 at 5 mV/s) and areal capacitance (153.6 mF/cm2 at 5 mV/s) values that were
greater than the literature values. Moreover, the authors demonstrated that by fabricating asymmetric
fMSCs using the GO/PANi as the positive electrode and a graphene-based negative electrode, the
voltage window can be widened from 0.8 to 1.2 V and improvements can be achieved in energy density
(from 3.36 to 4.83 mWh/cm3 ), power density (from 9.82 to 25.3 W/cm3 ), and cycling stability (from 75%
to 100% capacitance retention over 5000 cycles) compared with the symmetric counterpart.
4. Direct Ink Writing Technology of Graphene-Based Ceramic Pastes

DIW is among the most commonly used AM technique for the production of 3D parts from a
graphene-based paste. For obtaining a part with good properties by DIW a high graphene content paste
and with a suitable raw material is necessary [203]. Besides, a high colloid volume fraction in the paste
will minimize the drying-induced shrinkage after printing. Very often, the use of additives (binders,
viscosifiers, among others) is needed to provide a good dispersion of the graphene-based materials and
obtain a paste with appropriate viscoelastic properties. In DIW, the paste viscosity for printing, which is
related to the loss (i.e., viscous) modulus (G”), should be in the order of 103 –106 mPa·s, which are very
high values. On the other hand, the storage (i.e., elastic) modulus (G0 ) is associated with the paste
elastic property thus, high values of G0 are required, because the higher G0 the stiffer is the paste with
a solid-like response [165]. The yield stress and storage modulus G0 will be restored during ink exit
from the nozzle, i.e., will remain their shape and dimension.
In the state of the art of graphene-based/ceramic 3D printed composites by DIW, diverse works
with different applications as conductive ceramic nanocomposites [208,209], energy storage/conversion
systems, high-temperature filters, and others, can be found.
Roman-Manso et al. first reported the study of 3D architected graphene/ceramic composites
obtained by DIW. These composites are applied in energy storage/conversion systems, high-temperature
filters, or as catalyst supports, gas sensors, and acoustic metamaterials. These 3D objects were printed
starting from a paste containing homogeneous mixtures of SiC ceramic powders and up to 20 vol% of
graphene nanoplatelets (GNPs), and then, these objects were consolidated by Spark Plasma Sintering
(SPS), Figure 18 [208]. The paste was prepared as follows: three powder compositions were formulated
with diverse GNPs contents (5, 10 and 20 vol%). The ceramic powder was mainly composed of
b-SiC and using Al2 O3 and add Y2 O3 as sintering aids, and holding the SiC:Al2 O3 :Y2 O3 formulation
constant at a 93:2:5 (wt%) ratio for all the compositions. To obtain a homogeneous powder composition,
the aforementioned components were mixed in an attrition mill with alumina balls in an isopropyl
alcohol media. At the same time, a stable dispersion of GNPs in isopropanol was prepared by
sonication. Next, the ceramic composite and the GNPs dispersion were mixed and, finally, stirred
and sonicated. Subsequently, the solvent was removed in a rotary evaporator, and the mixture was
dried at 120 ◦ C and sieved through a 63 µm mesh. With aim of preparing the pastes, well-dispersed
suspensions of the as-obtained dried blend in an aqueous polymer solution of polyethylenimine (PEI),
methylcellulose (MC) and ammonium polyacrylate (APA) were obtained in a planetary centrifugal
mixer. In these suspensions, PEI, MC, and APA acted as a dispersant, viscosifying agent and flocculant,
respectively. The aqueous polymer composition for pastes with contents up to 10 vol%. of GNPs
was (4 wt% of PEI, 5 wt% of MC and 0.3 wt% of APA); while the paste with 20 vol%. a slightly
higher of the PEI concentration (5 wt%) to obtain the required pseudoplastic properties. Note that
the solids concentrations in the pastes were in the range of 69–71 wt% (42–44 vol%) in all cases. Next,
3D architected composites were manufactured using a DIW printer. After printing, the parts were
heated up to 415 ◦ C to burn out the organics and, then, the as-printed parts were sintered in an SPS
furnace at 1800 ◦ C and an Argon atmosphere. Sintered composites showed high porosity, ranging
from 1.6 to 0.9 g/cm3 for corresponding GNPs contents of 0 to 20 vol%, as compared with theoretical
values of the bulk compositions 3.28 g/cm3 and 3.03 g/cm3 for the monolithic SiC and for the 20 vol%
GNPs composites, respectively. Besides, the electrical conductivity of the scaffolds demonstrates
some anisotropy with the architecture character and grows with the GNPs volume fraction. It was
stated that, under such an approach, the values of up to 611 and 273 S/m for the longitudinal and
transverse orientations, respectively, of the structures relative to the extruded cylinders were obtained.
This anisotropy was determined by the design of the structure and also by the strong preferential
orientation of the
Nanomaterials 2020,GNP
10, x within the rod during the printing process. 29 of 48
Figure (a) (a)

18. 18.
Figure Patterned
Patternedstructure
structureused
usedforforscaffolds
scaffoldsdesigning
designing andand (b)
(b) scheme the contact
scheme of the contact area
area
between two orthogonal rods, where h, a, and Ø correspond to the distance between two equivalent
layers
layers in the
in the z direction,
z direction, thethe distance
distance betweentwo
between twoadjacent
adjacentrods,
rods, and
and the rod
rod diameter,
diameter,respectively.
respectively.
(c) Apparent
(c) Apparent viscosity
viscosity as aasfunction
a function
of of
thethe shear
shear ratefor
rate forthe
theGNPs/SiC
GNPs/SiCpastes
pastes formulated
formulated with
with0,0,5,5,10
10
and and 20 vol%
20 vol% GNPsGNPs in the
in the powder
powder compositions.(d)
compositions. (d)View
Viewof ofaa 10
10 vol%
vol% GNPs/SiC
GNPs/SiC sintered
sinteredscaffold.
scaffold.
Reproduced
Reproduced fromfrom [208],
[208], with with permission
permission from
from Elsevier,
Elsevier, 2016.
2016.
Tubio et al. proposed a scalable fabrication of rGO/Al2 O3 composites with complex mesoscale
architecture by DIW for their use in diverse applications [210]. The paste production involved three
basic steps: dispersion, mixing, and gelation. In the first step, an aqueous Al2 O3 colloidal suspension
with diverse graphene oxide concentration (0.5, 1 and 5 wt%) was prepared in a planetary mixer.
Then, the concentration of the as as-prepared suspension was increased by water evaporation at room
temperature and mixed again several times. Subsequently, hydroxypropyl methylcellulose (HPMC)
was added to increase the viscosity followed by other mixed steps. Next, polyethylenimine (PEI) was
added to facilitate the gelation followed by other mixed steps. The rheological tests under steady
and dynamic shear conditions were carried out to investigate the printability of as-prepared pastes.
The data results showed two important effects: all pastes have shear-thinning (i.e., pseudoplastic)
behavior, and the GO concentration influence on the viscosity data in the studied shear-rate range.
Moreover, the highest apparent viscosity was found in the paste with graphene oxide concentration of
5 wt% and this paste showed a storage modulus (G0 ) ~1 × 106 Pa, while the shear yield stress raised to
220 Pa from 20 Pa for paste with 0 wt% GO. Therefore, paste with 5 wt% GO content was used for the
fabrication of GO/Al2 O3 composites with complex mesoscale architecture by DIW. The rGO-Al2 O3
composites were sintered in a protective atmosphere (N2 ) at 1600 ◦ C. In another work, Moyano et al.
proposed a new formulation of graphene-based pastes for producing self-supported 3D architectures
by DIW. Here, the authors showed that is possible to obtain graphene-based pastes from just a single
surfactant to achieve a suitable high elastic modulus and a shear-thinning behavior at rest. At the
same time, the whole paste produce process is simple and scalable. Three aqueous graphene-based
pastes were created by mixing GO, GNP and their mixture (GNP (92.7 wt%) and GO (7.3 wt%)) with an
aqueous solution (30 wt% concentration) of Poloxamer 407, a triblock copolymer that contains 70 wt%
of PEO units. Pastes with 30 wt% solution of Poloxamer 407 display shear thinning characteristics.
The G0 values of the three inks were 8 × 105 Pa, 4 × 105 Pa and 3 × 105 Pa for GNP, GO and their mix,
respectively, Figure 19b [211]. These storage moduli values are larger compared with those reported
for equivalent water-based GNP and GO inks, which were prepared by utilizing polyelectrolytes
Figure 18. (a) Patterned structure used for scaffolds designing and (b) scheme of the contact area
(anionic and cationic) [212]. The yield stress, which is related to the change of the inks to a semi-liquid
state, stays between 1 and 4 kPa. Subsequently, the as-prepared pastes were used for the printing of
layers in the z direction, the distance between two adjacent rods, and the rod diameter, respectively.
3D structures. Next,
(c) Apparent the structures
viscosity achieved
as a function a very
of the shear high
rate for thecompressive strength
GNPs/SiC pastes (above
formulated with 2
0, MPa)
5, 10 after
thermally treated at 1200 ◦ C with a low density (0.12 g/cm3 ) and very high electrical conductivity
and 20 vol% GNPs in the powder compositions. (d) View of a 10 vol% GNPs/SiC sintered scaffold.
× 103 S/m)from
(above 4Reproduced for [208],
the mixwithGO–GNP
permissioncomposition.
from Elsevier, 2016.
Figure
Figure (a)(a)
19.19. 3D3Dprinted
printedGOGOstructure,
structure,(b)
(b)“a”
(a) dried 24
24 hh in
inair;
air;(c)
(c)Comparison
Comparisonofofstructures
structures obtained
obtained
after treatment
after treatment at at
1200
1200◦ C°C
from
fromGNP,
GNP,GOGOandandmix
mixcompositions;
compositions; (d) (d) Storage (G0 )and
Storage(G’) andloss
loss(G’’)
(G”) moduli
moduli
versus
versus shear
shear stress
stress for for
the the three
three inks:
inks: GO,GO,GNP GNPandand
mix.mix. Reproduced
Reproduced fromfrom [211],
[211], withwith permission
permission from
from Elsevier,
Elsevier, 2019. 2019.
The
Theprevious
previousexamples
examplesshowed
showedthat
thatthe
theclassic
classic production of graphene-based
production of graphene-basedceramic
ceramicpastes
pastes
involves thethe
involves useuse
of of
various
variouspolymers,
polymers,which
whichare
arelater
later removed getaacomposite
removed to get compositeofofboth
bothceramic
ceramic and
and
graphene-based materials. Different works have been carried out to develop new formulations and
methods of paste preparation to reduce the number of additives in them.
One solution can be to modify the paste rheological behavior to reach suitable viscoelastic
characteristics by adding some amount of silica. For example, Zhu et al. investigated the method
for manufacturing 3D graphene composite aerogel with periodic macropores for supercapacitor by
graphene-based materials. Different works have been carried out to develop new formulations and
methods of paste preparation to reduce the number of additives in them.
One solution
Nanomaterials can be to modify the paste rheological behavior to reach suitable viscoelastic
2020, 10, 1300 30 of 48
characteristics by adding some amount of silica. For example, Zhu et al. investigated the method for
manufacturing 3D graphene composite aerogel with periodic macropores for supercapacitor by DIW,
DIW,
FigureFigure 20 [213].
20 [213]. Here,Here, to prepare
to prepare a suitable
a suitable paste paste
for DIW for the
DIW GO the GO suspension
suspension (40 mg/mL)
(40 mg/mL) was
was mixed
mixed with hydrophilic fumed silica. Silica acted as a viscosifier that imparted
with hydrophilic fumed silica. Silica acted as a viscosifier that imparted both shear-thinning behavior both shear-thinning
behavior
and a shear andyield
a shear yieldtostress
stress the GO to the GO suspension
suspension to enhanceto enhance the printability
the printability of the of the GO-based
GO-based paste.
paste. Besides, the authors added several graphene nanoplatelets (GNPs)
Besides, the authors added several graphene nanoplatelets (GNPs) along with a reactant (resorcinol– along with a reactant
(resorcinol–formaldehyde
formaldehyde (R-F) solution) (R–F)to solution)
induce to induce post-printing
gelation gelation post-printing
via organicvia organic
sol-gel sol-gel chemistry.
chemistry. GNPs
GNPs
and SiOand SiO2 concentrations
2 concentrations ranged ranged
from from 0 towt%
0 to 16.7 16.7 wt% for both
for both materials.
materials. The results
The results demonstrated
demonstrated that
that the apparent viscosity of as-prepared composite paste (GO–GNP)
the apparent viscosity of as-prepared composite paste (GO–GNP) shows orders of magnitude higher shows orders of magnitude
higher than
than that ofthat of the
the GO GO suspension;
suspension; moreover, moreover,
both ofboth
them ofwere
themshear-thinning
were shear-thinning non-Newtonian
non-Newtonian fluids.
fluids. The presence
The presence of theand
of the GNP GNP andfillers
silica silicain
fillers in thegraphene
the pure pure graphene
oxide inkoxide
hasink
ledhas led to improved
to improved storage
storage
modulus modulus
and yieldand yield
stressstress
moremore thanthanone one order
order of of magnitude.The
magnitude. Themagnitudes
magnitudes of of these
these main
main
rheological
rheologicalcharacteristics
characteristicscoincide
coincide with
withthose stated
those for other
stated colloidal
for other inks fabricated
colloidal for DIW.
inks fabricated for In
DIW.order
In
to obtain the 3D graphene aerogel (GA) the printed composite was subjected
order to obtain the 3D graphene aerogel (GA) the printed composite was subjected to gelation, freeze- to gelation, freeze-drying
or supercritical-drying,
drying and etching
or supercritical-drying, and of the silica
etching with
of the hydrofluoric
silica acid. Although
with hydrofluoric in this work
acid. Although in thisefforts
work
were made
efforts wereto avoid
made the to addition
avoid the of polymer
addition additives,
of polymer the additives,
inclusion ofthe silica did not completely
inclusion of silica did solve
not
this problem, since a reactant was still used for gelation of the paste.
completely solve this problem, since a reactant was still used for gelation of the paste.
Figure
Figure20.20.Schematic
Schematic diagram
diagrampartpart
fabrication process:
fabrication Mixing
process: of SiOof
Mixing 2 , GNPs
SiO2, and
GNPs R-Fand
withR-Fthe aqueous
with the
GO suspension. Then, the as-prepared GO paste was extruded in an isooctane bath,
aqueous GO suspension. Then, the as-prepared GO paste was extruded in an isooctane bath, and the as-obtained
and the
part was gelled
as-obtained 85 ◦gelled
partatwas C, thenatdried using
85 °C, thensupercritical carbon dioxide.
dried using supercritical Finally,
carbon the silica
dioxide. fillers
Finally, thewere
silica
etched using diluted hydrofluoric acid. The scale bar is 10 mm. Reprinted Reproduced
fillers were etched using diluted hydrofluoric acid. The scale bar is 10 mm. Reprinted Reproduced from [213],
with
frompermission
[213], withfrom American
permission fromChemical
American Society, 2016.Society, 2016.
Chemical
Another approach to preparing pastes with appropriate rheological properties for ceramic/
Another approach to preparing pastes with appropriate rheological properties for
graphene composites manufacturing by DIW could be the use of preceramic polymers (PCP) [214].
ceramic/graphene composites manufacturing by DIW could be the use of preceramic polymers (PCP)
Preceramic polymers are polymeric compositions, particularly as organosilicon compounds
[214]. Preceramic polymers are polymeric compositions, particularly as organosilicon compounds
(e.g., polymers based on a Si backbone containing N, O, H, C, and B atoms), which under pyrolysis
(e.g., polymers based on a Si backbone containing N, O, H, C, and B atoms), which under pyrolysis
at above ~800 ◦ C in an atmosphere of argon or nitrogen are transformed into ceramic materials,
at above ~800 °C in an atmosphere of argon or nitrogen are transformed into ceramic materials, also
also referred to as polymer derived ceramics (PDCs) [215]. With the addition of PCPs into the
referred to as polymer derived ceramics (PDCs) [215]. With the addition of PCPs into the graphene-
graphene-based feedstock is possible to alter the properties, structures and phase of the material after
based feedstock is possible to alter the properties, structures and phase of the material after heat
heat treatment.
treatment.
Pierin et al. reported a method for the manufacturing of micro-sized SiOC ceramic components
by DIW using a preceramic polymer [216]. The mixing of siloxane resin dissolved in a solvent with
cross-linked preceramic grains ensured the appropriate rheological performance of pastes. Moreover,
for improved the structural stability via pyrolysis the low amount (0.025–0.1 wt%) of GO was added
Pierin et al. reported a method for the manufacturing of micro-sized SiOC ceramic components
by DIW using a preceramic polymer [216]. The mixing of siloxane resin dissolved in a solvent with
cross-linked preceramic
Nanomaterials 2020, 10, 1300 grains ensured the appropriate rheological performance of pastes. Moreover, 31 of 48
for improved the structural stability via pyrolysis the low amount (0.025–0.1 wt%) of GO was added
to the paste formulation, resulting in reduced shrinkage of the preceramic polymer. The resulting
to theafter
parts paste formulation,
pyrolysis at 1000resulting
°C showed in reduced shrinkage
an appropriate valueof the
of 2.5preceramic
MPa and 3.1 polymer.
MPa ofThe resulting
compression
parts after pyrolysis at 1000 ◦ C showed an appropriate value of 2.5 MPa and 3.1 MPa of compression
strength for a 64 vol % total porosity and after the addition of 0.1 wt% GO, respectively. Zhong et al.
strength
first for a 64GO/geopolymer
developed vol% total porosity and after
(GOGP) the additionstructures
nanocomposite of 0.1 wt%fabricated
GO, respectively.
by DIW,Zhong Figure et 21
al.
first developed GO/geopolymer (GOGP) nanocomposite structures fabricated
[209]. The authors noted that the addition of graphene oxide in the geo-polymeric water-based by DIW, Figure 21 [209].
The authors
mixture noted that the
(aluminosilicate and addition of graphene
alkaline-source oxide in
particles) the geo-polymeric
intensely modifies itswater-based mixture
rheology behavior
(aluminosilicate
allowing the DIW and alkaline-source
which would not particles)
be possible intensely
solely bymodifies its rheology
geo-polymer. Pastebehavior
preparation allowing the
involves
DIW which would not be possible solely by geo-polymer. Paste
the obtaining of geo-polymeric suspension by mixing of alkaline-source particles and preparation involves the obtaining of
geo-polymeric suspension
aluminosilicates particles by mixing in
(ASOPs) of alkaline-source particlesfor
water. After stirring and20aluminosilicates
min, suspensions particles
with (ASOPs)
diverse
in water. After stirring for 20 min, suspensions with diverse amounts
amounts of GO (4, 5, 10, and 20 wt%) were added into the as-prepared geo-polymeric suspension of GO (4, 5, 10, and 20 wt%)at
were added into the as-prepared geo-polymeric suspension at a temperature below 5 ◦ C. This low
a temperature below 5 °C. This low temperature avoids the geo-polymerization and the GO reduction
temperature
that avoidsatthe
could happen geo-polymerization
relatively and thewhich
high temperatures GO reduction
in turn can thatlead
couldto happen at relatively
heterogeneous high
structure
temperatures which in turn can lead to heterogeneous structure due
due to agglomeration of nanoparticles. When GO is added into geo-polymeric suspension, its to agglomeration of nanoparticles.
When GO isproperties
rheological added into geo-polymeric
change dramatically. suspension,
For the GOGPits rheological
with 4 wt% properties
of graphenechangeoxide dramatically.
the storage
0
(G’) and loss modulus (G’’) increased to ~1 × 10 Pa and ~1.5 × 10 Pa (at the stress of 50 Pa, that to
For the GOGP with 4 wt% of graphene oxide the
5 storage (G ) and 4 loss modulus (G”) increased is
~1 × 105 Pa
typically andin~1.5
used DIW)
4 Pa (at the stress of 50 Pa, that is typically used in DIW) that are over one
× 10that are over one and two orders of magnitude higher than the values of
and two(G’)
storage orders
andof magnitude
loss (G’’) moduli higher thangeopolymer,
of pure storage (G0 )In
the values ofrespectively. and loss (G”)
addition, themoduli of pure
yield stress of
geopolymer, respectively. In addition, the yield stress of the GO-based
the GO-based geo-polymeric suspension is as high as ~2000 Pa. When the GO concentration increases geo-polymeric suspension
is as
up to high
5 wt% asof~2000
GO the Pa.yield
When thedecrease
stress GO concentration
to ~1000 Pa,increases
while theup to 5 wt%
storage of GO
modulus the yield
increased stress
further.
decrease towhen
However, ~1000the Pa,concentration
while the storage of GO modulus increased further.
in nanocomposites increasesHowever,
above when
the rangethe concentration
of 10, and 20
of GO in nanocomposites increases above the range of 10, and 20 wt%,
wt%, a decrease of the modulus is showed, which is probably associated with the lubrication a decrease of the modulus effectsis
showed,
of GO. The which is probably associated
characterization with showed
of cured parts the lubrication
that GO effects of GO. The
nanosheets characterization
anchored themselvesofincured geo-
parts showed that GO nanosheets anchored themselves in geo-polymer
polymer and encapsulated individual geo-polymer grains, Figure 22 [209], in order to obtain a 3D and encapsulated individual
geo-polymer
network acrossgrains, Figure 22 [209], inThe
the nanocomposites. order to obtain acured
as-obtained 3D network across the
parts showed highnanocomposites.
mechanical properties The as-
obtained curedstrength
(compressive parts showed highwhile
> 30 MPa), mechanical properties
after sintering at (compressive
1000 °C the parts strength > 30 MPa),
achieved while after
a conductivity of
sintering at 1000 ◦ C the parts achieved a conductivity of 102 S/m.
10 S/m.
2
Figure 21. (a–f) 3D printing process and some 3D printed structures. (b–f) The colors of the printed
samples turn from
from brownish
brownishto toblackish
blackishwhen
whenthetheGO
GOloading
loadingincreased.
increased.(g)(g) The
The chemical
chemical structure
structure of
of geopolymer,
geopolymer, andand
(h) (h) schematic
schematic diagrams
diagrams of the
of the painting
painting process
process and and the composite
the composite structure
structure are
are also
also showed.
showed. Reproduced
Reproduced fromfrom
[209],[209],
withwith permission
permission fromfrom Elsevier,
Elsevier, 2017.2017.
Figure 22. SEM

Figure22. SEMimages
imagesof ofhydrated
hydratedgeopolymer
geopolymerparticles encapsulated
particles byby
encapsulated graphene
grapheneoxides sheets
oxides (a–d),
sheets (a–
and their models. With the increase of GO concentration from 4 wt% to 20 wt% in nanocomposites,
d), and their models. With the increase of GO concentration from 4 wt% to 20 wt% in nanocomposites,
the
theagglomerate
agglomerate sizesize
(showed by dotted-line
(showed circles)circles)
by dotted-line decrease. Reproduced
decrease. from [209],from
Reproduced with [209],
permission
with
from Elsevier,
permission 2017.
from Elsevier, 2017.
In
Inthe
thestate
stateof the
of theart ofartgraphene-based
of graphene-based ceramic 3D printed
ceramic composites
3D printed using preceramic
composites polymers,
using preceramic
interesting methods, which differ from the above examples in the way
polymers, interesting methods, which differ from the above examples in the way that ceramic phase that ceramic phase is introduced
in the 3D part,
is introduced in can
the 3D be part,
found. canCommonly in these solutions,
be found. Commonly a 3D graphene-based
in these solutions, a 3D graphene-basedpart is firstpart
manufactured
is first manufacturedby DIW; bythen,
DIW;itthen,is heated for polymer
it is heated removal
for polymer followed
removal by anby
followed infiltration step of
an infiltration stepa
ceramic precursor [217–219].
of a ceramic precursor [217–219].
Román-Manso
Román-Manso et et al.
al. developed
developed an an approach
approach to to manufacture
manufacture PDC/GO PDC/GO composites.
composites. In In this
this low-
low-
temperature method, the first 3D structures were fabricated by DIW
temperature method, the first 3D structures were fabricated by DIW using an aqueous GO paste with using an aqueous GO paste with
polymeric
polymeric additives.
additives. Then,Then, the the obtained
obtained graphene
graphene oxide oxide periodic
periodic structures
structures werewere dried
dried in in aa drying
drying
◦ ◦
furnace
furnaceat at~80
~80 °C C and
and immediately
immediately afterward
afterward frozenfrozenin inaarefrigerator
refrigeratorat at−20
−20 °C.C. This
This leads
leads to to prevent
prevent
the
theformation
formationof ofaa network
network of of evenly
evenly spaced
spaced cracks
cracks in in the
the composites
composites structure
structurecaused
causedby by the
the presence
presence
of water. Subsequently, the as-fabricated graphene oxide structures
of water. Subsequently, the as-fabricated graphene oxide structures were lyophilized to sublimate were lyophilized to sublimate the
ice. Finally,
the ice. in order
Finally, in orderto ensure
to ensure thethe diffusion
diffusion of of
thetheliquid
liquid into
intothethestructure
structurerods,
rods,highly
highlyporous
porous3D 3D
structures
structures were impregnated by immersion in a liquid organic-polysilazane (a compound of Si, C, H,
were impregnated by immersion in a liquid organic-polysilazane (a compound of Si, C, H,
N)
N) during
during several hours. For
several hours. Forcrosslinking
crosslinkingand andpyrolysis
pyrolysisthese these impregnated
impregnated structures
structures werewere placed
placed on
on ◦ C and 800–1000 ◦ C,
thethe
Pt Pt
foilfoil
in in alumina
alumina cruciblesinina atubular
crucibles tubularelectric
electricfurnace
furnaceand andheated
heated atat 200
200 °C and 800–1000 °C,
respectively,
respectively,in inNN22 atmosphere.
atmosphere. Figure Figure 23a23a [217],
[217], shows
shows the the printed
printed graphene
graphene oxideoxide andand pyrolyzed
pyrolyzed
composite
compositestructure
structurewhich whichhas hasremained
remainedthe theshape
shaperetention
retentionand andthe thehigh
highshrinkage.
shrinkage.
Figure
Figures23b,c,
23b and [217],
23c, exhibits viewsviews
[217], exhibits from fromabove of aofsublimated
above a sublimated GO GOstructure
structureatat different
different
magnifications. The linear shrinkage of the lattice was caused
magnifications. The linear shrinkage of the lattice was caused by quick-drying treatment. by quick-drying treatment.
Figure
Figure 23d–f,
23d–f, [217],
[217],showshowprinted
printedGO GOstructures
structuresafter afterthe thecomplete
completeinfiltration.
infiltration. No No substantial
substantial
cracking (Figure 23d,e, [217]) is detected in the infiltrated structures after pyrolysis (800–1000 ◦ C).
cracking (Figure 23d and 23e, [217]) is detected in the infiltrated structures after pyrolysis (800–1000
These PDC/GO
°C). These PDC/GO composites
composites imitate modeled
imitate modeled graphene
graphene oxideoxide skeleton
skeleton and,
and,while
whilethe theconductive
conductive
network
network (electrical conductivity in the range 0.2–4 S/cm) of the composite is provided by the presence
(electrical conductivity in the range 0.2–4 S/cm) of the composite is provided by the presence
of
of graphene.
graphene. The The ceramic
ceramic coating
coating serves
serves as as aa protective
protective barrier
barrier for for the
the graphene
graphene network
network against
against the the
atmosphere, ◦ C in the air) and even direct flame.
atmosphere,temperature
temperature(up (uptoto900
900 °C in the air) and even direct flame.
Figure23.
Figure 23.(a)
(a)3D
3D printed
printed scaffolds
scaffolds of of GO
GO (as-printed)
(as-printed) and
and the
the composite
compositestructure
structureGO/PSZ
GO/PSZpyrolyzed
pyrolyzed
atat800
800◦ C.
°C.SEM
SEMmicrographs
micrographs of of aa GO
GO lattice
lattice after
after dying/lyophilization
dying/lyophilization steps
stepsshowing
showingaatop topview
view(b)(b)
and the surface of an extruded filament (c). Analogous SEM images of a PSZ
and the surface of an extruded filament (c). Analogous SEM images of a PSZ infiltrated GO lattice infiltrated GO lattice
pyrolyzedatat800
pyrolyzed 800◦°C inN
C in N22,, (d)
(d) top
top view,
view, (e)
(e) filament
filament and
and (f)
(f) cross-section
cross-sectionat atdifferent
differentmagnifications.
magnifications.
Reproducedfrom
Reproduced from[217],
[217],with
withpermission
permissionfrom from Elsevier,
Elsevier,2018.
2018.
Similar
Similar work
work was was carried
carried out
out by
by Moyano et al. [218], in in which
which theythey studied
studied the the electrical,
electrical,
mechanicaland
mechanical andcapacitive
capacitive responses
responses of of aa strong
strong and light 3D ceramic/graphene
ceramic/graphene structurestructureobtained
obtained
throughaacontrollable
through controllableand andfast
fastinfiltration
infiltrationmethod
method usingusing aa preceramic
preceramic polymer.
Anotherinteresting
Another interesting approach
approach waswas reported
reported by et
by You You et al. In
al. [219]. [219].
this In thisthe
work, work,
authorsthe proposed
authors
aproposed
method fora method
the growthfor the growth
of SiC thatofit SiC that occurs
exactly it exactly occurs
in 3D in 3Dgraphene
printed printed graphene
scaffolds scaffolds
by meansby of
means of chemical vapor infiltration (CVI). The structures were fabricated
chemical vapor infiltration (CVI). The structures were fabricated using the addition of graphene to using the addition of
graphene
ethylene to ethylene
glycol glycol
butylether (EGB)butylether
in ethanol,(EGB) in ethanol,
followed followed
by sonication andbyaddition
sonication and addition
of dibutyl of
phthalate
dibutyl
(DBP) phthalate
and polyvinyl (DBP) and (PVB),
butyral polyvinyl butyral
resulting in (PVB), resultinggraphene-based
homogeneous in homogeneoussuspension.
graphene-based Next,
suspension.
the ethanol wasNext, the ethanolinwas
evaporated evaporated
a water bath at in 80
a water bathcontinuous
◦ C with at 80 °C with continuous
stirring. Thestirring. The
as-prepared
as-prepared suspension had a graphene concentration of 200 mg/mL. After,
suspension had a graphene concentration of 200 mg/mL. After, the graphene scaffolds were printed the graphene scaffolds
were the
using printed using the
as-prepared as-prepared
paste. paste. Subsequently,
Subsequently, the printed objects the printed objectsinwere
were located located
the Ar flow in the Ara
through
flow through a carbon tube furnace and
◦ heated to 1100 °C for thermal
carbon tube furnace and heated to 1100 C for thermal decomposition of organic-polymer. The polymerdecomposition of organic-
polymer. The polymer
decomposition allows adecomposition allows aarea
large specific surface largeofspecific surface
the scaffold area
that hasofathe scaffold
positive that on
effect hasthe
a
positive effect
densification andon thethe densification
in-situ growth of and the Thus,
the SiC. in-situthe
growth of the
SiC matrix wasSiC. Thus, the
introduced intoSiC
thematrix
pores ofwas
the
introduced into the pores of the 3D graphene scaffold by cracking methyltrichlorosilane
3D graphene scaffold by cracking methyltrichlorosilane (MTS) in the CVI process. The concentration (MTS) in the
CVIstructure
and process. of Thetheconcentration and structure
SiC in the composite of the SiC by
were monitored in adjusting
the composite were monitored
the holding time and gas by
adjustingwhich
pressure, the holding
are thetime
mainand CVIgas pressure, which are the main CVI parameters.
parameters.
Finally, the 3D graphene/SiC
Finally, the 3D graphene/SiC composites composites show show enhanced
enhanced mechanical
mechanical properties,
properties, especially
especially
compressive strength (193 ± 15.7 MPa) which is 394% higher compared to directly mixed products.
compressive strength (193 ± 15.7 MPa) which is 394% higher compared to directly mixed products.
Besides, the reconciling of the 3D graphene structure and SiC matrix produces a huge number of
Besides, the reconciling of the 3D graphene structure and SiC matrix produces a huge number of
conductive paths and gives a composite improved electrical conductivity compared to traditional
conductive paths and gives a composite improved electrical conductivity compared to traditional
ceramic materials.
ceramic materials.
Unfortunately, in these last three examples, it is not possible to directly obtain a 3D printed part
Unfortunately, in these last three examples, it is not possible to directly obtain a 3D printed part
from which a graphene-based/ceramic composite is obtained after sintering. In these examples, an
from which a graphene-based/ceramic composite is obtained after sintering. In these examples, an
additional step of ceramic material infiltration into the graphene skeleton is necessary.
additional step of ceramic material infiltration into the graphene skeleton is necessary.
As we have seen in this section, each of the discussed methods includes a preparing step of the
As we have seen in this section, each of the discussed methods includes a preparing step of
graphene-based paste that requires at least the presence of an additive, which is mainly utilized to
the graphene-based paste that requires at least the presence of an additive, which is mainly utilized
guarantee a homogeneous dispersion and to achieve the suitable viscoelastic properties. In the
to guarantee a homogeneous dispersion and to achieve the suitable viscoelastic properties. In the
majority of cases, the additives are eliminated either by a chemical etching or a thermal process at
majority of cases, the additives are eliminated either by a chemical etching or a thermal process at high
temperatures, which causes the appearance of pores in its structure that can negatively influence the
composite mechanical properties.
In recent years, attempts have been made to find new methods to minimize the presence of additives
in graphene-based paste formulations for DIW. For example, García-Tuñón et al. developed a clean,
flexible and robust approach to formulating pastes used in DIW that can be adapted to a wide range of
materials [29]. Thus, they prepared free additive pastes of diverse materials (polymer, ceramic and
metal), based only on the use of GO as the dispersant, rheological modifier, and binder. This procedure
was possible to realize thanks to the great similarities between GO and clay. These materials have
a flake-like shape with oxygen-containing functional groups on their basal planes and the edges
that promote the network connection between particles thanks to the electrostatic and noncovalent
interactions for clay and GO respectively. Clay has exceptional chemistry and structure that permit the
design of water-based suspensions for shaping with excellent viscoelastic behavior. For this reason,
it is added to ceramics suspensions to reach the required viscoelastic behavior for processing. On the
other hand, as for clay, the especial combination of GO sheets surface chemistry and structure in
contact with water under special conditions allow the preparation of a very stable GO paste with
proper viscoelastic behavior for different materials with have a broad variety of particle morphologies,
sizes, and chemistries. In this research, various kinds of graphene-based paste with ceramic (Al2 O3
powders and platelets, SiC powders) were prepared and, then, used for the printing of ceramic parts.
The increases of the paste concentration were reached by two different approaches: 1–redispersing
freeze-dried GO powders and 2–by evaporation of water at 70 ◦ C. In the two cases, pastes with a high
concentration of GO and the necessary viscoelastic behavior for printing were obtained without the
addition of any additive. Furthermore, in some cases of the paste preparations, certain amounts of
freeze-dried GO powder were added in order to achieve the necessary characteristics of viscoelasticity
and flow. Finally, the pastes prepared in this work were formed as indicated below: (1) 28.4 vol% SiC
with 0.4 vol% GO (10 mg/mL), (2) 23 vol% Al2 O3 platelets (0.8 vol% GO (23 mg/mL)) and (3) 27 vol%
Al2 O3 platelets (1.1 vol% GO (33 mg/mL)).
The authors found that GO suspensions with a concentration above ~2 vol% showed an increase
of the storage modulus (G0 , Figure 24a,b, [29]) as a result of a well-established and organized formed
structure in them (Figure 24d, [29]). The reorganization of the GO flakes occurs when the concentration
of the suspension increases thus creating a network like a liquid crystal, which produces growth of the
storage modulus (G0 ) up to 100 kPa (Figure 24b, [29]) and the yield stress up to 2300 Pa (Figure 24c, [29]).
Besides, the GO pastes with concentrations from 2.5 to 3.5 vol% have the necessary structure and
rheological properties for DIW (labeled 3D-printable in Figure 24a, [29]).
For the Al2 O3 platelets pastes, the concentration of 1.1 vol% GO and ~28 vol% platelets showed
the greatest behavior for printing (Figure 25, [29]). During extrusion an orientation of platelets and an
internal structure formation of printed filaments took place. The FESEM images of printed filament
cross-section and lateral view are shown in Figure 25c,d, [29]) respectively. In them is possible to see
how the platelets form a wall on the outside edge (Figure 25d, [29]), while the filament inside part has
a mixture of domains (Figure 25c, [29]). A more detailed observation demonstrated that GO sheets
are distributed over and across multiple Al2 O3 platelets interacting with a very strong form, binding
them together and forming bridges across them. After sintering, the structures made with GO had an
average porosity of 60% with only 2% closed pores and showed good handling strength, Figure 26 [29].
Viscoelastic behavior
behavior of
of pastes
pastes and 0 vs. Oscillation
Figure 24.
Figure 24. Viscoelastic and GOGO suspensions: Storage Modulus
suspensions: Storage Modulus (G (G′)) vs. Oscillation
Stress (a), and GO concentration influence on G0 (b), and yield stress (c). The proposed network created
Stress (a), and GO concentration influence on G′ (b), and yield stress (c). The proposed network
by GO flakes as concentration increases (d). A part of GO sheets form GO scrolls that together
created by GO flakes as concentration increases (d). A part of GO sheets form GO scrolls that together with the
sheets bring together forming a 3D liquid crystal structure with high G 0 (a). Reproduced from [29],
with the sheets bring together forming a 3D liquid crystal structure with high G′ (a). Reproduced from
with with
permission
Nanomaterials
[29], 2020, 10, x fromfrom
permission American Chemical
American Society,
Chemical 2017. 2017.
Society, 36 of 48
For the Al2O3 platelets pastes, the concentration of 1.1 vol % GO and ~28 vol % platelets showed
the greatest behavior for printing (Figure 25, [29]). During extrusion an orientation of platelets and
an internal structure formation of printed filaments took place. The FESEM images of printed
filament cross-section and lateral view are shown in Figures 25c,d, [29]) respectively. In them is
possible to see how the platelets form a wall on the outside edge (Figures 25d, [29]), while the filament
inside part has a mixture of domains (Figures 25c, [29]). A more detailed observation demonstrated
that GO sheets are distributed over and across multiple Al2O3 platelets interacting with a very strong
form, binding them together and forming bridges across them. After sintering, the structures made
with GO had an average porosity of 60% with only 2% closed pores and showed good handling
strength, Figure 26 [29].
Figure 25.
25. Printed
Printed objects
objectsfrom
fromGO/Al
GO/Al2O 3 platelets paste (a) and (b) and cross-section and lateral view
Figure 2 O3 platelets paste (a,b) and cross-section and lateral view of
of printed filament (c) and (d). Reproduced frompermission
printed filament (c,d). Reproduced from [29], with [29], with from
permission from
American American
Chemical Chemical
Society, 2017.
Society, 2017.
Figure 25. Printed objects from GO/Al2O3 platelets paste (a) and (b) and cross-section and lateral view
Nanomaterials 10, 1300 (c) and (d). Reproduced from [29], with permission from American Chemical
2020,filament
of printed 36 of 48
Society, 2017.
Figure 26.
26. Cylinder
Cylinderprinted
printedbybyDIW
DIWfromfromGO/Al 2O3 platelets paste and sintered at 1550 °C. (a−c).
GO/Al ◦ The
Figure 2 O3 platelets paste and sintered at 1550 C. (a–c).
SEM images show the cylinder microstructure with open porosity of 60% determined by Archimedes’
The SEM images show the cylinder microstructure with open porosity of 60% determined by Archimedes’
Principle (d,e).
Principle (d) and (e). Reproduced
Reproduced fromwith
from [29], [29],permission
with permission from American
from American Chemical
Chemical Society,Society,
2017. 2017.
The SiC
The SiC paste
paste also
also showed
showedsuitable
suitableprinting
printingbehavior.
behavior.Dried
Dried3D 3Dprinted
printedbars had
bars strengths
had strengths of ~1
of
MPa which demonstrates that in this case the GO also operates as a binding agent
~1 MPa which demonstrates that in this case the GO also operates as a binding agent between the between the SiC
particles.
SiC BarsBars
particles. printed fromfrom
printed GO/SiC pastepaste
GO/SiC and and
sintered at 2050
sintered °C for
at 2050 ◦ C2for
h showed a density
2 h showed a density of 3.21
of
g/cmg/cm
3.21 3 and reached
3 a bending
and reached strength
a bending of around
strength 212 MPa.
of around 212 MPa.
In both
In both cases,
cases, Al
Al22O
O33 and
and SiC
SiC were
were the
the unique
unique crystalline
crystalline phase
phase inin the
the sintered
sintered objects, and Raman
objects, and Raman
spectroscopy demonstrated
spectroscopy demonstratedthat thatnonocarbon
carbonresidues
residuesremained
remainedin inthe
thestructure.
structure. Note
Note that,
that, itit is
is possible
possible
to add potentially structural or functional properties to the sintered 3D object simply retaining the GO
in the structure after sintering
Summarizing, this method permits us to form complex 3D ceramic structures using DIW,
which have properties that are similar to alternative formulations, and demonstrates the possibility of
using 2D colloids in materials manufacturing.
5. Summary
In this review, it was shown that significant advances in additive technologies for 3D printing of
graphene-based ceramic composites have been made in recent years. The state of the art of different
additive techniques used for the manufacturing of both ceramic and graphene-based pieces was
analyzed. In addition, various examples of 3D printing of graphene-based ceramic composites were
discussed in detail.
First, a summary of existing additive technologies groups, techniques that are involved with
them, and of the most popular feedstock nowadays was made, (see Table 1). After that, it was
clear that not all AM technologies apply to the ceramic part manufacturing and even more for the
graphene-based materials.
The introduction of Additive Manufacturing to the production of ceramics is related to the need
to obtain complex parts that are not possible to produce using conventional methods since 3D printing
can manufacture complex structures in a fast, simple and inexpensive way. With the aim of a better
understanding, the AM technologies used in ceramic production were divided into three groups
(powder-, slurry- and bulk solid-based) taking into account the type of feedstock used. The state
of the art of AM technologies that are involved with these groups has been considered in detail
and demonstrated with symbolic examples. Moreover, several historical facts about each technique
were given.
The techniques (SLS, SLM, and BJ) are involved in the group of powder-based technologies for
the manufacture of 3D ceramic parts. SLS and SLM have a low surface finish, undesirable porosity,
and high shrinkage of parts that limit their application in many fields. Besides, the thermal gradients
and the high heating and cooling rates in the ceramic material produce cracks and distortions that are
not desired in the final part. On the other hand, in BJ the formation of pores and the contraction of
parts are related to the elimination of the binder used in the process. In BJ the mechanical properties of
parts are affected by pore formation, despite this, this technique is a good method used in biomedical
fields for the ceramic scaffold production.
The liquid-based group includes the SLA, DLP, TPP and IJP techniques. These methods proved
to be more promising than the powder-based ones as they can achieve high resolution, good surface
finish and required mechanical properties. Unfortunately, the high cost of the machines and the
photopolymers that are necessary for the manufacture of parts limit their wide application in the
industry. Furthermore, the working principle of TPP allows only the use of transparent polymers; i.e.,
the opaque polymers that were usually utilized in SLA and DLP are not applicable for TPP. On the
other hand, IJP is limited only to the production of miniaturized parts due to the low ink volume used
in each droplet.
In the third group are LOM, FDM and DIW techniques. In recent years, great development of the
LOM technique has not been observed and its application has been restricted only for the manufacture
of ceramic parts with simple geometry, and large sizes. On the contrary, FDM and DIW have found a
great application in the manufacture of macro-pore structures for the biomedicine application as the
production of scaffolds.
AM techniques have also been used for 3D printing of graphene-based materials thanks to the
combination of its properties with the advantages of slurry-based methods and techniques that use
a pseudoplastic feedstock. Additionally, the choice of such technologies is related to the fact that
graphene oxide, the main precursor of graphene, can be easily dispersed in water and other solvents,
which is not possible with graphene. Among the most used methods for printing graphene-based
material, we can find SLA, IJP, FDM, and DIW techniques.
The SLA method has been utilized to manufacture polymer-based composites that are used in the
production of scaffolds in biomedicine. On the other hand, IJP is one of the most used techniques in
the printing of graphene-based materials despite the low resolution and limitations that it presents.
It is possible to found polymer-based filaments with graphene fillers for FDM that are used in the
production of parts for biomedicine or in electronics and other areas of application. The disadvantage
of this method is its low precision and the quality of the surface.
DIW is the most studied technique and one of the most widely used for the manufacture of 3D
parts from a graphene-based feedstock thanks to the combination of the great possibilities of DIW with
the unique properties of graphene that has demonstrated remarkable printing capabilities with unique
viscoelastic properties. For DIW, the rheology of the suspension is very important, so it is essential to
establish the appropriate content of the components to obtain their homogeneous dispersion. After the
part is printed, a subsequent process is necessary for the removal of the solvent, which leads to the
appearance of pores in the structure. Similar structures are widely used in the production of biomaterial
scaffolds and energy storage fields.
Finally, a detailed study with some examples of printed composites from graphene-based ceramic
pastes by DIW is carried out. In this field, there is a tendency to reduce the number of additives
that are used for obtaining a homogeneous dispersion and very often produce undesired effects.
Some examples show that it is possible the use preceramic polymers for the reduction of additives and
to perform the characteristics of printed composites. Of great importance is the work carried out to
create ceramic pastes without any other additives than graphene oxide. Here it is appreciated how this
material can be used as a dispersant, rheological modifier and binder at the same time.
This work has tried to show that the DIW method is very promising in the printing of complex
graphene-based ceramic composites at reduced cost and in less time. We consider that this field should
continue to develop so that soon the manufacture of graphene-based ceramic composites will take its
place in the ceramic industry.
Author Contributions: Conceptualization, N.W.S.P., A.S. (Anton Smirnov); data curation, N.P., A.S. (Anton Seleznev);
formal analysis, N.W.S.P., N.P.; funding acquisition, P.P.; investigation, P.P., N.P.; methodology, A.S. (Anton Smirnov),
N.W.S.P.; project administration, N.W.S.P., P.P.; resources, N.W.S.P., N.P.; software, P.P., A.S. (Anton Seleznev);
supervision, N.W.S.P., A.S. (Anton Smirnov); validation, A.S. (Anton Seleznev), N.P.; visualization, P.P., A.S. (Anton
Smirnov); writing—original draft, N.W.S.P., A.S. (Anton Smirnov). All authors read and approved the final version of
the manuscript.
Funding: We would like to thank the Russian Science Foundation for supporting this work under grant
19–79–00355.
Conflicts of Interest: The authors declare no conflict of interest.
References
1. Kingery, W.D.; Bowen, H.K.; Uhlmann, D.R. Introduction to Ceramics, 2nd ed.; Wiley: New York, NY, USA,
1976; pp. 1–1056.
2. Carter, C.B.; Norton, M.G. Ceramic Materials: Science and Engineering; Springer: New York, NY, USA, 2013;
pp. 1–766.
3. Smirnov, A.; Kurland, H.-D.; Grabow, J.; Müller, F.A.; Bartolomé, J.F. Microstructure, mechanical properties
and low temperature degradation resistance of 2Y-TZP ceramic materials derived from nanopowders
prepared by laser vaporization. J. Eur. Ceram. Soc. 2015, 35, 2685–2691. [CrossRef]
4. Smirnov, A.; Beltrán, J.I.; Rodriguez-Suarez, T.; Pecharromán, C.; Muñoz, M.C.; Moya, J.S.; Bartolomé, J.F.
Unprecedented simultaneous enhancement in flaw tolerance and fatigue resistance of zirconia–Ta composites.
Sci. Rep. 2017, 7, 44922. [CrossRef] [PubMed]
5. Smirnov, A.; Bartolomé, J.F.; Kurland, H.-D.; Grabow, J.; Müller, F.A. Design of a new zirconia-alumina-Ta
micro-nanocomposite with unique mechanical properties. J. Am. Ceram. Soc. 2016, 99, 3205–3209. [CrossRef]
6. Bartolomé, J.F.; Smirnov, A.; Kurland, H.-D.; Grabow, J.; Müller, F.A. New ZrO2/Al2O3 nanocomposites
fabricated from hybrid nanoparticles prepared by CO2 laser Co-vaporisation. Sci. Rep. 2016, 6, 20589. [CrossRef]
7. Smirnov, A.; Bartolomé, J.F. Microstructure and mechanical properties of ZrO2 ceramics toughened by 5–20 vol%
ta metallic particles fabricated by pressureless sintering. Ceram. Int. 2014, 40, 1829–1834. [CrossRef]
8. Gutierrez-Gonzalez, C.F.; Smirnov, A.; Bartolomé, J.F. Cyclic fatigue life- and crack-growth behavior of
zirconia-niobium composites. J. Am. Ceram. Soc. 2013, 96, 1709–1712.
9. Bengisu, M. Engineering Ceramics; Springer: Berlin/Heidelberg, Germany, 2001; p. 620.
10. Richerson, D.W.; Lee, W.E. Modern Ceramic Engineering: Properties, Processing, and Use in Design, 4th ed.; CRC
Press: Boca Raton, FL, USA, 2018; pp. 1–791.
11. Pristinskiy, Y.; Solis Pinargote, N.W.; Smirnov, A. The effect of MgO addition on the microstructure and
mechanical properties of alumina ceramic obtained by spark plasma sintering. Mater. Today Proc. 2019, 19,
1990–1993. [CrossRef]
12. Chen, Z.; Li, Z.; Li, J.; Liu, C.; Lao, C.; Fu, Y.; Liu, C.; Li, Y.; Wang, P.; He, Y. 3D printing of ceramics: A review.
J. Eur. Ceram. Soc. 2019, 39, 661–687. [CrossRef]
13. Abdulhameed, O.; Al-Ahmari, A.; Ameen, W.; Mian, S.H. Additive manufacturing: Challenges, trends, and
applications. Adv. Mech. Eng. 2019, 11, 1–27. [CrossRef]
14. Gibson, I.; Rosen, D.; Stucker, B. Additive Manufacturing Technologies: 3D Printing, Rapid Prototyping, and Direct
Digital Manufacturing, 2nd ed.; Springer: New York, NY, USA, 2015; pp. 1–498.
15. International Organization for Standardization. ISO/ASTM 52900:2015 [ASTM F2792] Additive Manufacturing—
General Principles—Terminology; ISO: Geneva, Switzerland, 2015.
16. Diegel, O. A Practical Guide to Design for Additive Manufacturing; Series in Advanced Manufacturing; Springer:
New York, NY, USA, 2020; p. 226.
17. Coppola, S.; Nasti, G.; Vespini, V.; Ferraro, P. Layered 3D printing by tethered pyro-electrospinning.
Adv. Polym. Technol. 2020, 2, 1–9. [CrossRef]
18. Coppola, S.; Vespini, V.; Nasti, G.; Gennari, O.; Grilli, S.; Ventre, M.; Iannone, M.; Netti, P.A.; Ferraro, P.
Tethered pyro-electrohydrodynamic spinning for patterning well-ordered structures at micro- and nanoscale.
Chem. Mater. 2014, 26, 3357–3360. [CrossRef]
19. Coppola, S.; Nasti, G.; Todino, M.; Olivieri, F.; Vespini, V.; Ferraro, P. Direct writing of microfluidic footpaths
by pyro-EHD printing. ACS Appl. Mater. Int. 2017, 9, 16488–16494. [CrossRef]
20. Lewis, J.A.; Gratson, G.M. Direct writing in three dimensions. Mater. Today 2004, 7, 32–39. [CrossRef]
21. Martínez-Vázquez, F.J.; Perera, F.H.; Miranda, P.; Pajares, A.; Guiberteau, F. Improving the compressive
strength of bioceramic robocast scaffolds by polymer infiltration. Acta Biomater. 2010, 6, 4361–4368. [CrossRef]
22. Lewis, J.A. Direct ink writing of 3D functional materials. Adv. Funct. Mater. 2006, 16, 2193–2204. [CrossRef]
23. Revelo, C.F.; Colorado, H.A. 3D printing of kaolinite clay ceramics using the Direct Ink Writing (DIW)
technique. Ceram. Int. 2018, 44, 5673–5682. [CrossRef]
24. Martínez-Vázquez, F.J.; Pajares, A.; Miranda, P. A simple graphite-based support material for robocasting of
ceramic parts. J. Eur. Ceram. Soc. 2018, 38, 2247–2250. [CrossRef]
25. Ordoñez, E.; Gallego, J.M.; Colorado, H.A. 3D printing via the direct ink writing technique of ceramic pastes
from typical formulations used in traditional ceramics industry. Appl. Clay Sci. 2019, 182, 105285. [CrossRef]
26. Ahn, B.Y.; Duoss, E.B.; Motala, M.J.; Guo, X.; Park, S.I.; Xiong, Y.; Yoon, J.; Nuzzo, R.G.; Rogers, J.A.; Lewis, J.A.
Omnidirectional printing of flexible, stretchable, and spanning silver microelectrodes. Science 2009, 323,
1590–1593. [CrossRef]
27. Liu, D.-M. Influence of porosity and pore size on the compressive strength of porous hydroxyapatite ceramic.
Ceram. Int. 1997, 23, 135–139. [CrossRef]
28. Yao, Y.; Fu, K.K.; Yan, C.; Dai, J.; Chen, Y.; Wang, Y.; Zhang, B.; Hitz, E.; Hu, L. Three-dimensional printable
high-temperature and high-rate heaters. ACS Nano 2016, 10, 5272–5279. [CrossRef] [PubMed]
29. García-Tunñón, E.; Feilden, E.; Zheng, H.; D’Elia, E.; Leong, A.; Saiz, E. Graphene oxide: An all-in-one
processing additive for 3D printing. ACS Appl. Mater. Interfaces 2017, 9, 32977–32989. [CrossRef] [PubMed]
30. Lewis, J.A. Colloidal processing of ceramics. J. Am. Ceram. Soc. 2000, 83, 2341–2359. [CrossRef]
31. Xu, Z.; Gao, C. Aqueous liquid crystals of graphene oxide. ACS Nano 2011, 5, 2908–2915. [CrossRef] [PubMed]
32. Solis Pinargote, N.W.; Peretyagin, P.; Torrecillas, R.; Fernández, A.; Menéndez, J.L.; Mallada, C.; Díaz, L.A.;
Moya, J.S. Electrically conductor black zirconia ceramic by SPS using graphene oxide. J. Electroceram. 2017,
38, 119–124. [CrossRef]
33. Smirnov, A.; Peretyagin, P.; Bartolomé, J.F. Processing and mechanical properties of new hierarchical
metal-graphene flakes reinforced ceramic matrix composites. J. Eur. Ceram. Soc. 2019, 39, 3491–3497.
[CrossRef]
34. Gutierrez-Gonzalez, C.F.; Smirnov, A.; Centeno, A.; Fernández, A.; Alonso, B.; Rocha, V.G.; Torrecillas, R.;
Zurutuza, A.; Bartolomé, J.F. Wear behavior of graphene/alumina nanocomposite. Ceram. Int. 2015, 41,
7434–7438. [CrossRef]
35. Cascales, A.; Tabares, N.; Bartolomé, J.F.; Cerpa, A.; Smirnov, A.; Moreno, R.; Nieto, M.I. Processing and
mechanical properties of mullite and mullite–alumina composites reinforced with carbon nanofibers. J. Eur.
Ceram. Soc. 2015, 35, 3613–3621. [CrossRef]
36. André, J.C.; Le Mehauté, A.; De Witte, O. Dispositif Pour Réalizer un Modèle de Pièce Industrielle. Demande
de Brevet d’Invention FR 2567668, 16 July 1984.
37. Hull, C.W. Apparatus for Production of Three-Dimensional Objects by Stereolithography. U.S. Patent
4,575,330, 8 August 1984.
38. Ngo, T.D.; Kashani, A.; Imbalzano, G.; Nguyen, K.T.Q.; Hui, D. Additive manufacturing (3D printing)-A
review of materials, methods, applications and challenges. Compos. Part B Eng. 2018, 143, 172–196. [CrossRef]
39. Sachs, E.; Cima, M.; Cornie, J. Three-dimensional printing: Rapid tooling and prototypes directly from a
CAD model. CIRP Ann. Manuf. Technol. 1990, 39, 201–204. [CrossRef]
40. Kruth, J.P. Material incress manufacturing by rapid prototyping techniques. CIRP Ann. Manuf. Technol. 1991,
40, 603–614. [CrossRef]
41. Peretyagin, N.Y.; Pristinskii, Y.O.; Kuznetsova, E.V.; Peretyagin, P.Y.; Seleznev, A.E.; Solis Pinargote, N.W.;
Smirnov, A.V. Microstructure and properties of boron-carbide composites reinforced by graphene.
Russ. Eng. Res. 2020, 40, 94–96. [CrossRef]
42. Smirnov, A.; Solís Pinargote, N.W.; Peretyagin, N.; Pristinskiy, Y.; Peretyagin, P.; Bartolomé, J.F. Zirconia
reduced graphene oxide nano-hybrid structure fabricated by the hydrothermal reaction method. Materials
2020, 13, 687. [CrossRef] [PubMed]
43. Deckard, C.R. Method and Apparatus for Producing Parts by Selective Sintering. U.S. Patent 4,863,538,
17 October 1986.
44. Rossi, S.; Puglisi, A.; Benaglia, M. Additive manufacturing technologies: 3D printing in organic synthesis.
ChemCatChem 2018, 10, 1512. [CrossRef]
45. Liu, J.; Zhang, B.; Yan, C.; Shi, Y. The effect of processing parameters on characteristics of selective laser
sintering dental glass-ceramic powder. Rapid Prototyp. J. 2010, 16, 138–145. [CrossRef]
46. Gao, C.; Yang, B.; Hu, H.; Liu, J.; Shuai, C.; Peng, S. Enhanced sintering ability of biphasic calcium phosphate
by polymers used for bone scaffold fabrication. Mater. Sci. Eng. C 2013, 33, 3802–3810. [CrossRef]
47. Leu, M.C.; Pattnaik, S.; Hilmas, G.E. Investigation of laser sintering for freeform fabrication of zirconium
diboride parts. Virtual Phys. Prototyp. 2012, 7, 2536. [CrossRef]
48. Lakshminarayan, U.; Ogrydiziak, S.; Marcus, H. Selective laser sintering of ceramic materials. In Proceedings
of the International Solid Freeform Fabrication Symposium, Austin, TX, USA, 6–8 August 1990.
49. Shahzad, K.; Deckers, J.; Boury, S.; Neirinck, B.; Kruth, J.-P.; Vleugels, J. Preparation and indirect selective
laser sintering of alumina/PA microspheres. Ceram. Int. 2012, 38, 1241–1247. [CrossRef]
50. Sachs, E.M.; Haggerty, J.S.; Cima, M.J.; Williams, P.A. Three-Dimensional Printing Techniques. U.S. Patent
5,204,055, 8 December 1989.
51. Sachs, E.; Cima, M.; Williams, P.; Brancazio, D.; Cornie, J. Three dimensional printing: Rapid tooling and
prototypes directly from a CAD model. J. Eng. Ind. 1992, 114, 481–488. [CrossRef]
52. Meiners, W.; Wissenbach, K.; Gasser, A. Shaped Body Especially Prototype or Replacement Part Production.
Germany Patent DE 19649865, 2 December 1996.
53. Simchi, A. Direct laser sintering of metal powders: Mechanism, kinetics and microstructural features.
Mater. Sci. Eng. A 2006, 428, 148–158. [CrossRef]
54. Shishkovsky, I.; Yadroitsev, I.; Bertrand, P.; Smurov, I. Alumina–zirconium ceramics synthesis by selective
laser sintering melting. Appl. Surf. Sci. 2007, 254, 966–970. [CrossRef]
55. Deckers, J.; Meyers, S.; Kruth, J.; Vleugels, J. Direct selective laser sintering/melting of high density alumina
powder layers at elevated temperatures. Phys. Procedia 2014, 56, 117–124. [CrossRef]
56. Yap, C.Y.; Chua, C.K.; Dong, Z.L.; Liu, Z.H.; Zhang, D.Q.; Loh, L.E.; Sing, S.L. Review of selective laser
melting: Materials and applications. Appl. Phys. Rev. 2015, 2, 041101. [CrossRef]
57. Hao, L.; Dadbakhsh, S.; Seaman, O.; Felstead, M. Selective laser melting of a stainless steel and hydroxyapatite
composite for load-bearing implant development. J. Mater. Process Technol. 2009, 209, 5793–5801. [CrossRef]
58. Yves-Christian, H.; Jan, W.; Wilhelm, M.; Konrad, W.; Reinhart, P. Net shaped high performance oxide
ceramic parts by selective laser melting. Phys. Procedia 2010, 5, 587–594. [CrossRef]
59. International Organization for Standardization. ISO 17296–2:2015 Additive Manufacturing—General Principles—
Part 2: Overview of Process Categories and Feedstock; ISO: Geneva, Switzerland, 2015.
60. Kaur, M.; Srivastava, A.K. Photopolymerization: A Review. J. Macromol. Sci. Part C 2002, 42, 481–512. [CrossRef]
61. Griffith, M.L.; Halloran, J.W. Ultraviolet curable ceramic suspensions for Stereolithography of ceramics.
In Proceedings of the 1994 International Mechanical Engineering Congress and Exposition, Chicago, IL, USA,
6–11 November 1994; pp. 529–534.
62. Halloran, J.W.; Tomeckova, V.; Gentry, S.; Das, S.; Cilino, P.; Yuan, D.; Guo, R.; Rudraraju, A.; Shao, P.; Wu, T.
Photopolymerization of powder suspensions for shaping ceramics. J. Eur. Ceram. Soc. 2011, 31, 2613–2619.
[CrossRef]
63. Chen, Z.; Li, D.; Zhou, W.; Wang, L. Curing characteristics of ceramic Stereolithography for an aqueous-based
silica suspension. Proc. Inst. Mech. Eng. Part B J. Eng. Manuf. 2010, 224, 641–651. [CrossRef]
64. Zhang, X.; Jiang, X.; Sun, C. Micro-stereolithography of polymeric and ceramic microstructures. Sens. Actuators
A Phys. 1999, 77, 149–156. [CrossRef]
65. Kumar, S.; Bhushan, P.; Pandey, M.; Bhattacharya, S. Additive manufacturing as an emerging technology for
fabrication of microelectromechanical systems (MEMS). J. Micromanuf. 2019, 2, 175–197. [CrossRef]
66. Nakamoto, T.; Yamaguchi, K.; Abraha, P.A. Consideration on the producing of high aspect ratio micro parts
using UV sensitive photopolymer. In Proceedings of the MHS’96 Seventh International Symposium on
Micro Machine and Human Science, Nagoya, Japan, 2–4 October 1996; Institute of Electrical and Electronics
Engineers (IEEE): Piscataway, NJ, USA, 1996; pp. 53–58. [CrossRef]
67. Lu, Y.; Mapili, G.; Suhali, G.; Chen, S.; Roy, K. A digital micro-mirror device-based system for the
microfabrication of complex, spatially patterned tissue engineering scaffolds. J. Biomed. Mater. Res. Part A
2006, 77, 396–405. [CrossRef]
68. Murphy, S.V.; Atala, A. 3D bioprinting of tissues and organs. Nat. Biotechnol. 2014, 32, 773–785. [CrossRef]
69. He, R.; Liu, W.; Wu, Z.; An, D.; Huang, M.; Wu, H.; Jiang, Q.; Ji, X.; Wu, S.; Xie, Z. Fabrication of
complex-shaped zirconia ceramic parts via a DLP-stereolithography-based 3D printing method. Ceram. Int.
2018, 44, 3412–3416. [CrossRef]
70. Li, S.; Duan, W.; Zhao, T.; Han, W.; Wang, L.; Dou, R.; Wang, G. The fabrication of SiBCN ceramic components
from preceramic polymers by digital light processing (DLP) 3D printing technology. J. Eur. Ceram. Soc. 2018,
38, 4597–4603. [CrossRef]
71. Schwentenwein, M.; Schneider, P.; Homa, J. Lithography-Based Ceramic Manufacturing: A Novel Technique
for Additive Manufacturing of High-Performance Ceramics. Adv. Sci. Technol. 2014, 88, 60–64. [CrossRef]
72. Scheithauer, U.; Schwarzer, E.; Moritz, T.; Michaelis, A. Additive Manufacturing of Ceramic Heat Exchanger:
Opportunities and Limits of the Lithography-Based Ceramic Manufacturing (LCM). J. Mater. Eng. Perform.
2017, 27, 14–20. [CrossRef]
73. Lantada, A.D.; Romero, A.D.B.; Schwentenwein, M.; Jellinek, C.; Homa, J. Lithography-based ceramic
manufacture (LCM) of auxetic structures: Present capabilities and challenges. Smart Mater. Struct. 2016,
25, 54015. [CrossRef]
74. Scheithauer, U.; Schwarzer, E.; Ganzer, G.; Kornig, A.; Becker, W.; Reichelt, E.; Jahn, M.; Har-Tel, A.;
Richter, H.; Moritz, T.; et al. Micro-Reactors Made by Lithography-Based Ceramic Manufacturing (LCM).
Ceram. Trans. Ser. 2016, 258, 31–41. [CrossRef]
75. Wu, E.-S.; Strickler, J.H.; Harrell, W.R.; Webb, W.W. Two-photon lithography for microelectronic application.
Opt./Laser Microlithogr. V 1992, 1674, 776–782. [CrossRef]
76. Maruo, S.; Nakamura, O.; Kawata, S. Three-dimensional microfabrication with two-photon-absorbed
photopolymerization. Opt. Lett. 1997, 22, 132. [CrossRef]
77. Chu, W.; Tan, Y.; Wang, P.; Xu, J.; Li, W.; Qi, J.; Cheng, Y. Centimeter-Height 3D Printing with Femtosecond
Laser Two-Photon Polymerization. Adv. Mater. Technol. 2018, 3, 1700396. [CrossRef]
78. Sun, H.-B.; Kawata, S. Two-Photon Photopolymerization and 3D Lithographic Microfabrication. In Organic
Electronics; Springer Science and Business Media LLC: Berlin/Heidelberg, Germany, 2006; Volume 170,
pp. 169–273.
79. Fischer, J.; Wegener, M. Three-dimensional optical laser lithography beyond the diffraction limit.
Laser Photonics-Rev. 2012, 7, 22–44. [CrossRef]
80. Pham, T.A.; Kim, D.-P.; Lim, T.-W.; Park, S.-H.; Yang, D.-Y.; Lee, K.-S. Three-Dimensional SiCN Ceramic
Microstructures via Nano-Stereolithography of Inorganic Polymer Photoresists. Adv. Funct. Mater. 2006, 16,
1235–1241. [CrossRef]
81. Singh, M.; Haverinen, H.M.; Dhagat, P.; Jabbour, G.E. Inkjet Printing-Process and Its Applications. Adv. Mater.
2010, 22, 673–685. [CrossRef]
82. Le, H.P. Progress and trends in ink-jet printing technology. J. Imaging Sci. Technol. 1998, 42, 49–62.
83. Dong, H.; Carr, W.W.; Morris, J.F. An experimental study of drop-on-demand drop formation. Phys. Fluids
2006, 18, 72102. [CrossRef]
84. Lee, E.R. Microdrop Generation; CRC Press: Boca Raton, FL, USA, 2002; pp. 1–241.
85. Coppola, S.; Mecozzi, L.; Vespini, V.; Battista, L.; Grilli, S.; Nenna, G.; Loffredo, F.; Villani, F.; Minarini, C.;
Ferraro, P. Nanocomposite polymer carbon-black coating for triggering pyro-electrohydrodynamic inkjet
printing. Appl. Phys. Lett. 2015, 106, 261603. [CrossRef]
86. Grimaldi, I.; Coppola, S.; Loffredo, F.; Villani, F.; Nenna, G.; Minarini, C.; Vespini, V.; Miccio, L.; Grilli, S.;
Ferraro, P. Graded-size microlens array by the pyro-electrohydrodynamic continuous printing method.
Appl. Opt. 2013, 52, 7699–7705. [CrossRef]
87. Kyser, E.L.; Collins, L.F.; Herbert, N. Design of an impulse ink jet. J. Appl. Photogr. Eng. 1981, 7, 73–79.
88. Kawase, T.; Shimoda, T.; Newsome, C.; Sirringhaus, H.; Friend, R.H. Inkjet printing of polymer thin film
transistors. Thin Solid Film. 2003, 438, 279–287. [CrossRef]
89. Kawahara, Y.; Hodges, S.; Cook, B.S.; Zhang, C.; Abowd, G.D. Instant inkjet circuits. In Proceedings of
the 2013 ACM International Joint Conference, Zurich, Switzerland, 8–12 September 2013; Association for
Computing Machinery (ACM): New York, NY, USA, 2013; p. 363.
90. Nakamura, M.; Kobayashi, A.; Takagi, F.; Watanabe, A.; Hiruma, Y.; Ohuchi, K.; Iwasaki, Y.; Horie, M.;
Morita, I.; Takatani, S. Biocompatible Inkjet Printing Technique for Designed Seeding of Individual Living
Cells. Tissue Eng. 2005, 11, 1658–1666. [CrossRef] [PubMed]
91. Blazdell, P.F.; Evans, J.R.G.; Edirisinghe, M.J.; Shaw, P.; Binstead, M.J. The computer aided manufacture of
ceramics using multilayer jet printing. J. Mater. Sci. Lett. 1995, 14, 1562–1565. [CrossRef]
92. Seerden, K.A.M.; Reis, N.; Evans, J.R.G.; Grant, P.; Halloran, J.W.; Derby, B. Ink-Jet Printing of Wax-Based
Alumina Suspensions. J. Am. Ceram. Soc. 2001, 84, 2514–2520. [CrossRef]
93. Kunieda, M.; Nakagawa, T. Manufacturing of laminated deep drawing dies by laser beam cutting.
Adv. Technol. Plast. 1984, 1, 520–525.
94. White, D. Ultrasonic Object Consolidation. U.S. Patent 6,519,500, 23 March 2000.
95. Mekonnen, B.G.; Bright, G.; Walker, A. A Study on State of the Art Technology of Laminated Object
Manufacturing (LOM). In Proceedings of the 6th International Conference and Exhibition on Sustainable
Energy and Advanced Materials, Surakarta, Indonesia, 16–17 October 2016; Springer Science and Business
Media LLC: Berlin/Heidelberg, Germany, 2016; pp. 207–216.
96. Mathur, R. 3D printing in architecture. Int. J. Innov. Sci. Eng. Technol. 2016, 3, 583–591.
97. Mueller, B.; Kochan, D. Laminated object manufacturing for rapid tooling and pattern making in foundry
industry. Comput. Ind. 1999, 39, 47–53. [CrossRef]
98. Griffin, C.; Daufenbach, J.; McMillin, S. Solid freeform fabrication of functional ceramic components using a
laminated object manufacturing technique. Solid Freedom Fabr. 1994, 17–24. [CrossRef]
99. Windsheimer, H.; Travitzky, N.; Hofenauer, A.; Greil, P. Laminated object manufacturing of
preceramic-paper-derived Si-SiC composites. Adv. Mater. 2007, 19, 4515–4519. [CrossRef]
100. Gomes, C.M.; Gutbrod, B.; Travitzky, N.; Fey, T.; Greil, P. Preceramic paper derived fibrillar ceramics.
Ceram. Trans. 2010, 210, 421–426.
101. Weisensel, L.; Travitzky, N.; Sieber, H.; Greil, P. Laminated Object Manufacturing (LOM) of SiSiC Composites.
Adv. Eng. Mater. 2004, 6, 899–903. [CrossRef]
102. Griffin, E.; Mumm, D.; Marshall, D. Rapid prototyping of functional ceramic composites. Am. Ceram.
Soc. Bull. 1996, 75, 65–68.
103. Zhang, Y.; Han, J.; Zhang, X.; He, X.; Li, Z.; Du, S. Rapid prototyping and combustion synthesis of TiC/Ni
functionally gradient materials. Mater. Sci. Eng. A 2001, 299, 218–224. [CrossRef]
104. Gomes, C.; Travitzky, N.; Greil, P.; Acchar, W.; Birol, H.; Oliveira, A.P.N.; Hotza, D. Laminated object
manufacturing of LZSA glass-ceramics. Rapid Prototyp. J. 2011, 17, 424–428. [CrossRef]
105. Crump, S.S. Apparatus and Method for Creating Three-Dimensional Objects. U.S. Patent 5,121,329,
30 October 1989.
106. Rundle, G.A. Revolution in the Making; Affirm Press: South Melbourne, Australia, 2014; pp. 1–209.
107. Ahmad, A.; Darmoul, S.; Ameen, W.; Abidi, M.H.; Al-Ahmari, A. Rapid Prototyping for Assembly Training
and Validation. IFAC-PapersOnLine 2015, 48, 412–417. [CrossRef]
108. Wittbrodt, B.; Pearce, J.M. The effects of PLA color on material properties of 3-D printed components.
Addit. Manuf. 2015, 8, 110–116. [CrossRef]
109. 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, 442–458. [CrossRef]
110. Danforth, S. Fused Deposition of Ceramics: A New Technique for the Rapid Fabrication of Ceramic
Components. Mater. Technol. 1995, 10, 144–146. [CrossRef]
111. Iyer, S.; McIntosh, J.; Bandyopadhyay, A.; Langrana, N.; Safari, A.; Danforth, S.C.; Clancy, R.B.; Gasdaska, C.;
Whalen, P.J. Microstructural Characterization and Mechanical Properties of Si3N4Formed by Fused Deposition
of Ceramics. Int. J. Appl. Ceram. Technol. 2008, 5, 127–137. [CrossRef]
112. Allahverdi, M.; Danforth, S.; Jafari, M.; Safari, A. Processing of advanced electroceramic components by
fused deposition technique. J. Eur. Ceram. Soc. 2001, 21, 1485–1490. [CrossRef]
113. Yang, H.; Yang, S.; Chi, X.; Evans, J. Fine ceramic lattices prepared by extrusion freeforming. J. Biomed. Mater.
Res. Part B Appl. Biomater. 2006, 79, 116–121. [CrossRef]
114. Jafari, M.; Han, W.; Mohammadi, F.; Safari, A.; Danforth, S.C.; Langrana, N. A novel system for fused
deposition of advanced multiple ceramics. Rapid Prototyp. J. 2000, 6, 161–175. [CrossRef]
115. Sa, M.-W.; Nguyen, B.-N.B.; Moriarty, R.A.; Kamalitdinov, T.; Fisher, J.P.; Kim, J.Y. Fabrication and evaluation
of 3D printed BCP scaffolds reinforced with ZrO2 for bone tissue applications. Biotechnol. Bioeng. 2018, 115,
989–999. [CrossRef]
116. Pilleux, M.E.; Safari, A.; Allahverdi, M.; Chen, Y.; Lu, Y.; Jafari, M.A. 3-D photonic bandgap structures in the
microwave regime by fused deposition of multimaterials. Rapid Prototyp. J. 2002, 8, 46–52. [CrossRef]
117. Chen, Y.; Bartzos, D.; Lu, Y.; Niver, E.; Pilleux, M.E.; Allahverdi, M.; Danforth, S.C.; Safari, A. Simulation,
fabrication, and characterization of 3-D alumina photonic bandgap structures. Microw. Opt. Technol. Lett.
2001, 30, 305–307. [CrossRef]
118. Cesarano, I.; Segalman, R. Robocasting provides moldless fabrication from slurry deposition. Ceram. Ind.
1998, 148, 94–100.
119. Shen, A.; Caldwell, D.; Ma, A.W.; Dardona, S. Direct write fabrication of high-density parallel silver
interconnects. Addit. Manuf. 2018, 22, 343–350. [CrossRef]
120. Hartmann, K.; Krishnan, R.; Merz, R.; Neplotnik, G.; Prinz, F.B.; Schultz, L.; Terk, M.; Weiss, L.E. Robot-assisted
shape deposition manufacturing. In Proceedings of the 1994 IEEE International Conference on Robotics and
Automation, San Diego, CA, USA, 8–13 May 1994; Volume, 4, pp. 2890–2895.
121. Cesarano, J., III; Calvert, P.D. Freeforming Objects with Low-Binder Slurry. U.S. Patent 6,027,326,
28 October 1997.
122. Fu, K.; Wang, Y.; Yan, C.; Yao, Y.; Chen, Y.; Dai, J.; Lacey, S.; Wang, Y.; Wan, J.; Li, T.; et al. Graphene Oxide-
Based Electrode Inks for 3D-Printed Lithium-Ion Batteries. Adv. Mater. 2016, 28, 2587–2594. [CrossRef]
123. Farahani, R.D.; Dubé, M.; Therriault, D. Three-Dimensional Printing of Multifunctional Nanocomposites:
Manufacturing Techniques and Applications. Adv. Mater. 2016, 28, 5794–5821. [CrossRef]
124. Elsayed, H.; Colombo, P.; Bernardo, E. Direct ink writing of wollastonite-diopside glass-ceramic scaffolds
from a silicone resin and engineered fillers. J. Eur. Ceram. Soc. 2017, 37, 4187–4195. [CrossRef]
125. Feilden, E.; Blanca, E.G.-T.; Giuliani, F.; Saiz, E.; Vandeperre, L. Robocasting of structural ceramic parts with
hydrogel inks. J. Eur. Ceram. Soc. 2016, 36, 2525–2533. [CrossRef]
126. Rao, R.B.; Krafcik, K.L.; Morales, A.M.; Lewis, J. Microfabricated Deposition Nozzles for Direct-Write
Assembly of Three-Dimensional Periodic Structures. Adv. Mater. 2005, 17, 289–293. [CrossRef]
127. Schlordt, T.; Schwanke, S.; Keppner, F.; Fey, T.; Travitzky, N.; Greil, P. Robocasting of alumina hollow filament
lattice structures. J. Eur. Ceram. Soc. 2013, 33, 3243–3248. [CrossRef]
128. Simon, J.L.; Michna, S.; Lewis, J.A.; Rekow, E.D.; Thompson, V.P.; Smay, J.E.; Yampolsky, A.; Parsons, J.R.;
Ricci, J.L. In vivo bone response to 3D periodic hydroxyapatite scaffolds assembled by direct ink writing.
J. Biomed. Mater. Res. Part A 2007, 83, 747–758. [CrossRef] [PubMed]
129. Sun, K.; Wei, T.-S.; Ahn, B.Y.; Seo, J.Y.; Dillon, S.J.; Lewis, J.A. 3D Printing of Interdigitated Li-Ion Microbattery
Architectures. Adv. Mater. 2013, 25, 4539–4543. [CrossRef]
130. Eqtesadi, S.; Motealleh, A.; Miranda, P.; Lemos, A.; Rebelo, A.; Ferreira, J.M.F. A simple recipe for direct
writing complex 45S5 Bioglass® 3D scaffolds. Mater. Lett. 2013, 93, 68–71. [CrossRef]
131. Miranda, P.; Pajares, A.; Saiz, E.; Tomsia, A.P.; Guiberteau, F. Mechanical properties of calcium phosphate
scaffolds fabricated by robocasting. J. Biomed. Mater. Res. Part A 2008, 85, 218–227. [CrossRef]
132. Smirnov, A.; Peretyagin, P.; Pinargote, N.W.S.; Gershman, I.; Bartolomé, J.F. Wear Behavior of Graphene-
Reinforced Alumina–Silicon Carbide Whisker Nanocomposite. Nanomaterials 2019, 9, 151. [CrossRef]
133. Solis, N.W.; Peretyagin, P.; Seleznev, A.; Torrecillas, R.; Moya, J.S. Black zirconia-graphene nanocomposite
produced by spark plasma sintering. AIP Conf. Proc. 2016, 1785, 40074. [CrossRef]
134. Fokin, P.; Pinargote, N.W.S.; Kuznetsova, E.; Peretyagin, P.Y.; Smirnov, A. Effect of Drying Methods of
Alumina Powder and Graphene Oxide Mixture on the Mechanical and Electrical Properties of Sintered
Composites Fabricated by Spark Plasma Sintering. Inorg. Mater. Appl. Res. 2018, 9, 930–936. [CrossRef]
135. Grigoriev, S.; Peretyagin, P.; Smirnov, A.; Solís, W.; Diaz, L.; Fernández, A.; Torrecillas, R. Effect of graphene
addition on the mechanical and electrical properties of Al2 O3 –SiCw ceramics. J. Eur. Ceram. Soc. 2017, 37,
2473–2479. [CrossRef]
136. Novoselov, K.S.; Fal’Ko, V.I.; Colombo, L.; Gellert, P.R.; Schwab, M.G.; Kim, K. A roadmap for graphene.
Nature 2012, 490, 192–200. [CrossRef] [PubMed]
137. Gerstner, E. Nobel Prize 2010: Andre Geim & Konstantin Novoselov. Nat. Phys. 2010, 6, 836. [CrossRef]
138. Zhu, Y.; Murali, S.; Cai, W.; Li, X.; Suk, J.W.; Potts, J.R.; Ruoff, R.S. Graphene and graphene oxide: Synthesis,
properties, and applications. Adv. Mater. 2010, 22, 3906–3924. [CrossRef] [PubMed]
139. Nayak, T.R.; Andersen, H.; Makam, V.S.; Khaw, C.; Bae, S.; Xu, X.; Ee, P.-L.R.; Ahn, J.-H.; Hong, B.H.;
Pastorin, G.; et al. Graphene for controlled and accelerated osteogenic differentiation of human mesenchymal
stem cells. ACS Nano 2011, 5, 4670–4678. [CrossRef]
140. Munz, M.; Giusca, C.E.; Myers-Ward, R.L.; Gaskill, D.K.; Kazakova, O. Thickness-dependent hydrophobicity
of epitaxial graphene. ACS Nano 2015, 9, 8401–8411. [CrossRef]
141. Bagherzadeh, M.; Farahbakhsh, A. Surface functionalization of graphene. Graphene Mater. 2015, 25–65.
[CrossRef]
142. Sun, X.; Li, B.; Lu, M. A covalent modification for graphene by adamantane groups through two-step
chlorination-Grignard reactions. J. Solid State Chem. 2017, 251, 194–197. [CrossRef]
143. Qi, X.; Pu, K.Y.; Li, H.; Zhou, X.; Wu, S.; Fan, Q.L.; Liu, B.; Boey, F.; Huang, W.; Zhang, H. Amphiphilic
graphene composites. Angew. Chem. Int. Ed. 2010, 49, 9426–9429. [CrossRef]
144. Zaaba, N.I.; Foo, K.L.; Hashim, U.; Tan, S.J.; Liu, W.-W.; Voon, C.H. Synthesis of graphene oxide using
modified hummers method: Solvent influence. Procedia Eng. 2017, 184, 469–477. [CrossRef]
145. Singh, V.; Joung, D.; Zhai, L.; Das, S.; Khondaker, S.I.; Seal, S. Graphene based materials: Past, present and
future. Prog. Mater. Sci. 2011, 56, 1178–1271. [CrossRef]
146. Stankovich, S.; Piner, R.D.; Chen, X.; Wu, N.; Nguyen, S.T.; Ruoff, R.S. Stable aqueous dispersions of
graphitic nanoplatelets via the reduction of exfoliated graphite oxide in the presence of poly(sodium
4-styrenesulfonate). J. Mater. Chem. 2006, 16, 155–158. [CrossRef]
147. An, B.W.; Kim, K.; Kim, M.; Kim, S.Y.; Hur, S.H.; Park, J.U. Direct printing of reduced graphene oxide
on planar or highly curved surfaces with high resolutions using electrohydrodynamics. Small 2015, 11,
2263–2268. [CrossRef]
148. Zhang, J.-X.; Liang, Y.-X.; Wang, X.; Zhou, H.-J.; Li, S.-Y.; Zhang, J.; Feng, Y.; Lu, N.; Wang, Q.; Guo, Z.
Strengthened epoxy resin with hyperbranched polyamineester anchored graphene oxide via novel phase
transfer approach. Adv. Compos. Hybrid Mater. 2018, 1, 300–309. [CrossRef]
149. Yu, A.; Ramesh, P.; Itkis, M.E.; Bekyarova, E.; Haddon, R.C. Graphite nanoplatelet-epoxy composite thermal
interface materials. J. Phys. Chem. C 2007, 111, 7565–7569. [CrossRef]
150. Syurik, Y.V.; Ghislandi, M.G.; Tkalya, E.E.; Paterson, G.; McGrouther, D.; Ageev, O.A.; Loos, J. Graphene
network organisation in conductive polymer composites. Macromol. Chem. Phys. 2012, 213, 1251–1258.
[CrossRef]
151. Yan, J.; Wei, T.; Qiao, W.; Shao, B.; Zhao, Q.; Zhang, L.; Fan, Z. Rapid microwave-assisted synthesis of
graphene nanosheet/Co3O4 composite for supercapacitors. Electrochim. Acta 2010, 55, 6973–6978. [CrossRef]
152. Ahmad, J.; Majid, K. In-situ synthesis of visible-light responsive Ag2 O/graphene oxide nanocomposites and
effect of graphene oxide content on its photocatalytic activity. Adv. Compos. Hybrid Mater. 2018, 1, 374–388.
[CrossRef]
153. Acquah, S.F.A.; Leonhardt, B.E.; Nowotarski, M.S.; Magi, J.M.; Al-Hariri, L.A. Carbon nanotubes and
graphene as additives in 3D printing. In Carbon Nanotubes-Current Progress of Their Polymer Composites,
Mohamed Reda Berber and Inas Hazzaa Hafez; IntechOpen: London, UK, 2016.
154. Kim, H.; Miura, Y.; Macosko, C.W. Graphene/polyurethane nanocomposites for improved gas barrier and
electrical conductivity. Chem. Mater. 2010, 22, 3441–3450. [CrossRef]
155. An, X.; Butler, T.W.; Washington, M.; Nayak, S.K.; Kar, S. Optical and sensing properties of 1-pyrenecarboxylic
acidfunctionalized graphene films laminated on polydimethylsiloxane membranes. ACS Nano 2011, 5,
1003–1011. [CrossRef]
156. Chu, K.; Li, W.-S.; Jia, C.-C.; Tang, F.-L. Thermal conductivity of composites with hybrid carbon nanotubes
and graphene nanoplatelets. Appl. Phys. Lett. 2012, 101, 211903. [CrossRef]
157. Hicks, J.; Behnam, A.; Ural, A. A computational study of tunneling-percolation electrical transport in
graphene-based nanocomposites. Appl. Phys. Lett. 2009, 95, 213103. [CrossRef]
158. Zhang, H.-B.; Zheng, W.-G.; Yan, Q.; Yang, Y.; Wang, J.-W.; Lu, Z.-H.; Ji, G.-Y.; Yu, Z.-Z. Electrically conductive
polyethylene terephthalate/graphene nanocomposites prepared by melt compounding. Polymer 2010, 51,
1191–1196. [CrossRef]
159. Rafiee, M.A.; Rafiee, J.; Srivastava, I.; Wang, Z.; Song, H.; Yu, Z.-Z.; Koratkar, N. Fracture and fatigue in
graphene nanocomposites. Small 2010, 6, 179–183. [CrossRef] [PubMed]
160. Gong, L.; Young, R.J.; Kinloch, I.A.; Riaz, I.; Jalil, R.; Novoselov, K.S. Optimizing the reinforcement of
polymer-based nanocomposites by graphene. ACS Nano 2012, 6, 2086–2095. [CrossRef] [PubMed]
161. Lin, D.; Jin, S.; Zhang, F.; Wang, C.; Wang, Y.; Zhou, C.; Cheng, G.J. 3D stereolithography printing of graphene
oxide reinforced complex architectures. Nanotechnology 2015, 26, 1–9. [CrossRef]
162. Lin, D.; Richard, L.C.; Cheng, G.J. Single-layer graphene oxide reinforced metal matrix composites by laser
sintering: Microstructure and mechanical property enhancement. Acta Mater. 2014, 80, 183–193. [CrossRef]
163. Lin, D.; Ye, C.; Liao, Y.; Suslov, S.; Liu, R.; Cheng, G.J. Mechanism of fatigue performance enhancement
in a laser sintered superhard nanoparticles reinforced nanocomposite followed by laser shock peening.
J. Appl. Phys. 2013, 113, 133509. [CrossRef]
164. Verdejo, R.; Bernal, M.M.; Romasanta, L.J.; Lopez-Manchado, M.A. Graphene filled polymer nanocomposites.
J. Mater. Chem. 2011, 21, 3301–3310. [CrossRef]
165. Wang, J.; Liu, Y.; Fan, Z.; Wang, W.; Wang, B.; Guo, Z. Ink-based 3D printing technologies for graphene-based
materials a review. Adv. Compos. Hybrid Mater. 2019, 2, 1–33. [CrossRef]
166. Guo, H.; Lv, R.; Bai, S. Recent advances on 3D printing graphene-based composites. Nano Mater. Sci. 2019, 1,
167. Palaganas, N.B.; Mangadlao, J.D.; De Leon, A.C.C.; Palaganas, J.O.; Pangilinan, K.D.; Lee, Y.J.; Advincula, R.C.
3D printing of photocurable cellulose nanocrystal composite for fabrication of complex architectures via
stereolithography. ACS Appl. Mater. Interfaces 2017, 9, 34314–34324. [CrossRef]
168. Tumbleston, J.R.; Shirvanyants, D.; Ermoshkin, N.; Janusziewicz, R.; Johnson, A.R.; Kelly, D.; Chen, K.;
Pinschmidt, R.; Rolland, J.P.; Ermoshkin, A.; et al. Continuous liquid interface production of 3D objects.
Science 2015, 347, 1349–1352. [CrossRef] [PubMed]
169. Iftikhar, U. Nanoscribe Introduces Quantum X, A Two-Photon 3D Printer for Microoptics. Available
online: https://3dprintingindustry.com/news/nanoscribe-introduces-quantumx-a-two-photon-3d-printer-
for-microoptics-157656/ (accessed on 8 March 2020).
170. Palaganas, J.O.; Palaganas, N.B.; Ramos, L.J.I.; David, C.P.C. 3D printing of covalent functionalized graphene
oxide nanocomposite via stereolithography. ACS Appl. Mater. Interfaces 2019, 11, 46034–46043. [CrossRef]
171. Manapat, J.Z.; Mangadlao, J.D.; Tiu, B.D.B.; Tritchler, G.C.; Advincula, R.C. High-strength stereolithographic
3D printed nanocomposites-graphene oxide metastability. ACS Appl. Mater. Interfaces 2017, 9, 10085–10093.
[CrossRef]
172. Feng, Z.; Li, Y.; Hao, L.; Yang, Y.; Tang, T.; Tang, D.; Xiong, W. Graphene-reinforced biodegradable resin
composites for stereolithographic 3d printing of bone structure scaffolds. J. Nanomater. 2019, 2019, 1–13.
[CrossRef]
173. Hensleigh, R.M.; Cui, H.; Oakdale, J.S.; Ye, J.C.; Campbell, P.G.; Duoss, E.B.; Spadaccini, C.M.; Zheng, X.;
Worsley, M.A. Additive manufacturing of complex micro-architected graphene aerogels. Mater. Horiz. 2018,
5, 1035–1041.
174. Ren, Y.; Zhang, Y.; Fang, H.; Ding, T.; Li, J.; Bai, S.-L. Simultaneous enhancement on thermal and mechanical
properties of polypropylene composites filled with graphite platelets and graphene sheets. Compos. Appl.
Sci. Manuf. 2018, 112, 57–63. [CrossRef]
175. Bauer, J.; Schroer, A.; Schwaiger, R.; Kraft, O. Approaching theoretical strength in glassy carbon nanolattices.
Nat. Mater. 2016, 15, 438–443. [CrossRef] [PubMed]
176. Truby, R.L.; Lewis, J.A. Printing soft matter in three dimensions. Nature 2016, 540, 371–378. [CrossRef]
[PubMed]
177. Desai, J.A.; Biswas, C.; Kaul, A.B. Inkjet printing of liquid exfoliated, highly conducting graphene/poly(3,4
ethylenedioxythiophene):poly(styrenesulfonate) nanosheets for organic electronics. J. Vac. Sci. Technol. B
2017, 35, D112. [CrossRef]
178. He, Q.; Das, S.R.; Garland, N.T.; Jing, D.; Hondred, J.A.; Cargill, A.A.; Ding, S.; Karunakaran, C.; Claussen, J.C.
Enabling inkjet printed graphene for ion selective electrodes with postprint thermal annealing. ACS Appl.
Mater. Interfaces 2017, 9, 12719–12727. [CrossRef] [PubMed]
179. Nikolaou, I.; Hallil, H.; Conédéra, V.; Plano, B.; Tamarin, O.; Lachaud, J.L.; Talaga, D.; Bonhommeau, S.;
Dejous, C.; Rebiere, D. Electro-mechanical properties of inkjet-printed graphene oxide nanosheets.
Phys. Status Solidi A 2017, 214, 1600492. [CrossRef]
180. Saidina, D.S.; Eawwiboonthanakit, N.; Mariatti, M.; Fontana, S.; Herold, C. Recent development of
graphene-based ink and other conductive material-based inks for flexible electronics. J. Electron. Mater. 2019,
48, 3428–3450. [CrossRef]
181. Li, J.; Sollami Delekta, S.; Zhang, P.; Yang, S.; Lohe, M.R.; Zhuang, X.; Feng, X.; Ostling, M. Scalable fabrication
and integration of graphene microsupercapacitors through full inkjet printing. ACS Nano 2017, 11, 8249–8256.
[CrossRef]
182. Li, J.; Ye, F.; Vaziri, S.; Muhammed, M.; Lemme, M.C.; Östling, M. Efficient inkjet printing of graphene.
Adv. Mater. 2013, 25, 3985–3992. [CrossRef]
183. Dubowska-Sarapuk, L.; Kielbasinski, K.; Arazna, A.; Futera, K.; Skalski, A.; Janczak, D.; Sloma, M.;
Jakubowska, M. Efficient inkjet printing of graphene-based elements: Influence of dispersing agent on ink
viscosity. Nanomaterials 2018, 8, 602. [CrossRef]
184. Liu, Y.; Derby, B. Experimental study of the parameters for stable drop-on-demand inkjet performance.
Phys. Fluids 2019, 31, 032004. [CrossRef]
185. Sinar, D.M. Synthesis and Drop-on-Demand Deposition of Graphene Derivative Inks for Flexible Thin Film
Electronics. Ph.D. Thesis, The University of Western Ontario, London, ON, Canada, 2018.
186. Guo, J.; Asli, A.E.N.; Williams, K.R.; Lai, P.L.; Wang, X.; Montazami, R.; Hashemi, N.N. Viability of neural
cells on 3D printed graphene bioelectronics. Biosensors 2019, 9, 112. [CrossRef]
187. Asli, A.E.N.; Guo, J.; Lai, P.L.; Montazami, R.; Hashemi, N.N. High-yield production of aqueous graphene
for electrohydrodynamic drop-on-demand printing of biocompatible conductive patterns. Biosensors 2020,
10, 6. [CrossRef]
188. Delekta, S.S. Inkjet Printing of Graphene-Based Microsupercapacitors for Miniaturized Energy Storage
Applications. Ph.D. Thesis, KTH Royal Institute of Technology, School of Electrical Engineering and
Computer Science (EECS), Stockholm, Sweden, 13 September 2019.
189. Martinez-Flores, R.; Canto-Aguilar, E.J.; Rodriguez-Gattorno, G.; Oskam, G.; Meneses-Rodriguez, D.;
Ruiz-Gomez, M.A. Inkjet-printed reduced graphene oxide (rGO) films for electrocatalytic applications.
J. Electrochem. Soc. 2019, 165, 3279–3285. [CrossRef]
190. Bassetto, V.C.; Xiao, J.; Oveisi, E.; Amstutz, V.; Liu, B.; Girault, H.H.; Lesch, A. Rapid inkjet printing of high
catalytic activity Co3O4/N-rGO layers for oxygen reduction reaction. Appl. Catal. A Gen. 2018, 563, 9–17.
[CrossRef]
191. Li, L.; Secor, E.B.; Chen, K.-S.; Zhu, J.; Liu, X.; Gao, T.Z.; Seo, J.-W.T.; Zhao, Y.; Hersam, M.C. High-
performance solid-state supercapacitors and microsupercapacitors derived from printable graphene inks.
Adv. Energy Mater. 2016, 6, 1600909. [CrossRef]
192. Li, J.; Mishukova, V.; Östling, M. All-solid-state micro-supercapacitors based on inkjet printed graphene
electrodes. Appl. Phys. Lett. 2016, 109, 123901. [CrossRef]
193. Karim, N.; Afroj, S.; Malandarki, A.; Butterworth, S.; Beach, C.; Rigout, M.; Novoselov, K.S.; Casson, A.J.;
Yeates, S.G. All inkjet-printed graphene-based conductive patterns for wearable e-textile applications. J. Mater.
Chem. C 2017, 5, 11640–11648. [CrossRef]
194. Parandoush, P.; Lin, D. A review on additive manufacturing of polymer-fiber composites. Compos. Struct.
2017, 182, 36–53. [CrossRef]
195. Fraser, D.; Patoary, N.H.; Moore, A.L.; Weiss, L.; Radadia, A.D. Temperature-dependent electrical resistance
of conductive polylactic acid filament for fused deposition modeling. Int. J. Adv. Manuf. Technol. 2018, 99,
1215–1224.
196. Tambrallimath, V.; Keshavamurthy, R.; Saravanbavan, D.; Kumar, G.S.P.; Kumar, M.H. Synthesis and
characterization of graphene filled PC-ABS filament for FDM applications. AIP Conf. Proc. 2019, 2057, 020039.
197. Wei, X.; Li, D.; Jiang, W.; Gu, Z.; Wang, X.; Zhang, Z.; Sun, Z. 3D printable graphene composite. Sci. Rep.
2015, 5, 11181. [CrossRef]
198. Chen, Q.; Mangadlao, J.D.; Wallat, J.; De Leon, A.; Pokorski, J.K.; Advincula, R.C. 3D printing biocompatible
polyurethane/poly(lactic acid)/graphene oxide nanocomposites: Anisotropic properties. ACS Appl. Mater.
Interfaces 2017, 9, 4015–4023. [CrossRef]
199. Vernardou, D.; Vasilopoulos, K.C.; Kenanakis, G. 3D printed graphene-based electrodes with high
electrochemical performance. Appl. Phys. A 2017, 123, 623. [CrossRef]
200. Foster, C.W.; Down, M.P.; Zhang, Y.; Ji, X.; Rowley-Neale, S.J.; Smith, G.C.; Kelly, P.J.; Banks, C.E. 3D printed
graphene based energy storage devices. Sci. Rep. 2017, 7, 42233. [CrossRef] [PubMed]
201. Zhang, D.; Chi, B.; Li, B.; Gao, Z.; Du, Y.; Guo, J.; Wei, J. Fabrication of highly conductive graphene flexible
circuits by 3D printing. Synth. Met. 2016, 217, 79–86. [CrossRef]
202. Foo, C.Y.; Lim, H.N.; Mahdi, M.A.; Wahid, M.H.; Huang, N.M. Three-dimensional printed electrode and its
novel applications in electronic devices. Sci. Rep. 2018, 8, 7399. [CrossRef]
203. Huang, C.-T.; Kumar Shrestha, L.; Ariga, K.; Hsu, S.-H. A graphene-polyurethane composite hydrogel as
a potential bioink for 3D bioprinting and differentiation of neural stem cells. J. Mater. Chem. B 2017, 5,
8854–8864. [CrossRef]
204. Naficy, S.; Jalili, R.; Aboutalebi, S.H.; Gorkin, R.A., III; Konstantinov, K.; Innis, P.C.; Spinks, G.M.; Poulin, P.;
Wallace, G.G. Graphene oxide dispersions: Tuning rheology to enable fabrication. Mater. Horiz. 2014, 1,
205. Kim, J.H.; Chang, W.S.; Kim, D.; Yang, J.R.; Han, J.T.; Lee, G.W.; Kim, J.T.; Seol, S.K. 3D printing of reduced
graphene oxide nanowires. Adv. Mater. 2015, 27, 157–161. [CrossRef]
206. Liu, Y.; Zhang, B.; Xu, Q.; Hou, Y.; Seyedin, S.; Qin, S.; Wallace, G.G.; Beirne, S.; Razal, J.M.; Chen, J.
Development of graphene oxide/polyaniline inks for high performance flexible microsupercapacitors via
extrusion printing. Adv. Funct. Mater. 2018, 28, 1706592. [CrossRef]
207. Jakus, A.E.; Secor, E.B.; Rutz, A.L.; Jordan, S.W.; Hersam, M.C.; Shah, R.N. Three dimensional printing of
high-content graphene scaffolds for electronic and biomedical applications. ACS Nano 2015, 9, 4636–4648.
[CrossRef]
208. Roman-Manso, B.; Figueiredo, F.M.; Achiaga, B.; Barea, R.; Perez-Coll, D.; Morelos-Gomez, A.; Terrones, M.;
Osendi, M.I.; Belmonte, M.; Miranzo, P. Electrically functional 3D-architectured graphene-SiC composites.
Carbon 2016, 100, 318–328. [CrossRef]
209. Zhong, J.; Zhou, G.-X.; He, P.-G.; Yang, Z.-H.; Jia, D.-C. 3D printing strong and conductive geo-polymer
nanocomposite structures modified by graphene oxide. Carbon 2017, 117, 421–426. [CrossRef]
210. Tubio, C.R.; Rama, A.; Gomez, M.; del Rio, F.; Guitian, F.; Gil, A. 3D-printed graphene-Al2O3 composites
with complex mesoscale architecture. Ceram. Int. 2018, 44, 5760–5767. [CrossRef]
211. Moyano, J.J.; Gomez-Gomez, A.; Perez-Coll, D.; Belmonte, M.; Miranzo, P.; Osendi, M.I. Filament printing of
graphene-based inks into self-supported 3D architectures. Carbon 2019, 151, 94–102. [CrossRef]
212. de la Osa, G.; Perez-Coll, D.; Miranzo, P.; Osendi, M.I.; Belmonte, M. Printing of graphene nanoplatelets into
highly electrically conductive three-dimensional porous macrostructures. Chem. Mater. 2016, 28, 6321–6328.
[CrossRef]
213. Zhu, C.; Liu, T.; Qian, F.; Han, T.Y.-J.; Duoss, E.B.; Kuntz, J.D.; Spadaccini, C.M.; Worsley, M.A.; Li, Y.
Supercapacitors based on three-dimensional hierarchical graphene aerogels with periodic macropores.
Nano Lett. 2016, 16, 3448–3456. [CrossRef]
214. Shen, C.; Calderon, J.E.; Barrios, E.; Soliman, M.; Khater, A.; Jeyaranjan, A.; Tetard, L.; Gordon, A.; Seal, S.;
Zhai, L. Anisotropic electrical conductivity in polymer derived ceramics induced by graphene aerogels.
J. Mater. Chem. C 2017, 5, 11708–11716. [CrossRef]
215. Bernardo, E.; Fiocco, L.; Parcianello, G.; Storti, E.; Colombo, P. Advanced ceramics from preceramic polymers
modified at the nano-scale-a review. Materials 2014, 7, 1927–1956. [CrossRef]
216. Pierin, G.; Grotta, C.; Colombo, P.; Mattevi, C. Direct Ink Writing of micrometric SiOC ceramic structures
using a preceramic polymer. J. Eur. Ceram. Soc. 2016, 36, 1589–1594. [CrossRef]
217. Manso, B.R.; Moyano, J.J.; Perez-Coll, D.; Belmonte, M.; Miranzo, P.; Osendi, M.I. Polymer-derived
ceramic-graphene oxide architected composite with high electrical conductivity and enhanced thermal
resistance. J. Eur. Ceram. Soc. 2018, 38, 2265–2271. [CrossRef]
218. Moyano, J.J.; Mosa, J.; Aparicio, M.; Pérez-Coll, D.; Belmonte, M.; Miranzo, P.; Osendi, M.I. Strong and light
cellular silicon carbonitride–Reduced graphene oxide material with enhanced electrical conductivity and
capacitive response. Addit. Manuf. 2019, 30, 100849. [CrossRef]
219. You, X.; Yang, J.; Huang, K.; Wang, M.; Zhang, X.; Dong, S. Multifunctional silicon carbide matrix composites
optimized by three-dimensional graphene scaffolds. Carbon 2019, 155, 215–222. [CrossRef]
© 2020 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access
article distributed under the terms and conditions of the Creative Commons Attribution
(CC BY) license (http://creativecommons.org/licenses/by/4.0/).

Direct Ink Writing Technology (3D Printing) of Graphene-Based Ceramic Nanocomposites: A Review

Uploaded by

Copyright:

Available Formats

Direct Ink Writing Technology (3D Printing) of Graphene-Based Ceramic Nanocomposites: A Review

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Direct Ink Writing Technology (3D Printing) of Graphene-Based Ceramic Nanocomposites: A Review

Uploaded by

Copyright:

Available Formats

nanomaterials

Nanomaterials 2020, 10, 1300; doi:10.3390/nano10071300 www.mdpi.com/journal/nanomaterials

Table 1. Groups of additive manufacturing technologies by the International Organization for

2. Additive Manufacturing Processes for Ceramic and Their Principles

2.1.1. Selective Laser Sintering (SLS)

Figure 2. Schematic diagrams of powder-based additive manufacturing (AM) technologies main

2.1.2. Binder Jetting (BJ)

2.1.2. Binder Jetting (BJ)

2.1.3. Selective Laser Melting (SLM)

2.2. Slurry-Based Technologies

The first study

2.2.3. Two-Photon Polymerization (TPP)

2.3. Bulk Solid-Based

2.3.1. Laminated Object Manufacturing (LOM)

2.3.3. Direct Ink Writing (DIW)

3. Additive Manufacturing for Graphene-Based Materials

3.1. Graphene and Its Derivatives Materials

3.2. Additive Technologies for Graphene-Based Materials

3.2.1. Stereolithography (SLA)

3.2.2. In the current

4. Direct Ink Writing Technology of Graphene-Based Ceramic Pastes

Figure (a) (a)

Nanomaterials 2020, 10, 1300 29 of 48

Figure 22. SEM

You might also like