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Engineered Regeneration 3 (2022) 41–52

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Engineered Regeneration
journal homepage: http://www.keaipublishing.com/en/journals/engineered-regeneration/

3D Printing of Ceramic Biomaterials


Michael Ly, Sarah Spinelli, Shayne Hays, Donghui Zhu∗
Department of Biomedical Engineering, Stony Brook University, 100 Nicolls Rd, Stony Brook, NY 11794, United States

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

Keywords: Bioceramics are a popular class of materials used in biomedical applications due to their mechanical stability and
Extrusion biocompatibility. They exist in a variety of fields including hip joints for orthopedics, tooth fillings for dentistry,
Binder jetting and scaffolds for tissue engineering; however, the standard processes currently used to manufacture these ce-
Material jetting
ramic products can be time-consuming and costly. In response, current literature alternatively proposes additive
Powder bed fusion
manufacturing (3D printing) strategies to fabricate bioceramic materials in a cost-effective and efficient man-
Vat photopolymerization
ner. Herein, we briefly cover five common processes and materials used in additive manufacturing bioceramics:
fused deposition modeling, material jetting, binder jetting, powder bed fusion, and vat photopolymerization. Fur-
thermore, we discuss the potential of these 3D printed ceramic structures when applied to different biomedical
technologies such as bone tissue scaffolds and structural implants.

1. Introduction vide biocompatibility and bone repair attributes that metal devices lack
[5,6]. Structurally, ceramic morphology exists in crystalline or semi-
The emergence of bioceramic materials leads to exciting and innova- crystalline form, although there are exceptions depending on composi-
tive applications within biomedical engineering. Standard ceramic ma- tion and fabrication method. Examples include certain amorphous ce-
terials are hard, brittle, wear resistant, and corrosion resistant, which ramics like bioactive glasses [3].
all explain their orthopedic potential as medical implants like hip joint The growing demand for bioceramic devices and parts requires faster
prostheses [1]. Bioceramics are a subclass of ceramics developed in the and more accurate methods for creating ceramics. Subtractive manufac-
1970s. In addition to existing ceramic mechanical properties, bioce- turing technology is common albeit imperfect. Most methods for creat-
ramics include excellent biocompatibility and bioactivity potential [2]. ing ceramic scaffolds, by using polymer molds or foaming agents, are
Therefore, these biomaterials are also used in countless dental implants, created using subtractive methods. These methods unintendedly create
bone grafts, and scaffolds (see Fig. 1) to promote osteogenesis in the tis- the pores in the scaffold randomly, and therefore cannot provide the
sue engineering field [3]. same amount of control [7]. For other applications like orthopedics, a
Three commonly used bioceramics include alumina, zirconia, and computerized numerical control machine may subtract unwanted parts
hydroxyapatite. Alumina and zirconia are high density materials with of a material and leave only the desired shape. The subtracted material
great mechanical strength and corrosion resistance; albeit previous lit- may then fabricate other smaller components or is disposed of waste-
erature suggests zirconia is slightly weaker than alumina against cor- fully. The assembly of all these components produce a complete object.
rosion. The two are also biocompatible and bioinert, which may serve The advent of cost-effective additive manufacturing (AM) resolves these
hip and knee replacement parts. As a body implant, they may supply issues; 3D printers may construct complex objects in less parts with less
structural support preventing stress shielding and avoid adverse tissue wastage [8]. In 2018, General Electric followed an AM approach to re-
reactions to ion toxicity from metallic stents or prostheses. The third duce 855 car engine parts to only 12 parts. The simplification reduced
bioceramic, hydroxyapatite, is a calcium phosphate bioceramic, which engine weight by over 100 pounds and significantly improved fuel use
is a primary mineral component of teeth and bone. Hydroxyapatite is by 20% [9]. While subtractive techniques are standardized, newer ad-
known for its ability to interconnect with neighboring tissues and re- ditive manufacturing (AM) strategies may provide a higher degree of
pair damaged cells. It is both bioactive and bioresorbable, which means dimensional accuracy and precision for bioceramic fabrication under
osteogenesis will end with the material’s eventual dissolution in the shorter times. A general comparison between additive and subtractive
body. Hydroxyapatite is brittle and used for implant coating since they processes is shown in Fig. 2.
have a low load bearing resistance. For instance, coatings for metallic AM, or simply 3D printing, is renowned for its ability to create highly
biomedical devices like hip prosthetics and titanium tooth root pegs pro- customizable structures from diverse materials. In essence, a 3D printer
receives a computer-aided design (CAD) model for its compatible slicer


Corresponding author.
E-mail address: Donghui.Zhu@stonybrook.edu (D. Zhu).

https://doi.org/10.1016/j.engreg.2022.01.006
Received 22 December 2021; Received in revised form 21 January 2022; Accepted 21 January 2022
Available online 29 January 2022
2666-1381/© 2022 The Authors. Publishing Services by Elsevier B.V. on behalf of KeAi Communications Co. Ltd. This is an open access article under the CC
BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/)
M. Ly, S. Spinelli, S. Hays et al. Engineered Regeneration 3 (2022) 41–52

Fig. 1. Grand overview of potential 3D-printed ceramic scaffold applications in fields like tissue engineering and drug delivery. (Reprinted, with permission, from
[4].

by geometry and porosity may even be predicted using computation


modeling before the printing starts [7]. Although still a novel approach,
the 3D printing of bioceramics proves to be a promising alternative to
the conventional methods for scaffold creation.
AM may aid other applications other than scaffolds in bone regen-
eration. Dental implants and prosthetics require precise control during
manufacturing. The increased control and reproducibility that 3D print-
ing provides enables the customization and mass production of dental
parts [14]. Electronics and fluidics systems may also benefit from AM’s
ability to resolve cavities and channels at the micron scale [15].
In this review, we provide a cursory look at multiple strategies for
the additive manufacturing of bioceramic materials as well as several of
their applications.
Fig. 2. Additive manufacturing sequentially adds layers until the entire print is
formed. Subtractive manufacturing begins with a starting shape that is modified
2. Printing methods
until the desired form is made. Both methods may create the same end shape.

Additive manufacturing may construct identical 3D models with sim-


ilar morphology using diverse techniques. Each technique still maintains
software. Slicer programs, as in Fig. 3, provide further customization of the layer-by-layer method of printing that defines AM; however, varia-
print parameters such as infill, temperature, and print speed. They con- tions in printing method or materials may result in immense changes in
trol the overall print quality of the drawn object’s shape layer by layer features like mechanical strength, biocompatibility, porosity, and even
[10]. These shapes may be intricate and application-specific; however, cost. These features depend on the certain application, available bioce-
AM needs no molds or machining for complex construction of models ramic materials, and funding & equipment. Thus, there is no universal
like scaffolds. Furthermore, AM is not limited only to plastic materials. ‘best’ printing method for AM of bioceramics. Herein, we briefly cover
Present-day 3D printing technology incorporates alternative materials five common processes and materials used in additive manufacturing
including bioinks and of course, ceramics. This expansion elicits more bioceramics: fused deposition modeling, material jetting, binder jetting,
research strategies to effectively print materials for each application [8]. powder bed fusion, and vat photopolymerization.
The AM of ceramics can be extremely useful, as it allows for more
standardized and precise control over creating intricate bioceramic de- 2.1. Material extrusion
vices. These qualities are effective for fine-resolution scaffolds, osteo-
dental implants, as well as electronic devices and microfluidic chips. Extrusion-based printing, or Fused Deposition Modeling (FDM), is
In bone tissue engineering, scaffolds require fine resolution of their one of the more recognizable techniques. A device first receives an up-
pores. Scaffolds are bioactive matrices which provide structural support loaded 3D model and then begins the print by heating up the print-head
and encourage osteoregeneration. Scaffold porosity provides spaces for and print-bed. The nozzle then extrudes ceramic material layer by layer.
cellular growth and attachment [11]. The difficulty lies in achieving Each layer hardens as it is placed and becomes a solid product. FDM con-
the right degree of porosity using conventional scaffold-making tech- sumes low energy and costs less than a few of other AM techniques. For
nologies. In short, the procedure involves a foaming agent added to a this reason, they are desired for bone tissue engineering [16–18].
ceramic slurry, which is later burned out of the product to leave only
the ceramic matrix behind [12]. The 3D printing of bioceramics is a rel- 2.1.1. Selected materials
atively novel strategy that may fabricate such highly porous matrices Ceramic biomaterials are favored for their durability, biocompatibil-
with a higher degree of precision [13]. The scaffold’s success measured ity, and sintering window temperatures. For the FDM of scaffolds, bioce-

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M. Ly, S. Spinelli, S. Hays et al. Engineered Regeneration 3 (2022) 41–52

Fig. 3. (A) Slicer software like Ultimaker Cura, as used in extrusion-based printing, separates CAD models into distinct layers and estimates overall print time. (B)
Commercial material extrusion printers often focus on plastic materials; however, they may also print non-plastic materials like bioceramics in lieu of standard PLA
filament. (C) Slicers provide detailed control of printing parameters like infill, travel speeds, and build plate adhesion.

This softens the material in the chamber to lower viscosity and allow for
easier extrusion. The platform allows for easier adherence, less shrink-
age, and prevents curling from the temperature difference. The material
is pressure-driven through the nozzle at a designated velocity and onto
the print bed, layer by layer. These bioceramic composites may develop
into lattice shaped 3D structures like scaffolds for bone tissue engineer-
ing applications.
When fully printed, the model experiences post-processing. This may
include drying for up to 24 h to fully evaporate any solvents introduced
in the paste. Drying leaves behind a purer ceramic substance. To im-
prove ceramic mechanical strength, the body is sintered at temperatures
below 1650 degrees Celsius, the melting point of pure hydroxyapatite
Fig. 4. A generalized 5-step procedure of extrusion (fused deposition modeling). [16].
One of the primary reasons 3D printing hydroxyapatite scaffolds has
been so successful is because of the mathematical equations that are
ramic materials involved may include bioactive glasses or calcium phos-
fairly accurate at predicting the shrinkage of the mold after the sintering
phates such as hydroxyapatite. This material holds a nonlinear structure
and drying processes [21].
and succeeds at biocompatibility. Hydroxyapatite is often chosen for its
Most time spent in FDM printing is waiting for the material to dry
similarity to natural bone tissue. It has osteoconductive and osteoin-
and sinter. The sintering process can also increase prices due to the high
ductive properties and encourages cellular attachment within its pores
amount of heat needed to properly sinter the material. Overall, this pro-
[17,19].
cess takes about 2-3 days, depending on how long the actual printing
Pure hydroxyapatite may not be printed through heat and pressure
process takes for the scaffold structure.
extrusion alone. The material must first become softened to form the
desired shape. One method is to create a hydroxyapatite paste using
polyvinyl butyral (PVB) and polyethylene glycol (PEG) dissolved in
propan-2-ol solvent. PEG acts as a plasticizer to reduce viscosity and im-
prove flexibility of the material, whereas PVB acts as an adhesive binder
for the PVB and hydroxyapatite ceramic powder. About 60% of the paste 2.2. Material jetting
consists of hydroxyapatite. After the desired paste is developed, excess
solvent is evaporated until the desired ceramic paste is left [16]. An al- Material jetting is another AM technique that may include bioce-
ternative method uses melt blending between a ceramic filler and a PLA ramic materials. Its technology is popularly attributed to household
matrix. Micron-sized hydroxyapatite spheres are added to a screw mixer printers for color staining paper documents; however, material jetting
with melted PLA to form one highly loaded composite filament [17,20]. may also form complex 3D ceramic geometries without noticeable mi-
crostructural defects over glass [22]. With material jetting, picolitre
2.1.2. General process quantities of ceramic-suspended droplets are dispersed precisely onto a
Once a desired paste or filament for FDM is obtained, the material ex- substrate material or printing surface. These droplets then solidify either
trusion procedure as summarized in Fig. 4 may begin. First, the compos- through solvent evaporation, temperature-induced gelation, or chemical
ite filament or ceramic-laden paste is inserted into the extrusion cham- reactions [23]. The process repeats layer-by-layer until a 3D amalgama-
ber. The printer warms up both the printhead and the print platform. tion of the desired object is fabricated.

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M. Ly, S. Spinelli, S. Hays et al. Engineered Regeneration 3 (2022) 41–52

voltage creates regular vibrational disturbances to the stream at a spec-


ified frequency [25]. These disturbances divide the high-velocity inkjet
stream into monodisperse droplets due to Rayleigh instability. This in-
stability occurs when the wavelength is greater than the jet circum-
ference. Then, electrically conducting ink droplets are charged using
a nearby charging electrode. Diverse range of voltages provide differ-
ent charge levels for each droplet [26]. Deflector plates located below
these electrodes provide a fixed electric field which separates incoming
droplets by their level of charge. Lower charged droplets are deflected
to a catcher for recirculation while higher charged droplets bypass the
catcher and are directed to the substrate. To position droplet placement,
the substrate meticulously translates within the XY plane [25].
In a DOD system, the exact number of required ink droplets are re-
leased from an array of printheads and nozzles. This method is more
commonly used in ceramic industrial applications [23]. Actuators for a
DOD system are either piezoelectric, thermo, or a combination of both.
In a study conducted by Ainsley et al. [24], a piezoelectric jet head with a
heating jacket could adjust the extrusion characteristics of a droplet like
driving pulse amplitude, duration, peak shape, and fluid temperature.
In general, actuators create momentum within a fluid through dramatic
changes in cavity geometry. The fluid’s momentum causes droplet for-
mation outside of the selected nozzle. The ejected ink droplet is directed
down towards the print substrate [25].
Droplets formed by either CIJ, or DOD impact the print surface and
react with the substrate before the solidification process. The initial
Fig. 5. Material jetting printing can be divided into two major groups, con-
tinuous inkjet (CIJ) and drop-on-demand (DOD). They are further specified by
droplet reaches the substrate and forms a semi-spherical shape deter-
actuator type. CIJ uses charged inks to direct streams into a catcher or the sur- mined by the surface energy of the substrate and rheological properties
face region. Droplets in DOD systems fall directly to the printing surface. of the droplet. Behind the initial droplet are satellite droplets. Satellite
droplets are formed mid-fall due to the axial vibration and separation
of droplets from unstable jet streams [26]. These satellite droplets can
2.2.1. Selected materials merge with the initial droplet to form a larger shape.
Droplet mechanics are a major contributor to ceramic ink selection. Solidification typically occurs due to an evaporating solvent or a
As such, custom-made bioceramic inks can be created by suspending ce- phase change on substrate impact. Solvent evaporation is favored over
ramic particles into an aqueous medium using dispersants and a binder the latter in the construction of ceramic models because it generates a
to create a ceramic slurry [22]. In multiple studies performed by Ains- much denser structure than the latter. Regardless of the solidification
ley et al. [24], up to 40% by volume of alumina was suspended in a method, the layer must fully solidify continuing with the next. Other-
paraffin wax medium. The group learned lower percentages of ceramics wise, the droplets may fuse together unevenly [23].
were adequate to form small green bodies. Sadly, these bodies suffered The green bodies that result from an inkjet print must face post-
from distortion when sintering. processing to improve rigidity and strength; material jetting prints are
Purchasable graphic inks are often provided with recommended debinded and sintered [23]. Depending on the specific composition and
ranges of viscosity and surface tension values; however, they are not geometry of the print, the post-processing details may vary in value. One
an excellent model for ceramic-laden inks since they are generally less method performed by Cappi et al. [22], debinded green bodies com-
dense. Compatible ceramic inks depend on fluid behavior models like posed by Si3N4 suspensions at 500C for 2 h. They subsequently placed
Reynolds, Weber, and Ohnesorge numbers [23]. Simply put, there exists these green bodies in a Si3N4, YAG, and boron nitride powder bed to
a crucial balance between the volume percentage of ceramic particles avoid decomposition. Finally, they sintered the green bodies at 1780C
and the selected medium. Higher volume percentages reduce distortions for 2 h.
but increase the viscosity of the ink requiring high pressures to extrude Material properties of the models after post-processing can be re-
the ink [24]. viewed using scanning electron microscopy (SEM) and transmission
electron microscopy (TEM). These imaging techniques allow one to ob-
2.2.2. General process serve the microstructure and chemical composition of the sintered sam-
The exact mechanism by which material jetting functions depends ples. The resulting microstructures of these prints can be extremely ho-
highly on the general ink system. Material jetting printers pressurize mogeneous without any defects or flaws [22].
the ink from a reservoir up into the print head. Then, a controlled actu- CIJ and DOD both have their advantages and limitations in terms of
ator releases the fluid onto a printed surface in the desired location. The production. CIJ generates monodisperse droplets at a high throughput
mode of droplet transportation is classified into either continuous inkjet since the liquid streams can flow nonstop [26]. Unfortunately, a major
(CIJ) and drop-on-demand (DOD) systems. In a CIJ system, a printer issue with CIJ-type printers is contamination. While it is economic to
extrudes a stream of fluid composed of droplets. Selected droplets are recirculate unused droplets back into the system, this methodology is
electrically deflected to a desired position. The remainder recirculates prone to environmental hazards. Hence, it is not often used for many
into the system. In contrast, a DOD printer emits only the precise number ceramic applications. Conversely, DOD can produce accurate droplets
of droplets to print an object [24]. Most industrial applications prefer without fear of contamination but does not have the same processing
DOD systems over CIJ for printing functional parts. One reason is that speed as CJI. The slowdown is also attributed to high specificity in
the recirculated ink in CIJ may be contaminated thus limiting itself from droplet placement [24].
certain ceramic applications [23,24]. The process then repeats continu- In general, material jetting production is limited to small-scale appli-
ously for each layer until the overall object is formed as shown in Fig. 5. cations. Most results from studies conducted with material jetting print
In the CIJ system, typically a single jet releases a fluid stream toward in the centimeter or millimeter order of magnitude [26]. One reason
the printed surface. A piezoelectric transducer acting under a modulated is because the repeated process of waiting for solidification and start-

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Fig. 6. A generalized 7-step procedure for


binder jetting.

ing a new layer droplet-by-droplet is highly time-consuming. Other AM of low enough viscosity to perforate the ceramic powder [30]. The build
techniques like photopolymerization or FDM would be better suited for plate is lowered for the subsequent layer and the process repeats until
larger scale applications. the desired structure is fully complete [28]. The 3DP process is briefly
outlined in Fig. 6.
2.3. Binder jetting (3DP) Afterwards, the model enters a post-processing stage where the ma-
terial is dried and cured. Air is gently blown onto the product to remove
Binder jetting is another form of additive manufacturing capable of any unused powder collected on the model to be recycled into the over-
performing solid freeform fabrication of ceramic materials. 3DP is a flow bin. The product is then sintered for completion. If the product
poor abbreviation for binder jetting as it can be confused with three- is not sintered, it will be left in what is called a green state, where it
dimensional printing, which includes binder jetting. In 3DP, layers of is porous and not structurally strong. Eventual removal of the binder
bioceramic powders are evenly dispersed on a building platform. A car- will weaken mechanical stability; however, the structural drying and
riage drops binder fluid on the powder to bind layers of powder together. sintering process will help rebuild its integrity. Ceramic materials must
After completion, the developed ceramic is sintered for structural in- undergo this process before it may be used in any functional application
tegrity [27]. [29].

2.3.1. Selected materials 2.4. Powder bed fusion


Binder jetting operates using ceramic powders and polymeric
binders. The powders form the final ceramic structure, while the binder Besides using deposits from droplets, laser-based approaches to the
acts as temporary material to hold each layer together before sinteriza- AM of bioceramic materials exist. Selective laser sintering (SLS) is a
tion. powder-based method of AM. It uses a laser to partially melt ceramic
Like FDM, there exists flexibility in powder selection for 3DP. 3DP particles until they become bonded, or “sintered.” The powder is de-
may process a wide array of metal and ceramic materials including 316 posited layer by layer onto a bed. After each layer is deposited, an over-
SS, 420 SS, and alumina [27]. Binder jetting is relatively new with ce- passing laser scans the powder in a certain pattern [31]. This process
ramics, so there is much literature discussion on the optimal material is repeated for each layer until the final product is formed. The imme-
powder for each application. The powders are chosen based on their diate product that is produced from this process could be quite porous,
mechanical properties and structural shapes. The morphology and dis- making it an optimal choice for tissue engineering scaffolds.
tribution of ceramic powders by the roller determine the density and
stiffness of the preform. Generally, larger particle sizes pack better with 2.4.1. Selected materials
binder while smaller particles sinter faster [28]. The base material for this process is ceramic powder. The specific
The binder must complement the powder chosen. Ideally, the binder powder used determines the purpose of the final print. For instance,
fluid has low enough viscosity to separate into individual droplets. Ce- one study successfully created a bioactive glass 13-93 scaffold using
ramic particles may bind through two methods: In-Liquid and In-Bed this method. The powder’s particle size was 16 micrometers [32]. Other
binding. The binding agent in the In-Liquid method is found in the jetted bioactive glass powders include nano-58 S and hydroxyapatite [33,34].
liquid while in the In-Bed method, it occurs with the interaction between For orthopedic applications, a more structural ceramic may be formed
the liquid and powder bed. In-Liquid strategies decompose thermally in using alumina powder. Ball milling, dispersion polymerizations, and
post-processing; however, they may easily dry and clog the print-head thermally induced phase separation are several methods to create these
nozzle. Post-processing of In-Bed mechanisms tend to dissolve adhesive ceramic particles [35].
agents and leave a porous structure which may be beneficial for scaf- In addition to ceramic and bioactive glass powders, polymer binders
folds [29]. may optionally be incorporated within the powder to stabilize the ce-
ramic shape and function as a glue during sinterization [36]. They
2.3.2. General process usually have lower melting temperatures when compared to ceramics,
Ceramic powders are poured inside the printer’s material container. so they can eventually be removed later through firing. Furthermore,
When the printing process begins, a roller evenly disperses the material these binders can be made of nylon polymers, or other types of semi-
as a layer on the powder bed. Excess material that is spilled may be col- crystalline polymers. These semi-crystalline polymers have a clear melt-
lected by the overflow bin for recycling. Simultaneously, a carriage with ing and glass transition temperature window [35].
an array of print heads follows the roller and selectively deposits bind- One study used a Sinterization 2000 machine (DTM Corporation /
ing agents to adhere the powder together. These binding agents must be 3DSystems, USA), which had a carbon dioxide laser of 100 W of power.

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M. Ly, S. Spinelli, S. Hays et al. Engineered Regeneration 3 (2022) 41–52

one print bed. Production time can also be increased through speeding
up the laser’s scan speed, but that may decrease the number of particles
that are sintered within a scan, which can in turn cause other issues
[37]. Overall, SLS can be a beneficial technique for ceramic additive
manufacturing, as it can have a fast production time and bypasses the
need for scaffolding. However, it is still a process that can be researched
even more, as the relationships between powder particle size, powder
composition, laser intensity and more are not as understood even though
they impact the process significantly.

Fig. 7. A selective laser sintering setup for constructing flexible sinusoidal scaf- 2.5. Vat photopolymerization
folds. (Reprinted, with permission, from [36]).
Vat photopolymerization, or simply resin 3D printing, is another dis-
tinctive AM technique, which fabricates 3D ceramic objects freeform.
This laser had a wavelength of 10.6 micrometers and a diameter of 400 This strategy offers high resolution prints without any need for special
micrometers, and a scan speed and spacing of 300-1250 mm/s, 80-500 molds or tooling. Current vat photopolymerization methods have used
micrometers [35]. Laser sintering machines usually have a laser power ceramic materials mixed within resin for precise and fine-detailed prints
that ranges from 30 to 400 W (higher wattage is used for ceramics, as [43]. Simply put, a container filled with photosensitive resin is cured
well as metals). These lasers should also have a lower scan speed, which through UV light exposure one layer at a time. The resulting green body
increases the amount of powder that is melted with contact. Faster scan is then post-processed via sintering and debinding to establish rigidity
speeds will decrease the amount of powder that is melted, which can [44]. The method of UV exposure is distinguished as digital light pro-
cause balling and produce uneven surfaces. Shorter scan lengths are cessing (DLP) or stereolithography (SLA). As such, DLP and SLA share
also desired, as they prevent the sample from cooling before a second mostly the same experimental setup but differ in the general process.
pass [37]. If the powder sample cools, there is a greater opportunity
for polymer binder crystallization, which can then lead to warping and 2.5.1. Selected materials
distortion. In vat preparation, a ceramic powder is incrementally added to a UV
Finally, the particle powder size is especially important, as too small curing monomer made up of dispersant, crosslinker, and photoinitiator
of a particle will cause the powder to pack together and form clumps. to form a viscous slurry [45,46]. Ceramic materials involved in both DLP
However, particles that are too large can reduce the density of the pow- and SLA depend on the specific application which they are intended. For
der [38]. Therefore, the particle size of the powder is usually about 10– instance, investment casting may use a silica material while structural
150 micrometers [39]. Finding the balance between particle size and components may opt for alumina or silicon oxide [43]. Homogeneous
composition, as well as laser characteristics and scan time is essential to dispersion of the ceramic powder in suspension is essential for excellent
creating a successful powder ceramic part using this method. curing performance. Light-sensitive reagents and the dispersant first un-
dergo ultrasonic agitation. The gradual addition of ceramic material is
2.4.2. General process stirred slowly into the mix. Lastly, the photoinitiators are introduced
SLS operates through polymer binder crystallization, which is con- and ball milled [47]. The combination of all these material components
trolled by heating the powder bed before and during the printing pro- is entered in a tinted-color vat to prevent unintended exposures and pre-
cess. A visual representation of the SLS process in the context of scaffolds mature curing; these steps are all crucial in constructing green bodies
is shown in Fig. 7. Before the powder bed is preheated, a thin layer of with desired shape and structure.
the powder is deposited on the bed and then a roller is used to flatten the The suspension composition must ideally include a high percentage
powder [35]. The polymer binder eventually melts and forms a glassy of ceramic volume while adhering to optical and rheologic laws. The
phase around the ceramic powders. This phase helps stabilize the ce- method of green body formation is with UV light as it passes through
ramic when it is bonded by the overpassing laser beam, which partially the resin. Under the Beer-Lambert Law, the cure depth is influenced by
melts the particles. Upon melting by the laser beam, if the melted solu- particle size, exposure, ceramic volume percentage, and scattering effi-
tion is more viscous, it prevents the escaping of bubbles. This can com- ciency [43]. Ceramic suspensions made with fine particles typically are
promise the stability of the completed structure [40]. Once the bonding high in viscosity and cause issues printing smooth layers. Conversely,
is completed for a layer, a new layer of ceramic and polymer binder large-scale particles reduce viscosity but cause challenges during post-
powder is deposited, and the laser passes over once again. This process processing when sintering [44]. The choice between using aqueous
is repeated until a final product is formed. The body may then increase acrylamide-based and nonaqueous diacrylate-based UV-curable solu-
its density and structural stability with isostatic pressing. Afterwards, tions should also be kept in mind. For instance, ceramic binders are
the product is fired to debind any polymer binders [41]. often made up of acrylate polymers in SLA even though diacrylate is
A similar process to SLS is selective laser melting (SLM), which may more viscous and offers a higher refractive index/cure depth. Moreover,
be identified as a subset of SLS and a type of powder bed fusion. It is certain photo-monomers may hold viscosity values on the order of tens
an identical process to SLS except it requires no binders and uses high- to thousands of mPa∗ s. In terms of SLA, the suspension system’s vis-
energy lasers to fully melt ceramic particles together. Objects formed cosity should mimic the fluidity of convention resins (<3000 mPa∗ s) to
through SLM make for very dense structural ceramics. Therefore, the allow for proper layer recoating; although Griffith was referring to SLA,
technique is efficient since it bypasses post-processing modifications like the idea may hold true for DLP printers. High viscosity values may be
isostatic pressing to improve density. Unfortunately, SLM products are balanced with the introduction of optional nonreactive solvents [43].
prone to cracking. For instance, alumina powders are prone to both
transverse and longitudinal cracks from internal stresses and solidifi- 2.5.2. General process
cation shrinkage [42]. Like other AM procedures, vat photopolymerization requires users to
Although the cost may be higher, the production time for selective first create their desired 3D models within a computer aided design soft-
laser sintering is generally faster than other methods. It also does not ware. Once finished, the watertight mesh may be transferred to a digital
involve the printing of a support material like many additive manufac- slicing program as an STL file format. The model is then virtually di-
turing processes require. Of course, production time can be impacted vided into layers of user-defined thickness [48]. Thinner layers provide
by the final part’s size and how many parts that are being created from smoother surfaces and finer resolutions. In an experiment conducted

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M. Ly, S. Spinelli, S. Hays et al. Engineered Regeneration 3 (2022) 41–52

Fig. 8. Bottom-to-top configuration of a digi-


tal light processing printer. A projector emits
light through a lens that scatters UV in a broad
field. Regions circled in red at the surface layer
are cured simultaneously by the projector. The
platform is raised after each layer cures.

Fig. 9. Top-to-bottom configuration of a stere-


olithography printer. A set of mirrors direct the
path of a UV laser. Circled in red are resins that
were cured sequentially at the surface layer.
The platform translates downwards, and the
process repeats as shown.

by Diptanshu, Miao et al, fine powder ceramics were printed with a wards. This setup is commonly used in SLA setups for experiments like
50-micrometer layer thickness [44]. For SLA, polymers provide smooth that of Zhou et al [49]. Conversely, a bottom-to-top configuration would
surfaces and fine features at a > 150-micrometer thickness; ceramics begin the print’s first layer at the bottom of the vat. The print is made
require a minimum a 200-micrometer thickness [43]. Once sliced, the upside-down as the platform along with the model moves upwards after
model is converted into G-code which delivers numerical control of the each layer. This option is frequently used for vat photopolymerization
printing machine. The model is ready to begin the vat polymerization as it requires less resin and thereby costs less. Moreover, a Teflon layer
process [48]. at the bottom toward the projection reduces the UV radiation with neg-
In vat photopolymerization, structures are formed in a layer-by-layer ligible dispersion. This layer helps with DLP but does not aid SLA as
process where UV exposes the photosensitive resin from the bottom of much. Despite this, the top-to-bottom positioning is still preferred for
the vat in the pattern indicated within the uploaded G-code. Light can SLA since light dispersion issues are minimized [48].
only pass through a clear window for curing; light from external sources The result of ceramic vat photopolymerization is a cured green body
is blocked by tints which attempt to block UV light. When UV light that must be post-treated. Removal of excess or unwanted material is
exposes the photosensitive resin, a chemical reaction occurs between done using a chemical wash followed by a UV bath [48]. Afterwards,
the monomers and oligomers causing crossing linking to occur. DLP uses the green body may hold residual water that must be dried [49]. Photo-
a projector to shine UV light at all targeted locations simultaneously as sensitive resin functioned as a binder for the ceramic material and must
shown in Fig. 8. SLA is more specific and uses a combination of mirrors be removed to increase structural strength. The remaining material is
to direct the path of a laser to the target as shown in Fig. 9. After each then sintered to reach desired shape and density [47]. These processes
layer is cured, the stage will move clear from the window, or a blade will should be conducted carefully to reduce material deformation.
allow a fresh coating of uncured resin for the next layer. UV light then The drying process to remove residual water is the prerequisite step
polymerizes the layer once again so that the current layer is adhered to before any other post-processing techniques can be made. Tradition-
the previous. The entire process repeats until the entire model is drawn ally, a freshly made green body is left to the elements in an environ-
[48,49]. ment where the liquid can naturally evaporate. Certain procedures use
DLP and SLA both have the option to print either from top-to-bottom a stove to dry the bodies and remove any volatiles. An alternative tac-
or bottom-to-top configurations. In a top-to-bottom configuration, the tic uses liquid desiccants like PEG 400 to uniformly extract liquids in
light source exposes the first layer from the top of an entirely filled vat. multiple directions. This method would limit the possibility of uneven
As each layer cures, the platform along with the model moves down- evaporation and sample deformation [48,49].

47
M. Ly, S. Spinelli, S. Hays et al. Engineered Regeneration 3 (2022) 41–52

Table 1
3D Printing Method Classification and Comparison [4–6,13,15,41,43,48]

3D Printing
Technique Strategy Relative Cost Production Time Advantages Disadvantages

Extrusion Ceramic paste with Low – Moderate. Slow. Straightforward process. Limited resolution.
polymer binder and Flexible in porous scaffolds
plasticizer. or dense structures.

Binder Jetting Ceramic powder bed and Moderate – High. Moderate/ Great for larger, porous Challenging for very
polymer binder. Fast. ceramic structures. dense ceramics.
Requires few sacrificial
materials.

Material Jetting Ceramic-suspended Low – Moderate. Slow/ Beneficial for small models. Difficult for large
droplets on substrate. Moderate. Creates smooth surfaces. models.

Powder Bed Fusion Ceramic powder bed High. Fast. Flexible in porous scaffolds Distortion and
with laser. or dense structures. warping leading to
microcracks.
Vat Ceramic dispersed in Moderate. Moderate/ Precise. Requires extensive
Photopolymerization photosensitive resin. Fast. Creates smooth surfaces. post processing.

The debinding process is not required for all compositions but al- [4]. In addition, their complex porosity and interconnectivity is not eas-
lows for higher quality structures. Varghese et al. [48] sintered alumina ily replicable. Bioceramic materials hold great mechanical strength and
and 3-YSZ ceramic bodies separately and produced satisfactory quality wear resistance. They are also easily accommodative to complex struc-
ceramics. 8-YSZ, however, required a debinding route to prevent crack tures when 3D printed making them an excellent fit as a replacement
generation. In the debinding process proposed by Zhou et al. [49], a material. Currently, FDM, 3DP, SLS, and vat photopolymerization are
vacuum pyrolysis step is followed by air debinding for a zirconia ce- existing techniques that are commonly used for producing porous ce-
ramic body with minimal defects. First, the vacuum reduces the rate of ramic scaffolds [50].
organic decomposition and lowers the chance of crack and bubble for- The goal is to construct bioactive ceramic scaffolds that are porous
mation. Then, the air debinding purifies the bodies and extracts leftover enough to sustain a large amount of bioactivity and have decent me-
carbon residues. chanical properties like compressive strength. Oftentimes, the more
Sintering is the last and most crucial step of post-processing. The ce- porous a scaffold is the less strong it is, as a greater porosity and a
ramic material fuses together improving structural strength and density. smaller density go hand in hand. As of now, there are post-processing
The specific parameters such as temperature and time depend highly methods that can be used to solve this problem, such as sintering and
on the involved material and application. Li et al. [45,46] investigated the introduction of polymer coatings. However, there has been research
kaolin ceramic shells for precision casting. The group heated the bod- into ceramic-polymer composite materials that can be manufactured
ies at 375, 450, 500, and 1200C for 3 h each at either 0.5 or 2C/min without the need for other post-processing methods. One study found
heating rates before cooling. They observed fusion between layer bound- that a ceramic-polymer composite of poly-𝜀-caprolactone (PCL) and 𝛽-
aries and a reduction in crack defects. Other effects of general sintering tri-calcium phosphate (TCP), creating through the additive manufactur-
are increased bulk density, decreased porosities, and improved densities ing method of extrusion, had a high degree of biocompatibility with a
[44]. compressive strength of up to 90 MPa [18]. Finding a method of scaf-
In certain applications, vat photopolymerization can fabricate spe- fold construction that provides decent mechanical properties as well as a
cific objects much quicker than the traditional methods. For instance, suitable level of bioactivity, without lengthy post-processing techniques,
ceramic shells used in precision casting are manufactured using wax pat- is a promising future direction in this field.
tern preparation and slurry-stucco dip-coating. These methods of shell FDM is used with hydroxyapatite materials for many bone tissue en-
building are not only financially costly, but also are time-consuming. gineering applications for its great mechanical characteristics. A bone
The DLP process conducted by Li et al successfully printed out a com- graft constructed using FDM involves carbonated hydroxyapatite and
plex shell with minimal microstructural deformities [45,46]. polylactic acid materials. The microstructural analysis of these hybrid
scaffolds proved that the morphological blend provides a significantly
3. Applications greater toughness than a standard PLA scaffold. Composite scaffolds
studied by Corcione et al. [17,20] also determined that the stiffness val-
Fused deposition modeling, binder-jetting, powder bed fusion, mate- ues were much more compatible with that of bone tissue. Esslinger et al.
rial jetting, and vat photopolymerization are all useful technologies for [19] used an indirect approach of creating bioceramic scaffolds made of
the AM of ceramic materials. A brief comparison between these meth- bioactive glasses and tricalcium phosphates. In older experiments, they
ods is presented in Table 1. There are many diverse applications, most used direct binder jetting to manufacture scaffolds and learned that the
notably tissue engineering and implants, that each technique may be resulting green bodies were very fragile and would damage during de-
considered. Moreover, one approach may serve one specific application powdering. Therefore, the group decided to use an indirect approach
significantly greater than another. Decisions must therefore be made and print a PLA and ABS sacrificial thermoplastic mold in which a ce-
with great consideration to receive the desired print quality. ramic slurry would be placed within.
3DP is another common method of creating ceramic scaffolds us-
3.1. Tissue-engineered scaffolds ing 3D printing technology. Tarafder et al. [50] performed direct 3DP
on tricalcium phosphate to create micro-porosities of 27%, 35%, and
In the tissue engineering field, 3D-printed scaffolds derived from 41% for associated pore sizes of 500 micrometers, 750 micrometers, and
ceramics are increasingly desired. Ideal scaffolds are biocompatible, 1000 micrometers. After microwave sintering, maximum compressive
biodegradable, and bioactive; however, they hold low mechanical strengths of 10.95 +- 1.28 MPa and 6.62 +- 0.67 MPa were recorded.
strengths and prevent the longevity of the device under heavy loads

48
M. Ly, S. Spinelli, S. Hays et al. Engineered Regeneration 3 (2022) 41–52

in Fig.11. In the study, the group scanned a CT-based anatomical bone


model and used hydroxyapatite as reconstruction material. The result-
ing grafts are patient-specific with a comprehensive modulus ranging
from 33-200 MPa.
Material jet methods have also been employed in dental restoration.
Ebert et al. [52] modified a conventional DOD inkjet printer and devel-
oped a zirconia-based ceramic suspension with 27 vol% solid content.
The group printed a dense posterior crown with characteristic strengths
of 763 MPa and mean fracture toughness of 6.7 MPam0.5 . The printer
did face issues with clogged nozzles which explains any process-related
defects.
Researchers have also developed strategies for the SLM fabrication
of dental parts. Wilkes, Hagedorn et al. [53] investigated the limits SLM
face when printing freeform structures. Using a focused laser beam and
ZrO2 /Al2 O3 powder mixtures, the group discovered ceramics may be
printed close to 100% density without sintering or other post-processing.
Further, they exhibit no microcracks when the bed is preheated. Sadly,
these crack-free dental restoration framework suffer when melt escapes
the laser path. The resulting print may end with rough and uneven sur-
Fig. 10. SLS technique may fabricate biphasic calcium phosphate scaffolds with face.
∼61% porosity determined by Archimedes method. (Reprinted, with permission, Moin et al. [54] discusses a DLP approach to constructing zirconia
from [51].)
root analogue implants. The group took a CT scan of a human cadaver’s
mandible and recreated the structure the using CAD. The DLP projector
Bone formation due to scaffolding in the Sprague-Dawley rats justifies then cured the liquid photopolymer dispersed with ceramic material.
3DP as an excellent choice for making scaffolds. Superimposing the 3D printed tooth model with the original tooth and
Vat photopolymerization and SLS techniques are another option for CAD version revealed 1.55% and 4.86% of surface areas above threshold
scaffold fabrication. DLP is often used for its high printing accuracy and distance of 5 mm, respectively.
printing speed and is capable of printing 3D-printed scaffolds that may
even include human tissues like liver lobules. SLS also provides high 3.3. Implant coatings
accuracy and surface qualities which are also heavily desired in scaf-
fold engineering [4]. In addition, Shuai, Li et al. [51] conducted a study Perhaps, a more understudied area of research is the AM of bioce-
on the biological and mechanical properties of scaffolds made with cal- ramic hip coating. In biomedical devices, metal is used in stents, heart
cium phosphate ceramics. Their SLS print is shown in Fig. 10. The group pumps, orthopedic implants, dental parts, and more. Common metal
concluded a hydroxyapatite to 𝛽-tricalcium phosphate (70/30) ratio op- materials include titanium, stainless steel, and cobalt-chromiums. Sur-
timized the biological stability of an in vivo culture against material face modifications like micro- and macro-sized pores are made to metal
biodegradation. Further, it exhibited great fracture toughness at 1.33 implant surface to improve cellular attachment and growth through nu-
MPa m1/2 and compressive strength at 18.35 MPa. trient infiltration [55,56]. Unfortunately, long-term use of metallic im-
plants may produce certain metal ion toxins that damage neighboring
3.2. Bone grafts & dentistry cells and may lead to necrosis and cell death [57]. Porous bioceramic
coatings over these implants may be the solution to improve biocom-
Bioceramic materials are widely used in any bone tissue engineering, patibility at the implant-tissue interface while encouraging tissue inte-
specifically bone grafts and implants. In dentistry, bioceramics coupled gration. AM may provide finer control of the mechanical and biological
with AM make for excellent implants and restorations like crowns, in- capabilities of this bioceramic coating than traditional methods like dip
lays, and dentures. Bioceramics themselves are biocompatible, mechan- coating.
ically strong, and aesthetic as teeth. The inclusion of AM enables the Laser Engineered Net Shaping (LENSTM ) to AM. This printing strat-
printing of complex 3D parts that are difficult to manufacture through egy is similar to selective laser melting; however, it uses a deposition
conventional subtractive practices. Together, the AM of bioceramics head to release an appropriate amount of powder compared to having
provides a sustainable and tightly controlled method of delivering vi- an entire powder bed. Heer, Zhang et al. [58] performed a layer-by-layer
able solutions for numerous bone tissue applications. addition of Al2 O3 and SiO2 ceramics to a base Ti64 alloy as represented
One hot topic that benefits from 3D printed bioceramics is the devel- in Fig. 12. Under an additional laser pass over implant surface, the re-
opment of hip prosthetics used in orthopedic surgeries. Patients under- sulting Ti64 structure held improved wear resistance and hardened by
going replacement procedures for a hip joint provide unique morpholog- 186%. In another study using this technique, Zhang et al. [59] used
ical challenges for their surgeons. Hip joints are complex 3D structures LENS to coat a ceramic layer of Ti-Si-N over commercially pure tita-
that must be highly individualized to the patient’s anatomy. Currently, nium substrate. Their print exhibited graded microstructures and in situ
operating rooms provide variant shapes and sizes to fit in the hip struc- formed phases which explain its high hardness (90%) and wear resis-
ture; however, these non-customizable are not ‘one-size-fits all’ and lead tance.
to material waste. During a procedure, the lengthy time to find a suitable
part increases the patient’s risk of infection and may lead to intraoper- 4. Discussion
ative blood loss. Hip joints fabricated using FDM and gel-cast molding
have been proposed by Zhu, Liu et al. [1] to resolve these issues. While Bioceramic AM processes are not without fault. Research focus has
the ceramic material provided high biocompatibility with neighboring shifted to correct gaps in knowledge. With more studies completed, the
tissue and exhibits high wear resistance, the group mentions their initial material properties of many ceramics are evaluated, along with the lim-
issues with sintering caused irregular shrinkage. This would not do well itations and parameters of additive manufacturing processes [38]. The
with the specificity required of the site. more research completed, the greater understanding of how the mi-
Roopavath et al. [21] used computed tomography (CT) in combi- crostructure of ceramics, as well as several distinct aspects of the manu-
nation with extrusion-based printing to construct bone grafts as shown facturing process may be manipulated to produce desirable results. The

49
M. Ly, S. Spinelli, S. Hays et al. Engineered Regeneration 3 (2022) 41–52

Fig. 11. Computed tomography (CT) scans


may locate regions of defect bone. CAD and 3D
printing may create grafts for 3D bone recon-
struction through a virtual surgery. (Reprinted,
under Attribution 4.0 International (CC BY
4.0), from [21].)

Fig. 12. LENS method of coating titanium surfaces.


(Reprinted, with permission, from [58].)

AM of bioceramics is promising; however, there remain certain chal- shrinkage amounts albeit not always precisely. One necessary precau-
lenges engineers still face. tion to circumvent this issue is to combine the ceramic material with
Firstly, is the excessive cost. The initial purchase and operation cost other, non-ceramic materials. The resulting mixture stays together and
of a 3D printer is already significantly larger than other subtractive man- does not produce as much shrinkage. Unfortunately, this method may
ufacturing methods. With the cheapest of the printing techniques be- sacrifice important bioceramic characteristics, like biocompatibility and
ing in the thousands of dollars, successfully developing industrial sized osteogenic capability [60] Fig. 13.
equipment is not where it should be for efficient production. Further- Researchers have developed methods to limit shrinkage, distortion
more, prices rise higher when considering the cost of raw materials for and microcracking. One study photopolymerized a polysiloxane pre-
each line of production. Raw bioceramic materials come in powdered cursor to eventually form silicon oxycarbide microstructures. Polymer-
form and are fairly expensive compared to polymer materials like PLA derived ceramics created by this method involve pyrolysis of their green
used in other material prints. bodies. This method resulted in low porosity bodies with no recorded
Another issue with current production of 3D printed bioceramics is cracks or distortions and 30% shrinkage [61]. Recent studies incorporate
the high shrinkage rate and decrease in ceramic qualities after sinter- supplemental materials like polymers into the manufacturing process.
ing. A visual example exists in Fig. 11. Currently, when pure ceramic For example, vat photopolymerization methods like DLP as shown by Li
powder is used in the 3D printing process, the result usually undergoes et al. [45] may use a ceramic suspension of kaolin powder (solid load-
a sintering and drying process. An indirect result of this process is slight ing of 45% volume) in a UV-curable resin binder. This study reported a
shrinkage in the structure of the material. Calculations may estimate shrinkage of approximately 20%, with no microcracks. Other methods

50
M. Ly, S. Spinelli, S. Hays et al. Engineered Regeneration 3 (2022) 41–52

CRediT authorship contribution statement

Michael Ly: Conceptualization, Writing – original draft, Writing –


review & editing. Sarah Spinelli: Conceptualization, Writing – orig-
inal draft. Shayne Hays: Conceptualization, Writing – original draft.
Donghui Zhu: Supervision, Writing – review & editing.

References

[1] Y. Zhu, et al., 3D printed zirconia ceramic hip joint with precise structure and broad-
-spectrum antibacterial properties, Int. J. Nanomed. 14 (2019) 5977–5987.
[2] G. Daculsi, History of development and use of the bioceramics and biocomposites,
in: I.V. Antoniac (Ed.), Handbook of Bioceramics and Biocomposites, Springer Inter-
national Publishing, Cham, 2016, pp. 1–20. Editor.
Fig. 13. An example of shrinkage throughout the stages of post-processing. (a, [3] F. Baino, S. Hamzehlou, S. Kargozar, Bioactive glasses: where are we and where are
e) Green bodies. (b, d) Brown bodies. (c, f) Sintered bodies. (Reprinted, with we going? J. Funct. Biomater. 9 (1) (2018).
permission, from [47]). [4] M.V. Varma, B. Kandasubramanian, S.M. Ibrahim, 3D printed scaffolds for biomed-
ical applications, Mater. Chem. Phys. 255 (2020) 123642.
[5] S. Bose, S. Tarafder, A. Bandyopadhyay, 7 - Hydroxyapatite coatings for metallic
implants, in: M. Mucalo (Ed.), Hydroxyapatite (Hap) for Biomedical Applications,
of crack and distortion reduction employed include heating the bed in Woodhead Publishing, 2015, pp. 143–157. Editor.
powder-based additive manufacturing processes. One study conducted [6] M. Wang, L. Guo, H. Sun, Manufacture of biomaterials, in: R. Narayan (Ed.), Ency-
clopedia of Biomedical Engineering, Elsevier: Oxford, 2019, pp. 116–134. Editor.
by Wilkes, Hagedorn et al. [53] used selective laser sintering to melt
[7] A.P. Moreno Madrid, et al., Advances in additive manufacturing for bone tissue en-
together alumina and zirconia for applications like all-ceramic dental gineering scaffolds, Mater. Sci. Eng. C 100 (2019) 631–644.
restorations. The group found that preheating the powder bed reduced [8] S.C. Ligon, et al., Polymers for 3D printing and customized additive manufacturing,
thermal stresses helps prevent cracks and limit distortion. Chem. Rev. 117 (15) (2017) 10212–10290.
[9] A. Nazir, et al., The rise of 3D Printing entangled with smart computer aided design
3D printing failures may happen with any material, but common is- during COVID-19 era, J. Manuf. Syst. 60 (2021) 774–786.
sues related to bioceramic printing are sticking, splitting, dropping, and [10] N. Shahrubudin, et al., Challenges of 3D printing technology for manufacturing
flaking [62]. Sticking is the most common. In the case of DLP, sticking biomedical products: a case study of Malaysian manufacturing firms, Heliyon 6 (4)
(2020) e03734.
occurs when the build plate cures only the initial layer of resin since the [11] T. Ghassemi, et al., Current concepts in scaffolding for bone tissue engineering, Arch.
platform does not lower enough to accommodate further layers. Split- Bone Joint Surg. 6 (2) (2018) 90–99.
ting is when the printer continues to form new layers of the model de- [12] C. Gao, et al., Current progress in bioactive ceramic scaffolds for bone repair and
regeneration, Int. J. Mol. Sci. 15 (3) (2014).
spite not combining and sticking to one another. Splitting may occur [13] Y. Wen, et al., 3D printed porous ceramic scaffolds for bone tissue engineering: a
because of the material not sticking together or unwanted movement review, Biomater. Sci. 5 (9) (2017) 1690–1698.
in the base of the 3D printer. Depending on the AM technique and ma- [14] R. Galante, C.G. Figueiredo-Pina, A.P. Serro, Additive manufacturing of ceramics for
dental applications: a review, Dental Mater. 35 (6) (2019) 825–846.
terial used, the binding agent plays a key role in preventing splitting [15] M. Vaezi, H. Seitz, S. Yang, A review on 3D micro-additive manufacturing technolo-
within bioceramics. Specifically, it determines how much binding agent gies, Int. J. Adv. Manuf. Technol. 67 (5) (2013) 1721–1754.
is needed to prevent splitting without disrupting the actual functionality [16] G. Zhong, et al., Characterization approach on the extrusion process of bioceramics
for the 3D printing of bone tissue engineering scaffolds, Ceram. Int. 43 (16) (2017)
of the bioceramic being printed.
13860–13868.
[17] C. Esposito Corcione, et al., Highly loaded hydroxyapatite microsphere/PLA porous
5. Conclusion scaffolds obtained by fused deposition modelling, Ceram. Int. 45 (2 Part B) (2019)
2803–2810.
[18] B. Huang, et al., Polymer-ceramic composite scaffolds: the effect of hydroxyapatite
The bioceramics printing techniques presented herein each have spe- and 𝛽-tri-calcium phosphate, Mater. (Basel, Switzerland) 11 (1) (2018) 129.
cific characteristics that make them suitable for unique needs. In the AM [19] S. Esslinger, R. Gadow, Additive manufacturing of bioceramic scaffolds by combi-
nation of FDM and slip casting, J. Eur. Ceram. Soc. 40 (11) (2020) 3707–3713.
of bioceramics, there is no singular ‘best’ technique. Rather, it heavily [20] B.I. Oladapo, et al., 3D printing and morphological characterisation of polymeric
depends on the necessary constraints regarding a facility’s production composite scaffolds, Eng. Struct. 216 (2020) 110752.
and desired application. For example, smaller scale production could [21] U.K. Roopavath, et al., Optimization of extrusion based ceramic 3D printing process
for complex bony designs, Mater. Des. 162 (2019) 263–270.
be satisfied by the extrusion technique, whereas larger scale production [22] B. Cappi, et al., Direct inkjet printing of Si3N4: characterization of ink, green bodies
might require the binder jetting technique. and microstructure, J. Eur. Ceram. Soc. 28 (13) (2008) 2625–2628.
Furthermore, it is important to consider the microstructure, as well [23] B. Derby, Inkjet printing ceramics: from drops to solid, J. Eur. Ceram. Soc. 31 (14)
(2011) 2543–2550.
as the other material properties of the ceramics that are being printed.
[24] C. Ainsley, N. Reis, B. Derby, Freeform fabrication by controlled droplet deposition
Ceramic particle size and composition can affect overall homogeneity, of powder filled melts, J. Mater. Sci. 37 (15) (2002) 3155–3161.
porosity, and mechanical properties after sinterization. In addition, the [25] G.D. Martin, S.D. Hoath, I.M. Hutchings, Inkjet printing - the physics of manipulating
use of binder materials may also contribute to the stabilization of the liquid jets and drops, J. Phys. Conf. Ser. 105 (2008) 012001.
[26] P.F. Blazdell, J.R.G. Evans, Application of a continuous ink jet printer to solid
print and how the structure will hold after debinding. There are many freeforming of ceramics, J. Mater. Proc. Technol. 99 (1) (2000) 94–102.
more parameters to consider with each process, and further research is [27] J.A. Gonzalez, et al., Characterization of ceramic components fabricated using binder
needed to establish more standard protocols for controlling these param- jetting additive manufacturing technology, Ceram. Int. 42 (9) (2016) 10559–10564.
[28] A. Mostafaei, et al., Binder jet 3D printing-process parameters, materials, properties,
eters. A greater understanding of how bioceramic materials are affected modeling, and challenges, Prog. Mater. Sci. 119 (2021) 100707.
by the certain methods of an additive manufacturing process may help [29] M. Ziaee, N.B. Crane, Binder jetting: a review of process, materials, and methods,
understand and prevent prevalent issues like microcracking and distor- Additive. Manuf. 28 (2019) 781–801.
[30] X. Lv, et al., Binder jetting of ceramics: powders, binders, printing parameters, equip-
tion, as well as the tradeoff between bioactivity and desired mechanical ment, and post-treatment, Ceram. Int. 45 (10) (2019) 12609–12624.
properties. [31] F. Fina, et al., Selective laser sintering (SLS) 3D printing of medicines, Int. J. Pharm.
529 (1) (2017) 285–293.
[32] K.C.R. Kolan, et al., Effect of material, process parameters, and simulated body flu-
Declaration of Competing Interest ids on mechanical properties of 13-93 bioactive glass porous constructs made by
selective laser sintering, J. Mech. Behav. Biomed. Mater. 13 (2012) 14–24.
The authors declare that they have no known competing financial [33] C. Gao, et al., Enhancement mechanisms of graphene in nano-58S bioactive glass
scaffold: mechanical and biological performance, Sci. Rep. 4 (1) (2014) 4712.
interests or personal relationships that could have appeared to influence [34] C. Shuai, et al., Processing and characterization of laser sintered hydroxyapatite
the work reported in this paper. scaffold for tissue engineering, Biotechnol. Bioprocess Eng. 18 (3) (2013) 520–527.

51
M. Ly, S. Spinelli, S. Hays et al. Engineered Regeneration 3 (2022) 41–52

[35] J.P. Deckers, et al., Shaping ceramics through indirect selective laser sintering, Rapid [50] S. Tarafder, et al., Microwave-sintered 3D printed tricalcium phosphate scaffolds for
Prototyp. J. 22 (3) (2016) 544–558. bone tissue engineering, J. Tissue Eng. Regen. Med. 7 (8) (2013) 631–641.
[36] Z. Meng, et al., Design and additive manufacturing of flexible polycaprolactone scaf- [51] C. Shuai, et al., Optimization of TCP/HAP ratio for better properties of calcium
folds with highly-tunable mechanical properties for soft tissue engineering, Mater. phosphate scaffold via selective laser sintering, Mater. Charact. 77 (2013) 23–31.
Des. 189 (2020) 108508. [52] J. Ebert, et al., Direct inkjet printing of dental prostheses made of zirconia, J. Dent.
[37] R. Ganeriwala, T.I. Zohdi, Multiphysics modeling and simulation of selective laser Res. 88 (7) (2009) 673–676.
sintering manufacturing processes, Proced. CIRP 14 (2014) 299–304. [53] J. Wilkes, et al., Additive manufacturing of ZrO2-Al2O3 ceramic components by
[38] Zhang, H. and Leblanc S., Processing parameters for selective laser sintering or melt- selective laser melting, Rapid Prototyp. J. 19 (1) (2013) 51–57.
ing of oxide ceramics. 2018. [54] D. Anssari Moin, B. Hassan, D. Wismeijer, A novel approach for custom three-di-
[39] S.F.S. Shirazi, et al., A review on powder-based additive manufacturing for tissue en- mensional printing of a zirconia root analogue implant by digital light processing,
gineering: selective laser sintering and inkjet 3D printing, Sci. Technol. Adv. Mater. Clin. Oral Implants Res. 28 (6) (2017) 668–670.
16 (3) (2015) 033502. [55] S. Bose, S.F. Robertson, A. Bandyopadhyay, Surface modification of biomaterials and
[40] B. Qian, Z. Shen, Laser sintering of ceramics, J. Asian Ceram. Soc. 1 (4) (2013) biomedical devices using additive manufacturing, Acta Biomater. 66 (2018) 6–22.
315–321. [56] B.D. Boyan, et al., Role of material surfaces in regulating bone and cartilage cell
[41] Z. Chen, et al., 3D printing of ceramics: a review, J. Eur. Ceram. Soc. 39 (4) (2019) response, Biomaterials 17 (2) (1996) 137–146.
661–687. [57] G.M. Keegan, I.D. Learmonth, C.P. Case, Orthopaedic metals and their potential tox-
[42] Y. Zheng, et al., Cracks of alumina ceramics by selective laser melting, Ceram. Int. icity in the arthroplasty patient, J. Bone Joint Surg. Br. 89-B (5) (2007) 567–573
45 (1) (2019) 175–184. volume.
[43] M.L. Griffith, J.W. Halloran, Freeform Fabrication of Ceramics via Stereolithogra- [58] B. Heer, Y. Zhang, A. Bandyopadhyay, Additive manufacturing of alumina-silica re-
phy, J. Am. Ceram. Soc. 79 (10) (1996) 2601–2608. inforced Ti6Al4V for articulating surfaces of load-bearing implants, Ceram. Int. 47
[44] G.M Diptanshu, C. Ma, Vat photopolymerization 3D printing of ceramics: Effects of (13) (2021) 18875–18885.
fine powder, Manuf. Lett. 21 (2019) 20–23. [59] Y. Zhang, H. Sahasrabudhe, A. Bandyopadhyay, Additive manufacturing of Ti-Si-N
[45] F. Li, et al., Digital light processing 3D printing of ceramic shell for precision casting, ceramic coatings on titanium, Appl. Surf. Sci. 346 (2015) 428–437.
Mater. Lett. 276 (2020) 128037. [60] Huson, D. and Vaughan K., 3D printed ceramics: current challenges and future po-
[46] S. Li, et al., Additive manufacturing of SiBCN/Si3N4w composites from preceramic tential international conference on digital printing technologies, 2016. 2016.
polymers by digital light processing, RSC Adv., 10 (10) (2020) 5681–5689. [61] G. Konstantinou, et al., Additive micro-manufacturing of crack-free PDCs by
[47] R. He, et al., Fabrication of complex-shaped zirconia ceramic parts via a DLP- stere- two-photon polymerization of a single, low-shrinkage preceramic resin, Addit.
olithography-based 3D printing method, Ceram. Int. 44 (3) (2018) 3412–3416. Manuf. 35 (2020) 101343.
[48] G. Varghese, et al., Fabrication and characterisation of ceramics via low-cost DLP [62] Roach, M., et al. Mechanical challenges of 3d printing ceramics using digital light
3D printing, Bol. Soc. Esp. Cerám. Vidr. 57 (1) (2018) 9–18. processing. 2018. United States.
[49] M. Zhou, et al., Preparation of a defect-free alumina cutting tool via additive man-
ufacturing based on stereolithography – Optimization of the drying and debinding
processes, Ceram. Int. 42 (10) (2016) 11598–11602.

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