Accepted Manuscript

Binder jetting of ceramics: Powders, binders, printing parameters, equipment, and

post-treatment

Xinyuan Lv, Fang Ye, Laifei Cheng, Shangwu Fan, Yongsheng Liu

PII: S0272-8842(19)30822-3
DOI: https://doi.org/10.1016/j.ceramint.2019.04.012
Reference: CERI 21206

To appear in: Ceramics International

Received Date: 19 December 2018

Revised Date: 20 March 2019
Accepted Date: 1 April 2019

Please cite this article as: X. Lv, F. Ye, L. Cheng, S. Fan, Y. Liu, Binder jetting of ceramics: Powders,
binders, printing parameters, equipment, and post-treatment, Ceramics International (2019), doi: https://
doi.org/10.1016/j.ceramint.2019.04.012.

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Binder Jetting of Ceramics: Powders, Binders, Printing

Parameters, Equipment, and Post-Treatment

Xinyuan Lva, Fang Yea, Laifei Chenga,*, Shangwu Fana, Yongsheng Liua
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Science and Technology on Thermostructural Composite Materials Laboratory, Northwestern

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Polytechnical University, Xi’an, 710072, PR China

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∗ Corresponding author at: Science and Technology on Thermostructural Composite Materials

Laboratory, Northwestern Polytechnical University, Xi’an, 710072, PR China.

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Corresponding author E-mail address: chenglf@nwpu.edu.cn

Abstract
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Binder jetting is expected to become the universal process for preparing ceramic
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parts because it can overcome multiple problems, such as the difficulty to prepare
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complex-shaped ceramic parts and the shrinkage of the sintering process, which
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appear in conventional ceramic preparation process. This paper introduces principles,

steps, and applications of binder jetting printing ceramics. Furthermore, five key
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factors of binder jetting printing ceramics (powders, binders, printing parameters,

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equipment, and post-treatment process) have been investigated. Accordingly, effects

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of powders (including shape, particle size and distribution, and additives), binders

(including binding method, droplet-formation mechanism, and droplet-infiltration

kinetics), printing parameters (including layer thickness, saturation, solid binder, and

printing orientation), equipment, and post-treatment (including de-powdering process,

and densification process) on density, roughness, strength, accuracy, and resolution of

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ceramic parts have been discussed and summarized. This paper provides detailed

analysis of techniques and mechanisms of binder jetting of ceramics, giving guidance

on how to handle raw materials and select various processing parameters for

achieving desired performance.

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Keywords: Binder jetting; Powders; Binders; Printing parameters; Equipment;

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Post-treatment

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1. Introduction

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The American Society for Testing and Materials (ASTM) defines additive
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manufacturing (AM) as a layer-by-layer manufacturing method, which involves the
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addition of materials based on the data of a three-dimensional (3D) computer-aided

design (CAD) model [1]. AM is classified into seven categories as presented in Table
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1.
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AM can be used to fabricate parts of any complex shape without using molds and
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can rapidly fabricate small batch parts to shorten the development cycle, which

enables innovative ideas to be quickly realized [2-14]. AM is also cost-effective as it

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does not require molds and machining [4-8, 11, 14, 15]. These advantages have led to

the rapid development of AM since its emergence. It has found applications in the

fields of medical, automotive, aerospace, and architecture [2, 4, 5, 8, 9, 12, 14].

Ceramic materials exhibit many excellent properties, including high temperature

resistance, corrosion resistance, oxidation resistance, creep resistance, and high

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hardness, which make them play an unmatchable role in the fields of aerospace,

chemistry, metallurgy, electronics, machinery, and biomedical engineering. The

preparation process of ceramics involves two key steps of forming and sintering. The

conventional forming process is difficult to be used for manufacturing

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complex-shaped ceramic parts, whereas the requirement of molds makes the process

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cost intensive. On the other hand, the process of sintering causes shrinkage of final

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ceramic parts. Previous studies have shown that the multi-step AM, which refers to

the manufacturing process, in which various parts are fabricated in two or more steps,

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can solve these problems. The geometric shape of the parts can be obtained in the first
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step, while the desired material characteristics can be obtained post-treatment.
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Therefore, the ceramic raw materials can be first made into preforms of certain

geometrical shape using AM equipment and, then, combined with near-net size
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densification process, such as chemical vapor infiltration (CVI), precursor infiltration

and pyrolysis (PIP), reactive melt infiltration (RMI), or direct sintering to improve the
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strength and performance of the preforms. In analogy with the multi-step AM, the
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single-step AM refers to the manufacturing process, in which the parts can obtain
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desired geometrical shape and characteristics in a single step. Powder bed fusion

method is the only single-step AM method employed for preparing ceramics; however,

because of their high melting points, the method is not suitable for ceramics.

The above-mentioned seven AM methods can all prepare ceramic preforms.

However, binder jetting has distinct advantages compared to other methods. Firstly,
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the raw materials for binder jetting are ceramic powders, which are easier to prepare

than wires, sheets, or ceramic slurries. Secondly, for a particular application, raw

materials can be selected from a wide range of options. Theoretically, any ceramic

powder can be used to prepare ceramic preforms via the binder jetting method. Finally,

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binder jetting can also perform color printing, which renders the method vital and

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competitive with regards to other methods. In addition, as an AM method for multiple

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materials, binder jetting not only exerts its advantages when printing ceramics but

also is a major AM method for printing metals when combined with sintering [16-18]

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or sintering and infiltration processes [19-23]. The origin of binder jetting can be
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traced back to Emanual Sachs at the Massachusetts Institute of Technology (MIT),
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USA, who proposed the method in 1990 [24]. The method fabricates ceramic green

bodies by inkjet printing a binder phase onto a powder bed. Then, the binder phase
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collectively binds the ceramic powders where it has been printed and, finally, the

loose and unconsolidated ceramic powders are removed [25]. The schematic of binder
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jetting (Fig. 1) shows two principles, which are differentiated by the powder
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spreading mechanism: (a) a roller is used to spread powder through the height
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difference between the powder supply platform and the fabrication platform [5]; and

(b) a recoater is used to spread powder from a top hopper using vibration [17]. At

present, the ceramic parts fabricated using binder jetting involve bioceramics [26-61],

structural ceramics [28, 61-84], and functional ceramics [85-91].

However, the ceramic green body fabricated using binder jetting has low strength,
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whereas the ceramic parts have low accuracy. Previous studies have shown that the

accuracy and strength of ceramic parts are closely related to powder, binder, printing

parameters, equipment, and post-treatment. In the future, if the problem of accuracy

and strength can be solved, binder jetting can become a universal method for

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preparing ceramic parts, producing a preform of any complicated shape that does not

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shrink after post-treatment. Therefore, this paper will mainly focus on binder jetting,

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which is different from previous reviews on AM of ceramic parts [2, 4-7, 15, 25,

92-99], to assess the influence of the above-mentioned five factors on the

performance of ceramic parts.

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2. Steps and applications of binder jetting printing ceramics

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2.1 Steps
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The various steps involved in a typical binder jetting method for preparing

ceramic parts are shown in Fig. 2. The first step is the preparation of raw materials,
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which are powders. Different types of powders possess different shapes and
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physicochemical properties, whereas the printer's binder is usually non-optional. In

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order to make the powder and binder bond resistant while successfully spreading the

powder, the powder needs to be pretreated. Next, the as-prepared powders are printed

into a green body. Based on good binding of powder and binder and with the help of

the three-dimensional (3D) printing equipment and 3D graphics software, the

small-batch parts with arbitrarily complex shapes can be designed and manufactured.
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The third step is the strengthening of the green body. Even when the adhesion of

powder to binder is good, the strength of the green body is still relatively low. In some

cases, it is necessary to strengthen the green body in order to smoothly carry out the

subsequent steps. Usually, the green body is heated to a certain temperature (~

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200 °C), at which the binder will toughen the green body via polymerization,

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cross-linking, solvent evaporation, or some other mechanisms [7]. Afterward, the

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organics are removed via a de-binding process to obtain the preform. During the

de-bonding process, the heating rate, holding temperature, and holding time are

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controlled to ensure that the green body is subjected to low thermal stress. Finally, the
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ceramic parts are obtained after post-treatment. There are many post-treatment
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methods, including sintering, CVI [71], PIP [72], and RMI [61, 82]. The processing

parameters are controlled to obtain ceramic parts with the desired density,
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microstructure, strength, and functionalities.

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2.2 Applications
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Fig. 3 displays the current printable material and its application field. From the
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perspective of different applications, the ceramic materials produced using binder

jetting have made great progress in the field of biomedical engineering. Considering

hydroxyapatite [29, 30, 40-50, 56, 57, 100] and tricalcium phosphate (TCP) [31-39,

58-60] as representatives, the two materials have become the preferred choice for

bone substitute implants due to their excellent biocompatibility. The bone substitute
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implants printed using binder jetting have a complex shape and a loose, porous

internal structure, which are highly similar to those of human skeleton, and therefore,

have already been in use. According to technology readiness level (TRL), the research

on bioceramics has reached TRL8 (technology completed and qualified through tests

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and demonstrations). Nonetheless, further studies in this area still need to be

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conducted. For example, future work on obtaining the bone substitute implants with

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improved osteogenic capacity, biodegradability, bone repair capacity, and

osteoinductive activity by optimizing the composition and structure is still ongoing

[34, 40, 49, 58, 99].

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Although the structural ceramics printed using binder jetting are of types, they
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are still in TRL4 (component and/or validation in a laboratory environment). In this

regard, the Si [72, 84], SiC [70], plaster [79, 80], and TiC [61, 64, 69, 82, 83] powder
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materials have been used to print differently shaped parts. The density, strength, and

other properties of these parts, the difference between the adopted binder jetting
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process, and the traditional process have also been studied. The performance of many
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binder jetting printed structural ceramic parts has been compared with those of the
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parts prepared using traditional craftsmanship. However, their use is still limited in

terms of versatility, which implies researching advanced milling technology and

developing new binders matching the ceramic powders. Nevertheless, the structural

ceramic parts printed using binder jetting have great application potential in the fields

of mechanical design, toy entertainment, innovation education, and model production

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due to their low cost and rapid prototyping.

There are several types of printable materials that can achieve structural and

functional integration, including SiO2 [76-78, 87-89], Si3N4 [66, 71, 91], and Al2O3

[62, 63, 67, 68, 86-89]. The binder jetting method is less studied in the field of

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functional ceramics with the corresponding studies being in TRL4 as well. Si3N4

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exhibits excellent electromagnetic wave-transparent performance and is suitable for

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preparing some stealthy components with complex shapes. Al2O3 and SiO2 can act as

optical components with complex shapes. BaTiO3 [85, 90] can be used to make

ferroelectric dielectric capacitors.

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3. Determinants of binder jetting printing ceramics

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3.1 Powder
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The properties of the ceramic powders for binder jetting are particularly

important, especially the mechanical ones (flowability and bulk density). As shown in
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Fig. 4, the mechanical properties are influenced by the geometrical properties (shape
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and particle size distribution). Currently, the printable ceramic powders come in
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spherical and irregular shapes. However, the authors believe that the rod-like ceramic

powders also constitute a promising material, for example, whiskers can be used as

raw materials for binder jetting to fabricate a whisker-preform and, then, prepare

ceramic matrix composites (CMC). However, there is hardly any research on the

rod-like powders via binder jetting. The particle size distribution of the currently
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printable ceramic powders mainly includes monomodal and multi-modal distributions.

Sections 3.1.1, 3.1.2, and 3.1.3 will discuss the importance of mechanical and

geometrical properties of ceramic powders that mainly determine the properties of the

final ceramic parts.

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3.1.1 Flowability and bulk density of ceramic powders
To some extent, the flowability of ceramic powders determines their printability.

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An important step in the binder jetting process is to spread the powder. Whether each

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layer of ceramic powders can be evenly and smoothly spread determines if the
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ceramic parts can have a uniform and complete structure. If the flowability of the
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ceramic powders is not good, the powder will not be spread smoothly, the inside of

the ceramic parts will be defective, and the properties will be negatively affected. An
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improvement of flowability of ceramic powders can be achieved by controlling the

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shape and surface state. Currently, the methods used for controlling the shape and
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surface state are spray granulation [101-106] and surface coating modification,

respectively [107-110]. Furthermore, the addition of additives [111, 112] to ceramic

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powders can also contribute to enhancing their flowability.

The bulk density of ceramic powders mainly affects the composition and

performance of ceramic parts in the binder jetting process. When the ceramic powders

are printed, they are naturally deposited on the powder bed, whereas the powders are

not subjected to any extrusion. Therefore, the bulk density of ceramic powders
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approaches the green density according to Equation (1).

mg ρth
ρg ≈ (1)
ρb va

where mg is the mass of the green body, va is the apparent volume of the green body,

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whereas ρg, ρth, and ρb are the green density, theoretical density, and bulk density of

ceramic powders, respectively.

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For the ceramic parts densified using sintering, the green density will affect the

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sinterability, which represents the ability of a powder compact sintering and is

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assessed using Equation (2) [7].

ρs − ρ g
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ϕ= (2)
ρth − ρ g
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where φ is the sinterability, and ρg, ρs, and ρth are the green density, sintered

density, and theoretical density, respectively.

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For other near-net shape densification processes (CVI, PIP, and RMI), the bulk

density of ceramic powders will determine the volume fraction of the preform.
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Generally, the mechanical properties of as-prepared ceramics are enhanced when the
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volume fraction of preform is higher (25–40%). The volume fraction of the preform
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can be increased by increasing the bulk density of ceramic powders.

3.1.2 Shape of ceramic powders

The shape of ceramic powders mainly affects the flowability of powders, the tap

density, the powder bed (packing) density, the pore structure of the green body, and
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the contact mode between the particles. Generally speaking, spherical particles have

better flowability and higher tap densities than the irregular ones. However, during the

printing process, the powders will be slightly pressed by the spreading roller, which

means that the powders will not be compacted; thus, the contribution of spherical

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morphology to packing density will be reduced. In contrast, irregular powders have a

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relatively high packing density; Suwanprateeb et al. [45] reported that irregular

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hydroxyapatite has a higher packing density than spherical hydroxyapatite. As shown

in Fig. 5, this is because the spherical particles undergo a low uniaxial pressure, and

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their good flowability causes the particles to roll towards each other. Although the
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particles are re-arranged and slipped, they are still in point contact and, thus, cannot
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effectively reduce the pore volume. For irregular particles, after being re-arranged and

slipped, the larger internal friction causes them to combine and become compact,
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while the point contact between some of the particles becomes surface contact, which

can effectively reduce the pore volume. Therefore, the irregular powders will result in
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a higher green density than the spherically shaped ones. The green density is usually
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positively correlated with green strength. This higher green strength improves the
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handling characteristic of the as-fabricated green body.

In addition, the shape of ceramic powders has a great influence on the sintering

characteristics. Suwanprateeb [45] printed various parts using spherical and irregular

powders. After sintering at 1300 °C, the parts printed using irregular powders had 32%

higher sintered density than those obtained using spherical powders, whereas the
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porosity of parts from irregular powders was 20% lower than those from spherical

powders. Additionally, the flexural strength and modulus were almost doubled for

irregular powders than those of spherical ones. This is due to the reason that point

contact is not conducive to inter-particle sintering densification, whereas the surface

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contact facilitates the intra- and inter-particle sintering densification. It should be

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noted that the inter-particle pore structure of spherical particles is generally

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homogeneous, whereas it is mainly heterogeneous for irregular particles.

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3.1.3 Particle size and distribution of ceramic powders
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Binder jetting is a powder-based AM process. The particle size of the powder is
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usually between 0.2–200 µm [45, 113, 114]. The ideal particle size has not yet been

determined [39]. The particle size of the powder is a very important geometrical
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property, and its effect on the flowability of the powder, wettability with the binder,
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reactivity with the binder, surface roughness, resolution of the part, and the
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printability has been widely studied [39, 60, 115-123].

Generally, the fine powder has poor flowability, whereas the coarse powder
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exhibits good flowability. Many studies have reported that the quality of parts using

binder jetting is significantly different when coarse (≥ 20 µm) and fine (≤ 20 µm)

initial powders are used [120, 121]. Andre Butscher [60] used β-TCP to study the

effect of particle size on flowability. As shown in Fig. 6, as the median diameter

increased, the flowability became better. For dry powders with small particle size, the
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inter-particle force is dominated by van der Waals forces. [116]. For very fine

powders, these forces can even dominate gravitational forces and tend to form

irregular agglomerates, which significantly reduce flowability [39, 60]. Gravitational

forces are affected by density as well. Therefore, the particle size and density are the

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two critical factors affecting the flowability.

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Wettability is a key factor in the successful printing of binder jetting. The

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wettability of powders and binders are affected by many factors [124]. After the

droplets of binders are in contact with the ceramic particles, the droplets penetrate the

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pores through the ceramic particles under capillary force, and, at the same time, the
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ceramic particles around the droplets aggregate into a larger agglomerate under
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surface tension of the droplets [124]. As the droplets dry, the agglomerates are pulled

together more tightly. The ceramic particles in contact with the droplets are bound
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together. Therefore, the binders and the powders should have improved wettability,

which is beneficial to enhance mechanical properties and density of the green body.
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The wettability of fine powder may be low because it is easy to agglomerate.

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According to a previous study [60], the contact angle of coarse powder is small and
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presents good wettability, whereas the contact angle of fine powder is large and, thus,

corresponds to poor wettability (Fig. 7). In addition, the shape of ceramic powders,

the viscosity, and surface tension of the binders have a significant influence on the

wettability [60]. Irregularly ceramic powders have higher wettability because they

generally bind across the large flat faces with binder wetting, while spherical ceramic
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powders can only be bound together across a small amount of contact points with the

necks between the ceramic powders [124]. The viscosity of binders is required to be

as low as possible to facilitate the binder wetting with ceramic powders since low

viscosity binders penetrate more easily into the pores between the ceramic powders.

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Moreover, the binders with relatively large surface tension have better wettability,

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which can make the green body have higher density and strength [124].

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The reactivity of the powders with binders is also a crucial factor for the

successful printing of binder jetting. In theory, high specific surface area promotes

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high powder-binder reactivity [60], and, as a consequence, fine powder should be
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preferred. However, it turns out that the powder-binder reactivity of fine powder is not
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high. A previous study [39] demonstrated that the particle size affects the size and

distribution of voids in the powder bed (Fig. 8). The fine powder is easily
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agglomerated, thereby forming a large number of macro-voids inside the powder bed

since the binder droplets tend to flow through micro-voids through capillary forces.
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An increase in the radius of pores results in a decrease in the curvature of the flow
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front, which causes the droplet to significantly decelerate and even stop flowing into
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large pores [39]. In this case, the droplets of the binder must flow through micro-voids

around the macro-voids, leading to increased droplet penetration times. Slow

penetration rates delay the reaction of powder with the binder, affecting the

powder-binder interaction between adjacent layers and ultimately resulting in a low

printing resolution.
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Both the resolution and surface roughness constitute the essential criteria for

evaluating the properties of parts, whereas the powder size has an impact on the

resolution and surface roughness of the ceramic parts. The maximum particle size

determines the minimum layer thickness and resolution. Usually, fine powders have

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high resolution, while coarse powders exhibit low resolution. In order to facilitate the

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flow, the resolution should be at least twice the particle size [115], while the layer

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thickness is generally thrice the particle size [118]. In addition, Butscher [60] studied

the variations in particle size and surface roughness of parts (Fig. 9). The parts made

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from coarse powders showed high surface roughness, whereas fine powders also
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exhibited high surface roughness due to agglomeration. Only when the particle size
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was moderate (in the median range of coarse and fine particles), the surface roughness

of the obtained part was at the minimum.

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On the other hand, the particle size distribution also plays an important role in

the binder jetting process. The multi-modal powders are usually the mixture of fine
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and coarse powders in a certain ratio, whereas the fine powders are used to fill the
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gaps among coarse powders. Therefore, the overall packing density increases as well
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as the mechanical properties of the part are improved. Increasing the packing density

of the powder is also the main purpose of particle size gradation. It is well known that

the relative density of the part printed using binder jetting is very low, which leads to

low strength and difficulty in removing the powder [122, 125-128]. Furthermore,

particle size gradation is considered to be an effective way to overcome this problem

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[54]. Sun [54] studied the effect of the particle size distribution on the density and

mechanical properties of glass-ceramic materials (Fig. 10). After the sintering step,

the density and flexural strength of the part were determined to be 1.45 g/cm3 and 3.5

MPa, respectively, with a monomodal powder size of 45–100 µm. When mixed with

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40 wt.% of powders with the size of 1–25 µm, the density and flexural strength of the

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part increased to 1.60 g/cm3 and 13.8 MPa, respectively.

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In short, although there is currently no consensus about the optimal particle

shape, particle size, and particle size distribution of powders for binder jetting, it can

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be qualitatively concluded that the relationship among the properties of ceramic
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powders and the properties of ceramic parts is similar to the bucket effect. The
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powder's flowability, wettability, bulk density, and other properties determine the

properties of ceramic parts. It seems that it is not necessary to optimize all the
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properties of the powder. Instead, more attention should be paid to improve the lower

limit of the overall properties of the powder.

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3.1.4 Additives
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Adding different additives to the ceramic powders can also improve the

performance of ceramic parts by changing the composition and properties of the

powders. The addition of lecithin ensures the desired shape of parts and reduces the

flying of powders during printing [111]. The addition of SiO2 increases the packing

density of overall powders, reduces the voids between powders, and promotes the
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penetration of binders [111]. The addition of polyvinyl alcohol or cellulose reinforces

the powder bed [111], while the addition of Al2O3 or talc increases the flowability of

powders [112]. Adding an additive is relatively simple to implement; however, the

development of additives is unfortunately difficult. In addition, many additives are

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difficult to be removed after printing, which is undesirable for the parts, and require

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accurate control of composition. Furthermore, the addition of additives can reduce the

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packing density of base powders, thus leading to new issues, which would require

further challenge to be tackled.

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3.2 Binders
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Binder jetting is based on droplet jetting and powder bonding. Both the physical

and chemical properties of binders have a significant influence on the quality of

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ceramic parts. Therefore, Sections 3.2.2 and 3.2.3 will focus on the formation
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mechanism of binder droplets and droplet-infiltration kinetics.

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3.2.1 Binding method of the powder-binder

Table 2 presents the classification of binders for binder jetting. Binders can be
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divided into liquid binders and solid binders. Liquid binders can be further divided

into three types. The first type is a binder that cannot bond powder and triggers

powder reaction. The second type is a binder that has its binding effect. The third type

is a binder that can react with powders. Solid binders cannot be used alone and are
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usually used in combination with the first type of liquid binders. In order to meet the

performance requirements of the final ceramic parts, it is often necessary to add

additives, such as a coagulant, a flow promoter, a moisturizer, a lubricant, and a pH

adjuster to binders.

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Currently, the use of the first type of liquid binders in combination with solid

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binders is the most common. There are two types of combinations for these two

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binders. The first type is called the binder pre-mixing, which means that the solid

binder particles are mixed with ceramic powders, then milled and sieved. In this way,

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the powder feedstocks become a mixture of ceramic powders and solid binder
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particles [27, 64, 69]. The second type is called the binder pre-coating, which
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represents the dispersion of ceramic powders and solid binder particles in water,

followed by spray-drying [56] or drying, milling and sieving [61, 62, 67, 129].
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Additionally, ceramic powders with a surface coated with solid binder can be obtained.

When the liquid binder has been jetted, it triggers a binding reaction between the solid
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binder and the ceramic powders, strengthening the green body.

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3.2.2 Droplet-formation mechanism and design principles

Currently, the binders in use are not very versatile. For different kinds of ceramic

powders, the use of the same binder cannot ensure suitable strength and subsequent

operations (such as a de-powdering process) of the green body. In order to enable

more kinds of ceramic powders to be successfully printed, designing a new type of

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binder is a fundamental solution to the problem. The designing of the binder must

conform to certain principles in order to be printable: indeed, the binder must be able

to form droplets repeatedly and regularly at a certain frequency. Derby [92]

summarized these principles and reported that the fluid’s physical properties and the

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binder’s rheological properties should be within the proper range to achieve the

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desired results.

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Derby [92] pointed out that the behavior of binder droplets is mainly affected by

three physical parameters, namely the Reynolds number (Re), Weber number (We),

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and Ohnesorge number (Oh), which are given by Equations (3), (4), and (5),
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respectively.

vρ a
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Re = , (3)
η
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v2 ρ a
We = , (4)
γ
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We η
Oh = = , (5)
(γρ a )1 2
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Re

where ρ, η, and γ are the density, dynamic viscosity, and surface tension of binder
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drops, respectively, whereas v is the velocity, and a is the characteristic length.

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Fromm [130] first studied the droplet-formation mechanism and defined the

parameter Z=1/Oh to describe the printability of the binder. Reis and Derby [131]

further investigated the printable Z value interval, (10>Z>1) and reported that, when

Z<1, viscous dissipation prevents the ejection of droplets, whereas when Z>10, a large

number of satellite droplets (Fig. 11) are generated, which are accompanied by the
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ejection of the main droplets [132].

In addition, Derby [92] also pointed out two other conditions for the binder to

stabilize printing. The first condition is that the droplets must have a minimum speed

to overcome the surface tension and, thus, to be ejected from the nozzle [133]. This

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speed can be expressed based upon the minimum We and can be calculated using

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Equations (6) and (7).

4γ 1 2

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vmin = ( ) , (6)
ρ dn
ρ dn 1 2
We = vmin ( ) ＞4, (7)

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λ
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where dn is the nozzle diameter.

The second condition is that the droplets must have a maximum velocity to avoid
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splashing. Stow and Hadfield [134] proposed thresholds for droplet splashing, as
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represented by Equation (8).

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We1 2 Re1 4 ＞ f ( R) (8)

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where f(R) is the function of surface roughness.

Equations (5)–(8) define a parameter interval according to the Re and We values

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for the printability of droplets (Fig. 12) [92]. The parameter Z provides an effective
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guide for the design of binders. Nevertheless, it should be noted that the above

analysis assumes that the binder is a Newtonian fluid.

From the perspective of versatility, it is a challenge for binder jetting to print

different kinds of ceramic powders with sufficient green strength. To a large extent,

the green strength also depends on the strength provided by the binder. Due to this
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reason, the versatility of binder jetting depends on the versatility of the binder itself.

However, based on the droplet-formation mechanism, the composition of the binder

can be tuned according to the requirements. Zhao [73] used a mixed slurry of

nano-zirconia and ethanol as a binder to print calcium oxide (CaO). Unlike ordinary

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binders, a ceramic phase was introduced into the binder. The nano-zirconia can fill the

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voids of the green body and is sintered to form a high-melting-point CaZrO3 layer on

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the surface of CaO, which improves the hydration resistance of the ceramic parts.

Therefore, the versatility of the binder can be improved by optimizing the type and

content of various components.

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3.2.3 Droplet-infiltration kinetics

After the droplets have been ejected from the nozzle, a series of infiltration
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kinetic behaviors will occur, including impact, spreading, wetting, and penetration of
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droplets in powders. The droplet-infiltration kinetic behaviors are an important basis

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for optimizing the printing parameters and are a comprehensive reflection of powder

properties, binder properties, equipment construction, and printing parameters.

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Therefore, the droplet-infiltration kinetics is closely related to the roughness and

resolution of ceramic parts, while the rough surface and low resolution are also issues

that have not yet been effectively solved.

The impact of droplets on powders is very complicated since this process is

related to many factors, including droplet volume, initial velocity, viscosity, and
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roughness of the powder bed. The entire process is affected by inertial forces, surface

tension, and viscous forces. Agland [135] divided the impact of droplets on powders

into five types (Fig. 13). The value of We number of droplets increases from Fig. 13(a)

to 13(e).

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Range et al. [136] showed that, when We > 1000, the droplets splash and, thus,

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destroy the powder bed surface, due to which the properties of ceramic parts will be

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remarkably reduced. Therefore, droplet splashing must be avoided. To this end, Stow

and Hadfield [137] proposed a splash coefficient, K, as a criterion for whether the

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droplets would splash or not. The splash coefficient is given by Equation (9).
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1 1
K = We 2 Re 4 (9)
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At the same time, the discrimination coefficient Kc was also specified. When K <

Kc, splashing does not occur. Furthermore, rougher the surfaces is, smaller the Kc is,
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and easier it is for splashing to occur.

The spreading and wetting of droplets refer to the process, in which the radius of
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droplets gradually increases to maximum spreading radius. Mao [138] studied the
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spreading of droplets under different droplet velocities, viscosities, contact angles,

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and volumes. The results show that the viscosity and velocity of droplets have the

greatest influence on the maximum spreading radius. Fard [139] established a model

for the spreading process of droplets from the perspective of energy conservation. The

initial energy of the droplets is equal to the energy at any time during the spreading

process and is given by Equation (10).

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E1k + E1s = E 2d + E 2s (10)

The initial energy is the sum of the droplet kinetic energy E1k and the surface

energy E1s, whereas the energy during the spreading process is the sum of diffusion

energy E2d and the surface energy E2s. After calculations, the maximum spreading

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coefficient ζ of the droplets can be obtained (Equation (11)).

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d max We + 12 1
ζ= =[ ]2 (11)
d0 3(1 − cos θ ) + 4(We Re )

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where dmax is the maximum spreading diameter, d0 is the initial diameter of the

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droplets, and θ is the contact angle of the droplets with powders, respectively. The
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spreading coefficient ζ reflects the final shape of droplets, which can help determine

the DPI (number of dots printed per inch) of the nozzle.

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Bechtel [140] calculated the droplet-spreading time based on numerical

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simulations and proposed the following Equation (12).

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ρ d03
tspread = (12)
γ
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where all terms carry the same meaning and units as defined previously. Usually
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tspread <100 µs, which shows that the spreading of droplets is a very rapid process.
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Finally, the droplets penetrate the powders. Penetration refers to the process of

penetrating down to the maximum penetration depth after the droplets have been

spread. Fan [141] used a mathematical model to assess the penetration depth of

droplets in powders. Assuming that the droplets are Newtonian fluid and the inertial

forces are ignored, the penetration of droplets is believed to be caused by capillary

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forces and pressure gradients. The flow of droplets in a single pore can be simplified

to the model shown in Fig. 14. According to the Yang-Laplace equation and the

momentum conservation of the system, the penetration depth z can be calculated

using Equation (13).

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d 2 z dv Ap( z ) dz
2
= =− [ ρb ( ) 2 − F ( z )] (13)
dt dt m( z ) dt

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where Ap(z) is the size of the contact area, m(z) is the mass of the powders in the

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permeate zone, ρb is the average density of the powders, and F(z) is the resistance of

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the particles to the droplets. AN
It can be seen from Equation (13) that the penetration depth is mainly related to

droplet velocity and penetration resistance. The penetration resistance is mainly

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related to the porosity, shape, and packing density of the powders. Furthermore, the
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larger the porosity, the smaller is the penetration resistance. Similarly, smaller the
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packing density, lower is the penetration resistance. More spherical the powders,
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smaller is the penetration resistance.

For the penetration time, Lepoutre [142] analyzed the powders having uneven
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porosity and proposed Equation (14) to calculate the penetration time, as follows:
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Vτ 2µ
t penetration = ( )2 (14)
ε rγ cos θ

where V is the volume of the droplets penetrated in powders, ε is the porosity of

powders, r is the radius of the capillary, and τ is the unevenness coefficient of the

pores.
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The droplet-penetration time is usually 0.1–1 s. While the droplets are infiltrating,

the physical/chemical reactions are also carried out to dissolve or solidify the powders.

The research on the droplets infiltration kinetics can provide guidance to determine

the layer thickness and the time spent on each layer.

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3.3 Printing parameters
The core process of binder jetting is to use binders to precisely bind the powders.

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Numerous studies have shown that various printing parameters, such as layer

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thickness, binder saturation, volume fraction of solid binder, and printing orientation,
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have important effects on the core process, which in turn affects the accuracy, density,
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and strength of ceramic parts. Sections 3.3.1, 3.3.2, 3.3.3, and 3.3.4 will discuss the

effect of these printing parameters on the properties of ceramic parts.

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3.3.1 Layer thickness

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Layer thickness should be selected according to the particle size of ceramic

powders. Firstly, layer thickness should be higher than the maximum particle size of
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the ceramic powders [143]. Secondly, Sachs [144] proposed that layer thickness
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would be at least three times the particle size of ceramic powders to facilitate the flow.

Of course, it is also possible to prepare ceramic powders with suitable particle size

and matching the layer thickness.

Smale [46] used plaster to study the effect of layer thickness on the flexural
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strength and green density (Fig. 15). When the layer thickness is 200 µm, the flexural

strength of the green body suddenly drops, whereas the macro-photograph (shown in

Fig. 16) shows that the green body has disintegrated. However, the macro-photograph

analysis also suggests that the effect of layer thickness on the properties of the green

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body should be understood from the perspective of droplet-infiltration kinetics. For

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the same binder saturation, increasing the layer thickness results in insufficient

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binders to completely penetrate the current layer. Therefore, unpenetrated powders

will not bind together and lead to the disintegration of the green body. However, when

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the layer thickness is increased while increasing the binder saturation, the strength of
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the green body not obviously improves [46]. This is presumably because the
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penetration of binders proceeds simultaneously in the transverse and longitudinal

directions. However, not all of the increased amount of binders penetrates along the
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longitudinal direction. Moreover, excessive binders can result in the collapse and

deformation of the surface of the powder bed, which can seriously affect the accuracy
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and strength of ceramic parts. Therefore, the layer thickness should not be too large.
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According to the literature [46, 145-150], the properties of the green body are the
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most favorable when the layer thickness is in the range of 80–130 µm.

3.3.2 Binder saturation

Binder saturation (Ps) is defined as the ratio of the volume of jetted binders

(Vbinder) to the pore volume of the powder bed (Vair) in each layer (Equation (15)).
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Vbinder
Ps = (15)
Vair

Specifically, the binder saturation can be distinguished in shell saturation and

core saturation. The printer software divides each layer into two parts: the shell and

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the core (Fig. 17) [151]. The shell has high saturation, whereas the core has low

saturation. The default binder saturations level of shell and core are both 100%,

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whereas the corresponding shell and core saturations value are 0.23 and 0.12

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[152-154]. The purpose of dividing each layer into shell and core is to reduce the

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printing time, provide sufficient stability, and prevent oversaturation. However, the
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default binder saturation is usually not optimal with regards to the properties of the

green body and ceramic parts. Pereira [151] studied the effect of shell/core saturation
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on the properties of ceramic parts (Table 3). The results presented in Table 3 show that,
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within a certain range, as the shell/core saturation increases, both the bulk density and
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the compressive strength increase as well, whereas the porosity decreases. Similar
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results were reported in some other studies [46, 147]. According to Pereira [151], the

effect of binder saturation on the properties of ceramic parts is derived from its ability
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to promote the densification of the previous layer. As shown in Fig. 18, the binders
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deposited on the current layer (n) can drag ceramic powders into voids of the previous

layer (n-1). For low saturation situations, this phenomenon is insignificant.

Therefore, increasing the shell/core saturation within a certain range can improve

the mechanical properties of the green body and ceramic parts. However, it was found

that, as the binder saturation increases, the accuracy of ceramic parts decreases
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[149-151]. Therefore, finding the optimal binder saturation lies in finding the balance

between the accuracy and the mechanical properties of ceramic parts.

3.3.3 Volume fraction of solid binders

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Usually, liquid binders are used in combination with solid binders with the

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volume fraction of solid binders affecting the strength of ceramic parts.

Chumnanklang [56] prepared hydroxyapatite powders using pre-coating and studied

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the green strength and sintered strength under different volume fractions of solid

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binders (Fig. 19). Fig. 19 shows that, as the volume fraction of solid binders increases,
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both the green and sintered strengths of the ceramic parts increase as well.
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3.3.4 Printing orientation

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The fabricating direction of binder jetting is fixed in the Z direction. However,

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the parts can be placed in different orientations. For example, printing a rectangular
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part has at least three different placement orientations, as shown in Fig. 20.

Many studies [145, 146, 148-150] have shown that the ceramic parts with
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different printing orientations result in different properties. Castilho [148] pointed out
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that the printing orientation has a significant effect on the mechanical properties;

however, it has a slight impact on accuracy. Castilho [148] printed a cylinder in three

orientations to discover that the compressive strength is 13.18 MPa when the height

orientation (maximum scale orientation) is parallel to X-axis. Additionally, the value

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of compressive strength is 19.07 MPa when the height orientation is along the Y-axis.

Lastly, the value of compressive strength is 14.38 MPa when the height orientation is

along the Z-axis. It is worth mentioning that the Y-axis orientation of the printer used

by Castilho is the printhead moving orientation when it works. Similar results were

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reported in other studies [145, 146]. Mitra [146] explained this phenomenon

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according to the principle shown in Fig. 21. Indeed, the Z-printed parts have a smaller

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contact area of the successive layer than the X and Y orientations, which results in a

lower mechanical strength. Additionally, the X-printed parts have a larger bonding

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area along the cylindrical section than the Y-printed parts, which results in a higher
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integrity of successive layers and increases the mechanical strength. Furthermore, the
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X-axis orientation of the printer used by Mitra is the moving orientation of the

printhead.
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Li [149] investigated the effect of different printing orientations on surface

roughness. The results show that the planes parallel to the X-Y plane have lower
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surface roughness regardless of how the ceramic parts are placed. Other surfaces,
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especially the bevels, have greater surface roughness due to step effects, which are
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difficult to avoid.

Due to the variety of shapes of parts, it is difficult to propose a general theory for

optimal printing orientation. However, based on the qualitative analysis, two

principles can be formulated. Firstly, the X-Y plane should have the largest

cross-section area of the parts, and the maximum dimension orientation of this plane
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should be parallel to the moving orientation of the printhead, which can facilitate the

increase in mechanical strength of the ceramic parts. Secondly, the surfaces that

require a lower surface roughness should be parallel to the X-Y plane.

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3.4 Equipment

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With the invention and development of the binder jetting method, the binder

jetting equipment is continuously developing. Companies currently producing binder

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jetting equipment mainly include 3D Systems Inc. (California, USA), ExOne

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Americas LLC (Pennsylvania, USA) and Voxeljet AG (Friedberg, Germany).
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Summarizing the development of the past two decades, it has been found that the
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equipment determines the lower limit of the function and quality of the printed parts.

Table 4 presents the evolution of binder jetting equipment [155].

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Z Corporation (acquired by 3D Systems) designed and manufactured the first

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commercial color printer. Later, 3D Systems introduced a printer called ZPrinter850,

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which had five extruders and could produce 390,000 kinds of colors [156]. The

advent of color printers has greatly expanded the field of application of 3D printers,
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enabling them to create more realistic prototypes and directly manufacture products,

such as color toys and sand tables, without needing any subsequent coloring steps.

Multi-material additive manufacturing (MMAM) is a feature trending in 3D

printing equipment in recent years. For binder jetting, MMAM can be performed for

both the binder and the powder [93]. Beaman et al. [157] designed a two-binder
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system for binder jetting technology, in which one binder was traditional, while the

other one was carbon laden. This second material component (carbon) is introduced

into the powder layer. Sheydaeian et al. [158] designed a porogen insertion

mechanism (PIM) system (shown in Fig. 22), which selectively encapsulated

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sacrificial material particles into the powder layer to achieve the co-printing of two

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powder materials. Multi-material printers further expand the fields of application of

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3D printers, which makes it possible to print functionally graded materials (FGMs).

VXC800, produced by Voxeljet Company, is an infinitely continuous printer,

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which meets the requirement of mass production. In comparison, other printers can
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only produce small batch parts.
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In addition, the concept of hybrid AM has spawned new 3D printers. In 2000,

Objet Company invented the Polyjet technology, whose operating principle is similar
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to the combination of 3DP and stereolithography apparatus (SLA). Unlike the 3DP

technology, it sprays a photosensitive material and, then, cures it using ultraviolet

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light. This Polyjet technology enables colored multi-material printing and is a very
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popular AM technology.
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The above discussion shows that the equipment has a certain impact on the

function of printed parts, which means that powerful equipment can print more robust

parts.
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3.5 Post-treatment process

Binder jetting is a multi-step AM process. The as-printed parts usually obtained

the desired shape and size, but their mechanical properties are often insufficient. The

post-treatment process can give the desired properties and characteristics to the green

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parts. Post-treatment process mainly includes de-powdering and densification

processes. De-powdering process refers to the process of removing powders around

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green parts, and then, taking out the green parts. De-powdering has a significant effect

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on the surface roughness of ceramic parts, as this may distort the surface topography,

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such as residual or missing powder [60]. Although sintering is the most common
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densification method for binder jetting, there are also a few studies using CVI, PIP, or

RMI for densification. Sintering can quickly densify ceramic parts, saving time, but it
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inevitably shrinks. CVI, PIP, and RMI are near-net size densification processes that
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draw on the method of preparing CMC. However, the authors believe that the
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densification processes that best match the binder jetting are CVI, PIP, and RMI.
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Indeed, as an AM method, the most obvious advantage of binder jetting is that it can

easily prepare complex-shaped ceramic parts in near-net size. However, the shrinkage
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caused by sintering can destroy the expected size or shape.

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3.5.1 De-powdering process

The de-powdering process is a challenge for binder jetting in most cases,

especially for the parts having fine internal structures or complex cavities due to the

low strength of green parts. Therefore, it is necessary to develop solutions to resolve

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this problem.

Tancred [159] used the de-powdering method of applying force throughout the

vibration when printing hydroxyapatite and β-TCP. Sophie [100] printed

hydroxyapatite using binder jetting, whereas the de-powdering process was performed

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using compressed air directed using a syringe needle attached to the airbrush

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compressor. The patent of Sachs [160] provides a de-powdering method of boiling

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fluid inside the internal channels.

In addition, people can encapsulate sacrificial porogen particles at selected points

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of each layer during printing, which fills the cavity inside the part and makes
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de-powdering easier. However, this method requires the removal of porogen via
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multiple methods, such as leaching, dissolving or heat treatment [161-166].

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3.5.2 Densification process

Sintered density and shrinkage are common indicators for evaluating the
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sintering process performance. Sintering parameters, such as sintering temperature,

holding time, and heating rate, have crucial effects on the sintering behavior. Miyanaji
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et al.[26] studied the effects of these sintering parameters on the porosity and linear

shrinkage of parts using dental porcelain ceramics. The optimum sintering parameters

can be obtained by several sets of orthogonal experiments. However, the most

important factor for sintering is the self-characteristics of ceramic powders. The size

[19], shape [16, 45], and chemistry [16, 19] of ceramic powders have a significant
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impact on the sintering kinetics. Solid state sintering is driven by a reduction in

surface energy per unit volume; in other words, small size powders densify at a high

rate [19]. Nandwana [19] combined experiments and formulas to conclude that

smaller size particles would produce greater shrinkage during sintering. As mentioned

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in Section 3.1.2, the shape of ceramic powders also affects the sintering behavior.

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Previous studies [16, 45] have shown that irregular particles have a larger contact area

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(surface contact) than spherical particles (point contact) and, thus, favor the sintering

behavior (Fig. 5). Therefore, some researchers [128] tried to encapsulate spherical

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crystalline alumina particles into an amorphous alumina phase via the sol-gel process,
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as shown in Fig. 23. The spherical alumina as a core is designed to facilitate the flow,
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while an amorphous alumina shell promotes sintering. It was found that these

encapsulated particles enhance necking and increase diameter shrinkage. In fact,

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particle size and shape together determine the packing density, whereas lower packing

density results in weak bonding of particles and then in lower sintered density [16]. In
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addition, the presence of impurities on the surface of particles also affects the
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sintering behavior, resulting in low sintered density [16].

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Feng [71] employed binder jetting to print porous Si3N4 ceramics and, then,

introduced SiC matrix into porous ceramics via CVI to fabricate Si3N4-SiC composite

ceramics. SiC matrix prepared via CVI has high modulus, high purity, and high

temperature resistance. The infiltration time of SiC matrix is a major factor affecting

the performance of ceramics due to variation in the content of SiC matrix in ceramics
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with time. As shown in Fig. 24, when the infiltration time increases from 0 to 240 h,

the porosity decreases from 78% to 18%, while the volume fraction of the introduced

SiC matrix finally reaches the value of 59.5%.

Nan [61] printed TiC ceramics using binder jetting and introduced Si into TiC

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ceramics via RMI, finally fabricating Ti3SiC2-based ceramics. The parts made using

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RMI are usually highly densified. The infiltration temperature is an important factor

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affecting the performance of the parts. As shown in Fig. 25, when the infiltration

temperature is raised from 1600 °C to 1700 °C, the open porosity of the part is

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reduced from 8% to 2.4%, while the flexural strength is increased from 52 MPa to
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293 MPa.
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Duan [72] printed Si preform using binder jetting. The Si preform reacted with

nitrogen, and, then, polysiloxane (PSO) was introduced via PIP to finally prepare
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Si3N4-SiOC ceramics. PIP can be carried out at a lower preparation temperature to

modulate the composition of the precursor. The preparation temperature and the
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number of cycles are the major influencing factors of PIP. As shown in Fig. 26, with
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the increase in the PIP number of cycles from 1 to 4, the electrical conductivity (σdc)
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of Si3N4-SiOC ceramics significantly increases from 0.36 S/m to 45.3 S/m.

4. Future Challenges
Although research on binder jetting of ceramics has made great progress in

recent years, there are still many problems and new challenges needing further effort.
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These problems and challenges mainly originate from the five key factors of binder

jetting printing ceramics, as summarized below.

(1) Ceramic powders: There are very few types of ceramic powders that can be

printed at the moment, therefore, limiting the use of binder jetting technology in other

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fields. Ceramic milling technology has some disadvantages as well. A more advanced

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milling process to produce ceramic powders having excellent overall performance is

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urgently needed. Such a milling process should better match the binder jetting

technology and expand the types of printable ceramics.

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(2) Binders: At present, the strength of the green body printed using binder
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jetting is usually very low, which is related to the bonding force between the powders
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and the binders. It is necessary to develop a binder to achieve stronger powder

binding. On the other hand, a new binding mechanism needs to be explored. In order
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to obtain a high-strength green body, the addition of a monomer and a crosslinking

agent to binders, mixing the initiator with powders, and, then, initiating a crosslinking
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reaction at room temperature or after heating to cure the ceramic parts could prove
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helpful.
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(3) Printing parameters: The printing parameters have an effect on the binder

jetting of ceramics. In order to find the optimal printing parameters for printing a

certain ceramic powder, computer simulations need to be conducted and combined

with experiments. The essence of simulating the optimal printing parameters is to

establish the relationship between printing parameters and ceramic parts’ performance.
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In this regard, some work is currently ongoing

(4) Equipment: There is no doubt that the function of equipment often

determines the lower limit of the performance of ceramic parts. In recent decades,

various equipment of binder jetting has been continuously improved; however, some

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deficiencies still remain to be addressed in this regard. Developing more advanced

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equipment is a sign of progress in the 3D printing industry.

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(5) Post-treatment process: Post-treatment is independent of the AM process but

of great importance to binder jetting of ceramics. It is necessary to find a way to

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strengthen the green body so that it can be de-powdered and removed. It is also
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essential to develop near-net shape densification processes, such as CVI, PIP, and
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RMI to improve the properties of ceramics and extend their application field.
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5. Conclusions
This paper reviews the research progress in the field of binder jetting of ceramics
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in recent years from the perspective of technology and mechanism. The

developmental status of fabricating ceramic parts (including bioceramics, structural

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ceramics, and functional ceramics) using binder jetting was summarized. It was

pointed out that fabricating ceramic parts using binder jetting involves five key factors

(powders, binders, printing parameters, equipment, and post-treatment). The effect of

the properties of ceramic powders (including flowability, bulk density, and wettability)

on ceramic parts is similar to the bucket effect. More attention should be paid to
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improving the lower limit of the overall properties of ceramic powders. The binder

infiltration kinetics behaviors directly affect the strength and accuracy of the green

body, which in turn affects the properties of ceramic parts. Those behaviors are

affected by the properties of ceramic powders and printing parameters. Additionally,

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the composition of binders can be designed according to the formation mechanism of

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droplets and the printability principle. Printing parameters should be selected and

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tuned based on the properties of the ceramic powders and binder-infiltration kinetic

behaviors. The equipment can determine the lower limit of the functions and

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properties of ceramic parts as well. As the final step, the post-treatment process can
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greatly increase the strength of ceramic parts, making them more suitable for practical
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applications. Finally, several suggestions have been made to further develop binder

jetting printing ceramics.

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Acknowledgments
The authors acknowledge the financial supports from the National Key R&D

Program of China (Nos. 2017YFB1103500 and 2017YFB1103501) and the Chinese

National Foundation for Natural Sciences under the Contracts Nos.51632007 and

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51672218.

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Reference

[1] ISO/ASTM, 17296 Standard on Additive Manufacturing (AM) Technologies.

[2] M. Upadhyay, T. Sivarupan, M.E. Mansori, 3D printing for rapid sand casting—A review, Journal of
Manufacturing Processes, 29 (2017) 211-220.
[3] P. Kulkarni, A. Marsan, D. Dutta, A review of process planning techniques in layered manufacturing,
Rapid Prototyping Journal, 6 (2000) 18-35.

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[4] R.D. Farahani, M. Dubã©, D. Therriault, Three-Dimensional Printing of Multifunctional
Nanocomposites: Manufacturing Techniques and Applications, Advanced Materials, 28 (2016)
5794-5821.

RI
[5] T.D. Ngo, A. Kashani, G. Imbalzano, K.T.Q. Nguyen, D. Hui, Additive manufacturing (3D printing): A
review of materials, methods, applications and challenges, Composites Part B Engineering, 143 (2018).

SC
[6] N. Travitzky, A. Bonet, B. Dermeik, T. Fey, I. Filbert‐Demut, L. Schlier, T. Schlordt, P. Greil, Additive
Manufacturing of Ceramic‐Based Materials, Advanced Engineering Materials, 16 (2014) 729-754.
[7] W. Du, X. Ren, C. Ma, Z. Pei, Binder Jetting Additive Manufacturing of Ceramics: A Literature Review,

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ASME 2017 International Mechanical Engineering Congress and Exposition, 2017, pp. V014T007A006.
[8] L. Ferrage, G. Bertrand, P. Lenormand, D. Grossin, B. Ben-Nissan, A review of the additive
AN
manufacturing (3DP) of bioceramics: alumina, zirconia (PSZ) and hydroxyapatite, Journal of the
Australian Ceramic Society, 53 (2017) 1-10.
[9] H.H. Malik, A.R.J. Darwood, S. Shaunak, P. Kulatilake, A.A. El-Hilly, O. Mulki, A. Baskaradas,
M

Three-dimensional printing in surgery: a review of current surgical applications, Journal of Surgical

Research, 199 (2015) 512-522.
D

[10] S.F.S. Shirazi, S. Gharehkhani, M. Mehrali, H. Yarmand, H.S.C. Metselaar, N.A. Kadri, N.A.A. Osman,
A review on powder-based additive manufacturing for tissue engineering: selective laser sintering and
TE

inkjet 3D printing, Science & Technology of Advanced Materials, 16 (2015) 033502.

[11] S.L. Sing, J. An, W.Y. Yeong, F.E. Wiria, Laser and electron-beam powder-bed additive
manufacturing of metallic implants: A review on processes, materials and designs, Journal of
EP

Orthopaedic Research, 34 (2016) 369-385.

[12] T. Mühler, C.M. Gomes, J. Heinrich, J. Günster, Slurry-Based Additive Manufacturing of Ceramics,
International Journal of Applied Ceramic Technology, 12 (2015) 18-25.
C

[13] Z. Chen, Z. Li, J. Li, C. Liu, C. Lao, Y. Fu, C. Liu, Y. Li, P. Wang, Y. He, 3D printing of ceramics: A review,
Journal of the European Ceramic Society, 39 (2019) 661-687.
AC

[14] L.C. Hwa, S. Rajoo, A.M. Noor, N. Ahmad, M.B. Uday, Recent advances in 3D printing of porous
ceramics: A review, Current Opinion in Solid State & Materials Science, (2017) S1359028616301723.
[15] U. Kalsoom, P.N. Nesterenko, B. Paull, Recent developments in 3D printable composite materials,
Rsc Advances, 6 (2016).
[16] A. Mostafaei, J. Toman, E.L. Stevens, E.T. Hughes, Y.L. Krimer, M. Chmielus, Microstructural
evolution and mechanical properties of differently heat-treated binder jet printed samples from gas-
and water-atomized alloy 625 powders, Acta Materialia, 124 (2017) 280-289.
[17] A. Mostafaei, E.L. Stevens, J.J. Ference, D.E. Schmidt, M. Chmielus, Binder jetting of a
complex-shaped metal partial denture framework, Additive Manufacturing, (2018).
[18] A. Mostafaei, E.L. Stevens, E.T. Hughes, S.D. Biery, C. Hilla, M. Chmielus, Powder bed binder jet
 ACCEPTED MANUSCRIPT
printed alloy 625: Densification, microstructure and mechanical properties, Materials & Design, 108
(2016) 126-135.
[19] P. Nandwana, A.M. Elliott, D. Siddel, A. Merriman, W.H. Peter, S.S. Babu, Powder bed binder jet 3D
printing of Inconel 718: Densification, microstructural evolution and challenges☆, Current Opinion in
Solid State & Materials Science, 21 (2017) S1359028616300821.
[20] Paranthaman, M. Parans, Shafer, S. Christopher, Elliott, M. Amy, Siddel, H. Derek, McGuire, A.
Michael, Binder Jetting: A Novel NdFeB Bonded Magnet Fabrication Process, JOM, 68 (2016)
1978-1982.

PT
[21] L. Ling, A. Tirado, B.S. Conner, M. Chi, A.M. Elliott, O. Rios, H. Zhou, M.P. Paranthaman, A novel
method combining additive manufacturing and alloy infiltration for NdFeB bonded magnet fabrication,

RI
Journal of Magnetism & Magnetic Materials, 438 (2017) 163-167.
[22] A. Levy, A. Miriyev, A. Elliott, S.S. Babu, N. Frage, Additive manufacturing of complex-shaped
graded TiC/steel composites, Materials & Design, 118 (2017) 198-203.

SC
[23] Z.C. Cordero, D.H. Siddel, W.H. Peter, A.M. Elliott, Strengthening of ferrous binder jet 3D printed
components through bronze infiltration ☆, Additive Manufacturing, 15 (2017).
[24] E. Sachs, M. Cima, J. Cornie, Three-Dimensional Printing: Rapid Tooling and Prototypes Directly

U
from a CAD Model, CIRP Annals - Manufacturing Technology, 39 (1990) 201-204.
[25] B. Derby, Additive Manufacture of Ceramics Components by Inkjet Printing, Engineering, 1 (2015)
AN
113-123.
[26] H. Miyanaji, S. Zhang, A. Lassell, A. Zandinejad, L. Yang, Process Development of Porcelain
Ceramic Material with Binder Jetting Process for Dental Applications, JOM, 68 (2016) 831-841.
M

[27] Z. Fu, L. Schlier, N. Travitzky, P. Greil, Three-dimensional printing of SiSiC lattice truss structures,
Materials Science & Engineering A, 560 (2013) 851-856.
D

[28] A. Zocca, C.M. Gomes, E. Bernardo, R. Müller, J. Günster, P. Colombo, LAS glass–ceramic scaffolds
by three-dimensional printing, Journal of the European Ceramic Society, 33 (2013) 1525-1533.
TE

[29] J. Suwanprateeb, R. Sanngam, W. Suvannapruk, T. Panyathanmaporn, Mechanical and in vitro

performance of apatite–wollastonite glass ceramic reinforced hydroxyapatite composite fabricated by
3D-printing, J Mater Sci Mater Med, 20 (2009) 1281-1289.
EP

[30] H. Miyanaji, Y. Li, S. Zhang, A. Zandinejad, A preliminary study of the graded dental porcelain
ceramic structures fabricated via binder jetting 3D printing, Solid Freeform Fabrication Symposium,
2014.
C

[31] M.N. Birkholz, G. Agrawal, C. Bergmann, R. Schröder, S.J. Lechner, A. Pich, H. Fischer, Calcium
phosphate/microgel composites for 3D powderbed printing of ceramic materials, Biomedical
AC

Engineering, 61 (2016) 267-279.

[32] F.C. Fierz, F. Beckmann, M. Huser, S.H. Irsen, B. Leukers, F. Witte, Ö. Degistirici, A. Andronache, M.
Thie, B. Müller, The morphology of anisotropic 3D-printed hydroxyapatite scaffolds, Biomaterials, 29
(2008) 3799-3806.
[33] G.A. Fielding, A. Bandyopadhyay, S. Bose, Effects of silica and zinc oxide doping on mechanical
and biological properties of 3D printed tricalcium phosphate tissue engineering scaffolds, Dental
Materials, 28 (2012) 113-122.
[34] J.A. Inzana, D. Olvera, S.M. Fuller, J.P. Kelly, O.A. Graeve, E.M. Schwarz, S.L. Kates, H.A. Awad, 3D
printing of composite calcium phosphate and collagen scaffolds for bone regeneration, Biomaterials,
 ACCEPTED MANUSCRIPT
35 (2014) 4026-4034.
[35] U. Klammert, T. Reuther, C. Jahn, B. Kraski, A.C. Kübler, U. Gbureck, Cytocompatibility of brushite
and monetite cell culture scaffolds made by three-dimensional powder printing, Acta Biomaterialia, 5
(2009) 727-734.
[36] R. Lowmunkong, T. Sohmura, Y. Suzuki, S. Matsuya, K. Ishikawa, Fabrication of freeform
bone-filling calcium phosphate ceramics by gypsum 3D printing method, Journal of Biomedical
Materials Research Part B Applied Biomaterials, 90B (2010) 531-539.
[37] T.D. Roy, J.L. Simon, J.L. Ricci, E.D. Rekow, V.P. Thompson, J.R. Parsons, Performance of degradable

PT
composite bone repair products made via three‐dimensional fabrication techniques, Journal of
Biomedical Materials Research Part A, 66A (2010) -.

RI
[38] T.D. Szucs, D. Brabazon, Effect of Saturation and Post Processing on 3D Printed Calcium Phosphate
Scaffolds, Key Engineering Materials, 396-398 (2009) 663-666.
[39] Z. Zhou, F. Buchanan, C. Mitchell, N. Dunne, Printability of calcium phosphate: calcium sulfate

SC
powders for the application of tissue engineered bone scaffolds using the 3D printing technique,
Materials Science & Engineering C, 38 (2014) 1-10.
[40] E.M. Gonçalves, F.J. Oliveira, R.F. Silva, M.A. Neto, M.H. Fernandes, M. Amaral, M. Valletregí, M.

U
Vila, Three-dimensional printed PCL-hydroxyapatite scaffolds filled with CNTs for bone cell growth
stimulation, Journal of Biomedical Materials Research Part B Applied Biomaterials, 104 (2016)
AN
1210-1219.
[41] A. Kumar, K.C. Nune, R.D. Misra, Biological functionality of extracellular matrix-ornamented
three-dimensional printed hydroxyapatite scaffolds, Journal of Biomedical Materials Research Part A,
M

104 (2016) 1343-1351.

[42] C. Qian, J. Sun, Fabrication of the porous hydroxyapatite implant by 3D printing, Journal of
D

Ceramic Processing Research, 14 (2013) 513-516.

[43] H. Seitz, W. Rieder, S. Irsen, B. Leukers, C. Tille, Three‐dimensional printing of porous ceramic
TE

scaffolds for bone tissue engineering, Journal of Biomedical Materials Research Part B Applied
Biomaterials, 74B (2010) 782-788.
[44] J. Suwanprateeb, R. Sanngam, W. Suwanpreuk, Fabrication of bioactive hydroxyapatite/bis-GMA
EP

based composite via three dimensional printing, Journal of Materials Science Materials in Medicine,
19 (2008) 2637-2645.
[45] J. Suwanprateeb, R. Sanngam, T. Panyathanmaporn, Influence of raw powder preparation routes
C

on properties of hydroxyapatite fabricated by 3D printing technique, Materials Science & Engineering

C, 30 (2010) 610-617.
AC

[46] M. Smale, Influence of printing parameters on the transformation efficiency of 3D-printed plaster
of paris to hydroxyapatite and its properties, Rapid Prototyping Journal, 18 (2012) 490-499.
[47] J. Suwanprateeb, F. Thammarakcharoen, N. Hobang, Enhancement of mechanical properties of 3D
printed hydroxyapatite by combined low and high molecular weight polycaprolactone sequential
infiltration, Journal of Materials Science Materials in Medicine, 27 (2016) 171.
[48] Y.E. Wang, X.P. Li, C.C. Li, M.M. Yang, Q.H. Wei, Binder droplet impact mechanism on a
hydroxyapatite microsphere surface in 3D printing of bone scaffolds, Journal of Materials Science, 50
(2015) 5014-5023.
[49] H. Zhang, X. Mao, Z. Du, W. Jiang, X. Han, D. Zhao, D. Han, Q. Li, Three dimensional printed
 ACCEPTED MANUSCRIPT
macroporous polylactic acid/hydroxyapatite composite scaffolds for promoting bone formation in a
critical-size rat calvarial defect model, Science & Technology of Advanced Materials, 17 (2016)
136-148.
[50] S. Spath, P. Drescher, H. Seitz, Impact of Particle Size of Ceramic Granule Blends on Mechanical
Strength and Porosity of 3D Printed Scaffolds, Materials, 8 (2015) 4720-4732.
[51] J. Moon, A.C. Caballero, L. Hozer, Y.M. Chiang, M.J. Cima, Fabrication of functionally graded
reaction infiltrated SiC–Si composite by three-dimensional printing (3DP™) process, Materials Science
& Engineering A, 298 (2001) 110-119.

PT
[52] S.I. Roohaniesfahani, P. Newman, H. Zreiqat, Design and Fabrication of 3D printed Scaffolds with a
Mechanical Strength Comparable to Cortical Bone to Repair Large Bone Defects, Sci Rep, 6 (2016)

RI
19468.
[53] K.C.R. Kolan, C.L. Ming, G.E. Hilmas, M. Velez, Effect of particle size, binder content and heat
treatment on mechanical properties of 13-93 bioactive glass scaffolds, (2011).

SC
[54] C. Sun, X. Tian, L. Wang, Y. Liu, J. Günster, C.M. Wirth, D. Li, Z. Jin, Effect of Particle Size Gradation
on the Performance of Ceramic 3D Printing Process, Ceramics International, 43 (2017) 578-584.
[55] H. Miyanaji, S. Zhang, A. Lassell, A.A. Zandinejad, L. Yang, Optimal Process Parameters for 3D

U
Printing of Porcelain Structures ☆, Procedia Manufacturing, 5 (2016) 870-887.
[56] R. Chumnanklang, T. Panyathanmaporn, K. Sitthiseripratip, J. Suwanprateeb, 3D printing of
AN
hydroxyapatite: Effect of binder concentration in pre-coated particle on part strength, Materials
Science & Engineering C, 27 (2007) 914-921.
[57] S.H.I. Dr, B. Leukers, C. Höckling, C. Tille, H. Seitz, Bioceramic Granulates for use in 3D Printing:
M

Process Engineering Aspects, Materialwissenschaft Und Werkstofftechnik, 37 (2010) 533-537.

[58] C. Bergmann, M. Lindner, W. Zhang, K. Koczur, A. Kirsten, R. Telle, H. Fischer, 3D printing of bone
D

substitute implants using calcium phosphate and bioactive glasses, Journal of the European Ceramic
Society, 30 (2010) 2563-2567.
TE

[59] J.K. Sherwood, S.L. Riley, R. Palazzolo, S.C. Brown, D.C. Monkhouse, M. Coates, L.G. Griffith, L.K.
Landeen, A. Ratcliffe, A three-dimensional osteochondral composite scaffold for articular cartilage
repair, Biomaterials, 23 (2002) 4739-4751.
EP

[60] A. Butscher, M. Bohner, C. Roth, A. Ernstberger, R. Heuberger, N. Doebelin, P.R. von Rohr, R. Müller,
Printability of calcium phosphate powders for three-dimensional printing of tissue engineering
scaffolds, Acta Biomaterialia, 8 (2012) 373-385.
C

[61] B. Nan, X. Yin, L. Zhang, L. Cheng, Three‐Dimensional Printing of Ti3SiC2‐Based Ceramics,

Journal of the American Ceramic Society, 94 (2011) 969-972.
AC

[62] R. Melcher, S. Martins, N. Travitzky, P. Greil, Fabrication of Al 2 O 3 -based composites by indirect

3D-printing, Materials Letters, 60 (2006) 572-575.
[63] J.A. Gonzalez, J. Mireles, Y. Lin, R.B. Wicker, Characterization of ceramic components fabricated
using binder jetting additive manufacturing technology, Ceramics International, 42 (2016)
10559-10564.
[64] X. Yin, N. Travitzky, P. Greil, Near‐Net‐Shape Fabrication of Ti3AlC2‐Based Composites,
International Journal of Applied Ceramic Technology, 4 (2010) 184-190.
[65] B. Nan, X. Yin, L. Zhang, L. Cheng, Three-Dimensional Printing of Ti 3 SiC 2 -Based Ceramics.
[66] L. Rabinskiy, A. Ripetsky, S. Sitnikov, Y. Solyaev, R. Kahramanov, Fabrication of porous silicon
 ACCEPTED MANUSCRIPT
nitride ceramics using binder jetting technology, Materials Science and Engineering Conference
Series, 2016, pp. 012023.
[67] R. Melcher, N. Travitzky, C. Zollfrank, P. Greil, 3D printing of Al 2 O 3 /Cu–O interpenetrating phase
composite, Journal of Materials Science, 46 (2011) 1203-1210.
[68] J. Moon, J.E. Grau, V. Knezevic, M.J. Cima, E.M. Sachs, Ink‐Jet Printing of Binders for Ceramic
Components, Journal of the American Ceramic Society, 85 (2010) 755-762.
[69] X. Yin, N. Travitzky, P. Greil, Three‐Dimensional Printing of Nanolaminated Ti3AlC2 Toughened
TiAl3–Al2O3 Composites, Journal of the American Ceramic Society, 90 (2010) 2128-2134.

PT
[70] N. Travitzky, K. Zimmermann, R. Melcher, P. Greil, From Polysaccharides to Sisic Composites by 3D
Printing, John Wiley & Sons, Inc.2006.

RI
[71] 封立运, 殷小玮, 李向明, 三维打印结合化学气相渗透制备 Si3N4-SiC 复相陶瓷, 航空制造技
术, 400 (2012) 62-65.
[72] W. Duan, Z. Fan, H. Wang, J. Zhang, T. Qiao, X. Yin, Electromagnetic interference shielding and

SC
mechanical properties of Si3N4-SiOC composites fabricated by 3D-printing combined with polymer
infiltration and pyrolysis, Journal of Materials Research, 32 (2017) 1-8.
[73] H. Zhao, C. Ye, Z. Fan, C. Wang, 3D printing of CaO-based ceramic core using nanozirconia

U
suspension as a binder, Journal of the European Ceramic Society, 37 (2017).
[74] P. Lima, A. Zocca, W. Acchar, J. Günster, 3D printing of porcelain by layerwise slurry deposition,
AN
Journal of the European Ceramic Society, 38 (2018).
[75] ExOne, ExOne offers a variety of manufacturing quality materials that stand up to industrial use
and easy integration into existing processes, (2017) http://www.exone.com/Resources/Materials.
M

[76] E.M. Sivarupan T, Coniglio N, 3D printing process parameters and properties of additively
manufactured sand mold for rapid casting: strength and permeability, (2017).
D

[77] ExOne, Production Printers n.d, (2017).

[78] Voxeljet Sand casting molds - Rapid and economical n.d.
TE

http://www.voxeljet.de/en/materials/sand/ (accessed February 2, 2017).

[79] N. McKenna, S. Singamneni, O. Diegel, D. Singh, T. Neitzert, J. St George, A.R. Choudhury, P.K.
Yarlagadda, Direct Metal casting through 3D printing: A critical analysis of the mould characteristics,
EP

Global Congress on Manufacturing and Management (GCMM) Board, 2008.

[80] ZPrinter ® Consumables Catalogue (2013).
[81] B. Charbonnier, C. Laurent, D. Marchat, Porous hydroxyapatite bioceramics produced by
C

impregnation of 3D-printed wax mold: Slurry feature optimization, Journal of the European Ceramic
Society, 36 (2016) 4269-4279.
AC

[82] Y. Ma, X. Yin, X. Fan, L. Wang, P. Greil, N. Travitzky, Near‐Net‐Shape Fabrication of Ti3SiC2‐
based Ceramics by Three‐Dimensional Printing, International Journal of Applied Ceramic Technology,
12 (2015) 71-80.
[83] X. Yin, N. Travitzky, P. Greil, Three-dimentional printing of Ti-Al-O-C composites, Ceramic
Engineering & Science Proceedings, 27 (2006) 473-482.
[84] Z. Weng, Q. Zeng, C. Xie, J. Peng, J. Zhang, Porous Silicon Nitride Ceramics Prepared by 3D Printing
and Reaction Sintering, Materials Review, (2013).
[85] S.G.M.C.M. Aldaz, Analysis of ferroelectric ceramic fabricated by binder jetting technology,
Proceedings of Solid Freeform Fabrication Symposium, (2013) 859-868.
 ACCEPTED MANUSCRIPT
[86] S.A. Uhland, R.K. Holman, M.J. Cima, E.S.Y. Enokido, New Process and Materials Developments in
3-Dimensional Printing, 3DP™, Mrs Proceedings, 542 (1998).
[87] H.R. Wang, M.J. Cima, E.M. Sachs, Alumina-Doped Silica Gradient-Index (GRIN) Lenses by
Slurry-Based Three-Dimensional Printing (S-3DP™), Mrs Proceedings, 758 (2002) 360-367.
[88] H.E. Wang, M.J. Cima, B.D. Kernan, E.M. Sachs, Gradient㊣ndex (GRIN) Lenses and Other Optical
Elements by Slurrybased Three Dimensional Printing, John Wiley & Sons, Inc.2005.
[89] Wang, Hong-Ren, Gradient-Index (GRIN) lenses by Slurry-based Three-Dimensional Printing
(S-3DP), (2005).

PT
[90] S.M. Gaytan, M.A. Cadena, H. Karim, D. Delfin, Y. Lin, D. Espalin, E. Macdonald, R.B. Wicker,
Fabrication of barium titanate by binder jetting additive manufacturing technology, Ceramics

RI
International, 41 (2015) 6610-6619.
[91] L.N. Rabinskiy, S.A. Sitnikov, V.A. Pogodin, A.A. Ripetskiy, Y.O. Solyaev, Binder Jetting of Si3N4
Ceramics with Different Porosity, Solid State Phenomena, 269 (2017) 37-50.

SC
[92] B. Derby, Inkjet Printing of Functional and Structural Materials: Fluid Property Requirements,
Feature Stability, and Resolution, Annual Review of Materials Research, 40 (2010) 395-414.
[93] MohammadVaezi, SrisitChianrabutra, BrianMellor, ShoufengYang, Multiple material additive

U
manufacturing â “ Part 1: a review, Virtual & Physical Prototyping, 8 (2013) 19-50.
[94] P. Karandikar, M. Watkins, A. Mccormick, B. Givens, M. Aghajanian, Additive Manufacturing (3D
AN
Printing) of Ceramics: Microstructure, Properties, and Product Examples: Ceramic Engineering and
Science Proceedings, Volume 38, Issue 3, 2018.
[95] S.L. Sing, J. An, W.Y. Yeong, F.E. Wiria, Laser and electron‐beam powder‐bed additive
M

manufacturing of metallic implants: A review on processes, materials and designs, Journal of

Orthopaedic Research, 34 (2016) 369-385.
D

[96] A. Bhargav, V. Sanjairaj, V. Rosa, L.W. Feng, Y.J. Fuh, Applications of additive manufacturing in
dentistry: A review, Journal of Biomedical Materials Research Part B Applied Biomaterials, (2017).
TE

[97] E.C.E. Costa, J.P. Duarte, P. Bártolo, A review of additive manufacturing for ceramic production,
Rapid Prototyping Journal, 23 (2017) 00-00.
[98] K.U. Leuven, D. Pma, Celestijnenlaan, B. Heverlee, Additive Manufacturing of Ceramics: A Review,
EP

(2014).
[99] K. Qiu, G. Haghiashtiani, M.C. Mcalpine, 3D Printed Organ Models for Surgical Applications,
Annual Review of Analytical Chemistry, 11 (2018).
C

[100] S.C. Cox, J.A. Thornby, G.J. Gibbons, M.A. Williams, K.K. Mallick, 3D printing of porous
hydroxyapatite scaffolds intended for use in bone tissue engineering applications, Materials Science &
AC

Engineering C, 47 (2015) 237-247.

[101] M. Mapar, D.Q. Zhang, Z.H. Liu, W.Y. Yeong, C.K. Chua, B.Y. Tay, O. Geramifard, S. Maleksaeedi, F.E.
Wiria, Preparation and flowability characterization of ceramic powders for Selective Laser Melting,
(2014).
[102] S. Sathish, M. Geetha, S.S. Kumar, R. Asokamani, Granulation of Nano Alumina Powder for
Improved Flowability by Spray Drying, Transactions of the Indian Institute of Metals, 65 (2012)
485-490.
[103] B.P.C. Raghupathy, J.G.P. Binner, Spray Granulation of Nanometric Zirconia Particles, Journal of
the American Ceramic Society, 94 (2011) 139-145.
 ACCEPTED MANUSCRIPT
[104] P. Höhne, Utilization of an ultra sound atomizer for spray granulation of oxide ceramic fine
powder, (2017).
[105] R. Mirzajany, M. Alizadeh, M. Saremi, M.R. Rahimipour, Suspension preparation of Alumina
whiskers for spray granulation, Materials Letters, 228 (2018).
[106] S. Chiangka, S. Watcharamaisakul, B. Golman, Effect of Slurry Formulation on Morphology and
Flowability of Spray-Dried Alumina/Zirconia Composite Particles, Key Engineering Materials, 675-676
(2016) 531-534.
[107] L.J. Jallo, M. Schoenitz, E.L. Dreizin, R.N. Dave, C.E. Johnson, The effect of surface modification of

PT
aluminum powder on its flowability, combustion and reactivity ☆, Powder Technology, 204 (2010)
63-70.

RI
[108] V.R. Giampietro, C. Roth, M. Gulas, V. Wood, R.V.R. Philipp, Applying the Macroscopic Kinetic
Approach to Plasma Polymerization to the Plasma Surface Modification of Micropowders: Attempt of
Correlating Powder Flowability and Plasma Process Parameters, Plasma Processes & Polymers, 13

SC
(2016) 334-340.
[109] Y. Kudo, A. Uno, M. Yasuda, S. Matsusaka, Effect of Surface Modification with Silicon Compounds
on Flowability of Granulated Lactose, 54 (2017) 82-89.

U
[110] Xiaolin, Qiang, Zhang, Cang, Huang, Wang, Chaohe, Yang, Validation of surface coating with
nanoparticles to improve the flowability of fine cohesive powders, 颗粒学报(PARTICUOLOGY), 30
AN
(2017) 53-61.
[111] J.F. Bredt, T.C. Anderson, D.B. Russell, Three dimensional printing materials system, US, 2002.
[112] F.K. Feenstra, Method for making a dental element, US, 2005.
M

[113] C.B. Williams, J.K. Cochran, D.W. Rosen, Additive manufacturing of metallic cellular materials via
three-dimensional printing, International Journal of Advanced Manufacturing Technology, 53 (2011)
D

231-239.
[114] W.Y. Yeong, C.K. Chua, K.F. Leong, M. Chandrasekaran, Rapid prototyping in tissue engineering:
TE

challenges and potential, Trends in Biotechnology, 22 (2004) 643-652.

[115] J.P. Vacanti, L.G. Cima, M.J. Cima, Vascularized tissue regeneration matrices formed by solid free
form fabrication techniques, Children S Medical Center Corporation, (2001).
EP

[116] A. Spillmann, A. Sonnenfeld, P.R.V. Rohr, Flowability Modification of Lactose Powder by Plasma
Enhanced Chemical Vapor Deposition, Plasma Processes & Polymers, 4 (2010) S16-S20.
[117] M. Nebelung, B. Lang, Flowability of Ceramic Bulk Materials Part 2: Interaction of primary
C

particle properties and flowability, Ceramic Forum International, 86 (2009) E35-E38.

[118] B.R. Utela, D. Storti, R.L. Anderson, M. Ganter, Development Process for Custom
AC

Three-Dimensional Printing (3DP) Material Systems, China Printing & Packaging Study, 132 (2010)
165-174.
[119] A. Curodeau, E. Sachs, S. Caldarise, Design and fabrication of cast orthopedic implants with
freeform surface textures from 3‐D printed ceramic shell, Journal of Biomedical Materials Research
Part A, 53 (2015) 525-535.
[120] K. Lu, M. Hiser, W. Wu, Effect of particle size on three dimensional printed mesh structures,
Powder Technology, 192 (2009) 178-183.
[121] M. Turker, D. Godlinski, F. Petzoldt, Effect of production parameters on the properties of IN 718
superalloy by three-dimensional printing, Materials Characterization, 59 (2008) 1728-1735.
 ACCEPTED MANUSCRIPT
[122] A. Butscher, M. Bohner, S. Hofmann, L. Gauckler, R. Müller, Structural and material approaches
to bone tissue engineering in powder-based three-dimensional printing, Acta Biomaterialia, 7 (2011)
907-920.
[123] L. Qin, V. Rudolph, B. Weigl, A. Earl, Interparticle van der Waals force in powder flowability and
compactibility, International Journal of Pharmaceutics, 280 (2004) 77-93.
[124] E. Sachs, M. Cima, J. Cornie, D. Brancazio, J. Bredt, A. Curodeau, T. Fan, S. Khanuja, A. Lauder, J.
Lee, Three-Dimensional Printing: The Physics and Implications of Additive Manufacturing, CIRP Annals
- Manufacturing Technology, 42 (1993) 257-260.

PT
[125] D. Gilmer, E. Hong, A. Kisliuk, S.W. Cheng, A. Elliott, T. Saito, Enhanced green part strength in
binder jet additive manufacturing, Abstr. Pap. Am. Chem. Soc., 255 (2018) 2.

RI
[126] D. Gilmer, E. Hong, D. Siddel, A. Merriman, A. Kisliuk, S. Cheng, A. Elliott, T. Saito, Novel binder
development in binder jet additive manufacturing to improve green part strength, Abstr. Pap. Am.
Chem. Soc., 255 (2018) 2.

SC
[127] H. Miyanaji, M. Orth, J.M. Akbar, Y. Li, Process development for green part printing using binder
jetting additive manufacturing, Frontiers of Mechanical Engineering, 13 (2018) 504-512.
[128] W. Du, X. Ren, C. Ma, Z. Pei, Ceramic binder jetting additive manufacturing: Particle coating for

U
increasing powder sinterability and part strength, Materials Letters.
[129] A. Winkel, R. Meszaros, S. Reinsch, R. Müller, N. Travitzky, T. Fey, P. Greil, L. Wondraczek,
AN
Sintering of 3D-Printed Glass/HAp Composites, Journal of the American Ceramic Society, 95 (2012)
3387-3393.
[130] J.E. Fromm, Numerical calculation of the fluid dynamics of drop-on-demand jets, IBM Corp.1984.
M

[131] N. Reis, B. Derby, Ink Jet Deposition of Ceramic Suspensions: Modeling and Experiments of
Droplet Formation, Mrs Online Proceedings Library Archive, 625 (2000) 117-122.
D

[132] G.D. Martin, S.D. Hoath, I.M. Hutchings, Inkjet printing - the physics of manipulating liquid jets
and drops, 2008, pp. 012001.
TE

[133] P.C. Duineveld, E.I. Haskal, Ink-jet printing of polymer light-emitting devices, Proc Spie, 4464
(2002) 59-67.
[134] C.D. Stow, M.G. Hadfield, An Experimental Investigation of Fluid Flow Resulting from the Impact
EP

of a Water Drop with an Unyielding Dry Surface, Proceedings of the Royal Society of London, 373
(1981) 419-441.
[135] S. Agland, S.M. Iveson, The Impact of Liquid Drops on Powder Bed Surfaces, Chemeca Chemical
C

Engineering Solutions in A Changing Environment, (1998).

[136] R. Kai, F. Feuillebois, Influence of Surface Roughness on Liquid Drop Impact, J Colloid Interface
AC

Sci, 203 (1998) 16-30.

[137] C.D. Stow, M.G. Hadfield, An Investigation of the Condition for Splashing of Water Drops on Solid,
Dry Surfaces, Journal of the Meteorological Society of Japan, 58 (1980) 59-68.
[138] T. Mao, D.C.S. Kuhn, H. Tran, Spread and rebound of liquid droplets upon impact on flat surfaces,
Aiche Journal, 43 (1997) 2169-2179.
[139] M. Pasandideh〧ard, Y.M. Qiao, S. Chandra, J. Mostaghimi, Capillary effects during droplet
impact on a solid surface, Physics of Fluids, 8 (1996) 650-659.
[140] S.E. Bechtel, D.B. Bogy, F.E. Talke, Impact of a Liquid Drop Against a Flat Surface, Ibm Journal of
Research & Development, 25 (1981) 963-971.
 ACCEPTED MANUSCRIPT
[141] T. Fan, Droplet-powder impact interaction in three dimensional printing, Annales De Cardiologie
Et Dang└iologie, 39 (1996) 495-499.
[142] P. Lepoutre, LIQUID ABSORPTION AND COATING POROSITY, Pap Technol Ind, 19 (1978) 298-300.
[143] J.F. Bredt, S. Clark, G. Gilchrist, Three dimensional printing material system and method, US,
2006.
[144] E.M. Sachs, C. Hadjiloucas, S. Allen, H.J. Yoo, Metal and ceramic containing parts produced from
powder using binders derived from salt, EP, 2007.
[145] A. Farzadi, M. Solati-Hashjin, M. Asadi-Eydivand, N.A. Abu Osman, Effect of layer thickness and

PT
printing orientation on mechanical properties and dimensional accuracy of 3D printed porous samples
for bone tissue engineering, Plos One, 9 (2014) e108252.

RI
[146] M. Asadi-Eydivand, M. Solati-Hashjin, A. Farzad, N.A.A. Osman, Effect of technical parameters on
porous structure and strength of 3D printed calcium sulfate prototypes, Robotics and
Computer-Integrated Manufacturing, 37 (2016) 57-67.

SC
[147] M. Vaezi, C.K. Chua, Effects of layer thickness and binder saturation level parameters on 3D
printing process, International Journal of Advanced Manufacturing Technology, 53 (2011) 275-284.
[148] M. Castilho, M. Dias, U. Gbureck, J. Groll, P. Fernandes, I. Pires, B. Gouveia, J. Rodrigues, E.

U
Vorndran, Fabrication of computationally designed scaffolds by low temperature 3D printing,
Biofabrication, 5 (2013) 035012.
AN
[149] S.J. Li, S. Cao, Print Parameters Influence on Parts' Quality and Calibration with 3DP-Part I: Print
Parameters Influence on Parts’ Surface Topography, Advanced Materials Research, 399-401 (2012)
1639-1645.
M

[150] A.G. Arumaikkannu, B.N.A. Kumar, B.R. Saravanan, B.P. Student, STUDY ON THE INFLUENCE OF
RAPID PROTOTYPING PARAMETERS ON PRODUCT QUALITY IN 3D PRINTING.
D

[151] M. Pereira, J. Rodrigues, B. Gouveia, I. Pires, M. Castilho, The role of shell/core saturation level
on the accuracy and mechanical characteristics of porous calcium phosphate models produced by
TE

3Dprinting, Rapid Prototyping Journal, 21 (2015) 43 - 55.

[152] A.W.L. Yao, Y.C. Tseng, A robust process optimization for a powder type rapid prototyper, Rapid
Prototyping Journal, 8 (2014) 180-189.
EP

[153] E.M. Sachs, M.J. Cima, M.A. Caradonna, J. Grau, J.G. Serdy, P.C. Saxton, S.A. Uhland, J. Moon,
Jetting layers of powder and the formation of fine powder beds thereby, CA, 2003.
[154] M. Gatto, R.A. Harris, Non‐destructive analysis (NDA) of external and internal structures in 3DP,
C

Rapid Prototyping Journal, 17 (2011) 128-137.

[155] I. Gibson, D. Rosen, B. Stucker, Binder Jetting, 2015.
AC

[156] M. Yang, X. Lv, X. Liu, J. Zhang, Research on color 3D printing based on color adherence, Rapid
Prototyping Journal, (2017) 00-00.
[157] J.J. Beaman, C. Atwood, T.L. Bergman, D. Bourell, S. Hollister, D. Rosen, Additive/Subtractive
Manufacturing Research and Development in Europe, Additive/subtractive Manufacturing Research &
Development in Europe, 4 (2004) 595-599.
[158] E. Sheydaeian, E. Toyserkani, A system for selectively encapsulating porogens inside the layers
during additive manufacturing: From conceptual design to the first prototype, Journal of
Manufacturing Processes, 26 (2017) 330-338.
[159] D.C. Tancred, B.A. Mccormack, A.J. Carr, A synthetic bone implant macroscopically identical to
 ACCEPTED MANUSCRIPT
cancellous bone, Biomaterials, 19 (1998) 2303-2311.
[160] E.M. Sachs, M.J. Cima, J.F. Bredt, S. Khanuja, Process for removing loose powder particles from
interior passages of a body, US, 1996.
[161] M.J. Mondrinos, R. Dembzynski, L. Lu, V.K. Byrapogu, D.M. Wootton, P.I. Lelkes, J. Zhou,
Porogen-based solid freeform fabrication of polycaprolactone-calcium phosphate scaffolds for tissue
engineering, Biomaterials, 27 (2006) 4399-4408.
[162] Z. Ma, C. Gao, Y. Gong, J. Shen, Paraffin spheres as porogen to fabricate poly(L-lactic acid)
scaffolds with improved cytocompatibility for cartilage tissue engineering, Journal of Biomedical

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Materials Research Part A B, 67 (2003) 610-617.
[163] H.R. Lin, C.J. Kuo, C.Y. Yang, S.Y. Shaw, Y.J. Wu, Preparation of macroporous biodegradable PLGA

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scaffolds for cell attachment with the use of mixed salts as porogen additives, Journal of Biomedical
Materials Research Part A, 63 (2010) -.
[164] P.X. Ma, J.W. Choi, Biodegradable polymer scaffolds with well-defined interconnected spherical

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pore network, Tissue Engineering Part A, 7 (2001) 23-33.
[165] Y. Shanjani, J.N. De Croos, R.M. Pilliar, R.A. Kandel, E. Toyserkani, Solid freeform fabrication and
characterization of porous calcium polyphosphate structures for tissue engineering purposes, Journal

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of Biomedical Materials Research Part B Applied Biomaterials, 93B (2010) 510-519.
[166] J.M. Taboas, R.D. Maddox, P.H. Krebsbach, S.J. Hollister, Indirect solid free form fabrication of
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local and global porous, biomimetic and composite 3D polymer-ceramic scaffolds, Biomaterials, 24
(2003) 181-194.
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Figure Caption

Fig. 1 Schematic of binder jetting: (a) a roller is used to spread powder through the

height difference between the powder supply platform and the fabrication platform [5];

and (b) a recoater is used to spread powder from a top hopper using vibration [17].

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Fig. 2 Steps of binder jetting printing ceramics.

Fig. 3 Printable materials and application areas of binder jetting printing ceramics.

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Fig. 4 Relationship between the properties of the ceramic powder.

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Fig. 5 Changing mechanism of packing density of spherical and irregular ceramic

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powders after powder spreading.
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Fig. 6 Dependence of flowability (ffc) on median particle size. The symbols (○)

correspond to mean values, while the error bars represent standard deviations. The
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linear fit is based on ffc values of S, SPlasma, M, L, and XXL. The diamonds (◇)
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correspond to adjusted values according to the statistical model [60].

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Fig. 7 Relationship between the contact angle and median particle size (β-TCP
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powder fractions). The symbols (○) correspond to mean values, while the error bars

represent standard deviations [60].

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Fig. 8 Schematic illustrating the proposed droplet penetration behavior within

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homogeneously and heterogeneously distributed powder beds [39].

Fig. 9 Dependence of surface roughness (Sa) on median particle size. The symbols

(○) correspond to mean values, while the error bars represent standard deviations.

The diamonds (◇) correspond to adjusted values according to the statistical model

[60].
 ACCEPTED MANUSCRIPT

Fig. 10 Density and flexural strength of samples as functions of mass fraction of

Powder C (1 - 25 µm; fine powders) [54].

Fig. 11 A high-speed photographic image showing the satellite droplets (adapted from

[131]).

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Fig. 12 Printable region that facilitates the formation of stable droplets. The printable

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region is interlaced by four dotted lines. Outside of this region, the binder is not

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suitable for printing because of its high viscosity, splashing, producing satellite

droplets, and insufficient energy for drop formation [92].

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Fig. 13 Impact types of droplets on powders [134].
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Fig. 14 Model of droplet penetration in a single pore. R is the radius of the droplet. ∆P
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is the pressure gradient. θ is the contact angle between droplet and powders. dl/dt is

the flow rate of the droplet in a single pore. r is the radius of a single pore.
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Fig. 15 Flexural strength and green density at different layer thicknesses [46].

Fig. 16 Disintegration of the green body printed at the layer thickness of 200 µm [46].
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Fig. 17 Schematic of shell/core regions. The dark edges and the small regions in the
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inner zone are the shell regions with the higher binder saturation. The grey area in the
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inner zone is the core with lower saturation [150].

Fig. 18 Schematic illustration of the 3D-printed layers with nominal-and

high-saturations levels. Layer n-1 has been printed first, while layer n has been

printed last. [150].

Fig. 19 Influence of the ratio of maltodextrin to water on green and sintered strengths
 ACCEPTED MANUSCRIPT

[56].

Fig. 20 Different placement orientations for rectangular parts. The left, middle, and

right sides of the rectangular parts are respectively parallel to the bottom of the

building chamber [148].

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Fig. 21 The top view of samples in three orientations. X, Y, and Z represent the height

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direction of the samples parallel to the X, Y, and Z axes, respectively. The black frame

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region represents the sprayed binders that the printhead moves along the moving

orientation [145].

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Fig. 22 Schematic of the porogen insertion mechanism (PIM) system [157].
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Fig. 23 The SEM images of raw alumina particles (a) and encapsulated alumina
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particles (b) [127].

Fig. 24 Relationships among the infiltration time, porosity, and SiC volume fraction
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[71].

Fig. 25 Relationships among infiltration temperature, open porosity, and flexural

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strength [61].
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Fig. 26 Relationship between PIP’s number of cycles and σdc [72].

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Table 1 Classification of AMs and their comparison.

Table 2 Classification of binders used for binder jetting.

Table 3 Relationship between shell/core saturation and properties of ceramic parts

[150].

Table 4 Technical specifications of the binder jetting equipment [154].

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Table 1
Classification of AMs and their comparison

Method Feedstock Binding Mechanism Activation Source

Thermal reaction
Binder jetting Powder, liquid binder bonding, chemical Liquid binder
reaction bonding

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Directed energy Powder or wire Thermal reaction Laser, electron beam,
deposition (filler) bonding arc or plasma beam
Thermal bonding or

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Heat, ultrasound or
Material extrusion Wire or paste (filler) chemical reaction
chemical reaction
bonding

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Liquid photosensitive
Chemical reaction or Radiation source or
Material jetting resin or molten wax
curing temperature field
(filler)

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Thermal energy
Thermal reaction
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Powder bed fusion Powder (filler) (laser, electron beam,
bonding
infrared light)
Thermal bonding,
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Thermal, chemical
chemical reaction
Sheet lamination Sheet (filler) reaction or ultrasonic
bonding or ultrasonic
transducer
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connection
Photosensitive resin Chemical reaction
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Stereo lithography Ultraviolet light

(filler) curing
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Table 2
Classification of binders used for binder jetting

Binder Additives References

Water-based [29, 45, 64, 69, 70]

Tigger powder
reactive
Glycerol [27, 62, 67, 100]

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Methanol,
Phosphoric acid Ethanol, [34, 58]

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Polyethylene
Acrylic acid glycol, [66]
Liquid

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Glycerol, Citric
binder
Self-adhesive Polymer acid, Potassium [32]
aluminum
Phosphoric

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sulfate, [60]
acid & isopropanol
Isoamyl
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Commercial Zp-7 [129]

Self- and powder Acidic calcium

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[144]
reactive sulfate
Citric acid,
Solid Polyvinyl alcohol, Dextrin, Instant [27, 29, 45, 61, 62,
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Sodium
binder alveoline, Maltodextrin, Starch 64, 67, 69, 70, 129]
polyacrylate,
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Table 3
Relationship between shell/core saturation and properties of ceramic parts [150]

Binder Binder Compressive

Bulk density Apparent Total porosity
saturation saturation strength
(g/cm3) porosity (%) (%)
level (%) value (MPa)
Shell Core Shell Core

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200 100 0.47 0.23 1.39±0.04 47.30±1.26 55.73±0.74 3.74±0.37
100 200 0.23 0.23 1.20±0.02 54.44±1.38 61.76±0.58 2.40±0.15
200 400 0.47 0.47 1.78±0.04 31.98±2.13 43.09±1.39 23.80±4.57

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100 100 0.23 0.12 ﹣ ﹣ ﹣ 1.44±0.16
150 150 0.35 0.18 ﹣ ﹣ ﹣ 1.79±0.25

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200 200 0.47 0.23 ﹣ ﹣ ﹣ 3.74±0.26
250 250 0.59 0.29 ﹣ ﹣ ﹣ 5.26±0.79
350 350 0.82 0.41 20.33±3.95

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Table 4
Technical specifications of the binder jetting equipment [154]

Build size Resolution Layer thickness Number of Color/Monoch

Company Type 3
(l×w×h) (mm ) (dpi) (mm) nozzles rome Printing
ProJet 160 236×185×127 300×450 0.1 304 Monochrome
3D Systems ProJet 260C 236×185×127 300×450 0.1 604 Color

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ProJet 860Pro 508×381×229 600×540 0.1 1520 Color
Lab Platform 40×60×35 400×400 0.05~0.1 ﹣ ﹣
Flex Platform 400×250×250 400×400 0.1

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﹣ ﹣
Max Platform 1800×1000×700 300×300 0.28~0.5 ﹣ ﹣
ExOne
Innovent Platform 160×65×65 400×400 0.1 ﹣ ﹣

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Exerial Platform 2200×1200×600 300×300 0.28~0.5 ﹣ ﹣
S-Print Platform 800×500×400 400×400 0.28~0.5 ﹣ ﹣
VX200 300×200×150 300×300 0.15 256

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﹣
Voxeljet VXC800 850×500×300 600×600 0.15~0.4 2656 ﹣
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VX4000 4000×2000×1000 600×600 0.12~0.3 26560 ﹣
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Fig. 1 Schematic of binder jetting: (a) a roller is used to spread powder through the

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height difference between the powder supply platform and fabrication platform [5]; and

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(b) a recoater is used to spread powder from a top hopper using vibration [17].

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Fig. 2 Steps of binder jetting printing ceramics.

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Fig. 3 Printable materials and application areas of binder jetting printing ceramics.
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Fig. 4 Relationship between the properties of the ceramic powder.

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Fig. 5 Changing mechanism of packing density of spherical and irregular ceramic

powders after powder spreading.

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RI
Fig. 6 Dependence of flowability (ffc) on median particle size. The symbols (○)

correspond to mean values, while the error bars represent standard deviations. The

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linear fit is based on ffc values of S, SPlasma, M, L, and XXL. The diamonds (◇)

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correspond to adjusted values according to the statistical model [60].
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Fig. 7 Relationship between the contact angle and median particle size (β-TCP

powder fractions). The symbols (○) correspond to mean values, while the error bars

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represent standard deviations [60].

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Fig. 8 Schematic illustrating the proposed droplet penetration behavior within

homogeneously and heterogeneously distributed powder beds [39].

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Fig. 9 Dependence of surface roughness (Sa) on median particle size. The symbols

(○) correspond to mean values, while the error bars represent standard deviations.

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The diamonds (◇) correspond to adjusted values according to the statistical model

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[60].
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Fig. 10 Density and flexural strength of samples as functions of mass fraction of

Powder C (1-25 µm; fine powders) [54].

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Fig. 11 A high-speed photographic image showing the satellite droplets (adapted from

[131]).

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Fig. 12 Printable region that facilitates the formation of stable droplets. The printable

region is interlaced by four dotted lines. Outside of this region, the binder is not

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suitable for printing because of its high viscosity, splashing, producing satellite

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droplets, and insufficient energy for drop formation [92].
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Fig. 13 Impact types of droplets on powders [134].

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Fig. 14 Model of droplet penetration in a single pore. R is the radius of the droplet. ∆P

is the pressure gradient. θ is the contact angle between droplet and powders. dl/dt is

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the flow rate of the droplet in a single pore. r is the radius of a single pore.

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Fig. 15 Flexural strength and green density at different layer thicknesses [46].

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Fig. 16 Disintegration of the green body printed at the layer thickness of 200 µm [46].

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Fig. 17 Schematic of shell/core regions. The dark edges and the small regions in the

inner zone are the shell regions with the higher binder saturation. The grey area in the

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inner zone is the core with lower saturation [150].

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Fig. 18 Schematic illustration of the 3D-printed layers with nominal-and

high-saturations levels. Layer n-1 has been printed first, while layer n has been

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printed last [150].

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Fig. 19 Influence of the ratio of maltodextrin to water on green and sintered strengths

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[56].

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Fig. 20 Different placement orientations for rectangular parts. The left, middle, and

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right sides of the rectangular parts are respectively parallel to the bottom of the

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building chamber [148].

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Fig. 21 The top view of samples in three orientations. X, Y, and Z represent the height

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direction of the samples parallel to the X, Y, and Z axes, respectively. The black frame

region represents the sprayed binders that the printhead moves along the moving

SC
orientation [145].

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Fig. 22 Schematic of the porogen insertion mechanism (PIM) system [157].

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Fig. 23 SEM images of (a) raw alumina particles and (b) alumina particles

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encapsulated with amorphous alumina [127].

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Fig. 24 Relationships among the infiltration time, porosity, and SiC volume fraction

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[71].

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Fig. 25 Relationship among infiltration temperature, open porosity, and flexural

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strength [61].

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Fig. 26 Relationship between PIP’s number of cycles and σdc [72].

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