Ceramics International xx (xxxx) xxxx–xxxx

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Ceramics International
journal homepage: www.elsevier.com/locate/ceramint

Fabrication of dense zirconia-toughened alumina ceramics through a

stereolithography-based additive manufacturing
⁎
Haidong Wua,1, Wei Liua, ,1, Rongxuan Hea, Ziwei Wua, Qiangguo Jianga, Xuan Songb,
⁎
Yong Chenb, Lixia Chenga, Shanghua Wua,
a
School of Electromechanical Engineering, Guangdong University of Technology, Guangzhou 510006, Guangdong, China
b
Epstein Department of Industrial and Systems Engineering, University of Southern California, Los Angeles, CA, USA

A R T I C L E I N F O A BS T RAC T

Keywords: We report a novel approach to fabricate dense zirconia-toughened alumina (ZTA) ceramics with excellent
Additive manufacturing properties via an additive manufacturing process based on stereolithography. The XRD patterns show the ZTA
B. Microstructure sample consists of α-Al2O3 and t-ZrO2 with the dominance of α-Al2O3. The zirconia grain with the average size
B. Mechanical properties of 0.35 µm is small enough to trigger the toughening behavior of zirconia in the ZTA. The prepared ceramics
B. Toughness and toughening
showed a density, Vickers hardness, bending strength, and fracture toughness of 4.26 g/cm3, 17.76 GPa,
530.25 MPa, and 5.72 MPa m1/2, respectively. These properties are comparable to those for ceramics obtained
through conventional ceramic processing.

1. Introduction
Due to their excellent properties, e.g., their high hardness, high
strength, high fracture toughness, good mechanical strength at high
temperatures and good thermal shock resistance, zirconia-toughened
alumina (ZTA) ceramics have been widely used for various applications
such as cutting tools, biomedical implants and structural parts [1–3].
Conventional ceramic-shaping methods, such as dry pressing, isostatic
pressing, slip-casting, tape-casting [4–7] and injection molding [8],
have been used to fabricate ZTA ceramics for decades. However, these
conventional manufacturing techniques have limitations, and usually
cannot be used for the fabrication of parts with complex shapes
(internal holes, sharp corners, etc.) and parts requiring a high accuracy.
These processes are also rather time-consuming and of high cost
because they require the fabrication of a mold and a pots-machining
processing (cutting, grinding, etc.) after sintering. Therefore, it is
necessary to develop a more effective and economical approach to
fabricate complex ceramic parts.
Additive manufacturing (also referred to as 3D printing) is a rapid
prototyping technology and can be used to fabricate three-dimensional
(3D) parts very quickly, without molds, and offers a good alternative.
This new approach allows fabrication of ceramic parts with complex
geometries and is more efficient than conventional shaping methods.
In this approach, a ceramic part is directly produced from a virtual
model by gradually adding material to eventually form the final part.
This method not only saves time but also allows fabrication of parts
with arbitrary geometries [9].
Preparation methods of ceramics via 3D printing could be divided
to direct processing and indirect processing. For direct processing,
Selective Laser Melting (SLM) offers the opportunity to fabricate
complex shaped bulk ceramics directly from loose powder. For
instance, Hagedorn et al. [10,11] adopted the selective laser melting
technique to fabricate Al2O3-ZrO2 eutectic parts and were able to
achieve a density of almost 100%. Niu et al. [12] adopted a laser-based
net shaping method to fabricate Al2O3-ZrO2 eutectic ceramic structures
and reported that the fabricated ceramics showed mechanical proper-
ties similar to ceramics obtained through conventional methods.
However, Direct techniques immediately yield the sintered ceramic
parts but may produce a large number of defects due to internal
stresses induced by temperature gradients or the very rough surfaces.
Therefore, micro-cracks would occur easily in the samples due to the
high local stresses [13–15].
On the other hand, stereolithography (SLA), an indirect 3D printing
method which does not need a high energy laser beam, is based on the
photopolymerization of a liquid resin filled with ceramic particles
which could avoid the defects coming from the internal stresses and
offers several advantages such as a high accuracy and a good surface
finish of the products. However, most previous studies on SLA focused
on improving the rheological properties and the curing behaviors of the
suspension [16–22]. For instance, Griffith and Halloran discussed the

⁎
Corresponding authors.
E-mail addresses: 317127238@qq.com (W. Liu), swu@gdut.edu.cn (S. Wu).
1
Both authors contributed equally to this work.

http://dx.doi.org/10.1016/j.ceramint.2016.10.027
Received 17 September 2016; Received in revised form 3 October 2016; Accepted 4 October 2016
Available online xxxx
0272-8842/ © 2016 Elsevier Ltd and Techna Group S.r.l. All rights reserved.

Please cite this article as: Wu, H., Ceramics International (2016), http://dx.doi.org/10.1016/j.ceramint.2016.10.027
H. Wu et al. Ceramics International xx (xxxx) xxxx–xxxx

flow behavior of ceramic suspensions and raised the cure depth model
by employing a modified Beer-law [16]. Zhou et al. studied the
influence of the dispersant, the volume fraction of powder and particle
diameter in a new aqueous ceramic suspension [17]. Tomeckova et al.
investigated the critical energy for photopolymerization of silica and
alumina suspensions and spotted the relationship between critical
energy dose and inhibitors, photoinitiator concentration, inert dye
concentration, respectively [18]. To the best of our knowledge, the
production of ZTA ceramic parts by SLA with excellent mechanical
properties has not been achieved so far.
In this work, dense and crack-free ZTA ceramic was fabricated
through SLA and pressureless sintering. The XRD analysis was
conducted to identify the phase composition of the SLA-processed
ZTA. The microstructure of the ZTA sintered body and the grain size of
zirconia and alumina grains in ZTA body are characterized. Mechanical
properties such as the Vickers hardness, bending strength, and fracture
toughness were tested and compared with those obtained through
conventional shaping methods. In addition, dentoid ceramic parts were
produced as well to demonstrate the feasibility of the SLA approach to
fabricate complex parts and to underline the broad application
potential of this fabrication technique.
second layer was cured analogously. These steps were repeated until
the whole green body of the ZTA part was eventually obtained.
2.4. Post processing of the ZTA green body
1) Drying
After the green body was obtained, the residual water in the
sample had to be removed by drying. A novel drying approach
based on using PEG 400 as the liquid desiccant was adopted in this
study [23]. For the PEG-based extraction process, the sample was
immersed in PEG 400, which was expected to result in a uniform
extraction rate in all directions.
2) Debinding
A two-step debinding profile consisting of a vacuum debinding
step followed by an air pyrolysis debinding step was adopted to
remove the binders in the compact, which is shown as follows:
Firstly, the samples were heated at 600 °C for 3 h in vacuum with
the heating rate of 1 °C/min. Secondly, the samples after vacuum
debinding were heated at 1000 °C for 30 min in air with the heating
rate of 5 °C/min.
3) Sintering

2. Experimental procedure The samples were finally sintered at 1600 °C for 4 h in a furnace
(Thermconcept, HTK 16/18, Germany).
2.1. Powder mixture preparation

2.5. Characterization
First, the as-received alumina powder (TM-DAR, d50=200 nm,
BET=13.5 m2/g, TAIMEI CHEMICALS, Japan) and zirconia powder
The density of the prepared ZTA bodies was determined employing
(HWYA-N-1S, d50=200 nm, BET=12 m2/g, Guangdong Orient Zirconic
the Archimedes’ principle using a balance with an accuracy of 0.0001 g.
Ind. Sci. Tech. Co., China) were mixed together, with the weight ratio of
The theoretical density of the ZTA part used in this study was 4.28 g/
alumina/ zirconia=4:1. The mixture was then diluted in ethanol with
cm3. The Vickers hardness was tested using a Vickers hardness testing
ultrasound. After that, the mixture was ball-milled in a planetary ball
machine (HVS-30Z, Shanghai Precision Instrument Co., Ltd., China)
mill for 6 h using zirconia balls. The suspension was then dried in an
by applying a load of 98 N. The fracture toughness was assessed by
oven at 60 °C for 12 h. Finally, the dried powder was sieved through a
measuring the crack lengths produced by the Vickers indentation tests
100 mesh screen.
under a load of 98 N after 10 s. The fracture toughness was then
calculated using the following equation proposed by Niihara I [24]:
2.2. Preparation of the ceramic suspension
3
0.129 ⎛ c ⎞ 2 ⎛ H ⎞−0.4
−
The premixed solution used to prepare the ceramic suspension KIC = ⎜ ⎟ H a⎜ ⎟ (c / a > 2.5)
3 ⎝ a ⎠ ⎝ 3E ⎠
consisted of four components: acrylamide (23.75 wt%), N, N′ methy-
lenebisacrylamide (1.25 wt%), glycerine (10 wt%), and deionized water where E is the material’s Young's modulus, H is the hardness, P is the
(65 wt%). Then, the as-prepared powder was added to the premixed indentation load and c is the length of the indentation cracks. At least
solution with the volume fraction of 30 vol%, and polyvinyl pyrrolidone 10 indentation tests were performed for each sample at randomly
(PVP) K-15 was selected as 1.2 wt% of the powder, which was used as chosen spots. The radial crack lengths were measured using an optical
the dispersant to form the ceramic suspension. The ceramic suspension microscope. Ten specimens with dimensions of 25 mm (L)×2 mm
was then ball-milled for 12 h using zirconia balls. The suspension was (W)×1.5 mm (H) were fabricated for the flexural strength test. The
then de-gased for 30 min using a vacuum mixer. In order to produce a
UV-curable ceramic suspension, 2-hydroxy-2-methyl-1-phenyl-1-acet-
one was added to the ceramic suspension as initiator under ultrasound.
In this study, the mass fraction of the photoinitiator was selected to
1 wt% of the premixed solution.

2.3. Fabrication of the ceramic parts through stereolithography

The 3D model was created using the UG software, and then the
Magics software was employed to generate the supporting structure
and to slice the parts. The final data was then imported into the
stereolithography machine with its x-y resolution, laser beam diameter,
and layer thickness of 0.1 mm, 0.06 mm, and 0.07 mm, respectively.
The ZTA green body was obtained by stereolithography using the
ceramic suspension mentioned above. A schematic illustration of the
stereolithography process is shown in Fig. 1..
Each individual pattern layer was cured by the ultraviolet laser
selective scanning on the ceramic suspension. After the first layer was
cured, the supporting platform was moved down, and the ceramic
suspension was recoated on the cured surface with a blade. Then, the Fig. 1. Schematic illustration of the stereolithography process.

2
H. Wu et al. Ceramics International xx (xxxx) xxxx–xxxx

3. Results and discussion

3.1. Analysis of the phase composition and microstructure

Fig. 2 shows the XRD patterns obtained for the sintered ZTA
sample. The pattern indicates that the ZTA sample consists of two
phases – α-Al2O3 and t-ZrO2. The α-Al2O3 phase appears to be
predominant whereas the amount of t-ZrO2 in the sample seems to
be considerably smaller, which reflects the composition of the mixed
powder..
The microstructure of the polished surface of the sintered ZTA body
is revealed in Fig. 3(a). The zirconia particles were found to be well-
dispersed along the grain boundaries of the alumina grains, and some
of them were located at the triple junctions. In addition, the micro-
structure of the ZTA sample is very dense, with only a small number of
pores located at the grain boundaries. The grain size distributions for
the alumina and zirconia grains are shown in Fig. 3(b) and (c),
respectively. According to Fig. 3(b, c), the mean grain size of the
Fig. 2. XRD pattern obtained for the polished surfaces of the ceramic body after
alumina and the zirconia grains is 1.08 and 0.35 µm, respectively. The
sintering at 1600 °C.
zirconia grain size is small enough to trigger the toughening behavior of
zirconia in the ZTA body [25]. Regarding the toughening mechanism,
flexural strength of the sintered parts was determined through a three-
the fine ZrO2 particles located at the grain boundaries of the Al2O3
point bending test. The phase composition of the prepared ceramic
inhibit the movement of the Al2O3 grain boundaries and suppress the
parts was determined by X-ray diffraction (XRD, Bruker D8,
grain growth of Al2O3. Therefore, the improvement of the grain
Germany), and the microstructure of the sintered body was character-
boundary structure results in an enhancement of the mechanical
ized by scanning electron microscopy (SEM, Nova NanoSEM 430, FEI,
properties [26]..
Netherlands).

3.2. Mechanical properties

The density of the sintered ZTA sample was measured to be 4.26 g/

cm3, which corresponds to 99.5% of the theoretical density (T.D.%) of

Fig. 3. (a) Microstructure of the polished surface of the ceramic body after sintering at 1600 °C. (b) Grain size distribution of the alumina grains (c) Grain size distribution of the
zirconia grains.

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H. Wu et al.
Table 1
Systematic comparison of the mechanical properties of ZTA ceramic parts fabricated via stereolithography and other forming techniques.
Fabrication method Mass Ratio (Al2O3:ZrO2)
SLA (this work) 4:1
Dry-pressing pressureless sintering- ~ 98%
HIP[5]
SLM[10] 1.4:1
LENS[12] 1.4:1
CIM[27] 4:1
Dry-pressing Pressureless sintering[28] 4:1
Fig. 4. ZTA ceramic dentoid parts fabricated through stereolithography and pressureless
sintering.
the sintered ZTA body. The mechanical properties of the sintered ZTA
body are illustrated in Table 1. The average Vickers hardness, the
bending strength and the fracture toughness of the ZTA ceramic were
determined to be 17.76 GPa, 530.25 MPa and 5.72 MPa m1/2, respec-
tively.
The mechanical properties of the ZTA ceramics fabricated in this
study are essentially identical to those of ZTA ceramics produced via
the conventional fabrication routes mentioned above, and a systematic
comparison of the mechanical properties measured in the present
study with the corresponding properties of ZTA ceramics prepared
through other forming techniques is shown in Table 1 [5,10,12,27,28].
In addition, a complex shape could be easily prepared using the
presented SLA technique. As shown in Fig. 4, a net-shape dentoid part
can be obtained through SLA without any post-processing. Therefore,
the fundamental study of this paper offers an alternative approach with
complex shape and flexibility for fabricating structural ceramic parts..
4. Conclusions
In summary, we reported a new way to fabricate complex ZTA
ceramic parts with excellent properties via a 3D printing process based
on stereolithography. ZTA ceramic is composed of the majority of α-
Al2O3 and the minority of tetragonal YSZ according to the XRD
patterns. The zirconia particles were found to be well-dispersed along
the grain boundaries of the alumina grains, and the microstructure of
the ZTA sample is very dense, with only a small number of pores
located at the grain boundaries. The zirconia grain with the mean size
of 0.35 µm is small enough to trigger the toughening behavior of
zirconia in the ZTA body. The Vickers hardness, bending strength, and
fracture toughness of the sintered body were 17.76 GPa, 530.25 MPa,
and 5.72 MPa m1/2, respectively. These values are comparable to those
reported for ZTA ceramics prepared via conventional ceramic shaping
methods.
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Relative density Hardness Bending strength (MPa) Fracture toughness (MPa m1/2)
99.5% 17.76 ± 0.21(GPa) (GPa) 530.25 ± 29.57 5.72 ± 0.50
18.2(GPa) ~ 4.2
Nearly 100% ~ 500 ~
Nearly 100% 17.15(GPa) ~ 4.79
98% 1582.4HV ~ ~
~ 1516HV ~ 5.93
Acknowledgements
This work was financially supported by the Science and Technology
Project of Guangdong Province (Grant no. 2016B090915002), the
Research Fund for the Introduction of the Leading Talents of
Guangdong Province (Grant no. 40012001), the National Natural
Science Foundation of China (NSFC, Grant no. 51502041) and State
Key Laboratory of New Ceramic and Fine Processing Tsinghua
University (Grant no. KF201605).
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