Progress in Solid State Chemistry 41 (2013) 20e54

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Progress in Solid State Chemistry

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Transparent ceramics: Processing, materials and applications

S.F. Wang a, J. Zhang b, D.W. Luo a, F. Gu a, D.Y. Tang c, Z.L. Dong a, G.E.B. Tan a, W.X. Que d, T.S. Zhang e,
S. Li e, L.B. Kong a, *
a
School of Materials Science and Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
b
Temasek Laboratories, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
c
School of Electric and Electronic Engineering, Nanyang Technological University, 50 Nanyang Avenue, Singapore 639798, Singapore
d
Electronic Materials Research Laboratory, School of Electronic and Information Engineering, Xi’an Jiaotong University, Xi’an 710049, Shaanxi, PR China
e
School of Materials Science and Engineering, The University of New South Wales, Sydney, NSW 2052, Australia

a b s t r a c t
Keywords: Transparent polycrystalline ceramics have found various applications, such as laser hosts, infrared (IR)
Transparent ceramics windows/domes, lamp envelopes and transparent armors, instead of their single crystal counterparts,
Densification
due mainly to their processing flexibility in fabricating items with large sizes and complex shapes and
Microstructure
Optical property
more importantly cost-effectiveness. High optical transparent ceramics require high purity and high
Nanoceramics density. To achieve high purity final products, it is necessary to use high purity precursor powders. To get
Nanocomposite ceramics high density, various sintering technologies have been employed, such as high-pressure (HP) sintering,
high isostatic pressure (HIP) sintering, vacuum sintering and spark plasma sintering (SPS). At the same
time, various wet chemical synthesis routes have been used to produce precursor powders at submicron
or even nanometer scales, with significantly improved sinterability. Transparent ceramics for armor and
IR window/dome applications should have superior mechanical and thermal properties. Therefore,
nanosized ceramics and nanocomposite ceramics have attracted much attention more recently. This
review was aimed to summarize the latest progress in processing, materials and applications of trans-
parent ceramics. It is arranged by starting with a brief introduction, followed by a detailed description on
various sintering technologies used to develop transparent ceramics. After that, potential applications of
transparent ceramics, together with their optical, mechanical and thermal properties, will be discussed. It
will be concluded with discussions on future trend and perspectives, as well as some important issues, of
transparent ceramic materials.
Ó 2012 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .21
2. Transparent ceramics technologies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.1. Hot pressure (HP) sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 22
2.2. Hot iso-pressure (HIP) sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
2.3. Vacuum sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.4. Spark plasma sintering (SPS) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
2.5. Microwave sintering . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3. Materials of transparent ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.1. Oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.1.1. Al2O3 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
3.1.2. ZrO2 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
3.1.3. Sesquioxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
3.1.4. MgO . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
3.2. Complex oxides . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
3.2.1. YAG . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35

* Corresponding author. Tel.: þ65 67905032; fax: þ65 67909081.

E-mail address: elbkong@ntu.edu.sg (L.B. Kong).

0079-6786/$ e see front matter Ó 2012 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.progsolidstchem.2012.12.002
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54 21

3.3. MgAl2O4 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
3.4. ALON . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
3.5. Electro-optic ferroelectric ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.5.1. PLZT . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
3.5.2. Other ferroelectric ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 44
3.6. Mullite . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4. Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.1. Laser . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
4.2. Armor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 46
4.3. Lighting . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.4. Other applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.4.1. Scintillators . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.4.2. Transparent electro-optic ceramics devices . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
4.4.3. Optical systems (lens) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 47
5. Discussion and concluding remarks . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 48
Acknowledgement . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 49

1. Introduction machining of single crystals to meet the requirement of specific

applications is a difficult task. Other problems of single crystals
In the field of optics, transparency (also known as pellucidity or include difficulty of large-scale production and mechanical brit-
diaphaneity) is the physical property of materials of allowing light tleness of some materials. In this respect, transparent ceramics
to pass through it without being scattered. At macroscopic scale, become more and more important. Transparent ceramics have
where the dimensions investigated are much larger than the various advantages over single crystals, such cost-effectiveness,
wavelength of photons, the behavior of the photons follows the large-scale production, feasibility of shape controlling and better
Snell’s law. Translucency (also known as translucence or trans- mechanical properties.
lucidity), is a material optical property, which means it allows light Different from single crystals, ceramics have various sites to
to pass through, but does not necessarily follow the Snell’s law at scatter light, including mainly residual pores within the grains and
macroscopic scale. In this case, the photons could be scattered at the grain boundaries, grain boundaries, second phases (impuri-
either internally or at the interfaces where there is a change in ties) at the grain boundaries and double refraction from birefrin-
index of refraction. The opposite property of translucency is gent materials.
opacity. Transparent materials appear clear, with an overall The most significant factor to the transparency of a ceramics is
appearance of one color or any combination leading to a brilliant the porosity. The surface of a pore is a boundary between phases
spectrum of every color. When light shines a material, it can with sharply different optical characteristics, which therefore
interact with the material in several different ways. These inter- intensely reflects and refracts light. The presence of a large number
actions are closely dependent on both the wavelength of the light of pores makes ceramics opaque. Pores could be intergrain or
and the nature of the material. Photons interact with an object by intragrain. The elimination of intragrain pores, even if they are
some combinations of reflection, absorption and transmission. submicron in size, is a more difficult and much longer process than
Conventional optical transparent materials mainly include the elimination of closed intergrain pores. Intergrain pores are
glasses, polymers and alkali hydrides, which have been widely used located at grain boundaries, acting as sinks of vacancies, which
in industries and daily life. However, these materials have relatively makes it easier to remove them.
poor mechanical strengths and sometimes insufficient chemical and Ceramics consist of grains and grain boundaries. If there is
physical stabilities. More importantly, the conventional transparent difference in properties (e.g. compositions) between grains and grain
materials have a strong absorption in the IR range, making them not boundaries, the interfaces between them will become scattering
suitable for applications in this spectral range. Also, they usually cites of light. To be transparent, the difference in optical behaviors
possess relatively low melting temperatures (<600  C), so that they between grains and grain boundaries should be minimized. Trans-
cannot be used for applications at high temperatures. As a result, it is parent ceramics have less clear grain boundaries than opaque
desirable to develop new transparent materials that can be used for ceramics. The presence of a second phase at the grain boundaries is
applications operating in harsh and extreme environments. general the most common reason for opacity. Therefore, to fabricate
With the advancement in technologies in material growth, transparent ceramics, it is necessary to use raw material of high
single crystals of some compounds appeared as new transparent purity and to avoid any possible contamination during processing.
materials. Compared to the conventional transparent materials, Besides, carefulness should be taken when selecting additives. For
single crystals, such as sapphire (Al2O3) for IR windows, YAG example, the amount of additives must be as low as possible, so that
(yttrium garnet, Y3Al5O12) for lasers and PZNePT (lead zinc they completely dissolve to form solid solution with the main phase,
niobateelead titanate, PbZn1/3Nb2/3O3ePbTiO3) for electro-optics, without the presence of second phases.
addressed most of the problems that are encountered by the Crystal structure plays an important role in determining
conventional transparent materials. However, growth of single whether a ceramics can be optically transparent or not. In ceramics
crystals requires sophisticated facilities and is very time of optically anisotropic crystals, an additional scattering of light
consuming, thus leading to expensive products that are only used arises at the boundaries when the light travels from one grain to
in cases where cost is not necessarily considered. Furthermore, as- another. This is the reason why transparent ceramics generally have
grown single crystals usually have shapes determined by more a cubic lattice structure, which is isotropic, such as MgO, Y2O3, YAG,
their lattice structures and less by processing conditions. Therefore, and MgAl2O3 (spinel).
22 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Besides those internal factors, there are also external factors that
affect the transparency of a ceramic sample, including thickness
and surface finish. A rough surface means a significant diffuse
scattering, so the sample surface should be as smooth as possible.
Generally, transparency decreases with increasing thickness.
Thickness independent transparency is only possible when the
material reaches its theoretical maximum of in-line transmission.
In summary, the strategy to develop transparent ceramics is to
eliminate all possible scattering sites of light, including high
density (>99.9% of theoretical density), absence of pores at grain
boundaries or pores with size much smaller than the wavelength of
light, absence of second phase (impurity or glass phase) at grain
boundaries (negligible difference in optical property between
grains and grain boundaries), small grain size (as compared to the
wavelength of visible light) with uniform size distribution, isotropic
lattice structure and high surface finish.
This paper aims to provide an overview on the recent progress
in fabrication and characterization of transparent ceramics for
various applications. The techniques used to develop transparent
ceramics will be introduced first. After that, materials that are used
for transparent ceramics and their applications in various areas will
be described and discussed. The review will be ended with
concluding remarks.
2. Transparent ceramics technologies
Similar to that of general ceramics, the process of transparent
ceramics also consists of synthesis of precursor powder, compact-
ing, calcination/sintering and post-treatment (annealing,
machining and polishing). However, the process of transparent
ceramics has its special requirements, especially for the powder
synthesis and sintering. Because the synthesis of high quality
powders for transparent ceramics is not significantly different from
that for other materials, which can be found widely in the open
literature, here we only focus on the sintering techniques, including
Fig. 1. Schematic diagram of high-temperature high-pressure sintering facility.
hot pressure (HP), hot iso-pressure (HIP), vacuum sintering, spark
plasma sintering (SPS) and microwave sintering.
2.1. Hot pressure (HP) sintering
Hot pressure (HP) sintering is a high-pressure low-strain-rate
powder metallurgy process for forming of a powder or powder
compact at a temperature high enough to induce sintering and
creep processes. This is achieved by the simultaneous application of
heat and pressure. Densification at high pressure works through
particle rearrangement and plastic flow at the particle contacts. HP
is mainly used to fabricate hard and brittle materials. As a result,
HP has become an important technique to obtain transparent
ceramics. Fig. 1 shows a schematic diagram of typical high-
temperature high-pressure (HTHP) sintering facility. It consists of
a graphite furnace, sheathed by CaF2 and Pb foil. The CaF2 layer
crumbles at high pressure and thus acts a pressure-transmitting
medium. The Pb foil acts a lubricant for the furnace assembly
during the push-out after the experiment.
In 1977, translucent spinel with small grain size (w1 mm) was
prepared by using a low temperature (1400  C) and high-pres-
sure (70 MPa) hot pressing [1]. Since then, HP has been widely
used to prepare transparent spinel ceramics. For example, Cook
et al. [2] used HP process to fabricate MgAl2O4 transparent
ceramics, with a nearly 100% densification. Different from the
conventional sintering process which usually requires high sin-
tering temperatures (>1600  C), HP process is able to achieve
desired densification at relatively low temperatures, which is
therefore also called low-temperature high-pressure (LTHP)
process. Due to its low-temperature requirement, it can be used
to develop nanosized ceramics [3e6]. The sintering mechanism at
high pressures is entirely different from that at ambient pressure.
High pressure can restrain grain growth and initiate plastic
deformation to eliminate pores and/or additional phases existing
in triple junctions of the grains. However, the conventional
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
sintering process is controlled by grain growth to avoid imper-
fections between grain boundaries when preparing transparent
ceramics.
It has been reported that transparent MgAl2O4 spinel nano-
ceramics can be obtained at very low temperatures (500e700  C) at
high pressures (2e5 GPa) by using a hydrostatic press with high-
temperature-calcined nanosized powders [3]. The nanoceramics
were highly transparent even though their relative densities are
less than 99%, due to the low or negligible light scattering from the
nanosized grains and pores. The LTHP process is able to densify
nanosized powders without significant grain growth, which
becomes a key advantage for the development of transparent
ceramics, as discussed above.
Similar process was also successfully used to develop yttrium
aluminum garnet (Y3Al5O12 or YAG) transparent nanoceramics [7].
Fig. 2 shows a schematic diagram of the high-pressure cell. Disk
samples were placed in a capsule made of NaCl, which was used to
ensure the quasi-hydrostatic compression of the sample and to
prevent its contact with the graphite heater, and then contained in
the pyrophyllite high-pressure cell. The sample temperature in the
high-pressure cell was measured directly by using a standard Nie
Cr/NieSi thermocouple. The cell pressure was monitored by using
a calibrated oil pressure meter. Desired pressures were first applied
to the samples before raising the temperature. The pressure range
was 2.0e5.0 GPa and temperature range was 300  Ce500  C, with
holding time of 30 min. After that, the pressure was reduced to
ambient pressure first and then the samples were cooled down to
room temperature at a rate of 15  C/min. By doing in this way,
the residual stress of the samples could be readily released and
cracking could be avoided. Optimized processing parameters for
transparent YAG ceramics were 5 GPa and 450  C, as shown in
Fig. 3.
The application of HP allows for more freedom to optimize the
sintering parameters, which has been demonstrated when HP
sintering is used to fabricate transparent Y2O3 ceramics [8e10]. For
instance, Podowitz et al. [10] reported step-wise process to develop
Y2O3 transparent ceramics. The program included a high-
temperature ramp at constant pressure and a pressure ramp at
constant high temperature. After a dwell at 1150  C to outgas the
samples, a pressure of 10 MPa was applied to the samples, followed
by a temperature ramp at 8  C/min to 1580  C. After a 30 min dwell
at constant temperature and pressure, the pressure was ramped at
0.4 MPa/min to 40 MPa. The samples were then soaked at
maximum temperature and pressure for 8 h. The highest level of
transparency was found for 5 at.% Eu:Y2O3 hot pressed with a step-
Fig. 2. Schematic diagram of the sample assembly part in low-temperature high-pressure (LTHP) sintering experiments: (1), pyrophyllite, (2) dolomite, (3) ceramic tube, (4)
thermocouples, (5) graphite heater, (6) NaCl capsule, (7) hBN, (8) WC substrate, (9) NaCl sheet, (10) sample, (11) Mo sheet and (12) steel heater lead. Reproduced with permission
from Ref. [7], Copyright 2012, Elsevier.
23
wise application of pressure up to a maximum temperature of
1580  C.
HP sintering process is a very unique and feasible technique to
prepare transparent electro-optic ceramics, including PLZT [11e13],
PZNePLZT [14] and PMNePT [12,15], which contain volatile
element, Pb. In the early 1970s, Haertlin and Land synthesized
(Pb,La)(Zr,Ti)O3 (PLZT) ferroelectric ceramics by using HP
[11]. Highly transparent ceramics of La-doped 0.75Pb(Mg1/3Nb2/3)
O3e0.25PbTiO3 (PMNePT) were fabricated by using a two-stage
sintering method [15]. Green pellets were first sintered in an
oxygen atmosphere at different temperatures, which were then hot
pressed (HP) at temperatures of >1000  C for more than 8 h at
pressures of 50e100 MPa. The ceramics prepared in this way
exhibited a transparency of as high as 65% at infrared wavelength.
Large quadratic electro-optic coefficient of 66  1016 (m/v)2 was
obtained, which was the highest value reported in the literature for
the ceramics with similar compositions. SEM images indicated that
the PMNePT ceramics with higher transparency had more grains
with transgranular fracture behaviors. It is suggested that grain
boundary with an increased homogeneity and firm strength might
reduce the reflection and scattering of light at the grain boundaries
and thus improve the transparent property.
HP process was found to be the most feasible method to prepare
transparent or translucent a-sialon ceramics [16,17], which could not
be achievable by the conventional pressureless sintering. Single
phase a-sialon ceramics with high optical transmittance have been
prepared by using hot pressing [16]. HP was also used to tailor grain
morphologies and preferential texturing microstructures of a-sialon
ceramics [17e19]. Other examples include translucent MgO ceramics
fabricated by using hot pressing, using nanopowder of MgO con-
taining 2e4% LiF as a sintering aid [20]. HP process has even been used
to prepare fluoride ceramics (CaF2). Transparent Yb:CaF2 ceramics
processed by using HP were reported by Lyberis et al. [21,22].
2.2. Hot iso-pressure (HIP) sintering
Hot isostatic pressing (HIP) is a manufacturing process used to
reduce the porosity of metals and increase the density of various
ceramic materials. The HIP process subjects a component to both
elevated temperature and isostatic gas pressure in a high-pressure
containment vessel. The chamber is heated, causing the pressure
inside the vessel to increase. Many systems use associated gas
pumping to achieve the desired pressure levels. Pressure is applied
to the material from all directions.
24 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54

Fig. 3. Photographs of the YAG ceramics processed at various conditions (pressure/temperature) by using the LTHP sintering. Reproduced with permission from Ref. [7], Copyright
2012, Elsevier.

Materials are hot isostatically pressed (HIPed) in order to ach-
ieve the maximum possible densification, which is a key to
achieving high light transmittance. To reduce the fabrication cost,
hot isostatic pressing is usually used as the last step, although it has
been proved to be a critical step to prepare high quality transparent
ceramics, because HIPing is a high cost process needing critical
equipment and experimental conditions.
HIP process has been widely used to synthesize transparent
armor ceramics, such as alumina (Al2O3) [23e25] and spinel
(MgAl2O4) [26e28]. HIP process can be combined with HP. Hot
pressing followed by hot isostatic pressing (HIPing) proved to be
more feasible to fabricate transparent MgAl2O4 ceramics was
widely used [26e28]. Nowadays, HIP process was also used to
synthesize cubic sesquioxide ceramics, including Y2O3 [29], Sc2O3
[30] and Lu2O3 [31]. In these cases, vacuum sintering to remove
closed porosity with a subsequent HIP step was usually employed,
which provided an alternate processing route to the fabrication of
fully dense sesquioxide ceramics with less possibility for contam-
ination and reduction than hot pressing.
Highly transparent 8 mol% Y2O3eZrO2 (8YSZ) ceramics were
fabricated by using an improved hot isostatic pressing method [32].
Combined with pre-sintering treatment, microstructures, such as
positional difference in residual pores, inter- or intragranular pores,
of the 8YSZ ceramics could be well controlled. A microstructure
model for pore elimination by hot isostatic pressing was proposed,
as shown in Fig. 4. At low pre-sintering temperature, small inter-
granular pores are surrounded with fine grains, while at high pre-
sintering temperature, intergranular pores transform to intra-
granular ones with grain growth. It is probable that such inter-
granular pores are easily removed by hot isostatic pressing. The
model has been found to be applicable to many other oxide
ceramics [33,34].
The feasibility of HIP can be further demonstrated by the
following examples. Fully dense transparent garnet ceramics were
derived from cold pressed green bodies that were subsequently
vacuum sintered, with residual porosity being removed by hot
isostatic pressing [35]. Bhalla and Alberta reported the use of hot
isostatic pressing (HIPing) to enhance the electrical and optical
properties of PNNZT (50.0/15.5/34.5) [36]. After hot isostatic
pressing at 1100  C, the density was increased to more than 99%.
Schneider et al. [37] reported synthesis of mullite ceramics by
pressureless sintered and hot isostatically pressed (HIPed) process.
In the HIPed mullite, with porosity of <1%, a transmittance of 40%
was observed in the VIS range and up to 80% in NIR. Aubry et al.
showed that transparent Yb:CaF2 ceramics could be synthesized by
sintering and hot pressing powders that were derived by a soft
chemistry process [38]. Uematsu et al. applied HIP process to
consolidate hydroxyapatite (HAp) filter-cakes [39]. HAp ceramics

Fig. 4. Microstructure model for pore elimination by hot isostatic pressing. Reproduced with permission from Ref. [32], Copyright 2008, John Wiley & Sons.
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
were fully densified at 800  C after 2 h when a hot isostatic pressure
of 100 MPa was used. Besides, transparent a-sialon ceramics [40],
transparent magnesium oxide (MgO) ceramics [41] and transparent
La2Hf2O7 (LHO) ceramics [42] were also fabricated by using HIP
process.
2.3. Vacuum sintering
Vacuum sintering refers to a sintering processes carried out in
a vacuum equipment to achieve better results than those run at
atmospheric pressure. Vacuum sintering is typically used to fabri-
cate transparent garnet and rare-earth sesquioxides ceramics,
including Y2O3 [43e45] and Sc2O3 [46,47].
When using vacuum sintering to fabricate YAG ceramics, the
procedure usually consists of vacuum sintering followed by air
annealing [48e64]. For example, transparent polycrystalline
Nd:YAG ceramics can be synthesized by using solid-state reactive
sintering the mixture of Al2O3, Y2O3 and Nd2O3 in a tungsten mesh-
heated vacuum furnace (M60, Centorr Vacuum) at 5  106 Torr
during holding [61]. Fully dense transparent samples with average
grain sizes of w50 mm were obtained at 1800  C. The sintering
temperature was slightly affected by the concentration of Nd.
A small amount of SiO2 doping lowered the sintering temperature
by w100  C. SiO2 is usually introduced by using tetraethyl ortho-
silicate (TEOS). After sintering, the specimens were annealed at
1400  C for 2 h in air for decoloring.
2.4. Spark plasma sintering (SPS)
Spark plasma sintering (SPS) is a newly developed method for
obtaining fully dense and fine-grained transparent ceramics at low
temperatures within short time durations [65e74]. It is also known
as field-assisted sintering or pulsed electric current sintering. A
schematic diagram of SPS is shown in Fig. 5 [82]. In normal hot
pressing, heating is accomplished externally by heating a coil, while
SPS uses a high density current flux flowing through the sample
and the die to cause Joule heating within the sample. SPS technique
has a significant advantage over HIP and HP, because it can
complete the powder consolidation within a short time duration
[66]. Because of this, it is a potential technique to densify nanosized
Fig. 5. Schematic diagram of spark plasma sintering (SPS). Reproduced with permis-
sion from Ref. [82], Copyright 2010, Elsevier.
25
powders, without the presence of significant grain coarsening that
is unavoidable during the standard densification routes. The
densification process in SPS is generally divided into three stages
[67]. The first stage is characterized by the packing of the particles,
the second stage is related to a diffusion process accompanying the
neck formation and grain sliding, and the final stage is the removal
of pores mainly through the grain boundary. An applied pressure
strongly affects the initial packing and densification in the second
and third stages. A high pressure is constantly applied in common
SPS process. Heating rate is another important sintering parameter
for densification in the second and third stages.
It was recently reported that transparent alumina with fine
grains can also be obtained by using SPS technique [68e74]. Owing
to the advantage of rapid heating, the alumina ceramics obtained
by SPS had grain sizes and densities comparable to those of the
HIPed ones [75e81]. For example, a fully dense (a relative density of
w100%) alumina with a grain size of 0.5 mm was obtained at
1200  C by SPS [68].
Spark plasma sintering (SPS) technique can be employed not only
to sinter polycrystalline alumina disks but also to fabricate hemi-
spherical domes [83,84]. As demonstrated by Jiang et al. [85], the
fabrication of transparent polycrystalline alumina domes could be
obtained by combining sintering and forming into one step in
minutes instead of hours needed when using conventional
methods. This forming method provides an unprecedented oppor-
tunity to make optically transparent domes at much lower costs.
A two-step pressure profile was used to demonstrate the
feasibility of SPS [86]. At low pre-load pressure, 5 MPa, with the
normal characteristic fast heating rate (100  C/min), high in-line
transmittance of 51% at 550 nm and 85% at 2000 nm can be ach-
ieved. Sintering was carried out in vacuum (4e6 Pa) with a Dr.
Sinter 2050 SPS apparatus (Sumitomo Coal Mining Company Ltd.,
Japan). The temperature was increased to 600  C within 3 min and
then further increased to 1250  C in 6 min; the final stage of heating
to 1300  C was finished in 1 min. The dwell time for all experiments
was 3 min. Five pre-load pressures, P1 ¼ 5, 10, 20, 30, 50 and
100 MPa, were selected. It is obvious that the samples prepared at
P1 of 30, 50 and 100 MPa have a darker discoloration core of about
8 mm in size in the center, as shown in Fig. 6 [86]. The discoloration
was attributed to the dislocations formed during the fast densifi-
cation. Fig. 7 shows in-line transmittance of the samples. It was
concluded that a pre-load pressure P1 should not be >20 MPa to
Fig. 6. Photographs of the transparent of MgAl2O4 ceramics sintered at 1300  C for
3 min at different pre-loaded pressure P1: 5 MPa (1.79 mm), 10 MPa (1.99 mm), 20 MPa
(1.82 mm), 30 MPa (1.89 mm), 50 MPa (1.82 mm) and 100 MPa (1.60 mm). The samples
are 15 mm above the printed text and the thickness of each sample is indicated in
parentheses. Reproduced with permission from Ref. [86], Copyright 2009, Elsevier.
26 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 7. In-line transmittance spectra of the polycrystalline MgAl2O4 sintered by SPS at
different pre-load pressures P1. The theoretical transmittance of a single crystal
MgAl2O4 was calculated based on the refraction index as a function of wavelength.
Reproduced with permission from Ref. [86], Copyright 2009, Elsevier.
obtain acceptable optical transmittance approaching the theoret-
ical limit in the wavelength range of >1000 nm.
SPS can also be combined with doping of sintering aids and
variation of processing parameters [87e89]. For instance, according
to Morita et al. [89], heating rate had a significant effect on trans-
parency of fine-grained spinel polycrystalline ceramics, as shown in
Fig. 8. The sample prepared with heating rates of <10  C/min
possessed an in-line transmission of 47% at 550 nm wavelength and
a fracture strength of w500 MPa. The fact that low heating rate SPS
processing led to high transmission and strength can be attributed
to the reduction in the residual pores to <0.5%. SEM results (Fig. 9)
indicated that the average grain size was kept almost unchanged
for different heating rates, while the average area fraction of
porosity was dramatically increased with increasing heating rate.
Therefore, the heating rate had a strong effect on the porosity and
thus the in-line transmission of the spinel ceramics.
Transparent ceramics processed by using SPS, such as yttrium
aluminum garnet (YAG) [90,91], sesquioxides [67,92e101], ZrO2
[97,102,103], mullite [104], HAp [105e107], MgO [108], non-oxide
AlN [109] have been widely reported in the open literature. Simi-
larly, SPS is an effect method to process electro-optic ceramics, such
as lanthanum-doped lead zirconate stannate titanate (PLZSnT)
antiferroelectric ceramics [110], PbZrO3ePbTiO3ePb(Zn1/3Nb2/3)O3
ferroelectric ceramics [111] and lanthanum-doped lead zirconate
titanate (PLZT) ceramics [112].
2.5. Microwave sintering
Microwave sintering is a special sintering process that is
fundamentally different from the conventional sintering process
Fig. 8. Photographs showing the appearance of spinel SPS processed at 1300  C for
20 min and at heating rates: (a) 2  C/min, (b) 5  C/min, (c) 10  C/min, (d) 50  C/min
and (e) 100  C/min. Reproduced with permission from Ref. [89], Copyright 2008,
Elsevier.
and the processing techniques discussed above. In microwave
process, the processed materials themselves absorb microwave
power and then convert microwave energy to heat within the
samples, and hence the heating is very rapid. Microwave processing
of materials has major advantages of higher energy efficiency,
enhanced reaction and sintering rate, short cycle time and cost
savings. Comparatively, microwave sintering to obtain highly
transparent ceramics can be conducted at lower sintering
temperatures and much shorter sintering times.
In 1999, Roy et al. reported synthesis of single phase ALON by
using microwave sintering at 1650  C for 1 h [113], while fully dense
and transparent ALON ceramics were fabricated [114] at 1800  C for
1 h. A total transmission of 60% was achieved for a polished sample
with a thickness of 0.6 mm. Transparent mullite ceramics were
developed by using microwave sintering at about 1300  C [115]. The
microwave sintering was carried out in a 2.45 GHz, 900 W micro-
wave furnace. The samples were heated in the microwave field
directly from room temperature to 1300  C and held at this
temperature for 10 min, then allowed to cool down naturally. The
results indicated that aerogel of mullite stoichiometry, free of
agglomeration and highly active, was key factor to achieving the
transparent mullite. Microwave sintering has also been used to
process other transparent ceramics.
3. Materials of transparent ceramics
As stressed earlier, transparent ceramics are mostly derived
from materials with isotropic lattice structure, i.e. cubic structure.
There have been various transparent ceramics, including simple
oxides, sesquioxides, complex oxides and aluminum oxynitride.
3.1. Oxides
3.1.1. Al2O3
Alumina (Al2O3) exhibits many interesting properties, such as
high strength, high hardness and excellent corrosive resistance.
This makes transparent Al2O3 ceramics a promising candidate for
applications as electromagnetic windows, transparent armor
and envelopes of high-pressure metal halide lamps [76]. Sintered
Al2O3 ceramics with submicrometer grain size are the hardest
of all transparent armor (including sapphire). Transparent poly-
crystalline alumina is believed to be a promising replacement for
sapphire. Photographs of representative Al2O3 transparent
ceramics are shown in Fig. 10.
Traditional transparent Al2O3 ceramics were prepared by sin-
tering in hydrogen at temperatures of generally above 1700  C
[116,117]. The high sintering temperature caused extensive grain
growth, which in turn seriously affected mechanical strength and
hardness of the materials. The large grain size (up to 410 mm) led to
significant light scattering caused by the birefringence of the coarse
Al2O3 grains [118]. Therefore, its in-line transmission was typically
below 10%. The low strength and in-line transmission posed an
almost insurmountable obstacle for their applications in fields
where high transparence and good mechanical properties are
required.
Optical and mechanical properties of transparent Al2O3
ceramics are highly dependent on their grain size and residual
porosity. Various strategies have been employed to control the
grain sizes and minimize the residual porosity. For this purpose,
fine-grained transparent Al2O3 ceramics have recently attracted
much attention [24,70e72,118e121]. The fine-grained ceramics
demonstrated a significant improvement in mechanical strength
and optical transparency. It has been reported that typical fine-
grained transparent Al2O3 ceramics had strength of up to 600e
800 MPa and high in-line transmission of up to 60% [24,119].
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 9. SEM images of the transparent spinel ceramics SPS processed at 1300  C for 20 min and at heating rates: (a) 2  C/min, (b) 10  C/min and (c) 100  C/min. Reproduced with
permission from Ref. [89], Copyright 2008, Elsevier.
Various strategies and technologies have been used to fabricate
fine-grained transparent Al2O3 ceramics.
A multiple-step pressureless sintering to obtain high quality
transparent Al2O3 ceramics was reported by Li and Ye [122].
Nanosized Al2O3 ceramics with an average grain size of 70 nm and
a relative density of 95% were obtained by using two-step sintering.
In this case, a-Al2O3 powders with a mean particle size of about
10 nm and a weak agglomeration were synthesized by using an a-
Al2O3 seeded polyacrylamide gel method. The densification and the
suppression of the grain growth are realized by exploiting the
difference in kinetics between grain-boundary diffusion and grain-
boundary migration. The densification was proceeded by the
slower grain-boundary diffusion without promoting grain growth
in second-step sintering.
By float packing and sintering in air, transparent alumina with
submicrometer grains was obtained by Godlinski et al. [123].
Commercial a-alumina powder with high purity, submicrometer
particle-size and narrow particle-size distribution was used as
starting material. The powder was dispersed and stabilized in
a water-based suspension. Controlled consolidation and drying by
float packing led to homogeneous green compacts, which could be
densified without additives by sintering in air at 1275  C to trans-
parency, while the mean grain size remained to be 0.4 mm. The in-
line transmittance at wavelengths of 300e450 nm was comparable
to commercial polycrystalline alumina tubes for lighting technol-
ogies, whose grain sizes are larger by a factor of 40.
Liu et al. [124] used injection moulding and pressureless sin-
tering in hydrogen to manufacture translucent alumina ceramics.
Translucent alumina components with small size and high preci-
sion were fabricated in such a stable, efficient and low cost route.
Excellent rheological properties of the feedstocks for injection
moulding were obtained through a method of powder pre-treat-
ment with stearic acid induced by ball milling. The average grain
Fig. 10. Photographs of representative Al2O3 ceramics (Ø 12 mm): (a) undoped sample
with real in-line transmittance (RIT) of 7.8% and (b) sample doped with 450 ppm Mge
YeLa with RIT of 57%. Reproduced with permission from Ref. [82], Copyright 2010,
Elsevier.
27
size of the sintered body was 30e50 mm, with no significant pores
and abnormal grain growth observed. The real in-line transmission
was higher and more stable than those via other forming tech-
nologies and pressureless sintering reported in the literatures.
Another pressureless method was reported by Lee et al. [125].
Translucent alumina brackets were prepared by using powder
injection molding (PIM). The powders were mixed with a binder
consisting of a mixture of paraffin wax and polyethylene. After
injection molding, debinding was performed using the wicking
method and samples were sintered in a vacuum at 1700  C to
achieve high density. Sintering additives (MgO, La2O3 and Y2O3)
were used to decrease the porosity. An improvement in trans-
lucency by promoting grain growth during the pressureless sin-
tering was observed. After sintering, Vickers hardness, bending
strength, density, and transmittance of the fabricated parts were
found to be comparable to those of the commercially available
dental brackets.
Doping has been found to be an effective technique in fabri-
cating transparent ceramics. MgO doping, combined with pre-
sintering heat treatment, was used to accomplish a high trans-
lucency in polycrystalline Al2O3 ceramics sintered at 1700  C in
vacuum [127]. The concentrations of MgO were 140, 500 and
2500 ppm. A pre-sintering heat treatment was 800  C for 50 h in air.
It was found that the pre-sintering heat treatment improved the
sample transmittance in the visible range (400e700 nm) signifi-
cantly. This enhanced transmittance was explained in terms of the
removal of residual pores and the homogenization of the micro-
structure, due to the lowering of the boundary mobility, as a result
of the MgO addition and the suppression of local densification
through the pre-coarsening step.
Liu et al. [128] reported a novel approach to fabricate trans-
lucent alumina ceramics induced by doping additives via chemical
precipitation. In this approach, alumina powder was first mixed
with metal nitrates and dispersed by PEG-2000 as dispersant, and
then the pH value was controlled by introducing NH3∙H2O into the
suspension to favor the precipitation of Mg2þ and Y3þ onto the
Al2O3 matrix. It was found that the dopants were smaller in size and
more homogeneously dispersed through the chemical precipitation
in the translucent alumina sample as compared with those derived
from conventional ball milling. The samples prepared by doping
through chemical precipitation had much higher transparency.
Solid loading is a critical factor to the fabrication of ceramic
compacts with high densities by using ceramic injection molding.
Different from the traditional approaches in which stearic acid (SA)
was introduced just in the powder blending process, Xie et al. [129]
successfully prepared feedstock with a much higher solid loading
up to 64 vol% by a prior ball-milling treatment of ceramic powders
with a small amount of SA. It was because SA could be coated
homogeneously on the powder surfaces by a chemical reaction
induced by the ball-milling treatment. Highly translucent Al2O3
ceramics were fabricated from the precursors.
28 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54

Translucent alumina ceramics were also obtained through Commercially available alumina powder could be consolidated at
incorporating MgO/Y2O3/La2O3 additives using infiltration and 1150  C by using SPS at a heating rate of 100  C/min. The effects of
gelling technique, combined with sintering in H2 atmosphere [130]. pressure application mode were examined with respect to micro-
The improved microstructural homogeneity, finer grain size and structure, porosity and transparency. The pressure was applied in
enhanced transmission properties of infiltration processed samples two ways. In the first case, a constant pressure of 80 MPa was
over those processed by conventional ball-milling method were applied for the entire duration of the sintering process (hereinafter,
corroborated by experimental results. Triple doping via infiltration constant pressure). In the second case, an initial pressure of 35 MPa
appears to be significantly beneficial for achieving enhanced was applied, subsequently the pressure was increased in 3 min
transmission (36.3% at wavelength 800 nm for sample thickness of after the beginning of dwelling time (hereinafter, two steps pres-
0.75 mm). sure). The application of two-step pressure was found to be very
Hotta et al. [131] reported the effect of oligosaccharide alcohol effective to obtain homogeneously densified translucent alumina
addition to alumina slurry and translucent alumina produced by samples at high heating rate.
slip casting. Transmittance of the Al2O3 ceramics produced by slip The influences of SPS sintering pressure and temperature, as
casting using the slurry with both NH4ePMA and oligosaccharide well as Mg, Y and La single or co-doping (75e450 ppm), on the RIT
alcohol was higher than that of ceramics produced by slip casting and grain size of Al2O3 ceramics, were systematically studied [82].
using the slurry with NH4ePMA alone. The increased optical Using optimized sintering parameters, RITs of >50% were attained
property resulted from the low viscosity, which was attributed to in the visible wavelength (640 nm) for 0.8 mm thick samples for
the addition of oligosaccharide alcohol, at a high solid content. almost all doping strategies. The best RIT of 57% was for triple-
It was reported that by using HIP, the sintering temperature of doped samples at a total dopant level of 450 ppm. These results
Al2O3 could be reduced to 1200e1300  C, at which the porosity were best among those in the published SPS studies. It means that
could be easily decreased to less than 0.05% and the grain size was a combination of doping and SPS could produce transparent Al2O3
suppressed to be less than 1 mm [24,33,118]. Similarly, Petit et al. ceramics with improved performances.
[23] described a simple method to fabricate Al2O3 ceramics with Brosnan et al. [126] reported to develop transparent Al2O3
almost 100% relative density by using HIP, combined with colloidal ceramics by using microwave sintering at 2.54 GHz. With no hold at
dispersion casting and a natural pre-sintering step. The Al2O3 sintering temperature, microwave-sintered samples reached 95%
ceramics prepared in this way had 60% of relative transparency for density at 1350  C, versus 1600  C for conventionally heated
a 1 mm thick sample, which was enough to observe well-resolved samples. Fig. 11 shows a schematic diagram of the microwave sin-
pictures at several kilometers across such windows. The grain size tering with a special designed insulating casket. The hole on the top
was about 600 nm and the residual porosity was about 0.14%. The cover was used for infrared pyrometry. SiC powder was used as
properties of transparent Al2O3 ceramics are also related to the a microwave absorber, acting as a low-temperature microwave
characteristics of the starting Al2O3 powders [132].
Alvarez-Clemares et al. [75] prepared transparent alumina/ceria
nanocomposites by using SPS. It was found that the use of ceria
nanoparticles strongly enhanced the transparency of the SPS sin-
tered compacts, which was attributed to at least two factors. Firstly,
the ceria nanoparticles acted as powder lubricant, increasing the
initial density of the powder in the SPS die by about 15%. Secondly,
the ceria nanoparticles, having a very low solid solubility in the
alumina grains, located at grain boundaries, hindering alumina
grain growth by pinning during SPS sintering at 1430  C, 80 MPa for
2 min. However, this effect is found to be effective only under SPS
vacuum conditions.
Suarez et al. [80] reported grain growth control and trans-
parency in SPS sintered self-doped alumina materials. Highly
transparent Al2O3 ceramics were obtained by using SPS from both
pure and aluminum ethoxide-doped powders. It was found that the
porosity was reduced in the self-doped samples, when the doping
content is below 1%. In this case, the improvement in in-line
transmittance of the ceramics could be explained by considering
the grain- and pore-size distributions.
Effects of the nature of the dopants, thermal pre-treatment and
sintering temperature on spark plasma sintering of transparent
alumina were investigated by Durand et al. [69]. A slurry of a-Al2O3
was doped with Mg, Zr and La nitrates or chlorides, with concen-
trations of 150e500 weight ppm and then freeze-dried to produce
nanosized doped powders (w150 nm). The powders were sintered
by using SPS to yield transparent polycrystalline alumina ceramics.
Transparency of the nanosized Al2O3 ceramics was shown to
depend mainly on the way the powder was prepared, as well as the
nature of the dopants. RIT values at 640 nm of the samples doped
with ZrO2, MgO and La2O3 were 40.1%, 44.1% and 48.1% respectively,
as compared to 30.5% for pure alumina.
Very recently, a two-step pressure method was reported by Fig. 11. Schematic diagram of a microwave sintering with specially designed insulating
Sakka et al. [74], which enabled a significant improvement in casket. Reproduced with permission from Ref. [126], Copyright 2003, John Wiley &
in-line transmittance of high heating rate SPSed alumina. Sons.
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 12. Densities of the samples, sintered by using microwave sintering and
conventional sintering without holding at the sintering temperature, as a function of
sintering temperature. Reproduced with permission from Ref. [126], Copyright 2003,
John Wiley & Sons.
susceptor to preheat the Al2O3 samples because Al2O3 is a poor
microwave absorber at room temperature. Fig. 12 shows variations
in density of the samples as a function of sintering temperature.
The microwave-sintered sample was almost fully densified after
sintering at 1400  C, while the density of the sample sintered
through the conventional sintering was only about 50%. Microwave
sintering reduced the temperature for the samples by about 300  C.
In this study, the authors found that both the microwave sintering
and the conventional sintering exhibited a similar grain growth
behavior, as shown in Fig. 13. Therefore, they concluded that the
enhancement in densification of Al2O3 by microwave sintering was
not due to the fast heating rate. However, the microwave densifi-
cation corresponded to apparent activation energy of 85  10 kJ/
mol, much lower than the value of 520  14 kJ/mol for the
conventional sintering, meaning that there was a difference in
densification mechanism between the two sintering techniques.
As demonstrated by Krell et al. [24,25,120,133e136], the
strength of transparent Al2O3 ceramics is greatly affected by their
grain sizes and size distribution. Fine-grained transparent Al2O3
ceramics, with high optical and mechanical properties, can be
developed by using various methods and strategies, as discussed
above.
Fig. 13. Grain growth trajectories of the microwave-sintered and conventionally sin-
tered samples. Reproduced with permission from Ref. [126], Copyright 2003, John
Wiley & Sons.
29
Besides the applications for lighting and domes, transparent
nanostructured g-Al2O3 ceramic used as a humidity sensor was
reported by Sensgupta et al. [137]. Nanostructured g-Al2O3
ceramics were prepared from Al-Sec-Butoxide (C12H27AlO3)
through a solegel process. The sensors were stable up to 2 years.
3.1.2. ZrO2
Zirconia (ZrO2) has been widely used because of its exceptional
mechanical and functional properties, such as high toughness, high
oxygen diffusivity and low thermal conductivity. Based on these
virtues, transparent ZrO2 ceramics, especially yttria-stabilized
zirconia or YSZ, have been extensively and widely investigated. The
introduction of yttria can stabilize the cubic or tetragonal structure
of zirconia with the presence oxygen vacancies [103]. This improves
ionic conductivity and makes stabilized ZrO2 appropriate for use as
an electrolyte in solid oxide fuel cells. Recently, polycrystalline
transparent cubic yttria-stabilized zirconia (ZrO2e8 mol% Y2O3, c-
YSZ) ceramics have attracted increasing attention because of their
unique combination of mechanical and optical properties
[32,95,97,138e146]. Cubic zirconia has a refractive index of 2.2,
which has never been attained in optical glasses and is higher than
that of other oxides. Recently, there has been increasing interest in
transparent zirconia ceramics, because of their unique optical
properties [97,138]. In summary, high transparencies with large
refractive indices and dielectric constants are unique properties of
transparent zirconia ceramics [147]. Photographs of representative
ZrO2 transparent ceramics are shown in Fig. 14 [32,97,102].
At the early stage, there were only reports on translucent
zirconia ceramics. For example, Vahldiek [139] obtained trans-
lucent cubic zirconia (15 mol% Y2O3eZrO2) by using a high-pressure
hot pressing technique. Mazdiyas et al. [140] fabricated translucent
cubic zirconia (6 mol% Y2O3eZrO2) by using the conventional sin-
tering technique. Duran et al. [141] prepared translucent tetragonal
zirconia (3 mol% Er2O3eZrO2) by using the conventional sintering
technique, using powders synthesized through an alkoxides-
hydrolysis method. These studies indicated that sintering process
and sinterability of the starting powders are critical parameter for
translucency.
Gradually, reports on transparent zorconia ceramics started to
appear. Transparent polycrystalline c-YSZ could prepared with hot
isostatic pressing (HIP) [32,138,144]. It was found TiO2 was a good
additive for developing transparent c-YSZ by using HIP [144]. Fig. 15
shows in-line transmittance curves of the ZrO2 (10% Y2O3) ceramics
with different concentrations of TiO2 [138]. The transparent
ceramics were made from cubic stabilized ZrO2 (c-ZrO2) powder by
Fig. 14. Photographs of representative ZrO2 transparent ceramics. (a) YSZ 8% ceramics
densified at 1300  C and 200 MPa for 2 h by using high iso-pressure sintering,
reproduced with permission from Ref. [32], Copyright 2008, John Wiley & Sons. (b)
1 mm YSZ 8% ceramics densified at 1000  C and 600 MPa for 5 min by using SPS,
reproduced with permission from Ref. [97], Copyright 2007, John Wiley & Sons. (c)
0.6 mm YSZ 8% ceramics densified at 1300  C and 100 MPa for 5 min by using SPS,
reproduced with permission from Ref. [103], Copyright 2012, Elsevier.
30 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 15. In-line transmittance curves of the ZrO2 (10% Y2O3) ceramics with different
contents of TiO2. The transmission was measured on 6e9-mm thick specimen and
normalized to the thickness of 8.3 mm. Reproduced with permission from Ref. [138],
Copyright 2009, Elsevier.
sintering at vacuum (1  103 Pa) at 1650  C for 3 h, followed by
HIPing at 1750  C for 1 h at a pressure of 196 MPa. Post-thermal
annealing at 1000  C was conducted to oxidize the as-sintered
samples. The role of TiO2 was regarded as a grain growth
promoter and a pore scavenger. The optical properties of these
zorconia ceramics were comparable to those of their single crystal
counterparts. It was found that transmission performances of the
ceramics were sensitive to the microstructure of the pre-sintered
compacts. Microstructural features, such of fine grains and small
intergranular pores, were critical to achieving high transparency.
Therefore, high sintering temperatures of HIP produced samples
with large grains, which were not desirable in terms of mechanical
properties [32,138,144].
In this light, SPS is better than HIP to fabricate transparent c-YSZ
ceramics. For example, Lei et al. [103] synthesized nanosized cubic
yttria-stabilized zirconia (ZrO2e8 mol% Y2O3) powder by using
a glycine-nitrate process combining with high energy ball milling.
Consolidation of the nanopowder was carried out by using SPS at
1200e1350  C for 5 min. Transparent ceramics could be fabricated
at 1300  C. Zhang et al. [102] used high-pressure SPS to fabricate
translucent cubic zirconia ceramics at 1000e1200  C. In the SPS
samples, the total forward transmittance and in-line transmittance
were mainly affected by color centers with a limited contribution
from residual pores. In contrast, the changes in reflectance were
only related to the porosity. The amounts of color centers and
residual pores increased with increasing sintering temperature,
which reduced the total forward and in-line transmittance of the
as-sintered zirconia ceramics.
Klimke and Krell [148] reported a cost efficient technology for
development of larger quantities of transparent cubic ZrO2
ceramics. A multi-step sintering process was used. Yttrium-
stabilized ZrO2 powder was treated by dry-pressing with subse-
quent cold isostatic pressing. The obtained ZrO2 ceramics were
reported to be comparable to perovskite ceramics, which were
commercialized in 2004 as camera lens. The in-line transmittance
was related to the thickness of the samples. The real in-line
transmission of the unscattered transmitted light (wavelength of
640 nm) was measured to be 57% (4 mm thickness), 59% (3 mm
thickness) and 65% (2 mm thickness). Due to the high refractive
index of ZrO2, the reflection losses are 12% on both surfaces. Thus,
depending on the material thickness, the transmission of the 4 mm
plate is 0.75 of the theoretical maximum, and that of the 2 mm
plate is 0.85 which corresponds to 0.92 at 1 mm thickness. The
hardness HV10 (measured at a testing load of 10 kg) was 13 GPa and
represented the upper limit for ZrO2 ceramics. The mean grain size
of the examples was about 5 mm.
Although the transparent cubic ZrO2 ceramic is of interest
because of its high refractive index, its mechanical strength is
relatively low (<600 MPa). Tetragonal ZrO2 ceramics have
a strength of >900 MPa. Recent studies have shown that nearly
fully dense YSZ ceramics with a grain size <100 nm can exhibit
a fracture toughness of about 8 MPa m1/2, which is superior to
a typical cubic material with a toughness of 2.8 MPa m1/2. There-
fore, tetragonal ZrO2 ceramics deserve to be further developed
[145,149].
Klimke and Krell [150] conducted systematic investigation on
the influence of grain size and birefringence on the transparency of
partially Y2O3-stabilized tetragonal ZrO2 (YSZ) ceramics. It was
confirmed that optical birefringence was the main factor that
restricted the transparency of tetragonal pore-free ZrO2. They then
predicted the conditions to obtain transparent tetragonal ZrO2
ceramics (partially stabilized by yttria) by comparing the experi-
mental data for sintering of nanopowder with scattering calcula-
tions. The simulations were validated well by experimental data for
tetragonal ZrO2 (3 mol% Y2O3) ceramics made from a powder with
an initial particle size of w10 nm. The sintering was carried out in
air with hot isostatic pressing. A maximum in-line transmission of
about 77% was observed at IR wavelengths of 3e5 mm in the
samples.
Falk et al. [151] compared tetragonal and cubic polymorph ZrO2
ceramics prepared by electrophoretic deposition, sintering in air
and hot isostatic pressing (HIP). Tetragonal ZrO2 had grains of
<200 nm, but they were insufficiently dense to have transparency.
Munir et al. [97] and Casolco et al. [145] found that tetragonal ZrO2
ceramics with grain sizes of 50e55 nm could be obtained by using
SPS, which suppressed successfully the grain growth of the nano-
sized powders. These works further confirmed that dense tetrag-
onal ZrO2 ceramics are less transparent than cubic ones. By using
powders with finer particle sizes, Chaim and Hefetz [152] devel-
oped nanocrystalline 3YSZ ceramics with grain sizes of 22e45 nm
by using HIP. However, their samples had a significant amount of
monoclinic phase.
Munir et al. [97] prepared transparent samples of tetragonal
(3 mol% yttria) as well as cubic (8 mol% yttria) zirconia from
nanometric powders by using a pulsed electric current sintering
process. Both the tetragonal and cubic samples had an average
grain size of about 50 nm. Consolidation pressure was found to
show a positive effect on the transparency of both samples.
Transmittance of the samples with 1 mm thickness in the near-
infrared region was above the 60% for the cubic (8%YSZ) and above
50% for the tetragonal (3%YSZ) zirconia ceramics, representing
between 70 and 80% of the theoretical values of the two materials.
The samples had a yellowish brown color, which was attributed to
the presence of color centers. Annealing in oxygen improved the
transmittance initially, but prolonged annealing resulted in trans-
lucent samples.
3.1.3. Sesquioxides
3.1.3.1. Y2O3. Y2O3, as a promising optical material, has excellent
physical and chemical properties, such as high melting point
(2430  C), broad range of transparency (0.2e8 mm) and high
corrosion resistance. Y2O3 has a cubic crystal with group of Ia3.
Typical physical properties of Y2O3 include thermal conductivity of
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
13.6 W/mK at 300 K, refractive index of w1.935, density of 5.04 g/
cm3 and effective atomic number of 36.7 [153]. Due to its high
effective atomic number and high density, Y2O3 could be a more
effective scintillator than YAG (35 and 4.56 g/cm3, respectively)
[154]. Y2O3 possesses a higher thermal conductivity and a lower
thermal expansion coefficient than the widely used YAG, which is
critical for thermal management as laser powers continue to
increase and generate heat during operation [155,156]. Other
potential applications of Y2O3 include infrared-domes, nozzles,
refractories, components of semi-conductor devices and efficient
NIR-visible up-converter [157e159]. Due to its refractory nature,
Y2O3 has been mainly developed in transparent ceramics rather
than single crystals. The first transparent yttria ceramic was re-
ported by Lefever and Matsko in 1967 [160].
There have been several reports on Y2O3 transparent ceramics
by using pressureless sintering in vacuum or in H2 atmosphere
[43,161e166]. Jin et al. [162] reported a vacuum sintering to fabri-
cate transparent Y2O3 ceramics from commercial power by doping
with ZrO2. Fig. 16 shows photographs of the ZrO2-doped Y2O3
ceramics with different contents of ZrO2, after sintering at 1860  C
for 8 h. The samples with ZrO2 of above 2 mol% are all highly
transparent. The starting Y2O3 power had an average particle size of
2 mm, which was reduced to about 0.34 mm after ball milling in
ethanol for 12 h, as shown in Fig. 17. The powder with reduced
particle size was beneficial for densification. In-line transmittance
curves of the Y2O3 transparent ceramics are plotted in Fig. 18. It is
observed that 5 mol% ZrO2 was the optimum concentration in
terms of in-line transmittance. The optical properties of the
ceramics were well explained by using their enhanced densifica-
tion and suppressed grain growth behaviors due to the presence of
ZrO2. Representative cross-sectional SEM images of the samples
sintered at 1860  C for 8 h are demonstrated in Fig. 19. There was no
pore observed in the sample doped with 5 mol% ZrO2.
Greskovi and Chernoch [164] reported Y2O3 transparent
ceramics in hydrogen atmosphere with ThO2 as sintering aid.
Rhodes [165] used a two-step sintering in hydrogen atmosphere to
prepared La-doped Y2O3 transparent ceramics. Saito et al. [166]
obtained transparent Y2O3 ceramics at relatively low temperature
of about 1700  C in vacuum from carbonate-derived powder. The
transmittance of a 1-mm-thick sample was about 18% at 400 nm.
HP [8,10], HIP [29,167] and SPS [92e94,100] have been shown to
be effective methods to obtain transparent Y2O3 ceramics. Zhou
et al. [8] fabricated transparent Y2O3 ceramics by using HP at
1800  C for 20 h. Another example was reported by Podowitz et al.
[10] by using a uniaxial hot pressing at a maximum pressure of
40 MPa and a maximum temperature of 1580  C. Optical trans-
parency could be optimized through a step-wise application of
pressure. Ito et al. [100] reported the synthesis of transparent Y2O3
ceramics by using SPS at moderate temperature and pressure
profiles. The samples sintered at 1300  C and annealed at 1050  C
had a transmittance of 81.7% at wavelength of 2000 nm. Yoshida
et al. [92] used low-temperature SPS to synthesize yttria ceramics
with ultrafine grain sizes. The Y2O3 specimen sintered at 1050  C for
Fig. 16. Photographs of the ZrO2-doped Y2O3 transparent ceramics with different
contents of ZrO2, derived from commercial Y2O3 power through vacuum sintering.
Reproduced with permission from Ref. [162], Copyright 2010, Elsevier.
31
1 h exhibited an in-line transmittance of 6e46% in wavelength
range of 400e800 nm. Chaim et al. examined the effect of heating
rate and sintering temperature on properties of Y2O3 ceramics by
using SPS. High-pressure SPS was reportedly used to reduce the
sintering temperature of transparent yttria ceramics. For example,
transparent Y2O3 ceramics could be prepared at 1050  C for 1 h
with a heating rate of 20  C/min under a uniaxial pressure of
300 MPa [99]. The obtained samples possessed nanometric grains
(400 nm) and high density (>99.95%). 1 mm thick ceramics had in-
line transmittance of 68% at 700 nm and comparable performances
of single crystal yttria in the near-infrared wavelength region.
Various strategies, such as use of nanosized precursor powder,
introduction of sintering aids and adoption of multiple-step sin-
tering process, have been employed to obtain Y2O3 ceramics with
relatively high density, small grain size and high transparency. Wen
et al. [45] synthesized yttria nanopowders of 60 nm by using
a precipitation process. Transparent yttria ceramics were derived
from the nanosized Y2O3 powders by using vacuum sintering at
1700  C for 4 h, with optimized in-line transmittance of 52% at
wavelength of 1000 nm. Similar works were reported by Mori et al.
[161] and Huang et al. [168].
Jiang et al. [43] developed a new method, a combination of two-
step sintering and vacuum sintering, to fabricate transparent
lanthanum-doped yttrium oxide ceramics. The samples were firstly
sintered at an intermediate temperature T1 (1450  C) in air. Then
the temperature was decreased quickly to a lower point T2 (900e
1100  C) in air and held for more than 20 h in order to facilitate
densification with limited grain growth. Nanocrystalline yttria
ceramics with a high relative density were then obtained, which
could be further densified at higher temperature T3 (1700  C) in
vacuum condition. The final transparent yttria ceramics doped with
10% lanthanum, with an average grain size of about 25 mm, had
a transmittance of 77% at 580 nm. Microstructural analysis results
indicated that the mean particle size of the samples after the
second step was just slightly higher than that of those after the first
step processing with a relative density of over 90%. Because the
significant shrinkage was mainly observed in this step, pores were
isolated by grains. Therefore, grain-boundary diffusion was thought
to be the main matter transport mechanism. A similar two-step
sintering combined with HIP was reported by Ballato et al. [169].
Transparent yttria ceramics with an average grain size of 0.3 mm
exhibited a transparency of single crystals in the near-infrared
spectral region.
Effective sintering aids, used to fabricate transparent Y2O3
ceramics, include ThO2 [164], La2O3 [165], HfO2 [170], LiF [171] and
ZrO2 [172], as well as their combinations [173]. The presence of
sintering aids led to high grade Y2O3 ceramics with small grain sizes
by reducing the sintering temperatures. Doping technique has also
been used together with other strategies, such as slip casting,
vacuum sintering [162] and sintering in oxygen atmosphere [174].
For example, highly transparent Y2O3 ceramics, doped with the
addition of ZrO2 through slip casting and vacuum sintering could
achieve a transparency of 81.7%, very close to the theoretical value
of Y2O3.
Optical properties of Y2O3 ceramics doped with rare-earth ions
are of special interest for some applications. Fukabori et al. [154]
discussed fundamental physical and scintillation properties of
Y2O3 optical ceramics for X-ray scintillator applications. Hou et al.
[157] studied up-conversion luminescence properties of RE/Yb co-
doped Y2O3 transparent ceramic (RE ¼ Er, Ho,Pr, and Tm), which
demonstrated than Y2O3 transparent ceramics are a very efficient
NIR-visible up-converters.
3.1.3.2. Sc2O3. Sc2O3 (scandia) belongs to the cubic space group IA3
[175]. Its unit cell contains 16 f.u., with 32 cations that form 24 sites
32 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 17. SEM images of the commercial Y2O3 powders before (a) and after (b) ball milling. Reproduced with permission from Ref. [162], Copyright 2010, Elsevier.
of C2 symmetry and 8 sites of C3i symmetry. The C2 site is an
eightfold cubic structure with two oxygen vacancies on a face
diagonal, while the C3i site corresponds to a cube with two
vacancies on a body diagonal. The RE3þ dopants are assumed to
occupy randomly both sites, but the induced electric dipole tran-
sitions are allowed only for C2 centers. The cationic density
(3.338  1022 cm3) is rather high compared to other oxides. Sc2O3
has the smallest lattice parameter (0.986 nm), high melting point,
high bulk refractive index (nH ¼ 2.0, l ¼ 300 nm), high band gap
(5.7 eV, corresponding to an ultraviolet cutoff of 215 nm), high
thermal conductivity (17 W m1 K1) and high chemical stability
(in alkali metal steam). The combination of these excellent optical
and thermal properties makes Sc2O3 attractive for applications as
damage resistant and high reflection materials in light-emitting
diodes and high power pulsed ultraviolet lasers. It is also very
useful as infrared transmitting devices, host materials for high
power and ultrashort pulse solid-state lasers and heat-resistant
optical windows etc. [47,176e181]. Due to its high melting point
(2430  C), it is difficult to fabricate Sc2O3 single crystal. Therefore,
transparent polycrystalline Sc2O3 ceramics become more
important.
Vacuum sintering is the most widely used method to prepare
transparent Sc2O3 ceramics and nanosized precursor powders
have additional benefit to ensure high quality of the final materials
[46,47,179e182]. Various chemical routes have been used to
Fig. 18. In-line transmittance curves of the ZrO2-doped Y2O3 transparent ceramics
with different contents of ZrO2, sintered at 1860  C for 8 h in vacuum. Reproduced with
permission from Ref. [162], Copyright 2010, Elsevier.
synthesize nanosized Sc2O3 powders. Wang et al. [46] synthesized
nanocrystalline Sc2O3 powder by using a homogeneous precipi-
tation method. Li et al. [47] prepared highly reactive Sc2O3
powders through pyrolyzing at 1100  C a basic sulfate precursor,
(Sc(OH)2.6(SO4)0.2$H2O), precipitated from scandium sulfate solu-
tion with (CH2)6N4 as the precipitant. Similar reactive Sc2O3
powders were obtained through thermal pyrolysis of a scandium
sulfate salt, Sc2(SO4)3$7.8H2O [179]. The Sc2O3 ceramics obtained
by using vacuum sintering have relatively large grain sizes, due to
the significant grain growth during the final stage of sintering
[46,179e182].
Pressure-assisted sintering techniques have been used to
develop transparent Sc2O3 ceramics with smaller grain sizes. For
example, Ballato et al. [30] used HIP to fabricate erbium-doped
transparent Sc2O3 ceramics with an average grain size of 0.3 mm,
from solution-derived nanoparticles, using a two-step sintering
process. The two-step sintered ceramics showed a remarkable
decrease in grain size with relative density of over 98% before HIP.
After HIP, the Sc2O3 ceramics became highly transparent with
negligible grain growth. The samples exhibited an optical trans-
mittance of about 80%.
Spectroscopic properties of Sc2O3 ceramics doped with various
ions are attractive for different applications. Gheorghe et al. [175]
analyzed in detail the spectral characteristic of Ho3þ:Sc2O3 trans-
parent ceramics. A series of spectroscopic parameters, such as JO
intensity parameters, oscillator strengths, radiative transitions
probabilities, radiative lifetimes and branching ratios, were
derived. They also reported intensity parameters of Tm3þ-doped
transparent Sc2O3 ceramics as laser materials. They are potential
candidates to be used in diode-pumped solid-state laser emitting at
about 2 mm [183]. Trabelsi et al. [184] summarized the crystal field
analysis of Er3þ in Sc2O3 transparent ceramics, with which a theo-
retical trend was proposed for rare-earth ions in Sc2O3 in
comparison with Y2O3.
3.1.3.3. Lu2O3. Lu2O3 (lutetia) is an attractive host material for
various activators because of its wide band gap and favorable
properties, such as phase stability, low thermal expansion and
chemical stability. In particular, Lu2O3 is the one that can host the
highest doping concentration of Yb3þ, while maintaining high heat
conductivity, due to the comparable mass and ionic radius between
Lu3þ and Yb3þ [67]. The superiority of Lu2O3 to Y2O3 is its high
density (w9.42 g/cm3), as well as the high Z number of Lu (71),
which endows Lu2O3 with exceptionally high stopping power for
ionizing radiation. Lu2O3 ceramics doped with Nd or Yb are
promising high power ceramic laser materials. Europium-doped
Lu2O3 ceramic scintillator can find applications in digital X-ray
imaging technology, due to its high density resulting in high
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 19. Cross-sectional SEM images of the ZrO2-doped Y2O3 transparent ceramics with different contents of ZrO2: (a) 0 mol%, (b) 0.2 mol%, (c) 2 mol%, (d) 5 mol% and (e) 9 mol%.
Reproduced with permission from Ref. [162], Copyright 2010, Elsevier.
stopping power, efficient X-ray to visible light conversion of up to
90,000 photons/MeV [185], and visible emission at w600 nm
coupling well with the silicon CCD spectral response [185,186]. The
use of an optically transparent scintillator screen requires high
transparent Lu2O3:Eu to avoid excess background noise, loss of
resolution and scatter-induced ghosting.
An example of Lu2O3 transparent ceramics was reported by
Chen et al. [187]. The used a co-precipitation process to synthesize
highly sinterable Eu-doped Lu2O3 powders, using ammonium
hydroxide (NH3$H2O) and ammonium hydrogen carbonate
(NH4HCO3) as mixed precipitant. Highly transparent polycrystalline
Lu2O3 ceramics with a relative density of w99.9% were fabricated
by using pressureless sintering in flowing H2 atmosphere at 1850  C
for 6 h without any additives.
Goto et al. [101] used SPS to fabricate transparent Lu2O3
ceramics from commercially available powders. The effects of sin-
tering conditions, including temperature, pressure and holding
time, on the density and optical properties were systematically
studied. They found that the transparency of the Lu2O3 ceramics
could be further improved by adopting a two-step pressure profile
combined with a low heating rate [67]. The effects of pre-load
pressures from 10 to 100 MPa and heating rates from 0.03 to
33
1.67 K/s on microstructures and optical properties of the materials
were investigated. The samples obtained under a pre-load pressure
of 30 MPa at a heating rate of 0.17 K/s had transmittances of 60% at
550 nm and 79% at 2000 nm, showing a significant improvement.
It was found that vacuum sintering combined with HIP could be
used to sinter Eu:Lu2O3 ceramics without the risk of contamination
or oxygen vacancies [31]. Nanosized precursor powder was firstly
uniaxially pressed and sintered under high vacuum at tempera-
tures between 1575 and 1850  C to obtain densities ranging
between 94% and 99%. The sintered compacts were then subjected
to reach full density through HIP, which resulted in fully dense
highly transparent ceramics without the need of further air
annealing. The Eu:Lu2O3 ceramics showed about 4 times higher
light yield than commercially used scintillating glass, indicating
that transparent ceramics could be used for high energy radiog-
raphy devices with improved performances. Evolution of porosity
and microstructure was studied. Fig. 20 shows photographs and
scatterometry of the samples vacuum sintered at different
temperatures after HIP sintering at 1850  C. Vacuum sintering
above 1650  C led to rapid grain growth prior to densification,
rendering the pores immobile. Sintering between 1600 and 1650  C
resulted in closed porosity yet a fine grain size to allow the pores to
34 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54

Fig. 20. Photographs and scatterometry of compacts after hot isostatic pressing (HIPing) at 1850  C as a function of vacuum-sintering temperature, 1575e1850  C. Photograph is not
backlit. Reproduced with permission from Ref. [31], Copyright 2011, Elsevier.

be mobile during the subsequent HIPing step, resulting in a fully
dense highly transparent ceramic without the need for subsequent
air annealing.
SEM images of representative samples are shown in Fig. 21,
confirming that the residual porosity led to the difference between
the optically transparent and the opaque ceramics. As shown
Fig. 21(a), the pores were not completely closed after vacuum sin-
tering at 1575  C. Grain growth could not occur due to the signifi-
cant number of pores and the pores could not be removed because
they were filled with argon which was nearly insoluble in the
crystal matrix. Fig. 21(b) shows a nearly perfect pore-free micro-
structure of the sample, which was optically transparent after being
vacuum sintered at 1625  C prior to HIPing. Fig. 21(d) indicates that
the grain entrapped pores were not removed during the HIPing
step, resulting in residual porosity in the final ceramics vacuum
sintered at temperatures of above 1675  C.
3.1.4. MgO
MgO ceramic has excellent thermal and mechanical properties
with a high melting point (2800  C) and an isotropic cubic crystal
structure. Polycrystalline infrared transparent MgO is a potential
substitute for sapphire IR windows and protectors for sensors. Due
to the high sintering temperature required for full densification of
MgO, fabrication of transparent MgO ceramics is still a challenge.
Almost all techniques discussed above have been used to prepare
transparent MgO ceramics [188].
The use of sintering aids has been widely employed to improve
the sinterability of MgO. Rice [189] first reported fabrication of
transparent MgO ceramics with the addition of LiF by using pres-
sure sintering. It was found that MgO ceramics prepared in this way
had infrared optical transmission approaching to that of single
crystal. There are other reports using LiF as sintering aid to develop
MgO transparent ceramics at low temperatures [190,191].

Fig. 21. FE-SEM images of the compacts as HIPed at 1850  C. Prior to HIPing, the compacts were vacuum sintered at (a) 1575  C, (b) 1625  C, (c) 1675  C and (d) 1750  C. Reproduced
with permission from Ref. [31], Copyright 2011, Elsevier.
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
According to Hart and Pask [192], densification of MgO with LiF was
enhanced due to the formation of a liquid phase that acted initially
as a lubricant for the rearrangement of the MgO particles and later
a material transport medium to support pressure-enhanced liquid
phase sintering.
Although sintering aids can be used to reduce the sintering
temperature of MgO, they have negative effects on the intrinsic
properties of MgO. It was demonstrated by Itatani et al. [41] that
transparent MgO ceramics could be fabricated at 1600  C by using
an HIP technique. Before HIPing, MgO compacts were obtained by
using pressureless sintering. A non-agglomerated MgO powder
with an average primary particle size of 57 nm was used as
precursor. The relative density and average grain size of the MgO
compact pressureless sintered at 1600  C for 5 h were 96.7% and
10.7 mm, respectively. The as-sintered MgO ceramics had a relative
density of 98.1% with an average hardness of 6.8 GPa [188].
Transparent MgO ceramics have also been fabricated by using SPS
[108]. With SPS, fully dense optically transparent MgO ceramics
from nanocrystalline powders could be produced at 800  C and
150 MPa for 5 min.
3.2. Complex oxides
3.2.1. YAG
Yttrium aluminum garnet (Y3Al5O12 or YAG) is a crystalline
material of the garnet group. It is also one of the three phases of
yttriaealuminum composite, with the other two being yttrium
aluminum monoclinic (YAM) and yttrium aluminum perovskite
(YAP). YAG has a cubic crystal structure and belongs to the isometric
crystal system [193]. Due to the centrosymmetric cubic crystalline
structure, its optical properties are isotropic. Owing to its high
thermal stability, stable chemical properties and unique homoge-
nous optical properties, transparent YAG ceramics are not only an
important high-temperature structural material, but also an excel-
lent host material for fluorescence application and high power solid-
state lasers [194]. Nd- and Er-doped YAG ceramics are typical laser
Fig. 22. (a, b) XRD patterns of the 1% Er:YAG and 50% Er:YAG ceramics vacuum sintered at different temperatures for 2 h. (c, d) Photographs of the 1% Er:YAG and 50% Er:YAG
ceramics. Reproduced with permission from Ref. [48], Copyright 2011, Elsevier.
35
materials. Ce-doped YAG (Ce:YAG) is used as phosphor in cathode
ray tubes and white light-emitting diodes and as scintillator. Since
the first report transparent polycrystalline Nd:YAG ceramics for
laser media by Ikesue et al. [195,196] in 1995, more and more
attentions have been attracted on the fabrication of YAG [197].
Undoped YAG transparent ceramics have been fabricated by
various technologies, including vacuum sintering, HP and SPS.
Li et al. [198] synthesized ultrafine YAG powders through a co-
precipitation method using ammonium hydrogen carbonate as
precipitant and used the powders to obtain transparent YAG
ceramics under vacuum sintering at 1700  C for 1 h. Zych and
Brecher [199] derived YAG transparent ceramics from the mixture
of Y2O3 and Al2O3 by using HP at 1750  C for 4 h under a pressure
of about 300 atm. Spark plasma sintering was applied by Chaim
et al. [91] to fabricate YAG transparent ceramics at 1400  C for
3 min using nanocrystalline YAG powders as precursor. Fully
dense and transparent polycrystalline cubic YAG ceramics with
micrometer grain sizes were obtained. Liu et al. reported an HP
sintering process to prepare YAG transparent nanoceramics [7].
The nanostructured YAG compacts were prepared at high pres-
sures and modest temperatures (HPMT, 2.0e5.0 GPa and 300e
500  C). Prior to sintering, pellets were also heat treated in
vacuum. After the samples were treated at 2.0e5.0 GPa and
300  Ce500  C for 30 min, the pressure was reduced to ambient
pressure, and then the samples were quenched to room
temperature at a cooling rate of w15 C/min. The temperature
was found to be sufficiently low to prohibit the grain growth of
the YAG ceramics.
For practical applications, YAG ceramics should be doped with
different elements. An example was reported by Zhou et al. [48].
Highly transparent polycrystalline Er3þ:Y3Al5O12 (Er:YAG) ceramics
with contents of Er3þ ion from 1% to 90% were prepared by the
solid-state reaction and the vacuum-sintering technique. In-line
transmittances of mirror-polished Er:YAG ceramics were all up to
84% at 1100 nm wavelength, which were attributed to high density
of the samples.
36 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Phase evolution of the Er:YAG ceramics was carefully studied.
Fig. 22 shows XRD patterns and photographs of the 1% Er:YAG and
50% Er:YAG samples vacuum sintered at different temperatures for
2 h. For the 1% Er:YAG ceramics, YAG phase was formed at 1200  C
along with a bit of residual YAP (YAlO3). Single phase YAG was
achieved at 1600  C. As shown in Fig. 22(b), the concentration of
Er3þ has no dramatic effect on the phase formation of YAG struc-
ture. A solid solution, Er3Y3Al10O24, was finally obtained. The sin-
tering temperature for transparent samples was 1800  C, as shown
in Fig. 22(c) and (d).
Very recently, a two-step sintering process was developed by
Zhu et al. [200] to synthesize Nd:YAG ceramics. In this two-step
sintering process, the furnace temperature was first arisen to
a higher temperature T1 (1800  C), at a heating rate of 10  C/min,
and then the temperature was rapidly decreased to a certain sin-
tering temperature T2 (1550e1750  C) for 1e8 h in a vacuum
graphite tube furnace at 1.0  103 Pa during the holding process.
The transparent ceramics prepared by using this method exhibited
pore-free and homogeneous microstructure, with transparency of
up to 84.98% at the visible and near-infrared band and 87% in the
mid-infrared wavelength range. The absorption cross section of
a 0.3% Nd:YAG sample at 808 nm was 5.47  1020 cm2, while the
emission cross-section at 1064 nm was 4.66  1019 cm2.
To achieve full density and highest transparency, YAG ceramics
have also been prepared by using sintering aids [50,53,58,201e204].
Liu et al. [202] used MgO as sintering aid to produce Nd:YAG ceramics.
As shown in Fig. 23, the addition of small amount of MgO could reduce
the degree of agglomeration and particle size of the Nd:YAG precursor
powders. The MgO-doped Nd:YAG powders possessed better
dispersion characteristics as compared with the undoped powders.
The sample with 0.01 wt.% MgO was of spherical particles of 100 nm
in diameter. The well-dispersed precursor powders resulted in
ceramics with homogenous microstructure. Optimized ceramic
samples exhibited transmission of 82.6% at the wavelength of
1064 nm, which was comparable to that of Nd:YAG single crystals.
La2O3 is another effective sintering aid for Nd:YAG ceramics [50]. The
addition of 0.8 wt% La2O3 was optimized concentration, which led to
Fig. 23. SEM images of the Nd:YAG powders with various weight ratios of MgO. (a) Without MgO; (b) 0.008 wt.%; (c) 0.01 wt.%; and (d) 0.012 wt.%. Reproduced with permission
from Ref. [202], Copyright 2011, Elsevier.
Nd:YAG transparent ceramics having the highest transmittance in
the wavelength region from 400 nm to 1100 nm.
Co-doping with MgO þ SiO2 has been found to a promising
technique to improve the sinterability of YAGs [53,58,203]. By
optimizing the concentrations of the dopants, transparent YAG
ceramics with desired optical properties can be readily achieved.
For example, the Nd:YAG ceramic samples with 0.4 wt% TEOS
(precursor of SiO2) combined with 0.08 wt% MgO possessed the
highest transparency at 1064 nm [53]. Zhang et al. [58] found that
the function of SiO2 was to eliminate pores and remove secondary
phases, while MgO contributed to homogeneous microstructure of
the ceramics, which is demonstrated by the SEM images of repre-
sentative samples, as shown in Fig. 24.
It is well known that the sinterability of a ceramic precursor
powder is highly dependent on various characteristics, such as
particle size, size distribution, morphology and degree of agglom-
eration. This is also applicable to YAG transparent ceramics [205e
209]. A systematic study on the effect of powder properties on
the densification and performance of YAG transparent ceramics
was reported by Esposito and Piancastelli [208]. It was found that
the YAG ceramics derived from nanosized powder exhibited higher
optical transparency, due to their smaller grain size and less
residual pores. The properties of precursor powders could be also
modified by adjusting pH values when using co-precipitation
method [209]. pH values affected the performance of the final
Nd:YAG ceramics by influencing the morphology as well as the
(Nd þ Y):Al mole ratio of the powders. Optimized pH values were
found in the range of 7.9e8.2.
Fig. 25 shows EPMA images of the Nd:YAG ceramics with
different (Nd þ Y):Al mole ratios. If the (Nd þ Y):Al molar ratio was
much lower than 0.6, superfluous Al2O3 was present, while it was
much higher than 0.6, superfluous Y2O3 was present which led to
intermediate phases (YAP and YAM). The powders prepared within
the range of pH value of 7.9e8.2 had (Nd þ Y):Al molar ratio very
close to 0.6 (0.598 and 0.603). In this case, no secondary phases
were observed and fully dense Nd:YAG ceramics with homoge-
neous microstructures were obtained, as demonstrated in Fig. 25(b)
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54 37

Fig. 24. SEM images of polished surface and fractured surface of the samples with (a) SiO2, (b) SiO2 þ MgO and (c) MgO. Reproduced with permission from Ref. [58], Copyright 2012,
Elsevier.

and (c). The conclusion was further confirmed by the cross-
sectional SEM images shown in Fig. 26. The fracture styles of
samples with (Nd þ Y):Al molar ratios of 0.576 and 0.648 are both
intracrystalline because secondary phases and pores in them
enhanced strength of the grain boundaries. In contrast, the samples
from the powders with ratios of 0.598 and 0.603 possessed pore-
free microstructure and clean grain boundaries, thus having inter-
granular fracture behavior.
Other technologies used to further improve the quality of
precursor powers of transparent YAG ceramics include spray-
drying [64] and freeze-drying [57,210]. It has been demonstrated
that freeze-drying could play an important role in the synthesis of
high quality Nd:YAG nanosized powders [210]. With an optimized
calcination temperature of 1200  C, the powder showed lowest
agglomeration and could be used as precursor to obtain trans-
parent Nd:YAG ceramics.
Optical properties of rare-earth-doped YAG ceramics are
important requirements for practical applications, which has been
a subject of numerous studies in the literature [62,211e215]. For
example, Yagi et al. examined the influence of annealing on optical
properties of chromium-doped YAG ceramics [62]. As shown in
Fig. 27, the effect of annealing was quite significant. After annealing
at high temperatures, the absorption intensity was increased and
the two peak wavelengths shifted from 430 nm and 600 nm to

Fig. 25. EPMA micrographs of the Nd:YAG ceramics at various molar ratio of the (Nd þ Y):Al: (a) 0.576, (b) 0.598, (c) 0.603, (d) 0.648. Reproduced with permission from Ref. [209],
Copyright 2010, Elsevier.
38 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 26. EPMA micrographs of fracture surfaces of the Nd:YAG ceramics at various molar ratio of the (Nd þ Y):Al: (a) 0.576, (b) 0.598, (c) 0.603, (d) 0.648. Reproduced with
permission from Ref. [209], Copyright 2010, Elsevier.
approximately 465 nm and 612 nm, respectively, which was
attributed to valence changing from Cr3þ to Cr4þ. The presence of
Cr4þ ion was confirmed by emission measurement.
Nishiura et al. [212] reported properties of transparent Ce:YAG
ceramic phosphors for white LED. The Ce:YAG ceramics had a broad
emission band peaked at 530 nm due to the 5de4f transition of
Ce3þ. The transmittances of the samples were 70e87% at 800 nm.
The absorption coefficient and emission intensity of Ce3þ were
increased with increasing sample thickness. Under 465 nm LED
excitation, the color coordinates of the Ce:YAG ceramics shifted
from blue region to yellow region with increasing sample thickness,
passing nearby the theoretical white point in the chromaticity
diagram. The highest value of luminous efficacy of the ceramic
white LED was 73.5 lm/W. The LED’s current dependence of
Fig. 27. Absorption spectra of the 0.1 at.% Cr:YAG ceramics: (a) sintered with CaO, (b)
annealed at 1300  C, (c) annealed at 1500  C and (d) SiO2-doped and annealed at
1500  C. Reproduced with permission from Ref. [62], Copyright 2006, Elsevier.
luminous efficacy and luminous intensity for a 0.632 mm-thick
sample under 465 nm LED excitation is shown in Fig. 28. The
luminous efficacy was decreased from 74 lm/W to 44 lm/W, while
the luminous intensity was increased from 100 mCd to 1550 mCd
with increasing current.
When studying optical properties of transparent Eu3þ:Y3Al5(1-
x) 5xO12 ceramics, Shi et al. [213] found that a reduced peak
Sc
splitting of Eu3þ for 5D0e7F1 and 5D0e7F2 was observed when 10
at.% Al31 was substituted by Sc31. The enhanced symmetry of the Eu
sites in YAG lattice, which resulted from the expanded YASG lattice
due to the Sc31 doping, was the main reason for the reduced peak
splitting.
3.3. MgAl2O4
The crystal structure of magnesium aluminate “spinel”
(MgAl2O4) is based on an FCC close-packed oxygen sub-lattice, in
which a fraction of the octahedral and tetrahedral sites are filled. It
Fig. 28. LED’s current dependency of luminous efficacy and luminous intensity of the
Ce:YAG ceramics under 465 nm LED excitation (sample thickness: 0.632 mm).
Reproduced with permission from Ref. [212], Copyright 2011, Elsevier.
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
is characterized by magnesium ions tetrahedrally coordinated with
oxygen and aluminum octahedrally coordinated with oxygen. A
unit cell contains 32 oxygen ions, 16 octahedral cations, and 8
tetrahedral cations. Polycrystalline structure of the magnesia spinel
is optically isotropic. Magnesia spinel undergoes no polymorphic
transformations and hence is devoid of any thermally induced
phase changes [216].
Spinel is transparent to electromagnetic radiation from the
ultraviolet through the mid-infrared (0.2e5.5 mm). Spinel has
a distinct transmission advantage over sapphire and AlON from
4.5 to 5.5 mm, a region of particular importance for seeker and
electro-optic imaging systems. The combination of unique optical
and mechanical properties makes spinel one of the most
outstanding optically transparent ceramics.
Given its high strength and excellent transmittance properties
up to the mid-IR wavelength, spinel is a very attractive material to
manufacture high performance optical components, such as lenses,
IR windows and domes. Very good UVevis and medium
wavelength IR transparency coupled with high hardness and high
resistance to erosion makes spinel an excellent material for
protective windows for aircraft, ship and submarine IR sensors, as
well as missile domes. Spinel is also very promising for
applications as windows or windshields for military vehicles such
as large and bullet-proof windows, due to its mechanical and
ballistic properties [217].
Since it was shown to be transparent in early 1960s, spinel has
received considerable attention worldwidely [28,218]. Transparent
spinel is difficult to fabricate directly from high purity precursor
powders by using the conventional pressureless sintering tech-
niques [28,218,219]. Therefore, it is necessary to use HP, HIP or SPS
[27,28,86e89,223e225]. By the way, fine precursor powders,
together with sintering aids, such as B2O3 [34], CaO [218] and LiF
[220], have been shown to be very helpful in developing trans-
parent spinel ceramics.
It was reported that by using a combination process of pre-
sintering and HIP, fine-grained highly transparent spinel ceramics
could be obtained from powders with a wide range of properties
[222]. Clear transparent components with a thickness of up to
20 mm and lateral dimensions up to 240 mm were manufactured
equally successfully from both the spinel powders with lower
specific surface areas and the nanosized powders. Recently,
a similar process was developed to fabricate spinel ceramics with
large-scale production [223].
Kagawa et al. [27,28] used similar two-step process (HP followed
by HIP) to prepare optically transparent polycrystalline spinel
ceramics. The effect of HP temperature on optical properties of the
final ceramics HIP sintered at 1900  C for 1 h under a pressure of
189 MPa was studied. Three HP temperatures, 1400, 1450 and
1500  C in vacuum of 102 Pa for 1 h at 50 MPa, were examined.
Fig. 29 shows light transmittance curves of the sintered MgAl2O4
ceramics measured in the UVevis and near-IR wavelength regions.
The sample HP pre-sintered at 1400  C had the maximum trans-
mittance of over 60 and 70% in the UVevis and near-IR wavelength
regions, respectively. The light transmittance was well correlated
with the microcracked grain-boundary surface area per unit
volume of the samples.
Very recently, spark plasma sintering (SPS) has been proved to
an alternative technique for the fabrication of fine-grained
transparent spinel. Several studies have been conducted for
enhancing the transparency by using additives [87], controlling
heating rates [89,224], or applying two-step pressure profile
during sintering [86]. Although the transparency of the spinel
fabricated by SPS is lower than that by HIP at present, an
improvement for higher transmission can be made in SPS by
controlling the sintering parameters such as pressure,
39
Fig. 29. Light transmittance spectra of the sintered MgAl2O4 in the UVevis wavelength
range. Reproduced with permission from Ref. [28], Copyright 2003, Elsevier.
temperature, heating rate, atmosphere, and powder preparation.
Frage et al. [87] reported the spark plasma sintering of commer-
cial magnesium aluminate powder at the low heating rate of
10  C/min and investigated the effect of LiF additions on the
resulting optical properties of the consolidated transparent solids.
The presence of 1 wt.% LiF dopant affects dramatically the spinel
morphology, leads to the formation of large well-defined grains,
eliminates residual boundary phases and allows achieving rela-
tively high levels of light transmission. By employing low heating
rate, Morita et al. successfully demonstrated the densification of
a fine-grained high purity spinel only for a 20 min soak at the low
temperature of 1300  C without any sintering aids. For heating
rates of <10  C/min, the spinel exhibits an in-line transmission of
47% for a visible wavelength of 550 nm and a fracture strength of
>500 MPa. The high in-line transmission can be explained by the
lower residual porosity (<0.5%), as shown in Figs. 8 and 9 [89]. As
one of the techniques for enhancing the transparency, Kim et al.
[225] reported on the effects of preheating of powder before SPS.
The authors found that preheating resulted in an enhanced
transparency of the MgAl2O4 spinel.
One of the issues arisen when using the pressure-aided sintering
processes is contamination. For instance, as reported in Refs. [87,89],
the in-line transmittance of the samples did not approach the ex-
pected values, especially in the wavelength range of near/mid-
infrared (above 1 mm). It was attributed to the presence of
contamination or second-phase particles dispersed in the spinel
matrix. Bernard-Granger et al. [226] investigated influence of
graphite contamination on the optical properties of transparent
spinel obtained by spark plasma sintering. They found that residual
porosities and second-phase graphite particles had a strong nega-
tive influence on in-line transmittance of the ceramics. The carbon
contamination was proposed to be arisen from a CO-containing
residual atmosphere during the SPS experiments, because of the
graphite configuration of the equipment. During SPS, a rotary pump
was used to generate vacuum in which the residual gases gave rise to
an atmosphere containing CO2. Such an atmosphere infiltrated the
porous body at the beginning of sintering and CO2 was possibly
reduced to CO at high pressure within the shrinking pores, which
was finally carbonized into particles. The presence of such carbon
particles made the in-line transmittance to be less than theoretical
value of single crystalline MgAl2O4. Therefore, special carefulness
should be taken when using pressure-aided techniques to fabricate
transparent ceramics and more systematic studies should be carried
out on this important issue.
40 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Because the performance of spinel windows is also very sensi-
tive to the quality of the precursor materials (both purity and
morphology), there have been researches on this issue that can be
found in the open literature. To produce better spinel precursor
powders, various methods have been developed. Reimanis et al.
[216] reported a unique method to synthesize spinel powders from
boehmite, in which Mg2þ ion was metal exchanged onto the surface
of boehmite particles. In this method, particle size, size distribution,
purity and stoichiometry of the Mg-doped boehmite powders
could be well controlled. Such powders exhibited good sinterability
and resulted in spinel ceramics with desired optical properties.
Goldstein et al. [227] used flame spray pyrolysis to prepare fine
precursor powder so as to develop high quality spinel transparent
ceramics. The powder possessed excellent sinterability, allowing
the attainment of very high densification levels after the pre-
sintering stage at 1400  C. HIPing was necessary to attain high
transparency for t > 2 mm. The minimal HIPing conditions for
a reasonable transparency were 1400 C/80 h. A low-temperature
HIP processing, 1500  C, 3 h and 200 MPa, led to 2 mm thick
samples with a real in-line transmission of 63% (at 635 nm). The
samples had an average grain size of 2.2 mm and a hardness of
13.2 GPa.
An alternative method, by using Mg(OH)2, g-Al2O3 and AlOOH,
towards the direct production of transparent MgAl2O4 ceramics,
was reported by Sutorik et al. [228]. The samples derived from the
mixture of Mg(OH)2 and g-Al2O3 under optimized processing
conditions showed in-line transmittances of 84.2  1.0% at 550 nm,
with thicknesses of 3.5e4 mm. Typical mechanical properties
observed in the ceramics included Knoop hardness of w12 GPa,
elastic modulus of w280 GPa and biaxial flexural strength of 85e
136 MPa. There was a slight difference between g-Al2O3 and
AlOOH as the precursor components.
A simple reactive method named self-heat-sustained (SHS)
technique employing metallic aluminum as one of the reactants to
produce very high phase-purity magnesium aluminate powder
under rather mild experimental conditions was also developed by
Ping et al. [229]. Powders with small particle size- and narrow
particle size-distribution were obtained, which could be used to
fabricate spinel ceramics with high optical performances.
Another strategy for developing transparent spinel ceramics is
the use of sintering aids. According to Tsukuma [34], the addition of
a small amount of boron oxide (0.05e0.5 mass%) was very effective
in promoting the sintering behavior of a fine MgAl2O4 powder.
Experimental results indicated that the presence of B2O3 not only
reduced the sintering temperature of the precursor powder, but
also suppressed the grain growth of the ceramics which was
important to ensure high transparency. The optimal concentration
of B2O3 was 0.15 mass%, with which the samples could achieve
a high optical transmittance of 80% at 1 mm thickness.
Besides B2O3, LiF has also been widely used as a sintering aid for
spinel ceramics. By using 1 wt.% LiF, Reimanis et al. [216] obtained
MgAl2O4 transparent ceramics by HP process at a temperature of as
low as 1550  C for 2 h. The samples had an excellent visible
transmittance of w85%. The effect of LiF on sintering kinetics of
MgAl2O4 was investigated by Rozenburg et al. [221]. Powders with
0, 0.5 and 1.0 wt.% LiF were densified by using a vacuum HP under
a range of unaxial pressures. According to the sintering mecha-
nisms derived from the experimental studies, the vacuum HP
processing schedule could be further optimized.
According to MgOeAl2O3 phase diagram, spinel is the only
compound. However, the spine phase can act as a parent structure
type of solid solutions whose compositional range increases with
increasing temperature. The compositions can be expressed by the
formulation of MgO$nAl2O3, with n ¼ 1.0 corresponding to the
stoichiometry of MgAl2O4. At appropriate temperatures, n can
range from 0.8 (MgO-rich) to 3.5 (Al2O3-rich). Conceptually, as all
solid solution compositions share 1.0-spinel’s cubic crystal struc-
ture, they should all have the potential to be prepared as trans-
parent, single phase ceramics; however, exsolution of excess
alumina frequently undermines the formation of single phase
MgO$nAl2O3 solid solution polycrystalline ceramics. It has been
reported that MgO$nAl2O3 polycrystalline ceramics with Al-rich
compositions (n > 1) possess varied levels of light transmission at
infrared wavelengths, although generally the transmission in the
visible spectrum is low. As a consequence, there has been
increasing interest in MgO$nAl2O3 ceramics with n > 1 [26,27].
Sutorik et al. [26] used HP and HIP to prepare transparent spinel
ceramics with a composition of MgO$1.2Al2O3. The processing
consisted of HP at 1600  C for 5 h under vacuum and 20 MPa
uniaxial load for pre-sintering and HIP at 1850  C for 5 h under
200 MPa in argon. The samples obtained exhibited an average in-
line transmission of 84.8  2.7% at 550 nm and >82% throughout
the visible spectrum. Final grain sizes of the ceramics ranged
between 300 and 1000 mm, with flexural strength of
176.8  46.2 MPa, hardness of 12.3  0.2 GPa and elastic modulus of
292.9  7.5 GPa.
A detailed study on the relationship between composition and
mechanical properties of spinel transparent ceramics was reported
by Dericioglu et al. [27]. They also used HP and HIP, but with
commercial MgO and Al2O3 powders as the precursor. Three
compositions of MgO$nAl2O3 were investigated with n ¼ 1:0, 1.5
and 2.0. The spinel ceramic with MgO to Al2O3 molar ratio of 1:1
demonstrated the highest scattering coefficient due to its highest
amount of grain-boundary microcracking. Al2O3-rich compositions
possessed a specular transmission of 40e60% in the same wave-
length range. The spinel ceramic with n ¼ 2:0 exhibited the highest
fracture toughness with a mean value of w2.02 MPa m1/2. Based on
their optical and mechanical properties, the Al2O3-rich non-
stoichiometric polycrystalline spinel ceramics would be potential
candidates for engineering applications requiring high optical
transparency and fracture toughness.
Other studies on spinel transparent ceramics include the effect
of grain-boundary microcracking on optical performance, as
reported by Dericioglu and Kagawa [28] and nanoporosity effect
and elimination of precursor powders, as demonstrated by Krell
et al. [230]. Light transmittance losses occurred when the sintered
MgAl2O4 ceramics had microcracked grain boundaries which
facilitated light scattering [28]. It was recognized that the nano-
scale pores of <100 nm could be readily eliminated by using
pressure-assisted reactive sintering of MgOeAl2O3 mixtures,
starting with coarser powders with median particle sizes of 100e
200 nm instead of sintering pre-calcined raw spinel powders
<100 nm [230].
Due to the special requirement in mechanical properties for
some specific applications, such as armor [231], a new direction of
research on spinel transparent ceramics appeared recently, which
is nanocomposite transparent ceramics. This concept was well
demonstrated by Padture et al. in a recent publication [232]. In this
case, the nanocomposites were MgAl2O4 spinel matrix dispersed
with Si3N4 nanoparticles. The as-processed nanocomposites were
found to have a high transparency of >70% in the critical infrared
wavelength range of 3e4.5 mm and an acceptable transparency in
the visible region. The optical properties of the nanocomposites
remained almost unchanged upon heat treatment at 1000  C for 4 h
in air, which however resulted in a 29% increase in the average
strength, accompanied by almost doubling of the Weibull modulus
and an 85% increment in the indentation toughness. The
improvements in mechanical properties after the heat treatment in
these nanocomposites were attributed to surface-oxidation-
induced surface compression and flaw-healing.
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 30. (a) STEM image of the as-processed spinel/Si3N4 nanocomposite ceramics,
with the spinel grains and the Si3N4 nanodispersoids marked. (b) Indexed SAEDP from
the spinel grains (T denotes transmitted spot). (c) EDS spectrum from a Si3N4 nano-
dispersoid region (marked by a circle in (a)) showing the presence of Si, Al and Mg.
Reproduced with permission from Ref. [232], Copyright 2012, Elsevier.
As shown in Fig. 30, no residual porosity could be found in this
as-processed spinel/Si3N4 nanocomposite. The spinel grain size is
300 nm and the size of is about 100 nm. The nanosized Si3N4
particles were located both at grain boundaries and within the
spinel grains. Fig. 31 shows a landscape photograph taken through
the as-processed spinel/Si3N4 nanocomposite ceramics with
a thickness of 2 mm, showing good transparency in the visible
range. Therefore, this type of transparent ceramics could be used
for possible armor applications [232].
3.4. ALON
Aluminum oxynitride (ALON) has a defect cubic spinel crystal
structure with chemical formula of Al(64þx)/3O32xNx (2  x  5).
The addition of a small amount of nitrogen converts the rhombo-
hedral crystal structure of alumina into the cubic spinel structure of
ALON. Nitrogen stabilizes the cubic spinel crystal structure over
Fig. 31. Landscape photograph through as-processed spinel/Si3N4 nanocomposite half
disk (2 mm thickness). The distance between the camera lens and the sample is
w3 cm. Reproduced with permission from Ref. [232], Copyright 2012, Elsevier.
41
a wide range of compositions. ALON is optically transparent (80%)
over the region from near ultra violet to visible and near-infrared
wavelength of the electromagnetic spectrum. It is 4 times harder
than fused silica glass, 85% as hard as sapphire and nearly 15%
harder than MgAl2O4 spinel. Furthermore, the cubic structure of
AlON exhibits isotropic optical properties. Combined with its good
optical and mechanical properties, ALON can be used in fields of
defence and commercial applications, such as military aircraft and
missile domes, transparent armors, IR windows, hyper-
hemispherical domes, laser windows, military aircraft lenses,
semi-conductor processing applications and scanner windows
[233]. Over the years, several processing routes have been used to
produce fully dense transparent polycrystalline AlON ceramics.
Initial work was carried out by McCauley and Corbin [234] in 1979,
using reactive sintering of Al2O3eAlN mixtures. Then the reactive
sintering technique was widely used by other researchers [235].
The conventional fabrication of transparent AlON ceramics
involves several steps, including synthesis of precursor ALON
powder, forming green body with the powder and then sintering in
a nitrogen atmosphere at high temperatures (>1850  C) for
extended period (20e100 h). AlON precursor powders can be
synthesized by several methods, such as reaction of Al2O3 and AlN,
carbothermal reduction (CR) of Al2O3, solid-state reaction (SSR),
plasma arc synthesis and self-propagating high-temperature
synthesis (SHS) [236]. Among these methods, CR and SSR have been
the most widely used ones, because CR is very cost effective while
SSR is extremely simple. However, CR method has too many
influencing factors, making it difficult to synthesize pure AlON
powders without residual AlN or Al2O3 [237]. SSR method requires
high purity and fine AlN powders to ensure high sinterability. In
this respect, a combinational method of carbothermal reduction
and solid-state reaction synthesis of g-AlON powders was devel-
oped by Yuan et al. [238]. Ultrafine, phase pure and low cost g-AlON
powders were easily synthesized by using organic sucrose instead
of carbon black as a reducing agent.
Similar to other transparent ceramics, AlON ceramics have also
been processed by using various sintering techniques, such as
pressureless sintering [240], microwave sintering [114], HP [239],
HIP [240e242] and SPS [243]. For example, Zhang et al. [240]
proposed a new one-step pressureless sintering, using a-Al2O3
and aluminum powder as starting material. The starting material
was first nitridised into high activity AlN, from which Al23O27N5
was then synthesized in-situ by reacting with a-Al2O3. The optimal
one-step pressureless sintering process was observed to occur at
Fig. 32. XRD patterns of AlON samples SPS sintered at (a) 1500  C, (b) 1550  C, (c)
1580  C and (d) 1650  C for 30 min. Reproduced with permission from Ref. [243],
Copyright 2012, Elsevier.
42 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 33. Cross-sectional (a/b) and polished surface (c/d) SEM images of the AlON ceramics SPS sintered at 1550  C (a/c) and 1650  C (b/d) for 30 min. Reproduced with permission
from Ref. [243], Copyright 2012, Elsevier.
1750  C for 2 h, which resulted in samples with flexural strength of
as high as 321 MPa.
Very recently, Sahin et al. [243] reported a reactive SPS
method to prepare AlON transparent ceramics. Al2O3 and AlN
powder mixtures were used as precursors. Reactive SPS was
conducted at temperatures between 1400  C and 1650  C for 15e
45 min at 40 MPa under N2 gas flow. AlON phase formation was
initiated in the samples sintered above 1430  C, according to the
XRD analysis, as shown in Fig. 32. The complete transformation
from the precursor phases (Al2O3 and AlN) to AlON was observed
at 1650  C for 30 min at 40 MPa. High temperature and low
heating rate were favorable to the formation of AlON. Represen-
tative SEM images of the samples are shown in Fig. 33. The
highest value of hardness was recorded to be 16.7 GPa. The
sample with highest content of AlON possessed a fracture
toughness 3.95 MPa m1/2.
A two-step method to prepare AlON ceramics was developed by
Qi et al. [244] with nanosized Al2O3 and AlN as precursors. Single
phase AlON powder was obtained at 1750  C for 4 h in flowing
nitrogen atmosphere through direct reaction of the nanosized
Al2O3 and AlN. After ball milling, the powder had an average size of
several microns and showed quite high sintering activity. The high
reactive AlON powder was used to fabricate transparent ceramics at
1880  C.
By using MgO and Y2O3 as sintering aids, transparent AlON
ceramics were successfully prepared by solid-state reactive sin-
tering [245]. The effects of sintering aids and holding time on
densification of AlON ceramics were investigated. Co-doping of
MgO and Y2O3 was found to be more effective in enhancing the
densification of AlON than the doping of either MgO or Y2O3. It was
observed that, at a given doping level of Y2O3 (e.g. 0.08 wt.%),
transmission coefficient of the ceramics increased with increasing
concentration of MgO. A 1 mm thick sample, co-doped with 0.08 wt
% Y2O3 and 1 wt% MgO, sintered at 1950  C for 12 h in N2 atmo-
sphere, had an in-line transmittance of 60% at 600 nm.
3.5. Electro-optic ferroelectric ceramics
Opto-ceramics is a family of special transparent oxide materials.
Their crystallography structure is perovskite type with formulation
of ABO3. The typical representatives of this family include
Pb1xLax(ZryTi1y)1x/4O3 (PLZT), Pb(Mg1/3Nb2/3)O3ePbTiO3 (PMNe
PT) and Pb(Zn1/3Nb2/3)O3ePbTiO3 (PZNePT). The PLZT formula
assumes that La substitutes for Pb2þ in the A-site and the B-site
vacancies are created for electrical balance. To achieve highest
transparency and electro-optic coefficient, some elements, such as
Ba and/or La, are usually introduced into the solid solutions of PMNe
PT and PZNePT. Material synthesis and properties of transparent
electro-optic ceramics, including PLZT and PMNePT, were well
summarized by Jiang et al. [12].
3.5.1. PLZT
PLZT ceramics possess much higher electro-optic coefficient
than LiNbO3 single crystals. PLZT ceramics also have higher
transparency than other ferroelectric materials. Specifically,
Pb(1x)Lax(ZryTiz)1x/4O3 (i.e., PLZT 9/65/35) exhibits outstanding
electro-optic coefficients with little hysteresis and no remnant
polarization. Therefore, PLZT (9/65/35) ceramics are potential
candidates for applications in digital light modulators and large-
aperture light shutters [246].
Transparent PLZT ferroelectric ceramics were reported by
Haertling in 1971 [247]. The quality of transparent PLZT ceramics is
mainly determined by the properties of the precursors. High quality
powders should have small particle size, narrow size distribution
and no hard agglomeration. Several wet chemistry-based methods,
such as chemical co-precipitation, solegel processing, high energy
ball milling and hydrothermal processing, have been developed to
prepare PLZT powders [248e250]. Moreover, special sintering
techniques, such HP/HIP and atmosphere-controlled sintering, are
also very useful in fabricating high quality transparent PLZT
ceramics [247].
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Sintering atmosphere is demonstrated to be important in
determining the final microstructure of the PLZT ceramic because of
the volatility of lead oxide (PbO). Sun et al. [13] established
a controlled oxygen partial pressure sintering to obtain transparent
(Pb,La)(Zr,Ti)O3 ceramics. PLZT (7/60/40) ceramics with large
piezoelectric coefficients were prepared by using a two-step sin-
tering process with controlled oxygen partial pressure. At the first
step, the samples were sintered under a low-oxygen-pressure
(vacuum) at low temperature (1150  C), while they were then
processed under higher oxygen pressure (0.22 MPa) at higher
temperature (1250  C), at the second step. Fully densified trans-
parent PLZT ceramics with an average grain size of 3 mm could be
readily fabricated in this way. The samples possessed kp and d33 of
as high as 0.71 and 850  1012 C/N, respectively.
Kim et al. [246] fabricated transparent lanthanum-doped lead
zirconate titanate (PLZT) ceramics in air and in oxygen-gas atmo-
sphere by pressure sintering. The microstructure of the sintered
body was not uniform; it was completely dense near the surface,
but it was porous at the center. The thickness of the dense layer
increased with sintering time and oxygen-gas pressure in the sin-
tering atmosphere. Vaporization of PbO from the specimen surface
and resultant formation of lattice vacancies were attributed to this
microstructural evolution. Diffusion of the gas trapped in the pores
also was important in determining the thickness of the dense layer.
When the PLZT specimen was sintered in air at 1200  C for 8 h, the
thickness of the dense layer was 0.25 mm. Therefore, if the spec-
imen thickness was 0.5 mm, the whole specimen was dense and
transparent. When the specimen was sintered in an oxygen-gas
atmosphere under the same conditions, the specimen thickness
increased markedly.
Representative specimens of polished cross-sections of speci-
mens sintered in various atmospheres at 1200  C for 8 h are shown
in Fig. 34. When a specimen with the same composition was sin-
tered in argon, the thickness of the dense layer decreased
(Fig. 34(a)). Furthermore, it is apparent that the outer region was
not completely pore-free as was the case of the specimen sintered
in air. On the other hand, when the specimen was sintered in a 33%
oxygen-gas atmosphere, the dense layer became thicker than the
case of sintering in air, (Fig. 34(b)). As the oxygen partial pressure of
the sintering atmosphere was further increased, the dense layer
continued to grow until the whole specimen became dense in
a pure oxygen atmosphere, as shown in Fig. 34(c). The appearance
of the sample is shown in Fig. 35.
A modified HP method, namely a two-step controlled oxygen
pressure sintering process, was reported to fabricate fully densified
PLZT (7/60/40) ceramics with high piezoelectricity [13]. Specifically,
low-oxygen-pressure and low-temperature sintering were used in
the first step, followed by a high oxygen pressure, high-
Fig. 34. Optical micrographs of the PLZT ceramics sintered for 8 h in various atmospheres: (a) pure argon, (b) 33% oxygen-gas and (c) pure oxygen-gas. Reproduced with permission
from Ref. [246], Copyright 2001, John Wiley & Sons.
43
Fig. 35. PLZT specimens sintered in air at 1200  C for 8 h: (a) whole specimen with
thickness of 1 mm and (b) outer layer only. Reproduced with permission from Ref.
[246], Copyright 2001, John Wiley & Sons.
temperature sintering cycle. For the first step, after sintering
under low-oxygen-pressure (vacuum) and at low temperature
(1150  C), the PLZT ceramics were composed of small closed pores,
and the gas pressure inside the pores was low. For the second step,
after sintering under higher oxygen pressure (0.22 MPa) and at
higher temperature (1250  C), it was easy to obtain fully densified
PLZT ceramics with an average grain size of 3 mm. Correspondingly,
piezoelectric properties of the ceramics were improved; i.e., kp and
d33 were increased to as high as 0.71 and 850  1012 C/N,
respectively. Moreover, the piezoceramics were transparent, with
an optical transmittance of 15% (l ¼ 610 nm), for a sample of 1 mm.
Abe and Kakegawa [251] reported fabrication of optically trans-
parent PLZT ceramics by using a three-stage-atmosphere-sintering
technique. This technique consists of three stages: (1) sintering in
an oxygen atmosphere, (2) elimination of pores in a carbon dioxide
atmosphere, and (3) elimination of oxygen vacancies in an oxygen
atmosphere. The experimental results revealed that the use of
a carbon dioxide atmosphere effectively decreased the residual pores
and thus improved optical transmittance. From commercially avail-
able raw powders, an optical transmittance of 51% (wavelength of
550 nm) can be achieved for 0.7 mm thick polished PLZT (9/65/35)
ceramics using a carbon dioxide atmosphere, whereas the values
only 34% without a carbon dioxide atmosphere. The advantage of this
technique is that PLZT ceramics having high optical quality can be
obtained by using conventional sintering tools.
Kong et al. developed a simple and feasible method to obtain
transparent PLZT (9/65/35) ceramics through a repeated annealing
process [252]. The experiment was started from nanosized powder
44 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54

of PLZT, which was synthesized directly from commercially avail-

able constituent oxides by using a high energy ball milling at near
room temperature. Transparent PLZT ceramics were obtained by
annealing the samples pre-sintered at 1125  C for 6 h repeatedly for
4 times without using hot pressing or oxygen flow. The annealing
temperature was 1200  C. The optical properties together with the
electrical characteristics of the PLZT ceramics produced in this way
were comparable with the literature results. The most significant Fig. 36. Photographs of the Er3þ-doped PMNe0.25PT transparent ceramics (1.5 mm
aspect of this study is the low cost large-scale fabrication of the thick). The numbers in the photos are the Er3þ doping levels in mol.%. Reproduced with
PLZT nanosized powders, which is not available by most of the wet permission from Ref. [262], Copyright 2012, Elsevier.
chemical synthesis routes.
SPS has been confirmed to be a viable technique to synthesize transmittance was decreased to 28.0% in the sample with Er3þ of
PLZT transparent ceramics. An example was reported by Wu et al. 5.0 mol%, which was considered to be closely related to the
[112] to prepare PLZT (8/65/35) ceramics. The PLZT powder was formation of a trace of pyrochlore phase. By the way, the absorption
synthesized by using a wetedry combination method. Due to the edge shifted to higher energy as the doping concentrations were
contamination of carbon from the graphite mould, the samples <2.0 mol% and a red-shift was observed in the samples with higher
after the SPS sintering should be annealed in air or oxygen. Optical doping concentration (5.0 mol%). The observations were explained
properties of the samples were affected by the SPS temperature, as by considering the combined effects of ion polarization and local-
well as the post annealing temperature. It was found that 700  C ized defect energy level.
was the optimal sintering temperature when transmittance was Pb(Zn1/3Nb2/3)O3 (PZN) single crystal exhibits outstanding
considered. dielectric and electrostrictive properties and also shows a very
large electro-optic coefficient [263]. However, single phase PZN
3.5.2. Other ferroelectric ceramics ceramics cannot be prepared due to the thermodynamics inhibi-
Pb(Mg1/3Nb2/3)O3 (PMN) with perovskite-structure is known as tion. Therefore, it becomes a natural idea to combine PMN and
one of the best representative relaxor ferroelectrics [255]. However, PLZT, aiming at creating new compounds with advantages of both
the Curie point (TC) of PMN is below room temperature and the materials, such as excellent piezoelectric and dielectric properties,
synthesis of single PMN is always a challenge. Another perovskite- high optical transmittance in a wide range of wavelength, and
structure ferroelectric PbTiO3 (PT) has a high TC of about 490  C and strong electro-optical effect. Yin et al. [14] synthesized transparent
very phase stability. Incorporation of PT with PMN has been widely PZNePLZT ferroelectric ceramics by HP sintering in oxygen atmo-
used to form new solid solution PMNePT, which has TC of above sphere. Uniform cylindrical samples with diameter as large as
room temperature and is easy to be synthesized [253,254,256e 50 mm could be readily obtained. The product showed a pure
261]. More importantly, PMNePT has an isotropic minimum perovskite phase, thin grain boundaries and homogeneous dense
energy stable structure and a higher electro-optic coefficient than microstructures. The ceramics exhibited very good transparency
PLZT (about 10e30 times). To the same index change (or phase from near ultraviolet to infrared regions.
shift), the applied voltage onto PMNePT could be much lower than Besides ferroelectric transparent ceramics, there has also been
that required when using PLZT. Moreover, the electric hysteresis of reports on antiferroelectric ceramics. An example was demon-
PMNePT can be readily minimized [253]. In addition, PMNePT is strated by Zhou et al. [110]. They prepared lead zirconate stannate
the most promising nonlinear optical materials because of its titanate (PLZSnT) ceramics by using SPS at 900 Ce950  C. The
extremely high electro-optic (EO) coefficient and strong photo- samples had nearly full density and fine grain size (about 300 nm).
refractive effect [261]. Its EO effect is about 2e5 times higher than Compared with samples made by using conventional sintering (CS),
that of PLZT and nearly 100 times than that of LiNbO3 at room the SPS sintered samples showed higher permittivity and lower
temperature. The remarkably good transparency over a wide dielectric loss tangent, as well as special strain hysteresis loops
wavelength range of 500e7000 nm makes PMNePT suitable for similar to those of ferroelectric relaxors.
almost all the visible to mid-IR optical applications.
The first demonstration of PMNePT electro-optic ceramics was
reported in 2002 [254]. Detailed investigation on the optical char-
acteristics, including the electro-optic phase modulation, electric
hysteresis property and thermo-optic coefficient, of transparent
PMNePT electro-optic ceramics was carried out by Ye et al. [253].
A polarization independent electro-optic switch by using fiber
Sagnac interferometer (FSI) structure was built up with the PMNe
PT transparent ceramics.
Preparation and characterization of transparent ceramics of La-
doped PMNe0.25PT by a two-stage sintering method from
conventional raw materials were reported in Ref. [15]. Optical
characteristics of Er3þ-doped PMNePT transparent ceramics were
investigated by Wei et al. [262], with doping concentrations of 0.5,
1.0, 2.0 and 5.0 mol%. Figs. 36 and 37 show photographs of the
PMNePT ceramics and their transmittance curves, respectively. The
presence of Er3þ over 0.5e2.0 mol% could enhance the optical
transmittance of the samples and modify the optical absorption
near the band gap energy of the materials. Transmittance of the
undoped PMNe0.25PT in the visible region was estimated to be
43.0%. The transparent ceramics doped with Er3þ levels of 0.5, 1.0 Fig. 37. Transmittance curves of the PMNePT ceramics with different concentrations
and 2.0 mol% were 50%, 53% and 57%, respectively. However, the of Er3þ. Reproduced with permission from Ref. [262], Copyright 2012, Elsevier.
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
3.6. Mullite
Mullite, a crystalline aluminum silicate phase, with a stoichio-
metric composition of 3Al2O3$2SiO2, is a very interesting mineral
constituting silicate ceramics. It is one of the most widely used
ceramic materials because of its unique properties, like high-
temperature strength, thermal-shock resistance and low dielec-
tric constant [264]. It is also a good refractory material, due to its
high melting point (1850  C) [265], low thermal expansion coeffi-
cient, low thermal conductivity, high strength and good creep
resistance. Due to its low dielectric constant (ε ¼ 6.7, compared to
9.8 of Al2O3), it can be used as a promising candidate for substrates
in electronic packaging [266]. Moreover, mullite can be employed
as window materials, especially at high temperatures, because it
has a good transmission at high temperatures in the middle
infrared band. Low dielectric constant and optical transmittance of
fine-grained polycrystalline mullite could be a good host material
of solid-state laser activators [115].
Pore-free translucent mullite was reported by Mazdiyas and
Brown in 1972 by using HP sintering at 1500e1650  C and 30e
50 MPa, and vacuum HP, with high purity submicron mixed oxide
precursor powders derived from metal alkoxides [267]. Prochazka
and Klug prepared infrared transparent mullite ceramics with
72 wt% Al2O3 by using HP sintering at 1630  C and 76 wt% Al2O3 by
using HIP pressing at 1650  C [268]. Ohashi et al. fabricated visible
spectrum to infrared translucent mullite by using pressureless
sintering at 1750  C [269]. Schneider et al. obtained transparent
mullite by the combination of HIP pressing and pressureless sin-
tering using commercial fused-mullite [37]. Both processing
methods led to mullite ceramics with fine-grained microstructures
(mean grain size of 5e10 mm) with equiaxed grains and a narrow
grain-size distribution. The pressureless sintered mullite had
a porosity of 5.5% and a transmittance of 20% in the VIS and NIR
ranges, while the HIP sintered mullite showed a porosity of 1% and
a transmittance of 40% in the VIS range and up to 80% in NIR range.
This optically translucent mullite ceramics are suitable for optical
windows in the VIS and NIR ranges [37].
Zhang et al. [104] fabricated transparent mullite ceramics by
using SPS from monophasic precursors in mid-infrared and visible
light ranges by SPS. In this study, the effects of calcination
temperature, properties of precursor powders and sintering
parameters on microstructure and optical performances of the
mullite ceramics were systematically investigated. The samples
with a relative density of above 97.5% exhibited an infrared trans-
mittance of 75e82% in wavelength of 2.5e4.3 mm. It was found that,
as the precursor powders were calcined at temperatures of below
1100  C, the residual OH, H2O and organic compound could not be
completely eliminated, which in turn had negative effects on
optical properties of the final ceramics. However, if the calcination
temperature was too high, the precursors could not fully
densified, due to the absence of viscous flow of amorphous phase.
At a given calcination temperature, optical transmittance of the
mullite ceramics was decreased with increasing sintering temper-
ature above 1450  C owing to the elongated grain growth. In
addition, microwave sintering provided a rapid heating,
accelerated-mullitization, enhanced densification and limited grain
growth for developing transparent mullite ceramics with diphasic
gels [115].
4. Applications
The special optical transparency, combined with the general
properties of ceramics, makes transparent ceramics suitable for
various applications, such as lasers, armors and lighting, which will
be discussed in detail as follows.
45
4.1. Laser
Ceramic laser technology has emerged as an active research area
because of the numerous advantages of ceramics over single crys-
tals. First, ceramics can be produced in large volumes, which makes
them attractive for high power laser generation. Second, they can
provide a gain medium for fiber lasers with high beam quality and
can also be made into composite laser media with complicated
structures that would otherwise be difficult to fabricate by using
single crystals. Third, ceramics can be heavily and homogeneously
doped with laser-active ions when compared with single crystals.
Furthermore, the use of ceramics enables mass production, which
may lead to low cost commercial production of lasers or the
production of lasers with customized special functions.
Early in 1960s, effort to use ceramics as a laser gain medium was
begun with Dy:CaF2 in cryogenic conditions [270]. In the 1970s,
Nd:Y2O3eThO2 was successfully used for pulsed laser oscillation
[164,271], although the laser oscillation efficiency was relatively
low. The development of a practical ceramic laser started in 1995
when c.w. laser oscillation was developed by using polycrystalline
Nd:YAG ceramic laser gain medium [196], which showed that
ceramic materials could overcome both the technical and
economical problems of melt-growth single crystals. Since then,
a number of achievements, such as highly efficient laser oscillation
in compact devices, ease of control of the laser mode, and the
generation of highly focused coherent beams, have been made.
Ultrashort-pulsed laser (pico- to femtosecond) oscillation using
Nd:YSAG [272] and Yb:YSAG ceramics [273] were then demon-
strated. Subsequently, lasing at 1.47 kW was successfully generated
using an Nd:YAG ceramic rod [274], even though its oscillation
efficiency was 15% lower than that of single crystal one. More
recently, ceramic Nd3þ:YAG has been fabricated and used to
demonstrate lasers with output powers of 67 kW and even
>100 kW of at 1.06 mm.
Currently, rare-earth element-doped YAG is still the most
extensively studied and widely used ceramics for high power lasers
[275e277]. Ikesue and Aung [275] once summarized the progress
of polycrystalline Nd:YAG (Y3Al5O12), Nd:YSAG (Y3ScAl4O12),
Yb:YSAG ceramics with an almost pore-free microstructure by
using advanced ceramic processing. The laser conversion efficiency
of pore-free polycrystalline Nd- and Yb-doped ceramics was
extremely high and their optical qualities were comparable with
that of commercial high quality Nd:YAG single crystals. The c.w.
oscillation efficiency of the polycrystalline Nd:YAG ceramics was
very high and the beam quality was also sufficiently good. SHG
green and blue lasers were successfully generated by using the
Nd:YAG ceramics. A single longitudinal mode was achieved by
using the heavily doped Nd:YAG ceramics. The laser oscillation
efficiency was as high as 17%. Ps and fs mode-locked pulse lasers
were successfully realized by using the Nd:YSAG and Yb:YSAG
ceramics. Pulse width of the Yb:YSAG ceramics was as short as
280 fs.
Fig. 38 shows c.w. laser performances of the pore-free 1.0, 2.4,
and 3.6 at.% Nd:YAG polycrystal ceramics pumped with a Ti:Sap-
phire laser (808 nm) [275]. The threshold and the slope efficiency of
polycrystalline Nd:YAG ceramics generally depend on the concen-
tration of Nd in ceramics because fluorescence lifetime decreases
with increasing concentration of Nd ion. However, very high laser
conversion efficiency was achieved in all the ceramics because of
their pore-free microstructures. Although optical resonators were
not optimized in this oscillation, the slope efficiency (Z) of the
polycrystalline ceramics was as high as 65%, which was almost
equivalent to that of a single crystal.
Fig. 39 shows a photograph of a blue laser and a green laser,
together with a schematic diagram of a blue laser oscillator [275].
46 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 38. Laser performance of a commercial high quality 1 at.% Nd:YAG single crystal
and 1.0, 2.4 and 3.6 at.% Nd:YAG polycrystalline ceramics pumped with a Ti:Sapphire
(808 nm) laser. Reproduced with permission from Ref. [275], Copyright 2006, John
Wiley & Sons.
The main feature of this ceramic blue laser is its very compact
structure because coated mirrors are used instead of normal
mirrors. In this system, a 2.4 at.% Nd:YAG ceramic sample was used
as a laser gain medium. It was optically contacted with a KNbO3
single crystal as a secondary harmonic generation (SHG) device. A
diode laser was used as an exciting source. An SHG laser was
generated from the Nd:YAG ceramics.
Moreover, composite ceramics with complicated structures
could be fabricated without the need for precise polishing and
diffusion bonding. Fig. 40 shows laser characteristics of various
types of composite elements. Although the optical resonator was
not optimized, over 50% slope efficiency [275] could be achieved in
each composite and a high beam quality TEM00 mode was also
realized.
Maître et al. [278] investigated light scattering by pores in
transparent Nd:YAG ceramics for lasers. The correlations between
microstructure and optical properties were studied. This study
revealed that the pore contents affect the transparency and laser
efficiency of the ceramics. The porosity in Nd:YAG ceramics should
be lower than 104% to reach single crystal laser efficiency.
However, recent studies indicated that YAG is not the best host
material for high power laser operation systems due to its relatively
low thermal conductivity and high thermal expansion coefficient.
Instead, sesquioxides, such as Sc2O3, Y2O3 and Lu2O3, have been
shown to be very promising host materials for high power laser
applications, mainly due to their high thermal conductivity and
high absorption and emission cross-sections of trivalent rare-earth
ions [279]. One example is Yb3þ-doped Y2O3 which has excellent
Fig. 39. Appearance of ceramic blue and green lasers, together with a schematic diagram of a blue laser oscillator. (For interpretation of the references to colour in this figure legend,
the reader is referred to the web version of this article.) Reproduced with permission from Ref. [275], Copyright 2006, John Wiley & Sons.
potential as a laser material for high power lasers operating at 1 mm
[280].
Sanghera et al. [281] investigated laser properties of HP pro-
cessed Yb3þ:Y2O3 and Yb3þ:Lu2O3 ceramics. The laser output power
at 1076 nm was obtained by using c.w. pumping at 940 nm, based
on homogeneously doped 2%-Yb3þ:Y2O3 ceramic samples with
a thickness of 2 mm and diameter of 3 mm. Up to 600 mW output
power was demonstrated with a slope efficiency of 36.7% using a 2%
output coupler. When using a 5% output coupler, the slope effi-
ciency could reach 44.6%. In addition, pulsed lasing experiments
were performed by using the 2%-Yb3þ:Y2O3 ceramic samples.
Lasing occurred at 1077 nm with a slope efficiency of 46%. The laser
output power versus absorbed power measured by using a 5%
output coupler for the 10%-Yb3þ:Lu2O3 ceramics was examined. A
slope efficiency of 74% and output power of as high as 16 W were
observed at 1080 nm by pumping at 975 nm. This efficiency was
better than that of the best Nd3þ:YAG ceramic lasers [282].
4.2. Armor
Common applications for transparent armor include personnel
protection in the form of face shields and visors, windows for
ground vehicles and armored cars and windshields and lookdown
windows for aircrafts. The widely used glass-based transparent
armor windows are typically greater than five inches thick in order
to provide the required multi-hit ballistic protection. Not only does
this increase wear cost for tactical vehicles which are already
straining with their weight limits, but also the relatively soft glass
facing can be degraded in the field by rock damage and blowing
sand, leading to significant replacement cost. Therefore, there is
a compelling need to reduce the weight of the transparent armor
systems while simultaneously increase the ballistic protection
capabilities. There is also a need on large windows and domes for
multimode weapon systems that are exposed to harsh environ-
mental conditions. When both strength and hardness are the crit-
ical performance metrics, choices are often limited to a few
materials. These are the single crystals sapphire (sapphire),
aluminum oxynitride (AlON) and magnesium aluminate spinel
(spinel) [283e289]. Due to their high strength and hardness, these
three materials have long been considered as a potential replace-
ment for the ballistic glasses in transparent armor applications.
Recent ballistic testings have shown that spinel, AlON and sapphire
possess similar performance. However, as stated earlier, when
compared with sapphire single crystals, polycrystalline spinel
[286e289] and AlON [290,291] are superior. As window materials,
spinel is superior to sapphire and AlON due to its transparency up
to 5 mm wavelength. Its high optical and MIR transparency in the
range of 0.25e5.5 mm makes it an ideal candidate as windows and
domes for EO & IR sensors on various defence systems operating in
the environmental demanding conditions.
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 40. Laser performance of various types of composite elements. Reproduced with permission from Ref. [275], Copyright 2006, John Wiley & Sons.
4.3. Lighting
Transparent ceramic materials with appropriate thermal and
mechanical properties are very useful as envelopes for focused-
beam, short-arc lamps containing various fillers operating at
temperatures higher than the melting point of quartz. Coarse-
grained ceramics of translucent polycrystalline alumina have
been used for several decades as envelopes in discharge lamps.
Translucent polycrystalline alumina (PCA) doped with magnesia-
based additives discovered in 1960s has played an enabling role
in the lighting industry. It enabled the construction and wide-
spread use of high-pressure sodium lamps [292]. In 1990s, metal
halide lamps featuring translucent alumina tubes, cylindrical [293]
or round [294], were introduced for white light, general-
illumination applications, due to the nature of translucency of
regular translucent alumina. An improved “white” light is emitted
by metal halide lamps introduced by Philips in 1994. These lamps
run at a temperature close to 1200  C, which makes Al2O3 almost
irreplaceable as an envelope of outstanding chemical resistance
[295,296].
PCA of submicron grain size and high in-line transmittance (very
low residual porosity and small grains) was accomplished by using
HIP sintering of compacts consisting of nearly nanosize alumina
particles [24,33,295,297,298]. Other transparent ceramics as enve-
lope materials for improved beamer lamps included AlON, YAG,
Y2O3 and Dy2O3 [298]. A wide range of shapes (cylindrical, bulgy,
spherical and elliptical) can be fabricated by the aid of technological
advancements in ceramic powder synthesis, forming and sintering.
It is believed that there will be growing interest in developing and
manufacturing these new lighting ceramics [299e301].
4.4. Other applications
4.4.1. Scintillators
Scintillators are optical materials that emit pulses of visible
photons when excited with high energy radiations. Gamma ray
spectrometers providing high sensitivity and effective isotope
identification require high energy resolution, high effective atomic
number and scintillators that can be produced with large sizes.
Transparent ceramics, such as YAG(Ce) [302], LuAG [303] and
Lu2O3 [304], form a promising class of polycrystalline materials for
scintillator applications. By using transparent ceramics, not only
the production costs can be greatly reduced, but also the activator
concentration and homogeneity can be dramatically enhanced.
Transparent ceramics have become alternatives to replace single
crystals for scintillator applications, such as gamma ray spectros-
copy and radiography. The family of cerium-doped gadolinium
garnet (GYGAG(Ce)) scintillators appears to meet these require-
ments. A new gamma spectroscopy scintillator, with high light
47
yields and excellent phase stability, based on GYGAG(Ce) and
a radiography scintillator based on Lu2O3(Eu) have been reported in
the open literature [35,305].
4.4.2. Transparent electro-optic ceramics devices
A variety of devices have been designed by using transparent
electro-optical ceramic materials, including variable optical atten-
uators (VOA), polarization controllers (PC), sinusoidal filters,
dynamic gain flattening filters, tunable optical filters and Q-
switches, which have been described in detail in Ref. [12]. A brief
description is given some devices as follows.
Variable optical attenuator (VOA) is a device used to reduce the
power level of an optical signal, either in free space or in an optical
fiber. The basic types of optical attenuators are fixed, step-wise
variable and continuously variable. The type of devices has played
an important role in controlling the optical signal levels throughout
the network. Representative applications of VOA include pre-
emphasis, channel balancing and optical automatic gain control.
In dense wavelength-division multiplexing (DWDM) transmission
system, the optical powder between every two channels should be
equalized before they are combined and guided into a single optical
fiber. At add/drop network nodes, because the optical signals arrive
individually from different points in a network, all channels must
be equalized. In addition, VOA has found applications beyond the
usual networks [12].
Light is in nature an electromagnetic wave, with electric and
magnetic field components being perpendicular to each other and
to its propagation direction. Therefore, light is actually a polarized
electromagnetic field. As a result, light has distinct orientation in
space and its propagation in a media is dependent on the polari-
zation direction, which has exerted negative influence on the
transmission rates of DWDM systems, such as polarization
dependent loss (PDL) and polarization mode dispersion (PMD). To
solve these problems, it is necessary to have a good capability of
polarization management. A dynamic PC is used to overcome such
polarization related problems. In summary, PC can be used for
polarization mode dispersion compensation, polarization scram-
bling, polarization multiplexing, polarization generation and other
polarization management functions [12].
4.4.3. Optical systems (lens)
Markets for digital cameras and mobile phones with optic
equipment are increasing rapidly. Frequently, a compact and small
design of the lens systems is imperative for use and gives rise to
the search for new transparent materials with high refractive
index and high Abbé number. Optical glasses exhibit limits at
n ¼ 1.5e1.85 whereas higher values are known for a number of
crystalline ceramics that also exhibit a higher scratch and impact
resistance.
48 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 41. Photographs of a thin translucent organic material of 0.06 mm, a sintered
window of submicrometer Al2O3 (thickness 0.8 mm, real in-line transmission w60%)
and 6 mm thick almost fully transparent spinel for comparison. The characteristic
difference in transmission among the three samples is clearly demonstrated in (a),
while there is no clear difference due to the wrong positioning in (b). Reproduced with
permission from Ref. [306], Copyright 2009, Elsevier.
5. Discussion and concluding remarks
Various transparent ceramics have been developed by using
different sintering techniques, combined with the use of ultrafine
precursor powders with high sinterability. Although significant
progress has been made on the one hand, there are certain prob-
lems in the research of this area on the other, with which a detailed
discussion has been presented in Ref. [306]. Here, a brief delinea-
tion is used as discussion and concluding remarks of this review.
Fig. 42. Thickness effect (b / a) on in-line transmission of transparent of the transparent ceramics with an in-line transmission of <100%, due to the scattering and/or absorption.
“Real” in-line transmission is measured by using narrow measuring aperture (b). This thickness effect is absent as the transmission approaches the theoretical maximum (c).
Reproduced with permission from Ref. [306], Copyright 2009, Elsevier.
It is necessary to emphasize that a transparent component
means that when it is used as a window a clear image of subjects far
away from it can be formed. The prerequisite of such a clear image
is the absence of any scattering when the light travels through the
transparent window. Qualitative evidence by observation is usually
used to show the transparency of a transparent ceramics. The right
way to do this is to maintain a sufficiently large distance between
the objects and the transparent samples, as shown in Fig. 41(a).
By doing in this way, it is clearly demonstrate that the Al2O3
sheet is translucent, while the spinel and the organic samples are
transparent. However, more generally, samples have been laid on
background with a direct contact, as shown in Fig. 41(b). In this
case, all samples look like transparent. Another concern with the
accurate presentation of transparency is measurement. The aper-
tures of most commonly used photospectrometers are in the range
of 3e5 , with which the measured transparencies are usually
overestimated by including fairly large amount of the scattered
portion. For example, as the opening angle is increased from 0.5 to
5 , the recording area is increased by 100 times. Therefore, it is
urgent to establish an international standard for the measurement
of transparency of transparent ceramics.
Another important aspect is the so-called thickness effect if the
transparency of a material is below its theoretical maximum. As
shown in Fig. 42(a) and (b), the sample has a 60% of its theoretical
transparency. As the sample thickness is increased from (b) to (a),
the amount of scattered light is greatly increased. In other words,
the real in-line transparency of the sample is reduced with
increasing thickness. To exclude the contribution of the scattered
light, a narrow aperture should be used. Otherwise, the measured
transparency will be overestimated. Only when a material reaches
its theoretical maximum transparency, its transparency is not
affected by thickness, as shown in Fig. 42(c). In this respect, it is
always desired to fabricate transparent ceramics with maximum
transparency without any scattering or absorption. This is espe-
cially important for applications, such as armors, where a relative
large thickness is necessary to ensure sufficiently high ballistic
strengths.
As discussed earlier, the presence of various scattering losses is
the main contribution to the decrease in in-line transmission, with
respect to the theoretical maximum, of transparent ceramics, as
summarized in Fig. 43 [118,306]. Without the presence of these
losses, the theoretical maximum of transmission is 100% minus the
reflection on both surfaces of a piece of the material. At normal
incidence, the reflection R1 on one surface is related to the material
refractive index n, given by
 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54
Fig. 43. Light transmission through polycrystalline translucent ceramics (e.g. coarse
Al2O3). Loss in intensity of the incident light due to absorption, reflection on both
surfaces, diffuse scattering at pores and scattering caused by the birefringent splitting
(specifically for non-cubic materials). Reproduced with permission from Ref. [306],
Copyright 2009, Elsevier.
 
n1 2
R1 ¼ ; (1)
nþ1
and the total reflection loss, including multiple reflection, is
2R1
R2 ¼ : (2)
1 þ R1
Therefore, the maximum transmission is as follows:
2n
Tth ¼ 1  R2 ¼ : (3)
n2 þ 1
When all the factors are present, the real in-line transmission
(RIT) of a fully dense transparent ceramics can be described by the
following equation:
  2  ceramics. Scripta Materialia 2012;66(6):319e22.
Dn rd
RIT ¼ Tth exp  3p2 ; (4)
n l
2 structural and optical properties of Nd:Y2O3 transparent ceramic. Journal of
where Dn/n is the ratio of refractive index difference between
polarization perpendicular and parallel to c-axis to the average
index n, 2r is grain size of the ceramics, l is the wavelength of
incident light and d is thickness of the sample. This equation
implies that, at a given thickness, the RIT is closely related to the
Dn/n and r. The smaller the values of Dn/n and r, the high the RIT
will be. If Dn/n is an intrinsic property of the materials, r is an
extrinsic parameter that can be controlled through material pro-
cessing. Therefore, for give materials, the grain size of the ceramics
should be sufficiently small to achieve high RIT. For example, the
grain size of a highly dense sintered Al2O3 has to be about 0.5 mm
for RIT of 60e65% at l ¼ 640 nm and d ¼ 1 mm [306].
By the way, according to the definition of Tth, the transmission of
transparent ceramics can never be 100%. It is also necessary to
mention that the Tth in Eqs. (3) and (4) is calculated by assuming
that the reflection occurs on a theoretically perfect surface. Because
theoretically perfect surface is an ideal assumption, real ceramics
inevitably have a certain value of roughness. Therefore, technical
roughness gives rise to an additional loss e another mechanism
which decreases the real in-line transmission of products
depending on the quality of the surface preparation [306].
49
Traditional high tech ceramics (e.g. for hip implants or cutting
tools) are regarded as dense when their relative density reaches, e.g.
99.7%. However, the starting point of increase in real in-line trans-
mission is usually at residual porosities of <0.1e0.2%. The key
technology to achieve highly transparent ceramics is the use of high
sintering temperatures (>1700  C), even in the cases when sintering
facilities (HP, HIP or SPS) are used. As a result, transparent ceramics
often have extremely large grain sizes (50e300 mm), which is
detrimental to mechanical properties. In this light, development of
transparent ceramics with fine-grain microstructure remains
a challenge to the research community. A systematic knowledge on
the relationship among the properties of precursor powders, green
body preparation, as well as the combined use of various technol-
ogies, will be beneficial to the address this problem, which is
currently still lacking and thus deserves to be a subject of future
research in this area.
Acknowledgement
One of the authors (LBK) would like to acknowledge the finan-
cial support of Start-up Grant of the Nanyang Technological
University (2012), Singapore.
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