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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 hot pressure (HP), hot iso-pressure (HIP), vacuum sintering, spark
affect the transparency of a ceramic sample, including thickness plasma sintering (SPS) and microwave sintering.
and surface finish. A rough surface means a significant diffuse
scattering, so the sample surface should be as smooth as possible. 2.1. Hot pressure (HP) sintering
Generally, transparency decreases with increasing thickness.
Thickness independent transparency is only possible when the Hot pressure (HP) sintering is a high-pressure low-strain-rate
material reaches its theoretical maximum of in-line transmission. powder metallurgy process for forming of a powder or powder
In summary, the strategy to develop transparent ceramics is to compact at a temperature high enough to induce sintering and
eliminate all possible scattering sites of light, including high creep processes. This is achieved by the simultaneous application of
density (>99.9% of theoretical density), absence of pores at grain heat and pressure. Densification at high pressure works through
boundaries or pores with size much smaller than the wavelength of particle rearrangement and plastic flow at the particle contacts. HP
light, absence of second phase (impurity or glass phase) at grain is mainly used to fabricate hard and brittle materials. As a result,
boundaries (negligible difference in optical property between HP has become an important technique to obtain transparent
grains and grain boundaries), small grain size (as compared to the ceramics. Fig. 1 shows a schematic diagram of typical high-
wavelength of visible light) with uniform size distribution, isotropic temperature high-pressure (HTHP) sintering facility. It consists of
lattice structure and high surface finish. a graphite furnace, sheathed by CaF2 and Pb foil. The CaF2 layer
This paper aims to provide an overview on the recent progress crumbles at high pressure and thus acts a pressure-transmitting
in fabrication and characterization of transparent ceramics for medium. The Pb foil acts a lubricant for the furnace assembly
various applications. The techniques used to develop transparent during the push-out after the experiment.
ceramics will be introduced first. After that, materials that are used In 1977, translucent spinel with small grain size (w1 mm) was
for transparent ceramics and their applications in various areas will prepared by using a low temperature (1400  C) and high-pres-
be described and discussed. The review will be ended with sure (70 MPa) hot pressing [1]. Since then, HP has been widely
concluding remarks. used to prepare transparent spinel ceramics. For example, Cook
et al. [2] used HP process to fabricate MgAl2O4 transparent
2. Transparent ceramics technologies ceramics, with a nearly 100% densification. Different from the
conventional sintering process which usually requires high sin-
Similar to that of general ceramics, the process of transparent tering temperatures (>1600  C), HP process is able to achieve
ceramics also consists of synthesis of precursor powder, compact- desired densification at relatively low temperatures, which is
ing, calcination/sintering and post-treatment (annealing, therefore also called low-temperature high-pressure (LTHP)
machining and polishing). However, the process of transparent process. Due to its low-temperature requirement, it can be used
ceramics has its special requirements, especially for the powder to develop nanosized ceramics [3e6]. The sintering mechanism at
synthesis and sintering. Because the synthesis of high quality high pressures is entirely different from that at ambient pressure.
powders for transparent ceramics is not significantly different from High pressure can restrain grain growth and initiate plastic
that for other materials, which can be found widely in the open deformation to eliminate pores and/or additional phases existing
literature, here we only focus on the sintering techniques, including in triple junctions of the grains. However, the conventional

Fig. 1. Schematic diagram of high-temperature high-pressure sintering facility.


S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54 23

sintering process is controlled by grain growth to avoid imper- wise application of pressure up to a maximum temperature of
fections between grain boundaries when preparing transparent 1580  C.
ceramics. HP sintering process is a very unique and feasible technique to
It has been reported that transparent MgAl2O4 spinel nano- prepare transparent electro-optic ceramics, including PLZT [11e13],
ceramics can be obtained at very low temperatures (500e700  C) at PZNePLZT [14] and PMNePT [12,15], which contain volatile
high pressures (2e5 GPa) by using a hydrostatic press with high- element, Pb. In the early 1970s, Haertlin and Land synthesized
temperature-calcined nanosized powders [3]. The nanoceramics (Pb,La)(Zr,Ti)O3 (PLZT) ferroelectric ceramics by using HP
were highly transparent even though their relative densities are [11]. Highly transparent ceramics of La-doped 0.75Pb(Mg1/3Nb2/3)
less than 99%, due to the low or negligible light scattering from the O3e0.25PbTiO3 (PMNePT) were fabricated by using a two-stage
nanosized grains and pores. The LTHP process is able to densify sintering method [15]. Green pellets were first sintered in an
nanosized powders without significant grain growth, which oxygen atmosphere at different temperatures, which were then hot
becomes a key advantage for the development of transparent pressed (HP) at temperatures of >1000  C for more than 8 h at
ceramics, as discussed above. pressures of 50e100 MPa. The ceramics prepared in this way
Similar process was also successfully used to develop yttrium exhibited a transparency of as high as 65% at infrared wavelength.
aluminum garnet (Y3Al5O12 or YAG) transparent nanoceramics [7]. Large quadratic electro-optic coefficient of 66  1016 (m/v)2 was
Fig. 2 shows a schematic diagram of the high-pressure cell. Disk obtained, which was the highest value reported in the literature for
samples were placed in a capsule made of NaCl, which was used to the ceramics with similar compositions. SEM images indicated that
ensure the quasi-hydrostatic compression of the sample and to the PMNePT ceramics with higher transparency had more grains
prevent its contact with the graphite heater, and then contained in with transgranular fracture behaviors. It is suggested that grain
the pyrophyllite high-pressure cell. The sample temperature in the boundary with an increased homogeneity and firm strength might
high-pressure cell was measured directly by using a standard Nie reduce the reflection and scattering of light at the grain boundaries
Cr/NieSi thermocouple. The cell pressure was monitored by using and thus improve the transparent property.
a calibrated oil pressure meter. Desired pressures were first applied HP process was found to be the most feasible method to prepare
to the samples before raising the temperature. The pressure range transparent or translucent a-sialon ceramics [16,17], which could not
was 2.0e5.0 GPa and temperature range was 300  Ce500  C, with be achievable by the conventional pressureless sintering. Single
holding time of 30 min. After that, the pressure was reduced to phase a-sialon ceramics with high optical transmittance have been
ambient pressure first and then the samples were cooled down to prepared by using hot pressing [16]. HP was also used to tailor grain
room temperature at a rate of 15  C/min. By doing in this way, morphologies and preferential texturing microstructures of a-sialon
the residual stress of the samples could be readily released and ceramics [17e19]. Other examples include translucent MgO ceramics
cracking could be avoided. Optimized processing parameters for fabricated by using hot pressing, using nanopowder of MgO con-
transparent YAG ceramics were 5 GPa and 450  C, as shown in taining 2e4% LiF as a sintering aid [20]. HP process has even been used
Fig. 3. to prepare fluoride ceramics (CaF2). Transparent Yb:CaF2 ceramics
The application of HP allows for more freedom to optimize the processed by using HP were reported by Lyberis et al. [21,22].
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 2.2. Hot iso-pressure (HIP) sintering
Y2O3 transparent ceramics. The program included a high-
temperature ramp at constant pressure and a pressure ramp at Hot isostatic pressing (HIP) is a manufacturing process used to
constant high temperature. After a dwell at 1150  C to outgas the reduce the porosity of metals and increase the density of various
samples, a pressure of 10 MPa was applied to the samples, followed ceramic materials. The HIP process subjects a component to both
by a temperature ramp at 8  C/min to 1580  C. After a 30 min dwell elevated temperature and isostatic gas pressure in a high-pressure
at constant temperature and pressure, the pressure was ramped at containment vessel. The chamber is heated, causing the pressure
0.4 MPa/min to 40 MPa. The samples were then soaked at inside the vessel to increase. Many systems use associated gas
maximum temperature and pressure for 8 h. The highest level of pumping to achieve the desired pressure levels. Pressure is applied
transparency was found for 5 at.% Eu:Y2O3 hot pressed with a step- to the material from all directions.

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.
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- model for pore elimination by hot isostatic pressing was proposed,
ieve the maximum possible densification, which is a key to as shown in Fig. 4. At low pre-sintering temperature, small inter-
achieving high light transmittance. To reduce the fabrication cost, granular pores are surrounded with fine grains, while at high pre-
hot isostatic pressing is usually used as the last step, although it has sintering temperature, intergranular pores transform to intra-
been proved to be a critical step to prepare high quality transparent granular ones with grain growth. It is probable that such inter-
ceramics, because HIPing is a high cost process needing critical granular pores are easily removed by hot isostatic pressing. The
equipment and experimental conditions. model has been found to be applicable to many other oxide
HIP process has been widely used to synthesize transparent ceramics [33,34].
armor ceramics, such as alumina (Al2O3) [23e25] and spinel The feasibility of HIP can be further demonstrated by the
(MgAl2O4) [26e28]. HIP process can be combined with HP. Hot following examples. Fully dense transparent garnet ceramics were
pressing followed by hot isostatic pressing (HIPing) proved to be derived from cold pressed green bodies that were subsequently
more feasible to fabricate transparent MgAl2O4 ceramics was vacuum sintered, with residual porosity being removed by hot
widely used [26e28]. Nowadays, HIP process was also used to isostatic pressing [35]. Bhalla and Alberta reported the use of hot
synthesize cubic sesquioxide ceramics, including Y2O3 [29], Sc2O3 isostatic pressing (HIPing) to enhance the electrical and optical
[30] and Lu2O3 [31]. In these cases, vacuum sintering to remove properties of PNNZT (50.0/15.5/34.5) [36]. After hot isostatic
closed porosity with a subsequent HIP step was usually employed, pressing at 1100  C, the density was increased to more than 99%.
which provided an alternate processing route to the fabrication of Schneider et al. [37] reported synthesis of mullite ceramics by
fully dense sesquioxide ceramics with less possibility for contam- pressureless sintered and hot isostatically pressed (HIPed) process.
ination and reduction than hot pressing. In the HIPed mullite, with porosity of <1%, a transmittance of 40%
Highly transparent 8 mol% Y2O3eZrO2 (8YSZ) ceramics were was observed in the VIS range and up to 80% in NIR. Aubry et al.
fabricated by using an improved hot isostatic pressing method [32]. showed that transparent Yb:CaF2 ceramics could be synthesized by
Combined with pre-sintering treatment, microstructures, such as sintering and hot pressing powders that were derived by a soft
positional difference in residual pores, inter- or intragranular pores, chemistry process [38]. Uematsu et al. applied HIP process to
of the 8YSZ ceramics could be well controlled. A microstructure 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 25

were fully densified at 800  C after 2 h when a hot isostatic pressure powders, without the presence of significant grain coarsening that
of 100 MPa was used. Besides, transparent a-sialon ceramics [40], is unavoidable during the standard densification routes. The
transparent magnesium oxide (MgO) ceramics [41] and transparent densification process in SPS is generally divided into three stages
La2Hf2O7 (LHO) ceramics [42] were also fabricated by using HIP [67]. The first stage is characterized by the packing of the particles,
process. the second stage is related to a diffusion process accompanying the
neck formation and grain sliding, and the final stage is the removal
2.3. Vacuum sintering of pores mainly through the grain boundary. An applied pressure
strongly affects the initial packing and densification in the second
Vacuum sintering refers to a sintering processes carried out in and third stages. A high pressure is constantly applied in common
a vacuum equipment to achieve better results than those run at SPS process. Heating rate is another important sintering parameter
atmospheric pressure. Vacuum sintering is typically used to fabri- for densification in the second and third stages.
cate transparent garnet and rare-earth sesquioxides ceramics, It was recently reported that transparent alumina with fine
including Y2O3 [43e45] and Sc2O3 [46,47]. grains can also be obtained by using SPS technique [68e74]. Owing
When using vacuum sintering to fabricate YAG ceramics, the to the advantage of rapid heating, the alumina ceramics obtained
procedure usually consists of vacuum sintering followed by air by SPS had grain sizes and densities comparable to those of the
annealing [48e64]. For example, transparent polycrystalline HIPed ones [75e81]. For example, a fully dense (a relative density of
Nd:YAG ceramics can be synthesized by using solid-state reactive w100%) alumina with a grain size of 0.5 mm was obtained at
sintering the mixture of Al2O3, Y2O3 and Nd2O3 in a tungsten mesh- 1200  C by SPS [68].
heated vacuum furnace (M60, Centorr Vacuum) at 5  106 Torr Spark plasma sintering (SPS) technique can be employed not only
during holding [61]. Fully dense transparent samples with average to sinter polycrystalline alumina disks but also to fabricate hemi-
grain sizes of w50 mm were obtained at 1800  C. The sintering spherical domes [83,84]. As demonstrated by Jiang et al. [85], the
temperature was slightly affected by the concentration of Nd. fabrication of transparent polycrystalline alumina domes could be
A small amount of SiO2 doping lowered the sintering temperature obtained by combining sintering and forming into one step in
by w100  C. SiO2 is usually introduced by using tetraethyl ortho- minutes instead of hours needed when using conventional
silicate (TEOS). After sintering, the specimens were annealed at methods. This forming method provides an unprecedented oppor-
1400  C for 2 h in air for decoloring. tunity to make optically transparent domes at much lower costs.
A two-step pressure profile was used to demonstrate the
2.4. Spark plasma sintering (SPS) feasibility of SPS [86]. At low pre-load pressure, 5 MPa, with the
normal characteristic fast heating rate (100  C/min), high in-line
Spark plasma sintering (SPS) is a newly developed method for transmittance of 51% at 550 nm and 85% at 2000 nm can be ach-
obtaining fully dense and fine-grained transparent ceramics at low ieved. Sintering was carried out in vacuum (4e6 Pa) with a Dr.
temperatures within short time durations [65e74]. It is also known Sinter 2050 SPS apparatus (Sumitomo Coal Mining Company Ltd.,
as field-assisted sintering or pulsed electric current sintering. A Japan). The temperature was increased to 600  C within 3 min and
schematic diagram of SPS is shown in Fig. 5 [82]. In normal hot then further increased to 1250  C in 6 min; the final stage of heating
pressing, heating is accomplished externally by heating a coil, while to 1300  C was finished in 1 min. The dwell time for all experiments
SPS uses a high density current flux flowing through the sample was 3 min. Five pre-load pressures, P1 ¼ 5, 10, 20, 30, 50 and
and the die to cause Joule heating within the sample. SPS technique 100 MPa, were selected. It is obvious that the samples prepared at
has a significant advantage over HIP and HP, because it can P1 of 30, 50 and 100 MPa have a darker discoloration core of about
complete the powder consolidation within a short time duration 8 mm in size in the center, as shown in Fig. 6 [86]. The discoloration
[66]. Because of this, it is a potential technique to densify nanosized 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
Fig. 5. Schematic diagram of spark plasma sintering (SPS). Reproduced with permis- are 15 mm above the printed text and the thickness of each sample is indicated in
sion from Ref. [82], Copyright 2010, Elsevier. parentheses. Reproduced with permission from Ref. [86], Copyright 2009, Elsevier.
26 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54

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
Fig. 7. In-line transmittance spectra of the polycrystalline MgAl2O4 sintered by SPS at
temperature for 10 min, then allowed to cool down naturally. The
different pre-load pressures P1. The theoretical transmittance of a single crystal results indicated that aerogel of mullite stoichiometry, free of
MgAl2O4 was calculated based on the refraction index as a function of wavelength. agglomeration and highly active, was key factor to achieving the
Reproduced with permission from Ref. [86], Copyright 2009, Elsevier. transparent mullite. Microwave sintering has also been used to
process other transparent ceramics.
obtain acceptable optical transmittance approaching the theoret-
ical limit in the wavelength range of >1000 nm. 3. Materials of transparent ceramics
SPS can also be combined with doping of sintering aids and
variation of processing parameters [87e89]. For instance, according As stressed earlier, transparent ceramics are mostly derived
to Morita et al. [89], heating rate had a significant effect on trans- from materials with isotropic lattice structure, i.e. cubic structure.
parency of fine-grained spinel polycrystalline ceramics, as shown in There have been various transparent ceramics, including simple
Fig. 8. The sample prepared with heating rates of <10  C/min oxides, sesquioxides, complex oxides and aluminum oxynitride.
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 3.1. Oxides
processing led to high transmission and strength can be attributed
to the reduction in the residual pores to <0.5%. SEM results (Fig. 9) 3.1.1. Al2O3
indicated that the average grain size was kept almost unchanged Alumina (Al2O3) exhibits many interesting properties, such as
for different heating rates, while the average area fraction of high strength, high hardness and excellent corrosive resistance.
porosity was dramatically increased with increasing heating rate. This makes transparent Al2O3 ceramics a promising candidate for
Therefore, the heating rate had a strong effect on the porosity and applications as electromagnetic windows, transparent armor
thus the in-line transmission of the spinel ceramics. and envelopes of high-pressure metal halide lamps [76]. Sintered
Transparent ceramics processed by using SPS, such as yttrium Al2O3 ceramics with submicrometer grain size are the hardest
aluminum garnet (YAG) [90,91], sesquioxides [67,92e101], ZrO2 of all transparent armor (including sapphire). Transparent poly-
[97,102,103], mullite [104], HAp [105e107], MgO [108], non-oxide crystalline alumina is believed to be a promising replacement for
AlN [109] have been widely reported in the open literature. Simi- sapphire. Photographs of representative Al2O3 transparent
larly, SPS is an effect method to process electro-optic ceramics, such ceramics are shown in Fig. 10.
as lanthanum-doped lead zirconate stannate titanate (PLZSnT) Traditional transparent Al2O3 ceramics were prepared by sin-
antiferroelectric ceramics [110], PbZrO3ePbTiO3ePb(Zn1/3Nb2/3)O3 tering in hydrogen at temperatures of generally above 1700  C
ferroelectric ceramics [111] and lanthanum-doped lead zirconate [116,117]. The high sintering temperature caused extensive grain
titanate (PLZT) ceramics [112]. growth, which in turn seriously affected mechanical strength and
hardness of the materials. The large grain size (up to 410 mm) led to
2.5. Microwave sintering significant light scattering caused by the birefringence of the coarse
Al2O3 grains [118]. Therefore, its in-line transmission was typically
Microwave sintering is a special sintering process that is below 10%. The low strength and in-line transmission posed an
fundamentally different from the conventional sintering process 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
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 optical transparency. It has been reported that typical fine-
and (e) 100  C/min. Reproduced with permission from Ref. [89], Copyright 2008, grained transparent Al2O3 ceramics had strength of up to 600e
Elsevier. 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 27

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 size of the sintered body was 30e50 mm, with no significant pores
fine-grained transparent Al2O3 ceramics. and abnormal grain growth observed. The real in-line transmission
A multiple-step pressureless sintering to obtain high quality was higher and more stable than those via other forming tech-
transparent Al2O3 ceramics was reported by Li and Ye [122]. nologies and pressureless sintering reported in the literatures.
Nanosized Al2O3 ceramics with an average grain size of 70 nm and Another pressureless method was reported by Lee et al. [125].
a relative density of 95% were obtained by using two-step sintering. Translucent alumina brackets were prepared by using powder
In this case, a-Al2O3 powders with a mean particle size of about injection molding (PIM). The powders were mixed with a binder
10 nm and a weak agglomeration were synthesized by using an a- consisting of a mixture of paraffin wax and polyethylene. After
Al2O3 seeded polyacrylamide gel method. The densification and the injection molding, debinding was performed using the wicking
suppression of the grain growth are realized by exploiting the method and samples were sintered in a vacuum at 1700  C to
difference in kinetics between grain-boundary diffusion and grain- achieve high density. Sintering additives (MgO, La2O3 and Y2O3)
boundary migration. The densification was proceeded by the were used to decrease the porosity. An improvement in trans-
slower grain-boundary diffusion without promoting grain growth lucency by promoting grain growth during the pressureless sin-
in second-step sintering. tering was observed. After sintering, Vickers hardness, bending
By float packing and sintering in air, transparent alumina with strength, density, and transmittance of the fabricated parts were
submicrometer grains was obtained by Godlinski et al. [123]. found to be comparable to those of the commercially available
Commercial a-alumina powder with high purity, submicrometer dental brackets.
particle-size and narrow particle-size distribution was used as Doping has been found to be an effective technique in fabri-
starting material. The powder was dispersed and stabilized in cating transparent ceramics. MgO doping, combined with pre-
a water-based suspension. Controlled consolidation and drying by sintering heat treatment, was used to accomplish a high trans-
float packing led to homogeneous green compacts, which could be lucency in polycrystalline Al2O3 ceramics sintered at 1700  C in
densified without additives by sintering in air at 1275  C to trans- vacuum [127]. The concentrations of MgO were 140, 500 and
parency, while the mean grain size remained to be 0.4 mm. The in- 2500 ppm. A pre-sintering heat treatment was 800  C for 50 h in air.
line transmittance at wavelengths of 300e450 nm was comparable It was found that the pre-sintering heat treatment improved the
to commercial polycrystalline alumina tubes for lighting technol- sample transmittance in the visible range (400e700 nm) signifi-
ogies, whose grain sizes are larger by a factor of 40. cantly. This enhanced transmittance was explained in terms of the
Liu et al. [124] used injection moulding and pressureless sin- removal of residual pores and the homogenization of the micro-
tering in hydrogen to manufacture translucent alumina ceramics. structure, due to the lowering of the boundary mobility, as a result
Translucent alumina components with small size and high preci- of the MgO addition and the suppression of local densification
sion were fabricated in such a stable, efficient and low cost route. through the pre-coarsening step.
Excellent rheological properties of the feedstocks for injection Liu et al. [128] reported a novel approach to fabricate trans-
moulding were obtained through a method of powder pre-treat- lucent alumina ceramics induced by doping additives via chemical
ment with stearic acid induced by ball milling. The average grain 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
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
homogeneously on the powder surfaces by a chemical reaction
YeLa with RIT of 57%. Reproduced with permission from Ref. [82], Copyright 2010, induced by the ball-milling treatment. Highly translucent Al2O3
Elsevier. 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 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,
Fig. 12. Densities of the samples, sintered by using microwave sintering and
conventional sintering without holding at the sintering temperature, as a function of
which has never been attained in optical glasses and is higher than
sintering temperature. Reproduced with permission from Ref. [126], Copyright 2003, that of other oxides. Recently, there has been increasing interest in
John Wiley & Sons. transparent zirconia ceramics, because of their unique optical
properties [97,138]. In summary, high transparencies with large
susceptor to preheat the Al2O3 samples because Al2O3 is a poor refractive indices and dielectric constants are unique properties of
microwave absorber at room temperature. Fig. 12 shows variations transparent zirconia ceramics [147]. Photographs of representative
in density of the samples as a function of sintering temperature. ZrO2 transparent ceramics are shown in Fig. 14 [32,97,102].
The microwave-sintered sample was almost fully densified after At the early stage, there were only reports on translucent
sintering at 1400  C, while the density of the sample sintered zirconia ceramics. For example, Vahldiek [139] obtained trans-
through the conventional sintering was only about 50%. Microwave lucent cubic zirconia (15 mol% Y2O3eZrO2) by using a high-pressure
sintering reduced the temperature for the samples by about 300  C. hot pressing technique. Mazdiyas et al. [140] fabricated translucent
In this study, the authors found that both the microwave sintering cubic zirconia (6 mol% Y2O3eZrO2) by using the conventional sin-
and the conventional sintering exhibited a similar grain growth tering technique. Duran et al. [141] prepared translucent tetragonal
behavior, as shown in Fig. 13. Therefore, they concluded that the zirconia (3 mol% Er2O3eZrO2) by using the conventional sintering
enhancement in densification of Al2O3 by microwave sintering was technique, using powders synthesized through an alkoxides-
not due to the fast heating rate. However, the microwave densifi- hydrolysis method. These studies indicated that sintering process
cation corresponded to apparent activation energy of 85  10 kJ/ and sinterability of the starting powders are critical parameter for
mol, much lower than the value of 520  14 kJ/mol for the translucency.
conventional sintering, meaning that there was a difference in Gradually, reports on transparent zorconia ceramics started to
densification mechanism between the two sintering techniques. appear. Transparent polycrystalline c-YSZ could prepared with hot
As demonstrated by Krell et al. [24,25,120,133e136], the isostatic pressing (HIP) [32,138,144]. It was found TiO2 was a good
strength of transparent Al2O3 ceramics is greatly affected by their additive for developing transparent c-YSZ by using HIP [144]. Fig. 15
grain sizes and size distribution. Fine-grained transparent Al2O3 shows in-line transmittance curves of the ZrO2 (10% Y2O3) ceramics
ceramics, with high optical and mechanical properties, can be with different concentrations of TiO2 [138]. The transparent
developed by using various methods and strategies, as discussed ceramics were made from cubic stabilized ZrO2 (c-ZrO2) powder by
above.

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,
Fig. 13. Grain growth trajectories of the microwave-sintered and conventionally sin- reproduced with permission from Ref. [97], Copyright 2007, John Wiley & Sons. (c)
tered samples. Reproduced with permission from Ref. [126], Copyright 2003, John 0.6 mm YSZ 8% ceramics densified at 1300  C and 100 MPa for 5 min by using SPS,
Wiley & Sons. reproduced with permission from Ref. [103], Copyright 2012, Elsevier.
30 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54

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
Fig. 15. In-line transmittance curves of the ZrO2 (10% Y2O3) ceramics with different predicted the conditions to obtain transparent tetragonal ZrO2
contents of TiO2. The transmission was measured on 6e9-mm thick specimen and ceramics (partially stabilized by yttria) by comparing the experi-
normalized to the thickness of 8.3 mm. Reproduced with permission from Ref. [138], mental data for sintering of nanopowder with scattering calcula-
Copyright 2009, Elsevier.
tions. The simulations were validated well by experimental data for
tetragonal ZrO2 (3 mol% Y2O3) ceramics made from a powder with
sintering at vacuum (1  103 Pa) at 1650  C for 3 h, followed by an initial particle size of w10 nm. The sintering was carried out in
HIPing at 1750  C for 1 h at a pressure of 196 MPa. Post-thermal air with hot isostatic pressing. A maximum in-line transmission of
annealing at 1000  C was conducted to oxidize the as-sintered about 77% was observed at IR wavelengths of 3e5 mm in the
samples. The role of TiO2 was regarded as a grain growth samples.
promoter and a pore scavenger. The optical properties of these Falk et al. [151] compared tetragonal and cubic polymorph ZrO2
zorconia ceramics were comparable to those of their single crystal ceramics prepared by electrophoretic deposition, sintering in air
counterparts. It was found that transmission performances of the and hot isostatic pressing (HIP). Tetragonal ZrO2 had grains of
ceramics were sensitive to the microstructure of the pre-sintered <200 nm, but they were insufficiently dense to have transparency.
compacts. Microstructural features, such of fine grains and small Munir et al. [97] and Casolco et al. [145] found that tetragonal ZrO2
intergranular pores, were critical to achieving high transparency. ceramics with grain sizes of 50e55 nm could be obtained by using
Therefore, high sintering temperatures of HIP produced samples SPS, which suppressed successfully the grain growth of the nano-
with large grains, which were not desirable in terms of mechanical sized powders. These works further confirmed that dense tetrag-
properties [32,138,144]. onal ZrO2 ceramics are less transparent than cubic ones. By using
In this light, SPS is better than HIP to fabricate transparent c-YSZ powders with finer particle sizes, Chaim and Hefetz [152] devel-
ceramics. For example, Lei et al. [103] synthesized nanosized cubic oped nanocrystalline 3YSZ ceramics with grain sizes of 22e45 nm
yttria-stabilized zirconia (ZrO2e8 mol% Y2O3) powder by using by using HIP. However, their samples had a significant amount of
a glycine-nitrate process combining with high energy ball milling. monoclinic phase.
Consolidation of the nanopowder was carried out by using SPS at Munir et al. [97] prepared transparent samples of tetragonal
1200e1350  C for 5 min. Transparent ceramics could be fabricated (3 mol% yttria) as well as cubic (8 mol% yttria) zirconia from
at 1300  C. Zhang et al. [102] used high-pressure SPS to fabricate nanometric powders by using a pulsed electric current sintering
translucent cubic zirconia ceramics at 1000e1200  C. In the SPS process. Both the tetragonal and cubic samples had an average
samples, the total forward transmittance and in-line transmittance grain size of about 50 nm. Consolidation pressure was found to
were mainly affected by color centers with a limited contribution show a positive effect on the transparency of both samples.
from residual pores. In contrast, the changes in reflectance were Transmittance of the samples with 1 mm thickness in the near-
only related to the porosity. The amounts of color centers and infrared region was above the 60% for the cubic (8%YSZ) and above
residual pores increased with increasing sintering temperature, 50% for the tetragonal (3%YSZ) zirconia ceramics, representing
which reduced the total forward and in-line transmittance of the between 70 and 80% of the theoretical values of the two materials.
as-sintered zirconia ceramics. The samples had a yellowish brown color, which was attributed to
Klimke and Krell [148] reported a cost efficient technology for the presence of color centers. Annealing in oxygen improved the
development of larger quantities of transparent cubic ZrO2 transmittance initially, but prolonged annealing resulted in trans-
ceramics. A multi-step sintering process was used. Yttrium- lucent samples.
stabilized ZrO2 powder was treated by dry-pressing with subse-
quent cold isostatic pressing. The obtained ZrO2 ceramics were 3.1.3. Sesquioxides
reported to be comparable to perovskite ceramics, which were 3.1.3.1. Y2O3. Y2O3, as a promising optical material, has excellent
commercialized in 2004 as camera lens. The in-line transmittance physical and chemical properties, such as high melting point
was related to the thickness of the samples. The real in-line (2430  C), broad range of transparency (0.2e8 mm) and high
transmission of the unscattered transmitted light (wavelength of corrosion resistance. Y2O3 has a cubic crystal with group of Ia3.
640 nm) was measured to be 57% (4 mm thickness), 59% (3 mm Typical physical properties of Y2O3 include thermal conductivity of
S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54 31

13.6 W/mK at 300 K, refractive index of w1.935, density of 5.04 g/ 1 h exhibited an in-line transmittance of 6e46% in wavelength
cm3 and effective atomic number of 36.7 [153]. Due to its high range of 400e800 nm. Chaim et al. examined the effect of heating
effective atomic number and high density, Y2O3 could be a more rate and sintering temperature on properties of Y2O3 ceramics by
effective scintillator than YAG (35 and 4.56 g/cm3, respectively) using SPS. High-pressure SPS was reportedly used to reduce the
[154]. Y2O3 possesses a higher thermal conductivity and a lower sintering temperature of transparent yttria ceramics. For example,
thermal expansion coefficient than the widely used YAG, which is transparent Y2O3 ceramics could be prepared at 1050  C for 1 h
critical for thermal management as laser powers continue to with a heating rate of 20  C/min under a uniaxial pressure of
increase and generate heat during operation [155,156]. Other 300 MPa [99]. The obtained samples possessed nanometric grains
potential applications of Y2O3 include infrared-domes, nozzles, (400 nm) and high density (>99.95%). 1 mm thick ceramics had in-
refractories, components of semi-conductor devices and efficient line transmittance of 68% at 700 nm and comparable performances
NIR-visible up-converter [157e159]. Due to its refractory nature, of single crystal yttria in the near-infrared wavelength region.
Y2O3 has been mainly developed in transparent ceramics rather Various strategies, such as use of nanosized precursor powder,
than single crystals. The first transparent yttria ceramic was re- introduction of sintering aids and adoption of multiple-step sin-
ported by Lefever and Matsko in 1967 [160]. tering process, have been employed to obtain Y2O3 ceramics with
There have been several reports on Y2O3 transparent ceramics relatively high density, small grain size and high transparency. Wen
by using pressureless sintering in vacuum or in H2 atmosphere et al. [45] synthesized yttria nanopowders of 60 nm by using
[43,161e166]. Jin et al. [162] reported a vacuum sintering to fabri- a precipitation process. Transparent yttria ceramics were derived
cate transparent Y2O3 ceramics from commercial power by doping from the nanosized Y2O3 powders by using vacuum sintering at
with ZrO2. Fig. 16 shows photographs of the ZrO2-doped Y2O3 1700  C for 4 h, with optimized in-line transmittance of 52% at
ceramics with different contents of ZrO2, after sintering at 1860  C wavelength of 1000 nm. Similar works were reported by Mori et al.
for 8 h. The samples with ZrO2 of above 2 mol% are all highly [161] and Huang et al. [168].
transparent. The starting Y2O3 power had an average particle size of Jiang et al. [43] developed a new method, a combination of two-
2 mm, which was reduced to about 0.34 mm after ball milling in step sintering and vacuum sintering, to fabricate transparent
ethanol for 12 h, as shown in Fig. 17. The powder with reduced lanthanum-doped yttrium oxide ceramics. The samples were firstly
particle size was beneficial for densification. In-line transmittance sintered at an intermediate temperature T1 (1450  C) in air. Then
curves of the Y2O3 transparent ceramics are plotted in Fig. 18. It is the temperature was decreased quickly to a lower point T2 (900e
observed that 5 mol% ZrO2 was the optimum concentration in 1100  C) in air and held for more than 20 h in order to facilitate
terms of in-line transmittance. The optical properties of the densification with limited grain growth. Nanocrystalline yttria
ceramics were well explained by using their enhanced densifica- ceramics with a high relative density were then obtained, which
tion and suppressed grain growth behaviors due to the presence of could be further densified at higher temperature T3 (1700  C) in
ZrO2. Representative cross-sectional SEM images of the samples vacuum condition. The final transparent yttria ceramics doped with
sintered at 1860  C for 8 h are demonstrated in Fig. 19. There was no 10% lanthanum, with an average grain size of about 25 mm, had
pore observed in the sample doped with 5 mol% ZrO2. a transmittance of 77% at 580 nm. Microstructural analysis results
Greskovi and Chernoch [164] reported Y2O3 transparent indicated that the mean particle size of the samples after the
ceramics in hydrogen atmosphere with ThO2 as sintering aid. second step was just slightly higher than that of those after the first
Rhodes [165] used a two-step sintering in hydrogen atmosphere to step processing with a relative density of over 90%. Because the
prepared La-doped Y2O3 transparent ceramics. Saito et al. [166] significant shrinkage was mainly observed in this step, pores were
obtained transparent Y2O3 ceramics at relatively low temperature isolated by grains. Therefore, grain-boundary diffusion was thought
of about 1700  C in vacuum from carbonate-derived powder. The to be the main matter transport mechanism. A similar two-step
transmittance of a 1-mm-thick sample was about 18% at 400 nm. sintering combined with HIP was reported by Ballato et al. [169].
HP [8,10], HIP [29,167] and SPS [92e94,100] have been shown to Transparent yttria ceramics with an average grain size of 0.3 mm
be effective methods to obtain transparent Y2O3 ceramics. Zhou exhibited a transparency of single crystals in the near-infrared
et al. [8] fabricated transparent Y2O3 ceramics by using HP at spectral region.
1800  C for 20 h. Another example was reported by Podowitz et al. Effective sintering aids, used to fabricate transparent Y2O3
[10] by using a uniaxial hot pressing at a maximum pressure of ceramics, include ThO2 [164], La2O3 [165], HfO2 [170], LiF [171] and
40 MPa and a maximum temperature of 1580  C. Optical trans- ZrO2 [172], as well as their combinations [173]. The presence of
parency could be optimized through a step-wise application of sintering aids led to high grade Y2O3 ceramics with small grain sizes
pressure. Ito et al. [100] reported the synthesis of transparent Y2O3 by reducing the sintering temperatures. Doping technique has also
ceramics by using SPS at moderate temperature and pressure been used together with other strategies, such as slip casting,
profiles. The samples sintered at 1300  C and annealed at 1050  C vacuum sintering [162] and sintering in oxygen atmosphere [174].
had a transmittance of 81.7% at wavelength of 2000 nm. Yoshida For example, highly transparent Y2O3 ceramics, doped with the
et al. [92] used low-temperature SPS to synthesize yttria ceramics addition of ZrO2 through slip casting and vacuum sintering could
with ultrafine grain sizes. The Y2O3 specimen sintered at 1050  C for 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.
Fig. 16. Photographs of the ZrO2-doped Y2O3 transparent ceramics with different
contents of ZrO2, derived from commercial Y2O3 power through vacuum sintering. 3.1.3.2. Sc2O3. Sc2O3 (scandia) belongs to the cubic space group IA3
Reproduced with permission from Ref. [162], Copyright 2010, Elsevier. [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 synthesize nanosized Sc2O3 powders. Wang et al. [46] synthesized
eightfold cubic structure with two oxygen vacancies on a face nanocrystalline Sc2O3 powder by using a homogeneous precipi-
diagonal, while the C3i site corresponds to a cube with two tation method. Li et al. [47] prepared highly reactive Sc2O3
vacancies on a body diagonal. The RE3þ dopants are assumed to powders through pyrolyzing at 1100  C a basic sulfate precursor,
occupy randomly both sites, but the induced electric dipole tran- (Sc(OH)2.6(SO4)0.2$H2O), precipitated from scandium sulfate solu-
sitions are allowed only for C2 centers. The cationic density tion with (CH2)6N4 as the precipitant. Similar reactive Sc2O3
(3.338  1022 cm3) is rather high compared to other oxides. Sc2O3 powders were obtained through thermal pyrolysis of a scandium
has the smallest lattice parameter (0.986 nm), high melting point, sulfate salt, Sc2(SO4)3$7.8H2O [179]. The Sc2O3 ceramics obtained
high bulk refractive index (nH ¼ 2.0, l ¼ 300 nm), high band gap by using vacuum sintering have relatively large grain sizes, due to
(5.7 eV, corresponding to an ultraviolet cutoff of 215 nm), high the significant grain growth during the final stage of sintering
thermal conductivity (17 W m1 K1) and high chemical stability [46,179e182].
(in alkali metal steam). The combination of these excellent optical Pressure-assisted sintering techniques have been used to
and thermal properties makes Sc2O3 attractive for applications as develop transparent Sc2O3 ceramics with smaller grain sizes. For
damage resistant and high reflection materials in light-emitting example, Ballato et al. [30] used HIP to fabricate erbium-doped
diodes and high power pulsed ultraviolet lasers. It is also very transparent Sc2O3 ceramics with an average grain size of 0.3 mm,
useful as infrared transmitting devices, host materials for high from solution-derived nanoparticles, using a two-step sintering
power and ultrashort pulse solid-state lasers and heat-resistant process. The two-step sintered ceramics showed a remarkable
optical windows etc. [47,176e181]. Due to its high melting point decrease in grain size with relative density of over 98% before HIP.
(2430  C), it is difficult to fabricate Sc2O3 single crystal. Therefore, After HIP, the Sc2O3 ceramics became highly transparent with
transparent polycrystalline Sc2O3 ceramics become more negligible grain growth. The samples exhibited an optical trans-
important. mittance of about 80%.
Vacuum sintering is the most widely used method to prepare Spectroscopic properties of Sc2O3 ceramics doped with various
transparent Sc2O3 ceramics and nanosized precursor powders ions are attractive for different applications. Gheorghe et al. [175]
have additional benefit to ensure high quality of the final materials analyzed in detail the spectral characteristic of Ho3þ:Sc2O3 trans-
[46,47,179e182]. Various chemical routes have been used to 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
Fig. 18. In-line transmittance curves of the ZrO2-doped Y2O3 transparent ceramics
promising high power ceramic laser materials. Europium-doped
with different contents of ZrO2, sintered at 1860  C for 8 h in vacuum. Reproduced with Lu2O3 ceramic scintillator can find applications in digital X-ray
permission from Ref. [162], Copyright 2010, Elsevier. imaging technology, due to its high density resulting in high
S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54 33

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 1.67 K/s on microstructures and optical properties of the materials
90,000 photons/MeV [185], and visible emission at w600 nm were investigated. The samples obtained under a pre-load pressure
coupling well with the silicon CCD spectral response [185,186]. The of 30 MPa at a heating rate of 0.17 K/s had transmittances of 60% at
use of an optically transparent scintillator screen requires high 550 nm and 79% at 2000 nm, showing a significant improvement.
transparent Lu2O3:Eu to avoid excess background noise, loss of It was found that vacuum sintering combined with HIP could be
resolution and scatter-induced ghosting. used to sinter Eu:Lu2O3 ceramics without the risk of contamination
An example of Lu2O3 transparent ceramics was reported by or oxygen vacancies [31]. Nanosized precursor powder was firstly
Chen et al. [187]. The used a co-precipitation process to synthesize uniaxially pressed and sintered under high vacuum at tempera-
highly sinterable Eu-doped Lu2O3 powders, using ammonium tures between 1575 and 1850  C to obtain densities ranging
hydroxide (NH3$H2O) and ammonium hydrogen carbonate between 94% and 99%. The sintered compacts were then subjected
(NH4HCO3) as mixed precipitant. Highly transparent polycrystalline to reach full density through HIP, which resulted in fully dense
Lu2O3 ceramics with a relative density of w99.9% were fabricated highly transparent ceramics without the need of further air
by using pressureless sintering in flowing H2 atmosphere at 1850  C annealing. The Eu:Lu2O3 ceramics showed about 4 times higher
for 6 h without any additives. light yield than commercially used scintillating glass, indicating
Goto et al. [101] used SPS to fabricate transparent Lu2O3 that transparent ceramics could be used for high energy radiog-
ceramics from commercially available powders. The effects of sin- raphy devices with improved performances. Evolution of porosity
tering conditions, including temperature, pressure and holding and microstructure was studied. Fig. 20 shows photographs and
time, on the density and optical properties were systematically scatterometry of the samples vacuum sintered at different
studied. They found that the transparency of the Lu2O3 ceramics temperatures after HIP sintering at 1850  C. Vacuum sintering
could be further improved by adopting a two-step pressure profile above 1650  C led to rapid grain growth prior to densification,
combined with a low heating rate [67]. The effects of pre-load rendering the pores immobile. Sintering between 1600 and 1650  C
pressures from 10 to 100 MPa and heating rates from 0.03 to 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 3.1.4. MgO
dense highly transparent ceramic without the need for subsequent MgO ceramic has excellent thermal and mechanical properties
air annealing. with a high melting point (2800  C) and an isotropic cubic crystal
SEM images of representative samples are shown in Fig. 21, structure. Polycrystalline infrared transparent MgO is a potential
confirming that the residual porosity led to the difference between substitute for sapphire IR windows and protectors for sensors. Due
the optically transparent and the opaque ceramics. As shown to the high sintering temperature required for full densification of
Fig. 21(a), the pores were not completely closed after vacuum sin- MgO, fabrication of transparent MgO ceramics is still a challenge.
tering at 1575  C. Grain growth could not occur due to the signifi- Almost all techniques discussed above have been used to prepare
cant number of pores and the pores could not be removed because transparent MgO ceramics [188].
they were filled with argon which was nearly insoluble in the The use of sintering aids has been widely employed to improve
crystal matrix. Fig. 21(b) shows a nearly perfect pore-free micro- the sinterability of MgO. Rice [189] first reported fabrication of
structure of the sample, which was optically transparent after being transparent MgO ceramics with the addition of LiF by using pres-
vacuum sintered at 1625  C prior to HIPing. Fig. 21(d) indicates that sure sintering. It was found that MgO ceramics prepared in this way
the grain entrapped pores were not removed during the HIPing had infrared optical transmission approaching to that of single
step, resulting in residual porosity in the final ceramics vacuum crystal. There are other reports using LiF as sintering aid to develop
sintered at temperatures of above 1675  C. 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 35

According to Hart and Pask [192], densification of MgO with LiF was materials. Ce-doped YAG (Ce:YAG) is used as phosphor in cathode
enhanced due to the formation of a liquid phase that acted initially ray tubes and white light-emitting diodes and as scintillator. Since
as a lubricant for the rearrangement of the MgO particles and later the first report transparent polycrystalline Nd:YAG ceramics for
a material transport medium to support pressure-enhanced liquid laser media by Ikesue et al. [195,196] in 1995, more and more
phase sintering. attentions have been attracted on the fabrication of YAG [197].
Although sintering aids can be used to reduce the sintering Undoped YAG transparent ceramics have been fabricated by
temperature of MgO, they have negative effects on the intrinsic various technologies, including vacuum sintering, HP and SPS.
properties of MgO. It was demonstrated by Itatani et al. [41] that Li et al. [198] synthesized ultrafine YAG powders through a co-
transparent MgO ceramics could be fabricated at 1600  C by using precipitation method using ammonium hydrogen carbonate as
an HIP technique. Before HIPing, MgO compacts were obtained by precipitant and used the powders to obtain transparent YAG
using pressureless sintering. A non-agglomerated MgO powder ceramics under vacuum sintering at 1700  C for 1 h. Zych and
with an average primary particle size of 57 nm was used as Brecher [199] derived YAG transparent ceramics from the mixture
precursor. The relative density and average grain size of the MgO of Y2O3 and Al2O3 by using HP at 1750  C for 4 h under a pressure
compact pressureless sintered at 1600  C for 5 h were 96.7% and of about 300 atm. Spark plasma sintering was applied by Chaim
10.7 mm, respectively. The as-sintered MgO ceramics had a relative et al. [91] to fabricate YAG transparent ceramics at 1400  C for
density of 98.1% with an average hardness of 6.8 GPa [188]. 3 min using nanocrystalline YAG powders as precursor. Fully
Transparent MgO ceramics have also been fabricated by using SPS dense and transparent polycrystalline cubic YAG ceramics with
[108]. With SPS, fully dense optically transparent MgO ceramics micrometer grain sizes were obtained. Liu et al. reported an HP
from nanocrystalline powders could be produced at 800  C and sintering process to prepare YAG transparent nanoceramics [7].
150 MPa for 5 min. The nanostructured YAG compacts were prepared at high pres-
sures and modest temperatures (HPMT, 2.0e5.0 GPa and 300e
3.2. Complex oxides 500  C). Prior to sintering, pellets were also heat treated in
vacuum. After the samples were treated at 2.0e5.0 GPa and
3.2.1. YAG 300  Ce500  C for 30 min, the pressure was reduced to ambient
Yttrium aluminum garnet (Y3Al5O12 or YAG) is a crystalline pressure, and then the samples were quenched to room
material of the garnet group. It is also one of the three phases of temperature at a cooling rate of w15 C/min. The temperature
yttriaealuminum composite, with the other two being yttrium was found to be sufficiently low to prohibit the grain growth of
aluminum monoclinic (YAM) and yttrium aluminum perovskite the YAG ceramics.
(YAP). YAG has a cubic crystal structure and belongs to the isometric For practical applications, YAG ceramics should be doped with
crystal system [193]. Due to the centrosymmetric cubic crystalline different elements. An example was reported by Zhou et al. [48].
structure, its optical properties are isotropic. Owing to its high Highly transparent polycrystalline Er3þ:Y3Al5O12 (Er:YAG) ceramics
thermal stability, stable chemical properties and unique homoge- with contents of Er3þ ion from 1% to 90% were prepared by the
nous optical properties, transparent YAG ceramics are not only an solid-state reaction and the vacuum-sintering technique. In-line
important high-temperature structural material, but also an excel- transmittances of mirror-polished Er:YAG ceramics were all up to
lent host material for fluorescence application and high power solid- 84% at 1100 nm wavelength, which were attributed to high density
state lasers [194]. Nd- and Er-doped YAG ceramics are typical laser of the samples.

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.
36 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54

Phase evolution of the Er:YAG ceramics was carefully studied. Nd:YAG transparent ceramics having the highest transmittance in
Fig. 22 shows XRD patterns and photographs of the 1% Er:YAG and the wavelength region from 400 nm to 1100 nm.
50% Er:YAG samples vacuum sintered at different temperatures for Co-doping with MgO þ SiO2 has been found to a promising
2 h. For the 1% Er:YAG ceramics, YAG phase was formed at 1200  C technique to improve the sinterability of YAGs [53,58,203]. By
along with a bit of residual YAP (YAlO3). Single phase YAG was optimizing the concentrations of the dopants, transparent YAG
achieved at 1600  C. As shown in Fig. 22(b), the concentration of ceramics with desired optical properties can be readily achieved.
Er3þ has no dramatic effect on the phase formation of YAG struc- For example, the Nd:YAG ceramic samples with 0.4 wt% TEOS
ture. A solid solution, Er3Y3Al10O24, was finally obtained. The sin- (precursor of SiO2) combined with 0.08 wt% MgO possessed the
tering temperature for transparent samples was 1800  C, as shown highest transparency at 1064 nm [53]. Zhang et al. [58] found that
in Fig. 22(c) and (d). the function of SiO2 was to eliminate pores and remove secondary
Very recently, a two-step sintering process was developed by phases, while MgO contributed to homogeneous microstructure of
Zhu et al. [200] to synthesize Nd:YAG ceramics. In this two-step the ceramics, which is demonstrated by the SEM images of repre-
sintering process, the furnace temperature was first arisen to sentative samples, as shown in Fig. 24.
a higher temperature T1 (1800  C), at a heating rate of 10  C/min, It is well known that the sinterability of a ceramic precursor
and then the temperature was rapidly decreased to a certain sin- powder is highly dependent on various characteristics, such as
tering temperature T2 (1550e1750  C) for 1e8 h in a vacuum particle size, size distribution, morphology and degree of agglom-
graphite tube furnace at 1.0  103 Pa during the holding process. eration. This is also applicable to YAG transparent ceramics [205e
The transparent ceramics prepared by using this method exhibited 209]. A systematic study on the effect of powder properties on
pore-free and homogeneous microstructure, with transparency of the densification and performance of YAG transparent ceramics
up to 84.98% at the visible and near-infrared band and 87% in the was reported by Esposito and Piancastelli [208]. It was found that
mid-infrared wavelength range. The absorption cross section of the YAG ceramics derived from nanosized powder exhibited higher
a 0.3% Nd:YAG sample at 808 nm was 5.47  1020 cm2, while the optical transparency, due to their smaller grain size and less
emission cross-section at 1064 nm was 4.66  1019 cm2. residual pores. The properties of precursor powders could be also
To achieve full density and highest transparency, YAG ceramics modified by adjusting pH values when using co-precipitation
have also been prepared by using sintering aids [50,53,58,201e204]. method [209]. pH values affected the performance of the final
Liu et al. [202] used MgO as sintering aid to produce Nd:YAG ceramics. Nd:YAG ceramics by influencing the morphology as well as the
As shown in Fig. 23, the addition of small amount of MgO could reduce (Nd þ Y):Al mole ratio of the powders. Optimized pH values were
the degree of agglomeration and particle size of the Nd:YAG precursor found in the range of 7.9e8.2.
powders. The MgO-doped Nd:YAG powders possessed better Fig. 25 shows EPMA images of the Nd:YAG ceramics with
dispersion characteristics as compared with the undoped powders. different (Nd þ Y):Al mole ratios. If the (Nd þ Y):Al molar ratio was
The sample with 0.01 wt.% MgO was of spherical particles of 100 nm much lower than 0.6, superfluous Al2O3 was present, while it was
in diameter. The well-dispersed precursor powders resulted in much higher than 0.6, superfluous Y2O3 was present which led to
ceramics with homogenous microstructure. Optimized ceramic intermediate phases (YAP and YAM). The powders prepared within
samples exhibited transmission of 82.6% at the wavelength of the range of pH value of 7.9e8.2 had (Nd þ Y):Al molar ratio very
1064 nm, which was comparable to that of Nd:YAG single crystals. close to 0.6 (0.598 and 0.603). In this case, no secondary phases
La2O3 is another effective sintering aid for Nd:YAG ceramics [50]. The were observed and fully dense Nd:YAG ceramics with homoge-
addition of 0.8 wt% La2O3 was optimized concentration, which led to neous microstructures were obtained, as demonstrated in Fig. 25(b)

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.
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- high quality Nd:YAG nanosized powders [210]. With an optimized
sectional SEM images shown in Fig. 26. The fracture styles of calcination temperature of 1200  C, the powder showed lowest
samples with (Nd þ Y):Al molar ratios of 0.576 and 0.648 are both agglomeration and could be used as precursor to obtain trans-
intracrystalline because secondary phases and pores in them parent Nd:YAG ceramics.
enhanced strength of the grain boundaries. In contrast, the samples Optical properties of rare-earth-doped YAG ceramics are
from the powders with ratios of 0.598 and 0.603 possessed pore- important requirements for practical applications, which has been
free microstructure and clean grain boundaries, thus having inter- a subject of numerous studies in the literature [62,211e215]. For
granular fracture behavior. example, Yagi et al. examined the influence of annealing on optical
Other technologies used to further improve the quality of properties of chromium-doped YAG ceramics [62]. As shown in
precursor powers of transparent YAG ceramics include spray- Fig. 27, the effect of annealing was quite significant. After annealing
drying [64] and freeze-drying [57,210]. It has been demonstrated at high temperatures, the absorption intensity was increased and
that freeze-drying could play an important role in the synthesis of 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 luminous efficacy and luminous intensity for a 0.632 mm-thick
attributed to valence changing from Cr3þ to Cr4þ. The presence of sample under 465 nm LED excitation is shown in Fig. 28. The
Cr4þ ion was confirmed by emission measurement. luminous efficacy was decreased from 74 lm/W to 44 lm/W, while
Nishiura et al. [212] reported properties of transparent Ce:YAG the luminous intensity was increased from 100 mCd to 1550 mCd
ceramic phosphors for white LED. The Ce:YAG ceramics had a broad with increasing current.
emission band peaked at 530 nm due to the 5de4f transition of When studying optical properties of transparent Eu3þ:Y3Al5(1-
Ce3þ. The transmittances of the samples were 70e87% at 800 nm. x) 5xO12 ceramics, Shi et al. [213] found that a reduced peak
Sc
The absorption coefficient and emission intensity of Ce3þ were splitting of Eu3þ for 5D0e7F1 and 5D0e7F2 was observed when 10
increased with increasing sample thickness. Under 465 nm LED at.% Al31 was substituted by Sc31. The enhanced symmetry of the Eu
excitation, the color coordinates of the Ce:YAG ceramics shifted sites in YAG lattice, which resulted from the expanded YASG lattice
from blue region to yellow region with increasing sample thickness, due to the Sc31 doping, was the main reason for the reduced peak
passing nearby the theoretical white point in the chromaticity splitting.
diagram. The highest value of luminous efficacy of the ceramic
white LED was 73.5 lm/W. The LED’s current dependence of 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. 27. Absorption spectra of the 0.1 at.% Cr:YAG ceramics: (a) sintered with CaO, (b) Fig. 28. LED’s current dependency of luminous efficacy and luminous intensity of the
annealed at 1300  C, (c) annealed at 1500  C and (d) SiO2-doped and annealed at Ce:YAG ceramics under 465 nm LED excitation (sample thickness: 0.632 mm).
1500  C. Reproduced with permission from Ref. [62], Copyright 2006, Elsevier. Reproduced with permission from Ref. [212], Copyright 2011, Elsevier.
S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54 39

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 Fig. 29. Light transmittance spectra of the sintered MgAl2O4 in the UVevis wavelength
resistance to erosion makes spinel an excellent material for range. Reproduced with permission from Ref. [28], Copyright 2003, Elsevier.
protective windows for aircraft, ship and submarine IR sensors, as
well as missile domes. Spinel is also very promising for temperature, heating rate, atmosphere, and powder preparation.
applications as windows or windshields for military vehicles such Frage et al. [87] reported the spark plasma sintering of commer-
as large and bullet-proof windows, due to its mechanical and cial magnesium aluminate powder at the low heating rate of
ballistic properties [217]. 10  C/min and investigated the effect of LiF additions on the
Since it was shown to be transparent in early 1960s, spinel has resulting optical properties of the consolidated transparent solids.
received considerable attention worldwidely [28,218]. Transparent The presence of 1 wt.% LiF dopant affects dramatically the spinel
spinel is difficult to fabricate directly from high purity precursor morphology, leads to the formation of large well-defined grains,
powders by using the conventional pressureless sintering tech- eliminates residual boundary phases and allows achieving rela-
niques [28,218,219]. Therefore, it is necessary to use HP, HIP or SPS tively high levels of light transmission. By employing low heating
[27,28,86e89,223e225]. By the way, fine precursor powders, rate, Morita et al. successfully demonstrated the densification of
together with sintering aids, such as B2O3 [34], CaO [218] and LiF a fine-grained high purity spinel only for a 20 min soak at the low
[220], have been shown to be very helpful in developing trans- temperature of 1300  C without any sintering aids. For heating
parent spinel ceramics. rates of <10  C/min, the spinel exhibits an in-line transmission of
It was reported that by using a combination process of pre- 47% for a visible wavelength of 550 nm and a fracture strength of
sintering and HIP, fine-grained highly transparent spinel ceramics >500 MPa. The high in-line transmission can be explained by the
could be obtained from powders with a wide range of properties lower residual porosity (<0.5%), as shown in Figs. 8 and 9 [89]. As
[222]. Clear transparent components with a thickness of up to one of the techniques for enhancing the transparency, Kim et al.
20 mm and lateral dimensions up to 240 mm were manufactured [225] reported on the effects of preheating of powder before SPS.
equally successfully from both the spinel powders with lower The authors found that preheating resulted in an enhanced
specific surface areas and the nanosized powders. Recently, transparency of the MgAl2O4 spinel.
a similar process was developed to fabricate spinel ceramics with One of the issues arisen when using the pressure-aided sintering
large-scale production [223]. processes is contamination. For instance, as reported in Refs. [87,89],
Kagawa et al. [27,28] used similar two-step process (HP followed the in-line transmittance of the samples did not approach the ex-
by HIP) to prepare optically transparent polycrystalline spinel pected values, especially in the wavelength range of near/mid-
ceramics. The effect of HP temperature on optical properties of the infrared (above 1 mm). It was attributed to the presence of
final ceramics HIP sintered at 1900  C for 1 h under a pressure of contamination or second-phase particles dispersed in the spinel
189 MPa was studied. Three HP temperatures, 1400, 1450 and matrix. Bernard-Granger et al. [226] investigated influence of
1500  C in vacuum of 102 Pa for 1 h at 50 MPa, were examined. graphite contamination on the optical properties of transparent
Fig. 29 shows light transmittance curves of the sintered MgAl2O4 spinel obtained by spark plasma sintering. They found that residual
ceramics measured in the UVevis and near-IR wavelength regions. porosities and second-phase graphite particles had a strong nega-
The sample HP pre-sintered at 1400  C had the maximum trans- tive influence on in-line transmittance of the ceramics. The carbon
mittance of over 60 and 70% in the UVevis and near-IR wavelength contamination was proposed to be arisen from a CO-containing
regions, respectively. The light transmittance was well correlated residual atmosphere during the SPS experiments, because of the
with the microcracked grain-boundary surface area per unit graphite configuration of the equipment. During SPS, a rotary pump
volume of the samples. was used to generate vacuum in which the residual gases gave rise to
Very recently, spark plasma sintering (SPS) has been proved to an atmosphere containing CO2. Such an atmosphere infiltrated the
an alternative technique for the fabrication of fine-grained porous body at the beginning of sintering and CO2 was possibly
transparent spinel. Several studies have been conducted for reduced to CO at high pressure within the shrinking pores, which
enhancing the transparency by using additives [87], controlling was finally carbonized into particles. The presence of such carbon
heating rates [89,224], or applying two-step pressure profile particles made the in-line transmittance to be less than theoretical
during sintering [86]. Although the transparency of the spinel value of single crystalline MgAl2O4. Therefore, special carefulness
fabricated by SPS is lower than that by HIP at present, an should be taken when using pressure-aided techniques to fabricate
improvement for higher transmission can be made in SPS by transparent ceramics and more systematic studies should be carried
controlling the sintering parameters such as pressure, 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- range from 0.8 (MgO-rich) to 3.5 (Al2O3-rich). Conceptually, as all
tive to the quality of the precursor materials (both purity and solid solution compositions share 1.0-spinel’s cubic crystal struc-
morphology), there have been researches on this issue that can be ture, they should all have the potential to be prepared as trans-
found in the open literature. To produce better spinel precursor parent, single phase ceramics; however, exsolution of excess
powders, various methods have been developed. Reimanis et al. alumina frequently undermines the formation of single phase
[216] reported a unique method to synthesize spinel powders from MgO$nAl2O3 solid solution polycrystalline ceramics. It has been
boehmite, in which Mg2þ ion was metal exchanged onto the surface reported that MgO$nAl2O3 polycrystalline ceramics with Al-rich
of boehmite particles. In this method, particle size, size distribution, compositions (n > 1) possess varied levels of light transmission at
purity and stoichiometry of the Mg-doped boehmite powders infrared wavelengths, although generally the transmission in the
could be well controlled. Such powders exhibited good sinterability visible spectrum is low. As a consequence, there has been
and resulted in spinel ceramics with desired optical properties. increasing interest in MgO$nAl2O3 ceramics with n > 1 [26,27].
Goldstein et al. [227] used flame spray pyrolysis to prepare fine Sutorik et al. [26] used HP and HIP to prepare transparent spinel
precursor powder so as to develop high quality spinel transparent ceramics with a composition of MgO$1.2Al2O3. The processing
ceramics. The powder possessed excellent sinterability, allowing consisted of HP at 1600  C for 5 h under vacuum and 20 MPa
the attainment of very high densification levels after the pre- uniaxial load for pre-sintering and HIP at 1850  C for 5 h under
sintering stage at 1400  C. HIPing was necessary to attain high 200 MPa in argon. The samples obtained exhibited an average in-
transparency for t > 2 mm. The minimal HIPing conditions for line transmission of 84.8  2.7% at 550 nm and >82% throughout
a reasonable transparency were 1400 C/80 h. A low-temperature the visible spectrum. Final grain sizes of the ceramics ranged
HIP processing, 1500  C, 3 h and 200 MPa, led to 2 mm thick between 300 and 1000 mm, with flexural strength of
samples with a real in-line transmission of 63% (at 635 nm). The 176.8  46.2 MPa, hardness of 12.3  0.2 GPa and elastic modulus of
samples had an average grain size of 2.2 mm and a hardness of 292.9  7.5 GPa.
13.2 GPa. A detailed study on the relationship between composition and
An alternative method, by using Mg(OH)2, g-Al2O3 and AlOOH, mechanical properties of spinel transparent ceramics was reported
towards the direct production of transparent MgAl2O4 ceramics, by Dericioglu et al. [27]. They also used HP and HIP, but with
was reported by Sutorik et al. [228]. The samples derived from the commercial MgO and Al2O3 powders as the precursor. Three
mixture of Mg(OH)2 and g-Al2O3 under optimized processing compositions of MgO$nAl2O3 were investigated with n ¼ 1:0, 1.5
conditions showed in-line transmittances of 84.2  1.0% at 550 nm, and 2.0. The spinel ceramic with MgO to Al2O3 molar ratio of 1:1
with thicknesses of 3.5e4 mm. Typical mechanical properties demonstrated the highest scattering coefficient due to its highest
observed in the ceramics included Knoop hardness of w12 GPa, amount of grain-boundary microcracking. Al2O3-rich compositions
elastic modulus of w280 GPa and biaxial flexural strength of 85e possessed a specular transmission of 40e60% in the same wave-
136 MPa. There was a slight difference between g-Al2O3 and length range. The spinel ceramic with n ¼ 2:0 exhibited the highest
AlOOH as the precursor components. fracture toughness with a mean value of w2.02 MPa m1/2. Based on
A simple reactive method named self-heat-sustained (SHS) their optical and mechanical properties, the Al2O3-rich non-
technique employing metallic aluminum as one of the reactants to stoichiometric polycrystalline spinel ceramics would be potential
produce very high phase-purity magnesium aluminate powder candidates for engineering applications requiring high optical
under rather mild experimental conditions was also developed by transparency and fracture toughness.
Ping et al. [229]. Powders with small particle size- and narrow Other studies on spinel transparent ceramics include the effect
particle size-distribution were obtained, which could be used to of grain-boundary microcracking on optical performance, as
fabricate spinel ceramics with high optical performances. reported by Dericioglu and Kagawa [28] and nanoporosity effect
Another strategy for developing transparent spinel ceramics is and elimination of precursor powders, as demonstrated by Krell
the use of sintering aids. According to Tsukuma [34], the addition of et al. [230]. Light transmittance losses occurred when the sintered
a small amount of boron oxide (0.05e0.5 mass%) was very effective MgAl2O4 ceramics had microcracked grain boundaries which
in promoting the sintering behavior of a fine MgAl2O4 powder. facilitated light scattering [28]. It was recognized that the nano-
Experimental results indicated that the presence of B2O3 not only scale pores of <100 nm could be readily eliminated by using
reduced the sintering temperature of the precursor powder, but pressure-assisted reactive sintering of MgOeAl2O3 mixtures,
also suppressed the grain growth of the ceramics which was starting with coarser powders with median particle sizes of 100e
important to ensure high transparency. The optimal concentration 200 nm instead of sintering pre-calcined raw spinel powders
of B2O3 was 0.15 mass%, with which the samples could achieve <100 nm [230].
a high optical transmittance of 80% at 1 mm thickness. Due to the special requirement in mechanical properties for
Besides B2O3, LiF has also been widely used as a sintering aid for some specific applications, such as armor [231], a new direction of
spinel ceramics. By using 1 wt.% LiF, Reimanis et al. [216] obtained research on spinel transparent ceramics appeared recently, which
MgAl2O4 transparent ceramics by HP process at a temperature of as is nanocomposite transparent ceramics. This concept was well
low as 1550  C for 2 h. The samples had an excellent visible demonstrated by Padture et al. in a recent publication [232]. In this
transmittance of w85%. The effect of LiF on sintering kinetics of case, the nanocomposites were MgAl2O4 spinel matrix dispersed
MgAl2O4 was investigated by Rozenburg et al. [221]. Powders with with Si3N4 nanoparticles. The as-processed nanocomposites were
0, 0.5 and 1.0 wt.% LiF were densified by using a vacuum HP under found to have a high transparency of >70% in the critical infrared
a range of unaxial pressures. According to the sintering mecha- wavelength range of 3e4.5 mm and an acceptable transparency in
nisms derived from the experimental studies, the vacuum HP the visible region. The optical properties of the nanocomposites
processing schedule could be further optimized. remained almost unchanged upon heat treatment at 1000  C for 4 h
According to MgOeAl2O3 phase diagram, spinel is the only in air, which however resulted in a 29% increase in the average
compound. However, the spine phase can act as a parent structure strength, accompanied by almost doubling of the Weibull modulus
type of solid solutions whose compositional range increases with and an 85% increment in the indentation toughness. The
increasing temperature. The compositions can be expressed by the improvements in mechanical properties after the heat treatment in
formulation of MgO$nAl2O3, with n ¼ 1.0 corresponding to the these nanocomposites were attributed to surface-oxidation-
stoichiometry of MgAl2O4. At appropriate temperatures, n can induced surface compression and flaw-healing.
S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54 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
Fig. 30. (a) STEM image of the as-processed spinel/Si3N4 nanocomposite ceramics, synthesized by several methods, such as reaction of Al2O3 and AlN,
with the spinel grains and the Si3N4 nanodispersoids marked. (b) Indexed SAEDP from carbothermal reduction (CR) of Al2O3, solid-state reaction (SSR),
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.
plasma arc synthesis and self-propagating high-temperature
Reproduced with permission from Ref. [232], Copyright 2012, Elsevier. 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
As shown in Fig. 30, no residual porosity could be found in this influencing factors, making it difficult to synthesize pure AlON
as-processed spinel/Si3N4 nanocomposite. The spinel grain size is powders without residual AlN or Al2O3 [237]. SSR method requires
300 nm and the size of is about 100 nm. The nanosized Si3N4 high purity and fine AlN powders to ensure high sinterability. In
particles were located both at grain boundaries and within the this respect, a combinational method of carbothermal reduction
spinel grains. Fig. 31 shows a landscape photograph taken through and solid-state reaction synthesis of g-AlON powders was devel-
the as-processed spinel/Si3N4 nanocomposite ceramics with oped by Yuan et al. [238]. Ultrafine, phase pure and low cost g-AlON
a thickness of 2 mm, showing good transparency in the visible powders were easily synthesized by using organic sucrose instead
range. Therefore, this type of transparent ceramics could be used of carbon black as a reducing agent.
for possible armor applications [232]. Similar to other transparent ceramics, AlON ceramics have also
been processed by using various sintering techniques, such as
3.4. ALON pressureless sintering [240], microwave sintering [114], HP [239],
HIP [240e242] and SPS [243]. For example, Zhang et al. [240]
Aluminum oxynitride (ALON) has a defect cubic spinel crystal proposed a new one-step pressureless sintering, using a-Al2O3
structure with chemical formula of Al(64þx)/3O32xNx (2  x  5). and aluminum powder as starting material. The starting material
The addition of a small amount of nitrogen converts the rhombo- was first nitridised into high activity AlN, from which Al23O27N5
hedral crystal structure of alumina into the cubic spinel structure of was then synthesized in-situ by reacting with a-Al2O3. The optimal
ALON. Nitrogen stabilizes the cubic spinel crystal structure over one-step pressureless sintering process was observed to occur at

Fig. 31. Landscape photograph through as-processed spinel/Si3N4 nanocomposite half Fig. 32. XRD patterns of AlON samples SPS sintered at (a) 1500  C, (b) 1550  C, (c)
disk (2 mm thickness). The distance between the camera lens and the sample is 1580  C and (d) 1650  C for 30 min. Reproduced with permission from Ref. [243],
w3 cm. Reproduced with permission from Ref. [232], Copyright 2012, Elsevier. 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 3.5. Electro-optic ferroelectric ceramics
as high as 321 MPa.
Very recently, Sahin et al. [243] reported a reactive SPS Opto-ceramics is a family of special transparent oxide materials.
method to prepare AlON transparent ceramics. Al2O3 and AlN Their crystallography structure is perovskite type with formulation
powder mixtures were used as precursors. Reactive SPS was of ABO3. The typical representatives of this family include
conducted at temperatures between 1400  C and 1650  C for 15e Pb1xLax(ZryTi1y)1x/4O3 (PLZT), Pb(Mg1/3Nb2/3)O3ePbTiO3 (PMNe
45 min at 40 MPa under N2 gas flow. AlON phase formation was PT) and Pb(Zn1/3Nb2/3)O3ePbTiO3 (PZNePT). The PLZT formula
initiated in the samples sintered above 1430  C, according to the assumes that La substitutes for Pb2þ in the A-site and the B-site
XRD analysis, as shown in Fig. 32. The complete transformation vacancies are created for electrical balance. To achieve highest
from the precursor phases (Al2O3 and AlN) to AlON was observed transparency and electro-optic coefficient, some elements, such as
at 1650  C for 30 min at 40 MPa. High temperature and low Ba and/or La, are usually introduced into the solid solutions of PMNe
heating rate were favorable to the formation of AlON. Represen- PT and PZNePT. Material synthesis and properties of transparent
tative SEM images of the samples are shown in Fig. 33. The electro-optic ceramics, including PLZT and PMNePT, were well
highest value of hardness was recorded to be 16.7 GPa. The summarized by Jiang et al. [12].
sample with highest content of AlON possessed a fracture
toughness 3.95 MPa m1/2. 3.5.1. PLZT
A two-step method to prepare AlON ceramics was developed by PLZT ceramics possess much higher electro-optic coefficient
Qi et al. [244] with nanosized Al2O3 and AlN as precursors. Single than LiNbO3 single crystals. PLZT ceramics also have higher
phase AlON powder was obtained at 1750  C for 4 h in flowing transparency than other ferroelectric materials. Specifically,
nitrogen atmosphere through direct reaction of the nanosized Pb(1x)Lax(ZryTiz)1x/4O3 (i.e., PLZT 9/65/35) exhibits outstanding
Al2O3 and AlN. After ball milling, the powder had an average size of electro-optic coefficients with little hysteresis and no remnant
several microns and showed quite high sintering activity. The high polarization. Therefore, PLZT (9/65/35) ceramics are potential
reactive AlON powder was used to fabricate transparent ceramics at candidates for applications in digital light modulators and large-
1880  C. aperture light shutters [246].
By using MgO and Y2O3 as sintering aids, transparent AlON Transparent PLZT ferroelectric ceramics were reported by
ceramics were successfully prepared by solid-state reactive sin- Haertling in 1971 [247]. The quality of transparent PLZT ceramics is
tering [245]. The effects of sintering aids and holding time on mainly determined by the properties of the precursors. High quality
densification of AlON ceramics were investigated. Co-doping of powders should have small particle size, narrow size distribution
MgO and Y2O3 was found to be more effective in enhancing the and no hard agglomeration. Several wet chemistry-based methods,
densification of AlON than the doping of either MgO or Y2O3. It was such as chemical co-precipitation, solegel processing, high energy
observed that, at a given doping level of Y2O3 (e.g. 0.08 wt.%), ball milling and hydrothermal processing, have been developed to
transmission coefficient of the ceramics increased with increasing prepare PLZT powders [248e250]. Moreover, special sintering
concentration of MgO. A 1 mm thick sample, co-doped with 0.08 wt techniques, such HP/HIP and atmosphere-controlled sintering, are
% Y2O3 and 1 wt% MgO, sintered at 1950  C for 12 h in N2 atmo- also very useful in fabricating high quality transparent PLZT
sphere, had an in-line transmittance of 60% at 600 nm. ceramics [247].
S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54 43

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-
Fig. 35. PLZT specimens sintered in air at 1200  C for 8 h: (a) whole specimen with
sphere by pressure sintering. The microstructure of the sintered thickness of 1 mm and (b) outer layer only. Reproduced with permission from Ref.
body was not uniform; it was completely dense near the surface, [246], Copyright 2001, John Wiley & Sons.
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 temperature sintering cycle. For the first step, after sintering
and resultant formation of lattice vacancies were attributed to this under low-oxygen-pressure (vacuum) and at low temperature
microstructural evolution. Diffusion of the gas trapped in the pores (1150  C), the PLZT ceramics were composed of small closed pores,
also was important in determining the thickness of the dense layer. and the gas pressure inside the pores was low. For the second step,
When the PLZT specimen was sintered in air at 1200  C for 8 h, the after sintering under higher oxygen pressure (0.22 MPa) and at
thickness of the dense layer was 0.25 mm. Therefore, if the spec- higher temperature (1250  C), it was easy to obtain fully densified
imen thickness was 0.5 mm, the whole specimen was dense and PLZT ceramics with an average grain size of 3 mm. Correspondingly,
transparent. When the specimen was sintered in an oxygen-gas piezoelectric properties of the ceramics were improved; i.e., kp and
atmosphere under the same conditions, the specimen thickness d33 were increased to as high as 0.71 and 850  1012 C/N,
increased markedly. respectively. Moreover, the piezoceramics were transparent, with
Representative specimens of polished cross-sections of speci- an optical transmittance of 15% (l ¼ 610 nm), for a sample of 1 mm.
mens sintered in various atmospheres at 1200  C for 8 h are shown Abe and Kakegawa [251] reported fabrication of optically trans-
in Fig. 34. When a specimen with the same composition was sin- parent PLZT ceramics by using a three-stage-atmosphere-sintering
tered in argon, the thickness of the dense layer decreased technique. This technique consists of three stages: (1) sintering in
(Fig. 34(a)). Furthermore, it is apparent that the outer region was an oxygen atmosphere, (2) elimination of pores in a carbon dioxide
not completely pore-free as was the case of the specimen sintered atmosphere, and (3) elimination of oxygen vacancies in an oxygen
in air. On the other hand, when the specimen was sintered in a 33% atmosphere. The experimental results revealed that the use of
oxygen-gas atmosphere, the dense layer became thicker than the a carbon dioxide atmosphere effectively decreased the residual pores
case of sintering in air, (Fig. 34(b)). As the oxygen partial pressure of and thus improved optical transmittance. From commercially avail-
the sintering atmosphere was further increased, the dense layer able raw powders, an optical transmittance of 51% (wavelength of
continued to grow until the whole specimen became dense in 550 nm) can be achieved for 0.7 mm thick polished PLZT (9/65/35)
a pure oxygen atmosphere, as shown in Fig. 34(c). The appearance ceramics using a carbon dioxide atmosphere, whereas the values
of the sample is shown in Fig. 35. only 34% without a carbon dioxide atmosphere. The advantage of this
A modified HP method, namely a two-step controlled oxygen technique is that PLZT ceramics having high optical quality can be
pressure sintering process, was reported to fabricate fully densified obtained by using conventional sintering tools.
PLZT (7/60/40) ceramics with high piezoelectricity [13]. Specifically, Kong et al. developed a simple and feasible method to obtain
low-oxygen-pressure and low-temperature sintering were used in transparent PLZT (9/65/35) ceramics through a repeated annealing
the first step, followed by a high oxygen pressure, high- process [252]. The experiment was started from nanosized powder

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.
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 45

3.6. Mullite 4.1. Laser

Mullite, a crystalline aluminum silicate phase, with a stoichio- Ceramic laser technology has emerged as an active research area
metric composition of 3Al2O3$2SiO2, is a very interesting mineral because of the numerous advantages of ceramics over single crys-
constituting silicate ceramics. It is one of the most widely used tals. First, ceramics can be produced in large volumes, which makes
ceramic materials because of its unique properties, like high- them attractive for high power laser generation. Second, they can
temperature strength, thermal-shock resistance and low dielec- provide a gain medium for fiber lasers with high beam quality and
tric constant [264]. It is also a good refractory material, due to its can also be made into composite laser media with complicated
high melting point (1850  C) [265], low thermal expansion coeffi- structures that would otherwise be difficult to fabricate by using
cient, low thermal conductivity, high strength and good creep single crystals. Third, ceramics can be heavily and homogeneously
resistance. Due to its low dielectric constant (ε ¼ 6.7, compared to doped with laser-active ions when compared with single crystals.
9.8 of Al2O3), it can be used as a promising candidate for substrates Furthermore, the use of ceramics enables mass production, which
in electronic packaging [266]. Moreover, mullite can be employed may lead to low cost commercial production of lasers or the
as window materials, especially at high temperatures, because it production of lasers with customized special functions.
has a good transmission at high temperatures in the middle Early in 1960s, effort to use ceramics as a laser gain medium was
infrared band. Low dielectric constant and optical transmittance of begun with Dy:CaF2 in cryogenic conditions [270]. In the 1970s,
fine-grained polycrystalline mullite could be a good host material Nd:Y2O3eThO2 was successfully used for pulsed laser oscillation
of solid-state laser activators [115]. [164,271], although the laser oscillation efficiency was relatively
Pore-free translucent mullite was reported by Mazdiyas and low. The development of a practical ceramic laser started in 1995
Brown in 1972 by using HP sintering at 1500e1650  C and 30e when c.w. laser oscillation was developed by using polycrystalline
50 MPa, and vacuum HP, with high purity submicron mixed oxide Nd:YAG ceramic laser gain medium [196], which showed that
precursor powders derived from metal alkoxides [267]. Prochazka ceramic materials could overcome both the technical and
and Klug prepared infrared transparent mullite ceramics with economical problems of melt-growth single crystals. Since then,
72 wt% Al2O3 by using HP sintering at 1630  C and 76 wt% Al2O3 by a number of achievements, such as highly efficient laser oscillation
using HIP pressing at 1650  C [268]. Ohashi et al. fabricated visible in compact devices, ease of control of the laser mode, and the
spectrum to infrared translucent mullite by using pressureless generation of highly focused coherent beams, have been made.
sintering at 1750  C [269]. Schneider et al. obtained transparent Ultrashort-pulsed laser (pico- to femtosecond) oscillation using
mullite by the combination of HIP pressing and pressureless sin- Nd:YSAG [272] and Yb:YSAG ceramics [273] were then demon-
tering using commercial fused-mullite [37]. Both processing strated. Subsequently, lasing at 1.47 kW was successfully generated
methods led to mullite ceramics with fine-grained microstructures using an Nd:YAG ceramic rod [274], even though its oscillation
(mean grain size of 5e10 mm) with equiaxed grains and a narrow efficiency was 15% lower than that of single crystal one. More
grain-size distribution. The pressureless sintered mullite had recently, ceramic Nd3þ:YAG has been fabricated and used to
a porosity of 5.5% and a transmittance of 20% in the VIS and NIR demonstrate lasers with output powers of 67 kW and even
ranges, while the HIP sintered mullite showed a porosity of 1% and >100 kW of at 1.06 mm.
a transmittance of 40% in the VIS range and up to 80% in NIR range. Currently, rare-earth element-doped YAG is still the most
This optically translucent mullite ceramics are suitable for optical extensively studied and widely used ceramics for high power lasers
windows in the VIS and NIR ranges [37]. [275e277]. Ikesue and Aung [275] once summarized the progress
Zhang et al. [104] fabricated transparent mullite ceramics by of polycrystalline Nd:YAG (Y3Al5O12), Nd:YSAG (Y3ScAl4O12),
using SPS from monophasic precursors in mid-infrared and visible Yb:YSAG ceramics with an almost pore-free microstructure by
light ranges by SPS. In this study, the effects of calcination using advanced ceramic processing. The laser conversion efficiency
temperature, properties of precursor powders and sintering of pore-free polycrystalline Nd- and Yb-doped ceramics was
parameters on microstructure and optical performances of the extremely high and their optical qualities were comparable with
mullite ceramics were systematically investigated. The samples that of commercial high quality Nd:YAG single crystals. The c.w.
with a relative density of above 97.5% exhibited an infrared trans- oscillation efficiency of the polycrystalline Nd:YAG ceramics was
mittance of 75e82% in wavelength of 2.5e4.3 mm. It was found that, very high and the beam quality was also sufficiently good. SHG
as the precursor powders were calcined at temperatures of below green and blue lasers were successfully generated by using the
1100  C, the residual OH, H2O and organic compound could not be Nd:YAG ceramics. A single longitudinal mode was achieved by
completely eliminated, which in turn had negative effects on using the heavily doped Nd:YAG ceramics. The laser oscillation
optical properties of the final ceramics. However, if the calcination efficiency was as high as 17%. Ps and fs mode-locked pulse lasers
temperature was too high, the precursors could not fully were successfully realized by using the Nd:YSAG and Yb:YSAG
densified, due to the absence of viscous flow of amorphous phase. ceramics. Pulse width of the Yb:YSAG ceramics was as short as
At a given calcination temperature, optical transmittance of the 280 fs.
mullite ceramics was decreased with increasing sintering temper- Fig. 38 shows c.w. laser performances of the pore-free 1.0, 2.4,
ature above 1450  C owing to the elongated grain growth. In and 3.6 at.% Nd:YAG polycrystal ceramics pumped with a Ti:Sap-
addition, microwave sintering provided a rapid heating, phire laser (808 nm) [275]. The threshold and the slope efficiency of
accelerated-mullitization, enhanced densification and limited grain polycrystalline Nd:YAG ceramics generally depend on the concen-
growth for developing transparent mullite ceramics with diphasic tration of Nd in ceramics because fluorescence lifetime decreases
gels [115]. with increasing concentration of Nd ion. However, very high laser
conversion efficiency was achieved in all the ceramics because of
4. Applications their pore-free microstructures. Although optical resonators were
not optimized in this oscillation, the slope efficiency (Z) of the
The special optical transparency, combined with the general polycrystalline ceramics was as high as 65%, which was almost
properties of ceramics, makes transparent ceramics suitable for equivalent to that of a single crystal.
various applications, such as lasers, armors and lighting, which will Fig. 39 shows a photograph of a blue laser and a green laser,
be discussed in detail as follows. 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

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].
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 4.2. Armor
(808 nm) laser. Reproduced with permission from Ref. [275], Copyright 2006, John
Wiley & Sons. Common applications for transparent armor include personnel
protection in the form of face shields and visors, windows for
The main feature of this ceramic blue laser is its very compact ground vehicles and armored cars and windshields and lookdown
structure because coated mirrors are used instead of normal windows for aircrafts. The widely used glass-based transparent
mirrors. In this system, a 2.4 at.% Nd:YAG ceramic sample was used armor windows are typically greater than five inches thick in order
as a laser gain medium. It was optically contacted with a KNbO3 to provide the required multi-hit ballistic protection. Not only does
single crystal as a secondary harmonic generation (SHG) device. A this increase wear cost for tactical vehicles which are already
diode laser was used as an exciting source. An SHG laser was straining with their weight limits, but also the relatively soft glass
generated from the Nd:YAG ceramics. facing can be degraded in the field by rock damage and blowing
Moreover, composite ceramics with complicated structures sand, leading to significant replacement cost. Therefore, there is
could be fabricated without the need for precise polishing and a compelling need to reduce the weight of the transparent armor
diffusion bonding. Fig. 40 shows laser characteristics of various systems while simultaneously increase the ballistic protection
types of composite elements. Although the optical resonator was capabilities. There is also a need on large windows and domes for
not optimized, over 50% slope efficiency [275] could be achieved in multimode weapon systems that are exposed to harsh environ-
each composite and a high beam quality TEM00 mode was also mental conditions. When both strength and hardness are the crit-
realized. ical performance metrics, choices are often limited to a few
Maître et al. [278] investigated light scattering by pores in materials. These are the single crystals sapphire (sapphire),
transparent Nd:YAG ceramics for lasers. The correlations between aluminum oxynitride (AlON) and magnesium aluminate spinel
microstructure and optical properties were studied. This study (spinel) [283e289]. Due to their high strength and hardness, these
revealed that the pore contents affect the transparency and laser three materials have long been considered as a potential replace-
efficiency of the ceramics. The porosity in Nd:YAG ceramics should ment for the ballistic glasses in transparent armor applications.
be lower than 104% to reach single crystal laser efficiency. Recent ballistic testings have shown that spinel, AlON and sapphire
However, recent studies indicated that YAG is not the best host possess similar performance. However, as stated earlier, when
material for high power laser operation systems due to its relatively compared with sapphire single crystals, polycrystalline spinel
low thermal conductivity and high thermal expansion coefficient. [286e289] and AlON [290,291] are superior. As window materials,
Instead, sesquioxides, such as Sc2O3, Y2O3 and Lu2O3, have been spinel is superior to sapphire and AlON due to its transparency up
shown to be very promising host materials for high power laser to 5 mm wavelength. Its high optical and MIR transparency in the
applications, mainly due to their high thermal conductivity and range of 0.25e5.5 mm makes it an ideal candidate as windows and
high absorption and emission cross-sections of trivalent rare-earth domes for EO & IR sensors on various defence systems operating in
ions [279]. One example is Yb3þ-doped Y2O3 which has excellent the environmental demanding conditions.

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.
S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54 47

Fig. 40. Laser performance of various types of composite elements. Reproduced with permission from Ref. [275], Copyright 2006, John Wiley & Sons.

4.3. Lighting yields and excellent phase stability, based on GYGAG(Ce) and
a radiography scintillator based on Lu2O3(Eu) have been reported in
Transparent ceramic materials with appropriate thermal and the open literature [35,305].
mechanical properties are very useful as envelopes for focused-
beam, short-arc lamps containing various fillers operating at 4.4.2. Transparent electro-optic ceramics devices
temperatures higher than the melting point of quartz. Coarse- A variety of devices have been designed by using transparent
grained ceramics of translucent polycrystalline alumina have electro-optical ceramic materials, including variable optical atten-
been used for several decades as envelopes in discharge lamps. uators (VOA), polarization controllers (PC), sinusoidal filters,
Translucent polycrystalline alumina (PCA) doped with magnesia- dynamic gain flattening filters, tunable optical filters and Q-
based additives discovered in 1960s has played an enabling role switches, which have been described in detail in Ref. [12]. A brief
in the lighting industry. It enabled the construction and wide- description is given some devices as follows.
spread use of high-pressure sodium lamps [292]. In 1990s, metal Variable optical attenuator (VOA) is a device used to reduce the
halide lamps featuring translucent alumina tubes, cylindrical [293] power level of an optical signal, either in free space or in an optical
or round [294], were introduced for white light, general- fiber. The basic types of optical attenuators are fixed, step-wise
illumination applications, due to the nature of translucency of variable and continuously variable. The type of devices has played
regular translucent alumina. An improved “white” light is emitted an important role in controlling the optical signal levels throughout
by metal halide lamps introduced by Philips in 1994. These lamps the network. Representative applications of VOA include pre-
run at a temperature close to 1200  C, which makes Al2O3 almost emphasis, channel balancing and optical automatic gain control.
irreplaceable as an envelope of outstanding chemical resistance In dense wavelength-division multiplexing (DWDM) transmission
[295,296]. system, the optical powder between every two channels should be
PCA of submicron grain size and high in-line transmittance (very equalized before they are combined and guided into a single optical
low residual porosity and small grains) was accomplished by using fiber. At add/drop network nodes, because the optical signals arrive
HIP sintering of compacts consisting of nearly nanosize alumina individually from different points in a network, all channels must
particles [24,33,295,297,298]. Other transparent ceramics as enve- be equalized. In addition, VOA has found applications beyond the
lope materials for improved beamer lamps included AlON, YAG, usual networks [12].
Y2O3 and Dy2O3 [298]. A wide range of shapes (cylindrical, bulgy, Light is in nature an electromagnetic wave, with electric and
spherical and elliptical) can be fabricated by the aid of technological magnetic field components being perpendicular to each other and
advancements in ceramic powder synthesis, forming and sintering. to its propagation direction. Therefore, light is actually a polarized
It is believed that there will be growing interest in developing and electromagnetic field. As a result, light has distinct orientation in
manufacturing these new lighting ceramics [299e301]. space and its propagation in a media is dependent on the polari-
zation direction, which has exerted negative influence on the
4.4. Other applications transmission rates of DWDM systems, such as polarization
dependent loss (PDL) and polarization mode dispersion (PMD). To
4.4.1. Scintillators solve these problems, it is necessary to have a good capability of
Scintillators are optical materials that emit pulses of visible polarization management. A dynamic PC is used to overcome such
photons when excited with high energy radiations. Gamma ray polarization related problems. In summary, PC can be used for
spectrometers providing high sensitivity and effective isotope polarization mode dispersion compensation, polarization scram-
identification require high energy resolution, high effective atomic bling, polarization multiplexing, polarization generation and other
number and scintillators that can be produced with large sizes. polarization management functions [12].
Transparent ceramics, such as YAG(Ce) [302], LuAG [303] and
Lu2O3 [304], form a promising class of polycrystalline materials for 4.4.3. Optical systems (lens)
scintillator applications. By using transparent ceramics, not only Markets for digital cameras and mobile phones with optic
the production costs can be greatly reduced, but also the activator equipment are increasing rapidly. Frequently, a compact and small
concentration and homogeneity can be dramatically enhanced. design of the lens systems is imperative for use and gives rise to
Transparent ceramics have become alternatives to replace single the search for new transparent materials with high refractive
crystals for scintillator applications, such as gamma ray spectros- index and high Abbé number. Optical glasses exhibit limits at
copy and radiography. The family of cerium-doped gadolinium n ¼ 1.5e1.85 whereas higher values are known for a number of
garnet (GYGAG(Ce)) scintillators appears to meet these require- crystalline ceramics that also exhibit a higher scratch and impact
ments. A new gamma spectroscopy scintillator, with high light resistance.
48 S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54

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
Fig. 41. Photographs of a thin translucent organic material of 0.06 mm, a sintered its theoretical maximum transparency, its transparency is not
window of submicrometer Al2O3 (thickness 0.8 mm, real in-line transmission w60%) affected by thickness, as shown in Fig. 42(c). In this respect, it is
and 6 mm thick almost fully transparent spinel for comparison. The characteristic
always desired to fabricate transparent ceramics with maximum
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 transparency without any scattering or absorption. This is espe-
permission from Ref. [306], Copyright 2009, Elsevier. cially important for applications, such as armors, where a relative
large thickness is necessary to ensure sufficiently high ballistic
5. Discussion and concluding remarks strengths.
As discussed earlier, the presence of various scattering losses is
Various transparent ceramics have been developed by using the main contribution to the decrease in in-line transmission, with
different sintering techniques, combined with the use of ultrafine respect to the theoretical maximum, of transparent ceramics, as
precursor powders with high sinterability. Although significant summarized in Fig. 43 [118,306]. Without the presence of these
progress has been made on the one hand, there are certain prob- losses, the theoretical maximum of transmission is 100% minus the
lems in the research of this area on the other, with which a detailed reflection on both surfaces of a piece of the material. At normal
discussion has been presented in Ref. [306]. Here, a brief delinea- incidence, the reflection R1 on one surface is related to the material
tion is used as discussion and concluding remarks of this review. refractive index n, given by

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.
S.F. Wang et al. / Progress in Solid State Chemistry 41 (2013) 20e54 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
Fig. 43. Light transmission through polycrystalline translucent ceramics (e.g. coarse
research in this area.
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], Acknowledgement
Copyright 2009, Elsevier.
One of the authors (LBK) would like to acknowledge the finan-
cial support of Start-up Grant of the Nanyang Technological
University (2012), Singapore.
 
n1 2
R1 ¼ ; (1)
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