International Journal of Applied Glass Science 1 [3] 237–247 (2010)

DOI:10.1111/j.2041-1294.2010.00027.x

Glass–Ceramics: Engineering Principles and Applications

Akihiko Sakamoto and Shigeru Yamamoto*
Nippon Electric Glass Co. Ltd., 2-7-1 Seiran, Otsu, Shiga 520-8639, Japan

The history and typical achievements in the development of glass–ceramics are reviewed on the basis of the engineering
principles of crystallization in glass and its application. Bulk and surface crystallization phenomena and their practical ap-
plications are described as well as the forming process of glass–ceramics. In addition to conventional glass–ceramic materials
and processes, novel potentialities of glass–ceramics in next-generation devices are also indicated. Luminous glass–ceramics for
high-power lighting and display systems, and electrode materials for rechargeable batteries are emphasized. Recent develop-
ments on the position-selective laser crystallization of the glass surface and a glass–ceramic with anomalous thermal expansion
are also introduced.

Introduction hours, resulting in completely crystallized ‘‘porcelain’’

Glass is a stable noncrystalline material that has a
long history of several thousand years synchronized with
the history of humanity. It exhibits optical transparency,
hardness, gas and liquid impermeability, and formabil-
ity into various shapes. On the other hand, ceramics,
which also have a long history linked with human life,
show diverse properties as polycrystalline materials. For
a long time, researchers for glass and ceramics have
been attempting to develop a material that possesses
both natures of glass and ceramics. It is said that the first
experiment of the crystallization of glass dates back to
the work of Reaumur in 1739.1 He packed bottles of
soda-lime-silica glass inside and out with a mixture of
sand and gypsum, and heated the bottles for many
shyamamoto@neg.co.jp
r 2010 The American Ceramic Society and Wiley Periodicals, Inc.
articles. The crystallized glass, however, must have
been more fragile than the original glass, because of an
uncontrolled surface crystallization with coarse crystals
extending inward from the bottle surface.
After a long period of time, in the middle of the last
century, a new crystallized glass was developed by Stoo-
key with a new principle. He found that fine crystals,
such as lithium disilicate and barium disilicate, precip-
itate on noble metal colloids in glass formed by UV
irradiation.2 This was the discovery of the controlled
crystallization of glass based on the nucleation and
subsequent crystal growth, which is called ‘‘catalytic
crystallization’’. In 1956, on the basis of this principle,
Stookey invented an almost fully crystallized glass article
in Li2O–Al2O3–SiO2 or MgO–Al2O3–SiO2 systems
containing 2–20 mass% TiO2.3 These glasses were
homogeneously crystallized by heat treatment owing
to the thermal nucleation effect of TiO2. The glasses
238 International Journal of Applied Glass Science—Sakamoto and Yamamoto
after crystallization showed drastic changes in proper-
ties, such as mechanical strength and thermal expansion,
while they maintained the original shape of glass articles
even after the crystallization. This was the birth of the
first ‘‘glass–ceramic’’ possessing both properties of glass
and ceramics.
After Stookey’s invention, many glass–ceramic
products were developed by glass manufactures all
over the world. The Corning Glass Works company
(Corning Inc. at present) launched glass–ceramics for
heat-resistant tableware and nozzle cones of missiles4,5
with the trademark ‘‘Pyroceram’’. Shortly after, the
Nippon Electric Glass (NEG) company developed a
transparent low-expansion glass–ceramic ‘‘Neoceram’’
using ZrO2 as a nucleating agent, which was discovered
by Tashiro and Wada.6,7 A dark-colored glass–ceramic
panel containing transition metal ions was developed by
the Schott company for cook-top application.8 Nowa-
days, glass–ceramics is established as a firm basis in glass
science and industry, and new materials, technologies,
and applications relating to the glass–ceramics are con-
tinuously developing In this paper, the authors intro-
duce the engineering principles in manufacturing of
glass–ceramics, typical glass–ceramic products, and
novel glass–ceramic materials and technologies, together
with some prospects for the future.
Engineering Principles
The crystallization of glass involves nucleation and
crystal growth processes. The crystallization process is
divided into homogeneous and heterogeneous nucleation.
The homogeneous nucleation deals with the process that
nuclei precipitate in a homogeneous supercooled liquid.
On the other hand, the heterogeneous nucleation is ap-
plied to the process that nuclei form at the interface be-
tween a supercooled liquid and the other substance. The
actual crystallization process of glass can be divided into
several paths by the type of nucleation and the influence
of phase separation of glass. Stewart classified the crystal-
lization process of glass into four paths as shown in Fig. 1. 9
Each path is characterized as below.
 Path 1: Direct precipitation of the main phase
through homogeneous nucleation.
 Path 6–5: Nucleation through homogeneous
process and subsequent precipitation of the
main phase on the nucleus surface through het-
erogeneous process.
Vol. 1, No. 3, 2010
Fig. 1. Reaction paths between the initial glass and the final glass–
ceramic (after Stewart).9
 Path 2–3: Precipitation of the main phase through
homogeneous nucleation after phase separation.
 Path 2–4–5: Nucleation through homogeneous
process after phase separation followed by precip-
itation of the main phase on the nucleus surface
through heterogeneous process.
According to this classification, the homogeneous
nucleation is a common process to all paths that influ-
ences early stage of crystallization. The primitive nucleus
in the early stage (critical nucleus) is, however, too small
to directly observe its existence. Thus, the details of the
nucleus formation or the site for nucleation in homoge-
neous nucleation process are still mysterious. Recently,
through the in situ observation of the boson peak during
the crystallization of several glass–ceramics, it has been
pointed out that the homogeneous nucleation occurs in
molecularly denser regions that are already present in
as-quenched glass.10 This experimental result implies that
the crystallization process of glass is influenced by not
only glass composition but also structural homogeneity
or thermal history of glass and supercooled liquids.
To determine the heat-treatment condition for
crystallization of glass, it is essential to know the temper-
ature dependence of the nucleation rate and the crystal-
growth rate. These are expressed by equations expressed
below
I ¼ nns n exp½ðDE þ DG  Þ=kT  ð1Þ
U ¼ nlexpðDE=kT Þ½ð1  expðvDgv =kT Þ ð2Þ
The rate of nucleation, I, is the number of nuclei
formed within a certain period of time. n is the fre-
quency of atom, ns is the number of atoms surrounding
the critical nucleus, n is the number of atoms per unit
volume, DE is the activation energy of the atom to
traverse the interface, DG is the free energy change for
www.ceramics.org/IJAGS Glass–Ceramics: Engineering and Applications
the formation of the critical nucleus, k is Boltzmann’s
constant, and T is the temperature. The free energy
change for the formation of critical nucleus in the equa-
tion is detailed in the classical nucleation theory.11,12
U stands for the rate of crystal growth defined as the
distance of crystal growth within a certain period of
time. l is the thickness of the crystal per atom, v the
crystal volume formed by one atom, and Dgv the differ-
ence in free energy between the crystal and the melt per
unit volume. Equations (1) and (2) indicate that the
nucleation and crystal growth show a maximum rate for
each at a certain temperature. In general, the heat-treat-
ment condition for crystallization is determined in such
a way that these rates show maximum. The crystallinity
of glass, X, is defined by X 5 Vc/V, where Vc is the vol-
ume of the crystal in a glass–ceramic and V the total
volume of the glass–ceramic. The time dependence of
the crystallinity is expressed by the Johnson–Mehl–
Avrami equation as shown below12
X ¼ 1  expðkt m Þ ð3Þ
Here, m represents the Avrami constant that refers
to the morphology of the precipitating crystal, t the
crystallization time, and k a constant. m and k can be
determined from the slope and intercept in the equation
of ln [ln (1X)] 5 ln k1m  ln t.
The actual crystallization process of glass is much
more complicated than the theory mentioned above,
though it enables kinetic description of crystallization
phenomena in glass. The quantitative discussion on the
nucleation and crystal growth rates or crystallinity often
deviates from the theory. The nucleation and crystal
growth rates in Li2O–2SiO2 and Na2O–2CaO–3SiO2
systems show large discrepancies between the theoretical
and experimental values. The possible reasons for these
discrepancies are the difficulty in determination of
the nucleus-melt surface energy and Dgv for the critical
nuclei, and the effect of elastic stress on DG due to
density difference between glass and crystals. However,
the theory still provides a good qualitative description of
nucleation and overall crystallization data.
The crystallization conditions are usually designed
based on experimental studies. Figure 2 schematically
shows the time–temperature–transformation (T–T–T)
curves that indicate the relation between the time for
crystal deposition and heat-treatment temperatures. The
area inside the curve indicates time and temperature con-
ditions for crystal deposition (crystallization area). When
the glass precipitates plural crystalline phases, plural
239
Fig. 2. Schematic diagram of T–T–T curves. Shaded areas show
time and temperature conditions for crystal deposition. Arrow shows
heating profile for reheat forming process.
curves are drawn corresponding to each crystalline phase.
The T–T–T curve is effective to determine the time–
temperature condition for the crystal growth process;
however, the shape of the curve and the extent of the
crystallization area are significantly affected by the ther-
mal history at nucleation process of glass. In practical
study, therefore, tedious work that involves drawing a
T–T–T curve for each nucleation condition is needed to
determine the appropriate heat-treatment condition.
Typical Glass–Ceramic Products
Table I shows typical commercial glass–ceramic
products. They are roughly divided into two types by
crystallization nature: ‘‘bulk crystallization’’ and ‘‘sur-
face crystallization.’’ Furthermore, they can also be
divided by the type of forming process.
Bulk Crystallization Glass–Ceramics
The important principle for producing bulk crys-
tallization glass–ceramics is the use of nucleating agents,
such as TiO2 and ZrO2, found by early inventors of
glass–ceramics.3,6 In most of the glass–ceramics con-
taining nucleating agents, the composition of the pre-
cipitated crystal is different from that of the nucleus.
This means that the nucleation process involves both the
homogeneous and heterogeneous nucleation. This pro-
cess corresponds to the path 6–5 or 2–4–5 in Fig. 1.
First, nuclei of the nucleating agents form through the
homogeneous nucleation process, and then the nucle-
ation of the main crystal occurs with the heterogeneous
240 International Journal of Applied Glass Science—Sakamoto and Yamamoto Vol. 1, No. 3, 2010

Table I. Typical Commercial Glass–Ceramic Products

Glass System Application Crystallization site Forming
Li2O–Al2O3–SiO2 Heat-resistant materials Bulk Quenching
Fiber optic devices Reheat drawing
Li2O–SiO2 Hard disk substrate Quenching
K2O–Al2O3–SiO2 Dental materials Reheat pressing
CaO–SiO2 Building wall materials Surface Sintering
MgO–CaO–SiO2-P2O5–F Bioactive materials
MgO–CaO–SiO2 Dielectric substrate

process on the surfaces of the nuclei formed by the the microstructure as expressed below14
nucleating agents. After the nucleation, the precursor
Rayleigh 2 Gans model :
glass is treated at higher temperatures for crystal
growth. s ¼ ð8=9ÞpNk 4 r 6 ðnc DnÞ2 ð4Þ
A typical example of a bulk crystallization product
is a low-expansion glass–ceramic in a Li2O-Al2O3-SiO2
Quasi  continuum model :
system. In this system, two types of glass–ceramic can be
obtained from the same precursor glass by choosing s ¼ ð2=3Þ  103 k 4 y3 ðnc DnÞ2 ð5Þ
crystal growth temperature. A b-quartz solid solution
(ss) glass–ceramic, which exhibits optical transparency Here, s is the scattering coefficient, N is the par-
and a very small thermal expansion o5  107/1C, is ticle number density, r the particle radius, k 5 2p/l
obtained using a crystal growth temperature around
9001C. This process corresponds to the precipitation
of the first crystalline phase, phase 1 in Fig. 2. The other
type is a white porcelain-like b-spodumene ss glass–
ceramic obtained by crystallization at around 12001C,
which corresponds to the precipitation of the phase 2 in
the same figure. This glass–ceramic also shows small
thermal expansion (B10  107/1C), a high-tempera-
ture resistance and good mechanical property. These
low-expansion glass–ceramics have a large variety of
applications including fire-rated windows, tableware,
and cook-top panels.
The refractive indices of the crystalline and glassy
phases, as well as the crystal size, are the keys to
obtaining low-scattering glass–ceramics. A typical micro-
structure of the transparent Li2O–Al2O3–SiO2 glass–
ceramic is shown in Fig. 3. It is too fine to directly
measure the refractive indices of the crystalline and
glassy phases. Thus, a method for calculating the indi-
ces utilizing structural relaxation in the glassy phase has
been proposed.13 When a glass–ceramic is annealed, the
scattering coefficient changes due to fictive temperature
change in the glassy phase. The scattering coefficient of
glass–ceramics is described by the Rayleigh–Gans Fig. 3. Microstructure of transparent low-expansion glass–ceramic
model or the quasi-continuum model in relation to (Neoceram).7
www.ceramics.org/IJAGS Glass–Ceramics: Engineering and Applications 241

periodic changes in refractive index, the period of which

is shorter than the wavelength of light. In such solids, a
large compensating effect appears in scattering because of
the interaction of the scattering field. The Rayleigh–Gans
model is applied to the systems involving independent
scatterers embedded in a matrix. It is inferred from these
facts that the glass–ceramic shows the scattering behavior
close to the quasi-continuous solid due to its densely
packed structure with nanoscale crystals (Fig. 3).

Surface Crystallization Glass–Ceramics

The sintering crystallization of glass granules or

Fig. 4. Wavelength dependence of scattering coefficient of a powder enables the production of surface crystallization
transparent b-quarts glass–ceramic. The open circles and lines show glass–ceramics. In general, as Reaumur’s experiment
experimental and calculation results, respectively. Calculations were showed,1 it is difficult to obtain surface crystallization
carried out using the following data: nc 5 1.513, Dn 5 0.121, and glass–ceramics with practical mechanical strengths.
a 5 0.0210 mm. For the Rayleigh–Gans model, N 5 1900/mm3 and However, through the sintering crystallization process,
r 5 21 nm. For the quasi-continuum model, W 5 0.039 mm.15 strong panels of surface crystallization glass–ceramics
were commercialized for building interiors and exteriors
(Neoparies, NEG). The sintering crystallization is con-
where l is the wavelength, y the mean phase width sidered as a hybrid process of the paths 1 and 6–5 in Fig.
(r1W/2), and W the interparticle spacing. nc and Dn 1. That is, the interface of glass granules acts as the site
express the refractive index of the crystalline phase and for the homogeneous and the heterogeneous nucleation
the difference of the index between the crystalline and followed by crystal growth of the main phase. There-
glassy phases, respectively. As shown in both models, the fore, this process requires no nucleating agent though it
scattering coefficient is proportional to the second proceeds with heterogeneous nucleation process. Figure
power of ncDn. If the annealing temperature is much 5 illustrates the sintering crystallization process.16 First,
lower than the crystallization temperature, all of N, V, k, the granules of CaO–Al2O3–SiO2 glass with no
r, and y can be treated as constants. Thus, the refractive
indices can be calculated from either of the models by
measuring the scattering coefficient of specimens with
different fictive temperatures. The refractive index of the
glassy phase of this glass–ceramic was found to be
slightly higher (B1.6) than that of the crystalline phase
(B1.5) through this method.13,15
Once the refractive indices are known, applicability
of the scattering models can be evaluated. The scattering
coefficient in the Rayleigh–Gans model is proportional
to the sixth power of the particle radius, whereas that in
the quasi-continuum model is proportional to the third
power. The validity of these models was evaluated using
two specimens with different microstructures, which
were crystallized at 8501C and 8901C.15 As represented
in Fig. 4, it is clear that the scattering coefficient of this
glass–ceramic is proportional to the third power of the
crystal size, and the quasi-continuum model is much
more applicable than the Rayleigh–Gans model. The Fig. 5. Schematic drawing of sintering process of a surface
quasi-continuum model deals with the solids having crystallization glass–ceramic (Neoparies).16
242 International Journal of Applied Glass Science—Sakamoto and Yamamoto Vol. 1, No. 3, 2010

Fig. 7. Breakage patterns of Neoparies, marble, and a noncrystal-

line glass in a steel ball impact test.16 The weight of the ball is
535 g. t and h indicate the thickness of the specimen and the height
of the ball drop, respectively.

sintered surface crystallization glass–ceramics are used to

protect and decorate building walls all over the world.
Another important example of surface crystalliza-
tion glass–ceramics is a bioactive glass–ceramics.17 A
dense crack-free homogeneous glass–ceramic with apa-
tite and b-wollastonite can be obtained by sintering
MgO–CaO–SiO2–P2O5–F glass. This glass–ceramic
directly bonds to a living bone (Fig. 8) and is known
as glass–ceramic A–W. Glass–ceramic A–W forms an
apatite layer on its surface in biological applications and
Fig. 6. Microstructure of Neoparies produced by granule-sintering
process.16

nucleating agent are sintered at 8501C, and nucleation

occurs subsequently at the interface of the granules at
9501C. After the subsequent heat treatment at 11001C,
needle-shaped crystals of b-wollastonite grow inward
perpendicular to the interface. The microstructure of
Neoparies is shown in Fig. 6. Its crystallinity is approx-
imately 35 vol%. In the production of this glass–ce-
ramic, glass granules loaded in a ceramic mold are heat
treated in a continuous kiln, and then, the granules are
sintered and crystallized, resulting in dense flat glass–
ceramic panels. After lapping and polishing the surface,
a marblelike shiny texture appears, which is attributed to
the crystals grown in random orientation.
Neoparies shows a breakage pattern similar to that of
marble but differs from that of the noncrystalline glass,
because the interlocked structure of the needlelike crystals
and granule boundaries inhibits crack propagation. Fig-
ure 7 shows the breakage patterns obtained by the steel-
ball impact tests of Neoparies, marble, and the noncrys-
talline glass.16 Neoparies also shows a higher chemical
durability than natural stones. Nowadays, a number of Fig. 8. Interface of glass–ceramic A–W and rabbit bone.17
www.ceramics.org/IJAGS Glass–Ceramics: Engineering and Applications 243

bonds to a living bone through this layer. The bending

strength is 220 MPa, which is higher than that of the
human bone. This is attributed to a high fracture surface
energy due to the existence of needle-shaped b-wol-
lastonite crystals. This glass–ceramic has clinically been
the most widely used among bioactive glass–ceramics.
Low-temperature co-fired ceramics for multilayered
electronic circuit substrates are also produced by glass–
ceramic material through the sintering process.18 Both
low dielectric loss and high mechanical strength are
achieved using a glass–ceramic that is almost fully crys-
tallized with diopside.19 Precursor glass powder is
formed into flexible thin sheets with organic binders,
and then, the sheets with printed electronic circuits are
fired in multilayered structures.

Glass–Ceramics with New Forming Technology

In general, a melt of glass–ceramics is formed into

the final shape by quenching before the crystallization, Fig. 9. Inside flow of glass melt on the forming rollers.20
and then crystallized while maintaining the shape. This
utilizes the easiness of the forming of glass melt. In this
process, it is most important to prevent stone formation minimized by controlling the feeding path of the glass
(devitrification) from the glass melt. The melt of glass– melt onto the forming rollers. Figure 10 shows a jumbo
ceramics tends to cause devitrification compared with stone-free glass–ceramic shelf (4500 mm  2500 mm)
the melt of noncrystalline glass. This causes serious formed by this method, which is used in the heat treat-
problems in the production of glass–ceramics. ment of glass substrates for PDPs.
Recently, it has been reported that jumbo glass– A novel forming process for glass–ceramics with the
ceramic panels were successfully produced, preventing reheating of the crystallized preform was developed to
devitrification during the forming process.20 These produce precision products that cannot be accomplished
glass–ceramic panels are used as high-temperature-resis- by the use of direct forming of glass melt. In this
tant shelves in the production of flat panel displays, such process, a crystallized preform with a relatively low
as plasma display panels (PDPs). Rolling-out is a com-
mon method used to form a glass melt into sheets or
panels. A glass melt is fed between two forming rollers
and continuously pulled being quenched to a temper-
ature below the crystallization temperature. However,
because the melt of glass–ceramics crystallizes faster than
the melt of noncrystalline glasses, stones tend to be
formed in the mass of the glass melt that remains on the
rollers. Figure 9 shows a simulation result regarding
the inside flow of the mass of the glass melt. As shown in
the figure, there are two closed circular flows inside the
mass. When the melt is caught in these flows and re-
mains for a long time in the crystallization temperature
range, stones are formed in the melt, contaminating the
glass panel. This effect becomes more severe in larger Fig. 10. Jumbo low-expansion glass–ceramic shelf used in the
panels because the glass melt remains for a longer time on production of plasma display panels. The size of the shelf is
the rollers. To avoid this problem, the circular flows are 4500 mm  2500 mm.
244 International Journal of Applied Glass Science—Sakamoto and Yamamoto
Fig. 11. Neck down portion of the crystallized preform used for
reheat drawing.21
crystallinity is used so that the fluidity of the glass phase
can be utilized. Preform drawing is an effective method
of forming precision glass–ceramics. This method is
typically used for the production of noncrystalline op-
tical fibers and capillaries. Figure 2 also compares T–T–
T curves for the precursor glass of glass–ceramics and
the noncrystalline glass. Because the crystallization area
of the precursor glass is much larger than that of the
noncrystalline glass in nature, the precursor glass pre-
form causes a severe devitrification during the drawing
process as indicated with an arrow in the figure. To solve
this problem, a crystallized preform was developed for
drawing glass–ceramics.21 Figure 11 shows a neck-down
portion of a crystallized preform that was smoothly drawn
similarly to a noncrystalline glass, maintaining the crystals
inside. The preform was designed to contain 50 vol%
b-spodumene ss, and in such a way that no crystallization
or crystal growth proceeded during drawing. It is impor-
tant to prevent surface crystallization during the process,
because the increase in the specific surface area of the
preform caused by drawing may induce surface crystalli-
zation. This crystallized preform can be drawn into fibers,
Vol. 1, No. 3, 2010
capillaries, or ribbons, as shown in Fig. 12. No further
heat treatment for crystallization is required for the drawn
products. The precision glass–ceramic capillaries and
tubes are used in optical fiber devices.
There exists another example of glass–ceramics formed
with the crystallized preform. The preforms with lucite,
apatite, or lithium disilicate are formed by mold pressing
into tooth-shaped structures for dental application.22
Novel Glass–Ceramics and Technologies
In this section, some of novel glass–ceramic mate-
rials and technologies for next generation technologies
or systems are introduced. Luminous glass–ceramics for
solid-state lighting and display systems, glass–ceramics
for new energy technologies, laser crystallization, and a
new possibility of controlling the thermal expansion of
glass–ceramics are described.
Luminous Glass–Ceramics
Glass–ceramics can be used as wavelength converters
for white light-emitting diodes (LEDs). The SiO2–
Al2O3–Y2O3 glass doped with Ce2O3 precipitates an
yttrium–aluminum–garnet crystal containing Ce31 ions
(Ce:YAG) by heat treatment between 12001C and
15001C.23 The Ce: YAG crystal is in the nature of flu-
orescence that absorbs blue light and emits yellow light.
Thus, the Ce: YAG glass–ceramic can be used as a wave-
length converter to yield white light by mixing blue and
yellow lights. Figure 13 demonstrates white light emission
from the glass–ceramic illuminated by a blue LED. This
glass–ceramic is much more durable to high temperatures
and high-power optical irradiation than the conventional
wavelength converters composed of resin and phosphor
powders. The color temperature of the white light emitted
from the glass–ceramic can be controlled by the thickness
of the glass–ceramic. A high-power LED is applicable to
the back-lighting systems of liquid crystal displays or
lighting systems of automobiles as well as general light-
ing systems. The Ce:YAG glass–ceramic is one of the
promising candidate of the color converters for realizing
durable high-power white LED used in those new sys-
tems. Several studies on luminous glass–ceramics as wave-
length converters are in progress.24,25
Glass–ceramics containing nonlinear optical crys-
tals have the potential to realize full-color three-dimen-
sional displays based on second-harmonic generation.
Three-dimensional displays are of great interest in the
www.ceramics.org/IJAGS Glass–Ceramics: Engineering and Applications 245

Fig. 12. b-spodumene glass–ceramic products formed by preform drawing. (a) Cross-sectional view of a glass–ceramic capillary. The
eccentricity and roundness of the capillary are o0.5 mm and 1.0 mm, respectively. (b) Glass–ceramic ribbon wound around a reel. The width,
w, and the thickness, t, of the ribbon are 1.25 mm and 35 mm, respectively.

next generation of display systems. Recently, in a BaO–
TiO2–SiO2 system, a glass–ceramic containing a
Ba2TiSi2O8 crystal with a strong optical nonlinearity
has been reported.26,27 This crystal can be precipitated
by either femtosecond laser irradiation or heat treatment.
Because the glass–ceramic is transparent, it shows a
localized second harmonic generation at the focal point
of the laser inside the glass–ceramic when it is irradiated
by a tightly focused laser after the crystallization. This
indicates the possibility of space-selective visible emission,
which leads to three-dimensional full-color displays. The
lifetime of second-harmonic generation is so short
(B100 fs) that no ghost image is expected.
Glass–Ceramics for Energy
A glass–ceramic consisting of an olivine-type LiFe
PO4 crystal was developed as the cathode active material
of a lithium-ion rechargeable battery.28 This glass–
ceramic is obtained by crystallizing Li2O–Fe2O3–P2O5–
Nb2O5 precursor glass under reducing atmosphere. It is
known that the LiFePO4 crystal has a structure that
enables the intercalation of Li1 ions and acts as the
cathode material of the rechargeable battery. This crystal
is chemically stable against charge–discharge intercala-
tion cycles and does not contain any harmful or rare
element. Thus, it is attracting much attention as a cath-
ode material for realizing safe high-power rechargeable
batteries for next-generation automobiles.
The conventional LiFePO4 crystal, which is syn-
thesized by solid-state reaction, shows low electronic
conductivity. This leads to a low capacity or potential of
the battery, especially in high-rate discharge applica-
tions. Recently, it has been reported that the battery
fabricated with this glass–ceramic shows good cell per-
formance at high-rate discharge.29 Figure 14 shows the

Fig. 14. Discharge voltage of lithium-ion rechargeable batteries

Fig. 13. White light emission from the Ce: YAG glass–ceramic. with LiFePO4 glass–ceramic and ceramic.29
246 International Journal of Applied Glass Science—Sakamoto and Yamamoto
discharge voltage of the batteries at various current. The
battery with the glass–ceramic maintained a higher volt-
age at higher currents than the battery with the conven-
tional LiFePO4 ceramic. This indicates that the battery
with the glass–ceramic has lower internal resistance and
better high-rate discharge performance than the con-
ventional battery. This may be attributed to the
improved conductivity at the glass–ceramic surface, though
the detailed mechanism has not been clarified. It was
also confirmed that this glass–ceramic contains very few
metal impurities compared with the conventional ce-
ramic. This leads to suppression of the short-circuit
problem in battery systems. These new potentiality of
the glass–ceramic brought by the LiFePO4 glass–
ceramic will encourage extensive studies of glass–ceramics
for energy application.
Laser Crystallization
A novel crystallization method using laser irradia-
tion, which enables position-selective crystallization on
the surface of precursor glass, has been developed by
Komatsu et al.30 As mentioned earlier, in conventional
glass–ceramic production, precursor glass is heat treated
in its entirety for the nucleation and crystal growth in
accordance with the basic theory. A definitive difference
of the laser crystallization from the theory is that only
the crystal growth process occurs during laser scanning
without the nucleation. Figure 15 shows a LiNbO3 sin-
gle crystal line on the surface of Li2O–Nb2O3–SiO2
glass containing CuO formed by the scanning irradia-
tion of a continuous laser (wavelength: 1080 nm).31
Cu21 ions absorb the photon energy of the laser and
effectively convert it into heat. The temperature at the
Fig. 15. LiNbO3 single crystal on the surface of Li2O–Nb2O3–
SiO2–CuO glass formed by laser irradiation.31
Vol. 1, No. 3, 2010
irradiation point is estimated to be 47001C. The tem-
perature gradient between that point and the surround-
ing area is speculated to be responsible for the growth of
the oriented single crystal as well as the effect of scan-
ning speed. The second harmonic generation from this
crystal line has been confirmed.31 The application of
this technique to waveguide-type optical switching
devices is expected. The other crystals, such as
b0 -(Sm,Gd)2(MoO4)2 and CaF2 can also be formed
by a similar method of laser irradiation onto Sm2O3–
Gd2O3–MoO3–B2O3 and SiO2–Al2O3–CaO–NaF–
CaF2–NiO–ErF3 glasses, respectively.
Glass–Ceramics with Anomalous Expansion
A glass–ceramic that shows an anomalously low
thermal expansion has been found. In principle, the co-
efficient of thermal expansion (CTE) of glass–ceramics
is governed by the additivity rule, that is, the CTE is
determined from those of the crystalline and glassy
phases, and the crystallinity. However, an exception to
this rule was found in a Li2O–Al2O3–SiO2 glass–
ceramic containing b-spodumene (ss) with a crystalli-
nity of 45 vol%.32 The expansion curve is shown in Fig.
16 and compared with the curve calculated on the basis
of the rule. This glass–ceramic showed a CTE of
7  107/1C (30–3801C) that is much smaller than
the calculated value (39  107/1C) and is close to
that of silica glass despite the crystallinity of
Fig. 16. Anomalous thermal expansion of the b-spodumene glass–
ceramic. L and DL indicate the length of the specimen and the
change of the length, respectively. The temperature range for
coefficient of thermal expansion (CTE) measurement is
30–3801C.32
www.ceramics.org/IJAGS Glass–Ceramics: Engineering and Applications
o50 vol%. Although the details of the anomaly in CTE
are still unclear, the effect of the microstructure with
interstices on the expansion is suggested. If the CTE of
the glass–ceramic can be controlled independent of the
additivity rule, the degree of freedom in designing glass–
ceramics with a thermal function will be greatly en-
hanced.
Summary
Developments of glass–ceramic materials and tech-
nologies were described on the basis of the engineering
principles of glass crystallization and applications. The use
of a nucleating agent is a traditional method used to con-
trol bulk crystallization in glass, which enables the fabri-
cation of glass–ceramics with fine microstructures. A
transparent low-expansion glass–ceramic with a nano-
structure crystalline phase and its optical scattering prop-
erty were explained as an example of bulk crystallization
glass–ceramics. Sintered glass–ceramics applied to archi-
tecture, biomedics, and electronics were introduced as
successful examples of surface crystallization glass–ceram-
ics having practical mechanical strengths. Jumbo glass–
ceramic panels developed through a stone-free direct
forming method and thin glass–ceramic capillaries/rib-
bons developed through preform drawing are typical
examples that show progress in the forming technology
of glass–ceramics. For the prospective application of glass–
ceramics to next-generation devices, luminous glass–
ceramics for white LEDs and three-dimensional displays,
electrode materials for rechargeable batteries, and position-
selective laser-crystallized glass were introduced. All of
these examples show the great potential of glass–ceramic
materials in next-generation devices and technologies.
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