International Journal of Applied Glass Science, 5 [2] 93–103 (2014)

DOI:10.1111/ijag.12063

Milestones in Glass-Ceramics: A Personal Perspective

G. H. Beall*,†
Corning Incorporated, Corning, New York

Forward that three glass-ceramics had already been commercial-

Because of the author’s long association with
Corning Incorporated and with the development of
glass-ceramic products, this article will naturally con-
centrate on the history of commercial glass-ceramics
with some bias to those of special interest to Corning.
There are many landmark studies of nucleation and
crystallization of glasses that have advanced glass-cera-
mic science but are omitted in this paper as they are
not seen by the author, perhaps unwittingly, as directly
linked to the products described herein. The portions
of this paper which involve personal experiences of the
author are written in the first person to separate them
from the general history.
Early History: 1953–1963
I started with Corning Inc., then Corning Glass
Works, in October, 1962, as a newly minted PhD
from M.I.T. in geology with no background in materi-
als science or glass other than knowledge of the chemis-
try of natural rocks and volcanic glass. My first
objective was to learn from Don Stookey, the inventor
of glass-ceramics, and his prot
eg
e John MacDowell,
what had been discovered at Corning about the con-
trolled crystallization of glass. I was surprised to learn
*Life Member, The American Ceramic Society.
†
beallgh@corning.com
© 2014 The American Ceramic Society and Wiley Periodicals, Inc
ized, Code 8603, based on Li-silicates (LS), Code
9606, based on Mg-aluminosilicates (MAS), and Code
9608, based on Li-aluminosilicates (LAS). I will
attempt to point out key features and milestones in this
early work and how they led to subsequent advances.
Lithium Silicate (LS) Glass-Ceramics
I first heard of Stookey’s serendipitous experiment,
already legendary at Corning, which produced the first
glass-ceramic. While experimenting with lithium silicate
photosensitive glasses containing silver and ceria, he
had exposed a rectangular plate of glass to ultraviolet
radiation and then placed it in a furnace, set at 450°C
to precipitate silver. Instead, the furnace overheated to
above 850°C. Expecting to find a melted mass, Stoo-
key observed a dense white crystalline ceramic of
apparently identical shape as the original glass sample.
On accidentally dropping this plate on the floor, he
heard a metallic sound and observed that the plate
remained intact. There were several lessons to be
learned from this experiment. Firstly, silver particles
were effective as a nucleating agent for what turned
out to be lithium disilicate (Li2Si2O5) crystals. Sec-
ondly, a glass could be converted to a fine-grained
ceramic by simple thermal treatment. Thirdly, this
could be achieved while maintaining the shape of the
original glass article. Finally, the ceramic produced was
uniform and nonporous and apparently much stronger
than the original glass.
94 International Journal of Applied Glass Science—Beall
Continued research in this family of glasses led to
the understanding that dendritic crystals of lithium me-
tasilicate (Li2SiO3) were formed at lower temperatures
than those required for the development of the disili-
cate. Moreover, by exposure to ultraviolet light and
employing a mask, a pattern of clear glass and white
Li2SiO3 glass-ceramic was formed. As lithium metasili-
cate is much more soluble in dilute hydrofluoric acid
than the unexposed glass, a glass with patterned holes
could be made.1 This material was called Fotoformâ
and was used in various technical and decorative appli-
cations. By subsequent ultraviolet flood exposure, the
remaining glassy areas could then be heat-treated to
yield a strong lithium disilicate glass-ceramic with iden-
tical pattern to the original Fotoformâ. This was called
Fotoceramâ and was later used in various applications
including fluidic devices, magnetic recording head pads,
and as charge plates for ink-jet printing.
This work led to interest worldwide, and in the
United Kingdom, research at the General Electric Co.
(GEC) by McMillan, and Partridge2 revealed that
noble metals were not required to nucleate lithium sili-
cate glass-ceramics. Small additions of P2O5, from 0.5
to 3.0 wt.%, were shown to produce strong glass-
ceramics based on fine laths of closely packed Li2Si2O5
in high-lithia (~10 wt.%) glass-ceramics in the SiO2-
Li2O, SiO2-Li2O-(Al2O3), and SiO2-Li2O-(ZnO) sys-
tems. Flexural strengths of 350 MPa were measured, a
record at the time.
Lithium Aluminosilicate (LAS) Glass-Ceramics
After using silver nucleation to produce the first
internally nucleated Li-silicate glass-ceramics, Stookey
naturally tried to use silver and noble metals to nucle-
ate lithium aluminosilicate (LAS) crystal phases, such as
b-spodumene and b-eucryptite. These phases were
known at the time to have very low coefficients of ther-
mal expansion (CTE). Stookey envisioned the possibil-
ity of glass-ceramics with high resistance to thermal
shock. Silver and noble metals, however, simply did
not work as nuclei here, even when clearly present as
precipitates in the glass. Upon heating, the glasses
merely crystallized from the surface like ice cubes. Stoo-
key then tried TiO2 additions, based on his memory of
dense titania opal glasses, and internal nucleation was
achieved with about 4 wt.% TiO2.3 However, in
attempts to make practical SiO2-Al2O3-Li2O-TiO2
glass-ceramics based on low-CTE b-spodumene
Vol. 5, No. 2, 2014
(LiAlSi2O6-LiAlSi5O12 solid solution),4 an unusual and
persistent spiderweb cracking was encountered. This
was finally eliminated by replacement of some of the
Li2O by MgO, a substitution allowed in the b-spodu-
mene phase.
It was realized later that this type of cracking can
occur when the precipitation of the nucleating phase is
immediately followed by the major crystallizing silicate,
that is, when nucleation and crystallization are virtually
spontaneous. The parts of the glass article that reach
the nucleation temperature first, usually corners or
edges, will then crystallize, followed by an outward
wave of rapid crystallization exacerbated by the heat of
crystallization itself. The shrinkage on crystallization
cannot be accommodated in such cases, and a multi-
tude of cracks results, often in a radial pattern. This
phenomenon of avalanche cracking during crystalliza-
tion is most often encountered with glass compositions
that are close to the stoichiometry of the crystal and
where the viscosity of the glass at crystallization is large
(>1011 Pa.s).
Stookey’s substitution of MgO for some of the Li2O
in the LAS glass-ceramics eliminated the spiderweb
cracking by both increasing the temperature difference
between nucleation and crystallization and decreasing the
glass viscosity at the point of crystallization. In this way,
he was able to produce a viable Li-aluminosilicate glass-
ceramic cookware: CorningWareâ.
Magnesium Aluminosilicate (MAS) Glass-Ceramics
In the late 1960s, a need arose for a ceramic mis-
sile nosecone for a missile to be guided by an internal
antenna. This required a strong and refractory material
transparent to the microwave signals used for guidance.
Stookey3 investigated the composition area of the
SiO2-Al2O3-MgO (MAS) system in the vicinity of cor-
dierite (Mg2Al4Si5O16), a crystal of known low CTE
and good dielectric properties. To form this glass into a
radome (nosecone), the glass had to be centrifugally
cast into a mold at a relatively low viscosity, but it also
had to be stable enough to avoid crystallization. A stoi-
chiometric cordierite glass composition was too fluid
and unstable, so a composition closer to the eutectic
point (cordierite-enstatite-silica) was chosen. About 10
wt.% of TiO2 was added to this material for optimized
nucleation. The resulting glass-ceramic, Corning Code
9606, contained hexagonal cordierite (indialite) but also
accessory enstatite (MgSiO3), cristobalite, and rutile.
www.ceramics.org/IJAGS Milestones in Glass-Ceramics
The cristobalite component turned out to be impor-
tant, as this phase can be etched out in a hot caustic
(NaOH) solution, leaving a porous skin that resists the
propagation of handling flaws. This preserves the good
flexural strength (~250 MPa) required to resist stresses
caused by atmospheric friction and rain erosion.
Maurer5 studied the nucleation mechanism for this
glass-ceramic and was the first to demonstrate by optical
scattering studies the early stage sequence of nucleation,
and further x-ray diffraction (XRD) studies provided the
main crystallization sequence as follows: amorphous
nanophase separation?MgTi2O5 nuclei?“l-cordierite”
?a-cordierite. A somewhat analogous sequence was later
observed in the LAS-CorningWareâ composition6:
amorphous nanophase separation?Al2Ti2O7 nuclei?
“b-eucryptite”?b-spodumene solid solution (ss).
Sodium Aluminosilicate (NAS) Glass-Ceramics
In the early 1960s, MacDowell7 developed a soda
nepheline (NaAlSiO4) glass-ceramic suitable for manu-
facture of a new glazed tableware (Centuraâ). The
composition required about 7 wt.% TiO2 for good
nucleation. Nepheline is a framework silicate of high
thermal expansion (>10 9 10 6K 1), and a high CTE
is required to coat the surface with a lower CTE glaze
for compression and increased strength. On the other
hand, the CTE cannot be too high, or the thermal
shock resistance required for tableware cannot be met.
For this reason, sufficient barium oxide was added to
produce a secondary phase: celsian (BaAl2Si2O8), which
modified the CTE to the desired level (9 9 10 6K 1).
A borosilicate glaze with a CTE of 6 9 10 6K 1
was then applied to guarantee a good flexural strength
of about 250 MPa and to allow under-glaze
decoration.8
1963–1980
Transparent and Nanocrystalline Glass-Ceramics
My first assignment at Corning was to find a way
to remove the yellow-brown color and purple haze
from existing transparent “b-eucryptite” glass-ceramic
percolators, as these were said to “make coffee look like
motor oil.” These prototype vessels had been formed
by heating LAS glass-ceramics similar to Corning
Wareâ at temperatures high enough to cause metasta-
ble crystallization but not high enough to form the sta-
95
ble opaque glass-ceramics composed of b-spodumene
ss. The color of these early transparent glass-ceramics
was caused by the presence of TiO2 required for inter-
nal nucleation.
The approach I took was to completely replace the
nucleating agent TiO2 by ZrO2. It was found that on a
molar basis, the amount of ZrO2 required was only 2/3
of that needed for TiO2-induced nucleation. Zirconia
is not easily dissolved in LAS glasses, so the fact that
less was required was important.
In early 1963, I was able to produce a transparent
and colorless LAS glass-ceramic by substituting some
MgO and ZnO in place of about half the molar Li2O,
allowing improved solubility of ZrO2 in the glass. The
idea was to introduce this transparent glass-ceramic for
top-of-range ware, because, like Corning Wareâ, the
CTE was low, in fact close to zero. In addition, It was
found that this glass-ceramic could be strengthened by
K+ for Li+ ion exchange in a salt bath of 52 wt.% KCl
and 48 wt.% K2SO4 operating at 720°C. Modulus of
rupture (MOR) values of 275 MPa were measured
after abrasion, high enough for thin-blown-ware-like
coffee percolators. Moreover, because of the required
high temperature for this exchange, the compressive
stress at the surface was not decreased in long-term test-
ing on an electric range. Needless to say, I was disap-
pointed when this glass-ceramic was not put into
production. The major reason given for this decision
was that selling clear blown and pressed glass-ceramic
ware would cannibalize the market for Pyrexâ glass-
ware. We would wait another 15 years before a trans-
parent cookware line was introduced by Corning
France. Ironically, this material was to be intentionally
colored. Nonetheless, we learned a great deal from this
early effort including the following:
Both XRD and replica electron microscopy
revealed that these “b-eucryptite” glass-ceramics were
highly crystalline, about 90 volume%. The crystal com-
position could not be anywhere near the eucryptite
stoichiometry (LiAlSiO4), which has only 47.7 wt.%
SiO2, because the parent glass contains about 70 wt.%
SiO2 and the glass-ceramic is highly crystalline. More-
over, it was clear from studies of metastable phases in
the SiO2-MgAl2O4 system by Schreyer and Schairer9
and in the SiO2-LiAlO2 system by Roy10 that b-quartz
structures were easily crystallized from a wide variety of
glasses containing from 50 to 80 mole% SiO2 in the
SiO2-Al2O3-MgO-Li2O system. As a result of this
understanding, the terms “l-cordierite” and “b-eucryp-
96 International Journal of Applied Glass Science—Beall
tite” were replaced at Corning by “b-quartz solid solu-
tion (ss)” or “stuffed b-quartz.” Only those stable solid
solutions near the eucryptite (LiAlSiO4) stoichiometry
were referred to as b-eucryptite.
Highly crystalline glass-ceramics based on b-quartz
ss can be made from a variety of glasses in the basic
system SiO2-Al2O3-Li2O-MgO-ZnO, nucleated by
TiO2 or ZrO2 or a combination of both.11 There are
some restrictions. The atomic ratio (Li+½Mg+½Zn)/Al
must be near unity. This is because Al3+ replacing Si4+
in the helical network of tetrahedra of b-quartz must
be accompanied by “stuffing ions” such as Li+, Mg2+,
and Zn2+ that fit in the interstitial channels and main-
tain electrical neutrality. Nevertheless, some Zn2+ may
enter the network position if the composition is subalu-
minous (Li+½Mg+½Zn)/Al > 1, and some Al3+ may
enter the interstitial position if it is peraluminous
(Li+½Mg+½Zn)/Al < 1. The mole% SiO2 must be
above 50 to avoid Lowenstein’s rule forbidding Al-O-
Al bonding of tetrahedra, and below 80 to prevent
spontaneous inversion to a-quartz on cooling (insuffi-
cient stuffing). Transition metal ions may also enter the
crystal allowing coloring of the glass-ceramic.
The main advantages of stuffed b-quartz glass-
ceramics lie in their low CTE and uniform fine-grained
microstructure. The crystallites are often much smaller
(<100 nm) than the wavelength of visible light, thereby
allowing transparency. In addition, the wide composi-
tion variation inherent to b-quartz solid solutions
allows the tailoring of properties. For example, the
CTE can be varied in the range from 3 9 10 6K 1
to +4 9 10 6K 1. This composition flexibility is a key
factor in tailoring physical properties to required prod-
uct specifications, a feature normally attributed only to
glasses.
It became apparent to us in the early 1960s that
Corning was not the only company working on glass-
ceramics. Although I was not aware of it at the time,
Jurgen Petzoldt12 and his group at Schott Glaswerke in
Mainz and Tashiro and Wada13 at Nippon Electric
Glass were also mapping the extent of solid solutions
of b-quartz and were well aware of the potential for
their commercial development. Schott was aiming at a
suitable composition for telescope mirrors. Corning also
knew of this potential application and had developed a
candidate glass-ceramic composition. However, Corn-
ing already had a business in telescope substrates using
silica glass made by the chemical vapor deposition
(CVD) process and had been able to reduce its CTE to
Vol. 5, No. 2, 2014
near zero by doping it with titania. So it was decided
to stick with the glass approach.
The first successful commercial b-quartz ss glass-
ceramic available worldwide was introduced by Schott
in 1967 and named Zerodurâ.14 This material used a
combination of TiO2 and ZrO2 to produce ZrTiO4
nuclei, which had been shown to decrease b-quartz ss
grain size by about a factor of two (from about
100 nm with either single oxide to about 50 nm with
the best combination). Because of its nanocrystalline
grain size, the Zerodurâ glass-ceramic could be pol-
ished to the same smoothness as glass. It boasted a
CTE of 0  0.02 9 10 6 K 1 in the range of 0°C to
50°C, ideal for the dimensional stability required for
telescope mirror substrates. Remarkably, this glass-cera-
mic was capable of manufacture in sizes up to 10 m in
diameter weighing over 25 tons. The use of 6.5 wt.%
P2O5 in the composition, substituting for silica as
AlPO4, allowed sufficient glass fluidity and thermal sta-
bility to make such large castings.
It is often not the commercial potential of a new
material, but its appearance and novel properties that
excite scientific curiosity. I had such an experience after
just 2 months at Corning. While exploring in the
translucent Zn-stuffed b-quartz glass-ceramic composi-
tion field, I discovered that that ZrO2 levels higher
than that required for nucleation of b-quartz ss pro-
duced a haze-free transparent material. I sent this sam-
ple for XRD expecting to find a b-quartz pattern.
Instead, I was surprised to find the spinel pattern of
gahnite (ZnAl2O4) with broadened peaks indicating
smaller crystals than had been seen before. This was the
first glass-ceramic with a dominant oxide phase instead
of a silicate. As a geologist, I was aware of “ruby spi-
nel,” a red mineral known to contain chromium. I then
added 0.2 wt.% Cr2O3 to the glass batch and received
a bright green glass. Sure enough, on heat treatment,
this green glass turned into a red transparent glass-cera-
mic. This was exciting to me, and I shone an ultravio-
let lamp on it and found that it displayed a bright red
fluorescence. At the time, laser technology was in its
infancy, and there was interest in replacing ruby lasers
(Cr-doped alumina) with a less expensive material that
could be made in larger sizes. The fluorescence spec-
trum of this glass-ceramic, unfortunately, showed a
broad spectrum of many small peaks instead of a major
line as in ruby, and it therefore was not useful as a laser
material. Nevertheless, here was a new material of per-
haps future interest.
www.ceramics.org/IJAGS Milestones in Glass-Ceramics
Glass-Ceramics for Electric Rangetops
In the late 1960s, Corning introduced the concept
of cooking on a smooth white glass-ceramic by intro-
ducing The Counter That CooksTM. This product was
basically a polished b-spodumene ss version of Corning
Wareâ made by rolling the parent glass followed by a
crystallization heat treatment. For the final product,
heated from coils below, it was important to have an
insulating gap between the coils and the Li-ion-conduct-
ing glass-ceramic. The cooking surface was polished for
intimate contact with special bottom-polished Corning
Wareâ vessels. The material was improved in the early
1970s with higher temperature capability to allow cook-
ing with metal pans. In this case, a change in the com-
position was required to increase flexural strength at
stovetop use temperatures and to avoid staining by food.
It was found that adding 0.2 wt.% fluorine to the glass
created some surface compression, correlated with fluo-
ride volatilization from the surface and a relative densifi-
cation of the interior, where remaining fluoride aided
the precipitation of accessory dense spinel. The MOR
measured after abrasion was increased from 100 MPa to
about 140 MPa. Food staining was improved by replac-
ing the easily reduced rutile (TiO2-x) phase by the more
resistant polymorph: anatase.
Corning never deviated in the 1970s from the idea
of a white b-spodumene ss glass-ceramic cooktop.
Schott, however, was looking at translucent b-quartz ss
glass-ceramics with a zero CTE, perhaps because of the
success of Zerodurâ. They introduced a new “black”
rangetop glass-ceramic (Ceranâ),15 colored by cobalt
doping, which in b-quartz ss gives a dark purple in
transmitted light. Because this material had better infra-
red transmission than white opaque glass-ceramics,
heating of food was faster. In addition, the European
electric-range makers preferred black to white. The
result was a sharp increase in growth of this product.
Corning, who had by then exited the smaller white
market, returned with a dark rangetop in a joint ven-
ture with St. Gobain called Eurokera. They used a
zero-CTE b-quartz ss glass-ceramic doped with 0.1
wt.% V2O5. The advantage of vanadium- over cobalt
doping was improved infrared transmission and a dark-
red glowing appearance when the under-plate heat
source was a powerful tungsten-halogen lamp. Over the
years, electric cooking through dark glass-ceramic pan-
els became the standard, and this remains today the
largest market for glass-ceramics.
97
Transparent Glass-Ceramic Cookware
While Schott was working on dark stovetops in
the 1970s, Corning France developed a new transparent
and colored b-quartz ss glass-ceramic for rangetop
cookware. Under the Visionsâ label, this material was
introduced first in France as Visionâ and then across
the world. Both amber (from CoO-Cr2O3-doping) and
“cranberry” (from CoO-NiO doping) versions were
offered. The actual products included saucepans, deep-
dish casseroles, soup bowls, and even frying pans.
Machinable Mica Glass-Ceramics
In the late 1960s, as a former geologist with expe-
rience in field-work, I was thinking about ways of alter-
ing the microstructure of glass-ceramics to simulate
some of the unusual behavior of certain rocks. I was
aware that rocks like mica schist were soft and easily
drilled, yet difficult to fragment with dynamite. Could
mica, a layered mineral with excellent cleavage in its
basal (001) plane, be produced from a stable glass?
During World War II, there was a shortage of
mica used for radio capacitors. As a result, the U.S.
Bureau of Mines initiated research16 into the crystalliza-
tion of synthetic fluorine micas cooled slowly from the
melt. Fluoride was known by geologists to be capable
of at least partial substitution for hydroxyl in various
hydrous minerals such as micas and amphiboles. The
Bureau of Mines had the most success with fluoride
substitution in a certain variety of mica: phlogopite
[KMg3AlSi3O10(OH,F)2]. Based upon this work, I
tried to produce a stable glass containing the required
components and using MgF2 as a batch source of fluo-
ride. My approach was to add additional glass formers,
namely silica and alumina, to the KMg3AlSi3O10F2
stoichiometry. This resulted in an opal glass with one
phase rich in Mg and F. Upon heat treatment, MgF2
nuclei appeared and a fine-grained mica-containing
glass-ceramic developed. Unfortunately, the material
showed no obvious unique physical properties. The
electron microscope revealed no flake-like crystals, but
only thick books that resembled the geometry of typical
framework silicates, but the books did show some
cleavage on fracture surfaces. To try to change this
microstructure, B2O3 was added to the composition in
the hope that a lower viscosity glass might encourage
higher crystal growth rates that would favor a flake-like
morphology. This approach was successful in that it
98 International Journal of Applied Glass Science—Beall
produced tabular and partially interlocking crystals and
showed some machinability with a steel drill. Finally, I
thought of reducing the amount of potassium in the
glass to encourage the growth parallel to the basal
cleavage. The idea here was that by starving the glass in
the one element necessary to weakly bond the rigid
T-O-T sandwich layers (T = tetrahedral layer of SiO4
and AlO4, and O = octahedral layer of MgO6 and
MgO4F2), namely potassium, the flakes would grow
laterally yielding crystals with a higher aspect ratio.17
The result was a microstructure of flakes of high aspect
ratio, over 10:1. Thus, a random “house-of-cards”
microstructure was formed, causing blunting and
branching of cracks,18 and creating ease of machining
(drilling, turning, and sawing) with standard metal
tools.
Finally, a mica glass-ceramic optimized for glass
stability was released by Corning in 1970 as Macorâ
and found use in areas where machinability and excel-
lent dielectric and thermal insulating properties were
required. This included vacuum feed-through compo-
nents, ceramic prototypes, precision dielectric compo-
nents, medical components, and thermal insulating
supports at hinge points, windows and doors of the
Space Shuttle.
1980–1995
Chain Silicate Glass-Ceramics
After the development of glass-ceramics based on
layered silicates (Macorâ), I began considering whether
chain silicates might be used to reinforce glass-ceramics,
in analogy to glass reinforced with fibers of carbon or
silicon carbide. A fibrous variety of natural jade com-
posed of the chain silicate: nephrite, was known to be
strong and tough, but it contained no glass and was
formed at very high pressures. Would internally nucle-
ated rods or fibers really improve the mechanical prop-
erties of glass-ceramics, or, with no great advantage
likely in elastic modulus, would these acicular silicates
have any effect at all? Moreover, the simplest chain sili-
cates such as enstatite (MgSiO3), wollastonite
(CaSiO3), lithium metasilicate (Li2SiO3), and diopside
(CaMgSi2O6) are marginal glass formers because they
have Si:O ratios of 1:3 and contain only 50 mole% sil-
ica. Nevertheless, multiphase glass-ceramics containing
these phases had been developed at Corning and else-
where.
Vol. 5, No. 2, 2014
A search of natural chain silicate minerals turned
up one group of rock-forming double-chain silicates,
the amphibole group, with a particularly interesting
and possibly glass-forming mineral, richterite:
Na2CaMg5Si8O22(OH)2, and some rarer multiple
chain silicates such as canasite: K2Na4Ca5-
Si12O30(OH)4. These minerals had higher Si:O ratios
than single-chain silicates, namely 4:11 in the amphibo-
les and 6:15 for canasite. This suggested to me that
glasses would be more likely formed from these compo-
sitions, even though it would be necessary to use fluo-
ride as a replacement for hydroxyl.
Glass-Ceramics for Architectural Applications
White and gray glass-ceramics for architectural
cladding were introduced in Russia and Hungary in the
1960s. Rolled sheet was made from a variety of glasses
composed largely of metallurgical slag. These were heat
treated to form glass-ceramic products known as Slag-
Sitals19. Among the key crystal phases present were the
chain silicates: wollastonite and diopside. The nucleat-
ing agents involved were either sulfides or phosphates.
Nippon Electric Glass followed with a more deco-
rative glass-ceramic in the 1980s. Called NeopariesTM,20
this material resembles marble, and it is composed of
wollastonite and glass. Flat sheet in this case was made
by a process of sintering and crystallizing a coarse glass
frit. Oriented acicular crystals formed perpendicular to
the original frit interfaces, yielding a nodular and trans-
lucent texture on polishing.
Fire-resistant windows and doors based on
b-quartz ss glass-ceramics are also being manufactured
for their resistance to thermal shock. Schott Robaxâ,
Eurokera Keraliteâ, and NEG Neoceramâ are all
currently available.
Commercial Tableware Based on Potassium
Fluorrichterite
With the increased use of the microwave oven, it
became necessary to replace Corning’s Centuraâ table-
ware, which was largely based on the framework sili-
cate: soda nepheline (NaAlSiO4). Unfortunately, this
mineral contains sodium ions in channels that absorb
microwave energy and heat up faster in a microwave
oven than does the contained water. I was asked to try
to find a replacement with similar or better strength
and appearance.
www.ceramics.org/IJAGS Milestones in Glass-Ceramics
I knew of the two potential chain silicate candidate
crystals cited above and found that stoichiometric cana-
site not only formed an easily melted glass, but with
simple heat treatment to 850°C, it formed a glass-cera-
mic showing good flexural strength (300 MPa) and
fracture toughness (K1c = 4–5 MPa.m1/2). The micro-
structure as seen on fracture surfaces revealed interlock-
ing blade-shaped crystals with evident splintering,
accounting for the good toughness.21 Unfortunately,
glass-ceramics based on canasite crystallized from glass
only at relatively low viscosities (~109 Pa.s), and
pressed cups would not maintain their shape and would
sag during the crystallization heat treatment. This fact
prevented the use of these strong glass-ceramics for this
application.
Fortunately, I was able to hire a new PhD geolo-
gist, Linda Pinckney, who had written her doctoral the-
sis on chain silicates of the pyroxene group, and was
also very familiar with amphiboles. We were to become
long-term colleagues and close friends. We started this
project with a specific amphibole: potassium fluor-
richterite (KNaCaMg5Si8O22F2), which was chosen for
its glass-forming capability. We found that this glass
crystallized on heating to a fine-grained amphibole as
expected. However, it cracked in a complex spiderweb
fashion similar to that described earlier with stoichiom-
etric LAS glass-ceramics. This indicated that crystalliza-
tion of K-F richterite probably occurred at very high
viscosities. If we could eliminate the cracking, such a
glass-ceramic would not sag during crystallization, and
could allow manufacture of glass-ceramic tableware
without the use of expensive ceramic supports known
as “formers”. To eliminate the cracking, we increased
SiO2, lowered MgO, and added small amounts of
Al2O3, Li2O, BaO, and P2O5. These ingredients pro-
duced secondary phases in the K-F-richterite glass-cera-
mic, namely cristobalite and a mica (fluortaeniolite), as
well as about 20 wt.% residual glass.21 The acicular
nature of the K-F richterite helped increase the fracture
toughness of the glass-ceramic to 3.2 MPa.m1/2. More
importantly, the cracking was eliminated.
A secondary value of these composition modifica-
tions was a decrease in the liquidus temperature, thus
increasing the usable melt viscosity and allowing the
ample gob formation required for pressing large dinner
plates. After heating and crystallization, a surface glaze
of lower CTE than the glass-ceramic interior was
applied to increase strength (from 150 to 200 MPa)
and to allow under-glaze decoration. The final product,
99
called PyroceramTM Tableware, was sold for heavy-duty
use in hotels, restaurants, and institutions, and was also
used as cups and mugs to accompany the successful
Corelleâ line of thin opal plates.
Bio-Glass-Ceramics
Glass-Ceramics for Surgical Prostheses: One of the
most important developments in glass-ceramic technol-
ogy in the 1980s and early 1990s was the invention and
development of synthetic bone. Kokubo22 and his associ-
ates at Nippon Electric Glass used a compacted and sin-
tered glass powder of an appropriate formulation in the
SiO2-CaO(MgO)-P2O5-F system. Uniform crystalliza-
tion was achieved via surface nucleation, and the result-
ing product, Cerabone A-Wâ, became the most widely
used glass-ceramic for bone replacement. This material is
highly bioactive and forms a bond with living bone with-
out any connective tissue. Moreover, the bond is stronger
than the bone itself. The glass-ceramic is composed of
apatite: Ca5(PO4)3(OH,F), the inorganic crystal in
natural bone, and wollastonite (CaSiO3), a chain silicate
of acicular morphology. These two phases and glass are
present in the rough proportions of 3:2:2. The flexural
strength of this material is 215 MPa with a fracture
toughness of 2.0 MPa.m1/2.
The reaction mechanism that defines the bioactiv-
ity of Ceraboneâ involves a process in which Ca2+ ions
dissolve in simulated body fluid (SBF). Silanol (Si-OH)
groups on the surface of the glass-ceramic are favorable
sites for apatite nucleation. Additional Ca2+ ions and
phosphate groups are available through mass transport
from the surrounding body fluid. Cerabone A-Wâ has
been used successfully for artificial vertebrae, spacers,
and fillers. In the 1990s alone, 60,000 patients received
implants of this material.
Bioveritâ is 23a machinable glass-ceramic made by
Vitron Spezialwerkstoffe GmbH, Germany. It is com-
posed of fluormica and apatite and has been used for
middle-ear implants.
Glass-Ceramics for Dental Restoration: The first
glass-ceramic used for dental restorations was based on
a translucent fluormica referred to as tetrasilicic
(KMg2.5Si4O10F2) to distinguish from the trisilicic
phlogopite (KMg3AlSi3O10F2) used in Macorâ.
Named Dicorâ, 24this product was released in a
joint venture by Corning Inc. and Dentsply Interna-
tional. Though still machinable, this material was finer
100 International Journal of Applied Glass Science—Beall
grained and harder than Macorâ and also had the
proper translucency for simulating the appearance of
natural teeth. The flexural strength was given as
153 MPa, strong enough for complete crowns, but not
recommended for fixed partial dentures, abutments, or
dental bridges.
Ivoclar-Vivadent AG of Liechtenstein produced
surface-nucleated leucite (KAlSi2O6) glass-ceramic
ingots pressed from glass frit.25The lost-wax technique
was used to yield a suitable tooth mold. The glass-cera-
mic ingot was pressed into this mold at a viscosity of
1011 Pa.s. Over 33 million dental restorations have
been made from this material under the trade name
Empressâ since1991.
1995–2013
Lithium disilicate glass-ceramics, the first glass-
ceramic composition family dating back to the 1950s,
became the leading material for dental restorations as a
result of the research of my friend and frequent
co-author Wolfram H€oland and his collaborators at
Ivoclar-Vivident. The timeline of research on lithium
disilicate glass-ceramics, spanning several decades,
started with Corning’s photosensitive Fotoceramâ
(SiO2-Li2O-Al2O3-K2O) in the 1950s and was
expanded in the 1960s with phosphate-nucleated glass-
ceramics for electrical insulator materials (GEC, UK).
Following in the 1970s, research at Sandia National
Laboratories was aimed at high-CTE glass-ceramics
used to produce hermetic seals with metals.26 Then, in
the early 1990s, Corning attempted to make light-
weight, “self-glazing”, and strong lithium disilicate
glass-ceramics for airline service dishes using composi-
tions in the SiO2-Li2O-Al2O3-K2O-P2O5 system. Wol-
fram and his colleagues arrived at a similar composition
space for dental glass-ceramics at about the same time.
Ivoclar-Vivadent produced the first lithium disili-
cate dental product from a glass in the system SiO2-
Li2O-Al2O3-K2O-ZnO-La2O3 (Empress 2â). This
strong glass-ceramic was composed primarily of inter-
locking blade-like crystals. An improved product (IPS
e.maxâ) was developed in the composition system
SiO2-Li2O-Al2O3-K2O-ZrO2-P2O5, featuring finer
rod-like grains of Li2Si2O5 (1 lm 9 0.2 lm). This
glass-ceramic is suitable for molding and machining
and has excellent mechanical properties and chemical
durability. Flexural strength values of 530–670 MPa
Vol. 5, No. 2, 2014
and fracture toughness (K1c) of 3.1 MPa٠m½ were mea-
sured. As a result of this high strength and toughness,
IPS.e maxâ became the first glass-ceramic capable of
use as dental bridges, in addition to crowns, inlays, and
veneers.
Glass-Ceramics for Optical and Photonic
Applications
The application of nanocrystalline and transparent
glass-ceramics for cookware, telescope mirrors, and fire-
resistant windows were well known by the 1970s.
These applications all required a very low CTE for
dimensional stability and thermal shock resistance, and
the major crystal phase was always b-quartz solid solu-
tion. It was not until the late 1980s and 1990s that
applications requiring crystal luminescence or other
optical activity were considered, and it turned out that
b-quartz ss was a poor host for fluorescent cations and
the wrong space-group for optical activity.
This led to consideration of other nanocrystalline
glass-ceramics, some of which were curiosities discov-
ered in the 1960s. Such was the case for both ZrO2-
nucleated gahnite spinel (ZnAl2O4) and transparent
mullite (3Al2O3.2SiO2) glass-ceramics. The parent
glasses in both these systems were difficult to melt
below 1700°C. The glass-ceramics contained <50 per-
cent nanocrystals scattered in siliceous glass. Neverthe-
less, they could be doped with fluorescent cations such
as Ni2+ and Cr3+ that would partition faithfully into
the crystalline component. Pinckney27 was able to
develop a commercially meltable and formable trans-
parent spinel glass-ceramic composition by replacing
most of the nucleating agent ZrO2 with TiO2 and
some of the ZnO by MgO. Other additions were made
to help stabilize the parent glass against devitrification
during sheet rolling. This glass-ceramic, with a use tem-
perature >900°C and a CTE matching silicon, can be
considered as a substrate for polycrystalline photovoltaic
arrays. Similarly, mullite glass-ceramics were rendered
easier to melt by additions of B2O3 and K2O, and can
be doped with Cr3+ to produce short infrared fluores-
cence, allowing their consideration as luminescent solar
collectors.28
One of the major product requirements in optical
communications is increased bandwidth. To use more
of available spectral transmission allowed in silica glass,
broadband amplifiers are required. While Er3+ ions in
alumina-doped silica presently provide efficient lumi-
www.ceramics.org/IJAGS Milestones in Glass-Ceramics 101

nescence and adequate gain in the standard 1530– Improved Understanding of Nucleation via Advances
1570 nm telecommunication region, other host materi- in Instrumentation
als are required to improve gain at these wavelengths
X-ray diffraction (XRD), scanning and replica elec-
and to access a wider spectral region. Transparent glass-
tron microscopy (SEM, REM), transmission electron
ceramics containing fluoride nanocrystals, specifically
microscopy (TEM), and differential scanning calorime-
(Cd,Pb)F2,29 LaF3,30 and YF3,31 have been developed
try (DSC) have been the standard tools in understand-
to improve Er3+ gain and to access the 1300 nm tele-
ing nucleation and crystallization phenomena in glass-
communication band with Pr3+-doping. In addition,
ceramics. Recently, other important techniques have
upconversion can be achieved with Pr3+ in LaF3-con-
been developed, which shed further light on internal
taining glass-ceramics while quantum-cutting downcon-
nucleation phenomena, critical to integral glass-ceramic
version has been demonstrated by a combination of
formation. Two important examples of detailed work
Pr3+- and Yb3+-doping in b-YF3-containing glass-
are (i) nucleation and early phase development in the
ceramics.
IPS e.maxâ lithium disilicate dental product, and (ii)
Longer term exploratory research on transparent
nucleation of b-quartz ss in a composition closely
glass-ceramics doped with transition metals has indicated
related to the Schott Ceranâ rangetop product.
the potential of even wider bandwidth for future amplifi-
H€oland and associates at Ivoclar-Vivadent38 used
ers. For example, glass-ceramics based on Cr4+-doped
high-temperature XRD combined with DSC and NMR
forsterite32 (Mg2SiO4), a well-known laser crystal, dis-
to understand the sequence of events in nucleation and
play a wide fluorescence band from 1050–1350 nm, and
crystallization of their lithium disilicate dental glass-
lithium-aluminum-gallate spinel glass-ceramics doped
ceramics. The base glass was shown by29Si NMR to con-
with Ni2+ (LiGa5O8-LiAl5O8-Ga2O3: Ni)33 produce a
tain major quantities of Q3 (Si2O5)2 , with significant
band extending from 1200 nm to 1550 nm. Optical
Q4 (SiO2) and Q2 (SiO3)2 , but little Q1 (SiO4)4 Crys-
fiber waveguides were produced from each of these
tallization begins at 500°C with both lithium silicates
glass-ceramics. Together, these two in combination may
appearing, but with metastable Li2SiO3 predominant
produce amplification over the wide range: 1050–
over Li2Si2O5. The initial presence of Li2SiO3, which is
1550 nm.34
composed of Q2 units, is believed due to disproportion-
Glass-ceramics have also been developed for other
ation of Q3 in the parent glass to Q2 and Q4 units, the
photonic devices. Negative-CTE glass-ceramics were
latter forming residual siliceous glass. Surprisingly,
developed at Corning as a compensating substrate for
Li3PO4, long thought to be the nucleating phase in this
silica fibers in fiber-Bragg gratings. Sakamoto and
system, did not appear until 780°C. And yet, there is no
Wada35 have perfected dimensionally stable optical
internal nucleation without P2O5 present in this glass. In
connectors from b-spodumene glass-ceramics. Fujita et
fact, SEM photos taken from samples heated at 500°C
al36 have developed powder formed glass-ceramics
show easily etched spherical and noncrystalline phos-
based on Ce3+:-doped YAG garnet: (Y,Gd)5Al3O24.
phate-rich droplets in contact with primary nanoscaled
These materials show impressive broadband white fluo-
lithium silicate crystals. Therefore, it now appears that
rescence over the visible spectrum when excited by a
the original nucleation sites for crystallization are at the
blue LED at 465 nm.
interfaces between the phosphate-rich droplets and the
silicate glass matrix. The final microstructure of bladed
Glass-Ceramics for Solid Electrolytes in Lithium interlocking Li2Si2O5 with accessory Li3PO4 is devel-
Batteries oped at high temperatures near 850°C.
Bhattacharyya et al39 and H€oche et al40 have exam-
Interesting Li-conducting glass-ceramics (LiC-GCâ)
ined the nucleation sequence in a highly crystalline
based on the Nasicon structure have been developed
transparent b-quartz ss glass-ceramic composition
from multicomponent phosphosilicate glasses at Ohara,
related to the product Ceranâ, using cutting edge ana-
Inc.37 They can be formed as membranes by internal
lytical and imaging techniques performed in TEM.
nucleation or by tape casting and sintering of glass frit.
These studies indicate that nanocrystals of ZrTiO4, the
Conductivity values at room temperature have been mea-
nucleating crystal for b-quartz ss in this glass-ceramic,
sured up to 3 9 104 S/cm. The main crystal phase has a
form in about 30 min at 750°C reaching a small size of
composition given as Li1+xAlxGeyTi2-x-yP3O12.
102 International Journal of Applied Glass Science—Beall
4–5 nm in diameter. Increased treatment for 8 h does
not indicate any further growth of these crystals. This
unusual resistance to growth allows the nuclei to retain
their initial fine distribution and permits the develop-
ment of a nanocrystalline microstructure (40 nm) of
b-quartz ss in the final product. The reason for the
resistance to normal ripening of ZrTiO4 is explained by
the development of an observable alumina-rich shell
around the nuclei as they form. The shell is highly con-
centrated in Al2O3 for the first 1–2 nm and decreases
to the normal values in the bulk glass by about 8 nm.
This Al-rich zone is thought to prevent diffusion of Ti
and Zr species, thus prohibiting normal Ostwald
ripening. The effects of this shell may also cause the
first b-quartz ss crystals to be richer in alumina and
lower in silica than the b-quartz ss after full crystalliza-
tion. The question remains why does the alumina-rich
shell form in the first place? One likely possibility,
recently supported by TEM and x-ray absorption near-
edge-structure spectroscopy (XANES).38 is the existence
of an original amorphous nanophase separation rich in
Ti, Zr, and Al, from which the first crystalline ZrTiO4
nuclei precipitate upon heat treatment. Interestingly,
this result is in accordance with the Ti-Al-rich amor-
phous phase separation postulated in early studies of
nucleation in TiO2-nucleated b-quartz ss glass-ceram-
ics.5,6
Concluding Remarks
An important feature of commercial glass-ceramics
is their longevity. Of the glass-ceramics cited above,
Corning Wareâ was in continuous production for
40 years until Corning sold its Consumer Product Divi-
sion to World Kitchen Co. in the 1990s. It has been
recently re-introduced as Corning Wareâ PyroceramTM
by World Kitchen. Visionsâ transparent cookware, in
production from 1980 to 1995, has also been recently
brought back by the same company. Corning Code
9606, used for missile nosecones, has been in continuous
production for the past 55 years, and Macorâ machin-
able glass-ceramics, introduced in the early 1970s, has
been available for 40 years. Photosensitive glass-ceramics
like Fotoformâ are no longer made by Corning, but
Schott has introduced a similar material Foturanâ. Zero-
dur has been produced by Schott since the late 1960s,
and glass-ceramic electric cooktops have dominated the
electric-range market for the last 25 years.
Vol. 5, No. 2, 2014
Glass-ceramics have been increasingly used for den-
tal and surgical implants over the past 20 years. New
uses may include optical and photonic applications,
battery and fuel-cell components, substrates for semi-
conductors, and housings for mobile electronic devices.
Acknowledgment
The author thanks Dr. L. R. Pinckney for reading
and editing the manuscript.
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