International Journal of Research Studies in Science, Engineering and Technology

Volume 7, Issue 3, 2020, PP 1-16

ISSN : 2349-476X

Some Types of Glass-Ceramic Materials and their Applications

G. A. Khater1*, E.M. Safwat2, Junfeng Kang3, Yunlong Yue3, A.G. A. Khater4
1
National Research Centre, Glass Research Department, Cairo, Egypt
2
National Research Centre, Restorative and Dental Materials Department, Cairo, Egypt
3
School of Materials Science and Engineering University of Jinan, Jinan 250022, China
4
Ahram Canadian University, Faculty of Oral and Dental Medicine, Cairo, Egypt
*Corresponding Author: G. A. Khater, National Research Centre, Glass Research Department,
Cairo, Egypt.

ABSTRACT
Synthesis of glass-ceramics with tailored properties for diverse uses has always been a challenge for
scientist, a wide range of glass-ceramics was developed through combinations of different parent glass
compositions, along with, permutation of temperature, and time during the heat-treatment stage. Controlled
crystallization of glasses produces uniform reproducible fine-grain pores free, microstructures. Reinforcing
glass-ceramics and creating variable composites are conducted for obtaining the desired properties.
Several articles and books have been published discussing glass-ceramic production, properties and
applications. In this review article, a comprehensive study was made regarding the effect of different
synthesis protocols on the obtained glass-ceramic’s properties.
Keywords: glass-ceramic, properties, synthesis, reinforced glass ceramics, composites

INTRODUCTION Military, with products as wide ranging as fuel

cells through to safety glass and sup conductors.
The first glass-ceramic capable of being In the past decade, the use of glass-ceramics has
produced industrially was discovered in the
expanded in four major categories namely;
1950s by Stookey, 1960 [1] he was able to electronics, medicine and dentistry, optical
control the devitrification of glass by adding the materials and in severe thermal mechanical
nucleating agent TiO2. environments.
Several researches on sintered glass-ceramics
As for electronics, glass-ceramics have found
were published after Stookey’s discovery of the
major application in microelectronic packing,
controlled nucleation and crystallization of where as in medicine and dentistry, bio glass-
glass-ceramics [2][3]. ceramics have found wide use as implants.
However, as noted by McMillan [4], the sinter- In bone and in dental prostheses, as regards
crystallization was used even at the end of the optical materials, the dimensional stability,
nineteenth century. Glass-ceramic technology is lumine scence, or photosensitive characteristics
based on controlled crystal nucleation and of glass-ceramics can be exploited in a variety
growth in certain glass compositions, and has of new applications.
several advantages over conventional powder
processed ceramics, such as very low or null Whereas tough, fibrous glass-ceramics have
porosity, as well as uniformity and reproducibility been developed for severe thermal mechanical
of microstructure. environments. Figure 1 illustrates the steps of
glass-ceramics manufacturing process.
The crystalline phases precipitated in some
glass-ceramics have, for instance, low thermal Glass-ceramics demonstrating particularly
expansion coefficients coupled with high favorable properties were developed on the
thermal and chemical stability, high mechanical basis of two key advantages; the variation of the
strength and optical transparency [3]. chemical composition and of the microstructure
[3].
The Advanced ceramics industry supports many
industries, including, Aerospace, Automotive, These properties are briefly outlined and listed
Communication Computers, Medical, and in Tables 1 and 2.

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Some Types of Glass-Ceramic Materials and their Applications

Figure1. The glass-ceramic manufacturing process

Table1. Particularly Favorable Properties of glass-ceramics
Expansion can be controlled as desired, depending on the temperature, with zero
Thermal properties or even negative expansion being coefficients of thermal expansion possible
High-temperature stability
Transparency or translucency or opacity, Photo-induction is possible,
Optical properties
Pigmentation, Opalescence, fluorescence.
Chemical properties Durability, Biocompatibility, Bioactivity
Mechanical Properties Machinability, High strength and toughness.
Electrical and magnetic Isolation capabilities (low dielectric constant and loss, high resistivity and
properties breakdown voltage), Ion conductivity and superconductivity, Ferromagnetism
Table2. Particularly favorable combinations of properties of glass-ceramics (selection)
Mechanical property (machinability) + thermal properties (temperature resistance).
Thermal property (zero expansion + temperature resistance) + chemical durability.
Mechanical property (strength) + optical property (translucency) + Favorable processing properties.
Strength + translucency + biological properties + favorable processing properties.

GLASS-CERAMIC CONCEPTS or the free surface. If nucleation is formed at the

free surface, the resulting microstructure will
Two significant factors play the main role in the have large oriented crystals that are
production of fine-grained polycrystalline glass disadvantageous to mechanical properties but
ceramics. First, the compositions of the glass advantageous for piezoelectric and pyroelectric
utilized, as some glasses are difficult to devices [5] and machinable glass-ceramics[6].
crystallize, such as ordinary window glass, whereas However, for internal nucleation -also referred
others suffer uncontrolled crystallization
to as bulk nucleation- to occur, the chosen
resulting in undesirable microstructures. parent glass composition should contain species
Secondly, the heat treatment is critical to the to enhance the internal nucleation.
attainment of an acceptable and reproducible After formation of the stable nucleus, the
product. As will be discussed later, a range of crystals start to grow. The difference in volume
generic heat treatments procedures are used
or chemical free energy, ΔGv, between the glass
each of which has to be carefully developed and and crystalline states force atoms/molecules to
modified for a specific glass composition [3, 4] move from the glass, across the glass-crystal
The glass crystallization or devitrification, interface, and into the crystal.
process of glass represents one of the important The transport of atom/molecules across the
steps in glass ceramic preparation. This interface is thermally activated with an
heterogeneous transformation consists of two associated activation energy ΔGa. Models,
stages; the nucleation stage and the growth involving the terms ΔGv and ΔGa, have been
stage. developed for the temperature Dependence of
In the nucleation stage, small crystalline phases the growth rate and the form of the resulting
are formed at interfaces within the parent glass curve is given in Figure 2(a).

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Some Types of Glass-Ceramic Materials and their Applications

Figure2. Crystallization of a glass to form a glass-ceramic. (a) Insignificant overlap between nucleation and
growth rates (b) double-stage heat treatment.
TECHNOLOGIES OF GLASS - CERAMIC Modified Conventional Method (Single-
PREPARATION Stage)
Conventional Method (Two-Stage) The double-stage heat treatment of glass in the
conventional method is due to the limited
Devitrification of glass by two-stage heat overlap between the nucleation and growth rate
treatment is the conventional method for curves (Figure 2 (a). If there is extensive overlap
producing a glass-ceramic (Figure2 (b). The first of the rate curves then nucleation and growth
stage is a low temperature heat treatment at a can take place during a single-stage heat
temperature that gives a high nucleation rate treatment at temperature TNG as indicated in
(around TN in Figure 2a) thus forming a high Figure 3. The rate curves, particularly the
density of nuclei throughout the interior of the nucleation rate curve, is sensitive to composition,
glass. hence by optimizing the glass composition and
A high density of nuclei is important as it leads the included nucleating agents it is, in some
to a desirable microstructure consisting of a cases, possible to obtain the necessary overlap.
large number of small crystals. The second stage The pioneer glass-ceramic system utilized this
is a higher temperature heat treatment at around method is known as ―Silceram‖[7], as will be
temperature TG to produce growth of the nuclei explained in the next section.
at a reasonable rate.

Figure3. Crystallization of a glass to form a glass-ceramic by a single-stage heat treatment. (a) Temperature
dependence of the nucleation and growth rates with significant overlap (b) single-stage heat treatment.

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Some Types of Glass-Ceramic Materials and their Applications

Petrurgic Method DEVELOPMENT OF GLASS CERAMICS

It was found with ―Silceram‖ that it made little COMPOSITIONS
difference whether the glass was heated up to In recent years, new compositions, processing
TNG from room temperature or the molten glass methods and applications have begun to emerge.
was cooled to TNG [7]. This directed scientist to There are six basic composition systems which
produce certain glass-ceramics by a controlled, commercial glass-ceramics of economic
very slow cooling of the parent glass from the importance are made: (1) Li2O-Al2O3-SiO2,
molten state directly without a hold at an glass-ceramics of very low thermal expansion
intermediate temperature. coefficient; (2) MgO-Al2O3-SiO2 cordierite
With this method, referred to in the recent glass-ceramics of good mechanical, thermal, and
literature as the Petrurgic method [8], both dielectric properties; (3) Li2O-SiO2 glass-
nucleation and crystal growth can take place ceramics with photochemical etching capability;
during the cooling. Both the modified (4) Na2O-Al2O3-SiO2, nepheline glass-ceramics
conventional (single-stage) and the Petrurgic with high mechanical strength from
methods are more economical that the compression glazing; (5) K2O-MgO-Al2O3-
conventional method (two-stage). SiO2-F, machinablefluormica glass-ceramics;
and (6) CaO-MgO-Al2O3-SiO2, inexpensive
Powder Methods glass-ceramics from natural materials and
High temperature heat treatment (sintering) of slag[14].The following sections present details
cold-compacted powder is the common method of some of the above mentioned systems.
for the fabrication of ceramics and it has been Glass-Ceramics Based on Li2O-Al2O3-Sio2
likewise used for glass-ceramic manufacture [9,
10]. As there are limitations on the size and Glass-ceramics in the Li2O-AL2O3-SiO2 system
shape of components that may be cold have great commercial value because of their
compacted, and also a cost in producing a very low thermal expansion and excellent
powder, this method is only used if an obvious chemical durability[15]. These glass ceramics
benefit is identified. are based on either β-quartz or β-spodumene
solid solution crystal phases.The wide
In most cases there is little advantage in compositional range of these solid solutions
compacting and sintering a glass-ceramic allows one to tailor an essentially monophase
powder because a high sintering temperature is composition with only minor nucleant phases
required and the resulted glass-ceramics do not and residual glass.
have significant better properties than those
manufacturing by other techniques. Β-Quartz Solid Solution
It is more attractive to sinter a parent glass In the Li aluminosilicate system, a hexagonal
powder, which sinters by a viscous flow phase with β-quartz structure is known for
mechanism at lower temperatures [11]. It is compositions ranging from near SiO2 to
important to consider the rates of viscous flow LiAlSiO4. In other words, the β -quartz solid
sintering and crystallization and the interaction solution can be described as Li2O.Al2O3.nSi O 2
of these processes. , where n ranges from 2 to 10. Over most of this
range, β-quartz is actually a metastable phase.
If crystallization is too rapid the resulting high The Li-rich end member, LiAlSiO4 (β -
degree of crystallinity will hinder the low eucryptite), has an ordered arrangement of AI
temperature sintering leading to an unacceptable and Si, resulting in a doubling of its c axis, but
amount of porosity [12]. is otherwise structurally identical to the
Sol-Gel Precursor Glass intermediate members of this series;
compositions with n ≥ 4 have disordered Si/AI
So far only glasses produced from the molten distributions and are truly iso structural with β-
state have been considered but in the last SiO2.β-quartz glass-ceramics are made by
decades there has been considerable interest in crystallizing TiO2-or TiO2+ZrO2-nucleated Li
using sol-gel and colloidal techniques to obtain aluminosilicate glasses at 850-900°C[16].
the precursor glass in either powder or bulk Despite the metastability of β-quartz, these
form [13]. Glass-ceramics produced by all the glass-ceramics persist indefinitely and can
previous routes could be produced by sol-gel survive repeated thermal cycling provided that a
technique except that; they can’t be maximum temperature of about 900°C is not
manufactured from waste materials. exceeded. If heated about 900°C, β-quartz will

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Some Types of Glass-Ceramic Materials and their Applications

transform to β-spodumene. Table 3 lists the glass-ceramics from different manufactures and
compositions of three commercial β-quartz their areas of application [17].
Table3. Commercial glass-ceramics based on β-quartz solid solution (Wt.%)
Vision ZERODUR* Narumi*
Corning Schott Nippon Electric
SiO2 68.8 55.5 65.1
Al2O3 19.2 25.3 22.6
Li2O 2.7 3.7 4.2
MgO x1 1.8 1 0.5
ZnO 1 1.4
P 2O 5 7.9 1.2
F 0.1
0.2 0.5 0.6
Na2O
K 2O gl 0.1 0.3
BaO 0.8

2.7 2.3 2
TiO2 n
ZrO2 1.8 1.9 2.3

As2O3 f 0.8 0.5 1.1

0.1 0.03 0.03

Fe2O3
c
CoO 50 ppm
Cr2O3 50 ppm
Transparent Telescope Range tops,
cookware mirrors Stove windows
*As analyzed at Corning Glass Works, x1, oxides concentrated in crystal; gl, oxides concentrated in glass, n,
nucleating-agent oxides, f, fixing-agent oxide; c, colorant oxides.
Β-Spodumene (Keatite) Solid Solution obtained from heat treatment at temperatures in
excess of 1000°C [18].
β-spodumene is a tetragonal phase that is
isostructural with keatite which, like β-quartz, is Table 4 lists the composition of two commercial
a polymorph of SiO2. β-spodumene is therefore β-spodumene glass-ceramics, one used for
characterized by the same stoichiometry as β- cookware and one for ceramic regenerators in
quartz, although the compositional range of the turbine engines [19]showed that the Li F
solid solution is more restricted, with n ranging addition increased from 0 to 5% in the Li2O-
from 4 to 10. β-spodumene glass-ceramics can Al2O3-SiO2 system decreased the thermal
be made from the same glasses that yield (β - expansion coefficient from 8.3 x 10-7 to 5x10-7
quartz glass-ceramics simply by altering the /°C (25°C to 900°C). Table4. Composition of
heat treatment: β-quartz glass-ceramics are transparent glass-ceramics based on β-
formed by crystallizing at or below 900°C, spodumene Solid Solution (Wt.%) [17]
whereas β-spodumene glass-ceramic are
Table4. Commercial glass-ceramics based on β-spodumene solid solution
CORNING WARE CERCOR Corning
(Wt. %) (mol %) (Wt. %) (mol%)
SiO2 69.7 73.6 72.5 75.9
Al2O3 17.8 11 22.5 13.6
Li2O x1 2.8 5.9 5 10.5
MgO 2.6 4.1
ZnO 1 0.8
Na2O 0.4 0.4
gl
K2O 0.2 0.1

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Some Types of Glass-Ceramic Materials and their Applications

TiO2 4.7 3.7

n
ZrO2 0.1 0.1
Fe2O3 c 0.1 0.1
As2O3 f 0.6 0.2
Cookware, Heat exchangers,
hot plates regenerators
in crystal; gl, oxides concentrated in glass, n, nucleating-agent oxides, f, fixing-agent oxide; c, colorant oxides.
Mgo-Al2O3-Sio2 Glass-Ceramics Based on be present include cristobalite in the high silica
Cordierite compositions and clino-enstatite (MgO.SiO2) or
forsterite- (2MgO.SiO2) for compositions
Glass-ceramics of the magnesia-alumina-silica
having high magnesium oxide contents.
type are of importance because they combine
good electrical insulation characteristics with The advantages of the hexagonal form of the
high mechanical strength and medium to low cordierite based glass-ceramics are their high
thermal expansion coefficients. These desirable strength, excellent dielectric properties, good
properties arise largely as a result of the thermal stability, and thermal shock resistance.
presence of alpha-cordierite (2MgO. 2Al2O3 The commercial composition is the - missile
.5SiO2) as a principal phase in glass-ceramics of nose cones -standard glass-ceramic nucleated
this type. This crystal appears upon heat- with titanium, its major constituent is cordierite
treatment of compositions throughout the whole (Mg2AL4Si5O18 ) with some ―Mg-beryl‖ solid
glass-forming region. Other phases which may solution (Table5).
Table5. Commercial Cordierite Glass-Ceramics [17]
Composition wt.% mol% Phases
SiO2 56.1 58.1
Al2O3 x1 19.8 12.1 Cordierite
MgO 14.7 22.6 Cristobalite
Rutile
CaO 0.1 0.1
TiO2 n 8.9 6.9 Mg-dititanate
As2O3 f 0.3 0.1
Fe2O3 0.1 0.1
Use: Radomes

Nano-Crystalline Microstructures material. Although a number of definitions of

bioactivity have been reported, one by Hench
Glass-ceramics with crystallites’ size less than
[21]is especially simple: the property of an
100 nm are called nano-crystals. The
implanted material that allows it to bond to
development of glass-ceramics based on such
living tissue.
small crystallites was one of the earliest
examples of nanotechnology [20], a term now It has been reported [22]that, bioactive
applied in the fabrication of carbon nanotubes, ceramics, glasses and glass-ceramics, are able to
sintered ceramics, sol-gel glass, etc. the volume form a biologically active carbohydro xyapatite
percent of nano-crystals in glass-ceramics vary layer directly with bone, this layer is chemically
from very few volume percent to more than 90 and structurally correspondent to the mineral
vol. %.Usually, the nano crystals are surrounded phase of bone, thus provides a strong interfacial
by glass matrix. To achieve such a fine bonding. Bioactive glasses and glass-ceramics
microstructure, the nucleation rate must be very have been developed in response to the need to
high, but the secondary crystal growth must be suppress interfacial mobility in implanted
suppressed. bioinert ceramics.
SYNTHESIS OF FUNCTIONAL GLASS- Thus, in 1967, Hench proposed, to the US Army
CERAMICS Medical Research and Development Command,
to conduct research with a view to change the
Bioactive Glass-Ceramics chemical composition of glasses, in order to
The concept of bioactive material is midway enable their interaction with the physiological
between those of inert material and resorbable system and provide chemical bonding between

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Some Types of Glass-Ceramic Materials and their Applications

living tissue and the implant surface. This away, agents. The bioactivity of CeravitalR is roughly
in 1971, Hench et al. [23]showed, for the first one-half that of BioglassR 45S5 (5.6 versus
time, that a material made by the man could 12.5). At present, CeravitalR implants are
bond to bone through stimulating positive exclusively used to replace the ossicular chain in
biological reactions at the material/tissue the middle ear, where loads are minimal and the
interface.[24]. The invention, named BioglassR, mechanical properties of this material are thus
was the first bioactive glass material ever more than adequate.
developed.
Cerabone® A/W
According to Hench and Wilson [25], bioactive
One of the glass-ceramics of more clinical
materials include hydroxyapatite (HA) ceramics,
success, be probably the denominated A/W,
glasses, glass ceramics and surface-active
which is constituted by two crystalline phases:
composite materials.
oxyfluorapatitoCa10 (PO4)6(O,F2) and wollast
Bioactive Glass-Ceramic Compositions onite (β- CaSiO3) and a residual vitreous phase.
This was originally developed by Kokubo et
Most biomedical glass-ceramics are based on
al.[29]and is commercially available under the
compositions similar to those of Hench’s
trade name CeraboneR A/W.
bioactive glasses (BioglassR)[26], however, all
of them have very low contents in alkali oxides. Its composition is shown in the Table 6.After
Table 6 summarizes the properties of bioactive some failed attempts of producing a glass-
glass ceramics used in the clinical field as ceramic of the Ca3(PO4)2- SiO3-MgCa(SiO3)2
compared to those of BioglassR 45S5. system, starting from a monolithic glass or even
powdered glass, the glass-ceramic A/W was
Ceravital®
obtained by adding a small amount of CaF2 to
The earliest glass-ceramic material of clinical the original composition.
use was developed by Bromer and Pfeil in 1973
Glass ground to an average particle size of 5 μm
[27]and named CeravitalR. This designation,
was isostatically pressed at 200 MPa in the
however, includes a wide range of glass-ceramic
desired shapes and thoroughly densified at ca.
compositions. Originally, CeravitalR was
830 oC, which resulted in the precipitation of
believed to possess extraordinary properties as a
oxyfluorapatite and β- wollastonite at 870 and
replacement material even for bone in loaded
900 oC, respectively. The end-product was thus
zones and teeth.
a glass-ceramic with a very fine microstructure
However, as can be seen from Table 6, their free of cracks and pores.
mechanical properties, even for the optimum
The special microstructure of this glass-ceramic
compositions, they are below the 160 MPa of
endows it with the best mechanical properties
the human cortical bone and are similar to those
among all the materials shown on Table 6; thus,
of sintered dense hydroxyapatite (115
it’s of (220 MPa) is nearly twice that of dense
MPa).Also, long-term in vivo tests questioned
hydroxyapatite (115 MPa) and exceeds that of
the stability of these materials. However,
human cortical bone (160 MPa). In addition, its
subsequently Gross et al. [28]developed improved
tenacity is ca. 2.0 MPaAm–1/2 and its Vickers
compositions, the solubility of which was
hardness about 680 HV[30].
reduced by using various metals as nucleating
Table6. Composition and selected properties of glass-ceramics with clinical applications as compared to those
of Bioglass 45S5
Compound(wt.%) Bioglass45S5 Ceravital* Cerabone A/W Ilmaplant * Bioverit*
Na2O 24.5 5-10 0 4.6 3-8
K2O 0 0.5-3.0 0 0.2 0
MgO 0 2.5-5 4.6 2.8 2-21
CaO 24.5 30-35 44.7 31.9 10-34
Al2O3 0 0 0 0 8-15
SiO2 45.0 40-50 34.0 44.3 19-54
P2O5 6.0 10-50 6.2 11.2 2-10
CaF2 0 0 0.5 5.0 3-23
Apatite + Apatite +
Apatite +β-wollast.
Phases Glass Apatite +Glass β-wollast. Flogopite
+ Glass
+ Glass + Glass
Flexural Strength of 42 100 – 150 220 170 100 – 160

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Some Types of Glass-Ceramic Materials and their Applications

(MPa
CompressiveStrength
n.d 500 1060 n.d 500
(Mpa)
Young’s Modulus(GPa 35 n.d 117 n.d 70 - 88
n.d = not determined
Equally that in the bioactive glasses, an appetite nucleation and subsequent growth of the crystal
layer is formed on the surface of the glass- phases, by thermal treatment at 610 and
ceramic A/W in simulated body fluid and it is 1050oC.
also attributed to this layer the capacity of joint
The resulting product consists of residual glass
to bony tissue. Due to the chemical and
plus a mixture of apatite crystals (1-2 μm in
structural characteristics of this CHA, similar to
size) and a fluoroflogopite-like mica
the bony tissue, it is of expecting that, in the
(Na/KMg3[AlSi3O10F2]) which facilitates
interface with the bone, proliferate the
machining of the material.
osteoblasts preferably to the fibroblasts.
Subsequently, the same authors developed
However, unlike bioactive glasses, no
another family of also readily machined glass-
amorphous silica layer between the carbohydro
ceramics, which they called BioveritR II. As can
xyapatite (CHA) and the A/W glass-ceramics
be seen from Table 7 , the new materials
has been observed not even by high resolution
contained very little P2O5 relative to BioveritR
electron microscopy. In any case, Kokubo and
I. Like its predecessor, BioveritR II contains
coworkers believe that silanol groups formed at
fluoroflogopite-like mica, (whose crystals
the glass ceramic surface are those responsible
present a curved morphology that are not
for the formation of the CHA layer as they
encountered in nature), in addition to other
provide the favorable sites required for its
crystalline compounds, specially prominent
nucleation and growth.
among of cordierite (Mg2[Si5Al4O4]).
Their hypothesis relies on the following
Finally, Vogel and Holland[33]developed a
mechanism for the formation of the CHA layer
further family of glass-ceramics named
on A/W glass-ceramics: dissolution of calcium
BioveritR III (see Table 7) from a phosphate
ions from the glass-ceramic surface increases
glass containing no silica. To this end, they used
the ionic activity product of apatite in the
an inverted phosphate glass in the P2O5-Al2O3-
simulated body fluid, while hydrated silica at
CaO-Na2O system, consisting of mono- and
the glass-ceramic surface provides favorable
diphosphate structural units and doped it with
sites for CHA nucleation.
Fe2O3 or ZrO2. The end product consisted of
Imaplant-L1® residual glass in addition to apatite, berlinite
(AlPO4) and complex structures of phosphates
Berger et al. [31] developed this implant, which
of the varulite-like type (Na-Ca-Fe phosphate).
consists of apatite/wollastonite glass-ceramic.
As can be seen from Table III, it differs from The contents in crystalline phases and vitreous
A/W glass-ceramics in its alkali contents; matrix in BioveritR glass-ceramics can be
increased proportions of CaF2, SiO2 and P2O5; modified with a view to modulating their
and decreased content in CaO. Because of its physical properties and bioactivity by changing
low mechanical bending strength (see Table 6), the ingredient contents within the composition
its use is restricted to maxillofacial implants. ranges shown in Tables 6 and 7. Thus,
translucence in these materials is a function of
Bioverit®
the proportion of crystal phases, whereas
In 1983, Holland et al.[32], of the University of machinability depends on their mica content
Jena, developed a new series of bioactive glass- (e.g. BioveritR II is easier to machine than is
ceramics, which they called BioveritR I (Table BioveritR I). In addition, the material color can
6). BioveritR glass-ceramics can be readily be modified by addition of small amounts of
machined with standard tools and even oxides such as NiO, Cr2O3, MnO2, FeO, Fe2O3,
retouched in the operating theatre. etc.
These materials are obtained from a silicate- By the mid-1990s, more than one thousand bone
phosphate glass of complex composition in the replacement implants had been successfully
SiO2-Al2O3-MgO-Na2O-K2O-F-CaO-P2O5 fitted in various biomedical fields including
system. The procedure involves generating orthopedic surgery (e.g. acetabular reconstruction,
phase separation in the glass, through controlled vertebral replacement, tibial head osteoplastic,

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Some Types of Glass-Ceramic Materials and their Applications

joint plastic surgery) and head and neck surgery number of substrates, including dense alumina
(middle ear implants, orbital base repair, cranial [34], various types of stainless steel [35], cobalt-
base reconstruction, rhinoplasty, etc.). chromium alloys [36]and titanium alloys[37,
38]. This last alloy is especially attractive on
Bioactive Glass Coatings and Composites
account of its high strength, low elasticity
As noted earlier, the greatest constraint on a modulus and good biocompatibility.
wider use of bioactive glasses and glass-
The methods used to prepare the coatings range
ceramics is derived from their relatively poor
from immersion in the molten glass or in a
mechanical properties, especially in zones under
solution, suspension or gel (dip coating);
mechanical loads. This shortcoming has been
electrophoresis from a solution or suspension
circumvented by using various methods to
(the metal to be coated acting as an electrode),
increase the strength of these glass materials and
biomimetic coating growth or flame or plasma
facilitate their use as implants. One solution to
spraying. Plasma spraying is the method of
the problem is using bioactive glasses as a
choice when depositing a bioactive glass onto a
coating for materials with a high mechanical
metal substrate.
strength. This method has been used with a
Table7. Composition and selected properties of the Bioverit types II and III
Compound Bioverit II(wt.%) Bioverit III(wt.%)
SiO2 43 – 50 ---
Al2O3 26 – 30 6 – 18
MgO 11 – 15 ---
Na2O/K2O 7 – 10.5 11 – 18
F 3.3 – 4.8 ---
Cl 0.01 – 0.6 ---
CaO 0.1 – 3 13 – 19
P2O5 0.1 – 5 45 – 55
(MeO/Me2O5/MeO2)* --- 1.5 - 10
Density (gr/cm3) 2,5 2.7 – 2.9
Coefficient of Expansion (K-1) 7.5 – 12 ・ 10-6 14 – 18 ・10-6
Flexural strength (MPa) 90 – 140 60 – 90
Toughness (KIC) (MPa・m.) 1.2 – 1.8 0.6
Young’s Modulus (GPa) 70 45
Compressive strength (MPa) 450 ---
Vickers hardness (HV 10) up to 8000 ---
Hydrolytic Class (DIN 12111) 1-2 2–3
Roughness(after polishing) (μm) 0.1 ---
* (MnO, CoO, NiO, FeO, Fe2O3, Cr2O3, ZrO)
Another application of bioactive glasses is in the glass (CEL2) belongs to the system SiO2-P2O5-
production of composites, being reinforced the CaO-MgO-Na2O-K2O and has been synthesized
bioactive glass with a second phase. The by a conventional melting-quenching route.
materials thus obtained include ―biofibre glass‖ Slurry of CEL2 powder, polyvinyl alcohol and
and alumina, organic polymers or metal fibers. water has been prepared in order to coat, by
The former has fallen short of the original impregnation, the polymeric template. An
expectations as it seemingly releases large optimized thermal treatment was then used to
amounts of alumina powder that are detrimental remove the sponge and to sinter the glass
to tissues. The materials reinforced with metal powders, leading to a glass-ceramic replica of
fibers are those with the strongest potential. In the template. Morphological observations,
fact, metal fibers strengthen bioactive glasses image analyses, mechanical tests and in vitro
and improve their deformability. The most tests showed that the obtained devices are good
widely used procedure for producing these candidates as scaffolds for bone-tissue
materials is hot pressing [39]. engineering, in terms of pore-size distribution,
pore interconnection, surface roughness, and
Scaffolds for Bone Tissue Engineering
both bioactivity and biocompatibility. In
Macro porous bioactive Glass-ceramic scaffolds particular, a human osteoblast cell line (MG-63)
was developed for tissue engineering via seeded onto the scaffold after a standardized
polyurethane sponge template. The starting preconditioning route in simulated body fluid

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Some Types of Glass-Ceramic Materials and their Applications

showed a high degree of cell proliferation and a phases present in the microstructure to minimize
good ability to produce calcium nodules. The the light scattering. To achieve this objective,
obtained results were enhanced by the addition the targets are: 1) develop glasses with high
of bone morphogenetic proteins after cell refraction indexes, comparable to those of the
seeding [40]. reinforcing ceramic phases; 2) develop ceramic
composites infiltrated with glass under pressure;
Glass-Ceramics for Dental Hypersensitivity
3) study and understand the optical phenomena
Treatment
of light scattering of the new composites using
Dentin hypersensitivity is a common dental pain the Kubelka-Munk model; and 4) characterize
arises when subjecting tooth to thermal, the mechanical properties of composites [42].
chemical or tactile stimuli, it occurs due to loss
A recent study revealed comparable properties
of minerals from tooth, attempts to replace these
of mica glass ceramics containing 20 wt.% YSZ.
minerals was investigated. bioactive glasses was
particular, to the commercially available IPS
first used as a dental hypersensitivity treatment
emax Press and IPS emax CAD as regards
in SensodyneVR toothpaste containing
mechanical and chemical durability. [43]
BioglassVR 45S5 particulate named Nova Min
VR was in 2004. Transparent Glass-Ceramics
Bioactive glass-ceramics as BiosilicateVR was Some successful and many trial optical
also introduced, its composition[23, 24] applications have been proposed for transparent
23.75Na2O–23.75CaO–48.5SiO2-4P2O5 (wt %). glass-ceramics: cookware (Vision) that allows
its microstructure can be engineered to be continuous visualization and monitoring of the
composed of one or two crystalline phases cooking process); fireplace protection;
through controlled double-stage heat treatments, transparent eyeshields; transportation windows;
these two phases are: a sodium-calcium silicate substrates for LCD screens; ring laser
phase (Na2CaSi2O6) or both and sodium-calcium gyroscopes; rockets’ fronts; fiber grating
phosphate (NaCaPO4).[41] athermalization; precision photolithography;
printed optical circuits.
Infiltrated Ceramic Composites for Dental
Prostheses As for telescope mirrors (Zerodur), the
telescope’s optical components should resist
In the last years, many bioceramics and
distortions caused by temperature fluctuations.
processing methods for all-ceramic prosthesis
Therefore, they utilize glass-ceramics with zero
have been developed, because these materials
expansion.
can result in dental restorations with improved
biocompatibility, chemical stability, and Wavelength up-conversion devices for
aesthetic qualities compared to metals and europium-doped waveguide amplifiers uses
polymers restorations. The market of dental fluoride, chalcogenide and oxyfluoride-based
bioceramics is growing rapidly in Brazil and transparent glass-ceramics, doped with rare-
abroad. Despite the recent developments, earth ions. Transparent mullite, spinel,
bioceramics used as core materials still need to willemite, gahnite and gelenite based glass-
be improved in relation to their optical ceramics doped with transition-metal ions have
characteristics as well as to their mechanical been developed for use in tunable and infrared
properties. lasers, solar collector and high-temperature
lamp applications. Glass-ceramics that exhibit
The aim of this project is to develop a new
second harmonic generation and material with
method of preparation of ceramic composites
high kerr constant for electroopical devices have
infiltrated with glass with improved optical
been developed as well. The combination of
transmission and high mechanical properties for
several properties is the hallmark for their
use in dental prostheses. A new method for the
success [42].Other optically active applications
production of cores of ceramic-glass composites
include luminescent glass-ceramics for solar
is proposed, in which the infiltration of the glass
concentrators, up-conversion and amplification
in the partially sintered perform is conducted
devices; illumination devices using IR; heat-
under pressure. This method is a hybrid
resistant materials that absorb UV, reflect IR
technique between the systems In-Ceram Vita
and are transparent to visible light; materials
Zahnfabrik) and Empress (Ivoclar). Using this
that absorb UV and fluoresce in red/IR;
method, it is expected to develop translucent
substrates for arrayed waveguide grating; solid-
composites by decreasing the porosity and
state lighting – white light; and laser pumps.
matching the optical characteristics of the

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Some Types of Glass-Ceramic Materials and their Applications

To be transparent in the visible range, a glass- system, and the G–C commercial systems based
ceramics must have one or a combination of the on spodumene, cordierite, nepheline, and leucite
following characteristics: the crystal size must were melted and water quenched to obtain
be much less than the wavelength of visible powdered glasses (or frits). The glasses/frits
light (i.e., less than 200 nanometers); and the obtained were subsequently applied to
birefringence must be very low or there must be stoneware tiles , as is usual in the production of
negligible difference between the refractive ceramic pavements.
indexes of the residual glass matrix and the
An industrial fast firing to 1100°C for 30 min.
crystals.
was used, during which the (nucleation 1
This is the case in most existing transparent growth) stages were accomplished in the thin
glass-ceramics, as they have crystals size less layer of glassy coating (approx. 0.3 mm). In
than 200 nanometers and a crystallized fraction some cases, a complementary (nucleation 1
of only 1 to 70 percent. However, an interesting growth) thermal treatment was carried out, in
new discovery was recently reported by [44]. order to recrystallize the residual glassy phase
They developed a large grain (about 10-50 remaining after the fast-firing cycle.
micrometer), highly crystalline (97 percent) and
In these cases, the temperature used for the
transparent glass-ceramic.
additional thermal treatment was that of the
New Types of Glass-Ceramic Glazes main DTA exothermic crystallization peak
(DTA conditions: heating rate of 10°C/min. and
For many years, ceramists have known that
cooling rate of 30°C/min.). The final result was
certain glaze compositions are susceptible to
tiles with glass-ceramic glazes containing
large visible crystallization effects when they
several volume percent of crystals.[49]
are applied as coatings on decorative ceramic
ware[45]. Likewise, formerly, glass beads used The feldspar composition produced a very stable
to have opaque or opalescent heterogeneity glass with respect to nucleation and
colors and natural stones appearances due to crystallization, whereas the cordierite glass
crystallization in either the bulk or surface.[46]. showed two exothermic peaks at 800 and 920°C
Both controlled nucleation and crystallization of due to the precipitation of α- and β-cordierite
glasses have been widely developed since the phases.
1960s, due to the wide interest in the production
The difficulty of crystallization made it
and commercial exploitation of glass ceramic
necessary to introduce some nucleating
products in domestic and technological
agents[50] into several of the glassy
applications [2].
compositions considered here, mainly in the
Not much investigation, however, has been case of the most thermally stable glassy frits.
devoted to the production of glass-ceramics in Table 8 gives the glass systems investigated,
thin layers, although surface crystallization together with the crystalline phases precipitated
phenomena in glasses have been investigated after fast thermal treatment at 1000°C for 30
[47]. Yet, these studies considered surface min. As can be seen in Figure 4, the
crystallization a consequence of defects in crystallization microstructure of the surface of
glasses or a transitional stage during formation these glass-ceramic glazes is different
of bulk crystallization of glass-ceramics. depending on the crystalline phase and
composition of the original glassy matrix. SEM
In recent years, there has been a growing
observation of the microstructure of the cross
interest in ceramic glazes and frits for
section of the glaze/substrate interface revealed
developing new glaze compositions that can be
many bubbles indicating high volume of
crystallized in order to improve the mechanical
crystallization exists and coarse crystallization
and chemical properties of fast-fired glazed
in some thin layer glazes.
tiles. Nucleation and crystallization of thin
layers of certain glasses covering ceramic Therefore, in those cases where there was a high
substrates (glazes) to obtain high-performance tendency to crystallize, it was necessary to
glass-ceramic coatings[48], are scientific and dilute the original frits with some commercial
technological challenges due to the difficulties boro-zinc silicate frits, which likewise were
of controlling crystal growth homogeneously. phase separated [50]. This enabled the
Several parent glasses from a wide range of crystallization process to be better controlled, as
compositions in the CaO–MgO–Al2O3–SiO2 can be observed in the SEM micrograph shown
system, the Li2O–ZnO/BaO–Al2O3–SiO2 in Figure 5.

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Some Types of Glass-Ceramic Materials and their Applications

Table8. Glass Frits and Crystalline Phases Obtained After Blade Deposition and Fast Firing Over Ceramic
Substrates of Earthenware Tiles
Composition system Main crystal phase Microstructure
Spodumene rounded crystallites
cordierite dot crystals
Li2O-CaO-MgO-Al2O3-SiO2
diopside square/rounded crystals
diopside 1 anorthite elongated and prismatic crystals
Cordierite grained crystals
G-C commercial systems
spodumene prismatic crystals
Li2O-ZnO/BaO-Al2O3-SiO2 nepheline/celsian needle crystals
Li2O-K2O-Al2O3-SiO2 leucite as whiskers 1-2 mm crystals

Figure4. SEM micrographs from glass-ceramics glazes of (a) spodumene, (b) cordierite, (c) nepheline, and (d)
leucite.

Figure5. SEM micrograph obtained from a perpendicular cross section of the nepheline glass-ceramic glaze
diluted with a commercial frit.
This dilution advances the abrasion and and interfaces agrees well with the models of
hardness of the glaze surface through permitting surface nucleation recently developed by
a reticular crystalline microstructure embedded Schmelzer et al. [47]. Contrary to bulk glasses
in the original residual glassy phase to be crystallization mechanisms and comparable to
attained. In the case of the spodumene glaze, the sintered powdered glasses, this case has three
dilution allowed the precipitation of crystals different nucleating interfaces; viz., air/surface
between the cracks produced by the different of glaze, substrate/glaze interface, and frit/frit
expansion coefficient of the spodumene glassy interface. A wide range of crystallization
matrix and the solvent frit (Fig. 5). This type of microstructures has been achieved by this
nucleation of crystals associated with the cracks processing, depending on the original glass

12 International Journal of Research Studies in Science, Engineering and Technology V7 ● I3 ● 2020

Some Types of Glass-Ceramic Materials and their Applications

composition. However, the very short time for and preliminary irradiation stability. The phases
the growth step makes it difficult to obtain high identified in these glass ceramics were
percentages of volume crystallization. Crystals oxyapatite, powellite, cerianite, and lanthanide –
ranging in size from less than 1 mm to elongated borosilicate.[51]
crystallites larger than 20 mm precipitated in the
Glass-Ceramic Armor
glassy matrix of the coating were obtained.
Some patents have been filed and others have
been granted for inventions related to armor
material for the protection of people or
equipment against high speed projectiles or
fragments. Ceramic material is used particularly
in armors for which low weight is important:
bullet-proof vests; and armor for automobiles,
aircraft and helicopters, especially in cockpits or
seats and for protection of functionally
important parts. Hard, high modulus Al2O3,
despite its high density ( ~ 4 gm / cm3)remains
the gold standard ceramic armor material. Other
very hard, but less dense materials, such as SiC
and B4C, can be produced only at very high
temperatures by costly manufacturing processes
and are, hence expensive.
Inexpensive Glass-Ceramics Based On Slag
The principal proposed usage for basalt and slag
Figure6. Nucleation of spodumene star crystals, or derived glass ceramics is in the form tiles and
incipient dendrites, in the S2 glaze composition. pipes for the conveyance or storage of abrasive
Glass Ceramics for Nuclear Waste materials (e.g. coal) where the glass ceramics
Immobilization are much more resistant to abrasion than
alternative metals and out in the UK and the
Glass-ceramic waste form has been USA[52] a great deal of development and use
development to immobilize fission-product has been undertaken in Russia [53]. It is an
generated by the uranium extraction separations indication of its value that it is claimed that this
process. The glass ceramics were slow-cooled application may represent the greatest use of
and characterized in terms of phase assemblage glass ceramics worldwide.
Table9. Commercial glass-ceramic materials and their applications
Basic Chemical System Unique properties Product
Photosensitivity and differential solubility of Substrates; fine-mesh screens;
Li2O – SiO2 phases leads to ability to form intricate fluidic devices; printing-plate
patterns molds; spacers
Cookware; burner covers;
Li2O-Al2O3- SiO2 Low expansion, thermal shock resistance preheaters; mirror substrates; low
expansion housing; valve parts
MgO – Al2O3 – SiO2 High strength, good dielectric properties Radomes; antenna windows
Pacemater parts; welder’s fixture
K2O – MgO – Al2O3 –
Machinable holder; welding nozzles; circuit
B2O3 – SiO2 – F
bases
Industrial floor coverings, wall
CaO – MgO Fe2O3 –
Abrasion resistance facings; abrasion resistant linings;
Al2O3SiO2
high temperature insulators
Floor coverings; wall facings;
CaO – ZnO – Al2O3 – SiO2 Abrasion resistance
counter tops
Selective-ion evaporation at elevated
B2O3 – Al2O3 – SiO2 Semiconductor doping sources
temperatures
P2O5 –Al2O3 – SiO2 Elevated temperatures
Na2O – Al2O3 – SiO2 Good strength Dinnerware
Li2O – CeO2 – Al2O3 – Chemical durability; mechanical toughness Coatings for chemical reactor

International Journal of Research Studies in Science, Engineering and Technology V7 ● I3 ● 2020 13

 Some Types of Glass-Ceramic Materials and their Applications

SiO2 accessories
BaO – Al2O3 – SiO2 Specific expansion coefficient Alloy bonding
Li2O – BaO – SiO2 Dielectric properties Insulators in devices

CONCLUSIONS glass by the petrurgic method, Journal of

materials science letters, 21 (2002) 975-980.
 Glass-ceramic technology is based on [9] P. Hing, V. Sinha, P.B. Ling, The effects of some
controlled crystal nucleation and growth in processing parameters on the sinterability,
certain glass compositions. microstructures operties of sintered cordierite
glass ceramics, Journal of materials processing
 Technologies of glass-ceramic preparation
technology, 63 (1997) 604-609.
include:
[10] K. Lambrinou, O. Van der Biest, A. Boccaccini,
Conventional Method (Two-Stage) D. Taplin, Densification and crystallisation
behaviour of barium magnesium aluminosilicate
Modified Conventional Method (Single-Stage) glass powder compacts, Journal of the European
Petrurgic Method Ceramic Society, 16 (1996) 1237-1244.
[11] G.W. Scherer, Sintering of low‐density glasses:
Powder Methods
Part I. Theory, Journal of the American Ceramic
Sol-Gel Precursor Glass Society, 60 (1977 ) 239-243.
[12] E. Zanotto, M. Prado, Isothermal sintering with
 The basic composition systems which are concurrent crystallisation of monodispersed and
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BaO-AI2O3-SiO2. [15] H. Scheidler, E. Rodek, Li2O-Al2O3-SiO2 glass-
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 Glass-ceramics have different functions and (1989) 1926-1930.
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Citation: G. A. Khater, E.M. Safwat, Junfeng Kang, et al" Some Types of Glass-Ceramic Materials and
their Applications ", International Journal of Research Studies in Science, Engineering and Technology, vol.
7, no. 3, pp. 1-16, 2020.
Copyright: © 2020 G. A. Khater. This is an open-access article distributed under the terms of the Creative
Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any
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16 International Journal of Research Studies in Science, Engineering and Technology V7 ● I3 ● 2020