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Some Types of Glass-Ceramic Materials and their Applications

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

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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 glass or the free surface. If nucleation is formed

at the free surface, the resulting microstructure
Two significant factors play the main role in the will 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, However, for internal nucleation -also referred
whereas others suffer uncontrolled to as bulk nucleation- to occur, the chosen
crystallization resulting in undesirable parent glass composition should contain species
microstructures. Secondly, the heat treatment is to enhance the internal nucleation.
critical to the attainment of an acceptable and
reproducible product. As will be discussed later, After formation of the stable nucleus, the
a range of generic heat treatments procedures crystals start to grow. The difference in volume
are used each of which has to be carefully or chemical free energy, ΔGv, between the glass
developed and modified for a specific glass and crystalline states force atoms/molecules to
composition [3, 4] move from the glass, across the glass-crystal
interface, and into the crystal. The transport of
The glass crystallization or devitrification, atom/molecules across the interface is thermally
process of glass represents one of the important
activated with an associated activation energy
steps in glass ceramic preparation. This ΔGa. Models, involving the terms ΔGv and
heterogeneous transformation consists of two ΔGa, have been developed for the temperature
stages; the nucleation stage and the growth
stage. In the nucleation stage, small crystalline Dependence of the growth rate and the form of
phases are formed at interfaces within the parent the resulting 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
glass. composition, hence by optimizing the glass
A high density of nuclei is important as it leads composition and the included nucleating agents
to a desirable microstructure consisting of a it is, in some cases, possible to obtain the
large number of small crystals. The second stage necessary overlap. The pioneer glass-ceramic
is a higher temperature heat treatment at around system utilized this method is known as
temperature TG to produce growth of the nuclei ―Silceram‖[7], as will be explained in the next
at a reasonable rate. section.

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 There are six basic composition systems which

commercial glass-ceramics of economic
It was found with ―Silceram‖ that it made little
importance are made: (1) Li2O-Al2O3-SiO2,
difference whether the glass was heated up to
glass-ceramics of very low thermal expansion
TNG from room temperature or the molten glass
coefficient; (2) MgO-AI2O3-SiO2 cordierite
was cooled to TNG [7]. This directed scientist to
glass-ceramics of good mechanical, thermal, and
produce certain glass-ceramics by a controlled,
dielectric properties; (3) Li2O-SiO2 glass-
very slow cooling of the parent glass from the
ceramics with photochemical etching capability;
molten state directly without a hold at an
(4) Na2O-AI2O3-SiO2, nepheline glass-
intermediate temperature. With this method,
ceramics with high mechanical strength from
referred to in the recent literature as the
compression glazing; (5) K2O-MgO-AI2O3-
Petrurgic method [8], both nucleation and
SiO2-F, machinablefluormica glass-ceramics;
crystal growth can take place during the cooling.
and (6) CaO-MgO-AI2O3-SiO2, inexpensive
Both the modified conventional (single-stage)
glass-ceramics from natural materials and
and the Petrurgic methods are more economical
slag[14].The following sections present details
that the conventional method (two-stage).
of some of the above mentioned systems.
Powder Methods
Glass-Ceramics Based on Li2O-AL2O3-Sio2
High temperature heat treatment (sintering) of
Glass-ceramics in the Li2O-AL2O3-SiO2
cold-compacted powder is the common method
system have great commercial value because of
for the fabrication of ceramics and it has been
their very low thermal expansion and excellent
likewise used for glass-ceramic manufacture [9,
chemical durability[15]. These glass ceramics
10]. As there are limitations on the size and
are based on either β-quartz or β-spodumene
shape of components that may be cold
solid solution crystal phases.
compacted, and also a cost in producing a
powder, this method is only used if an obvious The wide compositional range of these solid
benefit is identified. In most cases there is little solutions allows one to tailor an essentially
advantage in compacting and sintering a glass- monophase composition with only minor
ceramic powder because a high sintering nucleant phases and residual glass.
temperature is required and the resulted glass-
Β-Quartz Solid Solution
ceramics do not have significant better
properties than those manufacturing by other In the Li aluminosilicate system, a hexagonal
techniques. It is more attractive to sinter a parent phase with β-quartz structure is known for
glass powder, which sinters by a viscous flow compositions ranging from near SiO2 to
mechanism at lower temperatures [11]. It is LiAlSiO4. In other words, the β -quartz solid
important to consider the rates of viscous flow solution can be described as Li2O.Al2O3.nSi O
sintering and crystallization and the interaction 2 , where n ranges from 2 to 10. Over most of
of these processes. If crystallization is too rapid this range, β-quartz is actually a metastable
the resulting high degree of crystallinity will phase. The Li-rich end member, LiAlSiO4 (β -
hinder the low temperature sintering leading to eucryptite), has an ordered arrangement of AI
an unacceptable amount of porosity [12]. and Si, resulting in a doubling of its c axis, but
is otherwise structurally identical to the
Sol-Gel Precursor Glass
intermediate members of this series;
So far only glasses produced from the molten compositions with n ≥ 4 have disordered Si/AI
state have been considered but in the last distributions and are truly iso structural with β-
decades there has been considerable interest in SiO2.β-quartz glass-ceramics are made by
using sol-gel and colloidal techniques to obtain crystallizing TiO2-or TiO2+ZrO2-nucleated Li
the precursor glass in either powder or bulk aluminosilicate glasses at 850-900°C[16].
form [13]. Glass-ceramics produced by all the Despite the metastability of β-quartz, these
previous routes could be produced by sol-gel glass-ceramics persist indefinitely and can
technique except that; they can’t be survive repeated thermal cycling provided that a
manufactured from waste materials. maximum temperature of about 900°C is not
exceeded. If heated about 900°C, β-quartz will
DEVELOPMENT OF GLASS CERAMICS transform to β-spodumene. Table 3 lists the
COMPOSITIONS compositions of three commercial β-quartz
In recent years, new compositions, processing glass-ceramics from different manufactures and
methods and applications have begun to emerge. their areas of application [17].

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Some Types of Glass-Ceramic Materials and their Applications

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
AI2O3 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
AI2O3 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

TiO2 n 4.7 3.7

International Journal of Research Studies in Science, Engineering and Technology V7 ● I3 ● 2020 5

Some Types of Glass-Ceramic Materials and their Applications

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.The
type are of importance because they combine
advantages of the hexagonal form of the
good electrical insulation characteristics with
cordieritebasedglass-ceramics are their high
high mechanical strength and medium to low
strength, excellent dielectric properties, good
thermal expansion coefficients. These desirable
thermal stability, and thermal shock resistance.
properties arise largely as a result of the
The commercial composition is the - missile
presence of alpha-cordierite (2MgO. 2Al2O3
nose cones -standard glass-ceramic nucleated
.5SiO2) as a principal phase in glass-ceramics of
with titanium, its major constituent is cordierite
this type. This crystal appears upon heat-
(Mg2AL4Si5O18 ) with some―Mg-beryl‖ solid
treatment of compositions throughout the whole
solution (Table5).
glass-forming region. Other phases which may
Table5. Commercial Cordierite Glass-Ceramics [17]
Composition wt.% mol% Phases
SiO2 56.1 58.1
AI2O3 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 [21]is especially simple: the property of an

implanted material that allows it to bond to
Glass-ceramics with crystallites’ size less than
living tissue.
100 nm are called nano-crystals. The
development of glass-ceramics based on such It has been reported [22]that, bioactive
small crystallites was one of the earliest ceramics, glasses and glass-ceramics, are able to
examples of nanotechnology [20], a term now form a biologically active carbohydroxyapatite
applied in the fabrication of carbon nanotubes, layer directly with bone, this layer is chemically
sintered ceramics, sol-gel glass, etc. the volume and structurally correspondent to the mineral
percent of nano-crystals in glass-ceramics vary phase of bone, thus provides a strong interfacial
from very few volume percent to more than 90 bonding.Bioactive glasses and glass-ceramics
vol. %.Usually, the nano crystals are surrounded have been developed in response to the need to
by glass matrix. To achieve such a fine suppress interfacial mobility in implanted
microstructure, the nucleation rate must be very bioinert ceramics.
high, but the secondary crystal growth must be
Thus, in 1967, Hench proposed, to the US Army
suppressed.
Medical Research and Development Command,
SYNTHESIS OF FUNCTIONAL GLASS- to conduct research with a view to change the
CERAMICS chemical composition of glasses, in order to
enable their interaction with the physiological
Bioactive Glass-Ceramics system and provide chemical bonding between
The concept of bioactive material is midway living tissue and the implant surface. This away,
between those of inert material and resorbable in 1971, Hench et al. [23]showed, for the first
material. Although a number of definitions of time, that a material made by the man could
bioactivity have been reported, one by Hench bond to bone through stimulating positive

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Some Types of Glass-Ceramic Materials and their Applications

biological reactions at the material/tissue versus 12.5). At present, CeravitalR implants are
interface.[24]. The invention, named BioglassR, exclusively used to replace the ossicular chain in
was the first bioactive glass material ever the middle ear, where loads are minimal and the
developed. According to Hench and Wilson mechanical properties of this material are thus
[25], bioactive materials include hydroxyapatite more than adequate.
(HA) ceramics, glasses, glass ceramics and
Cerabone® A/W
surface-active composite materials.
One of the glass-ceramics of more clinical
Bioactive Glass-Ceramic Compositions
success, be probably the denominated A/W,
Most biomedical glass-ceramics are based on which is constituted by two crystalline phases:
compositions similar to those of Hench’s oxyfluorapatitoCa10 (PO4)6(O,F2) and wollast
bioactive glasses (BioglassR)[26], however, all onite (β- CaSiO3) and a residual vitreous phase.
of them have very low contents in alkali oxides. This was originally developed by Kokubo et
Table 6 summarizes the properties of bioactive al.[29]and is commercially available under the
glass ceramics used in the clinical field as trade name CeraboneR A/W. Its composition is
compared to those of BioglassR 45S5. shown in the Table 6.After some failed attempts
of producing a glass-ceramic of the Ca3(PO4)2-
Ceravital®
SiO3-MgCa(SiO3)2 system, starting from a
The earliest glass-ceramic material of clinical monolithic glass or even powdered glass, the
use was developed by Bromer andPfeil in 1973 glass-ceramic A/W was obtained by adding a
[27]and named CeravitalR. This designation, small amount of CaF2 to the original
however, includes a wide range of glass-ceramic composition. Glass ground to an average
compositions. Originally, CeravitalR was particle size of 5 μm was isostatically pressed at
believed to possess extraordinary properties as a 200 MPa in the desired shapes and thoroughly
replacement material even for bone in loaded densified at ca. 830 oC, which resulted in the
zones and teeth. However, as can be seen from precipitation of oxyfluorapatite and β-
Table 6, their mechanical properties, even for wollastonite at 870 and 900 oC, respectively.
the optimum compositions, they are below the The end-product was thus a glass-ceramic with a
160 MPa of the human cortical bone and are very fine microstructure free of cracks and
similar to those of sintered dense hydroxyapatite pores.The special microstructure of this glass-
(115 MPa).Also, long-term in vivo tests ceramic endows it with the best mechanical
questioned the stability of these materials. properties among all the materials shown on
However, subsequently Gross et al. [28]developed Table 6; thus, it’s of (220 MPa) is nearly twice
improved compositions, the solubility of which that of dense hydroxyapatite (115 MPa) and
was reduced by using various metals as exceeds that of human cortical bone (160 MPa).
nucleating agents.The bioactivity of CeravitalR In addition, its tenacity is ca. 2.0 MPaAm–1/2
is roughly one-half that of BioglassR 45S5 (5.6 and its Vickers hardness about 680 HV[30].
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
(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

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Some Types of Glass-Ceramic Materials and their Applications

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

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Some Types of Glass-Ceramic Materials and their Applications

circumvented by using various methods to modulus and good biocompatibility. The

increase the strength of these glass materials and methods used to prepare the coatings range from
facilitate their use as implants. One solution to immersion in the molten glass or in a solution,
the problem is using bioactive glasses as a suspension or gel (dip coating); electrophoresis
coating for materials with a high mechanical from a solution or suspension (the metal to be
strength. This method has been used with a coated acting as an electrode), biomimetic
number of substrates, including dense alumina coating growth or flame or plasma spraying.
[34], various types of stainless steel [35], cobalt- Plasma spraying is the method of choice when
chromium alloys [36]and titanium alloys[37, depositing a bioactive glass onto a metal
38]. This last alloy is especially attractive on substrate.
account of its high strength, low elasticity
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 Slurry of CEL2 powder, polyvinyl alcohol and
production of composites, being reinforced the water has been prepared in order to coat, by
bioactive glass with a second phase. The impregnation, the polymeric template. An
materials thus obtained include ―biofibre glass‖ optimized thermal treatment was then used to
and alumina, organic polymers or metal fibers. remove the sponge and to sinter the glass
The former has fallen short of the original powders, leading to a glass-ceramic replica of
expectations as it seemingly releases large the template.
amounts of alumina powder that are detrimental
Morphological observations, image analyses,
to tissues.
mechanical tests and in vitro tests showed that
The materials reinforced with metal fibers are the obtained devices are good candidates as
those with the strongest potential. In fact, metal scaffolds for bone-tissue engineering, in terms
fibers strengthen bioactive glasses and improve of pore-size distribution, pore interconnection,
their deformability. The most widely used surface roughness, and both bioactivity and
procedure for producing these materials is hot biocompatibility.
pressing[39].
In particular, a human osteoblast cell line (MG-
Scaffolds for Bone Tissue Engineering 63) seeded onto the scaffold after a standardized
preconditioning route in simulated body fluid
Macroporous bioactive Glass-ceramic scaffolds
showed a high degree of cell proliferation and a
was developed for tissue engineering
good ability to produce calcium nodules. The
viapolyurethane sponge template. The starting
obtained results were enhanced by the addition
glass (CEL2) belongs to the system SiO2-P2O5-
of bone morphogenetic proteins after cell
CaO-MgO-Na2O-K2O and has been synthesized
seeding [40].
by a conventional melting-quenching route.

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Some Types of Glass-Ceramic Materials and their Applications

Glass-Ceramics for Dental Hypersensitivity develop ceramic composites infiltrated with

Treatment glass under pressure; 3) study and understand
the optical phenomena of light scattering of the
Dentin hypersensitivity is a common dental pain
new composites using the Kubelka-Munk
arises when subjecting tooth to thermal,
model; and 4) characterize the mechanical
chemical or tactile stimuli, it occurs due to loss
properties of composites [42].
of minerals from tooth, attempts to replace these
minerals was investigated. bioactive glasses was A recent study revealed comparable properties
first used as a dental hypersensitivity treatment of mica glass ceramics containing 20 wt.% YSZ.
in SensodyneVR toothpaste containing particular, to the commercially available IPS
BioglassVR 45S5 particulate named Nova Min emax Press and IPS emax CAD as regards
VR was in 2004. Bioactive glass-ceramics as mechanical and chemical durability. [43]
BiosilicateVR was also introduced, its
Transparent Glass-Ceramics
composition[23, 24] 23.75Na2O–23.75CaO–
48.5SiO224P2O5 (wt %). its microstructure can Some successful and many trial optical
be engineered to be composed of one or two applications have been proposed for transparent
crystalline phases through controlled double- glass-ceramics: cookware (Vision) that allows
stage heat treatments, these two phases are: a continuous visualization and monitoring of the
sodium-calcium silicate phase (Na2CaSi2O6) or cooking process); fireplace protection;
both Na2CaSi2O6 and sodium-calcium transparent eyeshields; transportation windows;
phosphate (NaCaPO4).[41] substrates for LCD screens; ring laser
gyroscopes; rockets’ fronts; fiber grating
Infiltrated Ceramic Composites for Dental
athermalization; precision photolithography;
Prostheses
printed optical circuits.
In the last years, many bioceramics and
As for telescope mirrors (Zerodur), the
processing methods for all-ceramic prosthesis
telescope’s optical components should resist
have been developed, because these materials
distortions caused by temperature fluctuations.
can result in dental restorations with improved
Therefore, they utilize glass-ceramics with zero
biocompatibility, chemical stability, and
expansion.
aesthetic qualities compared to metals and
polymers restorations. The market of dental Wavelength up-conversion devices for
bioceramics is growing rapidly in Brazil and europium-doped waveguide amplifiers uses
abroad. Despite the recent developments, fluoride, chalcogenide and oxyfluoride-based
bioceramics used as core materials still need to transparent glass-ceramics, doped with rare-
be improved in relation to their optical earth ions. Transparent mullite, spinel,
characteristics as well as to their mechanical willemite, gahnite and gelenite based glass-
properties. ceramics doped with transition-metal ions have
been developed for use in tunable and infrared
The aim of this project is to develop a new
lasers, solar collector and high-temperature
method of preparation of ceramic composites
lamp applications. Glass-ceramics that exhibit
infiltrated with glass with improved optical
second harmonic generation and material with
transmission and high mechanical properties for
high kerr constant for electroopical devices have
use in dental prostheses. A new method for the
been developed as well. The combination of
production of cores of ceramic-glass composites
several properties is the hallmark for their
is proposed, in which the infiltration of the glass
success [42].
in the partially sintered perform is conducted
under pressure. This method is a hybrid Other optically active applications include
technique between the systems In-Ceram Vita luminescent glass-ceramics for solar
Zahnfabrik) and Empress (Ivoclar). concentrators, up-conversion and amplification
devices; illumination devices using IR; heat-
Using this method, it is expected to develop
resistant materials that absorb UV, reflect IR
translucent composites by decreasing the
and are transparent to visible light; materials
porosity and matching the optical characteristics
that absorb UV and fluoresce in red/IR;
of the phases present in the microstructure to
substrates for arrayed waveguide grating; solid-
minimize the light scattering. To achieve this
state lighting – white light; and laser pumps.
objective, the targets are: 1) develop glasses
with high refraction indexes, comparable to To be transparent in the visible range, a glass-
those of the reinforcing ceramic phases; 2) ceramics must have one or a combination of the

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Some Types of Glass-Ceramic Materials and their Applications

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.
crystallization a consequence of defects in
As can be seen in Figure 4, the crystallization
glasses or a transitional stage during formation
microstructure of the surface of these glass-
of bulk crystallization of glass-ceramics.
ceramic glazes is different depending on the
In recent years, there has been a growing crystalline phase and composition of the original
interest in ceramic glazes and frits for glassy matrix. SEM observation of the
developing new glaze compositions that can be microstructure of the cross section of the
crystallized in order to improve the mechanical glaze/substrate interface revealed many bubbles
and chemical properties of fast-fired glazed indicating high volume of crystallization exists
tiles. Nucleation and crystallization of thin and coarse crystallization in some thin layer
layers of certain glasses covering ceramic glazes.
substrates (glazes) to obtain high-performance
Therefore, in those cases where there was a high
glass-ceramic coatings[48], are scientific and
tendency to crystallize, it was necessary to
technological challenges due to the difficulties
dilute the original frits with some commercial
of controlling crystal growth homogeneously.
boro-zinc silicate frits, which likewise were
Several parent glasses from a wide range of phase separated [50]. This enabled the
compositions in the CaO–MgO–Al2O3–SiO2 crystallization process to be better controlled, as
system, the Li2O–ZnO/BaO–Al2O3–SiO2 can be observed in the SEM micrograph shown
system, and the G–C commercial systems based in Figure 5.
on spodumene, cordierite, nepheline, and leucite

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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 crystallization mechanisms and comparable to
hardness of the glaze surface through permitting sintered powdered glasses, this case has three
a reticular crystalline microstructure embedded different nucleating interfaces; viz., air/surface
in the original residual glassy phase to be of glaze, substrate/glaze interface, and frit/frit
attained. In the case of the spodumene glaze, the interface. A wide range of crystallization
dilution allowed the precipitation of crystals microstructures has been achieved by this
between the cracks produced by the different processing, depending on the original glass
expansion coefficient of the spodumene glassy composition. However, the very short time for
matrix and the solvent frit (Fig. 5). This type of the growth step makes it difficult to obtain high
nucleation of crystals associated with the cracks percentages of volume crystallization. Crystals
and interfaces agrees well with the models of ranging in size from less than 1 mm to elongated
surface nucleation recently developed by crystallites larger than 20 mm precipitated in the
Schmelzer et al. [47]. Contrary to bulk glasses glassy matrix of the coating were obtained.

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

Some Types of Glass-Ceramic Materials and their Applications

Glass-Ceramic Armor
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.
Figure6. Nucleation of spodumene star crystals, or
Inexpensive Glass-Ceramics Based On Slag
incipient dendrites, in the S2 glaze composition.
The principal proposed usage for basalt and slag
Glass Ceramics for Nuclear Waste
derived glass ceramics is in the form tiles and
Immobilization
pipes for the conveyance or storage of abrasive
Glass-ceramic waste form has been materials (e.g. coal) where the glass ceramics
development to immobilize fission-product are much more resistant to abrasion than
generated by the uranium extraction separations alternative metals and out in the UK and the
process. The glass ceramics were slow-cooled USA[52] a great deal of development and use
and characterized in terms of phase assemblage has been undertaken in Russia [53].
and preliminary irradiation stability. The phases
It is an indication of its value that it is claimed
identified in these glass ceramics were
that this application may represent the greatest
oxyapatite, powellite, cerianite, and lanthanide –
use of glass ceramics worldwide.
borosilicate.[51]
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 – Coatings for chemical reactor
Chemical durability; mechanical toughness
SiO2 accessories
BaO – Al2O3 – SiO2 Specific expansion coefficient Alloy bonding
Li2O – BaO – SiO2 Dielectric properties Insulators in devices

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

 Some Types of Glass-Ceramic Materials and their Applications

CONCLUSIONS microstructures operties of sintered cordierite

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International Journal of Research Studies in Science, Engineering and Technology V7 ● I3 ● 2020 15

 Some Types of Glass-Ceramic Materials and their Applications

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
medium, provided the original author and source are credited.

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

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