Glass ceramic

By

Fatima shaker

Supervision

Dr. Elham Alali

:Glass ceramics
Glass-ceramics are fine-grained polycrystalline materials formed
when glasses of suitable compositions are heat treated and thus
undergo controlled crystallization to the lower energy,
.crystalline state
It has been shown that glass ceramics exhibit higher hardness
and scratch resistance then those of parental glasses or even
conventional ceramic
Unlike sintered ceramics, glass ceramics are inherently free
from porosity. However, in some cases, bubbles or pores
develop during the latter stages of crystallization. Glass-
:ceramics have, in principle, several advantages

.They can be mass produced by any glass-forming technique •

It is possible to design their nanostructure or microstructure for •
.a given application
.They have zero or very low porosity •
It is possible for them to combine a variety of desired •
.properties
Types of glass ceramics:
1-Glass-ceramics with minimal thermal expansion,These
products exhibit practically no physical expansion over a wide
temperature range.Main crystal phases of the glass-ceramics are
β-Spodumene solid solution or β-quartz solid solution.Because
of this minimal expansion coefficient, this glass-ceramic has a
very high resistance to thermal shock. The special properties of
this type of glass-ceramics allow these materials to be used in
the manufacture of consumer goods, such as kitchenware.
2-Glass-ceramics with special optical properties, β-quartzs.
glass-ceramics are also mentioned, because of their exceptional
optical properties which are requisite in products such as
Vision® (Corning Incorporated, USA) and Zerodur® (Schott AG,
Germany) an inorganic . Other types are glasses derived from
lithium metasilicate glass-ceramics to produce
microlenses.Three additional glass-ceramics were discussed: Cr-
doped mullite and oxyfluoride and Zn-spinel glass-ceramics. As
the crystals are embedded in the glass-ceramic in isolated form,
the glass-ceramic is transparent. This type of material can be
used in the electronics industry to produce photovoltaic
substrates.
3-Machinable glass-ceramics Macor, Dicor, Vitronit, Photoveel
and other brands of machinable glassceramics rely on mica
crystals in their microstructure. They exhibit zero porosity and,
in general, are excellent insulators at high voltages, various
frequencies and high temperatures. They can be machined to
complicated shapes and precision parts with ordinary metal
working tools, quickly and inexpensively. Machinable glass-
ceramics require no postfiring after machining. This means that
specifications can be met without having to resort to costly
machining with diamond tools. Typical Major applications
include insulators and supports for vacuum environment feed-
troughs; spacers, headers and windows for microwave tube
devices; sample holders for microscopes; aerospace
components; welding nozzles; fixtures; and medical equipment.
Some dental and some bioactive glassceramics also are
machinable using modern CAD–CAM techniques

MACOR ,High Temperature Machinable Glass/Ceramic

4-High-strength and high-toughness glass-ceramics,

Precipitating chain of sheet silicates in glass-ceramics allow the
development of high strength and high toughness materials. E.g.
for canasite glass-ceramcis, high KICtoughnesses of up to 5
MPa·m0.5were also established for this product.
5-Biomaterials,a wide range of different biomaterials has been
described. The largest group of bioactive materials is composed
of phosphate-containing glass-ceramics. Some of the restorative
materials used in dentistry also contain phosphate, however,
these contain a high concentration of additions that enhance
their chemical durability. Millions of products made of leucite-,
lithium disilicate of apatite glass-ceramics were produced as
dental restorative materials.
:The Glass Crystallization Process
The crystallization, or devitrification, of glass to form a glass-
ceramic is a heterogeneous transformation and as such consists
.of two stages, namely a nucleation stage and a growth stage
In the nucleation stage small, stable volumes of the product
(crystalline) phase are formed, usually at preferred sites in the
parent glass. The preferred sites are interfaces within the parent
glass or the free surface. The latter is usually undesirable as the
resulting glass-ceramic microstructure often consists of large
oriented crystals that are detrimental to mechanical properties.
In most cases internal nucleation, also known as bulk
nucleation, is required and the parent glass composition
is chosen to contain species that enhance this form of
nucleation. These species are termed nucleating agents and may
be metallic (e.g., Au, Ag, Pt, and Pd) or non-metallic
(e.g.,TiO2,P2O5 and fluorides). The rate of nucleation is very
temperature dependent as illustrated in Figure1(a)
Growth involves the movement of atoms/molecules from the
glass, across the glass-crystal interface, and into the
crystal. The driving force for this process is the difference in
,volume or chemical free energy
.ΔGv, between the glass and crystalline states
:Processing Routes for Glass-Ceramic Production
Conventional Method (Two-Stage)
The conventional method for producing a glass-ceramic is to
devitrify a glass by a two-stage heat treatment (Figure 1 (b)).
The first stage is a low temperature heat treatment at a
temperature that gives a high nucleation rate (around TN in
Figure 1a) thus forming a high density of nuclei throughout the
interior of the glass. A high density of nuclei is important as it
leads to a desirable microstructure consisting of a large number
.of small crystals
The second stage is a higher temperature heat treatment at
around temperature TG to produce growth of the nuclei at a
.reasonable rate
The parent glass may be shaped prior to crystallization
employing any of the well-established, traditional glass shaping
methods such as casting and forming or more special methods
such as extrusion . Glass production and the subsequent heat
treatments are in general energy intensive and therefore
. expensive
Modified Conventional Method (Single-Stage):
The reason for the two-stage heat treatment of the glass is a
consequence of the limited overlap between the nucleation and
growth rate curves (Figure 1 (a)). If there is extensive overlap of
the rate curves then nucleation and growth can take place during
a single-stage heat treatment at temperature TNG as indicated in
Figure 2. The rate curves, particularly the nucleation rate curve,
is sensitive to composition and hence by optimizing the glass
composition it is, in some cases, possible to obtain the necessary
overlap. By judicious choice of nucleating agents, this was first
achieved for the glass-ceramic system known as “Silceram”
Petrurgic Method
It was found with “Silceram” that it made little difference
whether the glass was heated up to TNG from room temperature
or the molten glass was cooled to TNG . This led to the
development of the production of certain glass-ceramics by a
controlled, usually very slow, cooling of the parent glass from
.the molten state without a hold at an intermediate temperature
With this method, referred to in the recent literature as the
petrurgic method , both nucleation and crystal growth can take
place during the cooling. Both the modified conventional
and the petrurgic methods are more economical )single-stage(
.that the conventional method(two-stage)

:Powder Methods
The shaping by cold-compacting a powder followed by a high
temperature heat treatment to sinter the compact is a common
route for the fabrication of ceramics and it has been also
employed for glass-ceramic production . As there are limitations
on the size and shape of components that may be cold
compacted, and also a cost in producing a powder, this method
is only used if an obvious benefit is identified. In most cases
there is little advantage in compacting and sintering a glass-
ceramic powder because a high sintering temperature is required
and the properties of the final product do not differ significantly
from those of glass-ceramics produced by the other routes. It is
more attractive to sinter a parent glass powder, which sinters by
a viscous flow mechanism at lower temperatures . It is important
to consider the rates of viscous flow sintering and crystallization
and the interaction of these processes. If crystallization
is too rapid the resulting high degree of crystallinity will hinder
the low temperature sintering leading to an unacceptable amount
of porosity . On the other hand, if sintering is fully completed
before crystallization, then the final product is unlikely to differ
significantly from those fabricated by other methods. With
appropriate rates it is possible in some cases to fabricate
a dense glass-ceramics by a sintering process in which both
densification and crystallization take 6 place simultaneously at
the same temperature. The technological significance of this
process as well as the theoretical complexities of its kinetics
have been discussed in the literature .Optimization of
composition and sintering temperature can lead to different
microstructures, and even different crystalline phases, compared
to those from the conventional method, and hence different
properties of the product. Pressure assisted densification
methods such as hot pressing and HIP pressing have also been
successfully applied for production of glass-ceramics from
.powders
Although these methods give improved products exhibiting near
full densification, they are more expensive than cold pressing
and sintering and thus unlikely to be employed for processing
wastes into monolithic glass-ceramics. Powder technology
facilitates the production of dispersion reinforced glass-ceramic
matrix composites . Fabrication of these particle-reinforced
composites involves intimately mixing the powdered parent
glass with the reinforcement in the required proportions. The
mixture is then shaped, sintered and crystallized. Hard and rigid
inclusions used as reinforcement hinder the sintering process.
The production of continuous fiber reinforced glass-ceramics is
more complex and requires dedicated apparatus . For both
particulate- and fiber-reinforced glass-ceramics the densification
is usually carried out by hot pressing and a final heat treatment
.is required to achieve crystallization of the glass matrix
?What are the characteristic properties of a glass ceramic
High strength-1
.High impact resistance-2
Low co-efficient of thermal expansion, sometimes even -3
.negative co-efficient of thermal expansion
.Good resistance to thermal shock-4
A range of optical properties, from translucent to opaque -5
.and sometime opalescence

:Differences between glass and glass ceramic

Glass Glass ceramic

Amorphous solid Crystalline or partially

crystalline structures
Silicon dioxide is the main Clay is the main component of
component of glass glass ceramic
Transparent Opaque
cheaper More expensive
A glass kiln have heating A glass ceramic kiln have
elements on the top heating elements on the side
References
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.Solids, ed. J.P. Roberts. Vol. 1
London: Academic Press Inc. (London) Ltd. (1979)
Hölland, W., Beall, G., Glass-Ceramic Technology, The .2
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Strnad, Z., Glass-Ceramic Materials. Elsevier, Amsterdam .3
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Pannhorst, W., Glass-ceramics: State-of-the-Art, J. Non- .4
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Glass-Ceramic Materials. Fundamentals and Applications. .5
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Pellacani and J. M. Rincon. Mucchi Editore, Modena, Italy
.(1997)
Beall, G. H., Design and Properties of Glass-Ceramics, Ann. .6
Review Mater. Sci. 22 (1992)
.91-119
Partridge, G., Transparent Ceramics and Glass-Ceramics, .7
Adv. Mater. 2 (1990) 553-556