Tripole university

Material and Metallurgical Department

Glass-Ceramic "MME660"


Home work "5"

Application of Glass -Ceramics


Prepared by :Hana Jamhour


D. Nibile Abed alwahab






PRESENT APPLI CATI ON OF GLASS-CERAMI CS I N SCI ENCE,
ENGI NEERI NG AND MEDI CI NE

The unique properties of glass-ceramics render them suitable for applications not only
in the technical engineering fields but also in production of consumer goods (1). The
first commercially viable glass-ceramics were developed in the aerospace industry in
the late 1950s were used to manufacture randomes to allow the use of and to protect
radar equipment (internal antennae) in the nose of aircraft and rockets. According to
McMillan (1979), materials used for this type application must exhibit a very
homogenous and low dielectric constant and low coefficient of thermal expansion ,
low dielectric loss, high strength, and high abrasion resistance. These properties are
also demonstrated by sintered Al
2
O
3
(2). In many cases, the selection of galas-ceramic
for particular application will rest primarily on one type physical characteristic and for
this reason the applications have been classified into groups depending on weather the
over-riding requirement is concerned with mechanical, thermal, or electrical
properties. Naturally, there will be some overlap in this classification and in those
cases, where a combination of properties is required, the classification has been made
on the basis of the more important physical characteristic for the particular
application. Many glass-ceramics have been produced in university and industrial
laboratories, but only a few have so far found commercial applications(2). And The
wide variety of applications include electric range tops, wood stove windows,
telescope mirrors, cooking utensils, dinnerware, building facing materials, precision
electronic parts, fluid amplifiers, inkjet printer heads, dental prostheses, and many
more can be grouped according to their type of crystal structure as shown in Table
"1"(3).



Table "1" glass-ceramic by primary crystal type and application






Some applications of glass-ceramic utilizing mechanical properties

1. Bearings
Glass-ceramics have potentialities for the manufacture of bearing and, a part
from the high mechanical strength which is necessary for this application, the
materials have other desirable properties including good abrasion resistance and
the ability to take a very smooth surface finish. In latter respect glass-ceramics
are superior to conventional ceramics, since the best surface finish attainable for
a 95 per cent alumina ceramic is 8 to 9 micro-inches where as glass-ceramics
have polished to have surface finishes of 1 to 2 micro-inches. The use of glass-
ceramics for bearing would probably be confined to application where the
operating conditions were particularly stringent. Glass-ceramic bearing surface
would be resistant to attack by corrosive liquids (e.g.-sea-water) and this might
therefore simplify the construction of bearing in pumps for handing such
liquids. The high abrasion resistance of glass-ceramics compared with certain
metal might permit bearings to operate with minimum lubrication and this
would be an advantage where lubrication is difficult due to inaccessibility of
the bearing during operation or under conditions where normal lubricants
would not function satisfactorily due to a high ambient temperature or other
cause. Wherever possible, of course, glass-ceramic bearings would be
lubricated by liquid or gas films. It is technically feasible to produced various
type of bearing such as ball or roller bearings or journal bearings using glass-
ceramics and to use techniques which permit metal shafts or housing to be clad
in glass-ceramic. Insufficient experience has yet been obtained to determine
which designs or techniques will give optimum results. In some cases the best
results may be achieved by having only one bearing surface made of glass-
ceramic, the other bearing surface being of a suitable metal. This would be in
accordance with normal practice for journal bearing where it is usual to make
the rotor and stator components from dissimilar metals to achieve minimum
wear.
2-Miscellaneous applications utilizing mechanical properties
Other applications where the abrasion resistance and durability of glass-
ceramics might be utilized with advantage include thread guides and godet
wheels in textile processing equipment. Spinnerets for the extrusion of synthetic
fibers might also be made from glass-ceramics. It has been suggested that half-
tone and intaglio printing plates could be made from to the desired from. The
use of glass-ceramics as binders for abrasives in the manufacture of grinding
wheels is also a distinct possibility. In this case, the glass-ceramic would
replace the usual glass bond and for certain types of grinding wheel this could
enable improved performance to be achieved. Another proposed application,
where the requirement is primarily for good mechanical characteristics, is the
use of glass-ceramic parts for internal combustion engines. Glass-ceramic
crowns for pistons may lead to engines. Glass-ceramic crowns for pistons may
lead to engines with increased life, and this possibility is being studied in
Russia (galina,1962) and elsewhere. Glass-ceramics, because of their durability
and the fact that they can be readily produced in a variety of shapes and sizes,
may find applications in architecture, especially as cladding or curtain walling
for buildings.
Some applications of glass-ceramic utilizing thermal properties
1-Cooking Wear
The largest application so far realized for glass-ceramics has been in the
production of cooking ware. One of the chief requirements here is for good
thermal shock resistance because of the rapid temperature changes which can
occur when heat is applied to removed from the cooking vessels. Glass-
ceramics, having thermal expansion coefficients less than 15x10
-7
and high
mechanical strengths, posses more than adequate thermal shock resistance. For
this application. The high mechanical strength compared with that of
borosilicate heat-resisting glass confers an additional advantage in reducing the
probability of accidental breakage due to mechanical shock. since the high
mechanical strength of glass-ceramic is inherent and is not dependent on the
existence of a surface compressive layer as is the case for toughened glass
cooking ware, the possibility of catastrophic failure due to accidental
overheating of the vessel is eliminated. The extremely hard and a abrasion-
resistant surface of the glass-ceramic coupled with a smooth finish renders it
very hygienic and easily cleaned. In this respect, the glass-ceramic ware can be
superior to glaze may sometimes occur after prolonged use, permitting
permanent staining to occur; with glass-ceramics, the smooth surface is a
characteristic of the material and is not dependent upon the application of a
separate glaze layer.
A related application of glass-ceramics is in the field of table ware. Here again,
the outstanding surface durability of glass-ceramics confers distinct advantages,
and special materials have been described for this application in British patent
no 869,315(1961). These materials are prepared by devitrifying glasses made
up from calcium phosphate, silica and alumina and it is claimed that the glass-
ceramics produced have the appearance and characteristics of bone-china. The
chief advantage of these materials over those traditionally used would be that
high-speed mass-production methods are available for the shaping of table ware
of exceptionally high strength is already beginning in the united states.
2- Sealing and Bonding Media
An application of glass-ceramics which depends upon their thermal
characteristics is as sealing media or thermo-setting comments for use in the
conduction of electronic tube of various design where it is necessary to make
vacuum- tight joints. These joints may be between glass or ceramic and metal,
or between two glass parts such as the face- plate and cone of cathode-ray tube .
Until fairly recently, the joints were made simply by fusing the glass locally so
that it flowed and sealed to the metal or to another glass component. There are
certain disadvantages associated with this method, however, since loss of
dimensional accuracy due to softening of the glass can occur and also the fairly
high temperatures involved may cause damage to the internal structure of
components of the electronic device. For this reason a technique developed
some years ago, known as solder glass sealing, has come into use. In this
process a very thin layer of a low- melting glass( often a lead-zinc-borate type)
is used as a jointing medium, and sealing between adjacent parts is achieved at
relatively low temperatures. The solder glass flows and" wets" the metal or
glass parts at temperatures where the main parts of the envelope are still rigid.
Thus deformation of the envelop, leading to loss of dimensional accuracy, can
be avoided. The disadvantage of solder glass sealing is that the seal produced
will not withstand reheating to very high temperatures because the solder glass
must be kept at temperatures well below its sealing temperature well below its
sealing temperature to avoid softening. If the solder glass were devitrified to
convert it into a glass-ceramic it would then be possible to heat the seal to a
considerably higher temperature and this would confer great technical
advantages because the attainment of a high vacuum is dependent upon being
able to outgas the electronic tube at the highest possible temperature.
In one process, described by S.A. claypool (1959), glasses of the lead-zinc-
borate type having approximate weight percentage compositions:
PbO:70-80,ZnO:10-15;B
2
O
3
:6.5-10
Together with certain minor constituents such as Al
2
O3and SiO
2
are used. The
glasses are employed in the form of fine powder which is made up into a
suspension with an organic vehicle and binder. The surfaces of the components
to joined are coated with this suspension by dipping or spraying. The coatings
may be prefired at this stage to increase their strength but the temperature for
this is controlled to avoid premature devitrification. The precoated surfaces are
placed in contact and the temperature is raised to the sealing temperature which
is in the range 430
o
c to 450
o
c; this temperature is maintained for about 30
minutes. During this time, flow of the glass occurs to accomplish sealing and
the glass devitrifies so that it becomes more refractory. Seals of this type can be
heated to temperatures within 20
o
c or so of the sealing temperature.
The lead-zinc-borate compositions are suitable for sealing together glasses
having thermal expansion coefficients in the range 80x10
-7
to 120x10
-7
and one
commercial application has been in the sealing of face-plate to cones in the
manufacture of color tevsion tubes. Other compositions suitable for sealing
together glasses or other materials having relatively low thermal expansion
coefficients in the range 30x10
-7
to 50x10
-7
are available. These glass-ceramic
compositions are based on zinc- borosilicate glasses having weight percentage
compositions in range ZnO:60-65B
2
O
3
:20-25;SiO
2
:10-15
Plus certain minor constituents.
Some applications of glass-ceramic utilizing electrical properties
1- Insulators
Although glass-ceramics have not yet been widely used for the manufacture of
insulators there is no doubt that they possess the characteristic required for this
application since they have high surface and volume resistivities and are
resistant to surface tracking under arcing conditions. Their high dielectric break
down and mechanical strengths, compared with those of normal electrical
porcelains, permit the use of thinner sections resulting in weight savings and
giving increased freedom to designer. The smooth surfaces of glass-ceramics
which do not required glazing constitute a most valuable feature, since
insulators which are required to operate under polluted conditions can easily be
cleaned to restore their insulating characteristics. In many cases, the glass-
ceramic would be used as a simple insulator in some required shape but very
often it is necessary to join the insulator to metal components. These
components may be required to act as conductors or as mechanical supports or
attachments. Examples of this type of insulator-metal construction include
hermetic or oil-light bushing for transformer and capacitors and also various
types of disc and pod insulators. Glass-ceramics possess a distinct advantage
for the manufacture of metal-insulator assemblies of this type since their
thermal expansion coefficients can be closely matched to those of suitable
metals. This ensures that stresses generated in the insulator during temperature
cycling will be low and also permits actual sealing of the insulating component
to the metal parts, thus giving more reliable joints than are obtainable with
cementing or other conventional techniques.
2-Capacitors
The production of dielectric layers giving high capacitance per unit volume is
achieved more easily with glass-ceramics than with conventional ceramic
material where the high permittivity ceramics can be produced by conventional
techniques, but the use of the glass-ceramic process offer certain advantages.
One of the principle advantages is that the glass-ceramic composition(special
glass-ceramics containing Ferro-electric crystal phases having high
permittivities),and in its glass state, can be drawn into a very thin film by a
continuous process, whereas the manufacture of very thin plate of conational
ceramics is extremely difficult than glass-ceramics.
The process for making a glass-ceramic capacitor comprises stacking alternate
layers of the thin glass sheet and of a conducting metal, heating the assembly to
soften the glass and to fuse the edges of the glass laminations together and
afterwards heat-treating the assembly to crystallize the Ferro-electric
compounds. The relatively low dielectric losses, high dielectric breakdown
strengths and good insulation resistance of suitable glass-ceramics of this type
are valuable additional characteristics for this application (2).


Some applications of glass-ceramic in medical
During the past 3040 years there has been a major advance in the
development of medical materials and this has been in the innovation of
ceramic materials for skeletal repair and reconstruction. The materials
within this class of medical implant are often referred to asBioceramics
and the expansion in their range of medical applications has been
characterised by a significant increase in the number of patents and
publications in the field and an ever increasing number of major
international conferences and themed meetings. Bioceramics are now used
in a number of different applications throughout the body. According to the
type of bioceramics used and their interaction with the host tissue, they can
be categorised as either bioinert or bioactive and the bioactive ceramics
may be resorbable or non-resorbable. The materials used include:
polycrystalline materials; glasses, glass ceramics and ceramic-filled
bioactive composites, and all these may be manufactured either in porous or
in dense form in bulk, as granules or in the form of coatings(4). Bioactive
glass-ceramics form in-situ a biologically active layer of hydroxycarbonate
apatite (the mineral phase of bone and teeth) that bonds to bone and teeth
and sometimes even to soft tissue. Moreover, load bearing applications
require excellent mechanical properties. Many products have reached
commercial success: Cerabone A-W (apatite wollastonite), Ceravital
(apatite-devitrite), BioveritI (micaapatite), Bioverit II (mica) and I
lmaplant L1 and AP40. They have been used as granular fillers, artificial
vertebrae, scaffolds, iliac spacers, spinous spacers, intervertebral spacers,
middle-ear implants and as other types of small-bone replacements. Some
of their interesting properties are listed in Table "2".

Table 2. relevant properties of bioactive glass-ceramic

Cerabone developed by Tadashi Kokubo and produced by Nippon Electric
Glass Co. Ltd. is probably the most widely used bioactive glass-ceramic for
bone replacement. Numerous clinical trials have shown intergrowth
between this glass-ceramic and human bone. Tadashi informed us in 2009
that about 50,000 successful implants already have been made using
Cerabone. Bioverits are machineable glass-ceramics that are very useful,
because they can be easily modified during clinical procedures. Bioverit II
is especially good in this respect. A different type of highly bioactive glass-
ceramic was developed by Peitl etal in 1995. This is a low-density glass-
ceramic in the Na-Ca-Si-P-O system that has a Youngs modulus closer to
that of cortical bone and much higher bioactivity than previous bioactive
glass-ceramics. This particular combination of properties is desired for
several applications. This glass-ceramic is about 30 to 50 percent
crystalline, and its main phase is Na
2
O.2CaO.3SiO
2
. The first clinical trials
for middle-ear bone replacements in 30 patients yielded very positive
results. Table I summaries the main properties of some bioactive glass-
ceramics. A new glass-ceramic based on the same Na-Ca-Si-P-O system
(Biosilicate) but with some compositional modifications and greater than
99.5 percent crystallinity recently was developed by Zanotto and
colleagues. This glass-ceramic is as bioactive as the gold standard
bioglass 45S5 invented by LarryHench. Clinical tests of treatment with
Biosilicate powder for dentin hypersensitivity in 160 sensitive teeth
conducted by dentist Jessica Cavalle are shown in Fig. 1. After the first
treatment, one-third of the teeth lost their sensitivity. After six applications
of Biosilicate powder, 94 percent of the teeth were cured. This powdered
glass-ceramic also can be useful for making small sintered bones and
bioactive scaffolds, such as those shown in the studies of Enrica Vern
and Aldo Boccaccini and their colleagues. Another interesting class of
bioactive glass-ceramics is heat-generating bioactive or biocompatible
glass-ceramics intended for use for hyperthermic treatment of tumors. For
instance, in one study by Koichiro et al., glass plates of he chemical
composition CaO-SiO
2
- Fe
2
O
3
-B
2
O
3
-P
2
O
5
were ceramized. The resulting
glass-ceramic containing magnetite and wollastonite crystals showed high-
saturation magnetization. This glass-ceramic formed a calcium- and
phosphorous-rich layer on its surface and tightly bonded with bone within
about eight weeks of implantation. The parent glass did not form the
calcium- and phosphorous-rich layer and did bond with bone at 25 weeks.
Under an external magnetic field, granules of this glassceramic filled in
rabbit tibias heated surrounding bone to more than 42C and maintained
this temperature for 30 minutes. Since then, this promising route for tumor
treatment has been followed by several authors. Several other compositions
have been and are presently being tested in various laboratories(5).



Figure " 1" micrographs of open and partially blocked dentin tubes Biosilicate glass-ceramic
powder. RHS-results of a clinical study of dentin sensitivity level of 160 teeth: initial and after 1to
6 applications of Biosilicate.).


FUTURE OF GLASS-CERAMIC

at the present time advances are being made in the technology of glass-
ceramics and it is not likely that the pace of development will slacken in the
immediate future. An obvious field concerns the development of glass-
ceramics prepared from inexpensive raw materials. Some of the important
present-day glass-ceramics contain lithium oxide which is a relatively
expensive constituent and the development of glass-ceramics based on more
conventional raw materials would give economic advantages. In addition,
some of the present glass-ceramics require relatively high melting
tempratures for the preparation of the parent glasses and these tend to be
rather corrosive towards available furnace refractory materials, so that again
it would be advantageous if more conventional glass compositions could be
used. A further point is that most glass shaping machinery has been
developed for conventional glasses having viscosity- temperature
characteristics falling within a fairly narrow range. Clearly, glass-ceramic
compositions which exhibited these characteristics would be advantageous.
Further development of glass-ceramic compositions for specialized
application can be expected. Magnetic glass-ceramics containing be
developed and have the advantage that they could readily of formed into
fibers or thin films which would be extremely difficult with more
conventional ferrite ceramics. Another possibility is the development of
semiconducting glass-ceramics for the manufacture of resistors and other
devices. An extremely important field for future development concerns
surface crystallization of glasses. Materials of very high strength have
already been produced and the extension of technique to other types of glass
will certainly occur.one aim will be to use glasses prepared from
inexpensive raw materials and having good melting and working
characteristics. In other developments, the production of surface crystallized
materials which are completely transparent could provide a high-strength
replacement for conventional glass in many applications. Continued growth
of applications for glass-ceramics can be expected. In some of these
applications they may tend to displace conventional ceramics and glasses,
but it is equally likely that the outstanding characteristics of glass-ceramics
will enable them to be used in new fields so that the overall effect will be to
create an expansion in the use of ceramic or glass-type materials. Expansion
of the use of glass-ceramics for technical applications is likely to occur and
important field include vacuum tubes, miniature electronic components, high
voltage electrical insulation, special types of bearings and refractory coating
for the protection of metals. In additionto these rather specialized
applications, glass-ceramics will find increasing use in more general fields.
In building construction, for example, the durability and strength of these
materials could be of great value. It is even possible that load-bearing
structural members might be made from the high strength surface-
crystallized glasses with the advantage that they would be completely stable
against corrosion. One of the important uses for glass is in the manufacture
of containers (bottles,jars,etc.) and it is likely that the superior properties of
glass-ceramics will suggest their use in the field. One of the chief factors
here is an economic one, but if low-cost glass-ceramics are developed there
is no reason why they should not be widely applied. The high-strength
surface-crystallized materials may be more suitable for this application and it
should be possible to produce containers which are considerably lighter and
stronger than those being made at present. Glass-ceramics have already
secured an important place in the general field of materials technology and it
is clear that the extensive research and development efforts, which are being
applied in many countries, will ensure continued growth of the significance
of these materials(2).

















Reference

1. Glass-ceramic technology /Second edition wolfram Hland george H. Beall/Copyright
2012 by The American Ceramic Society.

2. Glass-ceramics/PW McMillan/a cadmic press London New York/copyright second
printing 1964.
3.Hand Book of Ceramics, Glasses and Diamonds/ Charles. A. Harper. Editorin chief
/Copyright"1" 2001 by McGraw-Hill Companies/ http://books.google.com.ly.
4-Bioceramics: Past, present and for the future paper /science direct journal of European
ceramic society 2008 / Edited by S.M. Best
a
,, A.E. Porter
b
, E.S. Thian
a
, J. Huang
c

5- Emerging ceramics and glass technology/October/November 2010/by Americ Society.