228

Ceramics Basic Science

Introduction
The word ceramics in derived from the Greek Keramikos
which means earthen. A ceramic is therefore an earthy material,
usually of a silicate nature and may be defined as a combination of one
or more metals with a non-metallic elements usually oxygen (Gilman,
1967).

History
Ceramics are the earliest group of inorganic materials to be
structurally modified by man and his early history in principally traced
through these materials.

Glazed porcelain the origin of glazing in an interesting

advance. Glazed porcelain is the only restorative material from
which bacterial plaque can be easily removed.
The earliest glazing technique was a Sumerian invention made
famous about 4000BC as Egyptian Blue Faience.
European development of porcelain came in 18 t h century.
1788 DC Chemant published a book on artificial teeth.

229
The first ceramic artificial teeth where launched by an Italian
dentist in 1808 Guieppangelo Fanzi.
These where brittle
The dental profession did not really master the art of ceramics
until the end of 19 t h century.
Dr. Charles H. Land filed the first patient in 1889 for porcelain
Jarket corwn.
The old trick of basking porcelain J.C was reported in 1908.
In 1925 with Dr. Albert Le Gros book on ceramics in dentistry
porcelain became firmly established.
1962 the use of gold alloys for porcelain binging became
universal.
In 1963 Mclean and Hughes developed a technique for alumina
reinforced crowns.
This work was taken forward in 1976 by Mclean and Sied by
developing attachment of aluminium porcelain to platinum.
Other major advances were made in firing dental ceramics by the
use of vacuum firing techniques.

STRUCTURE

The larger oxygen atoms serve as a matrix with smaller metal

atoms tucked in to the spaces between the oxygen atoms.

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Atomic bonds in ceramic crystal have both a covalent and ionic
character. The stronger bonds are responsible for a greater
stability of ceramics and impart very useful properties such as
hardness high molecules of elasticity, resistance to heat and
chemical attack.
At the same time the nature of the bonding creates difficulties
for the dental ceramist since all ceramic materials are brittle.

THE NATURE OF GLASSES

Dental porcelains are glassy materials and in order to understand
their formulation knowledge of glass formation in essential.
Glasses may be regarded as super cooled liquids or as noncrystalline solids.
This distinguishes them from other solids and their atomic
structure

and

resultant

properties

depend

not

only

on

composition but also on thermal history.

Impure solutions are selected in solid and molten state. To
modify physical properties like viscosity, melting temperature,
chemical

durability,

devitrification.

Glass formation

thermal

expansion

and

resistance

to

231
O 2 ion is the principal anion present in all glasses which form
very stable bonds with small multivalent cation like Silica, Boron,
Germanium, Phosphorus giving rise to structural units such as the SiO 4
tetrahedral which form a random network in glass. Thus these ions are
termed glass formers.

1932, (Zachoriasen) Randam network theory of glass structures

a. Interatomic forces in glasses and crystals are similar.
b. Atoms in glass oscillate about definite equilibrium position.
c. In glass (like crystals) atoms must be linked in the form of 3dimensional network but because they do not give a sharp X-ray
differentiation spectra they could not be periodic.
d. The units of structure in glasses (SiO 4 tetrahedra) and crystals
are practically identical but in crystals these structural units are
built up to give a regular lattice and in glasses there is sufficient
distortion of bond angles to permit the structural units to be
arranged in a random network.

For dental purpose the two glass forming oxides used are Si, B.
They form the primary network around which dental glass can be built.
Alumina under certain circumstances may be regarded as a glass
forming oxide.

Dental porcelain

232
Dental porcelains use the basic Si-O network as the glass
forming

matrix

but

additional

properties

such

as

low

fusing

temperatures, high viscosity, and resistance to diversification are built

in by the addition of other oxides to the glass forming lattice and SiO 4 .
These oxides generally consist of K, Na, Ca, Al, Boric oxides.

Fluxes
K, Na, Ca oxides are used as glass modifies and act as fluxes by
interrupting the integrity of SiO 4 network.
The purpose of a fluxes is to lower the softening temperature of
a glass by reducing the amount of cross-linking between O 2 and
glass forming elements (e.g.) silicon
(E.g.) Soda (Na 2 O) is introduced into a silicate melt to produce
Sodium silicate glasses. Here structural changes occur.
Instead of bridging oxygen ion which formed the link between
the 2SiO 4 , there are now two non-bridging oxygen one of which
has been contributed by the Na 2 O.
Hence a gap is produced in the SiO 4 network and the Na + ions are
accommodated in the interstices or holes in the random network.
Increased Na + ion added Si-O-Si bonds are broken.
O: Si ratio is very important
It will affect the viscosity and thermal expansion of glass.

233
(e.g.) In dental porcelain used for bonding to metal, it is a usual
practice to increase the soda content to raise the thermal
expansion of porcelain near to that of Au alloys. Li, K oxides
also have a function Mg, Ca, B oxides may also act as same.
K, Na, Ca oxides introduced as carbonates revert to oxides on
heating.

Devitrification and thermal expansion

Vitrification development of a liquid phase by reaction or
melting which on cooling provides the glassy phase. This structure is
termed as vitreous.

When too many glass forming SiO 4 tetrahedra are disrupted in

dental porcelain the glasses may crystallize or devitrify.
Devitrification is generally seen in high expansion glasses since
the usual way of increased thermal expansion is by addition of
the alkalis (soda, potash) hence too many SiO 4 tetrahedra are
disrupted.
Devitrification of high expansion porcelain may be seen when
cloudiness develops in the porcelain and this can be accentuated
by repeated firings.
Once devitrified difficult to form a glazed surface.

234
Regular

or

aluminous

porcelain

are

more

susceptible

to

devitrification due to their higher silica: alkali ratio.

Glass modifiers
Addition will
Decrease softening point
Decrease viscosity

Addition results in the 3-dimensional silical network which

contains may linear chains of SiO 4 which are able to move easily at
lower temperature than are the atoms locked into the 3-dimensional
structure of SiO 4 .

Increased ease of movement

Greater fluidity
Decreased softening temperature

Manufacturers employ glass modifiers form to produce dental porcelain

with different fritting temperature.

High firing -

1290 1370C

Medium firing

1095 1260C

Low firing

870 1065 C

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Porcelain

with

less

firing

temperature

decreased

chemical

properties.

Water
Not added intentionally
Important glass modifier
Hedonism ions can replace the Ma + or metal ion
This fact accounts for the phenomenon of slow crack growth of
ceramics stored in moist environment.
May account for occasional long term failure of porcelain
restoration after 6 7 years.

Boric oxide fluxes

Boric oxide (B 2 O 3 ) powerful fluxes act as glass modifier.
It forms a 3-dimensional network of BO 3 triangles.
Bonds extend in 3 dimensions as opposed to 4 in SiO 4 . The
stability of B 2 O 3 structure is weaker i.e. decreased softening
temperature, viscosity and increased expansion. If B 2 O 3 is added
to glass it acts as a flux and the structure in a 3-dimensional
continuous network of SiO 4 tetrahedra and BO 3 triangles.
The addition of an extra oxygen atom can change the boron
coordination from 3 to 4, thus forming BO 4 (strong) tetrahedra
and producing a stable glass. This explains the boron anomaly

236
where at ratios of 12% B 2 O 3 the physical properties of glass
changes quite markedly.
Initial addition of B 2 O 3 BO 4 tetrahedra formed giving low
expansion and good chemical resistance.
Above 12% no BO 4 tetrahedra formed but less stable form BO 3
takes over. Boric oxide is therefore used in quantities below the
initial 12% value.
A twin lattice is formed with SiO 4 in which BO 4 tetrahedra still
acts as a flux by interrupting SiO 4 network but at the same time a
gross weakening of glass is not produced by formation of less
stable BO 3 triangles.
Intermediate oxides
Addition of glass modifiers or fluxes to the basic glass forming
network SiO 4 in dental porcelain will decrease the softening
temperature and viscosity.
Dental porcelains require a high of resistance to slump or
pyroplastic flow hence we need to produce glasses with high
viscosity and low firing temperature. This can be done by using
intermediate oxides which although not usually capable of
forming a glass can take part in the glass network.
The hardness and viscosity of glass can be increased by the use
of intermediate oxide such as Al 2 O 3 .

237
It cannot be considered as a true glass former because the
dimensions of the ion excludes the possibility of Al 2 O 3 being
formed and O: Al ratios precludes formation of AlO 4 tetrahedra.
In crystals the Al ion can be 4 or 6 coordinated with oxygen
giving rise to AlO4 and AlO 6 .
The tetrahedral group can replace SiO 4 in silicate lattices.
Each Al has +3
Each Si ion has charge of +4 hence an additional unit positive
charge must be present to obtain electro neutrality.

When metallic oxides such as Na 2 O are present, one alkali metal

ion per AlO 4 tetrahedra would satisfy this requirement and the
alkali metal ions could be accommodated in the interstices
between tetrahedral groups. In this way each Al + 3 ion replaces a
Si 4 + ion network and Na + ion is taken in to preserve neutrality.

This is found in many aluminosilicates like Feldspar and

zeolites.

Chemical composition of dental porcelain

The stability of glass is highly dependent on the Si-O lattice and
the covalent bonds must not be reduced too much, other wise
problem of hydrolytic stability and devitrification may arise.
Average dental porcelain 60% SiO 2
Balancing oxides, fluxes are carefully controlled to provide the
required properties such as resistance to pyroplastic flow,

238
hardness, hydrolytic stability, low melting temperature and
resistance to devitrification.
Fritting
The term frit is used to describe the final glass product.
Raw material powder (O 2 , CO 3 ) are mixed in a refractory
crucible and heated to a temperature will above their ultimate
maturing temperature.
Oxides melt to form a molten glass.
Gasses escape, the melt is then quenched in water.
The red hot glass strikes the cold water immediately breaks up
into fragments and is termed on frit.
Process of blending melting, quenching the glass components is
called fritting.

FELDSPATHIC PORCELAIN
Feldspar is the precursor of common clay
Natural feldspars are mixtures of albite Ma 2 Al 2 Si 6 O 1 0 and
orthoclase

or microline

(K 2 Al 2 Si 6 O 1 6 ) with free

crystalline

quartz.
They are a ratio of Soda and Pottash which may vary
High potash content feldspar is generally selected because of its
increased resistance to pyroplastic flow.

239
Potash feldspar has high viscosity and this will decrease only
relatively slowly with increased temperature.
When feldspar is melted at about 1250 0 C to 1300 0 C the alkali
unite with alumina and silica to form Na or K aluminium
silicates.
A glassy phase is formed with a free crystalline silica phase
Feldspar has been used to make dental porcelain for decades
(high fusing)
Natural feldspar 85%, Quartz 15%; Then demand for low
fusion temperature came into picture

Hence the feldspar was modified by the addition of glass

modifiers fluxes intermediate oxides. Chemical analysis of natural
feldspar shows that the elements necessary for glass making are present
in this mineral.

II. Feldspar in dental porcelain

Contain potash + alumina + silica
Used in preparation of nearly all dental porcelain designed for
metal

ceramic

ceramics.

crown

and

many

other

dental

glasses

and

240
When feldspar is mixed with various metal oxides and fired to
high temperature it can form a glass phase that is able to soften
and flow slightly at porcelain firing temperature.
The softening of glass phase during firing allows the porcelain
powder particles to coalesce together by sintering

It is a term that

refers to the fusing of particle together at high temperature without

complete melting.
Role in leucite formation
Feldspar has a tendency to form the crystalline mineral leucite
when it is melted.
Leucite is potassium aluminium silicate mineral with a large
coefficient of thermal expansion (20 to 25 x 10 6 / 0 C)
Feldspar when heated to temperatures of 1150 to 1530 undergoes
incongruent melting to give crystals of leucite in liquid phase
Incongruent melting is a process by which one material melts to
form a liquid plus a different crystalline material

Coloring and opacifying components

Basic

Dental porcelain material will vary in color depending

upon whether it is a single phase or multiphase glass (mixture)

If porcelain single phase glass then all oxides constituents are
completely taken into solution. The resultant product should be
as transparent as good window glass.

241
In case of fused feldspathic porcelain some manufacturer may
limit the degree of fusion and pyrochemical reaction in the frit to
the extent that a proportion of feldspar remains undissolved in
glass. These grains remain discretely in the glass matrix and
because of difference in RI the final glass frit may appear
opalescent or assume a gray blue translucency similar to
internal enamel.
Coloring pigments
Colored glasses are produced by fritting high temperature
resistant pigments generally metallic oxides into the basic glass
used in porcelain manufacturer.
Glass is then a highly color saturated and ground to a fine
powder.

Colour pigments used are Pink-Chromium tin or Chromium-alumin

This eliminates the greenish hue of glass and adds a warm tone
to the porcelain.
Yellow-Indium or praesodynium ,this gives a ivory shade
Blue-Cobalt salts ,produces enamel shades
Green Chromic oxide , not generally preferred
Grey- iron oxide or platinum grey, give an effect of translucency.

242
OPACIFYING AGENTS
These are added to produce a more life like tooth affect
An opacifying agent generally consists of a metal oxide ground
to a very fine particle size less than 5 m to prevent a speckled
appearance in the porcelain
Common

oxides

used

are-cerium

oxide,

titanium

oxide,

zirconium oxide.
STAINS AND COLOUR MODIFIERS
They are supplied in a kit.
A stain is more concentrated than a colour modifier
Stain used as surface colourent and to provide enamel check
lines, decalcification spots.
Colour modifier used for gingival effects.

Fluorescence
The usual procedure for producing fluorescence is by addition of
the uranium salt sodium di-urinate. This salt produces a strong
greenish yellow effect and when small amount of cerium is added
a bluish white fluorescence can be achieved.
The use of uranium has been banned.
New non-radioactive porcelains are available containing rare
earth oxides.

243
Advantages
1. Good aesthetics
2. Increased compressive strength
3. Good chemical durability
4. Biocompatible
Deficiencies
1. Decreased tensile strength
2. Brittleness
Nepheline synite
This material has been tried as a replacement for feldspar (1944)
Nephiline is the essential mineral of this syenite.
This never became popular for making dentalpocelain because of
its high pyroplasticity
Methods used to overcome the deficiencies of ceramics fall into two
categories
Strengthening the brittle materials
Designing components to minimize stress concentration and
tensile stress.

REFERENCES
1. Anusavice

KJ,

Philips

science

of

dental

materials.1998;

10thed:583-618.
2. .McLean JW, The science and art of dental ceramics, vol-I.1979;

244
1sted:55-112.
3. Hondrum SO: A review of the strength properties of dental
ceramics. J Prosthet Dent; 1992:67:859-865.
4. McLean JW, Odont D: Evolution of dental ceramics in the
twentieth century. J Prosthet Dent; 2001:85:61-66.