From: Introduction to Ceramics, kingery et al

Dr.
Dr Ir.
Ir Sotya Astutiningsih,
Astutiningsih M.Eng
M Eng
Ceramics phase equilibrium
y One component
y Two component
y Ternary
Two component system
y A system consisting of two components is called a
binary system or two‐component system. It is
controlled by three variables (pressure,
(pressure temperature
and composition) and it requires a 3D model ( a p‐T‐x
diagram)
g ) such as that shown schematicallyy in Fig.
g 3.
3
The condensed system
In many ceramic system, the vapour pressures of the liquid
and solid phases are negligible or so slight between the
room temp and 1500
1500‐2000C
2000C that the pressure variable is
ignored and the solid‐liquid phase relations are
determined atatmospheric pressure (p=constant). The
system is
i then
h called
ll d “condensed”
“ d d” system and d the
h phase
h
rule reverts to:
F C P+1 3 P.
F=C‐P+1=3‐P.
Fig. 1. Intersection off plane
l off constant pressure
with 3D (p‐T‐x) Binary system
In Fig
g 1.,, a plane
p has been passed
p through
g the diagram
g at
a position corresponding to a constant pressure at 1
atm. The intersection of this plane with the fusion
curves off theh endd members
b (pure
( A and
d pure B) and
d
with those of all the intermediate mixtures of A and B
results in the phase diagram for a two
two‐component
component
system at constant pressure (T‐x).
The elimination of the pressure variable leads to a
tremendous simplification of the viewpoint and
representation of a binary system. At constant
pressure,
pressure The phase Rule and degrees of freedom are
as follows:
y Three coexisting
g phases,
p F=3‐3=0,
33 invariant
y Two coexisting phases, F=3‐2=1, univariant
y One phase, F=3‐1=2, bivariant
The elimination of the vapour phase (p const)
(p=const),
tremendously simplifies the number and types of
p q
phases which would coexist in equilibrium. p
Temp‐
composition diagrams can be represented in a plane
and the need for 3D visualisation is eliminated.
H
However, in
i some cases, such
h simplification
i lifi ti is i nott
justified.
Two component, condensed (T (T‐x)
x) systems may be
classified as follows:
(the most extensive collections of diagrams in ceramics –
Am
A Ceram
C Soc
S
1. The simple eutectic
2 Intermediate compounds
2.
congruent melting
incongruent
g melting
g
dissociation
3. Solid solution
complete
partial
Th
Three ddi i l considerations
additional id i iin these
h bi
binary systems
are:
1.
1 Immiscibility in the liquid region
2. Unmixing of solid solutions or “exsolution”
3 Polymorphism of solids
3.
If the end members intermediate compounds or solid
end‐members,
solutions exist in two or more polymorphic forms, this
p p
phenomenon is superimposedp yp
on the three basic types
of diagrams listed above and they become, in some
cases, much more complex.
Eutectic
diagram
diagram,
BeO‐Al2O3
•The regions of ss (solid solution)
have not been determined
•The system: 3 simpler two comp
system (BeO‐ BeAl2O4; BeAl2O4 –
Be Al6O10 and BeAl6O10 – Al2O3)
•Assignment:
A i peform
f an isoplethal
i l h l
analysis for composition E
(heating)
•Lowering of T :
•Advantage: aid of firing at
lower T. Liq increases the ease
of densification
•Disadvantage: in refractory
Na2O‐SiO2
Lowering of T;
Advantage: Na2O‐SiO2 glass
composition can be melted at low
temp. The liquidus is lowered from
1710 in pure SiO2 to ~790 for
eutectic composition at approx
75% SiO2
CaO‐Al2O3
CaO‐Al2O3; (disadvantage) the
liquidus is strongly lowered by a
series of eutectics. In general,
strong basic‐oxides such as CaO
for a low‐melting eutectics with
amphoteric or basic oxides, and
these classes of materials cannot be
used adjacent to each other,
eventhough they are individually
highly reactive.
 l
Incongruent melting
= peritectic
A solid compound does not melt to
form a liquid of its own
composition but instead
dissociates to form a new solid
phase and a liquid.

Enstatite (MgSiO3) at 1557 Æ

Mg2SiO4 + liquid (61% SiO2).
Three phases present and temp
remains constant until the reaction
is complete
Another example Æ Fig 7.14 potash
feldspar
Peritectic
Potash feldspar
Phase separation
NiO‐CoO
When a liq or crystal solution
is cooled, it separates into 2
separate phases at the
consolute temp as long as the
excess enthalpy is positive (fig
7) Æ important to the
77‐7)
development of substructure
in glasses
Solid solution
Fig 7.15; 7.13; 7.16 (MgO‐CaO); 7.17
(MgO‐Cr2O3)
Steel plant refractories: directly
bonded magnesia – chromite brick
is formed at above 1600 as a results
of the partial solid solubility of the
constituents; exsolution occurs on
cooling
Almost all open hearth roofs are
formed of either direct‐bonded,,
rebonded fine grain or fusion‐cast
magnesia chromite refractories
In the basic oxygen –furnace
process for steel making, MgO –
CaO refractories bonded with
pitch are widely used, and the solid
solubility at high temp forms a
high‐tem
high tem bond.
in magnesia refractories, the lower
solid solubility of SiO2 as
compared with CaO in MgO
requires that excess CaO be added
to prevent the formation of low TM
intergranular silicates
MgO‐Al2O3
Extensive solubility of MgO and AL2O3 in spinel.
As spinel in this composition range is cooled, the solubility decreases and corundum precipitates as solid phase.
CaO – ZrO2
There are 3 fields of ss: tetragonal,
monoclinic and cubis.
Pure ZrO2 exhibits a mono‐tetra
phase transition at 1000C which
involves a large volume change and
makes the use of pure zirconia
impossible as a ceramic material.
Addition of lime to form the cubic
ss, which has no phase transition,
is one basis for stabilized zirconia,
a valuable refractory.
 l d
Complex diagram
Ba2TiO4 – TiO2
Combination of simple elements in
one system sometimes appear
frightening in their complexity but
actually offer no new problems in
interpretation.
There are 2 eutectics,
eutectics 3
incongruent TM, polymorphic
form of BaTiO3 and an area of
limited ss
 h
Three‐component
phase diagrams
Are fundamentally no different
from the two components
Complete graphical representation
is difficult
If P is held constant, composition
can be
b presented d on an equilateral
il l
triangle, the temp on the vertical
ordinate
For 2D representations, the temp is
projected on an equilateral
triangle, with the liquidus temp
represented by isotherms. The
diagram is divided into areas
representing equilibrium between
the liquidus and a solid phase.
Boundary curves represent
equilibrium between 2 solids and
the liquid. Intersection of 3
b
boundary
d curves iis the
h position
i i off
4 phases in equilibrium (invariant
point in the constant pressure
system)
K2O‐Al2O3‐SiO2
2D representation = constant temp
cut thru diagram
The basis for many porcelain
compositions
The eutectic in the subsystem
potashh – feldspar
f ld – silica
ili – mullite
lli
determine the firing behaviour
Na2O‐CaO‐SiO2
The basis in glass technology
Most compositions fall along the
border between the primary phase
of devitrivite Na2O.3CaO.6SiO2
and silica
Li id temp is
Liquidus i 900 to 1050
This is a compositional area of low
melting temp, but glasses formed
CaO for chemical resistance
Al2O3‐SiO2
Mullite: TM incongruent; although
the melting behaviour of mullite
has been controversial
Eutectic between mullite and
cristobalite at 1587 to form liq of 95
mole% SiO2
Solidus temp between mullite and
alumina at 1828
Factors affecting the fabrication
and use of several refractory:
•Refractory silica brick (0.2‐1.0 wt%
Al2O3)
•Clay products (35 – 50 wt% Al2O3)
•High
High‐alumina
alumina brick (60 – 90 wt%
Al2O3)
•Pure fused mullite (72 wt%
Al2O3)
•Pure fused / sintered alumina
(>90 wt% Al2O3)
Refractory silica brick (0.2‐1.0
(0 2‐1 0 wt% Al2O3)

y Widely used for furnace roofs; major application: as roof

brick for open hearth furnaces with operating temp of 1625
to 1650
y At this
h temp a part off the
h brick
b k is actuallyll in liq
l state
y A small amount of alumina are deleterious to brick
properties because the eutectic comp is close to the silica
end.
d C
Consequently,l even small ll addition
ddi i off aluminm
l i oxide
id
mean a substantial amount of liquid phase present at temp
above 1600
y For
F thi
this reason, supersilica
ili brick
b i kh having
i a lower
l alumina
l i
content through special raw material selection or
treatment is used in the structures that will be heated to
high temp
Clay products (35 – 50 wt% Al2O3) (fire clay bricks)
Hi h l i b
High‐alumina i k (60 – 90 wt%
brick t% Al2O3)

For comp without impurities the

equil phases present at temp below
1587 are mullite and silica
The relative amounts of these
phases present change with
composition and there are
composition,
corresponding changes in the
properties of the brick.
At temp above 1600, the amount of
q is sensitive to the alumina‐silica
liq
ratio, and for these high‐temp
applications the higher alumina
brick is preferred
Pure fused mullite (72 wt% Al2O3)
Pure fused / sintered alumina (>90 wt% Al2O3)
y Refractory properties of brick can be substantially
improved if sufficient alumina is added toincrease the
fraction of mullite.
y At >72 wt% alumina, the bric is entirely mullite or a
mixture of mullite plus alumina Æ no liq present up to
1828
8 8
y Fused mullite bricks Æhas superior ability to resist
corrosion and deformation at high temp
y Pure alumina Æ highest refractoriness
y Sintered alumina Æ for laboratory ware
y Fusion cast alumina Æ glass tank refractory
MgO‐Al2O3‐SiO2
The system is composed of several
binary compounds together with 2
ternary compounds: cordierite
2MgO.2Al2O3.5SiO2 and
sapphirine 4MgO.5Al2O3.2SiO2
both of which melt incongruently
The lowest liquidus temp is at the
tridymite – protoenstatite –
cordierite eutectic at 1345, but the
cordierite – enstatite – forsterite
eutectic at 1360 is almost as low
melting.
Ceramic compositio in this diagram:
ag es te refractories,
magnesite e acto es, forsterite
o ste te ce a cs,
ceramics,
steatite ceramics, special low loss steatites
and cordierite ceramics, in which the
composition is illustrated in the figure.
In all but magnesite refractories, the use of
clay and talc as raw materials is the basis for
the compositional developments. These
materials are valuable because of their ease
of forming; they are fine grained and platey
and are consequently plastic, nonabrasive
and easy to form.
On heating, clay decomposes at 90 to form
fine grained mullite in a silica matrix. Talc
decomposes and gives rise to a similar
mixture of fine ggrained p
protoenstatite
crystals, MgSiO3, n a silica matris at ~1000.
Further heating of clay give rise to increased
growth of mullite crystals; crystallization of
the silca matrix t cristobalite and formation
of eutectic liq at 1595.
Further heating of talc leads to crystal
growth of enstatite, and liq
g q is formed at
temp 1547. at this temp almost all the comp
melts since talc (66.6% SiO2, 33.4% MgO) is
not far from the eutecticcomp in the MgO –
SiO2 system
For firing to form a viterous
densified ceramic, about 20‐35% of
a viscous silicate liq is required.
Pure talc Æ no liq until 1547, when
the entire compliquifies
Thi can b
This be iimproved d using
i talc
l –
clay mixture (ex comp A of 90%
talc – 10% clay) Æ~30% liq is
formed abruptly at the liquidus
temp p of 1345
345 and the amount of liq q
increase quite rapidly with temp
making close control of firing temp
necessary … etc
Techniques for determining phase
equilibrium diagrams
y Dynamic methods
y Static methods
Dynamic methods
y Use the change in properties of a system when phases
appear or disappear
y Thermal
e a aanalysis
a ys s
Dynamics methods are suitable for determining the temp of
phase changes but give no info about the exact reaction
Phase identification before and after any phase change is
carried out by
y chemical determination of composition
y Determination of optical characteristics
y X ray determination of crystals
y Microscopic examination of phase amounts and distribution
Thermal analysis
Is the most common method
The temp of the phase change is determined from changes
in the rate of cooling or heating brought about by the
heat of reaction
Under the experimental
p conditions used,, the phase
p
change must take rapidly and reversibly at the equil
temp without undercooling, segregation or other non‐
equil effect
In silicate systems the rate of approach toward equil is
slow; as a result thermal analysis are less useful for
silicates than they are for metals
Static methods
y Use a sample held under constant conditions until
equil is reached, when the umber and composition of
the phases present are determined
1st
y Equil conditions are held at elevated T or P, the ample
is quenched to RT sufficiently rapid to prevent phase
changes during cooling
cooling, and then the specimen is
examined to determine the phases present.
By carrying out these steps at a number of different T
and P and compositions, the entire phase diagram can
be determined. Sometimes high T x‐ray & microscopic
exam can determine the phases present at high T,
making quenching unnecessary
2nd
y For silicate systems: slow approach toward equil and
the difficulty in ensuring that equil has actually been
reached
3rd
For most systems (common technique)
y Mix together carefully in the correct ratio to give the final
comp desired. These are held at a constant T in Pt foil; after
p cooling,
rapid g the mixture is reground
g is a mortar and
pestle and then heated a second time and quenched
y The phases present are examined, the sample mixture
remixed, rehated, and quencehd again.
again
y The resulting material is then reexamined to ensure that
the phase comp has not changed
Æ this
y ‐Æ hi process consumes much h time
i & effort,
ff since
i severall
thousands individual experiments may be necessary for
one ternary diagram Æ this is why only a few systems have
b
been completely
l l and d exhaustively
h i l studied!!
di d!!