Chapter 7 - Ceramics Phase Equilibrium Diagrams Kingery

264
6.2
D with Increasing pressurecfor
6.3. If diffusion anneal times re
6.4.
6 5 From data on ZnS d f n temperature to the meIUil
difuslon coemcient of 3 IO Z/ l USlO imcieIIIs were measured At

the basis
6.6
pIot ? (d) What is the to? (;) Would quenchlng the the
state of' the --..... energy experlmental) for Na+ diff
1:11
r
i
OF
MICRO'S'TR UCTURES
.I,N CERAMICS
The properties of ceramics are determined by the properties of each

phase present and by .the way in which these phases, including...Q___ orosity
and in many cases the are arranged. ln Part 11 we have
discussed the structure of crystalline materials, the structures of glasses,
imperfections in these structures, the characteristics of interfaces, and
how moility of to structural

properties of each phase present in more complex ceramics. ln Part 111 we
want to develop an understanding of the factors which determine the
phase distribution and how they in ceramic systems.
The development of microstructure proceeds on two fronts . First there
a tenden-cy to form an concentra-
tion of phases such as to minimize th
Phase-equilibrium diagrams are an economical method for des'cribing the
final state twards which the phase composition tends. ln our discussion
of phase diagrams we have limited ourselves to a maximum of three
and have developed the underlying thermodynamics only to
the minimum level necessary. In many actual more than three
components are important, but the of our treatment to this
mre complicated case uses the sam'e principles which have been
described and discussed. The primary difficulty with including a greater
number of components is not so much conceptual as in the easy
representation of a large body of data in concise diagrammatic form,. For
265
266 INTRODUCTION TO CERAMICS
ceramic students we have found that the most useful introductory
discussion to multicomponent systems is that given by A. Muan and E. F.
Osborn, Phase Equilibria in and among Oxides in Steelmaking. *
In addition to changes in the chemical constitution and amounts of
phases present physical factors are also important in determining the
direction in which changes proceed during the development of micro-
structure. achieved
surface and interface which occurs during the processes of
In addition there are
terms and surfce-energy terms associated with the formation of a new
phase which both its morphology and its tendency to appear. These
aspects of the driving forces toward minimizing the system s free energy
during microstructural development are discussed in 8 in rela-
tionship to phase transformations and in Chapter 10 in relationship to
grain growth and sintering. The physical changes occurring, such as the
decrease in porosity, the distribution in porosity, and the morphology of
the phases present, are equally as important as the chemical processes
related to phase equiIibria discussed in Chapter 7 and chemical equilibria
discussed in Chapter 9.
Only a small percntage of real ceramic systems are treated under con-
ditions such that equilibrium is achieved. Particularly with regard to the
small driving forces associated with surface and interface energy and for
systems in which the mobiIity of atoms is small, including many silicate
systems and almost all systems at moderate and low temperatures, the
way in whtch equilibrium is approached and the rate at which it Is
approached equally as important as the equilibrium being approached.
In the phase systems with which we are mostly concerned,
material processes may take place by or
or The
rate and kinetics by W1tich these processes are important in affecting the
development of are discussed in Chapter 8 with regrd to
phase transformations, in 9 with regard to solid-state reactions,
and in Chapter 10 with regard to owth and sinterng. A thorough
understanding f the way in which systemsnodify their microstructure in
the approach toward equilibrium is absolutely essential for understanding
the microstructur and therefore the properties of ceramic products.
In Chapter 11 some characteristic measurements necessary to describe
microstrcture together with typical examples of ceramic microstructur e
in a variety of real systems are discussed and described. In addition to the
specific systems described in Chapter t 1 we have been implicitly or
*Addison-Wesley Pu\ili shlna Cgmpa ny; Readlns, Mass .. 1965.
MICROSTRUCTURES IN CERAMICS
267

throughout Indeed, the development of microstructure, ltS InjlCnce on
the properties of ceramics, and its control by compositlqn and processIng
changes are a theme.
7
Ceramic Phase-
Equilibrium
Diagrams
At equilibrium a system is in it s lowest free energy state for the
composition, Wheh
a given set of system parameters is fixed, there is only one mixture of
phases that can be present, and the compostion of each of these phases is
determined. Phase-equilibrium diagrams provide a ciepr and concise
method of graphically representing this equilibrium situation and are an
invaluable tool for characterizing ceramic systems. They record the
composition of each phase present, the number of phases present, and the
amounts of each phase present at equilibrium.
The time that it takes to reach this equilibrium state from any arbitrary
starting point is highly variable and dependson factors other than the finaJ
equilibrium state. Particularl y for systems rich in silica the high viscosit y
of the liquid phase leads to slow reaction rates and very long times before
equilibrium is established ; equilibrium is rarel y achieved. For these
systems and for others, metastable equilibrium, in which the system tends
to a lower but not the lowest free energy state, becomes particularJy
Important.
It is obvious that the phases present and their composition are an
essentiaJ element in analysing, controlling, improving, and deveJoping
ceramic materials. Phase diagrams are used for determining phase and
composition change occurring when the partial pressure of oxygen or
other gases is changed, for evaluating the effects of heat treatments on
crystallizatiop and precipitation processes, for planning new composi-
tions. and for many other purposes. We have already seen the importance
of thermodynamic equilibrium in our discussions of single-phase systems:
crystalJi ne sQlid solutions (Chapter 2), crystalline imperfections (Chapter
4), structure of glasses (Chapter 3), and surfaces and interfaces (Chapter
5). In this chapter we concentrate our attention on equilibria invoJving
two or phases.
269
270 INTRODUCTlON .TO CERAMICS
7.1 Gibbss Phase Rule
When a system is in equilibrium, it is necessary that the temperature
and pressure be uniform throughout and that the chemical potential or
vapor pressure of each constituent be the same in every phase. Otherwise
there would be a for heat or material to be transferred from ooe
part of the system to some other part. ln 1874 J . Willard Gibbs* showed
that these equilibrium conditioos cao occur ooly if the relatiooship
P+V=C+2
is satished- This is known as the phase rule, with P being the number of
phases preseot at equilibrium, V the variaoce or oumber of degrees of
freedom, aod C the number of compooents. This relationship is the basis
for prepariog aod usiog phase-equilibrium diagrams.
A phase is defioed as aoy part of the system which is physicaIIy
homogeneous and bouoded by surface so that it is mechaoicaIIy
separable from other parts of the system. It oeed not be cootiouous; that
is, two ice cubes in a driok are ooe phase. The number of degrees .of
freedom or the variaoce is the number of ioteosive variables (pressure,
temperature, composition) that can be altered independently and arbitrar-
ily without bringiog about the di sappearance of a phase or the appearance
of a new phase. The oumber of componeots is the smaIIest oumber of
independeotly variable chemical coostitueots oecessary and sufficient to
express the compositioo of each phase present. The meaniog of these
terms wiII become clearer as they are applied to specific systems in the
foIIowiog sectioos.
Deductioo of the phase rule foIIows directl y from the requirement that
the chemical potential of each constituent i be the same in every phase
preseot at equilibrium. The chemical potential is equal to the partial molar
free energy G;,
; = T. P. n , . n
which is the change in free energy of a system at constant temperature
and pressure resulting from the addition of one mole of constituent i to
such a large quaotity of the system that there is no appreciable change in
the conceotratioo. In a system with C components we have ao indepen.
dent equation for each component represent"ing the equality of chemical
potentials: For a system containing P phases, we have
a b c P
= ... (7.2)
*Coll ecled Wq rks. Vol. 1, Lngmons. Green & Co .. Ll d .. LQndon" 1928.
CERAMIC PHASE.EQUILIBRUM DIAGRAMS
P
= = :: ". =
etc .
271
(7 .3)
constitute C(P - l) independent equatlons which serve to hx

phases
requires P
(C - 1)

terms, v
vp
imposed
conditions
of
temperature
and
pressure
gIve
Total nmber of
variables ==
P (C - 1) + 2
Variables fixed by equalityof
chemical
pteotials ==
C (P
- 1)
Variables
remainiog to be fixed ==
P (C - 1) + 2 - C (P - 1)
V==C-P+2
(7.4)
(7.5)
(7. 6)
(7.7)

that
equilibrium
does not exist), the
reverse is not always true-
That ls,
conformation
with the phase rule is not a
demonstration
of
equllibrillm
.

7.2
One.Componeot
Pbase
Diagrams

Rnd
different Phase
distributions
correspond
to Fig. 72a
to c. In actual
mctice
measurements
in which the vapor phase
is
unimportant
are
ugually
made at constant
atmospheric
pressure In a way similar to Fig.
7.Zd
Although
this is not an ideal closed
system, it closely
approximaFs

- , ( : > )
( q )
( l J )
T L ' S ! d
1 " 0
1
m
@
@
Z " Z
S 3 I I W H 3 3 O l N O I l 3 t M O R i N I
- q ! I ! n b : : l l j : > e : : l 1 0 1 p : : l J ! n b : : l J : : I J V - J O 8 u o ( 1 9 4 1 O S 3 J l l
U M O q S S U O ! I B W J O J S U B 1 1 J : : I q 1 0 : : I l j 1 . . ' : : I ( q ! S J : : I A : : I 1 p U B p ! d U J 5 1 o E L ! ; 1 1 3 U O ! I ! S U l I J I
Z l J B n b - : : I l . p 0 [ ' < : u O ! l : > : : I S U ! p d s s n : > S ! p s y ' U M O l j S S B 3 J B S 3 J I 1 1
- l U d d W : : I 1 U O m S U B J l d q l : : l J n s s : : l J d [ l V ' B : > ! [ ! S p ! n b ! ( p U B : : l 1 ! [ B q 0 1 S l J : : I
- f i Z l J B n b - l B l O : l : l O
. s : : l s B l j d P d S U : : I P U O : l : : l A y : : l J e : : I J : : I l j 1 . . U ! P ; l l B 1 1 S n m l n q
J O U ! W J O : : l j O J : : l l j l 0 1 S B d 1 n d s ! p ; l W O S 0 1 p d f q n s 1 I ! 1 S B : l ! l ! S J O
S : : l S B l j d : : l l j l : : l J e S U O ! l B : l ! j d d B 1 0 J l S d 1 : : l l U ! 1 d l B : : l J S J O
' p u n o J U d : : l q S B q a 1 ! a o t f S ! 1 s : : l S B l j d
M . : : I U J d l { l O U B O O [ : : l A O q B S : : l l O S S ; l l d J : : l l { S ! l { U : : l A : : I l Y ' S P B d W I
: : l l ! l O : : l l : : l W J O l j n S : : l J B S B ; l l O l B U U ! J O : > : l O 0 1 p u n o J U d : : l q S B l { l { : l ! l { M S J B d d d U
i J l ! S i J O : J : : l S B l { d M : : l U B 0 1 O E : : l A O q B S : : l J O S S : : I J d l Y ' L O ! S S ! : : l 1 O l
- B J : : l d W : : l l p U B : : I l O S S : : l J d l { 8 ! l { l B p : : l ! p n l S ( ; l A ! S U : : I 1 X ; l U : : l : : l q S B l { l { : > ! l { M W : : l l S S
J : : l l j l O U Y ' : : l l B J ( n J d s n B l B p : : l : : l : l O J d 0 1 U O ! p e d J : : l l { l J O J p d 1 ! n b : : l J S ! ( : : l ) { : l ! U
S B l j : > n s J O I S j B 1 B : : l P ! n b ! ( B J O : : l : : l u d S : : l J d : : I l { l U O ! l ! P P U
U [ ' t _ ' L U ! U M O l { S S B 1 B S S d : > ; l U d J B s d J n s s : : l J d p u e S : : l J n l B J : : I d w : : l 1
l j 8 ! H . W 0 1 J S p U O W e ! p : > ! l ; l l { l U S J O U O ! l : : l n p o J d
J O : : l l j l S ! : : l S : : l l { l J O J B j n : : l B p : : l d s l S O W ; l I H S d B l { l ; l d U !
S W B J 8 B ! P : : I S B l { d l U : : l u O d w O : : l - : : l u O J O s u o q B : : l ! ( d d e J O B : : l J e : : l J : : I q 1 . .
l B : > q 1 ; l A l S O W I B U : : l l J O : : l J e S : : l S B l { d P ! ( O S U : : l : : l M : l : : l q S : : l U ! { S U O ! l B W
- J O J S U B J l : : l S B l { d - p ; l S U ; l p U O : : l J O J I I B W S I I B n s n S ! A V ' : : l : : l U ! S ' : : l A ! l ! S O d I I B n S n
d J B S : : l A J O : > : : l S : : I l { l J O S : : l d O j S : : l l { l W J O J : : l J I 1 l B 1 ; l d W : : l l - l { S ! l { B 0 1 : : l J n l B 1 : : l d w : : l l
B W O J } u o : : l A ! l ! S O d I I B n S n S ! A V ' p u e : : I A ! l ! S O d S B M j B
S ! H V ' : : l : : l U ! S ' : : l J 0 1 B l : : l d W ; l 1 : : l l { l S ! 1 , p U B : : l W n j O A J B ( O W : : l I H S ! A V '
U O ! l B W J O } S U B 1 l J O U O ! l B Z P o d B A U o ! s n J J O l B : : l l { J e j O w : : l l { l S ! H V : : I 1 d q M
1 0 . 0
% m A Y a m
m - m d
i
i
W
F
(
-
H
J
%
T
U
m

O l l
A V ' 1 , l , p

u o q e n b ; l u 0 1 d d e ( J
- S n ! S n B j J : : l l { l q p : : l U ! W l ; l l : : l p l U ! O d U B l e S ! S : : I A J n : : l l e p U n O l - : : I S B q d
: : l S : : l q l J O : : l d O ( S : : l l j 1 . . ' l U ! O d i u ! ( ! o q : : l q l J o O O [ l e . S J n : l : l O 1 0 d B A p U l : l P ! n b ! (
J O : : l : : l U : : l l S ! X : : l O : : l ' l U ! O d 8 U ! Z ; l : : l J J d l { l J o O l B S J n : : l : : l O P ! n b ! ( p U B
P ! l O S : : l l { l U : : I : : I M l d q W n ! l q ! ( ! n b : : l [ ' L ' 8 ! d U ! U M O l { S S B : : l l O S S d J d [ l V
' : : I s B q d M ; ) U B J O d : : l U e l B d d d B
: : l l j l l n o q l ! M p d S U B q : l I ! l B l l N 1 B : : l q U B : : l d 1 0 1 B l : : l d W d l p u e ; ) l n s s : : I J d q l O q p U B
( 8 ' U
l = J \ l + [ = A + [ l + . J = ; : J \ + d
: J l B
S B l U : : I S d J d S ! : : l S B q d : : l U O { U O J I . ' I U : : I S d J d 0 1 : : l J B S d S B q d q l o q J ! L d 0 1
: : l 8 U B l { : l O S ( B l S n W ' d ' L l , 0 1 ' 1 , : : l 8 U B q : : l : : l M 1 1 ' : : I S B l { d B J O d : : l U B J B : : I d d B S ! P : : l l { l
p d 8 u B q : : l : : l q U B : : l l j l o q 1 0 U l n q : : l J n l B J : : I d W : : l l J O : : l J n s s : : l J d
J : : l l { l ! : : I l B 4 1 S U B : : I W S ! l { 1 . . ' : : l U O S ! d : : l U B ! l B A : : 1 4 1 p U B [ = A < : + 1 = A + l
: : > 1 1 V 1 I 3 : : > E L l
275
rium. The vapor pressure shown in the diagram is a measure of the
chemical potential of silica in the .different phases. and this same,kind of
diagram can be extended to include. the metastable forms of silica which
may occur (Fig. ,7.5). The phase with heavy
lines in the diagram) the equilibrium
phase. However, once formed, the transition between cristobalite arid
is so slu,ggish that -cristobalite commonly transforms on cooling
into a -cristobalite. Similarly, commonly transforms into a-
and -tridymite rather than into the equilibrium quartz forms. These are
the forms present in the refractory silica brick, for example. Similarly,
when cooled, the liquid forms silica glass, which can remain indefinitely in
this state at room temperature.
At any constant temperature there is always a tendency to transform
into another phase of lower free energy (lower vapor pressure), and ,the
reverse transition is thermodynamically impossible. It is not necessary,
however, to transform into the lowest energy form shown. For example,
at llOOo silica glass could transform into -cristobalite, -quartz, or
2-tridymite. Which of these transformations actually takes place is
i> \'!;'
phaS8 occurrina in the system SiG, .
--- y
;*?
y

CERAMIC PHASE-EQtJlLIBRIUM DIAGRAMS
LiqUl d
I Graphite

3000
'F (' Kl
phase diagram for carbon. From C
5000
1000
200
0
870'
1470. 1713'
Vapor
573.
1 atm
a-Quartz
@

"
"
Figo 7.4.
,
!
Temperature
Equilibrium diagram for SiO, .
r i

214
l
t
determined by the kinetics of these changes. In practice, when silica glass
is heated for a long time at this temperature, it crystallizes, or devitrifies,
to form cristobalite, which is not the lowest energy form but is structur-
ally the most similar to silica glass. On cooling, transforms
into
The silica system illustrates that the phase-equilibrium diagram graphi-
cally represents the conditions for minimum free energy in a system;
extension to include metastable forms also allows certain deductions
about possible nonequilibrium behavior. Almost always, however, a
number of alternative nonequilibrium courses are possible, but there is
only one equilibrium possibility.
7.3 Techniques for Determining Phase-Equilibrium Diagrams
The phase-equilibrium diagrams discussed in the last section and in the
rest of this chapter are the product of experimental studies of the phases
present under various conditions of temperature and pressure. In using
phase-equilibrium diagrams it is important to remember this experimental
basis. In critical cases, for example, diagrams should not be used without
referring directly to the original experimenter s description of exactly
how the diagram was determined and with what detail the measurements
were made. As additional measurements are carried out, diagrams are
subject to constant revision.
There is a large body of literature describing methods of determining
phase equilibrium. In general , any physical or chemical difference be-
tween phases or effect occurring on the appearance or disappearance of a
phase can be used in determining phase equilibrium. Two general
methods are used: dynamic methods use the change in properties of a
system when phases appear or disappear, and static methods use a sample
held under constant conditions until equilibrium is reached, when the
number and composition of the phases present are determined.
Dynamic Methods. The most common dynamic method is thermal
analysis, in which the temperature of a phase change is determined from
changes in the rate of cooling or heating brought about by the heat of
reaction. Other properties such as electrical conductivity, thermal expan-
sion, and have also been used. Under the experimental condi-
tions used, the phase change must take place rapidly and reversibly at the
equilibrium temperature without undercooIi ng, segregation, or other
nonequilibrium effects . .I n silicate systems the rate of approach toward
equilibrium is slow; as a result thermal-analysis methods are 1088 useful
for silicates than they are for metL\ls, for
CERAMIC PHASE-EQUlLlBRIUM DlAGRAMS
277
Dynamlc methods are suitable for determining the temperature Of

structure, and mICroscoplc examination of phase amounts and phase

consist of three steps- Eqmlibrim c.onditions are held at

and then the specimen is examined to determine the phases present - By

1t1e difRcult-- in ensuring that equllibrillm has actually been reached. For
most this means that statlc measurements are necessary A

rat io to These are held at a
lemPerature in platinum fml ; after rapid cooling, the mixture lS regrollL
in a mortar and pestle and then heatcd for a second time and

since several
individual experiments, such as those just described, may be
for one ternary dlagram, we can understand why only a few systems ave
general , the original experi-
menter investigating a partiClllar phase diagram is usually QOncerncd with
some limited region of composition, temperature, and pressure- His effort
is concentrated in that area, and the other parts of the diagram are
d@termined with much less precision and detail. As reported ln summarlz-
?;:

and compositions of individual lines or points on e
279
indicated by lines on the diagram. (l n binary diagrams two-phase regions
will often be shaded, single-phase regions not.) The intersection of a
constant-temperature tie line" with the phase boundaries gives the
compositions of the phases in equilibrium at temperature T. With two
phases present, P + V = C + 2, 2 + V = 2 + 2, V = 2. At an arbitrarily
..
fixed pressure, any arbitrary change in ither temperature or composition
of one of the phases present requires a corresponding change in the other
variable. The maximum number of phases that can be present where
pressure is arbitrarily fixed (V = 1) is
CERAMIC PHASE.EQUlLIBRIUM DIAGRAMS
P + V = C + 2, P + 1 = 2 + 2, P = 3.
When three phases are present, the composition of each phase and the
temperature are fixed, as indicated by the solid horizontal line at C.
Systems in Which a Gas Phase Is Not Important, Systems containing
only stable oxides in which the valence of the cations is fixed comprise a
large fraction of the systems of interest for ceramics and can adequately
be represented at a constant total pressure of 1 atm. At equilibrium the
chemical potential of each constituent must be equal in each phase
present. As a result the variation of chemical potential with composition
is the underlying thermodynamic consideration which determines phase
stability. If we consider a simple mechanical mixture of two pure
components, the free energy of the mixture G is
G
M
= XAGA +XBGB
[l nd under all conditions the free energy of the solution is less than that of
n mechanical mixture; the free energy curves for the solid and liquid
olutions and the resulting phase-equilibrium diagram are similar to those
nlready illustrated in Fig. 4.2. Since very dilute solu.tions approach ideal
bchayior, Eq. 7.10 requires that there is always at least some minute
ol\J bility on the addition of any solute t'o any pure substance.
Most concentrated solutions are not ideal , but many can be well
rcpresented as regul ar solutions in which the excess entropy of the
1s negligible, but the excess enthalpy or heat of mixing . H
xs
is
Jn this case the free energy of the regul ar solution is
(7.10) G
id
S
= G
M
- T . S
m
(7. 11)

a IIIJ
INTRODUCTION TO CERAMICS
represent
. These cautIOns are particularly appl.lcable to regions of llrnltcd crystal-
Jine at high temperatures sm for many systems exsolutlok

low often results ln submicroscopic phases which arc

278
(7.9)
For the simplest case, an ideal solution in which the heat of mixing and
changes in vibrational entropy terms are zero, random mixing gives rise to
[1 configurational entropy of mixing . Sm which has been derived in Eq.
4, 14; the free energy of the solution is
Two-Component Systems
1n two-component systems one variable, the composition, is
Introduced so that if only onc phase IS present, the variance is three:
2h4

and composltlOn gs variables A dlagram of this kind is shown in Fig 7.6
If one IS prFsent, both temperature and compositlOn can be
as for point A In the areas In which two
pases are present at equilibrIum, the composition of each phase is
7.4
}
m
a
E
7
/

QI?,-'
B
Smplc blrl ry diollfln1 ,
CompoSltiOl1
FiS. 7,6.
281
situation is illustrated in Fig. 7.7 d, in which the minimum system free
energy again consists of a mixture of the two solutions a and
When, for any temperature and composition, free-energy curves such
as shown in Fig. 7.7 are known for each phase which may exist , these
phases actually occur at equilibrium which give the lowest system free
energy consistent with equal chemical potentials for the components in
each phase. Thi s has been illustrated for an ideal solution in Fig. 4.2,
compound formation in Fig. 4.3, and phase separation in Fig. 3.10 and is
iIlustrated for a series of temperatures in a system in Fig. 7.8.
Systems in Which a Gas Phase Is Important. ln adjusting the oxygen
pressure in an experimental system, it is often convenient to use the
equilibria
CERAMIC PHASE-EQUILIBRIUM DIAGRAMS
The resulting forms of typical free-energy-composition curves for an
ldeal sqmuon and for regular solutions with positive or negative excess
enthalmes are shown iF Fig. 7-7 In Fig. 7.7c the Inmrnml
the system at compositions intermediate between a and consists of a
mxture of a and in which these two solution compositions have the
same chemical potential for component and a lower free energy than
lntermediate single-phase compositions ; that is, phase separanon occurs-
When differences of crystal struct ure occur (as discussed in Chapter 2), a
complete series of solld solutions between two components is not
possible, and the free energy of the solution increases sharply after an
initial decrease required by the configurational entropy of mixing. This
280
(7.12) I
CO+5oz=COz G
B
(7. 13)
In this case, with no condensed phase present, P + V = C + 2, 1 + V =
2 + 2. V = 3, and it is necessary to fix the temperature, system total
pressure, and the gas composition, that is, CO2/CO or H2/H20 ratio, in
order to fix the oxygen partial pressure. If a condensed phase, that is,
graphite, is in equilibrium with an oxygeri-containing vapor phase, P +
v = C + 2, 2 + V = 2 + 2, V = 2, and fixing any two independent variables
completely defines the system.
The most extensive experimenlal data available for a two-component
system in which the gas phase is important is the Fe-O system, in which a
number of condensed phases may be in equilibrium with the vapor phase.
A useful diagram is shown in Fig. 7.9, in which the heavy lines are
boundary curves separating the stability regions of the condensed phases
und the dash-dot curves are oxygen isobars. ln a single condensed-phase
region (such as wstite) P + V = C + 2, 2 + V = 2 + 2, V = 2, and both the
lemperature and oxygen pressure have to be fixed in order to define the
omposition of the condensed phase. ln a region of two condensed phases
(such as wstite plus magnetite) P + V = C + 2, 3 + V = 2 + 2, V = 1, and
f1 xing either the temperature or oxygen pressure full y defines the system.
Por thi s reason, the oxygen partial-pressure isobars are horizontal, that is,
in these regions, whereas they run diagonally across single
ondensed-phase regions.
An alternative metbod of representing the phases present at particul ar
oxygen pressures is shown in Fig. 7.9b. In thi s representation we do not

ihow the O/Fe rfl li o, that is, the compositi on of the condensed phases, but
nly the pressure- temperture nrnges for each stabl e phase.
H2+502 = H2O
G
A
B
Composition
(bl
~
(
A B
G
B
-T. Sm
G
M
+
!;,. H
%S
Compositi on
(al
~[
@
Z
A

@
B
A Q
Composftion

(C)
d)
Fig. 7.7. Free-energy-composition diagrams for (a ) ideal (b) Il nd (c )
solutions, and (d) incomplcte solld 5QlutiQn.
B
-T. S m
~
(
A
T.,
T
e
a
---m------ --------

a+

\
.
n

__________
1.

r

1,.1

A
,

B

f
X
s
7.8. Free-energy
ompositioq curves and the

,'-.'
dlagram for a eutectic syitem- From p. Gordon, PrinciPIes
oI Phase Dtagrains trl
Systems, McGrawSHill Book tCompany, New York, I%8.
n

f;') r
,'.:1
i; T,j

.'
,

'

J l'.,

\

* \ /
'\.
A
",
U\

4 : '\
magnetite
+
liquid

l
l O
6

-

wsti te
+
magnetite

-

- - - - ---!- IO _'::': '-

- .- .- -

+
magnet it e
\
liqu id
\
O\ ,

\
wustl te
+
il quid
" \
)' -l(on
+
wust ite
i}'
B
T
rF
l
o
X
s
A
A
T1
A
|
b
T
3
10
200
L_
l ",0 40 50 60 FeO.Fe20 380
Weight %
Fi
8

7.9. (a) Pha,se relations in the FeO-Fe,
O, system. Dash-dot lines.are oxygen isobars
Alternate solidiflcation paths for A are discussed in text. From A. Muan and E.
F: Osborn. Phase Equilibria among Oxides in Stee/making, Addison-Wesley Publishing
Company, Inc., Reading, Mass .. 1965 .
Fe20 :l
."
>,
,
, 1
90 30
!=

:.= 1 .t
,
1 t"

. H j:j!"
213
!
20
. ..
:-.:.=-
=
:.

t
X
B
A
2.3
5
T
T,

,
4l
|
A|
j
;, ? '1
A
285 CERAMIC PHASE-EQUILIBRIUM DIAGRAMS
INTRODUCTION TO CERAncs
284
Liquid
.A

\
\

+ BeO

2600
1700
Q
C
1200
1600
1500
Li quid oxide
Lt quid iron

7.0
i
'.. 6.0
e
o
6.5
m
o
o
BeO + 3 BeO Al 20 3
0

3

A${

for the
Fe-Fe2OI
SYStem-
- 2 - 4
- 8 -6
log p02(atml
60
3:1
Weight % A1
2
0
3
The binary system
O
BeO
lO be of limited extent, although this is uncertain, and are not shown in the
diagram. The system can be divided into three simpler two-cqmponent
ystems (BeO-BeAh04, BeAh04-BeAI60 IO, and BeAI60 ur-Ah03) in
0'
which the freezing' point of the pure material is lowered by addition of
the second component. The BeO-BeAhO. subsystem contains a com-
pound, Be3Ah06, which melts incongruently, as discqssed in the next
Icction. In the single.-phase regions there is only one phase present, its
mposition is obvious1y that of the entire system, and it comprises 100%
f the system (point A in Fig. 7: 10). In two-phase regions the phases
prcsent are indicated in the diagram (point B in Fig. 7.10); the composi-
of . ach phase is represented by the intersection of
i
,a constant
tcmperature tie 1ine and the phase-boundary 1ines. The amounts oLeach
phlll!e can aIso be determined from the fact that tbe sum t
,
he.
mpostion times the amount of each phase present must equa1 the
omposit ion f the entire system. For examp1e, at point C in Fig .. 7 .. 10,the
ntJre Ilystem ls of 29% A120 3 and cQnsists of two phases, BeO
ontlllnloi no
(which contains 58% Ah0 3). There

Phase-equilibrium
diagrams are
grgphical
representations
of experi-
mema! observanons
The most extenSIVe
collection
of diagrams
useful in

QIagrams
ca?
be classi6ed Into
several general
types-
Eutectic
When a second
component is added to a pure

the freezlng point is often lowered

A complete binary

conssts of lowered
curves for both end members, as illustrated

in Flg.
7.8
The. eutectlC
temperature
is the
temperature
at which the
liquidus
curves
lntFrsect
and
?s
tpe lowest
temperature
at Which liquid
occurs- The eutectlC
CompoF1tl?n IS the
composition
of the liquid at this
temperature, the llquid
coeXISUng
with two solid phases. At the eutectic
temperature
three phases are present, so the variance is
one- Since

6xed, the
temperature
cannot change
unless
qne phase

....
1:3 Al
2
Q3
Fill. 7.10
Two-Component
Phase
Diagrams
7.5
u aml l .t,
E M Levin, c.
R Robbins,
llnd H
F MCMurdie,
Phase Dtagrums
for
ican Ceramic Soclety, 1964: SUpplf ml!l lI , 1969.
must be 50% of each phase present for a mass balance to give the correct
overall composition. This can be represented graphically in the diagram
by the lever principle, in which the distance from one phase boundary to
the overall system composition, divided by the distance from that
boundary to the second phase boundary, is the fraction of the second
phase present. That is, in Fig. 7.10,
OC
;::;:. (1 00) = Per cent 3BeO'Ab03
OD
A little consideration indicates that the ratio of phases is given as
DC BeO
OC 3BeO' Ab03
This same method can be used for determining the amounts of phases
present at any point in the diagram.
Consider the changes that occur in the phases present on heating a
composition such as E, which is a mixture of BeAbO. and BeAI6 0 lO
These phases remain the only ones present until a temperature of 1850
0
C
is reached; at this eutectic temperature there is a reaction, BeAbO. +
BeAl6 0 lO = Liquid (85% Ab03), which continues at constant temperature
to form the eutectic liquid until all the BeAl6 0 lO is consumed. On further
heating more of the BeAbO. dissolves in the liquid, so that the liquid
composition changes along GF until at about 1875
0
C all the BeAbO. has
disappeared and the system is entirely liquid. On cooling this liquid,
exactly the reverse occurs during equilibrium solidification.
As an exercise ' students should calculate the fraction of each phase
present for different temperatures and different system compositions.
One of the main features of eutectic systems is the lowering of the
temperature at which liquid is formed. In the BeO-Ab03 system, for
example, the pure end members melt 'at temperatures of 2500
0
C and
2040
0
C, respectively. In contrast, in the two-component system a liquid is
formed at temperatures as low as 1835
0
C. This may be an advantage or
disadvantage for different applications. For maximum temperature use as
a refractory we want no liquid to be formed . Addition of even a smalJ
amount of BeO to Ab03 results in the formation of a substantial amount
of a fluid liquid at 1890
0
C and makes it useless as a refractory above thi
temperature\ ,However, if high-temperature applications are not of majQr
importance, 'it may be desirable to form the liquid as an aid to firing l
lower temperatures, since liquid increases the ease of densifi cati on. Thi
is true, for example, in the system Ti02- U0 2, in whi ch addition of 1%
Ti02 forms a eut ecti c liquid. which is a great aid in obtain ing hi gh
densities al low tcmperatures. Thc stl' ucture of thi s system. shown il1 I ig.
CERAMIC PHASE-EQUlLIBRIUM D1AGRAMS 287
7. 11, consist s of large grains of U02 surrounded by the eutectc composl-
t lOn.
The effectiveness of eutectic systems in lowering the melting point is
made use of in the N a20-Si0
2
system, in which glass compositions can be
melted at low temperatures (Fig. 7.12). The liquidus is lowered from
1710
0
C in pure Si0
2
to about 790
0
for the eutectic compositon' at
approximately 75% Si02- 25% Na20 .
Formation of low-melting eutectics also leads to some severe limita-
tions on the use of refractories . ln the system CaO-Ab03 the liquidus is
strongly lowered by a series of eutectics. In general , strongly basic oxides
such as CaO form low-melting eutectics with amphoteric or basic oxides,
and these classes of materials cannot be used adj acent to each other, even
though they are individually highly refractive.
Incongruent Melting. Sometimes a solid compound does not melt to
form a liquid of it s own composition but instead dissociates to form a new
i d phase and a liquid. This is true of enstatite (l4gSiO3) at I 5 5 7 c (Fig.
7 l3); this compound forms solid Mg2S:04 plus a liquid containing about
61 % Si0
2
. At this incongruent melting point or peritectic temperature there
1800
Tridymite + liquid
_-----....
Metastable
two,liquids ';
50
70 80 9O lQO
Weight Si"
sy5tem Na
2
SiO
,
-Si02. The dashed line shows
2900
1900
1700
1500 L__.1
O 1,0 20 30, 40 50 60
Mgo forsterite enstatlt!l
We1iht percent SiOa
Fi, 7.i blnary mtem r i
I J
....
CERAMIC PHASE-EQUILIBRlUM DIAGRAMS 289
are three phases present (two solids aid a lquid) , so that the temperature
remains fixed until the reaction is completed. Potash feldspar (Fig. 7.14)
also melts in this way.
Phase Separation. When a liquid or crystalline solution is it
separates into two separate phases at the consolute temperature as long as
the excess enthalpy is positive (see Fig. 7.7). This phenomenon is particu-
larly important relative to the development of substructure in glasses, as
discussed in Chapter 3 (Figs. 3.11, 3.12, 3.14 to 3.19). Although it has been
less fully investigated for crystalline oxide solid solutions, it is probably
equally important for these systems when they are exposed to moderate
temperatures for long periods of time, The system CoO-NiO is shown in
Fig. 7.15.
1800
1600
1400

:::J
m
gi
E
q
f- 1200
1000
Cristobalite + Li quid
o ' ' 20 40 60 80 100
Leucite Potash
feldspar
K2' AI 23'Si2
1.1 Weillht per S2
P1I , 7, 14, blnar . y. tem K10 ' AI
1
Q) ,/JSi02 (Ieycite)- SiO., From J , F, Schairer and N. L.
8owl n, 8u/l , Soc, 0101: FlnL, 20. 74 (1947), Two.pha8e reaion, are showI! shaded in this
dlqrm, r"- '" !.
1;:r---_ Liquid
-- -
1 -
--
---
-
---_------==-
r;...
1200
(Ni CoJ 50lid 5olution
1000
800
.8 Co
Mole fraction
Fig. 7.15. The binary system NiO-CoO.
m
@
3
@
g
E

Mg 55 + Ca 55
1800
1600
MgO
60
Weliht-" CO
FI, . 7.16. The blnary yllem M.O- C.O.
80
';,

100
CIIO
'"
CERAMIC PHASE-EQUILIBRIUM DIAGRAMS 291
Solid Solutions. As discussed in Chapter 4 and in Section 7.4, a
complete series of solid solutions occurs for some systems such as
illustrated in Fig. 4.2 and Fig. 7.15, and some minute or significant limited
solid solution occurs for all systems, as shown in Figs. 4.3, 7.13, and 7.15.
It has only been in the last decade or so that careful experimentation
has revealed the wide extent of solid solubility, reaching several percent
at high temperatures in many systems, as shown in Figs. 4.3, 7.13, and 7.15
and.for the MgO-CaO system in Fig. 7 16 and the MgO-Cr203 system in
Fig. 7.17. For steel-plant refractories directly, bonded magnesia-chromite
brick is formed when these materials are heated together at temperatures
above 1600
0
C as a reslJ.lt of the partial solubility of the constituents;
exsolution 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 temperatur.es forms a high-temperature bond.
In magnesia refractories the lower solid solubility of Si02 as compared
3900
2800
2600
2400

2om
1800
/ MgO 5.5. + MgCr2. 5.5
:
1400
."
....... "
1200
MgCr z4
40 60
Weight
Ei . 7.17. Tht blnll'Y IYltem
292
with CaO in MgO re9uirFS that excess CaO be added to prevent the
formation of low-melting intergranular silicates.

$

(Fig. 7.18)
This same sort of limited solid solution is observed in the Ca0-ZrCL
(Fig 7 19); in this system there are three diRerent 6elds of solid
somuon, the tetrFgonal form, the cubic form, and the monoclinic form.
Pure ZrO2 exhiblts a monodink tetragonal phase transition at
which lrwolves a largF mIume change and makes the llSe of pure zirconia
impoFsible as a CeramIC material. Addition of lime to form the cubic solid
somuon, which has no phase transition, is one basis for stabilized
zirconia, a valuable refractory.
d Complex Diagrams. AIl the basic parts of binary phase-equilibrium
lagrams have been Ulustfated ; readers should be able to identify the
of pha.sgs, compos1tl()n of phases, and amounts of phases present
at any composItlOn and temperature any of these diagrams with ease
and c?n5denge. If they cannot, thcy should consult one of the more
extensive treatments listed in the references.
Qf AhOI from

:J

E
Q
f- 1000
CERAMIC PHASE-EQUILIBRlUM DlAGRAMS
Li quid
10 20
Mole per cent CaO
50
ZrCa03
293
Fig.7.19. The binary system CaO-ZrO,. From P. Duwez, F. Odell, and F. H. Brown, Jr. ,
J. Am. Ceram. Soc. , 35, 109 (1952). Two-phase regions are shown shaded in this figure.
Combinations of simple elements in one system sometimes appear
frightening in their complexity but actually offer no new problems in
interpretation. In the system Ba2Ti04- Ti02 (Fig. 7.20), for example, we
find two eutectics, three incongruently melting compounds, polymorphic
forms of BaTiO), and an area of limited solid solution. AIl of these have
already been di scussed.
Generally phase di agrams are constructed at a total pressure of 1 atm
with temperature and composition as independent variables. Since the
interesting equilibrium conditions for many ceramics involve low oxygen
partlul pressures, phasc diogrums at a fixed lemperature but wi t h oxygen
. I l J U J Q l O - J : ' : > - : l . : : : J 0 1 . 1 L Q J O W S I : . l u ! d s
S H 4 : l I 1 S 4 0 ! I . I M S l U " l s s u I ' ( f - V ) I Z ' L
u ! U M o q s S ! t O d J O U O ! l 3 u n J R s e A 1 l A ! l 3 e ; ) 4 l ] 0 ( ' ( O l J ; )
7

- l U . I . i V ) l O O 3 6 0 ! N P u e
a ! I $

- O A l p g d g q s - s u g I a q i l e o - ! N - o J l O J e q ; ) O S S M O I . l S
Q 6 ' L 1 0 ] : . l s e q d $
j O J a ! l e u l g l I e l n J a s n g g m o 3 g q s a I q e ! j g A s e p u e
' W V ' f I l J g E
G Q l W d J J a d
" 6 t
S : J I W V H : F l : J 0 . 1 . N O I L : J a a O H . l . N I
" 0 d J o U O ! l : l U n J 1 1 1 1 , 0 ( 1 ^ I I O I l
( 0 O [ ( t ! : l q l p U l l U O ! l n ( O S P ! I O S : l p P ( O 3 4 1 U 3 3 M I 3 Q J O I ( t )
J O u o ! p u n J t ! S t ! s 3 s t ! q d p : l S U 3 p U O : l J O ( ( ) ' W 3 1 S S O - ! N - O : : > ( V ) Z ' L , ' S ,
( 1 : : ) ( 0 ) ( ! )

0 ' 1 8 ' 0 9 ' 0 t , . O ( : ' 0 0 l N 8 ' 0 9 ' 0 t . O
8 ' L -
-
m
N
/
t L
h
v
n u
9 9 -
0 : )
0 6
G O I
0 0 1
] ( :
1 1
1
Y
q P ; ) l U : . l S : . l 1 d : . l 1 S : . l l O l e 1 : . l d w : . l 1 S O p ! O b n : . l 1 . ( 1 1 . ( 1 ! M
u e u o P : . l l ; ) : . l f 0 1 d u e ; ) : . l 1 . ( 1 U O ! l e 1 U : . l S : . l 1 d : . l 1 I e U O ! S U : . l W ! P - O M 1
l O d ' Z Z ' L s e t p O S : . l s e l . ( d e 0 1 ; ) l e U ! p 1 0 I e ; ) ! l l : . l ^ e
u o : . l l O l e 1 : . l d w : . l 1 : . l 1 . ( 1 p u e : . l [ ! u e ! 1 1 l e 1 : . l l e l ! o b : . l u e u o P : . l 1 U : . l S : . l 1 d ; ) 1 : . l q u e ; ) S U O ! l
- I S o d w o ; ) 1 U e 1 S U O ; ) P I ; ) I . ( S ! : . l l O S S : . l l d : . l 1 . ( 1 ] ! 1 0 q S ! S W : . l 1 S S 1 e U 1 : . l 1
J O u O ! l e l U : . l S : . l 1 d : . l 1 1 U e ! l e ^ U 1 u e 0 1
s : . l s e l . ( d 1 0 0 J J O : . l ; ) u : . l s : . l 1 d : . l q 1 p : . l x y I ! l e 1 1 ! q 1 e S ! : . l l O S S : . l l d n ' ( p 1 ! 1 . ( 1 : . l 4 1 x y
4 ; ) ! I . ( M ) S l U ; ) u o d w o ; ) O M 1 ] 0 S U O ! l e 1 1 U : . l ; ) U O ; ) : . l 1 . ( 1 p u e : . l 1 0 1 e 1 : . l d w : . l 1 : . l l O S S : . l l d
- S : . l l q e ! l e A 1 U : . l p u : . l d : . l p u ! 1 0 0 ] : . l 1 : . l q 1 S W : . l 1 S S
1 U : . l 1 : . l , I J ! P q u w n U : . l w e p u o J
3 s u q d J U 3 u o d w o : : : > - 3 3 . 1 q . L
9 . '
' ) l o f L l 1 e U ! S U O ! l ! s o d w o ; ) : . l 1 . ( 1
( Z - q ) I Z ' L ' ! ! d U ! U M O I . ( S s l e q o S ! U : . l ! x o : . l q . 1
J O U O ! l e 1 1 U ; ) ; ) U O ; ) ; ) q 1 u o O l ( l ; ) ; ) d ) 1 0 ' ( O l ( l ; ) ; ) d ) + . 0 ( ( 1 ; ) ; ) d )
+ O ; ) d O ; ) d ; ) q s ; ) s e q d ; ) ( q e 1 S ; ) q 1 0 1 _
0 1
= ' o d
J ; ) l O S S ; ) l d U ; ) ! x o u e l V ' q 1 Z ' L ' ! ! d U ! U M O I . ( S S ! 1 e W : . l 1 S S
0
0
: )
( ( : )
S W V H ! ) V I a W a I H 8 n I f l : F l - : F l S V H d : J I W V H : F l : J S 6 t
297 CERAMIC PHASE-EQUILIBRIUM DIAGRAMS
z

m
a
g
g

{
x
Y
W W
Space diagram of (a) ternary eutectic and (b) complete series of solid solutions
Y
dimensional representation is to take a constant-temperature cut through
the diagram, indicating the phases at equilibrium at some fixed tempera-
ture.
lnterpretation of ternary diagrams is not fundamentally different from
that of binary diagrams. The phases in equilibrium at any temperature and
composition are shown; the composition of phase is given by the
phase-boundary surfaces or intersections ; the relative amounts of each
phase are determined by the principle that the sum of the individual phase
compositions must equal the total composition of the entire system. ln
Fig. 7.22 and Fig. 7.23, for example, the composition A falls in the primary
field of X. If we cool the liquid A, X begins to crystallize from the melt
when the temperature reaches T,. The composition of the liquid changes
along AB because of the loss of X. Along this line the lever principle
applies, so that at any point the percentage of X present is given by
100(BA/XB). When the temperature reaches T2 and the crystallization
path reaches the boundary representing equilibrium between the liquid
and two solid phases X and Z, Z begins to crystallize also, and the liquid
changes in composition along the path CD. At L, the phases in equilibrium
are a liquid of compostion L and the solids X and Z, whereas the overall
composition of the entire system is A. As shown in Fig. 7.23b, the only
mixture of L, X, and Z that gives a total corresponding to A is x A/x X
= Per cent X, z A/ zZ (100) = Per cent Z, IA/l L (1 00) = Per cent L
Tht 1s. the small er ;t ri angle XZL is a ternary system in which the
omposirion of A can be represented in terms of its three constituent s.
Fig.7.22
296
,

g
E

{
J
Fe20
Spihel
Wustite
T = 1573
0
K.
Fe30/
Fe20 3
-4

-6

Alloy + spinel
-16
0.4 0.6

(bJ
Fig. 7.2I (continued) (b) Fe-Cr-O system-(I) diagram and (2) oxygen
isobars for equiIibrimn between two phases. From A. pelton and H. SchIrialzried, Met. Trans.,
4, 1395 (1973).
Cr 0.8
Fe
isotherms. The diagram is divided into areas repre&enting equiIibrillm
between the liquid and a solid phase- Boundary curves represent equilib-
rillm bttween two solids and the liquid, an# intersegtions t Of three
of four phases in,
points in ' fhe constant-p'ess'ure system). meth_og, of two-
x
z
Z
Y
x
Composition
Fig.7.23. (a) Crystallization path ilustrated in 'Fig. 7.22a and (b) application of center of
gravity principle to a ternary system.
8i0
2
Cristobalite
20 Potash feldspar
K 20'A1
2
0
3
' 68i0
2
30
40
30
. 20 L
10
K
2
0

50 '60 70
Weiaht per cent;
'+
FfDml.
, _It T f! ';"'f-J. f
21'
CERAMIC: PHASE-EQUILIBRIUM DIAGRAMS . 299
Many ternary systems are of interest in ceramic science and technol-
ogy. Two of these, the K20-Ab03-Si02 system and the Na20-CaO-SiO:
system, are illQstrated in Figs. 7.,24 and 7.25. Another important system,
the system. is discussed in' Section 7.8. The
K20-Ab03-Si02 system is important as the basis for many porcelain
compositions. The eutectic in the subsystem potash-feldspar-
silica-mullite determines the firing behavior in many compositions. As
discussed in Chapter 10, porcelain compositions are adjusted mainly on
the basis of (a) ease in forming and (b) firing behavior. Although. real
systems are usually somewhat more complex, this 'terriary diagram
provides a 'good. description of the compositions used. The Na20-CaO-
Si02 system forms the basis for much glass technology. Most composi-
tions fall along the border between the primary phase of devitrite,
Na20.3CaO.6Si02, al)d silica; the liquidus temperature is 900 to 1050
o
C.
To Ca
m tM
A

Ma
m
o
9
i
a
N
Two liquids
2Na2'Ca' 3Si2
Na2SiOa
To Na2 Si2
50
Na 2SiOS
40 10

Weight per cent Na 2
Plli; 7.2'. The_Na.O- O- CaO-SiO. system. From G. W. Morey and N. L. Bowen. J. Soc.
CJ/cfll 232
This is a compositional area of low melting temperature, but the glasses
formed contain calcium oxide for reasonable resistance to
chemical attack. When glasses are heated for extended times above the
transition range, devitrite or cristobalite is the crystalline phase formed as
the devitrification product.
Very often constant-temperature diagrams are useful. These are illus-
trated for subsolidus temperatures in Figs. 7.24 and 7.25 by lines between
the forms that exist at equilibrium. These lines form composition triangles
in which three phases are present at equilibrium, sometimes called
compatibility triangles. Constant-temperature diagrams at higher temper-
atures are useful , as illustrated in Fig. 7.26, in which the 1200
0
isothermal
40
KS
2
Tridymite +
Li quid
/
50
To
K
2
0
Liquid
Leucite + KAS
2
Li quid L3
Si0
2
A1Z03 + Leucite +
KAS
z
To K
2
0

Single-phase region

F>. /:1 Three - phase regions
40
+ Tridymite +
Li quid L 1
Mullite + Leucite +
Li quid L 2
30 20
Weight per cent
Mullite + Leucite +
AloO

10 AI
2
0
3
Fig. 7.26. )sothcrmal cut in the 111 1200"_.
CERAMIC PHASE-EQUILIBRIUM DlAGRAMS 301
plane is shown for the K20-AbO,-Si02 diagram. The Iiquids formed in
this system are viscous; in order to obtain a substantial
amount of liquid must be present at the firing temperature From
isothermal diagrams the composition of liquid and amount of liquid for
different compositions can be easily determined at the temperaturc
selected. Frequently it is sufficient to determine an isothermal planc
rather than an entire diagram, and obviously it is much easier.
Altnough our discussion of three-component diagrams has been bri ef
and we do not discuss phase-equilibrium behavior for four or more
component systems ' at all , students would be well advised to becomc
familiar with these as an extra project.
7.7 Phase Composition versus Temperature
One of the useful applications for phase equilibrium diagrams in
ceramic systems is the determination of the phases present at different
temperatures. This information is most readily used in the form of plot s of
the amount of phases present versus temperature.
Consider, for example, the system MgO-Si02 (Fig. 7. 13). For a compos.
ition of 50 wt% MgO-50 wt% Si02 , the solid phases present at equilibrium
are forsterite and enstatite. As they are heated, no new phases are
until 1557
0
C. At this temperature the enstatite disappears and a composi .
tion of about 40% liquid containing 61% Si02 is formed . On furthcr
heating the amount of liquid present increases until the liquidus is reache<J
at some temperature near 1800
o
C. In contrast, for a 60% MgO-40o/r SiO:
composition the solid phases present are forsterite , Mg2SiO. , and peric-
lase, MgO. No new phase is found on heating until 1850
0
C. when
composition becomes nearly aJl liquid, since this temperature is near thc
The changes in phase occurring for these two
compositions are iJl ustrated in Fig. 7.27.
Several things are apparent from this graphical representation . One b
the large difference in liquid content versus for a relatively
small change in composition. For compositions containing greatcr th:.ll1
42% silica, the forsterite composition, liquids are formed at relatively low
temperatures. For compositions with silica contents less than 42% no
liquid is formed until 1 850
o
C. This fact is used in the treatment of
chromite refractories. The most common impurity present is scrpcntinc,
3MgO.2Si02 '2H20 , having a composition of about 50 wt% If
MgO is added to put thi s in the MgO- for sterite fi eld , it no longe r'
has a dcletcrious cffcct. Without thi s addition a li quid is formed al low
temperatures.
Another of Ihi s di l\Brum s n lhe of CQlllpt'l sitifls
302
1900
20 40 60 80 100 ---- 0 20 40 60 80 100
Weight per cent 01 each phase present Weight per cent 01 each phase present
(e) 65% Si02 (f) 70% Si0
2
Phase composition versus temperature for sampJes in the MgO-SiO, system.
1800
-
g
i
g
a
E
a
20 '40 60 80 100
Weight per cent 01 each phase present
(a) 40% Si02
1900

1700

1600
20 40 60 80 100
(c) 55% Si02
1900
1800
1700

Fig. 7.27.
1900
P
'"
1700

E
1600
20 40 60 80 100
(b) 45% Si02
E
@
1500
o 20 40 60 80 100
(d) 60% Si0
2
1900
1800
1700

1600
that pave desirable Rring characteristics It is necessary to form a
amount of for
or warps during 6rlng. The Iimits of liquid required vary with th@
propFrties of the liqpid but are in the range of 20 to 5O wt%. To have
sumclent range of hrlng temperature, it is desirable that the liquid conteM
not change much with temperature- Forsterite compositions b
6red until very high temperatures if the composjtjon is exactly 42% SifL
smce no liquid is formed below I 850@C Compositions in
enstatite field whj h are mainJy fOf S1Crite f orm a lt 1 557.1l C, nnd
CERAMIC PHASE-EQUILlBRIUM DIAGRAMS 303
since the liquidus curve is steep, the amount of liquid present changes but
slightly with temperature, as shown in Fig. 7.27. Consequently, these
compositions have a good firing range and are easy to vitrify. In contrast.
compositions that are mostly enstatite (55 , 60. 65o/c SiOJ form large
amounts of liquid at low temperature, and the amount of liquid present
changes rapidly with temperature. These materials have a limited firing
range and pose difficult control problems for economc production.
For systems in which the gas phase is important the way in which
condensed phases appear and their compositional changes on cooling
depend on the conditions imposd. Referring back to the Fe-O system
i1Justrated in Fig. 7.9, if the total condensed-phase composition remains
constant, as occurs in a closed nonreactive container with only a
negligible amount of gas phase present, the composition A solidifies along
the dotted line with a corresponding decrease in the system oxygen
pressure. In contrast, if the system is cooled at constant oxygen pressure,
the solidification path is along the dashed line. In one case the resulting
product at room temperature is a mixture of iron and magnetite ; in the
second case the resulting product is hematite. Obviously in such systems
the control of oxygen pressure during cooling is essential for the control
of the products formed.
For detai!ed discussions of paths in ternary systems the
references should be consulted. The following summary* can serve as a
revlew.
1. When a liquid is the first phase to appear is the primary
phase for that part of the system in which the composition of the melt is
represented.
2. The crystallization curve follows to the nearest boundary the
extension of the straight line connecting the composition of the original
liquid with that of the primary phase of that field . The composition of the
Ii quid within the primary fields is represented by points on the crystalliza-
tion curve. This curve is the intersection of a plane (perpendicular to the
base triangle and passing through the compositions of original melt and
the primary phase) with the liquidus surface.
3. At the boundary line a new phase appears which is the primary
phase of the adjacent field. The two phases separate together along this
boundary as the temperature is lowered.
4. The ratio of the two solids crystallizing is given by the intersection
() f the tangent to the boundary curve with a line connecting the composi-
' After E. M. Lvin. H F. McMurdi e. and F. P. HaJJ . P!wse Diagrallls for Ceramist s.
Scicty. CleveJand. Ohio. 1956.
304
tions of the two solid phases. Two things can occur. If this tangent line
runs between the compositions of the two solid phases, the amount of
each of these phases present increases. If the tangent line intersects an
extension of the line between solid compositions, the first phase de-
creases in amount (i s resorbed; Reaction A + Liquid = B) as crystalliza-
tion proceeds. ln some systems the crystallization curve leaves the
boundary curve if the first phase is completely resorbed, leaving only the
second phase. Systems in which this occurs may be inferred from a study
of the mean composition of the solid separating between successive
points on the crystallization path.
5. The crystallization curve always ends at the invariant point which
represents equilibrium of liquid with the three solid phases of the three
components within whose composition triangle the original liquid com-
position was found.
6. The mean composition of the solid Which is crystallizing at any point
on a boundary line is shown by the intersection at that point of the tangent
with a line joining the composition of the two solid phases which are
crystallizing.
7. The mean composition of the total solid that has crystallized up to
any point on the crystallization curve is found by extending the line
connecting the given point with the originalliquid composition to the line
connecting the compositions of the phases that have been separating.
8. The mean composition of the solid that has separated between two
points on a boundary is found at the intersection of a line passing through
these two points with a line connecting the compositions of the two solid
phases separating along this boundary.
7.8 The System Ah03-SiO
,
As an example of the usefulness of phase diagrams for considering
high-temperature phenomena in ceramic systems, the Ab03-Si0
2
system
illustrates many of the features and problems encountered. ln this system
(Fig. 7.28), there is one compound present, mullite, which is shown as
melting incongruently. (The melting behavior of mullite has been con-
troversial; we show the metastable extensions of the phase boundaries in
Fig. 7.28. For our purposes this is most important as indicative of the fact
that experimental techniques are difficult and time consuming; the diag-
rams included here and in standard references are sllmmari es of experi-
mental data. They usually include many interpol ations and
and have been compiled with greater or lesser care, dependiog 00 the
needs of the original investigator.) The utectC between ITI ullte and
CERAMIC PHASE-EQUILIBRIUM DIAGRAMS 30S
100
(
n
)
C
--- Stable equilibrium diagram
- ._.- Metastable extension 01
liquidus and solidus lines
Li quid
----_j_--------
I Alumina +
i mullite (88)
1700
Mullite (88) + liquid
1600
158r :t
1500
1400
Si02 10 20 30 40 60 70 80 90 A120
3
50
A1
2
0
3
(mole %)
Fig.7.28. The binary system AI,O,-Si02 From Aksay and Pask, Science, 183,69 (1974).
cristobalite occurs at 1587
0
C to form a liquid containing about 95 mole%
Si02 The solidus temperature between mullite and alumina is at 1828
0
C.
Factors affecting the fabrication and use of several refractory products
can be related to this diagram. They include refractory silica brick (0.2 to
1.0 wt% Ab03), clay products (35to 50 wt% Ab03), high-alumina brick(60
to 90 wt% Ab03), pure fused mullite (72 wt%' Ab03), and pure fused or
sintered alumina (> 90 wt% Ab03).
At one end of the composition range are silica bricks widely used for
furnace roofs and similar structures requiring high strength at high
temperatures. A major application was as roof brkk for open-hearth
furnaces in which temperatures of 1625 to 1650
0
C are commonly used. At
this temperature a part of the brick is actually in the liquid state. In the
development of silica brick t has found that small amounts of
aluml num oxldc are dcletcriou8 to brick properties because
306

eutectc compos ton s to the slca end of the dagram
consequently, even small addltIOns of aluminum oxide mean that sub-
stantial amounts of liquid phase are present at temperatures above
For thlS reason supersilica brick, which has a lower alumina
content through special raw-material selection or treatment, is used in
structures that will be heated to high temperatures.
Fre-clay brcks have a compostion rangng from 35 to 55% alumnum
oxide. For compositions without impurities the equilibrium phases pres-
ent at temperatures below are mullite and silica (Fig. 729). The
relatlve amounts of these phases present change with composition, and
there are corresponding changes in the properties of the brick. At
temperatures abo?e the amount of liquid phase present is sensitive
to the ratio, and for these high-temperature applications the
higher-alumina brick is preferred.
rig; crystals
CERAMIC PHASE-EQUILIBRIUM DIAGRAMS 307
Refractory properties of brck can be substantally improved if suffi-
cent alumina is added to increase the fraction of mullite present until at
greater than 72 wt% alumina the brick is entirely mullte or a mixture of
mullite plus alumina. Under these conditions no lquid is present until
temperatures above 1828
0
C are reached. For some applicatons fused
mullite brick is used; it has superor ability to resist corrosion and
deformation at high temperatures. The highest refractoriness is obtained
with pure alumina. Sintered Ab03 is used for laboratory ware, and
fusion-cast AbO, is used as a glass tank refractory.
7.9 The System MgO-AI20 3-Si02
A ternary system important in understanding the behavior of a number
of ceramic compositions is the MgO-AbOrSi02 system, iIlustrated in
Fig. 7.30. This system is composed of several binary compounds which
Al
2
0
3
7.30, The lcrry sys1cm Mlt!O- AI,O.- S01. Prom M. L. Keith and J. F. Schairer, J
IR2 or Nl1l1d sululion IIre nol shown; sce Figs. 4.3 and 7.13.
309
firing process, which is described in more detail in Chapter 12. On heating,
clay decomposes' at 980
0
C to form fine-grained mullite in a silica matrix.
Talc decomposes and gives rise to a similar mixture of fine-grained
protoenstatite crystals, MgSi03, in l). sili: a matrix at about 1000oC. Further
heating of clay gives rise to increased growth of mullite crystal s,
crystallization of the silica mat,rix as cristobalite, arid formation of a
eutectic liquid at .1 595
0
C. Further heating of pure falc leads to crystal
growth of the enstatite, and liquid is formed at a temperature of 1547
0
C.
At this temperature almost all the composition melts, since talc (66.6%
Si0
2
, 33.4% MgO) is not far from the eutectic composition in the
MgO-Si02
system (Fig. 7.13) .
The main feature which characterizes the melting behavior of cordier-
ite, steatite porcelain, and low-loss steatite compositions is the limited
firing range which results when pure materials are carried to partial
fusion. ln for firing to form a vitreous densified ceramic about 20
to 35% of a viscous silicate liquid is required. For pure talc, however, as
indicated in Fig. 7.32, no liquid is formed until 1547
0
C, when the entire
composition liquifies. This can be substantially improved by using talc-
clay mixtures. For example, consider the composition A in Fig. 7.31
which is 90% talc-IO% clay, similar to many commercial steatite composi-
tions. At this composition about 30% liquid is formed abruptly at the
liquidus temperature, I345
0
C; the amount of liquid increases quite rapidly
with temperature (Fig. 7.32), making close control of firing temperature
necessary, since the firing range is short for obtaining a dense vitreous
100
o
1200 1400 1500 1600
Temperature ("C)
Fla. 7.32. Amount of Iiquid present 111 different temperatures for compositions illustratcd
7.31.
1800 1300
havF a!ready been described, together with two ternary compounds,
cordlente, 2Mgp2Al2O3 5SiOz, and sapphirine, 4MgO5Al2O32SiOz, both
of whiFh melt lncongruently. The lowest liquidu5 temperature is at the
tridymlte-promFnstatite cordierite eutectic at I345
0
C, but the cordierite-
eutectic at 1360
0
C is l'!lmost as ---;
ceramlC that in large part appear on this diagram indlude
magnesite retractorles, ceramics, steatite ceramics, sa;;ial
low-loss steames, and cordlente ceramics. The general composition areas
of these products on thF ternary diagram are illustrated in Fig. 731. In all
but magnesite refractorles, the use of clay and talc as raw materials is the
basis for the compositional developments. These materials are valuabIe in
large part because of their ease in forming; they are 6ne-grained and
and are consequently plastic, nonabrasive, and easy to form. In
ddition, the fine-grained nature of these
MgO'
(enstatite)
/ Low-Ios.
Forster,te CeramlCS / st-"
compositions in the ternary system MaO- AI' OJ-S10.. See text ror
308
(
%
E
g
-
-
Periclase
8i0
2
17I3 %S.
body (this composition would be fired at 1350 to 1370
0
C). ln actual fact ,
however, the raw materials used contain Na20 , K20 , CaO BaO, Fe,O"
and TiO, as minor impurities which both lower and widen the fusion
range. Additions of more than 10% clay again so shorten the firing range
that they are not feasible, and only Ii rriited compositions are practicable.
The addition of feldspar greatly increases the firing range and the ease of
firing and has been used in the past for compositions intended as
low-temperature insulators. However, the electrical properties not
good.
For low-Ioss steatites, additional magnesia is added to combine with the
free silica to bring the composition nearer the composition triangle for
forsterite-cordierite-enstatite. This changes the melting behavior so that
a composition such as B in Fig. 7.31 forms about 50% liquid over a
temperature range of a few degrees , and control in firing is very difficult
(Fig. 7.32). In order to fire these compositions in practice to form vitreous
bodies, added flux is essential. Barium oxide, added as the carbonate, is
the most widely used.
Cordierite ceramics are particularly useful , since they have a very low
coefficient of thermal expansion and consequently good resistance to
thermal shock. As far as firing behavior is concerned, compositions show
a short firing range corresponding to a flat liquidus surface which leads to
the development of large amounts of liquid over a short temperature
interval. If a mixture consisting of talc and clay, with alumina added to
bring it closer to the cordierite composition, is heated, an initialliquidus is
formed at 1345
0
C, as for composition C in Fig. 7.3 1. The amount of liquid
rapidly increases; because of this it is difficult to form vitreous bodies.
Frequently when these compositions are not intended for electrical
applications, feldspar (3 to 10%) is added as a fluxing medium to increase
the firing range.
Magnesia and forsterite compositions are different in that a eutectic
liquid is formed of a composition widely different from the major phase
with a steep liquidus curve so that a broad firing range is easy to obtai n.
This is ilI ustrated for the forsterite D in Fig. 7.31 and t he
corresponding curve in Fig. 7.32. The initialliquid is formed at the 1360
0
C
eutectic, and the amount of liquid depends mainly on composition and
does not change markedly with temperature. Consequently, in contrast to
the steatite and cordierite bodies, forsterite ceramics present few prob-
lems in firing.
ln all these compositions there is normally prcscnt at thc fring
temperature an equilibrium mixture of crystalline anl.l Jiqu itl phscs.
is illustrated for a forsterite composition in Pig. 7.33. crystals
are present in a matrix of lquid si li cate 10 the Jiqlli dus
CERAMIC PHASE-EQUILlBRIUM DIAGRAMS
311
Fig. 7.33. Crystal-liquid structure of a forsterite composition (I 50x).
composition at the firing temperature. For other systems the crystalline
phase at the firing temperature is protoenstatite, periclase, or
and the crystal size and morphology are usually diRerent as well The
liquid phase frequently does not crystallize on cooling but forms a glass
(or a partly glass mixture) so that the triangle cannot be
for fixing the phases present at room temperature, but they must be
deduced instead from the firing conditions and subsequent heat treatment.
7.10 Nonequilibrium Phascs
The kinetics of phase transitions and solid-state reactions is considered
in the next two chapters; however, from our di scussion Qf glass structure
in Chapter 3 and atom mobility in Chapter 6 it is already apparent that the
lowest energy state of phase equilibria is not achieved in many practlcal
systems- For any change to take place in a system it is necessary that the
free energy be lowered. As a result the sort of free-energy curves
illustrated in Figs. 3.10, 4.2, 4.3, 7.7, and 7.8 for each of the possible
Dhases that might be present remain an important guide to metastable
Lquilibrillm In FIg 7 8, for example, if temperature T2 the solid
solution a were absent for any reason, the common tangent between the
liQuid and solid solution would determine the cOn1position of those
pGases ln which the have the same chemical pne ?f
thc types of noncquilibrium behavior in silicale systems IS the
slowneRR of cryslulliZHuon suQh that lhc liquid is supercooled. When thlS
energies required for their conversion into more stable phases cause a low
rate of transition. The energy relationships among three phases of the
same composition might be , represented as given in Fig. 7.34. Once any
one of these phases is formed, its rate of transformation into another
more stable phase is slow. In particular, the rate of transition to the lowest
energy state is specially slow for this system.
The kinetics of transformation in systems such as those iIIustrated in
Fig. 7.34 are discussed in Chapter 9 in terms of the driving force and
energy barrier. Structural aspects of transformations of this kind have
been discussed in Chapter 2. In general , there are two common ways in
which metastable crystals are formed. First, if a stable crystal is brought
into a new temperature or pressure range in which it does not transform
into the more stable form, metastable crystals are formed. Second, a
precipitate or transformation may form a new metastable phase. For
example, if phase 1 in Fig. 7.34 is cooled into the region of stability of
phase 3, it may transform into the intermediate phase 2, which remains
present as a metastable crystal.
The most commonly observed metastable crystalline phases not under-
going transformation are the various forms of silica (Fig. 7.5). When a
porcelain body containing quartz as an ingredient is fired at a temperature
of 1200 to 14OO
o
C, tridymite is the stable form but it never is observed ; the
quartz always remains as such. In refractory silica brick, quartz used as a
raw material must have about 2% calcium oxide added to it in order to be
transformed into the tridymite and cristobalite forms which are desirable.
The lime provides a solution-precipitation mechanism which essentially
eliminates the activation energy barrier, shown in Fig. 7.34, and allows
313 CERAMIC PHASE-EQUILIBRIUM DI-AGRAMS INTRODUCTION TO CERAMICS
happens, metastable phase separation of the liquid is quite common,
discussed in Chapter 3.
h G-lasses. OnF of the most common departures from equiIibrillIn be-
aVIor In CeramlC Systems is the ease with which many silicates are cooled
from the liquid state to form products. This requires that
the-dri?ing force for the liquid-crystal transformation be low and that thp
actwatIOn energy for the process be high Both of these conditions ar;
ful6lled for many sillcate systems- /
The rate of nucleation for a crystalline phase foriing from the nquid is
proportional to the product of the energy difference between the crystal
aFd liquid and the mobility ?f the constituents that form a crystal, as
dlscussed in Chapter 8. In sUlcate systcms, both of these factors change
so as to favor the formation of glasses as the silica content increases.
Although data for the diffusion coemcient are not generally available, the
!imiting mobility is that of the large network-forming anions and is

as shown in Table 7. 1.
312
Table 7.1.
B20 3

State 1
State 2
*
|1|
@
E
@
@
Comments
Good glass
formel
Good glass
former
Good glass
former
Poor glass
former
Very diffi -
cult to
form as
glass ,
Not aglass
former
Factors Glass-Forming Ability
(. Htl T mp) X

1.5X lO-
4 2 X 10-
5

(poise-
'
)
. HtlT
mp
T mp( oC) (cal/molej OK)
7.3
450
Compo-
sition
Si0
2
1 . 1 X 10-
6 1 X 10-
6
1. 1
1713
3. 7 X 10-
3
4.5 X 10-
2
0.74
345
5 X 10 4
5 X 10-
3
10-
1
50
7.4
9.2
7.4
6.9
874
800.5
1088
1544
Na2Si
2
0
S
Na
2
Si0
3
CaSi0
3
NaCI
State 3
Rate 01 transi tion 1-<>-2> 2-3 > 1--->> 3
lllus!nuion of energy barricrs bNween threc diTerenl SIICS of 11 syslem Fill, 7,34.

conditions ?f pressure, and composition of the system.
These remam present m a metastable state becauge the 8ctivati0l1
the stable phase to be formed . This is, in general , the effect of mineraliz-
ers such as fluorides , water, and alkalies in silicate systems. They provide
a fluid phase through which reactions can proceed without the activation
energy barrier present for the solid-state process.
Frequently, when high-temperature crystalline forms develop during
firing of a ceramic body, they do not revert to the more stable forms on
cooling. This is true for tridymite and cristobalite, which
never revert to the more stable quartz form. Similarly, in steatite bodies
the main crystalline phase at the firing temperature is the protoenstatite
form of MgSi03. 1n fine-grained samples this phase remains as a metasta-
ble phase dispersed in a glassy matrix after cooling. 1n large-grain samples
or on grinding at low temperature, protoenstatite reverts to the equilib-
riurn fOrm, clinoenstatite.
A common type of nonequilibrium behavior is the formation of a
metastable phase which has a lower energy than the mother phase but
not the lowest-energy equilibrium phase. This corresponds to the
tion illustrated in Fig. 7.34 in which the transition from the highest-energy
phase to an intermediate energy state occurs with a much lower activation
energy than the transition to the most stable state. It is exemplified by the
devitrification of silica glass, which occurs in the temperature range of
1200 to 1400
o
C, to form cristobalite as the crystalline product instead of
the mor stable form, tridymite. The reasons for this are usually found in
the structural relationships between the starting material and the final
product. 1n general , high-temperature forms have a more open' stri.l cture.
than low-temperature crystalline forms and consequently are more nearly
like the structure of a glassy starting material. These factors tend to favor
crystallization of the high-temperature form ffom a supercooled liquid or
glass, even in the temperature range of stability of a lower-temperature
modification.
This phenomenon has been observed in a number of systems. For
example, J. B. Ferguson and H. E. Merwin* observed that when calcium-
silicate glasses are cooled to temperatures below 1125
0
C, at which
wollastonite (CaSi03) is the stable crystalline form, the high-temperature
modification, pseudowollastonite, is found to crystallize first and then
slowly transform into the more stable wollastonite. Similarly, on cooling
compositions corresponding to N a20 . Ah03' 2Si02, the high-temperature
crystalline form (carnegieite) is observed to form as the reaction product,
even in the range in which nephelite is the stable phase ; transformation of
carnegieite into nephelite occurs slowly.
1n order for any new phase to form, it must be lower in free energy than
the starting material but need not be the lowest of all possible new phases.
*Am. J. Science, Series 4, 48. 16S (1 919).
CERAMIC PHASE-EQUILlBRIUM DlAGRAMS
315
me
the phase diagram, the liquidus curves of other phases on the
diagram must be extended to determine the conditions under whICh some
other phase becomes more than the starting solution and a possible
precipitate. This is illustrated for the potassium dlSilicate-silica system ln
Fig 7 35. Here, the compound KzO4SiO1 crystallizes only with- gregt
difRculty so that the eutechI corresponding to this prCQIPltatlOn lS
frequently not observed. Instead, the liquidus curves for sillCa and for
notassillm disilicate intersect at a temperature about below the true
Smectic temperature This nonequilibrium eutectic is the temperaturE at
whichi bth notassium disil1Cate and silica have a lower free energy tuan
the liquid COmposition corresponding to the false eutectic Actually, for
this sYstem the situation is complicated mor
cristobalite commonly crystallizes from the melt in plaFe of the
rillIn quartz phase. This gives additional possible behaVIors, as indicateu
by the dotted line in Fig. 7.35.
Extension of equilibrium curves on phase diagrams, such as has been
1400
1300
1200
1100

-;

"'

E
@

500
l
56 60
K
2
0.28i0
2
70
K
2
0.48i0
2
Liquid + Tridymite
Liquid + Quartz
Quartz + K8
4
Weight per cent 810
2
100
8i0
2
111(1 - 7.3' Equilibrlum und noncquilibrium liquidus curves in the pot!lssium di silicate- si lica
syMtcm
shown in Fig. 7.35 and a1so in Fig. 7.5, provides a genera1 method of using
equi1ibrium data to determine possib1e nonequilibrium behavior. It pro-
vides a highly useful guide to experimental observations. The actual
behavior in any sys'tem' may 'follow any one of severa1 possible courses,
so that an ana1ysis of the kinetics ofthese processes (or mre
experimental observations) is a1so required.
Incomplete Reactions. Probably the most common source of non-
equi1ibrium phases in ceramic systems are reactions that are not com-
pleted in:the time available during firing or heat treatment. Reaction rtes
in condensed' phases are discussed in Chapter 9. The main kinds of
incomp1ete reactions observed are incomp1ete solution, incomplete solid-
state reactiOIl-S, and in.comp1ete resorption or solid-liquid reactions. All of
these arise from the presence of re::iction products which act as
layers and prevent further reaction. Perhaps the most striking examp1e of
incmp1ete reactins is the entire metallurgical industry, since a1most all
meta1s are thermodynamically unstab1e in the atmosphere but oxidize.a:nd
corrode on1y slowly.
A particu1ar example of incomp1ete solution is the existence of quartz
grains which are undissolved in a porce1ain body, even after firing at
temperatures of 1200 to 1400
o
C. For the highly siliceous.liquid in contact
with the quartz grain, the diffusion coefficient is low, and there is no fluid
flow to remove the boundary layer mechanically. The situation is simi1ar
to diffusion into an infinite medium, illustrated in Fig. 6.5. To a first
approximation, the diffusion coefficient for Si02 at the highly siliceous
boundary may be of the order of 10-
8
to 10-
9
cm
2
/sec at 1400
o
C. With these
data it is 1eft as an exercise to estimate the thickness of the diffusion layer
after 1 hr of firing at this temperature.
The way in which incomp1ete solid reactions can lead to residual
starting material being present as nonequi1ibrium phases will be clear
from the discussion in Chapter 9. However, new products that arnot the
final equi1ibrium composition can a1s, be formed. For
mixtures.ofCaC03 and Si02 to form CaSi03, the first product
formed and te one that remains the major phase through most of the
reaction is the orthosilicate, Ca2Si04 Similarly, when BaC03 and Ti02 are
reacted to BaTi03, substantial amounts of Ba2Ti04 , BaTh07, and
BaTi0 9 are formed durng the reaction process, as might b<? expected
from the phase-equilibrium diagram (Fig. 7.20). When a series of inter-
mediate compounds is formed in a solid r eaction, the rate at which each
grows depends on the effectve diffusion coefficient through it. Those
layers for which the diffusion rate is high form most ' rapidly, For the
CaO- Si02 system this is the orthosilicate. For the BaO- Ti0 2 system the
most rapidly fQrming compound is again the orthotitanate{ BatTiO .
317
C
A AB
B
Fig, 7.36. Nonequilibrium crystallization path with (1 ) Liquid A, (2) A + liquid AB, (3)
Liquid AB, (4) Liquid AB + B, (5) Liquid AB + B+ C.
A final example of nonequilibrium conditions important in interpreting
diagrams is the incomplete resorption that may occur
whenever a reaction, A + Liquid = AB, takes place during crystallizatIon-
This is the case, for example, when a primary phase reacts with a liquid to
form a new compound during cooling. A layer tends to build up on the
surface of the original formirtg a batrie' to further reaction. As
the temperature is low'ered, the final products are not those anticlpated
from the equilibrium diagram. A nonequilibrium crystallization path for
incomp1ete resorption is schematically illustrated in Fig. 7.36.
Suggested Readi",g
1. E. M. Levin, C. R. Robbins, and H. F. McMurdie, Phase Diagrams for
Ceramists, American Ceramic Society, Columbus, Ohio, 1964.
2. E. M. Levn, C. R. Robbins, H. F. McMurdie, Phase Diagramsfor Ceramists,
1969 Supplement , American Ceramic Society, Columbus, Ohio, 1969.
3, A, M. AJper, Ed., Phase Diagrams: Mat erials Science and Tech_nology, Vol. 1,
Theory, PrincipJes, and Techniques of Phase Diagrams," Academic Press,
Inc .. New York, 1970; VoJ. ll. The U se of Phase Diagrams in Metal ,
Refractory, Ceramic, nd Cement Technology." Academic Press, Inc., New
318
York, 1970; Vol. III , The U se of Phase Diagrams in Electronic Material s and
Glass Technology," Academic Press , Inc., New York. 1970
4 A Muan and E F Osborn, Phase Equilibria among Oxides in Steelmaking,
Addison-Wesley, Publishing Company, Inc., Reading, Mass. , 1965.
5. A. Reisman, Phase Equilibria, Academic Press, Inc., New York. 1970.
6. P. Gordon, Principles of Phase Diagrams in Af.aterials Systems, McGraw HiII
Book Company, New York, 1968.
7. A. M. Alper, Ed., High Temperature Oxides, Part 1, Magnesia, Lime and
Chrome Refractories," Academic Press, Inc. New York, 1970: Part 11.
Oxides of Rare Earth, Titanium, Zirconium, Hafnium, Niobium, and Tan-
talum," Academic Press, New York, 1970; Part III , Magnesia, Alumina,
and Beryllia Ceramics: Fabricanon, Characterization and Properties,,J
Academic Press, Inc., New York; Part IV, Refractory Glasses, Glass-
Ceramics, Ceramics," Academic Press, New York, lnc. , 1971.
8. J. E. Ricci , The Phase Rule and Heterogeneous Equilibrium, Dover
New York, 1966. \
Problems
7. I. A power failure allowed a furnace used by a graduate student worklng in the K20-
Ca0-Si.Oi System to cool down over night For the fun of lt, the Student analyzed the
composition he was studying by X-ray ditrraction. To his horror, he found
2K
2
0'CaO.3Si02, and K
2
0 .2CaO.6Si0
2
in his
sample.
(a ) How could he get more than three phases?
(b) Can you tell him in which composition triangle hi s original composition was?
(C ) Can you predict the minimum temperature above whlCh hIS furnace was
ope_rating before .power failure?
(d) He thought at first he also had some questionable X-ray ditrraction evidence for
K20 .CaO.Si02, but after thinking it over he decided K
2
0.CaO.Si0
2
shOliId not
crystallize out of his sample. Why did he reach this concJusion?
7.2. According tO Alper, McNally, Ribbe, and DOman,* the maXlmum solubility of AlzOI m
MgO is 18 wt% at 1995
0
C and of MgO in MgAI
2
0 is 39% MgO, 51% AI
2
0 ,. Assuming
the Ni0-Al2O3 binary-ls similar to the Mg0-AlzO3 blnary, construct a ternary. Make
isothermal plots of this ternary at 2200
o
C, and 1700
o
C.
7.3. You have been assigned to the electrical properties of calcium metasilicate
by the director of the laboratory in which you work. If you were to make the
materlal synthetically, give a batch COInPOSItion of materlals commonly obtainable in
high purity. From a production standpoint, l0% liquid would increase the rate of
sintering and reaction. Adjust your composition accordingly. What would be the
expected firipg Should the boss ask you to explore th possibility f
lowering the 6rlng temperature and rnamain a white body, suggest the directIOn to
procede- What polymorphic transformations would you be conscious of in working
with the above systems?
*J. Am. Ceram. Soc. 45(6), 263-268 (1 962).
CERAMIC PHASE-EQUlLlBRIUM DlAGRAMS 319
7. 4. Discuss the importance of liquid-phase formation in the production and utilization of
refractory bodies. Considering the phase diagram for the MgO-Si02 system, comment
on the relative desirabiJi ty in use of compositions containing 50MgO-50Si02 by weight
and 6OMg0 -40Si02 by weight. What other characteristics of refractory bodies are
important in their use?
7.5. A binary silicate of specified composition is melted from powders of the separate
oxides and cooled in ditrerent ways, and the following observations are made:
Condition
(a) Cooled rapidly
(b) Melted for 1 hr, held
80
0
C below liquidus
for 2 hr
(c ) Melted for 3 hr, held
80
0
C below liquidus for
2 hr
(d) Melted for 2 hr, cooled
rapidly to 200
0
C below
liquidus, held for 1 hr,
and then cooled rapidl y
Observations
Single phase, no evidence of
crystallization
Crystallized from surface with
primary phases Si02 plus glass
Crystallized from surface with
primary phases compound AO.Si02
plus glass
No evidence of crystaJlization
but resulting glass is cloudy
Are all these observations self consistent ? How do you explain them?
7 6. Triaxial porcelains (flint-feldspar-clay) in which the equilibrium phases at the firing
temperature are mullite and a silicate liquid have a long firing range; steatite porcelains
(mixtures of talc plus kaolin) in which the equilibrium phases at the firing temperature
are enstiatite and a silicate liquid have a short firing range. Give plausible explanations
for ths ditrerence in terms of phases present, properties of phases, and changes in
phase composition and properties with temperature.
7.7. For the composition 40MgO-55Si02-5AJ,O" trace the equilibrium crystallization path
in Fig. 7.30. Also, determine the crystallization path if incomplete resorption of
forsterite along the forsterite-protoenstatite boundary. How do the composi-
tions and temperatures of the eutectics compare for the equilibrium and nonequilib-
rium cry,stallization paths? What are the compositions and amounts of each con-
stituent in the final product for the two cases ?
7. 11 . If a homogeneous glass having the composition I3Na20-13CaO-74Si02 were heated
10 1 050
0
C , 9OO
o
C, and 800
o
C, what would be the possible products
that might form? Explain.
7,9. The clay mineral kaolinite, AJ,Si,O,(OH) , when heated above 6OO
0
C decomposes to
AhSi,O, and water vapor. If thi s composition is heated to 1600
0
C and left at that
temperature until equilibrium is establi shed, what phase(s) will be present. If more
Ih!I Qne is present , what will be their weight percentages. Make the same calculations
ror I

Chapter 7 - Ceramics Phase Equilibrium Diagrams Kingery

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Chapter 7 - Ceramics Phase Equilibrium Diagrams Kingery

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264

The properties of ceramics are determined by the properties of each

ompositioq curves and the

(which contains 58% Ah0 3). There

the freezlng point is often lowered

curves for both end members, as illustrated

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