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IV. Phase Diagrams

6. Equilibrium Phase Diagrams

Phase: Physically homogeneous region in thermodynamic
equilibrium which is limited by a surface that allows to
separate it mechanically from other parts of the sample.
Phases may be distinguished by their different physical
character (structure etc.).
Component: Independently variable chemical constituent
(e.g. 2 in the case of Al2 O3 + SiO2 ).
Degree of Freedom: Number of intensive variables (e.g.
temperature, pressure, concentration) which have to be
fixed in order to define the system completely.
Phase rule (Gibbs)
f=cp+2

(6.1)

6.1. Monocomponent Systems

p=1:
p=2:
p=3:

f = 3 p
f = 2 (T and p are variable)
f = 1 (boarder lines IA, IB and IC in Fig. 6.1)
f = 0 (point I in Fig. 6.1)

I: Invariant or Triple Point

Boarder Lines: Univariant equilibria
Areas: Bivariant equilibria
AI: Sublimation curve (solid state + vapour coexist)
IC: Evaporation curve (liquid + vapour coexist)

Fig. 6.2 Pressure-temperature phase diagram of water.

Upper End: Critical Point (gas may not be liquified

above this temperature)
IB: Melting Curve (solid state and liquid coexist)
(variation of the melting point of the solid phase
with pressure change)
Metastability.
A metastable phase has always a higher vapour pressure
than another (more stable) phase at the same temperature.
A metastable phase is prepared by a specific procedure.
Example: Supercooled water may be only prepared by
decreasing the temperature of water, but not by
increasing the temperature of ice.

T
Fig. 6.1. Equilibrium - pressure temperature diagram of a
monocomponent system (general)

Fig. 6.3 Polymorphic phases of SiO 2 (allotropism)

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TiO2 , ZrO2

Fig. 6.4. Pressure-temperature diagram of SiO 2.

SiO2 :
As in the case of many other ceramic crystals: high
melting point, low vapour pressure (Figs. 6.3 and 6.4).

Fig. 6.7. Stable and metastable phases of TiO 2 as a function of

temperature.

Most stable state: Minimum of Gibbs energy G = H TS.

The entropy and enthalpy increase with increasing
temperature, but the Gibbs energy decreases (Figs. 6.5
and 6.6).

Fig. 6.8 Stable and metastable phases of ZrO2 as a function of

temperature.
M T at 1000 C, large volume change ( 7%).
T C at 2300 C, melting point: 2715 C

Carbon
Fig. 6.5 Gibbs energy, enthalpy and TS of SiO 2 as a function of
temperature (schematic).

Fig. 6.6 Temperature at which a transition from the to the

structure occurs (SiO 2) in view of the minimum of the Gibbs
energy.

Fig. 6.9. Phase diagram of carbon as a function of pressure and

temperature
Graphite Diamond: > 4000 C, p 150 kbar
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6.2. Two-Component Systems (Binary Systems)

3 variables: T, p, x
p-T-diagrams for the pure components A and B:
In most cases determination of the phase relations for p =
1 atm (Fig. 6.10).
In this case, the variables are T, x (Fig. 6.11).
ME: Liquidus-Line (no crystals exist above this
temperature)
FG: Solidus-Line (no liquid exists below this
temperature)
Phase rule:
p = 1 : f = 2 (T, x)
p = 2 : f = 1 (T or x)
Isothermal line through the 2-phase-region: Tie-Line
(conode). This line connects conjugated phases. Tie-

Fig. 6.12
Indication of the composition at S: The distance A-S and S-B
correspond to the amount of B and A, respectively.
The ratios may be given in mass-% or atom mol %.

Fig. 6.13 Liquidus lines ME, NE: Solubility limits of A, B in

the melt.

Line A3 -M 3 (Fig. 6.11): Liquid consists of 62 % B and

38% A.

Fig. 6.10 T, p, x-phase diagram of a binary system.

Binary Eutecticum
We consider the path X in Fig. 6.11. The addition of
component B to A decreases the freezing point
downward benditure of the liquidus line.
More crystals are being formed with decreasing
temperature which become separated from the melt. The
melt becomes more rich in component B with decreasing
temperature. At E the last remaining liquid crystallises.
The reaction of separation of a liquid into 2 crystalline
phases is called eutectic reaction; E is called "eutectic
point":
melt crystal A + crystal B
The reaction is an isothermal 3-phase reaction.

Fig. 6.11 Binary phase diagram A-B at constant pressure, e.g. 1

atm.

At the eutectic ratio, a characteristic microstructure is

being formed. This is frequently a lamellar structure.
Both phases grow simultaneously from the supercooled
melt. For example, first a nucleus of phase A is formed

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The velocity depends on the degree of supercooling and

the diffusion rates.
Practical application: Control of the electrical, magnetic,
optical, mechanical and thermal properties by controlled
microstructure.
6.3. Binary Systems with Intermediate Compounds

Fig.. 6.14 Microscopic description of the phases and liquid

formed upon cooling at 30% B.

which starts to grow (Fig. 6.16). Atoms A are taken from

the melt which becomes more rich in B and phase B
crystallizes. The region around B becomes more rich in A
which results in the formation of phase A again.
With the simultaneous growth of the lamellos in the melt,
a counter diffusion of A and B atoms along the
preceeding interface solid-melt takes place.

Classification with regard to the melting behaviour.

AB2 (Fig. 6.17) melts congruently since the compound
melts directly into a liquid of the same chemical
composition.
Congruently melting compounds separate a systems into
separate smaller binary systems (AB2 A und AB2 B;
both are simple eutectic systems).
Fig. 6.18 shows the reactions uponcooling of a sample at

Fig. 6.17 Formation of an intermediate phase AB2 which melts

congruently and separates the phase diagram into two separate
smaller binary systems.

Fig. 6.15 Formation of a lamella structure upon cooling a

eutectic mixture.

Fig. 6.18 Reactions upon cooling of a sample with constant

composition (35 w/o Al2O3, 65 w/o MnO)

Fig. 6.16 Microscopic description of the diffusion of A and B

atoms along the interface solid-liquid.

constant composition (35 w/o Al2 O3 , 65 w/o MnO):

1520+ C: 23 units of melt + 10 units of crystalls (MnO
Al2 O3 )
1520 C: 23 units of eutectic crystals + 10 units of
crystals (MnO Al2 O3 )
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Fig. 6.21 Microstructure with only partial reaction; Formation

of a nucleus
Fig.. 6.19 Microstructure upon cooling of a binary eutectic
systems.

Fig. 6.19: Microstructure at the composition x.

Incongruently melt ing compounds do not melt into one
liquid of the same composition but melt into another
liquid and form another crystalline phase.
Fig. 6.20: 3 phases are in equilibrium with each other
along the line PN:
810C

Cr2 O3 V2 O5 Cr2 O3 + melt.

This reaction of incongruent melting is being called
peritectic reaction.
P: Peritectic Point.
Temperature decrease at the composition x: Liquidus line
Cr2 O3 ; 810 C Cr2 O3 + melt Cr2 O3 V2 O5 .
The composition of the melt has not changed; however,
the amount of melt has been reduced. The disappearance
of Cr2 O3 is called resorption.
Rapid Quenching: Microstructure with only partially
reaction (Fig. 6.21). Formation of a central nucleus.

Fig. 6.22 Formation of an intermediate phase between

temperatures T 1 and T 2.

Fig. 6.23 Phase diagram with phase transformations of the

intermediate compound A2B.

Decomposition:
- Formation of 2 other crystalline phases (Fig. 6.22)
- Phase transformation (Fig. 6.23)
6.4. Solid Solutions.

Fig. 6.20 Binary phase diagram of a peridectic system.

Cooling along x (Fig. 6.24) increasing amount of solid

solution and change in the composition.
Counter Diffusion of Ni and Mg has to occur. Because of
the limited velocity, a concentration gradient is being
formed.
Solid solutions may also have maxima and minima
(Fig. 6.26). I: Indifferent or congruent point.
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Fig. 6.24 Binary phase diagram of a solid solution system with

liquidus and solidus line.

Fig. 6.25 Solidification of the melt upon passing through the

regime between the liquidus and solidus line.

Fig. 6.26

At I: Tangent of the liquidus curve = Tangent of the

solidus curve = Isothermal line.

A miscability gap may occur and may extend up to the

liquid phase and may form an eutectic system (Fig. 6.27).

Fig. 6.27 Growth of a miscability gap of a solid solution system A-B. Eventually a two-component system of immiscible components
A and B is being formed.
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Examples of phase diagrams with solid solutions are shown in Fig. 6.28

Fig. 6.28 Typical phase diagrams with solid solutions of the A and B phase

Fig. 6.29 shows a liquid immiscibility (example: ether

and water).
Cooling along x below MRT
L1 A + L2

Fig. 6.29 Phase diagram of an immiscibility of two liquids

(ether and water)

(liquid crystal + liquid)

(Monotectic reaction)
M: Monotectic point
MRT has to be isothermal (phase rule)

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6.5. Ternary Systems.

Fig. 6.30 shows a spinodal decomposition: The
microstructure shows diffuse boundary layers between
the phases.

f = 3 p + 2. Invariant point: 5 phases coexist:

p = const: 4 phases.
Representation of ternary systems: see Fig. 6.31.
Liquidus: Surface with hills and valleys. Sides: binary
systems with binary eutectic points f, g, h.
Eutectic point: E (invariant point, since 4 phases coexist.)
The ternary phase diagram consists of volumes or
spaces:
- Liquid-Space
- Spaces of primary crystallisation (A + liquid, B +
liquid, C + liquid; Fig. 6.32)
- spaces of binary crystallisation (A + B + liquid, A + C
+ liquid, B + C + liquid; Fig. 6.33)

Fig. 6.30 Spinodal Decomposition

Fig. 6.32 Description of the position in a ternary phase triangle.

The distance to the side lines corresponds to the amount of the
indicated components.

Fig.. 6.33 Description of the composition of a ternary phase

triangle according to the intersections along binary legs.

Fig. 6.31 Separation of a ternary phase diagram into sections of

primary and secondary crystallisation
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Presentation of the composition:

- The lengths of the lines perpendicular to the binary legs
of the triangle composed of the components A, B and C
are proportional to their concentrations (Fig. 6.32).
- Lines parallel to the legs of the triangle. The
intersections with the binary legs provide the relative
concentrations. This method is also applicable for nonequilateral triangles (Fig. 6.33).
Representation of the changes during cooling of a melt by
application of the planar projection of the liquidus plane
(Fig. 6.34). Temperature scale: Series of isothermal lines
along the liquidus planes. Projection of these isotherms
onto the basis plane.
The cooling path of each melt runs down to the eutectic
point E (Fig. 6.35). The areas BHEF, AFEG and CHEG
are called primary phase fields of B, A and C.

Fig. 6.35 Projection of the liquidus plane and isotherms of the

liquidus plane onto the basis plane.

Fig. 6.36 Boarder lines of the liquidus planes and Alkemadeline of a ternary system with a binary compound BC.

In the case of a melt with the composition in the primary

phase field B, the first crystal being formed is B. Along
the boarder lines HE, GE and FE, 2 crystalline phases are
in equilibrium with the melt.
A straight line which connects the compositions of the
primary crystals of 2 areas with common boarder line is
called Alkemade-line.

Fig. 6.34 3-dimensional representation of a ternary phase

In the case shown in the Fig. 6.36, an intermediate

compound BC with a primary phase field bc is being
formed. The line A - BC is a line connecting the
compositions of the primary crystals of two areas with
common boarder line (ED). A - BC is an Alkamade-line.
B - C is not an Alkamade-line.

diagram with liquidus planes, isothermal lines along the planes

and eutectic point E

Alkemade-Theorem: The intersection of a boarder line

between two liquidus planes with the corresponding
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Alkemade-line represents a temperature maximum along

the boarder line and a temperature minimum along the
Alkemade line. 3 boarder lines come together at a
common intersection at E and D (= eutectic points).
Compositional Triangles.
Alkemade-lines separate a ternary diagram into
compositional triangles. 3 Alkemaade lines generate a
compositional triangle. Alkemade lines never cross each
other. Upon cooling of a melt, a combination of crystals
with a composition of the corners of the compositional
triangles is being formed.
Example: The composition Y is within the triangle ABC-C in Fig. 6.37. The relative amounts are given by the
intersections of the lines parallel to the legs of the
compositional triangles. Eutectic point: D (30% A, 48%
BC, 22% C).
A - BC represents a true binary system.
If the Alkemade line does not cross the boarder line, there
will be no a true binary system being formed by the
Alkemade line.

Fig. 6.38 Isotherms of the ternary phase diagram shown in Fig.

6.37.

Isothermal Cuts
Fig. 6.38 shows the isotherm of Fig. 6.37. Fig. 6.39
shows the isothermal cut at 700 C. The areas with the
straight lines represent two-phase regions.
Fig. 6.40: 600 C,
Fig. 6.41: 400 C,
Fig. 6.42: 300 C
Fig. 6.39 Isothermal cut of the ternary system at 700 C.

Fig. 6.37 Representation of the composition Y within the 3phase equilibrium A-BC-B by drawing lines parallel to the legs
of the ternary region.

Fig. 6.40 Isothermal cut of the ternary system at 600 C.

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Fig. 6.44 Representation of polymorphic phases. The phase

transformations between the various structures of SiO 2
correspond to the isotherms of the corresponding transformation
temperatures.

Fig. 6.41 Isothermal cut at 400 C

Peritectic and Eutectic Reactions during Cooling.

Fig. 6.43: Before Solidification of the melt Y both a
peritectic and a eutectic reaction occur. The following
path is observed:
i) Crystals B, C and AB are being formed
ii) Cooling path: Cooling to the composition where the
crystals A, C and AB are in equilibrium with each
other.
Y is within the primary phase field B; accordingly B is
formed as the first crystal. The composition of the melt
changes along the line YG.
B and C are simultaneously formed while the
composition changes from G P.
At the temperature below that of P, a peritectic reaction
occurs, i.e. the melt reacts with one of the crystals in
order to form two different crystalline phases
After the peritectic reaction is completed, further cooling
results in the change of the composition along the boarder
line from P to E.

Formation of Intermediate Ternary Compounds.

Fig. 6.45: Formation of a congruently melting compound
ABC. Representation of the compound within the
primary phase field.
ABC forms 3 ternary subsystems: A-ABC-B, A-ABC-C
and B-ABC-C.
In case that ABC melts incongruently, the primary phase
field of this compound is separated from the position
which represents the compound.
The ternary subsystems are not true ternary systems
Ternary Solid Solutions.
Fig. 6.46: Complete solid solubility between the
components A and B under formation of the phase .
Limited solubility of C in A and C in B.
The eutectic points of the binary systems B-C and A-C
occur at E1 and E2 , which are connected to each other by
the 3 phase boundary E1 E2 .

Fig. 6.42 Isothermal cut at 300 C.

Phase-Transformations.
Formation of polymorphic crystalline phases. Example of
representation in ternary systems: Fig. 6.44. Since the
phase transformation occurs (in equilibrium) at a defined
temperature, the boarder line between two polymorphes
is in agreement with the corresponding isotherm. E.g. the
boarder line between Cristobalit and Tridymit agrees with
the 1470 C-isotherm.

Fig. 6.43 Cooling path and solidification of a melt Y with

peritectic and eutectic reactions.
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Example: System MgO-Al2 O3 -SiO2

Fig. 6.47: A large number of commercial products is
based on this diagram, especially electrical insulators.
Binary leg MgO-SiO2 : Periclas (MgO), Forsterit
(2MgOSiO2 ), Eustatit (MgOSiO2 ) = Magnesiummetasilicate, which is called Eustatit at low temperatures and is
transformed in its high temperature structure Protoenstatit
at 1040 C.
Ternary Compound: Cordierit (2MgO2Al2 O3 5SiO2 )
which shows good thermal shock resistance and high
electrical resistance.
Starting materials for the preparation of these materials:
Clay
(Al2 O3 2SiO2 2H2 O)
and
talcum
(3MgO4SiO2 H2 O).

Fig. 6.45 Formation of a congruently melting compound

ABC. This compound is formed within its primary phase
field.

Fig. 6.46 Ternary phase diagram of a system with solid

solubility between AB under formation of the phase with
limited solubility of C in A and C in B. The binary systems B-C
and A-C show eutectic points at E1 and E2.

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Fig. 6.47 Projection of the ternary phase diagram SiO 2, MgO and Al2O3

Isothermal Ternary Cut (Gibbs-Triangle)

Lines of equal
activity

Fig. 6.48 Representation of the single phase, 2-phase and 3phase regions of a ternary system ABC.

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6.6. Non-equilibrium Phases and Reactions

Fig. 6.49: Heating at X0 ; A and B are powders with a
microstructure shown in Fig. 6.50. T T2 : Melt with a
composition X1 and solid body A (in equilibrium).
First liquid phase eutectic composition.
The part of the melt which is in contact with A, will
dissolve further amounts of A.
This holds similarly also for B.
The simultaneous solution of A at a surface of the melt
and of B at the other surface generates gradients of the
composition in the melt Counter diffusion of A and B.
The melts will not reach saturation concentration. The
process of solution will be continued until all B is
consumed.
Fig. 6.52: Suppression of the formation of an
intermediate compound.
Example: Suppression of the formation of mullite SiO2 Al2 O3 -system.

Fig. 6.51 Formation of a melt in-between phases A and B with

diffusion of the two components in opposite direction for
equilibration.

Fig. 6.49 Binary phase diagram with heating of a mixture of

powders of A and B as shown in Fig. 6.50 at the composition
X0.

Fig. 6.52 Suppression of the formation of the intermediate

phase AB. The system takes up the phase diagram of a simple
binary system with an eutectic point.

Fig. 6.50 Starting distribution of grains of A and B when

heating at the composition X0 in Fig. 6.49.

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