1.1 Diagramas de Fases

Ingeniería de Materiales
Cerámicos 1
Diagramas de Equilibrio
Bibliografía
2010
2007
Página 2 Diagramas de Equilibrio E. Urday U.

Bibliografía
2003 1995
Phase Diagrams for Ceramists
•• Since many ceramics are oxides, the oxygen partial pressure,

, is an important variable.
• There is a lot of information about many metal-oxygen
systems.
• In part, this is due to interest in how to obtain metals by
direct reduction from their oxides.
• A frequent way of representing free energies of formation of
oxides as a function of and T is the Ellingham diagram, that
was popularized by Richardson and Jeffes for iron and steel
production.

DALTON’S LAW OF PARTIAL PRESSURES
PA = XAP
PA is the partial pressure of A.

XA is the mole fraction of A.
P is the total pressure of the gas mixture.

• Many ceramics are multicomponent materials and, hence,
many of the important phase diagrams involve three or more
components.
• Refractory silica brick:
– This was used for the roof of the open-hearth furnace,
which was once an important method for steel
production.
– Now silica refractories are used in coke ovens and as
roofs in glass tanks.
– Typical operating temperatures are 1625-1650°C.
– The phase diagram tells us that the SiO2 needs to be quite
pure (only 0.2-1.0 wt% Al2O3) or it will melt.
• Fire-clay brick:
– This is a classic clay product with composition close to
kaolinite.
– Although it is used at temperatures below 1587°C, the
phase diagram tells us that some liquid will often be
present since these ceramics contain 22-33 wt% Al2O3.
– This material is so important because it performs the task
very well and is cheap to produce.

• Barium titanate:
– Pure cubic BaTiO3 single crystals cannot be grown from a
melt of that composition because the hexagonal phase is
in equilibrium with the liquid at the solidification
temperature (1618°C).
– Although the hexagonal phase is transformed to the cubic
phase at 1460°C, the phase change is sluggish and thus
the hexagonal phase can exist at room temperature.
– The hexagonal form of BaTiO3 is not ferroelectric, which
is the property in which we are most often interested.

• Adhesion of metals in integrated circuits:
– Aluminum has been used for over 30 years as
interconnect and top level metallization in integrated
circuits.
– One of the reasons Al is so good is that it reduces SiO2 to
form interfacial metal–oxide bonds that promote adhesion
and stability.
– One of the problems with copper metallizations is that
SiO2 is more stable than Cu2O.
– Despite this difficulty, Cu has several significant
advantages over Al and is now used in many commercial
devices.
Phase Diagrams
Map of the phases in thermodynamic equilibrium that are

present in a system of materials at different pressures,
temperatures and compositions.
The phase diagrams provide the following information:
1. The phases present at equilibrium
2. The composition of the phases present at any time during
heating or cooling
3. The fraction of each phase present
4. The range of solid solubility of one element or compound in
another

Conceptos Básicos
Phase diagram of CO2

• There is no liquid CO2 at Troom and
ambient pressure.
• Gradient of P/T > 0, as it is in almost
all substances.
• Triple-point: gas, liquid and solid are at
equilibrium.
• At T below the triple point CO2 can
sublime:
gas solid (dry ice)
• Above Tc = 32°C and Pc =73 atm
supercritical CO2 fluid (used to extract
caffeine from coffee)
Gibbs Phase Rule
Phase diagrams are chemographic representations of the

famous Gibbs’ phase rule that relates the number of phases P,
the number of components C, and the number of degrees of
freedom F of a (closed) system by the simple equation
F=C–P+N (3.2)
The components C are defined as those simple oxides that
combine to constitute the phases P present at equilibrium; that
is, those portions of a system that are physically homogeneous
and mechanically separable.

Gibbs Phase Rule
The number of degrees of freedom, F, is the number of

variables that can be altered without changing the number of
phases present.
The number “2” in Eq. (3.1) is applicable when both
temperature and pressure have to be considered.
However, in systems of importance for ceramics, the vapor
pressure is very low over a wide range of temperatures; thus,
the pressure variable can be safely neglected.

Gibbs Phase Rule
Such systems with a reduced degree of freedom are termed

“condensed” systems, and Eq. (3.1) reduces to
P+F=C+1 (3.2)
also called the “ mineralogical phase rule ”.

Gibbs Phase Rule
• El número de fases es el número de porciones del sistema
distintas físicamente y separables mecánicamente, siendo
cada fase homogénea
• Sistema constituido por mezclas de CaCO3 (creta) y SiO2
(arena)
• Sistema constituido por mezclas de MgSiO3 (enstatita) y
Mg2SiO4 (forsterita)
• Sistema constituido por mezclas de dos polimorfos, α- y β-
Ca2SiO4, formas estable y metaestable, respectivamente
• Sistema constituido por una disolución sólida, AlCrO3

Gibbs Phase Rule
• El número de componentes es el número de constituyentes
del sistema que pueden sufrir variación independiente en las
diferentes fases. Alternativamente, puede ser definida como
el número mínimo de constituyentes necesarios para
describir completamente la composición de las fases
presentes en el sistema concreto.
• Todos los silicatos de calcio cristalinos pueden considerarse
constituidos a partir de CaO y SiO2
• Se forman cuatro fases cristalinas estables en el sistema
CaO-SiO2 : CS, C3S2, C2S y C3S

Gibbs Phase Rule
• El número de grados de libertad es el número de factores
variables independientes, tomados de entre la temperatura,
presión y composición de las fases. Es decir, es el número
de estas variables que deben especificarse para que el
sistema quede completamente definido.
• El sistema H2O(l) - H2O(v) es univariante, solo es necesario
un grado de libertad, presión o temperatura, para describir
completamente el sistema en equilibrio
• Una disolución sólida en el sistema Al2O3-Cr2O3 es
bivariante, es necesario especificar la composición y la
temperatura para describir el equilibrio del sistema

Gibbs Phase Rule
F=C–P+N

Gibbs Phase Rule
F=C–P+N

One-Component Phase Diagrams
• The number of independent variables in one-component

systems is only two, namely T and P, since the composition
is fixed (C = 1).
• Consequently, the system has two degrees of freedom (F =
2, bivariant) if only one phase is present, since T and P can
be varied widely without moving the system into another
phase field.
• As shown in Figure, this is the case for P, T conditions
within the stability fields of the solid phases A and B, and
the liquid and vapor phases.

• If two phases are present, the system is univariant (F = 1), as

represented by the five phase boundary lines – that is, the
melting curve B-E of phase B, the transition curve A-D
between the solid phases A and B, the sublimation curves F-
A (phase A) and A-B (phase B), and the vapor pressure
curve B-C of the liquid phase.
• Finally, if three phases are present, the system is invariant (F
= 0), as represented by the two triple points A (equilibrium
between solid A, solid B, and vapor) and B (equilibrium
between solid B, vapor, and liquid).

F=C–P+N
Figure 3.2 (a) General phase relations in a one - component system

• Figure follow shows the (hypothetical) equilibrium phase

diagram of silica, that is, the phase diagram without
metastable phases.
• The transformation temperatures between solid silica phases
are given at 100 kPa (1 bar) pressure.

Figure 3.2 (b) Hypothetical equilibrium phase diagram of silicon

dioxide
• Diagrama de P-T del SiO2

• Tiene cuatro fases cristalinas,
denominadas polimorfos
• Cada una de estas fases ocupa un
área o campo sobre el diagrama
cuando F = 2
• En estas áreas son necesarias la P
y T para describir el sistema
• Las regiones de fase única están
separadas de las vecinas por
curvas univariantes, con F=1

• Al variar una variable, tal como la P, la otra variable, T queda

fijada
• Como se puede observar al incrementar la P se observan dos
cambios principales
• La contracción del campo de la tridimita, desapareciendo a
~900 atm
• La desaparición del campo de la cristobalita a ~1700 atm
• Esta desaparición puede asociarse con la menor densidad de las
fases tridimita y cristobalita ( 2.298 y 2.334 g/cm3),
respectivamente) respecto al cuarzo (2.647 g/cm3)

• El polimorfismo a presión atmosférica se puede resumir

mediante


• As single-phase substances are heated or cooled, they can

undergo a number of polymorphic transformations.
• Polymorphs are different crystalline modifications of the
same chemical substance.
• These transformations are quite common and include
crystallization of glasses, melting, and many solid-solid phase
transformations.
• In general, there are two types of polymorphic
transformations,
• displacive and
• reconstructive

Reconstructive Transformations
• As shown schematically in Fig. reconstructive transformations
involve the breaking and rearrangement of bonds.
• Such transformations usually occur by nucleation and growth,
which in turn usually depend on the rate at which atoms
diffuse and consequently are relatively sluggish and easily
suppressed.
• The reconstructive transformations that occur in quartz,
specifically the α-β transformation are good examples.

Reconstructive Transformations

Displacive Transformations
• In contrast to reconstructive transformations, displacive
transformations do not involve the breaking of bonds, but
rather occur by the displacement of atomic planes relative to
one another.
• These reactions occur quite rapidly, and the resulting
microstructures are usually heavily twinned.
• In these transformations, the role of thermal entropy is
important since the enthalpies of the phases on either side of
the transformation temperature are quite comparable.

• It follows that the transformation usually results in the

formation of more open (less dense) structures at higher
temperatures, namely that the more open structures have
higher thermal entropies.
• Martensitic transformations in steel are probably the most
studied of these transformations.
• Examples in ceramic systems of technological importance
include the tetragonal-to-monoclinic transformation in ZrO2,
the cubic-to-tetragonal transformation in BaTiO3, and
numerous transformations in silica.


One - Component Phase Diagrams
Zirconia
Upon heating under 1 atm pressure, zirconia goes through the
following transformations:
It exhibits three well-defined polymorphs: a monoclinic phase, a

tetragonal phase, and a cubic phase.
The low-temperature phase is monoclinic, stable to 1170°C at
which temperature it changes reversibly to the tetragonal phase,
which in turn is stable to 2370°C.
Above that temperature the cubic phase becomes stable up to the

melting point of 2680°C.
The tetragonal-to-monoclinic (t → m) transformation is believed
to occur by a diffusionless shear process that is similar to the
formation of martensite in steels.
This transformation is associated with a large volume change
and undergoes extensive shear which is the basis for
transformation toughening of zirconia.


Barium titanate
Barium titanate goes through the following phase transitions
upon heating:
Above 130°C, the unit cell is cubic, and the Ti ions are centered
in the unit cell.
Between 130 and 0ºC, however, BaTiO has a distorted3
perovskite structure with an eccentricity of the Ti ions.


Silica
Silica has a multitude of polymorphs that undergo a number of
both displacive and reconstructive transformations, the most
important of which are summarized in Fig.
The displacive transformation from high to low quartz is
associated with a large volume change which, upon cooling, can
create large residual stresses and result in a loss of strength.

The best way to avoid the problem is to ensure that during

processing all the quartz is converted to cristobalite, which
because of its sluggish reconstructive transformation is
metastable at room temperature.
The volume change from high to low cristobalite is not as severe
as that for quartz.


Two-Component (Binary) Phase Diagrams
• Binary phase diagrams are very important for ceramics.

• The two most important cases for ceramics are the
combination of a metal plus oxygen and the combination of
two oxides.
• A model two-component system is shown in Figure 8.9 where
we are now using the third dimension to display the data.
• If there is one phase (X = 1) as at B, then the three variables
are P, T, and one other, for example, the composition (x/y
ratio).
• If there are two phases present (X = 2) such as the liquid and
one solid phase at A, then F = 2.

• If, for example, we fix P, we are free to vary T and move

along
• the liquid/solid phase boundary (a surface).
• The special feature is that we have introduced surfaces into
the phase diagram.
• In ceramic materials, the gas phase may be very important.
• This is where ceramics are particularly different from metals:
oxygen (or nitrogen or water vapor and hence hydrogen) may
be a component of the system.
• The gas phase is not important if the valence of the cations is
fixed and the total pressure, P, is fixed at 1 atm.

FIG. 8.9 A model binary phase diagram showing T, P, and composition as

variables.

• When two components are mixed together and allowed to

equilibrate, three outcomes are possible:
1. Mutual solubility and solid solution formation over the
entire composition range, also known as complete solid
solubility.
2. Partial solid solubility without the formation of an
intermediate phase
3. Partial solid solubility with the formation of intermediate
phases

Complete Solid Solubility
• In a substitutional solid solution, the solute ion directly
substitutes for the host ion nearest to it in electronegativity,
which implies, that cations will substitute for cations and
anions for anions.
• Needless to say, the rules for defect incorporation reactions
have to be satisfied at all times.

Substitutional solid solutions
For complete solid solubility to occur between two end members,
the following conditions have to satisfied:
1. Structure type. The two end members must have the same
structure type. For instance, SiO2 and TiO2 would not be
expected to form complete solid solubility.
2. Valency factor. The two end members must have the same
valence. If this condition is not satisfied, compensating
defects form in the host crystal in order to maintain charge
neutrality. Given that the entropy increase associated with
defect formation is not likely to be compensated for by the
energy required to form them over the entire composition
range, complete solid solubility is unlikely.
3. Size factor. As a result of the mismatch in size of the
solvent and solute ions, strain energy will develop as one is
substituted for the other. For complete solid solubility to
occur, that excess strain energy has to be low. Hence, in
general, the size difference between the ions has to be less
than 15 percent.
4. Chemical affinity. The two end members cannot have too
high a chemical affinity for each other. Otherwise the free
energy of the system will be lowered by the formation of an
intermediate compound.

• A typical phase diagram for two compounds that form a
complete solid solubility over their entire composition range
is shown in Fig. 8.4.
• Both NiO and MgO crystallize in the rock salt structure, and
their cationic radii are very similar.
• To illustrate the use and usefulness of phase diagrams, it is
instructive to take a composition in Fig. 8.4, say, 60% mol
MgO, and examine what happens as it is cooled from the melt.
• At T1, a solid solution of MgO and NiO (roughly 80% mol
Mg2+) will start solidifying.

•At T2 2500°C, two phases coexist: a solid solution of
composition Z (see top of Fig. 8.4) and a liquid solution of
composition X.
• The relative amounts of the each phase are given by the lever
rule:
• Note that as the temperature is lowered, the composition of

the solid solution moves along the solidus line toward NiO,
while that of the liquid moves along the liquidus line.

• At T3 ≈ 2400°C, the final liquid solidifies, and the
composition of the solid solution is now the same as the initial
composition.
Figure 8.4 MgO-NiO phase diagram

exhibiting solid solubility over entire
composition range.

Eutectic Diagrams with Partial Solid Solubility and No
Intermediate Compounds
• Given the numerous restrictions needed for the formation of
complete solid solutions, they are the exception rather than the
rule - most ceramic binary phase diagrams exhibit partial
solubility instead.
• Furthermore, the addition of one component to another will
lower the freezing point of the mixture relative to the melting
point of the end members.
• The end result is lowered liquidus curves for both end
members which intersect at a point.
• The point of intersection defines the lowest temperature at
which a liquid can exist and is known as the eutectic
temperature TE.
• This type of diagram is well illustrated by the MgO-CaO
system shown in Fig. 8.6, where MgO dissolves some CaO
and viceversa.
• The limited solubility comes about mostly because the size
difference between the Ca and Mg ions is too large for
complete solid solubility to occur.
• Beyond a certain composition, the increase in strain energy
associated with increasing solute content can no longer be
compensated for by the increase in configuration entropy.

•To illustrate the changes that occur upon cooling consider
what happens when a 40% mol CaO composition, depicted by
the dotted vertical line in Fig. 8.6, is cooled from the melt.
• Above 2600°C the liquid phase is stable.
• Just below 2600°C, a MgO solid solution (95% mol MgO
saturated with CaO) will start to precipitate out.
• At 2500°C, two phases will coexist: an MgO-CaO solid
solution and a liquid that is now richer in CaO (≈55% mol
CaO) than the initial composition.

• Upon further cooling, the composition of the liquid follows
the liquidus line toward the eutectic composition, whereas the
composition of the precipitating solid follows the solidus line
toward the point of maximum solubility.
• Just above TE, that is, at TE + δ, a solid solution of CaO in
MgO and a liquid with the eutectic composition XE 65% CaO
coexist.
• Just below TE, however, the following reaction
L => S1 + S2

• known as a eutectic reaction, occurs, and the liquid
disproportionates into two phases of very different
compositions - a calcia-rich and a magnesia-rich solid
solution.
• It is important to note here that the solution of one compound
in another is unavoidable - a perfectly pure crystal is a
thermodynamic impossibility for the same reason that a
defect-free crystal is impossible.
• The only legitimate question therefore is, How much
solubility is there?
• In many binary systems, the regions of solid solution that are
necessarily present do not appear on the phase diagrams
• For example, according to Fig. 8.7a or 8.8, one could conclude
incorrectly that neither Na2O nor A12O3 dissolves in SiO2.
• This is simply a reflection of the scale over which the results
are plotted - expanding the x-axis will indicate the range of
solubility that must be present.
• Note that in many applications and processes, this is far from
being a purely academic question.
• For example, the electrical and electronic properties of a
compound can be dramatically altered by the addition of a few
parts per million of impurities.

• Optical properties and sintering kinetics are also strongly
influenced by small amounts of impurities.
• This is especially true when, these impurities tend to segregate
at grain boundaries.

Partial Solid Solubility with Formation of Intermediate
Compounds
• One of the conditions for the existence of a wide solid
solution domain is the absence of a strong affinity of the end
members for one another.
• That is not always the case - in many instances, the two end
members react to form intermediate compounds.
• For instance, the compound AxByO2 can be formed by the
reaction

1.1 Diagramas de Fases

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Ingeniería de Materiales

Página 2 Diagramas de Equilibrio E. Urday U.

•• Since many ceramics are oxides, the oxygen partial pressure,

Página 4 Diagramas de Equilibrio E. Urday U.

PA is the partial pressure of A.

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Map of the phases in thermodynamic equilibrium that are

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Phase diagram of CO2

Phase diagrams are chemographic representations of the

Página 12 Diagramas de Equilibrio E. Urday U.

The number of degrees of freedom, F, is the number of

Página 13 Diagramas de Equilibrio E. Urday U.

Such systems with a reduced degree of freedom are termed

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• The number of independent variables in one-component

Página 20 Diagramas de Equilibrio E. Urday U.

• If two phases are present, the system is univariant (F = 1), as

Página 21 Diagramas de Equilibrio E. Urday U.

Figure 3.2 (a) General phase relations in a one - component system

Página 22 Diagramas de Equilibrio E. Urday U.

• Figure follow shows the (hypothetical) equilibrium phase

Página 23 Diagramas de Equilibrio E. Urday U.

Figure 3.2 (b) Hypothetical equilibrium phase diagram of silicon

• Diagrama de P-T del SiO2

Página 25 Diagramas de Equilibrio E. Urday U.

• Al variar una variable, tal como la P, la otra variable, T queda

Página 26 Diagramas de Equilibrio E. Urday U.

• El polimorfismo a presión atmosférica se puede resumir

Página 27 Diagramas de Equilibrio E. Urday U.

Página 28 Diagramas de Equilibrio E. Urday U.

• As single-phase substances are heated or cooled, they can

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• It follows that the transformation usually results in the

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It exhibits three well-defined polymorphs: a monoclinic phase, a

Above that temperature the cubic phase becomes stable up to the

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perovskite structure with an eccentricity of the Ti ions.

Página 38 Diagramas de Equilibrio E. Urday U.

Página 39 Diagramas de Equilibrio E. Urday U.

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The best way to avoid the problem is to ensure that during

Página 41 Diagramas de Equilibrio E. Urday U.

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• Binary phase diagrams are very important for ceramics.

Página 43 Diagramas de Equilibrio E. Urday U.

• If, for example, we fix P, we are free to vary T and move

Página 44 Diagramas de Equilibrio E. Urday U.

FIG. 8.9 A model binary phase diagram showing T, P, and composition as

Página 45 Diagramas de Equilibrio E. Urday U.