UNIDAD 2

DIAGRAMAS BINARIOS
2da. PARTE
 The first category of methods detects the phase boundaries
(transuses) by means of thermal, physical, chemical,
mechanical, or other property changes during cooling and/or
heating of an alloy, and therefore studies the approach of a
system to the equilibrium state,

 The other category of methods employs equilibrated alloys or

diffusion couple specimens, and therefore studies the behavior
of a system in an equilibrium or local equilibrium state. A
series of alloys with different compositions can be annealed at
a specific temperature. Some property is measured as a
function of composition to test for differences in the state of
equilibrium. For example, X-ray diffraction (XRD) may be used
for lattice parameter measurement, and the phase boundaries
 Equilibrium states and metastable states are
differentiated by their Gibbs energy.
 An equilibrium state (phase) is the lowest Gibbs
energy state (phase) a system can attain under
specific external constraints (i.e., temperature,
pressure, etc.). A metastable state (phase) has a
higher Gibbs energy than the equilibrium state, but it
is still stable against fluctuation (i.e., dG = 0)
 The experimentally determined, or thermodynamically
assessed, phase boundaries must not violate
thermodynamic laws, especially the First and Second Laws.

 The different approaches used by researchers to arrive at

the best judgment of the correct phase diagram features
and phase boundaries, in any system, should result in a
reasonable agreement.

 The three typical approaches to phase diagram

determination are
◦ through experimental determination of the actual phase
boundaries,
◦ through the use of measured thermodynamic quantities
followed by computations, or
◦ through thermodynamic modeling using carefully assessed
thermodynamic parameters.
 A: A two-phase field cannot be extended to become part of
a pure element side of a phase diagram at zero solute. In
example A, the liquidus and the solidus must meet at the
melting point of the pure element.
 B: Two liquidus curves must meet at one composition at a
eutectic temperature.
 C: A tie line must terminate at a phase boundary.
 D: Two solvus boundaries (or two liquidus, or two solidus,
or a solidus and a solvus) of the same phase must meet
(i.e., intersect) at one composition at an invariant
temperature. (There should not be two solubility values for
a phase boundary at one temperature.)
 E: A phase boundary must extrapolate into a two-phase field after

crossing an invariant point. The validity of this feature, and similar

features related to invariant temperatures, is easily demonstrated by

constructing hypothetical free energy diagrams slightly below and slightly

above the invariant temperature and by observing the relative positions of

the relevant tangent points to the free energy curves. After intersection,

such boundaries can also be extrapolated into metastable regions of the

phase diagram. Such extrapolations are sometimes indicated by dashed

or dotted lines.

 F: A phase boundary cannot cross the 0 at.% line except at a phase

transition (melting, allotropic transformation, etc.) point of the element A.

 G: The highest point of the γ phase must touch the invariant reaction line.

 H: In a binary system, an invariant temperature line should involve

equilibrium among three phases.

 I: There should be a two-phase field between two single-phase fields.

(Two single phases cannot touch except at a point. However, second-order

and higher-order transformations may be exceptions to this rule.)

 J: When two-phase boundaries touch at a point, they should touch at an

extremity of temperature.

 K: A touching liquidus and solidus (or any two touching boundaries) must

have a horizontal common tangent at the congruent point (Gibbs–

Konovalov rule [11]). In this case, the solidus at the melting point is too

“sharp”and appears to be discontinuous.

 L: A local minimum point in the lower part of a single-phase field (in this

case the liquid) cannot be drawn without an additional boundary in

contact with it. (In this case, a horizontal monotectic line is most likely

missing.)
 M: A local maximum point in the lower part of a single-phase field cannot

be drawn without a monotectic, monotectoid, syntectic, or syntectoid

reaction occurring below it at a lower temperature. Alternatively, a solidus

curve must be drawn to touch the liquidus at point M.

 N: The temperature of an invariant reaction in a binary system must be

constant. (The reaction line must be horizontal.)

 O: A phase boundary cannot terminate within a phase field. (Termination

due to lack of data is, of course, often shown in phase diagrams, but this

is recognized to be artificial.)

 P: The liquidus should not have a sharp peak with discontinuous slope at

the melting point of a compound. (This rule is not applicable if the liquid

retains the molecular state of the compound, i.e., in case of a strong

association.)
 Q: The compositions of all three phases at an
invariant reaction must be different.
 R: Initial slopes of the liquidus and solidus must have
the same sign (both up or down).
 S: A four-phase equilibrium is not allowed in a binary
system.
 T: Two separate phase boundaries that create a two-
phase field between two phases in equilibrium should
not cross one another.
 X: Two inflection points are located too closely to one

another.

 Y: An abrupt reversal of the boundary direction (more abrupt

than a typical smooth “retrograde”). This particular change

can occur only if there is an accompanying abrupt change in

the temperature dependence of the thermodynamic

properties of either of the two phases involved (in this case ε

or μ in relation to the boundary). The boundary turn at Y is

very unlikely to be explained by any realistic change in the

composition dependence of the Gibbs energy functions.

Problems Connected with Phase Boundary Curvatures

 Z: An abrupt change in the slope of a single-phase boundary.

This particular change can occur by an unrealistic abrupt

change in the composition dependence of the thermodynamic

properties of the single phase involved (in this case the ε

phase).

 If the abrupt change of slope is caused by an abrupt change

in the temperature dependence of the thermodynamic

properties of the ε phase, it is likely that the boundary of the

λ phase shows a curvature change at the same temperature.

Problems Connected with Phase Boundary Curvatures