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# Solutions

## If we mix two types of atoms, 3 possibilities

for attractive forces,

Ideal solutions

or

or

## Vapor pressure of pure metal A = pA*

Vapor pressure of A in solution = pA

## Fig. A. Vapor pressure pA of pure metal A in an

ideal solution as a function of composition [Alloy
Phase equilibria by A. Prince]

## In the composition range 0 XA 1, the vapor

pressure of A is linear function of composition if
the solution is ideal, hence
pA = XApA*
As aA = pA/pA* for an ideal solution, so
aA = XA
This is called Raoults law. The activity of a
solvent in an ideal solution is equal to its atomic
fraction.

Actual solutions

produced.

## Nucleation: As in solidification, nucleation

occurs most easily on surfaces already present
in the structure, thereby minimizing the surface
energy
term.
Thus,
the
precipitates
heterogeneously nucleate most easily at grain
boundaries and other defects.
Growth: Growth of the precipitates normally
occurs
by
long-range
diffusion
and
redistribution of atoms. Diffusing atoms must
be detached from their original locations
(perhaps at lattice points in a solid solution),
move through the surrounding material to the
nucleus, and be incorporated into the crystal
structure of the precipitate.

## Kinetics The overall rate, or kinetics, of a

transformation depends on both nucleation
and growth. If more nuclei are present at a
particular temperature, growth occurs from
a larger number of sites and the phase
transformation is completed in a shorter period
of time. At higher temperatures, the diffusion
coefficient is higher, growth rates are higher,
and again we expect the transformation to be
completed in a shorter time, assuming
an equal number of nuclei.
The rate of transformation is given by the
Avrami equation, with the fraction of the
transformation, f , related to time, t, by

## where c and n are constants for a particular

temperature. An incubation time, t0, is the time
required for nucleation to occur.

## The rate of atom or ion movement is

related to temperature or thermal energy by
the Arrhenius equation:

## where Q is the activation energy (in this case

for the phase transformation), R is the gas
constant, T is the temperature, and A is a
constant.

## Figure 12-3 (a) The effect of temperature on the

rate of a phase transformation is the product of
the growth rate and nucleation rate contributions,
giving a maximum transformation rate at a critical
temperature. (b) Consequently, there is a
minimum time (tmin) required for the
transformation, given by the C-curve.

Widmansttten patterns
Widmansttten Structure: The second phase
may grow so that certain crystallographic planes
and directions in the precipitate are parallel to
preferred planes and directions in the matrix,
creating a basket-weave pattern known as the
Widmansttten structure. This growth
mechanism minimizes strain and surface
energies and permits faster growth rates.
Widmansttten growth produces a characteristic
appearance for the precipitate. When a needlelike shape is produced [Figure 12-6(a)], the
Widmansttten precipitate may encourage the
nucleation of cracks, thus reducing the ductility
of the material. However, some of these
structures make it more difficult for cracks to
propagate, therefore providing good fracture
toughness.

Figure 12-6 (a) Widmansttten needles in a CuTi alloy (420). (From ASM Handbook, Vol. 9,
Metallography and Microstructure (1985), ASM
International, Materials Park, OH 44073.) (b)
Continuous y precipitate in an Al-4% Cu alloy,
caused by slow cooling (500).