Strengthening due to the presence of a

second phase

1. Precipitation hardening/ Age-hardening

2. Dispersed phase strengthening

Precipitation hardening was accidentally discovered by Alfred Wilm in Germany

in 1906. He attempted to harden an aluminum alloy (Al-2 at.%Cu), analogous to
steels by a quenching treatment.

The alloy was initially soft, but hardness increased with time at room
temperature after the quench, results were published in 1911 (no explanation).

Merica, Waltenberg & Scott attributed hardening due to precipitation.

- solubility of copper in aluminum reduced on cooling & quenching gives a
supersaturated solid solution.
 Precipitation hardening
At room temp. the stable state of Al-2
% at.Cu alloy is an aluminum rich solid
solution () and phase with a tetragonal
structure having nominal composition
CuAl2 ().
It was suggested that these fine
particles () were formed during aging
(similar precipitates for other systems).
When these precipitates were large
enough to be observed using a light
microscope, the hardness values
decreased.
Merica suggested a pre-precipitation
stage (tiny regions having different
compositions from the average were
Al-Cu phase diagram imagined to be in solid solution.

The mystery was solved first in Al-Cu alloys independently by Guinier and Preston in 1937 by careful
X-ray diffraction work. Small solute-enriched regions in the solid solutions where the lattice is identical or
somewhat perturbed from that of the solid solution Guinier-Preston Zones (GP zones)
Diffuse X-ray scattering by lattice
distortion ?
 Age-hardening curves for Al-Cu
Higher Cu contents result in higher
maximum hardness values - larger
volume fractions of precipitate are
possible.

There is a critical time beyond which

hardness does not increase, rather
starts decreasing.

Al-Cu precipitation sequence:

0 1 + GP-zones 2 + 3 +
4 +

GP zones mono-atomic layers of Cu on (001)Al

- thin discs, fully coherent with matrix
Hardness vs. time for various Al-Cu - disc-shaped, semi-coherent on (001) bct.
alloys at two different temperatures - incoherent interface, ~spherical, complex
body-centered tetragonal (bct).

Silcock, Heal and Hardy

Metastable & stable phases in Al-Cu systems

GP zone structure
 Metastable & stable phases in Al-Cu systems
Local contraction of the
host Al lattice on (100)
Superlattice of GP-I zones
(stacking of GP zones)
Coherent with matrix

Cu disks of
40 200 Stable-equilibrium
phase
Incoherent with
matrix
Tetragonal CuAl2
Semi-coherent with
matrix, tetragonal
distortion of cubic
fluorite structure
 GP-zones & ordinary precipitates
GP zones: compositional change in the solid solution with or without a
structural change. If there is a structural change, then it is a perturbation of
the structure of the solid solution.

- An ordinary precipitate gives an X-ray diffraction pattern characteristic of an

entirely different structure. They can be coherent, semi-coherent, or incoherent with
the matrix.

All types of precipitates may give hardening but GP zones and coherent
ord. precipitates give greater hardening.

In some systems such as Al-Cu, maximum hardening occurs due to GP

zones; For Al-Ag, maximum hardening is due to coherent ordinary
precipitates.

GP zones: Ideal or nonideal

The atomic sizes of zinc and silver differ little from that of aluminum, hence not much
distortion of the Al rich matrix, they form ideal zones.
Al-Cu is an example of forming nonideal zones.
 Cutting or bowing of dislocations
At small sizes, the dislocation cuts through the particle at a lower stress
than the Orowan bowing stress (and so this is what is observed). Larger
particles mean higher cutting stresses.

At large sizes, the dislocation bows around the particle more easily than it
cuts through it (so no cutting is observed). Larger particles mean fewer
particles (via coarsening) hence lower flow stresses.
Fewer and fewer particles,
Particles becoming stronger further apart

Variation of yield stress with aging time for age hardening alloys
 Particle coherency- shearing
If Upm is the specific particle-matrix interfacial energy, then the interfacial energy
which must be supplied at the circumference of the particle corresponds to the
repulsive force on the dislocation given by:
|Fpm|max ~ Upm b.

Particle shearing

Particle coherency: If the particle is coherent

with the matrix, the dislocation can pass
through the particle, cutting it. It is necessary
to provide surface energy for this as the
particle is sheared on the slip plane by an
amount equal to the Burgers vector.

Transmission electron micrograph of sheared Ni3Al particles in a 19%Ni-6%Cr Al alloy after 2 %

deformation in tension (H. Gleiter & E. Hornbogen, Goettingen)
 Shearing of ordered precipitates
If the particle is ordered, an antiphase boundary of energy UAPB is produced when
it is cut. This corresponds to the repulsive force, |FAPB|max ~ UAPB r0
A second dislocation however, restores the order and is thus attracted to the
particle.

Ordered Ni3Al precipitate cut by a perfect dislocation in the Ni (O) and Al ( ) matrix
producing an antiphase boundary.
 Precipitate-dislocation interactions

As in solid solution hardening, a precipitate can interact with a passing

dislocation parelastically by virtue of its distortion and dielastically (because
it has a different shear modulus from that of the matrix).
Then maximum interaction forces for a spherical particle of radius ro are
|Fp|max ~ Gbro||
&
|Fd|max ~ Gb2 ||/20
where, and are the differences in lattice parameter and shear modulus
between matrix and particle.

Strengthening due to elastic misfit stresses Internal strain hardening

(Mott-Nabarros theory of ppt. hardening)

rp
Let us define the misfit parameter: 1
rm

Where, rp = radius of the particle & rm = radius of the matrix atom

 Mott & Nabarros theory
(Internal strain hardening)
Assuming that the precipitate particle is spherical having a radius ro , then the shear
strain () at a distance R due to the presence of the precipitate is given by:
3
r
o
R

When R = ro , at the interface, strain is maximum.

Since the strain field is not constant, Mott and Nabarro suggested that an average
strain must be overcome by the gliding dislocations, and the avg. strain is given by:

8ro3 N
Where N = no.of precipitates/unit vol. of the alloy

And the shear stress is given by:

8ro3 N and 2c , if c = concentration of the solute/precipitate

 Extent of dispersion
The flow stress (shear stress, ) is dependent on the extent of dispersion of
the particles.

- existence of a critical dispersion where maximum hardening occurs.

- extent to which a dislocation can be bent

If r = radius of curvature of dislocation to which it can be bent;

b
r

Where ~0.5, = applied stress ~ /100 (for age hardened alloys), then, r ~ 50b

Case-1: when L<< r (~50b) (where L = spacing between particles)

(Const vol.fraction of particles)

- dislocation remains a straight line

- not much of hardening
 Extent of dispersion
(Const vol.fraction of particles)

Case-2: when L ~ r (~50b) (where L = spacing between particles)

- dislocation can bend between the particles,

- significant hardening can occur.

Case-3: When L>>r (~50b) (where L = spacing between particles)

- dislocation can bow between particles,
- again no much hardening.
(Orowan bowing may occur, which means, if Orowan mechanism is operative,
hardening will be quite less.
 Stacking fault energy strengthening

Differences in stacking fault energy: If the particle has a stacking fault

energy (p) different from that of the matrix (m) referred to the same crystal
structure, this can result in an interaction with the dislocation. The maximum
interaction force is, |Fsf|max ~ 2ro (m - p)

Eg: Al-Ag system, where (Al) ~ 200 mJ/m2 and (Ag) ~ 20 mJ/m2

Lower stacking fault energy of the particle implies higher strength

Note 1: The most relevant parameters are the strength, volume fraction, spacing, shape
and distribution of the particles.

Note - 2: Several elementary interactions are the same as in solid solution hardening
(excepting the concept of overageing of the alloy with the consequence of decrease in
strength determined by the Orowan process)
 Dispersion strengthening
Introduction of hard, non-deforming particles (2nd phase)
in to the matrix.

Particles are incoherent (separate crystal structure

separate interface that of the matrix)

Dislocations avoid these particles /bow between these

particles.

Eg: Ni-Thoria, Al-Al2O3

Orowan bowing/mechanism
dispersoid
Gliding dislocation

1 2
T b
2

Where = Orowan stress for bowing, and T =

Line tension, L = Spacing between the particles

Line tension exists to reduce the dislocation line length

and is the increase in energy/unit increase in length