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In The Name of
ALLAH
The Most Beneficent
The Most Merciful
06/19/2021
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DEVELOPMENT OF
MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS
(Equilibrium Cooling)
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Equilibrium Cooling)
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At this point it is instructive to examine the development
of microstructure that occurs for isomorphous alloys
during solidification.
We first treat the situation in which the cooling occurs
very slowly, in that phase equilibrium is continuously
maintained.
Let us consider the copper–nickel system (Figure 10.3a),
specifically an alloy of composition 35 wt% Ni–65 wt%
Cu as it is cooled from 1300°C.
The region of the Cu–Ni phase diagram in the vicinity of
this composition is shown in Figure 10.4
Figure 10.4 Schematic representation of the development of microstructure during the
equilibrium solidification of a 35 wt% Ni–65 wt% Cu alloy
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Equilibrium Cooling)
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Cooling of an alloy of this composition
corresponds to moving down the vertical
dashed line.
At 1300°C, point a, the alloy is completely liquid (of
composition 35 wt% Ni– 65 wt% Cu) and has the
microstructure represented by the circle inset in the figure.
As cooling begins, no microstructural or compositional
changes will be realized until we reach the liquidus line
(point b, ~1260°C).
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Equilibrium Cooling)
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At this point, the first solid α begins to
form, which has a composition dictated
by the tie line drawn at this temperature
[i.e., 46 wt% Ni–54 wt% Cu, noted as α(46 Ni)]; the
composition of liquid is still approximately 35 wt% Ni–65
wt% Cu [L(35 Ni)], which is different from that of the solid
α.
With continued cooling, both compositions and relative
amounts of each of the phases will change.
The compositions of the liquid and α phases will follow
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Equilibrium Cooling)
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Furthermore, the fraction of the α phase
will increase with continued cooling.
Note that the overall alloy composition
(35 wt% Ni–65 wt% Cu) remains unchanged during
cooling
even though there is a redistribution of copper and nickel
between the phases.
At 1250°C, point c in Figure 10.4, the compositions of the
liquid and α phases are 32 wt% Ni–68 wt% Cu [L(32 Ni)]
and 43 wt% Ni–57 wt% Cu [α(43 Ni)], respectively.
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Equilibrium Cooling)
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The solidification process is virtually
complete at about 1220°C, point d; the
composition of the solid α is approximately
35 wt% Ni–65 wt% Cu (the overall alloy composition),
whereas that of the last remaining liquid is 24 wt% Ni–76 wt
% Cu.
Upon crossing the solidus line, this remaining liquid
solidifies; the final product then is a polycrystalline α-
phase solid solution that has a uniform 35 wt% Ni–65 wt%
Cu composition (point e, Figure 10.4). Subsequent cooling
produces no microstructural or compositional alterations.
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DEVELOPMENT OF
MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS
(Non-equilibrium Cooling)
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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Conditions of equilibrium solidification and the
development of microstructures, as described in the
previous section, are realized only for extremely slow
cooling rates.
The reason for this is that with changes in temperature,
there must be readjustments in the compositions of the
liquid and solid phases in accordance with the phase
diagram (i.e., with the liquidus and solidus lines), as
discussed.
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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These readjustments are accomplished by diffusional
processes—that is, diffusion in both solid and liquid
phases and also across the solid–liquid interface.
Because diffusion is a time-dependent phenomenon, to
maintain equilibrium during cooling, sufficient time must
be allowed at each temperature for the appropriate
compositional readjustments.
Diffusion rates (i.e., the magnitudes of the diffusion
coefficients) are especially low for the solid phase and, for
both phases, decrease with diminishing temperature.
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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In virtually all practical solidification situations, cooling
rates are much too rapid to allow these compositional
readjustments and maintenance of equilibrium;
consequently, microstructures other than those previously
described develop.
Some of the consequences of nonequilibrium
solidification for isomorphous alloys will now be
discussed by considering a 35 wt% Ni–65 wt% Cu alloy,
the same composition that was used for equilibrium
cooling in the previous section.
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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The portion of the phase diagram near this composition is
shown in Figure 10.5; in addition, microstructures and
associated phase compositions at various temperatures
upon cooling are noted in the circular insets.
To simplify this discussion it will be assumed that
diffusion rates in the liquid phase are sufficiently rapid
such that equilibrium is maintained in the liquid.
Let us begin cooling from a temperature of about 1300°C;
this is indicated by point a′ in the liquid region.
Figure 10.5 Schematic representation of the development of microstructure during the
non-equilibrium solidification of a 35 wt% Ni–65 wt% Cu alloy
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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This liquid has a composition of
35 wt% Ni–65 wt% Cu [noted as L(35 Ni)
in the figure], and no changes occur while
cooling through the liquid phase region (moving down
vertically from point a′).
At point b′ (approximately 1260°C), α-phase particles
begin to form, which, from the tie line constructed, have a
composition of 46 wt% Ni–54 wt% Cu [α(46 Ni)].
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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Upon further cooling to point c′
(about 1240°C), the liquid composition has
shifted to 29 wt% Ni–71 wt% Cu;
furthermore, at this temperature the composition of the α
phase that solidified is 40 wt% Ni–60 wt% Cu [α(40 Ni)].
However, because diffusion in the solid α phase is
relatively slow, the α phase that formed at point b′ has not
changed composition appreciably—that is, it is still about
46 wt% Ni—and the composition of the α grains has
continuously changed with radial position, from 46 wt%
Ni at grain centers to 40 wt% Ni at the outer grain
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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Thus, at point c′, the average composition
of the solid α grains that have formed
would be some volume-weighted average
composition lying between 46 and 40 wt% Ni.
For the sake of argument, let us take this average
composition to be 42 wt% Ni–58 wt% Cu [α(42 Ni)].
Furthermore, we would also find that, on the basis of
lever-rule computations, a greater proportion of liquid is
present for these nonequilibrium conditions than for
equilibrium cooling.
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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The implication of this nonequilibrium
solidification phenomenon is that the solidus
line on the phase diagram has been shifted
to higher Ni contents—to the average compositions of the α
phase (e.g., 42 wt% Ni at 1240°C)—and is represented by
the dashed line in Figure 10.5
There is no comparable alteration of the liquidus line
inasmuch as it is assumed that equilibrium is maintained
in the liquid phase during cooling because of sufficiently
rapid diffusion rates.
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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At point d′ (∼1220°C) and for equilibrium
cooling rates, solidification should be
completed. However, for this nonequilibrium
situation, there is still an appreciable proportion of liquid
remaining, and the α phase that is forming has a composition
of 35 wt% Ni [α(35 Ni)]; also, the average α-phase
composition at this point is 38 wt% Ni [α(38 Ni)].
Nonequilibrium solidification finally reaches completion at
point e′ (∼1205°C).
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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The composition of the last α phase to
solidify at this point is about 31 wt% Ni;
the average composition of the α phase at
complete solidification is 35 wt% Ni.
The inset at point f′ shows the microstructure of the totally
solid material.
The degree of displacement of the nonequilibrium solidus
curve from the equilibrium one depends on the rate of
cooling; the slower the cooling rate, the smaller this
displacement—the difference between the equilibrium
solidus and average solid composition is lower.
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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Furthermore, if the diffusion rate in the
solid phase increases, this displacement
decreases.
There are some important consequences for isomorphous
alloys that have solidified under nonequilibrium
conditions.
As discussed earlier, the distribution of the two elements
within the grains is nonuniform, a phenomenon termed
segregation—that is, concentration gradients are
established across the grains that are represented by the
insets of Figure 10.5
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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The center of each grain, which is the first
part to freeze, is rich in the high-melting
element (e.g., nickel for this Cu–Ni system),
whereas the concentration of the low-melting
element increases with position from this region to the grain
boundary.
This is termed a cored structure, which gives rise to less
than the optimal properties.
As a casting having a cored structure is reheated, grain
boundary regions will melt first because they are richer in
the low-melting component.
DEVELOPMENT OF MICROSTRUCTURE IN
ISOMORPHOUS ALLOYS (Non-equilibrium Cooling)
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This produces a sudden loss in mechanical
integrity due to the thin liquid film that
separates the grains.
Furthermore, this melting may begin at a temperature
below the equilibrium solidus temperature of the alloy.
Coring may be eliminated by a homogenization heat
treatment carried out at a temperature below the solidus
point for the particular alloy composition.
During this process, atomic diffusion occurs, which
produces compositionally homogeneous grains.
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MECHANICAL PROPERTIES OF
ISOMORPHOUS ALLOYS
Mechanical Properties of Isomorphous Alloys
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We now briefly explore how the mechanical properties of
solid isomorphous alloys are affected by composition as
other structural variables (e.g., grain size) are held
constant.
For all temperatures and compositions below the melting
temperature of the lowest melting component, only a
single solid phase exists.
Therefore, each component experiences solid-solution
strengthening or an increase in strength and hardness by
additions of the other component.
Mechanical Properties of Isomorphous Alloys
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This effect is demonstrated in Figure 10.6a as tensile
strength versus composition for the copper–nickel system
at room temperature; at some intermediate composition,
the curve necessarily passes through a maximum.
Plotted in Figure 10.6b is the ductility (%EL)–
composition behavior, which is just the opposite of tensile
strength —that is, ductility decreases with additions of the
second component, and the curve exhibits a minimum.
Figure 10.6 For the copper–nickel system, (a) tensile strength versus composition and
(b) ductility (%EL) versus composition at room temperature.
A solid solution exists over all compositions for this system.
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