Solidification of Single Phase Metals and Alloys (I)

Solidification of Single Phase Metals
and Alloys (I)
.
In this chapter we will be concerned with the effect of
the different solidification variables (e.g. growth rate
and temperature gradient in the liquid) on the structure
and composition of the growing solid. In particular,
when we consider single-phase alloys, the way in which
the solute redistributed during solidification will be
examined as will the effects of this redistribution on the
micro and macro structure of the solidifying alloy.
Before examining the solidification process it is
essential to define clearly a terminology.
Terminology
• Growth Rate (R): is a measure of the rate of advance

of the interface between the liquid and the solid.
• Temperature Gradient (G) (in the liquid) is usually
taken to refer to the gradient in the liquid away from
the interface in the direction of growth. If the
temperature increases as we go into the liquid, the
temperature gradient is considered to be positive and
vice versa. Commonly, temperature gradients vary
from a few degrees centigrade per centimetre during
the growth of single crystals, to tens of degrees
centigrade per centimetre in castings and ingots, and
to hundreds of degrees centigrade per centimetre
during weld-pool solidification.
• Diffusivity (Diffusion Coefficient, D):
Determines the rate at which atoms can move in the
liquid. For virtually all metallic liquids D is of the order
of 5 x 10-5 cm2/sec. Diffusion rates in the solid are much
smaller ~10-8 cm2/sec. for common metals just below
their melting points. Thus solute redistribution in the
solid is usually ignored in comparison to solute
redistribution in the liquid.
• The equilibrium distribution coefficient, k0
İs defined by the phase diagram, assuming the liquidus
and solidus lines to be straight. The equilibrium
distribution coefficient is given by the ratio:
•If the
effect of the solute is to lover the liquidus
temperature then k0 < 1 and vice versa.
It is sometimes convenient to define an effective
distribution, kE as
Scheil Equation
fs: fraction solidified

• Slope of the liquidus line (m)
Positive (m) Negative (m)

Although this is contrary to normal mathematical practice, this
convention has been adhered to throughout the literature on
solidification.
• Unidirectional Solidification
(a) A casting boat (graphite) used for controlled directional

solidification (schematic). The metal is shown as partially solidified.
(b) Schematic view of the cross section of a partially solidified ingot
showing how the casting boat can be considered as a section of the
ingot.
• Cooling curves
(a) Cooling curve for a pure metal that has not been well-inoculated. The liquid cools as
specific heat is removed (between points A and B). Undercooling is thus necessary
(between points B and C). As the nucleation begins (point C), latent heat of fusion is
released causing an increase in the temperature of the liquid. This process is known as
recalescence (point C to point D). The metal continues to solidify at a constant
temperature (Tmelting). At point E, solidification is complete. The solid casting continues
to cool from this point. (b) Cooling curve for a well-inoculated, but otherwise pure,
metal. No undercooling is needed. Recalescence is not observed. Solidification begins at
the melting temperature.
Pure metals: Interface forms
(a) Area of solid and liquid
adjacent to the interface
showing positive
temperature gradients in the
liquid and solid (schematic).
Gsolid is steeper than Gliquid
because of the higher
thermal conductivity of the
solid. (b) Schematic
sequence showing the
formation of an unstable
protuberance which melts
because the local tip
temperature exceeds the
melting temperature.
(a) Area of solid and liquid
adjacent to the interface
showing a negative
temperature gradient in the
liquid and a positive
temperature gradient in the
solid (schematic.) (b)
Schematic sequence showing
the formation and
stabilisation of a protuberance
on the interface when it
projects into a region where
the local tip temperature is
below the melting
temperature.
When the temperature of the liquid is above the freezing
temperature, a protuberance on the solid-liquid interface will not
grow, leading to maintenance of a planar interface. Latent heat is
removed from the interface through the solid.
Planar Growth: When a well-inoculated liquid (i.e., a liquid
containing nucleating agents) cools under equilibrium
conditions, there is no need for undercooling since
heterogeneous nucleation can occur. Therefore, the
temperature of the liquid ahead of the solidification front
(i.e., solid-liquid interface) is greater than the freezing
temperature. The temperature of the solid is at or below
the freezing temperature. During solidification, the latent
heat of fusion is removed by conduction from the solid
liquid interface. Any small protuberance that begins to
grow on the interface is surrounded by liquid above the
freezing temperature The growth of the protuberance then
stops until the remainder of the interface catches up. This
growth mechanism, known as planar growth, occurs by the
movement of a smooth solid-liquid interface into the liquid.
(a) If the liquid is undercooled, a protuberance on the solid-liquid interface
can grow rapidly as a dendrite. The latent heat of fusion is removed by raising
the temperature of the liquid back to the freezing temperature. (b) Scanning
electron micrograph of dendrites in steel (x15).
Dendritic Growth: When the liquid is not inoculated and
the nucleation is poor, the liquid has to be undercooled
before the solid forms. Under these conditions, a small
solid protuberance called a dendrite, which forms at the
interface, is encouraged to grow since the liquid ahead of
the solidification front is undercooled. The word dendrite
comes from the Greek word dendron that means tree. As
the solid dendrite grows, the latent heat of fusion is
conducted into the undercooled liquid, raising the
temperature of the liquid toward the freezing
temperature. Secondary and tertiary dendrite arms can
also form on the primary stalks to speed the evolution of
the latent heat. Dendritic growth continues until the
undercooled liquid warms to the freezing temperature.
Any remaining liquid then solidifies by planar growth.
• difference between planar and dendritic growth arises because
The
of the different sinks for the latent heat of fusion. The container or
mold must absorb the heat in planar growth, but the undercooled
liquid absorbs the heat in dendritic growth. In pure metals,
dendritic growth normally represents only a small fraction of the
total growth and is given by
where c is the specific heat of the liquid. The numerator represents

the heat that the undercooled liquid can absorb, and the latent
heat in the denominator represents the total heat that must be
given up during solidification. As the undercooling ΔT increases,
more dendritic growth occurs. If the liquid is well-inoculated,
undercooling is almost zero and growth would be mainly via the
planar front solidification mechanism.
Typical form of cooling curve for pure metals showing the
regions in which the different growth phenomena occur.
Solute Redistribution Effects in Alloys
The growth of impure metals is much more complex because of the

redistribution of solute that occurs during solidification. This can
produce changes in the growth morphology and lead to solute
segregation on both a microscale and a macroscale. If we consider
the initial sequence of events during the solidification of an alloy of
composition C0, with distribution coefficient k0 < 1, it is clear from
the phase diagram that the first solid to form will have composition
of C0k0. Since k0 < 1 is a small localised increase in the solute content
of the liquid. First, the solute increase may disperse in the liquid by
diffusion only. Alternatively, conditions of complete mixing in the
liquid which rapidly spread the excess solute throughout the bulk of
the liquid.
• For solute concentrations (C0) higher than about 0.5 % the solute
pile-up effects are very marked and the physical nature of the
interface alters to a non-planar configuration.
Solute redistribution by diffusion
The solute profile ahead of the interface

during steady-state solidification with solute
Portion of a phase diagram for an alloy redistribution by diffusion only (k0 < 1)
of composition C0, with k0 < 1 showing
initial compositional changes.
Concentration-distance profiles for a bar solidified under
condition where solute transport in the liquid is by diffusion
only. (a) k0 < 1; (b) k0 > 1.

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Solidification of Single Phase Metals

and Alloys (I)

• Growth Rate (R): is a measure of the rate of advance

fs: fraction solidified

Positive (m) Negative (m)

(a) A casting boat (graphite) used for controlled directional

where c is the specific heat of the liquid. The numerator represents

The growth of impure metals is much more complex because of the

The solute profile ahead of the interface

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