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Department of Metallurgy and Materials Engineering

Materials Science III:


Phase Transformations in Metals

Dr. Mohamed Zaky Ahmed

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

Solidification of Metals and Alloys

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

Text Book

D.A. Porter, K.E. Easterling, Mohamed Y. Sherif “Phase


Transformations in Metals and Alloys”, Third Edition, CRC
Press, 2009.

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

Growth of a Pure Solid


Rough interfaces migrate by a continuous growth process while
flat interfaces migrate by a lateral growth process involving
ledges.

Solid/liquid interfaces: (a) atomically smooth, (b) and (c) atomically rough, or
diffuse interfaces.

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

Continuous Growth

Diffuse interfaces where it can be assumed that atoms can be


received at any site on the solid surface. For this reason it is
known as continuous growth. Such a mode of growth is
reasonable because the interface is disordered and atoms
arriving at random positions on the solid will not significantly
disrupt the equilibrium configuration of the interface.

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

Lateral Growth
The situation is, however, more complex when the equilibrium interface structure is
atomically smooth as in the case of many non-metals.

Atomically smooth solid/liquid interfaces with atoms represented by cubes.

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

The influence of interface undercooling (∆Ti on growth rate for atomically


rough and smooth interfaces).

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

Heat Flow and Interface Stability

In pure metals solidification is


controlled by the rate at which the
latent heat of solidification can be
conducted away from the
solid/liquid interface. Conduction
can take place either through the
solid or the liquid depending on the
temperature gradients at the
interface.

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

Heat Flow and Interface Stability

When a solid grows into a superheated liquid, a planar


solid/liquid interface is stable.

superheated liquid

(a) Temperature distribution for solidification when heat is extracted through


the solid. Isotherms (b) for a planar S/L interface, and (c) for a protrusion.

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

If a solid growing into supercooled liquid. If a protrusion forms


on the solid in this case the negative temperature gradient in the
liquid becomes even more negative. Therefore heat is removed
more effectively from the tip of the protrusion than from the
surrounding regions allowing it to grow preferentially. A
solid/liquid interface advancing into supercooled liquid is thus
inherently unstable.

a) Temperature distribution for solidification when heat is extracted through the


liquid. Isotherms (b) for a planar S/L interface, and (c) for a protrusion.
Materials Science III: Phase Transformations M.M.Z. Ahmed
Department of Metallurgy and Materials Engineering

Heat flow into the liquid, however, can only arise if the
liquid is supercooled below Tm. Such a situation can
arise at the beginning of solidification if nucleation
occurs at impurity particles in the bulk of the liquid.
Since a certain supercooling is required before
nucleation can occur, the first solid particles will grow
into supercooled liquid and the latent heat of
solidification will be conducted away into the liquid.

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

An originally spherical solid particle will therefore


develop arms in many directions as shown in Fig. 4.17.
As the primary arms elongate their surfaces will also
become unstable and break up into secondary and
even tertiary arms. This shape of solid is known as a
dendrite. Dendrite comes from the Greek for tree.
Dendrites in pure metals are usually called thermal
dendrites to distinguish them from dendrites in alloys.

It is found experimentally that the dendrite arms are


always in certain crystallographic directions: e.g. (100)
in cubic metals, and (1 1 00) in hcp metals.

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

dendrites

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

Temperature distribution at the tip of a


growing thermal dendrite.
The development of thermal dendrites: (a) a spherical nucleus; (b) the interface
becomes unstable; (c) primary arms develop in crystallographic directions (100) in
cubic crystals); (d) secondary and tertiary arms develop

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

dendrite of ice in
water

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

dendrites of water in ice

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

Dendrites of ice on window, Harbin, China


Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

Dendrite Videos

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

Alloy Solidification

The solidification of pure metals is rarely


encountered in practice. Even commercially pure
metals contain sufficient impurities to change the
characteristics of solidification from pure-metal to
alloy behaviour. We now develop the theory a step
further and examine the solidification of single-phase
binary alloys.

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

Solidification of Single-Phase Alloys


The way in which such alloys solidify in practice depends in
rather a complex way on temperature gradients, cooling rates
and growth rates.

Therefore let us simplify matters by considering the movement


of a planar solid/liquid interface along a bar of alloy as shown in
Fig. 4.20a.

Let us examine three limiting cases:


1. Infinitely slow (equilibrium) solidification
2. Solidification with no diffusion in the solid but perfect mixing
in the liquid
3. Solidification with no diffusion in the solid and only diffusional
mixing in the liquid
Materials Science III: Phase Transformations M.M.Z. Ahmed
Department of Metallurgy and Materials Engineering

Infinitely slow (equilibrium) solidification

Unidirectional solidification of alloy


A hypothetical phase diagram. k = Xs/ Xo. (a) A planar S/L interface and
XL is constant. axial heat flow. (b) Corresponding
composition profile at T2 assuming
where Xs and XL are the mole complete equilibrium. Conservation
fractions of solute in the solid and of solute requires the two shaded
liquid in equilibrium at a given areas to be equal.
temperature

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

No Diffusion in Solid, Perfect Mixing in Liquid

Fig. 4.21 Planar front solidification of alloy Xo in Fig. 4.19 assuming no diffusion in
the solid, but complete mixing in the liquid. (a) As Fig. 4.19, but including the mean
composition of the solid. (b) Composition profile just under T1 (c) Composition
profile at T2 (compare with the profile and fraction solidified in Fig. 4.20b.
(d) Composition profile at the eutectic temperature and below.

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

Effect of Grain Refiners

(a) (b)

Parts of transverse sections through two 6-in-diameter ingots of alloy


6063 (AI-0.7% Mg-0.4% Si) that were direct-chill semicontinuous cast.
Ingot section (a) was cast without the addition of a grain refiner; note
columnar grains and colonies of featherlike crystals near the center of the
section. Ingot section [b) was cast with the addition of a grain refiner and
shows a fine, equiaxed grain structure.
Ref: Principals of Materials Science and Engineering, William F. Smith

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

Solidification of Single Crystal-1

In industry single crystals of silicon 6 to 8 in (15 to 20


cm) in diameter have been grown for semiconducting device
applications.

One of the commonly used techniques to produce high-


quality (minimization of defects) silicon single crystals is
the Czochralski method.

In this process high-purity polycrystalline silicon is first


melted in a non-reactive crucible and held at a temperature
just above the melting point.

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

Solidification of Single Crystal-2


A high-quality seed crystal of silicon of the desired
crystallographic orientation is lowered into the melt while
it is rotated (2-35rpm).

Part of the surface of the seed crystal is melted in the


liquid to remove the outer strained region and to produce a
surface for the liquid to solidify on.

The seed crystal continues to rotate and is slowly raised


from the melt.

As it is raised from the melt, silicon from the liquid in


the crucible adheres and grows on the seed crystal,
producing a much larger diameter single crystal of silicon.

Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

Solidification of Single Crystal-3

In addition to the Si
wafers for semiconducting
devices, Single crystals
are useful in research in
the study of mechanical
properties since the
effects of grain
boundaries and randomly
oriented grains are
eliminated. Formation of silicon single crystal
using Czochralski Process

Ref: Principals of Materials Science and Engineering, William F. Smith

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

Photograph of a Czochralski furnace with a


grown 200 mm crystal
Materials Science III: Phase Transformations M.M.Z. Ahmed

Department of Metallurgy and Materials Engineering

Formation of silicon single crystal by Czochralski method


Ref: Principals of Materials Science and Engineering, William F. Smith

Materials Science III: Phase Transformations M.M.Z. Ahmed


Department of Metallurgy and Materials Engineering

Single crystal blade turbine from Ni base super alloy

Materials Science III: Phase Transformations M.M.Z. Ahmed