MMB 312 - 2016 - Lecture 3 - Solidification

SOLIDIFICATION
Introduction Overview:
Concept of Diffusion:
o
o
o
o
o
Self diffusion.
Vacancy diffusion.
Substitutional diffusion.
Factors influencing diffusion in materials.
Diffusion coefficient
Solidification in Metal Alloys.

o
o
o
o
Introduction - States of Matter.

Nucleation during solidification.
Nuclei growth mechanisms.
Solidification defects.
Part I - Diffusion Concept:

Thermodynamically any inhomogeneous
single phase system become homogeneous
=> equilibrium.
In-fact, many reactions & processes in the
treatment of materials rely on mass transport.
Hence, diffusion material transport by
atomic motion.
From an atomic perspective, atoms in solid
material are always in constant motion
change position.
For atoms to make such a move two
conditions MUST be met:
o There must be an empty adjacent site.
o Atom must have sufficient energy to break bonds
with neighbouring atoms cause lattice distortion.
Diffusion Concept Steady-State

Diffusion:

Diffusion time dependent =>

quantity of element transported
within another is a function of
time.
Often important to know how
fast diffusion occurs rate of
mass transfer diffusion flux (J).
In differential form:
M = mass (equivalently, no. of
atoms).
Flux for steady-state diffusion: ; D
= Diffusion Coefficient (Ficks 1st
Law Adolph Fick).
Concentrat
ion
Gradient,
Diffusion Concept Non-SteadyState Diffusion:

Most practical diffusion situation are non-steady; i.e. the

diffusion flux & concentration gradient vary with time.
This leads to a net accumulation or depletion of
diffusing species.
1st Law of Mass Transport can no longer hold; hence
Ficks 2nd Law:
If the diffusion coefficient is independent of
composition, the above expression then simplifies to:
Solutions to this expression concentration in terms of
position & time possible with some boundary conditions
specified.
For boundary conditions, we must first make some
assumptions:
Diffusion Concept Non-SteadyState Diffusion:

diffusion, diffusing solute
Before
distributed Concentration = C .
1.
atoms in the solid are uniformly
2. Value of x at the surface is zero increases with distance into solid.

3. Time before diffusion process begins taken to be zero.
. Thus; boundary conditions then become:
For t = 0, C = C0; at 0 x .
For t > 0, C = Cs (constant surface concentration); at x = 0.
C = C0; at x = .
. Application of these boundary conditions to Ficks 2nd Law above yields:
; where Cx represents the concentration at depth x after time t.
. The expression is known as the Gaussian Error Function, with values
given in some mathematical tables.
Factors Influencing Diffusion:

Diffusion increases exponentially with time:
D)
D0 = temp independent pre-exponential
constant.
Qd = Activation energy for diffusion.
Temperature: diffusion rate increases

rapidly with temp.
Diffusion mechanism: E.g. Interstitial
mechanism usually faster than vacancy
diffusion.
Host Species: D0 and Qd are different for
every solute and solvent pair.
Microstructure:
diffusion
faster
in
polycrystalline material than single crystals.
Types of Diffusion:
Self Diffusion: Migration of atoms within the
same matrix to an adjacent vacancy position.
Vacancy Diffusion: Mainly involves the
interchange of substitutional atoms from a
normal lattice position to an adjacent vacant
lattice site or vacancy. Thus, the extent to
which this mechanism can occur is dependent
on the presence or formation of vacancies in
the lattice.
Interstitial Diffusion: Involves migration of
atoms from an interstitial position to an
adjacent empty interstitial position. Mechanism
common in the diffusion of impurities in steel
alloys (e.g. hydrogen, carbon, nitrogen and
oxygen). It occurs much rapidly than vacancy
diffusion (impurity atoms are smaller & hence
more mobile).
Part II - Solidification:
State of Matter:
Metals exists as aggregates of
atoms or molecules; found in more
of three basic states:
Solid.
Liquid
Vapour (Gas).
Physicists sometimes consider forth

state of matter in plasma.
Normally, when a material solidifies,
multiple crystals begin to grow
(form) in the liquid; Nucleation.
That leads to a polycrystalline
(many crystals) solid forming.
Nucleation during Solidification:
Nucleation: Main mechanism of Phase

Transformation invariably accompanied by
large-scale atom rearrangement.
Phase transformation cannot occur if system
cannot decrease its free energy in the process.
System has to temporarily increase its energy
(G*) before gaining G in solidifying from
liquid to solid.
Phase
transformation
normally occurs at high temp

(G* - thermally activated).
If embryo forms randomly
within lattice homogeneous
nucleation (no preferred
position/direction).
System must have driving
force provided by the free
energy
change
of
transformation (G).
Nuclei formed randomly
arranged differently within
the lattice retarding
forces
from
interfaces
(surface energy - s).
Types of Nucleation:
Nucleation
can
either
be
homogeneous or heterogeneous.
Homogeneous Nucleation: New
phase or crystal embryo forms
spontaneously (randomly) within the
undercooled matrix.
Heterogeneous Nucleation: The new
phase forms selectively on specific
locations of the undercooled matrix
(e.g. on the walls of the container).
Nucleation: Driving and Retarding

Forces
total energy change for

The
solidification must incorporate the net

driving force of formation and the
energy required to overcome the
retarding forces.
Thus:
Solidification cannot occur at T = Tm.
Significant
undercooling
(supercooling) must be attained first
=> significant T.
Critical nucleus radius, r*, must be
achieved to form a stable embryo or
crystal.
Common Solidification Defects:
Critical Stages in Steel Production:

Video.
Summary Overview - Steel Production Process:

Smelting & Refining of Metal Ores and Scrap: In this process,
metals are extracted from their ores by melting them, followed by
some physical and chemical methods of selectively separating
them.
Sintering: Compressing and heating material into powder form.
Casting of Molten Metals: Involves pouring molten material into
a specific shape and then allowing it to cool and/or solidify into
that shape.
Pressing Metals (Hot & Cold Rolling): These are ways of forming
metal slabs or rods into required end materials. Improves
metallurgical properties of the material in the process.
Welding & Cutting Sheet Metal: Variety of techniques used to
finish metal production processes (joining, shaping, etc).

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SOLIDIFICATION

Solidification in Metal Alloys.

Introduction - States of Matter.

Part I - Diffusion Concept:

Diffusion Concept Steady-State

Diffusion time dependent =>

Diffusion Concept Non-SteadyState Diffusion:

Most practical diffusion situation are non-steady; i.e. the

Diffusion Concept Non-SteadyState Diffusion:

atoms in the solid are uniformly

2. Value of x at the surface is zero increases with distance into solid.

Factors Influencing Diffusion:

Diffusion increases exponentially with time:

Temperature: diffusion rate increases

Physicists sometimes consider forth

Nucleation during Solidification:

Nucleation: Main mechanism of Phase

normally occurs at high temp

Nucleation: Driving and Retarding

total energy change for

solidification must incorporate the net

Common Solidification Defects:

Critical Stages in Steel Production:

Summary Overview - Steel Production Process:

Summary Overview - Steel Production Process:

Summary Overview - Steel Production Process:

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