TOPIC 2:

SOLIDIFICATIONS, IMPERFECTIONS
IN SOLIDS & DIFFUSIONS

ISSUES TO ADDRESS...
• What are the solidification mechanisms?

• What types of defects arise in solids?

• Can the number and type of defects be varied

and controlled?

• How do defects affect material properties?

• Are defects undesirable?

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 Imperfections in Solids
• Solidification- result of casting of molten material
– 2 steps
• Nuclei form (nucleation : formation of stable nuclei)
• Nuclei grow to form crystals – grain structure
(nuclei: small particles of a new phase formed by a phase change
(i.e. solidification) which can grow until the phase change is
complete).
• Start with a molten material – all liquid

nuclei crystals growing grain structure

liquid Adapted from Fig.4.14 (b), Callister 7e.

• Crystals grow until they meet each other

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 Solidification: Nucleation Processes

• Homogeneous nucleation
– nuclei form in the bulk of liquid metal

• Heterogeneous nucleation
– much easier since stable “nucleus” is already
present
– The formation of very small regions of a new solid
phase at the interfaces of solid impurities.
• Could be wall of mold or impurities in the liquid
phase

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 Homogeneous nucleation
• Simplest case of nucleation
• Occurs when the metal itself provide the atoms to form nuclei.
– E.g. : The case of a pure metal solidifying. When a pure
liquid metal is cooled below its equilibrium freezing
temperature to a sufficient degree, numerous homogeneous
nuclei are created by slow-moving atoms bonding together.
– Requires a considerable amount of undercooling , ~ several
hundreds degrees (Undercooling: Cooling a metal below the
transformation temperature without obtaining the
transformation).
.
– For a nucleus to be stable so that it can grow into a crystal
and must reach a critical size**.
(the minimum radius which a particle of a new phase formed by
nucleation must have to become a stable nucleus).

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 Heterogeneous nucleation
• Nucleation that occurs in a liquid on the surfaces of
its container, insoluble impurities or other structural
material which lower the critical free energy required
to form a stable nucleus.
• Since large amounts of undercooling do not occur
during industrial casting operations (usually only ~
0.1-10oC), thus the nucleation must be
heterogeneous and not homogeneous.
• heterogeneous nucleation takes place more quickly
since the foreign particles act as a scaffold for the
crystal to grow on, thus eliminating the necessity of
creating a new surface and the incipient surface
energy requirements.

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 Cooling curve for pure metal (without impurities)
• Liquid cools as specific
heat is removed (A-B).
• Undercooling (B-C).
• Nucleation begins (C).
• Homogeneous nucleation.
Heat is released causing an
increase in the temp of the
liquid (C-D).
• Solidification continue at
constant temp. until
complete at E.

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Growth of crystals in liquid metal and formation of
grain structure
• After stable nuclei have been form in a
solidifying metal, these nuclei will grow into
crystals.
• When, solidification of the metal is completed,
the crystal join together in different
orientations and form crystal boundaries.
• Solidified metal containing many crystals is
called polycrystalline.

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 Polycrystalline Materials

Grain Boundaries
• regions between crystals
• transition from lattice of
one region to that of the
other
• slightly disordered
• low density in grain
boundaries
– high mobility
– high diffusivity
– high chemical reactivity
Adapted from Fig. 4.7, Callister 7e.

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 Solidification
Grains can be - equiaxed (roughly same size in all directions)
- columnar (elongated grains)
~ 8 cm

heat
flow

Shell of
Columnar in equiaxed grains
area with less due to rapid
undercooling cooling (greater
T) near wall
Adapted from Fig. 4.12, Callister 7e.

Grain Refiner - added to make smaller, more uniform, equiaxed grains.

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• Equiaxed grains: grains which are approximately
equal in all directions and which have random
crystallographic orientations. Commonly found
adjacent to a cold mold wall
• Columnar grains: long, thin grains in a solidified
polycrystalline structure. These grains are formed in
the interior of solidified metal ingots when heat flow is
slow and uniaxial during solidification. The columnar
grains have grown perpendicular to the mold faces
since large thermal gradients were present in those
directions.

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increase

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• Dendrite – The treelike structure of the solid
that grows as molten metal freezes (when an
undercooled liquid solidifies).

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Microstructure - dendrites

Cross
section
sample

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Effect of cooling rate (solidification rate)

• Rapid cooling leads to greater nucleation and more

smaller grains.

• Slow cooling leads to slower nucleus formation and

larger grains.

• More grains means more grain boundary.

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 Solidification defects (casting)
• Shrinkage: contraction of a casting during solidification

• Gas porosity – bubbles of gas trapped within a casting during solidification,

caused by the lower solubility of the gas in the solid compared with in the liquid.

• Mold material defects – wrong mold material selection

• Pouring metal defects – e.g. material freezing before it completely fills the mold
cavity.

• Metallurgical defects – hot tears and hot spots:

– Hot tears are failures in the casting that occur as the casting cools, because
the metal is weak when it is hot and the stresses in the material can cause
the casting to fail as it cools. Solution, proper casting design is needed.
– Hot spots: surface area of the casting that very hard because it chilled more
quickly than surrounding. Can be avoided by proper cooling practises or by
changing the chemical composition of the metal.

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 Continuous casting of steel ingots

(a) General setup; (b) closed up of the mold arrangement (After H. E.

McGannon (ed.), “ The making, shaping and treating of steel” ,United
States Steel Corp., 1971. 25
Defect in the crystalline structure
&
Diffusion of atom

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Defect in the crystalline structure

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 Imperfections in Solids
There is no such thing as a perfect crystal.
• What are these imperfections?
• Why are they important?

Many of the important properties of

materials are due to the presence of
imperfections.

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• Defect in the crystalline structure can have an
tremendous effect on a materials behavior.

• We can modify and improve many of the physical,

electrical, magnetic and optical properties of
crystalline materials by controlling the imperfections
in their lattice structure.

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 Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

• Casting defect Volume defect

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 (1). Point defects
Vacancies, Interstitial and substitutional
…move by diffusion

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Schottky and Frenkel defects in an ionic crystal
Schottky: a defect consisting of a cation and anion
vacancies pair.
Frenkel : In an ionic solid, a cation-vacancy and cation
interstitial pair. 32
 Point Defects
• Vacancies:
-vacant atomic sites in a structure.

Vacancy
distortion
of planes

• Self-Interstitials:
-"extra" atoms positioned between atomic sites.

self-
interstitial
distortion
of planes

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 Point Defects in Alloys
Two outcomes if impurity (B) added to host (A):
• Solid solution of B in A (i.e., random dist. of point defects)

OR

Substitutional solid soln. Interstitial solid soln.

(e.g., Cu in Ni) (e.g., C in Fe)
• Solid solution of B in A plus particles of a new
phase (usually for a larger amount of B)
Second phase particle
--different composition
--often different structure.

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 (2) Line Defects
Dislocations:
• are line defects,
• slip between crystal planes result when dislocations move,
• produce permanent (plastic) deformation.

Schematic of Zinc (HCP):

• before deformation • after tensile elongation

slip steps

Adapted from Fig. 7.8, Callister 7e.

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 Imperfections in Solids
Linear Defects (Dislocations)
– Are one-dimensional defects around which atoms are
misaligned
• Edge dislocation:
– extra half-plane of atoms inserted in a crystal structure
– b  to dislocation line
• Screw dislocation:
– spiral planar ramp resulting from shear deformation
– b  to dislocation line
Burger’s vector, b: measure of lattice distortion. Refer to
magnitude and direction of lattice distortion associated with
a dislocation.

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 Imperfections in Solids
Edge Dislocation

Fig. 4.3, Callister 7e.

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 Motion of Edge Dislocation
• Dislocation motion requires the successive bumping
of a half plane of atoms (from left to right here).
• Bonds across the slipping planes are broken and
remade in succession.

Atomic view of edge

dislocation motion from
left to right as a crystal
is sheared.

(Courtesy P.M. Anderson)

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 Imperfections in Solids
Screw Dislocation
Screw Dislocation

b
Dislocation
line
Burgers vector b (b)
(a)
Adapted from Fig. 4.4, Callister 7e.

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 Edge, Screw, and Mixed Dislocations
Mixed

Edge

Adapted from Fig. 4.5, Callister 7e.

Screw

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(3) Surface defects (area defects)
grain boundaries and material surface

The grain boundaries is a narrow zone

where the atoms are not properly spaced
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• Grain boundaries are:
– Boundaries between crystal
– Produced by the solidification process (e.g.)
– Have a change in crystal orientation across them
– Impede dislocation motion.

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 Imperfections in Solids
Dislocations are visible in electron micrographs

Adapted from Fig. 4.6, Callister 7e.

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 Dislocations & Crystal Structures
• Structure: close-packed view onto two
planes & directions close-packed
planes.
are preferred.
close-packed directions
close-packed plane (bottom) close-packed plane (top)

• Comparison among crystal structures: (more slip system:

more ductile)
FCC: many close-packed planes/directions;
HCP: only one plane, 3 directions;

• Specimens that Mg (HCP)

were tensile
tested. tensile direction
Al (FCC)
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 Microscopic Examination

• Crystallites (grains) and grain boundaries.

Vary considerably in size. Can be quite large
– ex: Large single crystal of quartz or diamond or Si
– ex: Aluminum light post or garbage can - see the
individual grains
• Crystallites (grains) can be quite small (mm
or less) – necessary to observe with a
microscope.

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 Optical Microscopy
• Useful up to 2000X magnification.
• Polishing removes surface features (e.g., scratches)
• Etching changes reflectance, depending on crystal
orientation.

crystallographic planes
Adapted from Fig. 4.13(b) and (c), Callister
7e. (Fig. 4.13(c) is courtesy
of J.E. Burke, General Electric Co.

Micrograph of
brass (a Cu-Zn alloy)

0.75mm
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 Optical Microscopy
Grain boundaries...
• are imperfections,
• are more susceptible
to etching,
• may be revealed as polished surface
dark lines,
• change in crystal surface groove
orientation across grain boundary
(a)
boundary. Adapted from Fig. 4.14(a)
and (b), Callister 7e.
ASTM grain (Fig. 4.14(b) is courtesy
of L.C. Smith and C. Brady,
size number the National Bureau of
Standards, Washington, DC

N = 2n-1 [now the National Institute of

Standards and Technology,
Gaithersburg, MD].)

number of grains/in2 Fe-Cr alloy

at 100x (b)
magnification 49
 Optical Microscopy

• Polarized light
– metallographic scopes often use polarized
light to increase contrast
– Also used for transparent samples such as
polymers

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 Microscopy
Optical resolution ca. 10-7 m = 0.1 m = 100 nm
For higher resolution need higher frequency
– X-Rays? Difficult to focus.
– Electrons
• wavelengths ca. 3 pm (0.003 nm)
– (Magnification - 1,000,000X)
• Atomic resolution possible
• Electron beam focused by magnetic lenses.

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 Scanning Tunneling Microscopy
(STM)
• Atoms can be arranged and imaged!
Photos produced from
the work of C.P. Lutz,
Zeppenfeld, and D.M.
Eigler. Reprinted with
permission from
International Business
Machines Corporation,
copyright 1995.

Carbon monoxide Iron atoms arranged

molecules arranged on a copper (111)
on a platinum (111) surface. These Kanji
surface. characters represent
the word “atom”.

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 Summary
• Point, Line, Area and volume defects exist in solids.

• The number and type of defects can be varied

and controlled (e.g., T controls vacancy conc.)

• Defects affect material properties (e.g., grain

boundaries control crystal slip).
• Defects may be desirable or undesirable
(e.g., dislocations may be good or bad, depending
on whether plastic deformation is desirable or not.)

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