Materials Science

Lecture #4

Solidification
Crystalline Imperfections in Solids
 Objectives

To answer the following;

• 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?

2
 Solidification of Metals

• Metals are melted to produce finished and semi-finished

parts.
• Two steps of solidification
➢ Nucleation : Formation of stable nuclei.
➢ Growth of nuclei : Formation of grain structure.

• Thermal gradients define the shape of each grain.

Grains
Nuclei

Crystals that will Grain Boundaries

Liquid Figure 4.2
Form grains
 Formation of Stable Nuclei
• Two main mechanisms:
Homogenous and heterogeneous.
• Homogenous Nucleation :
➢ First and simplest case.
➢ Metal itself will provide atoms to form nuclei.
➢ Metal, when significantly undercooled, has several slow
moving atoms which bond each other to form nuclei.
➢Cluster of atoms below critical size is called embryo.
➢ If the cluster of atoms reach critical size, they grow into
crystals. Else get dissolved.
➢ Cluster of atoms that are greater than critical size are
called nucleus.

4-3
Growth of Crystals and Formation of Grain Structure

• Nucleus grow into crystals in different orientations.

• Crystal boundaries are formed when crystals join
together at complete solidification.
• Crystals in solidified metals are called grains.
• Grains are separated by grain boundaries.
• More the number of
nucleation sites
available, more
the number of
grains formed.

Nuclei growing into grains

Forming grain boundaries
 Nucleation

Nuclei

6
 Growth of crystals

Formation of grain structure

Grains

Crystals Grain boundary

7
 3D view of grains and grain boundaries

Scanning electron microscope image

 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.

9
Formation of grain structure
 Complicated cases – Alloys
solidification of an Al-Mg-Si alloy

The evolution of the concentrations of Mg (left) and

Si (right), in both the liquid and the solid phases
 Polycrystals Anisotropic
• Most engineering materials are polycrystals.

Adapted from Fig. K,

color inset pages of
Callister 5e.
(Fig. K is courtesy of
Paul E. Danielson,
Teledyne Wah Chang
Albany)
1 mm

• Nb-Hf-W plate with an electron beam weld. Isotropic

• Each "grain" is a single crystal.
• If grains are randomly oriented,
overall component properties are not directional.
• Grain sizes typ. range from 1 nm to 2 cm
(i.e., from a few to millions of atomic layers).
12
 Single vs Polycrystals
• Single Crystals E (diagonal) = 273 GPa
Data from Table 3.3,
-Properties vary with Callister 7e.
(Source of data is R.W.
direction: anisotropic. Hertzberg, Deformation
and Fracture Mechanics
-Example: the modulus of Engineering
Materials, 3rd ed., John
of elasticity (E) in BCC iron: Wiley and Sons, 1989.)

E (edge) = 125 GPa

• Polycrystals
-Properties may/may not 200 mm Adapted from Fig.
4.14(b), Callister 7e.
vary with direction. (Fig. 4.14(b) is courtesy
of L.C. Smith and C.
-If grains are randomly Brady, the National
Bureau of Standards,
oriented: isotropic. Washington, DC [now
the National Institute of
(Epoly iron = 210 GPa) Standards and
Technology,
-If grains are textured, Gaithersburg, MD].)
anisotropic.

13
Directional solidification

14
15
 Crystals as Building Blocks
• Some engineering applications require single crystals:
--diamond single --turbine blades
crystals for abrasives Fig. 8.33(c), Callister 7e.
(Fig. 8.33(c) courtesy
(Courtesy Martin Deakins, of Pratt and Whitney).
GE Superabrasives,
Worthington, OH. Used with
permission.)

• Properties of crystalline materials

often related to crystal structure.
--Ex: Quartz fractures more easily
along some crystal planes than
others.
(Courtesy P.M. Anderson)

16
Single vs Polycrystals

17
 Metallic Solid Solutions
• Alloys are used in most engineering applications.
• Alloy is an mixture of two or more metals and
nonmetals.
• Example:
➢ Cartridge brass is binary alloy of 70% Cu and 30% Zinc.
➢ Inconel is a nickel based superalloy with about 10 elements.

• Solid solution is a simple type of alloy in which

elements are dispersed in a single phase.

• Two types: Substitutional and Interstitial

4-14
 Substitutional Solid Solution
• Solute atoms substitute for parent solvent atom in a
crystal lattice.
• The structure remains unchanged.
• Lattice might get slightly distorted due to change in
diameter of the atoms.
• Solute percentage in solvent
can vary from fraction of a
percentage to 100%

Solvent atoms
Figure 4.14
Solute atoms

4-15
 Substitutional Solid Solution (Cont..)
• The solubility of solids is greater if
➢ The diameter of atoms not differ by more than 15%
➢ Crystal structures are similar.
➢ No much difference in electronegativity (else compounds
will be formed).
➢ Have some valence.
• Examples:-
Atomic radius Electronegativity Solid
System Difference difference Solibility
Cu-Zn 3.9% 0.1 38.3%
Cu-Pb 36.7% 0.2 0.17%
Cu-Ni 2.3% 0 100%

4-16
 Interstitial Solid Solution
• Solute atoms fit in between the voids (interstices) of
solvent atoms.
• Solvent atoms in this case should be much larger than
solute atoms.

• e.g. Interstitial solid solution of carbon in γ iron (FCC) is

formed.
• A maximum of 2.8% of carbon can dissolve interstitially
in iron.

Figure 4.15a
4-17
 Interstitial Solid Solution

Iron atoms r = 0.129nm

Carbon atoms r = 0.075nm

Movement of small atoms (carbon) in a Fe crystal

structure (BCC)
 Crystalline Imperfections
• No crystal is perfect.
• Imperfections affect mechanical properties,
chemical properties and electrical
properties.
• Imperfections can be classified as
➢ Zero dimension (Point) defects.
➢ One dimension (line) defects.
➢ Two dimension (area) defects.
➢ Three dimension (volume) defects.

4-18
 Types of Imperfections

• Vacancy atoms
• Interstitial atoms Point defects
• Substitutional atoms

• Dislocations Line defects

• Grain Boundaries Area defects

• Cracks and Voids Volume defects

24
 Point Defects – Vacancy
• Vacancy is formed due to a missing atom.
• Vacancy is formed (one in 10000 atoms) during
crystallization or mobility of atoms.
• Energy of formation is 1 eV.
• Mobility of vacancy results in cluster of vacancies.
• Also caused due
to plastic deformation,
rapid cooling or particle
bombardment.

Figure: Vacancies moving to form vacancy cluster

 Equilibrium Concentration:
Point Defects
• Equilibrium concentration varies with temperature!

No. of defects Activation energy

 -Q 
= exp  
Nv v
No. of potential
N  kT 
defect sites.
Temperature
Boltzmann's constant
(1.38 x 10 -23 J/atom-K)
(8.62 x 10 -5 eV/atom-K)
Each lattice site
is a potential
vacancy site
26
 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

27
Point defects
 Point Defects - Interstitially
• Atom in a crystal, sometimes, occupies
interstitial site.
• This does not occur naturally.
• Can be induced by irradiation.
• This defects caused structural distortion.

Figure 4.16b
 Point Defects in Ionic Crystals
• Complex as electric neutrality has to be maintained.
• If two appositely charged particles are missing, cation-
anion di-vacancy is created. This is scohttky
imperfection.
• Frenkel imperfection is created when cation moves to
interstitial site.
• Impurity atoms are
also considered as
point defects.

Figure 4.17
 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.

31
 (c) 2003 Brooks/Cole Publishing / Thomson Learning
Figure 4.1 Point defects: (a) vacancy, (b) interstitial atom, (c) small
substitutional atom, (d) large substitutional atom, (e) Frenkel defect,
(f) Schottky defect. All of these defects disrupt the perfect
arrangement of the surrounding atoms.
32
Point Defects in Crystals

33
 Line Defects – (Dislocations)
• Lattice distortions are centered around a line.
• Formed during
➢ Solidification
➢ Permanent Deformation
➢ Vacancy condensation
• Different types of line defects are
➢ Edge dislocation
➢ Screw dislocation
➢ Mixed dislocation
 Line Defects
Edge Dislocation

Fig. 4.3, Callister 7e.

35
 EDGE DISLOCATION
Edge dislocation forms by the removal or
insertion of an extra half-plane

36
Dislocations are visible in electron micrographs

Adapted from Fig. 4.6, Callister 7e.

37
 Edge Dislocation
• Created by insertion of extra half planes of atoms.

• Positive edge dislocation

• Negative edge dislocation

Burgers vector
• Burgers vector
Shows displa-
cement of
atoms (slip).

Figure 4.18
After M. Eisenstadt, “Introduction to Mechanical Properties of Materials,” Macmillan, 1971, p.117
After A.G. Guy , “Essentials of Materials Science,” McGraw-Hill, 1976, p.153
 Line Defects
Screw Dislocation
Screw Dislocation

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

Chapter 4 - 39
 Screw Dislocation

Front View Top View

Chapter 4 - 40
 Screw Dislocation
• Created due to shear stresses applied to regions of
a perfect crystal separated by cutting plane.
• Distortion of lattice in form of a spiral ramp.
• Burgers vector is parallel to dislocation line.

After M. Eisenstadt, “Introduction to Mechanical Properties of Materials,” Macmillan, 1971, p.118

 Edge, Screw, and Mixed Dislocations
Mixed

Edge

Adapted from Fig. 4.5, Callister 7e.

Screw

42
 Mixed Dislocation
• Most crystal have components
of both edge and screw
dislocation.

Figure 4.21

• Dislocation, since have

irregular atomic arrangement
will appear as dark lines
when observed in electron
microscope. Figure 4.22
Dislocation structure of iron deformed
14% at –1950C
(After John Wolff et al., “Structure and Properties of Materials,” vol 3: “Mechanical Properties,” Wiley, 1965, p.65.
(After “Metals Handbook” vol. 8, 8th ed., American Society of Metals, 1973, p.164)
Dislocations, impurities and mechanical properties

• Dislocation creation
• Dislocation movement

• PURE Dislocation
• SMALL atoms.AVI
• Interstitial atoms.AVI
• LARGE atoms.AVI
 Planar Defects
• Grain boundaries, twins, low/high angle
boundaries, twists and stacking faults
• Free surface is also a defect : Bonded to
atoms on only one side and hence has higher
state of energy Highly reactive
• Nanomaterials have small clusters of atoms
and hence are highly reactive.
Formation of grains and grain boundaries
 Grain Boundaries
• Grain boundaries separate grains.
• Formed due to simultaneously growing crystals meeting
each other.
• Width = 2-5 atomic diameters.
• Some atoms in grain boundaries have higher energy.
• Restrict plastic flow and prevent dislocation movement.

Figure 4.25
3D view of
grains

Grain Boundaries
In 1018 steel

(After A.G. Guy, “ Essentials of materials Science,” McGraw-Hill, 1976.)

 Twin Boundaries
• Twin: A region in which mirror image of
structure exists across a boundary.
• Formed during plastic deformation and
recrystallization.
• Strengthens the metal.

Twin
Plane

Twin
 Twin boundary (plane)
– Essentially a reflection of atom positions across the twin
plane.

Adapted from Fig. 4.9, Callister 7e.

49
 Other Planar Defects
Small angle tilt boundary: Array of edge dislocations
tilts two regions of a crystal by < 10°

Stacking faults: Piling up faults during

recrystallization due to collapsing.
➢ Example: ABCABAACBABC FCC fault
 Observing Grain Boundaries - Metallography
• To observe grain boundaries, the metal sample must be
first mounted for easy handling
• Then the sample should be ground and polished with
different grades of abrasive
paper and abrasive solution.
• The surface is then etched
chemically.
• Tiny groves are produced
at grain boundaries.
• Groves do not intensely
reflect light. Hence
Figure 4.27
observed by optical
microscope.

After M. Eisenstadt, “Introduction to Mechanical Properties of Materials,” Macmillan, 1971, p.126

 Volume Defects
• Volume defects: Cluster of point defects join to
form 3-D void.