8.

NONCRYSTALLINE MATERIALS
The levels of atomic arrangement in various materials:

8.1 Gases

Fig. 8.1a: Inert gases have no regular ordering of atoms. [Adapted from D.R. Askeland]
The atoms or molecules have no order and are bonded together by very weak covalent
and Van der Waals bonding forces.

8.2 Liquids

Fig. 8.1b: Water has ordering of atoms only over a short distance. [Adapted from D.R.
Askeland]

The molecules have no order and are bonded together by stronger covalent and hydrogen
bonding forces.

8.3 Glassy Solids

Fig. 8.1: (c) Glass has ordering only over a short distance. (d) Crystalline solids such as
metals have a regular ordering of atoms that extends through the material. [Adapted from
D.R. Askeland]

The atoms or molecules are bonded together mainly by very strong ionic, covalent or
metallic bonding forces.

Fig. 8.2: Different levels of atomic arrangement in the formation of gas, liquid, and solid.
[Adapted from T.L. Richardson]

Also known as amorphous solids or supercooled liquids.

Eg. Crystalline SiO2 and amorphous SiO2.

Fig. 8.3: Two-dimensional illustration of the structure of (a) crystalline SiO2 and (b)
noncrystalline SiO2. [Adapted from W.D. Callister]
Lack a systematic and regular arrangement of atoms over relatively large atomic
distances; ie. no long-ranger order, only short-range order.
Have atomic or molecular structures that are relatively complex and become ordered only
with some difficulty; eg. plastics

Fig. 8.4: Illustration of the amorphous and semicrystalline polymers. [Adapted from T.L.
Richardson]

Fig. 8.5: Various structural forms of polymers. [Adapted from W.D. Callister]
Formation is favoured by rapid cooling of molten solids.

Fig. 8.6: Adapted from T.L. Richardson.

Splat-quenching of molten metals can lead to glassy metals.
Exhibit a glass-transition temperature (Tg); < Tg, glass, > Tg, supercooled liquid.

Fig. 8.7a: Plot of specific volume versus

temperature for crystalline solid and
glass. [Adapted from D.R. Askeland]

Fig. 8.7b: Plot of density versus

temperature for various forms of solid.
[Adapted from T.L. Richardson]

9. IMPERFECTIONS IN SOLIDS
All solids contain large number of imperfections or deviations from crystalline
perfection.
Only single crystals have a near perfect crystalline structure.
Presence of imperfections has a profound influence on the material properties (eg.
optical, electrical, thermal, chemical, mechanical, etc.)

9.1 Point Defects

9.1.1 Vacancies

Fig. 9.1: Point defects: (a) vacancy. [Adapted from D.R. Askeland]
Vacant lattice sites which increase the entropy or randomness of a crystal.
A vacancy is formed when an atom is missing from a normal site during solidification
from high temperatures or radiation damage.
The equilibrium number of vacancies (Nv) increases with temperature (T):
Qv
)
kT
where N = total number of atomic sites
Qv = energy required to form a vacancy
k = Boltzmanns constant (1.38x10-23 J/atom-K)
N v = N exp(

Example Problem 9.1

Calculate the equilibrium number of vacancies/m3 for copper at 1000C. The energy for
vacancy formation is 0.9 eV/atom; the atomic weight and density (at 1000C) for copper
are 63.5 g/mol and 8.4 g/cm3, respectively.
NA
(6.023 10 23 atoms / mol )(8.4 g / cm 3 )(10 6 cm 3 / m 3 )
=
63.5 g / mol
ACu
28
3
= 8.0 10 atoms/m
At 1000C (1273 K)

Q
0.9eV
N v = N exp( v ) = (8.0 10 23 atoms / m 3 ) exp

5
kT
(8.62 10 eV / K )(1273 K )
N=

= 2.2 1025 vacancies/m3

9.1.2 Self- Interstitials

Fig. 9.2: Self-interstitial and vacancy. [Adapted from W.D. Callister]

Host atoms that occupy interstitial sites and their presence can cause large distortions in
the surrounding lattice.

9.2 Impurities
Foreign atoms that occupy the lattice or interstitial sites of metals to form alloys.
Presence of impurity atoms can lead to formation of a solid solution and/or a new second
phase.
9.2.1 Solid Solutions

A solid solution is formed when foreign atoms are added to the host material.
The crystal structure of the host material is maintained and no new structures or phases
are formed.
(a) Substitutional solid solution

Fig. 9.3: Small and large substitutional atoms. [Adapted from D.R. Askeland]
Foreign atoms replace or substitute for the host atoms.
The degree of substitution depends on (a) the atomic size, (b) crystal structure, (c)
electronegativity and (d) valency of the foreign atoms.
Get complete solubility if the foreign has a similar atomic size (R 15%), crystal
structure, and electronegativity but higher or similar valency.
Eg. Copper/Nickel
Table 9.1: Characteristics of copper and nickel.
Cu
Atomic size (nm)
0.128
Crystal structure
FCC
Electronegativity
1.9
Valency
+1

Ni
0.125
FCC
1.8
+2

(b) Interstitial solid solution

Small foreign atoms (eg. C, N, H) fill the voids or interstitials among the host atoms.

Fig. 9.4: Interstitial atom. [Adapted from D.R. Askeland]

Eg. carbon (2%)-Iron (Steel)
RFe = 0.124 nm

RC = 0.071 nm

9.3 Line Defects

9.3.1 Dislocations
Line defects around which some of the atoms are misaligned.
Movement of dislocations leads to deformation in metals and ceramics.
The direction and distance that a dislocation moves in each step is known as the Burgers
vector (b).
(a) Edge Dislocation ()

Fig. 9.5: Edge dislocation. [Adapted from D.R. Askeland]

A dislocation introduced the lattice by adding an extra half plane of atoms.
The Burgers vector and the dislocation are perpendicular to each other.

Fig. 9.6: Slip system of an edge dislocation. [Adapted from D.R. Askeland]

(b) Screw Dislocation (3)

A dislocation produced by shearing a crystal so that one atomic plane produces a spiral
ramp about the dislocation.
The Burgers vector and the dislocation are parallel to each other.

Fig. 9.7: Screw dislocation. [Adapted from D.R. Askeland]

(c) Mixed Dislocation (,3)
A dislocation that contains partly edge components and partly screw components.

Fig. 9.8: Mixed dislocation. [Adapted from D.R. Askeland]

Fig. 9.9a: Dislocation loops. [Adapted from

Fig. 9.9b: Dislocation network. [Adapted

D.R. Askeland]

from D.R. Askeland]

Example Problem 9.2

A sketch of a dislocation in MgO, which has the sodium chloride crystal structure and a
lattice parameter of 0.396 nm is shown below. Determine the length of the Burgers
vector.

Fig. 9.10: Edge dislocation in MgO. [Adapted from D.R. Askeland]

d110 =

a
h2 + k 2 + l 2

0.396
= 0.280 nm
1 + 12 + 0 2
2

b= 0.280 nm

b = [110];

Example Problem 9.3

Calculate the length of the Burgers vector in copper ( a = 0.36151 nm).

Fig. 9.11: FCC structure in copper. [Adapted from D.R. Askeland]

The close-packed directions are <110> or along the face diagonals.
Face diagonal:

4R = a 2 = 2 (0.36151) = 0.51125 nm

1
b= 2R = (0.51125) = 0.25563 nm
2

9.4 Interfacial Defects

Boundaries that have two dimensions which separate regions of the materials that have
different crystal structures or crystallographic orientations.
9.4.1 External surfaces

Boundaries where the crystal structure terminates.

Due to incomplete bonding, surface atoms have higher energy and more reactive than the
bulk of the material.
9.4.2 Grain Boundaries

Fig. 9.12: Low-angle and high-angle grain boundaries. [Adapted from W.D. Callister]
Boundaries between two grains having has a different orientations in a polycrystalline
material.
There is lack of regular bonding and some atomic mismatch or disorder within the grain
boundary.
Hence grain boundaries have a higher energy state and are more chemical reactive than
the grains.
A small angle grain boundary is produced by an array of dislocations causing a small
misorientation of the lattice across the surface of the imperfection.

Fig. 9.13: Formation of a tilt boundary from edge dislocations. [Adapted from D.R. Askeland]
Tilt boundary formed by edge dislocations
Twist boundary formed by screw dislocations.

9.4.3 Twin Boundaries

Fig. 9.14: Formation of a twin boundary. [Adapted from D.R. Askeland]

Boundaries across the twins where there is a mirror image mis-orientation of the lattice.
Twins are formed from atomic displacements due to mechanical shear forces (mechanical
twins) or annealing heat treatments following deformation (annealing twins).
Mechanical twins are found in BCC and HCP metals.
Annealing twins are found in FCC metals.

9.4.4 Stacking Faults

Surface defects in FCC metals caused by the improper stacking sequence of close-packed
planes.
Eg. FCC lattice
Stacking fault

ABCABCABCABC..
ABCABABCBACA.

Table 9.2: Energies of surface defects in selected metals.

Surface Energy (J.m-210-3)
Surface Defect Al
Cu
Pt
Grain boundary 625
645
1000
Twin boundary 120
45
195
Stacking fault
200
75
95

9.5 Volume Defects

Cracks, pores, foreign inclusions and other phases.

Fe
780
190
-

10. ATOMIC MOVEMENT

Atoms move through a solid material by diffusion mechanisms, particularly at high
temperatures when a concentration gradient is present.

Fig. 10.1: Diffusion of copper atoms into nickel. Eventually, the copper atoms are
randomly distributed throughout the nickel. [Adapted from D.R. Askeland]
Two important mechanisms for atom movement are (a) vacancy diffusion, and (b)
interstitial diffusion.

Fig. 10.2: Diffusion mechanisms in materials: (a) vacancy diffusion, and (b) interstitial
diffusion. [Adapted from D.R. Askeland]
The rate of diffusion is governed by the Arrhenius relationship, ie. The rate increases
exponentially with temperature.
Rate = c o exp(

Q
)
RT

where co is a constant, R is the gas constant (8.314 J.mol-1K-1), T is the absolute

temperature (K) and Q is the activation energy (J.mol-1) required to cause the
imperfection to move.

Fig. 10.3: The Arrhenius plot of ln (rate) versus T-1 can be used to determine the
activation required for a reaction. [Adapted from D.R. Askeland]

Atom diffusion is of paramount importance, because many of the materials processing

techniques, such as sintering, powder metallurgy, and diffusion bonding require
diffusion.

Fig. 10.4: Diffusion processes during sintering and powder metallurgy. Atoms diffuse to
points of contact, creating bridges and reducing the pore size. [Adapted from D.R. Askeland]

Fig. 10.5: Diffusion processes in diffusion bonding: (a) Initially the contact area is small;
(b) application of pressure deforms the surface, increasing the bonded area; (c) grain
boundary diffusion permits voids to shrink; and (d) final elimination of the voids requires
volume diffusion. [Adapted from D.R. Askeland]
Furthermore, many of the heat treatments and strengthening mechanisms used to control
structures and properties in materials are diffusion-controlled.

Fig. 10.6: Grain growth occurs as atoms diffuse across the grain boundary from one grain
to another. [Adapted from D.R. Askeland]

-----------------------------------------------------------------------------------------------------------

References:
W.D. Callister, Jr. (2002). Materials Science and Engineering, An Introduction, 6th
Edn. Wiley.
D.R. Askeland (1998). The Science and Engineering of Materials, 3rd Edn. Stanley
Thornes.
T.L. Richardson (1989). Industrial Plastics: Theory & Application, 2nd Edn. Delmar.

Practice Questions (W.D. Callister):

4.1; 4.5; 4.14; 4.25
5.1; 5.3

Tutorial Questions
Chapters 3 & 4 (Callister, 6th Edition)
3.57
4.2
4.4