Revision of the main concepts in materials engineering - 3

Tessaleno C. Devezas

UNIVERSIDADE ATLÂNTICA
Crystalline defects
• The crystal structures studied up to this point were
considered "perfect"; in fact, crystalline imperfections of
some sort will always be present in any material, either in the
form of defects or as impurities.

• Although the number of defects in a "pure" crystal is

generally very small (± a defect in 106 - 1010 atoms!), These
defects can exert a great influence on the electrical
conductivity of the semiconductors, the ductility and the
mechanical resistance of metals and their alloys, in the
processing of materials and even in their colors!
Crystalline defects
• Classification

• Solid solutions
• Point defects (imperfections)
• a - Interstitial defects
• b - Substitutional defects
• Dislocations (linear imperfectios – 2D – 3D) - discordâncias
• Surface defects
• Importance of defects
Crystalline defects
• Solid solutions
• There are a very limited number of applications where metals
are used in pure form (99.99% purity). As examples may be
mentioned the copper used in electronic circuits (high
conductivity) and aluminum used in high-performance mirrors
(high reflectivity). Those high-purity materials are very
expensive, and their use is not justified in most of the more
common applications.

• The metals normally used in engineering applications always

have impurities remaining from ore processing; in addition,
they are often combined with other metals or non-metals in
order to get metal alloys with better properties (eg higher
resistance to corrosion, increased hardness, etc.) than the
original material.
Crystalline defects
• Solid solutions

• The simplest type of alloy is obtained through a solid

solution,
solution where two or more elements form a single
phase material. There are two types of solid solutions:

• Substitutional solid solution

• Interstitial solid solutions
Crystalline defects
Substitutional solid solutions

•In some binary alloys (formed by two elements) it is possible that

one element (solute) will replace the other in the positions of the
crystalline lattice without changing its original structure. There are
several examples of solid substitutional solutions; some very
common are:

•- Ag - Cu (sterling silver: 92.5% Ag + 7.5% Cu - fcc structure)

- Cu - Zn (brass/latão: fcc up to ± 38% Zn; pure Zn is hcp)
- Cu-Sn (bronze - ± 3% Sn)
- Cu - Ni (cupronickel - there is no solubility limit!)

•Two cases to distiguish: with solubility limit and without solubility

limit
Crystalline defects
Substitutional solid solutions

(brass)

(solid solution of Zn in Cu at 20%)

•The percentage of atoms in a metal that can be dissolved in

another can vary widely, depending on a set of conditions of
physico-chemical and geometric:
•Hume-Rothery rules
Crystalline defects

Hume-Rothery rules

1 - The crystalline structures of each element of the solid

solution must be identical;
2 - The size of the atoms of the elements shall not differ more
than 15%;
3 - The elements should not form compounds among
themselves, i.e. should not exhibit large differences in
electronegativity;
4 - The elements must have the same valence
Crystalline defects

Hume-Rothery rules

Example: Solubility of some elements in cupper

Crystalline defects

Interstitial solid solutions

•Another type of solid solution is the interstitial solid

solution, in which atoms of one element will occupy the
void spaces in the structure of another element.

•Interstitial solid solutions are formed when the solute is

a much smaller atom than the solvent. This requirement
is important because the voids in most of the crystalline
structures are relatively small.
Crystalline defects

For instance for a metal with fcc structure:

(4R)2 = a2 + a2 a = 2R + 2r

r = 0,414 R

Iron has an fcc structure between

912ºC and 1394ºC, and R = 0,129 nm

Then r = 0,414 x 0,129 = 0,053 nm

Carbon has r = 0,075 nm  solubility of 2,08 %!

Crystalline defects

This results in regions of the structure under compression:

In the bcc structure the void has only 0,036 nm  0,025%

Crystalline defects

Solid solutions in ionic crystals: mostly substitutional

Two main rules: the size of the atoms and the valence!
Crystalline defects

When there is difference of valence we have non-

stoichiometric compounds
Ex: FeO  Fe1-xO 0.04 < x < 0,12

(vavancy)
Crystalline defects
Point defects

Point defects are localized disruptions in otherwise

perfect atomic or ionic arrangements in a crystal
structure. Even though we call them point defects, the
disruption affects a region involving several atoms or
ions.

These imperfections may be introduced by movement of

the atoms or ions when they gain energy by heating,
during processing of the material, or by the intentional
or unintentional introduction of impurities.
Crystalline defects
Point defects – types

isolated vacancies

double vacancy
Crystalline defects
Point defects – types

interstitial defect in a metal structure

Crystalline defects
Point defects in ceramics

Schottky defect – absence of a pair

cation/anion

Frenkel defect – cation displaced

Crystalline defects
Resum:
Crystalline defects
Dislocations (discordâncias)

How to describe a linear dislocation?

- an extra line of atoms?

- the absence of a line of atoms?

Both descriptions are

equivalent!
Crystalline defects
Dislocations (discordâncias)

Screw dislocation

(discordância em espiral)
Crystalline defects
Dislocations (discordâncias)

(mixed dislocation)
Crystalline defects
Surface defects

Any surface is a structural defect – its existence implies in a

region where atomic bonding is incomplete and the atoms on
the surface are in an excited state (higher energy!)
Crystalline defects

Grain boundaries

When molten metal is

cooled, small particles
(embryos) form and
coalesce
Crystalline defects

Grain boundaries

Polycrystalline
microstructure

grain boundaries

The grain boundaries

are regions of higher
energy, where bonding
is discontinued, and then
are structural defects
through which cracks
will propagate
Crystalline defects

Importance of defects

It is important to point out that the main mechanisms

responsible for the plastic deformation of the materials involve
the propagation of defects (point defects and/or dislocations)
through its crystalline structure.

The movement of the dislocations is the main responsible for

the ductility and toughness observed in the metals, whereas in
the ceramic materials, where movement of the dislocations is
much more difficult, the plastic deformation mechanisms (at
high temperatures) involve the movement of vacancies and
defects of Schottky and Frenkel.