MATE 202: Introduction to Materials Engineering

Structure
Chapter 4

A computer generated hard-sphere model of twenty seven unit cells of the face-centered-cubic (FCC)
lattice (generated on the author’s iPad2). The hard-sphere model is commonly used to represent the pack-
ing within metallic crystal lattices, and the arrangement of the atoms can easily be seen and reproduced
with physical models.
The final packing of atoms within a crystal lattice depends on the nature of the atomic bond, the
electron structure, and how the material is cooled, or processed. Ultimately, the structure then dictates the
properties of the material, especially through defects and their mobility within the lattice.
The housing on the electronic device used to generate this graphic, for example, is made from an
aluminum alloy, which, if we could see inside the material would have the same atomic packing as shown
above! This particular structure, FCC, results in dense atomic packing which, in FCC metals, in turn leads
to low yield strength, high ductility, lack of a fatigue limit… and the list goes on!

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Chapter 4: Structure

The structure of materials represents one of the three cornerstones in the materials paradigm.
Understanding the structure of a material is the way we “get to know” a material, and be able to
predict its behaviour. Without understanding structure we have made very slow advances in ma-
terials development and processing (tens of thousands of years!). Blacksmiths and samurai
sword makers had intense knowledge of how to process materials to achieve incredible proper-
ties, but they did not know why! Recent advances in materials over the past 100 years can be
contributed to tools and techniques that have been developed to classify material structure.
Combining small scale structural information with processing knowledge, and ability to measure
properties, the past century has seen rapid advances in materials, and has enabled incredible
technological developments.
Issues to address
The importance of structure as it relates to atomic bonding
Crystals, Crystallographic Features, Imperfections, X-ray Diffraction

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 MATE 202: Introduction to Materials Engineering

Roadmap Atoms in melt

Condensation to solid
Type of atom, bonding type, and packing
determine nature of solid

Amorphous solid
Crystalline solid

Short range order (SRO), no Long SRO and LRO

range order (LRO) The lowest energy state of a
Not the lowest energy state material
of a material Unit cell, lattice parameters, and
Bond lengths are random atom placement can be
characterized by 14 Bravais Lattices
Miller Indices describe:
Points, directions, and planes
in crystals
Crystals are rarely perfect!

Atomic structure affects material properties

Open with ball bearing demonstration – arrangement, cooling, states of matter, defects, crystals,
glasses.

4.0 The importance of structure From the previous units we have seen that material response
is different from material to material. We learned that the primary bonding within classes of
materials is a major reason for the difference in behaviour between classes of materials.

Recall:
Material properties are determined by a material’s structure.
Understanding atomic structure of a material allows us to predict properties & to engineer
properties by engineering the structure.

Many material properties are determined by atomic scale structure:

Strong vs. tough
Brittle vs. ductile
Hard vs. soft
Electrical conductor vs. insulator
Thermal conductor vs. insulator
Transparent vs. opaque
Atomic scale structure:
Types of atoms present
Types of bonding between atoms
Packing of the atoms

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Chapter 4: Structure

We design materials to have a particular atomic scale structure and arrangement to

elicit the behaviour we want!
THIS IS MATERIALS ENGINEERING

4.1 Definitions
Structure: Order (arrangement) of atoms within a material. Equilibrium structure is ultimately
governed by:
1. the nature of the atoms,
2. their bond character, and
3. minimization of energy in the structure.
Short range order (SRO): regular arrangement of atoms about a central atom at a distance on
the order of one bond length. SRO is based on the number and type of nearest neighbors,
i.e. the coordination number.
Long range order (LRO): regular arrangement of atoms that extends beyond nearest neigh-
bors. Encompasses second and higher order neighbors (i.e. distances well beyond a single
bond length)
Gases (ideal): display neither SRO, nor LRO

condensed
Liquids: display SRO, usually not LRO
phases

Solids: display SRO, may display LRO

Crystallinity: 3-D structure where the material elements are arranged in a regular array that is
repeated at fixed intervals ad infinitum. Results in predictable order in 3-D.
*****Crystals have SRO AND LRO*****
Amorphous: a solid that is non-crystalline, exhibiting SRO but NO LRO. Glasses are amor-
phous (there are metallic, ceramic, and polymeric glasses).

The process of changing an amorphous solid into a crystalline solid is de-vitrification, and the
reverse is vitrification.

(Crystal) Structure is a major determinant of material properties

Most engineering materials are crystalline (metals, ceramics, some polymers, semiconductors)
though these can all be processed to be non-crystalline, or amorphous.

Summary of structure by class of materials

Metals: most are crystalline, and used in crystalline form
Ceramics: crystalline, amorphous, or a combination (e.g., glass ceramics – Corelle
plates are partially crystalline)
Polymers: amorphous, partially crystalline, or a combination
Semiconductors: most are crystalline, and used in crystalline form
Biological materials: amorphous, partly crystalline, usually a combination
Composites: depends on components – can be any combination really

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 MATE 202: Introduction to Materials Engineering

4.2 Levels of structure

Ultimately, the atomic level bond structure (atom to atom) gives rise to many properties
of materials. However, defects, of which many are present in materials, are the main
reason why materials do not behave as predicted from calculations based on pure atom-
atom interaction.

4.3 Review of Bonds and Their Strengths

Ionic bonding – ceramics

Covalent bonding – polymers,
Primary interatomic bonds (some ceramics)
Metallic bonding -- metals

BOND
Secondary bonds
van der Waals Bonding:
London dispersion force: instantaneous induced dipole-
induced dipole
Debye interaction: dipole-induced dipole (polarization)
Keesom force: permanent dipole-dipole (electrostatic)
(e.g., H-bonding)

Type Bond Energy Comments

Ionic Large ~4-5eV Nondirectional (ceramics)

Variable Directional
Covalent large-Diamond ~5-7eV semiconductors, ceramics
small-Bismuth polymer chains

Variable ~3-5eV
Metallic large-Tungsten Nondirectional (metals)
small-Mercury
Directional
Smallest ~0.1-1eV
Secondary inter-chain (polymer)
London, Debye ~0.1eV
Keesom (H) ~1eV inter-molecular

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Chapter 4: Structure

4.4 The bond-energy curve: U(r) The bond –energy curve is the most fundamental tool to ex-
plain the behaviour of materials response to various situations. You will understand so
much more about how materials behave if you spend the time to master the concepts of
these curves.
Using the bond-energy curve you should be able to:
 Derive the force distance curve from the energy curve and vice versa
 Indicate on a plot, and mathematically determine the:
 equilibrium bond separation distance
 binding energy
 theoretical bond strength
 bond stiffness
 Draw representative curves for ionic, covalent and metallic bond types (and materi-
als with different properties such as E, CTE, Tm)
 Write and explain the terms in the equations used to plot U(r)

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Bond-Energy Interatomic Separation Distance Curves (Potential Well Diagrams)

Properties from U(r) :

 Bond Energy ε [J, eV]

 Average Bond Length (Equillibrium

interatomic separation distance) r0
[nm]

 Elastic Modulus E[Gpa] & Bond

Stiffness S0 [N/m]

 Coefficient of Thermal Expansion

(linear) αth [ºC-1, K-1]

 Melting/Boiling point TMP, TBP [ºC, K]

4.4.1 Ionic Bond

 Ionic bonds are formed from separated charges (ions), with a strong Coulombic attraction/
interaction as described by:

( Z 1 e )( Z 2 e )
A
4 
Zi = Valence of ion i (i=1,2)
εo = Permittivity of vacuum
e = Electronic charge

Because ionic bonds require ions, the ionization energy required to produce the ions factors in to
the bond energy equation below. The ionization energy is a penalty or cost and is hence posi-
tive.

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Chapter 4: Structure

4.4.2 Covalent Bond (Similar to Metallic Bonds)

From the preceding curves there are some similarities:

1. Minimum energy is negative

2. Repulsive energy has a short rang interaction (effective over small distance, r)
3. Attractive energy has a long range interaction (effective over large distance, r)
4. Bond energy ε is the energy at the minimum of the well: U(ro)=ε
5. The average bond length ro is the equilibrium separation distance at which U(r) is a
minimum:

U
r r  ro 0

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 MATE 202: Introduction to Materials Engineering

4.5 Relation between Energy and Force

Bond stiffness is the slope of F(r) when r = ro (for small Δr about ro F is linear with respect to
Δr).
Bond stiffness, So, is related to Youngs Modulus! How?
F  aEr
F
Where a is the geometrical factor and E is Young’s Modulus. Rearranging we can say E 
ar
Recall that   E so, the force on a bond behaves similarly:
F
S r

E A  o o

r A
ro

and therefore E α So

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Chapter 4: Structure

If we evaluate the curvature of U(r) at U(ro) or the slope of F(r) at F(ro), both correlate to bond
Stiffness, So.
U
r
F  2U

F
2U  F S
 2r r
r 2 r r r r r o
o o

Example: Which material has a higher

Youngs Modulus? Material “a” or
material “b”?

Answer: Eb > Ea

But why?

The slope at ro of F(r) is greater for “b”

than for “a”.

This means that Sob>Soa.

Since So α E we deduce that if the

structure is similar, then Eb>Ea. If the
structure was not similar, then the
geometrical constants and area over
which the bonds exist would change,
and the comparison would be much
more complicated.

*Materials with high values of E have

high bond stiffness, So.

4.6 Coefficient of Thermal Expansion (CTE or αth)

As temperature increases, atoms gain energy, and the separation distance increases because the
bonds elongate.
For many metals the separation distance can be described as:
r  r0 1
 th   [°C-1 or K-1]
r0 (T  T0 )

This means the potential energy curve is assymetric about the equilibrium bond lenth!
Positive CTE means the material expands with increase temperature (the material becomes less
dense).

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MATE 202: Introduction to Materials Engineering

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Chapter 4: Structure

4.7 Melting and Boiling Points TMP, TBP

If enough enegy is supplied to fill U    kTBP

the well to zero energy, then we boil U  f  kTMP(k 1)
the material.

If enough energy is supplied to fill

some of the well to U ≤U(rmax) then
the material will melt. Usually less
than U(rmax) is required fo r melting, rmax
about:
r r
U U(r0 ( max 0 ))
4
In a molten state, the material is still
weakly bound!

4.8 Other forms of U(r)

a m a Where A is a constant = 4ε [J, eV],

U(r) A[  ( )  ( )n ] a is a constant [nm],
r r m,n are exponents which describe the nature of the bond.

4.9 Energy and packing

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4.10 Mass Density

Mass density is related to packing: nM

vN A
n= Number of atoms per unit cell (n can be 1, 2, 3...etc depending on unit cell type)
M= Molar Mass [g/mol]
v=volume of unit cell [cm3]
NA= Avogadro’s number [6.023 E23 atoms/mol]

The mass density of metals is so high because of their high molar mass and their dense packing
(due to non-directional bonding). We will discuss this at more length later in the chapter.

Reflection Question: Which is more dense, a crystalline or amorphous material (with fixed
composition)? Why?

Recall the exercise from the first lecture… your brain was pretty clever to deduce that the mate-
rials you had in hand were of different density, even though their masses were identical!

Four cylinders with the same diameter made from four different metallic alloys. The
similar mass (~48g) is undetectable by holding the cylinders in one’s hand, yet human percep-
tion identifies cylinder “D” on the right as the lightest. The different lengths demonstrate the
variation in density of the alloys.

A: Normalized AISI 1018 plain carbon steel; 7.87g/cm3

B: Oil Quenched and Tempered AISI 4140 low alloy carbon steel; 7.85g/cm3
C: Annealed Titanium Alloy Ti6Al4V; 4.43g/cm3
D: Precipitation Hardened Aluminum Alloy 6061-T6; 2.70g/cm3.

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Chapter 4: Structure

4.11 Crystal Systems

Crystal Structure for a crystalline material is the manner in which atoms, ions, or mole-
cules are arranged in space. It is defined in terms of the unit cell geometry and the atom po-
sitions within the unit cell.

Unit cell the smallest indivisible arrangement of atoms that is considered a repeat unit that
can build up a crystal if stacked in the same way. Think – the smallest lego block!

Lattice parameters are the edge lengths of the unit cell (a, b, c), sometimes called ao (for
cubic crystals)

Lattice is a 3D network of lattice points, the outlook from any point being the same to all
other points

Point lattice Unit cell

Crystal basis the repeat unit that is centered upon the lattice points. A basis can be a single
atom, a pair, or molecules etc.

Basis of two entities Example of complex basis (MC Escher)

Bravais Lattices – there are 4 types of unit cells, 7 crystal classes and 14 independent Bra-
vais Lattices, which are distinguished by relations between edge lengths (lattice parameters);
edge angles; and atom placement.

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MATE 202: Introduction to Materials Engineering

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Chapter 4: Structure

4.12 Common Metallic Crystals

FCC face centered cubic Fig 3.1 e.g. Al, Cu, Ag, Au, many stainless steels (austenitic)
BCC body centered cubic Fig 3.2 e.g. Fe, W, Mo, V, Nb
HCP hexagonal close packed Fig 3.3 e.g. Zn, Cd, Ti, Zr, Mg
(Some metals are also simple cubic.)
represent crystal structure by a part called the unit cell
A unit cell shows the relative position and spacing of the atoms and
When it is repeated indefinitely in 3 dimensions it gives the structure.
Calculations about the crystal can be made on the unit cell and will apply to the entire struc-
ture.

FCC (face centered cubic)

For all cubic systems we use a right-handed Cartesian system (thumb, first and second finger of
the right hand point in x, y and z directions), the cube edge is “a” the lattice parameter or
lattice constant.
FCC crystal structure can be represented by a cubic unit cell with atoms at each corner (8) and at
the center of each face (6).
Atoms touch along the face diagonals so 4R = √2 a. (Pythagoras).
For FCC we see that there are 4 atoms in the unit cell i.e. 8X1/8+6X1/2 =4.
Each atom touches 12 others, this is the co-ordination no. or no. of nearest neighbours. In fact
all atoms have identical surroundings so this is a Bravais lattice.

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 MATE 202: Introduction to Materials Engineering

BCC (body centered cubic)

cubic with atoms at corners and in cube center,
2 atoms per unit cell (8X1/8+1),
atoms touch along cube diagonal so 4R=√3 a.
Coordination no. (# nearest neighbours) = 8 and again this is a Bravais lattice so each atom has
identical surroundings.

HCP (hexagonal close packed) more complex

 7 atoms in close packing in top and bottom layer (directly above one another), -
middle layer - 3 atoms in hollows between atoms (also in close packing). (HCP is
not a Bravais lattice)
 Close packing also exists in FCC, which we can see if we remove a corner atom
in the unit cell.

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Chapter 4: Structure

4.13 Crystallographic Features (Packing of planes in HCP, FCC, and BCC)

We can think of HCP as a modification of FCC as follows based on the stacking sequence of
close packed planes:
“FCC is ABC”
“HCP is ABAB”
The stacking sequence of the close packed planes in HCP is ababab, since the third layer lies
directly above the first (and the fourth directly above the second etc.).
There are also close-packed planes in FCC, but these have stacking sequence abcabc etc., since
the fourth layer lies directly above the first etc.
With FCC there are actually 4 sets of close packed planes at different orientations rather than
just the one, and these planes are the slip planes for plastic deformation (planes in which
dislocations can move).
FCC tends to be more ductile than HCP since slip is not possible in directions perpendicu-
lar to the basal plane for some HCP metals (Zn or Mg for example), but slip is possible
in every direction in FCC since one of the slip systems will have significant components
in that direction.

A
B
C

FCC Unit cell

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Miller Indices are a way of describing points, lines, and planes in space. We will only study
indices with values of 0 and 1 in this course (however, any integer number is possible).

Directions
 For any vector of direction: subtract the co-ordinates of tail from co-ordinates of head, and
enclose in ‘[ ]’, no commas and no spaces, multiply or divide through to get the smallest
set of integers e.g. [200] becomes [100].

Procedure:
1.The vector is usually drawn from the origin of the coordinate system.
2.The length of vector is determined based on its projected length on each of the
three axes, which are measured in terms of unit cell dimensions, a, b, and c.
3.The projected length is modified by a common factor into the smallest integer val-
ues.
4.The vector is written as [uvw], u, v, w integers correspond to the reduced projects
along x, y, and z axes, respectively.
5.Negative indices are written as u rather than –u.
Any vector may be translated through the crystal lattice without alteration if parallel-
ism is maintained.

 All parallel vectors have the same Miller indices.

 Again: negative numbers are shown with a bar over the number e.g. [100] is the negative x-
direction. Read as “bar 1, zero, zero”

4.3.1.2 Planes
 The indices actually represent a set of parallel planes and their spacing. These sets of
planes produce diffraction in X-ray diffraction and electron diffraction, and this formulation
helps in understanding diffraction. This diffraction is very useful in getting information
about the structure and its defects.
 For a set of planes to find the Miller indices we take the intercepts of plane next to the
plane through the origin, calculate reciprocals and enclose in ‘( )’, no commas since
commas are reserved for co-ordinates.

Procedure
1. This applies to planes not through the origin. If the plane passes through the
origin, indices can be determined either by finding a parallel plane or by estab-
lishing a new origin.
2. Find the length of the planar intercept for each axis, and express the length in
terms of lattice parameter, a, b, c.
3. Take reciprocals of the length value. The reciprocal is zero for a plane parallel
to an axis
4. Cross multiply through to clear fractions (if necessary)
5. Write the indices as (hkl).
6.
Representations of a series each of (a) (001), (b) (110), and (c) (111) crystallographic planes.

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Chapter 4: Structure

Families of planes represent series of parallel planes with the same orientation in space, but separated by
the same distance apart in space. Examples are shown below. Equivalent planes can be drawn in other
unit cells, but of course the origin would need to be moved to the unit cell in question in order to deter-
mine the index values of the plane.

Note: A (222) plane is not a (111) plane because the spacing between the planes is different.

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 MATE 202: Introduction to Materials Engineering

Example: What are the Miller indices of the plane IKFG?

A
B
Intercepts: x= y =1 z=1/2

D C
K Reciprocals: 0 1 2

I Reductions: N/A

E F
Indicies: (012)

H G

REFERENCE SHEETS AND PRACTICE: MILLER INDICES

Starting Point: Adopt a coordinate system

right hand, Cartesian coordinate system

- align coordinate system with the edges of the unit cell (e.g. cubic unit cell)
- define origin at corner of the unit cell

Example: cubic unit cell

origin

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Chapter 4: Structure

POINTS

Individual points are designated using the coordinates h,k,l, where each value repre-
sents a fraction of the lattice parameter a,b,c, respectively. h,k,l correspond to x,y,z.

The values of h,k,l are limited to the range 0 to 1

Example: cubic unit cell

Label: O, A, G, F, D, 0,1,1

1,0,1 1,1,1
1/2,1,1/2
0,0,0
1,0,0 1,1,0

DIRECTIONS

1.) Select two points that lie in the direction of interest, h1,k1,l1, and h2,k2,l2.
Ideally, h1,k1,l1 should correspond to the direction’s origin.
2.) Subtract the coordinates: h2,k2,l2 - h1,k1,l1

Example (right), for direction OD: 1,1,1 – 0,0,0  (1-0), (1-0), (1-0) = 1,1,1

3.) Clear fractions from the differences, to give (lowest) integer values.
4.) Write indices in square brackets (no commas, no spaces): [111]
5.) Indicate negative values with overbar.

Example: Direction EO

Subtract: 0,0,0 – 1,1,0  -1,-1,0

Write in square brackets: [110]

Example: Direction AH

Subtract: 1/2,1,1/2 - 1,0,0  -1/2,

1,1/2

Clear fractions: -1,2,1

Write in square brackets: [121]

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PLANES

1.) Identify the coordinate intercepts of the plane.

a) If the plane is parallel to one of the coordinate axes, take the intercept as equal
to .
b) The plane of interest cannot pass through the origin. Thus, the origin may
have to be moved.

2.) Take the reciprocal of the intercepts.

3.) Clear fractions, but do not reduce to lowest integers.

4.) Cite planes in parentheses (hkl); use overbars for negative indices.

Examples
Plane A:
Intercepts = ,,1 (0 0 1)

Plane B:
Intercepts = 1,1,1 (1 1 1)

Plane C:
Intercepts = 1,1, (1 1 0)

Plane D:
Intercepts = ,,-1 (0 0 1)

TIPS for CUBIC units cells:

Planes that look like triangles will have all hkl because they will intersect all three axes. E.g.,
Plane B above, (111)

Planes that look like squares will have only 1 hkl value equal to an integer, and the others will
be zero. E.g., Plane A above (001).

Planes that look like rectangles will have two hkl values equal to an integer, the third will be
zero. E.g., Plane C above (110)

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Chapter 4: Structure

FAMILIES OF DIRECTIONS AND PLANES

DIRECTIONS
Families of directions are designated using angled brackets; for example <110>.

For cubic cells, the individual members of a family of directions can be determined by taking all
possible permutations (positive and negative) of the Miller indices.

Example: write the various [hkl] permutations for the <110> family of directions.
(12 permutations)
[110] [101] [011]

[110] [101] [011]

[110] [101] [011]

[110] [101] [011]

PLANES
Families of planes are designated using braces; for example {110}.

For cubic cells, the individual members of a family of planes can be determined by taking all
possible permutations (positive and negative) of the Miller indices.

Example: write the various (hkl) permutations for the {111} family of planes.

(8 permutations)
(111) (111) (111) (111)

(111) (111) (111) (111)

MILLER INDICES SUMMARY

Single notation Family notation

Points h,k,l * NONE
Directions [hkl] <hkl>
Planes (hkl) {hkl}

* h,k,l values for points are fractions of the unit cell length between 0 and 1 (also integers 0 and
1)

4.14 Crystal Calculations

4.14.1 Bulk Density

Recall that density is calculated by:

nM

VN A

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Example: What is the theoretical density of copper?

a = 3.61 x 10-10 m, structure = FCC
M = 63.54 g/mol
n = 4 atoms / unit cell
V (volume of unit cell) = a3 = (3.61 x 10-8)3 cm3

nM 4atoms  63.54 g / mol

  8 3
 8.97 g / cm 3
VN A (3.61  10 ) cm 3  6.023  10 23 atoms / mol

The measured value of the density of copper is 8.94 g/cm3. Why the difference? Well,
the above calculation assumes the atoms are hard spheres when in fact the electronic
orbital shells are not perfectly symmetric and can be distorted to yield an actual density
that may be slightly larger or smaller than the theoretical density. Other discrepancies in
density also become introduced via point and line defects (vacancies, grain boundaries,
dislocations) and even impurities.

4.14.2 Volumetric Atomic Packing Factor (aka: atomic packing factor: APF)

APF = volume of all atoms occupying the unit cell / volume of unit cell

Example An FCC unit cell.


4 R  2a , we get
4 atoms of volume 4/3πR3 in a volume of a3 so using 3 2 (=0.74) for the
atomic packing factor.

4.14.3 Linear Atomic Packing Factor (LPF)

 i.e. the fraction of a direction vector covered by atoms (considering only atoms whose cen-
ters are on the line).

length direction vector covered by atoms centered on direction vector

LPF 
length of direction vector

 A half of an atom will have a length of 1R, and a whole atom has an equivalent length of 2R,
etc.

Example
A cube edge in gold (FCC). The length of line is a (pink line), the length covered is 2R (sum
of dark red lines). So the fraction is 2R/a. For Gold, R= 1.442 Ǻ (Ǻ is the symbol for an Ang-
strom: 1 Ǻ = 10-10m) and a = 4.0786 Ǻ, so:

LPF = 2R/a = 2(0.357Ǻ)/4.0786 Ǻ = 0.707

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Chapter 4: Structure

Example

Direc on AH and AI for (111) of an FCC unit cell

4R 4R 2R
LPFAH    1
A
2a 2  2 2R 2R

2R 2R 2R
LPF   
AI AI 2 a  sin 60 3
2  2 2R 
2
H I F
2R 1
   0 . 577
R2 3 3

Line AH is a close packed direction. Notice that the packing cannot get any closer, the linear
packing factor is unity (thus a close packed direction can be defined as a direction in a unit cell
whose LPF =1. All of the length on a close packed direction is occupied by atoms.

4.14.3 Planar Atomic Packing Factor (PPF)

The fraction of the area of the plane covered by atoms whose centers lie in the plane.

area of atoms centered on a plane

PPF 
area of plane
The area of one atom is R2. Fractions of the atom can be summed to get whole fractions,
or fractional areas of an atom, depending on the plane of interest.

Example
Consider the BCC unit cell, and the plane (010).

 There area occupied by atoms centered on the plane is 4 x ¼ of an atom = 1 atom on the
plane (equivalent area = R2)
 The area of the plane is a2 (light red area), so the fraction is R2/ a2
 In BCC we know that 4R = √3a, so
PPF = R2/ a2 = R2/ (16R2/3) = 3/16 = 0.589

Now consider ‘close packed’ planes in BCC. There are no planes in which the atoms all have 6
nearest neighbours in the plane like in FCC; however, the plane joining cube edges diagonally
through the cube has 4 nearest neighbours and is the usual plane for slip. The family of (110)
planes:

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It’s more difficult to generate slip (plastic deformation) with no close packed plane and we need
thermal activation (i.e. some extra energy from thermal vibrations) for plastic deformation in
BCC crystals. Hence, there is a ductile-to-brittle transition as we lower the temperature in
BCC (recall the Charpy test). Since there is less thermal activation energy at lower T’s, slip is
more difficult and as the T is lowered eventually the increased stress produces cleavage!

Exercise: Show that the planar packing factor (PPF) for close packed planes is over 90%

4.15 Crystal Imperfections

Crystal imperfections (vacancies, impurity atoms either substitutional or interstitial and dislo-
cations) control diffusion and plasticity in the crystal (among other properties). Defects limit
the application of materials, and cause deviations from theoretical strength. Defects are
named by their dimensionality, point, line, interface, volume. Defects have energy associ-
ated with them, and in order to reduce total energy, the elimination of defects usually
occurs first (e.g., under heat grains will grow to reduce grain boundaries).

Point Defects
Vacancies, self interstitials, and solute atoms are called point defects because the
crystal disturbance is at a single point.

Vacancies
A vacancy is simply a vacant lattice site (empty site)

Vacancies occurs spontaneously at all T>0K. (because they increases entropy of mixing
(which enters free energy as the TS term in G=H-TS). Up to the point where the free
energy is minimized, vacancies occur spontaneously.

The number of vacancies (Nv) increases exponentially with T according to:

Nv   Qv 
( fraction of vacancies )  exp  
Nt  RT 
where Qv is the activation energy of formation of one mole of vacancies, R is the gas
constant and T is in Kelvin. Nt is the total number of lattice sites.

See Example Problem 4.1 in Callister.

The maximum fraction of vacancies in the solid occurs at the melting point (a homologous T of
1 : T/Tm) and is equivalent to 1 or 2 vacant sites in a total number of 104; the number falls rapid-
ly (exponentially) with T, e.g. to about 2 in 1010 at 300ºC for Ag.

There is a strain energy field centered on the vacancy because of the missing and strained
bonds.

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Chapter 4: Structure

Self-interstials an atom from

the lattice that is not on a lattice
point (i.e., it is in the empty
space (interstitial space) that
atoms don’t normally occupy in
the lattice. Lattice atoms do not
fit so easily into interstitial
space, and thus require addi-
tional energy to move off a lat-
tice point, so self-interstitals do
not often form spontaneously).

Solute Atoms A different type of atom (solute) dissolved in the crystal lattice (solvent). A solu-
tion is formed, but is a solid solution.

There are two kinds of solid solutions:

 substitutional - the atom replaces the solute on the lattice sites (occurs when the atoms
are of similar size , <15% difference in atomic radii, and similar valence to the host or sol-
vent atom). Depending on the size difference between solute and solvent atoms there will
be some strain energy associated with stretched bonds.

Nickel in gold (white gold) is an example of a substitutional solid solution.

 interstitial- the small atom (like H or C) goes in the spaces between the atoms in the lattice,
(solute size < 80% solvent size)

Similarly to vacancies there is a strain field near the solute because the nearest-neighbour dis-
tances are distorted – the atoms are either forced apart because the solute is either larger
or drawn together if the solute is smaller than the substitutional site.

Carbon in iron (plain carbon steel) is a classic example of an interstitial solute.

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Composition can be in weight or atomic percent (wt% (Ci), at% (Ci) respectively) and gives
information about concentrations of different components of an alloy. Ai is atomic
weight.

Atomic Vibrations
Atoms are vibrating about their lattice positions at the Debye frequency (~1013 Hz).
The amplitude of the vibration is proportional to kT where k is Boltzmann’s constant. As the
T goes up, the amplitude of the vibration increases.
It is this extra energy of the vibrating of atoms that is responsible for thermal activation i.e. it
is a source of extra energy to make things happen.

Line Defects in Metal Crystals (Dislocations)

Figure showing edge dislocation and how its glide causes slip.

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Chapter 4: Structure

The edge dislocation is a defect that occurs where a half-plane of atoms ends inside the crystal.
(There are other related types of dislocations such as screw and mixed, but here we just
consider edge dislocations)
Close to the dislocation line (along the end of the extra half plane), the atom positions are dis-
torted so there is a strain field (like stretched springs). Compression on the top, tension on
the bottom - the stored mechanical strain energy gives dislocations energy.
The motion of these dislocations produces slip (plastic deformation) so they’re important. Dislo-
cations are always present in significant numbers in industrial metals.
Significant numbers of additional dislocations are created during deformation and these can be
annealed out if the T is high enough as we discussed with creep.
Dislocations are reported as the dislocation density which is the line length in a unit volume.
(e.g., cm/cm3 which is then 1/cm2; cm-2). Typical dislocation densities in undeformed metals
are on the order of 107 cm-2 and can go as high as 1011cm-2 (which is 10 million kilometres of
dislocations in one cm3!)
We indirectly measure the dislocation density by a metal’s electrical resistivity; dislocations af-
fect the atomic packing order, which in turn results in scattering of electrons (high disloca-
tion density = high resisitivity).

Relation between dislocations and crystal structure

Dislocations move in close packed directions on close packed planes (or the
closest packed planes a crystal has) to cause plastic deformation.

The close packed directions and planes make up a slip system. Different crystal
structures then have different slip systems. We will discuss this in much more
detail in Chapter 6.

Interfacial Defects

The grain boundary is an area between two grains (crystals of different orientation)
where the atoms don’t fit perfectly into either grain and hence have higher energy. It
is narrow (2-3 atoms or 0.5 nm) and its properties are important to such phenomena as
grain boundary strengthening, vacancy formation and nucleation of phase changes.

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Volume defects are defects that have three-dimensionality to them such as voids (which are
an accumulation of atomic vacancies).

There are other defects associated with materials that will affect behaviour, such as porosity
(gas bubbles), cracks, impurities, inclusions etc., however the distinction is that such
other defects are not crystallographic imperfections.

4.16 Microscopy of materials at the small scale (especially for defects, impurities,
morphology, crystallography)

Microscopy. In optical microscopy the resolution is about the wavelength of the light
used - typically about 0.5 µm. Necessary to prepare a flat surface to a very good
(mirror-like) finish and to polish to remove scratches larger than 0.5 µm and then to
etch to produce contrast (the etchant grooves the grain boundary for example). To get
higher resolution, use transmission electron microscopy (TEM) the wavelength of the
electrons can be made smaller than 10-10 m.
SEM (scanning electron microscopy).
Like a television picture but at very high magnification, an electron beam is scanned
across the surface in a raster pattern and the electronic feedback from the sam-
ple is used to produce an image in a cathode ray tube scanning the same raster
pattern (like a closed circuit TV picture.
Because we can focus the electron beam into a very small region, we can obtain up
to 15 X more resolution than is possible in optical microscopy and also very
good depth of focus (about 100 X better) so we can look at rough surfaces e.g.
fracture.
It is also possible to do an analysis of the elements present under the electron
beam (volume of a micron cubed) by analyzing the X-rays given off by the at-
oms under the electron bombardment. Very useful to see the composition at
the different features. Widely used instrument.
TEM (transmission electron microscopy) The electrons pass through a foil of the sam-
ple and can be focused with magnetic lenses to form an image. The foil must be thin

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Chapter 4: Structure

and requires some skill to prepare. You can resolve dislocations and even atoms in
this microscope, very important in research.

Optical micrograph SEM micrograph TEM micrograph

Notice the scale bars!

4.17 X-ray diffraction is a technique used to determine crystal structure and inter-
planar spacing. X-ray diffraction is a scanning technique that produces a pattern of
scattered x-ray intensity as a function of incidence angle. Certain crystallographic
orientations will produce constructive or destructive inference.

Bragg’s law describes the interaction of x-rays and crystal lattices:

n  2d hkl sin 
where: n = integer number (1, 2, 3, etc.) related to the multiple of wavelengths
and plane of scattering. dhkl = interplanar spacing of plane (hkl)  = angle of incidence
diffraction angle).
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A diffractometer is used to collect the X-ray diffraction pattern, as seen below. Notice
that various (hkl) indices for planes are noted by the different peaks - each set of
crystallographic planes which contributes to the constructive interference of the x-
rays generates a peak at a specific value based on the interplanar spacing of the
(hkl).

Source: W.D. Callister

X-ray diffraction is a useful materials characterization tool, and can aid in determining
which materials are present in a specimen (since each crystal of certain composition
and structure has its own X-ray diffraction pattern, or fingerprint). X-ray diffraction can
also tell if a material is amorphous, since amorphous materials do not yield sharp in-
dividual peaks from crystallographic planes, but a broad hump corresponding to the
short range order in the structure (as seen below in the as received condition).

The x-ray diffraction patterns at left are from

the heat treatment of a bioactive glass (used
in the body to promote the growth of bone
tissue). The “as received” condition shows
that the glass was amorphous—no sharp
peaks exist in the pattern. The patterns pro-
gress vertically for different times at which the
glass was heated in a high temperature fur-
nace to crystallize the glass (devitrify the
glass T>700°C). Because the structure of the
as received glass was metastable (higher
energy) the thermal energy available at high
temperature permitted for atomic motion and
reorganization of the structure into a more
stable crystalline form, which then diffracted x
-rays from the crystallographic planes. Even-
tually the glass turned into a new phase
called combeite, the crystalline form of the
glass. The dashed lines and arrows show the
peak locations of the combeite phase in order
to show the progression from glass to crystal.

Source: S. Kashyap, MSc Thesis, University

of Alberta, 2010.

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