ES10: Intro to Material Science

Andrew Rosen

April 23, 2013

Contents
1 Introduction 3
1.1 Types of Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

1.2 Processes and Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

2 Atomic Structure and Interatomic Bonding 3

2.1 Basics of the Periodic Table . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

2.2 Electrons in Atoms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3

2.3 Bonding Forces and Energies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

2.4 Bonding . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3 Structures of Metals and Ceramics 4

3.1 Metallic Crystal Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3.1.1 Properties . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4

3.1.2 Terminology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.1.3 Atomic Packing Factor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.1.4 Simple Cubic (SC) Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.1.5 The Body-Centered Cubic (BCC) Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . 5

3.1.6 The Face-Centered Cubic (FCC) Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

3.1.7 The Hexagonal Close-Packed (HCP) Crystal Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

3.2 Density Computations - Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6

3.3 Ceramic Crystal Structure and Density . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.4 Carbon, Polymorphism, and Allotropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.5 Crystallographic Points, Directions, and Planes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.5.1 Miller Indices for Points and Vectors . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.5.2 Miller Indices for Planes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7

3.6 Linear and Planar Densities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

3.7 X-Ray Diraction: Determination of Crystal Structures . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

4 Polymer Structures 8
4.1 Degree of Polymerization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8

4.2 Molecular Structure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4.3 Tacticity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4.4 Thermal Behavior . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4.4.1 Thermoplastics - Think of Plastic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4.4.2 Thermosetting - Think of Proteins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4.5 Copolymers . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9

4.6 Crystallinity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

1
5 Imperfections in Solids 10
5.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

5.2 Point Defects in Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 10

5.3 Composition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

5.4 Point Defects in Ceramics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 11

5.5 Interfacial Defects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

5.6 Miscellaneous Imperfections . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

6 Diusion 12
6.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12

6.2 Steady-State Diusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

6.3 Nonsteady-State Diusion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

7 Mechanical Properties 13
7.1 Concepts of Stress and Strain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13

7.2 Stress-Strain Behavior and Elastic Properties of Materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

7.3 Mechanical Behavior Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

7.4 True Stress and Strain . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

8 Deformation and Strengthening Mechanisms 14

8.1 Dislocations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14

8.2 Mechanisms of Strengthening in Metals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

9 Phase Diagrams 15
9.1 Denitions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15

9.2 Binary Isomorphous System . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

9.3 Binary Eutectic Systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

10 Thermal Properties 16
10.1 Mathematics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 16

10.2 Trends . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 17

11 Electrical Properties 17

12 Optical Properties 18

2
1 Introduction
1.1 Types of Materials
 Metals are strong, ductile, have high thermal/electrical conductivity, are opaque, and are reective

 Polymers/plastics have secondary bonding, are soft, ductile, low strength, have low density, are thermal/electrical
insulators, and are optically translucent or transparent

 Ceramics have mostly ionic bonding. They are brittle, glassy, elastic, and insulators

 Semiconductors have covalent bonding and have electrical properties that are between conductors and insulators

 A composite consists of more than one material type

 Biomaterials have covalent and hydrogen bonding, ionic interactions, and hydrophobic interactions. They are exible,
hydrophilic, programmable, smart, and selective

 Nanomaterials have properties governed by size and also have high surface-to-volume ratios

1.2 Processes and Properties

 Adding impurity atoms to a metal, such as copper, can increase electrical resistivity

• Deformation can also cause increases resistivity

 Optical transmittance is dependent on material structure, such as single crystal vs. polycrystal and degree of porosity

• A single crystal of aluminum oxide will be transparent, a polycrystal with no porosity will be translucent, and a
polycrystal with some porosity will be opaque

 Stress and saltwater can cause deteriorative cracks

• Heat treatment slows crack speed in salt water

2 Atomic Structure and Interatomic Bonding

2.1 Basics of the Periodic Table
 The mass number of an atom is always a whole number (protons and neutrons)

 The atomic weight is a weighted average of the mass numbers of the isotopes of the given element

2.2 Electrons in Atoms

 The principal quantum number, n, denes the energy of an orbital and average distance of an electron from the nucleus
• Orbitals with the same n value form a shell

• n≥1
∗ Sometimes shells are designated with letters where n = 1 = K , n = 2 = L, etc.

 The subsidary number, l, signies the subshell and its shape

• l = 0 to n − 1
∗ The s orbital corresponds to l = 0, the p orbital for l = 1, the d orbital for l = 2, the f orbital for l = 3, etc.

 The magnetic quantum number, ml , describes the number of energy states for the orbital

• −l ≤ ml ≤ l
 The spin quantum number, ms , describes the spin moment of the electrons

1 1
• ms = + or −
2 2

3
2.3 Bonding Forces and Energies
 The bonding energy is the energy that is required to separate two atoms to an innite separation

 To calculate the attractive Coulombic force between charges

1 where Z1 and Z2 are the valences of the ions,

1 q1 q2 e2 Z1 Z2
FA = 2
= k0
4π0 r r2

• Note that e = 1.602 × 10−19 C

 To calculate the repulsive force ,

2
−bn
FR =
rn+1
 Energy and force are related as, ˆ ˆ
A B
Enet = FA dr + FR dr = − + n
r r

• Here, A = k0 e2 Z1 Z2 and B is found via an empirical plot

 In a plot of energy versus distance, the minimum is known as the equilibrium distance

• The magnitude of energy is the bonding energy

• Dense, ordered molecules with higher melting point in temperature have higher bonding energies and lower po-
tential energies; therefore, they are more stable

2.4 Bonding
 The percent ionic character of a bond between elements A and B is the following where X refers to the electronegativity
of an element ,
3
 h i
2
%IC = 1 − exp −(0.25) (XA − XB ) · 100%

 Metallic bonding and ionic bonding is non-directional while covalent bonding and secondary bonding are directional

 In order of increasing intermolecular force strength: uctuating induced dipole < polar molecule induced dipole <
hydrogen bonding (permanent dipole moment)

3 Structures of Metals and Ceramics

3.1 Metallic Crystal Structures
3.1.1 Properties
 Densely packed due to:

• Only one element is present, so all atomic radii are identical

• Metallic bonding is not directional
• Nearest neighbor distances are small and thus lower bonding energy
• Electron cloud shields cores from one another

 Metals have the simplest crystal structures

1 k = 8.99 × 109 N m2 /C 2
0
2 n ≈ 9 for ionic constant
3 This formula does not need to be memorized

4
3.1.2 Terminology
 A crystalline material has atoms arranged in a periodic array over large atomic distances

• All metals, many ceramics, and some polymers are crystalline

 Noncrystalline amorphous materials have no periodic packing

• This occurs for complex structures and under rapid cooling conditions

 Unit cells are small repeating entities of a crystalline material

3.1.3 Atomic Packing Factor

 The atomic packing factor is the following:

4 3
Volume of atoms in a unit cell 3 πR VS
APF= =N · =
Total unit cell volume a3 VC

3.1.4 Simple Cubic (SC) Structure

 There are N =1 atoms in an SC unit cell with R = 0.5a and coordination number of 6

4 3
1 · π (0.5a) 4
AP F = 3 = π · 0.53 ≈ 0.52
a3 3

3.1.5 The Body-Centered Cubic (BCC) Crystal Structure

 The BCC unit cell looks like the following:

 This unit cell thus follows √

4R = 3a

 Also, N =2 with a coordination number of 8 and an APF of 0.68

√ !3
4 3a
2· π √
3 4 8 3 3
AP F = = π 3 ≈ 0.68
a3 3 4

5
3.1.6 The Face-Centered Cubic (FCC) Crystal Structure
 The FCC unit cell is cubic with atoms located at each of the corners and the centers of all faces

 The cube length, a, and atomic radius, R, are related by,

√
4R = 2a
• This is√true because the diagonal of the unit cell face is 4R, and since it's an isosceles triangle, the ratio is
a:a: 2a

 N = 4 for FCC crystals (six face atoms and eight corner atoms) and has a coordination number of 12
√ !3
4 2a
4· π √
3 4 16 2 2
AP F = = π 3 ≈ 0.74
a3 3 4

3.1.7 The Hexagonal Close-Packed (HCP) Crystal Structure

 HCP crystal is not cubic:

 For HCP, N =6 with a coordination number of 12 and an APF of 0.74 just like FCC where 2R = a
√
2
√ 3 3 2
VHCP = 6R c 3 = a c
2

3.2 Density Computations - Metals

 Metals are dense because they have close packing due to metallic bonding and large atomic masses

 Ceramics have less dense packing since they are lighter and are made of covalent bonding

 Polymers have poor packing and use even lighter hydrocarbon elements

 Composites have intermediate densities

 The theoretical density of a metallic solid, ρ, is given by the following equation where n is the number of atoms
associated with each unit cell, M is the atomic weight, VC is the volume of the cell, and NA is Avogadro's Constant:
nM
ρ=
V C NA

 Since VC usually equals a3 ,

nM
ρ=
a3 NA

6
3.3 Ceramic Crystal Structure and Density
 For ceramics with ionic character, the magnitude of the electrical charge on each component ion and the relative size
of the ions play a role in determining the structure

• The charge indicates the ratio of ions since the crystal must be neutral
• The number of oppositely charged ion neighbors is maximized
rcation
 Coordination number increases with
ranion
 The density can be calculated as follows where the new variables are n0 (number of formula units within the unit cell),
AC (atomic weights of cations in formula unit), AA (atomic weights of anions in formula unit):

n 0 ( AC + AA )
P P
ρ=
VC NA
 In oxide structures, oxygen anions are larger than metal cations, the oxygen anions are closely packed (typically FCC),
and cations t into interstitial sites among the oxygen anions

3.4 Carbon, Polymorphism, and Allotropy

 The group IVA elements form structures known as diamond cubic crystals (e.g. carbon diamond)

 Graphite is more stable than diamond and is composed of layered hexagonal carbons

 Polymorphism is when a metal or nonmetal may have more than one crystal structure

• This is called allotropy for elemental solids

3.5 Crystallographic Points, Directions, and Planes

3.5.1 Miller Indices for Points and Vectors
 Crystallographic directions are vectors that pass through the origin. The length of the projection on each axis is
measured in terms of the unit cell dimensions a, b, and c. The three values are scaled to create the smallest integer
values. Then, the three indices are enclosed in a square bracket without commas - [uvw]
• A negative index will have a bar over the value
• Families of directions are expressed in angled brackets, < >
∗ There is the same packing density along a family of directions
∗ To nd dierent components of the family, one can switch the order of the three numbers and/or the sign

 In simpler terms, to nd the indices for a direction (vector), nd ∆x, ∆y , and ∆z , and then scale them to the nearest
integer

3.5.2 Miller Indices for Planes

1. If the plane passes through the origin, create a new origin

2. Read the intercepts of the plane with axes in terms of x, y , and z

(a) If it always intercepts, the value is ∞ (reciprocal is 0)
(b) A plane that parallels an axis may be considered to have ∞ intercept, too

3. Take the reciprocals of the intercepts

4. Reduce to smallest integer values

5. Enclose in parentheses without commas

(a) Families of planes are written with squiggly brackets, { }

i. There is the same packing density along a family of planes

(b) To describe a plane and a vector, use the format of [a b c] ⊥ (h j k)

7
3.6 Linear and Planar Densities
 Linear density is given by,

length of atoms centered on direction vector

LD = × 100%
length of direction vector
√
a 3 √
2R 3
• For instance, for BCC along [1 0 0], LD = = 2 = ≈ 86.6%
a a 2
 The planar density is given by,

area of atoms centered on a plane

PD = × 100%
area of plane

(1 1 0),
• For instance, for FCC along the plane goes through 1 whole and 4-quarters of atoms. Therefore , PD
4 =
√ !2
a 2
2π
4
2


2 πR
√ = √ ≈ 55.5%
a·a 2 a2 2

3.7 X-Ray Diraction: Determination of Crystal Structures

 The condition for diraction (Bragg's Law) is,
nλ = 2dhkl sin θ
• n is the order of reection (an integer)

 The diraction angle is given as,

Diraction Angle = 2θ
 The magnitude of the distance between two adjacent and parallel planes of atoms for a cubic symmetry crystal is,
a
dhkl = √
h2 + k 2 + l2
 To get a peak from FCC, the miller indices must be all odd or all even

 To get a peak from BCC, h+k+l must be even

 Larger miller indices indicate shorter distances between planes for the same a value, so then it corresponds bigger angle

4 Polymer Structures
4.1 Degree of Polymerization
 Polymers are made up of long chains of molecules of repeating chemical structure

 The amount of repeating units, n, is known as the degree of polymerization (does not have to be an integer)

Molar weight of polymer

n=
Molar weight of substituent

 Polymorphism is when two or more crystal structures are possible for a material of given composition

 The three steps of addition polymerization are initiation, propagation, and termination

 The molecular weight of polymers is an average can be found via two methods
P
• Number-average: M̄n = x i Mi (where xi is the fraction of the total number of chains within the corresponding
size range)
P
• Weight-average: M̄w = w i Mi (where wi is the weight fraction of molecules within the same size range)

• The value of Mi is the mean molecular weight within the size range
4 The area of the plane is simply base times height

8
4.2 Molecular Structure
 Linear polymers have repeat units joined together end to end in a single chain

 Branched polymers have side-branch chains connected to the main ones

 Crosslinked polymers have adjacent linear chains that are joined to one another at various positions by covalent bonds

 Network polymers are three-dimensional networks of multifunctional monomers

4.3 Tacticity
 Isotactic polymers have all the substituents located on the same side of the macromolecular backbone

 Syndiotactic polymers have alternating positions (up/down) along the chain

 Atactic polymers have substituents placed randomly along the chain

4.4 Thermal Behavior

4.4.1 Thermoplastics - Think of Plastic
 Soften when heated and harden when cooled

 Easily reshape and are recyclable due to presence of long chains that limits crosslinks

 Weak attractive forces between chains are broken by warming

 When cooled the weak forces reform the structure into a new shape

 Are linear and branched structured

4.4.2 Thermosetting - Think of Proteins

 Decompose when heated and thus cannot be reformed or recycled

 Extensive crosslinking due to covalent bonds induce decomposition upon heating and renders them brittle

 Bonds prevent chains moving relative to each other

 Are network polymers with cross-links

 Fast cooling yields a greater volume; slow cooling yields a smaller volume that is more rigid and dense

4.5 Copolymers
 Pure polymers are known as homopolymers

 Copolymers have dierent repeating units

• PE−C−PVC would be a copolymer (note that the C stands for copolymer and is not a carbon atom)

 Copolymers come in dierent types:

• Random copolymer: No pattern associated with copolymer (e.g. AABABBABAB)

• Alternating copolymer: Directly alternating sequence of units (e.g. ABABABABA)
∗ Therefore, alternating copolymers have chain fractions of 0.5 for each repeat unit type (assuming 2 repeat
types)

• Block copolymer: One block of identical repeating units followed by a block of the other unit (e.g. AAAABBB-
BAAAA)

• Graft copolymer: Where homopolymer side branches of one type are grafted onto homopolymer main chains that
are composed of a dierent repeating unit

9
4.6 Crystallinity
 Crystalline regions of polymers have chain folded structures

 Low density polymers have higher optical transparency while high density polymers are opaque

 Crystallized structures have higher indices of refraction than amorphous materials

 The degree of crystallinity can be given by the following equation where ρc is the density of a perfectly crystalline
polymer, ρa is the density of the totally amorphous polymer, and ρs is the density of the sample polymer

ρc (ρs − ρa )
% Crystallinity = × 100%
ρs (ρc − ρa )

• Heat treating increases % crystallinity

• Recall that number of repeat units per unit cell is,

ρVC NA
n=
A
 Electrical insulators, mechanically light, opaque or transparent, chemically inert, and are solid at room temperature

 The tendency of a polymer to crystallize decreases with increasing molecular weight because longer chains make it more
dicult to align adjacent chains in the correct atomic crystal array

5 Imperfections in Solids
5.1 Introduction
 Point defects are defects in one or two atomic positions

• A vacancy has an atom missing

• A self-interstitial site has an atom crowded in an interstitial site, which is a small void space that is unoccupied
under normal conditions

• Interstitials don't usually exist for anions due to their large size

 Line defects occur when some atoms of a lattice are misaligned and produce permanent (plastic) deformation

 Planar defects occur where the crystallographic direction of the lattice abruptly changes

 Bulk defects have voids and/or impurities that cluster together to form small regions of a dierent phase

 Solidication is the result of casting molten material where nuclei form and then grow to form crystals

5.2 Point Defects in Metals

 To nd the number of vacancies where N is the number of atomic sites and Qv is the energy required to form a vacancy,

 
Nv Qv
= exp −
N kT

NA ρ
N=
A

 For Frenkel and Schottky defects (see 5.3), the above equation uses 2kT in the denominator of the exponential instead
of kT

10
5.3 Composition
 Weight percent is dened as,
m1
C1 = × 100%
m1 + m2
 Atom percent is dened as,
nm1
C10 = × 100%
nm1 + nm2
 Converting weight percent to atom percent,

C 1 A1
C10 = × 100%
C1 A2 + C2 A1
 Converting from atom percent to weight percent,

C10 A1
C1 = × 100%
C10 A1+ C20 A2
 Converting weight percent to mass per unit volume,
 
00  C1 
C1 = 
 C1

C2 
+
ρ1 ρ2
 Converting weight percent to density,
100
ρave =
C1 C2
+
ρ1 ρ2
 Remember that for an alloy,
nAave
ρave =
VC NA
 Converting weight percent to atomic weight,
100
Aave =
C1 C2
+
A1 A2
 Converting weight percent to number of atoms per unit volume,

NA C 1
N1 =
C 1 A1 C2 A1
+
ρ1 ρ2
 Converting weight percent to number of atoms per unit volume,

100
C1 =
NA ρ2 ρ2
1+ −
N1 A1 ρ1

5.4 Point Defects in Ceramics

 Schottky defects consist of cation-anion vacancies

• Each defect must be electroneutral. So, if we have K2 O, each defect would have one O−
2 and two K+ vacancies

 Frenkel defects consist of a cation vacancy and cation interstitial pairs

 There are two types of impurities:

• Substitutional impurities have impurity atoms substituting the host atoms

∗ Needs similar atomic size (within ±15%), same crystal structure, similar electronegativities, and higher va-
lencies are favored

• Interstitial impurities have atoms lling the voids or interstices among the host atoms
∗ Therefore, the impurity atoms must have small atomic radii

11
5.5 Interfacial Defects
 There is the external surface boundary, which is a higher-energy state than atoms at interior positions since the surface
atoms are not bonded to the maximum number of neighbors

• This energy is termed surface energy, and it is stabilized by minimizing surface area

 A grain boundary separates two regions of a crystal that have dierent crystallographic orientations

• The magnitude of the grain boundary energy is directly related to the angle of misorientation
• These areas are more chemically reactive due to higher energies

 A twin boundary is a reection of atom positions across a plane

5.6 Miscellaneous Imperfections

 Dislocation: a linear or 1D defect around which some of the atoms are misaligned. It's dened by a dislocation line
and Burger's vector

→
−
 Burgers vector ( b ): The measure of lattice distortion

• The Burgers vector and dislocation line are perpendicular for edge dislocations, parallel for screw, and neither
parallel nor perpendicular for mixed

→
−
 Edge dislocation: an extra half-plane of atoms inserted into a crystal structure where b is ⊥ to the dislocation line

→
−
 Screw dislocation: a spiral planar ramp resulting from shear deformation where b is k to the dislocation line

 Mixed dislocation: a combination of screw and edge dislocations

 Interfacial defects (2D):

• External surfaces: surface atoms are not bonded to the maximum number of nearest neighbors, in a higher-energy
state than in the interior

∗ Materials minimize total surface area to minimize surface energy

• Grain boundary: the boundary separating two small grains or crystals having dierent crystallographic orientations
in a polycrystalline material

∗ Grain boundary energy will always be less than the surface energy since grain boundaries have some atoms
bonding across the boundary whereas the surface does not have this

 The ASTM grain size can be found via the following formula where n is grain sizes and N is the number of grains per
square inch at a magnication of 100x

N100 = 2n−1

 To convert NM to N100 , use

 2
Magnication
N100 = NM
100

6 Diusion
6.1 Introduction
 Interdiusion is when atoms tend to migrate from regions of high concentration to low concentration

 Self-diusion is diusion within an elemental solid where atoms migrate, but these atoms are all the same type

12
6.2 Steady-State Diusion
 Rate of mass transfer uses the variable J to indicate the diusion ux where M is mass, A is area, and t is time,

M
J=
At

 The concentration gradient is,

dC ∆C CB − CA
≈ =
dx ∆x XB − XA
 Fick's First Law states the following where D is the diusion coecient and the derivative is the concentration gradient,
dC
J = −D
dx
 
Qd
D = D0 exp −
RT

6.3 Nonsteady-State Diusion

 Non-steady state diusion is time-variant

 Fick's Second Law states

d2 C
 
dC
=D
dt dx2
 The following assumptions can be made to simplify the solution set:

• Before diusion, the diusing solute atoms are uniformly distributed

• The value of x at the surface is zero and increases with distance into the solid

• The time is taken to be zero the instant before the diusion begins
 
Cx − C0 x
= 1 − erf √
Cs − C0 2 Dt

 If it is desired to achieve some specic concentration of solute in an alloy (to produce the same concentration),

x2
= Constant
Dt
x2
• At constant temperature, this becomes, = Constant
t
• At constant composition, this becomes, Dt = Constant

7 Mechanical Properties
7.1 Concepts of Stress and Strain
 Engineering Stress is dened as,
F
σ=
A0
 Engineering Strain is dened as,
∆L
=
L0
 Sheer strength is given the same denition of Engineering Stress,

F
τ=
A0

13
7.2 Stress-Strain Behavior and Elastic Properties of Materials
 Stress and strain are proportional through the following equation where E is the modulus of elasticity (Young's Mod-
ulus),
σ = E

 Poisson's Ratio is dened as,

x y ∆d/d0
ν=− =− =
z z σ/E

• This is only valid for isotropic material

 Sheer strength, τ, and sheer strain, γ, are related via the following equation where G is the sheer modulus,

τ = Gγ

γ = tan θ

7.3 Mechanical Behavior Models

 From a stress-strain curve you can get the following information:

• Young's Modulus: Find slope of linear portion of curve (elastic range)

• σP (proportional stress limit): the σ value at the end of the linear curve

• σY (yield stress): Find the percent dierence in  at σ = 0 (x-intercept) extrapolating using the non-linear curve

• T.S. (tensile strength) is the maximum of the curve

• Toughness is the energy absorbed before fracture, and can be found from the area under the entire curve
• Resilience is the capacity of material to absorb energy when it deforms elastically and can be found from the area
under the linear portion of the curve

• Ductility can be found from elongation percent, which is dened as

lf − l0
× 100%
l0

7.4 True Stress and Strain

 True Strain is dened,
 
lf
T = ln
l0

 True Stress is dened as,

F
σT =
Ai
 Hardness is the resistance to localized plastic deformation

 There are two main hardness tests, and they are the Rockwell hardness test and the Brinell hardness test

8 Deformation and Strengthening Mechanisms

8.1 Dislocations
 Metals have the highest degree of dislocation motion due to non-directional bonding and close-packed directions for slip

 Covalent ceramics have a lower degree of motion due to directional bonding

 Ionic ceramics have the lowest degree of motion due to the need to avoid neighbors of identical electric charge

14
  Slip (plastic deformation) is when an edge dislocation slides over an adjacent plane

• These dislocations move along slip lines in a slip direction (same as Burgers vector) that is perpendicular to the
dislocation line

 Edge dislocations have an extra half-plane of atoms

 When two edge dislocations become aligned, a planar region of vacancies will exist between the dislocations

 For edge dislocations, dislocation line motion and direction of applied sheer stress are parallel. These directions are
perpendicular for screw dislocations and neither parallel nor perpendicular for mixed dislocations

 Yield stress increases as ρd increases

8.2 Mechanisms of Strengthening in Metals

 Barrier strength increases with increasing angle of misorientation

 Smaller grain sizes allow more barriers to slip but also create stronger/tougher materials since there is higher density
of atoms to prevent dislocations

• Small-angle grain boundaries are not as eective in interfering with the slip process as are high-angle grain
boundaries because there is not as much crystallographic misalignment in the grain boundary region for small-
angle, and, therefore, not as much change in slip direction

 The Hall-Petch equation states,

σyield = σ0 + ky d−1/2
 Twin boundaries will block slips and increase strength

 Impurity atoms distort the lattice and generate lattice strains that act as barriers to dislocation motion

 A small impurity atom will cause tensile strain while a larger one will cause compressive strain

• To reduce strains, surrounding atoms will surround a tensile lattice strain while surrounding atoms will repel
from compressive strains

 Strain hardening is when a ductile metal becomes harder/stronger as it plastically deforms (also known as cold working)

• Strain hardening decreases the ductility of the metal

• Strain hardening occurs because it increases the number of dislocations, but, simultaneously, this increased dislo-
cation density causes more resistance to dislocation motion

 The percent cold work is given by ,

5
∆A
%CW = − × 100%
A0

9 Phase Diagrams
9.1 Denitions
 The solubility limit is the maximum concentration for which only a single solution exists

 The microstructure is given by the number of phases, the proportions of substances, and how the substances are
distributed

 A solution is isomorphous if there is complete solubility and mixes evenly

 It is possible for two screw dislocations of opposite sign to annihilate one another if their dislocation lines are parallel

 For equilibrium to be reached, the free energy of the system must be at a minimum at the specic temperature, pressure,
and composition

5 Note: ∆ indicates nal minus initial. Since the book uses ∆A = A0 − Af (which is not standard), I have added a negative sign to this and a
few other equations

15
9.2 Binary Isomorphous System
 To nd the phases present, simply read o where the location of the data point is on the diagram

 To nd the phase compositions, construct a horizontal tie line

 To nd the phase mass fractions, utilize the lever rule

• Construct a tie line and locate alloy composition

• Take the length of the tie line from the overall composition to the other phase boundary and divide it by the total
tie length to nd the fraction of one phase

• The result is mass fraction when the x-axis is in weight percent

Wα
100
 To convert from mass fraction to volume fraction, Vα = Wα
ρα
Wβ
where ρα = C1(α) C2(α)
for components 1 and 2
ρα + ρβ ρ1 + ρ2

9.3 Binary Eutectic Systems

 The eutectic reaction is dened as L (CE )
α (CαE ) + β (CβE ) where E is the invariant point

 The phases present are the areas that the tie line touches

 Fast cooling yields cored structures while slow cooling yields equilibrium structures

 For composition CE , there is eutectic microstructure (also known as lamellar structure) with alternating layers of α
and β phases

• This is because atomic diusion occurs and the layering is the minimum diusion path length

 To nd the mass fraction of a eutectic component (let's say α), do WEα = Wα − Wα0 where primary α is found from a
Ceut − C0
tie line drawn from Cα to the eutectic point such that Wα 0 =
Ceut − Cα
 To nd the mass fraction of eutectic microconstituents, create a tie line from Cα to the eutectic point to Cα such that
C0 − Cα
We =
Ceut − Cα
 Eutectoid: One solid converts into two other solids

 Perictectic: A liquid and solid converts to a second solid

 Congruent phase transformations have no compositional changes while incogruent ones do

 Gibbs Phase Rule States, F = C+N −P where P is number of phases, F is degrees of freedom, C is number of
components, and N is number of non-compositional variables

10 Thermal Properties
10.1 Mathematics
dQ
 Heat capacity is dened as C=
dT
• Cp is always greater than or equal to Cv

 At low temperatures, the relationship between Cv and temperature is Cv ≈ AT 3

∆l
 The linear thermal expansion coecient, αl , is given by αl ∆T =
li
• The greater the bonding energy, the deeper and more narrow the potential energy trough is such that αl will be
lower

16
 ∆V
 The volume coecient of expansion can be found via αv ∆T =
V0
dT
 Also heat transfer can be found form, q = −k where k is the thermal conductivity
dx
dQ
• It is also true that = qAt
dT
k
 The Wiedemann-Franz Law states that L=
σT
• It is based on the assumption that free electrons are responsible for both electrical and thermal conduction

∗ Therefore, it is not valid for ceramics or polymers since free electrons only provide electrical conduction in
these systems

• σ can be approximated as the inverse of electrical resistivity

 The magnitude of stress resulting from a temperature change is σ = −Eαl ∆T

∆l
• This comes from the fact that σ = E where =
l0
σf k
 The thermal shock resistance of a material is dened as TSR =
Eαl

10.2 Trends
 Above the Debye temperature, θD , C v becomes independent of temperature at a value of approximately 3R
 The Debye temperature is typically below room temperature

 Thermal conductivities are higher for crystalline than for noncrystalline ceramics because, for noncrystalline, phonon
scattering, and thus the resistance to heat transport, is much more eective due to the highly disordered and irregular
atomic structure.

 Increase in temperature and decrease in porosity will increase conductivity

• Porous materials are less conductive because gases will ll the pores, and these gases are much poorer conductors
of electricity than the actual solid is

 For ceramics, the thermal conductivity rst decreases and then increases with temperature because the initial increase
in temperature causes scattering of lattice vibrations. Then, at higher temperatures, radiant heat transfer increases
across pores

 Pure materials will have a larger conductivity than alloys because impurities cause more free electron scattering

 Linear polymers are more thermally conductive because they have a higher degree of crystallinity

 Thermal stresses are induced by temperature changes because of the gradient between surface and interior temperature

 Cooling creates tensile stress, and heating creates compressive stress

11 Electrical Properties
 Ohm's Law states that V = IR
RA
 Electrical resistivity is ρ=
l
 Conductivity is σ = ρ−1
 Higher temperature means higher resistance for metals (opposite for semi conductors and no benet for insulators due
to large band gap)

17
 • Higher impurities and %CW increase resistivity

 Conductivity is also given by σ = n|e|µe + P |e|µn

 N-type semiconductors are doped with elements which have spare electrons in outer shells

 P-type semiconductors are doped with elements that have too few electrons in their out of shells

12 Optical Properties
hc
 E = hν =
λ
c
 n≡
v
 2
n−1
 Reectivity is measured by R=
n+1
 Amorphous and pore-free polymers have little scattering and are thus transparent

 Semicrystalline polymers have scattering and are opaque with high crystallinity

18