Valence (of an atom): no.

of electrons involved in bonding Electronegativity: tendency of atom to gain electron

· Metallic bonding: electrostatic attraction between (delocalized) valence electrons & positive nuclei; high young’s modulus
· Covalent bonding: sharing of valence electrons between atoms
· Ionic bonding: donation of valence electrons, electrostatic attraction binds ions together
· van der Waals bonding: secondary bond developed between atoms & molecules due to induced or permanent dipoles
London forces: between 2 dipoles in atoms / molecules
Keeson forces: between permanently polarized (charges on opposing ends → giving net dipole moment) molecules, due to polarization of
molecules / groups of atoms
Debye forces: induced dipole interacts with molecule with permanent dipole moment
· mixed bonding: 2 or more types of bonds (above)
· Interatomic spacing: equilibrium spacing between centers of 2 atoms (= min. interatomic energy of atoms / ions)
· Binding energy: energy to separate 2 atoms from equilibrium spacing to infinite distance apart (↑ bond energy = ↑ melting point = ↑ strength)
· Modulus of elasticity: slope of stress – strain curve in elastic region
· Yield strength: level of stress, above which will result in permanent deformation
· Coefficient of thermal expansion (CTE): amount by which material dimensions change when temperature changes
A B d dF d2
Einteratomic = − + n (+): repulsive (−): attractive F= [E ] Stiffness = = [E ]
r m r dr interatomic dr dr interatomic
steep curve + deep trough = low CTE

Material Classification

Monoatomic Amorphous liquid crystal crystalline (single / poly)

atoms/ions form regular, repeated 3D pattern
No order short range order short range order + long range (for small vol. only)
poly – : many smaller crystals (grains) w/ varying
orientations in space, short range
e.g. argon, e.g. plastics, e.g. Si, GaS (single crystalline)
neon glasses
e.g. LCD polymers e.g. metals, alloys, most ceramics (polycrystalline)

Metallic glasses: quenching metals on orders of 106 K ∙ s−1

Lattice: a periodic array of points in 3D space

Unit cell: smallest group of atoms (like a molecule) that is repeated to form the entire crystal
Basis: group of atoms that make up the unit cell, but does not necessarily describe the arrangement of the atoms
Crystal systems: unique arrangement of unit cells to fill in a 3D space – cubic / tetragonal / orthorhombic / trigonal / hexagonal / monoclinic / triclinic
Bravais lattice: 14 distinct arrangements of lattice points
Lattice parameters: describe size and shape of unit cell, including the dimensions of each side and angle between sides

Specific number of lattice points define each of the unit cells. Lattice points may be shared by more than 1 unit cell. Lattice per unit cell = no. of lattice
points owned by 1 unit cell, in light of the fact that lattice points are being shared by other unit cells. A lattice point at a corner of 1 unit cell is shared
1
by 8 cells, and of each corner belongs to 1 particular cell. At each face, the face center atom is shared between 2 cells.
8
 4r
Closed packed directions: directions in unit cell along which atoms are in continuous contact (simple cubic: a0 = 2r, BCC: a0 = , FCC: a0 = 2r√2)
√3

Coordination number: no. of atoms touching particular atom / no. of nearest neighbors for the particular atom (indicates how tightly / efficiently
packed atoms are)

Close – packed structure: packing fraction is highest with identical atoms of a fixed size
c
Hexagonal close – packed (HCP) structure: special form of hexagonal structure, where = 1.633 but will deviate slightly in real metals
a

Miller index

Directions Planes
· Deforms along planes that are most tightly packed
· metals deform easier in directions where atoms are in closest contact
· Surface energy of different faces depends on particular
· magnetic properties depend on crystallographic directions
crystallographic planes
· Set up coordinate system, where each length of the unit cell is 1, and
determine coordinates of points that lie along the direction
· Identify points where plane intercepts 𝑥, 𝑦, 𝑧 axes in terms of lattice
parameters (max. length = 1). * if plane passes through origin, then the
· For each direction, calculate vector (x⃗ ⃗ z) = (x2
y y2 z2 ) −
origin must be shifted
(x1 y1 z1 )
1 1 1
· Express column vector above in lowest terms / integers. · Take reciprocal of each axis intercept, express in the form: ( )
x0 y0 z0
· Enclose numbers in [square bracket] like this: [x⃗ y
⃗ z]. Represent any
· Clear fractions but do not reduce to lowest terms / integers
negative number with a ̅̅̅̅̅
bar
· Represent any negative (−) number with a ̅̅̅̅̅
bar
· Groups of equivalent directions  directions of a form, represented
with < > bracket
1 1 1 1 1 1
* [x⃗ y
⃗ z] = 𝑘[x⃗ y
⃗ z] *( ) = −( )
x0 y0 z0 x0 y0 z0

* [x⃗ y
⃗ z] ≠ −[x⃗ y
⃗ z] 1 1 1 1 1 1
*( ) ≠ 𝑘( )
x0 y0 z0 x0 y0 z0
SPECIAL CASE: hexagonal unit cell
𝑎1 → 120° → 𝑎2 → 120° → 𝑎3 → 120° → 𝑎1
To find directions,
1. use the 3 – axis coordinate system, and find the direction vector (∆x ∆y ∆z)𝑇
2. Convert the direction vector (∆x ∆y ∆z)𝑇 into (h′ k ′ 𝑙 ′ )𝑇
2h′ −k′ 2k′ −h′ h′ +k′
3. Convert into 4 component direction vector (h k i l)𝑇 where h = ; k= ; i=− ; l = l′
3 3 3

To find planes,
1. use the 4 axis coordinate system and obtain the intersection in each of the axes
1 1 1 1
2. Miller index is given by: ( )
a1 a2 a3 c

Plane density: no. of atoms per unit area whose centers lie on the plane, i.e. no. of atoms per face ÷ area of face
4πr3 4πnr3
Packing fraction: area of atoms ÷ area of plane = volume of atoms ÷ unit cell volume = no. of atoms in unit cell (n) × vol. of unit cell = 3
𝑎0
(assumes atoms are spherical & touch immediate neighbors)
|V1 −V2 |
∆ (vol. ) =
V1

Planes of a form  groups of equivalent planes that have their particular indices due to orientation of coordinates, represented by the { } bracket

In cubic systems, a direction that has the same indices as a plane is ⟂ that plane

Close – packed planes & directions [pg. 48]

Closed – packed planes in hexagonal unit cells are the (0001) and (0002) planes of the structure  ‘basal’ planes
̅̅̅̅ stacking sequence → atoms on plane B fit into spaces created by 2 ‘A’ planes
· ABABAB…. → AB
· ABCABCABC… → ABC̅̅̅̅̅̅ stacking sequence → ?

a0
Interplanar spacing: distance between adjacent planes of atoms with the same Miller indices (cubic: dhkl = where a 0 = lattice parameter)
√h2 +k2 +l2

Interstitial Sites
There exists gaps between ‘usual’ atoms where smaller atoms may fit
Interstitial site: location between ‘normal’ atoms / ions in crystal where another (different) atom / ion is placed, and size of interstitial location is
smaller than atom / ion to be introduced

· Interstitial atom / ion radius > interstitial site radius: may enter, pushing the surrounding atoms slightly apart
· Interstitial atom / ion radius < interstitial site radius not allowed inside, due to ‘rattling’ within the site
· Interstitial atom / ion radius >> interstitial site radius: atom / ion will look for site with larger coordination number

· Cubic site: an interstitial position with coordination number =8, i.e. atom / ion touches 8 other atoms / ions
· Octahedral site: an interstitial position with coordination number = 6, i.e. atom / ion touches 6 other atoms / ions
· Tetrahedral site: an interstitial position with coordination number = 4, i.e. atom / ion touches 4 other atoms / ions

Many ionic crystals can be viewed as being generated by close – packing of larger anions → cations can then be viewed as smaller ions that fit into
interstitial sites of close – packed anions

Crystal Structure Of Ionic Materials

·Many ceramic materials contain significant ionic bonding
·Factors to be considered – ionic radii, electrical neutrality, connection between anion polyhedral, visualization of crystal structures using computers
·Connection between anion polyhedral: corner sharing, edge sharing, face sharing
·Coordination polyhedra (formed by close packing of anions) will share corners, because electrostatic repulsion between cations is reduced
considerable in corner sharing polyhedral → more stable crystal structure

Common ceramic structures:

- Fluorite: FCC with anions (−) located at all 8 tetrahedral positions, with compound form AX2 , e.g. ZrO2 and ThO2
- Perovskite: crystal structure of mineral with compound form ABO3 , oxygen anions occupy face centers & A2+ ions occupy corners & B4+ occupy
octahedral site at the cube’s center
- Corundrum: oxygen anions arranged into hexagon, aluminum cations occupy some of the available octahedral positions

Diffraction Techniques For Crystal Structure Analysis

· 2 methods: x–ray diffraction , electron diffraction
· In a diffractometer, a moving x–ray detector records the angles at which the beam is diffracted, giving a characteristic diffraction pattern
𝜆
· Bragg’s Law: sin 𝜃 =
dhkl
Imperfection
· Basic types: point , line (dislocation) , surface
Vacancy: atom / ion missing from its regular crystallographic site
Interstitial defect: point defect due to atom inserted into crystal at an unoccupied point (compression / distortion @ surrounding crystal region)
Qv
Arrhenius type behavior: nvacancy = ninitial ∙ 𝑒 −𝑅𝑇

Substitutional defect

definition: point defect due to atom being removed from lattice point and replaced with a different atom
Frenkel effect Schottky effect
· cation leaves normal lattice site and occupies interstitial site · Equal number of cations and anions missing from regular lattice sites
· creates vacancy in regular lattice structure · found in: ionic, high coordination number & anion size ≅ cation size
· found in: ionic, low coordination number & anion size >> cation size
· density remains constant

Special case: iron ion of charge (A) replacing ion of different charge (B)
When divalent charge (2 +) replaces monovalent charge (+1), another monovalent charge must be removed, which creates a vacancy

1. charge balance must be maintained so crystal has 0 net charge 2. mass is conserved 3. no. of crystallographic sites is conserved

Dislocation

definition: a line imperfection, introduced during solidification / deformation & explains deformation & strengthening in metallic materials
Edge dislocation Mixed dislocation
Screw dislocation dislocation due to addition of ‘half a plane’ of a mix of both types
atoms between any 2 planes of atoms
lattice is sheared, so part of the lattice is offset
by a bit relative to the other
‘the linear defect that forms the extra half a
plane’  represented by ‘ᴛ’

Burgers vector

Right hand rule: thumb pointing into atom

Form a 4 sided loop, where each loop has same number of unit cell lengths (𝑛)
Identify the side that cannot be closed with (𝑛) unit cell lengths.
 ⃗ ) is the vector from the starting atom to the ending atom, i.e. the vector that completes the ‘circuit’ that is drawn around the
Burgers vector (b
dislocation

⃗ ⟂ the dislocation position (dislocation vector into / out of page)

LINE: b
SCREW: ⃗b is parallel to line of dislocation

Slip: movement of dislocation, causing metallic material to deform

Slip direction: direction in which dislocation moves
Slip plane: plane formed by ‘sweep’
Etch: tiny hole created at areas where dislocations meet surface
Slip line: visible line produced at surface of material by several thousand dislocations
Slip band: collection of many slip lines, often visible

Dislocations in metals  mechanism for plastic (permanent) deformation due to slip of numerous dislocations
Dislocation density: total length of dislocation line per cubic centimeter

Schmid’s Law

F0 · HCP metals: no cross slip (parallel slip planes)

λ: angle between σ & slip direction
τplane = σ cos λ cos Ф = cos λ cos Ф · FCC metals: high ductility ; polycrystalline HCP: brittle ;
A0 Ф: angle between σ & normal to slip plane
BCC: middle ground

Surface Defects
· boundaries / planes that separate material into regions, each with same structure but different orientation
· reduce grain size  number of grains, grain boundary area ↑  dislocation moves short distance before being stopped  strength increased
1
K
· Hall Petch equation: σy = σ0 +  from table of values, write out a column of values of d−2 and use linear approximation equation
√d
· small angle grain boundary: array of dislocations causing small misorientation of crystals across surface ; caused by edge: tilt boundary // caused by
screw: tilt boundaries
· twin boundary: plane across which there is a mirror image misorientation

Diffusion
· Definition: net flux of ions, electrons, holes & molecules
· Types:

1. Self–diffusion: random movement of atoms / vacancies within pure material from 1 lattice position to another
2. Interdiffusion: diffusion of atoms in different directions, diffusion of different atoms in materials
3. Vacancy diffusion: diffusion of atoms when atom leaves regular lattice position to fill vacancy in crystal → counter flow of atoms & vacancies
4. Interstitial diffusion: diffusion of small atoms from 1 interstitial position to another, smaller atoms → diffuse faster (no vacancy needed)

Activation energy for diffusion

· diffusing atom must ‘squeeze’ through surrounding atoms to reach new location, hence requires activation energy
· substitutional diffusion requires more energy than interstitial diffusion

Rate Of Diffusion
Q dc
dc
· Fick’s 1st Law: J = −D where D → diffusion coefficient (D = D0 ∙ e−RT ) and → concentration gradient (in atoms∙ 𝑐𝑚−3 or % atom∙ 𝑐𝑚−1 )
dx dx
· Flux: no. of atoms passing through plane of unit area per unit time
· Concentration gradient shows how composition of material varies with distance

Factors Of Diffusion [Crystalline Materials]

· Type of diffusion: volume (moving through crystal) , grain boundary (diffuse along boundaries & interface) , surface (moving along material surface)
· Time elapsed: long time to produce uniform structure
· Nature of bonding & crystal structure: interstitial diffusion > vacancy / substitutional diffusion, cations have ↑ D than anions, smaller cations = faster
· Dependence on concentration of diffusing substance and composition of matrix
* main mechanisms for atomic movement: interstitial & vacancy diffusion → substitutional atoms move by vacancy mechanism
* activation energy for self – diffusion increases with melting point of metals

Use Of Diffusion In Materials Processing

· Sintering: high temperature treatment to join small particles e.g. manufacture of ceramic materials
– lattice diffusion from bulk of particles into neck region causes densification

· Powder Metallurgy: used to produce monolithic metallic parts, similar to sintering

 · Grain growth: movement of grain boundaries by diffusion to reduce grain boundary area, causes
large grains to grow at the expense of smaller grains

· Diffusion bonding: joining technique where 2 surfaces are pressed at high pressure & temperature

· Melting & Casting: important in solidification of metals & alloys –

Phase Equilibria
Phase Diagram
Definition: shows phases (states of matter) and chemical compositions at any combination of temperature & pressure

Phase properties:
- Same atomic arrangement throughout
- Same properties throughout
- Defined interface between plane & adjoining phases

X: triple point

Gibbs Phase Rule

n(deg. of freedom) = n(variables to be fixed to specify temperature & composition of phase)
2+C=F+P

C : no. of components / substances P : no. of coexisting phases F : no. of independent variables that can be changed to maintain phase
Special case: either P or T is constant → 1 + C = F + P

Solubility
Unlimited: no limit to relative composition of substances and cannot be physically separated, e.g. water & alcohol
Limited: maximum relative composition between 2 substances, e.g. salt & water

‘line’ represents solubility limit

x–axis : % weight of additive, e.g. C y–axis : temperature (T)
(max. amount of additive that can dissolve into original solution @ given T)

Conditions for unlimited solubility (Hume Rothery Rules) in an alloy / ceramic system:

∆ (atomic radii) ≤ 15% same crystal structure equal valence approx. equal electronegativity

Solid Solution Strengthening

definition: increasing strength of metallic material via formation of solid solution
this is achieved by alloying with atoms with large ∆ (atomic radii) and different % weight of alloying substance

· Binary phase diagram: phase diagram with 2 (ternary → 3) components

· Isomorphous phase diagram: phase diagram where components display unlimited solid solubility
· Liquidus temperature: temperature at which 1st solid begins to form during solidification
· Solidus temperature: temperature below which all liquid has become solidified
· Freezing range: ∆= |Tliquidus − Tsolidus | ; 2 phases (solid & liquid) coexist in this range

Isomorphous Phase Diagrams

region above closed curve (or right of it): solid phase (α)
region bounded by closed curve: coexistence of solid (α) + liquid (L)
region below closed curve (or left of it): liquid phase (L)

tie – line: horizontal line within a 2 phase region (closed curve) drawn at
temperature of interest

in isomorphous system, tie–line connects liquidus & solidus points at specific

temperature, end of tie–line represents composition of the 2 phases in
equilibrium
Amount of each phase [Lever Rule]
purpose: to determine relative amounts of each phase (state of matter) present in the alloy
amounts expressed in units of % weight

1. from the tie – line, there are 2 phases at a given temperature which have 2 different compositions
2. overall amounts of compositions must add up to alloy’s overall composition
3. locate the fulcrum, which corresponds to the alloy’s overall composition (C0 )

opposite arm of lever Calculate % phase of left intersect → opposite arm of lever = length from fulcrum to right intersect
% phase = × 100%
length of tie line % phase of left intersect → % of alloy in liquidus

Solidification of solid – solution alloy

· when alloy is melted & cooled, solidification requires nucleation and growth
· intersection between tie–line & solubility curve between (closed region) and liquid → 1 𝑠𝑡 solid to form and its chemical composition
· to achieve equilibrium final structure, cooling rate must be very slow → permits alloy atoms to diffuse & produce compositions in phase diagram

Phase Diagrams Containing 3 – Phase Reactions

· many binary systems produce more complicated phase diagrams which contain 3 separate phases

SOLID α β γ
LIQUID L L1 L2
Eutectic: L → α + β Peritectic: α + L → β Monotectic: L1 → L2 + α Eutectoid: 𝛾 → α + β Peritectoid: α + β → 𝛾

horizontal line @ 3–phase

Notes: (-tic): solid ↔ liquid (-toid): solid ↔ solid Eutectoid = − Peritectoid
reactions

* proeutectoid phase: phase just before vertical line at 𝛾 → α + β

· miscibility gap: region in phase diagram where 2 phases of the same structure do not mix with each other

Eutectic Phase Diagram

· Isopleth: line on phase diagram that shows constant chemical composition
· Hypoeutectic alloy: alloy composition between ‘LHS of tie–line’ and the eutectic composition
· Hypereutectic alloy: alloy composition between ‘RHS of tie–line’ and the eutectic composition

Solvus: solubility curve that separates single solid phase region from a 2–solid phase
region in the phase diagram

To examine the solidification process, trace vertical line at specific % weight B and sketch
out processes that take place from liquid (L) to phase @ T = 0℃

Special case: eutectic structure – during solidification, characteristic structure of

alternating 𝛼 and 𝛽 layers (lamellae) form due to atomic diffusion over short distances
(same principal applies in eutectoid structure)

Hypoeutectic alloy
Formation: L → α + L → α + β
α: primary / proeutectic microconstituent
α + β: eutectic microconstituent

Eutectic Alloys
· colony size (grain): refine grain size to increase strength
· interlamellar spacing: distance from c.g. of 1 lamella to another; smaller distance = stronger alloy
· amount of eutectic microconstitutent: the more microconstituent, the stronger the alloy
· microstructure of eutectic: ?

Iron Carbon Eutectoid Reaction

· Austenite (γ): FCC crystal structure  always start from this phase
· Ferrite: BCC crystal structure that exists as α (low temp.) or δ (high temp.)
· Cementite (Fe3 C): hard & brittle; provides strengthening
· Pearlite: 2 phase lamellar microconstituent containing α and Fe3 C, ~0.77% C
Phase Transformation
· Nucleation: formation of 1st nano–sized crystalline from molten material
· Homogeneous nucleation: forming of critically sized solid by the clustering of large number of atoms at high undercooling
· critical radius: minimum size to be formed by atoms before solid particle is stable and able to grow
· undercooling: temperature where molten metal must cool below the freezing temperature, so that nucleation occurs
· nucleation occurs most easily on established surfaces, e.g. grain boundaries & other defects
𝑛
𝑓 = 1 − 𝑒 −𝑐𝑡

· Recrystallization: process of forming new grains by heat treating cold–worked material

Q
1
· growth (transformation) rate = 1 ÷ time taken for transformation = Ae−RT  plot ln(transformation rate) v. ( )
Temp.

· non–coherent: no relationship with crystal structure

· age hardening: solution treating at (Tsolvus < T < Teutectic )  quench to Troom to prevent precipitate from forming  aging at T < Tsolvus
· welding: fusion zone  (liquidus)  partial fusion zone  (solidus)  solution treated zone  over–aged zone  unaffected base metal
· Isothermal transformation: transformation under constant temperature
· Eutectoid reaction depends on: (1) amount of eutectoid, (2) austenite grain size, (3) cooling rate, (4) transformation temperature
· TTT diagram: diagram which shows the time required at a given temperature that allows phase transformation to take place
· coarse pearlite: relatively thick layers of ferrite and Fe3 C formed
· Martensite: metastable phase formed without diffusion and occurs very quickly  very hard
· Displacive transformation: phase transformation through small displacement of atoms / ions (no diffusion)  for ease of machining
· Tempering: low temp. heat treatment to reduce hardness of martensite by allowing some diffusion
· CCT: used for a mixture of phases within the material; ∆T from T1 to T2 → examine from t = 0 at T = T2 , but original products remain
 PART 2
MATERIAL DEFECTS

Permanent change in shape due to motion of dislocations (localized lattice disturbances)

Edge dislocation: burgers vector ⟂ dislocation line Screw dislocation: burgers vector is parallel to dislocation line

Slipping Twinning
Sliding of atoms over crystallographic plane (slip plane), in a particular Orientation difference across twin plane
direction (slip direction)
less than 1 atomic spacing
N.B. slip direction: closest packed direction
N.B. slip plane: plane of greatest atomic density Every atomic plane is involved

No orientation difference across plane happens due to:

1. restricted slip systems
occurs in multiples of atomic spacing 2. Twinning stress < slip stress

involves certain atomic planes

↑ slip systems = easier deformation (easiest to hardest: BCC, FCC, HCP)

5 strengthening mechanisms

1. Work / strain hardening – plastic deformation increases strength

- makes dislocation motion more difficult

- increases imposed stress to move dislocations
- can be used for materials that don’t respond to heat treatment e.g. pure metals & non–heat treatable alloys
A0 −Ad
- % cold work = × 100%
A0

2. Grain size strengthening

- grain size ↓
- ↑ no. of obstacles to motion of dislocations
K
- hall petch equation: σy = σ0 +  must memorize
√d
- fine grains can be obtained by: (1) rapid solidification from molten state, (2) using grain refiners during solidification, (3) plastic deformation followed
by suitable heat treatment

3. Solid solution strengthening

- adding solute atoms into lattice to form either substitutional solid solution (∆ atomic size ≤ 15%) OR interstitial solid solution (∆ atomic size ≥ 68%)
- impurity atoms increase lattice strain due to size mismatch  makes dislocation motion more difficult
- solute atoms segregate around dislocations to minimize overall energy  higher stress required to tear dislocations from solute atoms

4. Precipitation strengthening (alloys only)

- formation of 2nd phase particles (precipitates) by heat treating parent alloy

- introduces lattice distortions, impeding dislocation motions
- uniformly distributed precipitates pin the dislocations
- condition for alloy systems: (1) appreciable maximum solubility of one component in the other, (2) ∆T~∆ solubility
- steps: solutionizing (put 2nd phase in solution)  quenching  aging (smaller particles & inter–particle spacing)

5. Dispersion strengthening (alloys only)

- adding fine, hard and inert particles in matrix

- strengthening achieved through interaction between dispersoids and dislocations
- strengthening retained at higher temperatures

ANNEALING

During cold working, material experiences changes in:

- microstructure: ∆Estrain , more point & line defects, change in grain shape
- properties: ∆Ω, ∇ ductility, ∆ strength

annealing reverses the negative effects in 3 steps:

1. recovery: restoration of physical properties e.g. conductivities, no change in microstructure / mechanical properties, reduced residual stress
 2. recrystallization (0.3 – 0.7 Tm ): old grains replaced with strain free grains (dislocation density reduced)  hardness ↓ + ductility ↑
* if deformation is below a critical value, no annealing needed
3. grain growth: if new strain free grains are heated at T > 0.3 − 0.7 Tm , then ∆ grain size

Hot Working

- above recrystallization temperature - allows large deformation in the material - bad surface finish due to surface oxidation

Selection of materials – most cost effective, prediction of life

F F ∆L Lins.
σ= → σtrue = ε= → εtrue = ln ( )
Tensile Testing / Loading A Ains. L0 L0
For most commonly used structural materials
Compressive loading For brittle materials
Shear / Torsional Loading For cylindrical shafts / tubes

CHARACTERIZATION OF DEFORMATION
dF
Linearly elastic case: E ∝ |
dr r=r0
non–linear elastic behavior: secant modulus (line from origin to point of interest), tangent modulus in 𝜎 − 𝜀 curve

∆ temperature ~ ∇ E

E can be increased by: alloying, reinforcement, drawing (for polymers)

ultimate tensile strength: maximum stress material is able to withstand

uniform plastic deformation: uniform change in cross sectional area

non–uniform plastic deformation: characterized by formation of ‘neck’

ductility & brittleness: degree of plastic deformation that material can withstand before it fractures (unit: % area reduction OR % elongation)

toughness: ability to absorb energy before fracturing (unit: Pa ∙ √m) ; area under 𝜎 − 𝜀 curve up to point of fracture
* for material to be tough, it should be strong & ductile

IMPACT TESTING

Impact Testing: determines fracture characteristics & whether material exhibits ductile → brittle transition, carried out under high strain rate & 3–axis
stress state conditions

Ductile – Brittle Transition Temperature (DBTT):

1. Temperature where energy = 20 J (CVN energy)
2. Temperature at 50% brittle
3. Temperature at 100% ductility (most conservative approach)

Variables: grain size , composition of carbon content

FCC materials are safe, even @ low temperatures

HARDNESS / HARDNESS TESTING

definition: (1) resistance to penetration, (2) resistance to localized deformation

physical significance: indicates strength of interatomic bonds (& melting point)

measurement techniques: indenter forced into material  depth is measured  resulting indentation correlated with hardness number
*bigger indenter  bigger samples needed
*conditions: flat surface, sample thickness ≥ 10 indentation depth, indented on sample center, no stacking, indentations must be far apart

Used to: (1) assess quality of heat treated samples, (2) select materials in sliding applications to reduce wear, (3) assess ceramic’s fracture toughness

FATIGUE LOADING
σmin
stress ratio =
σmax

Definition: failure of material subjected to fluctuating stresses

Characteristics: fatigue failure occur suddenly fatigue failures are brittle may occur at σ < σy
 Factors: significantly large applied stress sufficiently big stress variation large no. of applied stress cycles
Modes of stress cycles: reversed repeated random
(R = −1 for reversed stress cycles)

Low High
- very short fatigue lives (< 104 to 105 cycles) - longer fatigue lives
Types of fatigue:
- very high applied stresses - low stress level
- elastic & plastic strains produced - completely elastic deformation

Steps involved in fatigue failure:

1. crack initiation: at point of concentration e.g. scratch / keyway / threat / dent

2. crack propagation: crack propagation along planes of high τ  crack propagation ⟂ σ  crack growth by repetitive plastic blunting &
sharpening
3. final failure: advancing crack has reached critical size (characterized by beachmarks & striations)
d𝑎
4. failure life governed by differential equation: = A(∆K)m from 𝑎0 (initial crack length) to 𝑎f (final crack length)
dN

improvement of fatigue failure:

- improving surface finish

- ↑ surface hardness
- introduce surface compressive stresses e.g. shot peening
- remove corrosion media
- careful designing to remove stress concentration (no sharp corner)

FRACTURE

ductile
brittle
· fracture after large plastic deformation
· fracture after little plastic deformation
· material subjected to σ > σUTS for long
· transgranular / intergranular in nature
time
mixed–mode
1. plastic deformation  stress
1. formation of neck and cavities
concentration ‘mixture of ductile & brittle fractures’
2. cavities  crack @ center  propagate
2. nucleation of voids  stress build up @
to surface (⟂ to σapplied )
obstacles
3. near surface, crack changes to 45° to
3. further stress  crack propagation
tensile axis  “cup & cone” fracture
Types:
thin sample: macroscopic appearance:
- less evidence of necking · fracture surface is flat, ⟂ to σapplied
- shear surface
- elongated dimples
thick sample: microscopic appearance:
- round dimples on flat surface · cleavage steps: joining of parallel cracks
- oval dimples near shear lip · river pattern: merging of cleavage steps
· cleavage tongue: formed due to local
fracture at twin–matrix interface
· herringbone structure: “spine – like”

CORROSION OF METALLIC MATERIALS

1. Fundamentals

definition: degradation of material in the environment

534 × M
m. p. y. =
D×A×T
m. p. y. : 10−3 inch M: mass lost (mg) D: density (g/cc) A: area of sample (in.2 ) T: exposure time (h)

DRY CORROSION (OXIDATION)

definition: reaction of material with oxygen to form oxide, i.e. material + oxygen + energy → oxide

Thermodynamic principle: if ∆G (free energy of formation) < 0, then reaction will proceed  indicates whether reaction is feasible, not rate
Mechanism: nucleation of oxide at metal – gas interface  transport of ions across metal–oxide / oxide–oxide / oxide–oxygen interface  oxide layer
grows laterally & along thickness due to diffusion of ions through solid oxide

Adherent (Protective) Oxide

Tight bonding between oxide ions prevent Non–Adherent (Non–protective) Oxide

diffusion through oxide Volatile (Non–protective) Oxide
Oxide types Volume contraction  cracking of scale
Good bonding between oxide and metal e.g. molybdenum oxide @ high T
due to crystal structure coherency e.g. Fe2 O3 / MgO

e.g. Al2 O3

PBR < 1: non – protective; tensile stress in oxide will lead to cracking
oxide vol.
Pilling–Bedworth Ratio (PBR) = PBR > 1: protective; compressive stress in oxide
oxidized metal vol.
PBR ≫ 1: non – protective; too much compressive stress

Linear Reaction Law

Condition: PBR < 1 or PBR ≫ 1 (non – protective oxides)
W = A×t+c
Mechanism: growth of film achieved through passage of gaseous oxygen through pores / fissures in oxide film
e.g. groups 1 & 2 metals
Parabolic Law
Condition: PBR > 1 (reasonably protective oxides)
W2 = B × t + c
e.g. Fe , Cu and Co at high temperatures
Logarithmic Law
condition: PBR > 1 (very protective oxide)
W = C lg(Dt + E)
e.g. Al , Fe or Ni near ambient / elevated temperatures

WET CORROSION

Electrochemical reaction
definition: chemical reaction due to current flow (exchange of electrons)
components: anodic (loses e− / dissolution rxn) , cathodic (gains H2 O) , overall

Application – iron corrosion in seawater:

· anodic: Fe → Fe2+ + 2e−
· cathodic: O2 + 2H2 O + 4e− → 4OH−
· overall: Fe2+ + 2OH − → Fe(OH)2 OR Fe3+ + 3OH− → Fe(OH)3  iron can exist as Fe2+ or Fe3+

factors that result in anodic & cathodic sites:

- contact of different metals (metal with a more negative E0 → anode → corrodes)
- change in O2 conc. (e.g. air has more O2 conc. → favors anodic + cathodic reactions → metal exposed to air = cathode)
- different conc. of metal ions in other species
- varying homogeneity of metal surface (macro → pits, scratches ; micro → presence of other phases)

Anodic & Cathodic Reactions

anodic: M → Mn+ + ne− (where M is the metal that corrodes by dissolution in the wet medium → forms oxides)
cathodic:
1. acidic solution (no O2 ): 2H+ + 2e− → H2 (0.00 V)
2. neutral / basic solution: 2H2 O + O2 + 4e− → 4OH − (0.40 V)
3. acidic solution (with O2 ): O2 + 4H+ + 4e− → 2H2 O (1.23 V)
4. ion reduction (impurities only): M3+ + e− → M2+
5. metal deposition (impurities only): M+ + e− → M
EMF & Galvanic Series
EMF series: electrode potential of various metals against hydrogen electrode at 25℃ (reactivity ↑ down the series)
Galvanic series: corrosion testing in unpolluted seawater
choose elements in the same bracket to minimize corrosion
active stainless steel: low O2 conc. and no Cr2 O3 protective covering
Passivity
definition: state of matter being resistant to corrosion as oxide has formed on surface (film)
film breakdown by: tensile stress, impact of foreign object, scratching, presence of aggressive ions such as halides (gp. 7)
preventing breakdown:
· alloying: adding molybdenum to stainless steel to improve resistance to halides
· heat treatment: to avoid compositional inhomogeneity
· proper design to minimize tensile stress
· processing: using amorphous films (no grain boundary) rather than crystalline films
 TYPES OF CORROSION

1. oxidation: [see – dry corrosion]

2. uniform / general: electrochemical reaction occur uniformly over exposed area → progressive thinning of material (predictable, eventual failure)
prevention: use proper material, coating, cathodic protection
3. intergranular: corrosion along grain boundaries
mechanism: near weld zone, [impurity / alloying substance] precipitates along grain boundaries, leading to ‘depletion zones’
prevention: heat treatment, use stabilizing elements (e.g. Ti), compositional adjustment
4. pitting: localized corrosion that causes pits
mechanism: initiation @ anodic site (scratches, inclusions, surface compositional inhomogeneity) → cathodic reaction at inert area → pit widens
prevention: alloying substances e.g. molybdenum, controlling electrode potential below pitting potential
5. crevice: localized corrosion where stagnant solution is in contact with metal crevices
mechanism: uniform surface corrosion → O2 depletion in crevices → crevices = anode
prevention: improve structural design (welded joints, design for complete drainage), alloying, seal gaps using non – absorbent material
6. galvanic: corrosion when 2 different metals are electrically connected in corrosive solution
mechanism: more reactive metal → anode → corrodes
prevention: reduce cathode area, use high purity metals, select single phase alloys, use 3rd metal which is anodic to both metals
7. stress corrosion cracking: combined action of tensile stress + corrosive environment
prevention: use material with low residual stress, remove residual stress by heat treatment, use inhibitors, induce compressive surface stress
8. erosion: rapid movement of corrosive environment (localized attack: elongated & comet shaped pits ; general attack: smooth wavy surface)
N.B. laminar → turbulent → impingement (fluid changing direction after striking surface; most severe erosion)
prevention: design for laminar flow, use coatings, select hard materials
9. microbiological: metabolic activity of aerobic / anaerobic micro–organisms
mechanism: creates electrolytic conc. cell near metal surface → alter resistance of metal film → influence rate of anodic / cathodic reactions

CORROSION PREVENTION

environment modification: ∇temp. of corroding medium + ∇speed through pipes // acid solution // drying air + ↓ air pollution

neutral solutions: deaeration (removal of O2 , no protective layer involved) + inhibitors (dissolves in corroding medium but forms protective layer at
anodic / cathodic areas)

modification of metal properties: alloying with Ni, Cr, P, Cu, Al, Mo, etc.

use of protective coatings: metallic coating (sacrificial anodic / noble for cathode), non–metallic (chemical / resinous and inorganic base)

cathodic protection: structure to be protected is the cathode (impressed DC / sacrificial anode)

corrosion protection by design: avoid pockets that collect dirt or water, avoid crevices, avoid dissimilar metal contact, streamlined tube for flows