Bonding and Crystal Structure: Phase Transformation and Kinetics in Materials

10/7/20
Lecture 2
Bonding and Crystal Structure
Mechanical and Materials Engineering

Phase Transform ation and Kinetics in M aterials M M E427/527 © 2015 Portland State University, All rights reserved.
Portland State University
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The Essence of Materials Science
• The field can be summarized in two sentences:

– Properties <= composition + microstructure
– Microstructure <= composition + processing
• Composition = kind and fraction of atoms present
• Microstructure = How those atoms are arranged

– Microstructure is not only essential to understanding properties
– Microstructure is often much more important than composition
– Example: bronze vs. iron weapons

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Atomic Resolution TEM Image:

Two Crystals (Grains) of Al
grain
boundary
-Eric Stach
NCEM/LBNL

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Crystalline compound (BaTiO3)
-Andy Minor
NCEM/LBNL

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Bonding
• Solids are made of atoms or molecules

• These stick together – “bonding”
• Understanding bonding is fundamental

– Microstructure
– Properties
• Some important properties are determined by the

nature of bonding alone

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Electron States in Atoms
• Pauli exclusion principle
• Quantum numbers
– n = orbit
– l = angular momentum [0(s)1(p)2(d)3(f)…n-1]
– m = z-component of l [-1,…,l]
– s = spin (1/2,-1/2)
• Configuration
– 1s22s22p63s23p64s23d104p6...

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The Periodic Table

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Composition of Human body

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The Periodic Table

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The Periodic Table

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Core and Valence States
• Valence electrons are outer-shell sp states

– Govern bonding
• Configurations
– H: 1s1 (z = 1)
– C: [1s2]2s22p2 (z = 4)
– Si: [1s 2s 2p ]3s 3p2
2 2 6 2
(z = 4)
– Fe: [1s22s22p63s23p63d6]4s2 (z = 2)
– Cu: 2 2 6 2 6 10
[1s 2s 2p 3s 3p 3d ]4s 1 (z = 1)

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Energy Level diagram

A complete energy level
diagram for the various shells
and subshells using the wave-
mechanical model.
Relative energies of the

electrons for the various shells
and subshells

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Schematic representation of
the filled and lowest unfilled
energy states for a sodium
atom.
• Sodium (Na) :
• atomic number 11
• 1s22s22p63s1
Na+

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Schematic representation of
the filled and lowest unfilled
energy states for a Chlorine
atom.
• Chlorine (Cl) :
• atomic number 17
• 1s22s22p63s23p5
Cl-

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Na Cl

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Bonding
• Bonding is primarily by valence electrons

• Bonding is electrostatic
• The “chemist’s model”

– Chemical bonds are localized between atoms
• The “physicist’s model”

– Electrons wander through the solid
– Electron states are gathered into “bands”

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Interatomic Bonding
• Electrostatic interaction
– Electron-nucleus
• Molecules or solids
– Electrons see multiple nuclei
– Interact with all
– Potential energy decreases
=> bonding

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Bonding
• Electrons between nuclei see both

=> attraction
• Closed inner shells overlap
=> repulsion
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The Chemist’s model:

Chemical Bonding
+ -
- +
- +
Shared Electron Bond Ionic bond Dipole bond

covalent
metallic
• Types of bonding
– Covalent => shared electron, saturated
– Metallic => shared electron, unsaturated
– Ionic => electrons exchanged to charge ions
– Dipole (Van der Waals) => transient or permanent dipoles

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Covalent Bonding
^^ ^^ ^^
^ Si :^Si ^
^Si ^ Si :^SiSi ^
^ •• •
•
^..^ ..
^^ ..^^
^Si :^Si :^Si ^
^..Si ^..Si ^..Si ^ ••
^^ ^^ ^^ ••
Si : Si : Si
• Valence electrons are shared to fill outer shell
• Examples:
– CH4
– C, Si, Ge (4/4); GaAs (3/5); ZnS (2/6)

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Properties of Covalent Materials
^^ ^^ ^^
^ Si ^ ^ Si ^
^ Si
.. :^Si
..Si :^Si
.. ^ •• •
•
^^ ^^ ^^
Si : Si : Si
^ .. ^ ..Si ^
^ Si
^ .. ^ Si ^ ^ •• ••
^Si
^ : Si
^^ : Si ^^
• Electrical:
– Semiconductors or insulators
• Mechanical:
– Hard, brittle

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Metallic Bond
= ion core
sea of
= valence
electrons
• Shared electrons, bonds unsaturated

– Excess electrons or excess neighbors
• Model:
– Ion cores float in an electron sea that glues them together

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Properties of Metallic Materials
= ion core
sea of
= valence
electrons
• Electrical:
– Good conductivity by electron flow
• Mechanical:
– Relatively easy to deform
– Ductile, not brittle

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Ionic Bonding
= Na+
-
= Cl
• Electrons are transferred to create ions

– Common for “almost filled” and “almost empty” shells
• Large difference in “electronegativity”
– Opposite charges bind together
• Ionic and covalent bonding can be mixed

– Dissimilar atoms always “transfer” some charge

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Properties of Ionic Materials
= Na+
-
= Cl
• Electrical
– Insulators
– Ionic conductors (diffusion of ion => current)
• Mechanical
– Tend to be brittle
– Interplanar slip forces unlike ions together

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Dipole Bonding
=O +
=H -
• Dipoles bond by alignment

– No charge transfer
• Permanent dipoles (H2O)

– “Hydrogen bonding” in organics
• Transient dipoles (He)

– “Van der Waals” bonding is always active

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Properties of Dipole Bonded Materials
=O +
=H -
• Electrical
– Insulators
– Weak conductors (“hopping” mechanisms)
• Mechanical
– Low strength
– Deformable (e.g., thermoplastic polymers)

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Permanent dipole bonds and Hydrogen bond

The strongest secondary bonding type, the hydrogen bond, is a special case of polar molecule bonding.

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Chemist’s model: shortcomings
Si
.. :^Si
..^ ^: ^Si
^ ..^ ^^^
Si ^ Si ^
^Si ^ Si ^ •• •
Si : : Si
.. ^^..^ ^ ^..^ ^ ^^^ •
Si ^ Si ^ Si ^ ••
Si :^^Si
^ :^Si ^ ^^
••
• Example: saturated covalent bonding

• Saturated bonds ⇒
– Electrons must reach excited states to conduct
– How much energy required for excitation?
• Much ⇒ insulator, less ⇒ semiconductor, none ⇒ metal
• “Chemist’s model” does not directly answer

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Bonding
• Bonding is primarily by valence electrons

• Bonding is electrostatic
• The “chemist’s model”

– Chemical bonds are localized between atoms
• The “physicist’s model”

– Electrons wander through the solid
– Electron states are gathered into “bands”

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Discrete Electron States in an Atom
• In an atom electron states have

– Particular energies (Ei)
– Discrete energy levels
– Separated by energy gaps
• Electrons confined
– “potential energy well” around nucleus

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The Physicist’s Model:

Atomic States Become “Energy Bands”
free
states
E excited
states
valence
states
core states
• Overlap decreases the potential between atoms

– Valence electrons travel through the solid
– Freely, or by quantum tunneling
• Atomic energy levels become “bands” of allowed states

– Separated by “energy gaps”
– Gaps are the energies electrons cannot have

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Why Atomic States Become

Energy Bands
• In a solid, atomic states interact, influence one another

– Create “electron energy bands”
– How to treat this?
• Many different approaches in physics texts
– Almost all of them are “right”

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Why Atomic States Become

Energy Bands
• Pauli exclusion principle

=> electrons must be in different states
– even electrons from the same atomic level
• Electrons from the same atomic state

– Since electrons move, they have momentum
– States in a band differ in momentum
E = E0 + p2/2m*
– m* is “effective” mass (resistance to motion)
– m* lower for higher E0
=> high-E bands are broader

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Change of Band Width with Separation
• Atomic states spread into bands as r decreases
• Valence bands broaden and overlap

– m* decreases as overlap makes electron movement easier
• Core bands remain narrow until cores overlap

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Band Structure Determines

Electrical Behavior
• Electrons fill low-energy states

– To “Fermi energy”, EF
• EF within a band => metal

– Empty states are accessible
– Electrons can flow with field
• Filled to band top => non-metal

– Must excite electrons across gap
– Small gap => semiconductor
– Large gap => insulator
* Fermi Energy : the energy difference between the highest and lowest occupied single-
particle states
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Change of Band Width with Separation:

Different Modes of Behavior
• In sodium, s and p-bands simply overlap
• In carbon, the s- and p-bands interact

– Create a new gap
– 4 states/atom in lower band, 4 in upper
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Drawing the Band Structure
• Show energy bands as a function of position

– Leave out potential
• Band identification
– Valence band contains valence electrons
– Conduction band is first band of excited states

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The Band Structures of Metals
• Natural metals - EF within a band

– Electron states are paired (spin up, spin down)
– Almost all odd-valence elements are natural metals (not sure)
• Exceptions are “molecular” solids with even total valence
• “Overlap” metals - EF in band overlap range
• Transition metals - EF in partially filled d-band

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The Periodic Table

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The Band Structure of Non-Metals
• Valence electrons fill band

=> EF in center of band gap
=> Poor conductor
• EG small (< ~ 2 eV)

=> semiconductor
• EG large (> ~ 3 eV)

=> insulator

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Importance of Crystal Structure:

Diamond vs. Graphite
• Carbon as diamond
– Each atom has four neighbors
– Covalent bonding in 3-D
– Electrical insulator
– Ultrahard material
• Carbon as graphite
– 3 neighbors in hexagonal plane
– Strong bond in-plane,
• weak bond between planes
– Electrical conductor (in-plane)
graphene – Mechanically weak (lubricant)
– Strong if loaded in-plane (fiber)

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Scientists have theorized about graphene for years. It
has unintentionally been produced in small
quantities for centuries, through the use of pencils
and other similar graphite applications.
It was originally observed in electron microscopes in

1962, but it was studied only while supported on
metal surfaces.
The material was later rediscovered, isolated, and

characterized in 2004.
The global market for graphene reached $9 million

by 2012 with most sales in the semiconductor,
graphene electronics, battery energy, and composites
industries.

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Microstructure
• Microstructure:
– Type and location of all atoms in solid
• All atom positions known in only two ideal cases

– Perfect order (“crystals” or “quasi-crystals”)
– Perfect disorder (“amorphous solids” or “glasses”)
• Almost all solids prefer the crystalline state

– But perfect crystals are not possible in nature
– Describe by basic crystal structure + “crystal defects”

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Two Crystals (Grains) of Al
grain
boundary
-Eric Stach
NCEM/LBNL

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Crystalline compound (BaTiO3)
-Andy Minor
NCEM/LBNL

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• Carbon as diamond
– Each atom has four neighbors
– Covalent bonding in 3-D
– Electrical insulator
– Ultrahard material
• Carbon as graphite
– 3 neighbors in hexagonal plane
– Strong bond in-plane,
• weak bond between planes
– Electrical conductor (in-plane)
– Mechanically weak (lubricant)
– Strong if loaded in-plane (fiber)

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Crystal Structure
Identical
atom groups
a2 Lattice points
a1
Unit cell
• Crystal lattice
– Periodic grid of positions in space (“lattice points”)
• Crystal structure
– Identical group of atoms placed at each lattice point
• Mathematical description: atom positions (Ri)

– Ri = hia1 + kia2 + t (hi, ki = integers, t = constant)
• Physical description:
– Infinitely repeatable unit cell that fills space

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a2
a1
A two-dimensional crystal. The lattice vectors are drawn. The unit cell is the shaded
parallelogram in the figure.

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a2
a1
An alternate crystal lattice and unit cell for the atom configuration

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a2
a1
A two-dimensional crystal made by repeating a two-atom cluster periodically over the plane.
The black dots are the lattice points. The open circles are the atoms. The unit cell is shaded.

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The structure re-drawn to show that the two atoms in the unit cell are located
on the lattice sites of two identical, interpenetrating lattices.

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Example:
2d Crystal of Diatomic Molecules
• Filled circles are lattice points

– a1, a2 = lattice vectors
a2
a1 • Open circles are atoms

– t1, t2 = basis vectors
• Shaded area is unit cell

a2 • Same atom arrangement
†1
†2
– at every lattice site
a1 – in every unit cell

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Primitive and Non-primitive Cells
• One lattice point/cell =>

“primitive lattice”
n = 4x(1/4) = 1 • Multiple lattice points/cell =>

“non-primitive lattice”
• One atom/cell =>

“primitive cell”
– Primitive lattice plus
one atom/lattice point
n = 4x(1/4) + 1 = 2

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The Five Two-Dimensional

“Bravais Lattices”
• Unit cell
– Chosen to reveal symmetry
– Even if non-primitive cell
• The five lattice cells:

– Parallelogram (primitive)
– Rectangle (primitive)
– Square (primitive)
– Hexagon
– Face-centered rectangle

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An arrangement of atoms generated by repeating the triangular cell. The cell does not
determine whether there are atoms in the shaded gaps in the pattern.

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Three Dimensional Crystal Structures
a3
a2
a1
a3
a2
a1
• Three non-collinear basis vectors (a1, a2, a3) define lattice
• Identical atom group at each lattice site:

– Ri = hia1 + kia2 + lia3 (h, k, l = integers)
• Primitive cell is a parallelepiped
• Distinguish 14 Bravais lattices to show symmetry

– Most engineering materials are cubic => simple properties

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Locating Points in a Cubic Crystal
• Edges of the cell define Cartesian

coordinates
• The unit of length is the cell edge
• (h,k,l) is the point with coordinates h, k and l

in this system
• {h,k,l} denotes all points of the same

geometric type
– Ex.: {1,0,0} is the set of cell corners

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Locating Directions in a Cubic Crystal
• The direction [hkl] is found as follows:

– Locate a point that lies along that direction
from the origin
– Find the coordinates of that point (a,b,c)
– Clear all fractions to find the simplest set of
whole numbers [hkl]
– If a coordinate is negative, place minus sign
Directions in a cubic crystal above it:
⎡⎣ hkl ⎤⎦ = [−hkl]
• <hkl> denotes the family of similar directions

(±h,±k,±l)
– Ex.: <111> is the set of directions pointing
toward cell corners
The family of <111> directions

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Locating Planes in a Cubic Crystal
• The “Miller Indices” of a plane are found as

follows:
– Draw the plane and find its intercepts (a,b,c)
with the coordinate axes
– Take the reciprocals: (1/a,1/b,1/c)
– Clear all fractions to find the simplest set of
Crystal showing (100) and (342) planes whole numbers (hkl)
– If a coordinate is negative, place minus sign
above it
• {hkl} denotes a family of geometrically

similar planes
– Ex.: {100} is the set of all cube faces
The (110) and (111) planes

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Locating Planes in a Cubic Crystal
• Ex: (100)
– Intercepts = 1, ∞, ∞
– Reciprocals = 1, 0, 0
– Miller indices are (100)
• Ex: (342)
– Intercepts = 2/3, 1/2, 1
– Reciprocals = 3/2, 2, 1
– With common denominator =
3/2, 4/2, 2/2
– Miller indices are (342)
Crystal showing (100) and (342) planes

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Three Advantages of Miller Indices
• (hkl) are the indices [hkl] of a perpendicular to the plane

=> Can easily find the angles between planes
• All parallel planes have the same Miller indices
• The distance between planes with Miller indices (hkl) is

a
d= (a = cell edge length)
h + k2 + l2
2

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Crystal Structures of Interest
• Elemental solids:
– Face-centered cubic (fcc)
– Hexagonal close-packed (hcp)
– Body-centered cubic (bcc)
– Diamond cubic (dc)
• Binary compounds
– Fcc-based (Cu3Au,NaCl, ß-ZnS)
– Hcp-based (α-ZnS)
– Bcc-based (CsCl, Nb3Sn)

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The Common Crystal Structures:

Body-Centered Cubic (bcc)
• Atoms at the corners of a cube plus one atom in the center

– Is a Bravais lattice, but drawn with 2 atoms/cell to show symmetry
– Bcc is not ideally close-packed
– Closest-packed direction: <111>
– Closest-packed plane: {110}
• Common in
– Alkali metals (K, Na, Cs)
– Transition metals (Fe, Cr, V, Mo, Nb, Ta)
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The Face-Centered Cubic (fcc) and

Hexagonal Close-Packed (hcp) Structures
• Fcc: atoms at the corners of the cube and in the center of each face
– Is a Bravais lattice, but drawn with 4 atoms/cell to show symmetry
– Found in natural and noble metals: Al, Cu, Ag, Au, Pt, Pb
– Transition metals: Ni, Co, Pd, Ir
• Hcp: close-packed hexagonal planes stacked to fit one another

– Does not have a primitive cell (two atoms in primitive lattice of hexagon)
– Divalent solids: Be, Mg, Zn, Cd
– Transition metals and rare earths: Ti, Zr, Co, Gd, Hf, Rh, Os

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fcc and hcp from Stacking

Close-Packed Planes
A A
B
C C
A A A
B B
C
A A
AB ABA = hcp
A
A A
• There are two ways to stack spheres C

B
C
A A A
• The sequence ABA creates hcp B

C
B
A A
• The sequence ABC creates fcc

ABC = fcc
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fcc and hcp from Stacking

Close-Packed Planes
A A
B
C C
A A A
B B
C
A A
AB ABA = hcp
A
A A
• There are two ways to stack spheres C

B
C
A A A
• The sequence ABA creates hcp B

C
B
A A
• The sequence ABC creates fcc

ABC = fcc
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Hexagonal Close-Packed
• HCP does not have a primitive cell

– 2 atoms in primitive cell of hexagonal lattice
– 6 atoms in cell drawn to show hexagonal symmetry
• Common in
– Divalent elements: Be, Mg, Zn, Cd
– Transition metals and rare earths: Ti, Zr, Co, Gd, Hf, Rh, Os
• Anisotropy limits engineering use of these elements

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Face-Centered Cubic Structure
ABC stacking Fcc cell View along diagonal (<111>)
• FCC is cubic stacking of close-packed planes ({111})

– 1 atom in primitive cell; 4 in cell with cubic symmetry
– <110> is close-packed direction
• Common in
– Natural and noble metals: Cu, Ag, Au, Pt, Al, Pb
– Transition metals: Ni, Co, Pd, Ir

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Between FCC and BCC, which crystal lattice is more corrosive?

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• For this, and others, need to identify interstices

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Interstitial Sites:
Octahedral Voids in fcc
• Octahedral interstitial site is equidistant from six atoms

– “Octahedral void”
– Located at {1/2,1/2,1/2} and {1/2,0,0}
• There are 4 octahedral voids per fcc cell

– One per atom

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Interstitial Sites:
Tetrahedral Voids in FCC
• Tetrahedral site is equidistant from four atoms

– “tetrahedral void”
– Located at {1/4,1/4,1/4} - center of cell octet
• There are 8 tetrahedral voids per fcc cell

– Two per atom

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The Diamond Cubic Structure
• Fcc plus atoms in 1/2 of tetrahedral voids

– Close-packed plane stacking is ...AaBbCc… or ... aAbBcC...
- Each atom has four neighbors in tetrahedral coordination
- Natural configuration for covalent bonding

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Interstitial Sites:
Voids between Close-packed Planes
A A
A A
B
B
C C
C C
A A A A A A
B B B B
C
C
A A A A
• In both FCC and HCP packing:

– Tetrahedral void above and below each atom (2 per atom)
– Octahedral void in third site between planes
• Stacking including voids:

– Fcc: ...(aAa)c(bBb)a(cCc)b(aAa)…
– Hcp: ...(aAa)c(bBb)c(aAa)… (octahedral voids all on c-sites)
=> Size and shape of voids are the same in fcc and hcp

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Properties of materials with the FCC and

HCP structures
Since each atom has twelve neighbors it is not possible to form saturated bonds.
FCC and HCP metals also tend to be malleable (easy deformed)
Atoms in the close-packed structures bond as if they were spheres, which suggests in
turn their energy is not strongly changed by the local distortions of the lattice that occur
during deformation
HCP structures are much less commonly used in engineering than those with the more
isotropic cubic structures.

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Unit cell of α-Ti (HCP) and β-Ti (BCC)

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Ti-V Phase diagram Ti-Al Phase diagram

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Titanium crystal structure

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THOM AS R. BIELER, P.D. NICOLAOU, and S.L. SEM IATIN
An Experimental and Theoretical Investigation of the Effect of Local

Colony Orientations and M isorientation on Cavitation during Hot
W orking of Ti-6Al-4V, M etallurgical and M aterials Transactions A,
vol.36A p129 (2005)

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Interstitial Sites:
“Octahedral” Voids in bcc Crystals
• Octahedral voids in face center and edge center

– Located at {1/2,1/2,0} and {1/2,0,0}
• Octahedral voids in bcc are asymmetric

– Each has a short axis parallel to cube edge (Ox, Oy, Oz)
– Total of six octahedral voids, three of each orientation

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Interstitial Sites:
“Tetrahedral” Voids in bcc Crystals
• Tetrahedral voids in each quadrant of each face

– Located at {1/2,1/4,0}
– 12/cell => 6/atom
• Tetrahedral voids in bcc are asymmetric

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• DC is the structure of the Group IV elements

– C, Si, Ge, Sn (grey)
– Are all semiconductors or insulators
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Reliability in Extreme Cold environment

Robert Scott South pole expedition
Karosene Can soldered with Tin solder was empty Napoleon 1812 Russian War
because the poor quality solder material Infantry solders wear Tin buttons. Those fall apart in the cold winter
β-Sn α-Sn
Below 13.2oC
(White Tin) (Grey Tin)
Ductile Brittle
7.31g/cm3 density 5.77g/cm3 density
Ductile β-Sn transforms into brittle α-Sn when the material is exposed below 13.2oC

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Reliability in Extreme Cold environment

Sn-0.5%Cu material, aged at -20oC. Y.Kariya et al., Soldering&Surface m ount Tech, 13(2000)
These α-Sn are potential reliability concerns when the solder joint is in cold environment

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Solid Solutions and Compounds
• Solid solution
– Solute distributed through solid
- Substitutional: solutes on atom sites
- Interstitial: solutes in interstitial sites
- Ordinarily small solutes (C, N, O, …)
• Ordered solution (compound)

– Two or more atoms in regular pattern (AxBy)
– Atoms may be substitutional or interstitial
on parent lattice
– “Compound” does not imply
distinguishable molecules

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Atomic Resolution Image of Gum Metal

Gum metal: Ti-23Nb-0.7Ta-2Zr-1.2O
TNTZ, is a unique titanium alloy with high elasticity, ductility, and yield strength. Applying cold work to gum
metal actually decreases its elastic modulus. At the same time, cold work increases gum metal's yield
strength. By using a heat treatment after this cold work, some elasticity can be sacrificed for even greater
strength, with yield strengths ranging as high as 2 gigapascals (290,000 psi), on par with some of the strongest
steels.

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Ordered Al3Li islands in an Al-Li solution
ordered Al3Li (Cu3Au)
disordered Al-Li solution (fcc)

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Binary Compounds: Examples
• Substitutional:
– Bcc: CsCl
– Fcc: Cu3Au
• Interstitial:
– Fcc octahedral: NaCl
– Fcc tetrahedral: ß-ZnS
– Hcp tetrahedral: α-ZnS
– Bcc tetrahedral: Nb3Sn (A15)

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Bcc Substitutional: CsCl
• Bcc parent
– Stoichiometric formula AB
– A-atoms on edges
– B-atoms in centers
– Either specie may be “A”
• Found in:
– Ionic solids (CsCl)
• Small size difference
to avoid like-ion contact
• RB/RA > 0.732
– Intermetallic compounds
• CuZn (ß-brass)

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Fcc Substitutional: Cu3Au
• Fcc parent
– Stoichiometric formula A3B
– B-atoms on edges
– A-atoms on faces
• Found in:
– Intermetallic compounds
– Cu3Au
– Al3Li
– As “sublattice” in complex ionics
• E.g., “perovskites”
– BaTiO3 (ferroelectric)
– YBa2Cu3O7 (superconductor)
• Lattices of + and - ions must
interpenetrate since like ions
A perovskite is any material with the same type of crystal structure as cannot be neighbors
calcium titanium oxide (CaTiO3), known as the perovskite structure, or
XIIA2+VIB4+X2−3 with the oxygen in the face centers.

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Fcc Octahedral Interstitial: NaCl
• Fcc parent
– A-atoms on fcc sites
– B-atoms in octahedral voids
– Either can be “A”
• Found in:
– Ionic compounds:
• NaCl, MgO (RB/RA ~ 0.5)
• “Perovskites” (substitutional
ordering on both sites)
– Metallic compounds
• Carbonitrides (TiC, TiN, HfC)

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Elastic Instabilities in TiC and TiN

TiC
• TiC has higher ideal strength
Stress (GPa)
than TiN or HfC.
• Despite HfC higher modulus
• TiN and HfC have an

engineering shear strain
instability that limits strength
TiN/HfC
Stress (GPa)
engineering shear strain

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101
Lattice instability in NaCl
[011] [001]
[001]
→ [011]
• Strength determined by “flip” when pulled on {110}

– Interstitial atoms jump to new sites during flip.
– Hence, there are two sequential instabilities
• Strength determined by first instability
– If lattice deformation initiates instability => high strength (TiC)
– If interstitials initiate instability => lower strength (HfC, TiN)

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Fcc Tetrahedral Interstitial: ß-ZnS
• Binary analogue of diamond cubic

– A-atoms on fcc sites
– B-atoms in 1/2 of tetrahedral voids
• AaBbCc
– Either element can be “A”
• Found in:
– Covalent compounds:
• GaAs, InSb, ß-ZnS, BN
• AgCl
• Large size difference (RB/RA < .414)

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103
Hcp Tetrahedral Interstitial: α-ZnS
• Hexagonal analogue of ß-ZnS

– A-atoms on hcp sites
• AaBbAaBb
• Found in:
• ZnO, CdS, α-ZnS, “Lonsdalite” C
• Silver halides

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Lonsdaleite (named in honour of Kathleen Lonsdale), also called hexagonal diamond in reference to the crystal
structure, is an allotrope of carbon with a hexagonal lattice. In nature, it forms when meteorites containing graphite
strike the Earth. The great heat and stress of the impact transforms the graphite into diamond, but retains graphite's
hexagonal crystal lattice.

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• Hexagonal analogue of ß-ZnS

– A-atoms on hcp sites
• AaBbAaBb
• Found in:
• ZnO, CdS, α-ZnS, “Lonsdalite” C
• Silver halides

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Bcc Tetrahedral Interstitial: A15
• A15: Complex bcc derivative

– Stoichiometric formula A3B
– B-atoms on bcc sites
– A-atoms in 1/2 of tetrahedral voids
• Form “chains” in x, y, and z
• Found in:
– A15 compounds:
• Nb3Sn, Nb3Al, Nb3Ge, V3Ga
– These are the “type-II” superconductors
– used in high-field magnets, etc.

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109
• For this, and others, need to identify interstices

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Bonding and Crystal Structure: Phase Transformation and Kinetics in Materials

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10/7/20

Mechanical and Materials Engineering

Mechanical and Materials Engineering

The Essence of Materials Science

• The field can be summarized in two sentences:

• Composition = kind and fraction of atoms present

• Microstructure = How those atoms are arranged

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Atomic Resolution TEM Image:

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Atomic Resolution TEM Image:

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• Solids are made of atoms or molecules

• Understanding bonding is fundamental

• Some important properties are determined by the

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Electron States in Atoms

• Pauli exclusion principle

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The Periodic Table

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Composition of Human body

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The Periodic Table

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The Periodic Table

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Core and Valence States

• Valence electrons are outer-shell sp states

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Energy Level diagram

Relative energies of the

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Energy Level diagram

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Energy Level diagram

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• Bonding is primarily by valence electrons

• The “chemist’s model”

• The “physicist’s model”

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• Electrons between nuclei see both

The Chemist’s model:

Shared Electron Bond Ionic bond Dipole bond

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• Valence electrons are shared to fill outer shell

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Properties of Covalent Materials

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• Shared electrons, bonds unsaturated

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Properties of Metallic Materials

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• Electrons are transferred to create ions

• Ionic and covalent bonding can be mixed

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Properties of Ionic Materials

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• Dipoles bond by alignment

• Permanent dipoles (H2O)