1
Whydowestudystructure?
C
Diamond Graphite
carbon
transparent, black,
hard, soft,
insulating, conducting,
expensive cheap
Chapter 3: Structure of Metals and Ceramics
Goals
Define basic terms and give examples of each:
Lattice
Basis Atoms (Decorations or Motifs)
Crystal Structure
Unit Cell
Coordination Numbers
Describe hard-sphere packing and identify cell symmetry.
Crystals density: the mass per volume (e.g. g/cm3).
Linear Density: the number of atoms per unit length (e.g. cm-1).
Planar Densities: the number of atoms per unit area (e.g. cm-2).
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Chapter3:StructureofMetalsandCeramics
Learning Objective
Know and utilize definitions to describe structure and
defects in various solid phases (crystal structures).
Compute densities for close-packed structures.
Identify Symmetry of Cells.
Specify directions and planes for crystals and be
able to relate to characterization experiments .
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ENERGYANDPACKING
typical neighbor
bond length
typical neighbor r
bond energy
typical neighbor
bond length
typical neighbor r
bond energy
Dense,regularpackedstructurestendtohavelowerenergy.
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Atomic PACKING
Crystalline materials...
atoms pack in periodic, 3D arrays
typical of: -metals
-many ceramics
-some polymers crystalline SiO2
Adapted from Fig. 3.18(a),
Callister 6e.
Si Oxygen
Noncrystalline materials...
atoms have no periodic packing
occurs for: -complex structures
-rapid cooling
"Amorphous" = Noncrystalline noncrystalline SiO2
Adapted from Fig. 3.18(b),
Callister 6e.
From Callister 6e resource CD.
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Crystalline Solids: Unit Cells
Fig. 3.1 Atomic configuration in
Its geometry!
Face-Centered-Cubic
Arrangement
Unit Cell: The basic structural unit of a
crystal structure. Its geometry and atomic R
positions define the crystal structure.
R R
A unit cell is the smallest component of the R
crystal that reproduces the whole crystal when
stacked together with purely translational a
repetition.
Note:
More than one unit cell can be chosen for a given
crystal structure but by convention/convenience
the one with the highest symmetry is chosen.
Several GIFS that follow were taken from Dr. Heyes (Oxford) excellent webpage.
http://www.chem.ox.ac.uk/icl/heyes/structure_of_solids/Strucsol.html
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Crystalline Solids: Unit Cells
A Space LATTICE is an infinite, periodic array of
mathematical points, in which each point has identical
surroundings to all others.
LATTICE
BASIS
Important Note:
Lattice points are a purely mathematical concept,
whereas atoms are physical objects.
So, don't mix up atoms with lattice points.
Lattice Points do not necessarily lie at the center of
atoms.
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Unit Cells and Unit Cell Vectors
Lattice parameters
axial lengths: a, b, c
interaxial angles:
unit vectors: a b c
c
In general: abc
b
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Possible Crystal Classes
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Possible Crystal Classes
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Unit Cells Types
A unit cell is the smallest component of the crystal that reproduces the whole
crystal when stacked together with purely translational repetition.
Primitive (P) unit cells contain only a single lattice point.
Internal (I) unit cell contains an atom in the body center.
Face (F) unit cell contains atoms in the all faces of the planes composing the cell.
Centered (C) unit cell contains atoms centered on the sides of the unit cell.
Primitive Face-Centered
Body-Centered End-Centered
Sometimes it is convenient to define a non-primitive unit cell to reveal overtly the higher symmetry.
Then, one has to count carefully "how many atoms are in unit cell" (see next).
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Unit Cells Types
Often its convenient to define a non-primitive unit cell to reveal overtly the higher symmetry.
Then, one has to count carefully "how many atoms are in unit cell" (see next).
Face-Centered
Primitive (with 1 atom/cell, no symmetry)
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The 14 Bravais Lattices!
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Why, for example do we not have a base-
centered tetragonal lattice?
FulllinesdelineateacellthatisC
centered.Butthedashedlinesshow
thatthecenteredarrangementisnot
reallyanewarrangementandthata
primitivecellcanbefound.Inthe
casebelow,theprimitivecellis
chosenbecauseitsvolumeissmaller.
Therefore,thereisnoneedtocreatea
Ccenteredtetragonallatticetype.
Counting Number of Atoms Per Unit Cell
Simple 2D Triangular Lattice Lattice showing primitive unit cell (in red)
and a square, non-primitive unit cell (in green).
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UNIT CELL - 3D Lattices
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Counting Number of Atoms Per Unit Cell
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Coordination Number of a Given Atom
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Unit Cells and Volume Packing
Atomic configuration in
What are basic structural parameters, Face-Centered-Cubic
e.g. lattice constant or side of cube? Arrangement
How many atoms per cell?
What is volume per cell? R
What is the atomic packing factor (APF)?
R
What is the closed-packed direction? R
R
What are (linear) densities of less
close-packed directions? a
What are planar densities of every plane?
2a 4R
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Atomic Packing Fraction for FCC
FaceCenteredCubic
Arrangement
APF=vol.ofatomicspheresinunitcell
totalunitcellvol.
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Basic Geometry for FCC
Geometry along close-packed direction give relation between a and R.
2 2R
2R
2a 4R 2 2R
a
a
4
Vunit _ cell a (2 2 R) 16 2 R
3 3 3 Vatoms 4 R 3
3
Geometry: a 2 2R
4 atoms/unit cell
Coordination number = 12
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Atomic Packing Fraction for FCC
FaceCenteredCubic
APF=vol.ofatomicspheresinunitcell Arrangement
totalunitcellvol.
Howmanyspheres(i.e.atoms)?4/cell
Whatisvolume/atom? 4R3/3
Whatiscubevolume/cell? a3 Unit cell contains:
HowisRrelatedtoa? 2a 4R 6 x 1/2 + 8 x 1/8
=4 atoms/unit cell
atoms volume
4 3
unit cell 4 (2a/4)
3 atom =0.74
APF =
volume
a3
unit cell IndependentofR!
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Summary APF for BCC
2a
Geometry: 4R a 3
2 atoms/unit cell
Coordination
number = 8
a 4R a 3
3
4 a 3
2
3
4
V 3
APF atoms 0.68
Vcell a3 8
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ABCABC.... repeat along <111> direction gives Cubic Close-Packing (CCP)
Face-Centered-Cubic (FCC) is the most efficient packing of hard-spheres of any lattice.
Unit cell showing the full symmetry of the FCC arrangement : a = b =c, angles all 90
4 atoms in the unit cell: (0, 0, 0) (0, 1/2, 1/2) (1/2, 0, 1/2) (1/2, 1/2, 0)
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FCCStacking
A
B Highlighting
thestacking
C
Highlightingthefaces
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FCC Unit Cell
Highlighting the
ABC planes and
the cube.
Highlighting the
hexagonal planes in
each ABC layer.
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A less close-packed structure is Body-Centered-Cubic (BCC).
Besides FCC and HCP, BCC structures are widely adopted by metals.
Unit cell showing the full cubic symmetry of the BCC arrangement.
BCC: a = b = c = a and angles = = 90.
2 atoms in the cubic cell: (0, 0, 0) and (1/2, 1/2, 1/2).
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Body-Centered-Cubic (BCC) can be template for more
Complex Structures: Lattice with Basis Atoms
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ABABAB.... repeat along <111> direction gives Hexagonal Close-Packing (HCP)
Unit cell showing the full symmetry of the HCP arrangement is hexagonal
Hexagonal: a = b, c = 1.633a and angles = = 90, = 120
2 atoms in the smallest cell: (0, 0, 0) and (2/3, 1/3, 1/2).
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HCPStacking
A
Highlighting
B thestacking
A
Layer A
Layer B
Highlightingthecell
Figure3.3
Layer A
SelfAssessment:Howmanyatoms/cell?
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ComparingtheFCCandHCPPlanesStacking
FCC HCP
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PackingDensitiesinCrystals:LinesPlanesandVolumes
Concepts
Planar Density:
No. of atoms per area of plane per area of plane
Versus
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LinearDensityinFCC
Number of atoms centered on a direction vector
LD =
Length of the direction vector
ANSWER
ASK
a. 2 atoms along [1 1 0]
a. How many spheres along blue line?
in the cube.
b. Length = 4R
b. What is length of blue line?
2atoms 1
LD110
4R 2R
XZ = 1i + 1j + 0k = [110]
Self-assessment: Show that LD100 = 2/4R.
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LinearPackingDensityinFCC
Number of radii along a direction vector
LDP=
Length of the direction vector
ASK ANSWER
a. How many radii along blue line? a. 2 atoms * 2R.
b. What is length of blue line? b. Length = 4R
2 * 2R
LPD110 1
4R
Fully CLOSE-PACKED.
Always independent of R!
a 2 2R
4R
2 1
Hence, PD
8 2R 2 4 2R 2
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PlanarPackingDensityinFCC
2R 2
4R Hence, PPD 0.555
8 2R 2 4 2
Always independent of R!
Self-assessment: Show that PPD100 = /4 = 0.785.
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Theoretical Density,
#atoms/unit cell Atomic weight (g/mol)
nA
Volume/unit cell Vc NA Avogadro's number
(cm3/unit cell) (6.023x 1023 atoms/mol)
Example: Copper
Data from Table inside front cover of Callister (see next slide):
crystal structure = FCC: 4 atoms/unit cell
atomic weight = 63.55 g/mol (1 amu = 1 g/mol)
atomic radius R = 0.128 nm (1 nm = 10 cm) -7
3
Result: theoreticalCu = 8.89 g/cm
Compare to actual:Cu = 8.94 g/cm3
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CharacteristicsofSelectedElementsat20C
At. Weight Density Crystal Atomic radius
Element Symbol (amu) (g/cm3) Structure (nm)
Aluminum Al 26.98 2.71 FCC 0.143
Argon Ar 39.95 ------ ------ ------
Barium Ba 137.33 3.5 BCC 0.217
Beryllium Be 9.012 1.85 HCP 0.114
Boron B 10.81 2.34 Rhomb ------
Adapted from
Bromine Br 79.90 ------ ------ ------ Table, "Charac-
Cadmium Cd 112.41 8.65 HCP 0.149 teristics of
Calcium Ca 40.08 1.55 FCC 0.197 Selected
Carbon C 12.011 2.25 Hex 0.071 Elements",
inside front
Cesium Cs 132.91 1.87 BCC 0.265 cover,
Chlorine Cl 35.45 ------ ------ ------ Callister 6e.
Chromium Cr 52.00 7.19 BCC 0.125
Cobalt Co 58.93 8.9 HCP 0.125
Copper Cu 63.55 8.94 FCC 0.128
Flourine F 19.00 ------ ------ ------
Gallium Ga 69.72 5.90 Ortho. 0.122
Germanium Ge 72.59 5.32 Dia. cubic 0.122
Gold Au 196.97 19.32 FCC 0.144
Helium He 4.003 ------ ------ ------
Hydrogen H 1.008 ------ ------ ------
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DENSITIESOFMATERIALCLASSES
metals>ceramics>polymers Metals/
Graphite/
Ceramics/ Polymers
Composites/
Alloys fibers
Metals have... 30
Semicond
close-packing Platinum
Based on data in Table B1, Callister
*GFRE, CFRE, & AFRE are Glass,
20 Gold, W
(metallic bonds) Tantalum Carbon, & Aramid Fiber-Reinforced
Epoxy composites (values based on
large atomic mass 60% volume fraction of aligned fibers
10 Silver, Mo in an epoxy matrix).
Cu,Ni
Ceramics have...
(g/cm3)
Steels
Tin, Zinc
less dense packing 5
Zirconia
Titanium
(covalent bonds) 4 Al oxide
Diamond
often lighter elements 3
Aluminum
Si nitride
Glass -soda Glass fibers
Concrete
Silicon PTFE GFRE*
2
Polymers have... Magnesium Graphite
Silicone
Carbon fibers
CFRE *
Aramid fibers
poor packing PVC
PET AFRE *
1 PC
(often amorphous) HDPE, PS
PP, LDPE
lighter elements (C,H,O)
0.5 Wood
Composites have... 0.4
intermediate values 0.3
Data from Table B1, Callister 6e.
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SUMMARY
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