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Engineering Materials

University of Georgia MCHE3310|Fall 2017

3: Crystalline structures

August 24, 2017

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Learning objective

Describe the difference in atomic/molecular structure between crystalline and noncrystalline materials

Understand basic terms: unit cell, lattice, crystal structure, coordination numbers

Describe hard-sphere packing and cell symmetry

Understand Miller indices

Today’s agenda

Unit cells

Atomic packing

Crystal structures and systems

Packing density

Point coordinates

Crystallographic directions

Crystallographic planes

Energy and packing

• Non dense, random packing

Energy and packing • Non dense, random packing Energy typical neighbor bond length r Energy typical
Energy typical neighbor bond length r
Energy
typical neighbor
bond length
r
Energy typical neighbor bond length
Energy
typical neighbor
bond length

r

typical neighbor bond energy

• Dense, ordered packing

r typical neighbor bond energy • Dense, ordered packing typical neighbor bond energy Dense, ordered packed

typical neighbor bond energy

Dense, ordered packed structures tend to have lower energies.

Materials and packing

Crystalline materials

• atoms pack in periodic, 3D arrays

• typical of:

-metals -many ceramics -some polymers

Noncrystalline materials

• atoms have no periodic packing

• occurs for:

-complex structures -rapid cooling

"Amorphous" = Noncrystalline

-rapid cooling " Amorphous " = Noncrystalline crystalline SiO 2 Adapted from Fig. 3.25(a), Callister

crystalline SiO2

Adapted from Fig. 3.25(a), Callister & Rethwisch 9e.

Si Oxygen
Si
Oxygen

noncrystalline SiO2

Adapted from Fig. 3.25(b), Callister & Rethwisch 9e.

Metallic crystal structures

How can we stack metal atoms to minimize empty space?

2-dimensions

How can we stack metal atoms to minimize empty space? 2-dimensions vs. Now stack these 2-D

vs.

How can we stack metal atoms to minimize empty space? 2-dimensions vs. Now stack these 2-D

Now stack these 2-D layers to make 3-D structures

Hard sphere model

Hard sphere model Atomic hard sphere model: hard sphere in a box Atoms (or ions) are

Atomic hard sphere model: hard sphere in a box

Atoms (or ions) are thought of as being solid spheres having well-defined diameters Spheres representing nearest-neighbor atom touch one another.

Crystalline solid: unit cells

Unit cell: the basic structural unit of a crystal structure. Its geometry and atomic positions define the crystal structure.

A unit cell is the smallest component of the crystal that reproduces the whole crystal when stacked together with purely translational repetition.

Note: more that one unit cell can be chosen for a given crystal structure but by convention, the one with highest symmetry is chosen.

a given crystal structure but by convention, the one with highest symmetry is chosen . Face-centered

Face-centered cubic structure

Crystalline solid: unit cells

A space LATTICE is an infinite, periodic array of mathematic points, in which each point has identical surroundings to all others.

which each point has identical surroundings to all others. A crystal structure is a periodic arrangement

A crystal structure is a periodic arrangement of atoms in the crystal that can be described by a LATTICE + ATOM DECORATION (BASIS).

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Crystalline solid: unit cells

Important notes:

Lattice points are a purely mathematic concept whereas atoms are physical objects

DON’T mix up atoms with lattice points

Lattice points do not necessarily lie at the center of atoms.

Unit cells

The parameters of the unit cell: (a,b,c) the length of three adjacent edges of the
The parameters of the unit cell:
(a,b,c) the length of three adjacent edges of the unit cell
(α,β,γ) three angles subtended by the lattice cell axes
The various unit cells are generated from the
different values of a, b, c and α, β, γ.
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Crystal systems & Bravais lattices

Seven possible combinations of a, b, c & α, β, γ, resulting in 7 crystal systems The seven crystal systems can be described using 14 point lattices, called Bravais Lattices (Proposed by French crystallographer Bravais in 1848)

90°

(simple)

by French crystallographer Bravais in 1848) 90 ° (simple) Bravais Face-centered cubic , body-centered cubic and

Bravais

Face-centered cubic, body-centered cubic and hexagonal close- packed are for most common metal

Cubic unit cell

In cubic unit cell:

Simple Cubic (SC)

Body-Centered Cubic (BCC)

Face-Centered Cubic (FCC)

a = b = c α = β = γ = 90°

unit cell: Simple Cubic (SC) Body-Centered Cubic (BCC) Face-Centered Cubic (FCC) a = b = c
unit cell: Simple Cubic (SC) Body-Centered Cubic (BCC) Face-Centered Cubic (FCC) a = b = c
unit cell: Simple Cubic (SC) Body-Centered Cubic (BCC) Face-Centered Cubic (FCC) a = b = c

Simple cubic structure (SC)

• Rare due to low packing density (only Po has this structure)

Close-packed directions are cube edges.

Coordination number = 6 (# nearest neighbors: each atom has the same number of nearest-neighbor or touching atoms)

Coordination number = 6 (# nearest neighbors: each atom has the same number of nearest-neighbor or
Coordination number = 6 (# nearest neighbors: each atom has the same number of nearest-neighbor or
Coordination number = 6 (# nearest neighbors: each atom has the same number of nearest-neighbor or

Counting number of atoms per unit cell in cubic

Atom in different position are shared by differing numbers of unit cells

Vertex atom shared by 8 cells 1/8 atom belongs to cell

Face atom shared by 2 cells

Body unique to 1 cell

1/2 atom belongs to cell

1

atom belongs to cell

Face atom shared by 2 cells • Body unique to 1 cell 1/2 atom belongs to
Face atom shared by 2 cells • Body unique to 1 cell 1/2 atom belongs to

Simple cubic

N=1

Atomic packing factor (APF): SC

Volume of atoms in unit cell*

APF =

Volume of unit cell

*assume hard spheres

• APF for a simple cubic structure = 0.52

a
a

R = 0.5a

close-packed directions contains 8 x 1/8 = 1 atom/unit cell

volume

atoms atom 4 unit cell 1 3 π (0.5a) 3 APF = a 3 volume
atoms
atom
4
unit cell
1
3 π (0.5a) 3
APF =
a 3
volume
unit cell

Body-centered cubic (BCC)

• Atoms touch each other along cube diagonals.

--Note: All atoms are identical; the center atom is shaded differently only for ease of viewing.

ex: Cr, W, Fe (α), Tantalum, Molybdenum

ease of viewing. ex: Cr, W, Fe ( α ), Tantalum, Molybdenum • Coordination # =

• Coordination # = 8

W, Fe ( α ), Tantalum, Molybdenum • Coordination # = 8 Adapted from Fig. 3.2,

Adapted from Fig. 3.2, Callister & Rethwisch 9e.

2 atoms/unit cell: 1 center + 8 corners x 1/8

Atomic packing factor (APF): BCC

• APF for a body-centered cubic structure = 0.68

R a
R
a
3 a a 2 a Close-packed directions: length = 4R = 3 a
3 a
a
2 a
Close-packed directions:
length = 4R =
3 a

atoms unit cell APF =

2
2

4

3 π ( 3a/4) 3

4 3 π ( 3 a /4) 3
4 3 π ( 3 a /4) 3
volume atom
volume
atom
volume a 3 unit cell
volume
a 3
unit cell

Face-centered cubic (FCC)

• Atoms touch each other along face diagonals.

--Note: All atoms are identical; the face-centered atoms are shaded differently only for ease of viewing.

atoms are shaded differently only for ease of viewing. ex: Al, Cu, Au, Pb, Ni, Pt,

ex: Al, Cu, Au, Pb, Ni, Pt, Ag

Coordination # = 12

ex: Al, Cu, Au, Pb, Ni, Pt, Ag • Coordination # = 12 Adapted from Fig.

Adapted from Fig. 3.1, Callister & Rethwisch 9e.

4 atoms/unit cell: 6 face x 1/2 + 8 corners x 1/8

Atomic packing factor (APF): FCC

• APF for a face-centered cubic structure = 0.74 maximum achievable APF

Close-packed directions:

length = 4R =

achievable APF Close-packed directions: length = 4 R = 2 a 2 a a Unit cell

2 a

2 a a
2 a
a

Unit cell contains:

6 x 1/2 + 8 x 1/8 = 4 atoms/unit cell

atoms unit cell APF =

x 1/2 + 8 x 1/8 = 4 atoms/unit cell atoms unit cell APF = 4
4
4

4

3 π ( 2a/4) 3

4 3 π ( 2 a /4) 3
4 3 π ( 2 a /4) 3

volume

+ 8 x 1/8 = 4 atoms/unit cell atoms unit cell APF = 4 4 3

atom

+ 8 x 1/8 = 4 atoms/unit cell atoms unit cell APF = 4 4 3
+ 8 x 1/8 = 4 atoms/unit cell atoms unit cell APF = 4 4 3
a 3
a 3
volume unit cell
volume unit cell

volume

unit cell

SC, FCC, BCC

20
20

Coordination number: each atom has the same

number of nearest-neighbor or touching atoms

number of atom per unit cell

FCC stacking sequence

• ABCABC

• 2D Projection

Stacking Sequence

B B B B C C C A A A B B B B B
B B
B B
C
C
C
A
A
A
B B
B
B
B
B B
C
C
C
C
C
C
B B
B B

A sites

B

B

sites sites

C sites

• FCC Unit Cell

A B C
A
B
C

Hexagonal close-packed structure (HCP)

• ABAB

Stacking Sequence

• 3D Projection c a
• 3D Projection
c
a

A sites

B sites

A sites

• Coordination # = 12

• APF = 0.74

c/a = 1.633

• Coordination # = 12 • APF = 0.74 • c / a = 1.633 6

6 atoms/unit cell:

3 atoms at center: 3(1)

2 atoms at face:

2(1/2)

12 atoms at corner: 12(

1/6

)

ex: Cd, Mg, Ti, Zn

Close packing of sphere

Comparison of Packing Efficiency

Close packing of sphere Comparison of Packing Efficiency Simple Cube Coordination #: 6 Atoms/Cell: 1 APF:

Simple Cube Coordination #: 6 Atoms/Cell: 1 APF: 52%

Simple Cube Coordination #: 6 Atoms/Cell: 1 APF: 52 % BCC Coordination #: 8 Atoms/Cell: 2

BCC Coordination #: 8 Atoms/Cell: 2 APF: 68%

1 APF: 52 % BCC Coordination #: 8 Atoms/Cell: 2 APF: 68 % FCC Coordination #:

FCC Coordination #: 12 Atoms/Cell: 4 APF: 74%

APF: 68 % FCC Coordination #: 12 Atoms/Cell: 4 APF: 74 % HCP Coordination #: 12

HCP Coordination #: 12 Atoms/Cell: 6 APF: 74%

FCC & HCP are the most close- packed structures, which can be described in term of close-packed planes of atoms

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Close packing of sphere

Stacking sequence of close-packed planes of atoms

FCC

C B A
C
B
A

The atoms in rows A and C are no longer aligned.

C

B

A

C

B

A

HCP

A B A
A
B
A

The atoms of the third plane are in exactly the same position as the atoms in the first plane.

B

A

B

A

B

A

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Theoretical density: ρ

Density = ρ =

ρ =

Mass of Atoms in Unit Cell

Total Volume of Unit Cell

n A

V C N A

where

n = number of atoms/unit cell A = atomic weight V C = Volume of unit cell = a 3 for cubic N A = Avogadro’s number = 6.022 x 10 23 atoms/mol

Theoretical density: ρ

R a
R
a

• Ex: Cr (BCC) A = 52.00 g/mol R = 0.125 nm n = 2 atoms/unit cell

A = 52.00 g/mol R = 0.125 nm n = 2 atoms/unit cell a = 4

a = 4R/ 3 = 0.2887 nm

atoms

nm n = 2 atoms/unit cell a = 4 R / 3 = 0.2887 nm atoms

unit cell

ρ =

2
2

52.00

g mol
g
mol

ρ theoretical

ρ actual

= 7.18 g/cm 3

= 7.19 g/cm 3

ρ theoretical ρ actual = 7.18 g/cm 3 = 7.19 g/cm 3 3 a 6.022 x
3 a
3
a

6.022 x 10 23

volume unit cell
volume
unit cell
ρ theoretical ρ actual = 7.18 g/cm 3 = 7.19 g/cm 3 3 a 6.022 x

atoms

ρ theoretical ρ actual = 7.18 g/cm 3 = 7.19 g/cm 3 3 a 6.022 x

mol

(g/cm 3 )

ρ

Densities of material classes

In general

ρ metals > ρ ceramics > ρ polymers

Why?

Metals have

• close-packing (metallic bonding)

• often large atomic masses

Ceramics have

• less dense packing

• often lighter elements

Polymers have

• low packing density (often amorphous)

• lighter elements (C,H,O)

Composites have

• intermediate values

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20

10

5

4

3

2

1

0.5

0.4

0.3

Metals/

Alloys

Graphite/

Ceramics/

Polymers

Semicond

Composites/

fibers

Ceramics/ Polymers Semicond Composites/ fibers Platinum Gold, W Silver, Mo Cu,Ni Steels Based

Platinum

Gold, W

Silver, Mo

Cu,Ni

Steels

Based on data in Table B1, Callister *GFRE, CFRE, & AFRE are Glass, Carbon, & Aramid Fiber-Reinforced Epoxy composites (values based on 60% volume fraction of aligned fibers in an epoxy matrix).

ZirconiaAl oxide Concrete Silicon Diamond Si nitride Glass -soda Graphite

Al oxide Zirconia Concrete Silicon Diamond Si nitride Glass -soda Graphite

ConcreteZirconia Al oxide Silicon Diamond Si nitride Glass -soda Graphite

Silicon

Diamond

Si nitride

Glass -soda

GraphiteZirconia Al oxide Concrete Silicon Diamond Si nitride Glass -soda

PTFESilicone PVC PET PC HDPE, PS PP, LDPE

SiliconePTFE PVC PET PC HDPE, PS PP, LDPE

PVCPTFE Silicone PET PC HDPE, PS PP, LDPE

PETPTFE Silicone PVC PC HDPE, PS PP, LDPE

PCPTFE Silicone PVC PET HDPE, PS PP, LDPE

HDPE, PSPTFE Silicone PVC PET PC PP, LDPE PTFE Silicone PVC PET PC PP, LDPE

PP, LDPE

Glass fibersGFRE* Carbon fibers Aramid fibers CFRE* AFRE* Wood

GFRE*Glass fibers Carbon fibers Aramid fibers CFRE* AFRE* Wood

Carbon fibers Glass fibers GFRE* Aramid fibers CFRE* AFRE* Wood
Carbon fibers

Aramid fibersGlass fibers GFRE* Carbon fibers CFRE* AFRE* Wood

CFRE*

AFRE*

WoodGlass fibers GFRE* Carbon fibers Aramid fibers CFRE* AFRE*

TantalumCarbon fibers Aramid fibers CFRE* AFRE* Wood Tin, Zinc Titanium Aluminum Magnesium Data from Table B.1,

Tin, Zincfibers Aramid fibers CFRE* AFRE* Wood Tantalum Titanium Aluminum Magnesium Data from Table B.1, Callister

TitaniumAramid fibers CFRE* AFRE* Wood Tantalum Tin, Zinc Aluminum Magnesium Data from Table B.1, Callister &

Aluminumfibers CFRE* AFRE* Wood Tantalum Tin, Zinc Titanium Magnesium Data from Table B.1, Callister & Rethwisch,

MagnesiumCFRE* AFRE* Wood Tantalum Tin, Zinc Titanium Aluminum Data from Table B.1, Callister & Rethwisch, 9e.

Data from Table B.1, Callister & Rethwisch, 9e.

Crystals as building blocks

Some engineering applications require single crystals:

-- diamond single crystals for abrasives

single crystals: -- diamond single crystals for abrasives (Courtesy Martin Deakins, GE Superabrasives, Worthington,

(Courtesy Martin Deakins, GE Superabrasives, Worthington, OH. Used with permission.)

• Properties of crystalline materials often related to crystal structure.

-- Ex: Quartz fractures more easily along some crystal planes than others.

-- turbine blades

Fig. 8.34(c), Callister & Rethwisch 9e.

(courtesy of Pratt and Whitney)

-- turbine blades Fig. 8.34(c), Callister & Rethwisch 9e. (courtesy of Pratt and Whitney) (Courtesy P.M.

(Courtesy P.M. Anderson)

-- turbine blades Fig. 8.34(c), Callister & Rethwisch 9e. (courtesy of Pratt and Whitney) (Courtesy P.M.

Polycrystals

Polycrystals • Most engineering materials are polycrystals. Anisotropic 1 mm Fig. K, color inset pages of

Most engineering materials are polycrystals.

Anisotropic

1 mm
1 mm

Fig. K, color inset pages of Callister 5e.

(Courtesy of Paul E. Danielson, Teledyne Wah Chang Albany)

. (Courtesy of Paul E. Danielson, Teledyne Wah Chang Albany) Isotropic • Nb-Hf-W plate with an

Isotropic

• Nb-Hf-W plate with an electron beam weld.

• Each "grain" is a single crystal.

• If grains are randomly oriented,

is a single crystal. • If grains are randomly oriented, overall component properties are not directional.

overall component properties are not directional.

• Grain sizes typically range from 1 nm to 2 cm

(i.e., from a few to millions of atomic layers).

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Single vs. polycrystals

• Single Crystals

-Properties vary with direction: anisotropic. -Example: the modulus of elasticity (E) in BCC iron:

E (diagonal) = 273 GPa

of elasticity ( E ) in BCC iron: E (diagonal) = 273 GPa Data from Table
of elasticity ( E ) in BCC iron: E (diagonal) = 273 GPa Data from Table

Data from Table 3.4, Callister & Rethwisch 9e.

(Source of data is R.W. Hertzberg, Deformation and Fracture Mechanics of Engineering Materials, 3rd ed., John Wiley and Sons, 1989.)

E (edge) = 125 GPa

200 μm
200 μm

• Polycrystals

-Properties may/may not vary with direction. -If grains are randomly oriented: isotropic.

direction. -If grains are randomly oriented: isotropic . ( E p o l y i r

(E poly iron = 210 GPa)

-If grains are textured, anisotropic.

o n = 210 GPa) -If grains are textured , anisotropic. Adapted from Fig. 4.15(b), Callister

Adapted from Fig. 4.15(b), Callister & Rethwisch 9e.

[Fig. 4.15(b) is courtesy of L.C. Smith and C. Brady, the National Bureau of Standards, Washington, DC (now the National Institute of Standards and Technology, Gaithersburg, MD).]

Polymorphism

• Two or more distinct crystal structures for the same material (allotropy/polymorphism)

titanium α, β -Ti

carbon diamond, graphite

iron system

liquid

BCC

FCC

BCC

liquid BCC FCC BCC 1538 ° C δ -Fe 1394 ° C γ -Fe 912 °
liquid BCC FCC BCC 1538 ° C δ -Fe 1394 ° C γ -Fe 912 °
liquid BCC FCC BCC 1538 ° C δ -Fe 1394 ° C γ -Fe 912 °
liquid BCC FCC BCC 1538 ° C δ -Fe 1394 ° C γ -Fe 912 °
liquid BCC FCC BCC 1538 ° C δ -Fe 1394 ° C γ -Fe 912 °
liquid BCC FCC BCC 1538 ° C δ -Fe 1394 ° C γ -Fe 912 °
liquid BCC FCC BCC 1538 ° C δ -Fe 1394 ° C γ -Fe 912 °
liquid BCC FCC BCC 1538 ° C δ -Fe 1394 ° C γ -Fe 912 °

1538° C δ-Fe

1538 ° C δ -Fe 1394 ° C γ -Fe

1394° C γ-Fe

liquid BCC FCC BCC 1538 ° C δ -Fe 1394 ° C γ -Fe 912 °

912° C

α-Fe
α-Fe
Crystallographic Indices
Crystallographic Indices

Labeling the crystal structures

Point Coordinates Direction Indices Plane Indices (Miller Indices) Miller-Bravais Indices
Point Coordinates
Direction Indices
Plane Indices (Miller Indices)
Miller-Bravais Indices

Point coordinates

Any point within a unit cell is specified as fractional multiples of the unit cell edge lengths

Position P specified as q r s; convention: coordinates not separated by commas or punctuation marks

coordinates not separated by commas or punctuation marks • Point P: q r s q (a

Point P: q r s

q (a fraction) qa (the distance)x axis

r (a fraction) rb (the distance)y axis

s (a fraction) sc (the distance)z axis

Point coordinates Example 1

Task: Locate the point 1/4 1 ½ x

y

z

(fractional multiples of the unit cell edge lengths)

coordinates Example 1 Task: Locate the point 1/4 1 ½ x y z ( fractional multiples

Point coordinates Example 2

Task: Specify point coordinates for all atom positions for a BCC unit cell

Example 2 Task: Specify point coordinates for all atom positions for a BCC unit cell BCC:

BCC: 8 corner atoms 1 center atom

Point coordinates Example 2

Task: Specify point coordinates for all atom positions for a BCC unit cell
Task: Specify point coordinates for all atom positions for a BCC unit cell

BCC: 8 corner atoms 1 center atom

Point coordinates Example 3

Task: Specify point coordinates for all atom positions for a FCC unit cell

z C8 C5 F5 C7 C6 F4 F1 F3 y F2 C1 C4 F6 C2
z
C8
C5
F5
C7
C6
F4
F1
F3
y
F2
C1
C4
F6
C2
C3

x

FCC: 8 corner atoms 6 face center atoms

C1: 0 0 0 C2: 1 0 0 C3: 1 1 0 C4: 0 1 0 C5: 0 0 1 C6: 1 0 1 C7: 1 1 1 C8: 0 1 1

F1:

F2:

F3:

F4:

F5:

F6:

Point coordinates Example 3

Task: Specify point coordinates for all atom positions for a FCC unit cell

z C8 C5 F5 C7 C6 F4 F1 F3 y F2 C1 C4 F6 C2
z
C8
C5
F5
C7
C6
F4
F1
F3
y
F2
C1
C4
F6
C2
C3

x

FCC: 8 corner atoms 6 face center atoms

C1: 0 0 0 C2: 1 0 0 C3: 1 1 0 C4: 0 1 0 C5: 0 0 1 C6: 1 0 1 C7: 1 1 1 C8: 0 1 1

F1: ½

0 ½

F2: 1

½

½

F3: ½

1 ½

F4: 0 ½

½

F5: ½

½

1

F6: ½

½

0

Point coordinates Example 4

Task: Specify point coordinates for diamond unit cell

4 Task: Specify point coordinates for diamond unit cell z C8 C5 F5 C7 C6 F4
z C8 C5 F5 C7 C6 F4 F1 F3 y F2 C1 C4 F6 C2
z
C8
C5
F5
C7
C6
F4
F1
F3
y
F2
C1
C4
F6
C2
C3

x

C8 C5 F5 C7 C6 F4 F1 F3 y F2 C1 C4 F6 C2 C3 x

F1: ½

0 ½

F2: 1

½

½

F3: ½

1 ½

F4: 0 ½

½

F5: ½

½

1

F6: ½

½

0

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Point coordinates Example 4

Task: Specify point coordinates for diamond unit cell

4 Task: Specify point coordinates for diamond unit cell 3 1 3 1 3 3 4

3

1

3

1

3 3

4 4 4
4 4 4
point coordinates for diamond unit cell 3 1 3 1 3 3 4 4 4 4

4 4 4

3 3

1

4 4 4
4 4 4
1 1 1
1 1
1

4 4 4

3 1 3 4 4 4 1 1 1 4 4 4
3
1
3
4
4 4
1
1
1
4
4 4
unit cell 3 1 3 1 3 3 4 4 4 4 4 4 3 3

4

4 4

1

3 3

3

3

1

unit cell 3 1 3 1 3 3 4 4 4 4 4 4 3 3

4

4

4

Point coordinates Example 5

Task: Specify point coordinates for atoms outside a unit cell

y
y

x

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