CHAPTER 3

The Structure of Crystalline Solids

Chapter 3-

ISSUES TO ADDRESS...
How do atoms assemble into solid structures?

(focus on metals)
How does the density of a material depend on

its structure?
When do material properties vary with the

sample (i.e., part) orientation?

Chapter 3- 1

Level of Structure in Metals

Macrostructure Microstructure Substructure Crystal Structure Electronic Structure Nuclear Structure 10 X 1500 X 105 X (SEM) X ray Spectrometer Nuclear Spectrometer
Chapter 3-

Material Structure Level &

Crystallization
Chapter 3-

How do atoms assemble into solid structures? (focus on metals) SOLID MATERIALS

Crystalline Materials

Non-Crystalline Materials

Single Crystal

Poly-Crystal
Chapter 3-

MATERIALS AND PACKING

Noncrystalline materials...

atoms have no periodic packing

occurs for: -complex structures -rapid cooling

Si

Oxygen

"Amorphous" = Noncrystalline noncrystalline SiO2

Chapter 3-

Single Crystal (Quartz)

Chapter 3-

MATERIALS AND PACKING

atoms pack in periodic, 3D arrays

Crystalline materials...

typical of: -metals -many ceramics -some polymers

Si

Oxygen

crystalline SiO2

Chapter 3-

METALLIC CRYSTALS
tend to be densely packed. have several reasons for dense packing:
-Typically, only one element is present, so all atomic

radii are the same. same. -Metallic bonding is not directional. directional. -Nearest neighbor distances tend to be small in order to lower bond energy. energy.

have the simplest crystal structures.

Chapter 3- 4

Metallic Solids (Imp. Props) High Strength Ductile High Density Good electrical and thermal conductivity Good workability

Chapter 3-

Crystal Structure Terminology

Crystal Lattice (Regular periodic arrangement of atoms)

Unit cell Lattice parameters

a , b, c

&

, ,
Chapter 3-

7 Crystal Systems
CUBIC TETRAGONAL ORTHORHOMBIC RHOBOHEDRAL MONOCLINIC TRICLINIC HEXAGONAL
Chapter 3-

CUBIC Crystal Structure

a=b=c

= = = 90
Chapter 3-

TETRAGONAL CRYSTAL STRUCTURE

a=bc

= = = 90
Chapter 3-

ORTHORHOMBIC Crystal Structure

abc

= = = 90

Chapter 3-

RHOMBOHEDRAL Crystal Structure

a=b=c

= = 90
Chapter 3-

MONOCLINIC Crystal Structure

abc

= = 90
Chapter 3-

TRICLINIC Crystal Structure

abc
90
Chapter 3-

HEXAGONAL Crystal Structure

a=bc

= = 90, = 120
Chapter 3-

SIMPLE CUBIC STRUCTURE

Chapter 3-

SIMPLE CUBIC STRUCTURE (SC)

Rare due to poor packing (only Po has this structure)

Ex.: Po structure
Chapter 3- 5

Effective No. of Atoms in a unit cell

a R=0.5a
close-packed directions contains 8 x 1/8 = 1 atom/unit cell
Chapter 3-

ATOMIC PACKING FACTOR

Volume of atoms in unit cell* APF = Volume of unit cell *assume hard spheres

Chapter 3- 6

Data for Simple Cubic Structure

Coordination No. (CN) 6 a-r Relation a=2r

Effective No. of atoms per unit cell (EN) 1/8 X 8 = 1 Atomic Packing Factor (APF) 0.5
Chapter 3-

Body Centered Cubic (BCC)

Chapter 3-

BODY CENTERED CUBIC STRUCTURE (BCC)

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

Ex Structure of Cr, Iron

Chapter 3- 7

Data for BCC Structure

Coordination No. (CN) 8 a-r Relation

4r = 3a

Effective No. of atoms per unit cell (EN) 1/8 X 8 + 1 = 2 Atomic Packing Factor (APF) 0.68
Chapter 3-

Face Centered Cubic (FCC)

Chapter 3-

FACE CENTERED CUBIC STRUCTURE (FCC)

--Note: All atoms are identical; the face-centered atoms are shaded

differently only for ease of viewing.

Ex.: Structure of Al, Cu, Au

Chapter 3- 9

Data for FCC Structure

Coordination No. (CN) 12 a-r Relation

4r = 2 a

Effective No. of atoms per unit cell (EN) 1/8(8)+1/2(6) = 4 Atomic Packing Factor (APF) 0.74
Chapter 3-

Hexagonally Packed Structure (HCP)

Chapter 3-

CLOSELY PACKED STRUCTURE (HCP)

Stacking A-B-A-B-A-B

A
Chapter 3-

HEXAGONAL CLOSE-PACKED STRUCTURE (HCP)

ABAB... Stacking Sequence 3D Projection

A sites B sites A sites

Ex.: Structure of Mg & Al
Chapter 3- 12

Data for HCP Structure

Coordination No. (CN) 12 a-r Relation a=2r

Effective No. of atoms per unit cell (EN) = 1/6(12) + (2) + 1(3) = 6 Atomic Packing Factor (APF) = 0.74
Chapter 3-

CLOSELY PACKED STRUCTURE (FCC)

Stacking A-B-C-A-B-C-A-B-C

C
Chapter 3-

FCC STACKING SEQUENCE

ABCABC... Stacking Sequence 2D Projection

A B C

Chapter 3-

Study of Crystallographic Points

Crystallographic Directions

Crystallographic Planes
Chapter 3-

Crystallographic Points

Chapter 3-

Point q r s
z b a

qrs c qa rb x
Chapter 3-

sc y

Locate 1 Point in a unit cell

z b = 0.46 nm a = 0.48 nm

1
c= 0.40 nm 0.12 0.46 x
Chapter 3-

0.20 y

Crystallographic Points in a SC Unit Cell

z b a 5 7 8

6 c 1 x 2

3
Chapter 3-

Concept of Set of Equivalent Points

Chapter 3-

Equivalent Crystallographic Points

are the points to arrive at same corresponding point by unit translations.

Chapter 3-

Set of Equivalent Points in a SC Unit Cell

0 0 0 All Corner Points

Chapter 3-

Crystallographic Points in a BCC Unit Cell

z b a 5 7 9 c 1 2 3
Chapter 3-

Set of Equivalent Points in a BCC Unit Cell

0 0 0 All Corner Points

All Body Centered

Chapter 3-

Lattice Points in a FCC Unit Cell

z b a 5 7 6 c 9 1 10 x 2 3
Chapter 3-

11 4 y

Set of Equivalent Points in a FCC Unit Cell

0 0 0 All Corner Points

0 All z-face centered 0 All y-face centered 0 All x-face centered
Chapter 3-

Crystallographic Direction (Vector)

Chapter 3-

Procedure to Draw a Crystal Direction in a Unit Cell

Note intercepts on x-, y- & z-axis in terms of edge lengths. Divide the intercepts by corresponding edge lengths Reduce them to smallest integers Enclose these integers in Sqr bracket e.g. [u v w]. Note [u v w] for one dirn, <u v w> for family of dirns. Negative index is noted by a bar on the top.

Chapter 3-

Crystallographic Direction in a cubic Unit Cell

z a a

a O y

OA [1 0 0]
Chapter 3-

Crystallographic Direction in a cubic Unit Cell

z a a

a O y

OA [1 1 0]
Chapter 3-

Crystallographic Direction in a cubic Unit Cell

z a a

OA [1 1 1]
Chapter 3-

Direction in a cubic Unit Cell

z a a

a A O a/2 y

OA [2 0 1]
Chapter 3-

Direction in a cubic Unit Cell

z a a

A O a/2 a/2 x

OA [1 2 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell OR Family of Directions

are the directions which are crystallographically equivalent; i.e. having same atomic packing (spacing)

Chapter 3-

Equivalent Directions in a cubic Unit Cell along edges of cube

z a a

a O y A x

OA [1 0 0]
Chapter 3-

Equivalent Directions in a cubic Unit Cell along edges of cube

z a a

a O y A x

AO [1 0 0]
Chapter 3-

Equivalent Directions in a cubic Unit Cell along edges of cube

z a a

a O y A x

OA [0 1 0]
Chapter 3-

Equivalent Directions in a cubic Unit Cell along edges of cube

z a a

a O y A x

AO [0 1 0]
Chapter 3-

Equivalent Directions in a cubic Unit Cell along edges of cube

z a a A a O y

OA [0 0 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell along edges of cube

z a a A a O y

AO [0 0 1]
Chapter 3-

Equivalent Directions along edges

Family Representation <1 0 0>

Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a

a O y

OA [1 1 0]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a

a O y

AO [1 1 0]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a

y A x O

OA [1 1 0]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a

y A x O

AO [1 1 0]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a A a O y

OA [1 0 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a A a O y

AO [1 0 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a A a

OA [1 0 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a A a

AO [1 0 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a A

y O x

OA [0 1 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a A

y O x

AO [0 1 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a A a

y O x

OA [0 1 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along face-diagonal of cube

z a a A a

y O x

AO [0 1 1]
Chapter 3-

Equivalent Directions along Face Diagonals

Family Representation <1 1 0>

Chapter 3-

Equivalent Directions in a cubic Unit Cell

along Body-Diagonal of cube

z a a A a

y O x

OA [1 1 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along Body-Diagonal of cube

z a a A a

y O x

AO [1 1 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along Body-Diagonal of cube

z a a A a

OA [1 1 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along Body-Diagonal of cube

z a a A a

AO [1 1 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along Body-Diagonal of cube

z a a A a

y O x

OA [1 1 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along Body-Diagonal of cube

z a a A a

y O x

AO [1 1 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along Body-Diagonal of cube

z a a A

OA [1 1 1]
Chapter 3-

Equivalent Directions in a cubic Unit Cell

along Body-Diagonal of cube

z a a A

AO [1 1 1]
Chapter 3-

Equivalent Directions along Body Diagonals

Family Representation <1 1 1>

Chapter 3-

Important Observation in Cubic Unit Cell

In case of cubic unit cell, directions having same indices irrespective of ORDER & SIGN are equivalent. E.g. [1 1 0], [0 1 1], [1 0 1] are equivalent

Chapter 3-

Draw a [1 1 0] direction in a Cubic Unit Cell

z a a

a -a O [1 1 0] [1 1 0] A x A
Chapter 3-

y O

Shift of Origin to accommodate ve direction in unit cell itself O) [u v w]

z a a 6 3 7 a 5

[- + + ] [+ - + ] [+ + -] [- - + ]
y

[+ - -] [- + -]

2 1 x 4

[- - -]
Chapter 3-

Crystallographic Planes

Chapter 3-

Procedure to Draw a Crystallographic Plane in a Unit Cell

Note intercepts on x-, y- & z-axis in terms of edge lengths. Divide the intercepts by corresponding edge lengths Write the reciprocals Reduce them to smallest integers Enclose these integers in parenthesis e.g. (h k l). Note (h k l) for one plane {h k l} for family of planes Negative indices are noted by a bar on the top

Chapter 3-

Crystal Planes in a cubic Unit Cell along faces of unit cell

z a a B

y A x D

ABCD (1 0 0)
Chapter 3-

Crystal Planes in a cubic Unit Cell along faces of unit cell

z a a C a D

y A x B

ABCD (0 1 0)
Chapter 3-

Crystal Planes in a cubic Unit Cell along faces of unit cell

z a a A C a D

ABCD (0 0 1)
Chapter 3-

Crystal Planes in a cubic Unit Cell

along face-Diagonal of cube

z a a B C

y D x A

ABCD (1 1 0)
Chapter 3-

Crystal Planes in a cubic Unit Cell along face-Diagonal of cube

z a a D C a

ABCD (1 1 0)
x B OR

ABCD (1 1 0)
Chapter 3-

Crystal Planes in a cubic Unit Cell along face-Diagonal of cube

z a a B C

ABCD (0 1 1)
Chapter 3-

Crystal Planes in a cubic Unit Cell along face-Diagonal of cube

z a a B a C

y D A

ABCD (0 1 1)
OR

ABCD (0 1 1)
Chapter 3-

Crystal Planes in a cubic Unit Cell along face-Diagonal of cube

z a a C B a

D x

ABCD (1 0 1)
OR
Chapter 3-

ABCD (1 0 1)

Crystal Planes in a cubic Unit Cell along face-Diagonal of cube

z B a a A

y O C x D

ABCD (1 0 1)
Chapter 3-

Crystal Planes in a cubic Unit Cell

along 3 face diagonals of a cube

z a a C a

y B x A

ABC (1 1 1)
Chapter 3-

Determine the Miller Indices for the plane ABCD

z a a

C a/2 a D B y

ABCD (0 1 2)
Chapter 3-

Construct a (0 1 1) plane within a Cubic Unit Cell

z a a

x
Chapter 3-

For (0 1 1) plane adjacent Unit Cell in ve ydirection is required

z a a

-y O

A
Chapter 3-

(0 1 1) plane w.r.t Cubic Unit Cell

z a a (0 1 1) a

-y O 0 x
Chapter 3-

Transfer the coordinate System to accommodate y axis

a a

a z -y x O y

Chapter 3-

(0 1 1) plane within a Cubic Unit Cell

a a B (0 1 1) z D -y x A
Chapter 3-

y O

Construct a (1 1 1) plane within a Cubic Unit Cell

z a a O a C

x
Chapter 3-

Construct a (1 1 1) plane within a Cubic Unit Cell

z a a O B a (1 1 1) y A

C
Chapter 3-

Equivalent Planes OR Family of Planes

are the planes which are Crystallographically equivalent; i.e. having the same atomic packing (spacing)

{1 0 0} {1 1 0} {1 1 1}
Chapter 3-

Important Observation in Cubic Unit Cell

In case of cubic unit cell, planes having same indices irrespective of ORDER & SIGN are equivalent. E.g. (0 0 1), (0 1 0), (1 0 0) are equivalent

Chapter 3-

Important Observation in Cubic Unit Cell

z a a B

y O A x D Miller indices are same for a plane and direction, which are perpendicular to each other

ABCD (1 0 0) OA [1 0 0]
Chapter 3-

Density of a crystal Structure

Chapter 3-

Theoretical Density of a crystal Structure

Th =
n A Vc Na

nA Vc N
A

Effective No. of atoms per unit cell Atomic weight, gram per mole Volume of unit cell Avogadro's No. = 6.023 X 1023
Chapter 3-

Theoretical Density of Cu
Data from Table inside front cover of Callister
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 = 10-7 cm) R = 0.128 x 10-7 cm

Vc = a3 ; For FCC, a = 4R/ 2 ; Vc = 4.75 x 10-23cm3

Result: theoretical Cu = 8.89 g/cm3 Compare to actual: Cu = 8.94 g/cm3

Chapter 3-

DENSITIES OF MATERIAL CLASSES

metals ceramics polymers
Why?
Metals have...
close-packing (metallic bonding) large atomic mass
30 20
Platinum Gold, W Tantalum Silver, Mo Cu,Ni Steels Tin, Zinc Titanium Aluminum Magnesium

Metals/ Alloys

Graphite/ Ceramics/ Polymers Semicond

Composites/ fibers

10

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

Ceramics have...

(g/cm3)

less dense packing (covalent bonding) often lighter elements

5 4 3 2

Glass fibers PTFE Silicone PVC PET PC HDPE, PS PP, LDPE GFRE* Carbon fibers CFRE* Aramid fibers AFRE*

Polymers have...
poor packing (often amorphous) lighter elements (C,H,O)
1

Composites have...
intermediate values

0.5 0.4 0.3

Wood

Chapter 3- 16

Atomic arrangements
(110) plane of FCC
C B A D E F A B C

F E D

Reduced sphere FCC unit cell with (110) plane

Atomic packing in (110) plane

Chapter 3-

 Atomic packing in (100) plane of FCC

Atomic Packing in (111) plane of BCC

Chapter 3-

Atomic arrangements (110) plane of BCC

B/ A/ C/ E/ D/ A/ C/ E/ B/

D/

Reduced sphere BCC unit cell with (110) plane

Atomic packing in (110) plane of a BCC structure

Chapter 3-

Atomic Packing Factor: BCC

APF for a body-centered cubic structure = 0.68
3a

a
2a
From Fig. 4.2(a) Callisters Materials Science and Engineering, Adapted Version.

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

atoms volume 4 3 ( 3 a/4 ) 2 unit cell atom 3 APF = volume 3 a unit cell

Chapter 3-

119

Atomic Packing Factor: FCC

APF for a face-centered cubic structure = 0.74 maximum achievable APF Close-packed directions: length = 4R = 2 a 2a Unit cell contains: 6 x 1/2 + 8 x 1/8 = 4 atoms/unit cell atoms 4 ( 2 a/4 ) 3 4 unit cell 3 APF = a3 volume atom volume unit cell 120
Chapter 3-

a
From Fig. 4.1(a), Callisters Materials Science and Engineering, Adapted Version.

LINEAR DENSITY

Chapter 3-

Linear Density formula

Number.of .atoms.centered .on.direction.vector LD = Length.of .Direction.Vector

Chapter 3-

Linear density in a SC unit cell along Edge <1 0 0>

z a a

LD<1 0 0> = 1/ a = 1/2R Chapter 3-

Linear density in a SC unit cell along Face Diagonal <1 1 0>

z a a

LD<1 1 0> = 1/ 2a = 1/2 2R

Chapter 3-

Linear density in a SC unit cell along Body Diagonal LD <1 1 1>

z a a

x LD<1 1 1> = 1/ 3aChapter = 1/2 3- 3R

Linear density in a BCC unit cell along Body Diagonal LD <1 1 1>
z a a

x LD<1 1 1> = 2/ 4RChapter = 1/ 32R

Linear Density
Linear Density of Atoms LD = [110] ex: linear density of Al in [110] direction a = 0.405 nm
Number of atoms Unit length of direction vector

# atoms a length

LD =

2 2a

= 3.5 nm

Chapter 3-

127

Linear density in a FCC unit cell along Face Diagonal LD <1 1 0>
z a a

LD<1 1 0> = 2/Chapter 2a= 1/2R 3-

PLANAR DENSITY

Chapter 3-

Planar Density Formula

Number.of . Atoms.centered .on.a.Plane PD = Area.of .a.Plane

Chapter 3-

Planar Density in a SC unit cell PD {1 0 0}

z a a

x PD{1 00}= 1 / a2 Chapter = 1/43R2

Planar Density in a SC unit cell PD {1 1 0}

z a a

PD{1 1 0}= 1 /a 2 a = 1/4R2 2

Chapter 3-

Planar Density in a SC unit cell PD {1 1 1}

z a a

PD{1 1 1}= 1/2 /( 3 a2/2) = 1/4R2 3 Chapter 3-

Planar Density in a BCC unit cell PD {1 0 0}

z a a

x PD{1 00}= 1 / a2 Chapter = 3/16 R2 3-

Planar Density in a BCC unit cell PD {1 1 0}

z a a

x PD{1 10}=2/ 2a2 = 3 2/16 R2 Chapter 3-

Planar Density in a BCC unit cell PD {1 1 1}

z a a

PD{1 1 1}= 1/2 /( 3 a2/2) = Chapter 33 /16R2

Planar Density in a FCC unit cell PD {1 0 0}

z a a

x PD{1 00}= 2 / a2 Chapter = 1/43R2

Planar Density in a FCC unit cell PD {1 1 0}

z a a

x
2 PD{1 10}=2/ 2a2 = 2/8R Chapter 3-

Planar Density in a FCC unit cell PD {1 1 1}

z a a

PD{1 1 1}= 2 /( 3 a2/2) = 1/2 3 R2

Chapter 3-

Polymorphism & Allotropy

Metals/Nonmetals may have more than one crystal structure. This phenomenon is called as polymorphism and the condition is called as allotropy

e.g.

1. Carbon: Graphite at ambient condition Diamond at extreme pressure 2. Iron: BCC Iron at room temperature FCC Iron at 912 oC.

Chapter 3-

DEMO: HEATING AND COOLING OF AN IRON WIRE

Demonstrates "polymorphism"
Temperature, C 1536 1391
longer heat up
FCC Stable Liquid BCC Stable

The same atoms can have more than one crystal structure.

914
Tc 768

BCC Stable

cool down

shorter! longer! magnet falls off shorter

Chapter 3- 22

ANISOTROPY
Directionality of a property is called as an ANISOTROPY. If properties are independent of direction, then material is called as ISOTROPIC material. Degree of anisotropy is dependent on structure symmetry. Higher the symmetry, lower the degree of anisotropy and lower the symmetry, higher the degree of anisotropy.
Chapter 3-

SUMMARY
Atoms may assemble into crystalline or amorphous structures. We can predict the density of a material, provided we know the atomic weight, atomic radius, and crystal geometry (e.g., FCC, BCC, HCP). Material properties generally vary with single crystal orientation (i.e., they are anisotropic), but properties are generally non-directional (i.e., they are isotropic) in polycrystals with randomly oriented grains.
Chapter 3- 23