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FundamentalStructure of CrystallineSolids

EnergyandPacking
Nondense,random packing Energy typicalneighbor bondlength typicalneighbor bondenergy Dense,ordered packing Energy typicalneighbor bondlength typicalneighbor bondenergy Dense,orderedpackedstructurestendtohave lowerenergies.
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MaterialsandPacking
Crystalline materials... atomspackinperiodic,3Darrays typicalof: metals manyceramics somepolymers

crystallineSiO2

Noncrystalline materials... atomshavenoperiodicpacking occursfor: complexstructures rapidcooling "Amorphous"=Noncrystalline

Si

Oxygen

noncrystallineSiO2

CrystalTerminalogy
Crystal:Regular,periodicandrepeatedarrangement Lattice:Threedimensionalarray ofpointscoincidingwithatom positions. Unitcell:smallestrepeatable entitythatcanbeusedto completelyrepresentacrystal structure.Itisthebuilding blockofcrystalstructure.

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A small group of lattice points which forms a repetitive pattern is called a unit cell.

7crystalsystems

14Bravais/spacelattices a,b,andc arethelatticeconstants

Classification of Crystal Systems: The angles ( ,,) between the lattice translation vectors and the distance(a,b,c) between two successive points along these vectors are used to classify the crystal structures into 7 systems

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SimpleCubicStructure(SC)
Rareduetolowpackingdensity (onlyPolonium(Po)hasthisstructure)

Coordination# =6 (#nearestneighbors)

(CourtesyP.M.Anderson) 9

AtomicPackingFactor(APF)
APF= Volumeofunitcell *assumehardspheres Volumeofatomsinunitcell*

volume atoms a R=0.5a unitcell APF= a3 volume unitcell APFforasimplecubicstructure=0.52

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4 1 3

atom (0.5a) 3

contains8x1/8= 1atom/unitcell Effectivenoofatoms/UC

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BodyCenteredCubicStructure(BCC)
Atomstoucheachotheralongcubediagonals. Note:Allatomsareidentical;thecenteratomisshaded differentlyonlyforeaseofviewing.

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

Coordination#=8

(CourtesyP.M.Anderson)

2atoms/unitcell:1center+8cornersx1/8
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AtomicPackingFactor:BCC
APFforabodycenteredcubicstructure=0.68

3a
a

2a
R Closepackeddirections: a 4 2 3 a3 volume unitcell
12

length=4R = volume atom

3a

atoms unitcell APF=

( 3 a/4 ) 3

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FaceCenteredCubicStructure(FCC)
Atomstoucheachotheralongfacediagonals. Note:Allatomsareidentical;thefacecenteredatomsareshaded differentlyonlyforeaseofviewing.

ex:Al,Cu,Au,Pb,Ni,Pt,Ag
Coordination#=12

4atoms/unitcell:6facex1/2+8cornersx1/8
(CourtesyP.M.Anderson) 13

AtomicPackingFactor:FCC
APFforafacecenteredcubicstructure=0.74 maximumachievableAPF Closepackeddirections: length=4R = 2a Unitcellcontains: 6x 1/2+8x 1/8 a atoms unitcell APF= a3 4 3 = 4atoms/unitcell 2a

( 2 a/4 ) 3

volume atom volume unitcell

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HexagonalClosePackedStructure (HCP)
2DProjection 3DProjection Asites Top layer

B sites Asites

Middlelayer Bottomlayer

a
Coordination#=12 APF=0.74 c/a =1.633
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6atoms/unitcell ex:Cd,Mg,Ti,Zn

Possible Bravais lattices: Cubic : Simple, BC, FC Hexagonal : Simple Tetragonal : Simple, BC Orthorhombic : Simple, Base C, Body-C, FC Monoclinic : Simple, BC Triclinic, Trigonal : Simple
Crystal System Cubic tetragonal Hexagonal Axial relationships a=b=c a=bc a=bc Interaxial Angles ===90o ===90o ==90 =120 ==90o ===90o ==90o 90o

Rhomohedral/try a=b=c gonal Orthorhombic Monoclinic triclinic a b c a b c a b c

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Allotropy

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THEORETICALDENSITY,
# atoms/unit cell

= nA VcNA Volume/unit cell

(cm3/unit cell)

Atomic weight (g/mol)

Avogadro's number (6.023 x 10 23 atoms/mol)

Example: Copper
Data from Table inside front page 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) 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

CharacteristicsofSelectedElementsat20C
At. Weight Element Symbol (amu) Aluminum Al 26.98 Argon Ar 39.95 Barium Ba 137.33 Beryllium Be 9.012 Boron B 10.81 Bromine Br 79.90 Cadmium Cd 112.41 Calcium Ca 40.08 Carbon C 12.011 Cesium Cs 132.91 Chlorine Cl 35.45 Chromium Cr 52.00 Cobalt Co 58.93 Copper Cu 63.55 Flourine F 19.00 Gallium Ga 69.72 Germanium Ge 72.59 Gold Au 196.97 Helium He 4.003 Hydrogen H 1.008 Density (g/cm3) 2.71 -----3.5 1.85 2.34 -----8.65 1.55 2.25 1.87 -----7.19 8.9 8.94 -----5.90 5.32 19.32 ----------Crystal Structure FCC -----BCC HCP Rhomb -----HCP FCC Hex BCC -----BCC HCP FCC -----Ortho. Dia. cubic FCC ----------Atomic radius (nm) 0.143 -----0.217 0.114 ----------0.149 0.197 0.071 0.265 -----0.125 0.125 0.128 -----0.122 0.122 0.144 ----------15

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metals ceramics polymers

Metals/ Alloys 30 20
Platinum Gold, W Tantalum Silver, Mo Cu,Ni Steels Tin, Zinc Titanium Aluminum Magnesium

DENSITIESOFMATERIALCLASSES
Graphite/ Ceramics/ Semicond Polymers Composites/ fibers
B ased 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 G raphite

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(g/cm3)

5 4 3 2 1

Glass fibers PTFE Silicone PVC PET PC H DPE, PS PP, LDPE GFRE* Carbon fibers CFRE * A ramid fibers AFRE *

0.5 0.4 0.3

Wood
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3.2

a)crystalSystem? Tetragonal b)CrystalStructure? BCT c)Density?ifAw=141g/mol

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Crystallographic Points Coordinates

Fractionalmultiplesofunitcell,edgelengths. Lessthanorequal1 Withoutseparationwithcommas(,)

z c

PointCoordinates
111

Pointcoordinatesforunitcell centerare a/2,b/2,c/2

a x

000

y b

Pointcoordinatesforunitcell cornerare111

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CrystallographicDirections
z Algorithm

1. Vector repositioned (if necessary) to pass through origin. 2. Read off projections in terms of unit cell dimensions a, b, and c y 3. Adjust to smallest integer values 4. Enclose in square brackets, no commas
x [uvw]

ex: 1 0 -1 1 1

=> 2 0 1 => [ 111 ]

=> [ 201 ] where overbar represents a negative index

families of directions <uvw>

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3.14

A) B) C) D)

How to draw the direction of [uvw] 1.Divide with the biggest integer among them. 2. Multiply with edge lengths.
3. Take corresponding length on ref. Axis/edges. 4. Farm a line by projection.

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_ 3.9: Draw a [211] direction in Orthorhombic unit cell?

1 2 3

U 2 2/2 a

V -1 -1/2 - b/2

W 1 1/2 c/2

4. Move along the edges / axis

_ 3.9: Draw a [211] direction in Orthorhombic unit cell?

1 2 3

U 2 2/2 a

V -1 -1/2 - b/2

W 1 1/2 c/2

4. Move along the edges / axis

c/2 -b/2 a

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HCPCrystallographicDirections

Algorithm

a2

a3 a1

1. Vector repositioned (if necessary) to pass through origin. 2. Read off projections in terms of unit cell dimensions a1, a2, a3, or c 3. Adjust to smallest integer values 4. Enclose in square brackets, no commas [uvtw]
a2
a2 2

-a3

ex:

, , -1, 0

=>

[ 1120 ]

a3
a1 2

dashed red lines indicate projections onto a1 and a2 axes

a1
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HCPCrystallographicDirections
HexagonalCrystals
4parameterMillerBravaislatticecoordinatesare relatedtothedirectionindices(i.e.,u'v'w')asfollows.
z

[ u ' v ' w ' ] [ uvtw ] u =

a2

1 3

( 2 u ' - v ')

v = -

1 3

( 2 v ' - u ')

a3 a1

t = - (u + v ) w = w '

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3.17

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Crystallographic Planes
Crystallographic planes are specified by Miller indices (hkl)

Indices are smallest Reciprocal of plane Intercepts with edges (Axis) of unit cell. Any two planes parallel to each other are equivalent and have identical indices.

Procedure: 1.Determine the intercepts made by the plane with the three axes. If the plane passes through the origin pick a parallel plane within the unit cell. 2. Calculate the reciprocals of the intercepts. 3. Divide by a common factor to convert to smallest possible integers. 4. Enclose in parentheses no commas i.e., (hkl)

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example 1. 2. 3. 4. Intercepts Reciprocals Reduction Miller Indices

a 1 1/1 1 1 (110)

b 1 1/1 1 1

c 1/ 0 0
a x c

y b

Example 2 1. 2. 3. 4. Intercepts Reciprocals Reduction Miller Indices

a 1 1/1 1 1 (111)

b 1 1/1 1 1

c 1 1/1 1 1

example z a 1. 2. Intercepts Reciprocals 1/2 1/ 2 3. 4. Reduction Miller Indices (634) 6 b 1 1/1 1 3 c 3/4 1/ 4/3 4 x a

b
y

Family of Planes {hkl} Same atomic arrangement Ex: {100} = (100), (010), (001), ( 100), (010), (001)

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3.22: Determine miller indices for the planes? Plane A 1. 2. 3. Intercepts Intercepts (in a,b,c) Reciprocals Miller Indices _ (111) h a 1 1 k b 1 1 l -c
-1

-1

Plane B

_ 3.19: a) Draw (021) plane for orthogonal unit cell? h 1. 2. 3 Indices Reciprocals Intercept par 0 k 2 1/2 b/2 l
-1

-1 -c

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3.19: b) (200) monoclinic

3.21: for cubic unit cell _ _ _ _ _ _ _ a) (101), b) (211) c) (012) d) (313) e) (111) f) (212) g) (312) h) (301)

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4.3) c/a = 1.633 in HCP

Atom at M is midway between the top and bottom so

Atom at M is midway between the top and bottom so

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Atomic Arrangements in planes

(110) For FCC

(110) For BCC

LinearDensity
Linear Density = number of atoms centered on direction vector length of direction vector
ex: linear density of FCC in [110] direction

[110]

a # atoms

LD =
length

1 2 = 2/a nm 2a
46

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BCC
[100] [110] [111]
R a

1/a 1/ 2 a 2/ 3 a

FCC
1/a 2/ a 1/ 3 a
a 2a

[100] [110] [111]

Planar Densities
Planar Density = number of atoms centered on a plane area of plane

(001) plane

# atoms

PD =
length

2 2 = 2 /a2 nm a2

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BCC
(100) (110) (111)
R a

1/a2 2 /a2 1/ 3a2

FCC
2/a2 2/ a2 4/ 3 a2
a 2a

(100) (110) (111)

Solution: AtT<912CironhastheBCCstructure.

PlanarDensityof(100)Iron
(100) 1/a2
2D repeat unit
a= 4 3 R

a Radius of iron R = 0.1241 nm

atoms 2D repeat unit

1 a2
=

Planar Density =
area 2D repeat unit

1 4 3
2

12.1

atoms atoms = 1.21 x 1019 2 nm2 m

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LinearDensityof[111]Iron
[111]
a= 4 3
Radius of iron R = 0.1241 nm R a

2/ 3a

atoms 2D repeat unit

2
= 4.029

linear Density =
length 2D repeat unit 3 4 R 3

atoms = nm

4.029

x 109

atoms m
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Highest planar & Linear density for FCC / CCP (Cubic Closed Pack) [110] 2/ a
2a

Closed packed directions

(111)

4/ 3

a2
a

Closed packed planes

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FCCSTACKINGSEQUENCE
ABCABC... Stacking Sequence 2D Projection A
B A sites B sites C sites FCC Unit Cell A B C B C B B C B B

A B C

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A A

B B C C

FCC Stacking sequence

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HEXAGONALCLOSEPACKED STRUCTURE(HCP)
ABAB... Stacking Sequence 3D Projection
A sites B sites A sites

2D Projection

Top layer Middle layer Bottom layer

12

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A B A

HCP Stacking sequence

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3.27: fallowing are the planes a) What is crystal system? b) What is crystal lattice? Tetragonal BCT

BCT

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4.20: fallowing are the planes a) What is crystal system? b) What is crystal lattice? Orthorambic

FCO

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c) Determine atomic wt if = 18.91 ?

# atoms/unit cell

= nA VcNA Volume/unit cell

(cm3/unit cell)

Atomic weight (g/mol)

Avogadro's number (6.023 x 10 23 atoms/mol)

4.10
TitaniumisHCPcrystalanddensity4.51gr/cm3 1) Vol ofunitcellinm3 ? 2) Ifc/aratiois1.58valueofa,c?

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4.12
Niobiumatomicradius0.143nm,density8.57g/cc DeterminewhetheritisaFCCorBCC

4.15

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Polymorphism
Twoormoredistinctcrystalstructuresforthe iron system samematerial(allotropy/polymorphism)
liquid

Titanium,Ti
BCC

1538C

-Fe
1394C

carbon diamond,graphite

FCC

-Fe
912C

BCC

-Fe

"Existence of an elemental solid into more than one physical forms is known as ALLOTROPY "
67

Existence of substance into more than one crystalline forms is known as "POLYMORPHISM".
Example: 1) Mercuric iodide (HgI2) forms two types of crystals. a. Orthorhombic b. Trigonal 2) Calcium carbonate (CaCO3) exists in two types of crystalline forms. a. Orthorhombic (Aragonite) b. Trigonal

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Allotropy

CRYSTALSASBUILDINGBLOCKS
Some engineering applications require single crystals: --diamond single crystals for abrasives --turbine blades

Crystal properties reveal features of atomic structure.

--Ex: Certain crystal planes in quartz fracture more easily than others.

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Polycrystals
Most engineering materials are polycrystals.

Anisotropic

1 mm

Nb-Hf-W plate with an electron beam weld. Each "grain" is a single crystal. If grains are randomly oriented,

Isotropic

overall component properties are not directional.

Grain sizes typ. range from 1 nm to 2 cm

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

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SinglevsPolycrystals
Single Crystals E (diagonal) = 273 GPa

-Properties vary with direction: anisotropic. -Example: the modulus of elasticity (E) in BCC iron:
Polycrystals E (edge) = 125 GPa

-Properties may/may not vary with direction. -If grains are randomly oriented: isotropic.
(Epoly iron = 210 GPa)

200 m

-If grains are textured, anisotropic.

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DEMO:HEATINGAND COOLINGOFANIRONWIRE
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

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Noncrystallinesolid
Noncrystalline materials... atomshavenoperiodicpacking occursfor: complexstructures rapidcooling "Amorphous"=Noncrystalline =supercooledliquid

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