Packing of Atoms in Solids [6]

¾ Metallic crystals－ are composed of bonded metal atoms.

Example: Ni, Cu, Fe, and alloys.

¾ Covalent crystals－consisted of an infinite network of

atoms held together by covalent bonds, no individual
molecules being present.
¾ Example: diamond, graphite, SiC and SiO2.

¾ Ionic crystals－consisted of an array of positive and

negative ions.
¾ Example: NaCl, MgO, CaCl2 and KNO3.

¾ Molecular crystals－are composed of individual

molecules. Example: Ar, CO2 and H2O.

1>
 Crystalline Solids
¾ Crystalline Solid is the solid form of a substance
in which atoms or molecules are arranged in a
definite, repeating pattern in three dimension.

¾ Single crystals, ideally have a high degree of

order, or regular 3D geometric periodicity,
throughout the entire volume of the material.

¾ Crystallography: The branch of science that deals

with the geometric description of crystals and
their internal arrangement. The word
"crystallography" derives from the Greek words
crystallon "cold drop, frozen drop", with its meaning
extending to all solids with some degree of
transparency, and grapho "I write".
http://en.wikipedia.org/wiki/Crystallography 2>
 Basic Crystallography

¾ Crystal Lattice:
¾ An infinite array of y
points in space,
B C D E
b α
¾ Each point has
O a A x
identical
surroundings to all
others.

¾ Arrays are arranged

exactly in a periodic
manner.

3>
 Basic Crystallography

¾ Crystal Lattice: can be obtained by attaching atoms,

groups of atoms or molecules which are called motif to
the lattice sides of the crystal lattice (points).
Crystal Structure = Crystal Lattice + Motif

4>
 2D Bravais Lattice
¾ Bravais lattice is an infinite array of discrete points with an
arrangement and orientation that appears exactly the same,
from whichever of the points
the array is viewed.

¾ Lattice must be
invariant under
translation.

¾ All 2D space
must be filled.

Bravais Lattices
in 2D

5>
 3D Unit Cell
¾ In three-dimensional space, there are 14 Bravais lattices.
These are obtained by combining one of the seven crystal
systems with one of the symmetry operations.
¾ Polyhedral shape: - cell edges (a, b, c)
- cell angles (α, β, γ)

6>
 A General Crystalline Solid

¾ The unit cell (Bravais Lattice) is the smallest, most

symmetrical repeat unit that, when translated in three
dimensions, will generate the entire crystal lattice.

http://www.chem.latech.edu/~upali/chem281/notes/C3-metals.htm
7>
 The Seven Crystal Systems
¾ A lattice system is generally identified as a set of lattices with
the same shape according to the relative lengths of the cell
edges (a, b, c) and the angles between them (α, β, γ).

¾ triclinic
¾ monoclinic
¾ orthorhombic
¾ tetragonal
¾ rhombohedral
¾ hexagonal
¾ cubic

Symmetry increases
8>
 ¾ 7 Crystal Systems
The Seven Crystal Systems

http://www.materials.ac.uk/elearning/matter/crystallography/3dcrystallography/7crystalsystems.html
linear and angular distortions

9>
 The Fourteen Bravais Lattices
The lattice types:
¾ Primitive (P)
¾ Body-Centered (I)
¾ Face-Centered (F)
¾ Base-Centered (A, B, or C) Rhombohedral (R)

P
P C
P C I F
P I
P I F
R
P

10>
The Fourteen Bravais Lattices

11>
 Body-Centered Cubic (BCC) elements

BCC elements: 16/90 (~18%) 12>

 Face-Centered Cubic (FCC) elements

FCC elements: 21/90 (~23%)

13>
 Hexagonal Close-Packing (HCP) elements

HCP elements: 31/90 (~34%) 14>

 Metallic Crystal Structures

¾ Tend to be densely packed.

¾ Reasons for dense packing:
¾ Typically, only one element is present, so all
atomic radii are the same.
¾ Metallic bonding is not directional.
¾ Nearest neighbor distances tend to be small in
order to lower bond energy.
¾ The “electron cloud” shields cores from each
other.
¾ They have the simplest crystal structures.

15>
 Metallic Crystal Structures
¾ Cubic Cell Units:

16>
 Crystal Structures

¾ Coordinatıon Number (CN): The Bravais lattice

points closest to a given point are the nearest
neighbours.

¾ Because the Bravais lattice is periodic, all points

have the same number of nearest neighbours or
coordination number. It is a property of the lattice.

¾ A simple cubic has coordination number 6; a body-

centered cubic lattice, 8; and a face-centered cubic
lattice,12.

17>
 Crystal Structures

¾ Atomic Packing Factor (APF): defined as

the volume of atoms (hard spheres) within
the unit cell divided by the volume of the
unit cell.

18>
 Simple Cubic Structure (SC)

¾ Rare due to low packing density (only Po has this structure)

¾ Close-packed directions are cube edges.

¾ Coordination Number = 6
(nearest neighbors)

19>
 Simple Cubic Structure (SC)

¾ APF for a simple cubic structure = 0.52

volume
atoms atom
unit cell
⎛4 3⎞
1 ⋅ ⎜ π (0.5) ⎟
a
APF = ⎝ 3 ⎠
R=0.5a 3
a
close-packed directions volume
unit cell
SC contains 8 x 1/8 = 1 atom/unit cell
20>
 Body-Centered Cubic Structure (BCC)

¾ Atoms touch each other along cube diagonals.

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

¾ Coordination Number = 8

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

21>
 Body-Centered Cubic Structure (BCC)
¾ APF for a body-centered cubic structure = 0.68
3a

2a

Close-packed directions:
R length = 4R = 3 a
a
⎛ 4 ⎛ 3 ⋅ a ⎞3 ⎞ volume
⎜
2⋅ π⎜ ⎜ ⎟ ⎟
atoms
⎜3 4 ⎠ ⎟ ⎟ atom
unit cell ⎝ ⎝ ⎠
APF =
a3 volume
unit cell 22>
 Face-Centered Cubic Structure (FCC)
¾ Atoms touch each other along face diagonals.
ex: Al, Cu, Au, Pb, Ni, Pt, Ag

¾ Coordination Number = 12

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

23>
 Face-Centered Cubic Structure (FCC)
¾ APF for a face-centered cubic structure = 0.74

FCC Close-packed directions:

length = 4R = 2 a
2a
FCC Unit cell contains:
6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
⎛ 4 ⎛ 2 ⋅ a ⎞3 ⎞ volume
⎜
4⋅ π⎜ ⎜ ⎟ ⎟
atoms
⎜3 4 ⎠⎟ ⎟ atom
unit cell ⎝ ⎝ ⎠
APF = 3
a volume
unit cell 24>
 Hexagonal Close-Packed Structure (HCP)

¾ HCP formed by compact planes (ABAB...)

ex: Ti, Co, Zr, Zn

2 atoms/unit cell: ¾ Coordination Number = 12

1 body + 1/2 basal plane x 2
25>
 Hexagonal Close-Packed Structure (HCP)

¾ APF for a hexagonal close-packed structure = 0.74

¾ In the HCP structure:
a = b = 2⋅r
2
c=4 ⋅r
3

r is the atomic radius of the atom.

¾ The volume of the HCP cell:

V = 8 2 ⋅ r3
4 3 4 3
2 × πr 2 × πr
AFP = 3 = 3 = 0.7405
3
V 8 2r 26>
 FCC – HCP Stacking Sequence

¾ HCP Stacking Sequence: ABABABABA....

27>
 FCC – HCP Stacking Sequence

¾ FCC Stacking Sequence: ABCABCABCA....

28>
 FCC – HCP Stacking Sequence

¾ HCP Stacking Sequence: ABABABA....

¾ FCC Stacking Sequence: ABCABCA....
https://www.youtube.com/watch?v=pdFqpDilLwY

https://www.youtube.com/watch?v=xyjW59-CYqk

https://www.youtube.com/watch?v=tgKC-awk6p4
29>
 Calculation of Theoretical Density (ρ)

¾ Determine the density of BCC iron, which

has a lattice parameter of 0.2866 nm.
SOLUTION:
Atoms/cell = 2, a0 = 0.2866 nm = 2.866 × 10-8 cm
Atomic mass = 55.847 g/mol
3
Volume of unit cell = a 0= (2.866 × 10-8 cm)3 = 23.54 × 10-24
cm3/cell
Avogadro’s number NA = 6.02 × 1023 atoms/mol

(number of atoms/cell)(atomic mass of iron)

Density ρ =
(volume of unit cell)(Avogadro' s number)
(2)(55.847)
ρ = − 24
= 7.882 g / cm
3

(23.54 × 10 )(6.02 × 10 ) 23

30>
 Allotropic or Polymorphic Transformations

¾ Allotropy: The characteristic of an element being able

to exist in more than one crystal structure, depending on
temperature and pressure.
¾ Polymorphism: Compounds exhibiting more than one
type of crystal structure.

Titanium Iron 31>

Allotropic or Polymorphic Transformations

32>
 Allotropic or Polymorphic Transformations
¾ Iron is BCC at 911oC with a lattice parameter of 0.2863
nm. At 913oC, iron is FCC, with a lattice parameter of
0.3591 nm. Determine the % change in volume.

SOLUTION: The volume of a unit cell of BCC iron before

transforming is:
VBCC = (0.2863 nm)3 = 0.023467 nm3
The volume of the unit cell in FCC iron is:
VFCC = (0.3591 nm)3 = 0.046307 nm3

But this is the volume occupied by four iron atoms, as there are
four atoms per FCC unit cell. Therefore, we must compare two
BCC cells (with a volume of 2 x (0.023467) = 0.046934 nm3)
with each FCC cell. The percent volume change during
transformation is:

(0.046307 - 0.046934)
Volume change = × 100 = −1.34%
0.046934
Fe (BCC) Æ Fe (FCC)
33>
 Interstitial Voids in FCC Cells

TETRAHEDRAL OCTAHEDRAL

¼ way along body diagonal At body centre

{¼, ¼, ¼}, {¾, ¾, ¾} FCC {½, ½, ½}
+ face centering translations + face centering translations
1
Vtetrahedron = Vcell Voctahedron
1
= Vcell
24 6
Note: Atoms are coloured differently but are the same 34>
 Interstitial Voids in FCC Cells

FCC- OCTAHEDRAL

Site for octahedral void

{½, ½, ½} + {½, ½, 0} = {1, 1, ½} ≡ {0, 0, ½}

Equivalent site for an
Face centering translation
octahedral void
Note: Atoms are coloured differently but are the same
35>
 Interstitial Voids Positions in FCC Cells

FCC voids Position Voids / cell Voids / atom

¼ way from each vertex of the cube

Tetrahedral along body diagonal <111> 8 2
→ ((¼, ¼, ¼))
• Body centre: 1 → (½, ½, ½)
Octahedral 4 1
• Edge centre: (12/4 = 3) → (½, 0, 0)
36>
 Interstitial Voids in FCC Cells

Size of the largest atom which can fit into the tetrahedral void of FCC

CV = r + x Radius of the
new atom
e 6
e=r+x
4
x ⎛ 3 ⎞
e = 2r ⇒ = ⎜⎜ − 1⎟⎟ ~ 0.225
r ⎝ 2 ⎠
Size of the largest atom which can fit into the Octahedral void of FCC

2r + 2x = a 2a = 4r
x
r
= ( )
2 − 1 ~ 0.414
37>
 Interstitial Voids in BCC Cells
Distorted TETRAHEDRAL Distorted OCTAHEDRAL**

a√3/2

a
a a√3/2

Coordinates of the void: Coordinates of the void:

{½, 0, ¼} (four on each face) {½, ½, 0} (+ BCC translations: {0, 0, ½})

rvoid / ratom = 0.29 rVoid / ratom = 0.155

** Actually an atom of correct size touches only
the top and bottom atoms
Note: Atoms are coloured differently but are the same 38>
 Interstitial Voids Positions in BCC Cells

Distorted
• Four on each face: [(4/2) × 6 = 12] → (0, ½, ¼) 12 6
Tetrahedral
Voids/cell Voids/atom
Distorted • Face centre: (6/2 = 3) → (½, ½, 0)
6 3 39>
Octahedral • Edge centre: (12/4 = 3) → (½, 0, 0)
 Interstitial Voids in BCC Cells

a BCC: Distorted Tetrahedral Void

a√3/2

a2 a2 5
From the right angled triange OCM: OC = + = a=r+x
16 4 4
4r
For a BCC structure: 3a = 4r ( a = )
3

5 4r x ⎛ 5 ⎞
= r + x ⇒ = ⎜⎜ − 1⎟⎟ = 0.29
4 3 r ⎝ 3 ⎠ 40>
 Interstitial Voids in BCC Cells
Distorted Octahedral Void
a 2a
OB = = 0.5a OA = = .707a
2 2
As the distance OA > OB the atom in the
void touches only the atom at B (body
centre).
⇒ void is actually a ‘linear’ void
a√3/2
This implies:
a
a OB = r + x =
2
4r
r+x= BCC : 3a = 4r
2 3

x ⎛2 3 ⎞
= ⎜⎜ − 1⎟⎟ = 0.1547
r ⎝ 3 ⎠
41>
 Relative Sizes of Voids in Cubic Cells

FCC o Void (Oct)

rFe
FCC = 1.292 A
FeFCC C
o
Fe
xFCC (oct ) = 0.534 A N

o O
r = 0.77 A
C

Relative sizes of voids w.r.t to atoms

BCC
o o Fe

(d .tet ) = 0.364 A
Fe xBCC (d .tet )
= 0.29
r Fe
BCC = 1.258 A xBCC Fe
rBCC

o Fe
xBCC (d .oct )
FeBCC x Fe
BCC (d .oct ) = 0.195 A Fe
rBCC
= 0.155

42>
 Interstitial Voids in Hexagonal Cells

TETRAHEDRAL OCTAHEDRAL

Coordinates : (0,0, 3 8 ), (0,0, 5 8 ), ( 2 3 , 1 3 , 18 ), ( 2 3 , 1 3 , 7 8 ) Coordinates: (⅓ ⅔,¼), (⅓,⅔,¾)

These voids are identical to the ones found in FCC

Note: Atoms are coloured differently but are the same

43>
 Interstitial Voids Positions in Hexagonal Cells

HCP voids Position Voids / cell Voids / atom

Tetrahedral (0,0,3/8), (0,0,5/8), (⅔, ⅓,1/8), (⅔,⅓,7/8) 4 2

Octahedral • (⅓ ⅔,¼), (⅓,⅔,¾) 2 1
44>
 Crystallographic Directions

¾ Lattice directions:

Miller Notation: [hkl] – a specific direction

<hkl> – a family of directions
45>
 Crystallographic Directions

¾ Examples of directions [hkl]:

210

X=1,Y=½,Z=0 X=½ ,Y=½,Z=1

[1 ½ 0] [2 1 0] [½ ½ 1] [1 1 2]

46>
 Crystallographic Directions

¾ Examples of directions [hkl]:

X=1,Y=0,Z=0 [1 0 0] X = -1 , Y = -1 , Z = 0 [110]

47>
 Crystallographic Directions

¾ Examples of directions [hkl]:

We can move vector to the origin. X =-1 , Y = 1 , Z = -1/6

[-1 1 -1/6] [6 6 1]

48>
 Crystallographic Planes

Miller Indices are a symbolic vector representation for

the orientation of an atomic plane in a crystal lattice
and are defined as the reciprocals of the fractional
intercepts which the plane makes with the
crystallographic axes.

To determine Miller indices of a plane, take the

following steps:
1) Determine the intercepts of the plane along each of
the three crystallographic directions;
2) Take the reciprocals of the intercepts
3) If fractions result, multiply each by the denominator
of the smallest fraction

Miller notation: (hkl) – a specific plane

{hkl} – a family of planes
49>
 Crystallographic Planes

Axis X Y Z
Intercept
points 1 ∞ ∞
Reciprocals 1/1 1/ ∞ 1/ ∞
Smallest
Ratio 1 0 0

Miller İndices (100)

(1,0,0)

50>
 Crystallographic Planes

Axis X Y Z
Intercept
points 1 1 ∞
Reciprocals 1/1 1/ 1 1/ ∞
Smallest
Ratio 1 1 0
(0,1,0)
Miller İndices (110)
(1,0,0)

51>
 Crystallographic Planes

Axis X Y Z
(0,0,1)
Intercept
points 1 1 1
Reciprocals 1/1 1/ 1 1/ 1
Smallest
(0,1,0) Ratio 1 1 1

(1,0,0) Miller İndices (111)

52>
 Crystallographic Planes

Axis X Y Z
Intercept
points 1/2 1 ∞
Reciprocals 1/(½) 1/ 1 1/ ∞
Smallest
(0,1,0) Ratio 2 1 0
(1/2, 0, 0)
Miller İndices (210)

53>
 Crystallographic Planes

[2,3,3] Plane intercepts axes at 3a , 2b , 2c

2 1 1 1
Reciprocal numbers are: , ,
3 2 2
c
b Indices of the plane (Miller): (2,3,3)
2
a Indices of the direction: [2,3,3]
3

(200)
(111)
(110) (100)

(100)

54>
 Family of Crystallographic Planes & Directions

¾ Directions:

¾ Planes:
{100} ≡ (100), (010), (001), (0 1 0), (00 1 ), ( 1 00)
{111} ≡ (111), (11 1 ), (1 1 1), ( 1 11), ( 1 1 1 ), ( 1 1 1), ( 1 1 1 ), (1 1 1 )

55>
 Atomic Density
ATOMIC DENSITY
(100) (110) (111)
(atoms/unit area)

SC (111) < (110) < (100)

a 2a 2a

FCC a a (110) < (100) < (111)

2a 2a

BCC (111) < (100) < (110)

a 2a 2a
56>
 Directions in HCP Crystal
z
Algorithm
1. Vector repositioned (if necessary) to
pass through origin.
2. Read off projections in terms of unit
a2 cell dimensions a1, a2, a3, or c
3. Adjust to smallest integer values
- 4. Enclose in square brackets, no
a3 commas
a2
a1 [uvtw]
Adapted from Fig. 3.8(a),
Callister & Rethwisch 8e.
a2 -a3
2

ex: ½, ½, -1, 0 => [ 1120 ] a3 a1

2
dashed red lines indicate
projections onto a1 and a2 axes a1
Miller notation: [hk.l] or [hkil] Where i = h + k
57>
 Crystallographic Planes in HCP Crystal

example a1 a2 a3 c
1. Intercepts 1 ∞ -1 1
2. Reciprocals 1 1/∞ -1 1
1 0 -1 1 a2

3. Reduction 1 0 -1 1
a3

4. Miller-Bravais Indices (1011) a1

Miller notation: (hk.l) or (hkil) Where i = h + k

58>
 Another Important Crystal Structures

¾ Sodium Chloride Structure Na+Cl-

¾ Cesium Chloride Structure Cs+Cl-
¾ Diamond Structure
¾ Zinc Blende (ZnS)

59>
Sodium Chloride Structure (NaCl)

60>
 Sodium Chloride Structure (NaCl)

¾ Many common salts have FCC arrangements of anions

with cations in OCTAHEDRAL HOLES
¾ Ion Count for the Unit Cell: 4 Na+ and 4 Cl-
¾ Na4Cl4 = NaCl
¾ Similar structures: LiF, NaBr ,KCl, MgO, FeO, etc…
61>
 Cesium Chloride Structure (CsCl)
Cesium chloride consists of equal numbers of cesium
and chlorine ions, placed at the points of a BCC cubic
lattice so that each ion has eight of the other kind as
its nearest neighbors.

rCs + 0.170
= = 0.939
rCl− 0.181

∴ Since 0.732 < 0.939 < 1.0,

cubic sites preferred
So each Cs+ has 8 neighbor Cl-

62>
 Diamond Structure (C)
¾ The diamond lattice is consist of two interpenetrating
face centered bravais lattices.
¾ There are 8 atoms in the structure of diamond.
¾ Each atom bonds covalently to 4 others equally
spread about atom in 3D.
142pm

335pm

graphite diamond
63>
Calcium Fluorite Structure (CaF2)
• Cations in cubic sites
• UO2, ThO2, ZrO2, CeO2
• Antifluorite structure –
positions of cations and
anions reversed

(c) 2003 Brooks/Cole Publishing / Thomson

Learning™
64>
 Zinc Blende Structure (ZnS)
¾ Zinc Blende is the name given to the mineral ZnS. It has a
cubic close packed (face centred) array of S and the Zn(II)
sit in tetrahedral (1/2 occupied) sites in the lattice.

65>
 Perovskite Structure

¾ ABX3 Crystal Structures

• Barium Titanate,
a complex oxide
BaTiO3

66>
X-Rays to Determine Crystal Structure

Bragg equation: nλ=2d.sinθ

67>
 X-Rays to Determine Crystal Structure
z z
c c

y y
a b (110) z a b
x c x
Intensity (relative)

(211)
y
a b
x (200)

Diffraction angle 2θ
Diffraction pattern for polycrystalline α-iron (BCC)

Bragg equation: nλ=2d.sinθ

68>
 References
¾ CALLISTER JR, W. D. AND RETHWISCH, D. G.
Materials Science and Engineering: An Introduction, 9th edition.
John Wiley & Sons, Inc. 2014, 988p. ISBN: 978-1-118-32457-8.
¾ HOSFORD, W. F.
Elementary Materials Science. ASM International. 2013, 180p. ISBN 978-1-62708-002-6.
¾ ASHBY, M. and JONES, D. R. H.
Engineering Materials 1: An Introduction to Properties, Applications and Design.
4th Edition. Elsevier Ltd. 2012, 472p. ISBN 978-0-08-096665-6.
¾ CALLISTER JR, W. D. AND RETHWISCH, D. G.
Fundamentals of Materials Science and Engineering: An Integrated Approach, 4th ed.
John Wiley & Sons, Inc. 2012, 910p. ISBN 978-1-118-06160-2.
¾ MITTEMEIJER, E. J.
Fundamentals of Materials Science: The Microstructure–Property Relationship Using
Metals as Model Systems. Springer-Verlag Berlin. 2010, 594p. ISBN 978-3-642-10499-2.
¾ ASKELAND, D. AND FULAY, P.
Essentials of Materials Science & Engineering, 2nd Edition.
Cengage Learning. 2009, 604p. ISBN 978-0-495-24446-2.
¾ ABBASCHIAN, R., ABBASCHIAN, L., AND REED-HILL, R. E.
Physical Metallurgy Principles, 4th Ed. Cengage. 2009, 750p. ISBN 978-0-495-08254-5.
¾ SMALLMAN, R. E. and NGAN, A.H.W.
Physical Metallurgy and Advanced Materials, 7th Edition.
Elsevier Ltd. 2007, 650p. ISBN 978-0-7506-6906-1.
Nota de aula preparada pelo Prof. Juno Gallego para a disciplina Ciência dos Materiais de Engenharia.
® 2015. Permitida a impressão e divulgação.
http://www.feis.unesp.br/#!/departamentos/engenharia-mecanica/grupos/maprotec/educacional/ 69