Indices de Miller

Crystallographic Notation

Miller Indices: Notation Interpretation

(hkl) crystal plane
{hkl} equivalent planes
[hkl] crystal direction
<hkl> equivalent directions
h: inverse x-intercept of plane
k: inverse y-intercept of plane
l: inverse z-intercept of plane
(Intercept values are in multiples of the lattice constant;
h, k and l are reduced to 3 integers having the same ratio.)
The procedure for determining the Miller indices for a
cubic crystal plane is as follows:
1. Choose a plane that does not pass through the origin at
(0, 0, 0).
2. Determine the intercepts of the plane in terms of the
crystallographic x, y, and z axes for a unit cube. These
intercepts may be fractions.
3. Form the reciprocals of these intercepts.
4. Clear fractions and determine the smallest set of whole
numbers that are in the same ratio as the intercepts.
These whole numbers are the Miller indices of the
crystallographic plane and are enclosed in parentheses
without the use of commas. The notation (hkl) is used
to indicate Miller indices in a general sense, where h, k,
and l are the Miller indices of a cubic crystal plane for
the x, y, and z axes, respectively.
 z 1. Select a crystallographic
coordinate system with origin not
on the plane

2. Find intercepts along 1 1 1

axes in terms of respective
lattice parameters
y 3. Take reciprocal 1 1 1
O

4. Convert to smallest integers in

x
the same ratio

5. Enclose in parenthesis
(111)
 Plane ABCD OCBE
origin O O*
z z
intercepts 1 ∞ ∞ 1 -1 ∞
E
reciprocals 1 0 0 1 -1 0

A Miller _
B Indices (1 0 0) (1 1 0)
O O*
y Bar
Zero represents
D that the plane is represents
C parallel to the a negative
intercept
x x corresponding axis

All parallel planes have the same Miller Indices

 z

E _ _ _
(h k l )  (h k l )
A
B
O
_
y (100)  (100)
D
C
x
{100}cubic = (100), (010), (001)
(100)
 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.
-Metallic bonding is not directional.
-Nearest neighbor distances tend to be small in
order to lower bond energy.

• have the simplest crystal structures. 74 elements

have the simplest crystal structures – BCC, FCC
and HCP

We will look at three such structures...

3
 The crystal lattice

A point lattice is made up of regular,

repeating points in space. An atom or
group of atoms are tied to each lattice
point
14 different point lattices, called Bravais lattices, make up the crystal system.
The lengths of the sides, a, b, and c, and the angles between them can vary for
a particular unit cell.
Three simple lattices that describe metals are Face Centered Cubic (FCC) Body
Centered Cubic (BCC) and Hexagonal Close Packed (HCP)
 SIMPLE CUBIC STRUCTURE (SC)
• Rare due to poor packing (only Po has this structure)
• Close-packed directions are cube edges.

• Coordination # = 6
(# nearest neighbors)

Click on image to animate

(Courtesy P.M. Anderson)

4
 ATOMIC PACKING FACTOR

• APF for a simple cubic structure = 0.52

Adapted from Fig. 3.19,

Callister 6e. 5
 FACE CENTERED CUBIC
STRUCTURE (FCC)
• Close packed directions are face diagonals.
--Note: All atoms are identical; the face-centered atoms are shaded
differently only for ease of viewing.

• Coordination # = 12

Adapted from Fig. 3.1(a),

Click on image to animate Callister 6e.

(Courtesy P.M. Anderson)

6
 ATOMIC PACKING FACTOR: FCC
• APF for a body-centered cubic structure = 0.74

Unit cell contains:

6 x 1/2 + 8 x 1/8
= 4 atoms/unit cell
a
Adapted from
Fig. 3.1(a),
Callister 6e.

7
Gem diamonds consist of pure carbon in the face-
centered cubic (fcc) crystal structure. If the lattice
constant a = 2.83 Å, what is the density of
diamonds?

1 AMU = 1.6605×10-27kg
 BODY CENTERED CUBIC
STRUCTURE (BCC)
• Close packed directions are cube diagonals.
--Note: All atoms are identical; the center atom is shaded
differently only for ease of viewing.

• Coordination # = 8

Adapted from Fig. 3.2,

Click on image to animate Callister 6e.

(Courtesy P.M. Anderson) 8

 ATOMIC PACKING FACTOR: BCC
• APF for a body-centered cubic structure = 0.68

Unit cell contains:

1 + 8 x 1/8
= 2 atoms/unit cell
R
Adapted from
Fig. 3.2,
a
Callister 6e.

9
Iron at 20◦C is BCC with atoms of atomic radius 0.124 nm. Calculate
the lattice constant a for the cube edge of the iron unit cell.

if a is the length of the cube edge, then √ 3a = 4R

where R is the radius of the iron atom.

T a = 4R /√3 = 4(0.124 nm) /√3 = 0.2864 nm

Characteristics of Selected Elements at 20C
At. Weight Density Atomic radius
Element Symbol (amu) (g/cm3) (nm)
Aluminum Al 26.98 2.71 0.143
Argon Ar 39.95 ------ ------
Barium Ba 137.33 3.5 0.217
Beryllium Be 9.012 1.85 0.114
Boron B 10.81 2.34 ------ Adapted from
Table, "Charac-
Bromine Br 79.90 ------ ------ teristics of
Cadmium Cd 112.41 8.65 0.149 Selected
Calcium Ca 40.08 1.55 0.197 Elements",
inside front
Carbon C 12.011 2.25 0.071 cover,
Cesium Cs 132.91 1.87 0.265 Callister 6e.
Chlorine Cl 35.45 ------ ------
Chromium Cr 52.00 7.19 0.125
Cobalt Co 58.93 8.9 0.125
Copper Cu 63.55 8.94 0.128
Flourine F 19.00 ------ ------
Gallium Ga 69.72 5.90 0.122
Germanium Ge 72.59 5.32 0.122
Gold Au 196.97 19.32 0.144
Helium He 4.003 ------ ------
Hydrogen H 1.008 ------ ------ 12
Volume density

Planar Atomic Density

Linear Atomic Density

For a BBC structure, what are the
Examples
 Quiz
Determine the plane and its Surface density

BCC
Identify the planes and directions in the figures a, b, c
Quiz
Calculate the surface density of atoms in the plane (100)

A.Avila 30
A.Avila 31
A.Avila 32
 Hexagonal

A.Avila 33
 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 commas
a3
[uvtw] a2
a1
a2 -a3
Adapted from Fig. 3.8(a), Callister 7e.
2

ex: ½, ½, -1, 0 => [ 1120 ] a3

a1
2
dashed red lines indicate a
1
projections onto a1 and a2 axes

A.Avila 34
 Quiz

( )?

A.Avila 35
 Rta

Intercepts → 1 1 - ½ 
Plane → (1 12 0)

(h k i l)
i = (h + k)

A.Avila 36
 (h k i l)
i = (h + k)

A.Avila 37
Does all the elements and compounds exist in one crystalline form?
 THEORETICAL DENSITY, 

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 -7cm)

Result: theoretical Cu = 8.89 g/cm3

Compare to actual: Cu = 8.94 g/cm3
11
 Density

Since the entire crystal can be generated by the repetition of the unit cell,
the density of a crystalline material, ρ= the
density of the unit cell = (atoms in the unit cell, n ) ×(mass of an atom, M)
/ (the volume of the cell, Vc)

Atoms in the unit cell, n = 2 (BCC); 4 (FCC); 6 (HCP)

Mass of an atom, M= Atomic weight, A, in amu (or g/mol) is given in

the periodic table. To translate mass from amu to grams we have to divide
the atomic weight in amu by the Avogadro number NA= 6.023 ×10 23
atoms/mol

The volume of the cell, Vc= a3(FCC and BCC) a = 2R√2(FCC); a =

4R/√3 (BCC) where R is the atomic radius
 DENSITIES OF MATERIAL
CLASSES
metals• ceramics• polymers
Why?
Metals have...
• close-packing
(metallic bonding)
• large atomic mass
Ceramics have...
• less dense packing
(covalent bonding)
• often lighter elements
Polymers have...
• poor packing
(often amorphous)
• lighter elements (C,H,O)
Composites have...
• intermediate values Data from Table B1, Callister 6e.
13
Silicio
 # of Electrons
1 2 3
Z Name 1s 2s 2p 3s 3p 3d Notation
1
1H 1 1s
2 He 2 1s 2
3 Li 2 1 1s 2 2s 1
4 Be 2 2 1s 2 2s 2
5B 2 2 1 1s 2 2s 2 2p1
6C 2 2 2 1s 2 2s 2 2p2
7N 2 2 3 1s 2 2s 2 2p3
8O 2 2 4 1s 2 2s 2 2p4
9F 2 2 5 1s 2 2s 2 2p5
10 Ne 2 2 6 1s 2 2s 2 2p6
11 Na 2 2 6 1 1s 2 2s 2 2p6 3s 1
12 Mg 2 2 6 2 1s 2 2s 2 2p6 3s 2
13 Al 2 2 6 2 1 1s 2 2s 2 2p6 3s 2 3p1
14 Si 2 2 6 2 2 1s 2 2s 2 2p6 3s 2 3p2
15 P 2 2 6 2 3 1s 2 2s 2 2p6 3s 2 3p3
16 S 2 2 6 2 4 1s 2 2s 2 2p6 3s 2 3p4
17 Cl 2 2 6 2 5 1s 2 2s 2 2p6 3s 2 3p5
18 Ar 2 2 6 2 6 1s 2 2s 2 2p6 3s 2 3p6

A.Avila 46
Usar http://www.doitpoms.ac.uk/tlplib/crystallography3/questions.php
• 14 electrons occupying the 1st 3 energy levels:
– 1s, 2s, 2p orbitals filled by 10 electrons
– 3s, 3p orbitals filled by 4 electrons
To minimize the overall energy, the 3s and 3p orbitals
hybridize to form 4 tetrahedral 3sp orbitals
Each has one electron and
is capable of forming a bond
with a neighboring atom

Unit cell:

A.Avila 47
 “diamond cubic” lattice

Unit cell:

• Each Si atom has 4

nearest neighbors

• lattice constant
= 5.431Å

A.Avila 48
 Unit cell:

View in <111> direction

View in <100> direction View in <110> direction

Number of atoms in a unit cell (lattice constant
= 5.431Å):
• 4 atoms completely inside cell
• Each of the 8 atoms on corners are shared among cells
 count as 1 atom inside cell
• Each of the 6 atoms on the faces are shared among 2
cells  count as 3 atoms inside cell
 Total number inside the cell = 4 + 1 + 3 = 8
• Cell volume:
(.543 nm)3 = 1.6 x 10-22 cm3
• Density of silicon atoms
= (8 atoms) / (cell volume) = 5 x 1022 atoms/cm3

A.Avila 50
Bonding
ATOMIC BONDING IN SOLIDS

54
Electron volt –
energy lost / gained when an electron is taken through a
potential difference of one volt.
E=qV

For q = 1.6 x 10-19 Coulombs

V = 1 volt

1 eV = 1.6 x 10-19 J

55
The energy that would
be required to separate
these two atoms to an
infinite separation

57
Table 1 gives list of bonding energies and melting temperatures for
various bond types. Increase in depth of the potential well, increases
the melting temperature Tm

58
Materials Sciences and Applications, 2011, 2, 97-104 doi:10.4236/msa.2011.22013 Published Online February59
2011
(http://www.SciRP.org/journal/msa)
 Types of Bonding

Primary Bonding: e- are transferred or shared

Strong (100-1000 KJ/mol or 1-10 eV/atom)

Ionic:
Example - Na+Cl
Strong Coulomb interaction between
a positive atom (lost an electron, Na+) and
a negative atom (an extra electron, Cl-)

Covalent: electrons shared between the atoms.

Example - H2

Metallic:
Atoms lose some electrons from valence band
Those electrons are shared by all the material

Secondary Bonding: no e- transferred or shared

Interaction of atomic/molecular dipoles
Weak (< 100 KJ/mol or < 1 eV/atom)

Fluctuating Induced Dipole (inert gases, H2, Cl2…)

Permanent dipoles (polar molecules - H2O, HCl...) 60

What is non directional?

The electrostatic charge are

Arranged symmetrically around
Each ion with the result that A ions
tend to sorround themselves with
B ions.

The pattern created depends on the

sizes of A and B ions
Metallic bond

The valence electrons are detached from their atoms and can
move freely between positive metallic ions

The electrostatic attraction between ions and elecrons is not

directional, the bonding is not localised between individual pairs
or groups
Mutual ionization by electron transfer
(remember electronegativity table)
•Anion = negatively charged atom
•Cation = positively charged atom

Ions are attracted by strong coulombic interaction

•Oppositely charged atoms attract
•An ionic bond is non-directional

Example: NaCl
Na has 11 electrons, 1 more than needed for a full outer
shell (Neon)
11 Protons Na 1S2 2S2 2P6 3S1 donates e-
11 Protons Na+ 1S2 2S2 2P6 10 e- left

Cl has 17 electron, 1 less than needed for a full outer shell

(Argon)
17 Protons Cl 1S2 2S2 2P6 3S2 3P5 receives e-
17 Protons Cl- 1S2 2S2 2P6 3S2 3P6 18 e-
63
 e-
Na Cl Na+ Cl-

• Electron transfer reduces energy of the system

• Na shrinks and Cl expands

Ionic bonding is termed nondirectional, that is, the magnitude

64
of the bond is equal in all directions around an ion
 Covalent Bonding

In covalent bonding stable electron configurations are assumed by the

sharing of electrons between adjacent atoms

molecule of methane (CH4)

Zc = 6 (1S2 2S2 2P2)
N´ valence electrons, an atom can covalently
bond with at most 8 -N´other atoms.
Example: Cl2 molecule. ZCl =17 (1S2 2S2 2P6 3S2 3P5)
N’ = 7, 8 - N’ = 1  can form only one covalent bond

65
Covalent bonds may be very strong, as in diamond, which is very hard
and has a very high melting temperature, 3550C (6400F), or they may
be very weak, as with bismuth, which melts at about 270C (518F)

66
 METALLIC BONDING

Valence electrons are detached from atoms

Spread in an 'electron sea'
that "glues" the “ions” together

Metallic bond is non-directional  atoms pack closely

Electron cloud from valence electrons

ion core

67
Examples of bonding in Materials:
Metals: Metallic
Ceramics: Ionic / Covalent
Polymers: Covalent and Secondary
Semiconductors: Covalent or Covalent / Ionic

68
 VAN DER WAALS BONDING

 10 kJ/mol (0.1 eV/atom)

Secondary bonding forces arise from atomic or molecular dipoles. In

essence, an electric dipole exists whenever there is some separation of
positive and negative portions of an atom or molecule

69
Permanent dipoles exist in some molecules
polar molecules: e.g. HCl, H2O
Due to asymmetry of positive and negative regions Strongest among
secondary bonds.

Polar molecule induces a dipole in adjacent non-polar molecule.

Attraction between the permanent and induced dipoles.

Fluctuations of electron density distribution in one atom A is felt by

the electrons of an adjacent atom:
Mutual dipoles induced (van der Waals)
This bond is the weakest (He-Ne, H2 - H2).

70
Example: hydrogen bond in water. The H end of the molecule is
positively charged and can bond to the negative side of another
H2O molecule (the O side of the H2O dipole)

“Hydrogen bond” – secondary bond formed between

two permanent dipoles in adjacent water molecules.

71
What Bond will form?

Ne and C

Ne+C
 Interprete the 4 properties presented in the fig 4.9 in terms of the
Information that you extract from the periodic table

http://periodic.lanl.gov/index.shtml
 PROPERTIES FROM BONDING: TM
• Bond length, r • Melting Temperature, Tm
F
F

• Bond energy, Eo

Tm is larger if Eo is larger.
 PROPERTIES FROM BONDING: E
• Elastic modulus, E
Elastic modulus

F L
=E
Ao Lo

• E ~ curvature at ro
Energy

unstretched length
ro E is larger if Eo is larger.
r
smaller Elastic Modulus

larger Elastic Modulus

 PROPERTIES FROM BONDING: a
• Coefficient of thermal expansion, a
coeff. thermal expansion

L
= a(T2-T1)
Lo

• a ~ symmetry at ro

a is larger if Eo is smaller.
 SUMMARY: PRIMARY BONDS
Ceramics Large bond energy
(Ionic & covalent bonding): large Tm
large E
small a

Metals Variable bond energy

(Metallic bonding): moderate Tm
moderate E
moderate a

Polymers Directional Properties

(Covalent & Secondary): Secondary bonding dominates
small T
small E
large a
 CERAMIC BONDING
• Bonding:
--Mostly ionic, some covalent.
--% ionic character increases with difference in
electronegativity.
• Large vs small ionic bond character:

Adapted from Fig. 2.7, Callister 6e. (Fig. 2.7 is adapted from Linus Pauling, The Nature of the
Chemical Bond, 3rd edition, Copyright 1939 and 1940, 3rd edition. Copyright 1960 by
Cornell University. 14
 IONIC BONDING & STRUCTURE
• Charge Neutrality:
--Net charge in the
structure should
be zero.

--General form:

• Stable structures:
--maximize the # of nearest oppositely charged neighbors.

Adapted from Fig. 12.1,

Callister 6e.

15
 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.

27
 SUMMARY: BONDING
Type Bond Energy Comments
Ionic Large! Nondirectional (ceramics)

Variable Directional
Covalent large-Diamond (semiconductors, ceramics
small-Bismuth polymer chains)

Variable
Metallic large-Tungsten Nondirectional (metals)
small-Mercury
Directional
Secondary smallest inter-chain (polymer)
inter-molecular

Material science. Cahill

Bonding Introduction

https://www.youtube.com/watch?v
=KjoQHqgzda8