Fundamentals on the structure of solids

3 Crystalline structures
3.1 Fundamentals on the structure of solids

solid body
crystalline semi-crystalline amorphous
e.g. metals e.g. certain thermoplasts e.g. glass

irregular distribution of
regular geometry on micro atoms on micro scale
both
and macro scale regular geometry on sub-
micro scale

In the liquid state atoms and molecules show little order. On the crossover to the solid this
disordered state remains (amorphous) or crystalline or even semi-crystalline structures develop
(see also Fig. 3.1). The bonds between atoms and molecules described in chapter 2 are the basis
for the resulting inter-atomic or inter-molecular structure.

semi-crystalline amorphous

Fig. 3.1 Schematic presentation of the difference between semi-crytsalline (left) and of a purely
amorphous (disordered) structure (right) of the macromolecule chains of a thermoplast
material.

Crystalline atomic structures are

 chains of atoms (or molecules) that repeat periodically with a characteristic symmetry
and
 are called crystal lattice, atomic lattice or spatial grid.

A liquid bulk is turned into a crystal by means of nucleation and growth of the nucleus. In Fig. 3.2
it is schematically shown how a single crystal growths starting from a single nucleus and how a
polycrystal forms at the presence of several nuclei.

Material Science and Engineering I / II 41

Status: 01.11.2017
 Fundamentals on the structure of solids

Fig. 3.2 Schematic view of nucleation and growth from the melt for a single-crystal and a
polycrystal.

The smallest structural unit (unit cell) is used to characterize the crystal (Fig. 3.3).

Simplest case: Most complicated case:

simple cubic lattice triclinic lattice

c0
c0
  

 
a0
a0
b0 b0
lattice parameters:
a0 = b0 = c0
a0  b0  c0
 =  =  = 90°


Fig. 3.3 Examples for unit cells (cubic und triclinic).

The entity of all possible atomic arrays can be divided into 7 crystal systems with a total of 14
lattice types the so called Bravais lattices.

Keep in mind: Real crystals always possess imperfections, they are never ideal.

Material Science and Engineering I / II 42

Status: 01.11.2017
 Crystal systems and Bravais lattice

3.2 Crystal systems and Bravais lattice

In all unit cells the center of mass of an atom is marked by a •.

3.2.1 Cubic lattice

a0 = b0 = c0; α = β = γ = 90°

1. simple cubic 2. body centered cubic 3. face centered cubic

Fig. 3.4 The three Bravais lattices for the cubic system (primitive (P); bcc (body centered cubic) (I)
and fcc (face centered cubic) (F).

3.2.2 Tetragonal lattice

a0 1.
= b0simple
≠ c0; α = β tetragonal
= γ = 90° 2. body centered tetragonal

1. simple tetragonal 2. body centred tetragonal

Fig. 3.5 The two Bravais lattices for the tetragonal system (simple or primitive (P) and body
centered (I)).

3.2.3 Orthorhombic lattice

a0 ≠ b0 ≠ c0; α = β = γ = 90°
1. orthorhombic 2. orthorhombic 3. orthorhombic 4. orthorhombic

simple base centered body centered face centered

Fig. 3.6 The four Bravais lattices for the orthorhombic crystal system (primitive (P); base
centered (C); body centered (I) and face centered (F)).

Material Science and Engineering I / II 43

Status: 01.11.2017
 Crystal systems and Bravais lattice

3.2.4 Monoclinic lattice

a0 ≠ b0 ≠ c0; α ≠ β = γ = 90°

1. simple monoclinic 2. base centered monoclinic

Fig. 3.7 The two Bravais lattices of the monoclinic crystal system (primitive (P) and base centered
(C)).

3.2.5 Triclinic lattice

a0 ≠ b0 ≠ c0; α ≠ β ≠ γ

Fig. 3.8 Presentation of the triclinic lattice (primitive).

3.2.6 Hexagonal lattice

a0 = b0 ≠ c0; α = β = 90°; γ = 120°

Fig. 3.9 Presentation of the hexagonal lattice (left) and of the hexagonal closest packed lattice (hcp)
2 1 1
(hexagonal closed packed) right) with occupation of the point locations (0,0,0) and ( , , ).
3 3 2
In both sketches three unit cells are plotted, while one unit cell is marked in red.

Material Science and Engineering I / II 44

Status: 01.11.2017
 Crystal systems and Bravais lattice

3.2.7 Rhombohedral lattice

a0 = b0 = c0; α = β = γ ≠ 90°

Fig. 3.10 Presentation of the rhombohedric lattice.

3.2.8 Nomenclature of the 14 Bravais lattices according to Pearson

Tab. 3. 1 Designation of the crystal systems with assignment of the Pearson symbols.
System Type Abbr. Examples
cubic simple cP α-Polonium, β-Manganese

face-centered cF Copper, Gold, Lead, Aluminum,

Carbon (Diamond), γ-Iron

body-centered cI α-Iron, Molybdenum, Tantalum,

Vanadium, Tungsten
tetragonal simple tP Boron, β-Uranium, β-Neptunium

base-centered tI β-Tin, Indium, Protactinum

orthorhombic simple oP α-Neptunium

base-centered oC Gallium, Phosphor (black)

face-centered oF γ-Plutonium, Sulphur

body-centered oI S2Si, CeCu2, B4Ta3, Al4U, Ga2Mg5,

Nb6Sn5
monoclinic simple mP α-Selenium, β-Selenium, Sulphur, α-
Plutonium
base-centered mC
β-Plutonium
triclinic simple aP HgK, ReSe2.δ-Al11Mn4, Fe7Se8, Al4Re
hexagonal simple hP α-Lanthanium
rhombohedral simple rP Stibium, Arsenic, Bismuth, Mercury

where P = primitive I = internal F = Face C = Cover

Material Science and Engineering I / II 45
Status: 01.11.2017
 Lattice directions and planes

3.3 Lattice directions and planes

3.3.1 Nomenclature of lattice directions
lattice directions  straight line in lattice containing atoms
nomenclature  internationally standardized using direction indices

Description by the aid of lattice vectors, pointing from the origin to the center of mass of an
arbitrary atom.

Illustration using the orthorhombic lattice

Fig. 3.11 Orthorhombic lattice with an example for the indexing of direction r.

Unit vectors i, j, k
dimension of the unit cell a0, b0, c0

𝒓 = 𝑢′ ∙ 𝑎 0 ∙ 𝒊 + 𝑣 ′ ∙ 𝑏0 ∙ 𝒋 + 𝑤 ′ ∙ 𝑐0 ∙ 𝒌 1)

𝒓 = 𝑝 ∙ (𝑢 ∙ 𝑎 0 ∙ 𝒊 + 𝑣 ∙ 𝑏0 ∙ 𝒋 + 𝑤 ∙ 𝑐0 ∙ 𝒌) 2)

where p in chosen in a way that u, v, w are relatively prime and integer

 lattice direction is defined through [uvw]

Examples
1) u‘ = v‘ = w‘ = 1: p=1 u=v=w= 1  [111]
2) u‘ = 2, v‘ = 1, w‘ = 0: p=1  u = 2, v = 1, w = 0  [210]
3) u‘ = 1/3, v‘ = 3/4, w‘ = 1/2:  p = 1/12  u = 4, v = 9, w = 6  [496]

Material Science and Engineering I / II 46

Status: 01.11.2017
 Lattice directions and planes

A graphical illustration of the individual lattice directions is shown in Fig. 3.12:

Fig. 3.12 Important directions in cubic lattices.

Note

1) negative indices are marked by an overline (for [11-1] it is written [111]).

2) directions of the same type are equivalent, the entity of them is addressed using angle
brackets, e.g. the edges of a cube [100], [010], [001] etc. are equivalent to <100>.
3) The rules of vector analysis apply.

3.3.2 Nomenclature of lattice planes

lattice planes  planes through the lattice containing atoms (atomic plane, crystallographic
plane, lattice plane)
nomenclature  internationally standardized using the so called Miller's indices

aim  definite description of a lattice plane that intersects the coordinate axes in x‘,
y‘ and z‘

Examples for the Indexing of lattice planes are shown in Fig. 3.13.

Fig. 3.13 Important planes in the cubic lattice.

Material Science and Engineering I / II 47

Status: 01.11.2017
 Lattice directions and planes

Procedure

1) intercepts with the coordinate axes in x‘, y‘, z‘

𝑥′ 𝑦′ 𝑧′
2) scale to the lattice dimensions , ,
𝑎0 𝑏 0 𝑐 0
𝑎 𝑏0 𝑐
3) transformation into conjugate ℎ ′ = 0 , 𝑘 ′ = , 𝑙 ′ = 0.
𝑥′ 𝑦′ 𝑧′
4) determination of relatively prime and integer
5) numbers h, k, l with
h‘ = ph, k´ = pk, l´ = pl (p = constant factor)

(h k l) are called Millers indices und describe the lattice planes definitely

One example for the designation of lattice planes is shown in

Fig. 3.14 .

Fig. 3.14 Schematic sketch for indexing lattice planes.

Example (cubic lattice):

1) x’= 1/3 a0, y’ = 1/2 b0, z’ = 1/4 c0: p=1  h = 3, k = 2, l = 4  (324)

2) x’ = 1/2 a0, y’ = 1 b0, z’ =  :  p = 1  h = 2, k = 1, l = 0  (210)
3) x’ = 1 a0, y’ = 2 b0, z’ =  :  p = 1/2  h = 2, k = 1, l = 0  (210)

 parallel planes have same indices

 planes parallel to one coordinate axes intersect the axis in infinity and thus the index is 0.

Note
1) negative intercepts lead to negative indices, marked by an overline (for (1-10) it
follows(110)).
2) the entity of all equivalent planes are grouped in curly brackets e.g. {100} = all planes of the
type (100) (cube faces).
3) a plane containing one or more coordinate axes is indicated using a parallel plane.
4) in cubic lattices the indices of a plane and its normal vector are equal.

Material Science and Engineering I / II 48

Status: 01.11.2017
 Lattice directions and planes

Material Science and Engineering I / II 49

Status: 01.11.2017
 Lattice directions and planes

As an example the indexing will be demonstrated for a cubic lattice:

In Figure Fig. 3.15 a plane is sketched that intercepts the x-axis in point (1, 0, 0), the y-axis in
point (0, 1/2, 0) and the z-axis in point (0, 0, 1/3).

Fig. 3.15 Example for the Indexing of a plane in the cubic crystal system.

One gets the number triple: (1, 1/2, 1/3). Through transformation into conjugate the following
presentation results: (123). Since as result of the transformation into conjugate only integer
numbers occur in the number triple the multiplication with the common denominator is
redundant.

3.3.3 Important planes and directions in the hexagonal lattice

In hexagonal structures for lattice directions and lattice planes a nomenclature with four indices
u*, v*, t* and w* resp. h*, k*, i* and l* is applied. By this means the symmetry of the lattice is
clearly visible.
For direction indices instead of [u v w] the indexing [u* v* t* w*] is used. For the indexing of
lattice planes instead of (h k l) the indexing (h* k* i* l*) is shown.

Fig. 3.16 Presentation of the hexagonal lattice with the axis a1, a2, a3 and c (left) and direction of view
along the c-axis to the basal planes (right).

Material Science and Engineering I / II 50

Status: 01.11.2017
 Lattice directions and planes

An arbitrary direction ruvw in the hexagonal system can be described as follows:

𝒓𝑢𝑣𝑤 = 𝑢 ∙ 𝒂1 + 𝑣 ∙ 𝒂2 + 𝑤 ∙ 𝒄 3)
With the three axes a 1, a2, a 3 and the c axis each direction can be describes by means of Miller-
Bravais-indices by:

𝒓𝑢𝑣𝑤 = 𝑢∗ ∙ 𝒂1 + 𝑣 ∗ ∙ 𝒂2 + 𝑡 ∗ ∙ 𝒂3 + 𝑤 ∗ ∙ 𝒄 4)
Under the condition that the vector sum of the three coplanar components a 1, a2, a3 result in 0,

𝒂1 + 𝒂2 + 𝒂3 = 0 5)
and through comparison of the coefficients from equations 3) and 4) the following conversion
for the direction indices is derived:

(2𝑢 − 𝑣)
𝑢∗ = 6)
3
(2𝑣 − 𝑢)
𝑣∗ = 7)
3
−(𝑢 + 𝑣)
𝑡∗ = 8)
3

𝑤∗ = 𝑤 9)
For obtaining integer indices the individual values from equations 6) - 9) must be multiplied
with the common denominator (three).

For indexing of the planes the indices are relatively prime reciprocal values of the plane
intercepts with the axes a 1, a 2, a 3 and c. The four indices depend on each other, since the
intercepts with the three coplanar axes are already sufficient for a definite characterization of
the planes. For this reason the following conditions must be fulfilled:

ℎ∗ = ℎ 10)

𝑘∗ = 𝑘 11)

𝑖 ∗ = −(ℎ ∗ + 𝑘 ∗ ) 12)

𝑙∗ = 𝑙 13)

Hence, (h k l) will become (h* k* -(h*+k*) l*) for indexing of hexagonal systems.

Material Science and Engineering I / II 51

Status: 01.11.2017
 Lattice directions and planes

Fig. 3.17 Important lattice planes and directions in the hexagonal lattice.

As example one selected plane of the hexagonal lattice will be indexed. In the following figure
(Fig. 3.18) a plane in the hexagonal lattice is displayed that intercepts the a1-axis in point
(1, 0, 0) and the a2-axis in point (0, 1, 0) and has no intercept with the c-axis („intercept“ in
(0, 0, „∞“)).

Fig. 3.18 Example for indexing of a lattice plane in the hexagonal crystal lattice.

The following number triple results: (1, 1, „∞“). By calculating the reciprocals the following
triple is obtained: (110). Again integer numbers result, hence the multiplication with the
common denominator is not needed.

In (hkil)-notation it results through application of equations 10) - 13) the designation (112̅0).

Material Science and Engineering I / II 52

Status: 01.11.2017
 Lattice directions and planes

3.3.4 Relationship between interplanar spacing and lattice

constants and Miller indices
Interplanar spacing = distance or space between two neighboring, parallel lattice planes.

a) orthorhombic lattice

1 ℎ 2 𝑘 2 𝑙 2
= ( ) + ( ) + ( ) 14)
𝐷2 𝑎0 𝑏0 𝑐0

b) tetragonal lattice
1 ℎ2 + 𝑘2 𝑙 2
= ( ) + ( )
𝐷2 𝑎 20 𝑐0 15)

c) cubic lattice
1 ℎ2 + 𝑘2 + 𝑙 2
= ( ) 16)
𝐷2 𝑎02

d) hexagonal lattice
1 4 ℎ2 + ℎ𝑘 + 𝑘 2 𝑙 2
= ∙ ( ) + ( ) 17)
𝐷2 3 𝑎 20 𝑐0

3.3.5 Interplanar spacing and density of occupancy

The lattice planes with the lowest indices show the largest interplanar spacing and the highest
density of occupancy!
Examples for the cubic-primitive lattice (traces of different lattice planes in the (001)-plane (see
Fig. 3.19).)

Fig. 3.19 Traces of different lattice planes in the (001)-plane of the cubic-primitive lattice.

Material Science and Engineering I / II 53

Status: 01.11.2017
 Most common lattice types for metals

3.4 Most common lattice types for metals

From the periodic table of elements it can be concluded that about 75% of all elements are
metals. From those about 90% crystallize in the bcc, fcc or hex lattice. Some examples are listed
in the following table:

Tab. 3. 2 Important representatives for lattice structures of metals.

fcc bcc hex

γ-Fe (> 911 °C) α-Fe (< 911 °C) Mg

Al Cr Ti
Cu Mo Co (< 450 °C)
Ni W Zn
Ag Nb Cd
Au Ta Zr

3.4.1 Features of the fcc lattice

3.4.1.1 Unit cell

Smallest structural units in the lattice

Examples:
Cu: a0 = 3,608·10-8 cm
Al: a0 = 4,041·10-8 cm
Ni: a0 = 3,562·10-8 cm

focus model real model

Fig. 3.20 Real- and focus (or center-of-mass) model of the fcc unit cell.

Material Science and Engineering I / II 54

Status: 01.11.2017
 Most common lattice types for metals

3.4.1.2 Coordination number (CN)

Fig. 3.21 coordination number in the fcc lattice.

 number of the nearest equidistant neighboring atoms

√2
 three {100}-planes with four atoms each with a spacing of 𝑎0 =
2

 and thus CNfcc = 12

3.4.1.3 Number of atoms per unit cell

Fig. 3.22 fcc unit cell.

 8 corner atoms are assigned to 8 unit cells, i.e. one corner atom counts 1/8

 6 face atoms are assigned to 2 unit cells and thus count ½

 and therefore nfcc = 8/8 + 6 /2 = 4

Material Science and Engineering I / II 55

Status: 01.11.2017
 Most common lattice types for metals

3.4.1.4 Density ratio DR

Fig. 3.23 Relationship between {100}-plane, atomic radius and lattice constant.

 The volume filled by atoms that are considered as rigid spheres in relation to unit cell
volumes of densest packed arrangement of rigid spheres of the same size is named the
closest packed sphere packing

For the density ratio (DR) the following relation is valid (with nfcc: number of atoms of the unit
cell, Vfcc: Volume of the atoms (considered as rigid spheres) inside the unit cell, VUC: Volume of
the cubic unit cell:

𝑛𝑓𝑐𝑐 ∙ 𝑉𝑓𝑐𝑐
𝐷𝑅 = ∙ 100 %. 18)
𝑉 𝑈𝐶

In case of the fcc lattice the following relations are valid:

𝑛𝑓𝑐𝑐 = 4 19)

𝑉 𝑈𝐶 = 𝑎 0 3 20)

4 4 𝑎0 3 𝜋 ∙ √2
𝑓𝑐𝑐 3 21)
𝑉𝑓𝑐𝑐 = 𝜋(𝑟𝑎𝑡𝑜𝑚 ) = 𝜋 ( ∙ √2) = ∙ 𝑎03
3 3 4 24

From equations 18) - 21) the density ration DR follows:

𝜋 ∙ √2
𝐷𝑅 = = 74 % 22)
6
This complies with the densest arrangement of spheres of equal size.
 Closest sphere packing

3.4.1.5 Voids

The fcc - lattice can be constructed by regular octahedrals and tetrahedrals. In their center there
is a lattice void, which is designated as tetrahedral or octahedral void, respectively. (see
Fig. 3.24).Octahedral void

Material Science and Engineering I / II 56

Status: 01.11.2017
 Most common lattice types for metals

The octahedral voids are situated in the center of the cube and on the center of the cube edges.
The latter can be assigned (or are shared) to (by) 4 unit cells.

𝑓𝑐𝑐 12
𝑛𝑜𝑐𝑡 = 1 + =4 23)
4

The available space is:

𝑓𝑐𝑐 𝑓𝑐𝑐
𝑎 0 = 2𝑟𝑜𝑐𝑡 + 2𝑟𝑎𝑡𝑜𝑚 24)

(from consideration of a cube edge in the {110} – plane intercept of the unit cell in the real
model, see also Fig. 3.25)

Tetrahedral void

 On room diagonals in the middle between corner atom and inner centered octahedral void

𝑓𝑐𝑐
𝑛𝑡𝑒𝑡𝑟𝑎 = 8 25)

The available space is:

√3 𝑓𝑐𝑐 𝑓𝑐𝑐
𝑎 0 = 𝑟𝑡𝑒𝑡𝑟𝑎 + 𝑟𝑎𝑡𝑜𝑚 26)
4

(from consideration of a room diagonal in {110} – plane intercept in the real model, see also Fig.
3.25)

a) b)

lattice atom places lattice atom places

octahedron places tetrahedron places

Fig. 3.24 Octahedral void (a)) and Tetrahedral void (b)) in the fcc-lattice.

A comparison between the available space of an octahedral void and a tetrahedral void is shown
in the following sketch:

Material Science and Engineering I / II 57

Status: 01.11.2017
 Most common lattice types for metals

Fig. 3.25 Available space in octahedral and tetrahedral void in the fcc-lattice.

3.4.1.6 Stacking sequence

As an equivalent approach to the unit cell concept the lattice can be considered as a sequenced
stack of specific lattice planes, e.g. close packed planes.

Example: {111}-planes, so called octahedral layer of the fcc - lattice.

stacking sequence of the {111}-planes is ABCABCABC... (triple sequence), i. e. in each fourth

layer the atoms are vertically aligned to the first one (see Fig. 3.26).

Fig. 3.26 stacking sequence of the {111}-planes in the fcc lattice.

Material Science and Engineering I / II 58

Status: 01.11.2017
 Most common lattice types for metals

3.4.1.7 Densest packed planes and directions

{111}- planes are close packed. Due to their low atomic roughness they can serve as slip planes.

<110>- directions are close packed. In the regime of plastic deformation they serve as slip
directions (see Fig. 3.27).

Fig. 3.27 {111}-planes and <110>-directions in the fcc lattice.

3.4.2 Comparison of the most important lattice types

Fig. 3.28 bcc lattice with atoms (), octahedral voids () and tetrahedral voids (∆).

Material Science and Engineering I / II 59

Status: 01.11.2017
 Most common lattice types for metals

Fig. 3.29 fcc lattice with atoms (), octahedral voids () and tetrahedral voids (∆).

Fig. 3.30 hex lattice with atoms (), octahedral voids () and tetrahedral voids (∆).

3.4.3 Stacking sequences in individual crystal lattices

Fig. 3.31 {112}-planes in the bcc lattice with an ABCDEF stacking sequence.

Material Science and Engineering I / II 60

Status: 01.11.2017
 Most common lattice types for metals

Fig. 3.32 {111}-planes in the fcc lattice with an ABC stacking sequence.

Fig. 3.33 {0001}-planes in the hex lattice with an AB stacking sequence.

Material Science and Engineering I / II 61

Status: 01.11.2017
 Most common lattice types for metals

3.4.4 Comparison of the most important lattice types

Atom loci and loci of voids

Tab. 3. 3 Comparison of the most important geometric propertied of the different lattice types

lattice type bcc fcc hex

characteristic V, Cr, α-Fe, Al, γ-Fe, Ni, Cu, Mg, Co

measures Nb, Mo, Ta, W Pd, Ag, Au, Pb

coordination number 8 12 12

atoms per unitcell 2 4 2

𝑎0 𝑎0 𝑎0
atomic radius r √3 √2
4 4 2

density ratio 68 % 74 % 74 %

octahedral voids per

unit cell 6 4 2

radius of octahedral
voids r0 0,155r 0,414r 0,414r

tetrahedral voids per

unit cell 12 8 4

radius of tetrahedral
voids rT 0,291r 0,225r 0,225r

no dense packing
stacking sequence ({112}-planes {111}: ...ABCABC... {0001}: ...ABABAB...
…ABCDEF…)

Material Science and Engineering I / II 62

Status: 01.11.2017
 Most common lattice types for metals

3.4.5 Allotropic element modifications

Some elements exist in different lattice structures depending on temperature (or pressure). This
effect is called polymorphism and the different structures are allotropes or modifications with
usually different properties

Tab. 3. 4 Example for some allotropic element modifications

Temperature range
Metal Phase designation Lattice type
[°C] at 1 bar
Iron α < 911 bcc
γ 911 … 1392 fcc
1392 … 1536
δ bcc

Cobalt α < 450 hex

β 450 … 1495 fcc
Titanium α < 882 hex
β 882 … 1668 bcc

The given temperature ranges are only valid for pure elements. Added alloying elements can
stabilize or destabilize particular modifications.

Important technical example: Austenitic steel (Fe + ≥ 8 Ma.-% Ni + ≥ 18 Ma-% Cr) exist as a fcc
lattice (γ) at room temperature.

3.4.6 Intermetallic compounds

Intermetallics or intermetallic phases can be found with metallic base elements and metallic
semi-metallic or nonmetallic atoms. They have metallic properties and can show both
stoichiometric (e.g. MgZn2) and non-stoichiometric (e.g. NaZn13) compositions.

There are some 1000 intermetallic phases with a wide variety of lattice structures with both
relatively simple cubic lattices with a low number of atoms per unit cell (e.g. 18, AlAs) and
extremely complex structures with

52 or 112 or 18 Atoms/unit cell

for Cu5Zn8 or CuZn13 or Mg3Cr2Al18

At present there are 106 known structure types with more than 5 representatives.

Material Science and Engineering I / II 63

Status: 01.11.2017
 Most common lattice types for metals

3.4.6.1 Intermetallic aluminides

Further important intermetallic compounds are aluminides. They are applied for the
development of materials for high temperature applications in components for mechanical
engineering on bases of Ni-, Fe- or Ti.

They feature
 Low weight
 Good mechanical properties
 Good oxidation characteristics

Examples:
 Ni3Al (fcc)
 NiAl, FeAl (bcc)
 γ-TiAl (tfc)

Material Science and Engineering I / II 64

Status: 01.11.2017