The Structure of Crystals

The properties of materials are directly related to their crystal structures. For example,
pure and undeformed magnesium (having one crystal structure) is much more brittle
than pure and undeformed gold (that has a different crystal structure). Also, the
permanent magnetic and ferroelectric behaviors of some ceramic materials are
explained by their crystal structures. Furthermore, significant property differences exist
between crystalline and noncrystalline materials having the same composition. For
example, noncrystalline ceramics and polymers normally are optically transparent, while
the same materials in crystalline form tend to be opaque or translucent.
 Fundamental Concepts
• A crystalline material is one in which the
atoms are situated in a repeating or periodic
array over large atomic distances. Long-
range order exists such that the atoms are
arranged in a repetitive (periodice) three-
dimensional pattern.

• Some of the properties of crystalline solids

depend on the type of crystal structure of
the material, i.e. the manner in which
atoms, ions, or molecules are spatially
arranged.

• When describing crystalline structures,

atoms (or ions) are thought of as being solid
spheres having well-defined diameters. This
is termed the atomic hard sphere model in
which spheres representing nearest-
neighbor atoms touch one another.

• Sometimes the term lattice is used in the

context of crystal structures. In this sense
‘‘lattice’’ means a three-dimensional array of
points coinciding with atom positions (or
sphere centers).
2
 Unit Cells
• In describing crystal structures it is often
convenient to subdivide the structure into
small repeat entities called unit cells.

• Unit cells for most crystal structures are

parallelepipeds or prisms having three sets
of parallel faces.

• A unit cell is chosen to represent the

symmetry of the crystal structure, wherein
all the atom positions in the crystal may be
generated by translations of the unit cell
integral distances along each of its edges.
Thus, the unit cell is the basic structural
unit or building block of the crystal
structure and defines the crystal structure
by virtue of its geometry and the atom
positions within.

3
The Crystal Lattice....unit cells

4
The Crystal Lattice....unit cells

5
 Lattice Parameters for Unit Cells
Lengths
a, b, c

Angles
a, b, g

6
Seven Crystal Systems

7
 14 Bravais Lattices

P – primitive cell

C – cell with a lattice point in

the center of two parallel
faces.

F – cell with a lattice point

in the center of each face

I – cell with a lattice point in

the center of the interior

R – rombohedral primitive
cell
 14 Bravais Lattices…..

a
Simple Cubic (P)

a=b=c a
a=b=g=
a
a Face-Centred
Cubic (F)
a=b=c
a=b=g= a

Body-Centred a
Cubic (I)
a=b=c
a=b=g= a

9
14 Bravais Lattices…..
Simple Tetragonal
(P) c
a=bc
a=b=g=
a

Body-Centred c
Tetragonal (I)
a=bc
a=b=g= a

10
14 Bravais Lattices…..
Simple c
Orthorhombic

abc
b
a=b=g=

Body-Centred c
Orthorhombic
(b)
b
abc
a=b=g=
a

11
14 Bravais Lattices…..

Base-Centred
Orthorhombic c
(C)
a  b c b
a=b=g=

Face-Centred
Orthorhombic c
(F)

a  b c
a=b=g= b

a
12
Rhombohedral
(R)
a=b=c
a=b=g a
a
a
a a
a

Hexagonal
(P)
c
a=bc
a=b=
g=
a 

a
13
 Simple
Monoclinic
(P)
c
a b  c
b
a=g=90b
b

Base-Centred
Monoclinic
(C)
a b  c c
a=g=90°b
b
b

c
Triclinic
(P)
a
a b c b b
abg
a g
14
 z

Does an atom belong to 0, ½, ½

y
a unit cell? a ½, 0, ½

0≤x<1
½, ½, ½
x
0≤y<1 000

0≤z<1

b
y

x
15
 Geometric Parameters
Relation between atomic radius and lattice parameter:

aFCC = 2R 2
R
4R
aBCC = R
3
aFCC aBCC

The number of nearest-neighbor atoms is the coordination number. For FCC the
coordination number is 12. For BCC the coordination number is 8.

The atomic packing factor (APF) is the fraction of solid sphere volume in a unit cell,
assuming the atomic hard sphere model.

volume of atoms in a unit cell

APF =
total unit cell volume
16
Geometric Parameters

17
 Example-1
Calculate the volume of an FCC unit cell in terms of the atomic radius R.

a + a = (4R)
2 2 2

a = 2R 2

( )
3
V C
FCC
= a = 2R 2
3
= 16R 3
2

18
 Example-2
Show that the atomic packing factor for the FCC crystal structure is 0.74.
volume of atoms in a unit cell
APF = z
total unit cell volume

4 3 y
0, ½, ½

VSphere =  R ½, 0, ½

3
½, ½, ½
x
4 3 16 3
= ( 4)  R =  R
000
VAtoms
3 3
z

V FCC
Cell = 16R 3
2
y

 16  3
  R
=  3
VAtoms 3
APF = = 0.74 x
VCell 16 R 2 19
 Density of Structures
If we know the crystal structure, we can determine the theoretical density r via:

nA
r=
VCell N A
Where:

N = number of atoms in the unit cell.

A = atomic weight

VCell = volume of the unit cell

NA = Avogadro’s number (6.023x1023 atoms/mol)

20
 Example-3
Copper has an atomic radius of 0.128nm, an FCC structure, and an atomic weight of
63.5 g/mol. Calculate its theoretical density and compare the answer with its measured
density.
nACu nACu
r= =
VCell N A (
16 R 3 2 N A )
r=
( 4 atoms/unit cell )( 63.5 g/mol )
16 2 (1.28 x10−8 )3 cm3  ( 6.023x1023 atoms/mol )
 
r = 8.89 g/cm3

The measured density of copper is 8.94 g/cm3.

21
 Examples of More Complicated Structures
Because ceramics are composed of at least two elements, their crystal structures are
generally more complex than those for metals. The atomic bonding in these materials
ranges from purely ionic to totally covalent, while many ceramics exhibit a combination
of these two bonding types.

For predominately ionic structures, 2 criteria influence the equilibrium structure:

1. Charge on the ions (the crystal must be electrically neutral).
2. The relative size of the ions.

For example, in calcium fluoride, each calcium ion

has a 2+ charge (Ca+2), and associated with each
fluorine ion is a single negative charge (F-). Thus,
there must be twice as many F- as Ca+2 ions, which
is reflected in the chemical formula CaF2 .

22
 Complicated Structures…
The second criterion involves the sizes or ionic radii of the cations and anions, rC and rA,
respectively. Because the metallic elements give up electrons when ionized, cations are
ordinarily smaller than anions, and the ratio rC/rA<1. Each cation prefers to have as many
nearest-neighbor anions as possible. The anions also desire a maximum number of
cation nearest neighbors.

anion

23
 Example-4
Show that the minimum cation-to-anion radius ratio for the
coordination number 3 is 0.155.

AP = rA AO = rA + rC

AP = cos a
AO

From simple geometry, a=30°.

AP rA 3
= = cos 30 =
AO rA + rC 2
3
rC 1 − 2
= = 0.155
rA 3
2
24
 Examples of More Complicated Structures…
Perhaps the most common AX crystal structure is the sodium chloride (NaCl), or rock
salt, type. The coordination number for both cations and anions is 6. There are 4
cations and 4 anions per unit cell. Some of the common ceramic materials that form
with this crystal structure are NaCl, MgO, MnS, LiF, and FeO.

25
 Examples of More Complicated Structures…
The cesium chloride (CsCl) structure has a coordination number of 8 for both ion
types. The anions are located at each of the corners of a cube, whereas the cube
center is a single cation. This is not a BCC crystal structure because ions of two
different kinds are involved.

26
 Examples of More Complicated Structures…
A third AX structure is one in which the coordination number is 4 so that all ions are
tetrahedrally coordinated. This is called the zinc blende or sphalerite structure (ZnS).
All corner and face positions of the cubic cell are occupied by S atoms, while the Zn
atoms fill interior tetrahedral positions. Each Zn atom is bonded to four S atoms, and
vice versa. Most often the atomic bonding is highly covalent in compounds exhibiting
this crystal structure which include ZnS, ZnTe, and SiC.

27
 Examples of More Complicated Structures…
If the charges on the cations and anions are not the same, a compound can exist with
the chemical formula AmXp, where m and/or p≠1. An example is AX2, for which a
common crystal structure is fluorite (CaF2). Calcium ions are positioned at the centers
of cubes, with fluorine ions at the corners. Other compounds that have this crystal
structure include UO2, PuO2, and ThO2.

28
 Examples of More Complicated Structures…
It is also possible for ceramic compounds to have more than one type of cation
(represented by A and B), such that the chemical formula may be designated as
AmBnXp . Barium titanate (BaTiO3), having both Ba2+ and Ti4+ cations falls into this
classification. This material has a perovskite crystal structure. Above 120°C the
structure is cubic. Ba2+ ions are situated at all eight corners of the cube and a single
Ti4+ is at the cube center, with O2- ions located at the center of each of the six faces.

29
 Density of Complicated Structures
If we know the crystal structure, we can determine the theoretical density r via:

n ' (  AC +  AA )
r=
VCell N A
Where:

n’ = number of formula units in the unit cell.

∑AC = sum of the atomic weights of all cations in the formula unit.

∑AA = sum of the atomic weights of all anions in the formula unit.

VCell = volume of the unit cell

NA = Avogadro’s number (6.023x1023 atoms/mol)

30
 Example-5
On the basis of crystal structure, compute the theoretical density for
sodium chloride. How does this compare with its measured density?
There are 8 atoms per unit cell: 4 cations and 4
anions, so we have 4 formula units of NaCl with:

∑AC = ANa = 22.99 g/mol

∑AA = ACl = 35.45 g/mol

( )
3
VCell = a 3 = 2rNa+ + 2rCl −

n ' ( ANa + ACl )

r=
( 2r )
3
Na +
+ 2rCl − NA
4 ( 22.99 + 35.45 )
r= = 2.14 g/cm3
 2 ( 0.102 x10−7 ) + 2 ( 0.181x10−7 )3 ( 6.023 x1023 ) 
 
The experimental value is 2.16 g/cm3. 31
 Examples of More Complicated Structures…
Carbon is an element that exists in various polymorphic forms, including the
amorphous state. Diamond is a metastable carbon polymorph at room temperature
and atmospheric pressure. Its crystal structure is a variant of the zinc blende, in which
carbon atoms occupy all positions (both Zn and S). Thus, each carbon bonds to four
other carbons, and these bonds are totally covalent. This is appropriately called the
diamond cubic crystal structure, which is also found for other Group IVA elements in
the periodic table [e.g., germanium,silicon, and gray tin, below 13°C].

32
 Examples of More Complicated Structures…
Graphite has a crystal structure distinctly different from that of diamond and is also
more stable than diamond at ambient temperature and pressure. The graphite
structure is composed of layers of hexagonally arranged carbon atoms; within the
layers, each carbon atom is bonded to three coplanar neighbor atoms by strong
covalent bonds. The fourth bonding electron participates in a weak van der Waals
type of bond between the layers.

33
 Crystallographic Directions
A crystallographic direction is defined as a vector between two points. The following
steps are utilized in the determination of the three directional indices:
1. A vector of convenient length is positioned such that it passes through the origin of
the coordinate system. Any vector may be translated throughout the crystal lattice
without alteration, if parallelism is maintained.
2. The length of the vector projection on each of the three axes is determined; these are
measured in terms of the unit cell dimensions.
3. These three numbers are multiplied or divided by a common factor to reduce them to
the smallest integer values.
4. The three indices, not separated by commas, are enclosed in square brackets [uvw].
The u, v, and w integers correspond to the reduced projections along the x, y, and z
axes, respectively.

34
 Example-6
Determine the indices for the direction in the figure:

35
 Example-7
Draw the vector 1 1 0 in a cubic unit cell.

36
 Equivalent Directions
For some crystal structures, several nonparallel directions with different indices are
actually equivalent. This means that the spacing of atoms along each direction is the
same.

For example, in cubic crystals all the directions represented by the following indices are
equivalent: [100], [100], [010], [010], [001], and [001]. Equivalent directions are grouped
together into a family, which are enclosed in angle brackets, thus: <100>.

Furthermore, directions in cubic crystals having the same indices without regard to
order or sign, for example, [123] and [213], are equivalent. This is not always true for
other crystal systems. For example, for crystals of tetragonal symmetry, [100] and [010]
directions are equivalent, whereas [100] and [001] are not.

[010]

[110]
[100]

37
 Hexagonal Directions
A problem arises for crystals having hexagonal symmetry in that some crystallographic
equivalent directions will not have the same set of indices. This is solved by using a
four-axis Miller–Bravais coordinate system. The three a1, a2, and a3 axes are all
contained within a single plane (called the basal plane), and at 120° angles to one
another. The z axis is perpendicular to this basal plane. Directional indices which are
obtained as described before are denoted by four indices, as [uvtw]. By convention, the
first three indices pertain to projections along the respective a1, a2, and a3 axes in the
basal plane.

11 20

1 100 38
 Conversion for Hexagonal Directions
Conversion from the three-index system to the four-index system, [u’v’w’] —> [uvtw] is
accomplished by the following formulas where primed indices are associated with the
three-index scheme and unprimed with the Miller–Bravais four-index system. n is a
factor that may be required to reduce u, v, t, and w to the smallest integers. For
example, using this conversion, the [010] direction becomes [1210].

u=
n
(2u '−v')
3
n
v = ( 2v '− u ' )
3
t = − (u + v )
w = nw '

Only use Miller-Bravais indices for hexagonal systems!!!

39
Crystallographic Planes

40
 ‫מצייני מילר של מישורים בסריג‬

‫משפחת מישורים מקבילים בגביש‬

‫מסוים ניתנת לתיאור‬
‫באמצעות שלישית מספרים‬
‫שלמים ‪ h, k, l,‬הנקראים‬
‫‪Z‬‬ ‫‪1‬‬ ‫מצייני מילר‪ ,‬והמראים כי‬
‫מישור מרחבי מסוים‪ ,‬מקצה‬
‫‪1/l‬‬ ‫קטעים של ‪ 1/h, 1/k, 1/l‬בהתאמה‬
‫על שלושת וקטורי היחידה‪.‬‬

‫‪1/k‬‬
‫‪Y‬‬
‫‪1/h‬‬ ‫‪1‬‬

‫‪X‬‬ ‫‪1‬‬
 Crystallographic Planes
The orientations of planes for a crystal structure are represented in a similar manner to
directions. Again, the unit cell is the basis using the three-axis coordinate system. In all
but the hexagonal crystal system, crystallographic planes are specified by three Miller
indices as (hkl). Any two planes parallel to each other are equivalent and have identical
indices. The procedure employed in determination of the h, k, and l index numbers is as
follows:

1. If the plane passes through the selected origin, either another parallel plane must be
constructed within the unit cell by an appropriate translation, or a new origin must be
established at the corner of another unit cell.
2. At this point the crystallographic plane either intersects or parallels each of the three
axes; the length of the planar intercept for each axis is determined in terms of the lattice
parameters a, b, and c.
3. The reciprocals of these numbers are taken. A plane that parallels an axis may be
considered to have an infinite intercept, and, therefore, a zero index.
4. If necessary, these three numbers are changed to the set of smallest integers by
multiplication or division by a common factor.
5. Finally, the integer indices, not separated by commas, are enclosed within
parentheses, thus: (hkl).

42
 Example-8
Determined the indices for:

Since the plane passes through the origin O, a new origin must be chosen at the corner
of an adjacent unit cell, taken as O and shown in sketch (b).

(0 1 2)

43
 Example-9
( )
Construct a 0 1 1 plane within a cubic unit cell.

44
 Crystallographic Planes
The atomic arrangement for a crystallographic plane, which is often of interest, depends
on the crystal structure. The (110) atomic planes for FCC structures are presented
below. A ‘‘family’’ of planes contains all those planes that are crystallographically
equivalent—that is, having the same atomic packing; and a family is designated by
indices that are enclosed in braces: {100}.

(111 )
(111)
( 111)
(1 1 1 ) {111}
(11 1 )
( 1 11)
( 11 1 )
(1 11)

45
 Hexagonal Planes
The four-axis Miller–Bravais system is also used for planes in hexagonal structures.
Planar indices which are obtained as described before are denoted by four indices, as
(hkil).

46
 Linear & Planar Density
•Linear Density: Relative length of a line through the ‘center’ of atoms.
•Planar Density: Relative area of a plane through the ‘center’ of atoms.

L1

Calculate the linear density of the [100] direction for BCC.

LAtoms = 2 R
LAtoms 2R
LD = = = 0.866
4R LTotal 4R / 3
LTotal = a =
3

47
 Example-10
Calculate the planar density for FCC (110).

( )( ) ( )
APlane = AC AD = (4R) 2R 2 = 8R2 2
1  1 
AAtoms = 4  Area  + 2  Area  = 2 R2
4  2 
AAtoms 2 R 2
PD = = 2 = 0.555
APlane 8R 2
48
 Close Packed Planes
B

A
A
C
B
B A

A
B
C A

Stacking sequence of (111) planes in FCC Stacking sequence of (0001) planes in HCP

49
‫בסריג קובי‬
 ‫מה למדנו?‬

‫‪.1‬השיעור שקיבלו אדם וחוה בנושא בחירת חומרים‬

‫‪.2‬תקופות הציוויליזציה על פי החומרים השימושיים‬
‫‪.3‬מצאי היסודות בטבע ומחיר חומרי גלם‬
‫‪.4‬חומרים הנדסיים ומקצת תכונותיהם‬
‫‪.5‬כמה מילים על הנדסת חומרים‬
‫‪.6‬קשרים בין אטומיים‬
‫‪.7‬סריגי ברווה‬
‫‪.8‬מבנים פשוטים של יסודות ותרכובות‬
‫‪.9‬הבדלי סדר האטומים בין מבנה ‪ FCC‬לבין ‪HCP‬‬
‫‪.10‬כוונים ומישורים במרחב הגביש‬
‫‪.11‬נוסחאות שימושיות למרחקים ולזוויות בין מישורים‬
‫במבנה קובי‬