How Do Atoms Arrange Themselves To Form Solids?: Chapter Outline

Introduction To Materials Science, Chapter 3, The structure of crystalline solids
Chapter Outline
How do atoms arrange themselves to form solids?
• Fundamental concepts and language

• Unit cells
• Crystal structures
¾Simple cubic
¾Face-centered cubic
¾ Body-centered cubic
¾ Hexagonal close-packed
• Close packed crystal structures
• Density computations
• Types of solids
Single crystal
Polycrystalline
Amorphous
University of Tennessee, Dept. of Materials Science and Engineering 1
Types of Solids
Crystalline material: atoms self-organize in a periodic
array
Single crystal: atoms are in a repeating or periodic array
over the entire extent of the material
Polycrystalline material: comprised of many small
crystals or grains
Amorphous: lacks a systematic atomic arrangement
Crystalline Amorphous
SiO2
1
Crystal structure
To discuss crystalline structures it is useful to consider
atoms as being hard spheres with well-defined radii. In this
hard-sphere model, the shortest distance between two like
atoms is one diameter.
We can also consider crystalline structure as a lattice of
points at atom/sphere centers.
Unit Cell
The unit cell is the smallest structural unit or building block
that can describe the crystal structure. Repetition of the unit
cell generates the entire crystal.
Example: 2D honeycomb net can

be represented by translation of
two adjacent atoms that form a unit
cell for this 2D crystalline structure
Example of 3D crystalline structure:
Different choices of unit cells possible, generally choose

parallelepiped unit cell with highest level of symmetry
2
Metallic Crystal Structures
¾ Metals are usually (poly)crystalline; although formation

of amorphous metals is possible by rapid cooling
¾ As we learned in Chapter 2, the atomic bonding in metals

is non-directional ⇒ no restriction on numbers or
positions of nearest-neighbor atoms ⇒ large number of
nearest neighbors and dense atomic packing
¾ Atom (hard sphere) radius, R, defined by ion core

radius - typically 0.1 - 0.2 nm
¾ The most common types of unit cells are the faced-

centered cubic (FCC), the body-centered cubic (BCC)
and the hexagonal close-packed (HCP).
The 14 Bravais ;attices grouped into 7 lattice types.

The restrictions on the lattice parameters (a,b,c) and
the angles of the unit cell are listed for each. What
are the most comon ?
3
Miller indices- h,k,l- for naming points in the crystal

lattice. The origin has been arbitrarily selected as the
bottom left-back corner of the unit cell.
(a) the coordinates of the six face centers

and the center of the cube, (b) the
location of the point ¼, ¾, ¼ which is
found by starting at the origin and
moving a distance ao/4 in the x-direction,
then 3 ao/4 in the y-direction, and finally
ao/4 in the z-direction.
4
Positions, Directions, and Planes

Z
x, y, z – u, v, w
X
Y
Lattice Positions and Directions:

1) Always establish an origin
2) Determine the coordinates of the lattice
points of interest
3) Translate the vector to the origin if
required by drawing a parallel line or
move the origin.
4) Subtract the second point from the first:
u2-u1,v2-v1,w2-w1
5) Clear fractions and reduce to lowest terms
6) Write direction with square brackets [uvw]
7) Negative directions get a hat.
Indices of Planes:
1) Identify the locations where the plane
intercepts the x, y, z axes as the fractions of
the unit cell edge lengths a, b, c.
2) Infinity if the plane is parallel.
3) Take the reciprocal of the intercepts.
4) Clear any fraction but do not reduce to
lowest terms.
5) Example: 1/3,1/3,1/3 is (333) not (111)!!!
6) Use parentheses to indicate planes (hkl)
again with a hat over the negative indices.
7) Families are indicated by {hkl}
Remember Terminology:
Defined coordinate system: x, y, z
Respective unit cell edge lengths: a, b, c
Direction: Denoted by [uvw]
Family of direction(s): Denoted by: <uvw>
Plane: Denoted by: (hkl)
Family of Plane(s): Denoted by: {hkl}
5
•Directions are always perp. to their respective planes, i.e. [111] perp. (111)
(for cubic systems)
•Families of equivalent planes are equal with respect to symmetrical
structures, they do not have to be parallel. Equivalent planes must be
translated to the correct atomic positions in order to maintain the
proper crystal symmetry.
• Families of directions are equivalent in absolute magnitude.
• (222) planes are parallel to the (111) planes but not equal.
• Intercepts for the (222) planes are 1/2,1/2,1/2
• Intercepts for the (333) planes are 1/3,1/3,1/3, remember this is in
what we call “reciprocal space”. If you draw out the (333) plane it is
parallel to the (111) plane but not equivalent.
)
-a 10
(1
(-1 b
-b 10
0,0,0 )
Representation of a series each of (a) (001),

(b) (110), and (c) (111) crystallographic planes.
6
Notation for lattice positions.

Lattice translations connect structurally

Equivalent positions (example shown is body
centered) in various unit cells.
7
Family of directions, <111>, representing

all body diagonals for adjacent unit cells
in the cubic system.
8
Miller-Bravis indicies, (hkil) for the hexagonal

System.
Simple Cubic
• Rare due to poor packing
(only Po has this structure)
• Close-packed directions are cube edges.
• Coordination # = 6
(# nearest neighbors)
(Courtesy P.M. Anderson)
Volume of atoms in unit cell*

APF =
Volume of unit cell
*assume hard spheres
volume
atoms atom
4
unit cell 1 π (0.5a)3
3
APF =
a3 volume
unit cell
9
Face-Centered Cubic (FCC) Crystal Structure (I)
¾ Atoms are located at each of the corners and on the

centers of all the faces of cubic unit cell
¾ Cu, Al, Ag, Au have this crystal structure
(Courtesy P.M. Anderson)
Two representations
of the FCC unit cell

Face-Centered Cubic Crystal Structure (II)
R
a
¾ The hard spheres or ion cores touch one another across a

face diagonal ⇒ the cube edge length, a= 2R√2
¾ The coordination number, CN = the number of closest
neighbors to which an atom is bonded = number of
touching atoms, CN = 12
¾ Number of atoms per unit cell, n = 4. (For an atom
that is shared with m adjacent unit cells, we only count a
fraction of the atom, 1/m). In FCC unit cell we have:
6 face atoms shared by two cells: 6 x 1/2 = 3
8 corner atoms shared by eight cells: 8 x 1/8 = 1
¾ Atomic packing factor, APF = fraction of volume
occupied by hard spheres = (Sum of atomic
volumes)/(Volume of cell) = 0.74 (maximum possible)
10
Face-Centered Cubic Crystal Structure (III)

¾ Corner and face atoms in the unit cell are equivalent
¾ FCC crystal has APF of 0.74, the maximum packing for
a system equal-sized spheres ⇒ FCC is a close-packed
structure
¾ FCC can be represented by a stack of close-packed
planes (planes with highest density of atoms)
Body-Centered Cubic (BCC) Crystal Structure (I)

Atom at each corner and at center of cubic unit cell
Cr, α-Fe, Mo have this crystal structure
R
a
¾ The hard spheres touch one another along cube diagonal
⇒ the cube edge length, a= 4R/√3
¾ The coordination number, CN = 8
¾ Number of atoms per unit cell, n = 2
Center atom (1) shared by no other cells: 1 x 1 = 1
8 corner atoms shared by eight cells: 8 x 1/8 = 1
¾ Atomic packing factor, APF = 0.68
¾ Corner and center atoms are equivalent
11
Hexagonal Close-Packed Crystal Structure (I)
¾ HCP is one more common structure of metallic crystals

¾ Six atoms form regular hexagon, surrounding one atom
in center. Another plane is situated halfway up unit cell
(c-axis), with 3 additional atoms situated at interstices of
hexagonal (close-packed) planes
¾ Cd, Mg, Zn, Ti have this crystal structure
Hexagonal Close-Packed Crystal Structure (II)

¾ Unit cell has two lattice parameters a and c. Ideal ratio
c/a = 1.633
¾ The coordination number, CN = 12 (same as in FCC)
¾ Number of atoms per unit cell, n = 6.
3 mid-plane atoms shared by no other cells: 3 x 1 = 3
12 hexagonal corner atoms shared by 6 cells: 12 x 1/6 = 2
2 top/bottom plane center atoms shared by 2 cells: 2 x 1/2 = 1
¾ Atomic packing factor, APF = 0.74 (same as in FCC)

¾ All atoms are equivalent
12
(b) Stacking of close-packed planes

Normal to
close-packed planes
(a) Stacking of close packed planes

Close-packed
planes A
B
Normal to C
A Close-
close-packed
packed
planes planes
Face centered cubic Hexagonal close-packed
Comparing HCP and FCC structures. The

difference between the two structures lies in the
different stacking sequences.
Close-packed Structures (FCC and HCP)

¾ Both FCC and HCP crystal structures have atomic
packing factors of 0.74 (maximum possible value)
¾ Both FCC and HCP crystal structures may be generated
by the stacking of close-packed planes
¾ The difference between the two structures is in the
stacking sequence
HCP: ABABAB... FCC: ABCABCABC…
13
FCC: Stacking Sequence ABCABCABC...
Third plane is placed above the “holes” of the first plane

not covered by the second plane
HCP: Stacking Sequence ABABAB...
Third plane is placed directly above the first plane of atoms
14
Density and Atom Packing
• Bulk Measurements
– Counting atoms within a unit
cell
• Area density in plane
– # atoms/nm2
• Linear density along direction
– #atoms/nm
Density Computations
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 × 1023 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
Thus, the formula for the density is: nA

ρ=
Vc N A
Atomic weight and atomic radius of many elements you

can find in the table at the back of the textbook front cover.
15
Polycrystalline Materials
• In polycrystalline materials,
grain orientations are random,
so bulk material properties are
isotropic
• Some polycrystalline materials

have grains with preferred
orientations (texture), so
properties are dominated by
those relevant to the texture
orientation
Polymorphism and Allotropy

Some materials may exist in more than one crystal
structure, this is called polymorphism. If the material is an
elemental solid, it is called allotropy.
An example of allotropy is carbon, which can exist as
diamond, graphite, and amorphous carbon.
Pure, solid carbon occurs in three crystalline forms – diamond,

graphite; and large, hollow fullerenes. Two kinds of fullerenes
are shown here: buckminsterfullerene (buckyball) and carbon
nanotube.
16
Single Crystals and Polycrystalline Materials
Single crystal: atoms are in a repeating or periodic array

over the entire extent of the material
Polycrystalline material: comprised of many small
crystals or grains. The grains have different
crystallographic orientation. There exist atomic mismatch
within the regions where grains meet. These regions are
called grain boundaries.
Grain Boundary
Atomistic model of a nanocrystalline solid by Mo Li, JHU
17
Simulation of annealing of a polycrystalline grain structure

Anisotropy
Different directions in a crystal have different packing. For

instance, atoms along the edge of FCC unit cell are more
separated than along the face diagonal. This causes
anisotropy in the properties of crystals, for instance, the
deformation depends on the direction in which a stress is
applied.
In some polycrystalline materials, grain orientations are

random, so bulk material properties are isotropic
Some polycrystalline materials have grains with preferred

orientations (texture), so properties are dominated by those
relevant to the texture orientation and the material exhibits
anisotropic properties
• Polycrystals
-Properties may/may not 200 µm
vary with direction.
-If grains are randomly
oriented: isotropic.
-If grains are textured,
anisotropic.
18
Anisotropy
• Properties of crystals may be

different along different directions,
because atomic periodicities are
different. E.g. in single crystal cubic
system: <111>
<110>
– <100> Cube edges

– <110> Face diagonals
– <111> Body diagonals
<100>
Modulus of Elasticity (Gpa)

Metal [100] [110] [111]
Aluminum 63.7 72.6 76.1
Copper 66.7 130.3 191.1
Iron 125.0 210.5 272.7
Non-Crystalline (Amorphous) Solids
In amorphous solids, there is no long-range order. But

amorphous does not mean random, in many cases there is
some form of short-range order.
Schematic picture of
amorphous SiO2 structure
Amorphous structure from

simulations by E. H. Brandt
19
Summary
Make sure you understand language and concepts:
¾ Allotropy
¾ Amorphous
¾ Anisotropy
¾ Atomic packing factor (APF)
¾ Body-centered cubic (BCC)
¾ Coordination number
¾ Crystal structure
¾ Crystalline
¾ Face-centered cubic (FCC)
¾ Grain
¾ Grain boundary
¾ Hexagonal close-packed (HCP)
¾ Isotropic
¾ Lattice parameter
¾ Non-crystalline
¾ Polycrystalline
¾ Polymorphism
¾ Single crystal
¾ Unit cell
20

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Introduction To Materials Science, Chapter 3, The structure of crystalline solids