Structure of metallic solids

on the basis of different pattern of 3d-

Close packing and resulting unit cells
Simple packing [ primitive unit cell]
Hexagonal close packing

Cubic close packing [ fcc unit cell]

Body centered close packing

[bcc unit cell]

2 D Hexagonal Closest Packing
3 D Hexagonal Closest Packing
Stacking Sequence AB-AB-AB-
now in 2nd
layer
YOU have
two
types of
dimples
[voids]
type A
type B

type A is
void on
sphere of
first layer
 Types of void on 2nd layer
Tetrahedral void Octahedral void
[B-type of void]
[C-type of void]
 Features of hexagonal close packing
This is an A-B, A- B type packing in which
every 3rd layer is similar to 1st layer in pattern of
packing
It is resulted from packing of 3rd layer point in
tetrahedral void of 2nd layer
No of atom [point] in one unit cell is 6
Co . No . of a lattice point[atom] is 12
6 from same plane and 3 from above and 3 from
below the plane
Packing efficiency is 74%
Cubic close packing
Stacking Sequence ABCABCABC

packing of 3 layer
rd

atoms in Octahedral void

[C-type of void] of 2nd
layer
 Closest Packing
Alternatively
we could
place the
third layer in
the C-type C C
site (void of
second layer
C A
above the
voids in 1st
layer )
 Closest Packing
Third layer:
If occupy C-type site
the layer ordering is
A-B-C-A-B-C and
creates a cubic
closest packed
structure (CCP)
Blue layer atoms are
now in a unique
position above voids
between atoms in
layers A and B
 Closest Packing
Third layer:
If occupy C-type
VOIDS the layer
ordering is A-B-C-
A-B-C and creates a
cubic closest packed
structure (CCP)
Blue layer atoms are
now in a unique
position above voids
between atoms in
layers 1 and 2
 Closest Packing
Third layer:
If occupy C-type site
the layer ordering is
A-B-C-A-B-C and
creates a cubic
closest packed
structure (CCP)
Blue layer atoms are
now in a unique
position above voids
between atoms in
layers A and B
 Closest Packing
View from the same side
shows the face-
centered cubic unit
cell that results.
A-layer
The atoms are slightly
shrunken to aid in
visualizing the
structure C-layer

B-layer

A-layer
 Closest Packing
Rotating toward a top
view
 Closest Packing
Rotating toward a top
view
 Cubic close Packing
You are looking at a top
yellow layer A with a
blue layer C below,
then a red layer B and
a yellow layer A again
at the bottom
FCC can be represented by a stack of close-packed
planes (planes with highest density of atoms)
 Address of Lattice point Contribution to one unit cell

Corner of cube 1/8

Edge centre of cube
Facecenter of cube
Body Center of cube 1

Address of Lattice point Contribution to one unit cell

Corner of Hexagonal unit cell 1/6

Facecenter of Hexagonal unit cell

Interior of Hexagonal unit cell 3

Edge centre of hexagonal 1/3

[only tv voids]
 Type of Relation Packing
UNIT Lattice Effective no. Coordination b/w effeicency Atoms in
CELL point Atoms number a and r contact
[Z]

Primitive 8 [1/8X8]=1 6 2r =a 52 On
corner
On body
digonal
Body
centred 9 [1/8X8]+[1X1]=2 8 4r = 68
Face On face
centred digonal
14 [1/8X8]+[1/4 X12]=4 12 4r= 74

Hexagonal [1/6X12]+[1/2X2]+3 Shortest In

17 12 a=2r 74 hexagonl
primitive =6 plane
What happens when RC/RA decreases?

The center cation becomes too small for the XII site
(as if a hard-sphere atom model began to rattle in
the XII site) and it drops to the next lower
coordination number (next smaller site).

It will do this even if it is slightly too large for the

next lower site.

It is as though it is better to fit a slightly large

cation into a smaller site than to have one rattle
about in a site that is too large.
Coordination Polyhedra

Click to run animation Case Klein animation

for Mineral Science, John Wiley & Sons
 The next smaller crystal site is:

Body-Centered Cubic
(BCC) with cation
(red) in the center of a
cube

Coordination number is
now 8 (corners of
cube)
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).
Set = 1
What is the RC/RA of that arbitrary
limiting condition?? since will
deal with
ratios

Diagonal length then = 2

 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.

Then a hard-sphere
cation would rattle
in the position, and it
would shift to the next
lower coordination
(next smaller site).

What is the RC/RA of that

limiting condition??

Rotate
 A central cation will remain in VIII coordination with
decreasing RC/RA until it again reaches the limiting
situation in which all atoms mutually touch.
Central Plane = 1 + 2 = 1.732
What is the RC/RA of that
limiting condition??

1.732 = dC + dA

=1
If dA = 1 (arbitrary)
then dC = 0.732

dC/dA = RC/RA
= 0.732/1 = 0.732
= 2
The limits for VIII coordination are thus between 1.0
(when it would by CCP or HCP) and 0.732

Note: BCC is not a = 1 + 2 = 1.732

cosest-packed
oxygen arrangement,
so it may not occur
in all ionic crystal
lattices
=1
(arbitrary)

= 2
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.732 the
cation will move to the next lower coordination: VI,
or octahedral. The cation is in the center of an
octahedron of closest-packed oxygen atoms
What is the RC/RA of that
limiting condition??

1.414 = dC + dA
= 2
=1
If dA = 1
then dC = 0.414

dC/dA = RC/RA
= 0.414/1 = 0.414
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
As RC/RA continues to decrease below the 0.414 the
cation will move to the next lower coordination: IV,
or tetrahedral. The cation is in the center of an
tetrahedron of closest-packed oxygen atoms
What is the RC/RA of the limiting
condition??

Center-to-corner distance of a
tetrahedron with edges of 1.0
= 0.6124 0.5 0.61
1
RC = 0.612 - 0.5 = 0.1124

RC/RA
= 0.1124/0.5 = 0.225
As RC/RA continues to decrease below the 0.22 the
cation will move to the next lower coordination: III.
The cation moves from the center of the tetrahedron to
the center of an coplanar tetrahedral face of 3 oxygen
atoms
What is the RC/RA of the
limiting condition??

cos 60 = 0.5/y y = 0.577

0.5 y
RC = 0.577 - 0.5 = 0.077 1

RC/RA
= 0.077/0.5 = 0.155
If RC/RA decreases below the 0.15 (a are situation) the
cation will move to the next lower coordination: II.
The cation moves directly between 2 neighboring
oxygen atoms
 Coordination Polyhedra
Consider coordination of anions about a
central cation
Halite
Na
Cl

Cl Cl

Cl
 Coordination Polyhedra
Na
Could do the opposite,
but conventionally Na Cl Na
choose the cation
Can predict the coordination Na

by considering the radius ratio:

RC/RA
Cations are generally smaller than anions so
begin with maximum ratio = 1.0
Homework Exercise
Use RC/ROxygen and the limits above to determine the
probable coordination of the following elements in
silicate and oxide minerals:

Si+4 Mg2+
Al3+ Ti4+
K+ Ca2+
Fe2+ Na+

Correct RC for cases in which the coordination is not VI (the

standard) and recalculate the ratio
 Formation of CCP
Layer 3 can now
occupy A-type site
(directly above
yellow atoms) or
C-type site (above
voids in both 1st
and 2nd layers)