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* Do not confuse these voids with microscopic/macroscopic voids/cracks in crystals or holes (semiconductors) or vacancies (missing atoms).
Note: in some cases the void within a crystal can be large enough to accommodate small/large molecules (e.g. in Metal Organic Frameworks)
→ we are not going to describe these voids in this set of slides.
This void space within the unit cell has a complicated shape, but (typically) we
only consider the plane faced polyhedron version of the voids.
There may be more than one type of such void polyhedra in a single unit cell.
These void polyhedra when put together fill space; however, in some cases only a
part of a given polyhedron may lie within a unit cell.
The size and distribution of voids* in materials plays a role in determining aspects
of material behaviour e.g. solubility of interstitials and their diffusivity.
The position of the voids of a particular type will be consistent with the symmetry
of the crystal (if a void of a particular type is located at (x,y,z), then all similar
voids can be obtained by the symmetry operations of the crystal).
In the close packed crystals (FCC, HCP) there are two types of voids tetrahedral
and octahedral voids (identical in both the structures as the voids are formed
between two layers of atoms)
The octahedral void has a coordination number 6 (should not be confused with 8 coordination!)
In the ‘BCC crystal’ the voids do NOT have the shape of the regular tetrahedron or
the regular octahedron (in fact the octahedral void is a ‘linear void’!!)
True Unit Cell of SC crystal Polyhedral model (Cube) Actual shape of the void (space)!
4-tetrahedra in view
VOIDS
Tetrahedral TV Octahedral OV
If ‘e’ is the edge length of the tetrahedron then CV = (6/4)e → see below in triangle ABC
6
DT erx e 2r 6
rrx
4 2
x 6
1 ~ 0.225
r 2
In tetrahedron ABCD
In triangle ABC AD 2 e2 AO 2 DO 2
e2 2 2
e AM 2
2 e
e DO 2
2 DO e
4 3 3
3 3
AM e DT DO
2 4
2 2 3 e
AO AM e 3 2 6
3 3 2 3 DT e e
4 3 4
Size of the largest atom which can fit into the Octahedral void of FCC
HCP VOIDS
TETRAHEDRAL OCTAHEDRAL
This void extends across 3
conventional unit cells and
hence is difficult to visualize
These voids are identical to the ones found in FCC (for ideal c/a ratio).
When the c/a ratio is non-ideal then the octahedra and tetrahedra are distorted (non-regular).
Important Note: often in these discussions an ideal c/a ratio will be assumed (without stating the same explicitly).
If c/a ratio is not the ideal one then the voids will not be ‘regular’ (i.e. regular octahedron and regular tetrahedron).
The other orientation of the tetrahedral void
Octahedral voids
Tetrahedral void
Check below
Octahedral void
Tetrahedral void
A
Further views with some models
There are NO voids in a ‘BCC crystal’ which have the shape of a regular
polyhedron (one of the 5 Platonic solids)
The voids in BCC crystal are: distorted ‘octahedral’ and distorted tetrahedral
→ the correct term should be non-regular instead of distorted (the ‘distortions’ are
‘pretty regular’ as we shall see shortly).
The distorted octahedral void is in a sense a ‘linear void’!
an sphere of correct size sitting in the void touches only two of the six atoms surrounding it
Carbon prefers to sit in this smaller ‘octahedral void’ for reasons which we shall
see soon.
BCC VOIDS
a3/2
a
a a3/2
Note: Atoms are coloured differently but are the same ** Actually an atom of correct size touches only
the top and bottom atoms
TV OV
{0, 0, ½})
Voids / Voids /
BCC voids Position
cell atom
Distorted
• Four on each face: [(4/2) 6 = 12] (0, ½, ¼) 12 6
Tetrahedral
a3/2
a2 a2 5
From the right angled triange OCM: OC arx
16 4 4
4r
For a BCC structure: 3a 4r ( a )
3
5 4r x 5
rx 1 0.29
4 3 r 3
Calculation of the size of the distorted octahedral void
This implies:
a
a
OB r x
2
4r
rx BCC : 3a 4r
2 3
* Point regarding ‘Linear Void’ x 2 3
Because of this aspect the OV along the 3 axes can be 1 0.1547
differentiated into OVx, OVy & OVz r 3
Similarly the TV along x,y,z can be differentiated
Where does the carbon atom sit in the BCC and FCC forms of iron? How does it affect
the solubility of carbon in these forms of Fe?
Surprising facts!
C dissolves more in the close packed structure (FCC, -Fe) (albeit at higher temperatures at
1 atm. pressure where FCC is stable) than in the open structure (BCC-Fe).
Solubility CCP Fe 2.06 wt.% at 1147ºC, BCC Fe 0.008 wt.% at RT & 0.025% at
723C.
C sits in the smaller octahedral void in BCC in preference to the larger tetrahedral void.
Fe carbon alloys are important materials and hence we consider them next.
The octahedral void in FCC is the larger one and less distortion occurs when
carbon sits there this aspect contributes to a higher solubility of C in -Fe.
The distorted (non-regular) octahedral void in BCC is the smaller one but
(surprisingly) carbon sits there in preference to the distorted tetrahedral void (the
bigger one) - (we shall see the reason shortly).
Due to small size of the voids in BCC the distortion caused is more and the
solubility of C in -Fe is small
this is rather surprising at a first glance as BCC is the more open structure
but we have already seen that the number of voids in BCC is more than that in
FCC i.e. BCC has more number of smaller voids.
See next slide for figures
Spend some time over this slide Relative size of voids, interstitials and Fe atom
FCC
Void (Oct) Void (Tet)
Size of Fe atom
CCP crystal
Fe
rFCC 1.292 A 0.77 A 0.534 A
FeCCP C
Size of the OV
Fe
xFCC (oct ) 0.534 A N r N 0.71 A
H r H 0.46 A
Size of Carbon atom
r 0.77 A
C
Relative sizes of voids w.r.t to atoms
(d .tet ) 0.364 A
Fe xBCC (d .tet )
x Fe
0.29
Size of the TV BCC rBCC
FeBCC Fe
xBCC (d .oct )
Size of the OV x Fe
BCC (d .oct ) 0.195 A Fe
rBCC
0.155
We had mentioned that the octahedral void in BCC is a linear one
(interstitial atom actually touches only two out of the 6 atoms surrounding it).
In the next slide we make a approximate calculation to see till what size will it
continue to touch only two Fe atoms
(these are ‘ideal’ simplified geometrical calculations and in reality other complications will have to be considered).
Ignoring the atom sitting at B and assuming the interstitial atom touches the atom at A
2a
OA r x A rFe
BCC 1.258 A
2
2 6r BCC : 3a 4r
r xA
3
xA 2 6
1 0.6329
r 3
OX xA 0.796 A OY xB 0.195A x Fe
BCC (d .tet ) 0.364 A
This implies for x/r ratios between 0.15 and 0.63 the interstitial atom has to push
only two atoms.
(xcarbon/rFe)BCC ~ 0.6
This explains why Carbon preferentially sits in the apparently smaller octahedral
void in BCC.
DC
In the DC structure out of the family of 8 (¼, ¼, ¼) type positions only 4 are occupied
[(¼, ¼, ¼), (¾, ¾, ¼), (¼, ¾, ¾), (¾, ¼, ¾)].
The other four are like void positions- which are all tetrahedral in nature.
Just because there is a large void space available, this does not imply that an atom can
actually occupy these void spaces– this depends on other factors including the type of
bonding in the crystal.
Other types of voids can also be envisaged for the DC crystal (not considered here for now).
rvoid / ratom
SC BCC FCC DC
Octahedral Not 0.155
present 0.414 Not present
(CN = 6) (non-regular)
Tetrahedral Not 0.29 1
present 0.225
(CN = 4) (non-regular) (½,½,½) & (¼, ¼, ¼)
Cubic
0.732 Not present Not present Not present
(CN = 8)
Funda Check Some points and checks on voids!
Voids should not be confused with vacancies- vacancies are due to missing atoms or ions in crystals.
Holes should also not be confused with voids- holes are ‘missing electrons’ from the valence band of
a solid.
In other contexts a ‘void’ could also imply a larger void* (of the size of nanometers or microns) and
not the void between atoms in a crystal structure.
Voids have complicated shapes- we usually use a polyhedral version – the coordination polyhedron
around a sphere of ‘correct size’.
Sometimes, as in the case of ‘octahedral void’ in the BCC- the second nearest neighbours are also
included in constructing the coordination polyhedron.
In ionic crystals, unlike metallic crystals the cation ‘does not sit’ in the void formed by the anions-
the cation is bigger than the anion. The void size calculation is to demarcate the regimes of various
coordination structures.
If an interstitial atom wants to jump from one metastable equilibrium position to another- it has to
cross an energy barrier.
Diffusivity of interstitial atoms (like C in Fe) is expected to be faster at a given temperature, as
compared to substitutional atoms. This is because, typically most of the interstitial sites are vacant
and hence an interstitial atom can jump from one site to neighbouring site.
The solubility of an interstitial element is often much smaller than the available void space. This is
due to the overall strain energy cost of introducing an interstitial solute.