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Voids in Crystals
Voids in Crystals
* 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 (they are non-regular octahedra and tetrahedra). (In fact- as we
shall see- the octahedral void is a ‘linear void’!!)
rx
( 3 1) 0.732
r
True Unit Cell of SC crystal Polyhedral model (Cube) Actual shape of the void (space)!
4-tetrahedra in view
VOIDS
Tetrahedral TV Octahedral OV
Voids / Voids /
FCC voids Position
cell atom
Now let us calculate the largest size sphere which can fit into these voids.
Size of the largest atom which can fit into the Octahedral void of FCC
A The atoms (primary and interstitial) will touch along AB rinterstitial x
This implies 2r 2 x a
As atoms touch along face diagonal in CCP 2a 4r
4r
2r 2 x a
2
B x
r
2 1 ~ 0.414
Size of the largest atom which can fit into the tetrahedral void of FCC
The distance from the vertex of the tetrahedron to the centroid (DT) is the distance spanned by radius of the atom and the
radius of the interstitial sphere.
DT = r + x x = rinterstitial = Radius of the interstitial atom (sphere)
If ‘e’ is the edge length of the tetrahedron then CV = (6/4)e → see below in triangle ABC
6 6
DT erx e 2r rrx
4 2
x 6
1 ~ 0.225 In tetrahedron ABCD
r 2 AD 2 e2 AO 2 DO 2
2 2
e
e DO 2
2 DO e
3 3
In triangle ABC DT
3
DO
4
e2
e AM 2
2
4 3 2 6
DT e e
3 4 3 4
AM e
2
2 2 3 e
AO AM e
3 3 2 3 Thus, the octahedral void is the bigger one and
interstitial atoms (which are usually bigger than
the voids) would prefer to sit here.
Funda Check How to add ‘face centering’ translations to get equivalent positions of the void?
The equivalent positions ‘within’ (or partly within) the unit cell, can be found by applying
the point group symmetry or by using fundamental lattice translations.
For the FCC lattice these translations are: (½, ½, 0), (½, 0,½), (0,½, ½). So we apply these to the
location of the voids.
Total: 8 nos.
(3/4,1/4,3/4)
Note: Atoms are coloured differently but are the same
HCP VOIDS
TETRAHEDRAL OCTAHEDRAL
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).
Further views
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 a3/2
Voids / Voids /
BCC voids Position
cell atom
Distorted
• Four on each face: [(4/2) 6 = 12] (0, ½, ¼) 12 6
Tetrahedral
Non-regular • Face centre: (6/2 = 3) (½, ½, 0)
6 3
Octahedral • Edge centre: (12/4 = 3) (½, 0, 0)
Calculation of the size of the distorted tetrahedral void
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
FCC Relative size of voids, interstitials and Fe atom
FeCCP Size of Carbon atom
0.77 A
r 0.77 A
C
Size of Fe atom
CCP crystal
rFe
FCC 1.292 A Void (Oct)
C
(oct ) 0.534 A
Fe 0.534 A
Size of the OV x FCC N r N 0.71 A
(tet ) 0.291 A
Void (Tet)
Size of the TV x Fe
FCC H r H 0.46 A
BCC
Note the difference in size of the atoms
FeBCC
Size of Fe atom Fe
BCC crystal r
BCC 1.258 A
Fe
xBCC (d .tet )
0.29
Size of the TV
Fe
xBCC (d .tet ) 0.364 A Fe
rBCC
Fe
(d .oct ) 0.195 A
Fe
xBCC (d .oct )
Size of the OV x BCC Fe
0.155
rBCC
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).
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.
(110)
Ignoring the atom sitting at B and assuming the interstitial atom touches the atom at A
OA r x A
2a rBCC 1.258 A
Fe
2
BCC : 3a 4r
2 6r
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
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
0.155
Octahedral Not (non-regular) 0.414
Not present
present
(CN = 6*) 6 voids/cell 4 voids/cell
Note comment below*
0.29
Tetrahedral Not 0.225 1
present
(non-regular)
(CN = 4) 8 voids/cell (½,½,½) & (¼, ¼, ¼)
12 voids/cell
Cubic
0.732 Not present Not present Not present
(CN = 8)
* In the case of a correct sized interstitial atom present in the OV of the ‘BCC crystal’, the coordination
number (CN) is only 2. Hence, the OV in BCC is actually a ‘linear void’.
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.