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MATERIALS SCIENCE

Part of & AALearners


LearnersGuide
Guide
ENGINEERING
AN INTRODUCTORY E-BOOK
Anandh Subramaniam & Kantesh Balani
Materials Science and Engineering (MSE)
Indian Institute of Technology, Kanpur- 208016
Email: anandh@iitk.ac.in, URL: home.iitk.ac.in/~anandh
http://home.iitk.ac.in/~anandh/E-book.htm
Interatomic Voids*
When an atom of an alloying element/impurity is added to a pure crystal, the atom
added may sit in a lattice/sublattice site in place of the host atom (e.g. Ag added
to Au sits in a FCC lattice site Ag is a substitutional alloying element) or go
into the space between atoms (e.g. C added to Fe C is a interstitial alloying
element). In some rare cases the atoms may be present both in the lattice and
interstitial sites (e.g. B in steel).
If the fit of the added atom in the available space is not too bad, then the
solubility of the added element in the host crystal is expected to be good.
In the hard sphere model of atoms, atoms are visualized as spheres. We have
already seen that as spheres cannot fill entire space. This implies that the packing
fraction (PF) < 1 (for all crystals).
This further implies there is void space between the atoms. Lower the PF, larger
the volume occupied by the void space.
We are mostly interested in the largest sphere which can fit into these voids.
The void space forms a continuous network across the whole solid. Part of this
void space lies within the unit cell (which when translated by the lattice translation vectors gives rise to the entire
void space).

* 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!!)

* Common way of referring to the void polyhedron/polyhedra.


SC
The simple cubic crystal (monoatomic decoration of the simple cubic lattice) has large void in the centre
of the unit cell with a coordination number of 8.
The actual space of the void in very complicated (right hand figure below) and the polyhedron version of
the void is the cube (as cube is the coordination polyhedron around a atom sitting in the void).
Voids in SC crystal are not often described in detail in text books as the only element crystallizing SC
structure is Polonium.
rx
( 3 1) 0.732
r

True Unit Cell of SC crystal Polyhedral model (Cube) Actual shape of the void (space)!

Later on we will talk about tetrahedral and octahedral


voids in FCC, BCC & HCP crystals:
Video:
Video:void
voidininSC
SCcrystal
crystal note that there are NO such tetrahedral and octahedral
voids in SC crystals and the only polyhedral void is
CUBIC (i.e. coordination number of 8)
FCC
Actual shape of the void is as shown below. This shape is very complicated and we use the polyhedral version of
the void. The polyhedra involved are the regular tetrahedron and the regular octahedron (referred to as the
tetrahedral and octahedral voids).

Actual shape of the void


Position of some of the atoms w.r.t to the void
FCC
The complicated void shown before is broken down in the polyhedral representation into two shapes: the
octahedron and the tetrahedron (which together fill space).
Note that a given tetrahedron (pink colour) is fully present within the unit cell, while only the octahedron (blue
colour) at the body centre is present within the unit cell. The octahedron with its centroid at centre of the edge of
the unit cell is shared by 4 unit cells (the cut faces are shown in green colur).

Octahedra and tetrahedra in an unit cell

Quarter of a octahedron which belongs to an unit cell

Video
Videoofofthe
theconstruction
construction
shown in this slide
shown in this slide

4-Quarters forming a full octahedron

Central octahedron in view- this is a full octahedron

4-tetrahedra in view
VOIDS

Tetrahedral TV Octahedral OV

Location of the void: Location of the void:


way along body diagonal {, , }, {, , At body centre {, , }
} + face centering translations
+ face centering
Calculation translations
shown later
rVoid / ratom = 0.414
rvoid / ratom = 0.225
1
1 Voctahedron Vcell
Vtetrahedron Vcell 6
24
Video:
Video:voids
voidsCCP
CCP
Note: Atoms are coloured differently but are the same Video: atoms forming the voids
Video: atoms forming the voids
More views
Tetrahedral TV Octahedral OV
Once we know the position of a void then we can use FCC- OCTAHEDRAL
the symmetry operations of the crystal to locate the
other voids. This includes lattice translations.

Site for octahedral void

{, , } + {, , 0} = {1, 1, } {0, 0, }
Equivalent site for an octahedral void
Face centering translation

Note: Atoms are coloured differently but are the same


There are 8 tetrahedral voids per cell and 4 octahedral voids per cell. The location of the voids and
number of voids per atom in the unit cell are to be noted from the table below.

FCC voids Position Voids / cell Voids / atom

way from each vertex of the cube


Tetrahedral along body diagonal <111> 8 2
((, , ))
Body centre: 1 (, , )
Octahedral Edge centre: (12/4 = 3) (, 0, 4 1
0)
Now let us calculate the largest size sphere which can fit into these voids.
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 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
r 2

In tetrahedron ABCD
In triangle ABC AD 2 e 2 AO 2 DO 2
e2 e
2 2
e AM 2
2
e DO 2
2 DO e
4 3 3
3 3
AM e DT DO
2 4
2 2 3 e 3 2 6
AO AM e DT e e
3 3 2 3 4 3 4
Size of the largest atom which can fit into the Octahedral void of FCC

2r + 2x = a Thus, the octahedral void is the bigger one


and interstitial atoms (which are usually
bigger than the voids) would prefer to sit
here
2a 4r
x
r

2 1 ~ 0.414
Note: Atoms are coloured differently but are the same

HCP VOIDS

TETRAHEDRAL OCTAHEDRAL
This void extends across 3
conventional unit cells and
hence is difficult to visualize

Coordinate s : (0,0, 3 8 ), (0,0, 5 8 ), ( 2 3 , 1 3 , 18 ), ( 2 3 , 1 3 , 7 8 ) Coordinates: ( ,), (,,)

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 occur in 1 orientation, tetrahedral voids occur in 2 orientations

Note: Atoms are coloured differently but are the same


Further views

This void extends across 3


conventional unit cells and hence
is difficult to visualize

Note: Atoms are coloured differently but are the same


Further views

Octahedral voids

Tetrahedral void

Note: Atoms are coloured differently but are the same


Voids/atom: FCC HCP
as we can go from FCC to HCP (and vice-
versa) by a twist of 60 around a central atom of
two void layers (with axis to figure) Central atom

Atoms in HCP crystal: (0,0,0), (, ,)

Check below

Voids /
HCP voids Position Voids / atom
cell
(0,0,3/8), (0,0,5/8), (, ,1/8),
Tetrahedral 4 2
(,,7/8)
Octahedral ( ,), (,,) 2 1
Further views

Various sections along the c-axis


of the unit cell
A

Octahedral void

Tetrahedral void

A
Further views with some models

Visualizing these voids can sometimes be difficult especially in the HCP


Video:
crystal. How the tetrahedral and octahedral void fill space? is shown in the Video:Polyhedral
Polyhedralvoids
voidsfilling
fillingspace
space
accompanying video
Voids in BCC crystal
Let us start with some surprising facts (which we shall list later as well):
(i) In a CCP crystal the octahedral void is bigger than the tetrahedral void the
reverse is true in BCC crystals.
(ii) In the case of Fe the solubility of C in close packed CCP structure is more than
the non-close packed BCC structure.
(ii) In BCC Fe, C sits in the smaller octahedral void in preference to the larger
tetrahedral void.
The solubility of C in Fe (both FCC & BCC) is much lower than the available
interstitial void space.

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

Distorted TETRAHEDRAL Distorted OCTAHEDRAL**

a3/2

a
a a3/2

Coordinates of the void:


{, 0, } (four on each face) Coordinates of the void:
{, , 0} (+ BCC translations: {0, 0, })
Illustration on one face only

rvoid / ratom = 0.29 rVoid / ratom = 0.155

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, })

Illustration on one face only


(due to symmetry all faces will be identical)

Voids / Voids /
BCC voids Position
cell atom

Distorted
Four on each face: [(4/2) 6 = 12] (0, , ) 12 6
Tetrahedral

Non-regular Face centre: (6/2 = 3) (, , 0)


6 3
Octahedral Edge centre: (12/4 = 3) (, 0, 0)
Calculation of the size of the distorted tetrahedral void

a BCC: Non-regular 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
r x 1 0.29
4 3 r 3
Calculation of the size of the distorted octahedral void

Non-regular Octahedral Void a 2a


OB 0.5a OA .707a
2 2
As the distance OA > OB the atom in the
void touches only the atom at B (body
centre).
void is actually a linear void*
a3/2

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).
C sits in the smaller octahedral void in BCC in preference to the larger tetrahedral void in
BCC.

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 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 r Fe
FCC 1.292 A 0.77 A
o o
0.534 A
FeFCC C
o
Size of the OV x Fe
FCC (oct ) 0.534 A N r 0.71 A
N

H r 0.46 A
H

Size of Carbon atom


r 0.77 A
C
Relative sizes of voids w.r.t to atoms

Note the difference in size of the atoms


BCC
Size of Fe atom
BCC crystal Fe
rBCC 1.258 A Fe
xBCC (d .tet )
Size of the TV x Fe
BCC (d .tet ) 0.364 A Fe
rBCC
0.29

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 r Fe
BCC 1.258 A
2
2 6r BCC : 3a 4r
r xA
3
xA 2 6
1
0.6329
r 3
o o
OX x A 0.796 A OY xB 0.195 A 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 (, , ) type positions only 4 are occupied
[(, , ), (, , ), (, , ), (, , )].
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.

Largest sphere which can sit in


the void in DC
Summary of void sizes

rvoid / ratom
SC BCC FCC DC
Octahedral Not 0.155
0.414 Not present
(CN = 6) present
(non-regular)
Tetrahedral Not 0.29 1
0.225
(CN = 4) present
(non-regular) (,,) & (, , )
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.

* Schematic of a large void implied under some circumstances