Lecture 9: Powder diraction

patterns
Contents
1 Introduction 1
2 Indexing pattern for cubic crystals 2
3 Indexing for non-cubic systems 5
4 Phase diagram determination 6
5 Super lattice structures 12
1 Introduction
The original reason for doing x-ray diraction is to identify the structure
of the unknown material. Single crystals are favorable but for most metals,
ceramics, intermetallics, single crystals are not necessarily available. For
such materials powder patterns from polycrystals are used for identifying
the crystal structure. Powder patterns give two useful information
1. The shape and size of the unit cell - this is from the position of the
diraction lines (2)
2. The arrangement of atoms in the unit cell - this is from the relative
intensities of the dierent lines.
To give an example, for a cubic system the lattice constant a determines the
values of 2 for the various planes. The arrangement of atoms in the cubic
system, whether simple cubic, bcc, or fcc, determines the relative intensities
and the absence and presence of some lines. Thus, given a structure it is
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easy to calculate the diraction pattern, especially for simple metals and in-
termetallics. But doing the reverse (which is what is expected from X-ray
diraction) is not easy. This is especially true for following phase transforma-
tions in multi component systems where more than one system, with closely
spaced diraction lines, is present. Finding the dierent phases and their
relative amounts becomes challenging. There are three major steps involved
in phase determination.
1. From the angular position (2) of the lines we get an idea of the shape
and size. We start by assigning a crystal system to the material (out
of 7) and based on that calculate Miller indices to the various lines. If
they dot t go back and reassign a new crystal system and iterate.
2. From the density, known chemical composition, and shape and size of
the unit cell the number of atoms per unit cell are calculated.
3. Finally, from the intensity of the lines the atom positions are calculated.
There are some sources of error in this approach.
1. Lack of truly monochromatic source - if the X-ray is not truly monochro-
matic, K

lines are also present along with the K

line then there will

be extra lines in the diraction pattern. Usually, these can be min-
imized by using the appropriate lters. Also, the extra lines have a
specic angular relation with the lines from the K

radiation which
can be calculated and then eliminated.
2. Impurities in the unknown material - any presence of crystalline impu-
rities in the sample will again cause extra lines. This depends on the
specimen properties and can be eliminated by processing.
2 Indexing pattern for cubic crystals
A cubic crystal gives diraction lines where the angle () obeys the following
relation
sin
2

h
2
+ k
2
+ l
2
=
sin
2

s
2
=

2
4a
2
= constant (1)
where a is the lattice constant, is the x-ray wavelength, and (hkl) refers to
the Miller indices of the plane. Equation 1 is obtained using Braggs law and
the fraction is a constant for diraction lines from a given x-ray source. Since,
hkl are integers s is also an integer and can only take certain values. The
values that s can take changes for the dierent cubic systems (sc, bcc, and
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Table 1: 2 values for Al. First 5 diraction lines
Intensity 2 (in deg)
100 38.37
45.4 44.61
23.0 64.90
22.7 77.97
6.2 82.14
Table 2: 2 values for Al with corresponding values of
sin
2

s
for the various
cubic systems
sin
2

s
Intensity 2 (in deg) d

A sin
2
sc bcc fcc
100 38.37 2.343 0.108 0.108 0.054 0.036
45.4 44.61 2.029 0.144 0.072 0.038 0.036
23.0 64.90 1.435 0.288 0.036
22.7 77.97 1.224 0.396 0.036
6.2 82.14 1.172 0.431 0.036
fcc) and this is based on the structure factor rules. The problem is nding
the values of s for the dierent 2 values. The s values for the dierent cubic
systems are
simple cubic - All (hkl): 1, 2, 3, 4, 5, 6, 8, 9, 10....
bcc - (h + k + l) = even: 2, 4, 6, 8, 10, 12 .....
fcc - (hkl) all even or odd: 3, 4, 8, 11, 12....
From the diraction lines it is possible to calculate the various values of s
using equation 1. This information is summarized graphically in gure 1 for
the dierent cubic systems. These can be tried against the dierent sets for
the cubic systems. If there is no match then the system is not cubic.
Consider the case of Al. The rst ve diraction lines for Al, in order of
increasing 2 are given in table 1. The radiation used is Cu K with wave-
length 1.54

A. Using equation 1 it is possible to calculate the values of
sin
2

s
taking dierent values of s for simple cubic, fcc, and bcc. These are tabulated
in table 2. From table 2 it is clear that only for the fcc system does
sin
2

s
become a constant as indicated in equation 1. Thus, Al crystallizes in a fcc
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Figure 1: Calculated diraction patterns for the various lattices. Taken from
Elements of X-ray diraction - B.D. Cullity.
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structure. The lattice spacing can be calculated using equation 1 where the
value of the constant from table 2 is 0.036.
sin
2

s
=

2
4a
2
= 0.036 (2)
From equation 2 the lattice constant a of Al is 4.06

A. Given that the density
of Al () is 2.7 gcm
3
it is possible to calculate the number of atoms per unit
cell, Z. This is given by the relation
=
Z. at.wt
a
3
N
A
(3)
where N
A
is Avogadros number. From equation 3 the value of Z is 4. Thus,
Al has a fcc structure with 4 atoms per unit cell.
3 Indexing for non-cubic systems
Cubic systems are easy to solve, since they have only one lattice constant
and the angle are all 90

. Things before more dicult if we have non-cubic

systems. Usually, graphical methods are used for solving these systems.
Consider a tetragonal system with a = b = c and all 3 angle 90

. The
relation between d spacing and the lattice constants for this system is
1
d
2
=
h
2
a
2
+
k
2
b
2
+
l
2
c
2
1
d
2
=
h
2
+ k
2
a
2
+
l
2
c
2
1
d
2
=
1
a
2
[(h
2
+ k
2
) +
l
2
(c/a)
2
]
(4)
Taking logarithm on both sides give
2 log d = 2 log a log[(h
2
+ k
2
) +
l
2
(c/a)
2
] (5)
If there are 2 planes with spacing d
1
and d
2
and Miller indices (h
1
k
1
l
1
) and
(h
2
k
2
l
2
) then equation 5 modies to
2 log d
1
2 log d
2
= log[(h
2
1
+ k
2
1
) +
l
2
1
(c/a)
2
] log[(h
2
2
+ k
2
2
) +
l
2
2
(c/a)
2
] (6)
Equation 6 shows that the logarithm of the dierence between d spacing for
2 planes in the tetragonal system depends only on the logarithm of the (c/a)
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ratio and the Miller indices. It is possible to make log plots of the second
term in the right hand side of equation 5 vs. (c/a) for all possible (hkl). This
will give a series of curves. The experimental pattern can be superimposed
on these curves and the (c/a) value can be obtained. Such types of curves
are called Hull-Davey curves. A partial Hull-Davey curve for the tetragonal
system is shown in gure 2. A complete one for the body centered tetrag-
onal system is shown in gure 3. Hull-Davey curves can be constructed for
dierent crystal systems taking into account the relation between the lattice
constants and the lattice angles. In the case of the hexagonal system the
relation between the d spacing and the lattice constants is
1
d
2
=
4
3
(h
2
+ k
2
+ hk)
a
2
+
l
2
c
2
(7)
After a similar manipulation followed for the tetragonal system, this can be
rearranged as
2 log d = 2 log a log[
4
3
(h
2
+ k
2
+ hk) +
l
2
(c/a)
2
] (8)
A Hull-Davey chart can be constructed similar to than for the tetragonal
system to get the lattice constants.
As the number of independent lattice constants of the of the crystal in-
creases (length and angles) it becomes more dicult to use the graphical
methods. Now, there are computer programs that are used to index patterns
by searching and matching with known databases. The powder diraction
patterns for known materials are stored in the ICDD (International Center
for Diraction Data) database. For unknown systems with more than one
type of atom in the unit cell we need the intensities of the lines to nd the
atom positions. This is done by relating then intensities to the structure fac-
tor, F, which is related to the atomic scattering factors, and atom positions.
This is usually a trial and error process, where an initial structure is assumed
and the diraction pattern calculated. This is matched with the experimen-
tal pattern and renement is carried out to the trial structure. This process
is repeated until there is a match. Sometimes, for complex molecules (e.g.
organic), single crystals are needed for structure determination.
4 Phase diagram determination
Another area where x-ray diraction is useful is in phase diagram determi-
nation. If we want to construct a phase diagram the classical way to do it is
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Figure 2: Partial Hull-Davey curve for the tetragonal system with the exper-
imental pattern superimposed. Taken from Elements of X-ray diraction -
B.D. Cullity.
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Figure 3: Complete Hull-Davey curve for the body centered tetragonal sys-
tem. Taken from Elements of X-ray diraction - B.D. Cullity.
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thermal analysis followed by microstructure information. But this does not
give structure information of the phases. For this we need diraction. The
diraction pattern for each phase is independent of the other phases. It is
also possible to get quantitative information on the relative amounts of the
various phases i.e. phase boundaries can also be constructed using XRD. It
is also important how the changing composition of the dierent phases can
aect the diraction patterns
1. If there is solid solubility then as the concentration increases the d-
spacing changes. This is because the lattice constant changes. There
can either be an increase or decrease in lattice constant depending on
the relative atomic sizes of the constituent elements. This leads to a
shift in the position of the lines.
2. If there is a 2 phase region then as the concentration change the relative
intensity of the dierent lines changes but there is no change in line
position.
The following are the principles for collecting x-ray diraction patterns for
phase diagram determination
1. Each alloy must be at equilibrium at the temperature of interest. For
high temperature phases not stable at room temperature there are two
options for studying the crystal structure.
(a) Quench to room temperature and do diraction.
(b) Use x-ray diraction with high temperature attachment for di-
rect determination. This option is preferred when available for it
eliminates the need for preparing large number of samples.
2. The phase sequence: a horizontal line (constant temperature)must pass
through a single phase region and 2 phase region alternatively. A
line cannot pass from one 2 phase region to the next without pass-
ing through a single phase region, can be a line compound.
These principles can be understood by looking at gure 4. If we draw a
horizontal line then the phases go from single phase to a mixture of +
and then a line compound . From we again get a two phase region
+ and then nally single phase . Within a single phase region as the
composition changes then line position changes but in the two phase region
the relative line intensities change. This information is captured in the series
of diraction patterns for the phase diagram shown in gure 4 and shown in
gure 5.
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Figure 4: Phase diagram and lattice constant of a hypothetical binary phase
diagram. Taken from Elements of X-ray diraction - B.D. Cullity.
In the single phase region where we have a solid solution, these can be of
two types
1. Interstitial - when solute atom is much smaller than the solvent atom
e.g. C, N, H, B atoms then we can have interstitial solid solutions. In-
terstitial solid solutions always lead to an increase in lattice parameters.
For non cubic structures not all lattice constant change equally.
2. Substitutional - These are of 3 types - random, ordered, or defect.
Random and ordered substitutional solid solutions are more common
than defect structures. Depending on the relative sizes of the two atoms
the lattice constants can increase or decrease. In defect structures the
increase in concentration of atom B is accompanied by creating holes
where A atoms are present. This is prevalent in compounds that have
partial covalent characteristics. They can aect the peak intensities by
aecting the structure factor. An example of a defect structure is in
NiAl which has a simple cubic structure with Ni atoms at the corner
and Al at the center. The phase exists over a composition range 45-61%
Ni. For o stoichiometry compositions there will be Ni or Al vacancies
in the lattice i.e. defect structures.
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Figure 5: XRD patterns for dierent alloys from the hypothetical binary
phase diagram in gure 4. Taken from Elements of X-ray diraction - B.D.
Cullity.
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Figure 6: Ordered and disordered conguration in AuCu
3
. Taken from Ele-
ments of X-ray diraction - B.D. Cullity.
5 Super lattice structures
These are also called order-disorder transformations. In this a substitutional
solid solution that has atoms located at random positions at high tempera-
ture transforms into an ordered structure where the dierent kinds of atoms
are located at specic positions. In x-ray diraction an order-disorder trans-
formation will not aect the positions of the peaks but relative intensities will
change. Sometime new peaks are also formed. Ordered structures are also
called super lattice structures. The new lines seen in the diraction pattern
are called super lattice lines. The original lines are called fundamental
lines.
To understand the formation of super lattice lines in XRD consider the ex-
ample of AuCu
3
. The disordered and ordered structure for this is shown in
gure 6. AuCu
3
has an fcc structure with 4 atoms per unit cell. From the
formula, there are 3 Cu atoms for 1 Au atom. In the disordered structure,
the 4 atoms are randomly located in the unit cell while in the ordered struc-
ture, Au atoms are located at the corners and the Cu atoms are located at
the face center positions. The order-disorder transition temperature for this
system is 390

C.
Consider the completely disordered structure. The probability of a site being
occupied by Au atom is
1
4
while the probability of occupation by Cu is
3
4
.
Hence it is possible to dene an average atomic factor term, f
av
that is given
by
f
av
=
1
4
f
Au
+
3
4
f
Cu
(9)
where f
Au
and f
Cu
are the atomic scattering factors for Au and Cu. The
disordered structure can be considered as a regular fcc structure so that the
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structure factor F
hkl
is given by
F
hkl
= f
av
[1 + exp(ih + k) + exp(ik + l) + exp(il + h)] (10)
The structure factor rules for the disordered structure are also similar to a
regular fcc lattice i.e. the structure factor F
hkl
vanishes when hkl are mixed
and is non-zero when they are all even or all odd. The dierence arises when
we have the ordered structure. Now the Cu and Au atoms are located at
specic positions and hence the structure factor is calculated by using these
specic positions. This gives the structure factor for the ordered structure
as
F
hkl
= f
Au
+ f
Cu
[exp(ih + k) + exp(ik + l) + exp(il + h)] (11)
Using equation 11 we can see that the structure factor does not vanish for
certain (hkl).
F = (f
Au
+ 3f
Cu
) when(hkl) are all evenor odd
F = (f
Au
f
Cu
) when(hkl) are mixed
Thus, the ordered structure has extra diraction lines, which are called super
lattice lines. This can be seen in the case of powder patterns of CuAu
3
in
gure 7 where extra lines are visible.
Complete order and complete disorder represent the two extremes. In most
cases, it is possible to get a mixture of both. In such cases, it is possible to
dene a long range order parameter, S, given by
S =
r
A
F
A
1 F
A
(12)
where r
A
refers to the fraction of A sites occupied by A atoms and F
A
refers
to the fraction of A atoms in the material. In the case of complete order r
A
= 1 and hence S = 1. In complete disorder r
A
= F
A
and S = 0. It is possible
to calculate the long range order parameter by comparing the intensity of the
super lattice lines with the expected intensity when there is complete order
(S = 1).
There are certain cases when the super lattice lines have a low intensity
and are not visible in the powder pattern. Consider the case of CuZn. The
disordered structure is a bcc unit cell with Cu and Zn atoms randomly located
either at the corner locations or the body center. In the ordered structure
the Cu atoms are located at the corner and the Zn atoms at the center. This
is shown in gure 8. In CuZn the order-disorder transformation takes place
at 460

C. The disordered structure behaves like a bcc structure with an
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Figure 7: Powder patterns of (a) disordered (b) partially ordered and (c)
completely ordered AuCu
3
. Taken from Elements of X-ray diraction - B.D.
Cullity.
Figure 8: Ordered and disordered structures in CuZn. Taken from Elements
of X-ray diraction - B.D. Cullity.
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average atomic scattering factor dened by the average of f
Cu
and f
Zn
. In
the ordered structure the scattering factor is given by
F
hkl
= f
Cu
+ f
Zn
[exp(ih + k + l)] (13)
Using equation 13 it is possible to calculate the structure factors for the
various values of (hkl)
F = (f
Cu
+ f
Zn
) when(h + k + l) is even Fundamental line
F = (f
Cu
f
Zn
) when(h + k + l) is odd Super lattice line
Since the super lattice line is given by the dierence of the atomic scattering
factors its intensity is very weak compared to the fundamental line. Since
intensity is directly proportional to the square of the structure factor
I
super
I
fundamental
=
(f
Zn
f
Cu
)
2
(f
Zn
+ f
Cu
)
2
(14)
For = 0 the atomic scattering factors are equal to the atomic numbers so
that f
Cu
= 29 and f
Zn
= 30. Substituting in equation 14 this gives the ratio
to be 3 10
4
. It is thus possible for the super lattice lines to be too weak to
be detected. Order-disorder transition is an example of long range ordering.
It is harder to detect short range order or clustering using x-ray diraction.
15