X-RAY DIFFRACTION (XRD)

WHAT XRD?
Figure caption :

(a) X-ray diffraction photograph for a single crystal of magnesium.

(b) Schematic diagram illustrating how the spots (i.e., the diffraction
pattern) in (a) are produced. The lead screen blocks out all beams
generated from the x-ray source, except for a narrow beam traveling in
a single direction. This incident beam is diffracted by individual
crystallographic planes in the single crystal (having different
orientations), which gives rise to the various diffracted beams that
impinge on the photographic plate. Intersections of these beams with
the plate appear as spots when the film is developed. The large spot in
the center of (a) is from the incident beam, which is parallel to a [0001]
crystallographic direction. It should be noted that the hexagonal
symmetry of magnesium’s hexagonal close-packed crystal structure is
indicated by the diffraction spot pattern that was generated.
 WHY XRD?

Much of our understanding regarding the atomic and molecular

arrangements in solids has resulted from x-ray diffraction investigations

X-ray powder diffraction is a unique in the sense that it is the analytical

technique which can provides both qualitative and quantitative information
about the compound present in a solid sample.

For example, the powder method can determine the percent of KBr and
NaCl in a solid mixture of these two compound, while other analytical
methods reveal only the percent of K+, Na+, Br- and Cl- in the sample.
WHY STUDY THE STRUCTURE OF CRYSTALLINE SOLIDS?

The properties of some materials are directly related to their crystal

structures.

For example, pure and un-deformed magnesium and beryllium, having one
crystal structure, are much more brittle (i.e., fracture at lower degrees of
deformation) than are pure and un-deformed metals such as gold and
silver that have yet another crystal structure.

Furthermore, significant property differences exist between crystalline

and non-crystalline materials having the same composition. For example,
non-crystalline ceramics and polymers normally are optically transparent;
the same materials in crystalline (or semi-crystalline) form tend to be
opaque or, at best, translucent.
Furthermore, significant property differences exist between crystalline and
non-crystalline materials having the same composition.

For example, non-crystalline ceramics and polymers normally are optically

transparent; the same materials in crystalline (or semi-crystalline) form
tend to be opaque or, at best, translucent.
 HOW DOES IT WORK?

The method of identification is based on the fact that an X-ray diffraction

pattern is unique for each crystalline substances.

Thus, if an exact match can be found between the pattern of an unknown

and an authentic sample, chemical identity can be assumed.
 THE DIFFRACTION PHENOMENON

Diffraction occurs when a wave encounters a series of regularly spaced

obstacles that:
(1) are capable of scattering the wave, and
(2) have spacings that are comparable in magnitude to the wavelength.

Furthermore, diffraction is a consequence of specific phase relationships

established between two or more waves that have been scattered by the
obstacles.
(a) Demonstration of how two waves (labeled 1 and 2) that have the same
wavelength and remain in phase after a scattering event (waves 1’ and 2’)
constructively interfere with one another. The amplitudes of the scattered waves
add together in the resultant wave.
Notes:

Consider waves 1 and 2 in Figure a which have the same wavelength

and are in phase at point O-O’ . Now let us suppose that both waves are
scattered in such a way that they traverse different paths. The phase
relationship between the scattered waves, which will depend upon the
difference in path length, is important.

One possibility results when this path length difference is an integral

number of wavelengths. As noted in Figure a, these scattered waves (now
labeled 1’ and 2’) are still in phase. They are said to mutually reinforce (or
constructively interfere with) one another; and, when amplitudes are
added, the wave shown on the right side of the figure results. This is a
manifestation of diffraction, and we refer to a diffracted beam as one
composed of a large number of scattered waves that mutually reinforce
one another.
(b) Demonstration of how two waves (labeled 3 and 4) that have the same
wavelength and become out of phase after a scattering event (waves 3’ and 4’ )
destructively interfere with one another. The amplitudes of the two scattered
waves cancel one another.
Notes:

Other phase relationships are possible between scattered waves that will
not lead to this mutual reinforcement. The other extreme is that
demonstrated in Figure b, wherein the path length difference after
scattering is some integral number of half wavelengths. The scattered
waves are out of phase —that is, corresponding amplitudes cancel or annul
one another, or destructively interfere (i.e., the resultant wave has zero
amplitude), as indicated on the extreme right side of the
figure.

Of course, phase relationships intermediate between these two extremes

exist, resulting in only partial reinforcement.
 X-RAY DIFFRACTION AND BRAGG’S LAW

X-rays are a form of electromagnetic radiation that have high energies and
short wavelengths, i.e. wavelengths on the order of the atomic spacings for
solids.

When a beam of x-rays impinges on a solid material, a portion of this beam

will be scattered in all directions by the electrons associated with each
atom or ion that lies within the beam’s path.

Let us now examine the necessary conditions for diffraction of x-rays by a

periodic arrangement of atoms.
A narrow beam of radiation strikes the crystal surface at an angle q,
scattering occurs as a consequence of interaction of the radiation with atoms
located at O, P, and R.
When an X-ray beam strikes a crystal surface at some angle q, a portion
is scattered by the layer of atoms at the surface. The un-scattered
portion of the beam penetrates to the second layer of atoms where
again a fraction is scattered, and the remainder passes on to the third
layer.

The cumulative effect of this scattering from the regularly spaced

centers of the crystal is diffraction of the beam in much the same way as
visible radiation is diffracted by a reflection grating.

Therefore, the requirements for X-ray diffraction are:

1. the spacing between layers of atoms must be roughly the same as
the wavelength of radiation;
2. the scattering centers must be spatially distributed in a highly
regular way.
Upon diffraction, the path length And :
difference between two constructive AP = PC = d sin q
waves have a distance : where d is the inter-planar
AP + PC = n l distance/spacing of particular
(hkl) crystal plane. Thus the
where n is an integer (which represent
conditions for constructive
the order of diffraction), the scattered
interference of the beam at
radiation will be in phase at OCD, and
angle q can be written as:
the crystal will appear to reflect the X-
radiation.
n l = 2 d sinq

This is called Bragg’s law,

which is of fundamental
importance.
The magnitude of the distance between two adjacent and parallel planes of
atoms (i.e., the interplanar spacing dhkl ) is a function of the Miller indices
(h, k, and l) as well as the lattice parameter(s).

For example, for crystal structures that have cubic symmetry,

in which a is the lattice parameter (unit cell edge length).

 DIFFRACTION TECHNIQUES

POWDER DIFFRACTION TECHNIQUE:

One common diffraction technique employs a powdered or polycrystalline

specimen consisting of many fine and randomly oriented particles that are
exposed to monochromatic x-radiation.

Each powder particle (or grain) is a crystal, and having a large number of
them with random orientations ensures that some particles are properly
oriented such that every possible set of crystallographic planes will be
available for diffraction.
Schematic diagram of an x-ray diffractometer:
T : x-ray source; S : specimen; C : detector, and O : the axis around which the
specimen and detector rotate.
Notes:

The diffractometer is an apparatus used to determine the angles at

which diffraction occurs for powdered specimens. A specimen S in the
form of a flat plate is supported so that rotations about the axis labeled
O are possible; this axis is perpendicular to the plane
of the page. The monochromatic x-ray beam is generated at point T,
and the intensities of diffracted beams are detected with a counter C in
the figure. The specimen, x-ray source, and counter are all coplanar.

The counter is mounted on a movable carriage that may also be rotated

about the O axis; its angular position in terms of 2q is marked on a
graduated scale.4 Carriage and specimen are mechanically coupled
such that a rotation of the specimen through is accompanied by 2q a
rotation of the counter; this assures that the incident and reflection
angles are maintained equal to one another.
Collimators are incorporated within the beam path to produce a well-
defined and focused beam.

Utilization of a filter provides a near-monochromatic beam. As the counter

moves at constant angular velocity, a recorder automatically plots the
diffracted beam intensity (monitored by the counter) as a function of 2q is
termed the diffraction angle, which is measured experimentally.

Other powder techniques have been devised wherein diffracted beam

intensity and position are recorded on a photographic film instead of
being measured by a counter.
Example: diffraction pattern for powdered lead. The high-intensity
peaks result when the Bragg diffraction condition is satisfied by some
set of crystallographic planes. These peaks are plane-indexed in the
figure.
One of the primary uses of x-ray diffractometry is for the determination of
crystal structure.

The unit cell size and geometry may be resolved from the angular
positions of the diffraction peaks;
whereas arrangement of atoms within the unit cell is associated with the
relative intensities of these peaks.

X-rays, as well as electron and neutron beams, are also used in other
types of material investigations. For example, crystallographic
orientations of single crystals are possible using x-ray diffraction (or
Laue) photographs.

Other uses of x-rays include qualitative and quantitative chemical

identifications and the determination of residual stresses and crystal size.
Example: Interplanar Spacing and Diffraction Angle Computations

For BCC iron, compute (a) the interplanar spacing, and (b) the
diffraction angle for the (220) set of planes. The lattice parameter for
Fe is 0.2866 nm. Also, assume that monochromatic radiation having
a wavelength of 0.1790 nm is used, and the order of reflection is 1.

Solution:
(a) The value of the interplanar spacing is determined using equation

with a = 0.2866 nm, and h =2, k =2 and l = 0 since we are considering

the (220) planes.
Therefore,

(b) The value of q may now be computed using equation n l = 2dsinq

with n =1 since this is a first-order reflection:

The diffraction angle 2q is or (2)(62.132o) = 124.26o

CRYSTAL SIZE MEASUREMENT

Scherrer’s equation:

0.9l
t
B cos q

where t is the average crystallite size, l is the X-ray wavelength, q is the

Bragg’s angle and B is the line broadening, based on full-width at half
maximum (FWHM) in radians.
Smaller Crystals Produce Broader XRD Peaks
For proper calculation, other aspects such as the broadening due to
strain in the sample should be considered. Therefore, the crystallite
sizes determined from XRD must be compared with those derived
from the transmission electron microscopy (TEM) analysis.