X-RAY DIFFRACTION

Mr. P.Prachet,
Assistant Professor,
Department of Pharmaceutical Analysis,
Chalapathi Institute of Pharmaceutical Sciences
Definition:
• A scattering of X-rays by the atoms of a crystal that produces an interference effect so that the
diffraction pattern gives information on the structure of the crystal or the identity of a
crystalline substance.

• Every crystalline substance gives a pattern; the same substance always gives the same pattern;
and in a mixture of substances each produces its pattern independently of the others.

• The X-ray diffraction pattern of a pure substance is, therefore, like a fingerprint of the
substance. It is based on the scattering of x-rays by crystals.

• It is a novel & non destructive method of chemical analysis and a variety of x –ray techniques
are available in practice.

These are

• X – Ray Absorption

• X-ray diffraction

• X-ray Fluorescence
X-ray absorption method:
These are analogous to absorption methods in the other regions of electromagnetic
spectrum. In these methods, a beam of x-rays is allowed to pass through the sample, and
the attenuation or fraction of x-ray photons absorbed is considered to be a measure of the
concentration of the absorbing substance.
X-ray absorption methods are only helpful in certain cases like elemental analysis and
thickness measurements. As compared with other x-ray methods these are least used.

X-ray diffraction methods:

These methods are based on the scattering of x-rays by crystals. By these methods one can
identify the crystal structures of various solid components. These methods are extremely
important as compared with x-ray absorption and x-ray fluorescence methods.

X-ray fluorescence method:

XRF (X-ray fluorescence) is a non-destructive analytical technique used to determine the
elemental composition of materials. XRF analyzers determine the chemical composition of a
sample by measuring the fluorescent (or secondary). X-ray emitted from a sample when it is
excited by a primary X-ray source.
Origin of X-Rays:

• The x-ray region of the electromagnetic spectrum consists of wavelengths in the region of
about 0.01 to 10nm.

• For analytical purposes the range of 0.7 to 2.0nm is the most useful region.

• X-rays are generated when high velocity electrons impinge on a metal target.

• The process of producing x-rays may be visualized in terms of Bohr’s theory of atomic
structure.
INSTRUMENTATION OF XRD:
Production of x-rays:

• X-rays are generated when a high velocity electrons impinge on a metal target.

• Approximately 1% of total energy of the electron beam is converted into X-radiation, the
remainder being dissipated as heat.

• Many types of x-ray tubes are available which are used for producing x-rays.
X-ray tube:

• In x-ray tube cathode is present and it is a filament of tungsten metal heated by a battery to
emit the thermionic electrons.

• This beam of electrons constitutes the cathode ray stream.

• If a positive voltage in the form of an anode having a target and is kept near these electrons,
the electrons are accelerated towards the target.

• On striking the target, the electrons transfer their energy to its metallic surface which then
gives off x-ray radiations.

• The choice of a target material depends upon the sample to be examined.

• As a rule, one should select the target material whose atomic number should be greater than
that of elements being examined in the sample.
• Another point about the selection of target material is that the energy of x-rays emitted by the
target material should be greater than that required to excite the elements being irradiated.

• Generally the target gets very hot in use. This problem has been solved to some extent by cooling
the tube with water.

• Another method to solve this problem is to rotate the target at high speed so that the production
of localized heating is reduced.

• One extra advantage of this method is that it permits the production of x-rays of intensity much
greater than that obtainable from stationary target.

• Disadvantage of the most of x-ray tubes is that there is lack of focusing of the electrons so that
whole surface becomes a source of x-rays.

• In one model, the small focus of electron beam has been achieved by using a spherical
electrostatic lens within the electron gun of the x-ray tube. By this method, electron beam smaller
than 1 micron in diameter can be produced.
Collimator:
Collimator:

• The x-rays produced by the target material are randomly directed.

• They form a hemisphere with a target at the center. In order to get a narrow
beam of x-rays , the x-rays generated by the target material are allowed to
pass through a collimator which consist of two sets of closely packed metal
plates separated by a small gap.

• The collimator absorbs all the x-rays except the narrow beam that passes
between the gap. A system for achieving a narrow beam of x-rays as shown
in figure.
Monochromator:
• In order to do monochromatization of x-rays , 2 methods are available.
• These are as follows.
1.Filters
2.Crystal monochromator
a) Flat crystal monochromator
b) Curved crystal monochromator

1.Filters:
• The x-ray beam may be partly monochromatized by the insertion of a suitable
filter.
• A filter is a window of material that absorbs undesirable radiation but allows
the radiation of required wavelength to pass.
• This method makes use of the large difference in the mass absorption co-
efficient on either side of an absorption edge.
• Example: zirconium filter is used for molybdenum radiation.
• When x-ray emitted from molybdenum are allowed to pass through a zirconium filter,
the zirconium strongly absorbs the radiation of molybdenum at short wavelengths but
weakly absorbs the Kα lines of molybdenum.
• Thus zirconium allows the kβ lines to pass. However the continuous or white radiation
will also be considerably reduced in intensity. In this case zirconium acts as β filter.
Crystal monochromator:
• A crystal monochromator is made up of a suitable crystalline material positioned in the x-rays
beam so that the angle of the reflecting planes satisfied the bragg’s equation (nλ=2d sin θ) for the
required wavelength.
• The beam is split up by the crystalline material into the component wavelengths in same way as a
prism splits up the white light into a rainbow. Such a crystalline substance is called an analyzing
crystal.
Crystal monochromators are of two types.
1.Flat crystal monochromator
2.Curved crystal monochromator
These crystals used in monochromators are made up of materials like sodium chloride, lithium
fluoride, quartz etc.
Detectors:

• The x-ray intensities can be measured and recorded either by photographic or counter methods.

• Both these types of methods depend upon the ability of x-rays to ionize matter and differ only in
the subsequent fate of the electrons produced by the ionizing process.

1.Photographic methods:

• in order to record the position and intensity of x-ray beam a plane or cylindrical film is used.

• The film after exposing to x-rays is developed. The blackening of the developed film is expressed in
terms of density units D given by

D = I0/I

Where, I0= Intensity of incident x-rays

I = Intensity of transmitted x-rays

• The quantity D is related to the total x-ray energy that causes the blackening of the
photographic film. The value of D is measured by the densitometer.

• The photographic method is mainly used in diffraction studies since it reveals the entire
diffraction pattern on a single film.

• But this method is time consuming and uses exposures of several hours.

• At the same time, the photographic method is rarely used for a quantitative measurement
because it involves the use of a densitometer, the operation of which can be both time
consuming and subject to considerable error.
Counter methods:

These are of following types.

a.Geiger-Muller tube detector:
• The Geiger tube is filled with an inert gas like argon and the central wire anode is maintained at
a positive potential of 800 to 2500 v.
• When an x-ray is entering the Geiger tube, this ray undergoes collision with the filling gas,
resulting in the production of an ion pair, the electron produced moves towards the central
anode while the positive ions moves towards the outer electrode.
• The electron is accelerated by the potential gradient and causes the ionization of a large number
of argon atoms, resulting the production of an avalanche of electrons that are travelling towards
the central anode.
• This results in an output pulse of 1 to 10v which can be measured very easily by employing a
simple circuit as shown in figure.
• The Geiger tube is inexpensive and is relatively trouble free detector. This tube gives the highest
signal for a given x-ray intensity.
Disadvantages:
• The Geiger tube is used for counting low rates.
• The efficiency of a Geiger tube falls off rapidly at wavelengths below 1 Angstroms.
• As the magnitude of the output pulse does not depend upon the energy of the x-ray which
causes ionization, a Geiger tube cannot be used to measure the energy of the ionizing radiation.
Proportional detector:

• Its construction is similar to a Geiger tube counter. A proportional counter is filled with a heavier
gas like xenon or krypton.

• The heavier gas is preferred because it is easily ionized.

• A proportional counter is dependent upon the intensity of x-rays falling on a proportional counter
with the proper electronic circuitry, one can count x-rays of a particular energy selectively.

• The dead time of the proportional counter is very short, it can be used to count high rates without
significant error.

• The sensitivity and efficiency of a proportional counter are comparable to that of a Geiger tube
counter.

• The main disadvantage of proportional counter is that the associated electronic circuit is complex
and expensive. Thus the advantages of the proportional counters outweigh the extra cost.
Scintillation detector:

• The scintillation detector is particularly useful for measuring x-rays of short

wavelengths but its usefulness drops off for x-rays of longer wavelengths.
• Crystals used in scintillation detectors include sodium iodide, anthracene,
naphthalene, and p-terpinol in xylene.
• The dead time of a scintillation counter is short and this allows for counting of
high rates.
Solid state semi conductor detector:

• In this type of detector, the electron produced by x-ray beam are promoted into
conduction bands and the current which flow is directly proportional to the incident
x-ray energy.

• The main disadvantage of a solid state semiconductor is that the semi conductor is
to be maintained at very low temperatures to minimize the noise and prevent
deterioration in the detector characteristics.

• Most semi-conductor detectors consist of a thin layer of n-type material on the

surface of a large piece of p-type material.
Semi conductor detector:

• When an x-ray falls on a semi conductor or a silicon lithium- drifted detector, it generates
an electronic (-ve) and a hole (+ve) in a fashion analogous to the formation of a primary ion
pair in a proportional counter.
• Based on this phenomenon semi conductor detectors have been developed and are now of
prime importance in both x-ray work and neutron activation analysis.
• The principle is similar to that of the gas ionization detector as used in a proportional
counter except that the materials used are in a solid state.
• In this system, a very pure silicon block is set up with a thin film of lithium metal plated
onto one end.
• The density of free electrons in the silicon is very low, constituting a p-type semi conductor.
• If the density of free electrons is high, then we have an n-type semi conductor.
Semiconductor detectors always operate with a combination of these two types.
• Under the influence of an applied voltage the electron moves towards the positive charge
and the holes toward the negative charge.
• The voltage generated is a measure of the x-ray intensity falling on the crystal.
• The process is analogous to that of the proportional counter. Upon arriving at the lithium
coating a pulse is generated.
• The voltage of the pulse equals Q/C, where Q is the total charge collected on the electrodes
and C is the detector capacity.
• The number of pulses is a direct measure of the number of x-ray photons falling on the
detector, which now provides a method of measuring x-rays intensity.
• Silicon-lithium drifted detectors are widely used.
Rotating crystal method:

The rotating crystal method was developed by schiebold in 1919.

The arrangement of this method is outline as follows.
The x-rays are generated in the x-ray tube and then the beam is made monochromatic by a filter.
From the filter, the beam is then allowed to pass through collimating system which permits a fine pencil of parallel x-
rays.
From the collimator, the x-ray beam is made up to fall on a crystal mounted on a shaft which can be rotated at a uniform
angular rate by a small motor.

Now the shaft is moved to put the crystal into slow rotation about a fixed axis. This causes the sets of planes coming

successively into their reflecting positions., i.e., the value of θ satisfies the bragg’s relation.

Each plane will produce a spot on the photographic plate. One can take a photograph of diffraction pattern upon a
photographic plate perpendicular to x-ray beam or upon a film in a cylindrical camera, the axis of which coincides with
the axis of rotation of the crystal.
One can take photographs in two ways.
1. Complete rotation method
2. Oscillation method.
Complete rotation method:

In this method there occurs a series of complete revolutions. It is observed that each set of planes in the crystal
diffracts four times during the rotation. These four diffracted beams are distributed into a rectangular pattern about
the central point of the photograph.

Oscillation method:

In this method, the crystal is oscillated through an angle of 15 or 20 degrees. The photographic plate is also moved
back and forth with a same period as that of the rotation of the crystal.

The position of a spot on the plate indicates the orientation of the crystal at which the spot was formed.

By the rotating crystal method, one ca measure the size of unit cell.
Powder crystal method:
• The powder method was devised independently by Debye and Scherrer in Germany and by hull in America at about
the same time.
• “A” is a source of x-rays which can be made monochromatic by a filter.
• Allow the x-ray beam to fall on the powdered specimen “P” through the slits S1 and S2. The function of these slits is
to get a narrow pencil of x-rays.
• Fine powder “P” struck on a hair by means of gum is suspended vertically in the axis of a cylindrical camera. This
enables sharp lines to be obtained on the photographic film which is surrounding the powder crystal in the form of a
circular arc.
• The x-rays after falling on the powder passes out of the camera through a cut in the film so as to minimize the
fogging produced by the scattering of the direct beam.
Working:
The produced specimen is mounted vertically on the axis of the cylindrical camera on the photographic film is held
around the camera in the form of circular arc. The diffracted beams are recorded as traces on the film and angle of
incidence θ can be calculated.

θ = 360 x l /𝜋𝑟
Where r = film radius
Value of θ can be substituted in bragg’s equation to get interpolar spacing d.
Advantages:
• It does not require sample preparation and quick method. Useful for analysis of cubic crystals complex
structures of metals and alloys can be differentiated.
• Different allotropes of same substance can be determined.
Applications:
1. To identify crystalline phases and orientation.
2. To determine structural properties.
3. To measure thickness of thin films and multilayers.
4. To determine atomic arrangement.
5. X-ray diffraction is most widely used for the identification of unknown crystalline materials. Eg. Minerals,
Inorganic materials.
6. Determination of unknown solids is critical to studies in geology, environmental science, material science,
engineering and biology.
7. Determination of unit cell dimensions measurement of sample purity.
Braggs equation:

• When a beam of x-ray is incident upon a crystal it get scattered by the electrons
constituting crystal atom.
• If the scattered x-rays undergo constitutive interference they are said to be
diffracted crystal plain.
• Each crystallization materials scatters the x-rays in a specific diffraction pattern
and does produces a fingerprint of its internal structure.
• The diffracted beams are called reflections. X-rays are diffracted only if bragg’s
law is satisfied.
• Bragg’s equation 𝑆𝑖𝑛𝜃 = 𝑛λ/2d
• 𝜃 = angle of incidence
• n = integer
• λ = wavelength
• d = interplanar distance of the crystal.
Derivation of bragg’s equation:
When an x-ray beam strikes crystal surface making an angle θ fraction of incident radiation gets scattered owing
to its interaction with atoms located at O,P and R.
Pathlength or distance between the plains l, m, n is identical and represented as D. when an x-ray beam strikes
the top crystal plain at O and other x-ray strikes 2nd crystal plain at P pathlength between x-rays is equal to
AP+PC.
AP+PC = nλ – Constructive interface
Two triangles OAP and OCP
< AOP = <COP
<OAP = <OCP = 90 °
According to ASA rule
<AOP & <OCP are similar.
AP=PC substituting in equation 1
PC+PC= nλ
2PC = nλ
PC= nλ/2 equation 2
<OPC
Sin 𝜃 = PC/OP X OPP/HYP
PC = OP sin 𝜃
Pc=d sin𝜃
𝑺𝒊𝒏𝜽 = 𝒏𝝀/2d hence proved.
Thank You