XRD

X – RAY
DIFFRACTION
 XRD

When beam of X radiation is incident upon a substance the

scattered waves coming from different reflection sites which
are arranged in a regular manner in a crystal lattice undergo
constructive interference ( provided Braggs law satisfies ) this
phenomenon is called diffraction .

Every crystalline substance scatters the X ray in its own unique diffraction
patter producing a finger print of its atomic and molecular structure
The condition for diffraction are governed by Bragg’s Law

Constructive interference of the reflected beams emerging from two

different planes will take place if the difference in the path lengths of
the two rays is equal to whole number of wavelengths.
Braggs equation n λ = 2d sin θ
d – is lattice spacing , θ is glancing angle n is an integer .
λ is the wavelength .
For Miller indices , the above equation becomes as n λ = 2dhkl sin θ ,
where dhkl is the spacing between the set of crystal planes
of Miller indices hkl .

On putting the integer n equal to 1 , 2 , 3 etc , a series of angle is obtained

at which reflections will occur for a given set of planes of spacing dhkl .
These reflections are referred to as first order , second order , third order etc
respectively .

Bragg’s equation is obeyed so well that it is possible to use this

equation for highly precise determination of lattice spacing dhkl .
 Diffraction techniques exploit the scattering of radiation from large
We will concentrate on scattering from atoms, groups of atoms
and molecules, mainly in crystals. There are various diffraction
techniques currently employed which result in diffraction patterns.
These patterns are records of the diffracted beams produced.

From diffraction patterns we can:

• measure the average spacing between layers or
rows of atoms;
• determine the orientation of a single crystal or
grain;
• find the crystal structure of an unknown material;
and
• measure the size, shape and internal stress of
small crystalline regions.
Phase Identification using XRD analysis
The identification of single or multiple phases in an unknown
sample is the main application of X-ray powder diffractometry.
Phase identification is widely used in many fields. Among
these is:
•Detection of polymorphs of a certain material – highly
important for the pharmaceutical industry.

X-ray powder diffraction (XRPD) is increasingly recognized

as a valuable tool for numerous application areas in the
pharmaceutical industry. These applications cover the entire
pharmaceutical process:
•Drug discovery
•Pre-formulation and formulation of drugs
•Manufacturing and quality assurance.
In all of these cases, XRPD is used to determine the
crystallographic constitution of the sample (under ambient or
non-ambient conditions) from which the physical properties
of an Active Pharmaceutical Ingredient (API) or an excipient
can be derived.
XRD is superior to other commonly used techniques because:
•It is non-destructive
•It allows analysis of the final oral dosage forms
•It enables the detection of any change in the morphology or
crystalline state of the active ingredient during the production
of the final product
 X-ray Methods

Diffraction can occur whenever Bragg's law is satisfied. With

monochromatic radiation, an arbitrary setting of a single crystal
in an x-ray beam will not generally produce any diffracted beams.
There would therefore be very little information in a single crystal
diffraction pattern from using monochromatic radiation.

This problem can be overcome by continuously varying  or  over

a range of values, to satisfy Bragg's law. Practically this is done by:

* using a range of x-ray wavelengths (i.e. white radiation), or

• by rotating the crystal or, using a powder or polycrystalline
specimen.
Recording X ray range specimen type Technique
Transmission Monochromatic Fixed Single Crystal Impractical

Transmission Monochromatic Rotating single crystal Rotating crystal method

Transmission Monochromatic Powder or poly crystals Powder method

Transmission White radiation Fixed Single Crystal Impractical

Transmission White radiation Rotating single crystal Impractical

Transmission White radiation Powder or poly crystals Laue method

Back Reflection Monochromatic Fixed Single Crystal Impractical

Back Reflection Monochromatic Rotating single crystal Rotating crystal method

Back Reflection Monochromatic Powder or poly crystals Powder method

Back Reflection White radiation Fixed Single Crystal Impractical

Back Reflection White radiation Rotating single crystal Impractical

Back Reflection White radiation Powder or poly crystals Laue method

Laue Method :

In the transmission Laue method, the film is placed

behind the crystal to record beams which are
transmitted through the crystal.
One side of the cone of Laue reflections is defined by
the transmitted beam. The film intersects the cone,
with the diffraction spots generally lying on an ellipse.

In the back-reflection method, the film is placed

between the x-ray source and the crystal.
The beams which are diffracted in a backward
direction are recorded.
One side of the cone of Laue reflections is defined by
the transmitted beam. The film intersects the cone,
with the diffraction spots generally lying on an
hyperbola.
Laue Method :

• A is a source of X ray , that emits a beam of continues wavelength ,

known as white radiation which is obtained from a tungsten target .
• B is an pin hole collimator , when X ray obtained from A
are allowed to pass through this pin hole collimator , a fine
pencil of X ray is obtained. The diameter of the pin hole is of
importance from the stand point of detail in diffraction pattern .
The smaller is the diameter , the sharper is the interference .

• C is a crystal whose internal structure is to be investigated . The

crystal is set on a holder to adjust the orientation .
• D is film cassette arranged on a rigid base . This film is provided
with beam stop to prevent direct beam from causing excessive
fogging of the film .
• The position of the crystal is held stationary in a beam of X rays ,
the X rays after passing through the crystals are diffracted and
recorded on a photographic plate .
On examining the the Laue photograph , it is observed that the the spots
actually occur at the positions to be expected from the diffraction law .
When X ray beam is passed along the axis of symmetry of crystal , the Laue
pattern would contain as series of “ spots ” whose loci are ellipses which
passes through the “ central image “ made by X –ray beam . The spots on
any one ellipse are produced by planes belonging to the same zone .
i. e . plane which are parallel to one common direction .
 Rotating crystal Method

1) The X ray are generated in X ray tube and then the beam
is made monochromatic by a filter .
2) From the filter , the beam is then allowed to pass through
collimating system which permits a fine pencil of parallel X-rays.
3) From the collimator , the X-ray beam is made to fall on a
crystal mounted in a shaft which can be rotated at a uniform
angular rate by a small motor .
4) Now the shaft is moved to put the crystal in to slow rotation
about a fixed axis . This causes the sets of planes coming
successively in their reflection positions ie the value of θ
satisfies the Bragg’s relation
Each plane will produce a spot on the photographic plate , one can take the
photograph of a diffraction pattern upon a photographic plate perpendicular to
X ray beam or upon a film in cylindrical camera , the axis of which coincides
with the axis of rotation of the crystal .

Braggs devised a spectrometer to measure the intensities of

X ray beam . The spectra obtained in this way can be employed
for crystallographic analysis . This method is based on Braggs
equation n λ = 2d sin θ.
Where n is an integer . The above equation gives the condition
which must be satisfied for reflection of X-ray from a set of
atomic planes
For a given set of lattice planes , d is a fixed value . If homogeneous X ray
of definite wavelength λ is used , then the possibility of getting maximum
reflection depends upon θ . If θ the angel the rays make with the
plane of crystal , regularly increased , a number of positions corresponding
to n = 1,2,3,…..etc will be found at which the reflections will be maximum
ie
θ = Sin –1 1 ( λ ⁄ 2 d )
θ = Sin –1 2 ( λ ⁄ 2 d )
θ = Sin –1 3 ( λ ⁄ 2 d )
.
.

θ = Sin –1 n ( λ ⁄ 2 d )
The reflection corresponding to n = 1 is called first order reflection : the
reflection corresponding to n = 2 is called second order reflection and so on.
From the above equation it follows that if the glancing angle θ are measured
From various order n , of maximum intensity , the distance d between
successive lattice plane of given type in the crystal can be calculated , if λ
is known . The study of the intensity of X ray spectra will give the required
information about the arrangement of planes of different atoms in space lattices .

In using the Braggs spectrometer , the crystal is mounted in such a position

that θ = 0 , and the ionization chamber is adjusted to receive the X –rays.

The crystal and ionization chamber are made to move in small steps so that the
angle through which the chamber is moved is twice the angle through which
crystal is rotated . The ionization at first fall as θ increases but for certain values
of θ it rises sharply . This corresponds to the direction of the X –ray spectrum .
X –ray spectrum is obtained by plotting a graph between the ionization current
and the glancing angle θ
Determination of crystal structure by Bragg’s Law

The X rays are allowed to fall on the crystal surface . Then the crystal is
rotated and X ray are made to reflect from various lattice planes . The
intense reflections are measured by Bragg’s X-ray spectrometer and the
glancing angle for each intense reflection is recorded .
On applying Bragg;s equation , ratio of lattice spacing for various groups
of planes can be obtained .
The ratio has been found to be different for different crystals .
Experimentally observed ratios are compared with the calculated ratios and
thus particular structure may be identified .

i) d100 : d110 : d111 = 1 : 1 ⁄ √ 2 : 1 ⁄ √ 3 for simple cubic lattice

ii) d100 : d110 : d111 = 1 : 1 ⁄ √ 2 : 2 ⁄ √ 3 for fcc crystal

iii) d100 : d110 : d111 = 1 : 2 ⁄ √ 2 : 1 ⁄ √ 3 for bcc crystal

The above method has been illustrated in the case of sodium chloride .
For the maximum intensity reflections , the glancing angles are 5.9 o , 8.4 o
and 5.2 o for ( 1 0 0 ) , ( 110 ) & ( 111 ) faces respectively for first order
reflection . Thus in case of NaCl

d100 : d110: d111 = 1 ⁄ Sin 5.9 : 1 ⁄ Sin 8.4 : 1 ⁄ Sin 5.2

= 1 ⁄ 0.1028 : 1 ⁄ 0.146 : 1 ⁄ 0.0906
= 1 : 0.704 : 1.155
= 1 : 1 ⁄ √2 :2 ⁄ √3
The above value is in full agreement with the values predicted
theoretically . Thus the crystal has a fcc lattice .
Powder crystal Method

If a monochromatic x-ray beam is directed

at a single crystal, then only one or two
diffracted beams may result.

If the sample consists of some tens of

randomly orientated single crystals, the
diffracted beams are seen to lie on the
surface of several cones. The cones may
emerge in all directions, forwards and
backwards.

sample of some hundreds of crystals (i.e.

a powdered sample) show that the diffracted
beams form continuous cones. A circle of film
is used to record the diffraction pattern as
shown. Each cone intersects the film giving
diffraction lines. The lines are seen as arcs on
the film.
 Powder crystal Method

In all the above described methods , a single crystal is required

whose size is much larger than macroscopic dimensions .
However in the powder method , the crystal sample need not be
taken in large quantity but is little as 1 mg of the material is
sufficient for the study .

1) A is a source of X ray which can be made monochromatic using a filter

2) Allow the X ray beam to fall on the powdered specimen P through the
slits S1 & S2 . The function of these slits is to get a narrow pencil of
X –rays.
3) Fine powder , P 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.
4 ) 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 .
5) On a flat photographic plate the diffraction pattern is recorded .

All the like orientations of the grains due to reflection for each
set of planes and for each order will constitute a diffraction
cone whose interaction with a photographic plate gives rise to
a traces . The crystal structure can be obtained from the
arrangement of the traces and their relative intensities .

If the angle of incidence is θ , the angle of reflection will be 2θ

If the film radius r , the circumference 2 π r corresponds to a scattering angle
of 360 o . Thus we can write
l ⁄ 2 π r = 2 θ ⁄ 360 θ = 360 * l ⁄ π r
From the above equation , the value of θ can be calculated and substituting
this value in Bragg’s equation the value of d can be calculated .
THANK YOU
X-ray diffraction methods Are generally used for investigating the int
structure

Laue Transmission Method is most suitable for investigation

of preferred orientation sheet or fibres , particularly if the
information is confined to the lower diffraction angles . This
method is also used in the determination of the symmetry of
single crystal.

Laue Back reflection Method : back reflection method is the only

method for investigation of large and thick specimen .

Disadvantage of Laue Method are that a big crystal is req

and further more there is uncertainty in the significance
of reflection intensities due to un homogeneous nature o
X-rays.
Brags X-ray Spectrometer Method :
λ , d can be measured
Determination of crystal structure .

Rotating crystal method : By rotating crystal method one can measure

the size of unit cell .

Powder crystal method : value of θ and d can be calcula

1) The method is most useful for cubic crystals
2) This method is used for determining the complex struc
of metal and alloys .
3) This method is useful to make distinction between the
allotropic modifications of the substances.
4) Determination of degree of crystallinity of the polymer
5) Particle size determination .