Qualitative Analysis and Determination of Samples Through XRD

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BIOCON RESEARCH LIMITED, BOMMASANDRA- JIGNI LINK ROAD BANGALORE.

Qualitative Analysis and Determination of Samples through XRD

PROJECT REPORT

Submitted by : Swathi Muralidhar (Summer Intern)


Supervisor: Pradeep Kumar Shetty , XRD Department, Quality Control
Biocon Research Limited

Biocon Research Limited, Bommasandra- Jigni Link Rd, Bangalore.


Page 2 of 86 Qualitative Analysis and Determination of Samples through XRD

ABSTARCT

Powder X-ray diffraction (XRD) is a powerful technique to study crystalline phase changes. The
method is based on the principal that the observed diffraction pattern is the sum of the individual
phases that compose the sample. By adding an internal standard (usually corundum) to both the
observed patterns and to those for individual pure phases (standards), all patterns can all be
normalized to an equivalent intensity based on the internal standard intensity. Using least-squares
refinement, the individual phase proportions are varied until an optimal match is reached. As the
fitting of full patterns uses the entire pattern, including background, disordered and amorphous phases
are explicitly considered as individual phases, with their individual intensity profiles or “amorphous
humps” included in the refinement. The method can be applied not only to samples that contain well-
ordered materials, but it is particularly well suited for samples containing amorphous and/or
disordered materials. In cases with extremely disordered materials where no crystal structure is
available for Rietveld refinement or there is no unique intensity area that can be measured for a
traditional RIR analysis, full-pattern fitting may be the best or only way to readily obtain quantitative
results.

HISTORY

The year 1912 marked the birth of two branches of physical sciences which was developed promptly
from Max von Laue’s discovery of the Diffraction of X-rays which is most closely linked with the
names of W. H. (Sir William) Bragg and W. L. (Sir Lawrence) Bragg of Bragg’s law fame and W. H.
Bragg, H. G. J. Moseley, M. de Broglie and Manne Siegbahn of X-ray spectroscopy fame.

Max Theodore Felix von Laue (1879-1960), in 1912, thought that X-ray has a wavelength similar to
inter atomic distances in crystals. Along with Walter Friedrich (research assistant) and Paul Knipping
(PhD grad student), he did the first diffraction experiment on CuSO4 crystal and won the Nobel Prize
in physics for the same in 1914.

Later on, in November 1912, W. L. Bragg (then still a student in Cambridge) produced his first papers
on Crystal Structure Analysis. Using the Laue diagram analysis of zinc blend, he determined the
correct lattice upon which the structure of this crystal is built. Soon afterwards he obtained the first
complete structure determinations, namely of NaCl, KCl, KBr and KI, a series of alkali halides having
similar structures. By this determination a scale for the measuring of atomic distances in crystals and,
simultaneously, of X-ray wave-lengths was obtained.
Page 3 of 86 Qualitative Analysis and Determination of Samples through XRD

Sir William Henry Bragg (father, 1862-1942) and Sir William Laurence Bragg (son, 1890-1971) (U of
Manchester), received the Nobel Prize for the same in 1915.

It led to the construction of the instrument devised by W. H. Bragg, the X-ray Spectrometer, with
which the majority of the early crystal structures were determined.

The quantitative determinations of atomic distances and bond angles were unobtainable until then and
with the advent of this instrument, finally access to super-stereo chemistry ushered and led to a close
link which subsists today between X-ray structure analysis and the physical and chemical problems of
chemical bond.

Moseley's early work had already showcased the underlying mechanisms of X-ray spectroscopy
(which deals with the emission and absorption of X-rays by and in matter) vaguely allowing the ‘then-
infant’ modern atomic theory to have a much simpler interpretation by finding an empirical
relationship between the strongest X-ray line emitted by atoms under electron bombardment and their
atomic number Z than those of the visible lights.

This gave invaluable support and guidance for the development of the principles of the quantum
theory of the atom. From this the whole of physics and chemistry profited, and again today, the
greatly refined methods of experimentation and discussion bring the research in X-ray spectroscopy
very close to the problems of chemical bond and energy band structure of solids.

Among the later consequences of von Laue’s discovery should be named the diffraction phenomena
obtained in crystals by using beams of electrons and neutrons, instead of X-rays.

These two applications of very nearly the same experimental procedures and theory as for X-ray
diffraction are rapidly developing along their own lines. Each of the means of obtaining diffraction-X-
rays, electrons, neutrons, and even atoms - has its own peculiarities in interacting with matter.
Therefore different information can be gained by using these methods judiciously; but they all spring
from the source Laue opened up.
Page 4 of 86 Qualitative Analysis and Determination of Samples through XRD

INTRODUCTION

X-rays

While exploring the path of electrical rays passing from an induction coil through a partially
evacuated glass tube, Wilhelm Roentgen, Professor of Physics in Wurzburg, Bavaria, noticed that a
screen covered in fluorescent material was illuminated by the rays though the tube was covered in
black paper and the room was completely dark. He later used a photographic plate instead of a screen,
and an image was captured. In this way an extraordinary discovery had been made- the possibility of
using electromagnetic radiation to create what we now know as the X-ray. The Nobel Prize was
awarded to him for the same in the year 1901.

Production and Characteristics of X-rays

X-ray is a form of electromagnetic wave with wavelength in the range of 10 to 0.01 nm and energies
in the range of 120 eV to 120 keV. X-rays are produced by bombarding a metal target (Cu and Mo
usually) with a beam of electrons emitted from a hot filament (often tungsten). The incident beam
will ionize electrons from the K-shell (1s) of the target atom and X-rays are emitted as the resultant
vacancies are filled by electrons dropping down from the L (2P) or M (3p) levels. This gives rise to
Ka and Kb lines.

Fig. 1

X-rays are electrically neutral and possess no mass. They cannot be optically focused and form a
poly-energetic or heterogeneous beam.

X-rays majorly are issued in two main varieties:


Page 5 of 86 Qualitative Analysis and Determination of Samples through XRD

1. Characteristic X-rays- When a high energy electron is collided with an inner orbital
electron, sufficient energy can lead to the electrons being ejected in different directions
leading to empty position in one of the shells. The remaining orbiting electrons will 'pack
down' to fill the hole, and when changing orbits will lose energy and emit this as radiation.
The energy emission will be characteristic of that atom. The energy will be mono-energetic
and so appear as a spike rather than a continuous spectrum.
Elements with higher atomic numbers have their K, L, M or N shells of sufficient energy to
be called 'X-rays'. The discrete characteristic radiation energies are equal to the difference in
the energy level of the outer and inner orbital electrons. The x-ray energy is proportional to
the atom's Z.

Fig. 2

2. Bremsstrahlung X-rays- The high speed electron impacts on the target and at the atomic
level approaches the nucleus. There is no actual collision between electron and nucleus
because the electron interacts with the Coulombic nuclear forces and its vector quantities of
direction and velocity are changed. Since kinetic energy derives from velocity
(KE=1/2mv^2), the change in energy is radiated as electromagnetic radiation. The amount of
energy means a short wavelength within the x-ray band.
Page 6 of 86 Qualitative Analysis and Determination of Samples through XRD

Fig. 3
As the electron is not destroyed, it can undergo multiple interactions, and even initial
interactions will vary from minor to major energy changes depending on the actual angle and
proximity of attack, and the point of 'impact' on the nucleus. As a result, Bremsstrahlung
radiation will have continuous spectrum where the maximum energy relates to the entire KE
of the electron but will be infrequent.
The probability of Bremsstrahlung production is proportional to the Z^2 of the target material,
and the efficiency of production is proportional to the target material Z and the tube voltage.

Fig. 4

As a result of characteristic and Bremsstrahlung radiation generation a spectrum of X-ray energy is


produced within the X-ray beam.
This spectrum can be manipulated by changing the X-ray tube current or voltage settings, or by
adding filters to select out low energy X-rays.
Page 7 of 86 Qualitative Analysis and Determination of Samples through XRD

Fig. 5

 As the atomic number Z of the target element increases, the energy of the characteristic emission
increases and the wavelength decreases. This relationship is defined well in the Moseley’s Law:

(c/l) 1/2 ∝ Z

Where,

c= energy of characteristic emission (m/s)

l= wavelength (lambda)

Z= atomic number

When the square root of frequencies of the characteristic X-rays from the elements is plotted against
the atomic number, a straight line is obtained.
Page 8 of 86 Qualitative Analysis and Determination of Samples through XRD

Fig. 6
(Moseley measured the x-ray emission of about 40 elements and plotted them against their respective
atomic numbers and showed that the graph of square root of frequency v/s atomic numbers was a
straight line.)

With insights from the Bohr model, Moseley’s empirical formula for K-alpha X-rays is as follows:

We can use this relationship to calculate approximate quantum energies and wavelengths for K-alpha
X-rays.
Page 9 of 86 Qualitative Analysis and Determination of Samples through XRD

Polarization of X-rays

Laue predicted that if x-rays were a form of short-wavelength electromagnetic radiation then they
should produce diffraction effects as they pass through crystals. This idea was put to the test by
Friedrich.

In the absence of strong external electric or magnetic fields, atomic systems of different magnetic
sublevels (but otherwise having the same principal and angular momentum quantum numbers) are
degenerated in energy. Measurement of the energies of the atomic transitions under such conditions
becomes impossible without the availability both quantum and magnetic numbers. The magnetic
quantum numbers are in relation to the spatial arrangement of the atoms.

Pronounced external symmetry makes spatial arrangement important. For example excitation in
cylindrically symmetric situations can lead to oriented or aligned systems where the magnetic
substrates with different angular momentum projections have the same energy but different
populations. If such a system undergoes a transition which results in a photon or electron emission the
emitted radiation will show anisotropic and polarized behaviour.

Transitions in highly charged ions usually involve the emission of photons in the X-ray region. This
fact offers an obvious choice of the use of X-ray analyzers (usually solid state detectors and crystal
spectrometers) for measuring.

Diffraction, Scattering and Reflection of X-rays

X-ray waves interact with matter through the electrons contained in atoms, which are moving at
speeds much slower than light. When the electromagnetic radiation (the X-rays) reaches an electron (a
charged particle) it becomes a secondary source of electromagnetic radiation that scatters the incident
radiation.

In accordance with the wavelength and phase relationships of the scattered radiation, we can refer to
elastic/inelastic process (depending if the wavelength changes or not) and to coherence/incoherence(
if the phase relationships are maintained or not maiantained over time and space)
Page 10 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 6 Fig. 7

Fig. 8
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XRD

Fig. 9

The refractive index of all materials in relation to X-rays is close to 1, so that the phenomenon of
refraction of X-rays is negligible. This explains why we are not able to produce lenses for X-rays and
why the process of image formation, as in the case of visible light, cannot be carried out with X-rays.

When a non-polarized X-ray beam (that is, when its electromagnetic field is vibrating at random in all
directions perpendicular to the propagation), interacts with an electron, the interaction takes place
primarily through its electric field. Thus, in a first approximation, we can neglect both the
magnetic and nuclear interactions. According to the electromagnetic theory of Maxwell, the electron
scatters electric waves which propagate perpendicular to the electric field, in such a way that the
scattered energy (which crosses the unit of area perpendicular to the direction of propagation and per
unit of time) is:

Ie (Ks) = I0 [e4 / R02 m2 c4] [(1 + cos2 2θ) / 2]

Fig.10
Page 12 of 86 Qualitative Analysis and Determination of Samples through
XRD

Where,

Ro= distance to the observation point

2Θ= incident direction and the direction where the scattering is observed

‘e’ and m are the charge and mass of the electron

‘c’ is the speed of propagation of radiation in the vacuum.

The binding forces between atom and electron are not considered in the model. It is assumed that the
natural frequencies of vibration of the electron are much smaller than those of the incident radiation.

The second factor (in brackets equation above) which depends on the θ angle, is known as
the polarization factor, because the scattered radiation becomes partially polarized, which creates a
certain anisotropy in the vibrational directions of the electron, as well as a reduction in the scattered
intensity (depending of the direction). The scattered intensity shows symmetry around the incident
direction. As the scattered wave is spherical, the inverse proportionality to the squared distance makes
the energy per unit of solid angle a constant.

Fig. 11

(A solid angle is the angle in three-dimensional space that an object subtends at a point. It is a
measure of how big that object appears to an observer looking from that point.
Metrically it is the constant ratio between the intersecting areas of concentric spheres with a cone, and
the corresponding squared radii of the spheres:
A1/R12 = A2/R22 = A3/R32 = ... = solid angle in steradians)

With regard to the phenomenon of diffraction and interference, it is important to consider the phase
relationship between two waves due to their different geometric paths. This affects the difference of
phase α of the resultant wave:
Page 13 of 86 Qualitative Analysis and Determination of Samples through
XRD

Φ = 2π (K0.r - ν.t + α)

In such a way that:

α = 2π (Ks - K0) rij + α’

Where

K0 = wave vector of incident wave

Ks = wave vector in the direction of propagation

rij = vector between the two propagation centres which produces the phase difference

If we have several disturbance centres whose phase differences are measured from a common origin,
and we consider the position vectors rj of their phase differences, the phase difference of one of the
centres can be written (using unit vectors in the directions of propagation with λK = s) as:

αj = 2π [(s - s0) / λ] rj + α '

This means that all rj points in which the product (s - s0) rj has a constant value (cte), will have the
same phase, given by:

α = (cte. 2π / λ) + α’

An atom that can be considered as a set of Z electrons (its atomic number) can be expected to
scatter Z times that which an electron does. But the distances between the electrons of an atom are of
the order of the X-rays wavelength, and therefore we can also expect some type of partial destructive
interferences among the scattered waves. In fact, an atom scatters Z times only in the direction of the
incident beam, decreasing with the increasing of the θ angle (the angle between the incident radiation
and the direction where we measure the scattering). And the more diffuse the electronic distribution of
electrons around the nucleus, the greater the reduction.
Page 14 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 12

(Phase relationships amongst electrons in an atom)

Fig. 13

( Diagram showing the variation of the amplitudes scattered by an electron, without considering the
polarization (left figure), and an atom (right figure). The amplitude scattered by an atom decreases
with increasing scattering angle.)

Therefore,

Atomic scattering factor = Amplitude scattered by an atom

Amplitude scattered by an electron

As the speed of electrons in the atom is much greater than the variation of the electric vector of the
wave, the incident radiation only sees an electronic cloud which is characterized by electron density
of charge i.e., ρ (r). If this distribution is considered spherically symmetric, it will just depend on the
distance to the nucleus, so that, with:
Page 15 of 86 Qualitative Analysis and Determination of Samples through
XRD

H = 2 sin θ / λ

(Which is the length of the scattering vector H = Ks- K0 = (s - s0) / λ):

f (H) = 4π∫(0 to inf.) r2 ρ(r) (sin H r / H r) dr

Thus, the atomic scattering factor will represent a number of electrons (the effective number of
electrons of a particular atom type) that scatter in phase in that direction, so that θ = 0 and f (0) = Z.
The hypothesis of isotropy, i.e. that this atomic factor does not depend on the direction of H, appears
to be unsuitable for transition momentum in which d or f orbitals are involved, nor for the valence
electrons.

By quantum-mechanics calculations we can obtain the values for the atomic scattering factors, and we
can derive analytical estimates of the type:

f (H) = Σ(1 to 4) ai exp [ -bi H2 ] + c

Fig. 14

(Atomic scattering factors calculated for several ions with the same number of electrons as Ne. One
can observe that the O-- has a more diffuse electronic cloud than Si 4+ and thus it shows a faster
decay.)
Page 16 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 15
(Atomic scattering factors calculated for atoms and ions with different numbers of electrons. Note that
the single electron of the hydrogen atom (H) scatters very little as compared with other elements,
especially with increasing θ. Hydrogen will therefore be difficult to see)

When the frequency of the incident radiation is close to the natural vibration of the electron linked to
the atom, we have to make some corrections (Δ) due to the phase differences that occur between the
individual waves scattered by electrons, whose vibration (due to the incident wave) is affected by that
linking. Thus:

f(H) = f0 + Δ' f + i Δ'' f


Also written as:

f(H) = f0 + f ' + i f ''

Where

f0= atomic scattering factor without ligation

‘i’= imaginary unit that represents the phase differences between individual scattered waves

This situation occurs for atoms with large atomic numbers (heavy atoms), or with atomic numbers
close (but smaller) to the metal atoms in the X-ray anode.
Page 17 of 86 Qualitative Analysis and Determination of Samples through
XRD

These corrections weakly depend on Θ angle so that this anomalous effect is better seen at larger
values of this angle, although this is where the scattered beams have lower intensity due to thermal
effects

Due to the movement of the atomic thermal vibrations within the material, the effective volume of the
atom appears larger, leading to an exponential decrease of the scattering power, characterized by a
coefficient B (initially isotropic) in the Debye-Waller (1913, 1923) exponential factor:
f(H) exp [ -Biso sin2θ / λ2 ]
(B is 8π2<u2>, <u2> being the quadratic average amplitude of thermal vibration in the H direction)

 In the isotropic model of vibration, B is considered to be identical in all directions (with


normal values between 3 and 6 Angstroms2in crystals of organic compounds)
 In the anisotropic model, B is considered to follow an ellipsoidal vibration model.
Unfortunately, these thermal parameters may reflect not only thermal vibration, as they are
affected by other factors such as atomic static disorder, absorption, wrong scattering factors,
etc.

Fig. 16

(Decrease of the atomic scattering factor due to thermal vibrations)

Scattering by a set of atoms- X-rays scattered by a set atoms produce X-ray radiation in all directions,
leading to interferences due to the coherent phase differences between the inter atomic vectors that
describe the relative position of atoms. In a molecule or in an aggregate of atoms, this effect is known
as the effect of internal interference, while we refer to an external interference as the effect that occurs
between molecules or aggregates. The scattering diagrams below show the relative intensity of each
of these effects:
Page 18 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 17

(Scattering diagrams of a monoatomic material in different states)

 In the intensity axis the background contribution is neglected


 The figures mainly represent the effect of the external interference, while the internal
interference (in this case due to a single atom only) is simply reflected by the relative
intensity of the maxima.
 The thermal movement in the liquid softens and reduces the scattering profile, and the
maxima produced by the glass also decreases.
 In the crystal, where the phase relations are fixed and repetitive, the scattering
profile becomes sharp with well defined peaks, whereas in the other diagrams the peaks are
broad and somewhat continuous.
 In the crystal case the scattering effect is known as diffraction.
 The scattering phenomenon reflects the internal order of the sample - the
positional correlations between atoms.

In the case of monoatomic gases, the effects of interference between atoms m and n lead (in terms of
the intensity scattered by an electron) to:

I (H) = Ie(H) ΣmΣn fm(H) fn(H) exp [2πi (s - s0) rm,n / λ]

Which, when averaged over the duration of the experiment and in all k directions of space, gives rise
to the Debye formula:

<I (H)> = Ie(H) ΣmΣn fm(H) fn(H) [ sin 2π|H| |rm,n| / 2π|H| |rm,n| ]
Page 19 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 18

(Geometry of the scattering produced by a set of identical atoms)

In the case of monoatomic liquids some effects appear at short distances, due to correlations between
atomic positions. If the density of atoms per unit of volume (at a distance r from any atom with
spherical symmetry) is, on average, ρ(r), then the expression 4π r2ρ(r) is known as the radial
distribution, and the Debye formula becomes:

<I (H)> = Ie(H) N f2(H) [ 1 + ∫(0 to inf.) 4πr2ρ(r) sin (2π|H| |r|) / 2π|H| |r| dr ]

All these relationships allow the analysis of the X-ray scattering in amorphous, glassy, liquid and
gaseous samples.

In brief, the X-ray scattering can be represented in this way:

X-rays are scattered by electrons contained


in atoms. This dispersion effect (which is
produced in the form of waves, scattered in
all directions of space) contains different
intensities (amplitudes), depending on the
number of electrons (electron density)
contributing to the scattered waves.

Fig. 19
Page 20 of 86 Qualitative Analysis and Determination of Samples through
XRD

Taking an origin in the atomic set and


considering a given direction of
dispersion, each of the waves scattered in
that direction can be represented by a
mathematical function (see figure at the
right), whose amplitude depends on the
electron density ρ(r) existing at the point
where the wave arises.

S is a magnitude which depends on the


angle at which the scattering occurs.

Fig. 20

The total scattered wave in each direction


is the sum of all the individual waves
which scatter in the same direction, f (S).
Its intensity (amplitude) will be governed
by the phase relationship between the
contributing waves, which depends
on r (the distance between the points
where they originate). This will happen for
all space directions.

Fig. 21

If we place a detector (such as a photographic


plate) to observe the scattered waves, f(S),
we obtain a distribution of intensities

Fig. 22
Page 21 of 86 Qualitative Analysis and Determination of Samples through
XRD

This "map" of scattered waves (shape


and intensities) contains information on
the distribution of atoms that are
producing the scattering. Mathematically
this map is represented by the
function f(S), which is the Fourier
transform of the atomic distribution
(electron density).

Fig. 23

When the set of atoms are arranged in


an orderly fashion, i.e., in the form of a
crystal, they behave as a very effective
dispersion amplifier.

Fig. 24

In these circumstances, scattering


effects concentrate in certain areas of
the detector, very well defined and
regularly distributed, known as
diffraction

The diffraction allows us to obtain


information about the electronic
distribution much richer than the one
produced by the scattering of a set of
disordered atoms

Fig. 25

Scattering by mono atomic lattices - When the set of atoms is structured as a regular three-
dimensional lattice (so that the atoms are nodes of the lattice), the precise geometric relationships
between the atoms give rise to particular phase differences. In these cases, cooperative effects occur
and the sample acts as a three-dimensional diffraction grid. Under these conditions, the effects
of external interference produce a scattering structured in terms of peaks with maximum intensity
which can be described in terms of another lattice (reciprocal of the atomic lattice) which
Page 22 of 86 Qualitative Analysis and Determination of Samples through
XRD

shows typical patterns, such as those you can see when you look at a streetlight through an umbrella
or a curtain.

Schematic diagram of diffraction patterns


from several two-dimensional point
distributions. The parameters of
repetition in the diffraction patterns
means a constant scale factor which
depends on the experiment. All points of
the diffraction pattern have the same
intensity, because it is assumed that the
used wavelength is much larger than the
points of the direct lattice

Fig. 26

Relationship between two 2-


dimensional lattices, direct
lattice (on the left) and
reciprocal lattice (on the right).

d01 and d10 are the corresponding


direct lattice spacing.

Note that the figures show a


direct unit cell and a reciprocal
unit cell only, corresponding to
the diffraction patterns shown
above.

Fig. 27

Structured in a lattice, any atom can be defined by a vector, referred to a common origin:

R j,m1,m2,m3 = m1 a + m2 b + m3 c

Where,
Page 23 of 86 Qualitative Analysis and Determination of Samples through
XRD

Rj represents the position of the j node in the lattice

m1, m2, m3, are integers

a, b and c are the vectors defining the lattice

According to this, the intensity scattered by a material would be:

I(H) = Ie(H) Σm1Σm'1Σm2Σm'2Σm3Σm'3 fj(H) fj'(H) exp [2πi (s - s0) rm,m' / λ]

Where,

(rm,m' = Rm1,m2,m3 - Rm'1,m'2,m'3 = (m1-m'1) a + (m2 - m'2) b + (m3 - m'3) c)

And calculating this sum we have:

I(H) = Ie(H) [ [ sin2 π(s - s0) M1 a / λ ] / [sin2 π(s - s0) a / λ ] ] .


[ [ sin2 π(s - s0) M2 b / λ ] / [sin2 π(s - s0) b / λ ] ] .
[ [ sin2 π(s - s0) M3 c / λ ] / [sin2 π(s - s0) c / λ ] ]

= Ie (H) IL(H)

Where,

M1, M2, M3 represent the number of unit cells contained in the crystal along the a, b and c directions

The total sample the number of unit cells would be M = M1.M2.M3 (around 1015 in crystals of an
average thickness of 0.5 mm).

IL(H) = factor of external interference due to the monoatomic lattice

.
Page 24 of 86 Qualitative Analysis and Determination of Samples through
XRD

Graphical representation of one of the products


of the IL(H) function between two consecutive
maxima

The transformation
from scattering to diffraction, that is, from
broad to very sharp peaks, as the number of
cells M1 increases.

The maxima are proportional to M12 and the


first minimum appears closer to the maximum
with increasing M1.

It consists of several products of type (sin2 Cx)


/ sin2 x, where C is a very large number

This function is almost zero for all x values,


except in those points where x is an integer
multiple of π, where it takes its maximum value
of C2.

The total value would be a maximum value only


when all three products are other than zero,
where it will take the value of M2

The diffraction diagram of the direct lattice is


another lattice that takes non-zero values in its
nodes and that, due to the Ie (H) factor, varies
from one place to another

Fig. 28

Diffraction by a single crystal

When the material is not structured in terms of a monoatomic lattice, but is formed by a group of
atoms of the same or of different types, the position of every atom with respect to a common origin is
given by:

R j,m1,m2,m3 = m1 a + m2 b + m3 c + rj
= Tm1,m2,m3 + rj
Page 25 of 86 Qualitative Analysis and Determination of Samples through
XRD

Reduction inside a unit cell of the


absolute position of an atom through
lattice translations

To go from the origin to the atom, at


position R, we first go, through
the T translation, to the unit cell origin,
and from there with the vector r we reach
the atom

Fig. 29

As the atom is always included within a unit cell, its coordinates referred to the cell are smaller than
the axes, and often are expressed as fractions of them:

r = X a + Y b + Z c = X/a a + Y/b b + Z/c c = x a + y b + z c

Where,

x, y, z, as fractions of axes, are now between -1 and +1.

Then, under the conditions initially raised, i.e. with a monochromatic and depolarised X-ray beam (as
a plane wave, formed by parallel rays of a common front wave), perpendicular to the propagation unit
vector s0 that completely covers the sample, the kinematic model of interaction indicates that the
sample produces diffracted beams in the direction s with an intensity given by:

I (H) = Ie(H) IF(H) IL(H)

where Ie is the intensity scattered by an electron, IL is the external interference effect due to the three-
dimensional lattice structure, and IF is the square of the so-called structure factor, a magnitude which
takes into account the effect of all internal interferences due to the geometric phase relationships
between all atoms contained in the unit cell. This internal structural effect is:

IF (H) = | F2(H) | = F(H) F*(H)

As a consequence of the complex representation of waves, mentioned at the beginning, the square of a
complex magnitude is obtained by multiplying the complex by its conjugate. Thus, specifically, we
give the name structure factor, F(H), to the resultant wave from all scattered waves produced by
all atoms in a given direction :
Page 26 of 86 Qualitative Analysis and Determination of Samples through
XRD

F (H) = Σ(1 to n) fj(H) exp [2π(s - s0) rj / λ]

As already stated, the phase differences due to geometric distances R are proportional to (s - s0) R / λ.

This means that if we change the origin, the phase differences will be produced according to the
geometric changes, in such a way that as the exponential parts of the intensity functions are conjugate
complexes, they will affect the intensities in terms of proportionality constant only. Thus, a change of
origin is not relevant to the phenomenon.

In the equation of the total intensity, I (H), the conditions to get a maximum lead to the following
consequences:

 The phenomenon of diffraction in crystal samples is discrete, spectral.

 The directions and the periodic repetitions in the reciprocal lattice do not depend on
the structure factors. They only depend on the direct lattice. The knowledge of these
directions give us the shape and size of the direct unit cell, which actually controls the
positions of the diffraction maxima.

 The intensity of the diffraction maxima depends on the structure factor in this direction (at
that reciprocal point), which only depend on the atomic distribution within the unit cell. In
other words, the diffraction intensities are only controlled by the atomic distribution within
the cell. Thus, through the intensities we can obtain information about the atomic structure
within the unit cell.

 The total diffraction pattern is the consequence of the diffraction of the different atomic
aggregates within the unit cell, sampled in the diffraction points produced by the crystal
lattice (the reciprocal points).

 In summary, structural crystallography by X-ray diffraction consists of measuring the


intensities of the largest possible amount of diffracted beams in the 3-dimensional diffraction
pattern, to get from them the amplitudes of the structure factors, and from these values
(through some procedure to allocate the phases for each of these structure factors) to build the
electronic distribution in the elementary cell (which can be described in terms of a function
whose maxima will give us the atomic positions).
Page 27 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 30

Diffraction patterns of: (a) a single molecule, (b) two molecules, (c) four molecules, (d) a periodically
distributed linear array of molecules, (e) two linear arrays of molecules, and (f) a two-dimensional
lattice of molecules. Note how the pattern of the latter is the pattern of the molecule sampled in the
reciprocal points

Collection of objects and their


corresponding diagrams of scattering /
diffraction: a molecule, a line of dots, a
line of molecules, a lattice of dots, and
finally a two-dimensional lattice of
molecules.

Fig. 31
Page 28 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 32

Fig. 33
Page 29 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 34

Fig. 35

Laue equations, Bragg's interpretation and Ewald's geometric diffraction model

The diffraction diagram of a direct lattice defined by three translations, a, b and c, can be expressed in
terms of another lattice (the reciprocal lattice) with its reciprocal translations: a*, b* and c*, and these
translation vectors (direct and reciprocal) meet the conditions of reciprocity:

a a* = b b* = c c* = 1 and a b* = a c* = b c* = 0

And they also meet that (for instance):

a* = (b x c) / V

(x means vectorial or cross product)

Where V is the volume of the direct unit cell defined by the 3 vectors of the direct cell, and therefore:
Page 30 of 86 Qualitative Analysis and Determination of Samples through
XRD

a* = N100 / d100

Where,

N100 is a unit vector perpendicular to the planes of indices h=1, k=0, l=0

d100 is the corresponding interplanar spacing.

And similarly with b* and c*.

In this way, any vector in the reciprocal lattice will be given by:

H*hkl = h a* + k b* + l c* = Nhkl / dhkl

In such a way that:


|H*hkl| dhkl = 1

On the other hand, we have seen that the maxima in the diffraction diagram of a crystal correspond to
the maximum function IL(H), meaning that each of the products that define this function must be
individually different from zero, as a sufficient condition to obtain a maximum for the diffracted
intensity. If we remember that H = (s - s0) / λ, this also means that the three so-
called Laue equations must be fulfilled:

H a = h, H b = k, Hc=l

where h, k, l are integers

Laue equations

These three conditions are met if the vector H represents a vector of the reciprocal lattice, so that:

H = h a* + k b* + l c*

Since due to the properties of the reciprocal lattice, it can be stated that:

Hhkl a = h, Hhkl b = k, Hhkl c = l

If these three conditions are fulfilled, and taking into account some relationships explained above, we
can write:
Page 31 of 86 Qualitative Analysis and Determination of Samples through
XRD

| H | = 2 sin θhkl / λ = | (s - s0) | / λ = | H*hkl | = 1 / dhkl

And this is Bragg's Law which can be rewritten in its usual form as:

λ = 2 dhkl sin θhkl

But remembering that

dhkl = n dnh,nk,nl

Equation will be transformed into:

n λ = 2 dhkl sin θnh,nk,nl

Where n is an integer number

Fig. 36

That is, when in the crystal-radiation interaction a


maximum of diffraction occurs, it is equivalent to
say that the incident beam reflects on the crystal
planes of indices hkl and interplanar spacing dhkl.
That's why in talking about diffraction maxima,
sometimes we use the phrase Bragg's reflection.

Moreover, this equation holds all the traditional


relations of reciprocity of diffraction,
between spacing-direction or position-momentum:
the shorter spacing, the larger angle and vice versa;
direct lattices with large unit cells produce very
close diffracted beams, and vice versa.
Page 32 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 37

Fig. 38
Page 33 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 39

Moreover, if the conditions of Laue are fulfilled all atoms located on the sequence of planes parallel
to the one with indices hkl at a given distance (DP) from the origin (DP being an integer multiple
of dhkl) will diffract in phase, and their geometric difference-of-phase factor will be:

(s - s0) r = n λ

And consequently a diffraction maximum will be produced in the direction:

s = s0 + λ H*hkl
Page 34 of 86 Qualitative Analysis and Determination of Samples through
XRD

Geometrical model to interpret the diffraction


(in phase) of all parallel planes with indices hkl
and a constant inter planar spacing dhkl, when
the Laue conditions (or their
equivalent, Bragg’s Law) are fulfilled.

Nhkl is the unit vector perpendicular to the


hkl planes and in the diffraction conditions is
given by:

Nhkl = H*hkl dhkl

The plane equation can, therefore, be written


as:

H*hkl r = H*hkl ri= |H*hkl| |ri| cos (H*hkl , ri) =


(1/dhkl) DP = n

Fig. 40

The figure geometrically describes the


direction of the diffraction beam due to
the constructive interference
between atoms located on the planes
with interplanar spacing d (hkl).
Fig. 41
Page 35 of 86 Qualitative Analysis and Determination of Samples through
XRD

The figure depicts a description of Bragg’s


model when different types of atoms are
located on their respective parallel planes
with Δd spacing. The separation between
blue and green planes creates interferences
and differences of phases (between the
reflected beams) giving rise to changes in
intensity (depending of the direction).
These intensity changes allow us to get
information on the structure of atoms that
form the crystal).

Fig. 42

On the other hand, we have seen that in general:

H = (s - s0) / λ = -s0/λ + s/λ

And this means that the vectors H can be considered as belonging to a sphere of radius 1/λ centred at
a point defined by the vector -s0/λ with respect to the origin where the crystal is. This is known
as Ewald's sphere (Ewald, 1921), which provides a very easy geometric interpretation of the
directions of the diffracted beams. When the H vectors belong to the reciprocal lattice and the end of
the vector (a reciprocal point) lies on that spherical surface, diffracted beam are produced, and
obviously the crystal planes are in Bragg's position.

Fig. 43

The above figure describes Ewald's geometric model. When a reciprocal point, P*(hkl), touches the
surface of Ewald’s sphere, a diffracted beam is produced starting in the centre of the sphere and
passing through the point P*(hkl). Actually the origin of the reciprocal lattice, O*, coincides with the
position of the crystal and the diffracted beam will start from this common origin.
Page 36 of 86 Qualitative Analysis and Determination of Samples through
XRD

This figure shows the whole reciprocal


volume that can give rise to diffracted
beams when the sample rotates.
Changing the orientation of the
reciprocal lattice, one can collect all
the beams corresponding to the
reciprocal points contained in a sphere
of radius 2/λ known as the limit sphere.
To obtain all possible diffracted beams
that a sample can provide, using a
radiation of wavelength λ, it is
sufficient to conveniently orient the
crystal and make it turn, so that its
reciprocal points will have the
opportunity to lay on the surface of
Ewald's sphere. In these
circumstances, diffracted beams will
Fig. 44 originate as described above. With
larger wavelengths, the volume of the
reciprocal space that can be explored
will be smaller, but the diffracted
beams will appear more separated.

According to Bragg's Law, the maximum angle at which one can observe diffraction will correspond
to the angle where the sin function is maximum (=1). This also means that the theoretical
maximum resolution that can be achieved is λ/2. In practice, due to the decrease of the atomic
scattering factors by increasing Bragg angles, appreciable intensities will appear only up to a
maximum angular value of θmax < 90º and the real maximum resolution reached will be dmin = λ/2
sin θmax.

Considering that the interplanar spacing dhkl are a characteristic of the sample, by reducing
the wavelength, Bragg's Law indicates that the diffraction angles (θ) will decrease; the spectrum
shrinks, but on the other hand, more diffraction data will be obtained, and therefore a better structural
resolution will be achieved.
Page 37 of 86 Qualitative Analysis and Determination of Samples through
XRD

According to Ewald's model, the


amount of reciprocal space to
be measured can be
increased by reducing the
wavelength, that is, by
increasing the radius of the
Ewald's sphere.

Fig. 45

Fig. 46

Fig. 47
Page 38 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 48
Page 39 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 49

Fig. 50
Page 40 of 86 Qualitative Analysis and Determination of Samples through
XRD

BUILD OF THE INSTRUMENT

Fig. 50 (Powder Diffractometer)

Fig. 51 (Bragg- Brentano Principle in XRD)


Page 41 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 52 (Schematic diagram of53


Fig. X-ray powder Diffractometer)
Page 42 of 86 Qualitative Analysis and Determination of Samples through
XRD

Essential Parts of Diffractometer

1. X-ray Tube: the source of X Rays


2. Incident-beam optics: condition the X-ray beam before it hits the sample
3. The goniometer: the platform that holds and moves the sample, optics, detector,
and/or tube
4. The sample & sample holder
5. Receiving-side optics: condition the X-ray beam after it has encountered the sample
6. Detector: count the number of X Rays scattered by the sample
a. point detectors
 observe one point of space at a time
 slow, but compatible with most/all optics
 scintillation and gas proportional detectors count all photons, within
an energy window, that hit them
 Si(Li) detectors can electronically analyze or filter wavelengths
b. position sensitive detectors
 linear PSDs
 observe all photons scattered along a line from 2 to 10° long
 2D area detectors observe all photons scattered along a conic section
 gas proportional (gas on wire; microgapanodes)
 limited resolution, issues with dead time and saturation
 CCD/Phosphors
 limited in size, expensive
 solid state real-time multiple semiconductor strips
 high speed with high resolution, robust
7. Monochromators remove unwanted wavelengths of radiation from the incident or
diffracted X-ray beam
 Diffraction from a crystal monochromator can be used to select one
wavelength of radiation and provide energy discrimination
 An incident-beam monochromator might be used to select only Kα1 radiation
for the tube source
 A diffracted-beam monochromator may be used to remove fluoresced
photons, Kβ, or W-contamination photons from reaching the detector
Page 43 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 54

Fig. 55
Page 44 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 56 (XRD)

Fig. 57 (Powder Diffractometer)


Page 45 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 58

Bruker XRD is used in our labs


1. The X-ray source technology is a key competence in the Bruker’s. Various fully integrated; state-
of-the-art X-ray sources are available to generate the X-rays.

i. The revolutionary METALJET, based on liquid metal jet technology, provides unmatched X-
ray source brilliance
ii. The TURBO X-RAY SOURCE (TXS) rotating anode provides highest intensities for line, spot
and micro focus applications
iii. The IµS micro focus X-ray source boosts the intensity on small spots while consuming only
very little power
iv. The patented TWIST-TUBE for fast and easy switching between line and spot focus
v. The cost effective ceramic sealed tube for line or spot focus
Page 46 of 86 Qualitative Analysis and Determination of Samples through
XRD

vi. These X-ray sources are combined with dedicated X-ray optics to efficiently capture the X-rays
and turn them into an X-ray beam optimized for your application.

Fig. 59 (Meta jet liquid metal jet X-ray source)

Fig. 60 (X-ray sources)


Page 47 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 61(X-ray sources)

2. X-ray optics are more and more important to meet the ever increasing needs of many
demanding applications in X-ray diffraction, X-ray fluorescence analysis, and
chemical or biological structure determination.
i. There are a large variety of purposes to use X-ray optics: increase the primary
beam flux or the flux density, improve the angular or energy resolution of a
set up, improve the peak-to-background ratio, and many more.
ii. In common it comes down to increasing the sample throughput and improves
the data quality.
iii. Bruker’s is the innovative supplier developing and supplying the entire range
of optical components, in particular the man-made nanometre multi-layer
optics, so called Goebel Mirrors and Montel optics.
iv. All types of these specific optics are high-tech, thin film devices. Their
preparation requires the highest accuracy, precision, and reproducibility.
v. To give an example, our unique Göbel mirror meets tolerances in the order of
1 mm over a distance of 600 km.
Page 48 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 62 (X-ray optics options provided by the Bruker)

3. Bruker’s offer a large portfolio of in-house developed Detectors to provide best


performance in all applications
i. To gain the full benefit from the intrinsic properties of a detector, such as a
high dynamic range or low noise level, proper manufacturing design is
essential.
ii. The LYNXEYE XE is the first energy dispersive 1-D detector operating at
room temperature for ultra-fast X-ray diffraction.
iii. The large VÅNTEC-500 is a true 2-D detector for collecting all diffraction
information from your sample in one shot.
Page 49 of 86 Qualitative Analysis and Determination of Samples through
XRD

iv. LYNXEYE XE detector overcomes the intensity losses and absorption edges
associated with secondary monochromator and metal filters. The LYNXEYE
XE therefore provides an enormous advantage in terms of intensity, peak-to-
background-ratio, lower limits of detection, and accurate profile fitting.
Thanks to its unparalleled filtering of fluorescence and K-beta radiation.
v. The large VÅNTEC-2000 is yet another 2-D detector that Bruker’s offer.

Fig. 63 (Types of Detectors by the Bruker’s)


Page 50 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 64 (Types of Detectors by the Bruker’s)

4. The range of Stages and Holders serve simple pressed powder sample needs, large machined
pieces, or 300 mm diameter wafer handling requirements as well.

i. Motorized sample stage allows for translation along X, Y and Z directions. It can be
mounted to any vertical D8 ADVANCE with DAVINCI. The stage is fully integrated
in the DIFFRACplus measurement software. The large support plane accommodates
a variety of sample holders; hence, it serves a wide range of applications.
ii. Specifications:
 63mm * 63mm support plane, with threads for mounting additional sample holders
 Travel range of 25 mm in X, Y and Z directions
 Load capacity up to 1 kg
 Bayonet fixture for alignment free switching to other sample stages

iii. Optional accessories to the sample holder :


 3” or 5” vacuum chuck, optionally with knife edge collimator
 Zeta/Xi tilt stage
 Capillary stage
 Goniometer head
 Double laser assembly for positioning
Page 51 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 65 (Types of Sample Holders)


iv. XRD non-ambient stages: Detailed knowledge of what happens to a sample at non-
ambient conditions is essential for optimizing industrial processes, performing quality
control, or for conducting research.
 D8 ADVANCE and D8 DISCOVER, enable fast data acquisition to
efficiently study kinetics and thermodynamics at non-ambient conditions. All
that is required is an additional, dedicated sample stage to study the effect of
the environment under which the sample is used as parameters like
temperature, atmosphere, humidity or pressure.
 Our large portfolio of stages covers a vast range of non-ambient conditions
such as, sample temperatures from 80 K up to 2300°C, different atmospheres
(vacuum to reactive gas or relative humidity and pressure), for reflection or
transmission geometry and fits seamlessly to the DAVINCI design.

Fig. 66 (Non- ambient Stages)

MECHANISM

Part 1: Preparing a powder specimen


Page 52 of 86 Qualitative Analysis and Determination of Samples through
XRD

 An ideal powder sample should have many crystallites in random orientations –the
distribution of orientations should be smooth and equally distributed amongst all orientations
•If the crystallites in a sample are very large, there will not be a smooth distribution of crystal
orientations. You will not get a powder average diffraction pattern. –crystallites should be
<10µm in size to get good powder statistics •Large crystallite sizes and non-random
crystallite orientations both lead to peak intensity variation –the measured diffraction pattern
will not agree with that expected from an ideal powder –the measured diffraction pattern will
not agree with reference patterns in the Powder Diffraction File (PDF) database
Ways to prepare a powder sample
 Top-loading a bulk powder into a well –deposit powder in a shallow well of a sample holder.
Use a slightly rough flat surface to press down on the powder, packing it into the well. •using
a slightly rough surface to pack the powder can help minimize preferred orientation •mixing
the sample with a filler such as flour or glass powder may also help minimize preferred
orientation •powder may need to be mixed with a binder to prevent it from falling out of the
sample holder –alternatively, the well of the sample holder can be coated with a thin layer of
Vaseline

Fig. 67
 Dispersing a thin powder layer on a smooth surface –a smooth surface such as a glass slide or
a zero background holder (ZBH) may be used to hold a thin layer of powder
 glass will contribute an amorphous hump to the diffraction pattern
 the ZBH avoids this problem by using an off-axis cut single crystal
 dispersing the powder with alcohol onto the sample holder and then allowing the alcohol to
evaporate, often provides a nice, even coating of powder that will adhere to the sample holder
powder may be gently sprinkled onto a piece of double-sided tape or a thin layer of Vaseline
to adhere it to the sample holder
 the double-sided tape will contribute to the diffraction pattern
 these methods are necessary for mounting small amounts of powder
 these methods help alleviate problems with preferred orientation
Page 53 of 86 Qualitative Analysis and Determination of Samples through
XRD

 the constant volume assumption is not valid for this type of sample, and so quantitative and
Rietveld analysis will require extra work and may not be possible
 Important characteristics of samples for XRD
 A flat plate sample for XRPD should have a smooth flat surface
 if the surface is not smooth and flat, X-ray absorption may reduce the intensity of low angle
peaks
 parallel-beam optics can be used to analyze samples with odd shapes or rough surfaces
 The sample, in general, should be:
 Densely packed
 Randomly oriented grains/crystallites
 Grain size less than 10 microns

Fig. 68

Part 2: XRD Log


The XRD is part of the MSE cost centre. The log MUST be filled out. It is recommended that this be
done before beginning a measurement as not to forget.

Part 3: Operation
1. Before the operation is started, the following has to be observed accurately without fail:
 The procedure has to be read thoroughly.
 The alarm light on the right side of the instrument has to be checked for.
 The XRD log spreadsheets on the desktop have to be filled in.

2. Loading of the Sample:


Page 54 of 86 Qualitative Analysis and Determination of Samples through
XRD

 The green ‘door open’ button present on the right hand side is pressed. If we wait to open the
door after we have pressed the green button, then the doors get relocked. The door should not be
yanked opened.
 The handles of the lead door are gently pulled outwards towards us and the doors slide open .
 The sample holder is placed in the respective numbered positions by holding the sample in place
with one hand and turning the stage anti-clockwise until it locks and a ‘tick’ sound appears.
 If the position of the detector and the sample stage is found to be at uncomfortable angles, then
one may move the drives in XRD Commander.
 The slits in Anti-scattering and detector positions are verified and the slit sizes are noted down.
 The slit, if need to be removed, are carefully slided out of the enclosure.
 To replace, the slit is slided into the place with the bevelled side down.
 The doors are then slided together and the handles are pressed gently so that they are interlocked.
 If the doors are slammed shut or if the handles are not interlocked properly, then the safety
circuit will trigger and the generator will shut down.
 Care has to be taken while opening and closing the lead doors.

3. On the computer, the ‘XRD Commander’ is expanded and the power is raised, if necessary, in the
following ways”:
 The kV is stepped up in increments of 10kV at 30s between steps until 40kV is reached. The <set>
button is pressed after each change.
 The mA is stepped from 5 to 10, and then from 10mA to 40mA is attained. The scan should not be
started before completing this step.
 It has to be made sure that the live and requested kV and mA match before starting to power up the
ramp.
 On the left hand side of window in XRD commander, the <shutter> and <x-ray> buttons are used to
open and close the shutter and turn on and off the x-ray. They SHOULD NOT be pressed. The
indicator to the right of the buttons gives the status of the shutter and x-ray.
 When the shutter light is green, the shutter is closed and the enclosure doors can be opened.

4. For a Quick Scan:


 In XRD Commander, the <adjust> tab at the bottom of the page is pressed, the scan parameters are
inputted and start and end 2Θ limits are set. (0-130-2Θ)
 The step size for quick scan is 0.5-0.1-2Θ
 The step time is typically 1s.
 The scan is started by pressing on the <start> tab.
Page 55 of 86 Qualitative Analysis and Determination of Samples through
XRD

 When the scan is complete, the file is names and saved by going to <File>, <save as> and file name.
 Data is not saved automatically in this mode.

5. For auto-saved Scan:


 The jobs tab is selected which is present at the bottom of the page in the XRD commander.
 ‘Create jobs’ icon on the toolbar is selected
 The sample ID, parameter file and raw file fields are filled in. The parameter files should be selected.
 The scan is started.
 The scan is observed in the adjust tab.
 Data is saved automatically.
 Once the scan of the sample is complete, it is removed. (The sample stage pressure unit should not be
yanked on, pulled or applied torque/force)
 Once it’s finished, the data is found in the ‘shortcut to scans’ file on the desktop.
 Always the samples should be removed without forgetting and the closure of the doors post the
completion of scan is very important.

6. Permanent parameter file creation for auto-saved scans:


 XRD Wizard is opened from the icon at the bottom of the desktop.
 The quick edit tab is selected.
 The portions are filled in with a white background as necessary
 OK is selected
 <file>, <Save as> is clicked and the file is named. It will automatically save in the parameters file.
 The pre-saved parameter files should not be over-written.

7. Other considerations:
 The materials, samples or sample holders should not be stored in XRD room.
 The sample holders should be cleaned thoroughly after use. The waste disposal should be taken care
of in an accurate way.
 The XRD commander should not be closed. It will prevent the machine from returning to stand-by
mode and can reduce the life of XRD tube.
Page 56 of 86 Qualitative Analysis and Determination of Samples through
XRD

1. 2Θ Start Position
2. 2Θ End position
3. Increment (step size)
4. Scan speed
5. kV, live display
6. kV, requested
7. mA, live display
8. mA, requested
9. Power ‘Set’ to change to
requested value
10. To move drives both
positions are checked off,
values are input in
requested field (30/60 is
level with the floor) and the
drive icon is selected.

Fig. 69

1. Job icon
2. Sample ID
3. Parameter File, press button
to select
4. Name raw data file
5. Start
6. Adjust tab

Fig. 70
Page 57 of 86 Qualitative Analysis and Determination of Samples through
XRD

1. XRD Wizard shortcut


2. User name
3. Informational only
4. Select Scan type
5. Select scan parameters
6. Adjust power
7. Select <OK> and save in the
parameters file

Fig. 71

Fig. 72 (A Search- Match routine)


Page 58 of 86 Qualitative Analysis and Determination of Samples through
XRD

INTERPRETATION:

Fig. 73 (A diffractogram)

Fig. 74 (Interpretation of the diffractogram)


Page 59 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 75 (Interpretation of the diffractogram)

Fig. 76 (Interpretation of the diffractogram)


Page 60 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 77 (Interpretation of the diffractogram)

Fig. 78 (Interpretation of the diffractogram)


Page 61 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 79 (Interpretation of the diffractogram)

Fig. 80 (Interpretation of the diffractogram)


Page 62 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 81 (Interpretation of the diffractogram)

Fig. 82 (Interpretation of Diffractogram)


Page 63 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 83 (Interpretation of the diffractogram)

Fig. 84 (Interpretation of the diffractogram)


Page 64 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 85 (Interpretation of the diffractogram)

Fig. 86 (Interpretation of the diffractogram)


Page 65 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 88 (Interpretation of the diffractogram)

Fig. 89 (Interpretation of the diffractogram)


Page 66 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 89 (Interpretation of the diffractogram)

Fig. 90 (Interpretation of the diffractogram)


Page 67 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 91

 Indexing patterns- It is the process of determining the unit cell dimensions from the peak
positions.
1. Manual indexing- it is time consuming yet useful.
2. Pattern matching/ Auto indexing- JADE or other computer based indexing software

 Relationship between diffraction peaks, miller indices and lattice spacing:


Taking an example of simple cubic material a = 5.0 Armstrong

Fig. 92

A diffractogram of cubic pattern


Page 68 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 93
A diffractogram of tetragonal crystal system

Fig. 94

A diffractogram of orthorhombic crystal system


Page 69 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 95

The following can be determined form XRD analysis:

1. Phase Determination
 Most commonly used in heterogeneous catalysis
 Each different crystalline solid has a unique X-ray diffraction pattern which acts like a
“fingerprint” .
 For e.g., the figure shown below is a diffractogram of TiO2.

Fig. 96
Page 70 of 86 Qualitative Analysis and Determination of Samples through
XRD

 TiO2 has three commonly occurring structures and phases with same chemical
composition also have different XRD patterns thereby enabling us for rapid
determination of the form. The diffractogram is matched against the reference data. (
the position of the peak and the intensities are compared).
 The reference could be an experimentally collected one or simulated diffraction pattern
 The matching process can also be manual or automated.
 In simulating XRD data for known crystals, previously reported structures in database
are searched for and the suitable .cif file is found and opened with viewing programs.
 Generally, all expected reflections should be seen in the diffractogram otherwise it is
not a valid match.

Fig. 97

Fig. 98

 Cell parameters are useful for comparative purposes. Bibliographic references should
include the preparations and experimental details.
 Temperature in which the data is collected in important as it affects both lattice
parameters and peak positions.
Page 71 of 86 Qualitative Analysis and Determination of Samples through
XRD

 R-value is indication of data quality.


 Low signal to noise ratio is expected.
 Weak reflections will not be visible.
 Different relative intensities with a systematic dependence on hkl is also expected.
 Deviations in relative intensities might occur due to ‘preferred orientations effect’. It
can be checked by applying a Rietveld fit including a preferred orientation model.
 Deviation in intensity might also occur due to a phenomenon called ‘isostructural
phase’ where the presence of substitutional impurities of similar atomic size but
differing Z. In such cases, the sample composition can be verified.
 Deviations in peak positions can occur due to thermal expansions and isostructural
phase.

2. Quantitative Phase Analysis

Determining the relative proportions of crystalline phase present in an unknown


sample is the quantitative phase analysis. The ratio of the peak intensities varies
linearly as a function of the weight fractions for any two phases (e.g., A and B) in a
mixture.

Fig. 99
 Quantification by whole pattern fitting using Rietveld method is more accurate but is a more
complicated approach.
 The amorphous content of a sample containing crystalline phase A is determined using
internal standard of known crystallanity. (Spiking / reference intensity ratio), an appropriate
XRD standard B is needed for the same. This known std B is added to the specimen
containing phase A.
 The standard B should have no overlap of reflections with the phase to be determined.
 It should possess high crystallanity and uniform particle size.
Page 72 of 86 Qualitative Analysis and Determination of Samples through
XRD

 Care should be taken while preparing such samples. Examples are, Corundum, Quartz, ZnO
etc.

L(hkl)A
= k (XA/XB)
L(hkl)B

3. Calculation of Lattice parameters

 Diffraction angle related to d-spacing via Bragg equation is calculated.


 The peaks are identified in the diffraction pattern
 The corresponding d-spacing are calculated.
 The pattern is indexed. Once hkl is determined, the lattice parameters a, b, c
is easy to calculate.
Page 73 of 86 Qualitative Analysis and Determination of Samples through
XRD

4. Analysis of crystalline size and strain

Fig. 100

Factors that determine peak profile:


 XRD peak profile shape and width are result of imperfections in both the experimental setup and
the sample.
 Instrumental broadening occurs due to sample size, slit widths, goniometer radius, function of 2
theta and measurement of a suitable reference.
 Sample broadening occurs due to periodicity in crystals. It is not infinite as crystals have a finite
size, esp. in crystals smaller than 100 nm.
 Finite size results in size broadening and lattice imperfections like dislocations, vacancies and
substitutional result in strain broadening.

(The below diffractograms belong to the same sample but are measured using different Diffractometer
with different optical configurations. Hence, instrumental contributions have to understood and
considered before determining the sample broadening.)

Fig. 101
Page 74 of 86 Qualitative Analysis and Determination of Samples through
XRD

5. Structure solution

 For the analysis of crystalline size, the term ‘size’ has to be carefully defined.

Fig. 102

 The Scherrer equation, published by Scherrer in 198 is used to relate peak width to crystalline domain
size:

Where,
B is the FWMH of a peak profile (corrected for instrumental broadening)
L is the volume average of crystal thickness in directions normal to reflecting planes
K is the constant of proportionality
Θ is the diffraction angle of reflection
ƛ is the wavelength

 Assumption is made that the crystal has a uniform size and shape
 The Scherrer constant K is dependent on the crystal shape ( for e.g., 0.94 for the spherical crystals
with cubic symmetry)

 Significance of apparent crystal thickness L- Volume averaged crystal thickened L is dependent on


the crystal shape. For example,

Cubic crystallite L= Lc = crystallite edge length


( for reflections of lattice planes parallel to the cube faces)
Page 75 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 102

Spherical crystallite L<= Lc = crystallite diameter, i.e, LVol = ¾ Lc (for all reflections)

Fig. 103

 The micro strain broadening analysis aka lattice strain arises from displacements of the unit
cells about their normal positions.

Fig. 104
Page 76 of 86 Qualitative Analysis and Determination of Samples through
XRD

 The reasons for the same are dislocations, surface restructuring, lattice vacancies, interstitials,
substitutional, etc.
 It is very common in nano crystalline materials.

Fig. 105

 Strain is usually quantified as :


Єo = Δd/ d, with d being the idealized d-spacing and Δd being the most extreme deviation
from d.
The peak broadening due to the strain is assumed vary as:

i. Several factors contribute to the observed peak broadening, Bobs :


Bobs = Binstr + Bsample = Binstr + Bsize + Bstrain

The instrumental broadening Binstr can be determined experimentally with


a diffraction standard or calculated with the fundamental parameters
approach.
The separation of the size and the strain effect on the sample broadening,
however, is more complicated and depends on the methods in use.
ii. Considering most methods, the following angular dependencies are put
into use:
Page 77 of 86 Qualitative Analysis and Determination of Samples through
XRD

Broadening may alter FWHM or the integral breadth of the peak (peak
shape)

iii. For crystal structure determination, Rietveld refinement is used which is


an automated procedure which stimulates the XRD patterns of the model
systems (theoretical or known)and calculates the difference of fit with the
measured data.

iv. The Rietveld refinement tells us about the following:

 Lattice parameters
 Quantitative phase analysis
 Atomic positions
 Crystallanity
 Atomic occupancy
 Phase transitions
 Structure factors
 Grain size

Fig. 106
Page 78 of 86 Qualitative Analysis and Determination of Samples through
XRD

v. Calculation of spectrum: To minimise residual function this accounts for


both intensity variation and for line broadnening.

Fig. 106

Accounts for intensity variation:

Accounts for line broadening:


Page 79 of 86 Qualitative Analysis and Determination of Samples through
XRD

vi. Profile Fitting


 Empirically fit experimental data with a series of equations is
used.
 Methods used are:
 Single peak
 Whole pattern – Complicated if more than one phase
 Rietveld – calculated structure
 Background is typically assumed to be linear.
 Precise peak parameters like position, intensity, FWHM and
shape are obtained.

Fig. 107
 Diffraction peaks usually contain both Gaussian and Lorentzian
contributions which is difficult to deconvolve.
 Most data fitted with a profile function combining both Gaussian
and Lorentzian components: The pseudo- Voigt (linear
combination) and Pearson VIII (exponential mixing).

vii. In situ XRD- XRD conducted under non-ambient conditions such as


elevated or reduced temperatures, pressure, and vacuum or defined gas
atmosphere.
Knowledge of structure can be determined unless of the structure
changes ‘under catalytic reactions conditions’.
Page 80 of 86 Qualitative Analysis and Determination of Samples through
XRD

We can determine temperature or pressure induced phase transitions. We


can also determine solid/ gas and solid/solid reactions and formation of
reaction intermediates.

Fig. 108

Fig. 109
Page 81 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 110

Fig. 111

Fig. 112
Page 82 of 86 Qualitative Analysis and Determination of Samples through
XRD

 Time resolved measurements and reaction kinetics can also be determined.


 In the context of catalysis, in situ XRD helps with characterization of the active catalyst,
activation / deactivation behaviour of the catalyst, characterization of catalyst precursor
materials, investigation of some catalyst preparation steps (in situ calcinations) and
investigation of catalyust material reactivity (oxidation, reduction and decomposition
reactions) and cues for understanding activity/ mechanisms.

A few examples are given below:

Fig. 113

Fig. 114
Page 83 of 86 Qualitative Analysis and Determination of Samples through
XRD

Fig. 115

viii. In operand XRD- To take the full advantage of in situ investigations on


catalysts under operation conditions, the catalytic activity must be
monitored simultaneously. Hence, this method provides with a common
scale to correlate the results of different in situ methods.
ix. Catalytic reactions usually occur at the surface of a heterogeneous
catalyst and the active sites often differ from ‘average’ structure.
x. The catalytically active phase may be XRD amorphous.
Page 84 of 86 Qualitative Analysis and Determination of Samples through
XRD

APPLICATIONS

 X-ray powder diffraction is most widely used for the identification of unknown crystalline
materials (e.g. minerals, inorganic compounds). Determination of unknown solids is critical to
studies in geology, environmental science, material science, engineering and biology.
 Other applications include:

 characterization of crystalline materials

 identification of fine-grained minerals such as clays and mixed layer clays that are difficult
to determine optically

 determination of unit cell dimensions

 measurement of sample purity

 With specialized techniques, XRD can be used to:

 determine crystal structures using Rietveld refinement

 determine of modal amounts of minerals (quantitative analysis)

 characterize thin films samples by:

 determining lattice mismatch between film and substrate and to inferring stress
and strain

 determining dislocation density and quality of the film by rocking curve


measurements

 measuring super lattices in multilayered epitaxial structures

 determining the thickness, roughness and density of the film using glancing
incidence X-ray reflectivity measurements

 make textural measurements, such as the orientation of grains, in a polycrystalline sample


Page 85 of 86 Qualitative Analysis and Determination of Samples through
XRD

CONCLUSION

X-ray diffraction is an important technique that provides compositional and structural information
about unknowns. It is well suited to the analysis of small samples such as those taken from works of
art and museum objects, whether they are homogeneous or multi-layer samples prepared as cross-
sections. X-ray diffraction has proven particularly valuable in the analysis of pigments and has
helped characterize pigments that were closely related chemically.

While the emphasis is increasingly placed on non-destructive methods, that is, methods which do
not require taking samples, for the scientific examination of works of art and museum objects, X-ray
diffraction provides information that is not easily obtainable otherwise.

Advances in instrumentation have made it possible to considerably reduce the sample size and there
is no doubt that the increased access to synchrotron facilities, which is foreseeable in the future, will
make it possible to study even smaller samples.

It is also possible that XRD analysis performed directly on objects, which is presently severely
restricted by equipment geometry and dependent on objects size and shape, may become more
practicable.
Page 86 of 86 Qualitative Analysis and Determination of Samples through
XRD

References:

1. http://prism.mit.edu/xray
2. http://www.youtube.com/watch?v=-mNQW5OShMA
3. JCPDS - International Centre for Diffraction Data 2004, Advances in X-ray Analysis,
Volume 47.
4. Von JurgenBeck, Phys. Z. (1939). 40,474.
5. Reibenspies & Bhuvanesh J. Pharm. Biomed. Analysis 37(2005) 611-614
6. http://www.iucr.org/publ/50yearsofxraydiffraction/full-text/introduction
7. http://www.nist.gov/pml/div684/grp01/x-ray-polarization.cfm
8. http://www.wikiradiography.net/page/Characteristics+and+Production+of+X-rays
9. http://www.xtal.iqfr.csic.es/Cristalografia/parte_05-en.html
10. http://www-conf.slac.stanford.edu/xray_polar/X-Ray%20presentations/Fabian.pdf
11. http://www.icdd.com/resources/axa/vol47/v47_02.pdf
12. Surface Science and Methods in Catalysis, 529-0611-00, Dr. Sharon Mitchell, Prof. Javier
Pérez-Ramírez Advanced Catalysis Engineering, Institute for Chemical and Bioengineering
ETH Zürich, Switzerland
13. Hanno zur Loye, South University of Carolina

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