CRYSTALLOGRAPHY
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CONTENTS:
Electromagnetic spectrum
Introduction to X rays
Discovery
Properties
Generation of X rays
Elementary crystallography
Unit cells
Lattice concepts
Miller indices
Bragg’s law
Powder diffraction
Applications
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DISCOVERY OF X-RAYS:
X-rays were first observed and documented in 1895
by Wilhelm Conrad Roentgen, a German scientist
who found them quite by accident when
experimenting with vacuum tubes.
He noticed a bright spot of light on a screen coated
with Barium pentocyanide which was placed 1 meter
away from the tube.
Then he deduced that the bright spot was not due to
cathode rays & realized that he had discovered a new
type of radiation which he named it as X rays.
He also analyzed for its properties by passing it
through several things.
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NATURE OF X-RAYS:
X-rays are electromagnetic radiation that have
wavelengths in the approximate range 0.1 Å to 100 Å
and corresponding energies in the range 120 to 0.25
KeV.
Units of X-ray wavelength is Angstroms (Å )
1 Å = 10-10m
Units of X-ray energy are electron volts (eV)
The relationship between energy (E) and wavelength ()
is:
E = hc ………...……… (1)
where:
h = Planck’s constant = 6.626 x 10-34 joules.sec-1
c = velocity of light in a vacuum = 2.998 x 108 m.sec-1
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Substituting for h and c, and expressing E in
keV (kilo electron volts) and in Å equation
(1) simplifies to:
E = 12.396 …………….. (2)
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Diagram of a water cooled X-ray tube. (simplified)
Thomas Edison
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GENERATION OF X-RAYS:
X-rays may be produced when a beam of electrons or X-ray
photons of sufficient energy interact with matter.
When electrons impinge on a target a number of possible
processes can occur:
Back scattering from the target. For high atomic number
elements (eg W) this accounts for approximately half the
incident electrons.
collisions with weakly bound valence or conduction band
electrons.
Many of these electrons are ejected from the target with
energies of < 50eV and are termed secondary electrons.
Most electrons not back scattered undergo this process.
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PRODUCTION OF X-RAYS
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In Bremsstrahlung the radiation is emitted when the
velocity of the electron shot at the tungsten changes.
This electron slows down after swinging around the
nucleus of a tungsten atom and loses energy by
radiating x-rays.
In the quantum picture, a lot of photons of different
wavelengths are produced, but none of the photons
has more energy than the electron had to begin with.
After emitting the spectrum of x-ray radiation the
original electron is slowed down or stopped.
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The incoming electron is accelerated and
strikes the tungsten at a high speed and has a
lot of energy. we call it as "braking radiation."
The electron might be slowed a little or a lot.
So the amount of "braking" determines which
wavelength of photons are emitted.
In the K-shell process, a heavy atom has lots of
electrons surrounding the nucleus in various
shells.
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When the high energy beam strikes the atom, one of
the innermost electron is knocked out.
The K-shell knock-out affects the innermost electron,
so its like having a hole in the bottom.
This "hole" causes a domino effect where the
electrons above it cascade down to fill the hole.
An x-ray photon has a lot of energy in it, and only
transitions of the inner electrons release that much
energy.
Transitions of the outer electrons, which can happen,
might be in the infrared or visible part of the
spectrum.
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Characteristic or line spectra are produced
when incident electrons or X-ray photons have
sufficient energy to remove electrons from the
inner shell of an atom.
The X-ray photons that result when outer
electrons fall into the vacancy have an energy
that is characteristic of a particular element.
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E Initial
EK
Vacant state
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Starting from the K shell the binding energy
decreases (ie binding energy K>L>M>N). Each shell
is defined by a set of quantum numbers (n,l and m).
K radiation - occurs when a vacancy is formed in the
K shell of an atom. All the transitions correspond to
electrons dropping into the K shell (n=1) from higher
quantum states (n=2, 3, …).
L radiation - occurs when a vacancy is formed in the
L shell of an atom. X-rays are produced from
transitions of electrons from n=3,4,…. to the L shell
(n=2).
M radiation - occurs when a vacancy is formed in the
M shell (n=3) and arises from electronic transitions
from n=4, 5, … down to n=3.
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X-ray Line Spectra K Series
Transitions in
X-ray Targets
Ka2 Ka1 Kb3 Kb1 Kb2 Kb5
K
I
L II
III
I
II
M III
IV
V
N V
VII
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For low atomic number elements only K
radiation is generated.
L and M radiation is only generated from
higher atomic number elements.Generally the
higher the atomic number the higher the energy
of the X-ray.
For a given element EK > EL > EM
The number of possible X-ray emission lines
increases with increasing atomic number (Z).
This can be explained by mosley’s law, which
says more the atomic number more intense
radiations are produced.
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When a vacancy is created in the K or L shell,
the atom can revert to its ground state in one of
two ways:
emission of an X-ray photon.
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Elementary crystallography
Types of crystals:-
Primitive unit cell (p)
Body Centered (I)
Face Centered (F)
End Centered (C)
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Primitive unit cell:
• The unit cell has the same type of atoms only
at the corners represented by symbol “p”.
• Otherwise the cell is called as non-primitive or
centered.
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Three types of Non –primitive cells :
a)Body centered (I) - corners and centre of
cell have same type of atoms.
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b)Face centered (F) -corners and the centres of
each of the 6 faces occupied by same type of
atoms .
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c) End centered or Base centred (c) corners of
the cell and intersection of face diagonals of
two opposite faces are occupied by the same
type of atoms.
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Lattice concepts:
Space Lattice -- atoms arranged in a pattern that
repeats itself in three dimensions.
Unit cell -- smallest grouping which can be
translated in three dimensions to recreate the
space lattice.
A crystal system is a category of space groups,
which characterize symmetry of structures in
three dimensions with translational symmetry in
three directions, having a discrete class of point
groups.
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A major application is in crystallography, to
categorize crystals.
Unit Cell Dimensions
- a, b and c are the unit cell edge lengths
- α, β and γ are the angles (a between b and c,
etc....)
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A UNIT CELL
b
γ
c
β
α
a
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CRYSTAL SYSTEMS
TETRAGONAL
CUBIC
RHOMBOHEDRAL
HEXAGONAL
ORTHORHOMBIC
MONOCLINIC
TRICLINIC
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The Bravais lattices
When the crystal systems are combined with the
various possible lattice centerings, we arrive at
the Bravais lattices.
They describe the geometric arrangement of the
lattice points, and thereby the translational
symmetry of the crystal.
In three dimensions, there are 14 unique Bravais
lattices which are distinct from one another in
the translational symmetry they contain.
All crystalline materials recognized until now
(not including quasicrystals) fit in one of these
arrangements.
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The fourteen three-dimensional lattices, classified by
crystal system, are shown to the right. The Bravais
lattices are sometimes referred to as space lattices.
The crystal structure consists of the same group of
atoms, the basis, positioned around each and every
lattice point.
This group of atoms therefore repeats indefinitely in
three dimensions according to the arrangement of one
of the 14 Bravais lattices.
The characteristic rotation and mirror symmetries of
the group of atoms, or unit cell, is described by its
crystallographic point group.
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The various parameters in seven basic crystal
systems are as follows:-
Sl. System Intercepts Crystal Angles Examples
No
1 Cubic a=b=c a=β =γ= 90° NaCl, Gold
Diamond
2 Tetragonal a=b=c a=β =γ= 90° SnO2, Sn
3 Orthorhombic a=b=c a=β =γ= 90° I2, KNO3
Monoclinic 3 2 13
Orthorhombic 3 4 59
Tetragonal 7 2 68
Rhombohedral
5 1 25
(Trigonal)
Hexagonal 7 1 27
Cubic 5 3 36
Total 32 14 230 34
MILLER INDICES: (CRYSTAL PLANE)
The lattice points forming a particular space –
lattice may be thought of occupying various
sets of parallel planes as illustrated in
following figure with reference to the axis of
the “unit cell”, each set of planes has a
particular orientation.
Often in dealing with crystalline solids we
have to specify this orientation w.r.t. the axis.
To do so we employ the so – called Miller
indices.
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The Miller indices of a face of a crystal are
inversely proportional to the intercepts of the
face on the various axis.
To determine Miller indices when face
intercepts are given, we have to consider the
law of a rational indices.
Miller indices are a notation system in
crystallography for planes and directions in
crystal lattices.
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LAW OF RATIONAL INDICES:
The intercepts of any face of a crystal along
the crystallographic axes are either equal to the
unit intercepts [a, b, c] or some simple whole
no. multiples [1,2,3,….etc.] of them.
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Let, OX ,OY,OZ be 3 crystallographic axis.
ABC-unit plane. The unit intercepts will be
OA=a unit intercept along X-axis
OB=b unit intercept along Y-axis
OC=c unit intercept along Z -axis
Then according to the above law, the intercept of any
face such as k, l, m, on the same 3 axis will be
multiples of a, b, c.
If OL=2a ,OM=2b , OK=3c, thus OL, OM, OK make
2, 2, 3, unit intercepts along the co-ordinate axes
respectively.
The reciprocals of these intercepts 1/2, 1/2, 1/3 in the
ratio 3, 3, 2 are known as “Miller Indices”
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PROCEDURE FOR FINDING MILLER
INDICES
To find out Miller indices of a plane we proceed as
follows:
1) We determine the intercepts of a plane with three
co-ordinate along the axes X, Y, Z in terms of a, b, c.
2) We take the reciprocals of these intercepts in order
3)We then find the least common denominator (l c d)
and multiply each by l c d.
Thus multiplying all reciprocals of intercepts by the
same number does not alter the orientation of the
plane
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Example: If we calculate MI of crystal planes having
intercepts 4, 1 and 2 on the three axes i.e [4a, 1b, 2c]
a b c
4 1 2
1/4 1/1 1/2 {Reciprocal is
taken and multiplied by l c d i.e 4}
We get 1, 4, 2.
Hence the MI of the plane is [142]
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Bragg’s law
When an X-ray beam strikes a crystal surface at
some angle, a portion is scattered by the layer of
atoms at the surface.
The un-scattered portion of the beam penetrates to
the second layer of atoms where again a fraction is
scattered and the remainder passes on to the third
layer.
The cumulative effect of this scattering from the
regularly spaced centers of the crystal is called
diffraction of the beam.
The requirement for x-ray diffraction are:-
AP = PC = d sin θ
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n is an integer determined by the order given,
λ is the wavelength of x-rays
d is the interplaner distance of the crystal.
θ is the angle between the incident ray and the
scattering planes
Thus, we may write that the conditions for
constructive interference of the beam at angle θ are
n λ = 2d sin θ
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Note that x-rays appear to be reflected
from the crystal only if the angle of
incidence satisfies the condition that
sinθ = n λ / 2d
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X-RAY DIFFRACTION METHODS
A - source of x-rays.
B - pinhole collimator.
C - crystal
D - film arranged on a rigid base.
When the x-ray beam is passed along the axis of symmetry of
the crystal, the Laue pattern would contain a series of “spot” .
This method is used in determination of the symmetry of
single crystals
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BACK – REFLECTION METHOD:
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The Braggs x-ray spectrometer method-
According to Laue , if a beam of x-ray is passed
through a crystal, the emitted x-rays by crystal, are
obtained on the photographic plate in the form of
pattern known as Laues photographs .
Using the photographs, Braggs analyzed the structure
of crystals of NaCl, KCl and ZnS.
Braggs devised a spectrometer to measure the
intensity of x-ray beam. The equation is as follows:
nλ = 2d sinθ
Where n is the integer , λ is the wavelength of x-ray
beam ,d is the distance between the crystal planes , θ
is the angle of incidence of x-ray beam.
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The various components of Braggs x-ray
spectrometer are as follows-
X-ray source
cathode A
slits B and B1
crystal C
vernier V
circular scale S.
Slit F
Ionization chamber E
Aluminum window W
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One plate of ionization chamber is connected to the
positive terminal of a H,T battery while the negative
terminal of H.T battery is connected quadrant
electrometer Q, which measures the strength of
ionization chamber.
The deflection in the electrometer is a measure of
ionization and consequently gives the intensity of
reflected X-ray i.e the strength of ionization current is
proportional to the intensity of the entering reflecting
x-rays.
In order to increase the ionization, the chamber is
sometimes filled with sulphur dioxide or methyl
iodide.
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WORKING-
In Braggs spectrometer the crystal is mounted in
such a position that θ = 0 degree and the ionization
chamber is adjusted to receive to the x-rays.
The crystals and the ionization chamber is made to
move in small steps so that the angle through which
the crystal is rotated.
The ionization at first falls, as θ increases but for
certain value of θ it rises sharply.
This corresponds to the direction of the x-ray
spectrum.
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ROTATING CRYSTAL METHOD-
a) The x-rays are generated in the x-ray tube
and then the beam is made monochromatic by
the filter.
b) From the filter the beam is allowed to pass
through collimating system which permits a
fine pencil of parallel x-rays.
c) From collimator, the x-ray beam is made to
fall on a crystal mounted on a shaft which can
be rotated at uniform angular rate by a small
motor.
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d) Now the shaft is moved to put the crystal
into slow rotation about a fixed axis. This
causes the sets of planes coming successively
in their reflecting positions i.e the value of θ
satisfies the Bragg’s law.
Each plate will produce a spot on a
photographic plate perpendicular to the x-ray
beam or upon a film in a cylindrical camera,
the axis of which coincides with the axis of
rotation of the crystal
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POWDER CRYSTAL METHOD:-
In this method little sample of 1 mg is required
as compared to other methods which requires
large sample.
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If r is film If θ is the angle of incidence, the angle of
reflection will be 2θ.
radius, the circumference 2πr corresponds to a
scattering angle of 360 degree.
Then we can :
1/ 2πr = 2θ
360
θ = 360 x 1/ πr
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Applications Powder crystal method has the
following applications;
1. The method is most useful for cubic crystals
2. This method is used for determining the
complex structures of metals and alloys.
3. Useful to make distinction between the
allotropic modification of the same substance.
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POWDER DIFFRACTOMETER :
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A flat specimen is mounted on a turn table around
which moves a detector.
The detector is connected to the specimen table and
geared in such a way that when the table rotates
through θ degree, the detector rotates through 2 θ
degree.
This results in the detector always being in the correct
position to receive the reflected rays.
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The resulting chart is a record of counts per standard
time versus. As the detector moves through each
degree (or half), a pulse is sent to a second pen.
Thus the scale and the diffraction pattern are recorded
at the same time.
The x-rays reaching the detector are registered and
displayed on a paper chart recorder as a series of
peaks on top of background due to white radiation.
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SAMPLE PREPARATION-
Grind powder finely in an agate mortar prior to
specimen preparation.
If there is sufficient sample, then powder can be
pressed into a disc or plate using a hydraulic press.
Or pack the powder in to the window of an
Aluminum holder backed by a glass slide.
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INSTRUMENTATION-
X-RAY TUBE –
X-rays are generated when the high velocity
electrons falls on a metal target, approximately
1 % of the total energy of the electron beam is
converted into x-radiation , the remainder
being dispersed as heat.
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MONOCHROMATORS-
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Crystal monochromators are of two types-
1)Flat crystal monochromators- A monocrystal
with one face cut parallel to a major of crystal planes
is often used in Bragg’s reflecting to obtain a
monochromatic x-ray beam.
2)Curved crystal monochromators- The crystals
used in monochromators are made up of materials
like sodium chloride, lithium fluoride and quartz.
They have high intensity compare to plane crystal
monochromators and focusing properties provide
high resolving power.
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DETECTORS-
Photographic film detector- In order to record the
position and intensity of x-ray beam, a plane or
cylindrical film is used.
1)Single –emulsion film-Here the AgBr in
photographic emulsion is coated on a supporting
material.
The emulsion layer is about 15 mm thick with a
protective gelatin layer, about 1 mm thick coated over
it.
2) Double–coated film-In this detector above coating
is done for two sides of the thin supporting material.
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Advantage- film require short exposure
Disadvantage- An x-ray beam incident on the
film produces a more intense blackening in the
first layer than in the second.
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PROPORTIONAL COUNTER
DETECTOR-
Its construction is similar to the Geiger tube
counter. A proportional counter is filled with
heavier gas like xenon or krypton.
The proportional counter is dependent upon
the intensity of x-rays falling on a proportional
counter.
The sensitivity and efficiency is same as that
of Geiger tube counter.
Disadvantage-complex and expensive.
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Geiger-MULLER TUBE COUNTER
DETECTOR-
This detector is filled with argon gas
Advantage - Inexpensive and trouble free
Disadvantage - Low efficiency
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SCINTILLATION COUNTER DETECTOR-
In the scintillation detector there is a large
sodium iodide crystal activated with a small
amount of thallium .
When the x-ray is incident on the crystal, the
pulses of a visible light are emitted which can
be measured by photomultiplier tube.
The scintillation detector is particularly useful
for measuring x-rays of short wavelengths.
Crystals used in scintillation detectors include
sodium iodide, anthracene, napthalene and p-
terphenol in xylene.
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SOLID STATE SEMI-CONDUCTOR DETECTOR-
In this type of the detector the electrons produced by
the x-ray beam are promoted into conduction bands
and the current which flows is directly proportional to
the incident x-ray energy.
Most of the semi-conductor detector consists of a thin
layer of n-type material on the surface of a large piece
of p-type material.
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MEDICINAL USES
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In some cases, the use of X-rays is debatable, such as
gallstones (which are rarely radiopaque) or kidney
stones (which are often visible, but not always).
Also, traditional plain X-rays pose very little use in
the imaging of soft tissues such as the brain or
muscle. Imaging alternatives for soft tissues are
computed axial tomography (CAT or CT scanning),
magnetic resonance imaging (MRI) or ultrasound.
Since 2005, X-rays are listed as a carcinogen by the
U.S. government.
Radiotherapy, a curative medical intervention, now
used almost exclusively for cancer, employs higher
energies of radiation.
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X-rays are relatively safe for investigation and
the radiation exposure is low.
But in pregnant patients, the benefits of the
investigation (x-ray) should be balanced with
the potential hazards to the unborn fetus.
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X-rays have been developed for their use in
medical imaging. Radiology is a specialized
field of medicine.
Radiologists employ radiography and other
techniques for diagnostic imaging.
This is probably the most common use of X-
ray technology.
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X-rays are also used in "real-time" procedures
such as angiography or contrast studies of the
hollow organs (e.g. barium enema of the small
or large intestine) using fluoroscopy acquired
using an X-ray image intensifier. Angioplasty,
medical interventions of the arterial system,
rely heavily on X-ray-sensitive contrast to
identify potentially treatable lesions.
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Each dot, called a reflection, in this diffraction
pattern forms from the constructive
interference of scattered X-rays passing
through a crystal.
The data can be used to determine the
crystalline structure.
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APPLICATIONS:
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Applications
Structure of crystals. The method is nondestructive
and gives information on the molecular structure of
the.
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