INTRODUCTION:

X-ray crystallography is a technique used for determining the atomic and molecular structure of
a crystal, in which the crystalline atoms cause a beam of incident X-rays to diffract into many
specific directions. By measuring the angles and intensities of these diffracted beams,
a crystallographer can produce a three-dimensional picture of the density of electrons within the
crystal. From this electron density, the mean positions of the atoms in the crystal can be
determined, as well as their chemical bonds, their crystallographic disorder, and various other
information.

Since many materials can form crystals—such as salts, metals, minerals, semiconductors, as well
as various inorganic, organic, and biological molecules—X-ray crystallography has been
fundamental in the development of many scientific fields. In its first decades of use, this method
determined the size of atoms, the lengths and types of chemical bonds, and the atomic-scale
differences among various materials, especially minerals and alloys. The method also revealed
the structure and function of many biological molecules, including vitamins,
drugs, proteins and nucleic acids such as DNA. X-ray crystallography is still the chief method
for characterizing the atomic structure of new materials and in discerning materials that appear
similar by other experiments. X-ray crystal structures can also account for
unusual electronic or elastic properties of a material, shed light on chemical interactions and
processes, or serve as the basis for designing pharmaceuticals against diseases.

X-ray crystallography is related to several other methods for determining atomic structures.
Similar diffraction patterns can be produced by scattering electrons or neutrons, which are
likewise interpreted by Fourier transformation. If single crystals of sufficient size cannot be
obtained, various other X-ray methods can be applied to obtain less detailed information; such
methods include fiber diffraction, powder diffraction and (if the sample is not crystallized) small-
angle X-ray scattering (SAXS). If the material under investigation is only available in the form
of nanocrystalline powders or suffers from poor crystallinity, the methods of electron
crystallography can be applied for determining the atomic structure.

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X-RAY CRYSTALLOGRAPHY

X-ray crystallography is a standard technique for solving crystal structures. Its basic theory was
developed soon after x-rays were first discovered more than a century ago. However, over the
years it has gone through continual development in data collection instrumentation and data
reduction methods. In recent years, the advent of synchrotron radiation sources, area detector
based data collection instruments, and high speed computers has dramatically enhanced the
efficiency of crystallographic structural determination. Today x-ray crystallography is widely
used in materials and biological research. Structures of very large biological machinery (e.g.
protein and DNA complexes, virus particles) have been solved using this method.

In x-ray crystallography, integrated intensities of the diffraction peaks are used to reconstruct the
electron density map within the unit cell in the crystal. To achieve high accuracy in the
reconstruction, which is done by Fourier transforming the diffraction intensities with appropriate
phase assignment, a high degree of completeness as well as redundancy in diffraction data is
necessary, meaning that all possible reflections are measured multiple times to reduce systematic
and statistical error. The most efficient way to do this is by using an area detector which can
collect diffraction data in a large solid angle. The use of high intensity x-ray sources, such as
synchrotron radiation, is an effective way to reduce data collection time.

One of the central difficulties in structural determination using x-ray crystallography is referred
to as the "phase problem", which arises from the fact that the diffraction data contains
information only on the amplitude but not the phase of the structure factor. Over the years many
methods have been developed to deduce the phases for reflections, including computationally
based direct methods, isomorphous replacement, and multi-wavelength anormalous diffraction
(MAD) methods.

X-ray crystallography uses the physical phenomenon of diffraction of electromagnetic radiation.

Diffraction occurs when light passes through a slit with size comparable to its wavelength. When
the light passes through the slit it is spread out. When several slits are present light from different
slits may hit the target no longer in phase. When the beams of light are in phase it causes high
intensity to be observed. When the light is out of phase by 180 degrees than the waves
destructively interfere with each other and causes no intensity to be detected. This constructive

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and destructive interference is observed when light passes through a series of slits. When this
situation occurs the pattern of differing intensities is called a diffraction pattern. This
phenomenon can be used to determine the placement of objects by determining the space in
between. Since crystals contain an ordered arrangement of atoms, a diffraction pattern can be
created. Using this diffraction pattern the arrangement of structures within the crystal can be
determined. The phenomenon is only experienced when the wavelength of the electromagnetic
radiation is comparable to the slit size. Because of this to determine the structure of molecules, in
a crystal, electromagnetic radiation with a wavelength of about 2- 20 Ð"... is used.
Electromagnetic radiation with this wavelength is in the x-ray region of the electromagnetic
spectrum.

Calculations allow the determination of the distance between the planes of a crystalline lattice.
The major equation that is used in crystallographic studies is the Bragg equation. The Bragg
equation is defined as nλ=2*d*sin θ; where n is the order of diffraction, d is the
distance between planes, λ is wavelength of the x-rays, and θ is the angle. Gathering
information at several angles and putting the information together allows the overall structure of
the crystal to be determined.

X-ray crystallography is not a product of this generation. The use of x-rays to determine a
crystalline structure was first explored by William and Lawrence Bragg in 1913. However, the
most famous use of early x-ray diffraction was the discovery of the alpha helix shape of DNA.
When x-ray crystallography was first performed the intensities of the x-rays was recorded using
photographic film. Now the use of semiconductor array detectors has made the data collection
process much faster and easier. Currently, the collection of x-ray diffraction data is much faster
because of the use of computers. To determine the structure, many data points must be collected
at many angles. Computers are also able to change the angle and store more information than in
the past.

One thing to consider when using this technique is the availability of an energy source. There are
several sources available to produce x-rays. The types of sources that are commonly used are x-
ray tubes, radioisotopes, and synchrotron radiation light sources. Several detectors are available
for use in x-ray crystallography. However, when x-ray crystallography was first used, the

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diffraction pattern was collected on film. The transition to electronic detectors allows a greater
degree of automation and speed compared to when film was used. Three types of detectors are
commonly used to detect the diffracted x-rays. These include gas filled, scintillation, and
semiconductor detectors. Most modern instruments use charge coupled device semiconductor
detectors.

X-ray crystallography experiments also have other uses than just to determine the crystalline
structure of a compound. This technique can be used on powdered crystalline samples. The
powdered crystals are packed into a capillary column or onto a flat surface. Because of the
random orientation of crystals in the powder, diffraction rings are generated instead of spots. The
position and intensity of these rings can be used to identify a crystalline compound. An example
of a powder diffraction spectrum is shown in figure one. The International centre for Diffraction
Data maintains a database with greater than 50,000 crystalline powder x-ray diffraction patterns.
Using this same concept, mixtures of crystalline powders can be identified. This does not work if
the crystals were formed in the presence of an impurity, because this impurity can change the
position and intensity of the diffraction lines.

The determination of the degree of crystallinity of a polymer is another essential use of x-ray
crystallography. The crystalline part of the polymer will create sharp peaks in intensity while the
amorphous part causes increased background because of scattering. The ratio of the peak height
to the background height is proportional to the ratio of crystalline to amorphous structures in the
polymer. To conduct this technique known standards must be used to calibrate the instrument.
Similarly, this technique can be used to determine the orientation of crystals in a polymer or
metal. If diffraction data is collected at different temperatures, phase transition studies between
amorphous and crystalline phases or different crystalline structures can be studied. Also, the
material's thermal expansion coefficient can be determined. This technique can be used to
determine the level of annealing a metal has undergone. If a metal is well annealed it will be
mostly crystalline, and therefore will have sharp diffraction lines.

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RECENTDEVELOPMENTS IN POLYMER CHARACTERIZATION

USING X-RAYDIFFRACTION

In the absence of an orientational force, the lamellae organize into spherulites (1-10 mm
indiameter). X-ray scattering can be used to ob-tain structural information at three lengthscales—
1, 10 and 100nm—using scattering atwide-, small- and ultra small-angles, respectively. A
continuum of structures between the ex-tremesof what are generally regarded as amorphous and
crystalline phases are present in areal polymer, and these entities have complex organization.
But, a model that describes these mi crystalline polymers in terms of two phases, an average
amorphous and an average crystalline phase, has been found to be adequate for many practical
purposes. The fraction of the material that is crystalline, the crystallinity or crystalline index, is
an important pa-rameter in the two-phase model. Crystallinity can be determined from a wide-
angle X-ray dif-fraction (WAXD) scan by comparing the area under the crystalline peaks to the
total scattered intensity. The accuracy and the precision of these measurements can be improved
by draw-ing a proper base-line, using an appropriate amorphous template, and by carefully
choosingthe crystalline peaks. The disorder in the crystalline domains can be evaluated by
measuring the crystallite sizes which are related to the radial widths D(2q) of the reflections at
ascattering angle 2q by the Scherrer equation. In reality, there are two contributions to the
width:one is the size and the other is the para crystallinity or microstrain.

REFERENCES

 Bijvoet JM, Burgers WG, Hägg G, eds. (1969). Early Papers on Diffraction of X-rays by
Crystals. I. Utrecht: published for the International Union of Crystallography by A.
Oosthoek's Uitgeversmaatschappij N.V.
 Bragg W L; Phillips D C & Lipson H (1992). The Development of X-ray Analysis. New
York: Dover. ISBN 0-486-67316-2.
 Ewald, PP, and numerous crystallographers, eds. (1962). Fifty Years of X-ray
Diffraction. Utrecht: published for the International Union of Crystallography by A.
Oosthoek's Uitgeversmaatschappij N.V. doi:10.1007/978-1-4615-9961-6. ISBN 978-1-
4615-9963-0.
 https://www.essays24.com/Miscellaneous/X-Ray-Crystallography/54370.html