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x-rays diffraction

1- INTRODUCTION
X-rays were discovered in 1895 by the German physicist Rntgen and were so
named because their nature was unknown at the time. Unlike ordinary light,
these rays were invisible, but they traveled in straight lines and affected
photographic film in the same way as light. On the other hand, they were much
more penetrating than light and could easily pass through the human body,
wood, quite thick pieces of metal, and other opaque objects.
It is not always necessary to understand a thing in order to use it, and x-rays
were almost immediately put to use by physicians and, somewhat later, by
engineers, who wished to study the internal structure of opaque objects. By
placing a source of x-rays on one side of the object and photographic film on
the other, a shadow picture, or radiograph, could be made, the less dense
portions of the object allowing a greater proportion of the x-radiation to pass
through than the more dense. In this way the point of fracture in a broken bone
or the position of a crack in a metal casting could be located. [1]
2- properties
X-rays have a wavelength ranging from 0.01 to 10 nanometers,
corresponding to frequencies in the range (31016 Hz to 31019 Hz) and
energies in the range 100 eV to 100 keV.
X-rays propagate at the velocity of light (c = 3 X 108 m/s), without
transference of mass, in straight lines undeflected by electric or magnetic
. fields.
x-rays are invisible and otherwise undetected by human senses.[2]
3-advantage
Nondestructive, fast, and easy sample preparation
_ High-accuracy for d-spacing calculations
_ Can be done in situ
_ Allows characterizing single crystal, polycrystal
_ Standards are available for thousands of material systems[
, low maintenance cost,
proper automation, easy data interpretation that could be used for both
qualitative and quantitative analysis, in wide range of applications.[3]
4 disadvantage
X-rays may cause ionization in gases, liquids, and solids, thereby
altering their electrical properties
.X-rays may cause permanent physical damage (radiation
damage)cracks, fissures, voids, scaling, etc.-in solids;
X-rays may kill, damage, and/or cause genetic change in biological
tissue-the basis of the x-ray health hazard.[4]
5-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[5]
6-Analytical Limitations of XRD
-Amorphous materials cannot be identified by XRD, so many
polymeric and glassy materials cannot be studied. XRD is not a trace
analysis technique.
Mixtures may be difficult to identify because of overlapping peaks
Requires tenths of a gram of material which must be ground into a
powder[3]
7-X-Ray Source and production
Three common methods of generating X-rays for analytical use in the
laboratory are:
1. Use of a beam of high-energy electrons to produce a broad band continuum
of X-radiation resulting from their deceleration upon impact with a metal target
as well as element-specific X-ray line radiation by ejecting inner core electrons
from the target metal atoms. This is the basis of the X-ray tube, the most
common source used in XRD and XRF.
2. Use of an X-ray beam of sufficient energy (the primary beam) to eject inner
core electrons from a sample to produce a secondary X-ray beam (XRF).
3. Use of a radioactive isotope which emits very high energy X-rays (also
called gamma radiation) in its decay process.[6]

7-1)Production of X-rays(x-ray tube)


any x-ray tube must contain (a) a source of electrons, (b) a high accelerating
voltage, and (c) a metal target When a high voltage with several tens of kV is
applied between two electrodes, the high-speed electrons with sufficient kinetic
energy, drawn out from the cathode, collide with the anode (metallic target). The
electrons rapidly slow down and lose kinetic energy.fig (1) show the x-ray tube.
Since the slowing down patterns (method of loosing kinetic energy) vary with
electrons, continuous X-rays with various wavelengths are generated. When an
electron loses all its energy in a single collision, the generated X-ray has the
maximum energy (or the shortest wavelength SWL). The value of the shortest
wavelength limit can be estimated from the accelerating voltage V between
electrodes.
eV =h max (1)

SWL = = (2)

Fig(1) cross section of x-ray tube

The total X-ray intensity released in a fixed time interval is equivalent to the area
under the curve in Fig. (2). It is related to the atomic number of the anode target
Z and the tube current i :
Icont = AiZV 2 (3)
where A is a constant. For obtaining high intensity of white X-rays, (3) suggests
that it is better to use tungsten or gold with atomic number Z at the target,
increase accelerating voltage V , and draw larger current i as it corresponds to
the number of electrons that collide with the target in unit time. It may be noted
that most of the kinetic energy of the electrons striking the anode (target metal)
is converted into heat and less than 1%is transformed into X-rays. If the electron
has sufficient kinetic energy to eject an inner-shell electron, and hat will produce
x-ray characteristic spectrum. for example, a K shell electron, the atom will
become excited with a hole in the electron shell. When such hole is filled by an
outer shell electron, the atom regains its stable state. This process also includes
production of an X-ray photon with energy equal to the difference in the electron
energy levels.[7]
Figure 2 X-ray spectrum
of molybdenum as a function
of applied voltage
(schematic). Line widths
not to scale

6-diffraction and bragg law


Diffraction arises from constructive interference of unmodified coherently
scattered x-rays. . A crystal may be defined as a solid in which the atoms or
molecules are closely packed in layers in a pattern having three-dimensional
periodicity. In Figure (3), x-ray beam of wavelength is directed at angle e (theta)
on a set of crystal planes having interplanar spacing d. A portion of the x-
radiation arriving at each plane is scattered in all directions. In most directions,
the scattered rays are out of phase and undergo destructive interference.
However, in certain directions, they may be in phase and mutually reinforce.
This phenomenon is diffraction, and a group of such reinforced rays in one
direction is a diffracted x-ray beam. The conditions for diffraction are: (I) the
angles made by the diffracting planes with the incident and diffracted beams
are equal; (2) the directions of the incident and diffracted beams and the normal
to the diffracting plane are coplanar; and (3) reflected rays from successive
planes differ in path length by an integral number of wavelengths. In Figure (4),
rays I and 2 are directed 'on two successive planes and scatter in all directions.
Of the scattered rays, only I- and 2- fill the conditions for diffraction. Rays I and
2 travel equal distances to AC, and rays I- and 2- travel equal distances beyond
AD. The path difference between rays 1A1' and 2B2' is then
CBD = CB + BD = 2AB sin = 2d sin
If these rays are to be in phase, this path difference must be an integral number
of wavelengths, that is,
n = 2dsin
This is the Bragg law, where n is the order of diffracted beam and is numerically
equal to the path difference, in wavelengths, for successive planes; d is the
interplanar spacing of the diffracting planes (A); and (, the Bragg angle, is the
angle between the incident x-rays and the diffracting planes. X-ray
spectrometers are usually calibrated in terms of 2 , the angle between the
diffracted beam and the undeflected incident beam [3].
The geometry of an X-ray diffractometer is such that the sample rotates in the
path of the collimated X-ray beam at an angle while the X-ray detector is
mounted on an arm to collect the diffracted X-rays and rotates at an angle of 2
. the figure (4) show the XRD diffractometer. The instrument used to maintain
the angle and rotate the sample is termed a goniometer. For typical powder
patterns, data is collected at 2 from ~5 to 70, angles that are preset in the
X-ray scan.
FIGURE (3). Diffraction by crystals, the Bragg law,
showing origin of Orders 2,3, and 4.

Fig(4) show the XRD diffractometer


reference

[1] B.D. Cullity, S.R. Stock-Elements of X-Ray Diffraction-Pearson Education


Limited (2014)
[2]-Eugene P. Bertin (auth.)-Introduction to X-Ray Spectrometric Analysis-
Springer US (1978)
[3]Ashish Chauhan1* and Priyanka Chauhan.Powder XRD Technique and its
Applications in Science and Technology. Chauhan and Chauhan, J Anal
Bioanal Tech 2014, 5:5
[4]ANDREI A. BUNACIU1, ELENA GABRIELA UDRISTIOIU2, and HASSAN
Y. ABOUL-ENEIN3X-Ray Diffraction: Instrumentation and Applications
[5] Barbara L Dutrow, Christine M. Clark, X-ray Powder Diffraction (XRD)
[6] James W. Robinson, Eileen M. Skelly Frame, George M. Frame II.
UNDERGRADUATE INSTRUMENTAL ANALYSIS Sixth EditionISBN 0-
203-99730-1 Master e-book ISBN
[7] Yoshio Waseda , Eiichiro Matsubara, Kozo Shinoda- subara
X-Ray Diffraction Crystallography Introduction, Examples and Solved Problems
Springer-Verlag Berlin Heidelberg (2011)