SUBJECT FORENSIC SCIENCE

Paper No. and Title PAPER No.4: Instrumental Methods and Analysis

Module No. and Title MODULE No.21: X-Ray Methods

Module Tag FSC_P4_M21

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 TABLE OF CONTENTS

1. Learning Outcomes
2. Introduction
3. General Theory
4. Instrumentation
5. Non- Dispersive X-Ray Absorption Method
6. Applications of X-Ray Absorption methods
7. X-Ray Diffraction
8. Applications of X-Ray Diffraction
9. Fluorescence Methods
10. Applications of Fluorescence methods
11. Crystal Tonography
12. Summary

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 1. Learning Outcomes

After studying this module, you shall be able to know about-

 Different X-ray techniques such as X-ray absorption, X-ray fluorescence and

X-ray diffraction methods
 General Theory about Origin of X-rays and Interaction of X-ray with matter
 Instrumentation related to X-rays
 Applications of X-Rays
 Crystal Tonography

2. Introduction
3.
A range of X-ray techniques and methods are in use but we shall categorize all methods
into three main categories. These are X-ray absorption, X-ray fluorescence and X-ray
diffraction methods.

a) X-ray Absorption Methods- These are analogous to absorption methods in the

other regions of electromagnetic spectrum. Quantity of X-ray photons absorbed is
considered to be a measure of the concentration of the absorbing substance. X-ray
absorption methods are useful in certain cases like elemental analysis and
thickness measurements. As compared with other X-ray methods, absorption
methods are the least used.

b) X-ray Diffraction Methods- Diffraction methods are based on the dispersion of

X-rays by crystals. By means of these methods, we can identify the crystal
structures of numerous solid compounds. These methods are extremely important
as compared to X-ray absorption and X-ray fluorescence methods.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 c) X-ray Fluorescence Methods- In this method, X-rays are produced by the
fluorescent sample. By measuring the wavelength and intensity of the produced
X-rays, qualitative and quantitative analysis can be performed. X-ray fluorescence
method is non-destructive. Moreover, it requires very little sample preparation
before the analysis is to be carried out.

Each of the mentioned method is applied to different fields of analysis and depends upon
different characteristics of the radiation. For example, x-ray absorption is employed to
analyze imperfections in the inner structure of a material through which it passes; x-ray
diffraction is applied to establish crystalline structure. X-ray fluorescence is utilized for
quantitative and qualitative elemental analysis. All three techniques are non-destructive.

3. General Theory
4.
Origin of X-rays: The X-ray region of the electromagnetic spectrum consists of
wavelengths in the region of about 0.1 to 100Ao. For analytical purposes, the range of 0.7
to 2.0Ao is the most valuable region. X-rays are produced when high velocity electrons
strike a metal target. The process of producing X-rays may be visualized in terms of
Bohr’s theory of atomic structure.

An atom is made up of a nucleus and numerous electrons. The electrons are arranged in
layers or shells with the valence electrons in the outer shell. The different shells, or layers
of electrons, are called the K shell, L shell, M shell, and so on. Whenever a rapid moving
electron impinges on an atom, it may knock out an electron completely from one of the
inner shells of that atom. Following the loss of inner-shell electron, one of the outer
electrons will fall into the vacant orbital, with the instantaneous emission of an X-ray
photon. The energy of the emitted X-ray photon is equivalent to the difference in energy
between the two levels involved.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 The X-ray spectrum of a copper target consists of a few sharp and intense lines
superimposed on a polychromatic background called “white radiation”. These sharp lines
are due to emitted X-ray photon, whose wavelength is equivalent to the difference in
energy between the two levels involved and are characteristic of that material.

Interaction of X-ray with Matter: The X-rays can interact with matter in three ways:
absorption, scattering and diffraction.

a) Absorption: If a beam of X-rays is permitted to penetrate through matter, it

loses energy partly by scattering and some due to absorption. The absorption
of X-rays means that the electrons of the atoms comprising the matter absorb
energy from these rays and get excited. Then, these excited electrons emit
secondary X-rays characteristic of those atoms.

b) Scattering and diffraction: This shall be discussed in following sections.

c) Fluorescence: If a sample is irradiated with an X-ray beam, and it irradiates

X-ray beams of different wavelength, the method is termed as X-ray
fluorescence. The wavelength of the X-ray fluorescence enables us to
establish the identity of the element. The intensity of the emitted X-rays forms
the basis of quantitative analysis. This method of elemental analysis is
independent of the molecular structure of the element. The method is non-
destructive in nature and requires very little sample preparation.

4. Instrumentation

X-ray absorption X-ray diffraction and X-ray fluorescence are the three main fields of X-
ray spectroscopy. Only optical system varies in each case although components of the
equipment are the same. The main components are described as follows:

1. Production of X-ray: X-rays are produced as high velocity electrons impinge on

a metal object. Approximately, 1 per cent of the entire energy of the electron
beam is transformed into X-radiation, the remainder being dissipated as heat.
Several types of X-ray tubes are used for producing X-rays.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 Figure 1: Schematic diagram of an X-ray source

2. Collimator. The X-rays produced by the object material are randomly directed.
They form a hemisphere with the target material at the center. The X-rays
produced by the target material are then permitted to pass through a collimator
that consists of two sets of closely packed metal plates divided by a small gap.
The collimator absorbs all the X-rays except the fine beam that passes between
the gaps.

Figure 2: Collimator system for achieving a narrow beam of X-rays

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 3. Monochromator. Monochromatic beams of X-rays can be obtained by two
methods.

a) Filter: A narrow wavelength range X-ray beam is obtained by inserting a suitable

filter in the path of wide range X-rays. A filter is made of a material which
absorbs all but desired radiations. A nearly monochromatic beam of radiation is
thus available. An interesting example is the zirconium filter which is employed
for molybdenum radiation.

b) Crystal Monochromator: A crystal monochromator is positioned in the path of

X-ray beam so that the angle of the reflecting planes satisfies the Bragg’s
equation for the required wavelength. The beam is split up by the crystalline
material into the component wavelengths in the similar way as a prism splits up
the white light into a rainbow. Such a crystalline material is called an analyzing
crystal.

4. Detectors: The X-ray intensities are calculated and recorded by photographic

plate, counter methods, scintillation detector and semi-conductor detector. These
types of methods depend upon the ability of X-rays to ionize matter and vary only
in the subsequent fate of the electrons formed by the ionizing process.

a) Photographic Methods: To record the position and intensity of X-ray beams a

cylindrical film is used. The film is developed after exposing to X-rays.

b) Counter Methods: These are of following types:

(i) Geiger-Muller tube: The Geiger tube is packed with an inert gas like argon and
the central wire anode is maintained at a positive potential of 800 to 2500 V. When an
X-ray enters the Geiger tube, this ray impacts the filling gas causing it to lose an
electron. This results in the production of an ion pair and the electron produced
moves towards the central anode while the positive ion moves towards the cylindrical
outer electrode.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 The electron is hastened by the potential gradient and causes the ionization of a large
number of argon atoms, resulting in the production of an avalanche of electrons that
are travelling in the direction of the central anode. This results in an output pulse of 1
to 10V which can be determined very easily by employing a simple circuit.

Figure 3: Geiger- Muller Tube

(ii) Proportional counter: Its construction is analogous to a Geiger tube counter with
lesser potential being maintained between the electrodes. A proportional counter is
packed with a heavier gas like xenon or krypton. The heavier gas is chosen because it
is easily ionized.

c) Scintillation detector: In a scintillation detector, there is a large sodium iodide

crystal activated with a small amount of thallium. When X-ray is incident upon the
crystal, the pulses of visible light are emitted which can be detected by a
photomultiplier tube.

d) Solid state semi-conductor detector: In this detector, the electrons generated by

X-ray beam are upheld to conduction bands. The current thus generated is directly
proportional to the incident X-ray energy.

e) Semiconductor Detectors: When an X-ray falls on a semiconductor or a silicon-

lithium-drifted detector, it generates an electron (-e) and a hole (+e) in a fashion
analogous to the formation of a ion pair in a proportional counter. These detectors are
of prime importance in both X-ray work and neutron activation analysis.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 5. Non-Dispersive X-Ray Absorption Method

In this apparatus, a tungsten X-ray tube is employed as a source, which operates at 15-45
Kv. A synchronous motor-driven chopper and an attenuator are placed between source
and sample/reference compartments, which alternately interrupt one-half of the X-ray
beams. There are duplicate reference and sample cells up to 65 cm in length. If liquids or
gases are to be analyzed, there are special arrangements for continuous flow of process
streams. Both halves of X-ray beam are permitted to descend on a common phosphor-
coated photomultiplier tube which is confined from visible light by a thin metallic filter.

Applications: This method is widely used to analyze any sample that contains one
element markedly heavier than the others. However, some selected applications are as
follows:

i) It can be used to determine chlorine in hydrogen, plastics and hydrocarbons.

ii) It can be used to determine barium fluoride in carbon and barium or lead in glass.

6. Applications of X-Ray Absorption Methods

The various applications are as follows:

a) Qualitative Analysis. This is based upon the simple fact that there is a large
difference in the mass absorption coefficient of one element from another.

b) Quantitative Analysis. Amount of X-rays absorbed is directly proportional to

the concentration of the element present. This characteristic is widely used to
detect broken bones, impurities, segregations, etc.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 7. X-Ray Diffraction

X-ray diffraction is commonly used for investigating the internal structures.

Determination of crystal structure by Bragg’s law: The X-rays are permitted to fall on
the crystal surface. Then the crystal is rotated and X-rays are made to diffract from
various lattice planes. The intense reflections are measured by Bragg’s X-ray
spectrometer and the glancing angle for each intense reflection is recorded.

(i) Rotating Crystal Method: The rotating crystal method was developed by Schiebold
in 1919.

(ii) Powder Crystal Method. In the above method, a single crystal is necessary whose
size is a lot larger than microscopic dimensions. However, in the powder method, as little
as 1 mg of the powered material is sufficient for the study. The powder technique was
devised separately by Debye and Scherrer in Germany and by Hull in America at about
the same time.

8. Applications of X-Ray Diffraction

1. Structure of Crystals: The analytical applications of X-ray diffraction are

numerous. The method is non-destructive and gives information about the
molecular structure of the sample. Perhaps its most vital use is to measure the size
of crystal planes.

2. Polymer Characterization: Powder method can be used to establish the degree

of crystallinity of the polymers.

3. Annealing of metals: Well annealed metals are in ordered crystal form and give
sharp diffraction lines. If the metal is subjected to drilling, hammering, or
bending, it becomes “worked,” or “fatigued,” that is, its crystals become broken
and the x-ray pattern becomes more diffused.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 4. Particle Size Determination: A range of X-ray techniques may be used to
determine the size of particles or crystallites. Following are the methods for
particle size determination:
a) Spot counting method.
b) Broadening of diffraction lines.
c) Low-angle scattering

Applications of Diffraction Methods to Complexes:

a) Determination of Cis-Trans Isomerism.

b) Determination of Linkage Isomerism.
c) Soil classification based on crystallinity.
d) Analysis of industrial dust.
e) Assess the weathering and degradation of natural and synthetic minerals.
f) Corrosion products of metals can be studied by this method.
g) Tooth enamel and dentine have been examined by X-ray Diffraction.
h) Effects of diseases on bone structure and tissue structure.
i) Identification of crystalline compounds.

9. Fluorescence Methods

Principle: The elements of the sample get excited by absorbing primary X-rays and
discharge their own X-rays of characteristic wavelength. This procedure is called x-ray
fluorescence.

Components of the Equipment

Instrumentation: The schematic diagram for an x-ray fluorescence system is shown.

The filtered primary X-rays from the tube hit the sample and produce the fluorescence
radiation characteristic of the elements in the sample. This radiation passes through a
collimator and on to the analyzing crystal. The wavelength is determined and recorded as
the synchronized detector rotates in an arc around the analyzing crystal.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 Figure 4: Schematic diagram of an X-ray Fluorescence system

10. Applications of X-Ray Fluorescence Spectroscopy

X-ray fluorescence is a method of elemental analysis used for qualitative analysis as well
for quantitative analysis.

1. This technique is used in agriculture for the determination of trace elements in

plants and food, detection of insecticides in fruit and leaves; determination of
phosphorus in fertilizers etc.
2. It is applied for direct determination of sulphur in protein, chloride in blood
serum, strontium in blood serum and bone tissue etc.
3. It is used for the examination of ores, tailings, concentrates and drilled cores;
determination of silica in flowing slurries of ores, determination of lead in lead-tin
alloys, etc.
4. Other applications includes the determination of additives in motor oil by
determining barium, zinc, phosphorus, calcium and chloride, and the
determination of lead or sulfur in gasoline.
5. It is used in rubber industry for the determination of vulcanizing elements.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 11. Crystal Tonography

There are numerous experimental diffraction techniques developed in current years,

which help in analyzing the microscopical defects in a crystals. Most crystals are far from
perfect and exhibit regions (grains) with somewhat differing orientations, or they may
contain individual defects such as dislocations or faults dispersed throughout the crystal.
Studies of these defects are important in understanding the nature of stress in metals, the
nature and behavior of “doped” crystals used in transistors, the production of “perfect”
crystals, and other phenomena.

Micro-radiographic techniques are based on absorption and the contrast in the images is
because of the differences in absorption coefficients from point to point. X-ray diffraction
topography depends on image contrast upon point-to-point changes in the direction or the
intensity of beams diffracted by planes in the crystal.

One much used method of X-ray diffraction topography is known as the Berg-Barrett
Method. The experimental arrangement is shown. The crystal is placed so as to reflect the
X-rays at the Bragg angle for some plane. Geometric resolutions of about 1 µm can be
achieved and single dislocations can be resolved. The dissimilarity on the film is owing
to variations of the reflecting power due to imperfections in the crystal.

Figure 5: Berg- Barrett method for X-ray diffraction topography

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods
 Another method for X-ray diffraction topography is known as the Lang method. A ribbon
X-ray beam is collimated to such a small angular divergence that only the characteristic
wavelength is diffracted by the crystal. Simultaneous movement of the crystal and film
allows a large area of the crystal to be investigated.

13. Summary

 A range of X-ray techniques in use are X-ray absorption, X-ray fluorescence and
X-ray diffraction methods.
 X-ray absorption is employed to analyze imperfections in the inner structure of a
material through which it passes; x-ray diffraction is applied to establish
crystalline structure. X-ray fluorescence is utilized for quantitative and qualitative
elemental analysis. All three techniques are non-destructive.
 X-rays are produced when high velocity electrons strike a metal target. The
process of producing X-rays may be visualized in terms of Bohr’s theory of
atomic structure.
 The main components of the equipment are as follows: Production of X-rays,
collimators, Monochromator and detectors.
 Applications of X-Ray Absorption methods are the Qualitative and Quantitative
analysis also used to detect broken bones, impurities, segregations, etc.
 Applications of the X-Ray Diffraction includes analysis of industrial dust, assess
the weathering and degradation of natural and synthetic minerals, corrosion
products of metals, effects of diseases on bone structure and tissue structure,
identification of crystalline compounds, etc.
 X- ray Fluorescence have applications in agriculture for the determination of trace
elements in plants and food, detection of insecticides in fruit and leaves;
determination of phosphorus in fertilizers, etc.
 X-ray diffraction topography depends on image contrast upon point-to-point
changes in the direction or the intensity of beams diffracted by planes in the
crystal.
 Methods of X-ray diffraction topography are the Berg-Barrett Method and the
Lang method.

FORENSIC SCIENCE PAPER No.4: Instrumental Methods and Analysis

MODULE No.21: X-Ray Methods