CHAPTER -3

METHODOLOGY

1. Petrography

Petrographic study is needed to examine the mineral content and the textural relationships within
the rock.The detailed analysis of minerals by optical mineralogy in thin section and the micro-
texture and structure are critical to understanding the origin of the rock. A petrographic thin
section is a 0.03mm thick slice of rock mounted on a glass slide. This slide is studied under
transmitted polarized light.

1.1 Sample preparation

First step involves cutting of sample using rock cutting machine to get a fresh part with flat
surface. It is followed by removal of roughness of the rock fragment by grounding them with
220,400, 800, 1000, grit carborundum powder and then with chromium oxide. Then polished
surface is glued to a glass slide with araldite and let it free for 8 hours to get cured. Then the
mounted specimen is cut using thin section preparation machine. After this the section is again
polish with different meshes of carborundum powder till the thickness become 0.03mm.

2. X-ray Fluorescence Spectrometer (XRF)

XRF is an analytical way to determine the chemical composition of all kinds of

material. It consists of a source which is an X-ray tube. The tube irradiates a sample and the
radiation coming from the sample is detected. The elements present in the sample will emit
fluorescent X-ray radiation with discrete energies that are characteristics of these elements.
These X-rays coming from the sample is detected by a detection system. In WDXRF, the
detection system is a set of collimators, a diffraction crystal and a detector. The X-ray coming
from the sample fall on the crystal and the crystal diffracts the X-ray with different wavelength
in different direction. By placing the detector at a certain angle, the intensity of the X-ray with a
certain wavelength can be measured.

Fig: Schematic diagram for Wavelength Dispersive spectrometer

In the Quantitative Analysis, the net intensities are converted into concentrations. The
usual procedure is to calibrate the spectrometer by measuring one or more reference materials.
The calibration determines the relationship between the concentration of elements and the
intensity of the fluorescent lines of those elements. Unknown concentration can be determined
one the relationship is known. The intensities of the elements with unknown concentrations are
measured, with the corresponding concentration being determined from the calibration.

2.1 X-ray Fluorescence theory

An electron can be ejected from its atomic orbital by the absorption of a light wave
(photon) of sufficient energy. The energy of the photon (hv) must be greater than the energy with
which the electron is bound to the nucleus of the atom. When an inner orbital electron is ejected
from an atom, an electron from a higher energy level orbital will be transferred to the lower
energy level orbital. During this transition a photon maybe emitted from the atom. This
fluorescent light is called the characteristic X-ray of the element. The energy of the emitted
photon will be equal to the difference in energies between the two orbital occupied by the
electron making the transition. Because the energy difference between two specific orbital shells,
in a given element, is always the same (i.e. characteristic of a particular element), the photon
emitted when an electron moves between these two levels, will always have the same energy.
Therefore, by determining the energy (wavelength) of the X-ray light (photon) emitted by a
particular element, it is possible to determine the identity of that element.

Fig X-ray fluorescence principle

For a particular energy (wavelength) of fluorescent light emitted by an element, the

number of photons per unit time (generally referred to as peak intensity or count rate) is related
to the amount of that analyze in the sample. The counting rates for all detectable elements within
a sample are usually calculated by counting, for a set amount of time, the number of photons that
are detected for the various analyses’ characteristic X-ray energy lines. It is important to note
that these fluorescent lines are actually observed as peaks with a semi-Gaussian distribution
because of the imperfect resolution of modern detector technology. Therefore, by determining
the energy of the X-ray peaks in a sample’s spectrum, and by calculating the count rate of the
various elemental peaks, it is possible to qualitatively establish the elemental composition of the
samples and to quantitatively measure the concentration of these elements

2.2 Sample preparation

Sample: Sample is the one which represent the whole outcrop by its chemistry, texture etc. For
XRF analysis sample should be

1) Homogenous
 2) As fine as possible
3) Representative of the outcrop
4) No surface irregularities.
Sample collection can be done by either a) Grab (random) sampling method or b) channel
sampling method. Quarter and coning method is done on each step of sampling to maintain
homogeneity and to avoid particle size effect.

The different processes in XRF sample preparation are Crushing, Grinding and
Pelletization.

Crushing and grinding are doing for grain size reduction of the sample.

1. Crushing:

The reduction in size of the sample was attained by using steel mortar. This steel mortar
should be clean and dry before using for crushing.

2. Grinding:

This can be achieved by using 1.Ball mill and 2.Cup mill

Ball mill was used to attain fine powder of the sample. Here at a time we used 30 gms of
sample after coning and quartering. The ball mill having 2 big balls, 6 medium sized balls and 32
small sized balls are used in ball mills. Homogenization is also more in this case. In cup mill we
have used 20 gm of sample at a time. This grinded sample is used for pellet preparation.

3. Pellet preparation:

Pellet preparation is done by using instruments known as Pelletizer. For making pellet
we have to take 3 gm of sample and mix that with one gram of boric acid, which act as a binding
material. The diameter of the pellet is 34 mm and boric acid is using as a backing material. The
sample is being uniformly sprinkled over the backing material inside the dye. Then apply 20 tons
of pressure using semi hydraulic automatic press for one minute. These are called as pressed
powder pellets. Boric acid is used as backing material because it is non hygroscopic, highly
compactable and cannot be analysed by XRF. These pressed powder pellets are used for XRF
analysis. Still there are some unsolved problems in pellet making process. The binding material
used for pellet is not adhesive to our samples. We have tried different ratios of sample and
binding material as 3:1, 4:2; 1:4, but in all the pellets sample powder is not sticking to binding
material. So we have prepared fusion bead.

3.X-RAY DIFFRACTOMETER (XRD)

Size and composition are the most fundamental attributes of sediments. Although
optical microscopy can be used to readily identify sand and coarse silt-sized crystalline material,
X-ray powder diffraction is the most common technique used to study the characteristics of
crystalline structure and to determine the mineralogy of finer grained sediments, especially clays.
As a method, X-ray diffractometry is attractive because of its speed and ease of performance,
and because it requires only small amounts of material, is nondestructive, and can be used to
perform semi-quantitative analyses of polymineralic mixtures.

The principles of diffractometry and descriptions of clay mineralogy condensed in

this report have very much important They are provided here solely to broaden the perspective
and understanding . Furthermore, only some of the preparatory and interpretive methods
presented

X-rays are electromagnetic radiation similar to light, but with a much shorter wavelength.
They are produced when electrically charged particles of sufficient energy are decelerated. In an
X-ray tube, the high voltage maintained across the electrodes draws electrons toward a metal
target (the anode). X-rays are produced at the point of impact, and radiate in all directions. Tubes
with copper targets, which produce their strongest characteristic radiation (K 1) at a wavelength
of about 1.5 angstroms, are
Commonly used for geological applications.

If an incident X-ray beam encounters a crystal lattice, general scattering occurs. Although
most scattering interferes with itself and is eliminated (destructive interference), diffraction
occurs when scattering in a certain direction is in phase with scattered rays from other atomic
planes. Under this condition the reflections combine to form newenhanced wave fronts that
mutually reinforce each other (constructive interference). The relation by which diffraction
occurs is known as the Bragg law or equation. Because each
crystalline material has a characteristic atomic structure, it will
diffract X-rays in a unique characteristic pattern.

The basic geometry of an X-ray diffractometer involves a source

of monochromatic radiation and an X-ray detector situated on
the circumference of a graduated circle centered on the powder
specimen. Divergent slits, located between the X-ray source and
the specimen, and divergent slits, located between the specimen and the detector, limit scattered
(non-diffracted) radiation, reduce background noise, and collimate the radiation. The detector
and specimen holder are mechanically coupled with a goniometer so that a rotation of the
detector through 2x degrees occurs in conjunction with the rotation of the specimen through x
degrees.
A curved-crystal monochromatic containing a graphite crystal is normally used to ensure that the
detected radiation is monochromatic. When positioned properly just in front of the detector, only
theK radiation is directed into the detector, and the Kß radiation, because it is diffracted at a
slightly different angle, is directed away. The signals from the detector are filtered by pulse-
height analysis, scaled to measurable proportions, and sent to a linear rate meter for conversion
into a continuous current.