SD9700016

X-RA Y DIFFRACTION ANALYSES OF CLAY STONES,

MUGLAD SEDIMENTARY BASIN .
SUDAN

A THESIS SUBMITTED IN PARTIAL

FULFILLMENT FOR THE DEGREE
OF MASTER OF SCIENCE IN
PHYSICS

BY
AMMAR ELSIDDIG ALI

DEPARTMENT OF PHYSICS
FACULTY OF SCIENCE
UNIVERSITY OF KHARTOUM

JANUARY 1997

-06
 We regret that
some of the pages
in this report may
not be up to the
proper legibility
standards, even
though the best
possible copy was
used for scanning
 ACKNOWLEDGMENT

Iwish to express may gratitude and indebtedness to my former supervisor

V

Dr. Osman Dawi Eisa for the insight he gave to me into my research and
laboratory work.
My gratitude is also due to Dr. Osman M. Abdullatif who carefully
supervised this work in the stage of writing; Mr. Hassan H. Elhussein for helping
me to master the XRD system and accessories; Dr. M. H. Shaddad for his help in
maintaining the lab printer and in changing the analyses program; Mr. Ali
Elssaied for his help in sample preparation; Mrs. Sadia Elsier for helping me
typing the thesis in the computer; Finally and before all my gratitude is due to my
family for the healthy atmosphere ana encouragement that they gifted to me.
 ABSTRACT

This study deals with the theoretical and experimental aspects of X-

ray diffraction (XRD) technique. Moreover, the XRD technique has been
used to investigate the clay mineral types and their distribution for samples
obtained from exploration wells in the Muglad sedimentary basin in
western Sudan. The studied samples range in depth from 1524m to
4572m.

The XRD analysis of samples shows that they consist of kaolinite,

smectite, illite, chlorite and the mixed - layer smectite / illite. Kaolinite has
higher abundance (15 - 72%) followed by illite (7 - 34%), smectite ( 1 1 -
76%) and the less abundance of chlorite and the mixed - layer smectite /
illife. Non-clay minerals found include quartz and cristabolite.

The clay mineral types and their vertical distribution reflect various
controls such as environmental, burial diagenesis, source rocks and
climatic influences in the Muglad sedimentary basin.
 4\\\ ...H V A>

JJJJ J j

.Ufti

J dulV Ao

j j j jSJLS Lxiikll j j t
 List of tables & Figs.

Page no.
Fig. II-1 Aunit cell 4
Fig. II-2 Aplane specified by the Miller indices 6
Fig. II-3 Diffraction of x-rays by a crystal 8
Fig. II-4 Coherent scattering of x-rays by asingle electron 11
Fig. III-l X-ray tube 15
Fig. III-2 The generation of x-rays of a line spectrum of copper due to the
transfer of electrons into the K shell 18
Fig III-3 Geoniometer 20
Fig. III-4 DACO-MP program 23
Fig. IV-1 Structure of clay minerals 30
Fig IV-2 Change of clay minerals with increasing depth of burial 31
Fig. IV-3 Vertical distribution of clay minerals 32
Table IV-1 Summary of behaviours of the clay minerals towards
identification treatments 33
Table IV-2 Clay mineral types percentages in sample measured 34
XRD charts 35
 CONTENTS
Page no.
Acknovvlegment i
Abstract ii
List of tables and figures iv

CHAPTER-I Introduction
Objective and scope 1
Methods 2

CHAPTER -II Theoretical background

II-O Crystal and crystal lattice 3
II-1 Crystal system 3
II-3 Miller indicies 3
II-4 X-ray diffraction 7
II-4-1 Introduction 7
II-4-2 Bragg low 7
II-4-3 DifFractiondirection 9
II-4-4 Scattering of x-rays by an electron 10
II-4-5 scattering of x-rays by atom 12
II-4-6 Scattering by a unit cell :.;13
II-4-7 Temperature factor 13
CHAPTER -III Experimental techniqes and data processing

Page no.

III-1 Introduction 14

III-2 Production of x-rays 14

III-3 The x-ray generator 16
111-4 The x-ray tube 17
III-5 The cooling system .':• 17
III-6 Monochromotization '. 17
III-7 The goniometer , 19
III-8 The detector 19
III-9 The DACO-MP 21
111-10 Sample preparation and separtion ,22
III-l 1 Data collection...., .7. 22
111-12 Data processing :..". 24

CHAPTER-IV Results,interpretations and conclusions

IV-1 Introduction 26
IV-2 Nature and crystal structure of clays 26
IV-3 Methods of interpretation 27
IV-4 XRD results 27
IV-5 Interpretation, discussion and conclusion 28

References 52
 CHAPTER(I)
INTRODUCTION

After the discovery of X- rays in 1895 it was realized that many of their
properties could be explained if they were subjected to electromagnetic
radiation with a wave-length much shorter than for ordinary light.
Van lane in 1912 discovered that crystals act as a diffraction gratings for
X-rays. Many experiments followed. For example, the experiment done by
Frederick and Knipping [Thewlis et al., 1962] lead to the use of X-ray
diffraction as a mean of studying the regular arrangement of atom and
molecules in crystals.
Since then X-ray diffraction (XRD) technique has proved to be a good
tool for investigating the fine structure of matter. At first (XRD) was used only
for the determination of crystal structure. Later on, other uses where developed,
and today the method is applied not only to structure determination, but to
such diverse problems as chemical analysis, stress measurement, the study of
phase equilibria, the measurement of particle size, the determination of the
orientation of crystal or the ensemble of orientation on polycrystalline
aggregate [Cullity 1978]
Methods or techniques of (XRD) were improved with time. Now it has the
advantage, with modern instrumentation, and complete automation, fast and
precise results are obtained. The theoretical and practical aspects of XRD, the
application and interpretation aspects and clay mineral identification and
quantification, all have been comprehensively treated in the literature
(Zussman, 1977; Tucker, 1988; Carol, 1970;Thorez, 1975).
In the mineralogical analysis of rocks (XRD) is a basic tool, and in the
case of fine grained sediments (clays) it is an essential one [Tucker 1991]. Clay
minerals are the most abundant minerals at the surface of the earth . This is
illustrated by the fact that they are, with quartz, the main constituents of
mudrocks which constitute between 45% to 75% of the total volume of
sediments [Tucker, 1991]. mud rocks can be deposited in different environments
such as river floodplains, lakes, deltas and deep sea. The data collected from
clay minerals is useful in understanding the geological processes
,environmental and climatic conditions as well as the control of successive
internal and surficial geodynamical factors (Tucker, 1991,Chamley,1989).
Objective and Scope :-
In this project the technique of (XRD) is used to investigate the clay
minerals of some collected subsurface clayston samples from Abu Gabra and
Sharaf formations in the Muglad sedimentary Basin in western Sudan. The
results of the samples analyses were analyzed to see the effect of vanes_ V
controlling factors on clay mineral types and their distribution .
Methods :
The samples investigated range in depth from 1524 to 4572m. These
samples represent sediments deposited mainly within lacustrine environments.
After sample preparation and separation, oriented mounts of the < 2 micron j>i
clay fraction were prepared.Then XRD analyses were measured by Siemens
diffractometer with its DACO-MP which uses a program called Analyses.
These analyses were carried out under normal (dry), ethylene glycol and
heating treatments. Then the clay minerals were identified and determined
qualitatively and semi-quantitatively according to change of basal spacing
under the three treatments and reJt.tive peak hights.
The thesis is written in four chapters, chapter (I) is the introduction,
chaptcr(II) is the theoretical background, chapter(III) is the experimental
technique and finally the results, discussion and conclusion are presented in
chapter (IV).
 Chapter (II)
THEORETICAL BACKGROUND

(II-O) INTRODUCTION :
This chapter deals with some concepts of solid state physics and the
intensity of diffraction and the factors which affecting this intensity.

(III) CRYSTAL AND CRYSTAL LATTICE :

A crystal is defined as "a solid composed of atoms arranged in a pattern
periodic in three dimensions'Mf one considers any point within the crystal,
then there are other points within the crystal that are in the same
conditions.The arrangement of these points constitute a crystal lattice.
The crystal is usually defined by three translation vectors a,b and c along
the three axis incline^to each other at angles a , P , y. The smallest unit of \
volume of the lattice with side equal to a, b and c is called a unit cell which
when repeated gives the crystal lattice [fig(II.l)].

(II-2) CRYSTAL SYSTEM:

When there are lattice points only at each corner of the unit cell, the unit
cell contains one basic unit of structure, which if repeated will build up the
crystal. Such a unit cell is called a primitive cell with symbol P.
Some unit cells contain more than one unit of structure and they are
referred to as non primitive (Cullity, 1978).
There are fourteen primitive and non primitive lattices, they are called
Bravias lattices. [Cullity 1978].
 *»* b

F
»g. H-l A unit cell
(II-3) MILLER INDICES :
The Miller indicics are defined as the reciprocals of fractional intercepts
which the plane makes with the crystallographic axis .If the Miller indices of
plane are (hkl) then [(hkl)]arQ the indices of the direction of the line passing
through the plane. The plane makes fraction intercepts 1/fi, 1/k ,1/1, with the
axis, and , if the axial lengths are a, b, c, the plane makes actual intercepts of
a/h , b/k , c/l, [fig(II.2)j. Parallel to any plane in any lattice, there is a whole
set of parallel equidistant planes, one of which passes through the origin. If a
plane is parallel to a given axis, its fractional intercept on that axis is infinity
and corresponding Miller index is zero .If the plane cuts a negative axis, the
corresponding index is negative and is written with a bar over it. Planes whose
indices are the negative of one another are parallel and lie on opposite sides of
the origin , e.g. ( 2 1 0 ) and ( 2 7 0).
The interplanear spacing dm > measured at right angles to the planes, is a
function of both the plane indices (hkl) and the lattice constants (a,b,c,a,P, y).
The exact relation depends on the crystal system involved and for the cubic
system forixample [Cullity, 1978]

dvM (cubic) =

for tetragonal
a
t {tetragonal) =-
>•*•!. '
Fig. 11-2 A plane specified by the Miller indices (hkl)
(II-4) X-RAY DIFFRACTION :
(II-4-1) INTRODUCTION :
A crystal is composed of regularly spaced atoms which act as scattering
centres of X-rays and since X-rays are of wave-length equal to.or close to the
interatomic distance in crystal , then diffraction of X-rays takes place by
crystal. This was in fact demonstrated by Van laue in 1912.
The diffracted beam may be defined as a beam composed of a large
number of scattered rays mutually reinforcing one another. The atoms of a
crystal scatter incident X-rays in all direction, but. some of these scattered
beams will be completely in phase and so reinforce each other to form
diffracted beams.

(II-4-2) BRAGG LAW:

Consider rays 1 and l a [fig (113)] striking the atoms K and P in the first
plane of the atom and scattered in direction 1 and l a . The difference in their
path length between the wave front XX and YY is equal to
QK-PR = PKcos8 - PK cos6 = 0

Also rays 1 and 2 scattered by atoms K & Land the path difference for
the rays lKl'and2L2 is

ML + LN -d sinO + d sine

If the scattered rays 1 and 2 are in phase and there' path difference is
equal to a whole number n of wave-length \, then

nX = 2d sin0
c-

Fig 11-3 Diffraction of X-ray by a crystal

 Where

X = wave-length.
d ~ spacing between planes .
9 = the angle between the incident beam and reflecting beam

This above relation is known as Bragg law, n is called the order of

reflection it takes integral values .For fixed values of X and d , there may be
several angles of incidence 9i, 62; O3, at which diffraction may occur,
corresponding to n = 1, 2, 3,
The form of Bragg law normally used is
K = 2dsin8
where d = ( d /n )

(II-4-3) DIFFRACTION DIRECTIONS :

Various diffraction angles can be obtained from the (100) planes and
produce first, second, third, order reflections.Also diffraction can be
produced by the (110) planes, the (111) planes, the (213) planes and so on. A
general relation which will predict the diffraction angle for any set of planes
can be obtained by combining Bragg equation (X = 2^sin6), and the
interplaner spacing d(wu> > for the cubic system.
Thus

4a1

This equation predicts, for cubic cell, all the possible Bragg angles at
which diffraction can occur from the planes (Jikl).
 (II-4-4) Scattering of X-rays by an electron :
The intensity of the scattered beam depend on the angle of scattering. The
intensity / of the beam scattered by single electron of charge e coulombs and
mass m Kg , at distance r meter from the electron, is given by

"Un

Where /„ is the intensity of the incident beam, ji o = 47rxlO"7mKc"2, K =

constant and a is the angle between the scattering direction and the direction of
the acceleration of the electron (Cullity 1978).If the incident beam is traveling in
the direction OX encounters an electron at O (fig II.4),then this will have an
electric vector E,which may be resolved into plane-polarized components Eyand

The Ey of the incident beam accelerates the electron in the direction OY. It
therefore gives rise to a scattered beam whose intensity at P is found to be

Since a = 7i/2, the intensity of the Z-component is given by

1 .

\
I
% io
Fig 11-4 Coherent scattering of x-rays by a single electron

II
 The total intensity nt P is givsn by

_/,,A"f 1 +cos 2 26

The quantity -(l + cos2 20) is known as the polarization factor.

(11-4 -5) SCATTERING BY AN ATOM :

The efficiency of scattering X-rays by a given atom in a given direction is
described by a quantity/called the atomic scattering factor, which is a ratio of
amplitudes

s=A-

Where Aa is the amplitude of the wave scattered by an atom and Ae is the

amplitude of the wave scattered by one electron. Since the intensity of the
scattered wave is proportional to the square of the amplitude then we have

Where /() and Ie is the intensity of the rays scattered by the atom and
electron respectively.

12
(11-4-6) SCATTERING BY A UNIT CELL :
Since the scattering from an atom depend'on the distribution of its electrons
and the scattering from a unit cell depend on the atomic arrangements, the most
important factor in the study of scattering by a unit cell is the structure factor
.This is defined as the ratio of the amplitude of the wave scattered by all atoms
in the cell to the amplitude of the wave scattered by one electron and is denoted
by i F {hkl) I

\F(hkf)\ =[(FcQsa)2+(Fs\na)2}>

Where a is the angle of the composite wave due to all kinds of atoms.

(II-4-7)TEMPERATURE FACTOR
Since / is the atomic scattering factor of an atom undergoing thermal
vibration, / , is the factor for an atom at rest then

/ = /(,exp[-B(sin0)2/^2]

Where B is called the temperature factor and depends on the type of the
atom and the orientation of the reflecting planes in the crystal ,6 is the Bragg
angle and X is the wavelength [Cullity 1978].

13
 Chapter (III)
EXPERIMENTAL TECHNIQUE
AND DATA PROCESSING

(III-l) INTRODUCTION :
This chapter describes how a Siemens diflxactometer, a DACO-MP and
an X-ray generator with its cooling system can be used to measure the
dilli actograms of the samples. The procedures of samples preparation and
separation shall also be presented.

(111-2) PRODUCTION OF X-RAYS :

X-rays are produced whenever high-speed electrons collide with a metal
target. The main constituents of the X-ray tube are source of electrons
(filament), a high accelerating voltage and a metal target. Because most of the
kinetic energy of the electrons is converted into heat in the target, the later is
almost always water cooled to prevent its melting. The tube used is a filament
tube consisting of an evacuated glass envelope which insulates the anode at one
end and the cathode at the other end ,[fig (IH-l)], the cathode being a tungsten
filament and the anode a cooled block of a desired target metal as small insert
at one end. One lead of the high voltage transformer is connected to the
filament and the other to the ground, the target being grounded by its own
cooling water connection. The filament is heated by a current of about 3 Amp
and it emits electrons which are rapidly drawn to the target by the high voltage
across the tube. Surrounding the filament is a~small metal cup maintained at
the same high (negative) voltage as the filament, it therefore repels the
electrons and tends to focus them into a narrow region of target called

14
 t

Fig.III-l Cross-section of sealed-of filament x-ray tube

15
focus them into a narrow region of target called the focal spot. X-rays are
emitted from the focal spot in all directions and escape from the tube through
beryllium windows.
The radiation escaping from beryllium windows consist of:
(
(I) Brcmestrahlung radiation which is abroad band of continuos radiation
produced by the electrons from the filament converting their kinetic energy into
X-rays when colliding with the atoms of the target.
(II) Characteristic radiations, which are number of discrete lines of varying
intensity representing the energy released by rearrangement of the orbital
electrons of the atoms of the target following the ejection of one or more
electrons during the excitation process. These lines are known as K, L,
M lines, the type of the line produced is determined by the orbital electrons
taking part in the arrangement [fig. (III.2)]

(IH-3) THE X-RAY GENERATOR :

The generator is a Siemens-K710 generator? Jt^supplies the X-ray tube s\
with negative polarity high voltage from 20 KV to 50 KV and a current of 5
mAmp to 40 mAmp.
It can function with any X-ray tube requiring a negative high voltage and
with a nominally rated filament between 5 V and 12 V. The generator has many
built-in protection circuits to monitor filament over or under current, X-ray tube
over voltage and over current.
Cooling water monitor for the protection of the X-ray tube, along with
many built-in temperature and circuit parameters monitor for the protection of
the generator.The generator water flow monitor is a factory set up to audibly
• warn and then shut the generator when the cooling water flow drops below 4
liters/min. for 10 seconds. The generator has a digital display for indicating tube
high voltage, tube anode current, tube filament current.
16
(III-4) THE X-RAY III BE :
The X-ray tube used in the system is FK 60 Cu anode type with the
following specifications Kx wave length of 0.1542 NM, excitation voltage of 9.0
KV, Ni Kp filter, operating voltage 25 KV- 45 KV (Siemens D500 / 501
diffractometcr manual, 1985)

(IH-5) THE COOLING SYSTEM :

The cooling system unit CKULVER is delivered with all componejTj^of the
cooling circuit such as circulating, pump, vaporization cooler, temperature
controller, temperature monitor, storage tank, safety valve for maximum
pressure limiting and connecting leads readily installed in such away that keeps 'S
and maintains the X-ray generator from over heating.

(1II-6) MONOCHROMOTIZATION :
A monochromatic beam of X-rays is desirable for certain diffraction
studies, when the sample is a powder one. The reason for this is that the Kp
component of the beam is sufficiently intense to produce its own diffraction
pattern. When this is superimposed on the Ka pattern, the difficulty of
interpreting the diffraction effects is materially increased.
The absorption effect offers means of moving the unwanted radiation to
leave a beam that is essentially monochromatic. The Nickel element (Ni) has an
absorption edge of I 49A°, which is intermediate between the wave length of
CuK«(1.5412A°) and Cu Kp(l .3922A°) radiation. This element is, therefore,
relatively transparent to the a-radiation and absorbs the P components of X-ray
beam and it can also reduce the intensity of the continuos spectrum. In this work
ci Ni filter with a Cu radiation is used.

17
 Kai

M shell

L
///// ^'ii;ii "VV$S

Ka,
Characteristic line spectrui
from Cu

Continuous spectrum

1
Wavelength X (A)
Maximum electron energy Kp 1.3922
Ka, 1.5405
Ko2 1.5408
IV

Electrons

Fii».lll-2 I lie generation of X-rays of a line spcotmm of copper due to tho transfer of

electrons into the K shell.

IR
(II1-7) THE GONIOMETER :
The D500 Siemens goniometer is constructed according to the Bragg-
Brentano para-focusing condition. The three components of primary interest
[fig(111.3)] are the anode of X-ray tube (B) emitting X-rays/ radiation, the >(
specimen carrier (P) in which r.he sample! be measured is placed and the y(
deiector (D) to pick up X-rays emanating from the sample.
In usual operation as a powder diffractometer, the X-ray hitting on the
sample diffract off the crystalline structure of the sample and cause peak
intensities to be recorded by the detector at the Bragg angle.
The goniometer is automatically controlled by DACO-MP which will be X
j ' \
described later.

(III-8) THE DETECTOR:

The detector used is a scintillation detector with a Nal(Tl) crystal 25 mm
diameter, approximately .1 mm thick .has a Beryllium window ,0.2mm thick,
a positive operating voltage of 1200 to 1300V, a maximum permissible voltage
of 1600V and a dead time < 10"6 second [Siemens D500/501 diffractometer
manual, 1985 ] .
Most of the X-ray quanta imping, on the scintillation crystal, are observed
by the crystal. The light flashes formed in the crystal cause a number of
electrons to be released from the directly coupled cathode of the multiplier .
The number of these electrons is greatly increased by multiplication at the
dynodes. The current pulse occurring at the anode when a quantum is
measured is ted, after amplification, by a charge sensitive pre-amplifier to the
compact measuring channel.

19
 /
' 1)1. 1
180" I

B Focus of the x-ray lube 3 Glancing angle

Bl.I,Il,]II Aperture diaphragms1 2S Diffraction angle
BI.IV Detector diaphragm cp Aperture angle
D Detector M Measuring circle
Kfl K/J filler F Focusing circle
I
P Specimen

Fig. 111-3 Focusing geometry of the diffractometer in case of 20/0 operation.

20
 (IH-9) T H E DACO-IYU':
• The DACO-MP is a micro-computer with standard controller interfaced to
: the Siemens D500 diffractometer. It has 32 Kbytes ROM and 23 kbytes of
; RAM. ll controls the diflractomctcr and the ditector while measuring. The
DACO-MP is connected to a printer which gives the out-put as a graph of
y intensity of diffracted rays versus 20 where 0 is the glancing angle and the
i corresponding d- spacing value.
•.*

t The DACO-MP firmware is logically made up of seven tasks that may

I potentially run in parallel :
1) The sequence of analytical program stored in a memory.
:, 2) The completion of time consuming commands.
f; 3) The initialization routings for commands from Ihe computer.
4) The computer input processor task.
5) The error message output task .
% 6) The display up data task .
% 7) The local terminal input processor and command initialization task.

; jjg Ihese tasks are controlled by the type of command used for performing
certian work. Bach command is associated with fixed flag sets, one for the par
command and the other for the command of one or more explicit arguments .
There are four buffers in the DACO-MP user RAM :
1) instruction buffer ( 1-buffer) .
2) Data buffer ( D-bulTer) .
3) Register buffer ( Regs ).
4) Secondary memory
[DACO- MP USER'S Reference m a n u a l ^ . I , V2.2 ,1985]
 (III-IO)SAMPLE PREPARATION AND SEPARATION:
The following/ procedure was used to separate the clay fractions (< 2 k
micron) needed tor XRD analyses :
a) About 10 gin of broken sample was dispersed in distilled water and then
disaggregated in a porcelain mortar.
b) Disaggregation was done gently and carefully without any grinding.
c) Hard samples were, further, disaggregated in the shaker and the
ultrasonic.
d) After the sample was disaggregated and brought into suspension, the
clay fraction (< 2micron ) was separated by the centrifuge at 2000 rotations per
min. for two minutes.
e) the clay fraction was filtered out from suspension by sucking filter, and
i

allowed to dry in the oven at 50 °C.

g) from the dry clay fraction oriented mounts were prepared on glass slides
for XRD analyses.

(III-ll) DATA COLLECTION :

The data collection was carried out using a program called Analyses. Fig.
(III.4 ) is a flow chart of that program.
The out put of the program is a graph of position (measured in
degrees)versus intensity ( measured in counts per seconds) with the d-spacing
measured in A°.
The XRD analyses were carried out for all samples under the following
treatments :-
1) Normal samples ( air-dried ).
2) Ethylene glycolated sample for 24 hours.
3) Heating to 550 °C for 4 hours.
 = Initialize
s Memory Partition
SA = Start Angle
EA = End Angle
SS = Step Size
CT 2 Counting Time
Y XS = X-Scale
I/P Y-S 3 Y-Scale
SA,EA.SS.CT SR s Sample Reference
X-S.Y-S PT • Peak Table
PS s Peak Search
PW = Peak Width
CD H Check Data
XO s Extended Operation
SM s Smoothing
PS = Background Subtraction
KS = K a o Stripping

OPEN
WINDOW
"DATA ARE

SMOOTHED

ONLY"
Y

I/P
PW / " DATA ARE
Y / SMOOTHED AND
"I BACKGROUND
/ SUBTRACTED"
Y N

i/P
TITLE f DATA ARE SMOOTHED,
Y /AND BACKGROUND
SUBTRACTED AND Ka
RUNOVER STRIPPED"
SHUT WINDOW;
('"SORRY NO
ANALYSIS
RL:ADY 'WERE MADE"/
FORXO

C END J

111-4 DACO-MP analysis program flow chart.

 In all treatments the scanning parameters are the same except for the starting
angle of the glycolated one where the 20 = 2 is used because the glycolation
shifts the d-spacing to lower position.
The imput parameters Cor scanning arc :
1) A title.
2) Starting angle 5°.
3) End angle 35°.
4) Step size 0.05.
5) Counting time 2 seconds.
6) Peak width 0.14.
7)X-sca!e 2° per cm.
8) Y-scale 100 counts per seconds.

(IH-12) DATA PROCESSING

1) Peak Search
DACO-MP detects the peaks of the intensity curve and the important
parameter for detecting a peak is the peak width ( Pkw). The peak width is
defined as the length of the interval placed symmetrically around each point in
order to compute its polynomial . The ( Pkw) value is given in degrees.
The peaks to be recognized should match the following condition (Getting
started with DACO-MP V2.1, V2.2, 1985)
1/2 ( FWHM) < Pkw < 2 ( FWHM )
Where FWHM is the chord of the peak at the relative intercept level The
number of points placed symmetrically around each data point is the integer
closest to ( Pkw / Slcp size ) . This integer is bounded to lie between 1 and
m
15. In some extreme situations, the adaptation of peak width will not be
possible because of the inadequacy of the step size.
2)The Kxrended Openi lions
The extended operations are, the curve smoothing, background subtraction

and K r i stripping. These operations are done to obtain good results and

analyses.
The argument called (Smol) is the interval for the curve smoothing
operation. The number of points placed symmetrically around each data point is
the integer closed to ( Smol.'Stepsize) .This integer is boundejjl'to lie between 1 •*,.
and 1 5. For each data point, a third degree approximation of the diffractogram is
derived from these points, and the point under consideration is replaced by the
coefficient of power 0 of the computed polynomia.(Getting started with
DACO-MP V2.1, V2.2, 1985)
The second argument As' called ( Pkg2 ) is used to adjust the background V
subtraction algorithm. Let Y(20) be the equation of the convex, linear by parts,
envelope of the diffractogram, the continuous background B(2B) is then
estimated to be
Yl
0(20) = Y(20) - Bkg2. [Y(20)]
The third argument called (Smo2) is the interval used to control the Kn 2
stripping algorithm . This algorithm is/work^
is [works' (or a third degree least square
approximation polynomia computed on a fraction of the diffractogram. The
length of this fraction is derived from (Smo2) as done with ( P k w ) and ( Smol )
for the peak search and for the curve smoothing. The K a 2 stripping algorithm is
derived from the Rachinger method (Getting started with DACO-MP
V2.1,V2.2, 1985)
In this work the smoothing and the background subtraction are used since
the information gain is enough for the determination of the samples components.
 CHAPTER IV
RESULTS, INTERPRETATIONS AND CONCLUSIONS

IV.1 Introduction :
This chapter presents the the results of clay minerals analyses of samples
investigated. Moreover, the clays were identified qualitatively and semi-
quantilatively. It also discusses the various factors controlling the clay mineral
types and their distributions.

* IV.2 Nature and crystal structure of clays :

Clay minerals are described as a hydrous aluminum silicates with a sheet
I or layered structurejthey are pivyilosilicates. The sheets of a clay mineral are of X,
two basic types. One is a layer of silicon-oxygen tetrahedral with three of
oxygen atoms in each tetrahedron shared with adjacent tetrahedron and linked
together to form a hexagonal network (fig. I V.I.a). The second type of layer
consists of aluminum in octahedral coordination with O"2 and OH"1 ions.
There are two basic groups of cirys, Kandite group and smectite group.
Kandite group have two layered structure consisting of silica tetrahedral sheet
linked to an alumina octahedral sheet by common O/OH ions (fig. IV. 1 .a). No
change in Kandite structure or transformation. Smectite group have a three
layered structure in which an aluminum octahedral layer is sandwiched
between two layers of silica tetrahedral (fig. IV. 1). The typical basal spacing is
14 A0 but smectites have the ability to adsorb water molecules and this changes
the basic spacing, it may vary from 9.6 to 21.4 A0 (Tucker 1992).
The common member of Kandite group is Kaolinite (K), its d-spacing is 7
A0. Other ciay minerals with three layered structure are Illite(I) and
Chlorite(C). Smectite have d-spacing of 14 A0, illite 10 A0 and chlorite with d-
spacing of 14 A0. Th'iie are mixed layer, clays between illite and smectite.
 7 *
(C),-Smectite have d-sn.ae'ing of 14 A^ittile 10 A0 and''chl«jrite>ntlf d-spacing y-y
f 14 ^,-There are nfixed kiyerj^tfys between iJJrfe and smectite.

(VI-3) Method Of Interpretation : \

To identify the clay minerals we have three runs (discussed in Ch.III) , the \
normal, glycolated and heated. The four principal clay minerals gives/certain d- X .]
spacing in the nonnal run. Kaolinite ha.c d-spacing 7A°, illite 10A°, smectite 12-
15 A0, chlorite 14 A0 and mixed layer between smectite / illite has intermediate
of high values of d-spacing (Tucker 1992). Because smectite and chlorite have
the same range of spacing we look in the glycolated run to distinguish between
them, smectite expands to d-spacing of about 17 A0 but chlorite remains as it is.
To give further distinction we must look at the heated run,we see that smectite f
collapses to 10A° and kaolinite is destroyedJTable IV. 1 shows the d-spacing of
any clay in different runs. (Thorez 1976).
The clay minerals types were identified qualitatively and semi
quantitatively according to Thorez(1976).
The percentages of the clay minerals were calculated from the length of
the peaks. The sum of the peak lengths of the clays is 100% , except the length
of Kaolinite which is divided by three and then added to the others, this because
Kaolinite grows rapidly three times faster than the other clay minerals (Thorez
1976).

( IV. 4) XRD Results :

Table IV.2 gives the depth of each sample and the percentage of the four
principal clays and mixed layer Sm/l for all samples. The starjiboye the peak A
means that the beak cannot seen clearly by the defector. Fig. IV.3 gives the / \
vertical distribution of clay minerals. Figs. 4 to 19 are the charts of the measured
samples. N, G and H refer to normal, glycolated and heated one respectively .
27
(IV. 5) Interpretation , Discussion and conclusion :
If we divide the samples into zones according to their depth , upper from
1524 to 2743 m. middle 2743 to 3353 m and lower 3353 to 4572 m, its clear
I*?
that from table IV. 1 the main clay in the samples is Kaolinite. Smectite is more /)/
abundant in the upper zone and it decreases in the middle and lower ones. Illite
percentage is lower in the upper zone, increases at the middle and the lower
one. In all zones there is a mixed-layer of smectite/illite. Chlorite increases in
the middle and lower zones but it decreases in the upper one.
The origin of clay minerals is attributed to three processes (a) inheritance
from detrital source, (b) neoformation (c) transformation by burial diageneses
(Tucker, 1992). Therefore, clay minerals may indicate environmental,
diagenetic, source rock and climatic influences (Chamley, 1989).
The vertical changes in clay mineralogy in the Muglad basin with the
increase in depth most probably reflects the effect of buriaf diagenesis. which
takes place principally through the rise in temperature accompanying increased
depth of burial (Chamley 1989). That is the main change is an alteration of
smectite to illite and chlorite via mixed-layer clays of smectite-illite and
smectite-chlorite (figs. IV.2, IV.3). This change usually occurs around 2-3km
between 70- 95 °C. The above depth and temperature conditions are provided
in the Muglad basin (fig.IV.3, fig. IV.2). The higher percentage of illite and
chlorite in the lower zones indicates the effect of burial diagenesis
(Tucker, 1992). Ramseyer and Boles (1986) reviewed the importance of the
various controlling factors on smectite transformation during burial, such as
temperature, potassium availability, inhibtor ions, permeability, smectite
composition and the residence time. Other studies, however, have indicated
that temperature is one of the principal factors in the transformation of smectite
during burial diagenesis (Hower et al., 1976; Burtner and Warner. 1986).

28
 The depth of burial of the sediments studied is more than 4500 m which is
quite sufficient to allow deep diagenetic processes to operate under the given
depth (4500m) and average geothermal gradient of 30 °C/km. Large part of the
sediments section must have been subjected to temperature greater than 100
°C (Fig.IV-3). Such burial diagenetic influences have been reported from the
Muglad basin (Abdullatif and Barazi, 1993).
Moreover, the high kaolinite abundance indicates the predominance
pedogenic processes over direct-rock weathering. This should testify to intense
chemical weathering and leaching under rather warm humid climate that
prevailed in the Muglad basin during most of the Cretaceous time. It is most
probably that the large proportion of the kaolinite encountered could have been
inherited through detrital from source rocks which subjected to intense
weathering. The high content of smeotite in the upper sediment section may
reflect dryer climatic intervals, limited hydrolysis and leaching (Chamley,
1989). Similar situation applies to the limited content o*fillite and chlorite.
Furthermore, this interpretation cannot exclude folly the partial formation of
some of the clay minerals encountered through neogenesis or neoformations,
since the physio-chemical and environmental conditions were favourable
(Chamley, 1989).
 ( ) anif ;."• ' O^O"1" Honn " amf • Silicon alolnj O Aluminnin.

8 0. kanlimla AljOj 2S.0, ?H?0 illila KAIjtOlM, lAlgijlO. 0 M | , 0 |

nlimiiM.i i
mtlKhliilinn nl Si Uy
Al in silica Inycrit

OM K"
inlC'lAyer K' tr>pnlliRr
w.lh some OM . re and Mg
li.is.il f.p.Tci'M) 7A
K'
basnl tpacing 10 A

basic loirnul.v 7AljO, 8ScD, 711,0 nil,O K" K' ~f»/Mg

oniM |M(j. CtlU AI,O, !>r,.O, «H,

cliloiit*

much Mjfi'hl'itinii of Sul»<ti(u(ion of A| Uy ft

M by Mq AIM! f r
H,0 M,0 b'ur.itc Uyei$ (Mg OM)
hnlvvflftu Al -Si shfiftti

tuil r>n.iiid^blt from basat tp^dng.14 A

9 G 10 21 1 A

Fig. IV-l Diagrams illustratiitg the structures of clay minerals

30
 Imrtnl ilhlo

bmi.il

yslalliniiyl

scrccife mulchloiiln

Fig. IV-2 Diagram ilhi.strating the changes of clay minerals with increasing
depth of burial and into mctamorphism
 Clay mineral %
10 20 30 IQ 50 60 70 frp 9Q 100
50°C o o * ^ 0 0
o o o o ©
po o

1&28 Jp:V oo
O ° o O O
c? o 0 o u o °
°
°
o _
O OO.

90°C
2134

2638 .;..;;.;;>.»:.VoVi-v:-4.

2 743 ^ . ^ ^ J f T ^

S 30A8
1 13(fC
3353 '

I
JC
CL

o
3658

3962

150°C
I
4262

4572

K I OO
Off Sm -Sm/I SC
Fig. IV-3 vertical distribution of clay minerals
3.:
 Table IV-1
Summary of behaviours of the clay minerals towards identification
treatments

d spacing in A
SYMBOL 7 B 9 10 11 ' 13 13 M 15 1« 1?

Kaolin ile K N
EG
N
EG
500

Swelling Chloiile Cg N EG
500
III,io N
EG
500
Smeclilcs 500 EG
(Monlmo'illoniles)

Vflfiniculile 500 IM
EG
PAL N
EG
500

Sopiolile SEP 500 N

EG

Values ol lite bnsnl r^ll^clmn in cl(A). lor the current clay minerals, after Ihe classical idenliliolion essays (N •• nulural.
unlreslcn1 sample ; EG - elliylone glycol ; 500 - hnnling lo 500"C).

33
*4 Table (IV.2) Clay mineral types percentages in samples measured .

No Depth in Smectite lllite % Knolinite Chlorite Smectite/

meters % % % lllite %

1 1603 76.5 7.65 15.8 — —

2 2243 — 27.9 23.1 — 48.91

3 2344 11.55 11.55 53.8 23.1 —

4 2499 — 23.1 ... 46.1 — 30.0

5 2646 35.5 13.47 50.2 — —

6 2682 — 23.1 34.6 23.1 19.2

7 2890 28.57 21.4 50.0 — —

'-A

8 3030 — 24.4 43.1 32.5 —

9 3167 25.0 16.6 33.3 25.0

10 3386 37.51 26.79 24.97 • 10.71 ---

11 3790 — 11.1 22.2 33.3 33.3

12 4252 21.5 32.25 35.48 10.75 —

13 4590 — 27.3 72.7 —

34
 no-:.

+ -•;' • • : • •-

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: 15 ^ i ^
» it tM t\

3.9141 28.

- 32 3.5731 2167.

35 3.2397. 832.

S i, 1 ; I

y -4^*|!pp?j?'v;-tX-

Fig.VI-4 sample no.l-N

35
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Fig.IV-5 sample no.l-G

36
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Fig.VI-6 sample no.l-H

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38
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Fig.lV-8 sample no,2-G

39

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SUH )?-A'JG-55 1 4 : 5 3 : 5 ? . •
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M. time: 2.000, S'.ep =iie: 0.050 [SSi
Start at 2Theta 2.000 Theta 1.000
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0. 200. 400. 600. 800. 1000. 1200. 1400.

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Fig.IV-10 sample no.3-N

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43

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Fig.IV-15 sample tao.8 -H

46
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48
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49
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50
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 REFRENCES

1- Abdullati£ O. M. and Barazi, N. (1993). Sedimentalogy and maturity

evaluation of the NW Muglad and Nile Rift basins, Sudan. In Thorweihe
and Schandelmeier(eds.). Geoscientific Research in NE Africa. Balkema.
395-399.

2- Alexander O.E Animalu (1977), Intermediate Quantum theory of

crystalline solids. Prentice - Hall, Jndia^ 11 ^ 5 | ^ | ^ ^ v.^ ^ ^ , «**-

3- Burtner, R. and Warner, M.A. (1986).Relationship between

illite/smectite diagenesis and hydrocarbon generation in lower t? - ,-
Cretaceous Mo wry and Skull Creek shalesi of tKe^ofthen Rock *
Mountain area. Clays and clay minerals, v34, No.4, p.390-402.

4- Carol, D. (1970). Clay Minerals: Aguide to their x-ray identification.

Geological Society of America, special paper 126.

5- Chamley, H. (1989) Clay sedimentoiogy, Springer - Verlag, Berlin

623 p p .

6- Cullity B.D, (1978), Elements of X-ray Diffraction, second edition,

Addison - Wesley Publishing Compciny .

7- DACO - MP User's V2.1 , V2.2 manual (1985). •

8- DACO - MP Getting start manual V2.1 , V2.2 manual (1985).

9- Diffrac -AT V3.1 Start up manual (1992).

10-Hower, J., Elsinger, E.V., Hower, M.E. and Perry, E.A.(1976) . Mech
a- -nism of burial metamorphism of argillaceous sediments: 1,
mineralogical and chemical evidence, Geological Society of America
Bull., V.89, p.725-737.

11-Idris, Hassan H. (1994). X-ray diffraction studies of clays and

minerals Msc. Thesis, Dcpt. of Physics, U. of K.
12- Klug, H. And Alexander, L. E., (1974), X-Ray diffraction procedures
for polycrystallijie and amorphous materials , Second edition, John Wiley
& Sons, Inc.

13- Ramseyer, K. and Boles, J. R. (1986). Mixed-layer illite/smectite

minerals in Tertiary Sandstones and Shales, San Joaquin basin,
California. Clay and clay minerals, V.34, No.2, 115-124.
14- Siemens D500 , D501 diffractometer operating instruction manual,
Model No. 79000- B3400 - C042-10 (1985).

15- Thewlis J., Hughes D.J. and Meetham A. R.(1962), Encyclopaedic

Dictionary of Physics.

16- Thorez, J. (1976). Practical Identification of Clay minerals. Editions

G. Lelotte, Dison Belgium.

17- Tucker (1988), Techniques in Sedimentology, Black well Scientific

publication Oxford 0X2 OEL 8 John street.

18- Tucker (1992), Sedimentary Petrology, An introduction to the origin

of sedimentary rocks , Black well Scientific publication Oxford O&2
OEL 8 John street.

19- Zussman, J. (ed) (1977). Physical methods in determinative

minerology (second edition), Academic press.