XRF & XRD Analysis

Principle
BY: Muhammad Nohman Mahmud
Sr.AM (QC)

Presented to the Quality

Control /Assurance staff of
Bestway Cement Group
 History of X-rays:

History of X-Rays :
X-rays were discovered in 1895 by the German scientist Wilhelm Conrad Roentgen
(1845-1923).
Working with a cathode ray tube (CRT) in a dark room he discovered a white spot on a
photographic film after development. As he did not know what kind of rays came from
the CRT he called those rays X-rays. Later he put his wifes hand between the CRT and
the photographic plate and after developing the photographic plate he saw the structure
of his wifes hand, including finger bones and the wedding ring, on the photographic
plate. So the application of X-rays for medical diagnostics were apparent from the
beginning. For his discovery he was awarded the first Nobel Prize for physics.
The properties of these X-rays were investigated and by 1912 the principles of
diffraction physics and reciprocal space were developed by Rontgen, von Laue,
Ewald,Sommerfeld and Brentano in Munich, Germany. It was in 1914 that father and son
Bragg (Leeds and Manchester, UK) introduced the crystallography. The principles of
powder diffractometry were described in 1916 by Debye and Sheerer (Gottingen,
Germany). In that same year the structure of LiF was reported. Hull (New Haven, USA)
published the structure of -Fe in 1917.The first principles of size-strain analysis were
published in 1918 by Sherrer.
Discoverer
 History of X-rays:

From 1917 to 1919 Brentano developed in Zrich, Switzerland the ideas of

the bent monochromator and focusing optics, but only in 1947 the first
commercial powder diffractometer was introduced by Philips in the
USA, after earlier developments of Le Galley (1935), Friedman (1945,
Washington, USA) and Parrish and Gordon (1947, USA).The Powder
Diffraction File (PDF) from Dow Chemical Company, started in the late 1930s,
was continued from 1950 onwards by the former Joint Committee for Powder
Diffraction Systems (JCPDS), now called International Centre for
Diffraction Data (ICDD), and issued yearly the PDF database on cards and
in books and later on micro-fiche, tape and now CD-ROM. Starting with a
1000 patterns, that database now contains a number of patterns in the
order of magnitude of 100000 and is the most important database in X-ray
powder diffraction. The development of calculation machines and computers
in the 1950s and 1960s brought about the full potential of the application of
single crystal and powder diffractometry, which also allowed a great deal of
automation. In the 1980s and 1990s new X-ray optics, like parallel beam
collimators, multi-crystal monochromators, graded mirrors and capillary
lenses were introduced, enabling an even larger range of applications.
 What are X-rays:
WHAT ARE X-RAYS?
X-rays can be seen as electromagnetic (EM) waves with their associated
wavelengths, or as beams of photons with associated energies. Both views
are correct, but one or the other is easier to understand depending on the
phenomena to be explained. Other electromagnetic wave includes light,
radio waves, and gamma rays. The wave lengths of x-rays are in the range
from 0.01 to 10nm, which corresponds to energies in the range from 0.125 to
125 keV. This region is bounded on the short wavelength side by Gamma
rays and on the long wavelength side by Ultra-Violet radiation. The wave
length of X-rays is inversely proportional to its energy, according to E*= hc,
E is the energy in keV and the wavelength in nm. The term is the product of
Plancks constant and the velocity of light and has, using keV and nm as
units, a constant value of 1.23985.The X-ray wavelength is given in (nm) or,
more commonly in the crystallographic world, in the older unit Angstrom
().1 = 0.1 nm 1 nm = 10
What are X-rays:
 X-rays Safety:
RADIATION
All kinds of radiation exists in and around us at all times. The question arises
what effect radiation has on us.
But first we have to answer the question what is radiation.
Radiation is phenomenon, which can be described as having wave properties,
but can also be described as particles. Some are ionising.
For some types of radiation we prefer the wave description, like Electro-
magnetic waves (photons), other radiation is best described as an emission
of particles from an atom or nucleus, like electrons, protons, neutrons or
complete atomic nuclei.
A lot of radiation types are harmless, but the more energetic radiation is
dangerous because of its ionising nature and other properties, see the next
section.
WARNING X-RAYS ARE DANGEROUS!!!
THEY CAN CAUSE SERIOUS PERSONAL INJURY IF SAFETY
INSTRUCTIONS AND RECOMMENDATIONS ARE NOT FULLY CARRIED
OUT
PROPERTIES OF SHORT WAVELENGTH ELECTRO-MAGNETIC RADIATION
 X-rays Safety:
The following properties make short wavelength (high-energy) Electro-
magnetic radiation a dangerous phenomenon:
_ They are not physically detectable by the human senses like smell, taste,
touch or vision
_ They are always transmitted in a straight line
_ They travel at the speed of light
_ There is almost no refraction by means of normal lenses or prisms
_ They penetrate in and through matter
_ They are ionising (generate charged particles)
_ They destroy and damage human tissue (burning, damage of the cell
genetic material, which can cause cancer)
RADIATION DOSE
Since it is known that radiation can be dangerous people have been
searching for criteria, which describe an amount of radiation that is still safe
or has to be considered dangerous. For this the general term dose is used.
The following terms and units have been or are still used for this:
 X-rays Safety:
_ Activity
This only describes the activity of radioactive material, being the number of atom
changes (emissions) per unit of time.
The unit in which the activity is expressed is Becquerel per second or Bq/s. The old
unit is the Curie or Ci (1 Ci=3.71010 Bq/s).
_ Exposure
Exposure is the quantity of released charge per kilogram of air.
The unit in which exposure is expressed is Coulomb per kilogram air or C/kg.
The old unit is the Roentgen or R. (1 R=2.5810-4 C/kg).
_ Absorbed dose
The absorbed dose is the absorbed energy per kilogram of material. The unit in
which absorbed dose is expressed is Gray or Gy (1 Gy =1 J/kg).The old unit is the
Radiation absorbed dose or Rad (1 Rad=0.01 Gy).
-Dose equivalent
The dose equivalent is the absorbed dose multiplied by a quality factor.This quality
factor is depending on the type of radiation and its relative damaging potential:
The unit in which dose equivalent is expressed is the Sievert or Sv (1 Sv =1 Gy=1
J/kg).
The old unit is the Rntgen Equivalent Men or REM
(1 REM=0.01 Sv).
 X-rays Safety:
EFFECTS ON THE HUMAN BODY
The overall effects on the human body depending on the total dose received are
of course very important. The following table gives an overview of the effects
and chance of survival after an exposure to a radiation source.
Total body exposure Effect on human body Chances of
survival
100 Sv Damage to central nerve system No chance/Only
few hours
10 Sv Damage to stomach, guts, bone marrow Little, <50%
1 Sv Change in blood composition Reasonable,
>50%
0.1 Sv no physical damage Complete recovery after about
6 weeks
 X-rays Legislation:
LEGISLATION
Country Official Documents Containing Regulations
Germany Verordnung ber den Schutz vor Schaden durch Rntgenstrahlen
UK The Ionising Radiation Regulation, 1985, United Kingdom
USA Radiation Safety for X-ray Diffraction and Fluorescence Analysis
Equipment, (NBS hand book 1977)Department of Health Education and
Welfare (DHEW), FDA 75 8003
Canada Radiation Emitting Devices Act, SOR/DORS/81-545,
Part XVIII: Cabinet of X-ray Equipment Consultative Document,
Part XIV: X-ray Diffraction Equipment
Australia Code of Practice for Protection against Ionising Radiation Emitted
from X-ray Analysis Equipment, (1984)
The approach of Philips is to take care of the user (customer) and provide
equipment that is better than the lowest permissible dose limit. These dose
limits are described in the legislation of the USA and the Netherlands and is
currently 2.5 micro Sv/hour.
 Theory of XRF:
Theory of XRF:
In XRF X-rays produced by a source irradiate a sample. In most case the source
is an X-ray tube. The element present in the sample will emit the fluorescent x-
ray radiation with discrete energies equivalent to color for optical light that are
characteristics for these elements. A different energy is equivalent to a
different color. By measuring the energies determining the color of the
radiation emitted by the sample it is possible to determine which elements are
present this step is called qualitative analysis. By measuring the intensities of
the emitted energies (colors) it is possible to determine how much of each
element is present in the sample. This step is called quantitative analysis.
Interaction of X-rays with matter:
There are three main interactions of x-rays with matter: Fluorescence,
Compton scatter and Rayleigh scatter. If X-ray fall on a material a
fraction will pass through the sample, a fraction is absorbed into the sample
and produce fluorescent radiation, and a fraction is scattered back. Scattering
can occur with loss of energy and with out loss of energy. The first is called
Compton scatter and the second Rayleigh scatter. The fluorescence and
scatter depends upon the thickness (d) and density () and composition of the
material and on the energy of the X-rays.
 Theory of XRF:
Production of Characteristic fluorescent radiation:
The classical model of an atom is a nucleus with positively charged protons and non-
charged neutrons, surrounded by electrons grouped in shells or orbitals. The
innermost shell is called the K-shell, followed by l-shells, M-shells etc travelling
outwards. The L-shell has 3 sub shells called L1, L11 and LIII. The M shell has 5 sub
shells. The K shell can contain 2 electrons, the L-shell 8 and the M-shell 18. The
energy an electron has depends on the shell it is in, and on the element to which it
belongs. Irradiating an atom, particles like X-ray photons and electrons with
sufficient energy can expel an electron from the atom.
This produces a hole in a shell, in the example a hole in the K-shell, putting the atom
in an unstable situation with a higher energy. The atom wants to restore the original
configuration, and this is done by transferring an electron from an outer shell e.g.
the l-shell to the hole in the K-shell. An L-shell electron has a higher energy than a K-
shell electron and when the L-shell electron is transferred to the K-shell, the energy
surplus is emitted as X-rays. In a spectrum, this is seen as a line. The energy of the
emitted X-rays depends on the difference in energy of the shell with the initial hole
and the energy of the electron that fills the hole. Each atom has its specific energy
levels, so the emitted radiation is characteristic for that atom. An atom emits more
than just one energy (or line), because different holes can be produced and different
electrons can fill up these holes. The collection of emitted lines is characteristic for
the element and is more or less a fingerprint of the element.
 Theory of XRF:
To expel an electron from an atom, the x-rays must have a higher energy than
the binding energy of the electron. If an electron is expelled, the incoming
radiation is absorbed and the higher the absorption the higher the fluorescence.
If on the other hand the energy is too high, many photons will pass the atom
and only a few electrons will be removed. If the energy is lower and comes
closer to the binding energy of the K-shell electrons, more and more radiation is
absorbed. The highest yield is reached when the energy of the photon is just
above the binding energy of the electron to be expelled. If the energy becomes
lower than the binding energy, a jump or edge can be seen: the energy is too
low to expel electrons from that shell, but is too high to expel electrons from the
lower energetic shells.
Not all incoming photons produce fluorescent photons. The fluorescence yield is
the ratio of the emitted fluorescent photons and the number of incoming
photons. the yield is low for the very light elements, explaining why it is so
difficult to measure these elements.
 Types of XRFs:
Types of Spectrometer Systems:
There are two types of XRF Systems ,Energy Dispersive XRF & Wave length
Dispersive XRF
EDXRF :
EDXRF Spectrometer have a detector that is able to measure the different energies of
the characteristics' radiation coming directly from the sample.The detector can
separate the radiation from the sample into the radiation from the elements in the
sample.
WDXRD:
WDXRF Spectrometer use an analyzing crystal to disperse the different energies. All
radiation coming from the sample fall on the crystal. The crystal diffracts the different
energies into different radiations ,similar to a prism that disperses colors into different
directions.
Is also possible to mount the detector on a goniometer and move it through an angular
range to measure the intensities of many different wave lengths. This system is called
as sequential systems because they measure the intensities of the different
wavelengths one After another. Simultaneous spectrometers are equipped with a set of
fixed detection system. Each detection system has its crystal and detector ,and each
system measures the radiation of a specific element .the intensities are measured all at
the same time,explaning why they are termed as simultaneous systems. combined
systems having an moving detector and fixed detectors are also available.
 Instrumentation:
As XRF Present in BCL CHK is WDXRF ,therefore we will focus on
WDXRF:
Cubix 2300 XRF :
The spectrometer comprises the following major assemblies.
Analyzer Containing:
Measuring Chamber
Element Channels & detectors
Sample Transport Assembley
Vacumn Pump
TT X-Ray Tube:
Controller Containing:
HT Supply
Internal Water Cooling System
CPU Board
Controller Board
Counting Electronics
 Instrumentation :
Measuring Chamber :
Measuring chamber is located in the analyzer.It consists of the measuring
chamber itself and 14 fixed measuring channels ,or optionally with a
maximum of 11 fixed channels.
Element Channel :
A fixed element channel comprises the following ,
Entrance Slit
Diaphragm
Curved Crystal Assembley
Exit slit
Detector
Scaler Circuit
Connecting Cables
Each channel has a high tension supply for the detector and when a gas flow
detector is used ,a controlled gas supply.
 Instrumentation :
Detector & Multi Channel Analyzer :
EDXRF mainly use solid state detector ,while WDXRF use gas filled detectors and
scintillation detectors.EDXRF detector is a wide range detector and measures all
elements from Na up to U.Gas filled detectors measures elements from Be upto Cu
and scintilllation detector from Cu upto U.All these detectors' produce an electrical
pulse when an X-Ray photon enters the detector ,and height of this pulse is
proportional to the energy of the incoming photon. The pulses are amplified and
than counted by Multi Channel analyzer.
There are 03 important parameters of detection system:
Resolution :
Is the ability of the detector to distinguish between different energy levels. A high
resolution means the detector can distinguish between different energies level.
Sensitivity :
Indicates how efficiently incoming photons are counted. Sensitivity is high if the
ratio of number of pulses against the number of incoming photons is high.
Dispersion :
Indicates the ability of the detector to separate X-rays with different energies. high
dispersion means different energies are separated well.
As in our XRF System there is gas filled detector system, therefore well focus on
them :
 Instrumentation :
Gas Filled Detector System:
The sealed gas detector is a hollow metal cylinder with an anode wire running
in the axial centre of the cylinder. The cylinder is sealed of and has a gas
mixture inside, containing the inert counting gas (Ne,Ar,Kr ,Xe and
occasionally He) and the quench gas Methane. On one side of the cylinder a
Be window is mounted through which the X-ray photons can enter. When an X-
ray photon enters the detector and collides with an inert gas atom an outer
electron may be knocked out forming an ion-electron pair. The number of ion-
electron pairs is depending on the energy of the X-ray photon. The electrons
from the ion-electron pair are then accelerated towards the anode wire by its
high potential. In its path such an accelerating electron can again knock out
an electron from an atom, forming another ion-electron pair etc.This will cause
an avalanche of electrons, the so-called gas amplification. When this
avalanche of electrons reaches the anode wire, a small voltage pulse is
produced. This voltage pulse is proportional to the energy of the X-ray photon
and the applied HT.If negative ions are produced also positive ions are
produced. These positive ions are attracted to the detector case at earth
potential and they will also cause an avalanche. To prevent this, the inert gas
is mixed with a quench gas, such as Methane. The quench gas has the effect
of neutralizing the positive ions without any other reactions.
 Instrumentation :
Gas Flow Proportional Detector:
It is used for X-Rays having energies between 0.28 KeV & 3 KeV.It is operated
with a continuous flow of gas .P10 Gas is used 90 % Argon & 10 % Methane
.The gas flow must be between 0.5 & 1 LITRE / HOUR.
The recommended use is for lighter elements from C to Mg.It is also possible
to use this detector for Al to Cr.
Neon Sealed Proportional Detector :
It is used for X-Rays having energies between 1.5 KeV & 3 KeV.The detector is
filled & sealed with Neon gas mixture.
The Neon sealed detector fitted with 25 Um window can be used to analyze
elements from Al upto P.A detector with a 50 um window is used to analyze
elements from S upto Cl.
Krypton Sealed Proportional Detector :
It is used for X-Rays having energies between 3 KeV & 8 KeV.The detector is
filled & sealed with Krypton gas mixture.
The Krypton sealed detector can be used to analyze elements from K upto Cu
(K Line).A & for the L-Line analysis of elements from Te to Ta.
 Instrumentation :
Xenon Sealed Proportional Detector :
It is used for X-Rays having energies between 6 KeV & 16 KeV.The detector is
filled & sealed with Xenon gas mixture.
The Xenon sealed detector can be used to analyze elements from Zn upto Y
(K Line). & for the L-Line analysis of elements from Ta to U.
COMPARISON OF DIFFERENT DECTECTORS
The resolution of gas filled and scintillation detectors are very poor, and they
are not suited for energy dispersive spectrometers. They can however be used
in wavelength dispersive spectrometers, because in these instruments the
resolution is achieved by the diffraction crystal. The sensitivity depends on the
type of detector and on the energy of the incoming X- rays. Gas filled
detectors have a high sensitivity for low energy and a low sensitivity for high
energies and are so best suited to detect low energies. The opposite applies
for scintillation detectors ,which are better suited for high energies than low
energies .Solid state detectors in general have a very low sensitivity for low
energies and high resolution for the higher energies.EDXRF Spectrometer
commonly use solid state detector ,while WDXRF spectrometers use a
combination of gas filled and scintillation detector.
 Instrumentation :

Lif 220 Crystal 2d = 0.2848 nm: used for elemental range V-U, high
resolution analysis
LiF200 Crystal :2d=0.4027 nm : used for elemental K-U ,routine
analysis.
Insb (111) Crystal 2d= 0.7477 : this is only used for silicon and gives
a higher sensitivity than PE with also an improved resolution
PE (002) Crystal 2d=0.8742 nm : Elemental range Al-Cl. Routine
analysis
PX1 Synthetic Multilayer 2d = 5 nm: Analysis range O-Mg
PX4 Synthetic Multilayer : 2d = 12nm used for analysis of carbon.

Counting & Control Electronics :

The Dual scaler board is used to count the detected pulses. This data is
passed to the SuperQ analytical software as raw count rate. The Dual scaler
board also sets the detector high voltage level .
 Instrumentation :
Detector High Voltage Supplies :
A high voltage supply is required for each type of detector.
A gas -flow or sealed detector is supplied with between 1000 to 3000 volts.
The detector high voltage supply is controlled by the Dual Scaler Board.
Chamber Atmosphere:
The inside of the chamber is kept under vacuum ,the vacuum ensures the
highest possible intensity for light elements. Whole of the sample transport
system and the measuring chamber is under vacuum.
HV Generator :
The high voltage supply is basically a 200 Watt high voltage
converter with negative polarity.
Routine X Rays Check :
Cleaning the Loading Opening
Cleaning the air dust Filter
Vacumn Pump Oil level Check
Vacumn Pump Oil Conditions Check
Fore line Trap Check
 Instrumentation :
X-Rays Tubes:
The basic design of X-Ray Tube contains a filament (wire) and an anode (target)
placed in an vacuum housing. An electrical current heats up the filament and
electrons are emitted, which hit the atoms in the anode which will expel the
electrons from theses atoms, causing emission of characteristics radiation. The
energy of this radiation is determined by the elements in the anode. The X-Rays
emitted escape through Be Window .There are two types of X-Ray Tube Side-Window
tubes & Target transmission Tubes .A high voltage (20.100Kv ) is applied across
the filament t and the anode ,and this high voltage accelerates the electrons
towards the anode.
The conversion of electrons into X-rays is a very inefficient process. About 1% of the
applied energy is converted to X-rays. The remainder of the energy is converted to
heat within the anode. Therefore, the backside of the anode is cooled with a high-
speed water jet of about 4 litres/ minute. A number of electrons are scattered from
the anode and strike other parts of the tube such as the window.
Therefore, the temperature of the window can rise to hundreds of degrees C.
The window is made of Beryllium (atomic weight 4) in order to minimize the
absorption of X-rays. The thickness of the window depends on the ability to conduct
heat from the window to the tube body to avoid fracture of the window

Instrumentation
Channels Specifications
Element Crystal Type Angle
Si Insb111 Flow 144.75
Al PE002 Flow 144.86
Fe LiF200 Sealed Kr 57.52
Ca LiF200 Sealed Kr 113.08
Mg PX1 Flow 22.56
K LiF200 Sealed Kr 136.69
Na PX1 Flow 27.48
S Ge111 Sealed Ne 110.68
Cl PE002 Sealed Ne 65.49
Equipment Details:
Max Min
Gas Flow 3.0 l / 0.5 l/hrs ,
hrs,1300 600 hpa
hpa
X-Ray Tube 50 kv,4 ma Cr 200 W
Vacumn 100 pa 0 pa
Temp 36.40 C 35.90 C
Compressed 6 Bar 4 Bar
Air
 Standardization of XRF:

STANDARDIZATION OF XRF ANALYSIS

Several standards are available to monitor quality assurance and certification of
XRF equipment performance and accuracy. A brief description of select materials
is given below:
Standard Reference Materials
A number of Certified Reference Materials (CRMs) and Reference Materials (RMs)
are available from many sources. The definitions for CRM and RM as listed in the
International Organization for Standardization's ISO Guide 30:1992, Terms and
Definitions Used in Connection with Reference Materials, are listed below.
Certified Reference Material (CRM). Reference material, accompanied by a
certificate, one or more of whose property values are certified by a procedure
which establishes its traceability to an accurate realization of the unit in which
the property values are expressed, and for which each certified value is
accompanied by an uncertainty at a stated level of confidence. CRMs are
certified by a recognized certifying organization using approved certification
procedures as instructed in
Standardization of XRF:

ISO Guide 35:1989, Certification of Reference Materials General and Statistical

Principles. The organization is usually a function of a federal government or
recognized by a federal government .A CRM is the highest level to which an
analytical reference material can be elevated.
Reference Material (RM): A material substance one or more of whose property
values are sufficiently homogeneous and well established to be used for the
calibration of an apparatus, the assessment of a measurement method, or
assigning values to materials. The RMs usually have been through inter laboratory
testing using many analysts and supplied with a certificate of analysis but do not
strictly follow the procedures of certification as indicated in ISO Guide 35:1989.
It is interesting to note that no cement raw mix standards exist and for good
reason. Mineralogy of the kiln feed is variable at different cement plants; some use
clay and limestone and others contain quartz, fly ash, bottom ash, and many other
materials. Significantly different results may result depending on the ingredients
when using pressed powders in analyses. However, if the fusion technique is used,
cement calibrations can be used effectively to analyze raw feed and
Standardization of XRF :

clinker as well. Careful attention to sulfur, alkalis , and chloride is still required.
Cement standards, available from NIST, vary in composition so they can be
used in calibration or qualification under ASTM C 114.3. Supplies usually last 15
years or more as thousands of samples are packaged and randomly tested for
homogeneity and composition to produce a Certificate of Analysis (COA). Other
reference material suppliers have one or two standards, which will add to the
number of samples used for calibration, or can supplement the qualification of
the test methods. Because the Cement and Concrete Reference Laboratory
(CCRL) samples are analyzed by 100 laboratories or more and statistically
evaluated, it is not uncommon for these samples to be used as standards in
calibration work. Caution is warranted in this practice because the results are
averages of many labs results, not certificate values. Nettles (1998)
proposed using pure compounds formulated to mimic the composition of the
1800 series cements using the fusion technique. Other sources of reference
materials can be found in Appendix E.
Drift standards. Drift standards correct for any instrumental changes such as
x-ray tube aging, detector sensitivity, etc. Such drift standards should be stable
materials free from changes due to exposure to x-rays and aging. Typically, drift
Standardization of XRF:

standards are fused beads for cement. Currently available are glass standards made by A.S.O.
Design specifically formulated for Portland cement manufacture concentration ranges.
Breitlander also supplies glass drift standards. In any case, the drift correction must be used if
chemical results indicate substantial evidence that the method is not providing results in
accordance with ASTM permissible limits. If the required accuracy on a major element is 0.1%
relative and the measured count rate fluctuates between -0.4% and +0.4% during a period of
one week, then one measurement a day is likely to be sufficient to obtain the required accuracy.
The PHD is the energy distribution of the pulses produced by a detector. The detector count
rates are displayed as a function of energy using the Check PHD function. Only those signals
which originate from the element of interest need to be processed from all the signals which are
detected. To define the appropriate signals, you must measure a pulse height distribution and
set the upper and lower levels between which the signal will be integrated for further
processing. The remaining signals are disregarded and only used for dead time correction.
Different settings are recommended for the upper and lower levels depending on which signal
you want to measure.
Pulse shift is an effect that is caused by incoming X-rays. At very high count rates the analyte
signal partially shifts outside the selected PHD window. The electronics in the spectrometer
correct for this effect using pulse shift correction which is designed to maintain stability. This
ensures linearity between the measured or reported count rate and the actually absorbed count
rate. The magnitude of pulse shift depends on both the energy and the count rate of the
absorbed flux (including the part which is not measured) in the detector.

 Theory of XRD
Diffraction Crystals & Collimators :
A crystal can be seen as a stack of thin layers all having the same thickness. If
a parallel beam of X-Rays falls on the crystal ,the first layer reflects a fraction
of the X-Ray. The remaining radiation penetrates the crystal and is reflected by
the subsequent layers. If the difference in path length between reflections from
layers is multiple of half the wave length of the radiation, the two reflected
beams vanish. If the difference is exactly an integer times the wavelength ,the
two reflected beams re inforce.The difference in path length is an integer times
,the wavelength if the following relation ,called Braggs law ,holds. N= 2d sin
()
At an angle ,all reflected radiation with a wavelength and obeying braggs law
are in phase and add up. All other wavelengths at the same angle will vanish,
A detector placed at angle can therefore measure the intensity of the
corresponding wavelength. Reflected wavelengths obeying braggs law for n=1
are called first order reflection ,for n=2 second order .At any specific angle
,only radiation with a wavelength obeying braggs law is reflected. Radiation
with slightly different wavelength will be reflected at slightly different angles
,but will still reach the detector and will interfere with the energy to be
measured. A collimator ,which is set of parallel plates ,is used to obtain a
parallel X-Ray beam that falls exactly at the required angle on the crystal. the
primary collimator is placed between the sample and crystal ,and on secondary
collimator can be placed between the crystal and the detector.
XRD:

Goniometer ,X Ray Tube (1)-5 to 85 ,Detector (-5 to 85 ) 2 0---167

X-Ray Tube (---- Geometry) (Copper ,2200 W)
Filter (Ni )
Diversion Slit (1)
Solar Slit (0.04 Radians)
Width Mask (10mm)
Sample
Fixed Anti scatter Slit (2)
Programmable Receiving Slit (0.1mm-3mm),Opening Increment 0.01
mm
Solar Slit (0.04 Radians)
X-Celerator Detector (Combination of 100 Solid State detectors
,therefore processing time is 100 times fast)
Equipment Details

Max Min
Water Flow 6.0 l / min 3.5 l/min
Water Input 50 PSI 115 PSI
Pressure
Water + 35 c + 20 C
Temperature
Compressed 6 Bar 4 Bar
Air
 Why use X-rays
There are various reasons why a choice is made for X-ray analysis:
_ Uniqueness of the method
X-ray diffraction is very often the only technique available to analyse material
properties, certainly when these depend on the crystalline state.
_ Speed of analysis
Each measurement (analysis) can take only a few minutes, which allows a high
through-put of samples.
XRF only takes one minute for analysis of 09 elements
While XRD Takes five & Half minutes for analysis of
C3S,C2S,C3A,C4AF,MaO.fCaO,K2SO4 CLASSICAL Method takes 06 Hrs for Cement
/ Clinker ,while at least 12 Hours for Raw Materials. (Excluding Alkalis)
Non-destructive analysis
Samples remain unchanged during and after measurement, which means that
other analysis techniques may be used on the same samples, or samples may
be preserved when needed.
_ Large range of materials
All element from atomic weight 4 (Beryllium) with the exception of Nitrogen can
be analysed with X-ray fluorescence.
All crystalline and semi-crystalline structures can be tested with X-ray
diffraction, however no liquids can be analysed.
 Why use X-rays
_ Accurate analysis
Relative accuracies of 0.1% to 0.3% are attainable.
_ Sensitivity
With X-ray fluorescence elements can be detected in concentrations from 0.1
PPM up to 100 % (PPM = parts per million).
With X-ray diffraction, crystalline structures can be analysed with a
concentration of typically 0.1% up to 100%. In exceptional situations
concentrations below 0.1% are attainable.
_ Range of sample types
Samples may be in many forms and shapes, with dimensions ranging from
tens of microns to meters.
_ Ease of use
Routine analyses do not require a high level of operator skills.
_ Automated operation
The whole process of sample taking, sample preparation and the final
measurement can
sometimes be highly automated ensuring a high throughput of samples.
Uses of XRD & XRF :

1. Calculation of actual C3S,C2S,Ortho C3A,Cubic C3A ,C4AF,Mgo

(Periclase) , Free Lime & K2S04 in Clinker.
2. Quartz in limestone. One major problem in cement manufacturing is
achieving proper grinding
and fineness of the material that is to enter the kiln. The presence of
coarse quartz in limestone
can have an impact on both the parameters. Assessment of coarse quartz
in raw feed can effectively be made by XRD in conjunction with acid
treatment of the sample and particle separation. The raw feed is treated
with dilute hydrochloric acid until all carbonates have been decomposed.
The residue is then filtered, dried, and analyzed by XRD. The XRD pattern
showing quartz peaks gives an estimation of insoluble quartz in the feed.
Figure shows the XRD pattern of a raw feed prepared by this procedure.
Reference pattern lines superimposed on the samples pattern indicate the
position and intensity for major quartz peaks.
Uses of XRD & XRF:
(XRD Pattern of KF treated with HCL Filtered & dried)
Uses of XRD & XRF:
Additionally, if the insoluble residue is sieved through a No. 325 sieve, and
the XRD pattern of the portion retained on the sieve is obtained,
abundance of quartz coarser than 45 m can be estimated from this
fraction. Figure shows the XRD pattern of a coarse fraction obtained after
acid treatment of a cement raw feed. It is apparent that this kiln feed
sample has a relatively high amount of coarse quartz .Because quartz is
harder to grind than other materials in the raw feed and is harder to burn,
it is likely that cement produced with this kiln feed will contain belite
clusters formed during clinkering process. Raw feed containing coarse
quartz will require more grinding energy to produce a quality clinker.
XRD pattern of kiln feed sample treated with diluted HCl,
filtered, dried, and sieved through a 45 m-size sieve.
Reference lines for quartz are shown.
 Uses of XRD & XRF:
Gypsum Rock
In the sense that gypsum is added to clinker during inter grinding in the finish mill, it is
considered a raw material in cement manufacturing. Its purpose is to control setting
when the cement starts to hydrate. Gypsum is generally secured from naturally
occuring deposits in the earth In natural gypsum deposits, it is most useful to scan the
source for naturally occurring anhydrite(CaSO4) or anhydrous calcium sulfate. Since
this form of calcium sulfate is not as readily soluble in water as is gypsum (CaSO4
2H2O), anhydrite can fail to control concrete setting appropriately. In addition,
anhydrite is much harder than gypsum and will not be ground as fine during finish
grinding; this will also reduce its rate of solubility. For these reasons, sources of
gypsum containing high amounts of anhydrite are usually avoided. However, if the
finish mill temperature is very high, dehydration of gypsum might produce too much
hemihydrate (CaSO4 12H2O), there by causing false set. In such a case, it may be
desirable to add some of the needed calcium sulfate as anhydrite. XRD provides a
quick method to detect anhydrite together with coexisting gypsum,hemihydrate, and
minor contamination such as calcite and quartz. Figure shows an XRD pattern of a
gypsum source. Naturally occurring anhydrite, sometimes referred to as insoluble
anhydrite, differs from soluble anhydrite in that they have different crystalline
arrangements and therefore have slightly different solubility in water. Soluble
anhydrite can result, for instance when gypsum is exposed to temperatures above
around 200C and loses its chemically bound water. This compound is not
XRD pattern of gypsum rock source for addition to clinker in cement
grinding. In addition to gypsum (reference lines shown), phases
identified include hemihydrate (Hh) and quartz (Qz). It must be
noticed that hemihydrate does not usually occur naturally. Its
presence in this pattern may result from sample preparation.
Uses of XRD & XRF:
easily distinguished from plaster by XRD in gypsum sources but is rapidly
soluble and usually causes no interference in controlling concrete setting.

Coal Characterization
The principal solid fuel used in cement manufacture is coal. In addition to
clay minerals, common impurities in coal are carbonates, iron sulfides such
as pyrite (FeS2) and other sulfides, chlorides ,and quartz (Bye, 1999). XRD
is a useful tool for detecting these compounds. Sulfides and chlorides can
cause a variety of problems when coal is burned in the kiln or in the
calciner. The use of coals(and fuels in general) is limited by the total sulfur
content, and some sulfur is in the form of crystalline sulfides, XRD will be a
useful tool for detecting these compounds. Chlorides also may be present
in crystalline structures like sylvite or halite that can easily be detected by
XRD. Pyrite is found in coal as a common impurity and in some limestone
deposits as well. Its XRD peaks are located at 33.0X, 56.27, 37.15, and
40.74 2.
Uses of XRD & XRF:

Dolomitic Limestones
Dolomite (CaMg(CO3)2) has limited use in cement manufacturing because the
clinker resulting from its use would be excessively high in free MgO or periclase
upon clinker cooling. Potential problems may arise with these cements because
of their excessive expansion. However, some cement producers have dealt
with high MgO clinkers by adjusting the raw mix chemistry to produce a clinker
with a lower MgO/Fe2O3 ratio. As a rule of thumb, when this ratio is lower,
more MgO can be tolerated without failing the autoclave expansion test. At
certain cement-making locations the only limestone readily available may
contain appreciable dolomite, and in such cases, careful characterization of the
limestone is required. In the example shown in Figure, the limestone contains a
rather high proportion of dolomite, whose XRD reference lines are shown in the
pattern. A cement or clinker suspected of containing high MgO should be
analyzed by XRD. Chemical analysis is also desirable. Clinkers or cements high
in MgO may contain as much as 8% or as little as 3.5% periclase by mass.
Figure shows a clinker sample with an unusual amount of periclase, readily
identified by the diffraction line at 42.9 2.
XRD pattern of a sample of limestone high in dolomite
used as a source in cement manufacturing. Reference lines
for dolomite are shown. Labels for quartz (Qz) and calcite
(Cc)main peaks are also shown.
XRD pattern of cement containing free MgO or crystalline
Periclase (reference lines shown). The oxide analysis
reported a total MgO of 3.9 wt.%.
Uses of XRD & XRF:
Clay
Clay materials from quarries used in cement manufacturing normally occur
together with feldspars,quartz, and carbonates (calcite or dolomite). The
XRD is an essential tool, aided by optical microscopy and chemical
analysis, to characterize and identify clay components in cement raw
materials. Clay minerals have a layered crystal structure and often occur
as thin sheets parallel to these crystal layers. Clays are often poorly
crystalline and often occur as very small grains. For these reasons, their
basal peak (from the crystal layer) is often the only recognizable peak and
may be quite broad. The d-spacing of the basal peak is usually quite broad,
a feature that is very helpful for their identification in the presence of
minerals like quartz, feldspars, or carbonates. For instance, a diffraction
peak at 12.3 2 identifies kaolinite, usually indicative of kaolin clay
present in the overburden of limestone quarries. Another clay commonly
found is illite. An example of the XRD pattern on clay minerals identified
ina clay source for cement manufacturing is shown in Figure.
 XRD pattern showing clay minerals identified on a clay
source for cement manufacturing. Cc: calcite, Qz: quartz,
Mm: montmorillonite, Ch: chlorite,Ab:
albite, Mt: margarite.
Uses of XRD & XRF:
Limestone
Limestone is the main raw material used in cement manufacturing. It
comprises from 70% to 95% of the raw meal fed to the kiln. Calcite
(CaCO3) is normally the most abundant phase in limestone; its strongest
diffraction peak is produced at 29.4 2 with Cu K radiation6. Quartz,
feldspars, and clay minerals are normally present as minor contaminants in
limestone deposits. Dolomite is also found in small amounts in some
limestones , as discussed later in this section. Figure shows a typical XRD
pattern of limestone.
XRD pattern of a limestone sample from a quarry. Calcite
(reference linesshown7) and quartz detected as main
phases. Aluminum line from sample holder is also shown
as an artifact.
Uses of XRD & XRF:
Bauxite
Bauxite may be used in cement manufacturing in cases where lime and/or
silica sources do not provide enough Al2O3 for the desired clinker
formulation. Bauxites mineralogical composition also includes different
polymorphs of aluminum oxide and hydroxide, such as gibbsite,
norstrandite, and bayerite, which are readily identifiable by XRD. Bauxite
may also contain hematite and magnetite, which incorporate iron into the
clinker. Corundum (Al2O3), is also readily identifiable. It is a very hard
mineral and its identification is a decisive factor for raw feed grindability
considerations. Al(OH)3, as the main phase in the sample. particular
sample is primarily composed of a mixture of gibbsite (reference lines
shown) and hematite (peaks at 33.1X, 35.67, 24.13 2). It also contains
anatase (TiO2), aluminum oxide
hydroxide, or boehmite (Al O(OH)), and traces of calcite, quartz, and
kaolinite.
 Bauxite alternative alumina source for cement
manufacturing. Reference lines shown identify gibbsite as
the main crystalline component in the sample.
XRD graph of an alternative alumina source for cement
manufacturing. The sample consists of a mixture of
gibbsite and hematite. Reference lines shown identify
gibbsite.
Bauxite Plot
Clay Plot
Gypsum Plot
Laterite Plot
Limestone Plot
Sand stone Low Purity
Sand stone High Purity
Raw Mix Quartz Test