Standard Test Methods

• IS 12803:1989: Method of Analysis of Hydraulic

Cement by X-Ray Fluorescence spectrometer
SPECTROMETER

• IS 3535: 1986 :The samples of cement shall be taken

according to the requirements of IS 3535 : 1986 and
the relevant standard specification for the type of
cement being tested. The representative sample of the
cement selected as above shall be thoroughly mixed
before using and about 100 g of sample from this
shall be taken for analysis.
 Calibration Theory
• Since characteristic x-rays are the main factor
in making an XRF measurement, it is essential
to be able to accurately measure their energies;
this can only be done after a calibration is
performed. In this case, the equipment needing
calibration is the detector and multi-channel
analyzer (MCA) system
 Calibration
• Calibration curves are expressions of the relation
between X-ray intensity and concentration. Because
X-ray intensity is converted to concentration,
changes in intensity may cause errors in the
following cases.
1. The measurement sample is smaller than the diameter of
the X-ray beam.
2. The surface of the measurement sample is uneven.
3. The position of the measurement sample is different
 Calibration Theory
• Once an x-ray impinges on the detector, the detector
sends an electrical pulse to the multi channel analyzer
(MCA). One can think of the MCA as a desktop coin
sorter. Just as the coin sorter will place each coin in
its appropriate bin depending on the coin’s size, the
MCA will “place” each x-ray in its appropriate
channel depending on the x-ray’s energy. The data
recorded is an array of numbers, each number
representing the total count of x-rays for that energy
(intensity). The number placement in the array
represents the channel number, in ascending order
 Calibration Theory
• A calibration is a process in which specific energy values are
assigned to the correct channel in the MCA. This is done by
sending x-rays of known energy values to the MCA; once the
user identifies the channels where the x-rays were sorted, he or
she can assign the known energy values to those channels.
Since it is not practical to assign energy values to each channel
manually, the calibration process consists of identifying six to
eight channels with known energy values and then applying a
curve fitting technique to those data points. Through this
method, all the channels in the MCA can be calibrated
indirectly.
 Calibration
• Pulse height Analyzer (PHA)
• Pure metal sample analysis
 Calibration Sample
• The calibration sample preferably contains an
adequate number of elements to provide
sufficient peaks for calibration;
• Peaks should be separated from other peaks to
avoid confusion in assigning peaks to their
corresponding elements.
 HISTORY OF XRF
 The history of XRF dates back all the way to 1895 when
German physicist Wilhelm Conrad Roentgen accidentally
discovered X-rays while studying cathode rays in high-
voltage, gaseous discharge tube.
 However, the possible use of X-rays for analysis went
unnoticed until 1913 when Henry Moseley established
the specific relationship between the wavelength of a
characteristic X-ray photon and the atomic number of the
excited element.
 In 1925 X-rays were used for the first
time to excite a sample, but the technique was only made
practical in 1940 and the first commercial XRF
spectrometers were produced in 1950.
 X-RAY FLUORESCENCE

An X-ray fluorescence (XRF) spectrometer is an x-ray

instrument used for routine, relative and non destructive
chemical analyses of rocks, minerals, sediments and
fluids.
One of the most widely used methods due to its relative
ease, low cost of sample preparation and the stability and
use of X- ray spectrometers.
One of the best analytical techniques to perform elemental
analysis in all kinds of samples, no matter if liquids, solids
or loose powders.
 APPLICATION FIELDS OF X-RAYS

X-RAY

ANALYTICAL
SECURITY MEDICAL

XRF XRD

WDX EDX
AIRPORT CARGO RADIOLOGY

SEQUENCIAL SIMULTENIOUS SIM/SEQ

SCHEMATIC DIAGRAM OF XRF
 ORIGIN OF XRF
 When an atom absorbs sufficient energy from an external source, an electron
may be knocked out of one of the inner shells.

 As a result, a hole(place of missing electron) is produced in a shell and the

atom is said to be in excited state.

 Atom returns to the ground state by transferring an electron from higher energy
state to the vacancy position created in the lower energy state and emits the
excess energy in the form of x-rays. This process is called x-ray fluorescence.

 The process of detecting and analyzing the emitted x-rays is called “X- ray
Fluorescence Analysis.”

 For example, if a hole is created in the K-shell and is filled by the electron
from L-shell then the difference in the energies of the two levels will be
emitted as x-rays.

X-RAYS
 PRINCIPAL OF XRF
BRAGG’S PRINCIPLE: n  2d.sin
where d is interplannar distance of planes,  is wavelength of the emitted line
 is scattering angle and n is integer

MOSELEY PRINCIPLE:   C( Z   )
where ν is frequency of the emitted line, Z is the atomic number (number of protons)
C & σ are constants
 Based on the characterstic atomic structure of each element,
chractestic X-ray emitted of the atom from excited state to
ground state.
 If bragg’s condition is satisfy within atomic structure,
coherent characterstic wave length or energy of emitted X-
rays emitted and identifed.
 Atomic number Z is measured based on the detected wave
length or energy by using moseley law. contd
 QULITATIVE/QUANTITAIVE ANALYSIS OF XRF

 X-ray fluorescence's spectroscopy provides a means of

identification of an element, by measurement of its
characteristic X-ray emission wave length or energy.
 The method allows the quantification of a given element
by first measuring the emitted characteristic line intensity
and then relating this intensity to elemental
concentration.
 The energy of the peaks leads to the identification of the
elements present in the sample (qualitative analysis).
 while the peak intensity provides the relevant or absolute
elemental concentration (semi-quantitative or
quantitative analysis).
 XRD Calibration
• Calibration of the X-ray Diffractometer will be
performed a minimum of once per month.
However, calibration is not limited to once per
month and can be performed as needed. Load
quartz standard slide into sample chamber.
Using “X-ray Diffraction Operation
Guidelines”, acquire a diffraction pattern for
the quartz standard.
 XRD Calibration
• Once the diffraction pattern is acquired, use “X-ray
Diffraction Operation Guidelines” and the “Materials
Data JADE XRD Pattern Processing” manual in
conjunction with the MDI JADE 5.0 software in
order to identify the diffraction pattern. Use the
Analyze and Find Peaks options to locate major
phases in the diffraction pattern (the default variables
are suitable for finding peaks). Use the Identify and
Search/Match options to identify the diffraction
pattern (search the Inorganics Subfile - all other
default variables are suitable for identification
purposes).
 XRD Calibration
• External standard and internal standard calibrations
are important procedures for achieving high accuracy
in X-ray powder diffraction studies. The theoretical
basis as well as procedures for obtaining calibration
curves are given. Methods and examples of selecting
Standard Reference Materials (SRMs) which are
produced and issued by the National Bureau of
Standards (NBS), and procedures of sample
preparation with these standards are also described.
Three examples are presented to indicate the value of
using SRMs.
K & L SPECTRAL LINES
 K-alpha lines: L shell e-transition
to fill a vacancy in K shell. Most
frequent transition, hence most
intense peak.

 K-beta lines: M shell e- transitions

to fill a vacancy in K shell.

 L-alpha lines: M shell e- transition

to fill a vacancy in L shell.

 L-beta lines: N shell e- transition to

fill a vacancy in L shell.
 Basic components of XRF spectrometer are x-ray source, sample
and detection system

 X-ray tube serves as x-ray source and excites the elements in the
sample to emit fluorescent radiation. The emitted fluorescent
radiation from the sample is collected and intensity is registered by
detection system

 There are two types of XRF spectrometers

Wavelength dispersive (WDXRF)
Energy dispersive (EDXRF)

 The difference between these two types lies in their detection system
 WDXRF
 A wavelength dispersive detection system physically separates
the X-Rays according to their wavelengths.
DETECTOR
SAMPLE

X-RAY
TUBE

 Fluorescent radiation from the sample is collimated and allowed to

fall on the diffracting crystal.
 Crystal reflects only those wavelengths which satisfies bragg’s
diffraction condition.
 P-10 gas (Ar+CH4 in 90:10 ratio) is used as detector for
characterstic wavelengths.
 EDXRF
EDXRF spectrometers uses a detector, that can separate different energies in the
characteristic radiation coming from the sample, elements in the sample can be identified

• A detector is used to convert X-ray energy into voltage signals; this information is sent to a
pulse processor, which measures the energy of the signals and passes them onto an
analyzer.

• They are sorted by energy with help of multi-channel analyzer (energy is characteristic for
each element) and frequency of appearance (characteristic for concentration) and sent to
data display and analysis.
• The most common detector now is Si(Li) detector cooled to cryogenic temperatures with
liquid nitrogen.
 COMPARISON OF EDXRF AND WDXRF SPECTROMETERS

Elemental EDXRF WDXRF

range Sodium to uranium Beryllium to uranium
Good for heavy elements
Good for all heavy
Detection limit and less optimal for light
elements
elements
Good for heavy elements Good for heavy elements
Sensitivity and less optimal for light and reasonable for light
elements elements
Good for heavy elements Good for light elements
Resolution and less optimal for light and less optimal for heavy
elements elements
Measurement Simultaneous Simultaneous / sequential
Costs Relatively inexpensive Relatively expensive
OVERVIEW FOR ELEMENTAL ANALYSIS BY XRF

 Instrument and lab preparation

 Instrument calibration

 Sample preparation for cement application

 Validation of calibration method

WHAT CAN BE ANALYSED BY X-RAY FLUORESCENCE?

Oils Polymers Ores and Raw Materials

Metals, Slags

Chemicals Ceramic Food Products

Glass
 INSTRUMENT AND LAB PREPARATION

 ASTM C-114 and IS 12803, “ Standard Test Methods for Chemical

Analysis of Hydraulic Cement”

 Whatever method of analysis is used in the cement lab, it must meet

specified performance criteria for
• Precision and
• Accuracy
 IS 12803 prescribe the procedure for sample preparation.
• Pressed powder pellets or glass fusion beads can be used.
• Cements are prepared according to the normal routine procedures
employed in the laboratory.
 PARAMETERS FOR INSTRUMENT

• Performance of instrument is determined by

parameters like repetability, reproducibilty, stability
and accuracy.
• Repeatability is the probability that an analytical
result remains the same for repeated measurments
in short period of time. (mesuring same sample min
7 times)
• Stability: above same for long period of time
• Reproducibility: capability to repeatedly deliver the
same result for the same sample (unloading and
reloading of same sample).
• Accuracy: is the ability to obtain the correct result
 GENERAL PROCEDURE
First step: the laboratory must demonstrate that it is capable of
preparing samples in a reproducible manner
 Prepare from a typical cement production sample
 10 pressed pellets or glass beads using the existing sample
preparation procedure.
• Ensure that the bulk sample used for this test is
homogeneous.
 Measure the intensity of elements in the 10 pellets/beads
• E.g. CaO, SiO2, Al2O3, Fe2O3, MgO, Na2O, K2O, Mn2O3,
SO3, TiO2, P2O5
 Determine the Standard Deviation of the repetitive counts for
each element.
 MAXIMUM PERMISSIBLE VARIATIONS IN DUPLICATES

Constituent Maximum
difference  The maximum permissible values for the
between
duplicates (%±)
SiO2 0.16
standard deviation are listed.
Al2O3 0.20
 The two most critical elements are CaO and
Fe2O3 0.10
CaO 0.20 SiO2.
MgO 0.16
SO3 0.10  If either of these elements exceeds the values
Na2O 0.03
K2O 0.03 shown the sample preparation procedure is
TiO2 0.02
P2O5 0.03 unacceptable and the cause of deviation must
Mn2O3 0.03
be sought and rectified.
• INSTRUMENT CALIBRATION
 CALIBRATION PROCEDURE
Constituent Typical Concentration Ranges for
portland cement
After success in the First step: SiO2 20 – 23
preparation of at least 7 NIST Portland Al2O3 3–6
cement reference materials can be Fe2O3 2–4
undertaken CaO 61 – 67
MgO 0.5 – 4
• NIST 1880a, 1881a, 1882, 1883, SO3 2.0 – 4.5
1884a, 1885a, 1886a, 1886b, 2689, Na2O 0.1 – 0.5
2691, 8486, 633, 634 K2O 0.1 – 1.3
Intensities of the elements are measured TiO2 0.2 – 0.3
P2O5 0.1 – 0.25
Calibration curves are derived through Mn2O3 0.05 – 0.3
correlation with the known concentrations
The prepared reference materials used for
calibration are analysed as unknowns.

CONCENTRATION
These analytical results constitute the first
set of test data.

CALIBRATION PLOT
INTENSITY
 MAXIMUM PERMISSIBLE VARIATIONS IN RESULTS FOR
RAPID ANALYTICAL METHODS
Constituent Instrument Errors %(±) Maximum difference Standard deviation (%±)
between duplicates
(%±) IS 12803
SiO2 0.05 0.2 0.2
Al2O3 0.05 0.2 0.1
Fe2O3 0.05 0.1 0.1
CaO 0.05 0.3 0.5
MgO 0.05 0.2 0.2
SO3 0.05 0.1 0.1
Na2O 0.005 0.05 0.05
K2O 0.005 0.05 0.05
TiO2 0.005 0.03 0.05
P2O5 0.005 0.03 0.03
Mn2O3 0.005 0.03 0.03

• One day later: A new set of the same reference materials used for calibration is
prepared and now analysed as Unknowns. These analytical results constitute the
second set of test.
• Precision of the method is calculated by the difference between the two sets of
analyses obtained on separate days. Differences between the results may not exceed the
maximum differences between duplicates shown here
 XRF technique is very sensitive , therefore choosing the sample
and preparing it for the analysis are very important. Only a few
grams of sample is analysed in this technique, so it should be chosen
in such a way that the sample should represent the entire bulk
material.

 Sample should be homogeneous, otherwise the obtained results may

deviate much from the actual values

 As the surface roughness of the sample affects the fluorescent

intensities, surface of the sample should be smooth

 Sample should be clean and uncontaminated

 SAMPLE PREPARATION METHODS
 There are different sample preparation methods depending on
the nature of the sample (powder , solid , liquid)
 There are two different methods for the preparation of powder
samples

1) Pressed pellet method

2) Fusion bead method
Both methods have their own advantages and disadvantages
Pressed powder Fused beads
Fast Slow
Cheap Expensive
Can be used for XRF & XRD Only XRF
More accurate
Better stability over time
PRESSED PELLET METHOD
 Finely ground powder is made into a tablet (pellet) by applying high pressure

 Care has to be taken to ensure clean surface

 This is easy and less expensive method

FUSION BEAD TECHNIQUE

 Powder is mixed with flux, generally lithium borates, and fused at high
temperatures to obtained glassy disc of the material

 Samples prepared in this way has several advantages over the samples
prepared by pressed pellet method

 Contamination from the flux and decrease in the line intensity due to dilution
are the main draw backs of this technique
TYPICAL SAMPLES FOR X-RAY FLUORESCENCE

PRESSED PELLETS

FUSION BEADS
 SOURCES OF ERROR RELATED TO SAMPLE
 Sample preparation method

 Grain size effects (ideally should be less than 50 µm)

 Mineralogical effects

 Line interference due to overlap of one X-ray line on another

 Absorption (100%): matrix effect

 Enhancement (10%): matrix effect

 Sample selection

 Sample deterioration (e.g filters, polymers, sedimentation in

3
liquids) 7
 GRAIN SIZE EFFECTS

10 μm
COARSE PARTICLES
~ 50 μm

When the particles are coarser, only a few particles will be analysed and the
sample may not represent the entire bulk material.
10 μm

FINE PARTICLES
~ 10 μm

When the particles are finer, then sufficient number of particles will be analysed
and the sample well represents the entire bulk material.
 MINERALOGY EFFECT
Mineralogical effect is defined as the difference of absorption of the
fluorescent radiation in the particles of minerals of different chemical
compositions.
E.g Calibration with OPC samples and analyse of PSC or 5% limestone addition
OPC or PPC samples
 INTERFERENCE ON XRF INTENSITY
In the case of interference on XRF intensity of one
element due to others in the sample, the equation
Y=Mx+C takes the form of Y=Mx+C+terms involving
interfernces.
Interfering elements are
Si by Mg and Al
Al by Mg and S
Fe by Ca and Si
Ca by K
Mg by Ca
 MATRIX EFFECTS
Intesity of a line not only depends on the concentration of the element from which it
is originating, but also on the presence of the other elements in the matrix

Absorption

Characteristic radiation emitted from an element is absorbed or scattered by any the

other element in the matrix. In this way part of characteristic radiation from a
particular element will be absorbed and its intesity decreases

Enhancement

Characteristic radiation of one element excites other element in the matrix and
enhances its signal
 CALIBRATION VALIDATION
• Calibration plot is validated by refernce
samples analysis (NIST).
• Validation of unknown sample results by
conventional chemical analysis method.
• Drift correction of the calibration curve, If
check sample analysis is not within the limits
of repeatability.
sample CaO SiO2 Al2O3 Fe2O3 MgO SO3 Na2O K2O LOI

638 62.09 21.48 4.45 3.55 3.83 2.34 0.13 0.59 0.95
638* 62.05 21.52 4.48 3.43 3.70 2.10 0.15 0.54 0.95
calibration
310
62.46 20.88 5.28 3.72 2.29 2.08 0.287 0.60 0.88
310’
conventional
62.20 21.09 5.36 3.78 2.33 2.11 0.29 0.61 0.89
 ACCURACY
Constituent Maximum difference of
• Accuracy of the method is the average of
duplicates from SRM
measured by calculating the Certificate value (%)
average value of the two separate SiO2 0.2
determinations for each element of Al2O3 0.2
each standard. Fe2O3 0.1
 The difference between this CaO 0.3

average and the certified value for MgO 0.2

the standard must not exceed the SO3 0.1

values tabulated in the appended Na2O 0.05

K2O 0.05
Table
TiO2 0.03
P2O5 0.03
 When all specifications of ASTM Mn2O3 0.03
C- 114 are met, the instrument and
method are qualified.
 EQUIPMENT RELATED ERROR SOURCES

Systematic errors Random errors

• Sample repositioning • Counting errors

• Goniometer repositioning • Tube and generator
• X-ray tube deterioration stability
• Short term drift • Electric/Electronic
• Long term drift stability
• Dead time correction
• Operating parameters selection
OTHER SOURCES OF ERRORS

 Operator
 Regression technique
 Standards accuracy
 Standards stability
 Standards composition
 Standards range
 Calculation philosophy

 But the biggest error comes from:

 SAMPLING
 APPLICATIONS OF XRF IN CEMENT INDUSTRY
Quarry guidance

Limestone stockpile monitoring and control

Chemical characterization of additives / corrective materials

Raw mix proportioning and quality control

Kiln feed monitoring

 Composition of clinkers, cements, pozzolanic, gypsum etc..,

Chemical characterization of build-ups, rings etc. in

rotary kilns
 QUICK

 ACCURATE

 SIMPLE (TO OPERATE)

 AMENABLE TO AUTOMATION

XRF FULFILLS ALL THE ABOVE REQUIREMENTS

 LIMITATIONS OF XRF TECHNIQUE

• Good standards are required for the calibration

• XRF analyses cannot distinguish ions of the same element in

different valence states

• This technique is not very suitable to find the low z (< 11) elements
CASE STUDY
QUALITY CONTROL SAMPLING POINTS
 MINES COMPOISTION
• Specific compliance of the avaliable materials and to ensure
that the major components will meet raw mix requirments
• Quality of the limestone deposited in the mines may not be
uniform and diffrent grades/types of limestone available at
diffrent locations.
• Blending of diffrent grades of limestones is controlled by
XRF in desired proportions and transpotrted to the stockpile.

Cconstituents % HG-LST MG-LST LG-LST

LOI
40.23 36.15 32.42
CaO 46.78 43.23 38.6
SiO2 6.74 15.12 21.69
Al2O3 0.66 1.23 2.45
Fe2O3 0.55 0.71 1.08
MgO 5.08 3.27 2.94
Na2O 0.06 0.07 0.24
K2O 0.15 0.36 0.69
Cl- 0.004 0.004 0.006
 STOCKPILE COMPOSITION
• Large quantity preseved/stored material for correct composition with
unifrom quality
• Pile quality is monitered by analysing the chemical analysis of
diffrent locations of samples and if quality is not upto desired level,
corrective action such as adding required quality of material in
desired quantity.
• General practice of pile quality parameter is Lime Saturation Factor
(LSF) and quick control/moniter technique is XRF analysis.
 RAW MATERIALS
Sample CaO SiO2 Fe2O3 MgO Na2O K2O Cl-
LOI (%) Al2O3 (%)
Code (%) (%) (%) (%) (%) (%) (%)

LST 35.16 41.68 12.92 1.16 0.68 3.56 0.08 0.32 35.16

IO 5.49 1.03 7.34 7.89 77.22 0.37 0.14 0.14 0.019

MS -5.49 0.68 0.53 0.09 97.55 0.26 0.13 0.04 0.013

BAX 17.59 0.17 7.49 33.13 36.14 0.05 0 0 0

Material Name
Raw Mix1
Limestone
95.4
Mill Scale 0.6
Bauxite 4.0

• The raw materials with desired weight proportions are conveyed to grinding mill and
percentages of these materials are designed based on the quality of the materials and quantity
of such materials is controlled/monitered by XRF
• Corrective actions are designed for quanity increase or decresed or addition of
sweetner/additive based on the quality of the materials.
 RAW MEAL
• The quality of raw meal is an
key parameter and it is
monitered and ensured by XRF
• If the quality of the material is
not meeting the required levels,
corrective action will be taken.

LOI SiO2 CaO MgO Fe2O3 Al2O3 LSF SM AM

(%)
(%) (%) (%) (%) (%)

RM-1
35.87 13.22 41.69 3.56 2.68 2.48 99.80 2.56 0.93
RM-2

35.93 13.12 41.59 3.74 2.52 2.57 100.2 2.58 1.02

 KILN FEED
• The quality of the material should be homogenious
for stable ruuning condition of kiln with desired
clinker quality.
• Raw Meal homogeneously mixed and extracted from
silo quality ensured by chemical analysis.
• Poor kiln feed quality and uniformity, caused by poor
raw mill control and low homogenization silo
efficiency leads to the undesired low clinker quality.
 CLINKER
SiO2 CaO MgO Fe2O3 Al2O3 SO3 Na2O K2O TiO2
(%) (%) (%) (%) (%) (%) (%) (%) (%)

CL-1 21.56 63.3 5.45 4.17 4.57 0.14 0.13 0.49 0.37

CL-2 21.43 63.23 5.72 3.94 4.71 0.14 0.16 0.52 0.38

Chemical analysis of material is used for process control in

clinker manufacture for demonstration specification
compliance and for relating chemical properties to
performance attributes.
 CEMENT
The control of the ground cement serves to ensure the designed cement quality
in terms of proportioning of constituents and achievement of the required
mechanical and physical properties.
Chemical constituents are related to other parameters
♦ Strength potential
♦ Cement expansion (Le Chatelier, autoclave)
♦ Cement reactivity
♦ Excessive heat consumption

SiO2 (%) CaO MgO Fe2O3 Al2O3 SO3 Na2O K2O TiO2
(%) (%) (%) (%) (%) (%) (%) (%)

OPC-1
21.02 61.66 5.21 3.98 4.40 2.02 0.13 0.47 0.35
OPC-2
20.90 61.59 5.46 3.76 4.53 2.02 0.16 0.50 0.36
 SUMMARY
• The defination of quality is the same product each time within
defined limits.
• Quality depends on how fast the measurment is done to enalble a
process/quality manager to assess whether the quality of the product
is maintained.
• Quality of the materials can be cntrolled by getting the analytical
results within reasonable time period and feedback given to
respective departement in order to take neccesary steps accordingly.
• Quality control and process optimization for cement maufacture
mainely depends on XRF
• Monitoring and controling the quality of materials from starting
stage to final product.
• XRF allows greater understanding of the quality of the material
within 30 mins and therefore greater control of the entire process
focusing on the ultimate quality of product of reduced costs.
• XRF plays a key role in on-line quality control of the final desired
product.
THANK YOU