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Quality control by X-ray analysis in the
Indian Cement industry
Mark Dirken
PANalytical
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Contents
Quality control by X-ray analysis in the
Indian Cement industry
XRF- WDS/EDS
WDSin I ndia
SimultaneousSequential
Alternative fuels/ Raw materials
EDS/bench tops
XRD
XRD in I ndia
Free lime - Rietveld
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Quality control by WDXRF
Status Indian cement industry
H ighly competitive
Considering use of alternative fuels and raw
materials (AFRs)
Optimizing plant operation
Careful look at investments,
also for quali ty control
Conservative
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WDXRF systems in India
Currently many Simultaneous WDXRF
systems for production control
I.e.
Wavelength dispersive, using Braggs law to
distinguish the energies
F ixed channels for measurement
Fast analyses
Reliable, (idiot) proof
Sample surface up
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Basics of Simultaneous XRF spectrometer
Simultaneous XRF
All elements are measured simultaneously,
In fixed optics for each element of interest (called channels)
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PANalytical history of simultaneous systems
PW1660
PW1606
MagiX FAST
XCem for
cement industry
N.B.: Many simultaneous WDXRF systems are still used
CubiX
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Current Simultaneous XRF spectrometer - CubiX
CubiX with 8 or 9 fixed channels Designed for automation,
Easy to operate, idiot proof
Low maintenance costs,
No water cooling
Sample surface up
14 fixed channels
11 fixed channels + 1 goniometer
Tmeas
= 60 to 120 seconds
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Cement Plant
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Overview Cement Line
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XRF Analysis frequency per Kiln
Raw mix 4/hour
Kiln feed 1/hour
Raw materials 1/day to 1/week
Clinker 1/hour
Cement 1/hour during dispatch
Combustibles 1/day to 1/month
Frequency of analyses
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Simultaneous WDXRF?
What to analyze in principle?
Only 8 elements + 1 Na, Mg, Al, Si, S, K, Ca, Fe and
Cl
Simultaneous WDXRF:
Elemental analysis optimized for selected set of elements
Adjustment to new requi rements via goniometer add-on?
No net intensities for trace analysis (alternati ve raw mater ials and
fuels, i.e. AFRs)
No liquid or loose powder samples (Alternati ve fuels)
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Analysis requirements?
For XRF 4 major compounds
CaO
SiO2
Al2O3
Fe2O3
And SO3
But primary materials.
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Primary materials - impurities
Limestone
MgO, fr om dolomites
SiO2fr om quartz
NaCl and KCl f rom salts
CaF2salt
Clay:
Na2O and K2O fromfeldspars
TiO2f rom bauxites and
other minerals
MnO from iron ores
Sand
Na2O and K2O from
feldspars
TiO2f rom clays
Iron ore
TiO2, MnO, Cr2O3
Bauxite
TiO2, Fe2O3
Combustibles
S from coal and oil
P2O5and Cl from
(biological) waste
Heavy trace elements
from all types of mater ials
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When demands are changing.Competitive situation = changing situations:
Ever more pressure on improving plant performance
H igher quali ty of product
Control of properties, which are a resul t of structural phases
- Better control of properties (workabil i ty) leads to better
planning of projects
Trends to stronger cements (f rom 32.5N to 42.5N and 52.5N)
More attention to impurities
Primary materials - impurities
More flexibility for XRF equipment
Trend towards sequential systems
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Basics of a Sequential XRF system
WD Sequential XRF : Sequential measurement of
elements, by selecting the angle and crystal
Bragg: n=2dsin
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Sequential XRF systems
Optimization for each element
Tube / close coupling tube sample
L ight element performance
(multi layer crystals)
No element/compound limitations
Sample surface down for flexibility
Reliable measurement of l iquids/oil !
Dust?
You must know what you are doing, but..
You do not have to know all analysis
requirements when you order the spectrometer!
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Axios-Cement: Sequential spectrometer
2.4 kW sequential ( Be - U )
Upgradeable to 4kW
Super sharp tube for long life time
Sequential optics with goniometer
Sample surface down (Versatility for sample types)
Dust collection device !!!
Dedicated cement analysis package
Configurable for:
Automation
S2-/SO32-analysis
I nvestigations - standardless analysis or
Trace element analysis (AFRs)
Tmeas
= 40 to
120 seconds
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Sampel surface down?
Built-in dust collection device
Avoids cross contamination
Improves up-time
Vacuum
Protects instrument mechanics
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Axios CementCement software
Dedicated for cement industry:
CEMOXI application and samples
XRD phase names to report Rietveld
analysis results
Default applications: Bead
PP = pressed pellet
PAN = measured example
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CEMOXI reference materials
Synthetic reference samples dedicated for
cement applications: Raw mix
Clinker
L ime stone
Gypsum
10 grams of each sample for beads
Covered compounds:
Na2O, MgO, Al2O3,SiO2, P2O5, SO3, K2O, CaO,
TiO2, Fe2O3, Mn2O3, ZnO, SrO
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CEMOXI: XRD analysis of sample
Mainly:
Lime
Quartz
No cement
or clinker
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CEMOXIproof?
Documentation/validation?
Per batch of CEMOXI samples
Tracing the concentr ations to pure mater ials
With resul ts of international standards (NIST)
Proof?
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Results cement : Al2O3Al2O3
y = 0.999x
R2
= 1.000
0
10
20
30
40
50
60
70
80
0 20 40 60 80
Certified
Meanmeas
ured
Al2O3 Certified
Mean
measured
Cert-
meas
BCS353 3.77 3.83 -0.06
BCS354 4.85 4.85 0.00
BCS372 5.35 5.38 -0.03
NIST-1880a 5.18 5.22 -0.04
NIST-1881a 7.06 7.18 -0.12
NIST-1882 38.60 38.25 0.35
NIST-1882a 39.14 39.28 -0.14
NIST-1883 71.20 71.21 -0.01
NIST-1883a 70.04 69.98 0.06
NIST-1884a 4.26 4.29 -0.03
NIST-1885a 4.03 4.01 0.01
NIST-1886a 3.88 3.85 0.02
NIST-1887 5.59 5.59 0.00
NIST-1887a 6.20 6.17 0.03
NIST-1888 5.35 5.36 -0.01
NIST-1888a 4.27 4.33 -0.07
NIST-1889 5.61 5.57 0.04
NIST-1889a 3.89 3.81 0.08
X0201 6.55 6.51 0.04
X0202 39.31 39.32 -0.01
X0203 5.21 5.22 -0.01
X0204 9.79 9.84 -0.05
X0205 3.94 3.97 -0.03
X0206 6.52 6.55 -0.03
X0207 4.97 5.01 -0.04
X0208 5.38 5.41 -0.03
Courtesy BGS
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Results cement: CaOCaO Certified
Mean
measured
Cert-
meas
BCS353 64.80 64.54 0.26
BCS354 70.00 69.02 0.98
BCS372 65.80 65.78 0.02
NIST-1880a 63.83 64.28 -0.45
NIST-1881a 57.58 58.13 -0.55
NIST-1882 37.60 37.25 0.35
NIST-1882a 39.29 38.89 0.40
NIST-1883 27.80 27.39 0.41
NIST-1883a 29.52 29.24 0.28
NIST-1884a 62.26 62.15 0.11
NIST-1885a 62.39 62.30 0.09
NIST-1886a 67.87 67.46 0.41
NIST-1887 62.88 62.88 0.00
NIST-1887a 60.90 60.48 0.42
NIST-1888 63.78 63.71 0.07
NIST-1888a 63.23 63.17 0.06
NIST-1889 65.08 64.65 0.43
NIST-1889a 65.34 65.07 0.27
X0201 60.56 60.44 0.12
X0202 38.01 38.02 -0.01
X0203 64.97 64.70 0.27
X0204 51.58 51.38 0.20
X0205 69.25 69.07 0.18
X0206 55.67 55.38 0.29
X0207 61.38 61.40 -0.02
X0208 56.04 56.13 -0.09
CaO
y = 0.997x
R2
= 0.999
0
10
20
30
40
50
60
70
80
0 20 40 60 80
Certified
Meanmeasu
red
Courtesy BGS
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Trace element analysis (AFRs)
Issues:
Accuracy = Net intensities needed:
Reference samples?
Time: does it fit in routine control
procedures?
Determination of Background intensities
L ine over laps
Suite of synthetic set up samples
YES (3040 min if optimized for key elements)
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(Pro-)Trace element analysis(AFRs):Sewage sludge
(P )T l t l i (AFR ) S l d
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(Pro-)Trace element analysis(AFRs):Sewage sludge
Methode Pro-Trace II
Herkomst analyseresultaten
Monsteromschrijving WZMLslib
WZMLslib
WZMLslib
WZMLslib
WZMLslib
WZMLslib
WZMLslib
WZMLslib
WZMLslib
WZMLslib
Monstercode 031 032 033 034 035 036 037 038 039 040
Sporenelementen g/g* g/g* g/g* g/g* g/g* g/g* g/g* g/g* g/g* g/g*
Arseen As 3.38 3.37 3.24 4.50 3.29 4.09 3.81 4.10 4.96 4.58
Barium Ba 402 412 393 400 399 395 397 400 389 394Cadmium Cd
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Conclusion on sequential systems
Sequential systems are reliable
Meet the norms (easily)
Goniometer for free selection of elements/compounds
(Future analysis requirements)
Sample sur face down for f lexibil i ty
Sequential systems are versatile
Meet demands in routine analysis
Ad hoc investigations
Trace element analysis (Control of AFRs)
EDS B h t ?
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EDS Bench tops?
EDS Bench tops
Used:
Small plants, grinding plants, quarr ies
Back up of larger systems (optimizing plant
operations)
Mi iP l 2
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MiniPal 2 Top of the Range - Bench Top
EDXRF Na - U
ppm to 100%
9W X-Ray Tube
12 position sample changer
Multiple Filters
Windows s/w Controlled
PIN detector
Spinner
XRD l i i I di t i d t ?
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XRD analysis in India cement industry?
Clinker analysis Free lime determination based on a
straight l ine calibration
Interest in full Rietveld analysis
for phase quantification
Phase analysis of
cement/clinker?
Why phase analysis in cement production?
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Why phase analysis in cement production?
Cement production norms are based on
Chemical composition
Physical/mechanical properties (strengths, setting time, etc.)
Physical properties are MAINLY depending on the
phase composition (not the elemental composition)of clinker
Better control of the clinker phases leads directly to morepredictable properties
Knowledge of properties in advance leads to a better
control in cement manufacturing Ki ln operation
Mil ling of clinker
Cement blending
Why phase analysis in cement production?
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Why phase analysis in cement production?
Hence, process control of the phase
composition enables optimization of plantoperations and final products
Microscopy?
XRD?
Speed of analysis?
Automation
Ph A l i i Cli k /C t (1)
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Phase Analysis in Clinker/Cement (1)
XRD Clinker/cement quantitative
analysis is not possible with a straight linecalibration, because of:
Calibration samples are often not stable
over time and very complex to obtain
Many phases are possible
I n XRD diagrams strong and pronounced
peak over laps are common
Peak shif ts due to composition changes
(solid solutions) happen often (= Con,
Pro= immobili zation of impur ities in cl inker)
O l i P k f Cli k Ph
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Overlapping Peaks of Clinker Phases
Ri t ld M th d O tli
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Rietveld Method - Outline
The Rietveld method uses all XRD peaks and the
complete profile for the analysis: For each phase present, the dif fraction pattern is
calculated
From the sum of all present phases, a total pattern is
generated
The dif ference between observed and calculated
patterns is minimized by varying the ref inement
parameters in the model
Rietveld is the only possible method to quantify
phases in clinker/cement
Riet eld Method Application
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Rietveld Method -Application
Rietveld is very precise, but not always accurate,
especially when used for clinker or cement
Cement/clinker are local products, with structures depending
on: Quar ry, ki ln operation (size, procedures, use of fuels,
AFRs),
PANalytical tunes the Rietveld method using data from
microscopy to obtain true referenced phase
concentrations.
Rietveld precision with microscopy accuracy gives
absolute quantification of phases True production control
Benefits of phase analysis:
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Benefits of phase analysis:
Absolute quantification allows prediction of product
properties for true production control: Reduction of clinker in cement (one 1% less clinker =
150kEuro per annum for an average plant)
Knowing clinker composition beforehand helps to
optimize the mil l operation
I ndividual character ization of sul fate phases
(Anhydrite, Bassani te and Gypsum) for better
prediction of the hydraul ic properties, leading to
improved performance and handling.
XRD phase analysis in cement manufacturing!
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XRD phase analysis in cement manufacturing!
Solution for quality control:
Rietveld method for phase analysis:
requires high quali ty measurement data (ful l
scan)
knowledge of phases and ref inement strategies.
High quality measurement data in time:
The RTMS XCelerator detector delivers high quality
XRD data with in minutes, enabling production
control
Reliable XRD system for productioncontrol:
XRD phase anal sis in cement man fact ring!
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XRD phase analysis in cement manufacturing!
Solution for quality control:
Rietveld method for phase analysis:
requires high quali ty measurement data (ful l
scan)
knowledge of phases and ref inement strategies.
High quality measurement data in time:
The RTMS XCelerator detector delivers high quality
XRD data with in minutes, enabling production
control
Reliable XRD system for productioncontrol:
CubiX FAST system with analysis knowledge
Qualitative Phase Analysis (Example)
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Qualitative Phase Analysis (Example)
1 minute
measurement time
Example Quantitative Rietveld Results
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Example Quantitative Rietveld Results
(4 main phases only)
2Theta
20
2Theta
30
2Theta
40
2Theta
50
Counts
1) C3A
2) C4AF
3) C3S
4) C2S
0
500
1000
1500
2000
0
100
-100
Quantitative Results for Main Phases
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Quantitative Results for Main Phases
NIST values are certified standard values (est. std. dev.) in [%]
Phase NIST(Microscopy)
XRD(Rietveld)
Alite 64.97 %(0.56 %)
65.2 %(0.2 %)*
Belite 18.51 %(0.58 %) 18.2 %(0.8 %)*Aluminate 4.34 %
(1.35 %)4.7 %
(0.2 %)*
Ferrite 12.12 %(1.50 %) 11.9 %(0.7 %)*
Quantitative Results of CEM II:
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Quantitative Results of CEM-II:Determination of Calcite and Sulfate phases
CEM II Results:
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CEM-II Results:
Phase Concentration in
CementCaCO3,
Calcite
5.4%
CaSO4,
Anhydrite
< 0.5%
CaSO4 . 0.5 H2O,
Bassanite
1.4%
CaSO4 . 2 H2O,
Gypsum
1.1%
Determination of Calcite and Sulfate phases
Benefits of phase analysis:
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Benefits of phase analysis:
Absolute quantification for true production control
allows prediction of product properties: Reduction of clinker in cement (one 1% less clinker =
150kEuro per annum for an average plant)
Knowing clinker composition beforehand helps to
optimize the mil l operation
I ndividual character ization of sul fate phases
(Anhydrite, Bassani te and Gypsum) for better
prediction of the hydraul ic properties, leading to
improved performance and handling.
Summary
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Summary
Quality control by X-ray analysis in the
Indian Cement industry
XRF- WDS/EDS
WDSin I ndia
SimultaneousSequential Alternative fuels/ Raw materials
EDS/bench tops
XRD
XRD in I ndia
Free limeRietveld analysis
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Quality control by X-ray analysis in the
Indian Cement industry
Mark Dirken
PANalytical
Thank you for your attention
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