Quality control by X-ray analysis in the Indian Cement industry

Mark Dirken
PANalytical

Contents
Quality control by X-ray analysis in the Indian Cement industry

XRF- WDS/EDS

WDS in India Simultaneous Sequential Alternative fuels/ Raw materials EDS/bench tops
XRD

XRD in India Free lime - Rietveld

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Quality control by WDXRF

Status Indian cement industry

Highly competitive Considering use of alternative fuels and raw

materials (AFRs) Optimizing plant operation Careful look at investments, also for quality control Conservative

WDXRF systems in India

Currently many Simultaneous WDXRF systems for production control I.e.

Wavelength dispersive, using Braggs law to

distinguish the energies

Fixed channels for measurement Fast analyses Reliable, (idiot) proof Sample surface up
4

Basics of Simultaneous XRF spectrometer

Simultaneous XRF All elements are measured simultaneously, In fixed optics for each element of interest (called channels)
5

PANalytical history of simultaneous systems

PW1606
MagiX FAST

PW1660

XCem for cement industry

CubiX

N.B.: Many simultaneous WDXRF systems are still used

6

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

Overview Cement Line

Frequency of analyses

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

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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 requirements via goniometer add-on? No net intensities for trace analysis (alternative raw materials and

fuels, i.e. AFRs) No liquid or loose powder samples (Alternative 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, from dolomites SiO2 from quartz NaCl and KCl from salts CaF2 salt Na2O and K2O from feldspars TiO2 from bauxites and other minerals MnO from iron ores

Iron ore

TiO2, MnO, Cr2O3 TiO2, Fe2O3

Bauxite
Combustibles

S from coal and oil P2O5 and Cl from (biological) waste Heavy trace elements from all types of materials

Clay:

Sand

Na2O and K2O from feldspars TiO2 from clays

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Primary materials - impurities When demands are changing. Competitive situation = changing situations:
Ever more pressure on improving plant performance Higher quality of product Control of properties, which are a result of structural phases
- Better control of properties (workability) leads to better planning of projects

Trends to stronger cements (from 32.5N to 42.5N and 52.5N)

More attention to 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 Light element performance
(multi layer crystals)

No element/compound limitations Sample surface down for flexibility Reliable measurement of liquids/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 Investigations - standardless analysis or Trace element analysis (AFRs)

Tmeas = 40 to 120 seconds

Sampel surface down?

Built-in dust collection device Avoids cross contamination Improves up-time

Vacuum Protects instrument mechanics

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Axios Cement Cement 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 Lime 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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CEMOXI proof?

Documentation/validation?

Per batch of CEMOXI samples

Tracing the concentrations to pure materials With results of international standards (NIST)

Proof?
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Results cement : Al2O3

Al2O3 BCS353 BCS354 BCS372 NIST-1880a NIST-1881a NIST-1882 NIST-1882a NIST-1883 NIST-1883a NIST-1884a NIST-1885a NIST-1886a NIST-1887 NIST-1887a NIST-1888 NIST-1888a NIST-1889 NIST-1889a X0201 X0202 X0203 X0204 X0205 X0206 X0207 X0208 Certified 3.77 4.85 5.35 5.18 7.06 38.60 39.14 71.20 70.04 4.26 4.03 3.88 5.59 6.20 5.35 4.27 5.61 3.89 6.55 39.31 5.21 9.79 3.94 6.52 4.97 5.38 Mean measured 3.83 4.85 5.38 5.22 7.18 38.25 39.28 71.21 69.98 4.29 4.01 3.85 5.59 6.17 5.36 4.33 5.57 3.81 6.51 39.32 5.22 9.84 3.97 6.55 5.01 5.41 Certmeas -0.06 0.00 -0.03 -0.04 -0.12 0.35 -0.14 -0.01 0.06 -0.03 0.01 0.02 0.00 0.03 -0.01 -0.07 0.04 0.08 0.04 -0.01 -0.01 -0.05 -0.03 -0.03 -0.04 -0.03
Al2O3 80 70

y = 0.999x R2 = 1.000

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Mean measured

50

40

30

20

10

0 0 20 40 Certified 60 80

Courtesy BGS

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Results cement: CaO

CaO BCS353 BCS354 BCS372 NIST-1880a NIST-1881a NIST-1882 NIST-1882a NIST-1883 NIST-1883a NIST-1884a NIST-1885a NIST-1886a NIST-1887 NIST-1887a NIST-1888 NIST-1888a NIST-1889 NIST-1889a X0201 X0202 X0203 X0204 X0205 X0206 X0207 X0208 Certified 64.80 70.00 65.80 63.83 57.58 37.60 39.29 27.80 29.52 62.26 62.39 67.87 62.88 60.90 63.78 63.23 65.08 65.34 60.56 38.01 64.97 51.58 69.25 55.67 61.38 56.04 Mean measured 64.54 69.02 65.78 64.28 58.13 37.25 38.89 27.39 29.24 62.15 62.30 67.46 62.88 60.48 63.71 63.17 64.65 65.07 60.44 38.02 64.70 51.38 69.07 55.38 61.40 56.13 Certmeas 0.26 0.98 0.02 -0.45 -0.55 0.35 0.40 0.41 0.28 0.11 0.09 0.41 0.00 0.42 0.07 0.06 0.43 0.27 0.12 -0.01 0.27 0.20 0.18 0.29 -0.02 -0.09
CaO 80 70 60

y = 0.997x R2 = 0.999

Mean measured

50 40 30 20 10 0 0 20 40 Certified 60 80

Courtesy BGS

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Trace element analysis (AFRs)

Issues:

Accuracy = Net intensities needed:

Determination of Line overlaps

Background intensities

Reference samples?

Suite of synthetic set up samples

Time: does it fit in routine control procedures?

YES (30 40 min if optimized for key elements)

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(Pro-)Trace element analysis(AFRs):Sewage sludge

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(Pro-)Trace element analysis(AFRs):Sewage sludge

Methode Herkomst analyseresultaten Pro-Trace II

WZML slib

WZML slib

WZML slib

WZML slib

WZML slib

WZML slib

WZML slib

WZML slib

WZML slib

Monsteromschrijving Monstercode Sporenelementen Arseen Barium Cadmium Kobalt Chroom Koper Kwik Molybdeen Nikkel Lood Antimoon Seleen Tin Thallium Vanadium Zink

As Ba Cd Co Cr Cu Hg Mo Ni Pb Sb Se Sn Tl V Zn

031 g/g* 3.38 402 <LLD 29.4 76.9 232 0.53 8.81 26.6 122 7.67 1.20 33.9 <LLD 34.9 881

032 g/g* 3.37 412 <LLD 36.2 78.1 239 0.20 9.05 26.6 125 8.25 1.06 34.5 <LLD 37.7 905

033 g/g* 3.24 393 <LLD 25.6 75.2 233 1.63 8.34 25.7 122 8.60 1.26 33.9 <LLD 32.8 880

034 g/g* 4.50 400 <LLD 50.3 73.9 232 <LLD 8.67 26.1 122 7.99 0.77 32.5 <LLD 34.5 879

035 g/g* 3.29 399 <LLD 29.1 72.5 231 <LLD 8.63 25.7 123 8.91 1.44 32.4 <LLD 33.0 875

036 g/g* 4.09 395 <LLD 32.2 73.3 232 <LLD 8.64 25.3 122 9.00 1.17 34.1 <LLD 31.1 877

037 g/g* 3.81 397 <LLD 27.3 73.2 231 1.30 8.57 26.6 122 7.71 1.26 32.9 <LLD 33.2 879

038 g/g* 4.10 400 <LLD 26.6 72.2 232 0.33 8.36 25.6 124 7.08 1.45 32.1 <LLD 33.6 878

039 g/g* 4.96 389 <LLD 33.4 76.4 230 4.42 8.79 25.2 122 7.37 1.22 32.3 <LLD 33.8 875

040 g/g* 4.58 394 <LLD 28.3 74.3 229 0.66 8.41 25.6 122 8.28 1.29 32.0 <LLD 33.1 866

WZML slib

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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 surface down for flexibility Meet demands in routine analysis Ad hoc investigations Trace element analysis (Control of AFRs)

Sequential systems are versatile

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EDS Bench tops?

EDS Bench tops Used:

Small plants, grinding plants, quarries Back up of larger systems (optimizing plant
operations)

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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

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XRD analysis in India cement industry?

Clinker analysis Free lime determination based on a

straight line calibration

Interest in full Rietveld analysis for phase quantification

Phase analysis of cement/clinker?

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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 more predictable properties Knowledge of properties in advance leads to a better control in cement manufacturing Kiln operation Milling of clinker Cement blending
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Why phase analysis in cement production?

Hence, process control of the phase composition enables optimization of plant operations and final products Microscopy?
Speed of analysis? Automation

XRD?

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Phase Analysis in Clinker/Cement (1)

XRD Clinker/cement quantitative analysis is not possible with a straight line calibration, because of:

Calibration samples are often not stable over time and very complex to obtain Many phases are possible In XRD diagrams strong and pronounced peak overlaps are common Peak shifts due to composition changes (solid solutions) happen often (= Con, Pro= immobilization of impurities in clinker)
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Overlapping Peaks of Clinker Phases

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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 diffraction pattern is calculated From the sum of all present phases, a total pattern is generated patterns is minimized by varying the refinement parameters in the model

The difference between observed and calculated

Rietveld is the only possible method to quantify phases in clinker/cement

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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: Quarry, kiln 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

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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 mill operation Individual characterization of sulfate phases (Anhydrite, Bassanite and Gypsum) for better prediction of the hydraulic properties, leading to improved performance and handling.

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XRD phase analysis in cement manufacturing!

Solution for quality control: Rietveld method for phase analysis: requires high quality measurement data (full

scan) knowledge of phases and refinement strategies.

High quality measurement data in time:

The RTMS XCelerator detector delivers high quality XRD data within minutes, enabling production control

Reliable XRD system for production control:

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XRD phase analysis in cement manufacturing!

Solution for quality control: Rietveld method for phase analysis: requires high quality measurement data (full

scan) knowledge of phases and refinement strategies.

High quality measurement data in time:

The RTMS XCelerator detector delivers high quality XRD data within minutes, enabling production control

Reliable XRD system for production control:

CubiX FAST system with analysis knowledge

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Qualitative Phase Analysis (Example)

1 minute measurement time

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Example Quantitative Rietveld Results

(4 main phases only)
Counts 1) 2) 3) 4) C3A C4AF C3S C2S

2000

1500

1000

500

0 100 0 -100 20 30 2Theta 40 50

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Quantitative Results for Main Phases

Phase NIST
(Microscopy)

XRD
(Rietveld)

Alite
Belite

64.97 % (0.56 %) 18.51 % (0.58 %) 4.34 % (1.35 %) 12.12 % (1.50 %)

65.2 % (0.2 %)* 18.2 % (0.8 %)* 4.7 % (0.2 %)* 11.9 % (0.7 %)*

Aluminate
Ferrite

NIST values are certified standard values (est. std. dev.) in [%]
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Quantitative Results of CEM-II:

Determination of Calcite and Sulfate phases

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CEM-II Results:
Determination of Calcite and Sulfate phases

Phase CaCO3, Calcite CaSO4, Anhydrite CaSO4 . 0.5 H2O, Bassanite CaSO4 . 2 H2O, Gypsum

Concentration in Cement 5.4% < 0.5% 1.4% 1.1%

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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 mill operation Individual characterization of sulfate phases (Anhydrite, Bassanite and Gypsum) for better prediction of the hydraulic properties, leading to improved performance and handling.

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Summary
Quality control by X-ray analysis in the Indian Cement industry

XRF- WDS/EDS

WDS in India Simultaneous Sequential Alternative fuels/ Raw materials EDS/bench tops
XRD

XRD in India Free lime Rietveld analysis

49

Quality control by X-ray analysis in the Indian Cement industry

Mark Dirken
PANalytical

Thank you for your attention

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