0322 panalytical

8/22/2019 0322 PANalytical

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Quality control by X-ray analysis in the

Indian Cement industry

Mark Dirken

PANalytical


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Contents



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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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



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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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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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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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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



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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



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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Mark Dirken

PANalytical

Thank you for your attention

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