1

X-Ray Diffraction and its

Application in the Industry

Sabine Verryn

Overview

� General & analytical procedures

� Iron ore sinters

� Ilmenite roasting

� Oxidation of Titania Slags

� Heavy Mineral Sands

� Coal & related materials

2

3

LiquidState

Crystalline(ordered)

SolidState

Atoms, ions, molecules

GaseousState

Amorphous(disordered)

Matter

The Crystalline State

4

Pyrite – FeS 2

Ruby - Al 2O3

The Crystalline State

3

X-Ray Diffraction (XRD)

� Each crystalline phase has a unique powder diffraction pattern

� Therefore it is possible to distinguish between compounds as the diffraction method is sensitive to structure and not just composition

� The powder diffraction pattern for the spinel MgAl2O4 looks different from the powder pattern of a MgO and Al2O3 mixture

� It is possible to distinguish between different polymorphic forms of the same compound

� Can distinguish between rutile and anatase (Both TiO2)

Crystallographic Planes

� nλ = 2d sin θ

4

What is XRD ?

� Result of an XRD measurement is a diffractogram, showing crystalline phases present (peak positions), phase concentrations (peak areas), amorphous content (background hump) and crystallite size/strain (peak widths).

Position [°2Theta] (Cobalt (Co))

20 30 40 50 60 70 80

Counts

0

5000

10000

15000

IronOreHematite 70.2 %Magnetite 4.9 %Goethite 14.3 %Quartz 10.6 %

7

PHASE IDENTIFICATION

� indirect method, like a police fingerprint

� Fingerprint � Database � Match found

� Identification �� More knowledge

� Distances between planes in a crystalline lattice are measured

Position [°2Theta] (Cobalt (Co))

20 30 40 50 60 70 80

Counts

0

5000

10000

15000

IronOreHematite 70.2 %Magnetite 4.9 %Goethite 14.3 %Quartz 10.6 %

8

5

XRD more info…

� X-ray diffraction has progressed significantly in the past decade from a mainly qualitative technique for the identification of crystalline materials to a quantitativetool

� Rietveld Analysis� The most reliable way for the quantification of crystalline (and

amorphous phases)� The method uses the full XRD pattern to refine the phase

quantities� Preferred orientation of particles can be modelled� Other important information such as particle size and lattice

strain can also be determined� The results are now very reliable – provided that they are

independently checked by other methods

Phase Quantification using XRD

� However… No textural features can be observed

� No distinction between primary and secondary minerals� Can distinguish phases of same composition (hematite, magnetite

and wuestite) (rutile, anatase) etc� A standard needs to be added to determine amorphous phase

content

� Aim: illustrate the possibilities of this method, but

also point out potential errors and pitfalls using

various industrial examples

6

2 theta / deg

I/ rel.

15 20 25 30 35 40 45 50 55 60 65 70

2443

1221

0

M3O5

002

020

021

022

111

112

023

004130 113

131 024

114

133

200

025

202

115

151 006

152

061

026223

204

241

224

136

064

J5.RAW

XRD - Structure

M3O5

• The XRD pattern is a direct representation of the structure of a phase

• Very similar patterns are possible when isomorphous replacement takes place, eg., replacement of Al for Cr, and Fe for Mg in spinelssuch as magnetite and chromite.

• The experimental XRD pattern is compared to the calculated one. The Rwp factor is an indication of the correspondence between the two.

Requirements for Rietveld Analysis

� Accurate crystal structure parameters

� Well prepared samples with sufficiently small particle sizes

� Sample presentation as random as possible, although preferred orientation can be corrected

� Well aligned instrumentation so that accurate data can be collected

� Data collected with sufficient resolution (~0.01°2θθθθ ) and adequate intensity (~10K counts per step)

� Elimination of sample micro-absorption by selection of suitable radiation

� Elimination of sample fluorescence by use of monochromators

� More routine use of internal standards to check the accuracy of refinement

7

Analytical method - XRD

� Crushing, splitting, milling, (micronizing)

� preparation for XRD analysis using back a loading method.

� Analysing using a PANalytical X’Pert Pro powder diffractometerwith X’Celerator detector and variable divergence- and receiving slits with Ni filtered Cu-Kα and Fe filtered Co-Kα radiation

� Phase identification using X’Pert Highscore plus software

� Quantification by Rietveld software using Fundamental Parameter Approach

� Addition of 15 to 20 per cent Si powder (Aldrich 99% purity), for verification of results or determination of non-crystalline phase content

� micronized in a McCrone micronizing mill

Example: Iron Ore Sinter Characterization

� When iron ores are crushed, large amounts of fines are

produced

� Reduce permeability of material in a blast furnace� Essential to introduce feed in a lumpy form

� Fines contain large amounts of iron units

� Discarding these fines would be a significant commercial loss to the steel making industry

� The ore fines can be agglomerated by sintering at

elevated temperatures (± 1300ºC)

� Sinters are the preferred blast furnace feedstock

because of feed homogeneity - resulting in better

steels

8

Sinters in Steelmaking

Heterogeneous assembly of mineral phases – dependent on temperature (coke addition), and composition

The Sinter Process

Heterogeneous assembly of mineral phases – dependent on temperature (coke addition), and composition

Heat supplied by the combustion of coke breeze – dependent on coke addition

9

Sinter Phases - Quality of the Sinter

� C2S can form a number of polymorphs.

� With decreasing temperature:

� α-polymorph - then α’ - then β - finally γ-C2S form.

� The transformation between the β and γ-C2S is accompanied with a large

volume increase, commonly causing a spectacular disintegration.

� Therefore the β -polymorph in sinters is undesirable

� Hematite – less desirable in the Blast Furnace� Breakdown of sinter due to reduction reaction :

� 3Fe2O3

+ CO = 2Fe3O4

+ CO2

∆V = 15-20%

� Other Calcium silicates and ferrites� Gehlenite (Ca

2(Al,Fe)(AlSi)O

7) is the preferred Ca silicate – no decrepitation

reaction

� Silicate bonding increases strength but lowers reducibility� CaO/SiO2 ratio optimized for that

� SFCA is the most elusive and difficult phase to characterize

SFCA

� SFCA (silico-ferrite of calcium and aluminium) are common phases in iron ore sinters

� SFCA M14+6n

O20+8n

(Aenigmatite str.)

� SFCA M14O20 (M/O = 0.700)

� SFCA-I M20O28 (M/O = 0.714)

� SFCA-II M26O36 (M/O = 0.722)

� Millions of tons are produced and sinter properties are dependent on SFCA type and quantity

10

Sinter Compositions• SFCA is a major

component. However,

small compositional

changes can affect the

phase assemblage

drastically

• We need to form SFCA-I

(Acicular SFCA) - this

phase has the highest Fe

content and forms the

strongest sinter

• Temperature and Al-

content are the most

important factors affecting

SFCA-I stability

Sinters: Phase composition - methods

� Modal analysis

� Method where textures are observed which are

important for sinter quality – but time consuming

and only on 2-dimensional space

� Automated optical image analysis based on

reflectivity

� 2-dimensional space

� SEM based image analysis based on grey level

and chemical composition

� Cannot easily distinguish between grey level of

hematite, magnetite and wuestite

11

Sinters: Phase quantification using XRD

However…

� No textural features can be observed

� No distinction between primary and secondary

hematite

� Can distinguish between hematite, magnetite

and wuestite

Evaluation of Mittal Sinters by XRD

� XRD not in general use to evaluate sinters. Point

counting is used

� Are our results (coming from ~500g of sample

representative of the samples we took on the plant?

� Starting with 2Kg Bulk plant sample� Whole sample crushed in a gyratory crusher� Whole sample milled in a ball mill for ½ hour� Riffled to 1 Kg� Ball milled� Riffled to 500g – used for XRD & XRF analysis� XRD analysis according to the method described in the

beginning

12

XRF Analysis

� Phases observed:

� magnetite, hematite, beta- di-calcium silicate, SFCA,

SFCA-II and minor quartz

XRF Analysis

0

10

20

30

40

50

60

70

80

SiO2 Al2O3 Fe2O3 MnO MgO CaO

%

Sample 1

Sample 2

Sample 3

Sample 4

Calculated XRD Patterns for SFCA-phases (CoKα)

Position [°2Theta]

10 20 30 40 50 60 70 80

Counts

0

1000

2000

0

200

400

600

0

200

400

600

SFCA1

SFCAII

SFCA

The structures of SFCA, SFCA-I and SFCA-II were determined at CSIRO by Mumme and co-workers

13

Analysis of Variance

� We need to test the reproducibility of our

Rietveld quantification – same mount

� We need to test the reproducibility of our

sample packing and sample presentation to

the beam- same sub-sample

� We need to test the homogeneity and

representativeness of our subsamples –

different sub-samples

Analysis of Variance

C2S Hematite Magnetite SFCA I SFCA SFCAII Silicon

Identical Sample Mount

Mean 9.30 8.91 23.81 3.54 15.31 22.46 16.22 Standard Deviation 0.54 0.16 0.51 0.98 1.54 1.37 0.26

Same Subsample - Different Sample Mount

Mean 9.35 9.01 23.80 3.25 15.56 22.46 16.17 Standard Deviation 0.49 0.23 0.57 0.61 1.28 1.46 0.36

Different Subsamples

Mean 9.16 9.04 23.76 3.53 15.54 22.35 16.19 Standard Deviation 0.54 0.43 0.52 0.97 1.69 1.37 0.43

14

Synthetic SFCA: EMP analysis

0.1

1

10

100

1 3 5 7 9 11 13 15 17 19 21 23 25

Analysis Spot Number

Wei

ght %

Mg

Al

Si

Ca

Fe

53.5210.492.311.620.5329.97Starting Composition

0.650.470.160.170.030.40Standard Deviation

53.2310.202.611.830.5931.98Mean

FeCaSiAlMgO

Synthetic SFCA: Rietveld refinement – SFCA

Rwp = 6.36

15

Synthetic SFCA: Rietveld refinement – SFCA + SFCA-II

Rwp = 4.68

Mixture

� 45 weight % SFCA (although refinement not

defined totally)

� synthesized

� 25 weight % natural magnetite

� Contains some ilmenite

� 15 weight % synthetic hematite

� 15 weight % synthetic C2S (larnite)

� Micronized in McCrone mill to obtain homogeneity

16

Mixture: Rietveld refinement (1)

Refinement No 1

05

101520253035404550

Larnite Hematite Ilmenite Magnetite SFCA

Wei

ght %

Standard

Larnite 15

Hematite 15

Magnetite 25

SFCA 45Rwp = 3.3

Mixture: Rietveld refinement (2)

Refinement No 2

05

10152025303540455055

Larnite Hematite Ilmenite Magnetite SFCA SFCAII TotalSFCA

Wei

ght %

Standard

Larnite 15

Hematite 15

Magnetite 25

SFCA 45

Rwp = 2.84

17

Conclusions - Iron Ore Sinters

� Iron ore sinters are very complex in spite of their high

iron content

� The SFCA phases are still poorly understood – in spite

of good work

� XRD has the potential to give accurate, reproducible

phase quantification of iron ore sinters – despite

uncertain SFCA characteristics

� With care, it can be used to examine and evaluate

plant performance

� More work necessary

Cluster Analysis – Statistical data evaluation

� Huge numbers of samples are analyzed for exploration, process

and quality control in industrial environments

� Large amount of data

� Time effective method needed for data analysis

18

Cluster Analysis – Statistical data evaluation

Cluster around the most representative

Clu

ster

Cluster Analysis – Statistical data evaluation

� Full pattern cluster analysis is a new feature added to our X-ray powder diffraction analysis software packages X’Pert HighScore and X’Pert HighScore Plus

� Cluster analysis is a method that greatly simplifies the analysis of large amounts of data by:1) Automatically sorting all scans of one or more experiments

into closely related classes. 2) Identifying the most representative scan of each class.3) Identifying the two most different scans of each class.4) Identifying outliers not fitting into any class.

19

Cluster Analysis – PCA plot

• 3D graphical view gives confirmation about clusters and outlier (100 samples)

High grade Low grade

Medium grade

Example: Ilmenite Purification

� Ilmenite is used as a feedstock for rutile pigment production

� Impurities such as Cr and V are undesirable as they colour the white pigment

� Other impurities such as Ca and Mg cause problems in the fluid bed chlorination of ilmenite or titania slag, produced from ilmenite

� Most plants use oxidative roasting to modify the magnetic properties of ilmenite, so that it can easily be purified

� The Fe2+ is oxidised to Fe3+ with the formation of anatase or rutile:

FeTiO3

+ O2⇒ TiO

2+ (Fe

2O3-FeTiO

3)ss

� The longer the oxidation – the more Fe-rich the solid solution

20

Ilmenite Roasting – Cell constants

9085807570656055504540353025201510

I / c

ps

400

350

300

250

200

150

100

50

0

D i f f e r e n c e s

2 T h e t a / °9 08 58 07 57 06 56 05 55 04 54 03 53 02 52 01 51 0

I / c

ps

2 0 0

1 5 0

1 0 0

5 0

0

- 5 0

- 1 0 0

- 1 5 0

- 2 0 0

CoKααααa = 5.0843(2)Å

c = 13.9955(6)Å

V = 313.3 Å3

� Ilmenite (FeTiO3) → roasting → Fe-rich ilmenite + rutile (TiO2)

Tracking Ilmenite Magnetization – Unit Cell Volume

This is the most reliable way to track the extent of oxidation

21

Differences in Ilmenite magnetic susceptibilty

Before roasting:

Ilmenite and chromite

cannot be separated using

magnetic separation

After Roasting:

Ilmenite and chromite

can be easily separated

Example - Oxidation of Titania Slags

400°C

Non-ambient temperature XRDOxidation behaviour!

22

Dimensional Changes in M3O

5

(Pseudobrookite) Lattice Constants

3.72

3.74

3.76

3.78

3.80

50 100 150 200 250 300 350

Temperature (°C)a-

axis

(Å)

9.4

9.6

9.8

10.0

10.2

b,c-

axis

(Å)

a axis

b axis

c axis

M = Fe, Al, Ti3+, Ti4+

� A good example of

the power of Rietveld

refinement!

� Rietveld refinements

were done every 10

degrees.

� One cell dimension

expands, one

contracts and one

expands very slightly.

� This causes strain in

the material, causing

it to crack

Titania slag disintegration problem

Reflection micrograph perpendicular to the [010] direction showing transformation domains along major cracks in a single crystal of M3O5. Secondary cracks form perpendicular to the triangular domains. The secondary cracks are parallel to the c-crystallographic axis.

23

Example - Heavy Mineral Sands

� Ilmenite, rutile and zircon are common minerals found all over the world, but not always in economic concentrations. � In heavy mineral sands such as in parts along the South African

coast these minerals are concentrated.

� The heavy minerals ilmenite, rutile and zircon which are separated from the free-flowing sand dunes go into the manufacture of a wide array of products which are essential to our modern lifestyle.

Current Analytical Methods

� The plant is controlled/informed of the proportions of minerals in the Heavy Mineral Concentrate (HMC according to their magnetic susceptibility –

� divided into fractions, i.e.� Mags (0.05 to 0.8A fraction)

� Mag-Others (> 2.4A)

� Non-Mags

� weights are measured in the Physical Laboratory

� Very time consuming and labor intensive

� therefore we aim to show that, using quantitative XRD we can group the minerals found into the traditionally accepted magnetic fractions.

24

Heavy Mineral Sands: Basic Classifications

Mag- othersEpidote, Pyroxene, Amphibole, Leucoxene, Monazite,

Apatite,

MagsIlmenite, Magnetite, Chromite, Altered ilmenite,

Hematite, Garnet+Spinel+Clays

Non-MagsZircon+ Rutile+Quartz+Feldspars+Titanite Anatase

Mineral GroupingsTraditional Descriptions

Heavy Mineral Sands: XRD – Major Phases

Position [°2The ta]

10 20 30 40 50 60 70

C ounts

0

1000

2000

3000

RBM _Total_HMC

Peak List 01-089-2811; Fe Ti O3; Ilmenite 01-081-0588; Zr ( S i O4 ); Zircon 01-071-0650; Ti O2 ; Rutile, syn 01-089-0596; Fe2 O3; Hematite, syn 00-009-0436; Na2 F e3 Fe2 S i8 O22 ( O H )2; Riebeckite 01-083-2465; S i O2 ; Quartz low, syn 01-082-0599; C a M g ( S i2 O6 ); D iopside

25

Heavy Mineral Sands: XRD - Minor Phases

Position [°2Theta]

10 20 30 40 50

Counts

0

500

1000

RBM_Total_HMC

Peak List 00-017-0514; Ca2 Al2 Fe ( S i O4 ) ( Si2 O7 ) ( O , O H )2; Epidote 00-004-0612; ( Ce , La , Y , Th ) P O4; Monazite 00-025-0177; Ca Ti O ( Si O4 ); Titanite, syn 00-041-1423; Fe3 +2 A l2 ( Si O4 )3; Almandine, syn 00-041-1486; Ca Al2 S i2 O8; Anorthite, ordered 01-071-1167; Ti O2; Anatase 01-086-1351; Fe2.936 O4; Magnetite

Heavy Mineral Sands: Magnetic Fractions

0

10

20

30

40

50

60

70

80

90

Actin

olite

Alm

an

din

e

An

ata

se

Dio

psid

e

Ep

ido

te

He

ma

tite

Ilme

nite

Ma

gn

etite

Mo

na

zite

Pla

gio

clase

Qu

artz

Ru

tile

Tita

nite

Zirco

n

HMC3_0.05Magn HMC4_0.05Magn HMC3_0.6ILM HMC4_06ILM HMC3_0.8ILM HMC4_0.8ILM

Ilmenite, Magnetite, Chromite,

altered Ilmenite, Hematite, Garnet, Spinel, Clays

26

Heavy Mineral Sands: Mag-other Fraction

0

5

10

15

20

25

30

35

40

45

Actinolite

Alm

andine

Anatase

Diopside

Epidote

Hem

atite

Ilmenite

Magnetite

Monazite

Plagioclase

Quartz

Rutile

Titanite

Zircon

HMC3_MO

Epidote, Pyroxene, Amphibole, Leucoxene,

Monazite, Apatite,

Heavy Mineral Sands: Non-Mag Fraction

0

10

20

30

40

50

60

Actin

olite

Alm

an

din

e

An

ata

se

Dio

psid

e

Ep

ido

te

He

ma

tite

Ilme

nite

Ma

gn

etite

Mo

na

zite

Pla

gio

clase

Qu

artz

Ru

tile

Tita

nite

Zirco

n

HMC3_NM HMC4_NM

Zircon, Rutile, Quartz, Feldspars, Titanite, Anatase

27

Conclusion – Heavy mineral sands

� Results indicate that X-ray diffraction, combined with Rietveld

quantification, can provide fast, valuable information for mining and

process control in the heavy minerals industry through standardless

quantification.

� Today’s optics, detectors, and software can provide rapid and accurate

analyses, suitable for process control environments as well as research.

� The data obtained from XRD-Rietveld analysis compare well with the

MLA method for the main economic minerals rutile, zircon and ilmenite.

Minor differences, especially between hematite and magnetite, have

been observed and need further investigation.

� The detection limits on XRD Rietveld analysis is about 0.5 wt%. To

overcome these high detection limits, XRD can be combined with XRF

analysis, using the two techniques in tandem to provide mineral

information as well as trace element or contaminant information in

routine operations.

� But – the quantification of alteration minerals like leucoxene has to be

addressed

Coal and Coal – related materials

� XRD methods and interpretations which I have

applied

� Work still in progress and will be refined as

going along and gaining experience

� Strong and weak points

� not about coal, coke .. graphite – only XRD

applied to those materials

28

Raw Coal

Position [°2Theta] (Cobalt (Co))10 20 30 40 50 60 70 80

Counts

5000

10000

Rawcoal_1

Peak List

Quartz low, syn; Si O2

Kaolinite 1\ITA\RG; Al2 ( Si2 O5 ) ( O H )4

Anatase, syn; Ti O2

Siderite; Fe ( C O3 )

Muscovite-3\ITT\RG; ( K , Na ) ( Al , Mg , Fe )2 ( Si3.1 Al0.9 ) O10 ( O H )2

Raw Coal

Dry Ash Content: 73 %

3 σ error

Anatase 1.79 0.3

Calcite 0.67 0.25

Dolomite 0.13 0.19

Graphite 28.27 2.97

Kaolinite 48.11 2.01

Muscovite 3.32 0.26

Pyrite 0 0

Quartz 15.59 0.72

Rutile 0.5 0.17

Siderite 1.62 0.19

AnataseCalciteDolomite_FeGraphite 2H_Kaolinite C1, ideal, BISHMuscovite_2M1PyriteQuartzRutileSiderite

Rawcoal_1

2 Theta / °908886848280787674727068666462605856545250484644424038363432302826242220181614121086

I / c

ps

2,000

1,800

1,600

1,400

1,200

1,000

800

600

400

200

0

Differences

2 Theta / °908886848280787674727068666462605856545250484644424038363432302826242220181614121086

I / c

ps

600

400

200

0

-200

-400

-600

29

Raw Coal

Differences

2 Theta / °9590858075706560555045403530252015105

I / c

ps

200

150

100

50

0

-50

-100

-150

-200

AnataseAnkerite Fe0.2CalciteDolomiteGraphite 2H_Gypsum_Kaolinite C1, ideal, BISHMagnetitePyriteQuartzRutileSiderite

Wits_Monnamme_Coal_E.raw - Coal_E

2 Theta / °9590858075706560555045403530252015105

I / c

ps

500

450

400

350

300

250

200

150

100

50

0

Anatase 0.583 %

Ankerite Fe0.2 4.23 %

Calcite 2.68 %

Dolomite 0.183 %

Graphite 2H_ 53.5 %

Gypsum_ 0.692 %

Kaolinite C1, ideal, BISH 26.6 %

Magnetite 0.873 %

Pyrite 1.57 %Quartz 7.23 %Rutile 0.233 %

Siderite 1.582 %

Char, Coke, Anthracite etc, LTA

2000

4000

Counts

Position [°2Theta] (Cobalt (Co))

10 20 30 40 50 60 70

Rachel_LTA_Exxaro_Char Rachel_Tihole_EXXARO_CHAR

Peak List 01-078-1252; Si O2; Quartz low, syn 01-080-0885; Al2 ( Si2 O5 ) ( O H )4; Kaolinite 1\ITA\RG 01-089-7194; Fe; Iron 01-081-2027; Ca ( C O3 ); Calcite, syn 00-025-1376; ( Fe , Mg ) ( Al , Cr , Fe , Ti )2 O4; Magnetite 01-071-1167; Ti O2; Anatase 01-073-2409; Ca Mg ( C O3 )2; Dolomite

30

Graphite

� XRD can be used to characterize the crystal structure of graphitic carbons� Structure governed by microstructure and this influences the

performance characteristics i.e electrical resistivity and conduction, coeff. of thermal expansion

� Graphitic carbons can be characterized in 3 dimensions (hkl indices) (002), (100), (101), (004), (110), (006)

� Intensity and sharpness of the peak give an indication of the degree of order compared to a pure graphite crystal

� d002

= measure of interlayer spacing between individual graphene layers (3.345Ǻ for pure graphite)� Can trace the degree of graphitization as a function of heat treatment

temperature

� Using the equation according to Maire & Mehring

the degree of graphitization (g) can be calculated

� g = (3.44-d002)/(3.44-3.354)

Diagram from: Introduction to Carbon Science, H Marsh, 1997

Crystallite development

Diagram from: Introduction to Carbon Science, H Marsh, 1997

2 theta / deg

I/ rel.

20 25 30 35 40 45 50 55 60 65 70 75 80 85 90

31

16

0

C2H

100

102

004

103

104

2 theta / deg

I/rel.

20 25 30 35 40 45 50 55 60 65 70 75 80 85 90

308

154

0

C2H

100

101

102

004

103

104

31

Graphite – indices of interest

� Lc

value – graphene layer stacking

height

� Determined from the FWHM of the

00l diffraction lines

� La

value – lateral diameter

(crystallite width)

� Determined by hk0 diffraction lines

� d002

interlayer spacing (002)

Lc

La

d002

Scherrer Equation

k = constant dependent on crystallite shape (0.89)λ = x-ray wavelengthβ = FWHM (full width at half max) or integral breadth (in

radians)θ = Bragg Angle

L = kλ/β cosθ

32

Scherrer Equation

� d002

= 3.460

Position [°2Theta] (Cobalt (Co))

10 20 30 40 50 60 70 80

Counts

0

5000

10000

15000

Graphite A

d = 3.460Ǻ, 29.98 º2θ

FWHM = 5.89 º2θ

d110 ~ 93º2θ

Lc = 0.89 * 1.798/ 0.1028 cos 0.099= 16 Ǻ

Crystallite Size

Raw Pitch

Graphite Natural Graphite

Scherrer 1.6 11.2 50.4

Autoquan 1.29 13.86 60.2

Highscore+ 1.9 14.0 55.5

d0023.49 3.42 3.36

10 20 30 40 50 60 70 80

Counts

0100020003000

0100002000030000

0

200000

400000

Raw Pitch

Graphite

Natural Graphite

� no size-strain

standard

� relative results

33

Flyash1 2 3 4

XRD

Amorphous

67.84 63.64 68.41 63.81

Calcite 0.26 0.34 0.3 0.26

Hematite 0.46 0.77 0.73 0.72

Mullite 23.91 21.46 20.52 21.88

Quartz 7.54 13.79 10.04 13.32

XRF

CaO 1.47 0.83 0.89 1.19

SiO2 60.9 62.3 62.3 56.8

Fe2O3 4.23 4.24 4.25 4.65

Al2O3 29.8 28.9 28.9 33.9

MgO 0.47 0.56 0.64 0.57

TiO2 0.29 0.29 0.3 0.31

Mn2O3 0.22 0.22 0.22 0.24

K2O 0.93 1.13 1.17 0.9

Amorphous Component Composition

CaO 1.21 0.49 0.59 0.93

SiO2 43.796 39.926 44.052 34.728

Fe2O3 4.046 3.932 3.958 4.362

Al2O3 15.454 16.024 16.588 20.772

MgO 0.47 0.56 0.64 0.57

TiO2 0.29 0.29 0.3 0.31

Mn2O3 0.22 0.22 0.22 0.24

K2O 0.93 1.13 1.17 0.9

Position [°2Theta]

10 20 30 40 50 60 70 80

Counts

0

2000

4000

6000

8000

0

5000

10000

0

5000

10000

0

5000

10000

1

4

3

2

Phase quantification does not

supply the entire picture!

XRD in the Cement Industry

34

35

Acknowledgements

� Prof Johan de Villiers

� University of Pretoria

� Theresa van den Berg

� Exxaro

� CSIR

� Prof Richard Kruger

� PANalytical

� …..