workshop for xrf-spectrometry anne wegner,...

Workshop for XRF-Spectrometry Anne Wegner, 2014 Dec 4th, Athens

X-ray fluorescence analysis (XRF) or X-ray spectrometry

• A method to do qualitative and quantitative analysis of the elemental composition by excitation of atoms and detection of their characteristic X-rays

X-ray fluorescence Spectrometry (XRF) Definition

04.12.2014 Workshop XRF Athens – Anne Wegner 2

X-ray fluorescence Spectrometry (XRF) Advantages

04.12.2014 3 Workshop XRF Athens – Anne Wegner

• Solid and liquid samples can be analysed directly

• Little or no sample preparation required

• non-destructive

• Sampling-analysis result time relatively short

• Elemental range: (Be) Na to U

• Linearity from ppm to 100%

• long term stability

• Quantitative, qualitative and semi-quantitative

X-ray fluorescence Spectrometry (XRF) Applications


Cement Minerals &

Mining Petrochemistry

Ceramics Geology Metals Chemistry

Research

Samples measured as

• Liquids

• directly

• Powders

• directly

• as pressed pellets

• as fused beads

• Bulks

• directly, after fitting into sample cups

X-ray fluorescence Spectrometry (XRF) Capabilities


• Qualitative Analysis

• Identification of elements

• „What’s inside?”

• Quantitative Analysis

• Determination of concentrations

• „How much is inside?”

• Semi-Quantitative Analysis

• Estimation of concentration

• „About how much?”

X-ray fluorescence Spectrometry (XRF) Capabilities


X-ray fluorescence Spectrometry (XRF) Principle


• Sample is excited by X-Rays

• Emission of X-ray Fluorescence from Elements inside the sample

• Energies of X-Ray Fluorescence charcteriastic for elements

• Energies = qualitative (Which Element?)

• Intensities = quantitative (How much of a certain element?)

XRF analysis covers the following energy- respective wavelength range:

• E = 0.1 – 60.0 keV

• l = 11.30 – 0.02 nm

• Elemental range from Berylium (Be) to Uranium (U)

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X-ray fluorescence Spectrometry (XRF) What are X-Rays?


X-ray fluorescence Spectrometry (XRF) What are X-Rays?

• X-rays are electromagnetic radiation having a dual character

• They have the properties of waves, i.e. they will show the typical characteristics like diffraction

• They have the properties of particles, i.e. they e.g. be able to collide with other particles and thus interact with them

• Subsequently, they are particles moving through space like a wave


X-ray fluorescence Spectrometry (XRF) Creation of X-Ray Fluorescence inside the sample


X-Ray Fluorescence

Fe

Cr

Ni

Fe

Cr

Ni

Fe

Cr

Ni

Fe

Cr

Ni Sample



K radiation



L radiation

Example Spectra of a Coin


• Spectra of 1 € Coin



Coherent Scatter

Incoherent Scatter Incident Beam

Diffraction

Absorption X-Ray Fluorescence

Fe

Cr

Ni

Fe

Cr

Ni

Fe

Cr

Ni

Fe

Cr

Ni Sample

X-ray fluorescence Spectrometry (XRF) Fluorescence Yield


• The actual number of X-ray photons produced from an atom is less than expected

• The ratio of the useful X-ray photons to the total number of primary photons is called the Fluorescent Yield (ω)

• Lower Intensities for lighter elements

wk(B) 10-4

wk(Fe) 0.35

wk(Te) 0.88

Different Setups for X-Ray Fluorescence

Different Setups for X-Ray Fluorescence WD-XRF vs ED-XRF

04.12.2014 17

• Wavelength-Dispersive XRF • Energy-Dispersive XRF

Workshop XRF Athens – Anne Wegner

• X-rays produced by a tube are directed to the sample • Causes sample to

produce X-rays that are characteristic of the atoms (elements) present

• Analyzer crystals are used

to separate the X-rays into their individual components

• Detectors are used to convert the X-ray energy into an electrical pulse that is counted

X-ray fluorescence analysis (XRF) WDXRF – sequential


X-ray fluorescence analysis (XRF) WDXRF – sequential


The Comparison of Wavelength and Energy Dispersive Spectrometers WD-XRF


n = 1, 2, 3,… (reflection order)

d = interplanar lattice spacing (nm)

θ = diffraction angle (°)

E = Energy of Photon (keV)

POLYCHROMATIC MONOCHROMATIC

nλ = 2d∙ sinθ

𝐴𝐵𝐶=2d∙ sinθ ′AC′

d= sin θ

′𝐴𝐶′ = d sin θ

′𝐴𝐶𝐵′ = 2d sin θ

′𝐴𝐶𝐵′ = nλ

λ = 1,24

𝐸

Three Analyzer Crystals • LiF 200 and PET are natural crystals

• XS-55 is a synthetic multilayer (sputtered)

X-ray fluorescence analysis (XRF) Basic Configuration


The Comparison of Wavelength and Energy Dispersive Spectrometers WD-XRF


Sample

Proportional detector

Crystal

Scintillation detector

• An analyzer crystal is used to

seperate the various

wavelangth λ (energies)

• The detector records the

number N of X-ray photons at

a given wavelength (energy)

• Two detectors are used to

cover the whole elemental

range

Propotional detector B to Cr

Scintillation detector Mn to U

• Same as for sequential WDXRF

• For each element there is one channel including analyzer crystal and detector

• No goniometer

• No scanning possible

Very Fast but less flexibile

X-ray fluorescence analysis (XRF) WDXRF – simultaneous


• Cheaper

• Smaller

• Mechanical simplicity

• Detector is used to detect both

• Energy of the incoming X-rays

• Intensity of the incoming X-rays

X-ray fluorescence analysis (XRF) EDXRF


Instrumentation for X-ray Spectrometry The Comparison of Wavelength and Energy Dispersive Spectrometers


Sample

• The detector is used to

record both

• the energy E

• the number N of X-ray

photons at a given energy.

• No Soller slits (collimators as

used in WD-XRF) and no

crystals are required.

X-ray fluorescence analysis (XRF) AXS Product Line

Wavelength-Dispersive

(WDXRF)

Simultaneous Sequential

Energy-Dispersive (EDXRF)

S8 LION S8 DRAGON

S8 TIGER S2 RANGER


• Large difference in resolution between WDXRF and EDXRF

• In WDXRF the combination crystal, collimator, detector gives us a much higher resolution

• In EDXRF the resolution only depends on the detector

X-ray fluorescence analysis (XRF) EDXRF vs. WDXRF – The Difference


• Steel sample with 0,31% Co

Co Ka1 line is overlapped by

Fe Kb1

Metal applications WDX

X-ray fluorescence analysis (XRF) EDXRF vs. WDXRF – The Difference

EDX

WDX


WDX

• High precision mechanics

• Higher capital

• Precision: <0.05%

• Higher resolution

• Sensitivities: down to the ppm level, but roughly one to two orders more sensitive

• Very fast analysis

• Highest sample throughput

X-ray fluorescence analysis (XRF) The Comparison of Wavelength and Energy Dispersive Spectrometers

EDX • Mechanical simplicity

• Cheaper

• Sensitivities: down to the ppm level

• Easy handling

• Smaller, “can be brought to the sample”

• Less Infrastructure necessary


The analytical performance of an X-ray

spectrometer is determined by:

• the range of elements

• the separation of elements (“resolution“)

• the sensitivity (kcps/%, cps/ppm)

• the peak to background ratio

• the lower limits of detection

• the reproducibility

These analytical parameters may define which type

of X-ray spectrometer needs to be sold/bought

X-ray fluorescence analysis (XRF)

Which instrument ?


S2 RANGER • Easy handling

• Easy applications Major, Minor

• Minerals Limestone, Cement, Slags, Glass

• Mining Ores

• Food Milkpowder, Biomass

• Petrochemical Oils, Additives, Minerals

• Coatings & Thin Films Cr passivation

Material specific calibration

Standards (CRMs or inhouse standards)

X-ray fluorescence analysis (XRF) Typical Applications


S8 TIGER

Standardless Method QUANT-EXPRESS

• Powerful tool for unknown samples

• Liquids, Powder, Pressed Pellet, Bulk samples

• All Materials

• Concentration range low PPM -100%

For highest precision / Trace Analysis

• Material specific calibrations

• Standards (CRMs or inhouse standards)



S8 TIGER 1K • All applications

• Lower Sensitivity longer measurement time

• Oil, Polymer, Coal

S8 TIGER 3K/4K

• All applications

• Higher Sensitivity High throughput

• Traces in geological samples, Metals, Ferro Alloy



Examples

Lightweight Matrices

Analysis of lightweight matrices


Linie Energie

(keV) Graphit Blei

Cd KA1 23.17 cm 14.46 µm 77.30

Mo KA1 17.48 6.06 36.70

Cu KA1 8.05 mm 5.51 20.00

Ni KA1 7.48 4.39 16.60

Fe KA1 6.40 2.72 11.10

Cr KA1 5.41 1.62 7.23

S KA1 2.31 µm 116.00 4.83

Mg KA1 1.25 20.00 1.13

F KA1 0.68 3.70 0.26

N KA1 0.39 0.83 0.07

C KA1 0.28 13.60 0.03

B KA1 0.18 4.19 0.01

Lightweight Matrices

• Organic Samples like Oils/Fuels, Coal, Polymers, Biomass

• Low Matrix Absorption compared to heavier matrices like steel

• saturation depths very high

• Not 100 % Sample can be measured

Sample Thickness has to be considered

Matrix has to be condidered

• Matrix is defined as all Compounds present in the Sample without the Analyte

• In XRF Matrix influence is quite big

• 100 ppm Pb in Polymer Matrix gives a different Intensity as 100 pm Pb in a Fe Matrix

• Influence can be either Absorption or Enhancement

Influence of the Matrix


Influence of the Matrix Matrix correction – Principle


Norm Ni

Alpha NiFe

Alpha NiFe,Cr

Stainless Steel

Enhancement ↔ Absorption

Matrix Correction Overview


Matrix Correction

Modells

Alpha Models

Fixed Alphas

Empirical

By Intensity

by Concentration

Theoretical

Variable Alphas

Internal Standard

By other Element

Compton Normalisation

Heavy Absorber

• Variable Alphas

• Big Concentration Ranges

• Iteration Process

• One Alpha determined for each concentration

• 100 % of sample must be known

• Fixed Alphas

• Theoratical Alphas

• Database Values

• Smaller Concentration Ranges

• 100 % of sample must be known

• Empirical Alphas

• Alphas determined only empirically from the calibration data

• Risky Standards have to be chosen well

• One additional degree of freedom for every correction Many Standards required

Matrix Correction Alpha Correction


Influence of the Matrix Alpha Models

1

1

where

).1.()..(

thus

.

where

)1.()..(

,

,)(

,

)(

,

,

--

i

j

i

ij

ji

nC

iC

nn

in

jjijLOiii

nn

in

jji

jLOiii

C

CIfImC

CM

MIfImC

ji

ji

a

a

a

Ci = concentration of element i

mi = inverse of the slope

Ii = net intensity for element i

f(LOi,j) = line overlap correction factor

for element j on element i

M = matrix correction

ai,j = matrix correction factor for

element j on i

Cj = concentration of element j

i = mass absorption coefficient of

element i at l of analysed

element

j = mass absorption coefficient of

element j at l of analysed

element


The regression analysis Calculating the calibration curve


• Let’s presume a 5 elements matrix

• Through an iteration process the concentrations will be calculated • Best fit for a minimum standard deviation

)1()(

)1()(

)1()(

)1()(

)1()(

,,,,,)(

,,,,,)(

,,,,,)(

,,,,,)(

,,,,,)(

llmkkmjjmiimmimimLOmmm

mmlkkljjliilmimilLOlll

mmkllkjjkiikmimikLOkkk

mmjlljkkjiijmimijLOjjj

mmillikkijjimimiiLOiii

CCCCIfImC

CCCCIfImC

CCCCIfImC

CCCCIfImC

CCCCIfImC

--

--

--

--

--

aaaa

aaaa

aaaa

aaaa

aaaa

Influence of the Matrix Matrix correction-Variable Alphas


Without matrix correction With matrix correction

• Cr in tool steel

Int. korrigiertInt. netto

Inte

nsität

(KC

ps)

Korr

igie

rte I

nte

nsität

(KC

ps)

Konz. (%)

0

10

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90

100

110

120

0

10

20

30

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50

60

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100

110

120

0 1 2 3 4 5 6 7 8 9 10 11

Int. korrigiertInt. netto

Inte

nsität

(KC

ps)

Korr

igie

rte I

nte

nsität

(KC

ps)

Konz. (%)

0

10

20

30

40

50

60

70

80

90

100

110

120

0

10

20

30

40

50

60

70

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100

110

120

0 1 2 3 4 5 6 7 8 9 10 11

• 0 – 11 % Cr, Std.Dev.: 0.51 % • 0 – 11 % Cr, Std.Dev.: 0.069 %

Anode Coke • Used in Aluminum Industry

• 1 t Aluminium requires 400 kg Anode material

Hall-Heroult-Process • Smelting of Aluminum

• Al2O3 is dissolved in molten Cryolite (Na3AlF6)

• Al3+ is reduced to Al0 at the cathode

Analysis of lightweight matrices Example Anode Coke

CC 3.0 de.wikimedia.org



Quality Control of Anode Coke

• Analysis of Trace elements

• Used Reference Materials

• S – 0.5 bis 5.0 %

• V – 20 bis 500 ppm

• Ni – 20 bis 500 ppm

• Na – 20 bis 200 ppm

• Ca – 20 bis 200 ppm

• Al – 20 bis 500 ppm

• Fe – 20 bis 500 ppm

• Si – 20 bis 500 ppm

• DIN ISO 12980


Certified Reference Materials

• 15 Standards

• Certified Values for S, V, Si, Fe, Na, Al, F, Ca, K, Mg, Ba, Cr, Cu, Mn, P, Pb, Sr, Ti, Zn

• Preparation as pressed pellets

• Homogeneous Particle Size Distribution

• Dried at 110C

• 7.0 g Sample + 1.4 g Wax

• Press at 20 t for 20 s



Conc. XRFInt. net

Inte

nsity (

Cps)

XR

F C

oncentr

ation (

%)

Concentration (%)

0

1000

2000

3000

4000

5000

6000

7000

8000

9000

10000

11000

0

1

2

3

4

0 1 2 3 4

S2 RANGER

• 10 kV, 100 s

• 0.89 – 4.69 %

• LOD: 17 ppm

• R2: 0.9964



Sulfur (Environmental)

S8 TIGER 1K

• 30 kV, 20 mA, XS-Ge-C, 0.23°

• Max. 6 s

• 0.89 – 4.69 %

• LOD: 15 ppm

• R2: 0.9967

Conc. XRFInt. net

Inte

nsity (

kcps)

XR

F C

oncentr

ation (

%)

Concentration (%)

0

10

20

30

40

50

60

70

80

90

100

110

120

130

0

1

2

3

4

0 1 2 3 4

Conc. XRFInt. net

Inte

nsity (

Cps)

XR

F C

oncentr

ation (

PP

M)

Concentration (PPM)

0

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

0

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

170

180

190

200

210

220

230

240

250

260

270

280

0 100 200

S2 RANGER

• 40 kV, 100 s, Al 500 µm

• 65 – 283 ppm

• LOD: 2.5 ppm

• R2: 0.9981

Nickel (Influence of Al-Quality)

S8 TIGER 1K

• 50 kV, 20 mA, LiF200, 0.23°

• Max. 10 s

• 65 – 283 ppm

• LOD: 1.5 ppm

• R2: 0.9994

Conc. XRFInt. net

Inte

nsity (

kcps)

XR

F C

oncentr

ation (

PP

M)

Concentration (PPM)

0

10

20

30

0

10

20

30

40

50

60

70

80

90

100

110

120

130

140

150

160

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190

200

210

220

230

240

250

260

270

280

0 100 200

C set as Matrix

Matrix Correction by variable Alphas used

Reproducibility – S2 RANGER (Measurement Time 12 Minutes)



Sample S

(%) Ni

(ppm) Si

(ppm) Fe

(ppm) Al

(ppm) V

(ppm) Ca

(ppm) Pb

(ppm) Zn

(ppm) Cr

(ppm) Mn

(ppm) Cu

(ppm)

A509-1 3.01 278 177 216 187 523 49 24 26 11 4 2

A509-2 3.01 279 214 219 192 535 44 25 27 9 4 2

A509-3 3.01 277 202 218 191 525 44 24 27 11 5 3

A509-4 3.00 277 190 214 181 530 44 23 27 12 5 2

A509-5 3.01 281 182 217 186 531 44 24 26 9 3 2

A509-6 3.01 281 178 214 156 527 44 24 27 11 4 2

A509-7 3.01 279 200 217 175 532 44 24 27 9 5 2

A509-8 3.01 282 195 215 193 536 44 25 27 9 4 3

A509-9 3.00 281 195 214 200 535 44 25 27 7 4 2

A509-10 3.02 278 202 214 194 527 44 24 27 10 4 3

Average 3.01 279 193 216 185 530 45 24 27 10 4 2

Std.Dev. 0.010 1.8 11.9 1.9 12.5 4.4 1.4 0.7 0.3 1.4 0.6 0.3

Rel.Std.Dev. 0.21% 0.63% 6.16% 0.88% 6.72% 0.83% 3.14% 2.82% 1.25% 14.65% 13.27% 12.38%

Reproducibility – S8 TIGER 1K (Measurement Time 14 Minutes)



Sample Na

(ppm)

Mg

(ppm)

Al

(ppm)

Si

ppm)

P

(ppm)

S

(%)

Cl

(ppm)

K

(ppm)

Ca

(ppm)

Ti

(ppm)

Cr

(ppm)

Mn

(ppm)

Fe

(ppm)

Ni

(ppm)

Zn

(ppm)

Pb

(ppm)

B404_F 36 6 43 80 21 0.57 241 13 66 11 9 6 127 3 570 449

B404_F 36 5 48 75 21 0.57 244 14 66 10 9 6 127 3 568 449

B404_F 36 5 45 72 21 0.57 241 13 66 10 9 7 126 3 569 447

B404_F 36 6 46 67 21 0.58 240 13 65 9 9 5 128 4 570 450

B404_F 36 5 47 53 21 0.57 244 14 66 11 9 6 126 3 568 448

B404_F 36 5 46 96 21 0.58 242 15 65 9 9 6 128 4 569 448

B404_F 36 5 45 93 21 0.58 241 14 66 10 9 5 127 4 569 448

B404_F 36 5 46 86 22 0.57 238 14 65 9 9 6 127 3 570 449

B404_F 36 5 45 83 21 0.57 241 14 66 10 9 7 126 3 570 449

B404_F 36 5 43 83 21 0.58 243 14 66 10 9 6 128 4 570 451

Average 36.0 5.2 45.4 78.8 21.1 0.57 241.5 13.8 65.7 9.9 9.0 6.0 127.0 3.4 569.3 448.8

Std.Dev. 0.0 0.4 1.5 12.0 0.3 0.00 1.7 0.6 0.5 0.7 0.0 0.6 0.8 0.5 0.8 1.1

Rel.Std.Dev. 0.00 7.69 3.30 15.29 1.42 0.85 0.72 4.35 0.70 7.07 0.00 10.54 0.61 14.41 0.14 0.24

Lab Report available

• Lab Report XRF 115 Quality control of anode cokes – trace analysis by WDXRF (J. Stelling, K. Behrens)

• S8 TIGER 1K

Lab Report


Heavy Metals in Soil Overview

• Low levels of heavy elements

• Simple sample preparation

• Measurement time less important

• Availablity of Certified Reference Materials

• Certified Reference Materials pourly described


Heavy Metals in Soil Concentration Range

Sum below 100 %

No Matrix Correction possible by fundamental Parameters

Use of Rh Compton Normalisation

Sum(%) V(PPM) Cr(PPM) MnO(PPM) Fe2O3(%) Co(PPM) Ni(PPM) Cu(PPM)

Min 0,18 0 0 201 1,9 0 0 0

Max 100 109 110 111 112 113 114 115

As(PPM) Rb(PPM) Sr(PPM) Y(PPM) Zr(PPM) Mo(PPM) Cd(PPM) Ba(PPM)

Min 0 41 28 13 110 1 0 185

Max 118 119 120 121 122 123 124 126


Compton Normalisation Properties – Compton & Rayleigh


• Elastic scattering • no energy loss after collision

of electrons

• Rayleigh effect is present

when electrons are strongly

bound

• Rayleigh is more present in

heavy matrices

• Inelastic scattering • energy loss after collision of

electrons

• Compton effect is present

when electrons are loosely

bound

• Compton is more present in

light matrices

l𝒄 > l𝒄 = l𝟎

01

02

03

04

05

06

07

08

09

01

00

11

01

20

13

01

40

15

01

60

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01

80

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02

00

21

02

20

23

02

40

25

02

60

27

02

80

KC

ps

1718192021222324

KeV

Physics of X-rays Properties – Compton & Rayleigh


0.033 Å

l𝒄 − l𝟎 = 𝟎. 𝟎𝟐𝟒𝟑(𝟏 − 𝒄𝒐𝒔 )

= 108° l𝒄 − l𝟎 = 𝟎. 𝟎𝟑𝟑 Å

Compton Peaks From Different Samples


• Scattered characteristic radiation from

the tube’s anode

• A measure for the sample’s matrix

• As average atomic number decreases,

Compton intensity increases

• Water (H2O) has an average atomic number

of 3.3

• Ethanol (C2H5OH) has an average atomic

number of 2.9

• Oil (CH2) has an average atomic number of

2.7

• C. factor = calculated C./measured C.

• Should be close to 1

• Use to adapt the matrix

Heavy Metals in Soil Example Fe


• Measurement Conditions

• Preparation Loose Powder 4 µm Prolene

• Atmosphere Helium

• Analysis Time approx. 20 min

• Special Crystal recommended LiF220

01

23

45

10

20

30

40

50

60

70

80

90

100

110

KC

ps

Rb K

A1

Rb K

B1 A

s K

B1

Sr

KA

1

Sr

KB

1Z

r K

A1

Zr

KB

1

Pb L

B1

Mo K

A1

11121314151617

KeV

Heavy Metals in Soil Example Fe

• SD = 0,27 %

• R² = 0,991

• LLD = 30 ppm

• SD = 0,46

• R² = 0,95

• LLD = 34 ppm

Konz. RFA

RF

A K

onzentr

ation (

%)

Konz. (%)

0

1

2

3

4

5

6

7

8

9

0 10 20 30 40 50 60 70 80 90 100

Konz. RFA

RF

A K

onzentr

ation (

%)

Konz. (%)

0

1

2

3

4

5

6

7

8

9

10

11

0 10 20 30 40 50 60 70 80 90 100

With Compton Normalisation Without Compton Normalisation


Heavy Metals in Soil Example Pb

• SD = 41 ppm

• R² = 0,996

• LLD = 2,4 ppm

• SD = 11 ppm

• R² = 0,9997

• LLD = 3 ppm

Konz. RFA

Konzentr

ation (

PP

M)

Konz. (%)

0

1000

2000

3000

0 10 20 30 40 50 60 70 80 90 100

Konz. RFA

Konzentr

ation (

PP

M)

Konz. (%)

0

1000

2000

3000

0 10 20 30 40 50 60 70 80 90 100



Heavy Metals in Soil Example Al

• SD = 1,15

• R² = 0,97

• LLD = 228 ppm

• SD = 2,09 %

• R² = 0,93

• LLD = 0,2 %


Konz. RFA

RF

A K

onzentr

ation (

%)

Konz. (%)

0

10

20

30

0 10 20 30 40 50 60 70 80 90 100 Konz. RFA

RF

A K

onzentr

ation (

%)

Konz. (%)

0

10

20

30

0 10 20 30 40 50 60 70 80 90 100


Example Quadratic Correlation-Electroplating

Electroplating

• Use Elecrical current to reduce the cations from the solution

• Coating on Electrode

• Cu needs to be determined in Cu-Sulphate bath

• Pretty high concentrations

• Low No. of Elements (S, Cu) inside the sample

• No high resolution necessary

• Energy dispersive XRF can be

used

CC 3.0 de.wikimedia.org



Cu(%) H2O(%)

Kal 1 4,6 80,4

Kal 2 5,12 79,88

Kal 3 5,65 79,35

Cu Bad_Blank 0 100

Kal 1 1-1 2,31 90,16

Kal 2 1-1 2,57 89,9

Kal 3 1-1 2,82 89,65

Kal 2 1-7 0,73 100

Kal 3 1-7 0,81 100

• Measurement Conditions

• Analysis Time < 5 min

• Voltage 40 kV

• Current Automatic

• Filter 500 µm Al



• SD = 0,49 %

• R² = 0,96

• LLD = 7 ppm

• SD = 0,029 %

• R² =0,9998

• LLD = 4,4 ppm

Conc. XRFInt. net

Inte

nsity

(C

ps)

XR

F C

once

ntra

tion

(%)

Concentration (%)

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

0

1

2

3

4

0 1 2 3 4 5

Conc. XRFInt. net

Inte

nsity

(C

ps)

XR

F C

once

ntra

tion

(%)

Concentration (%)

0

100

200

300

400

500

600

700

800

900

1000

1100

1200

1300

1400

0

1

2

3

4

5

0 1 2 3 4 5


• Excellent Calibration Curve

• 10-fold Preparation delivers excellent reproducibilty


Sample Cu (%)

Cu-Bath 1 4,471

Cu-Bath 2 4,472

Cu-Bath 3 4,47

Cu-Bath 4 4,473

Cu-Bath 5 4,475

Cu-Bath 6 4,465

Cu-Bath 7 4,468

AV 4,471

SD 0,003

RSD 0,074


Example Ni and Cr in potable Water

• Cr

• Concentration Range 1-10 ppm

• SD = 0,1 ppm

• LLD = 0,7 ppm

Conc. XRFInt. net

Inte

nsity

(C

ps)

XR

F C

once

ntra

tion

(PP

M)

Concentration (PPM)

-0,1

0

0,1

0,2

0,3

0

1

2

3

4

5

6

7

8

9

10

0 1 2 3 4 5 6 7 8 9 10

Conc. XRFInt. net

Inte

nsity

(C

ps)

XR

F C

once

ntra

tion

(PP

M)

Concentration (PPM)

0

1

2

3

4

0

1

2

3

4

5

6

7

8

9

10

0 1 2 3 4 5 6 7 8 9 10

• Ni

• Concentration Range 1-10 ppm

• SD = 0,1 ppm

• LLD = 0,1 ppm


Analysis of Geological Samples

XRF Applications for Geology, Mining, Minerals, Ceramics

• Wide range of XRF applications for

• Geological Surveys

• Mining: Exploration and Exploitation

• Industrial Minerals

• Cement: Raw Materials

• Ceramics and Refractories

• Glass

• Technical oxides: Fluid cracking catalysts (FCC) for petro industry

• Analysis of major and minor elements as oxides

• for grade control and product quality (purity) based on fused beads

• Analysis of traces

• for purity control and geological and environmental mapping based on pressed pellet


S8 TIGER GEO-QUANT M

• The advanced analytical

• solution for the accurate and

• precise analysis of major and

• minor elements developed for

• various XRF applications such

• as:

• Geology

• Mining

• Industrial minerals

• Exploration

• Exploitation

• Ceramics

• Refractories

• Glass


S8 TIGER GEO-QUANT M

• Reference calibration based on more than 20 certified reference materials:

• for 11 elements as oxides: Na2O, MgO, Al2O3, SiO2, P2O5, SO3, K2O, CaO, TiO2 MnO, Fe2O3

• matrix correction based on variable alpha model

• measurement time:

• 6 min for the default program S8 TIGER 4 K

• optimized sample preparation procedure as fused beads

• For optimum results of P and S:

• XS-GE-C


GEO-QUANT M Accurate and precise

Element

Low range

[%]

High range

[%]

Na2O 0.01 11.30

MgO 0.01 95.77

Al2O3 0.04 90.80

SiO2 0.41 99.88

P2O5 0.01 19.34

SO3 0.05 54.38

K2O 0.01 15.36

CaO 0.01 97.88

TiO2 0.01 7.79

MnO 0.01 0.88

Fe2O3 0.01 39.08


Wide calibration ranges

• Close to 100 % for most of the

elements

• best practice: based on fusion

sample preparation for accurate

results

• enhanced evaluation based on

unique matrix correction with the

variable alpha model

• intelligent measurement strategy for

high sample throughput and

shortest time-to-results

GEO-QUANT M Accurate and precise


Accurate calibrations for major oxides based on

fusion beads for best precision

Coverage of wide concentration ranges and materials

GEO-QUANT M The perfect match


0

20

40

60

80

100

0 10 20 30 40 50 60 70 80 90 100

SiO2 % (measured)

SiO

2 %

(c

ert

ific

ati

on

)

Evaluation of the accuracy for a wide range of

international reference materials

(Acceptance test samples included shown in yellow)

GEO-QUANT M The perfect match – again and again

Na2O MgO Al2O3 SiO2 P2O5 SO3 K2O CaO TiO2 MnO Fe2O3

certificate 1,48 2,59 19,18 63,23 0,18 0,41 3,13 2,06 0,80 0,09 7,06

Precision test 20 times alternated measurement

average 1,40 2,49 19,16 63,45 0,18 0,46 3,14 1,91 0,79 0,09 6,95

min. 1,39 2,47 19,13 63,32 0,18 0,45 3,14 1,91 0,78 0,09 6,94

max. 1,42 2,50 19,20 63,52 0,18 0,46 3,15 1,92 0,79 0,09 6,97

std. dev. 0,01 0,01 0,02 0,05 0,00 0,00 0,00 0,00 0,00 0,00 0,01

relative SD 0,52 0,40 0,10 0,07 0,00 0,49 0,10 0,19 0,56 0,00 0,10

repeatability test 18 measurement during 30 Days

average 0,11 0,36 64,26 17,88 0,27 0,20 0,39 2,71 2,91 0,04 10,49

min. 0,10 0,36 64,15 17,82 0,27 0,20 0,39 2,71 2,90 0,04 10,46

max. 0,12 0,37 64,36 17,92 0,28 0,21 0,39 2,72 2,91 0,04 10,53

std. dev. 0,01 0,00 0,05 0,03 0,00 0,01 0,00 0,00 0,00 0,00 0,02

relative SD 5,91 0,79 0,08 0,16 1,65 2,48 0,11 0,16 0,12 3,60 0,20


GEO-QUANT M Turn-Key Solution for the S8 TIGER


• The complete solution for

• the process and quality control

• by XRF for general oxides:

• Geological materials

• Industrial Minerals

• Ceramics, Refractories, Glass

• Including:

• 20 standard reference materials

• 3 acceptance test samples

• 3 glass drift monitor samples

• Operators manual

• Sample preparation manual

• Material safety data sheets

S8 TIGER GEO-QUANT T

• the trace element solution developed for various geological applications such as:

• limestone

• soils

• sediments

• industrial minerals

• ceramics

• in

• research

• monitoring

• exploration


S8 TIGER GEO-QUANT T

• Mastercalibration based on hundreds international certified reference materials:

• For 27 Elements: TiO2, MnO, Fe2O3, Sc, V, Cr, Co, Ni, Cu, Zn, Ga, As, Rb, Sr, Y, Zr, Nb, Mo, Sn, Sb, Cs, Ba, La, Ce, Pb, U, Th

• Automatic matrix correction

• Measurement time:

• typically 38 min for the default program S8 TIGER

• Optimized background handling with shared positions

• Optimized sample preparation procedure


Hunting for Traces in Geology Measurement method

Upper calibration range • Up to 3500 ppm

Matrix elements • TiO2, Fe2O3 and MnO calibrated up

to the % range to be used for the correction of interferences

• Automatic matrix correction based of Rh Compton method

Measurement time • 20 – 100 s • (counting statistical

optimization) Typical LOD • Down to the sub-ppm range


Hunting for Traces in Geology Master calibration Sr


Sr

Range : - 1500 ppm

LOD : 0.8 ppm

Std.Dev.: 5.9 ppm

Hunting for Traces in Geology Master calibration Pb


Pb

Range : - 2500 ppm

LOD : 1.4 ppm

Std.Dev.: 6.1 ppm

Hunting for Traces in Geology Optimized background handling

Shared background positions

• to modelize background

• to minimize measurement time


S8 TIGER GEO-QUANT M & T: User Benefits

• quantitative elemental analysis

• as easy as possible

• Well defined sample preparation methods

• Simple start of measurements

• accurate and precise analysis results

• right out of the box

• Ready-to-analyze for a wide range of geological trace applications

• A minimum of operator training required

• GEO-QUANT runs over years

• saves time and money!

• Quick start directly after installation

• no suite of expensive standards is needed

• No need for weeks of method development


workshop for xrf-spectrometry anne wegner,...

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