Direct measurement with XRF sampling but no sample preparation?

Bertil Magnusson

Content
an overview of direct XRF measurement will be presented using standard wavelength dispersive and energy dispersive instruments as well as handheld instrument
What we all know about XRF Direct measurement versus normal analysis in laboratory Elemental range Systematic effects Application of direct measurements 1. Quality control in nuclear power plant 2. Analysis of sediment and wood cores 3. Determination of thickness of coating

Direct measurement with XRF

We all know that XRF

can be regarded as a non-destructive technique but in most cases in order to get more reliable results with a lower measurement uncertainty a sample preparation step is performed for solid samples. The preparation can e.g. be homogenizing and subsequent briquetting or fusion into a bead. For liquid samples with no particles direct measurement is possible with reliable results
Direct measurement with XRF 3

We also know that XRF analysis.

can be performed directly on many samples with additional benefits such as less sample handling no sample transport to laboratory better spatial resolution lower response time higher sample throughput

But in most cases with a drawback of much higher measurement uncertainty

Direct measurement with XRF 4

Direct measurement versus normal analysis

normal analysisanalysis Direct Normal measurement Air/He Vacuum or helium Normally not Yes

Atmosphere Sample preparation Sample size

Few restrictions

< 5 cm No

Spatial resolution Yes

Drawbacks with measurement in air and no sample preparation

Direct measurement with XRF 5

Today light elements possible in air with short pathlengt example handheld XRF

Direct measurement with XRF

XRF measurement with no sample preparation

Measuring depth is dependent on energy of analytical line and mean atomic number in the matrix. With prepared sample that are homogeneous - no systematic effect
Sn Ka

Zn Ka Measuring depth

S Ka
Si Ka Na Ka

Direct measurement without sample preparation: Systematic effects for inhomogeneous samples!
Direct measurement with XRF 7

Measurement cycle

Client
Decision on result Client Issue

Can i sell this product?

Does the product fulfil the regulations?

Data presentation

Define issue

Report on measurement

Decision on measurement

Client
Interface
Measuring scientist

Evaluation Analysis

Sampling

Measuring scientist
Direct measurement with XRF 8

Direct measurement - building materials

Direct measurement with XRF

Direct measurement consumer goods

Metals in Plastics toys EU Toy directive (last March 2012) Presence of flame retardants e.g Br, Cl, Sb Electronics ROHS directive Cd, Cr(VI), Ni, Hg, Pb and org Br Jewellery e.g. Ni, Cd, Cr, Pb Co Textiles Isolation material Impregnated wood e.g As. Cr Today these tests are performed routinely at SP
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Direct measurement with XRF

Applications presented here

Quality control in nuclear power plant Analysis of deposits (crud) on nuclear fuel rods sampling on a filter. Analysis of sediment and wood cores XRF footprint along the core

Determination of thickness of coating on welding wire direct measurement

Direct measurement with XRF

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Measurement cycle nuclear power plant

Client
Decision on result Client Issue

Corrosion situation and..?

Data presentation

Define issue

Study crud deposits

Report on measurement

Decision on measurement

Client
Interface
Measuring scientist

Evaluation Analysis

Sampling

Measuring scientist
Direct measurement with XRF 12

Quality control analysis of deposits, crud

Crud sampling

Direct measurement with XRF XRF analysis on active samples Validation with synthetic samples and active test samples

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Crud* sampling
The crud is scraped or brushed from a defined area of the fuel rod Zircalloy The crud is collected on a filter membrane The crud/filter sample is analysed to determine: Quantity (g/m2) - XRF Elemental composition (g/m2): XRF

crud

Fe, Co, Cr, Mn, Ni, Cu, Zn, Pt

Sampling from fuel rod?- measurement of Zr Gamma activity of radioactive nuclides: Co60

ZrO2

*deposits on the nuclear rod

This application is presented courtesy to Eva Fredriksson & Pentti Hietala, Westinghouse

Crud* sampling
HOW
C Fuel crud is X sampled Side Orientation between Orientation X theSubbundle spacers 2 Spacer SP normally 5 or 6 Marking levels B 3 D

Sampling level
Top plate
SP 6

7
4

6
1

Spacer 6 Spacer 5 Spacer 4

SP 5

Water reference samples are takenD 10 1 Channel Center both before and 9 Marking 8 7 6 after 4each 2 3 5 4 3 assembly 2 3
1 C

5
A 4

SP 4

SP 3

SP 2

3 1
A B C D E F GH I J 2

Spacer 3
Spacer 2 Spacer 1

SP 1

2
B

*deposits on the nuclear rod

1
Direct measurement with XRF 15

Crud sampling
HOW

The fuel crud sampling equipment

Crud sampling process in a nuclear power plant

1. Sampling under water on a filter (Millipore) 2. Removing water by pressing air throught the filter

3. Removal with tool the upper part of filter holder

4. Mounting av cup with mylar film on top of filter 5. XRF-analysis using either or a calibration based on active standards Uniquant semiquantitative software

Analysis of crud in a nuclear power plant

XRFcontainer

ARL OptimX in a container

XRF measurement on radioactive samples

Issues with radioactive samples The radioactivity of the sample can lead to: Sample excitation resulting in XRF signal for several elements. Here we test X-ray tube off Higher background especially for lighter elements Samples in sample changer increasing background for measured sample

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Sample excitation from active samples ED-XRF with X-ray tube on&off?
Sample is a filter. Sampling 10 l water from primary cooling circuit in a nuclear power plant. Activity 25 S/cm close

Tube on

Tube off
Spectrum presented courtesy to Kari Moum and Torill Solheim Institutt for Energiteknikk/Halden Reaktor Prosjektet
Direct measurement with XRF 21

ED-XRF - tube off we see Cr Mn Fe Ni but no Co Cu and Zn

Cr Mn Fe Co Ni Cu Zn

Tube on

Iron background 2 g/cm2

Tube off

Direct measurement with XRF

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WD-XRF with X-ray tube off&on

NOTE: log scale

Tube on

Samples are crud from a nuclear power plant

Direct measurement with XRF

Tube off
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WD-XRF with X-ray tube off

Cr Ka

Mn Ka Green is ca 30 ug/cm2
Tube on

Samples are crud from a nuclear power plant

Direct measurement with XRF

Tube off
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Background increase with more crud

Red 20 mg crud or 5 mg/cm2 Blue 6 mg crud or 1.5 mg/cm2

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The background mystery

2009 was the first time we used XRF an a nuclear powr plant For a water blank sample we got very much higher background especially for Al & Si. A scan showed low background???

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New scan of water blank with samples and without samples in sample changer

No radioactive samples in sample changer

With no samples in sample changer less than 0.3 kcps

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Validation
Instrument calibrated with standardless software 1. Validation with synthetic crud samples prepared from pure metals Low recovery - < 80 % 2. Validation with synthetic crud samples grinded further recovery close to 100 % 3. Validation with active samples analysed with ICP-MS recovery close to 100 % for most elements

Direct measurement with XRF

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Validation with synthetic crud samples Fe, Co, Cr, Mn, Ni, Cu, Zn, Pt
Figure 1 Particle size distribution for crud 1. Surface weighted mean 3 m Figure 2 Particle size distribution for crud 1 after sample was further grinded. Surface weighted mean 1.2 m
1 m
Direct measurement with XRF 29

Low Recovery < 80 %

Particle size distribution

Recovery close to 100 %

Validation Fe up to 1 000 g or 250 g/cm2 XRF vs ICP-MS on active samples

crud samples

2010-08-17

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Validation Zn up to 600 g or 150 g/cm2 XRF vs synthetic crud

Residuals

crud samples

2010-08-17

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Validation Zn up to 100 g or 25 g/cm2 XRF vs ICP-MS on active samples year 2009

150 Resiidual ug

100
50 0
0 20 40 60 80 100 120

-50

Similar results were obtained 2010 Decision to use active crud samples for calibration
crud samples 2010-08-17

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Conclusions
Systematic effects yes. Validation with synthetic standards - The sample particles were finer than the synthetic crud standards (before further grinding) Validation with active test samples For most elements the recovery was close to 100 % comparing XRF Uniquant with ICP-MS results The Zn gave 150 % recovery when comparing with ICP-MS. No understanding of this effect so far. The ICP-MS were validated with synesthetic crud and gave excellent results

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Conclusions
New calibration performed with active crud samples, analysed with ICP-MS, to minimise systematic effects. For elements not found in crud synthetic samples were used. Interference from active samples Increased background with radioactive samples. No characteristic peaks found with WD-XRF Fitness for intended purpose Direct analysis now possible for elemental composition and amount using XRF for elements of interest
Direct measurement with XRF 34

Measurement cycle Increasing depth in harbour area

Client
Decision on result Client Issue

Can we dredge in the harbour area?

Will there be an environmental impact?

Data presentation

Define issue

Report on measurement

Decision on measurement

Client
Interface
Measuring scientist

Evaluation Analysis

Sampling

Measuring scientist
Direct measurement with XRF 35

Applications

Analysis of sediment and wood cores

Shale (norsk: skifer) sample was scanned with steps of 0.2 millimeters at 10 seconds using XRF. On top of the optical image is superimposed Si and Fe graphs.

Si (blue)

Fe (red)
This application is presented courtesy to Anders Rindby

50 mm

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Combined m-XRF, radiography and optical scanning

The Core Scanner moves the sample in steps.

Sample is irradiated with an X-ray tube with a well-defined beam. The fluorescence (XRF) and absorption (radiography) are measured. An camera system provides sample images.

Direct measurement with XRF

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Combined m-XRF, radiography and optical scanning

Camera XRF detector

profiler

Sample

Direct measurement with XRF

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XRF scan examples

820 mm

K profile

Ti profile

Fe profile

As profile

Br profile

Average atomic number

Direct measurement with XRF Sample with courtesy of Dr. Bernard Dennielou, Ifremer, France 39

Determination of thickness of coating on welding wire

Illustrations/graphs area

This application is presented courtesy to Gran Swemark, ESAB

Determination of thickness of coating on welding wire

Client
Decision on result Client Issue

Client need reporting in mg/dm2 Production need direct reporting

Data presentation

Define issue

Report on measurement

Decision on measurement

Client
Interface
Measuring scientist

Evaluation Analysis

Sampling

Measuring scientist
Direct measurement with XRF 41

Determination of thickness of coating on welding wire

Application of surface additives Lubricant MoS2 - thickness on wire 0.001-0.01m ( up to 0,3 mg/dm2) Ca (soap) 0,07 mg/dm2 Wet Chemical Analysis Analysis of Mo and Ca 4 m sample is leached in acetone in an ultrasonic bath to remove the MoS2 powder. The acetone is evaporated and the MoS2 is dissolved in aqua regia and Mo is determined by ICP.

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Sample Preparation of wires for XRF

Sample holder on the insert Sample ready for XRF-analysis

Illustrations/graphs area

Opening: 27 mm Analysed wire: 0.4-0.5 m Wire diameter: 1.0 -1.2 mm

Mo and S scan WD-XRF

Intensity versus 2

Illustrations/graphs area

Calibration curve Mo Lb
Intensity versus Mo (mg/dm2)

Illustrations/graphs area

Mo (mg/dm2) measured with ICP

Calibration curve Ca
Intensity versus Ca (mg/dm2)

Illustrations/graphs area

ED-XRF

Illustrations/graphs area

Mo and S scan ED-XRF

Intensity versus energy (channel number) 1.6 to 7.5 keV

Illustrations/graphs area

We measure S k alfa + partly Mo L alfa

Handheld XRF for screening

Using a general metal calibration The apparent sulfur concentration is used for screening if the product fulfils the specification

Illustrations/graphs area

Production control before respooling

Illustrations/graphs area

Conclusions - Application welding wire

At factory no wet chemical analysis XRF is a fast tool for deposited amount on the surface of MoS2 and Ca on welding wires For accurate analysis: Separate calibration curves / diameter WDXRF: Can separate Mo and S EDXRF: Analysis of S (Mo overlap) Handheld XRF: Analysis of S (Mo overlap) Fast production control on line Pass/Fail

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Direct measurement with XRF sampling but no sample preparation?

YES when we know our analytical technique & when we can demonstrate fitness for intended purpose
Bertil Magnusson

And I also would like to pay homage to Wilhelm Conrad Rntgen

Direct measurement with XRF

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