BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 1 © H. Kipphardt, BAM I.1 Characterisation of High Purity Metals as

BAM I Department for Analytical Chemistry; Reference Materials Berlin, November 2006, 1

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Characterisation of High Purity Metals as Primary Standards for Element

Determination

Bundesanstalt für Materialforschung und –prüfung

(BAM) H. Kipphardt, M. Czerwensky and R. Matschat


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High purity materials ...

… serve as primary standards for chemical measurements (mass or amount of substance of an identified substance)

... used for calibration… to establish SI traceability

SI

Primary standarde.g. BAM-Y001

(copper)

Primary calibration solution

e.g. PTB-001

traceable commercialcalibration solutions

Measurement result in field laboratorye.g. copper in tap water


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(1) Commercial calibration solutions1000 mg/l*

1000 mg/l*

1040 mg/l

1040 mg/l

960 mg/l

960 mg/l

Ca

CdCr

Cu

Fe

Mg

Mo

Ni

Pb


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Dissolution of high purity metals

purity BAM-B-primary-Cu-1‘nom. metallic’ 0.999 999 0.999 9

‘metallic' 0.999 997 0.999 978 ± 0.000 002 ± 0.000 010

total 0.999 44 0.999 969 ± 0.000 17 ± 0.000 010

BAM-A-primary-Cu-1


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Materials certified for purity ...

... hardly exist

... usually incompletely characterised using semi-quantitative measurement techniques

... no uncertainty statement


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Target: Primary standards ...

... of high metrological quality

... small uncertainty according to GUM

... serve as national standards for element analysis in Germany (with PTB)


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Primary standards of Type A ...

... intended for analyte calibration

(i.e. element amount standard)

... certified for the mass fraction of the matrix element in a ‘pure’ material

... for use within the NMIs multiplication to the field via cooperation


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Primary standards of type A

... w(E) known to better than 0.01 %

... measurement of total impuritiy content (bulk and surface)

... measurement of all impurity elements (including O, N ...)

... approach: 100 % - Imp


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Certification approach

ET and HG AAS

ICP OES, (INAA)

Gas andNon-metal analysis

HR ICP MS LA-ICP MS

FI-ICP MS

validationadditional information

CGHE; PAAnuclear methods

loweringdetection limits

combineduncertainty

(GUM)

certifiedvalue

check ofdissolution step

continuousnebulization

validationadditional information

consistency check


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BAM-Y001: overview of impurities

w(Cu, BAM-Y001)= 0.999 968 0.000 010 with k=2

BAM-A-primary-Cu-1LOT B27F17

matrix impurity sum 'above'sum/2 'below' not underin % in mg/kg in mg/kg in mg/kg relevant investigation

mass fraction 99,9968 32,33 22,38 9,95 (estimate)abs. uncertainty 0,0005 5,27 3,84 3,61

H He< 2,1 < 0,001

Li Be B C N O F Ne< 0,31 < 1,1 < 3,2 0,04 0,2 1 < 2 < 0,001

Na Mg Al Si P S Cl Ar 0,002 < 0,05 < 0,07 < 0,002 < 2 5,4 < 0,6 < 0,001

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr< 0,002 0,1 < 0,06 < 0,32 < 0,04 0,07 0,01 < 5 < 0,11 1,64 matrix 0,057 < 0,11 < 0,12 0,5 0,22 < 0,014 < 0,001

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe< 0,05 < 0,014 < 0,03 < 0,015 < 0,02 < 0,06 < 0,001 < 0,03 < 1,6 < 0,014 11,3 < 0,015 < 0,05 0,14 1 < 0,22 < 0,09 < 0,001

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn< 0,0057 < 0,017 < 0,002 < 0,003 < 0,003 < 0,12 < 0,009 < 0,004 < 0,007 < 0,007 < 0,008 < 0,03 < 0,005 0,47 0,23 < 0,001 < 0,001 < 0,001

Fr Ra Ac< 0,001 < 0,001 < 0,001

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu< 0,0057 < 0,002 < 0,21 < 0,001 < 0,007 < 0,003 < 0,001 < 0,001 < 0,001 < 0,001 < 0,001 < 0,001 < 0,001 < 0,002

Th Pa U< 0,02 < 0,001 < 0,001


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Measurements using different methods

HR ICP MSET AASICP-OESHE/PAAHE/IRPhotometrieINAA

mass fraction in mg/kg

0,01

0,1

1

10

100

Ag As Bi C Ca Cr Fe N Ni O Pb S Sb Se Si Sn


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BAM-Y001certificatio

nreport

BAM/HKi/01-27

I.1902 April 2004

Certification of the

mass fraction of copper

in Primary Reference Material

BAM-Y001

CERTIFICATION REPORT

Version of 2004-06-09

edited by Heinrich Kipphardt

Bundesanstalt für Materialforschung und -prüfung Richard-Willstätterstr. 11

12489 Berlin Germany

Warning: This report has been produced for internal use at BAM. It can only be quoted

with permission of the authors and referred to as a private communication.


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BAM-Y001

Certificate

Bundesanstalt für Materialforschung und -prüfung

Certificate for Primary Reference Material

BAM-Y001

high purity copper

(BAM-A-primary-Cu-1)

Certified quantity value

When applying the prescribed sample treatment as specified below, the mass

fraction w of copper in material BAM-Y001 is:

w(Cu) = (0,999 970 0,000 010)* kg/kg where the number following the symbol is the numerical value of an expanded

uncertainty U=kuc with k=2 estimated according the ISO/BIPM Guide to the expression of uncertainty in measurement.

Safety instructions: No special hazards are known. Handle with caution - as any chemical substance.

Sample description: The material is provided in compact form as spherical objects with a mass of about 12 g packed in glass bottles.

Recommendation for correct storing: The bottle should be kept closed at ambient conditions and in a clean environment.

Expiration of certificate: This certificate expires formally ten years after seal affixation on the certificate. (The material itself is assumed to be stable > 200 years).

* In line with the ISO 31-0 (1992) in this document the comma (and not the dot) is used as a decimal separator.


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Certified materials Element Value Uncertainty Upper limit estimates

BAM-Y001 Cu 0,999 970 0,000 010 -

BAM-Y002 Fe 0,999 862 0,000 044 P

BAM-Y003 Si 0,999 91 0,000 07 H, F, Cl, Br, I

BAM-Y004 Pb 0,999 92 0,000 06 H, P, Si, F, Cl, Br, I

BAM-Y005 Sn 0,999 91 0,000 06 H, Si, F, Cl, Br, I

BAM-Y006 W 0,999 81 0,000 10 H, F, Cl, Br, I

BAM-Y007 Bi 0,999 90 0,000 07 H, K, Si, S, F, Cl, Br, I

BAM-Y008 Ga 0,999 92 0,000 07 H, Si, F, Cl, Br, I

BAM-Y009 NaCl 0,999 84 0,000 09 H, F, K, Si, S

BAM-Y010 KCl 0,999 83 0,000 10 H, F, Si, S, Mn, Fe, As


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Elements under investigation ...

H He

Li Be B C N O F Ne

NaClKCl

KCl Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

Fr Ra Ac

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

ArAl Si P SNaCl Mg


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Materials of type B

... intended for matrix investigations (spectrometry)

... certified for very low metallic impurities (typically 1-50 g/kg)


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BAM Cu type B: overview of impurities

500 mg/kg oxygen !

BAM-B-primary-Cu-1LOT G24F31

matrix impurity sum 'above'sum/2 'below' not in % in mg/kg in mg/kg in mg/kg relevant

mass fraction 99,9438 562,16 557,93 4,23abs. uncertainty 0,0167 166,51 166,50 1,42

H He< < Li Be B C N O F Ne

< 0,08 < 0,045 < 0,75 0,3 1,1 555 < < Na Mg Al Si P S Cl Ar

< 0,3 < 0,065 < 0,12 < < 2 1,3 < < K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr< < < 0,06 < 0,33 < 0,04 < 0,06 < 0,25 < 0,48 < 0,11 < 0,4 matrix < 0,066 < 0,11 < 0,12 < 0,07 < < < Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe

< 0,05 < 0,014 < 0,03 < 0,015 < 0,02 < 0,06 < < 0,03 < 1,6 < 0,014 < 0,33 < 0,015 < 0,05 0,23 < 0,035 < 0,22 < < Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn

< 0,006 < 0,017 < 0,002 < 0,003 < 0,003 < 0,12 < 0,009 < 0,004 < 0,007 < 0,007 < 0,008 < < 0,005 < 0,07 < 0,009 < < < Fr Ra Ac< < <

Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu< 0,006 < 0,002 < 0,21 < < 0,007 < 0,003 < 0,001 < 0,001 < 0,001 < 0,001 < 0,001 < 0,001 < 0,001 < 0,002

Th Pa U< 0,02 < < 0,001


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Conclusion 1

• primary standards seem to be necessary,- also for analytical chemistry

• their realisation has been successfullydemonstrated

• realisation requires a variety of methodsand staying power


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CCQM-P62: Background

• Purity of Nickel with respect to six metallic analytes

• Quantity of interest:w(Ag)+w(Al)+w(Cu)+w(Fe)+w(Pb)+w(Zn)and interim results; expected range: 0.1 – 5.0 mg/kg

• Participants: 5 + BAM I, BAM II for homogeneity and IDMS NRC, for IDMS BAM

• Status: completed


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CCQM-P62: methods used

1 2 3 4 5 6 10

BAM I BAM II

Ag ICP-QMS

ICP-QMS

ICP-SFMS (MR)

ICP OES ICP-SFMS ET AAS ICP-QMS, INAA

Al ICP-QMS

ICP-QMS

ICP-SFMS (MR)

ICP OES ICP-SFMS ET AAS ICP-QMS

Cu ICP-QMS

ICP-QMS

ICP-SFMS (MR)

ICP OES ICP-SFMS (HR)

ET AAS ICP-QMS

Fe ICP OES

ICP-QMS

ICP-SFMS (MR)

ICP OES ICP-SFMS (MR)

ET AAS INAA

Pb ICP-QMS

ICP-QMS

ICP-SFMS, ET AAS

ICP OES ICP-SFMS ET AAS ICP-QMS

Zn ICP-QMS

ICP-QMS

ICP-SFMS (MR), ET AAS

ICP OES ICP-SFMS ET AAS ICP-QMS, INAA


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CCQM-P62: Additional IDMS experiments

Because of the inconsistent results in the pilot study, additionally IDMS was applied as ‘reference’:

• IDMS for Al is impossible • NRC: Ag, Pb, Zn• BAM: Pb, Zn, Cu, Fe • IDMS is not used to calculate mean of

CCQM-P62


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CCQM-P62: overview of IDMS results

w / mg/kgu / mg/kg

Ag Al Cu Fe Pb ZnNRC 1,03 - - - 0,259 1,08

0,02 0,008 0,05BAM - - 0,254 0,49 0,238 1,051

0,015 0,11 0,010 0,017

• Good consistency of results for Pb and Zn.• Some experimental problems with Fe measurements.• w(Ag+Cu+Fe+Pb+Zn) = (3,09 ± 0,12) mg/kg [without

Al]


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w(Pb) / mg/kg u Pb methodB IDMS BAM 0,238 0,010 IDMS5 BAM I 0,250 0,010 ICP-SFMS

10 0,254 0,010 ICP-QMSA IDMS NRC 0,259 0,008 IDMS6 BAM II 0,260 0,010 ET AAS3 0,31 0,07 ICP-SFMS(MR), ET AAS1 0,380 0,006 ICP-QMS2 0,460 0,019 ICP-QMS4 0,5 0,5 ICP OES

mean 0,34 0,18

CCQM-P62: results Pb

agreement < 30 %


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CCQM-P62: results Zn

agreement 30 %

w(Zn) / mg/kg u Zn10 0,91 0,04 ICP-QMS, INAA 6 BAM II 1,03 0,02 ET AAS B IDMS BAM 1,05 0,02 IDMS5 BAM I 1,08 0,04 ICP-SFMS A IDMS NRC 1,08 0,05 IDMS1 1,43 0,06 ICP-QMS 3 1,5 0,4 ICP-SFMS(MR) 4 1,70 0,25 ICP OES 2 1,77 0,12 ICP-QMS

mean 1,3 0,3


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CCQM-P62: results Ag

well agreement, one exception

w(Ag) /mg/kg u Ag10 0,93 0,03 ICP-QMS, INAA6 BAM II 0,95 0,02 ET AAS3 0,99 0,04 ICP-SFMS(MR)4 1,00 0,20 ICP OES5 BAM I 1,00 0,03 ICP-SFMSA IDMS NRC 1,03 0,02 IDMS1 1,05 0,06 ICP-QMS2 17,4 0,7 ICP-QMS

mean 3 6


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CCQM-P62: results Cu

problem: factor 5

w(Cu) / mg/kg u Cu5 BAM I 0,25 0,03 ICP-SFMS (HR) 6 BAM II 0,25 0,02 ET AAS B IDMS BAM 0,254 0,015 IDMS4 0,28 0,05 ICP OES

10 0,409 0,019 ICP-QMS 3 0,73 0,08 ICP-SFMS (MR) 1 1,29 0,05 ICP-QMS 2 1,35 0,09 ICP-QMS mean 0,7 0,5


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CCQM-P62: results Fe

problem: factor 10

w(Fe) / mg/kg u FeB IDMS-BAM 0,49 0,11 IDMS

6 BAM II 0,61 0,04 ET AAS 5 BAM I 0,77 0,05 ICP-SFMS (MR)

10 1,60 0,12 INAA 4 2,60 0,20 ICP OES 2 3,21 0,27 ICP-QMS 3 3,9 0,9 ICP-SFMS (MR) 1 6,0 0,6 ICP OES

mean 2,7 1,9


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CCQM-P62: results Al

problem: > factor 100

w(Al) / mg/kg u Al6 BAM II 0,03 0,03 ET AAS 5 BAM I 0,045 0,005 ICP-SFMS

10 0,086 0,005 ICP-QMS 4 0,5 0,5 ICP OES 2 1,21 0,05 ICP-QMS 3 4,5 2,1 ICP-SFMS (MR) 1 4,9 0,4 ICP-QMS mean 1,6 2,2


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CCQM-P62: results total

problem: factor 8

w(Imp) / mg/kg u totalA&B NRC&BAM 3,09 0,12 without Al!

6 BAM II 3,13 0,07 ET AAS 5 BAM I 3,40 0,08 ICP-SFMS

10 4,18 0,13 ICP-QMS, INAA 4 6,6 0,8 ICP OES 3 11,9 2,3 ICP-SFMS, ET AAS 1 15,1 0,7 ICP-QMS, ICP OES 2 25,4 0,8 ICP-QMS mean 10 8


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CCQM-P62: overview of results

level / mg/kg observed spread / %

max. contr. from homogen. / %

Ag 3 200 6

Al 2 3 orders of mag. 1

Cu 0.7 factor 5 20

Fe 2.7 factor 10 4

Pb 0.3 30 15

Zn 1.3 23 7

total 10 factor 8


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Conclusion 2: CCQM-P62• number of participants low

=> limited interest (or ability) concluded• discrepancies by a factor of 8 for the value of the target

quantity, not covered by the corresponding uncertainties• discrepancies based on discrepancies for individual

impurities• Results for a ‘rather simple task’

=> worldwide the characterisation of high purity materials is not to be comparable.

• few clusters of laboratories can be detected• 3 laboratories report rather low values• IDMS confirms the lower values for Pb, Zn, Ag, Cu, Fe

GDMS shows very low value for Al=> may be for some labs the blank is not fully under control


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END

Documents

BAM IDepartment for Analytical Chemistry; Reference Materials Berlin, November 2006, 1 © H. Kipphardt, BAM I.1 Characterisation of High Purity Metals as