BUREAU OF ANALYSED SAMPLES LTD

BRITISH CHEMICAL STANDARD CERTIFIED REFERENCE MATERIAL

CERTIFICATE OF ANALYSIS
4004
BCS-CRM No. 204/6
HIGH CARBON FERRO-CHROMIUM
Prepared under rigorous laboratory conditions and, AFTER CERTIFICATION ANALYSIS IN GREAT BRITAIN, BELGIUM,
CANADA, CHINA, ESTONIA, HUNGARY, INDIA, THE NETHERLANDS, SWEDEN and SPAIN
issued by the Bureau of Analysed Samples Ltd.

ANALYSES
Mean of 4 values - mass content in %.
Analyst C Si Mn P S Cr Ni Co Ti V N
1 8.5789 0.6917 0.2140 0.0182 0.0200 68.833 0.2740 0.0333 0.0602 0.0885 …
2 8.5460 0.7138 0.2197 0.0160 0.0175 68.963 0.2889 0.0336 0.0601 0.1012 0.0231
3 8.5116 0.6490 … … 0.0207 … … … … … 0.0245
4 8.6100 … … 0.0188 0.0175 68.749 … … 0.0555 0.0918 …
5 … 0.7650 0.2300 0.0165 … 68.508 0.2800 … 0.0560 0.0928 ….
6 8.6387 …. … … 0.0205 … … … … … …
7 8.4675 0.7330 0.2084 0.0158 0.0199 68.659 0.2791 0.0388 0.0602 0.1014 0.0233
8 8.5481 0.6872 … 0.0169 0.0183 68.710 0.2982 0.0334 … 0.0790 0.0227
9 8.5574 … … … 0.0195 … … … … … 0.0224
10 … 0.7476 … 0.0160 0.0188 … … … 0.0504 … …
11 … 0.7048 0.2314 0.0154 … 68.973 0.2852 0.0336 0.0517 0.0996 0.0175
12 8.6272 … … … 0.0189 … … … … … 0.0250
13 8.6575 … 0.2298 … 0.0172 68.777 0.2855 0.0346 0.0553 0.0901 …
14 8.5629 … 0.2273 0.0151 0.0203 … 0.2776 0.0345 0.0507 0.0949 …
15 8.6433 0.6803 0.2367 0.0170 0.0207 68.860 0.2841 … 0.0590 0.1001 0.0211
16 … 0.7245 … … … 68.985 0.2873 0.0360 0.0550 0.0963 ..
17 … 0.7357 0.2267 0.0167 … 68.529 0.2765 0.0346 0.0538 0.0935 …
18 8.5160 0.7088 0.2343 0.0164 0.0191 68.975 0.2855 0.0332 0.0559 0.0846 …
19 … 0.7514 … 0.0162 0.0203 68.672 0.2877 0.0351 … 0.0880 …
20 8.5573 … 0.2117 0.0172 0.0180 68.715 0.3154 0.0412 0.0606 0.0989 …
21 … … 0.2323 0.0158 … 68.645 0.2975 … 0.0573 0.0933 …
22 … …. … … … 68.960 … … … … 0.0231
23 … 0.7200 0.2375 0.0150 …. 68.768 0.3000 0.0400 0.0600 0.1000 0.0250
24 … … 0.2098 … … … 0.3120 0.0403 0.0620 0.0963 …
25 … … … … … 68.638 … … … ... …
26 … … … … 0.0157 … … … 0.0528 … ….

MM 8.5730 0.7152 0.2250 0.0164 0.0190 68.773 0.2891 0.0359 0.0565 0.0939 0.023

sM 0.0561 0.0314 0.0103 0.0011 0.0015 0.155 0.0119 0.0030 0.0037 0.0062
sw 0.0531 0.0105 0.0025 0.0004 0.0007 0.089 0.0020 0.0007 0.0015 0.0015
Values given in italics are for information only.
Additional Information: Analysts Nos. 2 & 16 reported values for Fe of 20.2% & 21.1% by ICP-OES and XRF respectively.
No. 16 also reported XRF values for Mg and Cu of 0.13% and 0.01% respectively.
MM: Mean of the laboratory mean values. sM: standard deviation of the laboratory mean values.. sW: average within laboratory standard deviation.
CERTIFIED VALUES (Cv)
mass content in %
C Si Mn P S Cr Ni Co Ti V
Cv 8.57 0.715 0.225 0.0164 0.0190 68.77 0.289 0.0359 0.0565 0.094
C(95%) 0.04 0.019 0.006 0.0006 0.0008 0.08 0.007 0.0017 0.0019 0.004
Minimum weight (g) 0.2 0.2 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1
The half width confidence interval, C(95%), is an expression of the uncertainty of the certified value. C(95%) = t × s M where “t” is
n
the appropriate two sided Student’s t value at the 95% confidence level for “n” acceptable mean values.
For further information regarding the confidence interval for the certified value see ISO Guide 35:2006 sections 6.1 and 10.5.2
NB: Although widely accepted within the industry “mass content in %” is neither an SI nor an IUPAC supported quantity.
Multiplication of the certified value (Cv) by 104 will yield the value in µg/g.

Page 1 of 4 Date of this edition: September 2017

(The current edition is available at www.basrid.co.uk)
 BCS -CRM 204/6
HIGH CARBON FERRO-CHROMIUM
CO-OPERATING ANALYSTS

1 BLUNDELL, P., ALS Inspection UK Ltd., Prescot.

2 HURDITCH, P., AMG Analytical Services Ltd, Rotherham.
3 SCRIMSHIRE, P. J., IncoTest, Hereford.
4, 25 HARGREAVES, C., Inspectorate International Ltd., Witham.
5 SIMPSON, P., Alfred Knight International Ltd., St Helens.
6 JAMIESON, S. N., NSG European Technical Centre, Lathom.
7 CROCKER, F. H., Pattinson & Stead (2005) Ltd., Middlesbrough.
8 JONES, S. J., Ridsdale & Co. Ltd., Middlesbrough.
9 SNOWDEN, Y., British Steel Testing Solutions, Scunthorpe.
10 RODUSHKIN, I., ALS Scandinavia AB, Luleå, Sweden.
11 HENRICH, A., Höganäs Sweden AB, Höganäs, Sweden.
12 LINDKVIST, L., Sandvik Heating Technology, Hallstahammar, Sweden.
13 WICHARDT, C., AB Sandvik Materials Technology, Sandviken, Sweden.
14, 26 GRANFORS, M., Swerea-Kimab, Kista, Sweden.
15 QUIRÓS, E. & PEREZ, D., Acerinox Europa SAU, Cadiz, Spain.
16 BOUCHARD, M., Claise, Quebec, Canada.
17 KICQ, P., CTP, Tournai, Belgium.
18 JIANG, J., Inspectorate (Shanghai) Ltd., Shanghai, China.
19 YARUSHKINA, M., Inspectorate Estonia AS, Tallinn, Estonia.
20 CHATTOPADHYAY, S., Inspectorate Griffith India PVT. Ltd., Bhubaneswar, India.
21 KONDOROSI, G., Dunaferr Labor Nonprofit Ltd., Dunaújváros, Hungary.
22 CULLEY, N., LMA CV, Sleeuwijk, The Netherlands.
23 BIJL, G., P., SGS Netherland BV, LA Spijkenisse, The Netherlands.
24 COLLINS, P., Tata Steel Technical, Swinden Laboratories, Rotherham.

Page 2 of 4
 BCS -CRM 204/6
HIGH CARBON FERRO-CHROMIUM
NOTES ON METHODS USED
CARBON
With the exception of Analysts Nos. 7 and 8 all of the Analysts determined carbon using combustion/infra-red methods, Nos. 1, 2, 3, 6, 9 and 15
calibrating with carefully selected CRMs (see below for details) and the rest with pure chemicals or stoichiometric compounds, Nos. 13, 14 and 19 by
following ISO 9556. Nos. 7 and 8 determined carbon gravimetrically following combustion in a stream of oxygen.
SILICON
Most of the Analysts determined silicon with Inductively Coupled Plasma – Optical Emission Spectroscopy (ICP-OES). Analyst No. 2 dissolved
the sample in HCl/HNO3 after an alkaline fusion and used standard addition, Nos. 11 and 18 used microwave dissolution (No. 18 following SN/T 3708-
2013), No.15 fused the sample and dissolved the melt in acid, No. 17 used an aqua-regia digestion combined with an alkaline fusion of the residue and
No. 23 fused the sample with peroxide. Analysts Nos. 5, 7, 8 and 19 used a gravimetric method, dehydrating with perchloric acid, No. 19 according to
ISO 4158-1978. No.10 used Inductively-Coupled Plasma – Mass Spectrometry (ICP-MS) and No. 16 used X-Ray Fluorescence Spectrometry (XRF).
MANGANESE
Analyst No. 24 determined manganese by ICP-MS, all of the rest used ICP-OES. No. 2 dissolved the sample in HCl/HNO3 after an alkaline fusion
and used standard addition, No. 11 used a microwave digestion, No. 13 used matrix matched bracketing standards, No. 14 a combination of HCl, HNO3
and HF, No. 15 fused the sample and dissolved in acid and No. 17 dissolved with aqua regia before using an alkaline fusion.
PHOSPHORUS
Most Analysts determined phosphorus using ICP-OES. No. 2 dissolved the sample in HCl/HNO3 after an alkaline fusion and used standard
addition, No. 11 used a microwave digestion, No. 14 a combination of HCl, HNO3 and HF, No. 15 fused the sample and dissolved in acid No. 18
followed SN/T 3708-2013 after microwave digestion and No. 23 used a peroxide fusion.
Analyst No.4 used XRF.
Analysts Nos.7, 8 and 21 determined phosphorus spectrophotometrically as phosphovanadomolybdate, Nos. 7 and 8 after solvent extraction and No.
21 without extraction.
Analyst No. 10 used ICP-MS whilst No. 20 determined phosphorus by acidimetric titration of ammonium phosphomolybdate, following IS 1559-
1961 and after fusion with Na2O2,
SULPHUR
Most Analysts determined sulphur by combustion/infra-red methods, Nos. 1, 2, 3, 6, 9 and 15 calibrating with carefully selected CRMs (see below
for details) and Nos. 4, 12, 13, 18, 19, 20 and 26 calibrating with pure chemicals or stoichiometric compounds, Analysts Nos. 12, 13, 19 and 26 using
ISO 4935 and No. 18 GB/T 4699.6-2008. No. 7 used an acid/base titration following combustion in a stream of oxygen. Nos. 8 and 14 used ICP-OES,
No. 14 digesting with a mixture of HCl/HNO3/HF whilst No.10 used ICP-MS.
CHROMIUM
Analysts Nos. 1, 5, 18, 20, 21, 22, 23 and 25 determined chromium by titration with Fe (II) after oxidation with persulphate. No. 1 used a
potentiometric titration, No. 18 GB/T 4699.2-2009, No. 20 IS 13452 (part 6) 1997 and Nos. 21, 22 and 23 according to ISO 4140. No. 25 used a
peroxide fusion.
Analysts Nos.2, 11 and 15 used ICP-OES, No. 2 dissolving the sample in HCl/HNO3 after an alkaline fusion and used standard addition, No. 11
after a microwave digestion and No. 15 after fusing the sample and dissolving in acid.
Analyst Nos. 4 and 16 used XRF.
Analysts Nos. 7, 8, 13 and 19 oxidised the chromium with persulphate, added excess Fe(II) and back titrated the excess Fe(II) with K2Cr2O7 in the
case of Labs 7, 8 and 13 (No. 13 following ISO 15355) and KMnO4 in the case of Lab 19 who followed GOST 21600.17-83.
NICKEL
With the exception of Analyst No. 24, who used ICP-MS after microwave dissolution with aqua regia,and No. 16 who use XRF, all of the Analysts
determined nickel using ICP-OES. No. 2 dissolved the sample in HCl/HNO3 after an alkaline fusion and used standard addition, No. 11 used a
microwave digestion, No. 13 used matrix matched bracketing standards, No. 14 a combination of HCl, HNO3 and HF, No. 15 fused the sample and
dissolved in acid, No. 17 dissolved with aqua regia before using an alkaline fusion, No. 18 followed TOP-04 after an acid dissolution, No. 19 followed
GOST R 53659-2009 after an alkaline fusion and No. 23 used a peroxide fusion.
COBALT
With the exception of Analyst No. 16, who used XRF and No. 24, who used ICP-MS after microwave dissolution with aqua regia, all of the
Analysts determined cobalt using ICP-OES. No. 2 dissolved the sample in HCl/HNO3 after an alkaline fusion and used standard addition, No. 11 used a
microwave digestion, No. 13 used matrix matched bracketing standards, No. 14 a combination of HCl, HNO3 and HF, No. 17 dissolved with aqua regia
before using an alkaline fusion, No. 18 followed TOP-04 after an acid dissolution, No. 19 followed GOST R 53659-2009 after an alkaline fusion and No.
23 used a peroxide fusion.
TITANIUM
With the exception of Analysts Nos. 4 and 16, who used XRF, and Nos. 10, 24 and 26, who used ICP-MS (No. 24 after microwave dissolution with
aqua regia), all of the Analysts determined titanium using ICP-OES. No. 2 dissolved the sample in HCl/HNO3 after an alkaline fusion and used standard
addition, No. 11 used a microwave digestion, Nos. 13 and 14 a combination of HCl, HNO3 and HF, No. 13 also used matrix matched bracketing
standards, No. 15 fused the sample and dissolved in acid, No. 18 followed TOP-04 after an acid dissolution and No. 23 used a peroxide fusion.
VANADIUM
With the exception of Analyst No. 24, who used ICP-MS after microwave dissolution with aqua regia, and Nos. 4 and 16, who used XRF, all of the
Analysts determined vanadium using ICP-OES. No. 2 dissolved the sample in HCl/HNO3 after an alkaline fusion and used standard addition, No. 11
used a microwave digestion, Nos. 13 and 14 a combination of HCl, HNO3 and HF, No. 13 also used matrix matched bracketing standards, No. 15 fused
the sample and dissolved in acid, No. 18 followed TOP-04 after an acid dissolution, No. 19 followed GOST R 53659-2009 after an alkaline fusion and
No. 23 used a peroxide fusion.
NITROGEN
With the exception of Analysts Nos. 7 and 8 all of the Analysts determined nitrogen using thermal conductivity, Nos. 2, 3, 9, and 15 calibrating with carefully selected CRMs (see
below for details) and the rest with pure chemicals or stoichiometric compounds, Nos. 11 following ISO 15351. Analyst No. 7 used a Kjeldahl digestion and steam distilled the ammonia
into Nessler’s reagent before completing spectrophotometrically. No. 8 also used a Kjeldahl digestion but followed the steam distillation by titrating the distillate with hydrochloric acid.

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 BCS -CRM 204/6
HIGH CARBON FERRO-CHROMIUM
DESCRIPTION OF SAMPLE
BCS-CRM 204/6 is sold in the form of finely divided material passing a nominal 150 micron aperture and packed
into bottles of 100g.
The preparation of representative samples for chemical analysis and the certification by co-operative analysis was
undertaken by Bureau of Analysed Samples Ltd.
Bureau of Analysed Samples Ltd is a United Kingdom Accreditation Service (UKAS) Accredited Reference
Material Producer, No.4004, and, as the Producer of BCS-CRM 204/6 as defined in BS EN ISO 17034:2016, is fully
responsible for assigning the certified values and their uncertainties.
INTENDED USE
BCS-CRM 204/6 is intended for the verification of analytical methods, such as those used by the participating
laboratories, for the calibration of analytical instruments, for establishing values for secondary reference materials and
for training purposes.
In order to ensure that a fully representative sample is taken users should take not less than the minimum weight
stated on the certificate for that element, this being the lowest sample mass used by any of the Co-operating Analysts
contributing to the certified value. Users of this material should be aware that the use of a smaller sub-sample size may
invalidate the certified values and the associated 95% confidence limits.
The sample should be mixed thoroughly before each use.
STABILITY
BCS-CRM 204/6 will remain stable provided that the bottle remains sealed and is stored in a dry atmosphere.
Once the bottle has been opened the lid should be secured immediately after use.
TRACEABILITY
The characterisation of this material has been achieved by chemical analysis involving inter-laboratory study, each
laboratory using the method of their choice, details of which are given above.
Most of the analytical methods used in the characterisation of this CRM were either international or national
standard methods or methods which are technically equivalent. With the exception of C, S and N all laboratories used
either stoichiometric analytical techniques or methods which were calibrated predominantly against pure metals or
stoichiometric compounds, ensuring traceability of the individual results to the SI.
For C, S and N results have been obtained using stoichiometric analytical techniques, methods which were
calibrated against pure metals or stoichiometric compounds or by calibration using 5 certified reference materials
carefully selected to be similar in composition to BCS-CRM 204/6 and all of which demonstrate full unbroken
traceability to the SI. Different Analysts used different combinations of CRMs. The CRMs used were as follows:
BCS-CRM 204/1, BCS-CRM 204/4, BS 130/1, DFS 1, DFS 2, ECRM 585-1, ECRM 585-2, ICRM F46, ICRM F47,
NCS HC25653.
MEASUREMENT UNCERTAINTY
The uncertainty of each of the certified values of BCS-CRM 204/6 has been established by multiplying the
standard error arising from the chemical analysis by the appropriate two sided Student’s t value at the 95% confidence
level for the number of results. Homogeneity has been assessed on the bulk material using one way ANOVA and has
been found to be acceptable. It has not, therefore, been included in the calculated measurement uncertainty. The
stability of this CRM and its transportation also make negligible contributions to the overall uncertainty of the certified
values.
COMMUTABILTY
BCS-CRM 204/6 is intended to be used in the same physical form as that used by the participating analysts and
therefore commutability is not of relevance in respect of this CRM.
Further information and advice on this or other Certified Reference Materials or Reference Materials produced by
Bureau of Analysed Samples Ltd may be obtained from the address below.

NEWHAM HALL, NEWBY For BUREAU OF ANALYSED SAMPLES LTD

MIDDLESBROUGH
ENGLAND R P MEERES,
TS8 9EA Managing Director
Email: enquiries@basrid.co.uk September 2017
Website: www.basrid.co.uk

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