GOST R ISO 6351-2015

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  ГОСТ Р ИСО 6351-2015

GOST R ISO 6351−2015 Nickel. Determination of silver, bismuth, cadmium, cobalt, copper, iron, manganese, lead and zinc. Spectrometric method of atomic absorption in the flame

GOST R ISO 6351−2015

Group B39

NATIONAL STANDARD OF THE RUSSIAN FEDERATION

NICKEL

Determination of silver, bismuth, cadmium, cobalt, copper, iron, manganese, lead and zinc. Spectrometric method of atomic absorption in the flame

Nickel. Determination of silver, bismuth, cadmium, cobalt, copper, iron, manganese, lead and zinc contents. Flame atomic absorption spectrometric method

OKS 77.120.40

AXTU 0709

Date of introduction 2016−01−01

Preface

1 PREPARED by the Technical Committee for standardization TC 145 «monitoring Methods of steel products» on the basis of authentic translation into the Russian language of the standard referred to in paragraph 4

2 recorded by the FSUE «the Central research Institute of ferrous metallurgy them.And.P.Bardeen"

3 APPROVED AND put INTO EFFECT by the Federal Agency for technical regulation and Metrology of April 21, 2015 N 279-St

4 this standard is identical to international standard ISO 6351:1985* «Nickel. Determination of silver, bismuth, cadmium, cobalt, copper, iron, manganese, lead and zinc. Spectrometric method of atomic absorption in the flame» (ISO 6351:1985 «Nickel — Determination of silver, bismuth, cadmium, cobalt, copper, iron, manganese, lead, and zinc contents — Flame atomic absorption spectrometric method»).
________________
* Access to international and foreign documents referred to here and hereinafter, can be obtained by clicking on the link to the site shop.cntd.ru. — Note the manufacturer’s database.

In applying this standard it is recommended to use instead of the referenced international standards corresponding national standards of the Russian Federation and interstate standards, details of which are given in Appendix YES

5 INTRODUCED FOR THE FIRST TIME

Application rules of this standard are established in GOST R 1.0−2012 (section 8). Information about the changes to this standard is published in the annual (as of January 1 of the current year) reference index «National standards» and the official text changes and amendments — in monthly information index «National standards». In case of revision (replacement) or cancellation of this standard a notification will be published in the upcoming issue of the monthly information index «National standards». Relevant information, notification and lyrics are also posted in the information system of General use — on the official website of the Federal Agency for technical regulation and Metrology on the Internet (www.gost.ru)

1 Purpose and scope

This standard specifies the flame atomic absorption spectrometric method for the determination of silver, bismuth, cadmium, cobalt, copper, iron, manganese, lead and zinc in high-purity, refined, wrought and cast Nickel within the ranges presented in table 1.

The method is applicable to an independent determination of any one or more of the listed items, without determining all the elements present in the standard solutions.

The lower limit of the range for determination of iron can be reduced, compared with 0,0025% indicated in table 1, if you have a Nickel for the preparation of standard solutions on 4.1 with iron content less than 0.0001% (mass). The upper limit of the determination of cobalt and copper can be increased to 2% (mass), slightly modifying the method (11.1).

About the possible effects see section 10.


Table 1 — Ranges of the contents of the designated elements

Item	Ranges of grades*, % (mass.)
	Methods And				Methodology In
Hell	From	0,0002	to	0,01	-
Bi	«	0,0010	«	0,01	-
Cd	«	0,0002	«	0,0025	From	0,01	to	Of 1.00
With	«	0,0010	«	0,01	«	0,01	«	Of 1.00
Si	«	0,0002	«	0,01	«	0,01	«	0,15
Fe	«	0,0025	«	0,01	«	0,01	«	0,20
MP	«	0,0005	«	0,01	-
Pb	«	0,0005	«	0,01	From	0,001	to	0,015
Zn	«	0,0002	«	0,0025
* Other ranges in the content of impurities is given in ISO 6283.

2 Normative references

The present standard features references to the following standards*:
_______________
* The table of conformity of national standards international see the link. — Note the manufacturer’s database.

ISO 385/1 oils. Burette. Part. General requirements (ISO 385/1, Laboratory glassware — Burettes — Part 1: General requirements)

ISO 648:2008 laboratory Glassware glass. Pipettes with one mark (ISO 648:2008, Laboratory glassware — Single-volume pipettes)

ISO 1042:1998 laboratory Glassware glass. Flasks volumetric with one mark (ISO 1042:1998, Laboratory glassware — One-mark volumetric flasks)

ISO 5725 Precision of test methods. Determination of repeatability and reproducibility of the method by interlaboratory tests (ISO 5725, Precision of test methods — Determination of repeatability and reproducibility by inter-laboratory tests)

3 the essence of the method

This method is based on dissolving the sample the investigated sample in nitric acid diluted 1:1, spraying the resulting solution in an air-acetylene flame atomic absorption spectrometer, the measurement of the absorption values of the resonance radiation of free atoms of each element emitted by the lamp with hollow cathode.

The obtained value of absorption compared with the absorption values of the calibration solutions of the same item cooked on the background of Nickel, used to prepare the calibration solutions.

4 Reagents

In the analysis, unless otherwise specified, use reagents of known analytical grade and distilled water or water of equivalent purity.

4.1 high-purity Nickel containing less than 0.0005% (mass.) iron and less than 0.0001% (mass.) each of the following elements: silver, bismuth, cadmium, cobalt, copper, manganese, lead and zinc.

4.2 Nitric acid (HNО), of 1.41 g/cm, diluted 1:1.

In all analysis procedures should be used the same batch of nitric acid.

4.3 Nitric acid (HNО), of 1.41 g/cm, diluted 1:19.

In all analysis procedures should be used the same batch of nitric acid.

4.4 Standard solutions of the identified elements

4.4.1 Basic standard solutions of detectable elements, each containing 1,000 g/DMAd, Bi, Cd, co, cu, Fe, Mn, Pb, Sb and Zn are prepared individually for each object.

Weighed 1,000 grams, weighed with accuracy to 0.001 g of each of high-purity metals [not less than 99.9% (mass.)] placed in a beaker with a capacity of 600 cmand dissolved in 40 cmof nitric acid (4.2). Was heated until complete dissolution of the sample, boil gently to remove oxides of nitrogen, cool and quantitatively transfer the solution into volumetric flasks with a capacity of 1,000 cmwith 160 cmof nitric acid (4.2). Bring to mark with water and mix.

The solutions were stored in polyethylene vessels, with the exception of the silver solution, which is stored in a vessel made of dark glass.

4.4.2 Mixture of standard solutions standard solution A, containing 20 mg/DMAg, Bi, Cd, co, cu, Fe, Mn, Pb and 10 mg/DMZn prepared as follows.

A pipette is taken at 20.0 cmof each of the basic solutions of silver, bismuth, cadmium, cobalt, copper, manganese, lead (4.4.1) and 10 cmbasic solution of zinc (4.4.1), transferred to volumetric flask with one mark capacity of 1000 smwith 160 cmof nitric acid (4.2). Bring to mark with water and mix. Store the solution in a glass vessel.

4.4.3 Mixture of standard solutions standard solution containing 100 mg/DMof each element, si, Fe, Mn, and 10 mg/DMZn prepared as follows.

Taken in 50.0 cmof each of the basic solutions of cobalt, copper, iron and manganese (4.4.1) and 5 cmcore solution of zinc (4.4.1), transferred to volumetric flask with one mark capacity of 500 cm, was adjusted to the mark with water and mix. Store the solution in a polyethylene vessel.

5 Instrument

Use conventional laboratory equipment and the following equipment.

5.1 Atomic absorption spectrometer

5.1.1 Atomic absorption spectrometer used in this method should satisfy the characteristic values of the instrumental parameters is given in Appendix A.

5.1.2 the Instrument shall be equipped with a burner head capable of working with a solution containing 25 g/lof Nickel in the form of nitrate and suitable for the air-acetylene flame.

5.1.3 Spectrometer when using single-element lamps hollow cathode or electrodeless discharge lamps must be operated at the currents recommended by the manufacturer.

5.2 Burette volume of 50 cm, graduated with divisions of 0.1 cm, in accordance with ISO 385/1, class A.

5.3 Pipettes, volume 5; 20; 25; 50 and 100 cm, in accordance with ISO 648, class A.

5.4 volumetric Flasks with a capacity of 200; 250; 500 and 1000 cm, in accordance with ISO 1042, class A.

6 Sampling and analyze the samples

6.1 Sampling and preparation of laboratory samples must be done in accordance with normal established procedures. In the event of a dispute use the appropriate international standard.

6.2 common laboratory sample is prepared in the form of powder, granules, chips obtained by milling or drilling, in an amount not in excess of the minimum.

6.3 If it is assumed that the laboratory sample is contaminated with oil or grease when milling or drilling, it is necessary to clean the sample by rinsing with high-purity acetone and air dry.

6.4 If the laboratory sample contains a significantly different size particles, the sample should be collected after pre-shredding of large particles.

7 analysis according to the method And

This method is applicable to determination of content of from 0.0005% to 0.01% (mass.) silver, bismuth, cadmium, cobalt, copper, iron, manganese, and lead, and from 0.0005% to 0.005% (mass.) zinc.

7.1 Preparation of the test solution

A portion of the analytical sample in the range from 4.9 g to 5.1 g with an accuracy of 0.01 g, placed in a clean beaker with a capacity of 600 cm. Add enough water to cover the sample and dissolve by adding small portions of 60 cmof nitric acid (4.2). Was heated until complete dissolution of the sample, boil gently to remove oxides of nitrogen, and then evaporated to a syrupy condition. Dissolve the resulting salt by adding 20 cmof nitric acid (4.2) and 100 cmof water. Was heated until complete dissolution of salts, cooled the solution and, if necessary, filtered through a filter of glass wool, previously washed with nitric acid, or through a cellulose filter into a measuring flask with one mark capacity of 200 cm. Washed the filter with water, collecting the washings in the same flask, adjusted to the mark with water and mix.

If it is assumed that the sample is not homogeneous, for analysis select a sample of larger size (from 10 to 50 grams). In this case, after dissolving the sample from the obtained solution should be selected aliquota part corresponding to the sample of 5 g, and further carried out the operation in accordance with this method, as described in 11.2.

7.2 Blank

As the blank experience is a null-solution in series of the calibration solutions (7.3), prepared using the same batch of nitric acid, which was used for the preparation of a standard solution of Nickel and solutions of analyzed samples. If it is not possible to use nitric acid from the same batch, it is necessary to prepare a second solution for a single experience, using the same Nickel metal (4.1). This solution blanks experience is compared with the zero solution and introduce the necessary amendments.

7.3 Preparation of a series of calibration solutions And

7.3.1 This series of solutions corresponds to the content (0; 0,2; 0,5; 1,0; 1,5; 2,0 and 2.5) mg/DMof each of the elements: Ag, Bi, Cd, Co, si, Fe, MP and Pb and (0; 0,1; 0,25; 0,5; 0,75; 1,0 and 1.25) mg/DMZn (table 2). All the solutions were prepared in a background of Nickel, the content of which is 25 g/DM.


Table 2 — Series calibration solutions And

N	The volume of the mixed analyte, cm, standard solution (4.4.2)	The concentration of analyte, mg/DM
		Ag, Bi, Cd, Co, Cu, Fe, Mn, Pb	Zn
1	0	0	0
2	2,0	0,2	0,1
3	5,0	0,5	0,25
4	10,0	1,0	0,5
5	15,0	1,5	0,75
6	20,0	2,0	1,0
7	25,0	2,5	1,25

7.3.2 Seven batches at 5.0 g, weighed with accuracy to 0.01 grams of Nickel metal (4.1) is placed in glasses with a capacity of 600 cmand dissolved as described in 7.1.

7.3.3 In seven volumetric flasks with a capacity of 200 cm, each of which previously placed a solution of Nickel (7.3.2), add from burette appropriate volumes of standard solution (4.4.2) in table 2. Dilute to the mark with water and mix.

7.3.4 the Zero solution in the series, which is not added standard solution And also serves as a blank solution experience (7.2).

7.4 Calibration and determination

7.4.1 Spectrometric measurements

7.4.1.1 the measurements using the spectral lines listed in table 3.


Table 3 — Spectral lines. Methods And

Item	Hell	Bi	Cd	With	Si	Fe	Mn	Pb	Zn
Wavelength, nm	321,1	223,1	228,8	240,7	324,7	Of 248.3	Of 279.5	217,0	213,9

7.4.1.2 Possible to use alternative, less sensitive lines listed in table 4.


Table 4 — Alternative spectral lines. Methods And

Item	With	Si	Fe	Mn	Pb
Wavelength, nm	241,2	327,4	252,7	403,1	Is 283.3

7.4.1.3 Set of requirements to the instrumental parameters must comply with the instructions of the manufacturers of spectrometers. Spray diluted (1+19) nitric acid (4.3) when lit the burner is continued until a thermal equilibrium. Use air-acetylene flame, depleted fuel.

7.4.1.4 performance of the instrument must meet the requirements shown in Appendix A.

Note — the Optimal set of instrumental parameters is different for different devices. To obtain the necessary definition can be used scale expansion.

7.4.1.5 Necessary that the temperature of the test solution (7.1) and a series of calibration solutions (7.3) differed by no more than 1 °C.

7.4.1.6 Sprayed nitric acid, dilute (1:19) and set the instrument reading to zero.

7.4.1.7 Sprayed analyte (s) solution (s) and record the instrument reading (value removals) that identifies its location in a series of calibration solutions A.

7.4.1.8 Sprayed nitric acid, diluted (1:19) to return readings to the original value. If necessary, set a zero value.

7.4.1.9 Sprayed a series of calibration solutions (7.3) and analyze (s) solution (s) in order of increasing analytical signal, starting from the zero solution. When obtaining a stable analytic signal register readings. The system was washed with dilute (1:19) nitric acid, between sprays of solutions, analyze or calibration.

Note — try to avoid spraying solutions with high concentration of Nickel over long periods of time without flushing system, otherwise possible clogging of the burner.

7.4.1.10 Repeat the absorbance measurement of a complete set of calibration solutions and analyzed two more times and record data.

7.4.2 Construction of calibration graphs

Applied to the graph of the average value of the readings regarding the concentration of analyte in the calibration solutions for each series of measurements. Perform the procedure as specified in section 9.

Notes

1 In this method, any effects of nonspecific absorption and light scattering kompensiruet alignment matrix of the calibration solutions and analyzed. Nitric acid, used for calibration and analyzed solutions must be from the same batch of reagents. Blank is included in the calibration schedule. The value of the absorption solution of the blank experience is not subtracted from the values of other calibration solutions, therefore, the calibration curve may not pass through the origin.

2 Some devices can be adjusted so that they give readings directly in concentration units analyte. To verify the correctness of the readings, it is recommended to plot the instrumental sensitivity relative to the analyte concentration.

8 analysis according to the method In

This technique is suitable for the determination of cobalt, copper, iron and manganese in the ranges [(0,01−0,25)% (wt.)] and in the range [(0,005−0,025)% (wt.)] for contents of zinc.

8.1 Preparation of the test solution

8.1.1 If the analyzed solution was prepared according to method A (7.1), then pipetted aliquot part of 100.0 cmof the solution in volumetric flask with one mark capacity of 250 cmand was adjusted to the mark with nitric acid (4.3). Continue implementation methods 8.1.2.

8.1.2 Sample laboratory sample (6.2) in range (1,9−2,1) d, taken with an accuracy of 0.005 g, is placed in a beaker with a capacity of 400 cm, and dissolved in 20 cmof nitric acid (4.2). Then do as described in 7.1.

8.2 Blank

The zero solution in the calibration series of solutions In (8.3) is a solution of the blank experience (7.2).

8.3 Preparation of a series of calibration solutions In

8.3.1 This series of solutions corresponds to the content (0; 2,5; 5,0; 10,0; 15,0; 20,0; 25,0) mg/DMof co, si, Fe, MP and (0; 0,25; 0,5; 1,0; 1,5; 2,0; 2,5) mg/DMZn (table 5). All the solutions were prepared in a background of Nickel, the content of which is 10 g/DM.


Table 5 — Series of calibration solutions In

N	The volume of the mixed analyte, cm, standard solution (4.4.3)	The concentration of analyte, mg/DM
		Co, Si, Fe, MP	Zn
1	0	0	0
2	5,0	2,5	0,25
3	10,0	5,0	0,5
4	20,0	10,0	1,0
5	30,0	15,0	1,5
6	40,0	20,0	2,0
7	50,0	25,0	2,5

8.3.2 the Seven batches at 2.00 g, weighed with accuracy to 0.01 grams of Nickel metal (4.1) is placed in glasses with a capacity of 400 cmand dissolved as specified in 8.1.2.

8.3.3 In seven volumetric flasks with a capacity of 200 cm, each of which previously placed a solution of Nickel (7.3.2), add from burette appropriate volumes of standard solution (4.4.3), are given in table 5. Dilute to the mark with water and mix.

8.3.4 Zero solution in the series, which is not added standard solution In the use solution of the blank experience (8.2).

Note — For convenience stock solution with the contents of Nickel nitrate 80 g/DMcan be prepared in the following way. Weighed 20 g of Nickel metal (4.1) is placed in a beaker with a capacity of 800 cm, add enough water to cover the sample and dissolve by adding small portions of 120 cmof nitric acid (4.2), followed by filtration through glass wool, washed with nitric acid (4.2), or through a cellulose filter into a measuring flask with one mark capacity of 250 cm. Aliquot portion (25,0 cm) of the obtained solution was evaporated and continue as specified in 8.1.2 and 8.3.3.

8.4 Calibration and determination

8.4.1 Spectrometric measurements

8.4.1.1 the measurements using the spectral lines listed in table 6.


Table 6 — Spectral lines. Methodology In

Item	With	Si	Fe	MP	Zn
Wavelength, nm	241,2	327,4	252,3	403,1	213,9

8.4.1.2 Continue the technique as described in 7.4.1.3 and 7.4.1.4.

8.4.1.3 continue to make 7.4.1.5−7.4.1.10 using a series of calibration solutions In (8.3) is a series of calibration solutions (7.3).

8.4.2 Construction of calibration graphs

The construction of the calibration graphs is carried out in accordance with 7.4.2.

9 processing of the results

9.1 Methodology And

9.1.1 Determine the concentration of analyte in the sample solution from the respective calibration graphs (7.4.2) in the readings of the spectrometer for each of the three measurements.

9.1.2 the content of the analyte expressed in % (mass.) according to the formula

, (1)

where g is the concentration of the analyte, in mg/lfound in the sample solution;

V — volume of the analyzed solution, cm;

m — mass of sample, g.

Note — the Average value of the results of the three readings calculated by 9.1.2 take a single result. Upon receiving the three results is possible to judge the precision of atomic absorption measurements.

9.2 Methodology In

9.2.1 Determine the concentration of analyte in the sample solution according to the relevant calibration curve (8.4.2) and readings of the spectrometer for each of the three measurements.

9.2.2 For the operation in 8.1.1, the content of the analyte expressed in % (mass.) according to the formula

, (2)

where 2.5 is the correction factor that takes into account the dilution.

9.2.3 During the processing of the results obtained in 8.1.2, use the formula (1).

9.3 Precision

In this standard, the results obtained by the interlaboratory test program involving 18 laboratories from nine countries. Were analyzed 12 samples covering the area of application of the method. Of these, nine samples were prepared using melting method and subsequent granulation, one — by chemical vapor deposition and two samples consisted of industrial products.

A statistical report of interlaboratory tests is presented in Appendix V. it Should be noted that the data on reproducibility include errors due to heterogeneity of samples for testing, and also due to participate in the experiment with different analysts, instruments and laboratories, so the data presented were obtained under conditions of greatest variability.

For optimal repeatability and reproducibility, atomic absorption spectrometer should match the operational characteristics specified in Annex A.

10 Disturbing effects and precautions

10.1 in the determination of silver is necessary to observe precautions to avoid contamination of the sample and calibration solutions of chloride ion.

10.2 Elements normally present in Nickel, do not have a hindering effect on the results of atomic absorption analysis.

10.3 the Full range of content of the determined elements is covered by two series of calibration solutions. One series of solutions were prepared in a background matrix of Nickel (25 g/DMNi) for analyte concentrations up to 0.01% (mass), for Zn and 0.005% (mass.) and the second series of solutions prepared in a matrix of Nickel (10 g/lNi) for concentrations of analytes in the range [(from 0.01 to 0.25)% (wt.)] for Zn [(0.005 to 0.025)% (wt.)].

10.4 the potential impact of background absorption is eliminated by the use of matrices that are similar in composition to the test sample prepared from high-purity Nickel.

10.5 Purity metallic Nickel can be checked by measuring specific and non-specific absorption of the solution matrix.

11 Special cases

11.1 High content of copper and cobalt

For samples of Nickel containing more than 0.25% (mass), but less than 2% (mass.) cobalt or copper are allowed other dilution of the test solution with nitric acid (4.3). The content of Nickel in the calibration and sample solutions should be the same.

11.2 the Heterogeneity of the sample

If the laboratory sample assumes some heterogeneity or contains relatively large particles of Nickel, for preparation of final analyzed solution it is advisable to take the increased weight. In this case, the recommended charge weight of 25 g samples after dissolution is transferred to the final volume 1000 cm. The amount of nitric acid should be increased in proportion to the increase of sample weight. You can use sample samples, even with a greater mass for the preparation of more concentrated analyte solutions of Nickel. However, the obtained concentrated solution should then be diluted to obtain the concentration of Nickel in a solution of 25 g/DMto meet their calibration solutions.

12 test Report

The test report should include the following information:

a) reference to this standard;

b) the results of the analysis;

c) the number of independent repeated definitions;

d) any unusual features noted during the analysis;

e) any operation not included in this standard or regarded as optional.

Annex a (mandatory). Verification of tool settings

Appendix A
(required)

Introduction

The operating characteristics of atomic absorption spectrometers manufactured by the same or different manufacturers, may vary in its instrumental parameters. It is therefore important to ensure that a particular device meets certain requirements for the performance characteristics of the device prior to its use as a means of measurement in the methods of the present international standard.

A. 1 the Initial setup of the device

A. 1.1 Set atomic absorption spectrometer for operation with air / acetylene flame, using odnoschelevye burner (usually about the size of 10 cm) for laminar flow of gas mixture through the burner head in accordance with the manufacturer’s instructions.

A. 1.2 as a radiation source using a single-element lamps with hollow cathode single-element electrodeless discharge lamp or other suitable lamp single element for each defined element. Working with the radiation source is carried out in accordance with the recommendations of the manufacturer of the device.

Note — to Use multi-element lamps are generally not recommended, despite the fact that some lamps with the cathode of binary alloys give a more stable radiation than single-element lamps.

A. 1.3 Include the burner and spray water to achieve thermal equilibrium. In the method of this standard as the atomizer is used the flame is starved of fuel.

A. 1.4 Spray the calibration solution and the average content of the analyzed element in the range used by a series of calibration solutions, achieving configuration of parameters the optimal values of absorption. Set the wavelength, slit width or bandwidth on the recommendations of the manufacturer for each designated item. If necessary, use the extension scale.

A. 1.5 wash the spray system of the burner of nitric acid diluted by 1·19 (4.3), bring the readings to zero and continue the test tool settings as specified in A. 2.2-A. 2.4.

Note — try to avoid spraying solutions with high concentration of salts over a long period of time without washing. Otherwise possible clogging of the burner.

A. 2 Verification of tool settings

A. 2.1 Solutions to test tool options

A calibration curve using seven calibration solutions, including the zero solution. To check the instrumental characteristics choose two pairs of calibration solutions, covering the bottom and the upper part of calibration curve so that the interval between two calibration solutions with the highest concentration equal to the interval between the comparison solution and the calibration solution with the lowest concentration, that is, use solutions 1, 3, 6 and 7, are shown in table 2, or 5.

A. 2.2 meter Reading device

A. 2.2.1 Spray two of the calibration solution with the highest concentration of the analyzed element, record the readings and calculate the difference between the obtained values.

A. 2.2.2 Divide the difference in readings of two calibration mixtures for 20. The readability of the readings for the two calibration solutions are acceptable if the result is not less than the smallest interval that can be read or estimated with readings of the instrument.

A. 2.3 the linearity of the analytical signal device

A. 2.3.1 subsequently sprayed zero and calibration solution with low concentration of the element (A. 2.1). Record the readings and calculate the difference.

A. 2.3.2 Divide the difference in readings of two of the calibration solutions with a high concentration of the element, obtained as in A. 2.2.1, the difference between the readings for the zero solution and the calibration solution with low concentration.

A. 2.3.3 the linearity of the analytical signal is acceptable when the obtained ratio is equal to 0.70 or more.

A. 2.3.4 If the ratio is less than 0.70, you should continue to configure the instrument to get acceptable results. Otherwise, the scope of the methodology will be reduced by reducing the concentration range in the upper part of calibration curve.

A. 2.4 Short term stability

A. 2.4.1 Spray of nitric acid (4.3) and set the readings to zero.

A. 2.4.2 Spray the most concentrated calibration solution and record the reading.

A. 2.4.3 Spray nitric acid (4.3).

Note — the instrument Reading should return to zero.

A. 2.4.4 Repeat the measurement of the calibration solution with the highest concentration six times, washing out the system with nitric acid (4.3) between sprays of the calibration solution, while not changing any other parameters of the device.

A. 2.4.5 Spread of readings VA with the measurements of absorbance of the most concentrated calibration solution, expressed in percent, is calculated by the formula

, (A. 1)

where Ais the mean value of the readings for the calibration solution with the highest concentration, calculated from the six readings;

A — the highest value of the absorption of the six readings;

A — the lowest value of absorption of the six readings.

Note — the estimate of the standard deviation.

A. 2.4.6 the device meets the requirements for minimum stability when the value VAis less than 1.5%.

Note — This test can be further applied to other points on the calibration chart. It can also be used to assess minimum stability value of zero readings.

Annex b (informative). A statistical report of interlaboratory tests

The App
(reference)

Introduction

In this standard included the results obtained by the program of interlaboratory tests conducted in 18 laboratories in nine countries. Twelve samples of Nickel metal were analyzed in the whole area of application of the methodology of this standard. Of these, 10 were specially prepared as materials for research, containing a complete set of contents of impurities, regulated by the standard, as it is not produced industrially. The test program was designed to determine intra — and inter-laboratory reproducibility on the methods adopted in ISO 5725.

B. 1 Normative references

ISO 3534 Statistics. Dictionary and symbols

ISO 5725 Accuracy (trueness and precision) of methods and measurement results.

B. 2 Definitions

In this application, the definitions in ISO 3534 are the following changes. The term «repeatability» should be replaced by «intralaboratory precision» due to the fact that the trial was not conducted in conditions of repeatability. Changed specialists and/or devices within each facility. The concept of «intralaboratory precision» takes into account the uncertainty in testing in terms of repeatability and of the effect on the test results of the factors arising due to the replacement of the operator or the instrument, change the time of testing, reagents, etc.

B. 3 Plan test program

V. 3.1 the test Program was designed to take into account when conducting the tests in one laboratory variances caused by the change of operator and/or atomic absorption spectrometer, while the test solution remained the same. Were analyzed by two sample from each sample by the same analyst on two different devices or two analysts on the same instrument.

V. 3.2 Samples for testing were chosen in such a way that it is possible to determine the lower limit of the concentration field determined by this method.

B. 4 Samples for testing

V. 4.1 Nine test specimens were specially prepared by melting high-purity Nickel with the addition of trace elements and subsequent granulation of the melt when spraying it in the water. The conditions were selected to obtain particles of a material such thin shavings resulting from drilling or milling metal.

V. 4.2 Fractions with different particle sizes in each of the nine samples were tested for homogeneity. Unfortunately, six of them (series R) copper was not evenly distributed. The fraction obtained by sieving the samples on the sieves of the Tyler in the size range of particles minus 28 plus 65 (plus or minus 0.6 mm 0.21 mm) were selected as homogeneous from each sample for subsequent testing. The fraction obtained by sieving of the material on the sieves of the Tyler, in the range of minus 14 plus 48 (1.2 mm plus minus 0.3 mm) was taken from the other three specially prepared samples (series J), covering the region in the upper part of the concentration range.

V. 4.3 One sample was prepared by the method of chemical deposition to determine the highest levels of cobalt and copper.

V. 4.4 the Remaining two test specimen was a industrial Nickel powder and milling shavings obtained from cast billet of a Nickel. Industrial high-purity Nickel powder was provided by each laboratory to prepare standard solutions.

B. 5 Statistical methods

V. 5.1 Computer program

For statistical data analysis used a computer program consistent with the requirements of ISO 5725. The program allows you to calculate the average value of the result, intra — and inter-laboratory standard deviation and corresponding limits of reproducibility. Various statistical tests were performed to exclude anomalous results of the analysis (outliers), which were excluded from the results for calculation of metrological characteristics.

V. 5.2 Statistical tests for the exclusion of emissions

For processing data obtained independently with a confidence level of 95%, was used the criteria of Cochran and Dixon in accordance with ISO 5725. The principle of the Cochran criterion is that the set of results constitutes a release, if the ratio of the sample variance the results of one analysis or the within-dispersion relative to the amount of other variances exceeds the table value of the criterion Cochran. The Dixon criterion to determine whether the average value of the results of the analyst or of the laboratory is too far from the average values of the results of other laboratories.

V. 5.3 calculation of the variances and the limits of reproducibility

Pair of results for each of the two analysts (or received on two devices) from each laboratory completing the testing program were processed in accordance with ISO 5725 and the resulting values of the intra-laboratory and inter-laboratory variance. Were calculated the corresponding limits of intra — and interlaboratory reproducibility. Thus, we have obtained the following information:

s — inter-laboratory variance;

s — inter-laboratory variance;

R — the limit intralaboratory reproducibility (taking into account the change analyst or device);

;

R — the limit of interlaboratory reproducibility;

.

V. 6 Results of statistical analysis

V. 6.1 the Results of statistical processing for each item covering the scope of this international standard are given in table A. 1 for methods A and b table A. 2 for methodology V.

V. 6.2 When evaluating these results it should be borne in mind that the samples for testing were prepared in the laboratory and may not be as homogeneous as prepared industrially. Furthermore, the method of calibration has been modified as the result of the test program so that for each measurement series was used separate calibration curve. It was assumed that this would improve the correspondence between the individual results.

V. 6.3 the Results obtained for elements that are not included in the scope of the standard are given for information. Also some laboratories have not fulfilled the full test program on all samples that had restricted the amount of data that could be used in the statistical processing of the results.


Table A. 1 — Results of statistical analysis. Methods And

Sample	The number of labora- torii	The number of accepted results, %	Found, g/t				R
Silver (Ad)
P45	10	100	4,3	0,12	0,42	0,3	1,2
P44	15	80	7,7	0,17	0,18	0,5	0,7
P46	16	94	9,5	0,41	0,31	1,16	1,5
Р41	12	83	19,1	0,30	0,53	0,8	1,7
J63	4	100	23,2	0,37	0,69	1,0	2,2
P43	12	92	28,3	0,59	0,49	1,7	2,2
J61	16	75	97,0	0,89	4,94	2,5	14,2
Bismuth (Bi)
P45	9	89	8,6	1,15	0,81	3,2	4,0
P46	10	100	9,9	1,20	2,49	3,4	7,8
P44	10	90	13,3	0,95	2,52	2,7	7,6
Р41	10	80	17,1	0,98	1,35	2,8	4,7
P43	10	90	24,5	Of 1.09	Of 1.34	3,1	4,9
J61	11	91	103,7	1.55 V	1,29	4,4	5,7
Cadmium (Cd)
P46	11	100	1,9	0,10	0,27	0,3	0,8
J63	4	75	2,5	0,06	0,30	0,2	0,9
J61	15	93	13,5	0,26	0,85	0,7	2,5
S65	Twelve	100	22,5	0,23	0,87	0,7	2,5
Cobalt (Co)
P46	15	87	3,2	0,16	1.Th*	0,5	3,1
P45	11	82	5,5	0,62	0,39	1,8	2,1
P43	12	83	10,5	0,26	0,52	0,7	1,6
P44	15	87	15,5	0,26	1,37	0,7	4,0
Р41	12	83	18,5	0,38	0,34	1,1	1,4
J62	16	81	50,8	0,80	0,71	2,3	3,0
J61	13	100	100,2	Of 1.34	1,64	3,8	6,0
Copper (C)
S65	12	100	7,9	0,41	0,65	1,2	2,2
J62	16	100	51,7	0,32	0,82	0,9	2,5
J61	15	87	100,6	0,32	1,40	0,9	4,1
Iron (Fe)
P46	15	80	24,1	0,70	Of 1.94	2,0	5,9
P45	11	72	29,8	1,16	1,78	3,3	6,0
P44	14	78	31,1	0,45	2,01	1,3	5,8
Р41	12	83	43,7	0,64	3,57	1,8	10,3
S65	11	82	47,4	0,91	Of 1.82	2,6	5,8
Manganese (MP)
P44	13	85	3,3	0,14	0,39	0,4	1,2
Р41	11	82	5,4	0,12	0,69	0,3	2,0
P46	16	94	7,0	0,16	0,69	0,5	2,0
P45	11	100	10,7	0,30	0,63	0,8	2,0
P43	11	91	20,0	0,18	0,47	0,5	1,4
J62	16	100	53,6	0,45	1,21	1,3	3.7 V
J61	12	92	102,8	0,97	1,57	2,7	5,2
Lead (Pb)
P45	10	100	3,9	0,64	0,68	1,8	2,7
Н79	6	83	7,8	0,12	0,58	0,3	1,7
P46	12	92	9,0	Of 1.07	0,67	3,0	3,6
Р41	11	100	20,2	1,13	1,25	3,2	4,8
Lead (Pb)
P44	12	92	25,2	0,84	0,35	2,4	2,6
J62	14	93	35,0	0,38	1,38	1,1	4,1
J63	4	100	36,5	0,61	0,00	1,7	1,7
J61	14	79	77,7	0,69	Of 1.47	2,0	4,6
Zinc (Zn)
Н79	6	100	2,9	0,14	0,52	0,4	1,5
P44	10	80	4,1	0,15	0,69	0,4	2,0
Р41	11	91	5,0	0,25	0,52	0,7	1,6
P46	13	100	6,2	0,27	0,24	0,8	1,0
S65	12	83	The 10.1	0,33	0,52	0,9	1,7
P43	12	100	11,7	0,33	0,93	0,9	2,4
P45	10	100	12,8	0,81	1,16	2,3	4,0
J62	13	100	26,9	0,51	0,67	1,4	2,4
The lower boundary of the range of contents is included for information only. The results of the determination of si in the series for P is not given, since these samples are not uniform in copper. s — inter-laboratory standard deviation. s — inter-laboratory standard deviation. R — intralaboratory reproducibility. R — interlaboratory reproducibility.

________________
* The text of the document matches the original. — Note the manufacturer’s database.


Table A. 2 — Results of statistical analysis. Methodology In

Sample	The number of labora- torii	The number of accepted results, %	Found, g/t				R
Cobalt (Co)
J61	11	100	0,010	0,0004	0,0005	0,0012	0,0017
Н79	14	86	0,106	0,0010	0,0025	0,0027	0,0076
S65	6	83	0,076	0,0017	0,0013	0,0047	0,0060
C1A	12	100	1,64	0,026	0,031	0,0074	0,11
Copper (C)
J61	12	92	0,010	0,0002	0,0005	About 0.0006	0,0014
Н79	14	86	0,113	0,0003	0,0031	0,0008	0,0089
C1A	12	100	0,467	0,0057	0,0190	0,016	0,056
Iron (Fe)
J61	14	86	0,012	0,0004	0,0012	0,0013	0,0036
Н79	15	73	0,137	0,0008	0,0035	0,0024	0,010
Manganese (MP)
J61	12	83	0,010	0,0002	0,0005	0,0005	0,0015
Н79	12	67	0,164	About 0.0006	0,0046	0.0016 inch	0,013
Zinc (Zn)
J62	11	82	0,0026	0,0001	0,0001	0,0002	0,0004
J61	15	87	0,0068	0,0001	0,0003	0,0004	0,0009
The upper limit of the range is included for information only. s — inter-laboratory standard deviation. s — inter-laboratory standard deviation. R — intralaboratory reproducibility. R — interlaboratory reproducibility.

App YES (reference). Information about the compliance of the referenced international standards reference the national standards of the Russian Federation and acting in this capacity interstate standards

App YES
(reference)

Table YES.1

Marking the reference international standard	The degree of compliance	Designation and name of the relevant national, international standard
ISO 385/1:1984	MOD	GOST 29251−91 (ISO 385−1-84) «oils. Burette. Part 1. General requirements"
ISO 648:1977	MOD	GOST 29169−91 (ISO 648−77) «oils. Pipette with one mark"
ISO 1042:1998	-	*
ISO 5725−1:1994	IDT	GOST R ISO 5725−1-2002 «Accuracy (trueness and precision) of methods and measurement results. Part 1. General provisions and definitions"
ISO 5725−2:1994	IDT	GOST R ISO 5725−2-2002 «Accuracy (trueness and precision) of methods and measurement results. Part 2. The basic method for the determination of repeatability and reproducibility of a standard measurement method"
ISO 5725−3:1994	IDT	GOST R ISO 5725−3-2002 «Accuracy (trueness and precision) of methods and measurement results. Part 3. Intermediate indicators the precision of a standard measurement method"
* The corresponding national standard is missing. Prior to its adoption, it is recommended to use the translation into Russian language of this international standard. The translation of this international standard is the Federal information Fund of technical regulations and standards. Note — In this table the following symbols have been used the degree of conformity of standards: — IDT — identical standards; — MOD — modified standard.

UDC 669.14:620.2:006.354	OKS 77.120.40	B39	AXTU 0709
Key words: Nickel; content of silver, bismuth, cadmium, cobalt, copper, iron, manganese, lead and zinc; spectrometric method; atomic absorption