GOST 6012-98

• gost-6012-98.pdf (1.38 MiB)
  ГОСТ 6012-98

GOST 6012−98 Nickel. Methods of chemical-atomic-emission spectral analysis (with Change No. 1)

GOST 6012−98

Group B59

INTERSTATE STANDARD

NICKEL

Methods of chemical-atomic-emission spectral analysis

Nickel. Methods of chemical-atomic-emission spectral analysis

ISS 77.040
AXTU 1732

Date of implementation 2000−01−01

Preface

1 DEVELOPED by the Technical Committee TC 370 «Nickel. Cobalt"

INTRODUCED by Gosstandart of Russia

2 ADOPTED by the Interstate Council for standardization, Metrology and certification (Protocol No. 14 dated November 12, 1998)

The adoption voted:

3 Resolution of the State Committee of the Russian Federation for standardization and Metrology dated March 1, 1999 N 52 inter-state standard GOST 6012−97 introduced directly as state standard of the Russian Federation from January 1, 2000

4 REPLACE GOST 6012−78

5 EDITION (November 2001) as Amended (ICS 1−2000, 9−2000)


The Change N 1, approved and put into effect by the Protocol of MGS from 01.11.2001 N 20

Change No. 1 made by the manufacturer of the database in the text IUS N 8, 2002

1 Scope

This standard specifies the chemical-atomic-emission spectral analysis techniques with DC arc and inductively coupled plasma as a source of excitation spectrum for determination of mass fractions of elements in Nickel GOST 849, Nickel powder according to GOST 9722 and Nickel and Nickel alloys according to GOST 492 and GOST 19241.

2 Normative references

The present standard features references to the following standards:

GOST 8.315−97 GSI. Standard samples of composition and properties of substances and materials. The main provisions of the

GOST 12.0.004−90 SSBT. Organization of training safety. General provisions

GOST 12.1.004−91 SSBT. Fire safety. General requirements

GOST 12.1.005−88 SSBT. General hygiene requirements for working zone air

GOST 12.1.007−76 SSBT. Harmful substances. Classification and General safety requirements

GOST 12.1.016−79 SSBT. The air of the working area. Requirements for measurement techniques of concentrations of harmful substances

GOST 12.1.019−79 SSBT. Electrical safety. General requirements and nomenclature of types of protection

GOST 12.1.030−81 OCCUPATIONAL SAFETY STANDARDS. Electrical safety. Protective grounding, neutral earthing

GOST 12.2.007.0−75 SSBT. Products electrical. General safety requirements

GOST 12.3.002−75 SSBT. The process of production. General safety requirements

GOST 12.3.019−80 OCCUPATIONAL SAFETY STANDARDS. Test and measurement electrical. General safety requirements

GOST 12.4.009−83 SSBT. Fire fighting equipment for protection of objects. Principal. The accommodation and service

GOST 12.4.021−75 SSBT. System ventilation. General requirements

GOST 61−75 acetic Acid. Specifications

GOST 83−79 Sodium carbonate. Specifications

GOST 123−98 Cobalt. Specifications

GOST 195−77 Sodium sanitarily. Specifications

GOST 244−76 Sodium thiosulfate crystal. Specifications

GOST 492−73 Nickel, alloys Nickel and copper-Nickel, processed by pressure

GOST 804−93 primary Magnesium ingots. Specifications

GOST 849−97 Nickel primary. Specifications

GOST 859−2001 Copper. Brand

GOST 860−75 Tin. Specifications

GOST 1089−82 Antimony. Specifications

GOST 1467−93 Cadmium. Specifications

GOST 2789−73 surface Roughness. Parameters and characteristics

GOST 3118−77 hydrochloric Acid. Specifications

GOST 3640−94 Zinc. Specifications

GOST 3778−98 Lead. Specifications

GOST 4160−74 Potassium bromide. Specifications

GOST 4198−75 Potassium phosphate. Specifications

GOST 4204−77 sulfuric Acid. Specifications

GOST 4212−76 Reagents. Preparation of solutions for colorimetric and nephelometric analysis

GOST 4461−77 nitric Acid. Specifications

GOST 4530−76 Calcium carbonate. Specifications

GOST 5494−95 aluminum Dust. Specifications

GOST 5817−77 tartaric Acid. Specifications

GOST 6008−90 metallic Manganese and nitrated manganese. Specifications

GOST 6709−72 distilled Water. Specifications

GOST 6836−80 Silver and silver alloys. Brand

GOST 8655−75 red Phosphorus technical. Specifications

GOST 9147−80 Glassware and equipment lab porcelain. Specifications

GOST 9428−73 Silicon (IV) oxide. Specifications

GOST 9722−97 Nickel Powder. Specifications

GOST 9849−86 iron Powder. Specifications

GOST 10157−79 Argon gaseous and liquid. Specifications

GOST 10298−79 Selenium technical. Specifications

GOST 10484−78 hydrofluoric Acid. Specifications

GOST 10928−90 Bismuth. Specifications

GOST 11069−74 Aluminium primary. Brand

GOST 11125−84 nitric Acid of high purity. Specifications

GOST 14261−77 hydrochloric Acid of high purity. Specifications

GOST 17299−78 ethyl Alcohol technical. Specifications

GOST 17614−80 Tellurium technical. Specifications

GOST 18300−87 ethyl rectified technical. Specifications

GOST 18337−95 Thallium. Specifications

GOST 19241−80 Nickel and alloyed Nickel alloys treated under pressure. Brand

GOST 19627−74 Hydroquinone (paradoxians). Specifications

GOST 19908−90 Crucibles, bowls, beakers, flasks, funnels, test tubes and caps made of transparent quartz glass. General specifications

GOST 22860−93 Cadmium high purity. Specifications

GOST 22861−93 Lead of high purity. Specifications

GOST 23148−78 Powder metal. Methods of sampling and sample preparation

GOST 24104−2001 laboratory Scales. General technical requirements

GOST 24231−80 non-ferrous metals and alloys. General requirements to selection and preparation of samples for chemical analysis

GOST 25086−87 non-ferrous metals and alloys. General requirements for methods of analysis

GOST 25336−82 Glassware and equipment laboratory glass. The types, basic parameters and dimensions

GOST 25664−83 Metol (4-methylaminophenol). Specifications

ST SEV 543−77 Number. Record rules and rounding

(Changed edition, Rev. N 1).

3 General requirements

3.1 General requirements for methods of analysis should correspond to GOST 25086.

3.2 Selection and preparation of samples of Nickel and Nickel alloys is carried out according to GOST and GOST 849 24231, Nickel powder according to GOST 23148 and GOST 9722.

3.3 To establish the calibration according to recommended to use at least four standard samples (CO) according to GOST 8.315 composition of Nickel or at least four calibration solutions.

(Changed edition, Rev. N 1).

3.4 Analysis carried out on two parallel definitions.

3.5 the result of the analysis represent a numeric value, which must end with a digit of the same category as the numeric value of the error guaranteed by the application of methods of analysis (hereinafter, error analysis methods) defined in this standard.

In the preparation of quality document production on the basis of the results of the analysis allowed a test result of chemical composition to represent a numeric value with the same number of significant figures as in the tables of chemical composition GOST 849, GOST 9722, GOST 492 and GOST 19241.

3.6 Rules for rounding of numbers shall conform to the requirements of ST CMEA 543.

4 safety Requirements

4.1. All work should be carried out on appliances and electrical installations, the relevant regulations for electrical installations, approved by Gosenergonadzor, and the requirements of GOST 12.2.007.0.

4.2. In the operation of instrumentation and electrical installations need to comply with the requirements of GOST 12.3.019, rules of technical operation of electrical installations and safety rules at operation of electrical installations, approved by Gosenergonadzor.

4.3. All instruments and appliances must be equipped with devices for grounding in accordance with the requirements of GOST 12.2.007.0 and GOST 12.1.030. Grounding must conform to the rules of arrangement of electrical installations, approved by Gosenergonadzor.

4.4. When the works are used and are formed of substances which have a deleterious effect on the human body: Nickel powder, aerosols of metal oxides, carbonaceous dust, oxides of nitrogen and carbon, vapors of hydrochloric and nitric acids and ethyl alcohol. Storage and use of hazardous substances and materials shall comply with the requirements, regulated in the normative documents for these substances and materials.

4.5. In analysis of Nickel produced in buildings equipped with General dilution ventilation system according to GOST 12.4.021.

4.6. To prevent contact with the air, oxides of carbon, nitrogen and aerosols of metal oxides in quantities exceeding the maximum allowable GOST 12.1.005, as well as protection from UV radiation of each excitation source must be placed inside devices equipped with local exhaust ventilation and protective screen according to GOST 12.1.019.

4.7. Grinding machine carbon electrodes should have a suction device to prevent the ingress of coal dust in the air of working zone in quantities exceeding the maximum allowable.

4.8. Control of content of harmful substances in the air of working zone should be carried out in accordance with the requirements of GOST 12.1.007, GOST 12.1.005 and GOST 12.1.016.

4.9. The recycling, disposal and destruction of hazardous wastes from the production of Nickel analyses should be carried out in accordance with normative document [1].

4.10. Learning organisation, working to the requirements of labour safety — according to GOST 12.0.004.

4.11. Requirements to professional selection and testing of knowledge of employees — according to GOST 12.3.002.

4.12. The premises of the laboratory must comply with the fire safety requirements of GOST 12.1.004 and have a extinguishing media in accordance with GOST 12.4.009.

4.13. Laboratory personnel must be provided with premises at the IIIA group of the production processes according to the normative document [2].

4.14. Laboratory personnel should be provided with overalls, special footwear and other means of individual protection according to the normative document [3].

5 Chemical-atomic-emission spectral method with the DC arc as excitation source spectrum

5.1 measurement Method

The ranges of detectable concentrations of the elements are, %:

The method is based on the excitation spectrum globalnoi arc DC with the subsequent registration of radiation of spectral lines photographic, or photoelectric means. The analysis uses the dependence of the intensities of spectral lines of the elements from their mass fraction in the sample. The sample is pre-transferred to the metal oxides.

Items and options that apply only to photographic or photoelectric method of registration of the spectrum, marked respectively, «FG» and «FE».

(Changed edition, Rev. N 1).

5.2 measurement Means, auxiliary devices, materials, reagents, solutions

A multichannel photoelectric spectrometer type IFS-8 (FE) or a type spectrograph STE-1 (FG) or any other spectrometer or spectrograph for ultraviolet region of the spectrum with an inverse linear dispersion of 0.6 nm/mm.

Power source DC arc type, UGE-4, or any other, providing a voltage up to 400 V and currents up to 20 A.

Microphotometer geregistreerde of any type (FG).

Gas analyzers of the 2nd class of accuracy of any type with an accuracy of weighing according to GOST 24104.

Libra technical of any type, providing for weighing masses up to 500 g.

The composition of the Nickel produced in accordance with Appendix A or other method approved in the prescribed manner.

Muffle furnace of any type with thermostat providing temperatures up to 850 °C.

Press which provides sufficient force for tabletting the crushed metal oxides.

Mold alloy steel punch with a diameter of 4−8 mm. in the manufacture of the plunger and the inner surface of the matrix, hardened, cemented and sanded. The roughness parameter of the working surfaces in the manufacture of molds should be no more than 0,160 µm according to GOST 2789.

The machine with a set of shaped cutters for sharpening carbon electrodes.

Rods of high purity graphite grades, C-2, C-3 or C-3M with a diameter of 6 mm as an upper electrode and a diameter of 6−15 mm as electrodes-coasters.

Wool.

Buxy according to GOST 25336 or porcelain boat type L3 by GOST 9147.

Caps glass or plastic to protect from contamination prepared for analysis of tablets samples WITH and sharpened electrodes.

A pair of tweezers.

The Jasper or agate mortar with a pestle.

Photographic plates spectrographic contrast (FG).

Varicellae bowls or crucibles made of quartz glass according to GOST 19908 or bowls, crucibles and cups of glassy carbon for dissolution of samples, evaporation of the solution and calcination of a mixture of salts. Allowed for dissolution and evaporation apply flask and glasses from chemically and thermally resistant glass according to GOST 25336. Allowed for the analysis of samples of Nickel marks N3 and N4, electrolytic Nickel powder and Nickel alloys to use bowls and crucibles made of porcelain to GOST 9147.

Distilled water according to GOST 6709, further purified by distillation or otherwise.

Nitric acid of high purity according to GOST 11125 brand or GRADE according to GOST 4461, or marks chda GOST 4461, further purified by distillation or otherwise, and diluted 1:1.

Hydrochloric acid according to GOST 3118, diluted 1:10.

The technical rectified ethyl alcohol according to GOST 18300 or technical ethyl alcohol according to GOST 17299, further purified by distillation or otherwise.

Sodium salitsilovaya, solution in ethyl alcohol with a mass concentration of 60 g/DM(FG).

The developer consisting of two solutions (FG).

5.3 Preparation for assay

Weighed samples weighing 5−10 g were placed in a bowl of quartz glass or another utensil to dissolve. To remove accidental contamination of samples with iron is recommended in the analysis of Nickel cathode marks N-0, N-1U N-1 sample pre-processing 30−50cmof hydrochloric acid, diluted 1:10, stirring for 1 min. Acid is drained by decantation and rinsed with sample 2−3 times with water in portions of 50 cmby decantation.

The sample poured in portions of 3−5 cmof nitric acid, diluted 1:1, until complete dissolution of the sample when heated. If you want to determine the mass fraction of selenium in dilute nitric acid is replaced by concentrated.

The solution was evaporated in a bowl of quartz glass or other utensils to remove the excess of nitric acid to the receipt of dry salts, to prevent any decomposition of the nitrate salts to oxides (the appearance of dark inclusions in the sample material). A bowl of dry salt is placed in a muffle furnace, heated to a temperature of (825±25)°C and maintained at this temperature for 15−20 min the resulting oxides is cooled, then comminuted to obtain a powder in a mortar or other method eliminating contamination of sample material.

From powder taken three hitch weight 0,200−1,000 g depending on the conditions of analysis and a mass fraction of detectable elements, and their tableted with a press and mold.

Mold clean residue from the sample with cotton wool soaked with ethyl alcohol. Consumption of ethanol is 10 cmon the sample.

WITH the composition of Nickel in the form of metal prepared for analysis in the same way as the sample. WITH the composition of Nickel in the form of oxides prepared for analysis, not by swiping them through a stage of dissolution in nitric acid.

(Changed edition, Rev. N 1).

5.4 analysis

Preparing the spectrometer to the measurements carried out in accordance with the manual for operation and maintenance of the spectrometer (FE).

Recommended analytical lines and ranges of detectable concentrations of elements are given in table 1.


Table 1 — Recommended analytical lines and ranges of detectable concentrations of the elements

Allowed to use other analytical lines, if they provide a determination of mass fraction of elements in the specified range with an error not exceed this standard.

Tablet samples or placed on the electrode stand. The upper electrode should be sharpened to a truncated cone.

The electrode pre-calcined in the arc of DC for 10−20 seconds at a current of 6−10 A, including as the anode of the arc. The electrodes ultraclean nitric acid is allowed to be heated up.

The shape and dimensions of the electrodes and their location during the analytical exposure is shown in figure 1.

Figure 1. The shape and dimensions of the electrodes and their location during the analytical exposition

and — before exposure; b — at the anode the polarity of the sample; in — at the cathode the polarity of the sample

Figure 1

The spectrogram is removed through a three-stage attenuator. When working in a narrow range of detectable concentrations of the elements of shooting can be performed without the attenuator (FG).

The electrode stand is placed on it pill sample or include as the anode of the arc. The spectrum starts only after the transition of the anode spot of the arc on the melt sample. Transition speed up shutdown current after a few seconds of arc and re-enabling until the melt has not yet had time to cool down. Originally established arc gap adjusted periodically throughout the exposure on a zoomed image of the arc on the screen of the objective lens of the lighting system or with a special short throw projection lens. The spectrum carried out under the following conditions: the width of the entrance slit of the spectral device of 0.010−0.015 mm, the illumination slits being a condenser, the aperture height in the middle of the condenser lens is 5 mm, current intensity And 5−10, the exposure is from 40 to 60, weight pills 0,200−1,000 g On measurements obtained at the first step determine the volatile elements bismuth, cadmium, arsenic, tin, lead, selenium, silver, antimony, thallium, tellurium, zinc and phosphorus.

Formed during the first stage, the Wren is placed on sweetalicious the stand and include it as the cathode of the arc. The spectrum begins after the transition of the cathode spot of the arc from the cradle to the molten portion of the bead and hold it under the following conditions: the width of the entrance slit of 0.010−0.015 mm, the illumination slits being a condenser, the height of the diaphragm middle lens of the condenser is 3 mm, current And 3−6, the exposure of 20−40 C. the measurements obtained in the second stage, determine the semi-elements — aluminum, iron, calcium, cobalt, silicon, magnesium, manganese, copper and tantalum.

Allowed to carry out the second stage without removing the bead from the base at the end of the first stage, automatically changing the polarity of the electrodes and the current arc (FE).

When determining the mass fraction of selenium and the need to reduce detection limits of volatile elements analytical lines with wavelengths less than 230 nm, the additional third stage. Photographic plates are treated in a solution of sodium salicylanilide for 60 s and dried. Tablet samples or include as the anode of the arc. Conditions of registration of the spectrum: the width of the slit of a spectrograph is 0.018−0.020 mm, the illumination slits being a condenser, the aperture height in the middle of the condenser lens is 5 mm, the current strength 18−20 And 45−60 with exposure, electrode stand with a diameter of 15 mm with a recess on the end of the 1.5 mm, weight pills 0,700−1,000 g (FG).

Photographic plates showing within 4−6 min at a temperature of 18−20°C, fixed, washed and dried (CF).

Optimization of conditions for the analysis of a specific type or brand of products is carried out by selection of the values of variables parameters (mass of tablets, arc current, exposure, width of the entrance slit of the spectral device), selection of optimum analytical lines, of the type of photographic plates, the shape of the upper electrode, etc.

(Changed edition, Rev. N 1).

5.5 processing of the results

In the spectra of samples WITH measured intensity of analytical lines of the elements and lines of comparison of Nickel. Permitted instead of the intensity of the comparison lines to use the undecomposed light intensity (PE) and the minimum value of the optical density of the background measured near the analytical line (FG).

While photographic registration of the spectrum in the spectrograms of the samples and measure the blackening of analytical lines of the determined elements and lines comparison, choosing the level of attenuation with optimum values of pucherani. On the measured values calculates the difference pucherani and their arithmetic average for each and every parallel assay. Before averaging, it is recommended to check the suitability of the measurement results in accordance with Annex B.

According to calculated values for co and the corresponding values of the mass fraction of detectable elements to build calibration graphs in the coordinate .

Values for samples find the mass fraction of detectable elements on the respective calibration graphs.

By the photoelectric registration of spectrum according to the obtained results of measurements of the intensity of the analytical lines of the determined elements calculate an arithmetic average for each and every parallel assay. Before averaging, it is recommended to check the suitability of the measurement results in accordance with Annex B.

According to calculated values for co and the corresponding values of the mass fraction of detectable elements to build calibration graphs in the coordinate or .

Values or samples to find the mass fraction of detectable elements on the respective calibration graphs.

When working on the spectrometer with a computer the values of the mass fraction of elements WITH their corresponding arithmetic means of the measurements of the intensities of the analytical lines of the determined elements introduced in the computer that generates the equation of the calibration dependence. Allowed to enter the processing algorithm of the results of the analysis in the analytical program and read from the monitor or printing device values of the mass fraction of detectable elements.

For the results analysis be the arithmetic mean of results of parallel measurements, if the difference does not exceed the permissible differences given in 5.6.

When the divergence of the results of parallel measurements more acceptable analysis is repeated. If during the re-analysis of the differences between the results of parallel measurements exceeds the allowable, the sample is replaced with new, obtained upon repeated sampling.

The discrepancy between the results of the analysis of the same samples obtained in two laboratories and one reference laboratory, but under different conditions (different time, different performers) should not exceed the permissible discrepancy of the two results of the analysis .

If the result of the analysis differs from branded content to a value less than or equal to the value of the error of the method, it is recommended to conduct re-analysis. The final result of the analysis in this case should be the arithmetic mean of initial and repeat analysis results, if the difference between them does not exceed the permissible differences given in 5.6.

(Changed edition, Rev. N 1).

5.6 Control of accuracy of analysis

The control accuracy of the analysis carried out in accordance with GOST 25086 at least once a quarter. As standard for the control of accuracy using error analysis method , are shown in table 2.

Standards of operational control — the permissible discrepancy between two parallel definitions and allowable discrepancies between the two analysis results are given in table 2.


Table 2 — Standards for monitoring and error analysis method (under confidence probability =0,95)

Percentage

For intermediate values of the mass fraction of elements, calculate values , and is carried out by linear interpolation.

(Changed edition, Rev. N 1).

6 Chemical-atomic-emission spectral method with inductively coupled plasma as the excitation source spectrum

6.1 measurement Method

The ranges of detectable concentrations of the elements are, %:

The method is based on the excitation spectrum of inductively coupled plasma and subsequent radiation of spectral lines photoelectric method. The analysis uses the dependence of the intensities of spectral lines of the elements from their mass fraction in the sample. The sample is dissolved in a mixture of hydrochloric and nitric acids.

6.2 measurement Means, auxiliary devices, materials, reagents, solutions

The automated spectrometer (or monochromator polychromator) atomic emission with inductively coupled plasma as the excitation source spectrum with all accessories.

Gas analyzers of the 2nd class of accuracy of any type with an accuracy of weighing according to GOST 24104.

Argon according to GOST 10157.

Distilled water according to GOST 6709, further purified by distillation or otherwise.

Nitric acid of high purity according to GOST 11125 brand or GRADE according to GOST 4461, or marks chda GOST 4461, further purified by distillation or otherwise, and diluted 1:1 and 1:10.

Hydrochloric acid of high purity according to GOST 14261.

A mixture of acids: 800 cmof water was added 300 cmof hydrochloric acid and 100 cmof nitric acid.

Aluminium GOST 11069 or aluminum powder according to GOST 5494.

Cadmium GOST 1467 or GOST 22860.

Potassium phosphate according to GOST 4198, dried at a temperature of (105±2)°C for 1 h.

Cobalt GOST 123.

Magnesium primary GOST 804.

Manganese GOST 6008.

Copper according to the GOST 859.

Sodium acid 9-aqueous.

Sodium carbonate according to GOST 83, a solution with a mass concentration of 200 g/DM.

Iron powder brand MLB-1 according to GOST 9849 or carbonyl iron of special purity, or iron restored.

Nickel powder carbonyl group «U» or «0» according to GOST 9722 or Nickel stamps N-0 GOST 849, dened by mass fractions of elements.

Zinc GOST 3640.

6.3 Preparation for analysis

6.3.1 Preparation of solutions of known concentration

The solution of Nickel with a mass concentration of 200 g/DM:

The suspension of Nickel powder or Nickel with a mass of 100.00 g were placed in a glass with a capacity of 1000 cm, add 50 cmof water and in portions of 5−10 cmpour 400 cmof nitric acid. The solution was evaporated to a volume of 250−300 cm, cooled, transferred to a volumetric flask with a capacity of 500 cmand topped to the mark with water. When using the Nickel powder in the solution was filtered through a filter medium density, pre-washed with nitric acid, diluted 1:10.

Solution of iron and cobalt mass concentration of 1 g/DM:

The weight and iron weight 0,5000 g was dissolved with heating in 30 cmof a mixture of acids, boil for 5−10 minutes, cooled and transferred to volumetric flask with a capacity of 500 cm. A portion of the cobalt weight 0,5000 g was dissolved with heating in 25 cmof nitric acid, diluted 1:1, the solution was cooled, transferred to the same volumetric flask and topped to the mark with water.

Solution of manganese and copper with a mass concentration of 1 g/DMand of magnesium mass concentration of 0.1 g/DM:

Sample of manganese and copper for weight 0,5000 g of magnesium with a mass 0,1000 g separately dissolved by heating in 25 cmof nitric acid, diluted 1:1, boil for 5−10 minutes, cool, each solution was transferred to volumetric flasks with a capacity of 100 cmand then filled to the mark with water. In a volumetric flask with a capacity of 100 cmis taken at 20 cmobtained solutions of manganese and copper, and 10 cmof a solution of magnesium and topped to the mark with water.

Solution of aluminum with a mass concentration of 1 g/DM:

A portion of the aluminum or aluminum powder weighing 0,4000 g was dissolved with heating in 25 cmof hydrochloric acid diluted 1:1, transferred into a volumetric flask with a capacity of 100 cmand then filled to the mark with water. In a volumetric flask with a capacity of 100 cmselect the 25 cmof this solution and topped up to the mark with water.

The solution of cadmium and zinc mass concentrations of 0.02 g/land phosphorus mass concentration of 0.04 g/DM:

Sample of cadmium and zinc by mass 0,1000 g separately dissolved by heating in 25 cmof nitric acid, diluted 1:1, cooled, each solution was transferred to volumetric flasks with a capacity of 500 cmand topped to the mark with water. Weighed potassium phosphate mass 0,4393 g dissolved in water, the solution was transferred to volumetric flask with a capacity of 500 cmand topped to the mark with water. In a volumetric flask with a capacity of 100 cmtaken at 10 cmthe obtained solutions of cadmium and zinc, and 20 cmof a solution of phosphorus and topped to the mark with water.

A solution of silicon with a mass concentration of 0.5 g/DM:

A portion of silicate of sodium with a mass 2,5297 g dissolved in 50 cmof sodium carbonate solution, the solution was transferred to volumetric flask with a capacity of 500 cmand topped to the mark with water.

For the preparation of solutions with known concentrations of elements use oxides or salts of stable composition, as well as state standard samples of solutions of metals.

Solutions with known concentrations of elements stored in a plastic container. The conditions of storage and use of the solutions — in accordance with GOST 4212.

6.3.2 Preparation of the calibration solutions

For the preparation of the calibration solutions 1−11, the recommended composition of which is given in table 3 in volumetric flasks with a capacity of 100 cmselect the calculated volumes of solutions with known concentrations of elements and topped to the mark with water. If necessary, make amendments to the mass fraction of element in carbonyl Nickel powder or Nickel, is used for preparation of a solution of Nickel. The calibration solutions are stored in a container made of polyethylene and is used for no more than three months.


Table 3 — Composition of the calibration mixtures 1−11

Mass concentration of Nickel in the calibration solutions 1 to 5 is 50 g/DM, 6−11 calibration solution — 20 g/DM.

6.3.3 Preparation of solutions samples

A portion of the sample with a mass of 5,000 grams are placed in a beaker with a capacity of 250−400 cm, dissolved in 100 cmof the mixture of acids, adding the mixture in portions of 5−10 cm, the solution was evaporated to a volume of 25−30 cm, transferred into a volumetric flask with a capacity of 100 cmand then filled to the mark with water. The initial a sample solution is used for the determination of cadmium, zinc and phosphorus.

In a volumetric flask with a capacity of 100 cmselect 20 cmof the primary sample solution and topped up to the mark with water. The diluted sample solution used for determination of cobalt, iron, copper, manganese, silicon, aluminum and magnesium.

6.4 analysis

Preparing the spectrometer to the measurements carried out in accordance with the instruction manual and maintenance spectrometer. The parameters of the spectrometer and the flow rate of argon is set within the range for maximum sensitivity to determine the mass fractions of elements.

Recommended analytical lines and ranges of detectable concentrations are given in table 4.


Table 4 — Recommended analytical lines and ranges of detectable concentrations of the elements

Allowed to use other analytical lines, if they provide a determination of mass fraction of elements in the specified range with an error not exceed this standard.

When working at the monochromator position check of the analytical lines, using the calibration solution of 5 or 10.

The calibration dependence for cadmium, zinc and phosphorus is found using the calibration solutions 1 to 5, and cobalt, iron, manganese, copper, magnesium, aluminum and silicon — calibration solutions 6−11.

For each calibration solution perform at least five parallel measurements of the intensities of the analytical lines of the determined elements. By calculating the average of the values of the intensities and their corresponding mass concentrations of the elements determined the parameters of the calibration graphs, which are introduced into the computer memory at the stage of creating analytical programs.

Before the beginning of measurements and after every two hours of operation of the device adjust the calibration graphs for the two calibration solutions of 2 and 5 or 7 and 11.

Day of each of the sample solution and perform three parallel measurements and read from the screen or the tape printing device values of the mass concentrations of determined elements in the sample solution and their average arithmetic values.

6.5 processing of the results

Mass fraction of the element in the sample in % is calculated by the formula

, (1)

where is the mass concentration of element in sample solution, mg/DM;

 — the volume of the analyzed solution, cm;

 — weight of sample, g;

 — the dilution factor.

Allowed processing of the results of the analysis to enter in the analytical program and read from the monitor or printing device values of the mass fraction of detectable elements.

For the results analysis be the arithmetic mean of results of parallel measurements, if the difference does not exceed the permissible differences given in 6.6.

When the divergence of the results of parallel measurements more acceptable analysis is repeated.

If during the re-analysis of the differences between the results of parallel measurements exceeds the allowable, the sample is replaced with new, obtained upon repeated sampling.

If the result of the analysis differs from branded content to a value less than or equal to the value of the error of the method, it is recommended to conduct re-analysis. The final result of the analysis in this case should be the arithmetic mean of initial and repeat analysis results, if the difference between them does not exceed the permissible differences given in 5.6.

6.6 accuracy Control analysis

The control accuracy of the analysis carried out in accordance with GOST 25086 at least once a quarter. As standard for the control of accuracy using error analysis method given in table 5.

Standards of operational control — the permissible discrepancy between two parallel definitions and allowable discrepancies between the two analysis results are given in table 5.


Table 5 — Standards for monitoring and error analysis method (under confidence probability =0,95)

Percentage

For intermediate values of the mass fraction of elements, calculate values , and is carried out by linear interpolation.

Annex a (recommended). The method of preparation of standard samples

APPENDIX A
(recommended)

_____________

* Changed the wording, Rev. N 1.

Standard samples for the calibration represent the crushed Nickel oxide with additives introduced the identified elements. Part of developing a given mass fraction of elements in the analyzed products. Metrological characteristics WITH adjusted in accordance with the requirements of GOST 8.315.

A. 1 measurement Means, auxiliary devices, materials, reagents, solutions

Gas analyzers of the 2nd class of accuracy of any type with an accuracy of weighing according to GOST 24104.

Muffle furnace of any type with thermostat providing temperatures up to 850 °C.

Bowl varicellae quartz glass according to GOST 19908 or glassy carbon.

The Jasper or agate mortar with a pestle.

Distilled water according to GOST 6709, further purified by distillation or otherwise.

Nitric acid of high purity according to GOST 11125 brand or GRADE according to GOST 4461, or marks chda GOST 4461, further purified by distillation or otherwise, and diluted 1:1 and 1:2.

Sulfuric acid according to GOST 4204, diluted 1:2.

Tartaric acid according to GOST 5817.

The technical rectified ethyl alcohol according to GOST 18300 or technical ethyl alcohol according to GOST 17299, further purified by distillation or otherwise.

Bismuth GOST 10928.

Cadmium GOST 1467 or GOST 22860.

Calcium carbonate according to GOST 4530.

Cobalt GOST 123.

Silicon (IV) oxide according to GOST 9428, crushed and sifted through a sieve with cell size 0,074 mm, or tetraethyl ester of silicic acid solution in ethyl alcohol.

Magnesium primary GOST 804.

Manganese GOST 6008.

Copper cathode according to the GOST 859.

Arsenic according to the normative document [4].

Aluminum powder according to GOST 5494.

Iron powder brand MLB-1 according to GOST 9849 or carbonyl iron of special purity, or iron restored.

Nickel powder carbonyl group «U» or «0» according to GOST 9722 or Nickel stamps N-0 GOST 849 with established mass proportions of the identified elements.

Tin GOST 860 or powder tin.

Lead at 3778 or GOST GOST 22861.

Silver GOST 6836.

Antimony GOST 1089.

Thallium GOST 18337.

Tellurium GOST 17614.

Red phosphorus according to GOST 8655 or potassium phosphate according to GOST 4198, dried at a temperature of (105±2)°C for 1 h.

Zinc GOST 3640.

Selenium GOST 10298

Hydrofluoric acid according to GOST 10484

Tantalum according to the normative document [5].

For the preparation of solutions of the input elements use oxides or nitrate salt of stable composition, as well as state standard samples of solutions of metals.

A. 2 Production of material WITH

To prepare the solution the basics WITH a sample of Nickel powder or Nickel estimated mass is dissolved by heating in nitric acid, diluted 1:1.

Sample the calculated masses of iron, cobalt, copper, magnesium, manganese, aluminum powder, zinc, lead, bismuth, cadmium, silver, thallium, phosphorus and calcium carbonate is dissolved by heating in nitric acid, diluted 1:1. Antimony is dissolved in the presence of tartaric acid at a weight ratio of antimony and tartaric acid 1:5. Arsenic, selenium and tellurium is dissolved in hot nitric acid. Potassium phosphate is dissolved in water.

The solutions were transferred to volumetric flasks and topped up to the mark with nitric acid, diluted 1:2. The shelf life of solutions of known concentration according to GOST 4212.

Tin dissolves in sulphuric acid, the solution was transferred to volumetric flask and topped to the mark with sulfuric acid diluted 1:2.

Powder of tin dissolved in nitric acid, diluted 1:2, in an ice bath with stirring, the solution is used within 1 h.

Tantalum is dissolved in a mixture of nitric and hydrofluoric acids followed by repeated Stripping of the fluoride ion hot nitric acid.

The resulting solution was cooled, transferred to a volumetric flask and topped to the mark with a solution of tartaric acid with a mass concentration of 0.15 g/cm.

The estimated volumes of solutions with known content of elements enter into the solution of Nickel and mixed. If necessary, take into account the mass fraction of impurities in the metal used to prepare the solution of Nickel.

After that injected silicon in the form of an aqueous slurry of silicon oxide or solution tetrachloro ester of silicic acid in ethyl alcohol, the solution is used within 1 h.

The resulting solutions evaporated to dry salts and calcined in a muffle furnace at a temperature of (825±25)°C. the Calcined mixture of oxides is cooled, crushed to a powder in a mortar or other method that prevent pollution of material. The average material mixing and is used for determining the metrological characteristics.

The material is stored in tightly closed cans or buksh under conditions that exclude contamination and moisture.

Appendix A. (Revised edition, Edit. N 1).

APPENDIX B (recommended). The procedure for verifying the suitability of the results of the parallel measurements with the calculation result of the determination

APPENDIX B
(recommended)

Three values of the differences pochernenija (or intensities) of the analytical spectral lines find the mass fraction of the determined elements in the calibration schedule. Suitable are measurements for which the condition

, (B. 1)

where , and are the values on the mass fraction of the element corresponding to highest, lowest and average values of the differences pochernenija (or intensity);

 — relative value allowable discrepancies between and below for the designated items.

the subscript number index — number of dimensions.

If this condition is not met, it is allowed to exclude the result, the most remote of the average. The remaining two dimensions are considered suitable, if the condition

. (B. 2)

If this condition is not met, the measurement is repeated from the new tablets of the same sample.

For aluminium, bismuth, cadmium, calcium, silicon, magnesium, copper, arsenic, selenium, silver, antimony, thallium, tellurium and phosphorus, the value is equal to 0.50; for the remaining items of 0.33.

Appendix B. (Amended, Rev. N 1).

ANNEX b (informative). Bibliography

THE APP
(reference)

Appendix C (Revised edition, Edit. N 1).


________________________________________________________________________________________
UDC 669.24:543.42:006.354 ISS 77.040 B59 AXTU 1732

Key words: Nickel, spectral analysis, measuring instruments, reagent, solution, test, result