GOST 25278.10-82

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  ГОСТ 25278.10-82

GOST 25278.10−82 Alloys and alloys of rare metals. Methods for determination of zirconium (with Amendments No. 1, 2)

GOST 25278.10−82

Group B59

STATE STANDARD OF THE USSR

ALLOYS AND ALLOYS OF RARE METALS

Methods for determination of zirconium

Alloys and foundry alloys of rare metals. Methods for determination of zirconium

AXTU 1709

Valid from 01.07.83
to 01.07.93*
_______________________________
* Expiration removed
according to the Protocol of the Intergovernmental Council
for standardization, Metrology and certification
(IUS N 2, 1993). — Note the manufacturer’s database.

INFORMATION DATA

1. DEVELOPED AND INTRODUCED by the Ministry of nonferrous metallurgy of the USSR

PERFORMERS

Yu. A. Karpov, E. G. Nembrini, V. G., Miscreants, G. N. Andrianov, E. S. Danilin, M. A. Desyatkova L. I. Kirsanova, T. M. Malyutina, Y. F. Markov, V. M. Mikhailov, L. A. Nikitina, L. G. Obruchkova, N. Rasnitsyn, N. Suvorova, L. N. Filimonov

2. APPROVED AND put INTO EFFECT by Decision of the USSR State Committee for standards from 26.05.82 N 2120

3. The period of examination — 1993

The frequency of inspection — 5 years

4. INTRODUCED FOR THE FIRST TIME

5. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS

6. Validity extended until 01.01.93 by the Resolution of Gosstandart of the USSR from 29.10.87 N 4096

7. REPRINT (November 1988) with amendment No. 1, approved in October 1987 (ICS 1−88).

The Change No. 2 adopted by the Interstate Council for standardization, Metrology and certification (Protocol No. 12, 21.11.97). The state developed by Russia. By the resolution of Gosstandart of Russia dated 06.04.98 No. 107 enacted in the territory of the Russian Federation with 01.07.98

Change No. 2 made by the manufacturer of the database in the text IUS N 6, 1998


This standard establishes methods for determination of zirconium:

photometric:

from 0.2 to 5% for alloys (alloys) on the basis of niobium (components of aluminium not more than 20%, vanadium not more than 0.5%, tungsten not exceeding 25%, molybdenum not more than 25%, carbon not more than 0.2%);

from 0.5 to 5% for alloys (ligatures) based on vanadium (components: niobium, not more than 40%, of yttrium is not more than 30%);

spectral (from 0.3 to 3%) for alloys based on niobium and vanadium;

chelatometric:

from 1 to 5% for alloys (ligatures) based on vanadium, which does not contain niobium;

80 to 90% for binary alloys zirconium-aluminium;

from 5 to 30% for alloys based on niobium containing no aluminum;

from 1 to 30% for alloys based on niobium containing aluminum, and for alloys based on vanadium-containing niobium.

1. GENERAL REQUIREMENTS

1.1. General requirements for methods of analysis and security requirements — according to GOST 26473.0−85.

(Changed edition, Rev. N 1).

2. THE PHOTOMETRIC METHOD FOR THE DETERMINATION OF ZIRCONIUM IN ALLOYS BASED ON NIOBIUM

The method is based on formation of colored complex compounds of zirconium and selenology orange in sulfuric acid 0.2 mol/DMsolution. The hydrolysis of niobium (base alloy) to prevent the introduction of hydrogen peroxide. Absorption of complexes of niobium, of tungsten and molybdenum with selenology orange take into account, by measuring the total absorption of complexes of niobium, tungsten, molybdenum and zirconium in relation to the other equal aliquots of the sample in which it is added Trilon B, masking only zirconium.

The definition does not interfere up to 2 mg of aluminium, up to 7 mg of yttrium, up to 10 mg of molybdenum 3 mg of tungsten, and up to 50 µg of vanadium in fotometriya solution.

(Changed edition, Rev. N 1).

2.1. Apparatus, reagents and solutions

Photoelectrocolorimeter FEK-56 or similar device.

Tile electric.

Muffle furnace with thermostat providing temperatures up to 1000 °C.

Analytical scale.

Libra technical.

Volumetric flasks with a capacity of 50, 100 and 200 cm.

Pipettes without division into 1, 2, 5 and 10 cm.

Microburette with a capacity of 5 cm.

The chemical glasses with a capacity of 100 cm.

Watch-glasses.

The quartz crucibles high capacity of 40 cm.

Ammonium sulfate according to GOST 3769−78.

Potassium preservatory according to GOST 7172−76.

Sulfuric acid GOST 4204−77 and diluted 1:1, 1:5 and a solution of 0.5 mol/DM.

Hydrogen peroxide according to GOST 10929−76.

Salt is the disodium Ethylenediamine-N, N, N', N'-tetraoxane acid; 2-water (Trilon B) according to GOST 10652−73, solution 0,05 mol/l; prepared as follows: 18.6 g Trilon B dissolved in water with heating (if the solution is turbid, it is filtered), transferred to a volumetric flask with a capacity of 1 DM, is cooled and adjusted to the mark with water.

Selenology orange, an aqueous solution of 1 mg/cm.

Zirconium metal containing at least 99.9% of the zirconium in the form of a powder or fine shavings.

Standard solution zirconium (spare) containing 1 mg/cmZirconia: 0.1 g of metallic zirconium is placed in a quartz crucible, add 2−3 g of potassium persulphate and fused in a muffle at 800 °C until a clear melt. The smelt is dissolved by heating in 6 cmof sulphuric acid (1:1), transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water.

A solution of zirconium (working) containing 10 µg/cmof Zirconia, prepared on the day of use by dilution of a standard solution sulfuric acid 0.5 mol/DM1

00 times.

2.2. Analysis

A portion of the sample-based alloy of niobium with a mass of 0.1 g depending on the carbon content dissolved in one of the following methods.

2.2.1. When the mass fraction of carbon not more than 0.03%

A portion of the sample is dissolved by heating into a heat-resistant glass, covered with glass, 3.5 cmof concentrated sulfuric acid with addition of 1 g of ammonium sulfate. After the complete decomposition of a sample of the melt is cooled, poured 0.3 cmof hydrogen peroxide, about 30 cmof water, heated until complete dissolution of water; the resulting solution was cooled, transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water.

2.2.2. When the mass fraction of carbon more than 0.03%

A portion of the sample placed in a quartz crucible, add 4 g of potassium persulfate, a few drops of concentrated sulphuric acid and fused in a muffle furnace at a temperature of 800−900 °C to produce a clear float. The smelt is dissolved by heating in 6 cmof sulphuric acid (1:1) containing 0.3 cmof hydrogen peroxide.

The solution was transferred to volumetric flask with a capacity of 100 cm, cooled, adjusted to the mark with water (the acidity of the solution of 0.5 mol/lfor sulphuric acid). The expected content of zirconium more than 1% of the resulting solution was diluted again: take 10 cmof solution in a volumetric flask with a capacity of 100 cmand adjusted to the mark with sulphuric acid of 0.5 mol/DM(consider the second dilution in the calculation of the mass fraction of zirconium in claim 2.3).

For the determination of zirconium in two volumetric flasks with a capacity of 50 cmis taken equal aliquote parts of a solution containing 15−35 µg of zirconium, diluted to 20 cmof sulphuric acid 0.5 mol/DM. In one of the flasks is introduced 0.2 cmof the solution Trilon B, mix. Then both flasks poured 1 cmof solution kylinalove orange, bring to the mark with water and mix. After 20 minutes (colored solutions are stable not more than 40 min after addition of the reagents) and measure the optical density of a solution containing Trilon B, relative to solution of Trilon B in the photoelectrocolorimeter at 536 nm in a cuvette with the thickness of the light absorbing layer 30 mm.

The mass of zirconium find the calibration schedule.

(Revised edition, Edit

. N 1).

2.2.3. Construction of calibration curve

In a volumetric flask with a capacity of 50 cmis injected from microburette from 1.0 to 4.0 cmof the working solution of zirconium at intervals of 0.5 cm. All the flasks were poured 20 cmof sulphuric acid 0.5 mol/DM, 1 cmof solution kylinalove orange, stirring after adding each reagent, adjusted to the mark with water and mix. In one of the flasks poured all reagents with the exception of zirconium (zero solution). After 30 min measure optical density of solutions on the photoelectrocolorimeter at 536 nm in a cuvette with the thickness of the light absorbing layer 30 mm in relation to the zero solution. According to the obtained results build a calibration curve in the coordinates: the optical density is the mass of zirconium. Separate test points of the graph along with the analysis of samples

.

2.3. Processing of the results

2.3.1. Mass fraction of zirconium () in percent is calculated by the formula

,

where is the mass of zirconium was found in the calibration graphics mg;

 — aliquotes volume of the solution taken for the determining, cm;

 — capacity volumetric flasks, cm;

 — the weight of the portion of the sample,

2.3.2. Discrepancies between the results of two parallel determinations and the results of the two tests should not exceed the values of permissible differences given in table.1.

Table 1

(Changed edition, Rev. N 1).

3. THE PHOTOMETRIC METHOD FOR THE DETERMINATION OF ZIRCONIUM IN ALLOYS BASED ON VANADIUM, WHICH DOES NOT CONTAIN NIOBIUM

The method is based on formation of colored complex compounds of zirconium and selenology orange in sulfuric acid 0.2 mol/DMsolution.

The definition does not interfere up to 10 mg of yttrium and 5 mg of vanadium when the content of zirconium in fotometriya the amount of not less than 25 micrograms.

3.1. Apparatus, reagents and solutions

Photoelectrocolorimeter FEK-56 or similar device.

Tile electric.

Muffle furnace with thermostat providing temperatures up to 1000 °C.

Analytical scale.

Libra technical.

Volumetric flasks with a capacity of 50, 100 and 200 cm.

Pipettes without division into 1, 2, 5 and 10 cm.

Microburette with a capacity of 5 cm.

Measuring cylinders with a capacity of 50 cm.

The quartz crucibles high capacity of 40 cm.

Ammonium sulfate according to GOST 3769−78.

Potassium preservatory according to GOST 7172−76.

Sulfuric acid GOST 4204−77 and diluted 1:1, 1:5 and a solution of 0.5 mol/DM.

Salt is the disodium Ethylenediamine-N, N, N', N'-tetraoxane acid, 2-water (Trilon B) according to GOST 10652−73, solution 0,05 mol/l; prepared as follows: 18.6 g Trilon B dissolved in water with heating (if the solution is turbid, it is filtered), transferred to a volumetric flask with a capacity of 1 DM, is cooled and adjusted to the mark with water.

Selenology orange, an aqueous solution of 1 mg/cm.

Zirconium metal containing at least 99.9% of the zirconium in the form of a powder or fine shavings.

Standard solution zirconium (spare) containing 1 mg/cmZirconia: 0.1 g of metallic zirconium is placed in a quartz crucible, add 2−3 g of potassium persulphate and fused in a muffle at 800 °C until a clear melt. The smelt is dissolved by heating in 6 cmof sulphuric acid (1:1), transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water.

A solution of zirconium (working) containing 10 µg/cmof Zirconia, prepared on the day of use by dilution of a standard solution sulfuric acid 0.5 mol/DM.

(Redrafted From

M. N 1).

3.2. Analysis

A portion of the sample weight of 0.1 g in the form of a small chip placed in a quartz crucible, add 2−4 g of potassium persulphate and fused in a muffle at a temperature of 900 °C to obtain a homogeneous melt. The smelt is dissolved by heating in 36 cmof sulphuric acid (1:5), the solution was cooled and transferred to volumetric flask with a capacity of 200 cm, adjusted to the mark with water.

To determine zirconium in a volumetric flask with a capacity of 50 cmis taken aliquot part of the solution, containing 25−35 µg of zirconium, diluted to 20 cmof sulphuric acid 0.5 mol/DM, pour 1 cmof solution kylinalove orange, bring to the mark with water and mix. After 20 minutes, measure the optical density of the solution on photoelectrocolorimeter at 536 nm in a cuvette with the thickness of the light absorbing layer 30 mm in relation to the zero solution.

The mass of zirconium find the calibration schedule is constructed according to claim 2.2.3.

(Changed edition, Rev. N 1)

.

3.3. Processing of the results

3.3.1. Mass fraction of zirconium () in percent is calculated by the formula

,

where is the mass of zirconium was found in the calibration graphics mg;

 — aliquotes volume of the solution taken for the determining, cm;

 — capacity volumetric flasks, cm;

 — the weight of the portion of the sample,

3.3.2. Discrepancies between the results of two parallel determinations and the results of the two tests should not exceed the values of permissible differences given in table.2.

Table 2

(Changed edition, Rev. N 1).

4. THE PHOTOMETRIC METHOD FOR THE DETERMINATION OF ZIRCONIUM IN ALLOYS BASED ON VANADIUM-CONTAINING NIOBIUM

The method is based on formation of colored complex compounds with selenology orange in sulfuric acid 0.2 mol/DMsolution. Hydrolysis of niobium to prevent the introduction of ammonium sulfate. The absorption of a complex of niobium with selenology orange take into account, by measuring the total absorption of complexes of niobium and zirconium selenology orange in relation to another is equal aliquots of the sample in which it is added Trilon B, masking only zirconium. The definition does not interfere up to 10 mg of niobium and up to 5 mg of vanadium when the content of zirconium in fotometriya the amount of not less than 25 micrograms of zirconium.

4.1. Apparatus, reagents and solutions

Photoelectrocolorimeter FEK-56 or similar device.

Tile electric.

Analytical scale.

Libra technical.

Muffle furnace with thermostat providing temperatures up to 1000 °C.

Volumetric flasks with a capacity of 50, 100 and 200 cm.

Pipettes without division into 1, 2, 5 and 10 cm.

Microburette with a capacity of 5 cm.

The quartz crucibles high capacity of 40 cm.

Measuring cylinders with a capacity of 50 cm.

Potassium preservatory according to GOST 7172−76.

Sulfuric acid GOST 4204−77, and diluted 1:1, 1:5 and a solution of 0.5 mol/DM.

Salt is the disodium Ethylenediamine-N, N, N', N'-tetraoxane acid, 2-water (Trilon B) according to GOST 10652−73, solution 0,05 mol/l; prepared as follows: 18.6 g Trilon B dissolved in water with heating (if the solution is turbid, it is filtered), transferred to a volumetric flask with a capacity of 1 DM, is cooled and adjusted to the mark with water.

Selenology orange solution of 1 mg/cm.

Zirconium metal containing at least 99.9% of the zirconium in the form of a powder or fine shavings.

Standard solution zirconium (spare) containing 1 mg/cmZirconia: 0.1 g of metallic zirconium is placed in a quartz crucible, add 2−3 g of potassium persulphate and fused in a muffle at 800 °C until a clear melt. The smelt is dissolved by heating in 6 cmof sulphuric acid (1:1), transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water.

A solution of zirconium (working) containing 10 µg/cmof Zirconia, prepared on the day of use by dilution of a standard solution sulfuric acid 0.5 mol/DM100 times.

(Redrafted From

M. N 1).

4.2. Analysis

A portion of the sample weight of 0.1 g in the form of a small chip placed in a quartz crucible, add 2−4 g of potassium persulphate and fused in a muffle at a temperature of 900 °C to obtain a homogeneous melt. The smelt is dissolved by heating in 36 cmof sulphuric acid (1:5) containing 5 g of ammonium sulfate, the solution was cooled and transferred to volumetric flask with a capacity of 200 cm, adjusted to the mark with water.

For the determination of zirconium in two volumetric flasks with a capacity of 50 cmis taken equal aliquote parts of a solution containing 25−35 µg of zirconium, diluted to 20 cmof sulphuric acid 0.5 mol/DM. In one of the flasks is introduced 0.2 cmof the solution Trilon B and mix. Then both flasks poured 1 cmof solution kylinalove orange, bring to the mark with water and mix. After 20 minutes (colored solutions are stable for no more than 30 min after addition of the reagents) and measure the optical density of a solution containing Trilon B, relative to solution of Trilon B in the photoelectrocolorimeter at 536 nm in a cuvette with the thickness of the light absorbing layer 30 mm.

The mass of zirconium find the calibration schedule is constructed according to claim 2.2.3.

(Changed edition, Rev. N 1)

.

4.3. Processing of the results

4.3.1. Mass fraction of zirconium () in percent is calculated by the formula

,

where is the mass of zirconium was found in the calibration graphics mg;

 — capacity volumetric flasks, cm;

 — aliquotes volume of the solution taken for the determining, cm;

 — the weight of the portion of the sample,

4.3.2. Discrepancies between the results of two parallel determinations and the results of the two tests should not exceed the values of permissible differences given in table.3.

Table 3

(Changed edition, Rev. N 1).

5. SPECTRAL METHOD FOR THE DETERMINATION OF ZIRCONIUM IN ALLOYS BASED ON NIOBIUM AND VANADIUM

Method is based on the intensity of spectral lines of zirconium from its mass fraction in the analyzed sample in the excitation spectrum in the condensed spark discharge.

5.1. Apparatus, materials and reagents

The diffraction spectrograph DFS-8 with the grating 600 gr/mm (complete installation with a universal tripod) or similar device.

The spark generator IG-3 or a similar generator.

Muffle furnace with thermostat, providing a temperature of 800−900 °C.

Microphotometer MF-2 or similar device.

Spectromancer of PS-18 or similar type.

The quartz crucibles or cups platinum.

Analytical scale.

Libra torsion type VT-500 or similar type.

A device for sharpening graphite electrodes.

Mortar and pestle agate.

Graphite electrodes b-3, with a diameter of 6 mm with a spherical recess in the end face (the radius of the sphere is 5 mm, depth 1 mm) and sharpened on the convex hemisphere with a radius of 5 mm.

Vaseline.

Measurer — plate 4 mm thick with drilled hole 5 mm in diameter.

Plate glass size 9x12 for mixing of the sample with vaseline.

Spectral photographic plates 9x12 type 2 CHUV. 15 units or equivalent, providing normal blackening of analytical lines.

Vanadium pentoxide, containing zirconium at a level of 0.05%.

Niobium pentoxide-containing Zirconia at the level of 0.05%.

Of zirconium dioxide.

Industry standard sample of alloy 5 VIC CCA 48−4-1−90 (1−78).

Set the industry standard samples of composition of the alloy niobium-zirconium (set of 2) CCA 48−4 (12−17)-87.

The technical rectified ethyl alcohol GOST 18300−87.

The developer according to GOST 10691.1−84.

Ammonium chloride according to GOST 3773−72.

Fixer: 300 g chernovetskogo sodium, 20 g of ammonium chloride according to GOST 3773−72растворяют respectively 700 and 200 cmof water, poured the resulting solutions together and the total volume was adjusted with water to 1 DM.

Stopwatch.

Wool to wipe the spatula, mortar, pumps, weights.

Tracing paper for making bags.

Spatula for taking of test portions.

A scalpel for cutting tracing paper.

Tweezers to install the electrodes in the holders of a tripod before shooting.

Lamp infrared ikz-500 with voltage regulator type RNO-250−0,5 or controller of the same type.

(Changed edition, Rev. N 1, 2).

5.2. Preparation for assay

5.2.1. Preparation of a primary reference sample (OOS), containing 6% Zirconia

1,3442 g of niobium pentoxide or 1,6780 g of vanadium pentoxide mixed in an agate mortar under a layer of alcohol (50 cm) for 1.5−2 h with 0,0810 g of Zirconia. (Before taking batches oxides calcined at 400 °C to constant weight).

The mixture is dried under an infrared lamp to constant weight.

(Changed edition, Rev. N 1).

5.2.2. Sample preparation comparison (OS)

The comparison samples are prepared by successive dilution of the primary reference sample, and then each subsequent sample with niobium pentoxide or vanadium.

Mass fraction of zirconium (in percent based on the metal content in the alloy) and the mass added to the mixture of the batches are shown in table.4.

Table 4

The mixture is ground in a mortar under a layer of alcohol (50 cm) for 1.5−2 h and dried under an infrared lamp.

Samples of comparison on the basis of vanadium pentoxide was placed in a quartz or platinum crucibles cups, put in a muffle furnace at a temperature of 850 °C and held for 1−1,5 h. the Crucible (a Cup) with the melt, taken from the muffle furnace, cooled in air, wetting the melt 10 cmof alcohol. Slightly deforming the walls of the Cup (when using a platinum Cup), remove the melt and thoroughly mix it with 10 cmof ethanol in an agate mortar. The mixture is dried under an infrared lamp to constant weight.

The comparison samples stored in plastic jars or packets.

In the analysis of the niobium alloy samples of comparison is allowed to use industry-standard samples of the composition of the niobium-zirconium (set of 2).

(Changed edition, Rev. N 1).

5.3. Analysis

A portion of the sample weighing 0.5 g was placed in a quartz crucible or a platinum Cup and calcined in a muffle until constant mass at 850 °C. the Oxide is removed from the crucible or platinum cups, as specified in clause 5.2.2, and triturated. Weighed on a torsion scale 40 mg of the prepared sample and mix it with vaseline, taken using the measuring device, on a glass plate with a spatula. The resulting mixture is applied with a spatula on a three-electrode with a spherical recess at the end. The electrode with the sample installed in the lower holder tripod. In the upper holder set carbon electrode, sharpened to a convex hemisphere. The index of the scale of the wavelength of the spectrograph is mounted so that a part of the spectrum around 320 nm appeared in the middle of the spectrogram. Intermediate diaphragm on the condenser are selected such as to ensure the normal blackening of analytical lines. Between the electrodes ignite the spark.

If the sensitivity of the photographic plates do not provide a normal pucherani analytical lines, the one place photographic plates to take pictures of spectra from the two pairs of electrodes. The same operations are performed with samples of comparison spectra being photographed on the same photographic plate. The spectrum of each test sample (or reference sample) photographed three times. On the same photographic plate, in the case of analysis of niobium alloys, photographed six spectra of the oxidized sample an industry-standard alloy composition 5 VIC.

(Changed edition, Rev. N 1).

5.4. Processing of the results

5.4.1. Each of the obtained spectrograms with photoretrieval find the blackening of analytical lines of Zirconia () and compare () (table.5) and calculate the difference pucherani .

On three values , , obtained three spectrograms taken for each sample, find the arithmetic mean ().

The results of electrophoretic spectra of comparison samples to build calibration graphs in the coordinate , where is the logarithm of the mass fraction of the element in the reference sample.

Table 5

(Changed edition, Rev. N 1).

In the case of the analysis of niobium alloys find mean value () for the standard sample of the alloy 5 of the VIC, find the coordinate system of the position of the point ; where is the concentration of niobium in the analyzed alloy; 0.85 and the content of zirconium in the standard sample, 92 — mass fraction of niobium in a standard sample, and through this point parallel conduct schedule a schedule built on samples comparison (coefficient takes into account the change in the concentration of niobium in the alloy analyzed on the content of niobium in a standard sample). Mass fraction of zirconium find the results of electrophoretic spectra using a calibration chart.

5.4.2. Discrepancies between the results of three parallel measurements (the difference between larger and smaller) and the results of the two tests should not exceed the values of permissible differences given in table.6.

Table 6

(Changed edition, Rev. N 1).

5.4.3. (Deleted, Rev. N 1).