GOST 19863.13-91

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  ГОСТ 19863.13-91

GOST 19863.13−91 Alloy of titanium. Methods for determination of zirconium

GOST 19863.13−91

Group B59

STATE STANDARD OF THE USSR

ALLOYS OF TITANIUM

Methods for determination of zirconium

Titanium alloys.
Methods for the determination of zirconium

AXTU 1709

Date of introduction 1992−07−01

INFORMATION DATA

1. DEVELOPED AND INTRODUCED by the Ministry of aviation industry of the USSR

DEVELOPERS

V. G. Davydov, doctor of engineering. Sciences; V. A. Moshkin, PhD. tech. Sciences; G. I. Friedman, PhD. tech. Sciences; L. A. Tenyakova; M. N. Gorlova, PhD. chem. Sciences; L. V. Antonenko, O. L. Sikorska, PhD. chem. Sciences

2. APPROVED AND put INTO EFFECT by Decision of the USSR State Committee on management of quality and standards from 5.05.91 N 626

3. REPLACE GOST 19863.13−80

4. The frequency of inspection — 5 years

5. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS

The designation of the reference document referenced	Item number
GOST 3118−77	4.2
GOST 3759−75	4.2
GOST 3760−79	3.2
GOST 3772−74	2.2
GOST 3773−72	3.2
GOST 4204−77	2.2; 3.2
GOST 4461−77	4.2
GOST 5456−79	3.2
GOST 5457−75	4.2
GOST 9656−75	4.2
GOST 10484−78	4.2
GOST 10652−73	3.2
GOST 10929−76	2.2
GOST 17746−79	3.2
GOST 22867−77	2.2
GOST 25086−87	1.1
THAT 6−09−1678−86	2.2; 3.2
THAT 6−09−3986−76	3.2
THAT 95−259−88	4.2

This standard specifies the gravimetric (mass fraction in from 0.5 to 20.0%), photometric (with a mass fraction of from 0.02 to 0.5%) and atomic absorption (at a mass fraction of from 0.5 to 20.0%) methods for determination of zirconium.

1. GENERAL REQUIREMENTS

1.1. General requirements for methods of analysis GOST 25086 with the Supplement.

1.1.1. For the results analysis be the arithmetic mean of results of two parallel measurements.

2. GRAVIMETRIC METHOD FOR THE DETERMINATION OF ZIRCONIUM

2.1. The essence of the method

The method is based on dissolving the sample in sulfuric acid, the precipitation of zirconium phosphate dwuzameshchenny ammonium in the presence of hydrogen peroxide, calcining the precipitate at a temperature of (1000±10) °C to the zirconium pyrophosphate and weighing the calcined residue.

2.2. Apparatus, reagents and solutions

Muffle furnace with thermostatic control.

Ashless filters on the other 6−09−1678.

Sulfuric acid according to GOST 4204 density 1.84 g/cm, mortar 1:3 and 1:4.

Hydrogen peroxide according to GOST 10929.

Ammonium disodium phosphate according to GOST 3772, a solution of 100 g/DM.

Ammonium nitrate according to GOST 22867, a solution of 50 g/DM.

The washing liquid in the conical flask with a capacity of 1 DMis placed 100 cmof solution dosagedosage ammonium phosphate, poured 900 cmof sulfuric acid solution 1:4 and stirred.

2.3. Analysis

2.3.1. A portion of the sample in accordance with table.1 is placed in a conical flask with a capacity of 250 cm, flow 50 cmof sulfuric acid solution 1:3 and heated to complete dissolution of the sample, maintaining the initial volume with water.

Table 1

Mass fraction of zirconium, %	The weight of the portion of the sample, g
From 0.5 to 5.0 incl.	0,5
SV. 5,0 «10,0 «	0,25
«10,0» 20,0 «	0,1

The solution was cooled to room temperature, poured 150 cmof water, 20 cmof hydrogen peroxide, while stirring, in small portions of 20 cmof solution dosagedosage ammonium phosphate, then heated to 40−50 °C, mix thoroughly with a glass rod and allowed to settle at room temperature for at least 3 hours.

The precipitate was filtered off through a filter medium density («white ribbon»), washed eight times with wash liquid and three times with ammonium nitrate solution (the precipitate and the filter must be completely washed from the yellow color).

The filter with precipitate was placed in brought at a temperature of (1000±10) °C to constant weight and weighed porcelain crucible, dried, carefully incinerated, not allowing to ignite the filter paper, calcined in a muffle furnace at a temperature of (1000±10) °C for 30 min, cooled in a desiccator and weighed.

2.4. Processing of the results

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

, (1)

where is the mass of the crucible with the sediment, g;

 — weight of crucible, g;

 — weight of sample, g;

0,344 — the ratio of pyrophosphate Zirconia to zirconium.

2.4.2. Discrepancies in the results must not exceed the values given in table.2.

Table 2

Mass fraction of zirconium, %	The absolute allowable difference, %
	results of parallel measurements	the results of the analysis
From 0.50 to 1.00 incl.	0,05	0,07
SV. Of 1.00 to 2.50 «	0,07	0,10
«With 2.5» and 5.0 «	0,1	0,2
«5,0» 10,0 «	0,2	0,3
«10,0» 20,0 «	0,3	0,4

3. THE PHOTOMETRIC METHOD FOR THE DETERMINATION OF ZIRCONIUM

3.1. The essence of the method

The method is based on dissolving the sample in sulfuric acid, the formation of an orange-red complex compound of zirconium kylinalove orange and measuring the optical density of the solution at a wavelength of 536 nm.

3.2. Apparatus, reagents and solutions

Muffle furnace with thermostatic control.

Spectrophotometer or photoelectrocolorimeter.

Filters obestochennye on the other 6−09−1678.

Sulfuric acid according to GOST 4204 density 1.84 g/cm, mortar 1:4 and 0.05 mol/DM.

Hydroxylamine hydrochloride according to GOST 5456, a solution of 200 g/DM.

Ammonium chloride according to GOST 3773.

Ammonium nitrate according to GOST 3761, a solution of 200 g/DM.

Ammonia water according to GOST 3760.

Salt is the disodium Ethylenediamine — N, N, N', N'-tetraoxane acid, 2-water (Trilon B) according to GOST 10652, solution 0,025 mol/DM: 9.3 g Trilon B, is placed in a beaker with a capacity of 400 cm, 200 cm pouredwater and dissolved with stirring.

The solution is filtered through a folded filter from filter paper into a measuring flask with a capacity of 1 DM, made up to the mark with water and mix.

Selenology orange solution of 1 g/DM, freshly prepared.

Titanium sponge according to GOST 17746* stamps TG-100.
_______________
* On the territory of the Russian Federation GOST 17746−96. — Note the manufacturer’s database.

Zirconium sulfate on the other 6−09−3986.

Standard solutions of zirconium

Solution a: 3.9 g of zirconium sulfate was placed in a conical flask with a capacity of 250 cm, flow 50 cmof water and dissolve the sample, then carefully poured 25 cmof sulphuric acid, cool, transfer the solution into a measuring flask with volume capacity of 1000 cm, made up to the mark with water and mix.

1 cmof the solution contains 0.001 g of zirconium.

Set the mass concentration () of a standard solution of zirconium: aliquot part of the solution is 25 cmis placed in a beaker with a capacity of 300 cm, a flow of 70−80 cmof water, add 1 g of ammonium chloride, heated to 60−70 °C and added dropwise with stirring to ammonia aroma.

Solution and the precipitate was heated to boiling, incubated 20 minutes in a warm place at a temperature of 40−50 °C, then filtered through the filter medium density («white ribbon»).

The filter cake is washed five times with ammonium nitrate solution. The filter with precipitate was placed in brought at a temperature of (1000±10) °C to constant weight and weighed platinum crucible, dried, carefully incinerated and calcined in a muffle furnace at a temperature of (1000±10) °C for 1 h, cooled in a desiccator and weighed.

The mass concentration of a standard solution of zirconium (), g/cm, is calculated by the formula

, (2)

where is the mass of the sediment after ignition, g;

0,7403 — the ratio of zirconium dioxide to zirconium;

 — the volume of a standard solution of zirconium taken for the determination of zirconium, cm.

Solution B: 10 cmstandard solution And transferred with a pipette into a measuring flask with volume capacity of 1000 cm, add 0.05 mol/DMsulfuric acid solution to the mark and mix.

1 cmof the solution contains 0,00001 g of zirconium

.

3.3. Analysis

3.3.1. A portion of sample weighing 0.25 g was placed in a conical flask with a capacity of 100 cm, poured with a pipette 15 cmsulphuric acid 1:4, the beaker cover watch glass or funnel and heated to dissolve the sample, maintaining the initial volume with water. At the same time under the same conditions dissolve 0.25 g of titanium sponge.

The resulting solution was added dropwise a solution of hydroxylamine hydrochloride to the bleaching solution and 2−3 drops in excess, poured 20 cmof water and boil for 1−2 min. the flask with the solution was cooled to room temperature, the solution was transferred to volumetric flask with a capacity of 100 cm, made up to the mark with water and mix.

3.3.2. Aliquot part of the solution according to the table.3 is placed in a volumetric flask with a capacity of 50 cm, flow of 0.05 mol/DMsolution of sulphuric acid to a volume of 20 cm(tab.3), 2.5 cmof a solution of hydroxylamine hydrochloride, 2 cmof mortar kylinalove orange, made up to the mark with water and mix.

Table 3

Mass fraction of zirconium, %	Aliquota part of the solution, see	The volume of 0.05 mol/DMsolution sulphuric acid, see
From 0.02 to 0.05 incl.	20	-
SV. 0,05 «0,10 «	10	10
«To 0.10» to 0.25 «	5	15
«0,25» 0,50 «	2,5	17,5

3.3.3. Optical density of the solution is measured after 15 min at a wavelength of 536 nm in a cuvette with a layer thickness fotometricheskogo 30 mm.

Solution comparison is a compensatory solution: corresponding aliquota part of test solution with all reagents, in which before adding the orange kylinalove administered 0.5 cmof the solution Trilon B.

3.3.4. Mass fraction of zirconium calculated according to the calibration schedule.

3.3.5. Construction of calibration curve

In six conical flasks with a capacity of 100 cmpour 10 cmof a solution of Titan, five of them measure 1,0; 2,0; 3,0; 4,0; 5,0 cmstandard solution B, which corresponds to the 0.00001; 0,00002; 0,00003; 0,00004; 0,00005 g zirconium, and then go accordingly 10,0; 9,0; 8,0; 7,0; 6,0; 5,0 cmof sulfuric acid solution 0.05 mol/DMand continue the analysis on PP.3.3.2 and 3.3.3.

Solution comparison is the solution to which is not entered zirconium.

According to the obtained values of optical density of the solutions and the corresponding mass of zirconium to build a calibration curve.

3.4. Processing of the results

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

, (3)

where is the mass of zirconium in the sample solution found by the calibration schedule g;

the sample mass in the corresponding aliquote part of the solution,

3.4.2. Discrepancies in the results must not exceed the values given in table.4.

Table 4

Mass fraction of zirconium, %	The absolute allowable difference, %
	results of parallel measurements	the results of the analysis
From 0.020 to 0.050 incl.	0,006	0,010
SV. 0,05 «0,10 «	0,01	0,02
«To 0.10» to 0.30 «	0,02	0,03
«To 0.30» to 0.50 «	0,03	0,05

4. ATOMIC ABSORPTION METHOD FOR THE DETERMINATION OF ZIRCONIUM

4.1. The essence of the method

The method is based on dissolving the sample in hydrochloric and bridgestation acids and measurement of atomic absorption zirconium at a wavelength 360,1 nm in a flame acetylene — nitrous oxide.

4.2. Apparatus, reagents and solutions

Spectrophotometer of atomic absorption with a radiation source for zirconium.

Acetylene according to GOST 5457.

Nitrous oxide medical.

Hydrochloric acid according to GOST 3118 density of 1.19 g/cm, a solution of 2:1.

Nitric acid according to GOST 4461 density of 1,35−1,40 g/cm.

Boric acid according to GOST 9656 and a saturated solution.

Hydrofluoric acid according to GOST 10484.

Acid bridgestation: 280 cmhydrofluoric acid at a temperature of (10±2) °C add portions 130 g of boric acid and stirred. The reagent is prepared and stored in a plastic container.

Aluminium chloride according to GOST 3759, a solution of 100 g/DM.

The zirconium metal of high purity on the other 95−259.

Standard solutions of zirconium

Solution a: 1 g of metallic zirconium is placed in a Teflon beaker with a capacity of 100 cm, add four drops of water to wet the sample and cautiously, in small portions pour 10 cmof a mixture consisting of one part hydrofluoric and one part of nitric acid. Dissolution of lead in the cold. After dissolution of the sample add 50 cmof the saturated solution of boric acid and allowed to stand for 10 min. the Solution was stirred and transferred to a volumetric flask with a capacity of 100 cm, adjusted to the mark with water, mixed and transferred to the glass, which had a dissolution.

1 cmof solution A contains 0.01 g of zirconium.

Solution B: 10 cmsolution And placed in a volumetric flask with a capacity of 100 cm, add 20 cmof a hydrochloric acid solution, adjusted to the mark with water, mix.

1 cmof the solution contains 0.001 g qi

Rania.

4.3. Analysis

4.3.1. A portion of the sample weight in accordance with table.5 is placed in a conical flask with a capacity of 100 cm, flow 20 cmof a hydrochloric acid solution, 5 cmbridgestation acid and dissolved with moderate heating.

Table 5

Mass fraction of zirconium, %	The weight of the portion of the sample, g
From 0.5 to 5.0	0,5
SV. Of 5.0 to 20.0	0,25

After dissolution of the sample solution was cooled to room temperature and transferred to a volumetric flask with a capacity of 100 cm. Add 10 cmbridgestation acid, 10 cmof a solution of aluminum chloride, made up to the mark with water and mix.

4.3.2. The solution in the reference experiment is prepared according to claim 4.3.1.

4.3.3. Construction of calibration curve

4.3.3.1. When the mass fraction of zirconium from 0.5 to 2.0%

Five conical flasks with a capacity of 100 cmplaced at a 0.5 g sample of alloy, similar in composition analyzed, but not containing zirconium, and conduct dissolution as specified in claim 4.3.1, and in four of them measure 2,5; 5,0; 7,5; 10,0 cmstandard solution B, which corresponds to RUB 0.0025; to 0.005; 0,0075; 0.01 g zirconium, and then perform operations according to paragraph 4.3.1.

4.3.3.2. When the mass fraction of zirconium of more than 2.0 to 5.0%

Five conical flasks with a capacity of 100 cmplaced at a 0.5 g sample of alloy, similar in composition analyzed, but not containing zirconium, and conduct dissolution as specified in claim 4.3.1, and in four of them measure 1,0; 1,5; 2,0; 2,5 cmstandard solution A, which corresponds to 0,01; 0,015; 0,02; 0,025 g zirconium, and then perform operations according to paragraph 4.3.1.

4.3.3.3. When the mass fraction of zirconium in excess of 5.0 to 12.0%

In six conical flasks with a capacity of 100 cmis placed on a 0.25 g sample of the alloy, similar in composition analyzed, but not containing zirconium, and conduct dissolution as specified in claim 4.3.1, and in five of them measure 1,0; 1,5; 2,0; 2,5; 3,0 cmstandard solution A, which corresponds to 0,01; 0,015; 0,02; 0,025; 0,03 g zirconium, and then perform operations according to claim 4.3.1.

4.3.3.4. When the mass fraction of zirconium in excess of 12.0 to 20.0%

In six conical flasks with a capacity of 100 cmis placed on a 0.25 g sample of the alloy, similar in composition analyzed, but not containing zirconium, and conduct dissolution as specified in claim 4.3.1, and in five of them measure 3,0; 3,5; 4,0; 4,5; 5,0 cmstandard solution A, which corresponds to 0,03; 0,035; 0,04; 0,045; 0.05 g zirconium, and then perform operations according to claim 4.3.1.

4.3.4. The sample solution, solution control experience and solutions to build the calibration curve is sprayed into the flame of acetylene — nitrous oxide (recovery) and measure the atomic absorption of the Zirconia at a wavelength 360,1 nm.

According to the obtained values of atomic absorption and corresponding mass concentration of zirconium to build a calibration curve in the coordinates «Value of atomic absorption — Mass concentration of zirconium, g/cm».

The mass concentration of zirconium in the sample solution and in the solution of control and experience determined by the calibration schedule.

4.5. Processing of the results

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

, (4)

where is the mass concentration of zirconium in the sample solution found by the calibration schedule, g/cm;

 — mass concentration of zirconium in solution in the reference experiment, was found in the calibration schedule, g/cm;

 — the volume of the sample solution, cm;

 — weight of sample, g

.

4.5.2. Discrepancies in the results must not exceed the values given in table.6.

Table 6

Mass fraction of zirconium, %	Absolute tolerance, %
	results of parallel measurements	the results of the analysis
From 0.50 to 1.00 incl.	0,05	0,10
SV. Of 1.00 «to 2.50 «	0,10	0,15
«Of 2.50» and 5.00 «	0,15	0,20
«5,0» 10,0 «	0,2	0,3
«10,0» 20,0 «	0,3	0,4