GOST 19863.4-91
GOST 19863.4−91 Alloy of titanium. Methods for determination of tungsten
GOST 19863.4−91
Group B59
STATE STANDARD OF THE USSR
ALLOYS OF TITANIUM
Methods for determination of tungsten
Titanium alloys.
Methods for the determination of tungsten
AXTU 1809
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; A. I. Korolev, 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
3. REPLACE GOST 19863.4−80
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 |
2.2; 3.2; 4.2 |
| GOST 4147−74 |
2.2 |
| GOST 4204−77 |
2.2; 3.2 |
| GOST 4328−77 |
2.2; 3.2 |
| GOST 4461−77 |
2.2; 3.2 |
| GOST 5457−75 |
4.2 |
| GOST 9656−75 |
3.2; 4.2 |
| GOST 10484−78 |
3.2; 4.2 |
| GOST 10929−76 |
4.2 |
| GOST 11125−84 |
4.2 |
| GOST 17746−79 |
2.2; 3.2 |
| GOST 18289−78 |
2.2; 3.2 |
| GOST 25086−87 |
1.1 |
| GOST 27067−86 |
2.2; 3.2 |
| THAT 6−09−1678−86 |
2.2; 3.2 |
| THAT 48−19−69−80 |
2.2; 3.2 |
| THAT 48−19−57−78 |
4.2 |
This standard specifies the photometric (with a mass fraction of from 0.1 to 6.0%) and atomic absorption (at a mass fraction of from 0.5 to 6.0%) methods for determination of tungsten.
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. The PHOTOMETRIC METHOD for the DETERMINATION of TUNGSTEN (at a mass fraction of tungsten of 1.0 to 6.0%)
2.1. The essence of the method
The method is based on dissolving the sample in sulfuric acid solution, the formation of yellow complex compound of pentavalent tungsten with radamisty ammonium after pre-reduction of the hexavalent tungsten trichloride titanium and measuring the optical density of the solution at a wavelength of 400 nm.
Titanium, iron, Nickel, and chromium are pre-separated with sodium hydroxide. The influence of molybdenum at a ratio of molybdenum and tungsten is not more than 1:1 can be eliminated by adding the appropriate mass fraction of molybdenum in the construction of calibration curve.
2.2. Apparatus, reagents and solutions
Spectrophotometer or photoelectrocolorimeter.
Muffle furnace with thermostatic control.
Filters obestochennye on the other 6−09−1678.
Adsorbent (materiana paper): 100 g of crushed filters (red ribbon) is placed in a beaker with a capacity of 500 cm, 300 cm poured
water and stirred with a stirrer to obtain a homogeneous mass.
Sulfuric acid according to GOST 4204 density 1.84 g/cm, mortar 1:1 and 1:3.
Hydrochloric acid according to GOST 3118 density of 1.19 g/cmand a solution of 2:1, 1:1 and 1:4.
Nitric acid according to GOST 4461 density of 1,35−1,40 g/cmand a solution of 1:5.
A mixture of acids: 300 cmof hydrochloric acid poured 100 cm
of nitric acid and stirred.
Sodium hydroxide according to GOST 4328, solutions of 20 g/DMand 200 g/DM
.
Ammonium radamisty according to GOST 27067, a solution of 500 g/DM.
Titan according to GOST 17746* stamps TG-100.
_______________
* On the territory of the Russian Federation GOST 17746−96, here and hereafter. — Note the manufacturer’s database.
Titanium trichloride, a solution of 10 g/DM, 1 g of titanium was placed in a conical flask with a capacity of 250 cm
, 50 cm pour the
hydrochloric acid solution of 2:1, cover with a watch glass or funnel and dissolved by heating, maintaining a constant volume of the same solution of hydrochloric acid.
The solution was cooled to room temperature, transferred to a volumetric flask with a capacity of 100 cm, is poured a solution of hydrochloric acid 2:1 to the mark and mix. The solution is ready for use within 4 days if stored in a dark place in the flask with a cork.
Sodium volframovich 2-water according to GOST 18289.
A standard solution of tungsten: 1,7941 volframovich g of sodium is placed in a conical flask with a capacity of 250 cm, pour 100 cm
of sodium hydroxide solution 20 g/l
and dissolved at a moderate heat.
The solution was cooled to room temperature, transferred into a measuring flask with volume capacity of 1000 cm, is poured a solution of sodium hydroxide 20 g/DM
up to the mark and mix. The solution was stored in a plastic container.
1 cmof the solution contains 0.001 g of tungsten.
To establish the mass concentration of tungsten aliquots of 50 cmstandard solution of tungsten placed in three beakers with a capacity of 400 cm
, flow 15 cm
of nitric acid and evaporated to a volume of 5−6 cm
. Then pour in 100 cm
of boiling water, boil for 15 min, add maseribane paper and shaken.
The precipitate was filtered off through a filter medium density (white ribbon) and washed 5−6 times with a solution of nitric acid, heated to 30−40 °C.
The filter with precipitate was placed in brought at a temperature of 750−800 °C to constant weight and weighed porcelain or platinum crucible, dried, carefully incinerated at a temperature of 400−500 °C, calcined in a muffle furnace at a temperature of 750−800 °C for 1 h, cooled in a desiccator and weighed.
Simultaneously conduct control experience for contamination of reagents.
Mass concentration volframovich sodium on tungsten () in g/cm
is calculated by the formula
where is the mass of the crucible with the sediment, g;
— weight of crucible, g;
— the volume of a solution of sodium volframovich taken to establish the mass concentration, cm
;
0,7930 — the ratio of tungsten trioxide to tungsten.
Iron (III) chloride 6-water according to GOST 4147, solution 100 g/l: 100 g of iron (III) chloride were placed in a glass with a capacity of 1000 cm
, and dissolved in 200 cm
of a hydrochloric acid solution 1:4, poured 700 cm
of water and stirred.
Molybdenum metal of high purity on the other 48−19−69 containing not less than 99.5% molybdenum.
A standard solution of molybdenum, 1 g of molybdenum was placed in a conical flask with a capacity of 250 cm, and dissolved in 30 cm
of a mixture of acids. Then pour the 30 cm
of sulfuric acid solution 1:1 and evaporated until the appearance of white vapors. The solution was cooled to room temperature, pour the 50 cm
of water, heated to dissolve the salts; the solution was cooled to room temperature, transferred 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 molybdenum.
Methyl orange: 0.1 g of the reagent dissolved in 100 cmof water with a weak to
greaney.
2.3. Analysis
2.3.1. A portion of sample weighing 0.25 g was placed in a conical flask with a capacity of 250 cm, flow 40 cm
of sulfuric acid solution 1:3 and heated to complete dissolution. The solution was added dropwise nitric acid until the disappearance of violet colour, three drops in excess, is evaporated until the appearance of dense white fumes and continue heating for 3 min.
The solution was cooled to room temperature, poured 40 cmof water and heated to dissolve the salts, mix, add 10 cm
of a solution of iron (III) chloride, 40 cm
of sodium hydroxide solution 200 g/l
and stirred.
The solution was transferred in portions of 10 cmin a volumetric flask with a capacity of 250 cm
, containing 50 cm
of sodium hydroxide solution, heated to a temperature of 80−85 °C. the Flask is washed with 10 cm
of hot sodium hydroxide solution 200 g/l
, stirred, cooled to room temperature in running water, made up to the mark with water and mix.
Sediment is allowed to settle for 15−20 min, the solution was filtered through a filter medium density (white ribbon) in a conical flask with a capacity of 250 cm, discarding the first portions of the filtrate.
Aliquot part of the solution in accordance with the table.1 is placed in a volumetric flask with a capacity of 100 cm, pour 2 cm
of a solution of ammonium Rodenstock, 45 cm
of a hydrochloric acid solution of 2:1, stirred and cooled to a temperature of 15−17 °C.
Table 1
| Mass fraction of tungsten, % |
The volume aliquote part, see |
| From 1.0 to 3.0 incl. |
10 |
| SV. The 3.0 «and 6.0 « |
5 |
The cooled solution was poured fifteen drops (in portions of five drops) of the solution trichloride titanium. In the case of the presence in the alloy of molybdenum titanium trichloride poured in portions of four drops to the disappearance of the red-orange color of the complex compound of molybdenum with thiocyanate ions and five drops in excess. 5 min after formation of stable yellow-green color is poured a solution of hydrochloric acid 1:1 to the mark and mix.
2.3.2. Optical density of the solution measured after 5 min, but not later than 30 min at a wavelength of 400 nm in a cuvette with a layer thickness fotometricheskogo 30 mm. Solution comparison the solution serves as the reference experiment, which is prepared according to claim 2.3.1 all used in the analysis reagents.
2.3.3. Mass fraction of tungsten is calculated according to the calibration schedule.
2.3.4. Construction of calibration curve
In seven conical flasks with a capacity of 250 cmis placed hinge titanium with a weight of 0.25 g In six of them measure 2,5; 5,0; 7,5; 10,0; 12,5; 15,0 cm
standard solution tungsten, which corresponds to 0,0025; 0,005; 0,0075; 0,01; 0,0125; 0,015 g tungsten, poured 40 cm
of sulfuric acid solution 1:3 and then continue according to claim
In the presence in the alloy of molybdenum in eight conical flasks with a capacity of 250 cmmeasured to the standard solution of molybdenum in the amount corresponding to the mass fraction of molybdenum in the sample. Solution comparison is the solution, in which tungsten is not entered.
According to the obtained values of optical density of the solutions and their corresponding masses of tungsten to build a calibration curve.
2.4. Processing of the results
2.4.1. Mass fraction of tungsten () in percent is calculated by the formula
where is the mass of tungsten in the sample solution found by the calibration schedule g;
— the weight of the portion of the sample in the appropriate aliquote part of the solution,
2.4.2. Discrepancies in the results must not exceed the values given in table.2.
Table 2
| Mass fraction of tungsten, % | The absolute allowable difference, % | |
| results of parallel measurements |
the results of the analysis | |
| From 1.00 to 2.00 incl. |
0,10 |
0,15 |
| SV. 2,00 «4,00 « |
0,20 |
0,25 |
| «Of 4.00» to 6.00 « |
0,30 |
0,35 |
3. The PHOTOMETRIC METHOD for the DETERMINATION of TUNGSTEN (at a mass fraction of tungsten of from 0.1 to 1.5%)
3.1. The essence of the method
The method is based on dissolving the sample in a mixture of hydrochloric and bridgestation acids, the formation of yellow complex compound of pentavalent tungsten with radamisty ammonium after pre-reduction of the hexavalent tungsten trichloride titanium and measuring the optical density of the solution at a wavelength of 400 nm.
The influence of molybdenum at a ratio of molybdenum and tungsten is not more than 1:1 can be eliminated by adding the appropriate mass fraction of molybdenum in the construction of calibration curve.
The method is applicable to alloys with a mass fraction of tungsten not more than 1.5%.
3.2. Apparatus, reagents and solutions
Spectrophotometer or photoelectrocolorimeter.
Muffle furnace with thermostatic control.
Filters obestochennye on the other 6−09−1678.
Adsorbent (materiana paper): 100 g of crushed filters (red ribbon) is placed in a beaker with a capacity of 500 cm, 300 cm poured
water and stirred with a stirrer to obtain a homogeneous mass.
Sulfuric acid according to GOST 4204 density 1.84 g/cm.
Hydrochloric acid according to GOST 3118 density of 1.19 g/cm, mortar 1:1 and 2:1.
Nitric acid according to GOST 4461 density of 1,35−1,40 g/cm, a solution of 1:5.
Hydrofluoric acid according to GOST 10484.
Boric acid according to GOST 9656.
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.
Ammonium radamisty according to GOST 27067, a solution of 150 g/DM.
Titan according to GOST 17746 grade TG-100.
Titanium trichloride, a solution of 10 g/DM, 1 g of titanium was placed in a conical flask with a capacity of 250 cm
, 50 cm pour the
hydrochloric acid solution of 2:1, cover with a watch glass or funnel and dissolved by heating, maintaining a constant volume of the same solution of hydrochloric acid.
The solution was cooled to room temperature, transferred to a volumetric flask with a capacity of 100 cm, is poured a solution of hydrochloric acid 2:1 to the mark and mix.
Sodium hydroxide according to GOST 4328, solution 20 g/DM.
Sodium volframovich 2-water according to GOST 18289.
Standard solution of tungsten according to claim 2.2.
Molybdenum metal of high purity on the other 48−19−69 containing not less than 99.5% molybdenum.
A standard solution of molybdenum —
claim 2.2.
3.3. Analysis
3.3.1. A portion of the sample weight in accordance with table.3 is placed in a conical flask with a capacity of 100 cm, flow 20 cm
of hydrochloric acid of 1 cm
bridgestation acid and heated until complete dissolution.
Table 3
| Mass fraction of tungsten, % |
The weight of the portion of the sample, g |
| From 0.1 to 0.5 incl. |
0,5 |
| SV. 0,5 «1,5 « |
0,2 |
The solution was cooled to room temperature, transferred to a volumetric flask with a capacity of 100 cm, made up to the mark with water and mix. Aliquot part of the solution 10 cm
is placed in a volumetric flask with a capacity of 100 cm
, flow 10 cm
Rodenstock solution of ammonia, fifteen drops (in portions of five drops) of the solution trichloride titanium, add a solution of hydrochloric acid 1:1 to the mark and mix.
3.3.2. Optical density of the solution is measured after 10 min, but not later than 30 min at a wavelength of 400 nm in a cuvette with a layer thickness fotometricheskogo 30 mm.
Solution comparison is the solution of the reference experiment: a portion of the titanium in accordance with the table.3 is placed in a conical flask with a capacity of 100 cmand continue the analysis according to claim
3.3.3. Mass fraction of tungsten is calculated according to the calibration schedule.
3.3.4. Construction of calibration curve
In nine conical flasks with a capacity of 100 cmplaced sample of titanium in accordance with the table.3. Eight of them measure 0,5; 1,0; 1,5; 2,0; 2,5; 3,0; 3,5; 4,0 cm
standard solution tungsten, which corresponds to 0,0005; 0,001; 0,0015; 0,002; 0,0025; 0,003; 0,0035; 0,004 g tungsten, poured 20 cm
of hydrochloric acid of 1 cm
bridgestation acid and continue the analysis according to claim
In the presence of the molybdenum alloy in nine conical flasks with a capacity of 100 cmmeasured to the standard solution of molybdenum in the amount corresponding to the mass fraction of molybdenum in the sample.
Solution comparison is the solution, in which tungsten is not entered.
According to the obtained values of optical density of the solutions and their corresponding masses of tungsten to build a calibration curve.
3.4. Processing of the results
3.4.1. Mass fraction of tungsten () in percent is calculated by the formula
where is the mass of tungsten in the sample solution found by the calibration schedule g;
— the weight of the portion of the sample in the appropriate 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 tungsten, % |
The absolute allowable difference, % | |
| results of parallel measurements |
the results of the analysis | |
| From 0.10 to 0.25 incl. |
0,04 |
0,05 |
| SV. Of 0.25 «to 0.75 « |
0,08 |
0,10 |
| «0,75» 1,50 « |
0,10 |
0,15 |
4. ATOMIC ABSORPTION METHOD FOR THE DETERMINATION OF TUNGSTEN
4.1. The essence of the method
The method is based on dissolving the sample in hydrochloric and bridgestation acids and measuring the nuclear absorption of tungsten at a wavelength 255,1 nm in a flame acetylene — nitrous oxide.
4.2. Apparatus, reagents and solutions
Spectrophotometer of atomic absorption with a radiation source for tungsten.
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 11125 density of 1,35−1,40 g/cmand a solution of 1:5.
Hydrofluoric acid according to GOST 10484.
A mixture of hydrofluoric and nitric acids in the ratio 1:1.
Boric acid according to GOST 9656.
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.
Hydrogen peroxide according to GOST 10929.
Tungsten of high purity on the other 48−19−57.
Standard solutions of tungsten
Solution a: 5 g of tungsten was placed in a Teflon beaker, add 75 cmof a mixture of hydrofluoric and nitric acids in the ratio 1:1. After dissolution, the sample solution was transferred to volumetric flask with a capacity of 500 cm
, made up to the mark with water and mix. The solution was stored in a plastic container.
1 cmof solution A contains 0.01 g of tungsten.
Solution B: 10 cmsolution And placed in a volumetric flask with a capacity of 100 cm
, made up to the mark with water and mix. The solution was stored in a plastic container, prepare before use.
1 cmof the solution contains 0.001 g wolfra
mA.
4.3. Analysis
4.3.1. A portion of sample weighing 0.5 g is placed in a conical flask with a capacity of 100 cm, add 20 cm
of a hydrochloric acid solution of 2:1, 1 cm
bridgestation acid and dissolved with moderate heating. The solution was cooled to room temperature, add 1 cm
of hydrogen peroxide, 10 cm
bridgestation acid and transferred to volumetric flask with a capacity of 100 cm
, made up to the mark with water and mix.
4.3.2. The solution in the reference experiment is prepared according to claim
4.3.3. Construction of calibration curve
4.3.3.1. When the mass fraction of tungsten 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 does not contain tungsten, and conduct dissolution according to claim 4.3.1, and in four of them measure 2,5; 5,0; 7,5; 10,0 cm
standard solution B, which corresponds to RUB 0.0025; to 0.005; 0,0075; 0.01 g of tungsten, and then continue the analysis at step
4.3.3.2. When the mass fraction of tungsten over 2.0 to 6.0%
Five conical flasks with a capacity of 100 cmplaced at a 0.5 g sample of alloy, similar in composition analyzed, but does not contain tungsten, and conduct dissolution according to claim 4.3.1, and in four of them measure 1,0; 2,0; 3,0; 4,0 cm
standard solution A, which corresponds to 0,01; 0,02; 0,03; 0,04 g of tungsten, and then perform operations according to claim
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 tungsten at a wavelength 255,1 nm.
According to the obtained values of atomic absorption and corresponding mass concentrations of tungsten to build a calibration curve in the coordinates «Value of atomic absorption — Mass tungsten concentration, g/cm».
The mass concentration of tungsten in the sample solution and in the solution of control and experience determined by the calibration schedule.
4.4. Processing of the results
4.4.1. Mass fraction of tungsten () in percent is calculated by the formula
where is the mass concentration of tungsten in the sample solution found by the calibration schedule, g/cm
;
— mass concentration of tungsten 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
.
4.4.2. Discrepancies in the results must not exceed the values given in table.5.
Table 5
| Mass fraction of tungsten, % |
The absolute allowable difference, % | |
| results of parallel measurements |
the results of the analysis | |
| From 0.50 to 1.00 incl. |
0,05 |
0,10 |
| SV. 1,00 «2,00 « |
0,10 |
0,15 |
| «2,00» 4,00 « |
0,15 |
0,20 |
| «Of 4.00» to 6.00 « |
0,25 |
0,30 |
