GOST R 51013-97
GOST R 51013−97 Alloys heat-resistant, corrosion-resistant, precision Nickel-based. Methods for the determination of titanium (amended)
GOST R 51013−97
Group B39
STATE STANDARD OF THE RUSSIAN FEDERATION
ALLOYS HEAT-RESISTANT, CORROSION-RESISTANT, PRECISION
NICKEL-BASED
Methods for determination of titanium
Nickel based fire-resistant, corrosion-resistant, precision alloys.
Methods for titanium determination
OKS 77.100.20*
AXTU 0709
_______________
* In the index «National standards» 2008 ACS
Note the manufacturer’s database.
Date of introduction 1997−07−01
Preface
1 DEVELOPED AND SUBMITTED by the Technical Committee TC 145 «monitoring Methods of steel products"
2 ADOPTED AND put INTO EFFECT by the Resolution of Gosstandart of Russia of 22 January 1997 No. 10
3 INTRODUCED FOR THE FIRST TIME
4 Annex a contains the full authentic text of international standard ISO 11433−93 «Nickel alloys. The determination of titanium. Spectrophotometric method diantipyrylmethane"
AMENDED, published in the IUS N 8, 1997
An amendment made by the manufacturer of the database
1 SCOPE
This standard sets the photometric method for the determination of titanium in heat-resistant, corrosion-resistant and precision alloys based on Nickel with a mass fraction of titanium from 0.15 to 3.0%.
Allow the definition of titanium by spectrophotometry according to the method of international standard ISO 11433, given in Appendix A.
2 NORMATIVE REFERENCES
The present standard features references to the following standards:
GOST 3118−77 hydrochloric Acid. Specifications
GOST 3765−78 Ammonium molybdate. Specifications
GOST 4204−77 sulfuric Acid. Specifications
GOST 4461−77 nitric Acid. Specifications
GOST 5817−77 tartaric Acid. Specifications
GOST 6552−80 orthophosphoric Acid. Specifications
GOST 7172−76 Potassium preservatory. Specifications
GOST 11125−84 nitric Acid of high purity. Specifications
GOST 14261−77 hydrochloric Acid of high purity. Specifications
GOST 14262−78 sulphuric Acid of high purity. Specifications
GOST 19807−91 Titanium and titanium wrought alloys. Brand
GOST 28473−90 Iron, steel, ferroalloys, chromium and manganese metal. General requirements for methods of analysis
3 GENERAL REQUIREMENTS
3.1 General requirements for methods of analysis GOST 28473.
4 PHOTOMETRIC METHOD FOR THE DETERMINATION OF TITANIUM (0,15−3,0%)
4.1 the essence of the method
The method is based on formation of yellow colored coordination compounds of titanium with diantipyrylmethane in the environment of hydrochloric acid and measuring the optical density of the solution at a wavelength of 395 nm.
Iron (III) and vanadium (V) is reduced with ascorbic acid.
Tungsten and niobium mask, respectively, phosphoric and tartaric acids.
4.2 Apparatus and reagents
Spectrophotometer or photoelectrocolorimeter, allowing to carry out measurement of light absorption of the solution at a wavelength of 390 nm.
The hydrochloric acid according to GOST 3118 or GOST 14261, solution 1:1, 1:9, 1:100.
Nitric acid according to GOST 4461 or GOST 11125.
Sulfuric acid according to GOST 4204 or GOST 14262, diluted 1:1, 1:2, 1:5.
Orthophosphoric acid according to GOST 6552.
Tartaric acid according to GOST 5817, solution mass concentration of 200 g/DM.
Ascorbic acid according to GOST 5817, solution mass concentration of 40 g/DM, prepared on the day of application.
Diantipyrylmethane, solution mass concentration of 40 g/DM.
4 g diantipyrylmethane dissolved in 100 cmof hydrochloric acid, diluted 1:6.
Titanium metal according to GOST 19807.
Standard titanium solution: 0.1 g of titanium metal is placed in a beaker with a capacity of 250−300 cm, flow 50 cm
of sulphuric acid (1:2) and dissolved by heating. Then added dropwise nitric acid to the bleaching solution and evaporated until the appearance of dense sulphuric acid fumes. The solution was cooled. Gently wash the side of the Cup with water and again evaporated to the appearance of sulphuric acid fumes. After cooling, the solution is poured into a measuring flask with a capacity of 1 DM
, made up to the mark with sulphuric acid (1:5) and stirred.
1 cmof the solution contains 0.0001 g of titanium.
Potassium preservatory according to GOST 7172.
Ammonium molybdate according to GOST 3765, solution: 1,8402 g of ammonium molybdate was placed in a beaker with a capacity of 300 cmand dissolved in water when heated. After cooling, the solution is transferred to a volumetric flask with a capacity of 1 DM
, made up to the mark with water and mix.
1 cmof the solution contains 0.001 g of molyb
Dan.
4.3 analysis
4.3.1 Preparation of test solution for the alloys not containing tungsten and niobium
A sample of 0.1 g was placed in a beaker with a capacity of 100−150 cm, add 20 cm
of hydrochloric acid and 5 cm
of nitric acid and dissolved by heating. Add 15 cm
of sulphuric acid (1:1), evaporated the solution until vapors of sulphuric acid and cooled. Add 20 cm
of hydrochloric acid (1:9) and dissolve the salt when heated.
4.3.2 Preparation of test solution for alloys containing tungsten and niobium
Weighed samples of 0.1 g were placed in a glass with a capacity of 100−150 cmand dissolved by heating in 30 cm
of hydrochloric acid, 15 cm
of sulphuric acid (1:1) and 3 cm
of phosphoric acid. Add 5−7 cm
of nitric acid and evaporated to fumes of sulfuric acid. The glass solution was cooled, poured 15 cm
of tartaric acid solution, 20 cm
of hydrochloric acid (1:9) and dissolve the salt by heating
.
4.3.3 in the presence of the insoluble residue, the solution obtained in accordance with 4.3.1 or 4.3.2, filtered through the filter medium density («white ribbon»), washed the filter twice with hydrochloric acid (1:100) and then with water. Retain the filtrate (primary filtrate). The filter with precipitate was placed in a platinum crucible, dried, incinerated, and calcined at 600−700 °C and fused with 1 g of potassium peacemaking. The cooled crucible was placed in a beaker with a capacity of 150 cmand dissolve the melt by heating in 20−30 cm
of hydrochloric acid (1:9).
The crucible is removed and washed with hydrochloric acid (1:9).
The resulting solution was attached to the main filtrate.
4.3.4 the development of the painting
The solution obtained in accordance with 4.3.1, 4.3.2 or 4.3.3, is poured into a measuring flask with a capacity of 200 cm, made up to the mark with hydrochloric acid (1:9) and stirred.
In two volumetric flasks with a capacity of 100 cmeach placed aliquote part of the solution in accordance with table 1.
Table 1
| Mass fraction of titanium, % | Aliquota part of the solution, see |
| From 0.15 to 1.0, incl. |
20 |
| SV. 1,0 «2,0 « |
10 |
| «2,0» 3,0 « |
5 |
To each flask add 5 cmof a solution of ascorbic acid, the solutions mixed and allowed to stand for 5−10 minutes Add 15 cm
of hydrochloric acid (1:1) and in one of the flasks poured 10 cm
of the solution diantipyrylmethane. The solutions in flasks topped up to the mark with water, mix and leave to stand for 40 min.
The optical density of the resulting solutions is measured on the spectrophotometer at a wavelength of 395 nm in a cuvette with a layer thickness of fluid 1 cm or photoelectrocolorimeter with a filter having maximum transmission in the wavelength range of 390−405 nm, choosing the sample chamber, thus to obtain the optimal value of optical density.
As a solution comparison, using aliquot part of the solution, containing all reagents except diantipyrylmethane.
Simultaneously with the analysis of spend control experience for contamination of reagents.
The titanium content found by the calibration schedule.
4.4 Construction of calibration curve
Six glasses with a capacity of 100−150 cmeach poured 1,0; 2,0; 4,0; 6,0; 8,0 and 10,0 cm
standard solution titanium. If the analyzed alloy contains molybdenum, in each glass add a solution of ammonium molybdate in the amount corresponding to the molybdenum content in the analyzed alloy. The seventh glass is used for the reference experiment. Further analysis is carried out as described in section 4.3. The volume aliquota part is 20 cm
. In the measurement of optical density as a solution comparison solution is used in the reference experiment. Build a calibration graph of optical density from the content of titanium in the calibration solutions.
4.5 Processing of results
Mass fraction of titanium , %, is calculated by the formula
where is the mass of titanium in the sample was found in the calibration schedule g;
— the mass of titanium in a control experiment, was found in the calibration schedule g;
— the weight of the portion of alloy, suitable aliquote part of the solution,
Norms of accuracy and norms of control are shown in table 2.
Table 2
| Allowable difference, % | |||||
| Mass fraction of titanium, % |
The error analysis results |
two average results, in different conditions |
two parallel definitions |
three parallel definitions |
the results of the analysis of standard sample and certified values |
| From 0.15 to 0.20 incl. | 0,02 | 0,03 | 0,02 | 0,03 | 0,01 |
| SV. The 0.20 «to 0.50 « | 0,04 | 0,04 | 0,04 | 0,04 | 0,02 |
| «To 0.50» and 1.0 « | 0,05 | 0,06 | 0,05 | 0,06 | 0,03 |
| «1,0» 2,0 « | 0,07 | 0,09 | 0,07 | 0,09 | 0,04 |
| «2,0» 3,0 « | 0,11 | 0,14 | 0,11 | 0,14 | 0,07 |
Annex a (mandatory). ISO 11433−93 Nickel alloys. The determination of titanium. Spectrophotometric method diantipyrylmethane
APPENDIX A
(required)
A. 1 Scope
This standard specifies a spectrophotometric method for determining titanium in the range of from 0.3 to 5.0% () in Nickel alloys. Allowed the spread of this method to the lower boundary of 0.05% of titanium.
The method allows for the determination of titanium in alloys containing tungsten and/or tantalum.
A. 2 Normative references
The present standard features references to the following standards:
GOST 1770−74 laboratory Glassware measuring glass. Cylinders, beakers, flasks, test tubes. Specifications
GOST 7565−81 Iron, steel and alloys. Methods of sampling for chemical analysis
GOST 29169−91 Laboratory glassware. Pipette with one mark
GOST 29251−91 Laboratory glassware. Burette. Part 1. General requirements
A. 3 the essence of the method
The test sample is dissolved in hydrochloric and nitric acids.
Hydrochloric and nitric acid is removed by evaporating the solution to fumes of sulfuric acid. Form a complex compound of titanium with diantipyrylmethane and measure the absorbance of test solution at a wavelength of 390 nm.
A. 4 Reagents
In the analysis using reagents of analytical purity unless otherwise specified, and distilled water or water of equivalent purity.
Hydrochloric acid, =1.18 g/cm
.
Hydrochloric acid, =1.18 g/cm
, a solution of 1:1.
Sulphuric acid =1.84 g/cm
, diluted 1:1. Slowly and with constant stirring, add 100 cm
of sulphuric acid to 100 cm
of water.
Nitric acid, =1,41 g/cm
.
Ammonium hydroxide, solution = 0.88 g/cm
.
Ascorbic acid solution: 20 g of ascorbic acid (CH
O
) dissolved in water, diluted to 200 cm
and mixed.
Acidic potassium sulfate (KHSO).
Oxalic acid solution: 10 g dvukhfaznoi oxalic acid [(COOH)·2H
O] was dissolved in water and diluted to 200 cm
and mixed.
Diantipyrylmethane, solution: 4 g diantipyrylmethane monohydrate (CH
N
O
·H
O) was dissolved in water containing 25 cm
of hydrochloric acid solution 1:1 diluted to 200 cm
and mixed.
Sodium chloride, a solution of 117 g of sodium chloride (NaCl) dissolved in water and diluted to 500 cmand mixed.
Titan, the main standard solution (0,200 g/DM): 0,739 g of potassium titanyl oxalate dvukhfaznogo [K
TiO (C
O
)
·2H
O] was dissolved in water, add 50 cm
of dilute sulfuric acid and evaporated to fumes. Cooled and diluted with water. Transfer the cold solution in a volumetric flask with a capacity of 500 cm
, made up to the mark with water and mix.
Titanium, standard solution (25 cm/DM): 25,0 cm
primary standard solution is transferred to a volumetric flask with a capacity of 200 cm
, add 20 cm
of dilute sulfuric acid. The solution was cooled, made up to the mark with water and mix.
A. 5 Instrument
Conical flasks with a capacity of 125 cm.
Volumetric flasks with a capacity of 50, 100, 200, 250 and 500 cmaccording to GOST 1770.
A pipette with a capacity of 5 cmaccording to GOST 29169.
Microburette with a capacity of 10 cm, graduated with divisions of 0.02 cm
according to GOST 29251.
A molecular absorption spectrometer, allowing to measure the absorbance at a wavelength of 390 nm.
A. 6 Sampling and sample preparation
A. 6.1 Selection and preparation of laboratory samples should be held at regular agreed-upon methods or, in case of disagreement, in accordance with GOST 7565.
A. 6.2 Laboratory test is normal in the form of a milling or drilling swarf and does not require further preparation.
A. 6.3 If it is suspected that the laboratory sample is contaminated with oil or grease in the process of milling or drilling, it must be cleaned by washing in high purity acetone and air dried.
A. 6.4 laboratory If the sample contains particles or pieces of widely varying sizes, the test sample shall be obtained by dividing.
A. 7 analysis
A. 7.1 Preparation of test solution
A. 7.1.1 Mounting the test sample
A portion of the test sample weighed to the nearest 0.1 mg in accordance with table A. 1.
Table A. 1
The expected titanium content, %, ( |
Weight of sample, g |
| From 0.3 to 3.0 incl. | 0,19−0,21 |
| SV. 3,0 «5,0 « | 0,099−0,11 |
A. 7.1.2 Dissolution of the test sample in acid
The test sample is placed in a conical flask with a capacity of 125 cm. Add 10 cm
of hydrochloric acid and 3cm
of nitric acid.
Heated to start the reaction and heating was continued until complete dissolution. If the alloy is not soluble, needs to be an adjustment of the mixture of acids. Add hydrochloric acid to increase its content by 1 cm, and heating was continued to dissolve the test sample.
A. 7.1.3 Preparation of the final test solution
Add 7 cmof dilute sulfuric acid and evaporated the solution until the appearance of white vapors. Cool the contents and act further in accordance with A.
A. of oxalic acid and heated to dissolve the salts. The solution was cooled and alloys not containing tungsten, the analysis continues as described in A.
A. of hydrochloric acid. The solution was cooled, and continue the analysis as described in A.
A. of water, heated to dissolve salts and cooled again. The solution is filtered through a folded filter with filtrowanie ground. The precipitate is washed with warm water. The filtrate is saved. Put the filter with the precipitate in a platinum crucible, incinerated at 800 °C and cooled. Add 1 g acid potassium sulphate, cover the crucible with a platinum lid and gently melted over a flame. The cooled crucible was placed in a beaker with a capacity of 150 cm
, with 20 cm
solution of oxalic acid, and gently heated to dissolve the melt. A platinum crucible is removed and washed. Connect the oxalate solution with the initial filtrate and continue as described in A.
A. 7.1.4 Dilution
A. )
Transfer the test solution (A. , made up to the mark with water and mix.
A. )
Transfer the test solution (A. , made up to the mark with water and mix.
A. 7.2 the development of the painting
A. 7.2.Aliquot 1 part of test solution (A. pipetted and placed into two volumetric flasks with a capacity of 50 cm
each.
A. 7.2.2 In two volumetric flasks add 5.0 cmof dilute hydrochloric acid (solution 1:1), 5.0 cm
of a solution of ascorbic acid and 20 cm
of sodium chloride solution. The solutions were mixed and allowed to stand for a few minutes.
A. 7.2.3 In one of the volumetric flasks add 10,0 cmsolution diantipyrylmethane.
A. 7.2.4 Solution in both flasks topped up to the mark with water and allowed to stand for 40 min.
A. 7.3 Spectrometer measurements
A. 7.3.1 Measure the absorbance of both solutions, obtained in accordance with A. 7.2.4, relative to water as a solution of comparison on a molecular absorption spectrometer at a wavelength of 390 nm in a cuvette of 1 cm.
A. 7.3.2 the Absorbance of the test solution was subtracted from the absorbance of the test solution containing diantipyrylmethane complex.
A. 7.4 Control experience
In parallel with the definition of spend control experience for contamination of reagents using the same procedure of analysis and the same quantities of reagents.
A. 7.5 Calibration
A. 7.5.1 In six volumetric flasks with a capacity of 50 cmeach with microburette put 0; 1,0; 2,0; 3,0; 4,0 and 5,0 cm
standard solution titanium.
A. 7.5.2 Add the diluted solutions of hydrochloric acid, ascorbic acid and sodium chloride as in A.
A. 7.5.Add 3 to solutions of 10.0 cmsolution diantipyrylmethane. The solutions were topped up to the mark with water, mix and leave to stand for 40 min. This series corresponds to 0:0, 0:1, 0:2, 0:25 mg/cm
of titanium.
A.
Subtract the absorbance of the calibration solution not containing titanium, the absorption of the other calibration solutions.
A. 7.5.5 Build a calibration graph of absorbance from the content of titanium in the calibration solutions.
A. 7.6 the Number of definitions
The definition of Titan perform minimally in two parallel batches.
A. 7.7 Control analysis
The method can be controlled by parallel determination of titanium in one or more samples of the same alloy, the titanium content in which it is known, using the same procedure performed.
A. 8 Handling of results
A. 8.1 the Calculation
A. 8.1.1 Determine the concentration of titanium in the test solution (A. 7.3.2) and in a control experiment from the calibration graph (A. 7.5.5).
A. 8.1.2 calculate the titanium content , %, by formula
where is the concentration of titanium in the test solution (A. 8.1.1), µg/cm
;
concentration of titanium in a control experiment (A. 8.1.1), µg/cm
;
— volume of test solution (A.
;
is the mass of the test portion (A. 7.1.1),
A. 8.2 Precision
A. 8.2.1 Laboratory tests
Eleven laboratories in four countries participated in testing this method of analysis, using four samples, the chemical composition of which is given in table A. 2. Each sample was analyzed twice on different days.
Table A. 2 — Chemical composition of test specimens, % ()
| Sample | AI | With | SG | Fe | Hf | Mo | Nb | The | Ti | W | Ni |
| RE-1 | 5,5 | 10 | 9 | - | 1,6 | - | - | 2,6 | 1,5 | 10 | The rest |
| RE-2 | 0,5 | 0,5 | 20 | 18 | - | 3 | 5 | - | 1,0 | - | « |
| RE-3 | 1,9 | 19 | 22 | - | - | - | 1 | 1,4 | 3.7 V | 2 | « |
| RE-4 | 3,0 | 10 | 14 | - | - | 4 | - | - | 5,0 | 4 | « |
A. 8.2.2 Statistical analysis
The results of the interlaboratory test program was evaluated using the average of two results. The data were statistically processed using the criteria of Cochran and Dixon.
A. 8.2.3 Repeatability and reproducibility were calculated with a confidence level of 95%. The results of the statistical analysis are given in table A. 3.
Table A. 3 — Results of statistical analysis
| Standard sample | The average value of the results |
Intralaboratory standard deviation | Interlaboratory standard deviation | Convergence | Reproducibility |
| RE-1 | 1,49 | 0,015 | 0,026 | 0,041 | 0,084 |
| RE-2 | 0,37 | 0,007 | 0,012 | 0,019 | 0,038 |
| RE-3 | 3,69 | 0,018 | 0,026 | 0,050 | 0,089 |
| RE-4 | 5,09 | 0,022 | 0,044 | 0,063 | 0,139 |
A. 9 Interference
If Nickel alloys molybdenum is present, it may be the cause of the overstatement resulting values of Titan (A. 8.1.2) to 0,001% () Ti for each 1,0% (
) Mo.
