GOST 12365-84
GOST 12365−84 Steel alloyed and high alloy. Methods for determination of zirconium
GOST 12365−84
Group B39
STATE STANDARD OF THE USSR
STEEL ALLOYED AND HIGH-ALLOYED
Methods for determination of zirconium
Steels alloyed and highalloyed.
Methods for the determination of zirconium
AXTU 0809
Valid from 01.01.85
to 01.01.95*
______________________________
* Expiration removed
Protocol N 4−93 inter-state Council
for standardization, Metrology and certification
(IUS N 4, 1994). — Note the manufacturer’s database.
DEVELOPED by the Ministry of ferrous metallurgy of the USSR
PERFORMERS
N. P. Liakishev, V. T. Ababkov, S. M. Novokshenova, M. S. Dimova, T. F. Rybin, V. D. Shuvalov
INTRODUCED by the Ministry of ferrous metallurgy of the USSR
Member Of The Board V. G. Antipin
APPROVED AND put INTO EFFECT by decision of the USSR State Committee on standards of 19 January 1984, N 234
REPLACE GOST 12365−66
This standard specifies the methods for determination of zirconium:
direct photometric reagent kylinalove orange when the mass fraction of zirconium from 0.10 to 1.0% for steels containing no molybdenum and niobium;
the photometric reagent, arsenazo III with mass fraction of zirconium from 0.01 to 0.50%, with prior separation of zirconium from interfering elements;
gravimetric phosphate in a mass fraction of zirconium from 0.10 to 1.0%.
1. GENERAL REQUIREMENTS
1.1. General requirements for methods of analysis GOST 20560−81.
2. PHOTOMETRIC METHOD WITH REAGENT KYLINALOVE ORANGE
2.1. The essence of the method
The method is based on formation of colored complex compounds of zirconium (IV) with selenology orange in the sulfuric acid solution with molar concentration of equivalent of 0.3−0.4 mol/DMand measuring the light absorption of the solution at a wavelength of 540 nm. Iron (III) reduced to iron (II) ascorbic acid.
To account for the influence of related elements of the optical density of the colored solution with a complex compound of zirconium is measured relative to the same solution containing Trilon B.
2.2. Apparatus, reagents and solutions
Spectrophotometer or photoelectrocolorimeter.
Hydrochloric acid by the GOST 3118−77, diluted 1:1 with the mass concentration equivalent of 1 mol/DM.
Nitric acid GOST 4461−77.
A mixture of hydrochloric and nitric acids in the ratio 3:1; prepared before use.
Sulfuric acid GOST 4204−77 and diluted 1:10, 1:100.
Hydrofluoric acid according to GOST 10484−78.
Ascorbic acid, a solution with a mass concentration of 100 g/DM.
Selenology orange, mark «Chemapol», a solution with a mass concentration of 1 g/ DM.
Salt is the disodium Ethylenediamine-N, N, N', N'-tetraoxane acid, 2-water (Trilon B) according to GOST 10652−73, a solution with a mass concentration of 10 g/DM.
Ammonium chloride according to GOST 3773−72, a solution with a mass concentration of 30 g/DM.
Potassium preservatory according to GOST 7172−76.
Zirconium metal, ideny.
Zirconium sulfate, standard solution with the mass concentration of the zirconium of 0.001 g/cm: charge metal zirconium of 0.1 g was placed in a platinum Cup and dissolved in 10 cm
hydrofluoric acid when heated. The solution is oxidized with 2−3 drops of nitric acid. After cooling, the contents of the Cup poured 10 cm
of sulphuric acid and evaporated until the appearance of sulphuric acid fumes.
The solution was cooled, carefully wash off the walls of the Cup with water and again evaporated to fumes of sulfuric acid. After cooling in a Cup add 25−30 cmof water and dissolved salt. The solution was transferred to a volumetric flask with a capacity of 100 cm
, made up to the mark with water and mix.
Zirconium sulfate, standard solution with a mass concentration of zirconium of 0.0001 g/cm: 10 cm
standard solution of zirconium and the mass concentration of 0.001 g/cm
transferred to a volumetric flask with a capacity of 100 cm
, made up to the mark with water and mix; prepare before use.
Zirconium (IV) oxychloride 8-water, a standard solution with a mass concentration of the zirconium of 0.001 g/cm: linkage 0,8832 g of zirconium oxychloride were placed in a glass with a capacity of 250−300 cm
, flow 40 cm
of hydrochloric acid (1:1) and dissolve in low heat. The solution was transferred to a volumetric flask with a capacity of 250 cm
, made up to the mark with water and mix.
Check the mass concentration of a standard solution of zirconium oxychloride: 25 cmsolution is placed in a beaker with a capacity of 250−300 cm
and conduct the deposition of zirconium hydroxide with ammonia. Solution and the precipitate was allowed to stand for 20−25 min, then the precipitate was filtered off on filter «white ribbon» and washed 4−5 times with a solution of ammonium chloride.
The filter with precipitate was placed in a calcined to constant weight porcelain or platinum crucible, dried, incinerated and calcined at 1000−1050 °C to constant weight. Simultaneously conduct control experience for contamination of reagents.
The mass concentration of a solution of zirconium oxychloride (), expressed in g/cm
of zirconium, calculated by the formula
where is the mass of the crucible with the precipitate of zirconium dioxide, g;
— weight of crucible without sediment, zirconium dioxide, g;
— the mass of the crucible with the sediment in a control experiment, g;
— weight of crucible without the sediment in a control experiment, g;
0,7403 — the ratio of zirconium dioxide to zirconium; — the volume of solution of oxychloride of zirconium taken for analysis, cm
.
Zirconium (IV) oxychloride, 8-water, a standard solution with a mass concentration of zirconium of 0.0001 g/cm; 10 cm
of a standard solution of zirconium and the mass concentration of 0.001 g/cm
transferred to a volumetric flask with a capacity of 100 cm
, made up to the mark with hydrochloric acid with the mass concentration equivalent of 1 mol/l
and stirred; prepared prior to use.
2.3. Analysis
2.3.1. A sample of steel weighing 0.25 g were placed in a glass or flask and is dissolved by heating in 30−50cmof hydrochloric acid and 5−7 cm
of nitric acid. If the sample is not soluble in hydrochloric acid with addition of nitric acid, the portion dissolved in 30−50 cm
of a mixture of hydrochloric and nitric acids.
The beaker or flask is cooled and poured sulphuric acid (1:1) in an amount shown in table.1, and evaporate the solution until fumes of sulfuric acid.
The solution was cooled, washed away the walls of the beaker or flask with water and again evaporated to fumes of sulfuric acid.
Table 1
Mass fraction of zirconium, % |
|
|
|
The weight of the portion of steel in aliquote part of the solution, g |
From 0.10 to 0.50 incl. |
20 |
200 |
10,0 |
0,0125 |
| SV. Of 0.50 to 0.70 |
25 | 250 | 10,0 | 0,01 |
| SV. Of 0.70 to 1.00 |
50 | 250 | 5,0 | 0,005 |
The contents of the beaker or flask is cooled, poured 80−120 cmof water and heated to dissolve the salts.
The precipitate is filtered off, the filter «white ribbon» and the filter residue was washed 4−5 times with hot water. The filtrate and washings retain (primary filtrate).
The filter with precipitate was placed in a platinum crucible, dried, incinerated and calcined at 700−800 °C. To the contents of the crucible, add a few drops of water, 2−3 drops of sulphuric acid, 2−3 cmhydrofluoric acid and evaporated to remove sulfuric acid. The residue was calcined at 700−800 °C and fused with 1 g of potassium peacemaking. The melt is cooled, dissolved in 20−30 cm
of sulphuric acid (1:100), the solution was filtered through a filter «white ribbon» in a glass or flask with the main filtrate.
The combined filtrates is evaporated and transferred in a volumetric flask with capacity of depending on the mass fraction of zirconium is determined by the table.1, made up to the mark with water and mix.
Two aliquote part of the obtained solution in accordance with the table.1 is placed into two volumetric flasks with a capacity of 50 cmeach.
The solutions in flasks, heated to 70−80 °C, cool, add 2 cmof ascorbic acid solution and mix thoroughly. After 5 minutes in each flask poured 20 cm
of water into one of the flasks pour 2 cm
of the solution Trilon B in each flask from microburette add 2cm
of a solution kylinalove orange. The contents of the flask topped up to the mark with water and mix. The solution in the flask with Trilon B is solution comparisons.
After 20−25 min, the optical density of the solution measured on a spectrophotometer at a wavelength of 540 nm or photoelectrocolorimeter with a filter having a maximum transmittance at a wavelength (540±10) nm in a cuvette with the thickness of the absorbing layer 30 mm.
Simultaneously with the execution of the analysis carried out control experience for contamination of reagents.
The content of zirconium find the calibration schedule subject to amendments the reference experiment.
2.3.2. Construction of calibration curve
To build a calibration curve of seven beakers or flasks were placed 0.25 g of carbonyl iron or steel, similar in composition to the analyzed and do not contain zirconium. Six of cups or flasks sequentially poured 2,5; 5,0; 7,5; 10,0; 12,5 and 15.0 cmof a standard solution of zirconium and the mass concentration of 0.0001 g, which corresponds to 0,0000125; 0,000025; 0,0000375; 0,00005; 0,0000625 and 0,000075 g Zirconia 50 cm
fotometricheskogo solution. The seventh beaker or flask serves for the control experience.
All beakers or flasks go for 30−50cmof hydrochloric acid, 5−7 cm
of nitric acid and further analysis is carried out as specified in clause
, aliquot part of the solution are taken at 10 cm
.
From the values of optical density of analyzed solutions is subtracted the value of optical density in the reference experiment. According to the obtained values of optical density and the respective concentrations of the zirconium building a calibration curve.
2.4. Processing of the results
2.4.1. Mass fraction of zirconium () in percent is calculated by the formula
where is the mass of zirconium was found in the calibration schedule g;
the weight of steel, suitable aliquote part of the solution,
2.4.2. Allowable absolute discrepancies in the results of parallel measurements at p = 0.95 does not exceed the permissible values given in table.2.
Table 2
Mass fraction of zirconium, % |
Allowable absolute differences, % |
From 0.01 to 0 020 incl. |
0,005 |
| SV. 0,02 «0,050 « |
0,007 |
| «0,05» 0,10 « |
0,010 |
| «To 0.10» to 0.20 « |
0,015 |
| «To 0.20» and 0.40 « |
0,025 |
| «And 0.40» to 1.00 « |
0,04 |
3. PHOTOMETRIC METHOD WITH THE REAGENT, III ARSENAZO
3.1. The essence of the method
The method is based on formation of colored complex compounds of zirconium, arsenazo III in hydrochloric acid solution with molar concentration of equivalent of 2 mol/DMand measurement of optical density at a wavelength of 665 nm. The Zirconia is pre-separated from chromium, molybdenum, tungsten deposition with ammonia, using as a collector of iron hydroxide. Iron (III) reduced to iron (II) ascorbic acid.
3.2. Equipment, reagents, solutions
Spectrophotometer or photoelectrocolorimeter.
Hydrochloric acid by the GOST 3118−77, diluted 1:1, 1:5 with molar concentration of equivalent of 2 mol/DM.
Nitric acid GOST 4461−77.
A mixture of hydrochloric and nitric acids in the ratio 3:1, prepare before use.
Sulfuric acid GOST 4204−77, diluted 1:100.
The acid chloride.
Hydrofluoric acid according to GOST 10484−78.
Potassium preservatory according to GOST 7172−76.
Ascorbic acid according to GOST 4815−76, a solution with a mass concentration of 100 g/DM.
Tartaric acid according to GOST 5817−77, a solution with a mass concentration of 150 g/DM.
Ammonia water according to GOST 3760−79.
Gelatin GOST 11293−78, a solution with a mass concentration of 10 g/DM.
Salt is the disodium Ethylenediamine-N, N, N', N'-tetraoxane acid, 2-water (Trilon B) according to GOST 10652−73, a solution with a mass concentration of 10 g/DM.
Arsenazo III, the solution with a mass concentration of 1 g/DM; linkage, arsenazo III equal to 0.1 g was dissolved with heating to 50−60 cm
of water, the solution was transferred to volumetric flask with a capacity of 100 cm
, add 15 cm
of hydrochloric acid (1:5) and adjusted to the mark with water. The solution was stirred and filtered through a filter «white ribbon»; cook before eating.
Standard solutions of zirconium and the mass concentration of 0.001 and 0.0001 g/cmis prepared from a metallic zirconium oxychloride or zirconium, as mentioned in paragraph 2.2.
A standard solution of zirconium and the mass concentration of 0.00005 g/cm: 10 cm
solution of zirconium and the mass concentration of 0.001 g/cm
transferred to a volumetric flask with a capacity of 200 cm
, made up to the mark with water and mix; cook in front of u
consumption.
3.3. Analysis
3.3.1. A sample of steel weighing 0.25 g were placed in a glass or flask and is dissolved by heating in 30−50cmof hydrochloric acid and 5−7 cm
of nitric acid. If the sample is not soluble in hydrochloric acid with addition of nitric acid, the portion dissolved in 30−50 cm
of the mixture of acids.
The solution was poured 15−20 cmof perchloric acid and heated until complete oxidation of the chromium ions (the solution becomes orange in color). In the absence of ions the solution is heated for 5−7 min. after starting your selection, vapor perchloric acid.
The solution was cooled, poured 90−100 cmof water and heated to dissolve the salts.
The precipitate is filtered off, the filter «white ribbon», and the filter residue thoroughly washed with hot water at least 5−6 times to completely remove the ions of perchloric acid. The filtrate and washings retain (primary filtrate).
The filter with precipitate was placed in a platinum crucible, dried, incinerated and calcined at 700−800 °C. To the contents of the crucible, add a few drops of water, 2−3 drops of sulphuric acid, 2−3 cmhydrofluoric acid and evaporated to remove vapors of sulfuric acid.
The residue was calcined at 700−800 °C and fused with 1 g of potassium peacemaking. The melt is cooled, dissolved in 20−30 cmof sulphuric acid (1: 100) and the obtained solution was filtered by adding the filtrate to the main filtrate.
To the obtained solution poured ammonia until the precipitation of iron hydroxide and 2−3 cmin excess. Solution and the precipitate was heated to boiling and allowed to stand in a warm place for 10−15 min.
The precipitate was filtered off on filter «white ribbon» and the filter residue thoroughly washed at least 6−8 times with hot water to remove ions of perchloric acid.
The filter cake is dissolved in 80 cmof hot hydrochloric acid (1:1) with a mass fraction of zirconium up to 0.10% or 200 cm
for the mass concentration of zirconium in excess of 0.10%. The filter is washed with hot water, collecting the solution in a glass, which conducted the deposition.
The solution was boiled down to 70−80 cmor cm 200−220
depending on capacity of volumetric flasks, used in the next stage of the analysis. A glass or flask with the solution was cooled. The solution was transferred to a volumetric flask with a capacity of 100 cm
for the mass concentration of zirconium up to 0.10% or less in a volumetric flask with a capacity of 250 cm
for the mass concentration in excess of 0.10%, made up to the mark with water and mix.
In two volumetric flasks with a capacity of 50 cmeach, taken at 20 cm
of the resulting solution. The contents of the flask are heated to 70−80 °C, cooled and poured into each flask 2 cm
of a solution of ascorbic acid. The solutions are thoroughly mixed, after 5 minutes in each flask pour 3 cm
of a solution of gelatin. Then one flask is poured 1 cm
of the solution Trilon B, and each of the flasks add 5 cm
of the solution, arsenazo III. The contents of the flask topped up to the mark with water and mix. The solution in the flask with Trilon B is used as a solution of comparison.
After 20−25 min, the optical density of the solution measured on a spectrophotometer at a wavelength of 665 nm or photoelectrocolorimeter with a filter having maximum transmission at the wavelength (665±10) nm in a cuvette with the thickness of the absorbing layer is 50 mm.
Simultaneously with the execution of the analysis carried out control experience for contamination of reagents.
The content of zirconium find the calibration schedule subject to amendments the reference experiment.
3.3.2. Construction of calibration graphs
To construct the calibration curve for the mass concentration of zirconium from 0.01 to 0.10% to the seven beakers or flasks were placed 0.25 g of carbonyl iron or steel, similar in composition to the analyzed and do not contain zirconium. Six glasses consistently poured 0,5; 1,0; 2,0; 3,0; 4,0 and 5,0 cmstandard solution of zirconium and the mass concentration of 0.00005 g/cm
, which corresponds to 0,000005; 0,00001; 0,00002; 0,00003; 0,00004; 0,00005 g Zirconia 50 cm
fotometricheskogo solution. The seventh beaker or flask serves for the control experience.
To construct the calibration curve in mass fraction of zirconium from 0.10 to 0.50% of six beakers or flasks were placed 0.25 g of carbonyl iron or steel, similar in composition to the analyzed and do not contain zirconium. In five glasses poured consistently 2,5; 5,0; 7,5; 10,0 and 12,5 cmof a standard solution of zirconium and the mass concentration of 0.0001 g/cm
, which corresponds to 0,00002; 0,00004; of 0.00006; and 0,00008 0,0001 g Zirconia 50 cm
fotometricheskogo solution. The sixth beaker or flask serves for the control experience.
All beakers or flasks go for 30−50cmof hydrochloric acid at 5−7 cm
of nitric acid and further analysis is carried out as specified in clause 3.3.1
From the values of optical density of analyzed solutions is subtracted the value of optical density in the reference experiment. According to the obtained values of optical density and the respective concentrations of the zirconium building a calibration curve.
3.4. Processing of the results
3.4.1. Mass fraction of zirconium () in percent is calculated by the formula
where is the mass of zirconium was found in the calibration schedule g;
the weight of steel, suitable aliquote part of the solution,
3.4.2. Allowable absolute discrepancies in the results of parallel measurements at p = 0.95 does not exceed the permissible values given in table.2.
4. GRAVIMETRIC METHOD
4.1. The essence of the method
The method is based on the deposition of zirconium in the form of a phosphate of zirconium and calcining it to pyrophosphate.
From interfering elements zirconium pre-separated by cupferron.
4.2. Reagents and solutions
Hydrochloric acid by the GOST 3118−77 and diluted 5:95.
Nitric acid GOST 4461−77.
A mixture of hydrochloric and nitric acids in the ratio 3:1.
Sulfuric acid GOST 4204−77 and diluted 1:4, 1:9.
N-nitroso-N-phenylhydroxylamine ammonium salt (cupferron) according to GOST 5857−79, the solution with mass concentration 60 g/DM.
The washing liquid: 1 DMwater poured 10 cm
of sulphuric acid, cooled and poured 20 cm of a solution of cupferron.
Ammonium disodium phosphate according to GOST 3772−74, a solution with a mass concentration of 100 g/DM.
Ammonium nitrate according to GOST 3761−65, a solution with a mass concentration of 50 g/DM.
Potassium preservatory according to GOST 7172−76.
Hydrogen peroxide according to GOST 10929−76, solutions with a mass concentration of 30 and 300 g/DM.
The anhydrous sodium carbonate according to GOST 83−79, and the solution with a mass concentration of 50 g/DM.
4.3. Analysis
The weight became 2 g when the mass fraction of zirconium from 0.10 to 0.50% or 1 g for the mass concentration from 0.50 to 1.0% is placed in a flask or beaker with a capacity of 250−300 cmand dissolved by heating in 30−50cm
of hydrochloric acid. Then pour 5−7 cm
of nitric acid and boil to remove oxides of nitrogen. If the steel does not dissolve in hydrochloric acid by oxidation with nitric acid, the portion dissolved in the mixture of acids.
The contents of the flask or beaker is cooled, poured 10 cmof sulphuric acid and evaporated until the appearance of sulphuric acid fumes. After cooling, the solution was poured 150−170 cm
of water and dissolved salts when heated.
The precipitate is filtered off, the filter «white ribbon» containing ashless paper pulp. The filter cake was washed 4−5 times with hot hydrochloric acid (5:95). The filtrate and washings retain (primary filtrate).
The filter with precipitate was placed in a platinum crucible, dried, incinerated and calcined at 800−900 °C. the Contents of the crucible fused with 3−4 g of sodium carbonate at 1000−1100 °C for 20 min.
The melt is cooled, dissolved in 50−70 cmof water, the solution boiled for 10−15 min, filtered the insoluble residue on the filter «blue ribbon» containing a small amount of ashless paper pulp and washed 6−8 times with hot sodium carbonate solution. The precipitate is dried, calcined and fused with 1−2 peacemaking potassium at 800−850 °C.
The smelt is leached in 50 cmof sulphuric acid (1:9) and the solution attached to the main filtrate.
The combined solution was cooled to 12−15 °C, add a small amount of ashless paper pulp and pour the solution cupferron, stirring constantly, until beginning of deposition of the brown precipitate of iron cupferron, which indicates the completeness of separation of cupferron zirconium. The residue was allowed to stand for 30−35 min and filtered on the filter «white ribbon». Precipitate was washed 5−6 times with wash liquid, placed in a porcelain crucible, dried, incinerated and calcined for 20−30 minutes at 800−850 °C.
The contents of the crucible fused with 2−3 g of potassium peacemaking at 800−850 °C and cooled. The smelt is dissolved by heating in 100 cmof sulphuric acid (1:4).
The solution was filtered into a glass with a capacity of 400−500 cmthrough the filter «white ribbon». The filter was washed 4−5 times with hot water and dilute the solution with water to 200 cm
.
To the obtained solution add 2−5 cmof hydrogen peroxide solution with the mass concentration of 300 g/DM
, 20 cm
of a solution of phosphate of ammonia, stirred and maintained at 65−70 °C for 3 hours, watching over the preservation of the excess of hydrogen peroxide in solution.
In the analysis of steels containing titanium, the precipitation of the zirconium phosphate of ammonium is carried out without the addition of hydrogen peroxide.
The precipitate of zirconium phosphate is filtered off on the filter «blue ribbon» containing a small amount of ashless paper pulp and washed 10−12 times with cold ammonium nitrate solution. The filter with precipitate was placed in a porcelain crucible, dried, incinerated and calcined at 950−1000 °C for 20−25 min. the Contents of the crucible fused with 4−5 g of potassium peacemaking. The smelt is dissolved in 100 cmof sulphuric acid (1:4) and precipitated zirconium phosphate ammonium as described above.
Filter the precipitate of zirconium phosphate is placed in a calcined to constant weight and weighed porcelain crucible, dried, incinerated and calcined at 950−1000 °C to constant weight.
Simultaneously with the execution of the analysis carried out control experience for contamination of reagents.
4.4. Processing of the results
4.4.1. Mass fraction of zirconium () in percent is calculated by the formula
where is the mass of the crucible with the precipitate of zirconium pyrophosphate, g;
— weight of crucible without the precipitate of zirconium pyrophosphate, g;
— the mass of the crucible with the precipitate obtained from the reference experiment, g;
— weight of crucible without the sediment in a control experiment, g;
0,3440 — pyrophosphate ratio of zirconium to zirconium;the weight of steel,
4.4.2. Allowable absolute discrepancies in the results of parallel measurements at p = 0.95 does not exceed the permissible values given in table.2.
