GOST 22517-77

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  ГОСТ 22517-77

GOST 22517−77 Hafnium ideny. Specifications (with Amendments No. 1, 2)

GOST 22517−77

Group W51

INTERSTATE STANDARD

HAFNIUM IDENY

Specifications

Hafnium-iodide metal. Technical requirements

GST 17 6536

Date of introduction 1979−01−01

INFORMATION DATA

1. DEVELOPED State of the order of the October revolution, the scientific-research and design Institute of rare metals industry «Giredmet"

INTRODUCED by the Ministry of nonferrous metallurgy of the USSR

2. APPROVED AND put INTO EFFECT by Decision of the USSR State Committee for standards from 10.05.77 N 1169

3. INTRODUCED FOR THE FIRST TIME

4. REFERENCE NORMATIVE AND TECHNICAL DOCUMENTS

5. Limitation of actions taken by Protocol No. 3−93 Interstate Council for standardization, Metrology and certification (ICS 5−6-93)

6. EDITION with Amendments No. 1, 2 approved in April 1983, June 1988 (IUS 8−83, 10−88)

This standard applies to ideny hafnium used for technical and research purposes.

1. MARKS AND TECHNICAL REQUIREMENTS

1.1. Ideny hafnium release GFI1 in accordance with the requirements of this standard with the chemical composition given in table.1.

Table 1

Note. Mass fraction of molybdenum in the hafnium by weight of molybdenum wire embedded in the process should be not more than 0.1%.


(Changed edition, Rev. N 1, 2).

1.2. Ideny hafnium is produced in the form of bars.

1.3. On the surface of the bars must not be of iodine and iodine compounds.

2. ACCEPTANCE RULES

2.1. Ideny hafnium accept parties. The party must consist of bars of the same brand, obtained in one technological cycle and one decorated by a quality document, which must include:

is the trademark or name and trademark of manufacturer;

— name of the product and its brand;

— the net weight of the batch in kilograms;

— the batch number;

— date of manufacture;

— the results of the analysis;

— the number of seats in the party;

— the stamp of the technical control Department;

— the designation of this standard.

The document about quality investing in ground No. 1;

The mass of the party — not more than 30 kg.

2.2. Control of the chemical composition of hafnium is carried out on each rod.

2.1, 2.2. (Changed edition, Rev. N 1).

2.3. Surface quality control on each rod.

2.4. (Deleted, Rev. N 1).

3. TEST METHODS

3.1. From each bar selected spot samples. Selection of point samples produced by the drilling swarf a drill with a diameter of 3.5−4.5 mm to a depth exceeding the radius of the rod by 1−2 mm. Drilling is carried out at a speed that does not cause oxidation (tint). Chips taken from three points: from the ends of the rod at a distance of 10−15 cm from the middle of the rod. Spot samples are combined. The mass of the joint sample shall be not less than 20 g. Chips treated with magnet mix thoroughly and divide into equal parts. One sample sent to the laboratory for analysis, the other stored in the Department of technical control within six months.

Samples placed in glass jars with tight-fitting lids or double bags made of polyethylene film according to GOST 10354, each of which are carefully knotted. Banks stick or put between layers of plastic bags with a label indicating:

— the name of the product and its brand;

— batch number;

— date of sampling;

the stamp of the technical control Department.

3.2. The determination of the amount of hafnium and zirconium

Mass share of the amount of hafnium and zirconium is determined conventionally as the difference between 100% and sum of impurities (without molybdenum).

3.3. The determination of carbon

The carbon content is determined by a gas-volume method according to GOST 9853.3*. Thus as the flux using silicon dioxide according to GOST 9428 brand h. d. a. when the ratio of the mass of sample to the mass flux 1:1; the temperature of combustion of the sample of hafnium 1100−1200 °C.
_______________
* Standards 9853.3−96. — Note the manufacturer’s database.

3.4. Determination of aluminium, iron, silicon, magnesium, manganese, Nickel, titanium and chromium spectral method

The spectral method is preceded by the translation of the sample in the hafnium dioxide.

The method is based on measuring pucherani analytical lines of the elements of the impurities in the arc spectra, obtained by evaporation of a sample of hafnium dioxide mixed with chloride of silver and sulphur from the vents carbon electrode (anode) in the flame of the arc DC. Overall spectrogram simultaneously determine the content of all impurities on a pre-constructed calibration graphs in the coordinate: the difference between pucherani analytical lines and the surrounding background is the logarithm of the concentration of the element in percent.

3.4.1 Equipment, materials and reagents

The diffraction spectrograph DFS-13 with grating of 600 or 1200 lines/mm with a three-lens Achromat lighting system.

A constant current source providing a voltage of at least 200 V and a load of not less than 20 A.

Microphotometer type MF-2.

Spectromancer the SS-18.

Muffle furnace with temperature of 300 to 1200 °C.

Analytical scale.

Libra torsion bar type W-500.

Mortar pestle agate and organic glass.

Box of organic glass.

Devices made of organic glass (racks of electrodes, spatulas, «Nobuaki»).

Cups and crucibles of platinum.

The coals of graphite for high purity spectral analysis 7−3, with a diameter of 6 mm. the Cathode is sharpened to a cone. The diameter of the crater of the anode 3.8 mm, depth 6 mm.

Plate photographic spectral JS1 and JS2.

Silver chloride, H. h

Sulphur elementary OS.h.

Titan ideny.

Silicon dioxide according to GOST 9428, h.d. a.

Iron oxide in the NTD, h.d. a.

Aluminum oxide, anhydrous, for spectral analysis, H. h

Magnesium oxide according to GOST 4526, h.d. a.

Chrome oxide.

Manganese dioxide according to GOST 4470.

Nickel oxide black GOST 4331, h

Hafnium oxychloride, OS.h.

Of hafnium dioxide, OS.h.

Sanitarily sodium (sodium sulfite) in the NTD crystal.

Hydrochloric acid according to GOST 3118.

Sulfuric acid according to GOST 14262, OS.h.

Acetic acid according to GOST 61.

Hydrofluoric acid, OS.h.

Nitric acid according to GOST 11125, OS.h.

The technical rectified ethyl alcohol according to GOST 18300.

The developer according to GOST 10691.1.

Chernovetskiy sodium (sodium thiosulfate) according to GOST 27068, h.d. a.

Fixer; is prepared as follows: 400 g chernovetskogo sodium are dissolved in 400 cmof water (solution A). 300 cmwater dissolve 200 g of crystalline sodium sulphite and the resulting solution is gradually poured with stirring 7 cmof acetic acid (solution B). After 10−15 min, the solution B is poured into solution A and water to bring the liquid volume up to 1 DM.

(Changed edition, Rev. N 2).

3.4.2. Preparation for assay

3.4.2.1. Preparation of the buffer mixture

7 g of silver chloride and 3.5 g of sulfur are mixed in a Styrofoam mortar for 1 h.

3.4.2.2. The preparation of calibration samples

To prepare the set of calibration samples previously prepared two major examples A and B, the mechanical mixing and serial dilution which hafnium dioxide (the Foundation) get a set of working calibration samples. The mixing is carried out in buxe. The basic pattern And consists of oxides of the respective elements, and contains (based on metals) for 8% of iron, silicon, Nickel, aluminum and magnesium, 4% chromium, 0.8% manganese and 55.2% of hafnium. It is prepared by careful grinding of the oxides and mixing in an agate mortar while adding a purified distillation of ethyl alcohol. The total mass of the mixture 3−5 g mixing time is 2−3 h. then the mixture is dried, transferred to a platinum Cup and calcined in a muffle furnace at 1100−1200 °C for 1 h. After cooling again ground in an agate mortar.

The basic pattern B consisting of titanium dioxide and hafnium, respectively, and 2.7 and 97.3% (based on metals), prepared from solutions of the platinum Cup in two steps. Initially, a portion of iodide of titanium in the form of chips is dissolved in hydrofluoric acid with the addition of a small amount of nitric acid, then add sulphuric acid and evaporated until the appearance of sulphuric acid fumes. After this, the solution is cooled and added the calculated amount of solution of oxychloride of hafnium in a minimum volume of water. The common solution is slowly evaporated to dryness. The contents of the Cup is carefully separated from the walls in the center of the Cup and calcined to constant weight in a muffle gradually raising the temperature from 300 to 1200 °C. After cooling, the resulting mixture was transferred into an agate mortar, ground and mixed. Some portions of core samples A and B, taken in the ratio 1:3, mixed in an agate mortar in the same manner as in preparing sample A. the thus obtained sample No. 1 contains 2 percent iron, silicon, Nickel, aluminum, magnesium and titanium, 1% chromium and 0.2% manganese, the rest is hafnium. A portion of sample No. 1 was placed in a mortar made of organic glass and stir, gradually adding three times the amount of dioxide of hafnium and thus obtaining sample No. 2 with a mass fraction of manganese of 0.05%, chromium 0.25% and other impurities at 0.5%. Serial dilution of the source of hafnium dioxide sample, N 2 2−2,5 times to get a set of calibration samples shown in table.2. The samples obtained are dried and placed in a hermetically closed plastic cans.

Table 2

3.4.3. Analysis

A sample of hafnium selected for analysis are treated with hydrochloric acid diluted 1:1 at room temperature for 30 min, washed with water, then with alcohol and dried. In a platinum crucible placed 1 g of shavings and calcined in a furnace at a temperature of 900−1200 °C. complete oxidation of the metal is controlled by the gain: 1 g of metal forms 1,179 g of hafnium dioxide. The oxidized sample is transferred in a Styrofoam mortar, mix and grind to the state of powder for 5 min.

100 mg of each calibration sample and samples mixed by grinding for 5 min in a Styrofoam mortar with 75 mg of a mixture consisting of chloride of silver and sulphur.

The mixture is then placed in the craters of three carbon electrodes 35 mg in each and seal the rod of plexiglass. Before putting the batches of the craters bottom electrode — anode burn for 10−15 seconds in the arc DC 15 A so that the crater depth was reduced to 5 mm. the Upper electrode before applying calcined under the same conditions. The distance between vertically placed electrodes when the arc is 2 mm. Photographing spectra is carried out at a current of 12 A through the diffraction spectrograph DFS-13 (with grating of 600 or 1200 lines/mm) being the illumination system of the slit. The width of the slit of the instrument is 0.02 mm. When photographing spectra in the first order reflection of the grating in the middle of the cutout of the cassette combined with division 290 nm on the drum of wavelengths. In the magazine, respectively, includes two photographic plates: SP-2 in the shortwave and SP-1 in the wavelength regions of the spectrum.

In the intermediate condenser install a cutout intermediate diaphragm to the blackening of analytical lines and the background was in the field of pochernenija emulsion. The exposure time of 45 s,

The resulting spectrograms photometric blackening of analytical lines and the nearby background and calculate their difference . The analytical lines and the interval of the designated impurities shown in table.3. Obtained for each calibration sample three values of the analytical lines and the background, calculate the average difference pucherani and build a calibration curve in the coordinates where  — mass fraction determined by the impurities in the calibration sample, in percent. The values of the same analytical lines and the background spectrum obtained for the unknown samples, find the contents according to the schedule determined by impurities.

Table 3

3.4.4. Processing of the results

The result is the arithmetic mean of three parallel measurements.

The differences between the highest and lowest of the three results of the parallel definitions should not exceed 50% of the average of the three matched definitions.

Discrepancies between the results of the analyses should not exceed 25% of the arithmetic average of the two matched analyses at a confidence level =0,95.

3.5. Spectral method for the determination of zirconium

The method is based on establishing the relationship between the difference pucherani analytical lines of zirconium and hafnium in the spark spectra obtained with the discharge of the high-voltage condensed spark on the graphite pill containing the analyzed hafnium dioxide, and a mass fraction of zirconium in percent. The content of zirconium set for the calibration graphs constructed in the coordinates . Quantitative determination of zirconium in hafnium is carried out by the «method of three standards».

3.5.1. Standard are prepared and analyzed samples

Standard and analyzed the samples prepared in the form of tablets with a diameter and a height of 4 mm, pressed in a steel mold using a hydraulic press at a pressure of 39.2 x 10PA (4,000 kg/cm) of a mixture with the ratio of sample to the cleaned steel graphite 1:3. As elektrogerate tablets use a carbon electrode with an outer diameter of 6 mm, inner (crater) of 4.1 mm and a depth of 1 mm. Upper carbon electrode has a diameter of 4 mm. the distance between the surface of the tablet and the upper end of the electrode is 2 mm.

3.5.2. Apparatus, materials and reagents

Spectrograph ISP-28 or ISP-30 being the illumination system, the slit width of 0.015 mm.

Generator IG-2, enabled by a complex scheme, the capacitance of 0.005 microfarads, the inductance of 0.15 mH, the current in the primary circuit, 1.0 A, analytical interval of 2 mm, the auxiliary gap of 3 mm. Nature of charge — discharge in one half-cycle of current.

Microphotometer MF-2.

Spectromancer the SS-18.

The graphitized carbons for the spectral analysis of the brand-3.

Libra torsion bar type W-500.

Hydraulic press (lab) 5 t

Mold steel for pressing tablets with diameter of 4 mm.

A device for sharpening carbon electrodes.

Mortars and pestles, agate or Jasper.

Metallurgical colloidal graphite (cleaned of impurities).

Plate photographic spectral SP2.

Standard samples of mixtures of the oxides of zirconium and hafnium for spectral analysis N 589−74−592−74 on the State registry of measures and measuring instruments of the USSR.

3.5.3. Analysis

On one photographic plate photographed three times the spectrum of each standard and test sample. Exposure time (45−90 C) is selected depending on the optical spectrograph data of the class used photographic plates so that the blackening of analytical lines was in the region of normal pochernenija for the entire range of the designated concentrations.

3.5.4. Processing of the results

The resulting spectrograms photometric blackening of analytical lines of zirconium and hafnium. The calibration graphs are built in coordinates , using for calculations the mass fraction of Zirconia analytical lines given in table.4.

Table 4

Concentration index (=0) of the calibration graphs built by these pairs of lines equal to, respectively, 0.6 and 0.5%.

The relative standard deviation of a single determination performed on the calibration graph and the results of the photometry of the spectrum of the sample must be 0.05.

Permissible differences between results of two parallel definitions should not exceed 15% of the arithmetic average of these two results. The allowable discrepancies between the two tests should not exceed 10% of the average of the two matched analyses; in both cases =0,95.

3.6. Spectral method for determination of calcium

The method is based on measuring pucherani analytical lines of calcium and of the background in arc spectra obtained by evaporation of a sample of hafnium dioxide in a mixture of chloride of silver in the flame of the arc DC. The content of calcium is determined by calibration graphs constructed in the coordinates: the difference pucherani analytical lines and background () is the logarithm of the concentration of the analyzed element (). Quantitative determination of calcium is carried out by the «method of three standards».

3.6.1. Apparatus, materials and reagents

The diffraction spectrograph DFS-13 with grating of 600 or 1200 lines/mm with a three-lens Achromat illumination system of the slit.

A constant current source providing a voltage not less than 220V and current of at least 20 A.

Microphotometer MF-2.

Spectromancer the SS-18.

Electrodes, carbon, high purity 7−3, with a diameter of 6 m. the Cathode is confined to the cone. The diameter of the crater of the anode 3.8 mm, depth 7 mm.

Libra torsion W-500.

Mortar Plexiglas.

Silver chloride, H. h

Hafnium dioxide with a mass fraction of calcium is not more than 0.001%.

Calcium carbonate according to GOST 4530.

The technical rectified ethyl alcohol according to GOST 18300.

The developer according to GOST 10691.1.

Acetic acid according to GOST 61.

Chernovetskiy sodium (sodium thiosulfate) according to GOST 27068, h.d. a.

Sanitarily sodium (sodium sulfite) in the NTD crystal.

Fixer; is prepared as follows: 400 g chernovetskogo sodium are dissolved in 400 cmof water (solution A); 300 cmwater dissolve 200 g of crystalline sodium sulphite and the resulting solution is gradually poured with stirring 7 cmof acetic acid (solution B). After 10−15 min, the solution B is poured into solution A and water to bring the liquid volume up to 1 DM.

3.6.2. The preparation of calibration samples

The basic calibration sample with a mass fraction of calcium in hafnium 10% prepared by rubbing calcium carbonate to dioxide of hafnium, which are the basis.

Serial dilution obtained of the head of the calibration sample made of a series of calibration samples with a mass fraction of calcium in the hafnium of from 0.01 to 0.2%. All of the calibration samples and the silver chloride is stored in a desiccator.

3.6.3. Analysis

100 mg of each calibration sample and the sample mixed for 5 min with 50 mg of silver chloride; 35 mg of the mixture placed in a recess of the anode and slightly tamped. The sample should not remain on the stands of the electrode.

The scale of the wavelength set to 290 nm division. The width of the slit of a spectrograph 0.020 mm, the distance between the electrodes is 2 mm.

Between the electrodes ignite the arc, fed by a constant current of 15 A. the Shooting is performed in the longwave region of the spectrum on the plate type JS1, exposure time 45 s. the Analysis is performed on three parallel samples (photographed on three of the spectrum of each calibration sample and to each sample). A photographic plate showing and record in standard conditions.

3.6.4. Processing of the results

Based on the results of the photometry data lines of the spectra of the calibration samples and the background close to the lines to build calibration graphs in the coordinate . Chart find the calcium content in the analyzed samples. The result of the analysis taking the arithmetic mean of results of three parallel measurements. In table.5 shows the analytical line and the interval defined by the mass fraction of calcium.

Table 5

The relative standard deviation of a single determination performed on the calibration graph and the results of the photometry of the spectrum of the sample must be 0,15.

The differences between the highest and lowest result of the parallel definitions should not exceed 50% of the arithmetic average of the three matched definitions. The differences between the two analyses should not exceed 25% of the average of the two matched analyses. Confidence probability =0,95.

3.7. Determination of nitrogen content

Nitrogen in metals is contained primarily in the form of nitrides and carbonitrides. Upon dissolution of metals in acids chemically bound nitrogen is transferred into the corresponding ammonium salt. The definition of done acidometry in the presence of the mixed indicator after the distillation of ammonia from alkaline solution (by the method of Kjeldahl).

3.7.1. Apparatus, materials and reagents

Setup for the determination of nitrogen (see drawing).

1 — flask-trap with sulfuric acid; 2 — flask-trap with water; 3 — hot plate;
4 — distillation Kjeldahl flask of the type of heat-resistant glass with a capacity of 500 cm
with ground stopper, equipped with a drip funnel with a tap;
5 — refrigerator 6 — vessel for collecting ammonia; 7 — microburette

Sulfuric acid according to GOST 4204, diluted 1:1, and 0.01 n solution.

Hydrochloric acid according to GOST 3118, diluted 1:1.

Hydrofluoric acid according to GOST 10484.

Sodium hydroxide (caustic soda) according to GOST 4328, h. e. a., the solution is prepared as follows: 400 g of sodium hydroxide dissolved in small portions in 100 cmof water, to the solution was added 2−3 pieces of granulated zinc and a few crystals of copper sulphate, mix and boil for 1 hour adding water to maintain the initial volume. The resulting solution was stored in a tightly sealed plastic jar. The solution is prepared based working with him for 5−6 days.

The technical rectified ethyl alcohol according to GOST 18300.

The mixed indicator is prepared by dissolving 0,062 g methyl red and 0,041 g of methylene blue, produced by NTD, in 100 cmof ethanol. The solution was stored in a flask made of dark glass.

(Changed edition, Rev. N 2).

Bidistilled water, freshly distilled.

The jet pump.

3.7.2. Analysis

A portion of the hafnium with a mass of 1.0 g (powder or thin shavings) is placed in a platinum Cup, poured 20 cmof hydrochloric acid diluted 1:1, 2 cmof hydrofluoric acid and left until complete dissolution of the metal. To the solution was added to 50 cmof water.

Before transferring the solution into the distillation flask pre-cleaning alkali solution and the entire system from traces of ammonia. For this purpose in a distillation flask and pour 50 cmof sodium hydroxide solution and 50 cmof water. The vessel for trapping of ammonia poured 25−30 cmof water and 1−2 drops of the solution mixed indicator. Assemble setup (see drawing). Using leak-tested the system flow of purified air using the water-jet pump. Distilling flask with sodium hydroxide solution heated and boiled for 5−10 min. the Completeness of ammonia removal is controlled by a colour change of the mixed indicator. Add from burette drop by drop of 0.01 n sulfuric acid solution to restore the violet color of the solution. The cleanup is complete, if the purple color persists After 3−5 minutes lye cleaning turn off the hotplate and after a few minutes transfer the solution carefully in small portions through a funnel with stopcock to the distillation flask. The vessel, which was the sample, and a funnel is washed with several small portions of water. The washings poured through the same funnel into the distillation flask. The tap of the funnel is closed and the contents of the flask are thoroughly mixed, gentle circular movements. The flask is heated to boiling and within 45 minutes produce a distillation of ammonia, supporting the continuous boiling of the solution.

As Stripping of ammonia the color of the mixed indicator changes from violet-red to green. After appearance of green colouring quickly poured from the burette drop by drop of 0.01 n sulfuric acid solution before re-appearing purple-red color of the solution.

The Stripping finished, if the solution in the vessel for trapping ammonia continues to maintain a weak purple-red color within 5 min.

Determination of nitrogen, since dissolution of the sample and ending with the Stripping, should be done in the premises, which is not conducted any work with ammonia and its salts.

Simultaneously with the analyzed breakdown through all stages of the analysis carried out control experience, using the same quantities of reagents as in the analysis of the test sample.

3.7.3. Processing of the results

Mass fraction of nitrogen (a) percentage calculated by the formula

,

where  — volume of 0.01 n of sulfuric acid solution consumed for titration of ammonia in the analyzed sample, cm;

 — the volume of 0.01 n of sulfuric acid solution consumed for titration of the solution in the reference experiment, cm;

 — the mass of sample, g;

0,00014 — titer of 0.01 N. the solution HSO, expressed in grams of nitrogen.

The result of the analysis taking the arithmetic mean of results of three parallel measurements.

The allowable divergence between the extreme results of parallel measurements at a confidence level =0.95 does not exceed the values given in table.5.

Table 5

3.8. Determination of molybdenum content

Molybdenum content is determined by the ratio of the mass of molybdenum wire is embedded in the process, the weight of the product obtained.

3.9. The absence of the surface rods of iodine and iodine compounds checked by visual inspection without the use of magnifying devices.

4. MARKING, PACKAGING, TRANSPORTATION AND STORAGE

4.1. Bars godenovo of hafnium form in packs not exceeding 30 kg, Packed in sack paper grades M-70 or M-80 according to GOST 2228, or wrapping paper according to GOST 8273 and placed in stout wooden boxes, type 1 according to GOST 2991 size 700х200х200 mm.

Hafnium ideny designed for long-term storage, are Packed in wooden boxes type III-1 according to GOST 2991.

4.2. Transport marking under GOST 14192.

4.3. To the shipping container is applied to the data on the Packed products:

— name and brand of the product;

— the batch number;

— date of manufacture;

the mark of the technical control Department.

4.4. Products transporterowych by rail in covered wagons small shipments in accordance with the rules of transportation, loading and fastening of goods, operating in railway transport.

The stacking of cargo according to GOST 24597 flat universal pallets according to GOST 9078 by using a steel tape according to GOST 3560 or wire according to GOST 3282 diameter not less than 5 mm.

Overall dimensions and weight of package must not exceed the limits established by GOST 24597.

Allowed transportation by air transport in accordance with goods transportation regulations applied to this type of transport, and postal parcels.

4.5. Ideny hafnium stored in the manufacturer’s packaging in covered warehouses in the absence of vapors of acids and alkalis.

Sec. 4. (Changed edition, Rev. N 1).