GOST 9853.21-96
GOST 9853.21−96 Titan spongy. Methods for determination of hydrogen
GOST 9853.21−96
Group B59
INTERSTATE STANDARD
TITANIUM SPONGE
Methods for determination of hydrogen
Sponge titanium. Methods for determination of hydrogen
ISS 77.120*
AXTU 1709
_______________
* In the index «National standards» 2008 ACS 77.120,
Note the manufacturer’s database.
Date of introduction 2000−07−01
Preface
1 DEVELOPED by the Interstate technical Committee for standardization MTK 105, Ukrainian research and design Institute of titanium
SUBMITTED to the State Committee of Ukraine for standardization, Metrology and certification
2 ADOPTED by the Interstate Council for standardization, Metrology and certification (Protocol No. 9 dated April 12, 1996)
The adoption voted:
| The name of the state | The name of the national authority standardization |
| The Republic Of Azerbaijan | Azgosstandart |
| The Republic Of Belarus | Gosstandart Of Belarus |
| The Republic Of Kazakhstan | Gosstandart Of The Republic Of Kazakhstan |
| Russian Federation | Gosstandart Of Russia |
| Turkmenistan | The main state inspection of Turkmenistan |
| Ukraine | Gosstandart Of Ukraine |
3 Resolution of the State Committee of the Russian Federation for standardization and Metrology dated 19 October 1999 No. 353-St inter-state standard GOST 9853.21−96 introduced directly as state standard of the Russian Federation from July 1, 2000.
4 INTRODUCED FOR THE FIRST TIME
1 Scope
This standard establishes, chromatographic (when the mass fraction of hydrogen is from 0.001% to 0.1%) and spectral (at a mass fraction of hydrogen from 0.002% to 0.1%) methods for determination of hydrogen in titanium sponge according to GOST 17746.
Chromatographic method based on high temperature extraction of hydrogen from the titanium in a stream of nitrogen followed by its determination using thermo-chemical detector.
The spectral method is based on excitation spectrum samples the low-voltage pulsed discharge with the subsequent registration of the intensities of the spectral lines of hydrogen photographic or photoelectric method and the determination of the mass fraction of hydrogen, with calibration parameters.
2 Normative references
The present standard features references to the following standards:
GOST 8.315−97 State system for ensuring the uniformity of measurements. The standard samples. The main provisions, the order of development, certification, approval, registration and application
GOST 83−79 Sodium carbonate. Specifications
GOST 195−77 Sodium sanitarily. Specifications
GOST 244−76 Sodium thiosulfate crystal. Specifications
GOST 859−78* Copper. Brand
______________
* On the territory of the Russian Federation GOST 859−2001, here and hereafter. — Note the manufacturer’s database.
GOST 3022−80 Hydrogen technical. Specifications
GOST 3956−76 Silica gel technical. Specifications
GOST 4160−74 Potassium bromide. Specifications
GOST 6709−72 distilled Water. Specifications
GOST 9245−79 Potentiometers DC measurement. General specifications
GOST 9293−74 (ISO 2435−73) Nitrogen gaseous and liquid. Specifications
GOST 13033−84 State system of industrial devices and automation means. Instrumentation and automation electrical analog. General specifications
GOST 14261−77 hydrochloric Acid of high purity. Specifications
GOST 17433−80 Industrial purity. Compressed air. Classes of contamination
GOST 17746−96 spongy Titanium. Specifications
GOST 18300−87 ethyl rectified technical. Specifications
GOST 19627−74 Hydroquinone (paradoxians). Specifications
GOST 21241−89 Tweezers medical. General technical requirements and test methods
GOST 22056−76 insulating Tube of PTFE 4D and 4ДМ. Specifications
GOST 23780−96 spongy Titanium. Methods of sampling and sample preparation
GOST 25086−87 non-ferrous metals and their alloys. General requirements for methods of analysis
GOST 25664−83 Metol (4-methylaminophenol sulfate). Specifications
GOST 28498−90 Thermometers liquid-in-glass. General technical requirements. Test methods
GOST 28723−90 the high-speed flow Meters, electromagnetic and vortex. General technical requirements and test methods
GOST 29298−92* cotton and mixed household. General specifications
______________
* On the territory of the Russian Federation GOST 29298−2005, here and hereafter. — Note the manufacturer’s database.
3 General requirements
3.1 General requirements for methods of analysis GOST 25086.
3.2 Selection and preparation of samples is carried out according to GOST 23780.
3.3 Mass fraction of hydrogen find in two batches.
3.4 the construction of calibration curve each point is based on the average of the results of four measurements.
4 Chromatographic method
4.1 measuring instruments, accessories and reagents
The gas chromatograph of the type «Gaschrom-3101», equipped with a thermo-chemical detector, or similar device.
Micro-doser gas containing graded doses from 1 to 18 mm(kit with chromatograph «Gazprom-3101» as a separate dispenser).
Rod crane-dispenser containing the calibration doses from 0.125 to 0.5 cm(completed with a chromatograph «Gazprom-3101»).
Automatic digital meter parameters of chromatographic peaks (integrator) according to the current normative document.
Automatic potentiometer KSP-4 according to GOST 9245.
Electric tubular socket type SUOL.
Type autotransformer Latr-1M.
Millivoltmeter-type M-45300 thyristor regulator according to GOST 13033.
Stopwatch, class 3, graduation of the second scale 0.2 s according to the current normative document.
Flowmeter soap-foam according to GOST 28723.
The reactor quartz from quartz of double melting (figure 1). The wall thickness shall not be less than 1 mm.
Figure 1. The reactor quartz from quartz of double melting
Figure 1
The quartz capsule (figure 2).
Figure 2. Capsule quartz
Figure 2
Connection for PTFE reactor (figure 3), consisting of: 1 fitting, Union nut 2, rubber gasket 3, the clutch 4, a quartz reactor flange 5.
Figure 3. Connection for PTFE reactor
Figure 3
Regulator pressure: 
The regulator of the gas flow from 20 to 1000 cm/min.
A set of soil sieves, fractions from 0.1 to 2.0 mm.
Pipe: polyvinyl chloride (5,0−6,0)/1,0 according to the current normative document.
PTFE tube (chromatography column) according to GOST 22056, (3,5−4,0)/0,6,
3 m.
Nitrogen gas RF GOST 9293.
Hydrogen grade B according to GOST 3022.
The air is compressed according to GOST 17433 or air line with the air pressure not lower than 0.5 MPa.
Ethanol (ethyl alcohol) rectified technical GOST 18300.
The activated carbon (for gas purification) according to the current normative document.
The silica gel fraction of 0.5 to 1.0 mm (for gas purification) according to GOST 3956.
Zeolite CAA (5A), the fraction from 0.25 to 0.50 mm.
Zeolite NaX (13X), fraction from 0.5 to 1.0 mm (for gas cleaning).
Hydrochloric acid according to GOST 14261, diluted 1:4.
Standard samples of titanium GOST 8.315.
Calibration gas mixtures with certified volumetric proportion of hydrogen.
4.2 preparation for measurement
The test portion of the titanium should be in the form of slices or chips of a thickness not exceeding 0.5 mm and a length of 1.0 mm, obtained by mechanical treatment of the sample.
Prior to analysis of the quartz reactor, and the capsules are washed with a solution of hydrochloric acid, with water until neutral environment and ethanol. The reactor and capsules dried and calcined at a temperature of 1373 K in a muffle or tubular furnace. In the reactor with the wide collar proshlifovat to obtain a flat surface.
Zeolites CAA and NaX pre-regenerated by heating in a vacuum, raising the temperature at a speed of 50−60 deg/min up to 653 K, and kept at this temperature for 3−4 h.
Installation assemble according to figure 4. The device for determination of hydrogen in titanium consists of: filters nitrogen 1A, 2A, 3A; of air filters 1B, 2B, 3B, respectively, are filled activated charcoal, silica gel and molecular sieves NaX; flow controllers nitrogen 4A; pressure regulators air 4B; microdontia 5; rod of the valve 6; 7 reactor; 8 furnace; 9 chromatographic column filled with zeolite CAA (5A); thermochemical detector 10 with two chambers; the potentiometer 11 and the integrator 12.
Figure 4. The device for determination of hydrogen in titanium
Figure 4
Nodes installation connect the PVC pipe. The node connecting the reactor to the installation assemble in accordance with figure 3. With the help of pressure regulators and flow 4B and 4A (figure 4) install air flow in both lines at 60 cm/min, the nitrogen flow rate in both lines at 60 cm
/min the Temperature of heating furnace 8 and the quartz reactor 7 set (1323±50) K. the Junctions of the reactor should not be located in the heating zone. Gas chromatograph, potentiometer, integrator include according to the user’s manual. Set the current bridge detector 150 mA. Tightness test by clamping the output of carrier gas and supplying the working pressure on installation. In the case of a drop in operating pressure recorded by the manometer, the connection nodes opilivayut soap solution. Eliminate gas leakage.
4.3 measurements
4.3.1 the weight and mass of 0.03−0.1 g was placed in a quartz capsule. The reactor is placed in a horizontal plane and open. Using tweezers according to GOST 21241 quartz capsule was placed in the reactor and close by screwing the cap nut on the coupling. After 4−5 minutes turn the reactor around the axis by 90° (wide end of the reactor is at the top) capsule with the suspension is introduced into the heating zone. The chromatographic peak of hydrogen recorded on the tape recording potentiometer. The area of the chromatographic peak of cheated by using the integrator. Identification is performed by comparing absolute retention time of hydrogen in the sample, standard sample and calibration gas mixtures used in the calibration.
A control experiment is conducted under the same conditions with an empty quartz capsule.
4.3.2 According to the obtained values of the area of the chromatographic peak of hydrogen in a sample and the values of the control experiment calculate the mass percent of hydrogen in the sample.
4.3.3 Graduation the installation is carried out in pure hydrogen (99.99%) or calibration gas mixtures with certified volumetric proportion of hydrogen, while using micro-doser containing graded doses of N 5−7, and rod crane-dispenser with replaceable calibration doses from 0.125 cmand above. After the installation mode and achieve a stable zero line on the chart tape recording of the potentiometer to the «entrance» of the calibration gas microdosage using PVC pipe is the supply of hydrogen (from the tank, out of line).
The calibration is carried out (when the mass fraction of hydrogen is from 0.001% to 0.02%), consistently dosing hydrogen microdonation using N doses 5, 6, 7, which corresponds to 8; 11; 17 mmof hydrogen, and stalowym tap-dispenser, using doses of 0.125 and 0.25 cm
. When the mass fraction of hydrogen from 0.02% to 0.10%, the calibration is carried out using rod of valve, using doses of 0,125; 0,25; 0,375 and 0.5 cm
.
According to the obtained area values of chromatographic peak count absolute calibration coefficient or calibration curve built in accordance with GOST 25086.
The calibration coefficient , g/(µv·s), is calculated by the formula
where is the volume of the dosed amount of hydrogen, cm
;
2 — the mass of one mole of hydrogen, g; — the area of the chromatographic peak with a given scale factor, mV·s;
22400 — the volume of one mole of hydrogen under normal conditions, cm.
When using test gas mixtures for calibration setup the absolute calibration coefficient , g/(µv·s), is calculated by the formula
where — volume fraction of hydrogen in the calibration gas mixture, %.
Allowed use for the calibration of the standard installation of the samples of titanium. The procedure of measurement for , g/(µv·s), in this case, is calculated by the formula
where — weight of standard sample, g;
— certified value of the mass fraction of hydrogen in the standard sample, %;
— area of chromatographic peak of hydrogen for the standard sample, mV·s.
For a single definition of the calibration coefficient must ensure
The calculated value of the calibration coefficient is used to quantify hydrogen content in the sample.
4.4 Processing of measurement results
Mass fraction of hydrogen , %, is calculated by the formula
where is the absolute calibration coefficient, g/(µv·s);
— area of chromatographic peak of hydrogen in the sample, mV·s;
— area of chromatographic peak of hydrogen in a control experiment, µv·s;
— the weight of the portion,
4.5 Permissible error of measurement
4.5.1 the discrepancy between the measurement results and analysis results (at a confidence probability of 0.95) shall not exceed the permissible values given in table 1.
Table 1
Percentage
| Mass fraction of hydrogen | The permissible discrepancy between the results of the parallel measurements |
The permissible discrepancy between the results of the analysis | The margin of error of measurement | ||||
| From | 0,0010 | to | 0,0030 | incl. | 0,0005 |
0,0008 | About 0.0006 |
| SV. | 0,0030 | « | 0,0100 | « | 0,0010 |
0,0014 | 0,0010 |
| « | 0,010 | « | 0,030 | « | 0,003 |
0,005 | 0,004 |
| « | 0,030 | « | 0,100 | « | 0,010 |
0,014 | 0,010 |
4.5.2 Control of accuracy of analysis results
Control of accuracy of analysis results is carried out according to the standard model that has not been used for calibration of the instrument, in accordance with GOST 25086.
Allowed to monitor the accuracy of analysis results by varying the sample sample.
4.6 skill Requirements
To perform analysis allowed the analyst qualification not less than 4th level.
5 Spectral method
5.1 measuring instruments, accessories and reagents
Set of standard samples with a range of hydrogen content, covering the outside of the hydrogen content in the spongy titanium.
Lathe type TV-16 or similar machines.
Copper rod grade M-0, M-1 according to GOST 859 for the manufacture of protivoelektrodom with a diameter of 6 mm.
Ethanol (ethyl alcohol) rectified technical GOST 18300.
Calico and cambric GOST 29298.
A generator of low voltage pulses. The generator is an electric device that allows you to obtain low-voltage (~300 V) impulse discharges between the analyzed sample and the counter. The principle of operation of the generator based on the charge of the forming line, consisting of serially connected U-shaped filter, to a predetermined voltage and then discharge in summing up the samples counter to the breakdown distance.
Spectrograph with glass optics ISP-51 and a camera with a focal length of 270 mm.
Microphotometer type MF-2, IPV-460 or similar devices.
Spectromancer of PS-18, MMP-2 or similar devices.
Spectral records «Infra» according to the current normative document.
Thermometer laboratory according to GOST 28498.
Fotocity or other vessels for processing photographic plates.
Developer.
Solution A:
— distilled water according to GOST 6709 — 1000 cm;
— metol according to GOST 25664 — 1 g;
— sodium sulfite (sodium sanitarily) according to GOST 195: crystalline — 52 g, anhydrous — 26 g;
— hydroquinone according to GOST 19627 — 5 g.
Solution B:
— distilled water according to GOST 6709 — 1000 cm;
— sodium carbonate (sodium carbonate) anhydrous GOST 83 — 20 g;
— potassium bromide (potassium bromide) according to GOST 4160 — 1,
Before the manifestation of the solutions A and B mixed in a volume ratio of 1:1.
Fixer:
— distilled water according to GOST 6709 — 1000 cm;
— sodium thiosulfate GOST 244 — 300 g;
— sodium sulfite (sodium sanitarily) anhydrous GOST 195 — 26 g.
Photovoltaic steamer FES-1 with a registered device (EPS-154, EPS-164 or the digital voltmeter is of type b-4−14).
5.2 preparation for measurement
For the determination of hydrogen content specimens obtained from the molded billet according GOST 23780 prepared for mechanical testing.
Before analysis copper protivoelektrodom, analyzed and standard samples are treated on a lathe. The ends of the samples and copper protivoelektrodom carefully treated with a finishing cutter with a roughness of the processed surface is not more than 10 µm and sharp edges removed (chamfer). On the end surface of samples are not allowed cracks, holes, scratches, nonmetallic inclusions and other defects. Copper counter after sharpening needs to have a sharp cone with a smooth forming surface with the apex angle (60±5)°.
5.3 procedures for measuring
5.3.1 measurements on a photographic installation of ISP-51 is carried out at a slit width of 0.03−0.04 mm; charging voltage 250−300 V, the analytical line — 656,28 nm.
Photographed spectra of the standard samples and the sample analyzed on one photographic plate. The spectrum of a single pulse discharge.
5.3.2 measurements on the FES-1 is carried out when the width of the entrance slit is 0.04 mm and the exit slit is 0.12 mm. Scale accumulation (1:1 to 1:5) is determined by the value of the signal.
On the exit slit is set to the analytical line of hydrogen 656,28 nm.
Analytical gap between the sample and the copper counter — 0,2 mm, charging voltage from 250 to 300 V.
Uses a single pulse without pre-sparking.
5.3.3 allowed to use other devices, equipment, materials, modes of excitation and registration of spectral lines of hydrogen subject to receipt of the metrological characteristics meet the requirements of this standard.
5.4 the Processing of the measurement results
5.4.1 Mass fraction of hydrogen at the work on the spectrograph ISP-51 determine fotometriya spectrogram on microphotometer.
In each spectrogram, measure the blackening of analytical lines of hydrogen and calculate the difference of the blackening
of analytical lines and background.
Calibration curve constructed in the coordinates 
is the mass fraction of hydrogen in a standard sample taken from the certificate on the standard sample;
— the average value of the difference of the blackening of analytical lines and the background hydrogen in the standard model.
Obtained for each sample the values for the calibration schedule find define mass fraction hydrogen in the test specimen.
5.4.2 Mass fraction of hydrogen when operating the FES-1 is determined by building calibration curve in the coordinates 
— mass fraction of hydrogen, specified in the certificate on standard designs;
— the readings of the output of the measuring device, proportional to the intensity of the spectral lines of hydrogen.
In the constructed calibration schedule find define mass fraction of hydrogen.
5.4.3 the use of other coordinate systems is subject to receipt of the metrological characteristics meet the requirements of this standard.
5.5 Permissible error of measurement
5.5.1 the difference between the definitions and the results of the two tests
shall not exceed (with confidence probability
of 0.95) of the values given in table 2. The error analysis results (at a confidence probability
of 0.95) does not exceed the limit
given in table 2.
Table 2
Percentage
| Mass fraction | The permissible divergence | The margin of error of measurement | |||||
| From | 0,002 | to | 0,005 | incl. | 0,001 |
0,002 | 0,002 |
| SV. | 0,005 | « | 0,010 | « | 0,003 |
0,004 | 0,003 |
| « | 0,010 | « | 0,020 | « | 0,007 |
0,008 | 0,007 |
| « | 0,020 | « | 0,050 | « | 0,012 |
0,014 | 0,011 |
| « | 0,05 | « | 0,10 | « | 0,02 |
0,03 | 0,02 |
5.5.2 Control of accuracy of analysis results
Control of accuracy of analysis results is carried out by comparison with the results of the analysis performed by physicochemical methods.
The results of the analysis are believed to be accurate, if the condition
where the result of analysis of control samples obtained by the present method;
— the result of the analysis of the same samples obtained by physicochemical method;
,
is governed by the standards of the permissible differences between results of the analyses for respectively the spectral and physico-chemical methods.
5.5.3 Operational control of accuracy of analysis results is carried out before the beginning of the shift or at the same time analysis of batch production samples. For control purposes, choose the standard two sample values of the mass fraction of hydrogen in the lower and upper limits of the measuring range, carry out the measurement of hydrogen content in each standard sample. If at least one standard sample analysis result at the operational control differs from the value of the mass fraction of hydrogen at a given point of the calibration characteristics is more than 0.5 , adjust the calibration characteristics.
5.6 qualifications
To perform analysis allowed spectroscopist qualification not less than 4th level.
