GOST 23902-79

• gost-23902-79.pdf (2.83 MiB)
  ГОСТ 23902-79

GOST 23902−79 Alloys of titanium. Methods of spectral analysis (with Amendments No. 1, 2)

GOST 23902−79*

Group B59

STATE STANDARD OF THE USSR

ALLOYS OF TITANIUM

Methods of spectral analysis

Titanium alloys. Methods of spectral analysis

AXTU 1809

Date of introduction 1981−07−01

Resolution of the USSR State Committee on standards of 21 November 1979, N 4443 time of the introduction set with 01.07.81

Proven in 1985 by the Resolution of Gosstandart from 20.12.85 4508 N validity extended to 01.07.91**

________________

** Expiration removed by the resolution of Gosstandart of the USSR from 29.04.91 N 609 (IUS N 8, 1991). — Note the manufacturer’s database.

* REISSUE (October 1988) with amendment No. 1 approved in August 1986 (IUS 3 to 86).

The Change N 2 approved and put into effect by the Decree of the USSR State Committee on management of quality and standards from 29.04.91 N 609 from 01.09.91

Change No. 2 made by the manufacturer of the database in the text IUS N 8, 1991


This standard specifies the methods of spectral analysis to determine the mass fraction of alloying elements and impurities: aluminium, vanadium, iron, silicon, manganese, molybdenum, tin, chromium, Nickel, zirconium, copper in wrought and cast titanium alloys.

1. GENERAL REQUIREMENTS

1.1. Mass fraction of alloying elements and impurities in titanium alloys is determined by the calibration graphs. Will use two methods of calibration instruments:

the method of «three standards»;

the method of «controlling standard».

Registration of spectra of photographic or photoelectric.

The analysis of the photographic method of calibration graphs constructed in the coordinates:

,

where is the difference of pochernenija lines of the designated element and an element of comparison;

 — mass fraction of the element in the standard sample (CO).

The analysis of the PV method, the calibration graphs constructed in the coordinates:

, , ,

where is the indication of the output of the measuring device;

 — mass fraction of the element.

1.2. For evaporation of the sample and the excitation spectrum using spark and arc sources of light.

1.3. For the calibration of instruments used state standard samples of GSO NN 1641−79 — 1645−79, 1792−80 — 1796−80, 2194−81 — 2198−81, 2881−84 — 2885−84, 3047−84 — 3050−84.

(Changed edition, Rev. N 1).

1.3.1. It is permitted to use industry standard sample (CCA 5−84 — 7−84, 20−84 — 28−84), standard samples of enterprises, as well as newly-issued standard samples of the composition of titanium alloys in all categories.

(Added, Rev. N 1).

1.4. Sampling produce according to normative-technical documentation.

1.5. Check of correctness of definition of a mass fraction of elements is carried out by comparing the results of spectral analysis with the results of the analysis performed by chemical methods according to GOST 19863.1−80* — GOST 19863.13−80*. The permissible value of the absolute differences in percent must be calculated by the formula
________________
* On the territory of the Russian Federation there are GOST 19863.1−91, GOST 19863.13−91. Here and hereinafter. — Note the manufacturer’s database.

,

where the result of analysis of sample made by chemical method, %;

 — the result of a sample analysis performed by the spectral method, %;

the value of reproducibility of spectral analysis;

the value of reproducibility of the chemical method of analysis.

(Changed edition, Rev. N 1, 2).

2. PHOTOGRAPHIC METHOD OF SPECTRAL ANALYSIS

2.1. Analysis of monolithic samples

2.1.1. The essence of the method

The method is based on the excitation spectrum of the sample arc or spark discharge, with subsequent registration on the photographic plate by a spectrograph.

2.1.2. Apparatus, materials and reagents

The average dispersion spectrograph with quartz optics type ISP-30.

Light sources: spark generator type IG-3 or IVS-23 or arc generator type DG-2 or IVS-28.

Microphotometer type MF-2 or IPV-460.

The three-stage attenuator.

Coals spectral pure grades of C-2 or C-3, with a diameter of 6 mm.

Bars brands of magnesium MG-95 MG-90 GOST 804−72*, with a diameter of 6−8 mm.
______________
* On the territory of the Russian Federation GOST 804−93. — Note the manufacturer’s database.

Bars copper marks M00, M1 or M2 according to GOST 859−78, with a diameter of 6 mm.
________________
* On the territory of the Russian Federation GOST 859−2001. Here and hereinafter. — Note the manufacturer’s database.

Photographic plates of the spectral types 1, 2, ES, SP-1 or OFS-3 sensitivity from 3 to 10 units.

Developer N 1.

Fixer is acidic.

The lathe, bench type ТВ16.

Grinding machine type ET-62.

A device for sharpening carbon electrodes.

Absorbent cotton wool GOST 5556−81.

The technical rectified ethyl alcohol GOST 18300−87.

Allowed to use other equipment, equipment and materials subject to receipt of the accuracy of the analysis, not lower than this standard.

(Changed edition, Rev. N 2).

2.1.3. Sample preparation

For analysis use samples of the following forms and sizes:

round bars or square cross-section with a diameter (side) of from 10 to 40 mm, length from 20 to 100 mm;

profiles, strips, disks with a minimum thickness of 2 mm;

sheets of thickness not less than 0.5 mm;

chips with a thickness of 0.7 to 1.5 mm, width from 12 to 15 mm, length 15 mm.

Permitted use of samples obtained by pressing chips or melting it in an inert atmosphere.

Ubeskrivelig the surface of the samples sharpen on a plane on a lathe or grinding machine; parameter of surface roughness should be not more than 20 µm according to GOST 2789−73. In the analysis chips use it smooth side, which is pre-wipe with alcohol.

Ubeskrivelig on the surface of samples are not allowed shell scratches, cracks, slag inclusions, Nadira, waviness, colors of tint.

Preparation for assay and analyzed samples (AO) must be similar for this series of measurements. Protivoelektrodom sharpen on a hemisphere with a radius of 3 to 6 mm truncated cone with an apex angle of 60−90° and a platform with a diameter of 1.0−1.5 mm, or a cone with an apex angle of 120°.

2.1.4. Analysis

The conditions of analysis of the photographic method are given in table.1.

Table 1

Equipment, materials and control parameters	The conditions of analysis
	monolithic samples				solutions
	elements	impurities			alloying elements and impurities
Spectrograph	Type ISP-30
Generator	Types of IG-3, IVS-23 (advanced scheme)	Types DG-2, IVS-28		Types of IG-3, IVS-23 (advanced scheme)	Type IG-3 (advanced scheme)
The width of the slit of a spectrograph, mm	0,010−0,020	0,007−0,020		0,010−0,020	0,020
Illumination system slit	Being
Capacitance, µf	0,01	-		0,01	0,01
Inductance, mg	0−0,05	-		0,15	0,05
The strength of the current, And	1,8−3,0	2,0−10,0		2.0 to 3.0	2,0
Voltage, V	220
The analytical gap, mm	2.0 to 2.5	1,5−2,0		2,0	2,0
Defining the gap gap, mm	3,0	0,5−0,9		3,0	3,0
Pre-search,	30−60	5		30	30−60
The counter	Coal, copper and magnesium				Coal
Photographic plates	Types 1, ES, UFS-3 or SP-1				Types 2, UFS-3
Coordinates of calibration curve			, *

________________

* Consistent with the original. — Note the manufacturer’s database.

Notes:

1. Options set within the specified values.

2. The exposure time is set depending on the sensitivity of the used photographic plates; it should be at least 15 C.

3.  — the difference between pucherani analytical lines and the background near the line.


Wavelength of analytical spectral lines and ranges of detectable concentrations are given in table.2.

Table 2

The designated element	Type of test	Wavelength of lines of the designated element, nm		Wavelength comparison lines, nm		The range of detectable concentrations, %
Aluminium	Monolith	I 396,15 I 394,40 III 360,16		I 394,78 II 356,16		0,2−0,7 From 2.0−8.0
		I 309,27*		I 310,62 II 304,88 II 303,87		0,5−7,0
		II 281,62**		II 284,19 II 282,00		From 2.0−8.0
		I 257,51		I 243,41		0,004−0,2
	Solution	I 394,40		I 394,86		0,2−8,0
Vanadium	Monolith	II 326,77		II 326,37 II 303,87 II 299,02		0,2−3,0
		II 310,23 II 309,31 II 303,38		II 304,88 II 303,87		1,0−6,0
		II 289,33 II 288,25		II 282,00		1,0−6,0
		II 268,80		Background		0,002−0,2
	Solution	(II) 296,80		II 303,87		0,1−6,0
Iron	Monolith	II 259,94 II 259,84 I 248,42		II 288,60 II 284,19 (II) 257,26 I 255,60 I 243,83		Of 0.1−2.0 Of 0.01−0.2
	Solution	I 259,94		I 261,15 II 257,26		Of 0.1−2.0
Silicon	Monolith	I 288,16		288,60 II 284,19 II 282,00		0,05−0,5
		I 251,43 I 250,69		(II) 257,26 II 255,60 I 252,05
		I 251,43		I 243,83		0,002−0,03
		I 243,52		I 243,41		0,03−0,1
	Solution	I 288,16		II 299,02		0,05−0,5
Manganese	Monolith	II 294,92 II 293,93		I 310,62 II 303,87		0,5−1,5
		II 261,02 II 260,57 II 257,61		288,60 (II) 257,26 II 255,60		0,5−2,0
		II 261,02		Background		0,007−0,5
		II 257,61		Background		0,0005−0,007
	Solution	II 293,31		II 299,02		0,5−2,0
Molybdenum	Monolith	II 287,15 II 284,82		II 303,87 288,60 II 284,19 II 282,00		0,5−10,0
		II 268,41		Background		0,006−0,5
	Solution	II 287,15 II 284,82		II 299,02		1,0−10,0
Tin	Monolith	I 303,41 I 300,91	*	II 303,87		1,0−5,0
		II 266,12 I 242,95		II 255,60 I 252,05 II 245,04		1,0−5,0
		I 242,95		I 243,83		0,003−1,0
	Solution	I 284,00		II 299,02		1,0−5,0
Chrome	Monolith	II 284,32		II 303,87 288,60 II 284,19 II 282,00		0,2−3,0
		II 268,71		Background		0,02−0,2
		II 267,72		Background		0,004−0,02
	Solution	II 284,98		II 299,02		0,2−3,0
Cubic Zirconia	Monolith	II 355,19 II 349,62 II 343,82		II 350,03 I 341,17		1,0−5,0
		II 343,05
		II 339,20		II 303,87		3,0−10,0
		II 273,49		II 303,87 Background		0,1−5,0
		II 270,01		II 299,02		1,0−5,0
		II 243,41		0,006−0,1
		II 257,14		(II) 257,26 II 255,60		1,0−5,0
Cubic Zirconia	Solution	II 273,84 II 256,89		II 299,02 (II) 257,26		0,1−10,0
Copper	Monolith	I 324,75		II 327,53		0,0009−0,01
		II 224,70		I 224,47		0,01−0,25
Nickel	Monolith	I 341,48		I 342,89		0,01−0,10
		II 239,45		I 243,41		0,10−0,25

________________

* Used in the analysis of alloys not containing vanadium.

** Used in the analysis of alloys not containing molybdenum.

Notes:

1. Spectral lines, limited in the table paranteza may be respectively combined in any analytical pair.

2. When used in spray-spark method as an internal standard for nitrate of Nickel per line comparison take line Nickel 309,91 nm or 277,31 nm.

3. Roman numerals before the values of the wavelength represent the accessory lines:

I — the neutral atom;

II — once the ionized atom;

III doubly ionized atom.


When working according to the method of «three standards» perform the following operations:

choose at least three FROM the analyzed alloy;

spectra of co and AO are photographed on the same photographic plate at the selected conditions of analysis with randomization of the order of shooting. Spectra each WITH and AO photographed 2−3 times;

measure the blackening of the selected analytical lines and lines of comparison, to compute the value of the difference of pochernenija for the analytical line pairs, and the arithmetic mean of two or three spectra;

build a calibration curve in the coordinates . This schedule is suitable for the analysis of those samples, the spectra of which are filmed along with on a single photographic plate;

according to the calibration schedule find the mass percent of an element in AO.

The exposure time is selected such in which, provided the normal blackening of analytical lines.

If you are working on a method of «control reference» in addition to FROM which to construct a primary calibration curve, use of SOPS, which must satisfy the following requirements:

in chemical composition it needs to be as close as possible to mid-range concentrations specified in regulatory technical standards on the alloy;

on physico-chemical properties (the method of casting, processing), the shape and size of the DIS must meet the AO.

The work begins with the construction of the basic calibration curve. On one photographic plate spectra photographed WITH this alloy, together with the spectra of the DIS. Spectra each WITH SOP and photographed three to five times. The average difference values of pucherani build permanent calibration schedule of the main photographic plates in the coordinates: .

In the analysis of production samples on the plate working together with the spectra of AO photographed spectra SOP 2−3 times each. Determine the difference pucherani analytical line pairs for SOP and AO (and ) as the average of the corresponding number of spectra. multiply the magnitude of conversion factor .

The conversion factor is introduced to account for the properties of the emulsion working plates, calculated by the formula

,

where is the difference of pochernenija auxiliary line pair titanium or difference pucherani line of titanium for the two steps of the attenuator, calculated for several spectra of the core plates;

 — the difference between pochernenija the same auxiliary lines titanium or pochernenija of the line titanium for the same steps of the attenuator, calculated for a working photographic plates.

Through the point with coordinates ; conduct work schedule, parallel to the main, and carried on it the definition of a mass fraction in JSC using the value .

For calculation of the coefficient it is recommended to use the following pairs of lines of the Titan (in nanometers):

257,10 Ti — Ti 257,26;

Of 252.00 Ti — Ti 255,60;

257,10 Ti — Ti 255,60

or I and II steps of the attenuator (line 356,16 Ti; Ti 303,

87).

2.1.5. Processing of the results

2.1.5.1. The final result of the analysis be the arithmetic mean of three parallel measurements obtained on the three spectrograms, if the condition:

,

where is the greatest result of the parallel measurements;

 — the lowest result of the parallel measurements;

 — relative standard deviation describing repeatability of measurements;

 — the arithmetic mean calculated from parallel measurements (3).

When carrying out the Express analysis allowed to calculate the result of the analysis on two parallel measurements and provided that

.

2.1.5.2. The repeatability of the photographic method of analysis, characterized by relative standard deviation , and correlation are given in table.3.

Table 3

The designated element	The range of detectable concentrations, %	Photographic method				Photovoltaic method
		monolith		solution
		no more
Manganese, copper	0,0005−0,001	0,20	0,20	-	-	0,15	0,15
Aluminum, vanadium, iron, silicon, manganese, copper	0,001−0,01	0,15	0,15	-	-	0,10	0,10
Molybdenum, tin, chromium, Nickel, zirconium	0,01−0,10	0,08	0,08	0,07	0,06	0,06	0,06
Aluminum, iron, silicon, manganese, molybdenum, chromium, Nickel, zirconium	0,1−0,5	0,05	0,045	0,05	0,045	0,04	0,035
Aluminum, vanadium, iron, manganese, molybdenum, tin, chromium, zirconium	0,5−2,0	0,04	0,03	0,04	0,03	0,03	0,03
Aluminium, vanadium, molybdenum, tin, zirconium	2,0−5,0	0,04	0,03	0,03	0,03	0,03	0,03
Aluminium, vanadium, molybdenum, chromium	5,0−10,0	0,03	0,03	0,03	0,03	0,03	0,03

2.1.5.3. Calculation methodology and reference is given in Annex 1.

2.1.5.2, 2.1.5.3 (Revised edition, Edit. N 1).

2.2. The sample analysis translated into the solution

2.2.1. The essence of the method

The method is based on transforming a metal sample in solution is injected spray in the spark. Spectra recorded on the photographic plate.

2.2.2. Apparatus, materials and reagents

The average dispersion spectrograph with quartz optics type ISP-30.

Spark generator of the type IG-3 or IVS-23.

Air compressor type KVM-8 electric (0,2−0,3 kW) and a receiver at a pressure of 50−200 kPa.

Dispenser with reverse camera condensation (Fig.1).

1 — atomizer; 2 — rubber tube; 3 — liquid capillary; 4 — air capillary

Damn.1

Microphotometer type MF-2 or IPV-460.

Lathe for sharpening electrodes of the type of TV 16.

A device for sharpening carbon electrodes.

Spectral clean coal grades of B3 or C3 with a diameter of 6 mm.

Photographic plates of the spectral type I, II or ES sensitivity from 3 to 20 units.

Rubber hose.

Porcelain crucibles.

Platinum crucibles.

Plastic utensils.

Filters ashless, medium density («white ribbon») and dense («blue ribbon») on the other 6−09−1678.

Muffle furnace with thermostatic control.

Ammonia water according to GOST 3760−79, 25% solution.

Sulfuric acid GOST 4204−77, diluted 1:3.

Hydrochloric acid by the GOST 3118−77.

Hydrofluoric acid according to GOST 10484−78.

Nitric acid GOST 4461−77.

Hydroxylamine hydrochloride according to GOST 5456−79, a solution of 100 g/DM(hydroxylamine hydrochloride).

Sodium hydroxide according to GOST 4328−77, 0.1 N. solution.

Sodium silicate (NaSiO·9HO) on the other 6−09−5337.

Titanium sponge stamps ТГ1−00 GOST 17746−79*.
______________
* On the territory of the Russian Federation GOST 17746−96. — Note the manufacturer’s database.

Aluminium primary the A95 according to GOST 11069−74*.
______________
* On the territory of the Russian Federation GOST 11069−2001. — Note the manufacturer’s database.

Manganese metal brands Mr-00 GOST 6008−82*.
______________
* On the territory of the Russian Federation GOST 6008−90. — Note the manufacturer’s database.

Tin metal stamps 01 according to GOST 860−75.

Nickel metal stamps NP1 GOST 492−73.

Molybdenum metal, vanadium metal (mass fraction of the base element not less than 99.5%).

Metal chrome brand X00 GOST 5905−79*.
______________
* On the territory of the Russian Federation GOST 5905−2004. — Note the manufacturer’s database.

Iron metal has been restored.

Zirconium oxychloride (ZrOCl zirconium chloride·8HO).

Distilled water GOST 6709−72.

Standard solutions: titanium with 0.02 g/cm; aluminum from 0.01 g/cm; vanadium from 0.01 g/cm; iron with 0.01 g/cm; silicon 0,001 g/cm; manganese from 0.01 g/cm; molybdenum from about 0.001 g/cm; Nickel of 0.01 g/cm; tin from 0.01 g/cm; chromium from 0.01 g/cm; zirconium, with 0.001 g/cm.

Preparation of standard solutions is described in the mandatory application

s 2.

2.2.3. Sample preparation

Analyzed the sample weight of 1 g was dissolved with heating in 50 cmof sulphuric acid (1:3), adding to oxidize a few drops of concentrated nitric acid or solutions of hydroxylamine hydrochloride, 100 and 200 g/DM. After complete dissolution of the sample solution was transferred to volumetric flask with a capacity of 100 cm, the volume was adjusted solution to the mark with water and mix thoroughly.

2.2.2, 2.2.3. (Changed edition, Rev. N 2).

2.2.4. Analysis

2−3 cmof the solution prepared according to claim 2.2.3 is placed in the chamber of the spray gun 1 (see the devil.1) and close the spray hole of the rubber stopper 2, in which is inserted a carbon electrode (Fig.2).

Damn.2

The sprayer 1 (Fig.3) secured to the holder tripod spectrograph 2. Include a compressor 6, blocking the access of air to the atomizer clip 3. Upon reaching the system pressure of 70−80 kPa, as measured by the pressure gauge 4, and remove the clip 3. Air enters the atomizer starts the supply of the aerosol into the discharge gap and the spectrum.

1 — the atomizer with the tube and electrode; 2 — holders of the electrodes of the spark stand; 3 — terminal;
4 — gauge 100−200 kPa; 5 — hose; 6 — air compressor with electric

Damn.3

The conditions of analysis are given in table.1.

Wavelength of analytical spectral lines and ranges of detectable concentrations are given in table.2.

Charting solutions are used for calibration (WG) prepared from standard solutions of the individual elements.

The amount of the standard solution , cm, is necessary for preparation of the WG, is calculated by the formula

,

where  — prigotavlivaemy number RG, cm;

 — total mass fraction of elements in WG, g/DM;

 — mass fraction of the element in RG based on the metal, %;

 — mass concentration of a standard solution of the element, g/cm.

Values , and specify, based on the specific analytical tasks.

For the preparation of RG allowed to use the set WITH or one WITH. If you are using one WITH the solutions of samples and RG is introduced as an internal standard 15 cmof Nickel nitrate in 100 cmof solution.

The WP © percentage made from one, calculated by the formula

,

where  — mass fraction of the element in the metal, %;

 — weight, g;

 — mass of test portion, g.

Analysis of the sample solution is carried out by the method of «three standards».

2.2.2−2.2.4. (Changed edition, Rev. N 1).

2.2.5. Processing of the results

2.2.5.1. Processing of the results is given in section 2.1.5.

2.2.5.2. The reproducibility of the method and convergence are given in table.3.

(Changed edition, Rev. N 1).

3. THE METHOD OF PHOTOELECTRIC SPECTRAL ANALYSIS

3.1. The essence of the method

The method is based on the excitation spectrum of the arc or spark discharge with the registration of the intensity of the lines using the photovoltaic installation.

3.2. Equipment and reagents

Installation of photovoltaic (quantometer) type DFS-10M, DFS-36, DFS-41 or MFS-4.

Generator type geu-1, UGE-4, IVS-1, «ARKUS» or IG-3.

Coals spectral pure brand C2 or C3, with a diameter of 6 mm.

Rods of copper of brand of M00, M1 or M2 according to GOST 859−78, with a diameter of 6 mm.

Lathe type of TV 16.

A device for grinding coal.

The grinding machine.

Allowed to use other equipment, equipment and materials subject to receipt of the accuracy of the analysis, not lower than this standard.

3.3. Sample preparation

The samples prepared as described in step 2.1.3.

3.4. Analysis

Analysis carried out by the method of «three standards» or «control standard».

The conditions of analysis are given in table.4.

Wavelength of analytical spectral lines are given in table.5.

The analytical lines chosen depending on the mass fraction of the element in the sample, the possibility of placing the output of cracks on the slide quantometer, etc. the use of other analytical lines, provided that they provide accuracy and sensitivity to meet the requirements of this standard.

Mass fraction of elements in AO are determined using a calibration curve constructed in the coordinates: or 2−3 parallel measurements.

While working on quantometer by the method of «reference standard» construction of calibration curve in the coordinates of the do as specified in claim 2.1.4 ( — reading device proportional to the logarithm of the intensity). When this calibration curve carried out in coordinates ; parallel to the main schedule.

When building a calibration curve in the coordinates of the recorded spectra, averaged samples to build a calibration curve and continue to the intersection with the axis mass fraction ( — reading device, is proportional to the intensity). The intersection point is the «pivot point» calibration curve (assuming the constancy of the «zero» reading device via the appropriate channel).

Before analysis the samples of the recorded spectra SOP 3−5 times, through the point of rotation and the coordinates ; conduct a working calibration curve, which determine the mass fraction of the element in

AO.

3.5. Processing of the results

3.5.1. Processing of the results is given in section 2.1.5.

3.5.2. The reproducibility of the photoelectric method of analysis and convergence are given in table.3.

(Changed edition, Rev. N 1).

Table 4

Control parameters	The conditions of analysis
	Quantometer DFS-10M, generator powerplant-1	Quantometer DFS-36, generator UGE-4	Quantometer DFS-41, generator IVS-1	Quantometer MFS-4
				generator
				ARCUS	IG-3
	Alternating current arc		Pulse aperiodic discharge high voltage	Alternating current arc	High voltage spark
The voltage, V	220
The strength of the current, And	1−3	1−2	5,5	1,1−1,8	2,5
Control method	Phase
Phase of ignition, deg.	90
Capacitance, µf	-	-	16	-	0,01
Inductance, mg	-	-	500	-	0,01
The discharge gap, mm	-	-	-	5,5	3,0
The analytical gap, mm	1,5	1,5	5,0	1,5	2,0
The width of the entrance slit, mm	0,02−0,06
Width of output slit, mm	0,04−0,20	Are selected depending on the concentration of the element and the degree of alloying of the alloy
The roasting	7−10	7	25	5−30	20
The exhibition, with	30	30	25	30	20
The counter	Coal of 6 mm in diameter, sharpened to a hemisphere or on a cone with apex angle 120°
Coordinate system			,

Notes:

1. The parameters selected in the range of specified values.

2. For alloy grade ВТ5Л you can use a dummy copper electrode with a diameter of 4 mm, sharpened to a truncated cone with an area of 1 mm.

3. The analysis on quantometer DFS-41 with generator IVS-1 should use a resistance of 11.5 Ohms.

Table 5

The designated element	Wavelength of lines of the designated element, nm	Range of determined mass concentrations, %
Aluminium	I 265,2 III 360,1 I 396,15 I 394,40 I 308,21	0,004−10,0
Vanadium	I 572,70 I 437,92 I 326,77 I 318,54 II 311,84	0,002−6,0
Iron	II 271,41 II 259,94 II 259,84 II 238,20	0,01−2,0
Silicon	I 288,1	0,002−0,5
Manganese	II 294,92 II 293,31	Of 0.0005 to 2.0
Molybdenum	I 553,30 I 386,41 II 277,54 284,8 II	0,006−10,0
Tin	I 326,23 I 317,50 I 284,00	0,005−5,0
Chrome	I 534,58 I 425,43 II 296,17 I, II 284,92 II 267,72	0,004−3,0
Nickel	I 341,48	0,01−0,25
Cubic Zirconia	I 477,23 I 349,62 II 343,82 II 339,20	0,006−10,0
Copper	I 324,75	0,001−0,25

Notes:

1. As a comparison, using the lines of Titan: I 453,32 nm; I 363,55 nm; II 324,19 nm; II 271,62 nm; I 334,9 nm or undecomposed light.

2. The line of vanadium II 311,84 nm cannot be used in the presence of chromium.

3. The line of aluminum I 308,21 nm cannot be used in the presence of vanadium.

ANNEX 1 (reference). TO EVALUATE THE ACCURACY OF SPECTRAL ANALYSIS

ANNEX 1
Reference

1. The accuracy of spectral methods of analysis — the quality of measurements that reflects the closeness of their results to the true value of the measurand is determined by the value of systematic and random errors provided that the failures are excluded from the calculations (random errors obey the normal distribution law).

(Changed edition, Rev. N 2).

2. When properly configured, the spectral instrument and the implementation of the recommendations of the standard procedure of analysis the main sources of systematic errors are errors associated with the influence of structure and chemical composition of samples on the results of the analysis.

These errors should be identified by comparison of the results of the analysis of samples, performed chemical and spectral methods of the analysis of a large sample (at least 30 samples) and corrected by adjustment of the position of the calibration graphs according to SOP. Validation of chemical analysis results carried out in accordance with GOST 19863.1−80 — GOST 19863.13−80.

3. The result of the analysis of the sample obtained as the arithmetic mean, for example, from two (three) of parallel measurements, i.e. in two (three) spectra should be regarded as one definition.

4. Reproducibility of spectral analysis — the quality of measurements that reflects the closeness to each other of the results of measurements in different conditions (at different times, different places, different methods and means) — is characterized by the value of the relative mean square error (relative standard deviation) of a single definition .

(Changed edition, Rev. N 2).

5. For calculation choose at least five samples of one brand of alloy having approximately the same chemical composition, and within 5 days conduct their analysis series (one series per day). Spectra in each series is carried out in a different sequence, i.e. randomization. One series of spectra recorded on the same photographic plate. On each photographic plate to receive three of the spectrum of each sample and three FROM each spectrum. The latter is necessary for the construction or adjustment of the calibration graphs.

By the photoelectric registration prior to the measurement adjustments of the calibration graphs, and then spectra.

Just from each sample get for 5 days for 15 measurements (five definitions).

For each sample calculate the standard deviation by the formula

, (1)

where is the average mass fraction of the element in the sample is calculated from five determinations;

 — mass fraction of the element at the -th definition in the sample is calculated from three measurements;

 — the number of definitions (5).

Then compute the standard deviation by the formula

, (2)

where is the standard deviation calculated respectively for first, second, etc. samples according to the formula (1);

 — the number of samples (5).

The relative standard deviation characterizing the reproducibility of the analysis calculated by the formula

, (3)

where is the average mass fraction of element in the samples, calculated according to the formula

, (4)

where is the average mass fraction of element respectively in the first, second, etc. samples, calculated from 5 determinations.

6. The convergence of the results of the measurements the quality of measurements that reflects the closeness to each other of the results of the measurements performed in the same conditions, is characterized by a value of relative mean square error of a single measurement.

(Changed edition, Rev. N 2).

7. The value of the find in series of 20 parallel measurements of one sample with correctly configured equipment.

First calculate the standard deviation by the formula

*, (5)

where is the average mass fraction of element in the sample is calculated from 20 parallel measurements;

* — mass fraction of element in the sample computed from the -th measurement;

 — the number of measurements in the series (20).
________________
* Formula and explication to it correspond to the original. — Note the manufacturer’s database.

Next calculate the relative standard deviation characterizing the repeatability of measurements, according to the formula

. (6)

8. When conducting analyses, it is often necessary to estimate the error of the result of the analysis and assessment of confidence limits. At p = 0.95 and excluded systematic error is calculated by the formula

, (7)

where is the number of definitions by which the computed result of the analysis of the sample (usually in the spectral analysis of 1 or 2);

the result of analysis of the sample, calculated according to the definitions.

Computed value means that with a reliability of 95% the true value of the designated value lies in the interval between the values

and .

The most likely result of the analysis is the value .

9. The offset of the calibration curve relative to the base (drift level SOP) is considered significant if it exceeds the standard deviation of the results of 4 measurements calculated according to the SOP, i.e. when the necessary adjustments to the schedule, where is the number of parallel measurements for SOP, which is controlled by the position of the chart (=4);

 — mass fraction of the element in the SOP.

The position of the calibration chart, it is recommended to monitor 1−2 SOP 2−3 times per shift.

10. If the difference between the analysis result and one of the limit values of the mass fraction of element for the alloy specified in GOST 19807−74*, in absolute value less than or equal to , the analysis is carried out by chemical method according to the GOST and GOST 25086−87 19863.1−80 — GOST 19863.13−80, where is the number of samples (1 or 2);

where  — the average result of the analysis of one or two definitions.

______________
* On the territory of the Russian Federation there are GOST 19807−91. — Note the manufacturer’s database.

11. A comprehensive assessment of the operation of the generator excitation spectrum, the spectral device and electronic measuring device it is recommended to periodically (1−2 times per month) carried out by determining the relative standard deviation for a series of 20 parallel measurements according to the formula (5).

The value found is compared , i.e. the standard deviation, which was calculated previously, when you configured the instrument. The comparison produced by criterion.

If more than the table value , it indicates that the instrument requires tuning. At confidence probability 0.95 and the number of measurements in the series (20) of 2.1.

ANNEX 2 (mandatory). PREPARATION OF STANDARD SOLUTIONS

ANNEX 2
Mandatory

1. A standard solution of titanium with a mass concentration of 0.02 g/cm: 2 g of titanium sponge was dissolved with heating in 25 cmof sulphuric acid (1:3), maintaining a constant volume of water. Upon completion of the dissolution, the titanium is oxidized to the tetravalent state by the addition of a few drops of a solution of hydroxylamine hydrochloride 200 g/DM. The solution was transferred to volumetric flask with a capacity of 100 cm, its volume adjusted to the mark with water and mix.

(Changed edition, Rev. N 2).

2. A standard solution of aluminum with 0.01 g/cm: 1 g of primary aluminum is dissolved with moderate heating in 30 cmof hydrochloric acid (1:1). Upon completion of the dissolution solution was cooled, transferred to a volumetric flask with a capacity of 100 cm, its volume adjusted to the mark with water and mix.

3. A standard solution of vanadium from 0.01 g/cm: 1 g of metallic vanadium dissolved in 20 cmof concentrated nitric acid. After dissolving, the solution was transferred to volumetric flask with a capacity of 100 cm, its volume adjusted to the mark with water and mix.

4. Standard solution of iron with 0.01 g/cm, 1 g of the recovered metal iron is dissolved in 40 cmof hydrochloric acid (1:1). After dissolving, the solution was transferred to volumetric flask with a capacity of 100 cm, its volume adjusted to the mark with water and mix.

5. Standard solution of silica of 0.001 g/cm: 10 g sodium silicate (NaSiO·9HO) is dissolved in water, add 20 drops of sodium hydroxide solution 0.1 mol/DM, filtered through a folded filter of «blue ribbon» in a volumetric flask with a capacity of 1 DM, adjusted its volume to the mark with water and mix. The solution was stored in a plastic container.

Set the mass concentration of the solution in a porcelain Cup to 50 cmaliquote parts of sodium silicate add 10 cmsulphuric acid (1:1), gently stirred and evaporated to dryness. Then add 10 cmof concentrated hydrochloric acid and 150 CCof water, mix and leave in a dark place for 40 minutes to coagulate. The precipitate is filtered at the filter «white ribbon» with absorbent, and washed eight times with hot hydrochloric acid (1:99). The filter with the sediment is dried, incinerated in a platinum crucible and calcined in a muffle furnace at a temperature of 1000−1100 °C for 40 min. the Crucible is cooled and weighed. The calcined precipitate is treated with 10−20 drops of hydrofluoric acid, one drop of concentrated sulfuric acid and heated to stop the allocation of the vapour of sulphuric anhydride. The crucible with the precipitate is calcined again in a muffle furnace at a temperature of 1000−1100 °C for 10 min, cooled and weighed.

The mass concentration of a standard solution of silicon in g/cm, is calculated by the formula

,

where is the mass of the sludge before treatment with hydrofluoric acid, g;

 — the mass of the precipitate after treatment with hydrofluoric acid, g;

0,4675 — the ratio of silicon dioxide on silicon;

 — the volume of a standard solution taken for the determination of silicon, cm.

6. A standard solution of manganese from 0.01 g/cm: 1 g of metallic manganese is dissolved in 30 cmof nitric acid (1:1). The solution was boiled to remove oxides of nitrogen. Upon completion of the dissolution solution was cooled, transferred to a volumetric flask with a capacity of 100 cm, its volume adjusted to the mark with water and mix.

7. A standard solution of a molybdenum 0.001 g/cm: 0.1 g of a metallic molybdenum dissolved in 10 cmof nitric acid (1:1), one adds 20 cmof sulphuric acid (1:2), evaporated to the appearance of dense white fumes of sulphuric anhydride and continue to heat for 3 min. Then pour 50 cmof water and again evaporated to dense white fumes. Then pour 50 cmof sulphuric acid (7:93), cooled, transferred to a volumetric flask with a capacity of 100 cm, the volume was adjusted solution to the mark with the same acid and stirred

.

8. A standard solution of Nickel and 0.01 g/cm: 1 g of metallic Nickel dissolved in 40 cmof a mixture of hydrochloric and nitric acids (1:1). After dissolution the solution was transferred to volumetric flask with a capacity of 100 cm, its volume adjusted to the mark with water and mix.

9. A standard solution of tin from 0.01 g/cm: 1 grams of powdered tin metal was dissolved with heating in 20 ml of concentrated hydrochloric acid in a platinum Cup. After dissolution, the solution was cooled, transferred to a volumetric flask with a capacity of 100 cm, its volume adjusted to the mark with water and mix.

10. Chromium standard solution with a 0.01 g/cm: 1 g of chromium metal is dissolved in 40 cmof hydrochloric acid (1:1). After dissolving, the solution was transferred to volumetric flask with a capacity of 100 cm, its volume adjusted to the mark with water and mix.

11. A standard solution of zirconium and 0.001 g/cm: 3,53 g of zirconium oxychloride (ZrOCl·8HO) is dissolved in 80 cmof concentrated hydrochloric acid. The solution was transferred to volumetric flask with a capacity of 1 cm, its volume adjusted to the mark with water and mix.

Set the mass concentration of a standard solution of zirconium: 50 cmaliquote part of the solution is placed in a beaker with a capacity of 150 cm, 70 cm pourhot water, precipitated Zirconia 25% ammonia solution before the strong smell and put in a warm place for 20 minutes to coagulate the precipitate. The precipitate was filtered off on the filter «white ribbon» and was washed with ammonia water (5 cmof a 25% ammonia solution in 1 litre of water) 10 times. The sediment filter is placed in a weighted porcelain crucible, dried and calcined at (1100±10) °C for 40 min to constant weight. The crucible with residue was cooled and weighed.

Mass concentracao standard solution zirconium , g/cm, is calculated by the formula

,

where is the mass of the sediment after ignition, g;

0,7403 — the ratio of zirconium dioxide to zirconium;

 — the volume of a standard solution of zirconium taken for the determination of zirconium, cm.

Appendix 2. (Changed edition, Rev. N 1).