GOST R ISO 16918-1-2013
GOST R ISO 16918−1-2013 Steel and cast iron. Mass-spectrometric method with inductively coupled plasma. Part 1. Determination of tin, antimony, cerium, lead and bismuth
GOST R ISO 16918−1-2013
NATIONAL STANDARD OF THE RUSSIAN FEDERATION
STEEL AND CAST IRON
Mass-spectrometric method with inductively coupled plasma. Part 1. Determination of tin, antimony, cerium, lead and bismuth
Steel and iron. Inductively coupled plasma mass spectrometric method. Part 1. Determination of tin, antimony, cerium, lead and bismuth content
OKS 77.080.20
Date of introduction 2014−10−01
Preface
1 PREPARED AND SUBMITTED by the Technical Committee for standardization TC 145 «monitoring Methods of steel products"
2 APPROVED AND put INTO EFFECT by the Federal Agency for technical regulation and Metrology, dated 22 November 2013 No. 2054, art.
3 this standard is identical with ISO 16918−1* «Steel and cast iron. Mass-spectrometric method with inductively coupled plasma. Part 1. Determination of tin, antimony, cerium, lead and bismuth». (ISO 16918−1:2009 «Steel and iron — Determination of nine elements by the inductively coupled plasma mass spectrometric method — part 1: Determination of tin, antimony, cerium, lead and bismuth»).
________________
* Access to international and foreign documents referred to here and hereinafter, can be obtained by clicking on the link to the site shop.cntd.ru. — Note the manufacturer’s database.
In applying this standard it is recommended to use instead of the referenced international standards corresponding national standards of the Russian Federation and interstate standards, details of which are given in Annex C*
________________
* Probably, the error of the original. Should read: application, YES. — Note the manufacturer’s database.
4 INTRODUCED FOR THE FIRST TIME
Application rules of this standard are established in GOST R 1.0−2012 (section 8). Information about the changes to this standard is published in the annual (as of January 1 of the current year) reference index «National standards» and the official text changes and amendments — in monthly information index «National standards». In case of revision (replacement) or cancellation of this standard a notification will be published in the upcoming issue of the monthly information index «National standards». Relevant information, notification and lyrics are also posted in the information system of General use — on the official website of the Federal Agency for technical regulation and Metrology on the Internet (gost.ru)
1 Scope
This standard specifies a method for determining in the steel and iron trace content of tin, antimony, cerium, lead and bismuth using inductively coupled plasma mass spectrometry (ICP-MS). The method is applicable for the determination of trace elements content in the following ranges of mass fractions:
tin — Sn — from 5 to 200 µg/g;
— antimony Sb — 1 to 200 µg/g;
— cerium CE — from 10 to 1000µg/g;
— lead Pb — 0.5 to 100 µg/g;
— bismuth Bi, from 0.3 to 30 µg/g.
Interference free determination of trace elements using ICP-MS are listed in Appendix B.
2 Normative references
This standard uses the regulatory references to the following international standards*:
_______________
* The table of conformity of national standards international see the link. — Note the manufacturer’s database.
ISO 648:1977 Laboratory glassware. Pipette (Mohr) with the specified capacity (ISO 648:1977, Laboratory glassware — One-mark pipettes)
ISO 1042:1998 Laboratory glassware. Volumetric flask with one mark (ISO 1042:1998, Laboratory glassware — One-mark volumetric flasks)
ISO 5725−1:1994 Accuracy (trueness and precision) of methods and measurement results. Part 1. General provisions and definitions (ISO 5725−1:1994, Accuracy (trueness and precision) of measurement methods and results — Part 1: General principles and definitions)
ISO 5725−2:1994 Accuracy (trueness and precision) of methods and measurement results. Part 2. The basic method for the determination of repeatability and reproducibility of a standard measurement method (ISO 5725−2:1994, Accuracy (trueness and precision) of measurement methods and results — Part 2: Basic method for the determination of repeatability and reproducibility of a standard measurement method)
ISO 5725−3:1994 Accuracy (trueness and precision) of methods and measurement results. Part 3. Intermediate indicators the precision of a standard measurement method (ISO 5725−3:1994, Accuracy (trueness and precision) of measurement methods and results — Part 3: Intermediate measures of the precision of a standard measurement method)
ISO 14284 Steel and iron. Selection and preparation of samples for the determination of chemical composition (ISO 14284, Steel and iron — Sampling and preparation of samples for the determination of chemical composition).
3 the essence of the method
The analytical sample is dissolved in mixture of acids: hydrochloric, nitric and hydrofluoric, microwave heating, or hot plate. Diluted solutions of the samples are sprayed into a plasma mass spectrometer (ICP-MS) using a peristaltic pump. Simultaneous measurement of the intensity of the elements in units of atomic mass (mass spectrum) is carried out using the spectrometer ICP-MS. The blank solution experience for calibration and calibration solutions must match matrix component in the composition of the major elements in steel and the mineral acids, used for the decomposition of the sample. Internal standards are used in all operations to compensate for any instrumental drift.
4 Reagents
Unless otherwise indicated, use only reagents of high purity, with a mass fraction of less than 0.0001% of each element, or equivalent purity. The following symbols, in percent refer to the mass fraction of the elements.
4.1 Hydrochloric acid (HCI), 30%, density — 1.15 g/cm
or 38%, density
is 1,19 g/cm
.
4.2 Nitric acid (
is 1.42 g/cm
.
4.3 Hydrofluoric acid (HF), 49%, density — 1,16 g/cm
.
4.4 Nitric acid (
— 1.40 g/cm
.
4.5 ultra-pure water obtained in cleaning system that can clean water up to the value of the resistance of 18 M
/cm.
4.6 Flushing solution for NSP-MS.
In a plastic bottle (e.g. plastic) with a capacity of 500 cm400 cm pour
purified water (4.5), add 15 cm
of hydrochloric acid (4.1), 5 cm
of nitric acid (4.2), 2.5 cm
hydrofluoric acid (4.3) and the volume was adjusted to 500 cm
of water (4.5). The quality of the acids can be checked, before their use by the scanning of the mass spectrum of the solutions on the instrument ICP-MS. It is recommended to prepare a solution of the following composition: 0.30 cm
(300 µl) HCI (4.1) + 0,10
(100 µl)
(50 µl) HF (4.3) and approximately 3 cm
of water (4.5), then the solution was brought (water) to volume of 10 cm
. If the spectrum peaks are identified (bands) of the analyzed elements, you need to take acid from another vessel and again to check the solution in the presence of the same elements.
4.7 Nitric acid (
In a volumetric flask with a capacity of 100 cmpour about 70 cm
of water (4.5), then add 10 cm
of concentrated
4.8 sodium Hydroxide (NaOH), a solution concentration of 7.5 mol/DM, density
is only 1.33 g/ cm
.
4.9 sodium Hydroxide (NaOH) solution of concentration 0.2 mol/DM.
Placed in a volumetric flask with a capacity of 100 cm2.7 cm
of NaOH solution concentration of 7.5 mol/DM
(4.8) and adjusted water (4.5) to the mark.
Solutions of NaOH should be stored in vessels made of polyethylene or similar material.
4.10 Aqua Regia (HCI + 
Prepare Aqua Regia in a beaker with a capacity of 30 cm(or close in size), placing them in a glass 9 cm
HCl (4.1), 3cm
4.11 Aqua Regia solution, diluted 4:10.
Placed 100 cmof water (4.5) in a flask with a capacity of 150 cm
, then add 40 cm
of a solution of Aqua Regia (4.10) and mix. Do not bring to mark.
4.12 Nitric acid (
In a volumetric flask with a capacity of 100 cmpour about 30 cm
of water (4.5), then add 50 cm
of concentrated
4.13 Perchloric acid (
— 1.68 g/cm
.
4.14 Hydrochloric acid (HCI), a density of 1.19 g/ cm
(4.1), diluted 1:1.
In a volumetric flask with a capacity of 100 cm, pour about 30 cm
of water (4.5), then add 50 cm
of concentrated HCI (4.1) and dilute to the mark with water (4.5).
4.15 the high-purity Iron, containing less than 0,0001% of the mass fraction of each element.
4.16 standard solutions containing 1000 mg/DMof each object
4.16.1 Tin Sn, the primary standard solution
100,0 mg of high-purity tin (mass fraction of tin is not less than 99.9%) was dissolved in 3 cmHCI (
— 1,19 g/cm
) (4.1) and 1 cm
. The contents of the Cup gently warmed until complete dissolution, cooled and quantitatively transferred to a volumetric flask with a capacity of 100 cm
, the solution was adjusted to the mark with water (4.5) and mixed well.
Store a standard solution of tin in a plastic (PET) container.
4.16.2 Antimony Sb, a primary standard solution
A 100.0 mg of metallic antimony of high purity (mass fraction of antimony is not less than 99.9%) was dissolved in 3 cmHCI (
— 1,19 g/cm
) (4.1) and 1 cm
. The contents of the Cup gently warmed until complete dissolution, cooled and quantitatively transferred to a volumetric flask with a capacity of 100 cm
, the solution was adjusted to the mark with water (4.5) and mixed well. Store a standard solution of tin in a plastic container.
4.16.3 Cerium CE, the primary standard solution
288,5 mg of pure sulphate of cerium (IV) CE 
of a solution of dilute Aqua Regia (4.11) in a volumetric flask with a capacity of 100 cm
. After complete dissolution of sulfate added to a solution of Aqua Regia (4.11) up to the mark and mix well.
Store a standard solution of cerium in PET container.
4.16.4 Lead, primary standard solution
A 100.0 mg of metallic lead of high purity (mass fraction of lead not less than 99.9%) dissolved in 20 cm
. The glass is gently heated until complete dissolution of lead, the solution was cooled and quantitatively transferred to a volumetric flask with a capacity of 100 cm
, adjusted to the mark with water (4.5) and mixed well. Store a standard solution of lead in PET container.
4.16.5 Bismuth Bi, the primary standard solution
A 100.0 mg of metallic bismuth of high purity (mass fraction of bismuth is not less than 99.9%) was dissolved in 3 cmHCI (
— 1,19 g/cm
) (4.1) and 1 cm
. The glass is gently heated until complete dissolution of bismuth, the solution was cooled and quantitatively transferred to a volumetric flask with a capacity of 100 cm
, adjusted to the mark with water (4.5) and mixed well. Store a standard solution of bismuth in PET container.
4.16.6 Rhodium Rh, a primary standard solution
203,6 mg of pure chloride of rhodium (III) (a
of freshly prepared solution of Aqua Regia (4.10) in a volumetric flask with a capacity of 100 cm
. After complete dissolution of the sodium chloride solution diluted to the mark with water (4.5) and mixed well.
A standard solution of rhodium are stored in a PET container.
4.16.7 Yttrium Y, primary standard solution
127,0 mg of pure trioxide of yttrium (
to 6 cm
of freshly prepared Aqua Regia (4.10). After complete dissolution the solution was diluted to the mark with water (4.5) and mixed well.
Standard solution of yttrium stored in a PET container.
4.16.8 Lutetium Lu primary standard solution
113.7 mg of pure trioxide, lutetium (
to 6 cm
of freshly prepared Aqua Regia (4.10). After complete dissolution the solution was diluted to the mark with water (4.5) and mixed well. Standard solution lutetium stored in a PET container.
4.16.9 Titanium Ti, a primary standard solution
A 100.0 mg of titanium metal of high purity (mass fraction of titanium is not less than 99.9%) is dissolved in 30 cmHCI (
— 1,19 g/cm
), diluted 1:1 (4.14) and 0.2 cm
HF (4.3) in a beaker with a capacity of 250 cm
. The glass is gently heated until complete dissolution of titanium, the solution was cooled and quantitatively transferred to a volumetric flask with a capacity of 100 cm
, adjusted to the mark with water (4.5) and mixed well. Store a standard solution of titanium in PET container.
4.17 Iron Fe matrix solution, 10,000 mg Fe/DM
0.5 g of iron of high purity (4.15) is weighed with an accuracy of 0.01 mg and placed in a beaker with a capacity of 250 cm. Add 20 cm
of water (4.5), then 0.1 cm
HCI (4.1) and add 5 cm
, made up to the mark with water (4.5) and mixed well.
Solution of iron stored in polyethylene vessel.
4.18 Calibration (by weight) solution containing 100 mg/lof each of the elements Ti, Y, Rh, Sb, CE, Pb and Bi
Pour about 50 cmof water (4.5) in a measuring flask with volume capacity of 1000 cm
, then add 0.10 cm
(100 µl) of each of the standard solutions of Ti (4.16.9), Y (4.16.7), Rh (4.16.6), Sb (4.16.2), CE (4.16.3), Pb (4.16.4) and Bi (4.16.5). Bring to mark with water (4.5) and well stirred solution.
5 Instrument
5.1 Laboratory glass and plastic ware
Use the following laboratory glassware and plastic glassware: volumetric flasks, hourglass, glasses, polyethylene bottles (vessels), plastic pipette tips, test tubes, polystyrene.
All glass volumetric glassware should be class A (1st class) in accordance with ISO 648 and ISO 1042.
5.2 Micropipettes
The capacity of the micropipette should be: 5 to 40, from 50 to 200, 100 to 1000 ál, and 1 to 5 cm.
Note — 1 µl corresponds to 0.001 cm.
5.3 satellite microwave equipment
For sample digestion use a laboratory microwave oven and a rotary table (carousel) or other holder for vessels made of polytetrafluoroethylene (PTFE), designed for high pressure.
Allowed to apply step by step-a temporary program when performing wet decomposition that determines the pressure and temperature (reaction vessels), parameters can be register or watch on the monitor.
5.4 ICP-MS instruments
5.4.1 Magnetobacteria ICP-MS (high resolution ICP-MS)
5.4.2 Quadrupole ICP-MS (low resolution ICP-MS)
5.4.3 Time-of-flight ICP-MS (ICP-TOF-MC)
For the optimal functioning of the ICP-MS instrument is necessary to comply with the instructions for each type of ICP-MS.
In all three types of instruments ICP-MS as the plasma-forming gas used argon to ensure the operation of the argon plasma. Before analysis the plasma includes argon and left on for 30−60 min to stabilize the instrument. During this time the water spray (4.5) or flushing solution (4.6) via nebulizer and burner. The stabilization time depends on the type of instrument ICP-MS.
The calibration mass must be performed each morning before the start of the analysis that choose the seven elements [Ti, Y, Rh, Sb, CE, Pb and Bi (4.18)] in the order of their arrangement in the periodic table. For the calibration solution can be used, and other elements, but the content (in atomic mass units), they shall overlap concentration area to be analyzed.
Usually, the analysis connects the device automatic sampling by a peristaltic pump for the automatic introduction of samples into the plasma. You can also use manual input of samples. The devices are configured for optimum sensitivity. It is very important to adjust operating parameters, such as frequency, output power, plasma gas flow, auxiliary gas flow rate, gas flow rate to sprayer speed spray of the sample, method of detection, the integration time/peak, the number of points/peak number of replications and time of washing. In practice, the sensitivity will optimize the introduction of the calibration solution (e.g., a calibration solution of rhodium 100 µg/DMor any other suitable solution) into the plasma, and then configure the operating parameters.
6 measurement Techniques
6.1 Minimum precision (RSD)
Calculated relative standard deviation for 10 measurements of each analyzed element (concentration of each element, 10 µg/DM) in the selected matrix solution. The minimum precision (RSD) must not exceed 5%.
6.2 the Limit of detection (LD) and quantification limit (LQ)
The limit of detection (LD) and quantification limit (LQ) is calculated by the following formulas:
where is the standard deviation of the intensity for 10 measurements of the blank solution experience;
— the average intensity value for 10 measurements of a standard solution;
— the concentration of the standard solution, mg/l
;
— the average intensity value for 10 measurements of the blank solution experience.
7 Sampling
Sampling is carried out in accordance with ISO 14284 or national standards for sampling of steel.
8 Preparation of dishes
All glassware and plastic ware is kept in nitric acid (4.4), not less than 12 hours and then washed with water (4.5). Laboratory glassware should be stored in a dust-free place.
9 analysis
9.1 Linkage (analytical test)
As an analytical sample, weigh 100 mg of sample with accuracy of 0.01 mg.
Note — this standard specifies the method in which the nominal weight of 100 mg, but you can also use the sample of smaller mass, such as 10 mg.
9.2 Solution of a blank experiment (sample solution for the blank experience)
In parallel with the analysis of samples with unknown composition of the analyzed solution of the blank experience. The solution of the blank experience should contain the same quantities of reagents as in the analyzed solutions, and the same number of high-purity iron (4.15) as in the linkage sample.
9.3 Preparation of test solution
9.3.1 Analyze the solution to determine the elements Sn, Sb, Pb and Bi
Re-9.3.1.1 the Method of sample digestion in a microwave device
Weighed sample is placed in a vessel resistant to high pressure (further — a vessel for high pressure) PTFE (up to 120 cm) and add 3 cm
Hcl (4.1), 1 cm
HF (4.3). The lid of the vessel tightly screwed down. However, acid can be added in a loosely closed vessel and left for the night. This usually improves the process of wet decomposition.
Wet decomposition takes place in the system of microwave devices for the decomposition. Pressure vessels of PTFE is placed on a rotary table (carousel) or in a special holder placed in a laboratory microwave, and the decomposition is carried out under the influence of microwave radiation.
Wet decomposition performed in accordance with the three-step program, namely: the decomposition is conducted at a low temperature (about 50°C) for 10 min, and then at a temperature of about 100 °C also for 10 min and finally increasing the temperature to 150°C-200°C, decompose another 10 min.
Three-step program you can do a simple power adjustment of a microwave oven. If the decomposition in a microwave device lasts 30 minutes or longer, the pressure vessel of PTFE must be cooled to remove them from the microwave oven. The temperature in the pressure vessel of PTFE before opening them should not exceed 50 °C. the Operator, opening the vessels for high pressure, must wear plastic gloves.
Note — you Cannot open the door of the microwave oven immediately after running the program, because there is always a risk that the protective membrane in the pressure vessel of PTFE can break and miss the hot acid.
After cooling, the contents of the vessel are transferred into a plastic bottle or volumetric flask with a capacity of 100 cm, carefully washed vessel for high pressure PTFE with water (4.5) and combine the washings with the main solution. Bring the volume in the bottle or flask with water (4.5) to the mark and mix well.
9.3.1.2 Method of sample digestion on a hot plate in open vessels
Weighed samples were placed in a glass of PTFE or quartz with a graphite bottom with a capacity of 50 cm. Add 3 cm
HCI (4.1), cover the beaker watch glass and gently warmed until the termination of the reaction of dissolution. Add 1 cm
HF (4.3) and heated for 5 minutes If necessary, cool and add 5 cm
Cover a glass watch glass and continue heating, maintaining temperature at which condensation of white fumes of perchloric acid rises up the walls of the glass. Heating was continued until no allocation of fuming vapors of perchloric acid. The cooled solution is quantitatively transferred to a volumetric flask with a capacity of 100 cm, washing the walls of glass of water (4.5). Solution top up with water (4.5) to the mark and mix well.
Note — Cups PTFE with graphite bottom can easily deteriorate with increasing temperature, so temperature is necessary to raise very slowly.
9.3.2 Analyze the solution to determine the CE
9.3.2.1 Method of sample digestion in a microwave device
The sample is quantitatively placed in a vessel for high pressure PTFE (with a capacity of approximately 120 cm), poured 3 cm
HCI (4.1) and 1 cm
A three-step procedure can be performed by simply adjusting the power of the microwave oven. The whole process of autopsy samples in a microwave device takes 30 minutes and another 30 minutes is required for cooling vessels made of PTFE before they can be removed from the microwave oven. The temperature inside the vessels of PTFE before they are opened should be less than 50 °C. Plastic gloves should protect the hands of the operator when opening vessels made of PTFE.
Note — you Cannot open the door of the microwave oven immediately after the end of the program, since there is always the risk of rupture of the safety membrane of the reaction vessel made of PTFE for high pressure and ejection of hot acid.
After cooling, the contents of reaction vessels made of PTFE for high pressure quantitatively transferred into polyethylene bottle with a capacity of 100 cmor a volumetric flask of the same volume. Carefully washed walls of the reaction vessel with water (4.5), combining the washings with the main solution, the volume was adjusted to the mark with water (4.5) and mixed well.
9.3.2.2 decomposition of the sample on a hot plate using open vessels
Put a portion in a glass or quartz glass with a capacity of 100 cm. Add 3 cm
HCI (4.1), cover the beaker watch glass and gently warmed until the termination of the reaction of dissolution. Added to the reaction mixture 1, see
Cover the watch glass and continue heating at a temperature at which it forms a stable white pair of perchloric acid, the condensation which rises on the walls of the glass. Heating was continued until white pair inside the glass. Cool the solution and transfer it quantitatively into a measuring flask with a capacity of 100 cm, wash the side of the Cup with water (4.5) and combine the washings with the main solution. The volume was adjusted solution to the mark with water (4.5) and mixed well.
10 Standard solutions
Three standard solution is prepared and used further for preparing calibration solutions.
10.1 multi-element standard solutions includes the elements Sn, Sb, Pb and Bi
Preparation of multi-element standard solutions for the four elements described above, starting from the primary standard solution for each element (4.16.1, 4.16.2, 4.16.4, 4.16.5).
10.1.1 Preparation of solutions in the test tubes of polystyrene
Preparation of standard solutions directly in a test tube made of polystyrene with a capacity of 10 cmis convenient and saves time. Solutions adjusted water (4.5) to the desired volume. Prepare two standard solutions described
10.1.1.1 Preparation of multi — element solution-multistandarda concentration of 10 mg/DM
From each of the four primary standard solution (4.16.1, 4.16.2, 4.16.4, 4.16.5) taken at 0,10(100 µl) and added to a test tube made of polystyrene with a capacity of 10 cm
containing about 5 cm
of water (4.5). Multi-element solution was adjusted with water (4.5) to the desired volume by controlling the mass of a solution weighing
. Seal the test tube with a film parafilm and mixed standard solution (table 1).
____________________Is controlled by the net mass of the solution in the test tube.
Table 1 — Multistandard
The volume of each standard solution primary Standard |
Weight, micrograms | The volume of the test tube, cm |
The concentration of each element in the test tube after dilution, mg/DM |
| 0,10 (100) |
100 | 10 | 10 |
10.1.1.2 Preparation of multi-element solution — multistandardconcentration of 0.1 mg/DM
Select 0,10(100 µl) multi-element solution multistandard
in a test tube made of polystyrene with a capacity of 10 cm
. Prepare a solution by diluting with water (4.5) to the desired volume, determine the mass of a solution weighing
. Close the test tube with a film parafilm and mixed standard solution (table 2).
_______________Is controlled by the net mass of the solution in the test tube.
Table 2 — Multistandard
The volume of multistandard |
Weight, micrograms | The volume of the test tube, cm |
The concentration of each element in the test tube after dilution, mg/DM |
| 0,10 (100) | 1,0 | 10 | 0,10 |
10.1.2 Preparation of solutions in volumetric flasks
The standard solutions can be prepared in a volumetric flask with a capacity of 100 cm.
All solutions was adjusted to the mark with water (4.5). Multi-element solutions prepared in accordance with
10.1.2.1 Preparation of multi-element solution — multistandarda concentration of 10 mg/DM
From each of the four primary standard solutions (4.16.1, 4.16.2, 4.16.4, 4.16.5) select aliquot part of 1.0 cmand added to a volumetric flask with a capacity of 100 cm
containing about 50 cm
of water (4.5). Multi-element solution in the flask was diluted with water (4.5) to the mark and mixed well (table 3). A standard solution stored in a volumetric flask.
Table 3 — Multistandard
The volume of each standard solution primary Standard |
Weight, micrograms | Volume volumetric flasks, cm |
The concentration of each element in a volumetric flask after dilution, mg/DM |
| 1,0 |
1000 | 100 | 10 |
10.1.2.2 Preparation of multi — element solution-multistandardconcentration of 0.1 mg/DM
Make a 1.0 cmof multistandard
in a volumetric flask with a capacity of 100 cm
, diluted to the mark with water (4.5) and mixed well (table 4).
Table 4 — Multistandard
The volume of multistandard |
Weight, micrograms | Volume volumetric flasks, cm |
The concentration of each element in a volumetric flask after dilution, mg/DM |
| 1,0 | 10 | 100 | 0,10 |
10.2 Standard solutions of CE element
The CE element should be defined separately, because there is a risk of loss as sediment if the use of hydrofluoric acid. A standard solution of Se-the standard
should be prepared strictly according to the method, following the dilution scheme, starting with
11 Preparation of internal standard solution (internal standards) Y, Rh and Lu
11.1 Preparation of solutions in tubes made of polystyrene
In case the recommendation is to use internal standards in the analysis of multiple samples is necessary to account for instrumental drift if subjected to wet decomposition of steel samples with a complex matrix.
Internal standard elements Y, Lu and Rh is prepared in three separate test tubes made of polystyrene. In each of the three test-tubes with a capacity of 10 cmpour about 3 cm
of water (4.5). One of them added 0.10 cm
(100 µl) of the primary standard solution Rh (4.16.6), the second tube add 0.10 cm
(100 µl) of the primary standard solution Y (4.16.7) and the third test-tube add 0.10 cm
(100 µl) of the primary standard solution Lu (4.16.8). In all three test tubes get the right amount, diluting the solutions with water (4.5) and by determining the mass of a solution weighing. Then the test tube is closed with a film parafilm and mix the solutions. Solution concentration of internal standard in each tube of polystyrene should be 10 mg/DM
. Further, dilution will be necessary in accordance with the procedure of preparation of standard solutions (for Rh and Y —
.
11.2 Preparation of solutions in volumetric flasks
If the recommended use of internal standards in the analysis of several samples, it is necessary to take into account instrumental drift, especially in the wet decomposition of steel samples with a complex matrix.
Solutions of internal standards of the elements Y, Lu and Rh is prepared in three separate volumetric flasks with a capacity of 100 cmeach. In each of the three volumetric flasks pour approximately 50 cm
of water (4.5). One should add 1.0 cm
of the primary standard solution Rh (4.16.6) in the second volumetric flask, add 1.0 cm
of the primary standard solution Y (4.16.7) and the third volumetric flask add 1.0 cm
of the primary standard solution Lu (4.16.8). In all three flasks add water (4.5) to the mark and mix the solutions. The concentration of the internal standard in each volumetric flask is 10 mg/DM
. In the future will need dilution. The method of dilution in accordance with the scheme for standard solutions (Y and Rh —
.
12 Calibration solution blank experience and calibration solutions
Calibration solutions and a calibration blank solution experience for Sn, Sb and Pb is prepared for the concentration region from 0.4 to 200 mg/lin accordance with the methodology in the parts 12.1 and 12.2. Calibration solutions for the CoE needs to cover the region of concentrations from 5 to 1000 mg/l
, while for Bi, from 0.3 to 40 mg/DM
. The calibration blank solution experience and at least five calibration solutions shall be prepared to construct the calibration curve. Calibration curve must cover the concentration area of the analyzed samples with unknown composition. All calibration solutions must comply with the content of iron, acids used for wet decomposition of the samples, the same contents as in the solutions of analyzed samples of steel. To be added to the calibration solutions of iron as a matrix using a solution 10000 mg Fe/DM
(4.17). At the end add the internal standards solutions: Y, Rh and Lu for multi-element calibration solution blank experience (for the elements Sn, Sb, Pb and Bi) are also suitable, as for five multi-element calibration solutions (for the elements Sn, Sb, Pb and Bi). Lu as the internal standard for the calibration blank solution experience. also suitable for the five calibration solutions of CE.
12.1 Preparation of solutions in volumetric flasks
Prepare six volumetric flasks with a capacity of 100 cmeach, which are then used to prepare the calibration blank solution experience and calibration solutions for constructing the calibration curve. The concentrations of elements in the calibration solutions should be chosen to cover the concentration area in the analyzed samples.
Preparation of standard solutions in volumetric flasks perform in accordance with the methodology 12.1.1 and
12.1.1 Preparation multi-element calibration solution blank experience and multi-element calibration solutions of Sn, Sb, Pb and Bi
To build a calibration chart, the calibration requires the solution of the blank experience and at least five calibration solutions.
In six volumetric flasks with a capacity of 100 cmeach pour approximately 50 cm
of water (4.5), then prepare solutions in accordance with the procedure below, adding a matrix solution of iron (4.17), mineral acids and multielement standard solutions. Solutions of internal standards (Y and Rh) are added in such quantities to match the concentrations of the elements in the analyzed solution. Then the solutions were brought to volume with water (4.5) and stirred (see table 5).
12.1.2 Preparation of the calibration solution blank of experience on Se and Se calibration solutions
To build a calibration chart, the calibration requires the solution of the blank experience and at least five calibration solutions.
In six volumetric flasks with a capacity of 100 cmeach pour approximately 50 cm
of water (4.5), then prepare solutions in accordance with the procedure below, adding a matrix solution of iron (4.17), mineral acids and standard solutions of Se. The solution of the internal standard Lu is added in such an amount that is consistent with the CE concentration in the analyzed solution. Then the slurry was adjusted to the mark with water (4.5) and stirred (see table 6).
Note — HF is not added.
12.2 Preparation of solutions in the test tubes of polystyrene
Prepare not less than six test tubes made of polystyrene with a capacity of 10 cm, which are then used to prepare the calibration blank solution experience and calibration solutions for constructing the calibration curve. The concentrations of elements in the calibration solutions should be chosen to cover the concentration area of the analyzed samples.
Preparation of standard solutions in the test tubes is performed in accordance with the methodology 12.2.1 and
12.2.1 Preparation multi-element calibration solution blank experience and multi-element calibration solutions of Sn, Sb, Pb and Bi
To build a calibration chart, the calibration requires the solution of the blank experience and at least five calibration solutions.
In six test tubes of polystyrene pour about 3 cmof water (4.5), then prepare solutions in accordance with the procedure below, adding a matrix solution of iron (4.17) mineral acids and multielement standard solutions. Solutions of internal standards Y and Rh is added in such quantities to match the concentrations of the elements in the analyzed solution. Then adjusted to the desired volume with water (4.5), determining the mass of a solution weighing, close the test tube with a film parafilm and stirred (see table 7).
12.2.2 Preparation of the calibration solution blank of experience on Se and Se calibration solutions
To build a calibration chart, the calibration requires the solution of the blank experience and at least five calibration solutions.
In six test tubes of polystyrene pour about 3 cmof water (4.5), then prepare solutions in accordance with the procedure below, adding a matrix solution of iron (4.17), mineral acids and standard solutions of cerium. The solution of the internal standard Lu is added in such quantities to match the concentration of Se in the analyzed solution. Then the solutions were brought to volume with water (4.5), determining the mass of a solution weighing, close the test tube with parafilm foil and stirred (see table 8).
Note — HF is not added.
Table 5 — Preparation multi-element calibration solution blank experience and multi-element calibration solutions of Sn, Sb, Pb and Bi
Matrix solution |
HCI (4.1), see |
|
HF |
Size of primary standard solutions |
The amount of multi- |
The amount of multi- |
The concentration of each element in the calibration solution, mg/l |
The mass of each of the elements mg |
| 10 |
3 | 1 | 0,5 | 0 | 0 | 0 | 0 | 0 |
| 10 |
3 | 1 | 0,5 | 50 | 0 | 0 | 500 | 50 |
| 10 |
3 | 1 | 0,5 | 20 | 0 | 0 | 200 | 20 |
| 10 |
3 | 1 | 0,5 | 0 | 1000 | 0 | 100 | 10 |
| 10 |
3 | 1 | 0,5 | 0 | 500 | 0 | 50 | 5 |
| 10 |
3 | 1 | 0,5 | 0 | 200 | 0 | 20 | 2 |
| 10 |
3 | 1 | 0,5 | 0 | 100 | 0 | 10 | 1 |
| 10 |
3 | 1 | 0,5 | 0 | 50 | 0 | 5 | 0,5 |
| 10 |
3 | 1 | 0,5 | 0 | 20 | 0 | 2 | 0,2 |
| 10 |
3 | 1 | 0,5 | 0 | 0 | 1000 | 1 | 0,1 |
| 10 |
3 | 1 | 0,5 | 0 | 0 | 500 | 0,5 | 0,05 |
| 10 |
3 | 1 | 0,5 | 0 | 0 | 200 | 0,2 | 0,02 |
| ||||||||
(4.2), see
Table 6 — Preparation of the calibration solution blank of experience on Se and Se calibration solutions
Matrix solution |
HCI |
|
The volume of primary standard solution of Se (4.16.3), MKL | The volume of a standard solution of Se — the standard |
The concentration of CE in calibration solution, mg/l |
Mass of CE, mg |
| 10 |
3 | 1 | 0 | 0 | 0 | 0 |
| 10 |
3 | 1 | 200 | 0 | 2000 | 200 |
| 10 |
3 | 1 | 100 | 0 | 1000 | 100 |
| 10 |
3 | 1 | 50 | 0 | 500 | 50 |
| 10 |
3 | 1 | 20 | 0 | 200 | 20 |
| 10 |
3 | 1 | 0 | 1000 | 100 | 10 |
| 10 |
3 | 1 | 0 | 500 | 50 | 5 |
| 10 |
3 | 1 | 0 | 200 | 20 | 2 |
| 10 |
3 | 1 | 0 | 100 | 10 | 1 |
| 10 |
3 | 1 | 0 | 50 | 5 | 0,5 |
| 10 |
3 | 1 | 0 | 20 | 2 | 0,2 |
| ||||||
Table 7 — Trade mnogoletnego of the calibration blank solution and multiple element experience Gradirovsky solutions on Sn, Sb, Pb and Bi
Matrix solution |
HCI |
|
HF |
The amount of multi- |
The amount of multi- |
The concentration of each element in the calibration solution, mg/l |
The mass of each of the elements mg |
| 1,0 |
300 | 100 | 50 | 0 | 0 | 0 | 0 |
| 1,0 |
300 | 100 | 50 | 500 | 0 | 500 | 5,0 |
| 1,0 |
300 | 100 | 50 | 200 | 0 | 200 | 2,0 |
| 1,0 |
300 | 100 | 50 | 100 | 0 | 100 | 1,0 |
| 1,0 |
300 | 100 | 50 | 50 | 0 | 50 | 0,5 |
| 1,0 |
300 | 100 | 50 | 0 | 2000 | 20 | 0,2 |
| 1,0 |
300 | 100 | 50 | 0 | 1000 | 10 | 0,1 |
| 1,0 |
300 | 100 | 50 | 0 | 500 | 5 | 0,05 |
| 1,0 |
300 | 100 | 50 | 0 | 200 | 2 | 0,02 |
| 1,0 |
300 | 100 | 50 | 0 | 100 | 1 | 0,01 |
| 1,0 |
300 | 100 | 50 | 0 | 50 | 0,5 | 0,005 |
| |||||||
Table 8 — Preparation of the calibration solution blank of experience on Se and Se calibration solutions
Matrix solution |
HCI |
|
The volume of a standard solution of Se — the standard |
The volume of a standard solution of Se — the standard |
The concentration of CE in calibration solution, mg/DM |
Mass of CE, mg |
| 1,0 |
300 | 100 | 0 | 0 | 0 | 0 |
| 1,0 |
300 | 100 | 2000 | 0 | 2000 | 20,0 |
| 1,0 |
300 | 100 | 1000 | 0 | 1000 | 10,0 |
| 1,0 |
300 | 100 | 500 | 0 | 500 | 5,0 |
| 1,0 |
300 | 100 | 200 | 0 | 200 | 2,0 |
| 1,0 |
300 | 100 | 100 | 0 | 100 | 1,0 |
| 1,0 |
300 | 100 | 50 | 0 | 50 | 0,5 |
| 1,0 |
300 | 100 | 0 | 2000 | 20 | 0,2 |
| 1,0 |
300 | 100 | 0 | 1000 | 10 | 0,1 |
| 1,0 |
300 | 100 | 0 | 500 | 5 | 0,05 |
| 1,0 |
300 | 100 | 0 | 200 | 2 | 0,02 |
| ||||||
13 Preparation of instrument ICP-MS to work
Calibration of the instrument at mass, made the consistent introduction of mass calibration solution (4.18), is crucial for good preparation. In order to optimize the signal detector, enter the calibration solution with the concentration of Sb 100 mg/lduring setup of the operating parameters of the device. These two procedures should be performed daily.
Prior to ICP-MS measurements, the system of tubes and glass apparatus should be rinsed by pumping through the system for 5 min, wash solution (4.6).
14 ICP-MS measurement
Start the measurement with the calibration blank solution experience, then measured five calibration solutions, starting with the lowest concentration and ending with the element of highest concentration. Next measure the blank solution experience to analyze solutions of (9.2) to test the value of the idle experience for the analyzed samples and to determine if any memory effects from the calibration solution with the highest concentration. If so, increase the washing time between measurement samples. After the solution of the blank experience is measured ten analyzed samples and the next calibration standard solution (control sample). Repeat this procedure again with the ten analyzed samples and the calibration standard solution and so on. Thus, every tenth sample should be a calibration solution (control sample) and the last measured sample should be the calibration solution, even if the measured throughput is less than ten.
The concentration area of the elements in the calibration solutions should cover the concentration of elements in analyzed samples.
Note — the Calibration standard solution (control sample) is measured as the test sample, for example, a solution concentration of 100 µg/DMneeds to give the same intensity as obtained on the calibration curve. A certified standard sample (GSO) can also be used as a control sample.
15 the Construction of calibration graphs
It is necessary to prepare a new calibration curve for each series of determinations. Blank, when using pure metals and reagents, should not make any significant changes in the values of signal mass spectrum.
Calibration curve (calibration curve) must be based on the intensity values of mass spectra (usually expressed in counts per second, cps) of the calibration solutions with respect to the mass of element concentrations in the calibration solutions (mg/l). The value of the blank subtracted experience. In addition, the calibration curves should be calculated using one or two internal standards, and mass concentration of elements must be in the same range as that of the test sample.
Build gabonamong graphics and calculations of concentrations of the test sample is carried out automatically using a software instrument ICP-MS. Linearity of calibration curve should be checked by calculating regression coefficient, and its value shall be not less than 0,999.
The value of the intensities of the mass spectra of the analyzed samples is measured by subtracting the blank values. Concentrations of elements in the analyzed samples is found by a calibration curve.
If the intensity value of the blank on the spectrum experience the same or higher than that of the calibration solutions and the sample solution should be taken precautions. In this case, it is important that the intensity value for a single curve was very stable, as this value is later subtracted. A high intensity value in the spectrum of the idle experience may be due to mutual influence or several influences that can be reduced or even completely eliminated if you select a different isotope. However, in the case monoisotopic elements this is not possible and requires a more effective control for background signal.
16 Presentation of results
16.1 calculation Method
The concentration of each determined element, expressed through the intensity (in seconds or millivolts) of the analyzed solution and the blank solution experience, respectively. On the calibration graph all the results are obtained after subtraction of blank results of experiment (section 15).
Mass fraction w of each element µg/g is calculated according to the formula:
where is the mass of the analyzed element (mg) in the sample solution, obtained from the calibration curve, µg;
— the weight of the portion,
16.2 Precision
The precision of the present method was determined by tests carried out in ten laboratories for 10−12 grade levels for each item (depending on the analyzed element), thus, each laboratory performed three definitions (notes 1 and 2) of each item.
Note 1 — Two of the three definitions was conducted under the conditions of repeatability (ISO 5725−1, ISO 5725−2 and ISO 5725−3), i.e., single operator, same equipment at identical operating conditions, the same calibration and the minimum period of time.
Note 2 — the Third definition was made at a different time (the next day) by the same operator, as stated above, in note 1, using the same equipment, but with a new calibration.
Three of the results obtained in accordance with notes 1 and 2, repeatability , intralaboratory repeatability
and reproducibility
were calculated in accordance with ISO 5725−3 (Appendix C, section C. 1.).
Samples used for testing are listed in table A. 1 for Sn, in tables A. 2 and A. 3 for Sb, in tables A. 4 and A. 5 for Behold, in tables A. 6 and A. 7 for Pb and in tables A. 8 and A. 9 for Bi. The table presented along with the logarithmic graphs of the five investigated elements (Annex A).
The obtained results were processed statistically in accordance with ISO 5725−1, ISO 5725−2 and ISO 5725−3.
The data obtained showed a logarithmic dependence between the mass fraction of the five elements, and respectively: repeatability , reproducibility
and inter-laboratory reproducibility
of the test results. The data presented in tables: 9 — Sn, table 10 for Sb, in table 11, for Se, table 12, for Pb and in table 13 for Bi.
Table 9 — Repeatability and reproducibility for Sn
| Mass fraction of tin, ág/g | The frequency of occurrence |
Inter-laboratory reproducibility |
Reproducibility |
| 5 |
0,77 | 1,96 | 3,18 |
| 10 |
1,33 | 3,16 | 5,74 |
| 30 |
3,13 | 6,72 | 14,63 |
| 50 |
Of 4.66 | Of 9.55 | Of 22.60 |
| 100 |
8,00 | Of 15.39 | Of 40.78 |
| 150 |
10,97 | Of 20.33 | 57,59 |
| 200 |
Of 13.73 | 24,78 | Of 73.57 |
Table 10 Repeatability and reproducibility for Sb
| Mass fraction of antimony, ág/g | The frequency of occurrence |
Inter-laboratory reproducibility |
Reproducibility |
| 1 | 0,14 | 0,32 |
0,57 |
| 5 | 0,56 | 1,35 |
2,42 |
| 10 | 1,01 | 2,52 |
4,50 |
| 20 | Of 1.82 | 4,72 |
8,36 |
| 40 | 3,28 | Of 8.82 |
15,56 |
| 70 | 5,27 | 14,61 |
25,68 |
| 100 | 7,15 | 20,15 |
35,34 |
| 150 | 10,09 | 29.06 m |
50,80 |
| 200 | 12,89 | 37,66 |
65,73 |
Table 11 — Repeatability and reproducibility for CE
| The mass fraction of cerium, µg/g | Repeatability |
Intralaboratory reproducibility, |
Reproducibility |
| 10 | 0,92 | Of 1.07 |
4,19 |
| 40 | 2,65 | 3,72 |
13,97 |
| 70 | 4,05 | 6,15 |
22,71 |
| 100 | 5,32 | 8,47 |
30,96 |
| 200 | Of 9.02 | 15,78 |
56,52 |
| 300 | 12,29 | 22,70 |
Of 80.38 |
| 500 | 18,14 | 35,91 |
125,56 |
| 700 | 23,44 | 48,56 |
167,78 |
| 1000 | 30,76 | Of 66.89 |
228,69 |
Table 12 — Repeatability and reproducibility for Pb
| Mass fraction of lead, mg/g | The frequency of occurrence |
Inter-laboratory reproducibility |
Reproducibility |
| 0,5 | 0,12 |
0,32 | 0,42 |
| 1 | 0,20 |
0,52 | 0,78 |
| 2 | 0,35 |
0,85 | 1,44 |
| 4 | 0,60 |
1,38 | 2,65 |
| 7 | 0,94 |
2,03 | 4,35 |
| 10 | 1,24 |
2,61 | 5,95 |
| 20 | 2,15 |
Of 4.23 | 10,97 |
| 50 | 4,43 |
8,00 | 24,60 |
| 100 | 7,67 |
12,98 | 45,32 |
Table 13 — Repeatability and reproducibility for Bi
| Mass fraction of bismuth, mg/g | The frequency of occurrence |
Inter-laboratory reproducibility |
Reproducibility |
| 0,3 | 0,05 |
0,07 | 0,12 |
| 0,6 | 0,10 |
0,14 | 0,25 |
| 1 | 0,14 |
0,23 | 0,42 |
| 2 | 0,26 |
0,44 | 0,88 |
| 6 | 0,63 |
1,24 | Of 2.81 |
| 10 | 0,96 |
Of 2.00 | 4,83 |
| 20 | 1,70 |
3,84 | 10,05 |
| 30 | 2,37 |
Of 5.62 | In 15.43 |
17 test report
The test report must contain:
a) all information necessary for sample identification, the laboratory and date of testing;
b) Reference to this standard;
C) results of tests and form of their presentation;
g) any deviations and peculiarities that occurred in the process definition;
e) any operations not specified in this standard, or any additional operations that may affect the results.
Annex a (informative). For more information about conducting international trials
Appendix A
(reference)
Precision graphics data represented in the figures: A. 1 for Sn A. 2 for the Sb, A. 3 for Behold A. 4 for Pb in figure A. 5 for Bi in accordance with table A. 1 (Sn), tables A. 2 and A. 3 (Sb), tables A. 4 and A. 5 (CE), tables A. 6 and A. 7 (Pb), and tables A. 8 and A. 9 (Bi), respectively.
Studies were performed to fully cover the concentration area of 1 to 1000 µg/g in relation to the range of concentrations for five of the identified elements, respectively, given in section 1 of this standard.
Not all certified standard samples (CRMs) were used for each element, moreover, there are non-certified values, or approximate values in a certified sample (CRM), these values are marked with «?».
Values presented in tables A. 1-A. 9, obtained as a result of international tests in 2001−2005 for 12 samples of steel and 5 spike-in samples of steel in 10 laboratories in 6 countries.
Used samples are listed in tables A. 1-A. 9.
Figure A. 1 — Logarithmic plot between the mass fraction of tin and repeatability or reproducibility
X — mass fraction of Sn, mg/g
Y — precision, µg/g
1 — authentic ;
2 — authentic — ;
3 — authentic — ;
4 — ;
5 — ;
6 — ;
Figure A. 1 — Logarithmic plot between the mass fraction of tin and repeatability or reproducibility
Table A. 1 — Mass fraction of Sn — authentic samples
In milligram per gram
| Sample identification | Certifica- purpose value |
The obtained average value | Repeatability |
Nutrilab- |
To play DVDs. - |
| ECRM 090−1, BAS carbon steel (WG53−1) |
44 | 49,2 | 1,86 | 3,14 | Led light bulbs 26,95 |
| ECRM 295−1, BAS high-alloy steel (WG53−2) |
25 | 29,7 | 3,28 | 7,50 | 8,83 |
| ECRM 179−2, BAS tool steel (WG53−3) |
? | 102 | 23,60 | 23,60 | 36,57 |
| ECRM 188−1, IRSID Low alloy steel (WG53−4) |
? | 15,2 | 1,14 | 5,57 | Of 6.98 |
| JK1C, JK/SIMR Low alloy cast iron (WG53−5) |
24 | 25,6 | 1,56 | 5,40 | 11,05 |
| JK37, JK/SIMR high-alloy steel (WG53−6) |
20 | 16,9 | 1,67 | 5,91 | 10,19 |
| NIST 361 (AIS14340) Low alloy steel (WG53−7) |
100 | 97,2 | 4,73 | Of 12.33 | Accounting period 32.85 |
| ECRM 187−1, YOU Low-alloy steel (WG53−8) |
110 | 110 | To 10.43 | To 10.43 | 54,49 |
| GBW01222, SBQTS Carbon steel (WG53−9) |
260 | 264 | 18,62 | 50,53 | 106,04 |
| GBW01619, SBQTS high temperature Nickel-based alloy (WG53−14) |
103 | 107 | 12,38 | 15,92 | 44,47 |
| GBW01622, SBQTS high temperature Nickel-based alloy (WG53−15) |
1040 | 1072 | 47,78 | 87,37 | 328,81 |
| JSS 175−5, ISIJ Low alloy steel (WG53−17) |
? | 5,92 | 2,20 | 2,65 | 5,34 |
Figure A. 2 — Logarithmic relationship between the mass fraction of antimony and repeatability or reproducibility
X — mass fraction of Sb, ug/g;
Y — precision, ug/g;
1 — authentic ;
2 — authentic — ;
3 — authentic — ;
4 spike ;
5 spike ;
6 — spike ;
7 — ;
8 — ;
9 — ;
Figure A. 2 — Logarithmic relationship between the mass fraction of antimony and repeatability or reproducibility
Table A. 2 — Mass fraction of Sb — authentic samples
In milligrams per gram
| Sample identification | Certifica- purpose value |
The obtained average value | Repeatability |
Nutrilab- |
Of rehabilitation |
| ECRM 090−1, BAS carbon steel (WG53−1) |
9,0 | 10,3 | 0,99 | 1,40 | Of 6.52 |
| ECRM 295−1, BAS high-alloy steel (WG53−2) |
25 | 7,8 | 1,43 | 1,71 | 3,83 |
| ECRM 179−2, BAS tool steel (WG53−3) |
17,5 | 19,5 | 3,94 | 3,94 | Of 8.39 |
| ECRM 188−1, IRSID Low alloy steel (WG53−4) |
4,8 | 5,15 | 0,77 | 0,92 | 1,98 |
| JK1C, JK/SIMR Low alloy cast iron (WG53−5) |
1,7 | 1,69 | 0,38 | 0,69 | 0,69 |
| JK37, JK/SIMR high-alloy steel (WG53−6) |
20 | 16,9 | 1,67 | 5,91 | 10,19 |
| NIST 361 (AIS14340) Low alloy steel (WG53−7) |
42 | 42,7 | 1,71 | 9,10 | 17,51 |
| ECRM 187−1, YOU Low-alloy steel (WG53−8) |
? | 28,1 | 3,15 | 6,87 | 10,62 |
| GBW01222, SBQTS Carbon steel (WG53−9) |
? | The 10.1 | 0,78 | 2,11 | 3,91 |
| GBW01619, SBQTS high temperature Nickel-based alloy (WG53−14) |
204 | 212 | Of 18.57 | 42,57 | 95,39 |
| GBW01622, SBQTS high temperature Nickel-based alloy (WG53−15) |
7,4 | 7,66 | 0,63 | 4,97 | 4,97 |
| JSS 175−5, Low-alloy steel ISIJ (\М353−17) |
190 | 204 | 10,00 | 43,83 | 63,40 |
Table A. 3 — Mass fraction of Sb — spike samples
In milligrams per gram
| Sample identification | Certifica- purpose value |
The obtained average value | Repeatability |
Nutrilab- |
Of rehabilitation |
| ECRM 295−1, BAS high Alloyed steel spike 1b (WG53−2) |
7 | Of 9.61 | 0,94 | 3,23 | 5,02 |
| ECRM 179−2, YOU tool steel spike 2b (WG53−3) |
17,5 | 20,6 | 2,15 | 2,47 | Of 7.93 |
| JK1C, JK/SIMR Low alloy cast iron spike 3b (WG53−5) |
1,7 +1000 |
1080 | 53,56 | 204,12 | 204,12 |
| GBW01622, SBQTS high temperature Nickel-based alloy spike 4b (WG53−15) |
7,4 | 8,3 | 0,69 | 1,85 | 4,65 |
| JSS 175−5, Low-alloy steel ISIJ spike 5b (WG53−17) |
1,7 | 1,95 | 0,14 | 0,67 | 40,79 |
Figure A. 3 — Logarithmic relationship between the mass fraction of cerium and repeatability or reproducibility
X — mass fraction of Se, ug/g;
Y — precision, ug/g;
1 — authentic ;
2 — authentic — ;
3 — authentic — ;
4 spike ;
5 spike ;
6 — spike ;
7 — ;
8 — ;
9 —
Figure A. 3 — Logarithmic relationship between the mass fraction of cerium and repeatability or reproducibility
Table A. 4 — Mass fraction of Se — spike — samples
In milligrams per gram
| Sample identification | Certifica- purpose value |
The obtained average values | Repeatability |
Nutrilab- |
To play DVDs. - |
| ECRM 090−1, BAS carbon steel (WG53−1) |
<0,045 | - | - | - | - |
| ECRM 295−1, BAS high-alloy steel (WG53−2) |
? | - | - | - | - |
| ECRM 179−2, BAS tool steel (WG53−3) |
? | - | - | - | - |
| ECRM 188−1, IRSID Low alloy steel (WG53−4) |
? | - | - | - | - |
| JK1C, JK/SIMR Low alloy cast iron (WG53−5) |
<0,2 | - | - | - | - |
| JK37, JK/SIMR high-alloy steel (WG53−6) |
1230 | 1150 | Of 19.83 | Is 40.87 | 128,15 |
| NIST 361 (AIS14340) Low alloy steel (WG53−7) |
40 | 39,52 | 1,48 | 2,22 | Of 2.83 |
| ECRM 187−1, YOU Low-alloy steel (WG53−8) |
? | - | - | - | - |
| GBW01222,SBQTS Carbon steel (WG53−9) |
8,5 | 7,33 | 1,11 | 1,20 | 7,86 |
| GBW01619, SBQTS high temperature Nickel-based alloy (WG53−14) |
83 | 64,3 | 56,00 | 56,00 | 61,98 |
| GBW01622, SBQTS high temperature Nickel-based alloy (WG53−15) |
0,36 | - | - | - | - |
| JSS 175−5, ISIJ Low alloy steel (WG53−17) |
? | - | - | - | - |
Table A. 5 — Mass fraction of Se — spike samples
In milligrams per gram
| Sample identification | Certifi- qualified value |
The obtained average values | Repeatability |
Nutrilab- |
To play DVDs. - |
| ECRM 295−1, BAS high Alloyed steel spike 1b (WG53−2) |
? +110 |
133 | 9,39 | For 36.05 | 62,62 |
| ECRM 179−2, YOU tool steel spike 2b (WG53−3) |
<0,3 +11 |
12,6 | 0,59 | 2,25 | 8,31 |
| JK1C, JK/SIMR Low alloy cast iron spike Зb (WG53−5) |
<0,2 +0,1 |
- | - | - | - |
| GBW01622, SBQTS high temperature Nickel-based alloy spike 4b (WG53−15) |
? +400 |
477 | To 24.99 | To 24.99 | 157,25 |
| JSS 175−5, Low-alloy steel ISIJ spike 5b (WG53−17) |
<0,2 +800 |
896 | 32,50 | 92,00 | 389,06 |
Figure A. 4 is a Logarithmic dependence between the mass fraction of lead and repeatability or reproducibility
X — mass fraction of Pb, ug/g;
Y — precision, ug/g;
1 — authentic ;
2 — authentic — ;
3 — authentic — ;
4 spike ;
5 spike ;
6 — spike ;
7 — ;
8 — ;
9 — ;
Figure A. 4 is a Logarithmic dependence between the mass fraction of lead and repeatability or reproducibility
Table A. 6 — Mass fraction of Pb — authentic samples
In milligrams per gram
| Sample identification | Certifica- purpose value |
The obtained average values | Repeatability |
Nutrilab- |
Of rehabilitation |
| ECRM 090−1, BAS carbon steel (WG53−1) |
23,9 | 22,8 | 1,70 | 1,75 | Of 5.71 |
| ECRM 295−1, BAS high-alloy steel (WG53−2) |
? | - | - | - | - |
| ECRM 179−2, BAS tool steel (WG53−3) |
1,3 | 1,43 | 0,29 | 0,65 | 0,72 |
| ECRM 188−1, IRSID Low alloy steel (WG53−4) |
<1 | - | - | - | - |
| JK1C, JK/SIMR Low alloy cast iron (WG53−5) |
<0,3 | - | - | - | - |
| JK37, JK/SIMR high-alloy steel (WG53−6) |
1,29 | 1,30 | 0,12 | 0,56 | 0,63 |
| NIST361 (AIS14340) Low alloy steel (WG53−7) |
0,25 | - | - | - | - |
| ECRM 187−1, YOU Low-alloy steel (WG53−8) |
? | 0,52 | 0,13 | 0,57 | 0,57 |
| GBW01222, SBQTS Carbon steel (WG53−9) |
? | - | - | - | - |
| GBW01619, SBQTS high temperature Nickel-based alloy (WG53−14) |
12 | 12,3 | 1,79 | 2,43 | 9,32 |
| GBW01622, SBQTS high temperature Nickel-based alloy (WG53−15) |
2,2 | 1.52 m | 0,62 | 2,46 | 2,89 |
| JSS 175−5, ISIJ Low alloy steel (WG53−17) |
? | 2,12 | 0,26 | 0,82 | 1,21 |
Table A. 7 — Mass fraction of Pb spike samples
In milligrams per gram
| Sample identification | Certifica- purpose value |
The obtained average values | Repeatability |
Nutrilab- |
Monito- |
| ECRM 295−1, BAS high Alloyed steel spike 1b (WG53−2) |
? +40 |
45,7 | 2,39 | 2,67 | 18,48 |
| ECRM 179−2, YOU tool steel spike 2b (WG53−3) |
1,3 | 1.55 V | 0,42 | 0,42 | 1,36 |
| JK1C, JK/SIMR Low alloy cast iron spike 3b (WG53−5) |
<0,3 +0,1 |
- | - | - | - |
| GBW01622, SBQTS high temperature Nickel-based alloy spike 4b (WG53−15) |
2,2 +540 |
567 | To 23.17 | 102,86 | 307,30 |
| JSS 175−5, Low-alloy steel ISIJ spike 2b (WG53−17) |
<0,3 +1100 |
1230 | 101,76 | 101,76 | 424,71 |
Figure A. 5 is a Logarithmic dependence between the mass fraction of bismuth and repeatability or reproducibility
X — mass fraction of Bi, ug/g;
Y — precision, ug/g;
1 — authentic ;
2 — authentic — ;
3 — authentic — ;
4 spike ;
5 spike ;
6 — spike ;
7 — ;
8 — ;
9 — ;
Figure A. 5 is a Logarithmic dependence between the mass fraction of bismuth and repeatability or reproducibility
Table A. 8 — Mass fraction of Bi — authentic samples
In milligrams per gram
| Sample identification | Certifica- rovanie values |
The obtained average values | Repeatability |
Nutrilab- |
Of rehabilitation |
| ECRM 090−1, BAS carbon steel (WG53−1) |
<0,2 | - | - | - | - |
| ECRM 295−1, BAS high-alloy steel (WG53−2) |
? | - | - | - | - |
| ECRM 179−2, BAS tool steel (WG53−3) |
<0,3 | - | - | - | - |
| ECRM 188−1, IRSID Low alloy steel (WG53−4) |
<0,2 | - | - | - | - |
| JK1C, JK/SIMR Low alloy cast iron (WG53−5) |
<0,1 | - | - | - | - |
| JK37, JK/SIMR high-alloy steel (WG53−6) |
0,32 | 0,33 | 0,03 | 0,09 | 0,14 |
| NIST 361 (AIS14340) Low alloy steel (WG53−7) |
4 | 5,10 | 0,39 | 0,69 | 2,50 |
| ECRM 187−1, YOU Low-alloy steel (WG53−8) |
? | - | - | - | - |
| GBW01222, SBQTS Carbon steel (WG53−9) |
? | - | - | - | - |
| GBW01619, SBQTS high temperature Nickel-based alloy (WG53−14) |
4,2 | 4,54 | Of 1.08 | 0,96 | 0,96 |
| GBW01622, SBQTS high temperature Nickel-based alloy (WG53−15) |
0,5 | 0,52 | 0,15 | 0,15 | 0,26 |
| JSS 175−5, ISIJ Low alloy steel (WG53−17) |
?* | 2,12 | 0,26 | 0,82 | 1,21 |
___________________
* Consistent with the original. — Note the manufacturer’s database.
Table A. 9 — Mass fraction of Bi — spike samples
In milligrams per gram
| Sample identification | Certifi- qualified values |
The obtained average values | Repeatability |
Nutrilab- |
To play DVDs. - |
| ECRM 295−1, BAS high Alloyed steel spike 1b (WG53−2) |
? +200 |
237 | Of 12.40 | 30,20 | 185,65 |
| ECRM 179−2, YOU tool steel spike 2b (WG53−3) |
<0,1 +0,1 |
13,5 | 1,12 | 3,48 | 9,62 |
| JK1C, JK/SIMR Low alloy cast iron spike 3b (WG53−5) |
<0,1 +0,1 |
- | - | - | - |
| GBW01622, SBQTS high temperature Nickel-based alloy spike 4b (WG53−15) |
? 0,5 |
- | - | - | - |
| JSS 175−5, Low-alloy steel ISIJ spike 5b (WG53−17) |
<0,1 +1000 |
1210 | By 45.45 | 223,75 | 635,71 |
Annex b (informative). Isotopes, hampering the definition of the elements Sn, Sb, CE, Pb and Bi using the method ICP-MS
The App
(reference)
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App YES (reference). Information about the compliance of the referenced international standards national standards of the Russian Federation (and acting in this capacity inter-state standards)
App YES
(reference)
Table YES.1
| Marking the reference international standard: | The degree of compliance | Designation and name of the relevant national standard |
| ISO 648−1977 | MOD | GOST 29169−91 (ISO 648−77) oils. Pipette with one mark |
| ISO 1042:1998 | IDT | * |
| ISO 5725−1:1994 | IDT | GOST R ISO 5725−1-2002 Accuracy (trueness and precision) of methods and measurement results. Part 1. General provisions and definitions |
| ISO 5725−2:1994 | IDT | GOST R ISO 5725−2-2002 Accuracy (trueness and precision) of methods and measurement results. Part 2. The basic method for the determination of repeatability and reproducibility of a standard measurement method |
| ISO 5725−3:1994 | IDT | GOST R ISO 5725−3-2002 Accuracy (trueness and precision) of methods and measurement results. Part 3. Intermediate indicators the precision of a standard measurement method |
| ISO 14284:1996 | IDT | GOST R ISO 14284−2009 Steel and cast iron. Selection and preparation of samples for the determination of chemical composition |
| Note — In this table the following symbols have been used the degree of conformity of standards: — IDT — identical standards; — MOD — modified standards | ||
| UDC 669.14:620.2:006.354 | OKS 77.080.20 |
| Key words: steel, cast iron, determination of content, tin, antimony, cerium, lead, bismuth, mass-spectrometric method with inductively coupled plasma | |
