GOST 23862.9-79
GOST 23862.9−79 Neodymium, gadolinium, terbium, dysprosium, holmium, erbium, thulium and their oxides. Chemical-spectral method of determination of impurities of oxides of rare earth elements (with Change No. 1)
GOST 23862.9−79
Group B59
INTERSTATE STANDARD
NEODYMIUM, GADOLINIUM, TERBIUM, DYSPROSIUM, HOLMIUM, ERBIUM, THULIUM AND THEIR OXIDES
Chemical-spectral method of determination of impurities of oxides of rare earth elements
Neodymium, gadolinium, terbium, holmium, erbium, thulium and their oxides. Chemical-spectral method of determination of impurities in oxides of rare-earth elements
ISS 77.120.99
AXTU 1709
Date of introduction 1981−01−01
The decision of the State Committee USSR on standards on October 19, 1979 N 3988 date of introduction is established 01.01.81
Limitation of actions taken by Protocol No. 7−95 Interstate Council for standardization, Metrology and certification (ICS 11−95)
EDITION with Change No. 1, approved in April 1985 (IUS 7−85).
This standard specifies the chemical-spectral method of determination of impurities of oxides of rare earth elements neodymium, gadolinium, terui, dysprosium, holmium, arbie, the thules and their oxides.
The method is based on extraction-chromatographic concentration of rare-earth dopants, depositing them with the filler, oxide of yttrium and subsequent spectral analysis of the obtained concentrate.
Intervals determined by a mass fraction of impurities of oxides:
| in the neodymium and its oxide: | |
| gadolinium |
4·10 |
| terbium |
from 1·10 |
| dysprosium |
4·10 |
| holmium |
4·10 |
| erbium |
2·10 |
| thulium |
2·10 |
| ytterbium |
2·10 |
| Lutetia |
2·10 |
| in gadolinium and its oxide: | |
| terbium |
from 1·10 |
| dysprosium |
4·10 |
| holmium |
4·10 |
| erbium |
2·10 |
| thulium |
2·10 |
| ytterbium |
2·10 |
| Lutetia |
2·10 |
| in terbia and its oxide: | |
| Lantana |
7·10 |
| cerium |
from 1·10 |
| praseodymium |
from 1·10 |
| neodymium |
7·10 |
| Samaria |
7·10 |
| europium |
from 1·10 |
| gadolinium |
from 1·10 |
| dysprosium |
7·10 |
| holmium |
from 1·10 |
| erbium |
7·10 |
| thulium |
from 1·10 |
| ytterbium |
7·10 |
| Lutetia |
from 1·10 |
| in holmium and its oxide: | |
| Lantana |
4·10 |
| cerium |
4·10 |
| praseodymium |
4·10 |
| neodymium |
4·10 |
| Samaria |
4·10 |
| europium |
4·10 |
| gadolinium |
from 1·10 |
| terbium |
4·10 |
| dysprosium |
from 1·10 |
| erbium |
from 1·10 |
| thulium |
from 1·10 |
| ytterbium |
4·10 |
| Lutetia |
from 1·10 |
| in tuliya and its oxide: | |
| Lantana |
2·10 |
| cerium |
2·10 |
| praseodymium |
2·10 |
| neodymium |
2·10 |
| Samaria |
2·10 |
| europium |
2·10 |
| gadolinium |
from 5·10 |
| terbium |
2·10 |
| dysprosium |
from 5·10 |
| holmium |
from 5·10 |
| erbium |
from 5·10 |
| ytterbium |
2·10 |
| Lutetia |
4·10 |
| in dysprosium and its oxide: | |
| Lantana |
2·10 |
| cerium |
2·10 |
| praseodymium |
2·10 |
| neodymium |
2·10 |
| Samaria |
2·10 |
| europium |
2·10 |
| gadolinium |
from 5·10 |
| terbium |
2·10 |
| holmium |
from 1·10 |
| erbium |
from 1·10 |
| thulium |
4·10 |
| ytterbium |
2·10 |
| Lutetia |
4·10 |
| in erbie and its oxide: | |
| Lantana |
4·10 |
| praseodymium |
4·10 |
| neodymium |
4·10 |
| Samaria |
4·10 |
| europium |
4·10 |
| gadolinium |
from 1·10 |
| terbium |
4·10 |
| dysprosium |
from 1·10 |
| holmium |
from 1·10 |
| thulium |
from 1·10 |
| ytterbium |
4·10 |
| Lutetia | from 1·10 |
1. GENERAL REQUIREMENTS
1.1. General requirements for method of analysis according to GOST 23862.0−79.
2. APPARATUS, MATERIALS AND REAGENTS
Column chromatography of molybdenum glass with a height of 600−800 mm from the water jacket (see GOST 23862.7−79, damn.1).
A quartz column with an inner diameter of 15 mm and height 35 mm.
Evaporators made of molybdenum glass (see the devil.2 GOST 23862.7−79).
The thermostat TS-16 or similar, ensure the water temperature up to (40±2) °C.
Potentiometer LPU-01, or similar for measurement of pH in the range of 1−11.
Ball mill metal with a diameter of 210 mm, height 200 mm, weight 4 kg.
Metal balls with a diameter of 30 mm, 25 PCs.
Sieves of metal.
Drying oven with thermostat providing temperatures up to 200 °C.
Muffle furnace with thermostatic control, providing temperature up to 1000 °C.
Motor sewing DSS-2.
The diffraction spectrograph DFS-13 with a grating 1200 lines/mm, operating in first order of reflection, with single lens and three-lens Achromat lighting system.
The arc generator type DG-2 with optional rheostat or similar, suitable for ignition of the arc DC high-frequency discharge.
Spectromancer PS-18 or similar.
Rectifier 250−300, 30−50 A.
Microphotometer geregistreerde type MF-2 or similar.
Analytical scale.
Libra torsion type VT-500 or similar.
The machine tool for sharpening of electrodes.
Tile electric.
Water jet pump laboratory glass according to GOST 25336−82.
Camera of quartz, consisting of a cylinder with a height of 40−45 mm, a diameter of 50 mm, made of optical quartz and two round plates with a diameter of 70 mm made of technical quartz. Quartz cylinder lies freely on the bottom plate, the upper plate is lowered onto the cylinder. In each of the plates has an outlet pipe for gas supply and the opening for the electrodes.
The flowmeters type RS-3.
Reducers oxygen.
Pressure gauges according to GOST 2405−88 1−4 kgf/cm.
Coals spectral high purity-7−3 with a diameter of 6 mm.
The electrodes are machined from high purity coals spectral-7−3, sharpened to a truncated cone with an apex angle of 15° and a platform with a diameter of 1.5 mm.
The electrodes are machined from high purity coals spectral-7−3 with a side height of 1 mm.
The electrodes are machined from high purity coals spectral-7−3 with a channel depth of 5 mm, a diameter of 2 mm and a wall thickness of 1 mm.
Graphite powder of high purity according to GOST 23463−79.
Photographic plates type size 1 9х24 or equivalent, providing normal blackening of analytical lines in the spectrum.
Bath water.
A Buchner funnel with a diameter of 132 mm, 120−140 mm.
Separating funnel with a capacity of 1000, 2000 cm.
Micropipettes 0.1 cm, hydrophobized with dimethyldichlorosilane. For this inside part of the pipette 2−3 times washed with dimethyldichlorosilane and dried at 120 °C.
Burettes with a capacity of 25 cm.
A glass bulb with a capacity of 1,000 cmwith a reflux condenser.
Glass propeller stirrer.
The quartz crucibles with a capacity of 10−15 cmhydrophobized inner wall of the quartz crucible is washed with dimethyldichlorosilane and dried at 120 °C.
A device for distillation flask furca, with a capacity of 500, 1000 cm.
Tube rubber.
The polyethylene film.
Paper universal indicator pH 1−10.
Silica gel brand KSK N 2 or 2.5.
Ftoroplast-4 (Teflon), powder with grain size ~0.1 mm.
The wool is Teflon.
Oxides of rare earth elements: lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium, yttrium, clean-defined impurities.
Copper sulfate 5-water according to GOST 4165−78, 0.5 mol/DMsolution.
Standard solutions of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium containing 10 mg/cmof one of REE in the calculation of the oxide. Each solution is prepared separately, 1 g of the appropriate oxide of re is placed in a beaker with a capacity of 100 cm
, add 10 cm
of hydrochloric acid (1:1) and heated until complete dissolution of the oxide; the solution was then cooled, transferred to a volumetric flask with a capacity of 100 cm
and the volume was adjusted to the mark with water.
The solutions of internal standard containing 1 mg/cmcerium or 1 mg/cm
erbium; prepared by diluting 10 cm
of a standard solution of cerium (10 mg/cm
) or 10 cm
standard solution erbium (10 mg/cm
) ten times 1 mol/DM
hydrochloric acid solution.
A solution of 1 containing 0.1 mg/cmof lanthanum, cerium, praseodymium, neodymium, samarium, europium, calculated on oxide: 1 cm
of each standard solution (10 mg/cm
) of lanthanum, cerium, praseodymium, neodymium, samarium, europium is placed in a volumetric flask with a capacity of 100 cm
and the volume was adjusted up to the mark of 1 mol/DM
hydrochloric acid solution.
Solution 2 containing 0.1 mg/cmof gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, based on the oxide: 1 cm
of each standard solution (10 mg/cm
) of gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium is placed in a volumetric flask with a capacity of 100 cm
and the volume was adjusted up to the mark of 1 mol/DM
hydrochloric acid solution.
Sodium acetate according to GOST 199−78, H. h, a saturated solution.
Sodium chloride according to GOST 4233−77, solutions with concentrations of 100 g/land 20 g/DM
.
Sodium hydroxide according to GOST 4328−77, H. h, 0,1; 0,5; 1; 2; 3 mol/DMsolutions.
Hydrochloric acid by the GOST 3118−77, H. h, concentrated and titrated solutions: 0,01; 0,1; 0,3; 0,4; 0,5; 0,8; 1; 1,1; 1,2; 1,5; 2; 2,2; 2,4; 2,5; 3; 4; 5; 7 mol/DM.
Hydrochloric acid double-distilled, a 1.5 mol/DMsolution.
Oxalic acid according to GOST 22180−76, H. h, a saturated solution.
Nitric acid GOST 4461−77, H. h, concentrated, 3,5; 7 mol/DMsolutions.
Hydrofluoric acid according to GOST 10484−78, H. h, concentrated and 1 mol/DMsolution.
Ammonia water according to GOST 3760−79, H. h, concentrated, 5% solution.
Hydrogen peroxide according to GOST 10929−76.
Acetone according to GOST 2603−79.
Arsenazo III solution with a concentration of 0.2 g/DM.
For NTD phenolphthalein, alcohol solution with a concentration of 10 g/DM.
Di (2-ethylhexyl) phosphoric acid (D2EHPA), technical (50−70%) and improved (at least 95%).
D2EHPA 100%: produced from technical D2EHPA or D2EHPA improved cleaning for GOST 23862.7−79.
The ethyl ether.
The technical rectified ethyl alcohol GOST 18300−87.
The dimethyldichlorosilane.
Carbon tetrachloride according to GOST 20288−74.
The dimethyldichlorosilane solution in carbon tetrachloride (1:4).
Benzene according to GOST 5955−75.
Polystyrene.
A solution of polystyrene in benzene with a concentration of 20 g/lprepared on the day of use.
Sec. 2. (Changed edition, Rev. N 1).
3. PREPARATION FOR ASSAY
3.1. References (OS) is prepared immediately before photographing spectra with mixing in 1:1 ratio of samples for graphite powder (UCP) and clean at the designated impurities of an oxide of yttrium.
3.2. Samples on graphite powder (UCP) is prepared by mixing powder of graphite with oxides of rare earth elements. To prepare ОГП1 containing 1% (by weight) of the oxides of gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium, in a Jasper mortar place of 1.82 g of graphite powder and 20 mg svezhepoymannyh oxides of gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium and lutetium. The content was stirred for 30 min, the alcohol is added as supporting a pasty mass. After mixing the alcohol burn and the mixture stirred for 3 min. Samples of UCP 2 and UCP 10 prepare a serial dilution of UCP 1, and then each subsequent sample of powdered graphite, each time repeating the procedure of mixing and burning the alcohol as described for the preparation of sample 1 UCP. The content of each of the designated impurities in the samples of the UCP 1-UCP 10 and added to the mixture of graphite powder sample and the previous sample are shown in table.1.
Table 1
| Marking sample |
The mass fraction of each impurity determined based on the content of oxides in the mixture of oxides and powdered graphite, % | The mass of charge, g | |
| powder graphite |
the previous sample (in parentheses symbol) | ||
| UCP 1 |
1,0 |
- | - |
| UCP 2 |
5·10 |
0,885 |
0,885 (UCP 1) |
| UCP 3 |
2·10 |
1,155 |
0,770 (UCP 2) |
| UCP 4 |
1·10 |
0,940 |
0,940 (UCP 3) |
| UCP 5 |
5·10 |
0,880 |
0,880 (UCP 4) |
| UCP 6 |
2·10 |
1,140 |
0,760 (UCP 5) |
| UCP 7 |
1·10 |
0,900 |
0,900 (UCP 6) |
| UCP 8 |
5·10 |
0,800 |
0,800 (UCP 7) |
| UCP 9 |
2·10 |
0,900 |
0,600 (UCP 8) |
| UCP 10 |
1·10 |
0,500 |
0,500 (UCP 9) |
3.3. The mixtures with the internal standard
The mixture powder of graphite and cerium dioxide (OGC), containing 4% of cerium dioxide, is prepared by mixing 960 mg graphite powder and 40 mg of cerium dioxide in agate mortar for 30 min with the addition of alcohol, maintaining a mushy state of mass. Then the alcohol burn and the mixture was stirred for 3 min.
A mixture of oxides of yttrium and of cerium dioxide (JRC), containing 4% of cerium dioxide, is prepared by mixing 960 mg of yttrium oxide and 40 mg of cerium dioxide in agate mortar and then do as in the preparation OGC.
4. ANALYSIS
4.1. Analysis of neodymium oxide or its
Determination of oxides of gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium
Concentrates impurities get in an extraction-chromatographic column with a water jacket. The inner diameter of the column 16 mm. Column filled with sorbent (25 g of silica gel with a grain size of 0.06−0.07 mm+15 cm100% D2EHPA, the free volume of the sorbent 40 cm
). Filling of the column section.3 23862.7 GOST-79. A portion of metal neodymium with a mass of 0.86 g or 1 g of its oxide was placed in a beaker with a capacity of 50 cm
, add 6−8 cm
7 mol/DM
of hydrochloric acid, 0.5 cm
of hydrogen peroxide and heated to dissolution. The solution is evaporated to wet salts; chlorides of rare earth elements is dissolved in 30 cm
0.1 mol/DM
hydrochloric acid and passed through an extraction-chromatographic column. The technique works on an extraction-chromatographic column according to sect.3 23862.7 GOST-79.
The glass in which was dissolved the sample was washed with 0.7 mol/DMhydrochloric acid with a volume of 5 cm
. Flushing solution passed through the column. Then passed through a column of 0.7 mol/DM
hydrochloric acid, 90 cm
eluate collected in a beaker (solution of neodymium). Next, the eluate collected in vials in portions of 5 cm
, in each of which detect the presence of a neodymium sec. 3 23862.7 GOST-79. The portions of eluate not containing neodymium, are transferred into the evaporator and is evaporated with subsequent portions of the eluate. Subsequent portions of the eluate receive, passing through a column of 300 cm
7 mol/DM
of hydrochloric acid. The eluate is evaporated in the evaporator to a volume of 15−20 cm
and transferred into a beaker with a capacity of 50 cm
(concentrate of impurities REE).
The concentrate of REE impurities are added 20 mg of yttrium oxide, was heated until complete dissolution, prepare for the spectral analysis in sect.3 GOST 23862.7−79 and analyzed by the method given in claim 4.8 of this standard.
Mass fraction of the oxides of gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium () in percent is calculated by the formula
where — mass fraction determined by impurities in the obtained oxide of yttrium enriched with impurities of REE, %.
4.2. Analysis of gadolinium or of its oxides
Determination of oxides of terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium
Concentrates impurities get in an extraction-chromatographic column with a water jacket. The inner diameter of the column 16 mm. Column filled with sorbent (25 g of silica gel with a grain size of 0.06−0.07 mm+15 cm100% D2EHPA, the free volume of the sorbent 40 cm
). Filling of the column section.3 23862.7 GOST-79.
Sample of gadolinium metal with a mass of 0.87 g or 1 g of its oxide was placed in a beaker with a capacity of 50 cm, add 6−8 cm
7 mol/DM
of hydrochloric acid, 0.5 cm
of hydrogen peroxide and heated to dissolution. The solution is evaporated to wet salts, the chlorides of REE is dissolved in 30 cm
of 0.83 mol/DM
of hydrochloric acid and passed through an extraction-chromatographic column. The technique works on an extraction-chromatographic column according to sect.3 23862.7 GOST-79.
The glass in which was dissolved the sample was washed with 1.4 mol/DMhydrochloric acid with a volume of 5 cm
. Flushing solution passed through the column. Then passed through the column with 1.4 mol/DM
hydrochloric acid. 100 cm
eluate collected in a beaker (solution of gadolinium). Next, the eluate is collected in portions of 5 cm
, in each of which detects the presence of gadolinium in sect.3 23862.7 GOST-79. The portions of eluate not containing gadolinium, are transferred into the evaporator and is evaporated with subsequent portions of the eluate. Subsequent portions of the eluate receive, passing through a column of 300 cm
7 mol/DM
of hydrochloric acid. The eluate is evaporated in the evaporator to a volume of 15−20 cm
and transferred into a beaker with a capacity of 50 cm
(concentrate of impurities REE).
The concentrate of REE impurities are added 20 mg of yttrium oxide, was heated until complete dissolution, prepare for the spectral analysis in sect.3 GOST 23862.7−79 and analyzed by the method given in claim 4.8 of this standard.
Mass fraction of oxides of terbium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium () in percent is calculated by the formula
where — mass fraction determined by impurities in the obtained oxide of yttrium enriched with impurities of REE, %.
4.3. Analysis of the terbium or its oxide
Determination of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, dysprosium, holmium, erbium, thulium, ytterbium, lutetium
Concentrates impurities REE get in an extraction-chromatographic column with a diameter of 26 mm. Column filled with sorbent (100 g of silica gel with a grain size of 0.06−0.07 mm+60 cm100% D2EHPA, the free volume of the column 160 cm
). Filling of the column section.3 23862.7 GOST-79.
A sample of terbium metal with a mass of 1.28 g or 1.5 g of its oxide was placed in a beaker with a capacity of 50 cm, add 6−10 cm
of concentrated hydrochloric acid and heated until complete dissolution. The solution is evaporated to wet salts, chlorides, rare earth elements are dissolved in 45 cm
1 mol/DM
of hydrochloric acid and passed through an extraction-chromatographic column. Engineering work on the column sec. 3 23862.7 GOST-79.
The glass in which was dissolved the sample was washed with 1 mol/DMhydrochloric acid with a volume of 30 cm
. Flushing solution passed through the column. Then through a column flow of 1.2 mol/DM
hydrochloric acid. The first 100 cm
of the eluate, including the volume of sample solution and wash solution, is discarded, the next 200 cm
eluate is collected in a measuring cylinder with a capacity of 500 cm
. Next, the eluate is collected in test tubes in portions of 10 cm
, in each of which determine the presence of terbium sec. 3 23862.7 GOST-79.
The portions of eluate not containing terbium was added to the main portion of the eluate in a graduated cylinder, is evaporated in the evaporator to a volume of 15−20 cmand transferred into a beaker with a capacity of 50 cm
(concentrate I). Once in the eluate is detected terbium, passed through a column of 2 mol/DM
hydrochloric acid. The first 60 cm
of the eluate is discarded, the following 300 cm
of the eluate collected in a beaker (solution of pure terbium). Next, the eluate is collected in test tubes in portions of 10 cm
, in each of which determine the presence of terbium sec. 3 23862.7 GOST-79. The portions of eluate not containing terbium is transferred to the evaporator and is evaporated with subsequent portions of the eluate. Subsequent portions of the eluate receive, passing through a column of 1500 cm
7 mol/DM
of hydrochloric acid. The eluate is evaporated in the evaporator to a volume of 15−20 cm
and transferred into a beaker with a capacity of 50 cm
(concentrate II).
In concentrate I determine the content of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium;
concentrate II — oxides of dysprosium, holmium, erbium, thulium, ytterbium, lutetium.
The concentrate I add 20 mg of yttrium oxide in the concentrate II — 20 mg of terbium oxide, heated to full dissolution and prepared for spectral analysis by the method given in sec. 3 23862.7 GOST-79.
The obtained oxide of yttrium and terbium enriched in REE impurities, is subjected to spectral analysis GOST 23862.1−79.
Mass fraction of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium () in percent is calculated by the formula
where — mass fraction of oxide of the element in the enriched yttrium oxide, %.
Mass fraction of oxides of dysprosium, holmium, erbium, thulium, ytterbium, lutetium () in percent is calculated by the formula
where — mass fraction of oxide of the element in the enriched oxide terbium, %.
4.4. Analysis of dysprosium oxide or
Determination of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, holmium, erbium, ytterbium, lutetium
Concentrates impurities get in an extraction-chromatographic column with a water jacket. The inner diameter of the column 33 mm. Column filled with sorbent (150 g of silica gel with a grain size of 0.06−0.07 mm+90 cm100% D2EHPA, the free volume of the sorbent 240 cm
). Filling of the column section.3 23862.7 GOST-79.
A portion of the metal dysprosium mass of 0.87 g or 1 g of its oxide was placed in a beaker with a capacity of 50 cm, add 6−8 cm
7 mol/DM
of hydrochloric acid, 0.5 cm
of hydrogen peroxide and heated to dissolution. The solution is evaporated to wet salts, the chlorides of REE is dissolved in 30 cm
to 1.1 mol/DM
of hydrochloric acid and passed through an extraction-chromatographic column. Engineering work on the column sec. 3 23862.7 GOST-79.
The glass in which was dissolved the sample was washed with 1.6 mol/DMhydrochloric acid with a volume of 30 cm
. Flushing solution passed through the column. Then passed through a column of 1.6 mol/DM
hydrochloric acid. The first 150 cm
of the eluate, including the volume of sample solution and wash solution, is discarded, the next 550 cm
eluate is collected in a measuring cylinder with a capacity of 1000 cm
. Next, the eluate is collected in test tubes in portions of 10 cm
, in each of which determine the presence of dysprosium in sect.3 23862.7 GOST-79. The portions of eluate not containing dysprosium, is added to the main portion of the eluate in a graduated cylinder, is evaporated in the evaporator to a volume of 15−20 cm
and transferred into a beaker with a capacity of 50 cm
(concentrate I). Once in the eluate is detected dysprosium, passing through a column of 2.4 mol/DM
hydrochloric acid, 600 cm
eluate collected in a beaker (solution of pure dysprosium).
Next, the eluate is collected in test tubes in portions of 10 cm, in each of which determine the presence of dysprosium in sect.3 23862.7 GOST-79.
The portions of eluate not containing dysprosium is transferred to the evaporator and is evaporated with subsequent portions of the eluate. Subsequent portions of the eluate receive, passing through a column of 2600 cm7 mol/DM
of hydrochloric acid. The eluate is evaporated in the evaporator to a volume of 15−20 cm
and transferred into a beaker with a capacity of 50 cm
(concentrate II).
In concentrate I determine the content of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium;
concentrate II — holmium, erbium, thulium, ytterbium, lutetium.
Concentrate I is divided into two equal parts by volume of each was transferred to a beaker with a capacity of 50 cm. In one Cup add of 0.02 cm
of the internal standard solution erbium (1 mg/cm
) — concentrate REE. Another added of 0.02 cm
of the internal standard solution of cerium (1 mg/cm
) concentrate heavy REE. Each of the concentrates prepared for spectral analysis and analyze according to sect.3, 4 23862.8 GOST-79.
To the concentrate II is added 20 mg of yttrium oxide, was heated until complete dissolution, prepare for the spectral analysis in sect.3 GOST 23862.7−79 and analyzed by the method given in claim 4.8 of this standard.
Mass fraction of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium () in percent is calculated by the formula
where is the mass determined by impurities, mcg;
— hanging samples,
Mass fraction of oxide of holmium () in percent is calculated by the formula
where — mass fraction of oxide of holmium in the resulting yttrium oxide enriched with impurities of REE, %.
Mass fraction of oxides of erbium, thulium, ytterbium, lutetium () in percent is calculated by the formula
where — mass fraction determined by impurities in the obtained oxide of yttrium enriched with impurities of REE, %.
4.5. Analysis of holmium oxide or
Determination of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, erbium, thulium, ytterbium, lutetium
Concentrates impurities get in an extraction-chromatographic column with a water jacket. The inner diameter of the column 33 mm. Column filled with sorbent (150 g of silica gel with a grain size of 0.06−0.07 mm+90 cm100% D2EHPA, the free volume of the sorbent 240 cm
). Filling of the column section.3 23862.7 GOST-79.
A portion of holmium metal with a mass of 0.44 g, or 0.5 g of its oxide was placed in a beaker with a capacity of 50 cm, add 6−8 cm
7 mol/DM
of hydrochloric acid, 0.5 cm
of hydrogen peroxide and heated to dissolution. The solution is evaporated to wet salts, chlorides, rare earth elements are dissolved in 15 cm
of 1.3 mol/DM
of hydrochloric acid and passed through an extraction-chromatographic column. The technique works on an extraction-chromatographic column according to sect.3 23862.7 GOST-79.
The glass in which was dissolved the sample was washed with 1.8 mol/DMhydrochloric acid with a volume of 15 cm
. Flushing solution passed through the column. Then passed through a column of 1.8 mol/DM
hydrochloric acid. The first 150 cm
of the eluate, including the volume of sample solution and wash solution, is discarded, the next 900 cm
eluate is collected in a measuring cylinder with a capacity of 2000 cm
. Next, the eluate is collected in test tubes in portions of 10 cm
, in each of which determine the presence of holmium in sect.3 23862.7 GOST-79.
The portions of eluate not containing holmium was added to the main portion of the eluate in a graduated cylinder, is evaporated in the evaporator to a volume of 15−20 cmand transferred into a beaker with a capacity of 50 cm
(concentrate I). Once in the eluate is detected holmium, passed through a column of 3.5 mol/DM
hydrochloric acid. 450 cm
eluate collected in a beaker (solution of pure holmium). Next, the eluate is collected in test tubes in portions of 10 cm
, in each of which determine the presence of holmium in sect.3 23862.7 GOST-79. The portions of eluate not containing holmium is transferred to the evaporator and is evaporated with subsequent portions of the eluate. Subsequent portions of the eluate receive, passing through a column of 2600 cm
7 mol/DM
of hydrochloric acid. The eluate is evaporated in the evaporator to a volume of 15−20 cm
and transferred into a beaker with a capacity of 50 cm
(concentrate II).
In concentrate I determine the content of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium;
concentrate II — erbium, thulium, ytterbium, lutetium.
Concentrate I is divided into two equal parts by volume of each was transferred to a beaker with a capacity of 50 cm. In one Cup add of 0.02 cm
of the internal standard solution erbium (1 mg/cm
) — concentrate REE, in the other add 0,02 cm
of the internal standard solution of cerium (1 mg/cm
) concentrate heavy REE. Each of the concentrates prepared for the spectral analysis in sect.3, 4 23862.8 GOST-79.
To the concentrate II is added 20 mg of yttrium oxide, was heated until complete dissolution and prepare for the spectral analysis in sect.3 GOST 23862.7−79, and then analyzed according to the method specified in claim 4.8 of this standard.
Mass fraction of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium () in percent is calculated by the formula
Mass fraction of oxide of dysprosium () in percent is calculated by the formula
where is the mass determined by impurities, mcg;
— the weight of the portion of the sample,
Mass fraction of oxides of erbium, thulium, ytterbium and lutetium () in percent is calculated by the formula
where — mass fraction of oxides of erbium, thulium, ytterbium, lutetium in the oxide of yttrium is enriched with impurities of REE, %.
4.6. Analysis of erbium oxide or
Determination of oxides of lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, thulium, ytterbium, lutetium
Concentrates impurities get in an extraction-chromatographic column with a water jacket. The inner diameter of the column 33 mm. Column filled with sorbent (150 g of silica gel with a grain size of 0.06−0.07 mm+90 cm100% D2EHPA, the free volume of the sorbent 240 cm
). Filling of the column section.3 23862.7 GOST-79.
A portion of metallic erbium with a mass of 0.44 g, or 0.5 g of its oxide was placed in a beaker with a capacity of 50 cm, add 6−8 cm
7 mol/DM
of hydrochloric acid, 0.5 cm
of hydrogen peroxide and heated to complete dissolution. The solution is evaporated to wet salts, chlorides, rare earth elements are dissolved in 15 cm
of 2.1 mol/DM
of hydrochloric acid and passed through an extraction-chromatographic column. The technique works on an extraction-chromatographic column according to sect.3 23862.7 GOST-79.
The glass in which was dissolved the sample was washed with 2.1 mol/DMhydrochloric acid with a volume of 15 cm
. Flushing solution passed through the column. Then through a column flow of 2.4 mol/DM
hydrochloric acid. The first 150 cm
of the eluate, including the volume of sample solution and wash solution, is discarded, the next 700 cm
eluate is collected in a measuring cylinder with a capacity of 1000 cm
. Next, the eluate is collected in test tubes in portions of 10 cm
, in each of which determine the presence of erbium sec. 3 23862.7 GOST-79. The portions of eluate not containing erbium, added to the main portion of the eluate in a graduated cylinder, is evaporated in the evaporator to a volume of 15−20 cm
and transferred into a beaker with a capacity of 50 cm
(concentrate I). Once in the eluate is detected erbium, passed through a column of 4.4 mol/DM
hydrochloric acid, 400 cm
eluate collected in a beaker (solution of pure erbium). Next, the eluate is collected in test tubes in portions of 10 cm
, in each of which determine the presence of erbium sec. 3 23862.7 GOST-79.
The portions of eluate not containing erbium is transferred to the evaporator and is evaporated with subsequent portions of the eluate. Subsequent portions of the eluate receive, passing through a column of 2000 cm7 mol/DM
of hydrochloric acid. The eluate is evaporated in the evaporator to a volume of 15−20 cm
and transferred into a beaker with a capacity of 50 cm
(concentrate II).
In concentrate I determine the content of oxides of lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, concentrate II — thulium, ytterbium, lutetium.
To concentrate I add 0.04 cmof a solution of internal standard cerium (1 mg/cm
), prepared for spectral analysis and analyze according to sect.3, 4 23862.8 GOST-79.
To the concentrate II is added 20 mg of yttrium oxide, was heated until complete dissolution, prepare for the spectral analysis in sect.3 GOST 23862.7−79 and analyzed by the method given in claim 4.8 of this standard.
Mass fraction of oxides of lanthanum, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium () in percent is calculated by the formula
where is the mass determined by impurities, mcg;
— the weight of the portion of the sample,
Mass fraction of oxides of thulium, ytterbium and lutetium () in the sample in percent is calculated by the formula
where — mass fraction of oxides of thulium, ytterbium, lutetium in the oxide of yttrium is enriched with impurities of REE, %.
4.7. Analysis of thulium or its oxide
Determination of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium, ytterbium, lutetium
Concentrates impurities get in an extraction-chromatographic column with a water jacket. The inner diameter of the column 33 mm. Column filled with sorbent (150 g of silica gel with a grain size of 0.06−0.07 mm+90 cm100% D2EHPA, the free volume of the sorbent 240 cm
). Filling of the column section.3 23862.7 GOST-79.
A sample of thulium metal with a mass of 0.88 g or 1 g of its oxide was placed in a beaker with a capacity of 50 cm, add 6−8 cm
7 mol/DM
of hydrochloric acid, 0.5 cm
of hydrogen peroxide and heated to dissolution. The solution is evaporated to wet salts, the chlorides of REE is dissolved in 30 cm
3 mol/DM
of hydrochloric acid and passed through an extraction-chromatographic column. The technique works on an extraction-chromatographic column according to sect.3 23862.7 GOST-79.
The glass in which was dissolved the sample was washed with 3.5 mol/DMhydrochloric acid with a volume of 30 cm
. Flushing solution passed through the column. Then passed through a column of 3.5 mol/DM
hydrochloric acid. The first 150 cm
of the eluate, including the volume of sample solution and wash solution, is discarded, the next 750 cm
eluate is collected in a measuring cylinder with a capacity of 1000 cm
. Next, the eluate is collected in test tubes in portions of 10 cm
, in each of which determine the presence of thulium in sect.3 23862.7 GOST-79. The portions of eluate not containing thulium, are added to the main portion of the eluate in a graduated cylinder, is evaporated in the evaporator to a volume of 15−20 cm
and transferred into a beaker with a capacity of 50 cm
(concentrate I). Once in the eluate is detected Tullius, passed through a column of 6 mol/DM
hydrochloric acid, 400 cm
eluate collected in a beaker (solution of pure thulium). Next, the eluate is collected in test tubes in portions of 10 cm
, in each of which determine the presence of thulium in sect.3 23862.7 GOST-79. The portions of eluate not containing thulium, transferred to the evaporator and is evaporated with subsequent portions of the eluate. Subsequent portions of the eluate receive, passing through a column of 2000 cm
7 mol/DM
of hydrochloric acid. The eluate is evaporated in the evaporator to a volume of 15−20 cm
and transferred into a beaker with a capacity of 50 cm
(concentrate II).
In concentrate I determine the content of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium;
concentrate II — ytterbium, lutetium.
Concentrate I is divided into two equal parts by volume of each was transferred to a beaker with a capacity of 50 cm. In one Cup add of 0.02 cm
of the internal standard solution erbium (1 mg/cm
) — concentrate REE, to another beaker was added to 0.02 cm
of the internal standard solution of cerium (1 mg/cm
) concentrate heavy REE.
Each of the concentrates prepared for spectral analysis and analyze according to sect.3, 4 23862.8 GOST-79.
To the concentrate II is added 20 mg of yttrium oxide, was heated until complete dissolution and prepare for the spectral analysis in sect.3 GOST 23862.7−79, and then analyzed according to the method specified in claim 4.8 of this standard.
Mass fraction of oxides of lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, terbium, dysprosium, holmium, erbium () in percent is calculated by the formula
where is the mass determined by impurities, mcg;
— the weight of the portion of the sample,
Fraction of total mass of ytterbium and lutetium () in percent is calculated by the formula
where — mass fraction of oxides of ytterbium, lutetium in the oxide of yttrium is enriched with impurities of REE, %.
4.8. Performing spectral analysis
15 mg samples enriched yttrium oxide is mixed with 15 mg of graphite powder containing 4% of cerium dioxide (OGC). The resulting mixture divided into two equal parts (15 µg) and placed with a spatula and a metal rod in the craters of two graphite electrodes. 15 mg each of the samples on the graphite powder (10 UCP-UCP 1) was mixed with 15 mg of an oxide of yttrium, containing 4% of cerium dioxide (JRC). The resulting mixture divided into two equal parts (15 mg) and placed in the craters of two graphite electrodes.
The electrode with the sample or the reference sample serves as the anode, the upper electrode, sharpened to a cone — cathode. Between electrodes to ignite an arc DC current of 10 A. the exposure Time from 60 to 120 sec (until complete evaporation of the material).
The spectra are photographed on a spectrograph DFS-13 with a grating 1200 lines/mm operating in the first order reflections from being lighting system. The width of the slit of a spectrograph 15 microns. In the cassette of the charge spectrograph of the plate type I.
Spectra of each sample and each reference sample is photographed on the photographic plate twice in the region 310−340 nm. Exposed photographic plates show 3 min, rinsed with water, fixed, washed in running water for 15 min and dried.
5. PROCESSING OF THE RESULTS
5.1. In each spectrogram photometric blackening of analytical lines of the designated element and cerium (comparison lines)
(see table.2) and calculate the difference of pochernenija
and
obtained two spectrograms taken for each sample, find the average value
. The values of
and
for sample comparison build a calibration curve in the coordinates (
,
).
Table 2
| Basis |
The designated element |
Wavelength of analytical lines, nm |
Wavelength comparison lines (cerium), nm |
The mass fraction of the designated oxides of REE, % |
| Neodymium |
Gadolinium |
310,05 |
310,40 |
1·10 |
| 310,05 |
310,34 |
5·10 | ||
| Terbium |
332,44 |
332,47 |
5·10 | |
| 332,44 |
333,30 |
5·10 | ||
| Dysprosium |
340,78 |
340,80 |
2·10 | |
| 340,78 |
340,41 |
5·10 | ||
| Holmium |
341,65 |
341,67 |
1·10 | |
| 317,49 |
317,69 |
1·10 | ||
| Erbium |
326,48 |
326,56 |
1·10 | |
| 326,48 |
325,98 |
5·10 | ||
| 326,48 |
326,39 |
1·10 | ||
| Tullius |
313,13 |
313,82 |
1·10 | |
| 313,13 |
313,67 |
1·10 | ||
| Ytterbium |
328,94 |
328,88 |
1·10 | |
| 346,44 |
346,69 |
5·10 | ||
| 319,29 |
319,40 |
1·10 | ||
| Lutetium |
331,21 |
331,14 | 1·10 | |
| 331,21 |
331,40 |
1·10 | ||
| 331,21 |
331,22 |
5·10 | ||
| Gadolinium | Terbium |
332,44 |
332,48 |
5·10 |
| 332,44 |
332,55 |
5·10 | ||
| Dysprosium |
340,78 |
340,68 |
5·10 | |
| 340,78 |
340,61 |
1·10 | ||
| Holmium |
345,60 |
345,67 |
1·10 | |
| 345,60 |
347,68 |
1·10 | ||
| Erbium |
323,06 |
322,81 |
2·10 | |
| 323,06 |
323,35 |
5·10 | ||
| 323,06 |
323,42 |
1·10 | ||
| Ytterbium |
328,94 |
328,87 |
1·10 | |
| 328,94 |
329,02 |
2·10 | ||
| 328,94 |
328,55 |
1·10 | ||
| Tullius |
313,13 |
313,83 |
1·10 | |
| 313,13 |
312,77 |
1·10 | ||
| 313,13 |
316,42 |
1·10 | ||
| Lutetium |
335,96 |
335,69 |
2·10 | |
| 335,96 |
335,73 |
2·10 | ||
| Dysprosium | Holmium |
345,60 |
346,34 |
5·10 |
| 345,60 |
342,62 |
2·10 | ||
| Erbium | 323,06 |
322,81 |
2·10 | |
| 323,06 |
322,57 |
1·10 | ||
| 323,06 |
322,71 |
1·10 | ||
| Tullius |
336,26 |
336,88 |
2·10 | |
| 329,10 |
329,03 |
1·10 | ||
| 329,10 |
328,52 |
1·10 | ||
| Lutetium |
331,21 |
331,14 |
2·10 | |
| 331,21 |
331,15 |
2·10 | ||
| 331,21 |
331,47 |
1·10 | ||
| Holmium | Erbium |
323,06 |
322,35 |
2·10 |
| 323,06 |
323,22 |
1·10 | ||
| 323,06 |
322,93 |
1·10 | ||
| Tullius |
313,13 |
312,93 |
1·10 | |
| 313,13 |
312,36 |
5·10 | ||
| 313,13 |
312,77 |
5·10 | ||
| Ytterbium |
328,94 |
328,88 |
1·10 | |
| 328,94 |
329,50 |
5·10 | ||
| 347,88 |
347,90 |
1·10 | ||
| Lutetium |
331,21 |
331,35 |
2·10 | |
| 331,21 |
330,48 |
5·10 | ||
| 331,21 |
331,47 |
1·10 | ||
| Erbium | Tullius |
336,26 |
335,77 |
1·10 |
| 336,26 |
335,64 |
1·10 | ||
| 313,39 |
313,76 |
1·10 | ||
| Ytterbium |
328,94 |
329,03 |
1·10 | |
| 328,94 |
329,51 |
5·10 | ||
| 347,63 |
347,90 |
1·10 | ||
| Lutetium |
335,96 |
335,78 |
2·10 | |
| 335,96 |
335,39 |
5·10 | ||
| 335,96 |
335,64 |
5·10 | ||
| Tullius | Ytterbium |
328,94 |
328,87 |
1·10 |
| 346,44 |
346,48 |
1·10 | ||
| 319,29 |
319,34 |
1·10 | ||
| Lutetium |
331,21 |
331,14 |
1·10 | |
| 331,21 |
331,15 |
1·10 | ||
| 325,43 |
325,77 |
5·10 |
The contents of the designated impurities find the calibration schedule as an average for the sample.
Discrepancies in the results of the two tests (ratio greater outcome to a lesser) should not exceed the value of permissible differences, is equal to 2.1.
5.2. Under the control of the reproducibility of parallel measurements on two parallel values and
obtained two spectrograms taken for each sample, the calibration schedule to find the value
and
the results of each of the parallel definitions of the impurities in the sample. The ratio of the greater of these results to smallest should not exceed 1.5.
