AU2021102203A4 - Method for quickly determining yttrium content in steel by using full spectrum spark direct reading spectrometry - Google Patents
Method for quickly determining yttrium content in steel by using full spectrum spark direct reading spectrometry Download PDFInfo
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- 229910052727 yttrium Inorganic materials 0.000 title claims abstract description 159
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 title claims abstract description 159
- 229910000831 Steel Inorganic materials 0.000 title claims abstract description 107
- 239000010959 steel Substances 0.000 title claims abstract description 107
- 238000001228 spectrum Methods 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 29
- 238000004611 spectroscopical analysis Methods 0.000 title claims abstract description 9
- 238000001514 detection method Methods 0.000 claims abstract description 39
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 claims abstract description 38
- 238000004458 analytical method Methods 0.000 claims abstract description 37
- 229910052761 rare earth metal Inorganic materials 0.000 claims abstract description 35
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 33
- 238000005070 sampling Methods 0.000 claims abstract description 20
- 238000005520 cutting process Methods 0.000 claims abstract description 19
- 239000012086 standard solution Substances 0.000 claims abstract description 17
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 24
- 239000012085 test solution Substances 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 20
- 239000011159 matrix material Substances 0.000 claims description 19
- 230000003595 spectral effect Effects 0.000 claims description 18
- 239000002994 raw material Substances 0.000 claims description 13
- 230000005284 excitation Effects 0.000 claims description 12
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 230000007613 environmental effect Effects 0.000 claims description 10
- 238000010438 heat treatment Methods 0.000 claims description 10
- 239000012535 impurity Substances 0.000 claims description 10
- 239000000203 mixture Substances 0.000 claims description 10
- 238000010926 purge Methods 0.000 claims description 10
- 239000000126 substance Substances 0.000 claims description 10
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 claims description 9
- 239000000395 magnesium oxide Substances 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 8
- 239000000243 solution Substances 0.000 claims description 8
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 claims description 7
- 238000013178 mathematical model Methods 0.000 claims description 7
- 230000006698 induction Effects 0.000 claims description 5
- 238000004364 calculation method Methods 0.000 claims description 4
- 238000003756 stirring Methods 0.000 claims description 4
- 239000002245 particle Substances 0.000 claims description 3
- 238000005266 casting Methods 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 229910052758 niobium Inorganic materials 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- 229910052698 phosphorus Inorganic materials 0.000 claims description 2
- 238000004381 surface treatment Methods 0.000 claims description 2
- 229910052718 tin Inorganic materials 0.000 claims description 2
- 238000007670 refining Methods 0.000 abstract description 2
- 238000005096 rolling process Methods 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 89
- 238000012360 testing method Methods 0.000 description 26
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 10
- 239000011259 mixed solution Substances 0.000 description 9
- 229910052742 iron Inorganic materials 0.000 description 8
- 150000003839 salts Chemical class 0.000 description 8
- 239000000779 smoke Substances 0.000 description 8
- 239000012488 sample solution Substances 0.000 description 7
- 238000002844 melting Methods 0.000 description 4
- 230000008018 melting Effects 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 230000003252 repetitive effect Effects 0.000 description 4
- 239000010421 standard material Substances 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 3
- 238000005259 measurement Methods 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- QIVUCLWGARAQIO-OLIXTKCUSA-N (3s)-n-[(3s,5s,6r)-6-methyl-2-oxo-1-(2,2,2-trifluoroethyl)-5-(2,3,6-trifluorophenyl)piperidin-3-yl]-2-oxospiro[1h-pyrrolo[2,3-b]pyridine-3,6'-5,7-dihydrocyclopenta[b]pyridine]-3'-carboxamide Chemical compound C1([C@H]2[C@H](N(C(=O)[C@@H](NC(=O)C=3C=C4C[C@]5(CC4=NC=3)C3=CC=CN=C3NC5=O)C2)CC(F)(F)F)C)=C(F)C=CC(F)=C1F QIVUCLWGARAQIO-OLIXTKCUSA-N 0.000 description 2
- HFGHRUCCKVYFKL-UHFFFAOYSA-N 4-ethoxy-2-piperazin-1-yl-7-pyridin-4-yl-5h-pyrimido[5,4-b]indole Chemical compound C1=C2NC=3C(OCC)=NC(N4CCNCC4)=NC=3C2=CC=C1C1=CC=NC=C1 HFGHRUCCKVYFKL-UHFFFAOYSA-N 0.000 description 2
- 238000003723 Smelting Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
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- XULSCZPZVQIMFM-IPZQJPLYSA-N odevixibat Chemical compound C12=CC(SC)=C(OCC(=O)N[C@@H](C(=O)N[C@@H](CC)C(O)=O)C=3C=CC(O)=CC=3)C=C2S(=O)(=O)NC(CCCC)(CCCC)CN1C1=CC=CC=C1 XULSCZPZVQIMFM-IPZQJPLYSA-N 0.000 description 2
- 238000010561 standard procedure Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- KMIOJWCYOHBUJS-HAKPAVFJSA-N vorolanib Chemical compound C1N(C(=O)N(C)C)CC[C@@H]1NC(=O)C1=C(C)NC(\C=C/2C3=CC(F)=CC=C3NC\2=O)=C1C KMIOJWCYOHBUJS-HAKPAVFJSA-N 0.000 description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000011088 calibration curve Methods 0.000 description 1
- 238000009614 chemical analysis method Methods 0.000 description 1
- 229910052729 chemical element Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000000265 homogenisation Methods 0.000 description 1
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- 238000000691 measurement method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000003801 milling Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- AYOOGWWGECJQPI-NSHDSACASA-N n-[(1s)-1-(5-fluoropyrimidin-2-yl)ethyl]-3-(3-propan-2-yloxy-1h-pyrazol-5-yl)imidazo[4,5-b]pyridin-5-amine Chemical compound N1C(OC(C)C)=CC(N2C3=NC(N[C@@H](C)C=4N=CC(F)=CN=4)=CC=C3N=C2)=N1 AYOOGWWGECJQPI-NSHDSACASA-N 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012925 reference material Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 238000010183 spectrum analysis Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010301 surface-oxidation reaction Methods 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- 238000013076 uncertainty analysis Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3563—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing solids; Preparation of samples therefor
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C33/00—Making ferrous alloys
- C22C33/04—Making ferrous alloys by melting
- C22C33/06—Making ferrous alloys by melting using master alloys
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/001—Ferrous alloys, e.g. steel alloys containing N
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/005—Ferrous alloys, e.g. steel alloys containing rare earths, i.e. Sc, Y, Lanthanides
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/008—Ferrous alloys, e.g. steel alloys containing tin
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/02—Ferrous alloys, e.g. steel alloys containing silicon
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/04—Ferrous alloys, e.g. steel alloys containing manganese
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/06—Ferrous alloys, e.g. steel alloys containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/12—Ferrous alloys, e.g. steel alloys containing tungsten, tantalum, molybdenum, vanadium, or niobium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C38/00—Ferrous alloys, e.g. steel alloys
- C22C38/14—Ferrous alloys, e.g. steel alloys containing titanium or zirconium
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/40—Concentrating samples
- G01N1/4022—Concentrating samples by thermal techniques; Phase changes
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
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Abstract
The invention discloses a detection method for quickly determining yttrium content in
steel by using full spectrum spark direct reading spectrometry, which comprises the following
steps: refining steel ingots with different yttrium contents by changing the addition amount of
rare earth yttrium, and rolling into steel billets. A standard sample is taken from one section of
billet, and the uniformity of the standard sample is detected by spark direct reading instrument,
and the sample with the best uniformity is selected as the standard sample. Sampling drill
cuttings on standard samples, preparing standard solutions, and determining yttrium content in
the standard solutions by ICP-AES. The standard sample is excited and calibrated to obtain the
strength ratio, and the standard analysis curve of rare earth yttrium element is formed by fitting
the strength ratio with yttrium content. The method can quickly detect the yttrium content in
steel, and has important practical scientific value and economic and social significance for
researching and popularizing the application of yttrium in steel.
1/1
FIGURES
A
Poish chanfi
Fig 1
A -AZ content
NewFunction (User) Fit of content
0.06
0 2
0.02
0.00
0 1000000 2000000 3000000 4000000
light intensity
Fig.2 a
a b c Statistics
Value Error Value Error Value Error Reduced Chi-Sqr Adj R-Square
content -1.97843E-15 3.53869E-16 285535E-B 128482E-9 -0002 706773E-4 9.37421E-7 0.99881
Fig.2 b
Description
1/1
Poishchanfi
Fig 1
A -AZ content NewFunction (User) Fit of content
0.06
0 2
0.02
0.00
0 1000000 2000000 3000000 4000000 light intensity
Fig.2 a
a b c Statistics Value Error Value Error Value Error Reduced Chi-Sqr Adj R-Square content -1.97843E-15 3.53869E-16 285535E-B 128482E-9 -0002 706773E-4 9.37421E-7 0.99881
Fig.2 b
Method for quickly determining yttrium content in steel by using full spectrum
spark direct reading spectrometry
The invention belongs to the technical field of rare earth yttrium detection methods,
and particularly relates to an on-line rapid detection method of rare earth yttrium content
in steel.
Rare earth elements play an increasingly prominent role in molten steel, which is
expected to become an important element in developing new high value-added steel
materials in the 21st century. Adding a small amount of heavy rare earth yttrium into
steel can significantly improve the mechanical properties and mechanical properties of
steel. However, there is no relevant standard method for the determination of yttrium
content (mass fraction) in steel in domestic and foreign standards at present. The standard
of EDTA titration is adopted for the single rare earth content in GB/T 14635 "Chemical
Analysis Methods of Rare Earth Metals and Their Compounds". This method is
cumbersome and cannot meet the requirements of on-line rapid detection in the
production practice, and it is difficult to meet the requirements of yttrium content (mass
fraction) detection in steel.
Spark direct reading spectrum analysis is one of the important means of rapid
metallurgical analysis, but it is also a relative measurement method, which must be
compared with corresponding standard materials, and at the same time, special channels
and spectral lines for rare earth yttrium detection are needed. At present, there are relatively few standard materials for metallurgical analysis containing rare earth elements in China, especially the standard materials for steel containing yttrium, which are not available in the market and have not been reported at home and abroad However, the traditional spark direct reading spectrometer has not developed a special channel and spectral line for measuring yttrium, which leads to the bottleneck of studying the action and mechanism of yttrium in steel. Full-spectrum spark direct reading spectrometer can realize full-spectrum scanning without channel limitation and solve the problem of no yttrium channel. However, there is no yttrium detection method for full spectrum spark direct reading spectrometer. Therefore, the research and development of yttrium containing steel reference materials and rapid detection methods have important practical scientific value and economic and social significance for the research and popularization of the application of yttrium in steel.
In view of the above-mentioned prior art, the object of the present invention is to
provide a detection method for rapidly determining yttrium content in steel by using full
spectrum spark direct reading spectrometry. The method can quickly detect the yttrium
content in steel, and has important practical scientific value and economic and social
significance for researching and popularizing the application of yttrium in steel.
In order to achieve the above purpose, the invention adopts the following technical
scheme:
The invention provides a detection method for rapidly measuring yttrium content in
steel by using full spectrum spark direct reading spectrometry, which comprises the
following steps:
(1) By changing the amount of rare earth yttrium, steel ingots with different yttrium
contents are refined and rolled into billets.
(2) Taking a plurality of samples on one section of each billet obtained in the step
(1) and carrying out surface treatment, selecting the best working spectral line of the full
spectrum spark direct reading spectrometer according to the principle of minimum
interference of elements, detecting the uniformity of the samples by using the best
working spectral line, and selecting the sample with the best uniformity as a standard
sample.
(3) Sampling drill cuttings on the standard sample obtained in step (2), preparing a
standard solution, and calibrating the yttrium content in the standard solution by ICP
(4) Performing excitation calibration on the standard sample obtained in step (2) to
obtain an intensity ratio, establishing a corresponding relationship between the intensity
ratio and the yttrium content obtained in step (3), and drawing a rare earth yttrium
element standard analysis curve; The mathematical model of yttrium is obtained by
fitting the standard analysis curve, and the steel with unknown rare earth yttrium content
is detected by using the standard analysis curve of rare earth yttrium.
Preferably, in step (1), the steel billet is prepared by the following method:
SOL. a magnesium oxide crucible is built in a medium frequency induction furnace,
baked and washed with matrix raw materials; The addition amount of matrix raw
materials and pure rare earth yttrium is determined by proportioning calculation, and the
raw materials are polished, weighed and put into a magnesium oxide crucible.
S02. start vacuumizing and slowly raise the temperature, keeping the vacuum degree
at 6.67x10-1 Pa. When the base material is completely melted, pure rare earth yttrium is
added and kept warm, and then poured into a casting mold after melting, forged after
demoulding, and rolled into a billet with a thickness of 30mm.
Preferably, in step S01, the purity of the rare earth yttrium is 99.9%.
Preferably, in step SO1, the matrix material consists of the following chemical
components in percentage by mass:
C 0.09%, Mn 1.34%, S 0.006%, P 0.021%, Si 0.2%, Als 0.027%, N 0.0044%, Nb
0.029%, Ca 0.0013%, Ti 0.011%, Sn 0.0044% and the balance Fe.
Preferably, in step (3), the working conditions of the spark direct reading instrument
are as follows: the discharge frequency is 400-500 Hz. The argon flow rate is 220-2301/h.
Environmental temperature 25°C/ light room temperature 20°C, humidity 5 0 - 6 0 %,
purging time is 1, the excitation time is 12s, and the precombustion time is 4s.
Preferably, in the step (2), the uniformity detection is that a full spectrum spark
direct reading spectrometer is used to dot and scan the surface of a standard sample, and
each standard sample is marked with 8 dots, and the uniformity of the sample is judged
by the relative standard uncertainty of the intensity ratio.
According to the standard uncertainty (UA1) and relative standard uncertainty
(U(rel,A1)) of repetitive test data, the stability of the data is checked. The smaller the
relative standard uncertainty (U(rel,A1)), the smaller the data difference, the better the
stability, that is, the better the uniformity.
Preferably, in step (2), the working spectral line is XY=371.029nm.
Preferably, in step (3), the standard solution is prepared by the following method:
Al. Take 0.50g of steel scrap, add 25mL of mixed solution prepared by water,
hydrochloric acid and nitric acid according to the mass ratio of 1: 1: 3 until the steel scrap
is completely dissolved, add 5mL of perchloric acid, heat until perchloric acid smokes,
and continue heating until the volume of test solution remains 1-2 ml.
A2. Add 20mL of water and 5mL of hydrochloric acid after cooling the test solution,
heat and dissolve until the test solution is clear and free of impurities, and cool to room
temperature to obtain standard solution.
Preferably, in step (3), sampling is carried out according to the method specified in
GB/T20066-2006, and the surface of the sample is ground after sampling, and the particle
size of the ground material is 0.124-0.25 mm.
Sampling method: sampling is respectively carried out on a cross section of the billet
prepared in step (1) and a quarter of the diagonal line of the cross section, and the
distance between the edge of the sample and the edge of the cross section is 1mm.
Sampling diagram is shown in Figure 1.
Preferably, in step (4), the standard analysis curve is that the mathematical model is
y=1.94724*10 8 x2 +3.16856*10 7 x+89329.93426, where x is the element content, Y is the
intensity ratio.
The invention has the beneficial effects that:
According to the invention, yttrium-containing steel calibration samples are
researched and developed. The standard analysis curve of yttrium was drawn by full
spectrum spark direct reading spectrometer, and the content of yttrium in steel was
determined. The detection method provided by the invention is rapid, accurate, good in repeatability and stability, and has important practical scientific value and economic and social significance for researching and popularizing the application of yttrium in steel.
Fig. 1: Sampling diagram of sample uniformity test;
Fig. 2: A is the standard analysis curve of yttrium, and B is the fitting parameter;
It should be noted that the following detailed description is exemplary and is
intended to provide further explanation for this application. Unless otherwise specified,
all technical and scientific terms used herein have the same meanings as commonly
understood by those of ordinary skill in the technical field to which this application
belongs.
As introduced in the background section, adding a small amount of heavy rare earth
yttrium into steel can significantly improve the mechanical properties and mechanical
properties of steel. However, there is no relevant standard method for the determination
of yttrium content (mass fraction) in steel in domestic and foreign standards at present.
Due to the low content of yttrium in steel, it is difficult to detect the content of yttrium in
steel by the existing technology.
Based on this, the purpose of the present invention is to provide a detection method
for on-line rapid determination of yttrium content in steel by full spectrum spark direct
reading spectrometry. The method comprises the following steps: firstly, establishing a
standard material for steel containing yttrium, developing a standard analysis curve of
yttrium, and establishing a mathematical model of yttrium.
Working principle of full spectrum spark direct reading spectrometer:
Discharge between the prepared block sample and the counter electrode under the
action of spark light source generates plasma in high temperature and inert atmosphere.
When the atom of the measured element is excited, the electrons transition between
different energy levels in the atom, and when the transition from high energy level to low
energy level is the generated characteristic spectral line, measure the spectral intensity of
the selected analysis element and internal standard element characteristic spectral line.
According to the relationship between spectral line intensity and concentration of the
measured element in the sample, the content of the measured element is calculated by
calibration curve.
Based on the above working principle, the relationship between the strength ratio
and the content of yttrium element is established, and the standard analysis curve of rare
earth yttrium element is formed, thus realizing the accurate customization of the standard
analysis curve.
The method realizes on-line rapid detection of yttrium content in steel. At the same
time, the standard samples of iron and steel containing yttrium were prepared. The
method solves the problem of how to accurately hit the required yttrium content in steel
in yttrium content detection, that is, how to accurately hit the target component. In order
to achieve this goal, multi-heats smelting is adopted, from which the best choice is made.
The medium frequency induction melting furnace used in preparing the calibration
sample has electromagnetic stirring function, which can effectively promote the full and
uniform mixing of all components in steel. The yttrium content in the steel ingot cannot
be directly obtained by adding yttrium with different qualities to the steel ingot in step 1
of the invention, because yttrium will burn to different degrees in the smelting process, and the yield of yttrium in each furnace steel cannot be guaranteed to be completely the same. Different amounts of rare earth yttrium are added for refining standard samples with different yttrium contents, and the yttrium content in each furnace steel has a gradient through different addition amounts. The value of yttrium content in refined steel ingot cannot be determined, so it needs to be determined by ICP-AES. This method is a chemical analysis method, which can determine the content of all chemical elements in theory, and has a mature technical development. However, compared with spark direct reading spectrum detection, ICP-AES detection takes a long time and has low efficiency, which can not meet the demand of online rapid detection in the production process. In actual detection, the composition of the steel containing yttrium (Y) does not have to be exactly the same as the chemical composition and content of the raw materials in the invention, but the chemical composition and content of the raw materials are different, which has no obvious influence on the detection of yttrium content. The method of the invention can quickly detect the content of Y in steel and achieve the purpose of quick analysis and detection required by the production line. And it is not a destructive test, which can keep the integrity of steel.
In order to enable those skilled in the art to understand the technical scheme of this
application more clearly, the technical scheme of this application will be described in
detail with specific examples below.
Test materials used in the embodiments of the invention are all conventional test
materials in the field and can be purchased through commercial channels.
Example 1
Step 1: Sample preparation
Using medium frequency induction furnace, steel ingots with different yttrium
contents were refined and rolled into billets by changing the addition amount of rare earth
yttrium. Eight standard samples were smelted in total, and the sample numbers were Z1,
Z2, Z3, Z4, Z5, Z6, Z7 and Z8 respectively.
Operation steps are as follows:
The crucible in the medium frequency induction furnace is a crucible with built-in
magnesium oxide, which is baked and washed with matrix raw materials. The addition
amount of matrix raw materials and pure rare earth yttrium is determined by batching
calculation, grinding raw materials, weighing, putting matrix raw materials into crucible,
putting rare earth pure Y into silo, wherein the purity of rare earth yttrium is 99.9%, the
chemical composition of magnesium oxide crucible is shown in Table 1, and the
chemical composition of substrate is shown in Table 2.
Start vacuumizing and slowly raise the temperature, keeping the vacuum degree at
6.67x101 Pa. The melting state of matrix raw materials was observed, and the total
melting time was about 70mins. Add rare earth into that silo, keep the temperature for
about 2mins, and carry out electromagnetic stirring. Electromagnetic stirring is beneficial
to the homogenization of temperature and alloy composition, ensures the uniformity of
the calibration sample, confirms the molten state, pours it into the corresponding mold,
knocks the ingot after demoulding, and rolls it into a steel plate with a thickness of
mm.
Table 1 Chemical composition of crucible chemical MgO SiO 2 A1 2 0 3 CaO Fe203 composition content >97.5 <0.70 <0.10 <1.10 <0.460
The selection of crucible has a certain influence on the preparation of steel ingot, so
the magnesium oxide crucible is selected to reduce the influence of crucible on the
preparation of steel ingot.
Table 2 Chemical composition of substrate element C Mn S P Si Als
content (
0.09 1.34 0.006 0.021 0.2 0.027
element N Nb Ca Ti Sn others
content ( The 0.0044 0.029 0.0013 0.011 0.0044 allowance isFe
Step 2: Uniformity test
Sampling is carried out at 1/4 of the diagonal line of one side of each billet refined in
step one and 1mm away from the edge of the side, and four samples with specifications
of 20mm*20mm*10mm are obtained from each calibration sample, as shown in Figure 1.
And the samples are numbered. In order to prevent the surface oxidation and pollution of
steel samples from affecting the accuracy and precision of data, a milling machine is used
to grind the surface of the samples, and the particle size of the grinding material is 0.2
mm.
In this experiment, SPECTROLAB S spark direct reading instrument is used to test
the uniformity of standard samples. The working conditions of SPECTROLAB S spark
direct reading instrument are: discharge frequency 450Hz. The argon flow rate is 2201/h.
Environmental temperature 25°C/ light room temperature 20°C, humidity 50-60%,
Purging time is Is. The excitation time is 12s, and the precombustion time is 4s.
According to the above working conditions, the upper surface of the sample is scanned
with SPECTROLAB S spark direct reading instrument to measure its intensity ratio.
According to the principle of minimum interference of elements, the working spectral
line is selected from the measuring spectral lines recommended by the instrument. the
working spectral line selected in this experiment isXY=371.029nm. The full spectrum
spark direct reading spectrometer is used to scan the upper surface of the sample by
dotting. Each sample is randomly selected from one side, and 8 points are punched. The
uniformity of the sample is judged by the relative standard uncertainty of intensity ratio,
and a sample with the best uniformity is selected as the standard sample in each group for
drawing the standard analysis curve. Eight steel plates Z1-Z8 prepared in step one, and
the strength ratio of each steel plate for uniformity detection is shown in Table 3.
Table 3 Strength ratio of uniformity samples Sample S RSD U (A, 1) Urel (A, 1) No. Zi 45706 1136.82 2.49 401.93 0.0088 Z2 49594 903.28 1.82 319.36 0.0064 Z3 141804 5037 3.55 1780.85 0.0126 Z4 177574 4079.22 2. 3 1442.22 0.0081 Z5 261809 5998.8 2.29 92563.46 0.3511 Z6 520329 12208.28 2. 35 4316.28 0.0083 Z7 754800 8114.46 1.08 2868.9 0.0038 Z8 986454 16926.24 1. 72 5984. 33 0.0061
The data of 8 points measured on each calibration sample are investigated, and the
data stability is checked by calculating the standard uncertainty (UAl) and the relative
standard uncertainty (U(rel,Al) of repetitive test data. The smaller the relative standard
uncertainty (U(rel,Al)), the smaller the data difference, the better the stability, that is, the
better the uniformity.
Standard uncertainty of passing repeatability test:
The relative standard uncertainty of repeatability test is:
S U(rei,A1)=" (1.2)
In which: S is the standard deviation of the sample to be measured;
N: determination times of a single sample;
X: the average value of the sample to be measured.
The measured standard uncertainty (UAl) and relative standard uncertainty
(U(rel,Al)) of calibration sample data and data repeatability test are shown in table 3 below.
Judging the uniformity of the data in Table 3, we can see that the relative standard
deviation (RSD) is less than 5%, which meets the requirement that the absolute value
between the two test results should not exceed the probability of 95% under the
conditions of repeatability and reproducibility. It shows that the data fluctuation of 8
points of each calibration sample is small, which proves that the uniformity of the refined
calibration sample is good and that the calibration sample is desirable.
The closer the relative standard uncertainty (U(rel,Al)) is to 1, the worse the data
stability is. The relative standard uncertainties(U(rel,Al)) in the table are all less than 1, and
the values are all small, which proves that the uniformity of the refined calibration
samples is good again.
Step 3: ICP fixed value of yttrium content in steel
Through the uniformity test in step 2, four samples were taken out from each steel
plate from Z Ito Z8, and one of the four samples with the best uniformity was selected as
the standard sample of the numbered steel plate, and eight standard samples respectively
correspond to Z1 to Z8. Drilling cuttings were sampled at a quarter of the standard samples (pay attention not to over-high bit temperature during sampling), and 0.50g of steel cuttings was taken, add 25mL mixed solution of water-hydrochloric acid-nitric acid
(1: 1: 3) and slowly heat it until the sample is completely dissolved, add 5mL perchloric
acid, heat it to smoke with perchloric acid, and continue heating until the volume of the
test solution remains 1 ml ~ 2 ml. Cool, add 20mL of water and 5mL of hydrochloric
acid, dissolve the salts with slight heat, and cool to room temperature, when the test
solution is clear and free of impurities. The obtained standard solutions correspond to
steel plates Z1-Z8 one by one, and the standard solutions are numbered X1, X2, X3, X4,
X5, X6, X7 and X8.
The yttrium content in standard solution was determined by ICP-AES, and the
standard solution was used to calibrate ICP-AES, and the sample was determined under
the condition of good accuracy and stability of ICP-AES. The content of yttrium in steel
samples from ZI to Z8 can be obtained by detecting the standard solution (X1
corresponds to the content of yttrium in steel samples from Z1, and so on). The yttrium
content measured by ICP-AES is shown in table 4.
Table 4 yttrium content in standard solution measured by ICP-AES Standard X1 X2 X3 X4 X5 X6 X7 X8 solutionNo. Yttrium content 0.0023 0.0024 0.012 0.01 0.021 0.042 0.062 0.075 (wt/%)
Step 4: Drawing the standard analysis curve
Use the working spectral lines screened in step 2 to excite each standard sample
respectively, use SPECTROLAB S spark direct reading instrument to excite and calibrate
the standard samples with different rare earth yttrium content, establish a database corresponding to the intensity ratio and rare earth yttrium content in the spectrometer, as shown in Table 5, and perform linear fitting on the data to form a rare earth yttrium standard analysis curve (see Figure 2), thus realizing accurate customization of the standard spectral lines.
The mathematical model of yttrium is: y=1.94724*108
x 2+3.16856*10 7 x+89329.93426
Table 5 Corresponding relationship between intensity ratio measured by Spectrolab S spark direct reading instrument and rare earth yttrium concentration Sample Zi Z2 Z3 Z4 Z5 Z6 Z7 Z8 No. strength 145177 160860 511194 457703 833727 1713390 2864766 3533816 ratio
Content% 0. 0023 0. 0024 0. 012 0.01 0.021 0.042 0.062 0.075
Example 2
Eight points were randomly selected from yttrium-bearing steel, and dot scanning
was performed by full spectrum spark direct reading spectrometer. Set the working
conditions of full spectrum spark direct reading spectrometer: discharge frequency
400Hz. The argon flow rate is 2201/h. Environmental temperature 25°C/ light room
temperature 20°C, humidity 50-60%, purging time is Is. The excitation time is 12s and
the precombustion time is 4s. Dot scanning is performed on the surface of the sample by
using a spark direct reading spectrometer to obtain the intensity ratio, and the yttrium
content in the sample is calculated according to the standard analysis curve obtained in
step 4 of Example 1.
The intensity ratio measured by dot scanning of full spectrum spark direct reading
spectrometer is 410040, and the mathematical model of yttrium introduction is: y=1.94724*10 8 x 2+3.16856*10 7 x+89329.93426, and the yttrium content is
0.00956%.
Determination of yttrium content by ICP-AES: adopt the above yttrium-containing
steel, sample the drill cuttings at 1/4 of the sample of yttrium-containing steel (pay
attention to the bit temperature not to be too high during sampling), take 0.50g sample of
steel cuttings, add 25mL mixed solution of water-hydrochloric acid-nitric acid (1: 1: 3)
and slowly heat it until the sample is completely dissolved, add 5mL perchloric acid, heat
it to smoke, and continue heating until the volume of the test solution remains 1. Cool,
add 20mL of water and 5mL of hydrochloric acid, dissolve the salts with slight heat, and
cool to room temperature, when the test solution is clear and free of impurities. The
yttrium content in the sample solution to be tested was determined by ICP-AES, and the
standard solution was used to calibrate ICP-AES. When the accuracy and stability of
ICP-AES were good, the yttrium content in the steel sample to be tested was 0.0087%.
Example 3
Eight points were randomly selected from yttrium-bearing steel, and dot scanning
was performed by full spectrum spark direct reading spectrometer. Set the working
conditions of full spectrum spark direct reading spectrometer: discharge frequency
500Hz. The argon flow rate is 2301/h, environmental temperature 25°C/ light room
temperature 20°C,humidity 50-60%, purging time is Is. The excitation time is 12s and the
precombustion time is 4s. Dot scanning is performed on the surface of the sample by
using a spark direct reading spectrometer to obtain the intensity ratio, and the yttrium
content in the sample is calculated according to the standard analysis curve obtained in
step 4 of Example 1.
The intensity ratio measured by dot scanning of full spectrum spark direct reading
spectrometer is 265096, and the standard analysis curve of yttrium is:
y=1.94724*10 8 x 2+3.16856*10 7 x+89329.93426, and the yttrium content is
0.00537%.
Determination of yttrium content by ICP-AES: use the above steel, sample the drill
cuttings at 1/4 of the yttrium-containing steel sample to be measured (during sampling,
pay attention to the bit temperature not to be too high), take 0.50g of steel cuttings, add
mL of mixed solution of water-hydrochloric acid-nitric acid (1: 1: 3) and slowly heat it
until the sample is completely dissolved, add 5mL of perchloric acid, heat it to smoke,
and continue heating until the volume of the test solution remains 1 ml. Cool, add 20mL
of water and 5mL of hydrochloric acid, dissolve the salts with slight heat, and cool to
room temperature, when the test solution is clear and free of impurities. The yttrium
content in the sample solution to be tested was determined by ICP-AES, and the standard
solution was used to calibrate ICP-AES. When the accuracy and stability of ICP-AES
were good, the yttrium content in the steel sample to be tested was 0.0053%.
Example 4
Eight points were randomly selected from yttrium-bearing steel, and dot scanning
was performed by full spectrum spark direct reading spectrometer. Set the working
conditions of full spectrum spark direct reading spectrometer: discharge frequency
420Hz. The argon flow rate is 2201/h, environmental temperature 25°C/ light room
temperature 20°C, humidity 50-60%, purging time is Is. The excitation time is 12s and
the precombustion time is 4s. Dot scanning is performed on the surface of the sample by
using a spark direct reading spectrometer to obtain the intensity ratio, and the yttrium content in the sample is calculated according to the standard analysis curve obtained in step 4 of Example 1.
The intensity ratio measured by dot scanning of full spectrum spark direct reading
spectrometer is 707314, and the standard analysis curve of yttrium is:
y=1.94724*10 8 x 2 +3.16856*10 7 x+89329.93426, and the yttrium content is 0.0176%.
Determination of yttrium content by ICP-AES: use the above steel, sample the drill
cuttings at 1/4 of the yttrium-containing steel sample to be measured (during sampling,
pay attention to the bit temperature not to be too high), take 0.50g of steel cuttings, add
mL of mixed solution of water-hydrochloric acid-nitric acid (1: 1: 3) and slowly heat it
until the sample is completely dissolved, add 5mL of perchloric acid, heat it to smoke,
and continue heating until the volume of the test solution remains 1 ml. Cool, add 20mL
of water and 5mL of hydrochloric acid, dissolve the salts with slight heat, and cool to
room temperature, when the test solution is clear and free of impurities. The yttrium
content in the sample solution to be tested was determined by ICP-AES, and the standard
solution was used to calibrate ICP-AES. When the accuracy and stability of ICP-AES
were good, the yttrium content in the steel sample to be tested was 0.017%.
Example 5
Eight points were randomly selected from yttrium-bearing steel, and dot scanning
was performed by full spectrum spark direct reading spectrometer. Set the working
conditions of full spectrum spark direct reading spectrometer: discharge frequency
440Hz. The argon flow rate is 2301/h, environmental temperature 25°C/ light room
temperature 20°C, humidity 50-60%, purging time is Is. The excitation time is 12s and
the precombustion time is 4s. Dot scanning is performed on the surface of the sample by using a spark direct reading spectrometer to obtain the intensity ratio, and the yttrium content in the sample is calculated according to the standard analysis curve obtained in step 4 of Example 1.
The intensity ratio measured by dot scanning of full spectrum spark direct reading
spectrometer is 1065743, and the standard analysis curve of yttrium is:
y=1.94724*10 8 x 2 +3.16856*10 7 x+89329.93426, and the yttrium content is 0.0265%.
Determination of yttrium content by ICP-AES: use the above steel, sample the drill
cuttings at 1/4 of the yttrium-containing steel sample to be measured (during sampling,
pay attention to the bit temperature not to be too high), take 0.50g of steel cuttings, add
mL of mixed solution of water-hydrochloric acid-nitric acid (1: 1: 3) and slowly heat it
until the sample is completely dissolved, add 5mL of perchloric acid, heat it to smoke,
and continue heating until the volume of the test solution remains 1 ml. Cool, add 20mL
of water and 5mL of hydrochloric acid, dissolve the salts with slight heat, and cool to
room temperature, when the test solution is clear and free of impurities. The yttrium
content in the sample solution to be tested was determined by ICP-AES, and the standard
solution was used to calibrate ICP-AES. When the accuracy and stability of ICP-AES
were good, the yttrium content in the steel sample to be tested was 0.0274%.
Example 6
Eight points were randomly selected from yttrium-bearing steel, and dot scanning
was performed by full spectrum spark direct reading spectrometer. Set the working
conditions of full spectrum spark direct reading spectrometer: discharge frequency
460Hz. The argon flow rate is 2201/h, environmental temperature 25°C/ light room
temperature 20°C, humidity 50-60%, purging time is Is. The excitation time is 12s and the precombustion time is 4s. Dot scanning is performed on the surface of the sample by using a spark direct reading spectrometer to obtain the intensity ratio, and the yttrium content in the sample is calculated according to the standard analysis curve obtained in step 4 of Example 1.
The intensity ratio measured by dot scanning of full spectrum spark direct reading
spectrometer is 2013699, and the standard analysis curve of yttrium is:
y=1.94724*10 8 x 2 +3.16856*10 7 x+89329.93426, and the yttrium content is 0.0471%.
Determination of yttrium content by ICP-AES: use the above steel, sample the drill
cuttings at 1/4 of the yttrium-containing steel sample to be measured (during sampling,
pay attention to the bit temperature not to be too high), take 0.50g of steel cuttings, add
mL of mixed solution of water-hydrochloric acid-nitric acid (1: 1: 3) and slowly heat it
until the sample is completely dissolved, add 5mL of perchloric acid, heat it to smoke,
and continue heating until the volume of the test solution remains 1 ml. Cool, add 20mL
of water and 5mL of hydrochloric acid, dissolve the salts with slight heat, and cool to
room temperature, when the test solution is clear and free of impurities. The yttrium
content in the sample solution to be tested was determined by ICP-AES, and the standard
solution was used to calibrate ICP-AES. When the accuracy and stability of ICP-AES
were good, the yttrium content in the steel sample to be tested was 0.045%.
Example 7
Eight points were randomly selected from yttrium-bearing steel, and dot scanning
was performed by full spectrum spark direct reading spectrometer. Set the working
conditions of full spectrum spark direct reading spectrometer: discharge frequency
480Hz. The argon flow rate is 2301/h, environmental temperature 25°C/ light room temperature 20°C, humidity 50-60%, purging time is Is. The excitation time is 12s and the precombustion time is 4s. Dot scanning is performed on the surface of the sample by using a spark direct reading spectrometer to obtain the intensity ratio, and the yttrium content in the sample is calculated according to the standard analysis curve obtained in step 4 of Example 1.
The intensity ratio measured by dot scanning of full spectrum spark direct reading
spectrometer is 2211772, and the standard analysis curve of yttrium is:
y=1.94724*10 8 x 2 +3.16856*10 7 x+89329.93426, and the yttrium content is 0.051%.
Determination of yttrium content by ICP-AES: use the above steel, sample the drill
cuttings at 1/4 of the yttrium-containing steel sample to be measured (during sampling,
pay attention to the bit temperature not to be too high), take 0.50g of steel cuttings, add
mL of mixed solution of water-hydrochloric acid-nitric acid (1: 1: 3) and slowly heat it
until the sample is completely dissolved, add 5mL of perchloric acid, heat it to smoke,
and continue heating until the volume of the test solution remains 1 ml. Cool, add 20mL
of water and 5mL of hydrochloric acid, dissolve the salts with slight heat, and cool to
room temperature, when the test solution is clear and free of impurities. The yttrium
content in the sample solution to be tested was determined by ICP-AES, and the standard
solution was used to calibrate ICP-AES. When the accuracy and stability of ICP-AES
were good, the yttrium content in the steel sample to be tested was 0.0492%.
Example 8
Eight points were randomly selected from yttrium-bearing steel, and dot scanning
was performed by full spectrum spark direct reading spectrometer. Set the working
conditions of full spectrum spark direct reading spectrometer: discharge frequency
450Hz.The argon flow rate is 2251/h, environmental temperature 25°C/ light room
temperature 20°C, humidity 50-60%, purging time is Is. The excitation time is 12s and
the precombustion time is 4s. Dot scanning is performed on the surface of the sample by
using a spark direct reading spectrometer to obtain the intensity ratio, and the yttrium
content in the sample is calculated according to the standard analysis curve obtained in
step 4 of Example 1.
The intensity ratio measured by dot scanning of full spectrum spark direct reading
spectrometer is 389,569, and the standard analysis curve of yttrium is:
y=1.94724*10 8 x 2+3.16856*10 7 x+89329.93426, and the yttrium content is
0.00898%.
Determination of yttrium content by ICP-AES: use the above steel, sample the drill
cuttings at 1/4 of the yttrium-containing steel sample to be measured (during sampling,
pay attention to the bit temperature not to be too high), take 0.50g of steel cuttings, add
mL of mixed solution of water-hydrochloric acid-nitric acid (1: 1: 3) and slowly heat it
until the sample is completely dissolved, add 5mL of perchloric acid, heat it to smoke,
and continue heating until the volume of the test solution remains 1 ml. Cool, add 20mL
of water and 5mL of hydrochloric acid, dissolve the salts with slight heat, and cool to
room temperature, when the test solution is clear and free of impurities. The yttrium
content in the sample solution to be tested was determined by ICP-AES, and the standard
solution was used to calibrate ICP-AES. When the accuracy and stability of ICP-AES
were good, the yttrium content in the steel sample to be tested was 0.0091%.
The measured values (spark direct reading measured values) of the method
according to the present invention in Examples 2 to 8 were compared with the detected results (ICP measured values) of the ICP measuring method, and the results are shown in
Table 6.
Table 6 Comparison of test results
ICP estimated Spark direct Deviation Deviation Y value wt% reading measured value wt% rate
% value wt%
Example2 0.0087 0.00956 0.00086 0.098850575 Example 0.0053 0.00537 0.0000700 0.013207547 Example4 0.017 0.0176 0.0006 0.035294118
Example5 0.0274 0.0265 -0.0009 0.032846715
Example 0.045 0.0471 0.0021 0.046666667
Example7 0.0492 0.051 0.0018 0.036585366
Example8 0.0091 0.00898 -0.00012 0.013186813
At present, the determination of yttrium content mainly adopts ICP method, but the
process of detecting yttrium content by this method is very complicated, and destructive
detection is needed for the sample to be detected, which takes a long time. It can be seen
from Table 6 that compared with ICP method, the deviation value of the method of the
present invention is very small, which is basically negligible. However, the detection
method of the invention does not need to destroy the sample to be detected, and the
detection speed is fast. And is suitable for popularization and application.
Test example: uncertainty test
The uncertainty analysis was carried out on the detection results of Examples 2-8.
Uncertainties are mainly divided into two categories: Class A uncertainty and Class
B uncertainty. By calculating the uncertainty, the influencing factors of the determination
results are determined.
1. uncertainty caused by test results ((U(rel,Al)))
Reference formula (2.1) for calculating standard uncertainty and relative standard
uncertainty introduced by repetitive test
U(rei,A1)=-: (2.1)
Table 7 Relative standard uncertainty of repeatability test of y
Y Example2 Example3 Example4 Example5 Example6 Example7 Example8 average value 0.009560 0.005370 0.017600 0.026500 0.047100 0.051000 0.008980 S 0.000173 0.000747 0.000316 0.000469 0.000200 0.000300 0.000200 U(A,1) 0.000061 0.000264 0.000112 0.000166 0.000071 0.000106 0.000071 U(A,1)averag 0.000121 e value Urel(A,1) 0.006386 0.049198 0.006352 0.006255 0.001501 0.002080 0.007874 Urel(A,1)aver 0.011378 age value
According to the analysis in Table 7, the uncertainty calculated by repetitive test is
0.0001. The smaller the uncertainty, the smaller the deviation value of the measured
results, the better the test accuracy and the higher the use value of the values. The
uncertainty of yttrium is only 0.0001, and the uncertainty values are all small, which
shows that the measurement results are of good quality and high reliability.
2. Uncertainty brought by steel matrix(U(rel,B))
It is known that the content of each element in steel is based on iron matrix as
internal standard. In the testing process, the content of iron matrix in the calibration
sample and the sample to be tested should be the same or basically the same. The
difference of iron matrix content between the sample to be tested and the calibration
sample will bring uncertainty to the measurement results. Generally, the difference of
iron matrix content between the calibration sample and the sample to be tested is not
more than 1% (according to experience, every 1% difference in iron matrix content will bring about an error of 0.3), and the standard uncertainty caused by evenly distributed iron quantity difference is as follows:
According to the determination of content analysis, assuming that the average
concentration of iron is 98%, then
0.3 UB1 0.18 (1)
Urei,B1 0.0018 98 (2)
According to the analysis, the uncertainty of yttrium caused by steel matrix is
0.0018.
Evaluation of synthetic uncertainty (Urei)
The uncertainty brought by different reasons is judged by the uncertainty brought by
the test results, the uncertainty brought by the nonlinearity of calibration spectral lines
and the uncertainty brought by steel matrix, and the whole experimental test results are
judged by calculating the combined uncertainty. The calculation process is as follows:
Urei = Urei,A1 2 + UreIB1 2 (3)
Table 9 Evaluation of Synthetic Uncertainty Y Al/wt% 0.000121 Bi/wt% 0.001800 Urel/wt% 0.001804
The measurement result is judged by calculating the uncertainty of class a and class
b. If the confidence level of 95% is taken, then the factor k=2 is included, then in the test
sample:
UYttrium=. 001804 X 2=0. 003608 (4)
According to the above formula, the uncertainty of yttrium is 0.003608, that is, the
fluctuation range of yttrium detection results is 0.003608%.
In an embodiment, the deviation values of the values measured by ICP-AES and full
spectrum spark direct reading spectrometry are 0.00086, 0.00007 and 0.0006,
respectively, and the deviation rates are all less than the uncertainty of yttrium
(0.003608), so it can be concluded that the accuracy of the values measured by full
spectrum spark direct reading spectrometry is better and meets the detection
requirements.
The above is only a preferred embodiment of this application, and is not used to
limit this application. For those skilled in the art, this application can be modified and
varied. Any modification, equivalent substitution, improvement, etc. made within the
spirit and principle of this application shall be included in the protection scope of this
application.
Claims (10)
1.Method for quickly determining yttrium content in steel by using full spectrum
spark direct reading spectrometry, which is characterized by comprising the following
steps:
(1) By changing the addition amount of rare earth yttrium, steel ingots with different
yttrium contents are refined and rolled into billets.
(2) Taking a plurality of samples on one section of each billet obtained in the step
(1) and carrying out surface treatment, selecting the best working spectral line of the full
spectrum spark direct reading spectrometer according to the principle of minimum
interference of elements, carrying out uniformity detection on the samples by using the
best working spectral line, and selecting the sample with the best uniformity as a standard
sample.
(3) Sampling drill cuttings on the standard sample obtained in step (2), preparing a
standard solution, and calibrating the yttrium content in the standard solution by ICP
AES;
(4) Performing excitation calibration on the standard sample obtained in step (2) to
obtain an intensity ratio, establishing a corresponding relationship between the intensity
ratio and the yttrium content obtained in step (3), and drawing a rare earth yttrium
element standard analysis curve; The mathematical model of yttrium is obtained by
fitting the standard analysis curve, and the steel with unknown rare earth yttrium content
is detected by using the standard analysis curve of rare earth yttrium.
2. The detection method according to claim 1, characterized in that in step (1), the
billet is prepared by the following method:
SO. a magnesium oxide crucible is built in a medium frequency induction furnace,
baked and washed with matrix raw materials; The addition amount of matrix raw
materials and rare earth yttrium is determined by proportioning calculation, and the raw
materials are polished, weighed and put into a magnesium oxide crucible;
S02. start vacuumizing and slowly raise the temperature, keeping the vacuum degree
at 6.67x10-1 Pa. When the matrix raw materials are completely melted, rare earth yttrium
is added, the temperature is kept, electromagnetic stirring is carried out, melted, poured
into a casting mold, forged after demoulding, and rolled into a billet with a thickness of
mm.
3. The detection method according to claim 2, wherein in step SO1, the purity of the
rare earth yttrium is 99.9%.
4. The detection method according to claim 2, characterized in that, in step SO1, the
matrix material consists of the following chemical components by mass fraction:
C 0.09%, Mn 1.34%, S 0.006%, P 0.021%, Si 0.2%, Als 0.027%, N 0.0044%, Nb
0.029%, Ca 0.0013%, Ti 0.011%, Sn 0.0044% and the balance is Fe.
5. The detection method according to claim 1, which is characterized in that, in step
(2), sampling is carried out according to the method specified in GB/T20066-2006, and
the surface of the sample is ground after sampling, and the particle size of the ground
material is 0.124-0.25 mm.
6. The detection method according to claim 1, which is characterized in that in step
(2), the working conditions of the full spectrum spark direct reading instrument are as
follows: the discharge frequency is 400-500 Hz. The argon flow rate is 220-2301/h, environmental temperature 25°C/ light room temperature 20°C, humidity 50-60%.
Purging time is Is. The excitation time is 12s, and the precombustion time is 4s.
7. The detection method according to claim 1, characterized in that, in step (2), the
uniformity detection is as follows: spot scanning is performed on the surface of the
sample by using a full spectrum spark direct reading spectrometer, 8 spots are made for
each sample, and the uniformity of the sample is judged by the relative standard
uncertainty of the intensity ratio.
8. The detection method according to claim 1, characterized in that in step (2), the
best working spectral line isXY=371.029nm.
9. The detection method according to claim 1, characterized in that in step (3), the
standard solution is prepared by the following method:
Al. Take 0.50g of steel scrap and add 20mL of hydrochloric acid solution with a
density of 1.19g/mL. After the steel scrap is completely dissolved, add 5 drops of
perchloric acid with a density of 1.67g/mL, heat until the perchloric acid smokes
completely, and continue heating until the volume of the test solution remains 1-2 ml.
A2. Cool the test solution, dilute it to constant volume, mix well, and then let it
stand until the test solution is clear and free of impurities, thus obtaining the standard
solution.
10. The detection method according to claim 1, characterized in that in step (4), the
mathematical model is y=1.94724*10 8 x 2 +3.16856*107 x+89329.93426, where x is the
element content, y is the intensity ratio.
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