CN107356618A - A kind of method of covering agent component content in x-ray fluorescence spectrometry - Google Patents
A kind of method of covering agent component content in x-ray fluorescence spectrometry Download PDFInfo
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- CN107356618A CN107356618A CN201710521274.9A CN201710521274A CN107356618A CN 107356618 A CN107356618 A CN 107356618A CN 201710521274 A CN201710521274 A CN 201710521274A CN 107356618 A CN107356618 A CN 107356618A
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- Prior art keywords
- covering agent
- ray fluorescence
- component content
- fluorescence spectrometry
- sample
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Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N23/00—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00
- G01N23/22—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material
- G01N23/223—Investigating or analysing materials by the use of wave or particle radiation, e.g. X-rays or neutrons, not covered by groups G01N3/00 – G01N17/00, G01N21/00 or G01N22/00 by measuring secondary emission from the material by irradiating the sample with X-rays or gamma-rays and by measuring X-ray fluorescence
-
- 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
- G01N1/36—Embedding or analogous mounting of samples
-
- 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
- G01N1/36—Embedding or analogous mounting of samples
- G01N2001/366—Moulds; Demoulding
Abstract
The invention provides a kind of method of covering agent component content in x-ray fluorescence spectrometry, and specifically detect SiO2、CaO、MgO、Al2O3And Fe2O3Content.Compared with prior art, the present invention realizes the technological break-through of covering agent chemical constituents determination in measure, covering agent chemical composition in being determined using x-ray fluorescence method, the shortcomings that the method overcome the defects of original wet chemical analysis method is present and being verified without standard sample, with the advantages of analyze speed is fast, precision is high and the degree of accuracy is good, the Accurate Determining of covering agent chemical composition suitable for steel-making use.Meanwhile method is simple to operate, safety, print preparation time is short, and can preserve for a long time.
Description
Technical field
The invention belongs to technical field of analysis and detection, and in particular to covering agent in a kind of x-ray fluorescence spectrometry
The method of component content, and specifically detect SiO2、CaO、MgO、Al2O3And Fe2O3Content.
Background technology
In casting process, tundish plays the important function taken over from the past and set a new course for the future.Molten steel is dispensed into different crystallizers by it
And make molten steel that there is the hydrostatic head of relatively low stabilization, but also be a refining vessel, it can be used for improving the quality of molten steel.Its
In, the effect of tundish covering flux increasingly attracts people's attention.
The original function of tundish covering flux is insulation, prevents that temperature drop is excessive in casting process, but is wanted with steel quality
More and more higher is sought, the metallurgical function of tundish covering flux tends to be extensive：It is incubated, prevents air to the secondary oxidation of molten steel, absorption
Floating field trash in molten steel, do not avoid polluting molten steel with molten steel reaction, prevent molten steel from returning sulphur etc..
Tundish covering flux mainly has acid, neutral, the alkaline and double-deck type of slag four.The chemical composition of middle covering agent
Including SiO2、CaO、MgO、Al2O3And Fe2O3Deng the detection no ready-made national standard or professional standard of, its chemical composition, lead to
Frequently with the wet chemical analysis method such as volumetric method and photometry.
The defects of wet chemical analysis method generally existing is：Simultaneous determination of multiponents is unable to, cumbersome, molten sample formality
It is numerous and diverse, analytical cycle length.Need to use substantial amounts of chemical reagent during analysis, certain pollution is caused to environment.Meanwhile do not have
Commercially available middle covering agent national standard sample, the accuracy of its composition measurement result can not effectively be verified.Cause
This, tends not to provide fast and accurately composition measurement result, and serious influence is caused to electric furnace production.
Therefore it provides a kind of high, the simple to operate middle covering agent chemical constituents determination method of accuracy is compeling for industry
It is essential and asks.
The content of the invention
In order to solve the above technical problems, the present invention provide in a kind of x-ray fluorescence spectrometry covering agent chemistry into
The method divided, can quick detection SiO2、CaO、MgO、Al2O3And Fe2O3Content.
The method of covering agent chemical composition in a kind of x-ray fluorescence spectrometry provided by the invention, including it is following
Step：
1) from silica, high-alumina brick, clinker and standards for iron ore material and standard reagent, be configured to concentration gradient and
With the series of calibration sample of content range；
2) first high temperature sintering processing, removes the reducing substances in calibration sample；
3) then, calibration sample, flux and releasing agent are mixed, high-temperature fusion, are prepared into calibration sample sheet glass；
4) calibration sample sheet glass product are carried out with Xray fluorescence spectrometer to be detected, obtains SiO2、CaO、MgO、Al2O3With
Fe2O3Content and fluorescence intensity relation, obtain making calibration curve；
5) it is put into Xray fluorescence spectrometer, is examined using test sample made of the preparation method same with calibration print
Survey and the calibration curve of x ray fluorescence spectrometry is established according to calibration sample, you can SiO in covering agent in acquisition2、CaO、
MgO、Al2O3And Fe2O3Content.
Further, high-temperature process refers to described in step 2)：Weigh 1g samples to be placed in constant weight container, 1000 ± 20
Calcination lh in DEG C Muffle furnace, taking-up are cooled to room temperature, are placed in standby in drier.
High-temperature fusion refers to described in step 3)：20min~30min is melted in 1100 DEG C~1200 DEG C.
Step 3) alignment sample, the mass ratio of flux are：1:10.
The solvent is selected from anhydrous lithium tetraborate；
The releasing agent is selected from ammonium bromide.
The present invention uses X-ray fluorescence spectra (XRF) analytic approach detection elements content, is a kind of important chemical composition analysis
Means, there is the advantages that quick, easy, accurate, analytical element is more, and the content range of measure is wide, and precision is high.Pass through high temperature simultaneously
MTG YBCO bulk method, selection standard sample addition primary standard substance or different standard samples according to a certain percentage, can be artificial synthesized
Series of calibration sample, solves the problems, such as no respective standard sample.
Compared with prior art, the present invention realizes the technological break-through of covering agent chemical constituents determination in measure, realizes
A variety of chemical composition contents in covering agent determined with x-ray fluorescence method simultaneously in.Due to SiO in middle covering agent2、CaO、
MgO、Al2O3And Fe2O3Content is different, has height difference, by controlling the mass ratio of sample, flux to be：1:10, it can take into account
The accuracy of the detected value of different element different contents.1100 DEG C~1200 DEG C of sample melts 20min during preparing sheet glass
~30min, takes into account SiO2、CaO、MgO、Al2O3And Fe2O3The accuracy of detection.Higher than this temperature, energy consumption is increased, and composition is waved
Hair influences detection accuracy；Less than this temperature, composition can not melt completely, influence accuracy in detection；Meanwhile the melting of this temperature is most
Energy-conservation, reduces cost.It the method overcome and be unable to simultaneous determination of multiponents and without mark existing for original wet chemical analysis method
The defects of quasi- sample checking, there is the advantages of analyze speed is fast, precision is high and the degree of accuracy is good, lid is coated suitable for steel-making use
The Accurate Determining of agent chemical composition.Meanwhile method is simple to operate, safety, print preparation time is short, and can preserve for a long time.
Embodiment
Embodiment 1
The method of covering agent component content, comprises the following steps in a kind of x-ray fluorescence spectrometry：
1) selection of calibration sample
From the standard substances such as silica, high-alumina brick, clinker, iron ore and standard reagent, synthesis according to a certain ratio has one
Determine the series of calibration sample of concentration gradients.Synthesis series of calibration sample is shown in Table 1, and each element measurement range is shown in Table 2.
Table 1 synthesizes series of calibration sample
The each component measurement range of table 2
| Component | Measurement range, % |
| SiO2 | 0.10-60.00 |
| CaO | 0.10-99.90 |
| MgO | 0.05-60.00 |
| Al2O3 | 0.05-60.00 |
| Fe2O3 | 0.05-20.00 |
2) preparation of sample and calibration sample
2.1) pre-treatment of sample
Weigh 1g samples to be placed in constant weight container, the calcination lh in 1000 ± 20 DEG C of Muffle furnaces, taking-up is cooled to room temperature, puts
It is standby in drier.The mode of calibration sample pretreatment is consistent with sample.Each element content is pressed in pretreated sample
Row formula (1) calculates：
C=C0/ (100-IL) % (1)
In formula：C-- be pretreatment after each element content, %；
C0-- for the constituent content indicated on standard specimen bottle, %；
IL-- is the burning decrement indicated on standard specimen bottle, %.
Calibration sample pre-processes：
Weigh 1g calibration samples to be placed in constant weight container, the calcination lh in 1000 ± 20 DEG C of Muffle furnaces, taking-up is cooled to room
Temperature, it is placed in standby in drier.
2.2) preparation of standard sample
Weigh 7.0000g Li2B4O7Flux is in weighing disk, then weighs 0.7000g standard sample in weighing disk,
After fully mixing, it is transferred in platinum yellow crucible, adds 0.5-0.5ml20% NH4Br releasing agents, are put into high temperature Muffle furnace,
5min is melted under 1150 DEG C of high temperature.Take out after shaking up and driving bubble away, place into high temperature Muffle furnace, continue to melt 20min.Take
Go out to shake up, cool down after be stripped, be put into standby in drier.
It is prepared by test sample：
Weigh 7.0000g Li2B4O7Flux is in weighing disk, then weighs 0.7000g test sample in weighing disk,
After fully mixing, it is transferred in platinum yellow crucible, adds 0.5-0.5ml20% NH4Br releasing agents, are put into high temperature Muffle furnace,
5min is melted under 1150 DEG C of high temperature.Take out after shaking up and driving bubble away, place into high temperature Muffle furnace, continue to melt 20min.Take
Go out to shake up, cool down after be stripped, be put into standby in drier.
3) calibration curve makes
The series of calibration sample prepared with table 1, the normal glass sample prepared by the same method of step 2) mother glass piece
Piece, condition test is carried out on Xray fluorescence spectrometer, select suitable crystal, collimater, voltage and current, 2 θ and pulse
Highly distribution etc., to select the optimal analysis condition of instrument.The fluorescence that 6 calibration samples are determined with Xray fluorescence spectrometer is strong
Degree, after overlap of spectral lines and basal image, linear relationship is determined according to intensity and content, carries out linear regression, is made
Go out calibration curve, and be stored in the quantitative analysis software of computer.Instrumental conditions see the table below 3.
The instrumental conditions of table 3
4) measure
The test sample being prepared into is put into Xray fluorescence spectrometer, x ray fluorescence spectrometry is established with standard sample of photo
Working curve measure, after Xray fluorescence spectrometer detects, calculate the content of each component in sample automatically, and lead to
Formula (1) conversion obtains SiO in primary sample in crossing 2.1)2、CaO、MgO、Al2O3And Fe2O3Etc. the content of component.
To verify the degree of accuracy of this method, the accuracy of this method is verified from 5 production samples, as shown in table 4.By chemistry
Value and XRF are worth contrast to understand, two methods analysis result difference very little, show that this method has good accuracy.
The accuracy test result % of the method for table 4
Meanwhile in order to verify the precision of this method, the same melt sample preparation behaviour of continuous 10 times is carried out to same sample
After work, the measurement intensity of each component is measured on Xray fluorescence spectrometer, calculates its average value, standard deviation and relative standard
Deviation.
Precision (n=10) KCPS of the method for table 5
| Sequence number | Al2O3 | SiO2 | CaO | Fe2O3 | MgO |
| 1 | 7.649 | 1.928 | 5.119 | 17.853 | 40.401 |
| 2 | 7.624 | 1.923 | 5.137 | 17.142 | 40.422 |
| 3 | 7.619 | 1.917 | 5.109 | 17.261 | 40.420 |
| 4 | 7.640 | 1.919 | 5.137 | 17.233 | 40.392 |
| 5 | 7.633 | 1.972 | 5.121 | 17.193 | 40.360 |
| 6 | 7.660 | 1.915 | 5.153 | 17.515 | 40.373 |
| 7 | 7.659 | 1.924 | 5.155 | 17.210 | 40.374 |
| 8 | 7.630 | 1.910 | 5.134 | 17.054 | 40.409 |
| 9 | 7.637 | 1.930 | 5.091 | 17.323 | 40.375 |
| 10 | 7.642 | 1.919 | 5.103 | 17.314 | 40.322 |
| Avg | 7.639 | 1.921 | 5.126 | 17.210 | 40.368 |
| S | 0.016 | 1.009 | 0.025 | 0.185 | 0.040 |
| RSD% | 0.570 | 0.655 | 0.997 | 0.203 | 0.105 |
By the as shown by data of table 5, MgO, SiO2、Fe2O3And Al2O3Relative standard deviation all within the scope of less,
Illustrate that this method has good precision.
Claims (6)
1. a kind of method of covering agent component content in x-ray fluorescence spectrometry, it is characterised in that methods described includes
Following steps：
1) from silica, high-alumina brick, clinker and standards for iron ore material and standard reagent, it is configured to concentration gradient and and contains
Measure the series of calibration sample of scope；
2) first high temperature sintering processing, removes the reducing substances in calibration sample；
3) then, calibration sample, flux and releasing agent are mixed, high-temperature fusion, are prepared into calibration sample sheet glass；
4) calibration sample sheet glass product are carried out with Xray fluorescence spectrometer to be detected, obtains SiO2、CaO、MgO、Al2O3And Fe2O3
Content and fluorescence intensity relation, obtain making calibration curve；
5) it is put into using test sample made of the preparation method same with calibration print in Xray fluorescence spectrometer, detection is simultaneously
The calibration curve of x ray fluorescence spectrometry is established according to calibration sample, you can SiO in covering agent in acquisition2、CaO、MgO、
Al2O3And Fe2O3Content.
2. the method for covering agent component content in x-ray fluorescence spectrometry according to claim 1, its feature exist
In high-temperature process refers to described in step 2)：Weigh 1g samples to be placed in constant weight container, the calcination in 1000 ± 20 DEG C of Muffle furnaces
Lh, taking-up are cooled to room temperature, are placed in standby in drier.
3. the method for covering agent component content in x-ray fluorescence spectrometry according to claim 1, its feature exist
In high-temperature fusion refers to described in step 3)：20min~30min is melted in 1100 DEG C~1200 DEG C.
4. the method for covering agent component content in x-ray fluorescence spectrometry according to claim 1, its feature exist
In step 3) alignment sample, the mass ratio of flux are：1:10.
5. the method for covering agent component content in the x-ray fluorescence spectrometry according to claim 1 or 4, it is special
Sign is that the solvent is selected from anhydrous lithium tetraborate.
6. the method for covering agent component content in the x-ray fluorescence spectrometry according to claim 1 or 4, it is special
Sign is that the releasing agent is selected from ammonium bromide.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108414556A (en) * | 2018-01-26 | 2018-08-17 | 武汉科技大学 | A kind of preparation method of XRF cobalts internal standard analysis coating flux piece |
| CN110261420A (en) * | 2019-07-04 | 2019-09-20 | 包头钢铁（集团）有限责任公司 | The method of x-ray fluorescence spectrometry serpentine chemical component |
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| CN103743769A (en) * | 2013-12-31 | 2014-04-23 | 马钢(集团)控股有限公司 | Method for determining the content of harmful elements in iron ore by using X-ray fluorescent spectrometry |
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2017
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101713751A (en) * | 2009-12-07 | 2010-05-26 | 巨石集团有限公司 | Method for detecting chemical components of alkali-free glass by mixing X-ray fluorescence spectrometry with compression method |
| CN102135508A (en) * | 2011-01-25 | 2011-07-27 | 唐山建龙实业有限公司 | Method for testing chemical constituents in coal or coke ash by X-ray fluorescence spectrum analysis method |
| CN102156142A (en) * | 2011-05-19 | 2011-08-17 | 马鞍山钢铁股份有限公司 | Method for analyzing ferrosilicon alloy components for X-ray fluorescence spectrum analysis |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108414556A (en) * | 2018-01-26 | 2018-08-17 | 武汉科技大学 | A kind of preparation method of XRF cobalts internal standard analysis coating flux piece |
| CN110261420A (en) * | 2019-07-04 | 2019-09-20 | 包头钢铁（集团）有限责任公司 | The method of x-ray fluorescence spectrometry serpentine chemical component |
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Address after: 243003 intellectual property department, technology center, No. 8 Hunan West Road, Yushan, Ma'anshan, Anhui Applicant after: Ma'anshan Iron and Steel Co., Ltd. Address before: 243003 intellectual property department, technology center, No. 8 Hunan West Road, Ma'anshan, Anhui Applicant before: Ma'anshan Iron and Steel Co., Ltd. |
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Address after: 243003 8 Jiuhua Road, Yushan, Ma'anshan, Anhui Applicant after: Ma'anshan Iron and Steel Co., Ltd. Address before: 243003 intellectual property department, technology center, No. 8 Hunan West Road, Yushan, Ma'anshan, Anhui Applicant before: Ma'anshan Iron and Steel Co., Ltd. |
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