CN108051467A - A kind of method that X fluorescence spectrometer measures the primary and secondary quantitative elements in manganese ore - Google Patents
A kind of method that X fluorescence spectrometer measures the primary and secondary quantitative elements in manganese ore Download PDFInfo
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- CN108051467A CN108051467A CN201810002720.XA CN201810002720A CN108051467A CN 108051467 A CN108051467 A CN 108051467A CN 201810002720 A CN201810002720 A CN 201810002720A CN 108051467 A CN108051467 A CN 108051467A
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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
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- 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
- G01N1/286—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q involving mechanical work, e.g. chopping, disintegrating, compacting, homogenising
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Abstract
The invention belongs to analysis and testing technology fields, the method for disclosing the primary and secondary quantitative elements that a kind of X fluorescence spectrometer is measured in manganese ore, using the high-pressure powder sample making technology for reducing powder effect, granularity effect, mineral effect, method of preparing sample as manganese ore XRF analysis, simultaneously with the interference of absorption enhancement effect, background interference, matrix effect between instrumental quantitative analysis software correction element, a kind of high-pressure powder tabletting X-ray fluorescence spectra analytic approach for measuring various ingredients in manganese ore is established.The present invention intends using the method for preparing sample that can obviously reduce the high-pressure powder sample making technology of powder effect, granularity effect, mineral effect as XRF analysis manganese ore, realize that high-pressure powder tabletting XRF disposably quickly measures the major and minor component in manganese ore, avoid the mating series methods using traditional manganese ore, manpower and cost are saved, testing efficiency and economic benefit are improved, while can realize the environmental protection concept of green analysis.
Description
Technical field
The primary and secondary in manganese ore is measured the invention belongs to analysis and testing technology field more particularly to a kind of X fluorescence spectrometer
The method of secondary element.
Background technology
In conventional manganese ore analysis, in addition to main manganese, ferro element, usually also need to Hubeiwans such as CaO, MgO,
SiO2、Al2O3、K2O、Na2O、TiO2, the impurity such as P, S, As, BaO and association metallic element Cu, Co, Ni, V etc. carry out the same time-division
Analysis.Each national standard substantially establishes the classical way on the basis of the chemical analysis method individually detected in each element.The nineties
After, with icp ms (ICP-MS), inductively-coupled plasma spectrometer (ICP-AES), X-ray
The appearance of the large-scale precisions analytical instrument such as Fluorescence Spectrometer (XRF) simultaneously, is quickly measured in manganese ore using these large-scale instruments
Various elements become hot spot.
But ICP-MS and ICP-AES analysis methods improve wherein micro, trace components measuring accuracy, realize to manganese
The Accurate Analysis of impurity and rare element in ore deposit.But two methods are solution sample introduction, thus still need sample pre-treatments mistake
Journey.
Major and minor component comparative maturity in x-ray fluorescence spectrometry manganese ore.Generally use high temperature fuse piece sample preparation.
But contain since manganese ore water imbibition is relatively strong and often the crystallization water, be easy to generate bubble when sheet glass is melted, and be difficult to catch up with to the greatest extent, this
Operator is required to possess very high experience, the print reappearance for being otherwise susceptible to preparation is bad.In addition high temperature fuse piece-X is penetrated
Also there are 2 shortcomings for major and minor component in line fluorescence spectrum method for measuring manganese ore：First, sample preparation speed is relatively slow, no
Batch samples is suitble to measure；Second is that low content component, since flux dilution causes accuracy to be deteriorated, can test scope it is small.
In conclusion problem existing in the prior art is：
Print is prepared using powder pressing method, the multielement report in x-ray fluorescence spectrometry manganese ore sample is non-
It is often few.This is mainly due to manganese ore ingredient is extremely complex, principal component content is higher, and excursion is big, makes matrix variation greatly, right
X-ray fluorescence analysis adversely affects, and in particular by conventional powders pressed disc method (sample preparation pressure is in 200kN-600kN), deposits
In serious " powder effect ", " grain dispersion ", " mineral effect ", cause to carry out manganese ore analysis in usual powder pressing method
When, accuracy is high not as good as chemical method.
The content of the invention
In view of the problems of the existing technology, the primary and secondary in manganese ore is measured the present invention provides a kind of X fluorescence spectrometer
The method of secondary element.
The present invention is achieved in that a kind of method that X fluorescence spectrometer measures the primary and secondary quantitative elements in manganese ore, described
X fluorescence spectrometer measures the method for the primary and secondary quantitative elements in manganese ore to measure the high-pressure powder tabletting of various ingredients in manganese ore
X-ray fluorescence spectra analytic approach；
The method is using reduction powder effect, granularity effect, the high-pressure powder sample making technology of mineral effect as manganese ore
The method of preparing sample of stone XRF analysis；
Simultaneously with absorption enhancement effect, background interference, the matrix effect between instrumental quantitative analysis software correction element
Interference.
Further, the method for the primary and secondary quantitative elements in the X fluorescence spectrometer measure manganese ore specifically includes：
The first step, the preparation of print：It weighs in 105 DEG C of drying sample 4.5g in agate mortar, mixed grinding 5min；To
0.2g microcrystalline cellulose adhesives are added in ground sample, are put in after mixing in grinding tool, it is rebasing with polyethylene fringing, add
1000KN pressure is allowed into diameter 32mm disks, and number, which is put into drier, to be stored；
Second step, the foundation of standard curve：15 country-level manganese ore standard sample GBW07261 of selection,
GBW07262、GBW17263、GBW07264、GBW07265、GBW07266、GBW(E)070093、GBW(E)070094、GBW(E)
070095、GBW(E)070096、GBW(E)070097、GBW(E)070098、GBW(E)070099、GBW(E)070100、GBW
(E) 070101 and mixed by standard sample by different proportion 4 from sample mixing product GBW07261：GBW07262(1:
1)、GBW17263：GBW07264(1:1)、GBW07265：GBW07266(1:1)、GBW07262：GBW07266(1:1) and
GBW07261：GBW07264(1:1) standard curve is established；
3rd step, machine measures on instrument：The optimization of each analytical element instrument parameter is carried out, including narrow on WD-XRF
The optimization of seam, measurement voltage, electric current, angle, filter disc, PHD instrument parameters；Using the absorption between fundamental parameters method element correction
Enhancement effect, background interference, matrix effect.
Further, the bearing calibration of the absorption enhancement effect between element includes：
Ii=Pi+Sij
In formula, IiFor the intensity of i elements in unknown sample, I(i)It represents the intensity of i element pure elements, is obtained by calculating；Ii,s
Represent the intensity of i elements in standard sample；Subscript m s represents that actual measurement is value；Cal represents calculated value；PiRepresent first order fluorescence intensity,
SijRepresent second-order fluorescence intensity, μi,λThe mass-absorption coefficient for the incident light that representing sample i is to wavelength；Δ λ represents that incidence X is penetrated
Relevant wavelength difference with incoherent scattering of the wavelength of line in scattering object；RiRepresent relative intensity；
Introduce Di,λAnd Dj,λ, numerical value is 0 and 1, and simple X-ray spectrum wavelength is in short-wavelength limit and element to be measured and matrix member
Between the absorption limit of element, Di,λIt is otherwise 0 for 1；Equally, when matrix element j wavelength be more than element to be measured absorption prescribe a time limit,
Dj,λFor 0, otherwise the absorption less than element to be measured is prescribed a time limit, Dj,λFor 1；
For a certain feature X-ray spectral line of a certain element, EiFor a constant, when XRF instruments are consolidated
PeriodicallyIt is constant with csc Ψ 1, thus GiIt is just constant；For pure material, Cj=1.
Further, from opposite Strength co-mputation sample to be tested element content, use iterative method；The process of iteration includes：
A. by it is measuring or from formula 5. in the sample relative intensity that is calculated, be denoted asAs each component concentration
Initial estimate Ci；
B. by CiIn substituting into formula 3., the relative intensity of each component is calculated, calculated value is denoted as Ri；
C. by the relative intensity value of theoretical calculationWith the relative intensity value measuredIt is compared, as the following formula to previous
Secondary concentration is modified：C in formulaiFor previous estimate, Ci' it is correction value；
D. by revised concentration value Ci', then compared, then correct ..., so Xun Huan is until Ci' until convergence.
Further, the fundamental parameters method uses the basic calculating method of Rousseau：
Wherein, CiRepresent the concentration of element i to be measured, Wi(λk) represent weight factor, αij, εij, δijRepresent the suction between element
Receive enhancement effect, i.e., it is theoretical to influence coefficient, μiAnd μjThe mass-absorption coefficient for the incident light that representing sample i or j is to wavelength, I0
Representing the intensity of incident light, Δ λ represents relevant wavelength difference with incoherent scattering of the wavelength of incident X-rays in scattering object,
RiRepresent relative intensity.
Another object of the present invention is to provide the primary and secondary quantitative elements in a kind of X fluorescence spectrometer measure manganese ore to be
System.
Advantages of the present invention and good effect are：
The present invention establishes a kind of achievable quick, various ingredients in Accurate Determining manganese ore high-pressure powder tabletting X and penetrates
Line fluorescence spectrum analysing method.
Object is analyzed for manganese ore, pressure selection, dwell time and the sample granularity during high-pressure powder sample preparation are to method
Accuracy and the impact analysis of precision are one of key technologies that the present invention needs emphasis solution.
Absorption enhancement effect in X fluorescence spectrum analysis between each element is very serious, reduces matrix effect and background correction
It is another key technology in the present invention.
The application of this technology of high-pressure powder sample preparation of the present invention belongs to the starting stage at home, and applied to ore sample
It is not had been reported that also in the analysis of product, in blank in terms of manganese ore analysis, the present invention, which intends using, can obviously reduce " powder effect
Should ", the method for preparing sample of " granularity effect ", the high-pressure powder sample making technology of " mineral effect " as manganese ore XRF analysis, realize height
Pressed powder XRF is pressed disposably quickly to measure the major and minor component in manganese ore, avoids the mating series using traditional manganese ore
Method has saved manpower and cost, improves testing efficiency and economic benefit, while can realize the environmental protection reason of " green analysis "
It reads.
Description of the drawings
Fig. 1 is the method flow for the primary and secondary quantitative elements that X fluorescence spectrometer provided in an embodiment of the present invention is measured in manganese ore
Figure.
Specific embodiment
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiments, to the present invention
It is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, it is not used to
Limit the present invention.
At present, print is prepared using powder pressing method, the multielement report in x-ray fluorescence spectrometry manganese ore sample
Road is considerably less.This is mainly due to manganese ore ingredient is extremely complex, principal component content is higher, and excursion is big, changes matrix
Greatly, x-ray fluorescence analysis is adversely affected, in particular by conventional powders pressed disc method, (sample preparation pressure is in 200kN-
600kN), there are serious " powder effect ", " grain dispersion ", " mineral effect ", cause to carry out in usual powder pressing method
When manganese ore is analyzed, accuracy is high not as good as chemical method.
The application principle of the present invention is described in detail below in conjunction with the accompanying drawings.
The method that X fluorescence spectrometer provided in an embodiment of the present invention measures the primary and secondary quantitative elements in manganese ore, in high-pressure powder
During last sample preparation, pressure, dwell time and sample granularity are made choice；X fluorescence spectrum analysis in, carry out reduce matrix effect and
Background correction.
As shown in Figure 1, X fluorescence spectrometer provided in an embodiment of the present invention measures the side of the primary and secondary quantitative elements in manganese ore
Method specifically includes：
S101：The preparation of print：It weighs in 105 DEG C of drying sample 4.5g in agate mortar, mixed grinding 5min, to disappear
Except inhomogeneous broadening effect；0.2g microcrystalline cellulose adhesives are added in into ground sample, are put in after mixing in grinding tool, with poly- second
Alkene fringing is rebasing, and 100t pressure is added to be allowed into diameter 32mm disks, and number, which is put into drier, to be stored.
S102：The foundation of standard curve：15 country-level manganese ore standard sample GBW07261, GBW07262 of selection,
GBW17263、GBW07264、GBW07265、GBW07266、GBW(E)070093、GBW(E)070094、GBW(E)070095、
GBW(E)070096、GBW(E)070097、GBW(E)070098、GBW(E)070099、GBW(E)070100、GBW(E)
070101 and mixed by standard sample by different proportion 4 from sample mixing product GBW07261：GBW07262(1:1)、
GBW17263：GBW07264(1:1)、GBW07265：GBW07266(1:1)、GBW07262：GBW07266(1:1) and
GBW07261：GBW07264(1:1) standard curve is established.
S103：Machine measures on instrument：Carry out the optimization of each analytical element instrument parameter, including on WD-XRF slit,
Measure the optimization of voltage, electric current, angle, filter disc, PHD instrument parameters；Absorption enhancement effect, background interference between element, base
The correction of bulk effect.
The application principle of the present invention is further described with reference to specific embodiment.
The first step：The preparation of print.It weighs in 105 DEG C of drying sample 4.5g in agate mortar, mixed grinding 5min, with
Eliminate inhomogeneous broadening effect.0.2g microcrystalline cellulose adhesives are added in into ground sample, are put in grinding tool after mixing, with poly-
Ethylene fringing is rebasing, and 100t pressure is added to be allowed into diameter 32mm disks, and number, which is put into drier, to be stored.
Second step：The foundation of standard curve.15 country-level manganese ore standard sample GBW07261 of selection,
GBW07262、GBW17263、GBW07264、GBW07265、GBW07266、GBW(E)070093、GBW(E)070094、GBW(E)
070095、GBW(E)070096、GBW(E)070097、GBW(E)070098、GBW(E)070099、GBW(E)070100、GBW
(E) 070101 and mixed by standard sample by different proportion 4 from sample mixing product GBW07261：GBW07262(1:
1)、GBW17263：GBW07264(1:1)、GBW07265：GBW07266(1:1)、GBW07262：GBW07266(1:1) and
GBW07261：GBW07264(1:1) standard curve is established.
3rd step：Machine measures on instrument.
(1) optimization of each analytical element instrument parameter is mainly carried out, including slit, the measurement electricity on WD-XRF
The optimization of the instrument parameters such as pressure, electric current, angle, filter disc, PHD；
(2) corrections such as the absorption enhancement effect between element, background interference, matrix effect.Mainly with instrument quantitative point
Software is analysed to correct；
1. usually it should be considered to absorb come timing with this and also with absorption enhancement effect between fundamental parameters method element correction
Consider enhancement effect, should together consider by first order fluorescence and with second-order fluorescence, i.e.,
Ii=Pi+Sij ①
In formula, IiFor the intensity of i elements in unknown sample；I(i)It represents the intensity of i element pure elements, is obtained by calculating；Ii,s
Represent the intensity of i elements in standard sample；Subscript m s represents that actual measurement is value；Cal represents calculated value.
Will from opposite Strength co-mputation sample to be tested component content, it is necessary to use iterative method.The process of iteration is as follows：
A. by it is measuring or from formula 5. in the sample relative intensity that is calculated (be denoted as), as each component concentration
Initial estimate Ci。
B. by CiIn substituting into formula 3., calculating the relative intensity of each component, (calculated value is denoted as Ri)。
C. by the relative intensity value of theoretical calculationWith the relative intensity value measuredIt is compared, as the following formula to previous
Secondary concentration is modified：C in formulaiFor previous estimate, Ci' it is correction value.
D. by revised concentration value Ci', then compared, then correct ..., so Xun Huan is until Ci' (can until convergence
First provide a convergence, the concentration value difference for such as setting front and rear secondary calculating is no more than 0.005%, but all components all need to reach
This standard).
2. theory influences the basic calculating method that leveling factor method uses Rousseau：
Wherein, Wi(λk) represent weight factor, αij, εijRepresent the absorption enhancement effect between element, i.e., it is theoretical to influence coefficient.
(3) accuracy of method, precision.Using established analysis method, to being not included in the manganese ore of standard series
The sample of stone national standard substance or known constituent content is tested, the accuracy of discussion method, precision；
(4) actual sample test, method validation, result compare.Mainly actual sample is tested, with verification method
Practicability, while carried out to score using other analysis methods (such as traditional chemical method, ICP-MS or ICP-AES etc.)
Analysis, the reliability of verification method.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all essences in the present invention
All any modification, equivalent and improvement made within refreshing and principle etc., should all be included in the protection scope of the present invention.
Claims (6)
1. a kind of method that X fluorescence spectrometer measures the primary and secondary quantitative elements in manganese ore, which is characterized in that the X fluorescence spectrum
Instrument measures the method for the primary and secondary quantitative elements in manganese ore to measure the high-pressure powder tabletting x-ray fluorescence of various ingredients in manganese ore
Spectra methods；
The method is using reduction powder effect, granularity effect, the high-pressure powder sample making technology of mineral effect as manganese ore XRF
The method of preparing sample of analysis；
Simultaneously between instrumental quantitative analysis software correction element absorption enhancement effect, background interference, matrix effect it is dry
It disturbs.
2. the method that X fluorescence spectrometer as described in claim 1 measures the primary and secondary quantitative elements in manganese ore, which is characterized in that
The method that the X fluorescence spectrometer measures the primary and secondary quantitative elements in manganese ore specifically includes：
The first step, the preparation of print：It weighs in 105 DEG C of drying sample 4.5g in agate mortar, mixed grinding 5min；To grinding
0.2g microcrystalline cellulose adhesives are added in good sample, are put in after mixing in grinding tool, it is rebasing with polyethylene fringing, add 1000KN
Pressure is allowed into diameter 32mm disks, and number, which is put into drier, to be stored；
Second step, the foundation of standard curve：15 country-level manganese ore standard sample GBW07261, GBW07262 of selection,
GBW17263、GBW07264、GBW07265、GBW07266、GBW(E)070093、GBW(E)070094、GBW(E)070095、
GBW(E)070096、GBW(E)070097、GBW(E)070098、GBW(E)070099、GBW(E)070100、GBW(E)
070101 and mixed by standard sample by different proportion 4 from sample mixing product GBW07261：GBW07262(1:1)、
GBW17263：GBW07264(1:1)、GBW07265：GBW07266(1:1)、GBW07262：GBW07266(1:1) and
GBW07261：GBW07264(1:1) standard curve is established；
3rd step, machine measures on instrument：Carry out the optimization of each analytical element instrument parameter, including on WD-XRF slit, survey
Measure the optimization of voltage, electric current, angle, filter disc, PHD instrument parameters；Using the influx and translocation between fundamental parameters method element correction
Effect, background interference, matrix effect.
3. the method that X fluorescence spectrometer as claimed in claim 2 measures the primary and secondary quantitative elements in manganese ore, which is characterized in that
The bearing calibration of absorption enhancement effect between element includes：
Ii=Pi+Sij
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In formula, IiFor the intensity of i elements in unknown sample, I(i)It represents the intensity of i element pure elements, is obtained by calculating；Ii,sRepresent mark
The intensity of i elements in quasi- sample；Subscript m s represents that actual measurement is value；Cal represents calculated value；PiRepresent first order fluorescence intensity, SijIt represents
Second-order fluorescence intensity, μi,λThe mass-absorption coefficient for the incident light that representing sample i is to wavelength；Δ λ represents the ripple of incident X-rays
Grow the relevant wavelength difference with incoherent scattering in scattering object；RiRepresent relative intensity；
Introduce Di,λAnd Dj,λ, numerical value is 0 and 1, and simple X-ray spectrum wavelength is in short-wavelength limit and element to be measured and matrix element
Between absorbing limit, Di,λIt is otherwise 0 for 1；Equally, when matrix element j wavelength be more than element to be measured absorption prescribe a time limit, Dj,λFor
0, on the contrary the absorption less than element to be measured is prescribed a time limit, Dj,λFor 1；
For a certain feature X-ray spectral line of a certain element, EiFor a constant, when XRF instruments are fixedIt is constant with csc Ψ 1, thus GiIt is just constant；For pure material, Cj=1.
4. the method that X fluorescence spectrometer as claimed in claim 3 measures the primary and secondary quantitative elements in manganese ore, which is characterized in that
The content of element, uses iterative method from opposite Strength co-mputation sample to be tested；The process of iteration includes：
A. by it is measuring or from formula 5. in the sample relative intensity that is calculated, be denoted asAs the initial of each component concentration
Estimate Ci；
B. by CiIn substituting into formula 3., the relative intensity of each component is calculated, calculated value is denoted as Ri；
C. by the relative intensity value of theoretical calculationWith the relative intensity value measuredIt is compared, as the following formula to previous
Concentration is modified：C in formulaiFor previous estimate, C 'iFor correction value；
D. by revised concentration value C 'i, then compared, then correct ..., so Xun Huan is until C 'iUntil convergence.
5. the method that X fluorescence spectrometer as claimed in claim 3 measures the primary and secondary quantitative elements in manganese ore, which is characterized in that
The fundamental parameters method uses the basic calculating method of Rousseau：
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Wherein, CiRepresent the concentration of element i to be measured, Wi(λk) represent weight factor, αij, εij, δijRepresent that the absorption between element increases
It is potent to answer, i.e., it is theoretical to influence coefficient, μiAnd μjThe mass-absorption coefficient for the incident light that representing sample i or j is to wavelength, I0It represents
The intensity of incident light, Δ λ represent relevant wavelength difference with incoherent scattering of the wavelength of incident X-rays in scattering object, RiTable
Show relative intensity.
6. a kind of X fluorescence spectrometer as described in claim 1 measures the X fluorescence spectrum of the method for the primary and secondary quantitative elements in manganese ore
The system that instrument measures the primary and secondary quantitative elements in manganese ore.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108872283A (en) * | 2018-09-11 | 2018-11-23 | 中国科学院寒区旱区环境与工程研究所 | Using the method for wavelength dispersion X-ray fluorescence spectrometer measurement plant sample |
| CN110082379A (en) * | 2019-04-09 | 2019-08-02 | 湛江出入境检验检疫局检验检疫技术中心 | The method that MTG YBCO bulk-X-ray fluorescence spectra surveys 14 kinds of major and minor components in chrome ore |
| CN111650231A (en) * | 2020-06-08 | 2020-09-11 | 天津钢铁集团有限公司 | Method for analyzing content of main elements in low-silicon ferrosilicon by X-ray fluorescence spectrum |
| CN112415034A (en) * | 2020-10-09 | 2021-02-26 | 湖南省生态环境监测中心 | XRF (X-ray fluorescence) measurement and analysis method of solid waste |
| CN113866203A (en) * | 2021-09-26 | 2021-12-31 | 广东韶钢松山股份有限公司 | Method for detecting primary and secondary elements of crude zinc powder of rotary hearth furnace |
| CN113866203B (en) * | 2021-09-26 | 2024-03-12 | 广东韶钢松山股份有限公司 | Method for detecting primary and secondary elements of coarse zinc powder of rotary hearth furnace |
| CN114441574A (en) * | 2022-02-11 | 2022-05-06 | 山东钢铁集团永锋临港有限公司 | Method for measuring contents of potassium, sodium, lead and zinc in iron ore |
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