CN108680593A - A kind of X-ray fluorescence spectra quickly measures primary and secondary in granite, the method for micro constitutent - Google Patents
A kind of X-ray fluorescence spectra quickly measures primary and secondary in granite, the method for micro constitutent Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 40
- 239000010438 granite Substances 0.000 title claims abstract description 38
- 238000004876 x-ray fluorescence Methods 0.000 title claims abstract description 27
- 238000001228 spectrum Methods 0.000 title claims abstract description 19
- 238000001514 detection method Methods 0.000 claims abstract description 21
- 230000004907 flux Effects 0.000 claims abstract description 19
- 238000002360 preparation method Methods 0.000 claims abstract description 19
- IIPYXGDZVMZOAP-UHFFFAOYSA-N lithium nitrate Chemical compound [Li+].[O-][N+]([O-])=O IIPYXGDZVMZOAP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 230000000694 effects Effects 0.000 claims abstract description 12
- 239000000126 substance Substances 0.000 claims abstract description 10
- 238000012937 correction Methods 0.000 claims abstract description 7
- XZXYQEHISUMZAT-UHFFFAOYSA-N 2-[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenol Chemical compound CC1=CC=C(O)C(CC=2C(=CC=C(C)C=2)O)=C1 XZXYQEHISUMZAT-UHFFFAOYSA-N 0.000 claims abstract description 6
- 229940107816 ammonium iodide Drugs 0.000 claims abstract description 6
- 238000010521 absorption reaction Methods 0.000 claims abstract description 5
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 5
- PSHMSSXLYVAENJ-UHFFFAOYSA-N dilithium;[oxido(oxoboranyloxy)boranyl]oxy-oxoboranyloxyborinate Chemical compound [Li+].[Li+].O=BOB([O-])OB([O-])OB=O PSHMSSXLYVAENJ-UHFFFAOYSA-N 0.000 claims abstract description 4
- HZRMTWQRDMYLNW-UHFFFAOYSA-N lithium metaborate Chemical compound [Li+].[O-]B=O HZRMTWQRDMYLNW-UHFFFAOYSA-N 0.000 claims abstract description 4
- 238000002844 melting Methods 0.000 claims description 17
- 230000008018 melting Effects 0.000 claims description 17
- 238000012360 testing method Methods 0.000 claims description 17
- 239000012925 reference material Substances 0.000 claims description 12
- 238000002156 mixing Methods 0.000 claims description 11
- 230000003647 oxidation Effects 0.000 claims description 10
- 238000007254 oxidation reaction Methods 0.000 claims description 10
- 238000007689 inspection Methods 0.000 claims description 7
- 241000282376 Panthera tigris Species 0.000 claims description 6
- 238000011088 calibration curve Methods 0.000 claims description 6
- 239000006185 dispersion Substances 0.000 claims description 6
- 229910052656 albite Inorganic materials 0.000 claims description 5
- 238000001816 cooling Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- 239000002689 soil Substances 0.000 claims description 5
- DLHONNLASJQAHX-UHFFFAOYSA-N aluminum;potassium;oxygen(2-);silicon(4+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Al+3].[Si+4].[Si+4].[Si+4].[K+] DLHONNLASJQAHX-UHFFFAOYSA-N 0.000 claims description 4
- 230000004927 fusion Effects 0.000 claims description 4
- 238000007493 shaping process Methods 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 230000008021 deposition Effects 0.000 claims description 3
- 229910052703 rhodium Inorganic materials 0.000 claims description 3
- 239000010948 rhodium Substances 0.000 claims description 3
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000470 constituent Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract description 10
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 abstract description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 abstract description 8
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 8
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 abstract description 8
- CPLXHLVBOLITMK-UHFFFAOYSA-N Magnesium oxide Chemical compound [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 abstract description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 abstract description 6
- 239000000377 silicon dioxide Substances 0.000 abstract description 5
- 229910052726 zirconium Inorganic materials 0.000 abstract description 5
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 abstract description 4
- CHWRSCGUEQEHOH-UHFFFAOYSA-N potassium oxide Chemical compound [O-2].[K+].[K+] CHWRSCGUEQEHOH-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001950 potassium oxide Inorganic materials 0.000 abstract description 4
- 238000002203 pretreatment Methods 0.000 abstract description 4
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 abstract description 4
- 229910001948 sodium oxide Inorganic materials 0.000 abstract description 4
- 239000004408 titanium dioxide Substances 0.000 abstract description 4
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 3
- 239000005864 Sulphur Substances 0.000 abstract description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052788 barium Inorganic materials 0.000 abstract description 3
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 abstract description 3
- 230000008901 benefit Effects 0.000 abstract description 3
- 239000003153 chemical reaction reagent Substances 0.000 abstract description 3
- 239000000395 magnesium oxide Substances 0.000 abstract description 3
- 229910052701 rubidium Inorganic materials 0.000 abstract description 3
- IGLNJRXAVVLDKE-UHFFFAOYSA-N rubidium atom Chemical compound [Rb] IGLNJRXAVVLDKE-UHFFFAOYSA-N 0.000 abstract description 3
- 229910052712 strontium Inorganic materials 0.000 abstract description 3
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 abstract description 3
- 239000011573 trace mineral Substances 0.000 abstract description 3
- 235000013619 trace mineral Nutrition 0.000 abstract description 3
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 abstract description 2
- 239000000292 calcium oxide Substances 0.000 abstract description 2
- ODINCKMPIJJUCX-UHFFFAOYSA-N calcium oxide Inorganic materials [Ca]=O ODINCKMPIJJUCX-UHFFFAOYSA-N 0.000 abstract description 2
- 238000002189 fluorescence spectrum Methods 0.000 abstract description 2
- 229910052593 corundum Inorganic materials 0.000 abstract 1
- 238000000921 elemental analysis Methods 0.000 abstract 1
- 238000007500 overflow downdraw method Methods 0.000 abstract 1
- 238000004846 x-ray emission Methods 0.000 abstract 1
- 229910001845 yogo sapphire Inorganic materials 0.000 abstract 1
- 238000005259 measurement Methods 0.000 description 7
- 239000005357 flat glass Substances 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 229910052500 inorganic mineral Inorganic materials 0.000 description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 4
- 239000011707 mineral Substances 0.000 description 4
- 235000010755 mineral Nutrition 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- 230000003595 spectral effect Effects 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 239000011575 calcium Substances 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011435 rock Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 229910021521 yttrium barium copper oxide Inorganic materials 0.000 description 3
- UKFWSNCTAHXBQN-UHFFFAOYSA-N ammonium iodide Chemical compound [NH4+].[I-] UKFWSNCTAHXBQN-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000013049 sediment Substances 0.000 description 2
- 239000005995 Aluminium silicate Substances 0.000 description 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 1
- 229910013178 LiBO2 Inorganic materials 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 238000003723 Smelting Methods 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- 235000012211 aluminium silicate Nutrition 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- -1 basalt Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033558 biomineral tissue development Effects 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- NLYAJNPCOHFWQQ-UHFFFAOYSA-N kaolin Chemical compound O.O.O=[Al]O[Si](=O)O[Si](=O)O[Al]=O NLYAJNPCOHFWQQ-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000005464 sample preparation method Methods 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
Classifications
-
- 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
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Analysing Materials By The Use Of Radiation (AREA)
Abstract
The invention belongs to fluorescence spectrum detection fields, and in particular to a kind of X-ray fluorescence spectra quickly measures primary and secondary in granite, the method for micro constitutent.The present invention uses fusion method sample preparation, sample to select mass ratio for 12 after lithium nitrate pre-oxidizes:22 lithium tetraborate and lithium metaborate mix reagent prepares fuse piece as flux using ammonium iodide as releasing agent.Using standard substances such as granite as calibration sample, and elemental analysis range is further expanded by artificial synthesized sample, by the absorption enhancement effect between the Theoretical Alpha Coefficient Method element correction of variation, the x ray fluorescence spectrometry of silica in granite, alundum (Al2O3), potassium oxide, sodium oxide molybdena, iron oxide, calcium oxide, magnesia, manganese oxide, phosphorus pentoxide, titanium dioxide, barium, strontium, sulphur, 15 kinds of rubidium, zirconium components is established.This method have many advantages, such as pre-treatment is simple, detection speed is fast, it is at low cost, can analyze primary and secondary and trace element simultaneously, significant increase detection efficiency.
Description
Technical field
The invention belongs to fluorescence spectrum detection fields, and in particular to a kind of X-ray fluorescence spectra quickly measures in granite
Primary and secondary, the method for micro constitutent.
Background technology
Each element assay and analysis are of great significance to the research of its mineralization in granite, are the weights of geological prospecting
Want basic work.Granite is by silica, alundum (Al2O3), potassium oxide, sodium oxide molybdena, iron oxide, titanium dioxide, oxidation
The primary and secondarys such as calcium, magnesia, phosphorus pentoxide, manganese oxide and micro constitutent composition.It is traditional according to the difference of its component content
Detection method mainly uses volumetric method, gravimetric method, spectrophotometry, atomic absorption spectrophotometry and inductively coupled plasma
Emission spectrometry etc., there are detection cycles, and long, cumbersome, reagent consumes greatly, with test request quick and precisely, environmentally protective
There are larger gap, it has been difficult to meet analysis detection demand.Therefore, square to adapt to mineral prospecting, exploitation, trade and smelting etc.
The detection demand in face, fast and accurately inspection technology system of establishing are particularly important.
To solve the above problem existing for granite traditional detection method, the present invention utilizes X-ray fluorescence spectra technology
（XRF）Establish a kind of pre-treatment is simple, detection speed is fast, it is at low cost, can analyze simultaneously primary and secondary and trace element detection side
Method can complete silica, alundum (Al2O3), potassium oxide, sodium oxide molybdena, iron oxide, calcium oxide, oxygen in granite in 30min
Change the measurement of magnesium, manganese oxide, phosphorus pentoxide, titanium dioxide, barium, strontium, sulphur, rubidium, zirconium totally 15 kinds of components.
Invention content
In view of the above-mentioned deficiencies in the prior art, it is an object of the present invention to which providing a kind of X-ray fluorescence spectra quickly measures flower
Primary and secondary, the method for micro constitutent in the rock of hilllock.This method pre-treatment is simple, detection speed is fast, it is at low cost, primary and secondary can be analyzed simultaneously
And trace element, significant increase detection efficiency.
To achieve the purpose of the present invention, it adopts the following technical scheme that：
A kind of X-ray fluorescence spectra quickly measures primary and secondary in granite, the method for micro constitutent, includes the following steps：
1）Sample preparation：After mixing by sample and mixed flux, lithium nitrate solution is added, after pre-oxidation；It is with ammonium iodide
Releasing agent, heating melting；Fusant is poured into warmed-up mold, take out fuse piece after cooling and shaping, performed and mark and put
Enter to be measured in drier；
2）The selection of series of calibration sample：Choose granite, granodiorite, quartzy sandstone, shale, basalt, water system deposition
Object, soil, potassium feldspar, albite, siliceous sandstone, kaolinic certified reference material, and using these certified reference materials as base
Plinth mixes two of which or more than two standard substances in any proportion, increases the quantity of calibration sample, and makes each element
Content is distributed in certain gradient, to obtain being suitble to the series of calibration sample of granite inspection；By series of calibration sample according to
Step 1）Method sample preparation；
3）Using S8 Tiger types wavelength dispersion X-ray fluorescence spectrometers as detecting instrument, with step 2）Series of calibration after sample preparation
Sample is detection object, is optimized to the determination condition of each element in granite, determines the test condition of each element, and used
Absorption enhancement effect between the Theoretical Alpha Coefficient Method element correction of variation；
4）According to step 3）Determining test condition measures all calibration prints after sample preparation, and draws calibration curve；
5）In step 3）Under determining test condition, to step 1）Treated waits for that test sample is detected, and obtains result.
Step 1）Described in mixed flux be by lithium tetraborate and lithium metaborate in mass ratio 12:22 mixing, through 500 DEG C
Manufactured flux after 4 h of calcination.
Step 1）The mass ratio of middle sample and mixed flux is 1:10.
Step 1）Described in lithium nitrate solution mass fraction be 22%, addition be 1 mL；The addition of ammonium iodide is
0.05g。
Step 1）The pre-oxidation is：700 DEG C of pre-oxidation 5min are warming up in high frequency fusion machine.
Step 1）Described in heating melting be：Temperature is risen into 1050 DEG C of 4 min of melting, then waves 6 min of melting.
Step 2）In, the constituent content of certified reference material directly uses certificate sign value, mixes the element of calibration sample
Content is directly calculated according to the actual ratio of each certified reference material.
Step 3）The instrument of middle S8 Tiger type wavelength dispersion X-ray fluorescence spectrometers is characterized as：Rhodium target, maximum power
4KW, maximum working voltage 60KV, maximum operating currenbt 150mA.
Step 2）In, the selection of calibration sample is specially：
Calibration sample includes that granite, granodiorite, quartzy sandstone, shale, basalt, sediments, soil, potassium are long
Certified reference materials such as stone, albite, siliceous sandstone, kaolin, and based on above-mentioned certified reference material, by will wherein
Two or more standard substances mixes in any proportion can further increase the quantity of calibration sample and make each element content
It is distributed in certain gradient, to obtain the calibration sample series for being suitble to granite inspection.
Calibration sample of the present invention totally 29, see the table below 1.Wherein mixing -1 uses 1：1 GBW07312 and
GBW03116 is mixed, i.e., weighs 0.3g GBW07312 and 0.3g GBW03116 respectively, aforementioned molten sample system is used after mixing
Preparation Method is prepared.Mixing -2 and mixing -3 are made using similar approach.
Table 1
The present invention has the following advantages compared with the prior art：
The present invention detection method have pre-treatment is simple, detection speed is fast, it is at low cost, primary and secondary and micro member can be analyzed simultaneously
The advantage of element, can complete silica, alundum (Al2O3), potassium oxide, sodium oxide molybdena, iron oxide, oxidation in granite in 30min
The measurement of calcium, magnesia, manganese oxide, phosphorus pentoxide, titanium dioxide, barium, strontium, sulphur, rubidium, zirconium totally 15 kinds of components.
Specific implementation mode
Further to disclose rather than the present invention is limited, the present invention is described in further detail below in conjunction with example.
A kind of X-ray fluorescence spectra quickly measures primary and secondary in granite, the method for micro constitutent, is as follows：
1.1 key instruments and measuring condition
S8 Tiger types wavelength dispersion X-ray fluorescence spectrometer (German Bruker AXS companies)：Rhodium target, maximum power 4KW, most
Big operating voltage 60KV, maximum operating currenbt 150mA；Analymate V4D type high frequency fusion machines（The quiet remote century science and technology in Beijing has
Limit responsible company）.
Select the calibration print with certain representative content（29 calibration samples being shown in Table in 1）To the measurement of each element
Condition optimizes, and determines that the test condition of each element is shown in Table 2.
Table 2
1.2 reagent
Li2B4O7-LiBO2Mixed flux（Top pure grade, m:m=12:22）Be placed in drier through 500 DEG C of 4 h of calcination store it is standby
With；LiNO3、NH4I is that analysis is pure；Sample is dried at 105 DEG C to constant weight.
1.3 calibration sample
According to the type and element content range of mineral to be measured, this research selects granite, granodiorite, quartzy sandstone, page
The standard substances such as rock, basalt, sediments, soil, potassium feldspar, albite, siliceous sandstone are as calibration sample.Its middle part
Divide the concentration gradients of element to change greatly, cannot be satisfied X-ray fluorescence spectra calibration curve requirement, to make each element content be in one
Fixed gradient distribution, the present invention also above-mentioned standard specimen of selected section and by a certain percentage intersection, which are prepared, to be obtained being suitble to granite inspection
Calibration sample series, amounts to 29 calibration samples, and content range is shown in Table 1.
1.4 sample preparation
Accurate to weigh 0.6000g samples, 6.000g mixed fluxs are placed in platinum-gold crucible and after mixing, addition 1mL
22wt% lithium nitrate solutions are warming up to 700 DEG C of pre-oxidation 5min in high frequency fusion machine；Then 0.05g ammonium iodides are added to demould
After agent, temperature is risen into 1050 DEG C of 4 min of melting, then wave 6 min of melting.It takes out and fusant is poured into warmed-up mold
In, fuse piece is taken out after cooling and shaping, is performed and is marked and be put into be measured in drier.
2 results and discussion
2.1 sample preparation methods
Pressed disc method and fuse piece method are that X-ray fluorescence spectra analyzes most common two kinds of method for making sample.Due to different types of colored hilllock
Its phase structure of rock is not quite similar, and is difficult to ensure the consistency of sample and calibration sample granularity, therefore pressed disc method sample preparation is by mine
The influence of object effect and grain effect is more serious.Based on chemical breakdown reaction of the MTG YBCO bulk under high temperature, break original object
Phase structure, by the borate product that each object inversion of phases in sample is glassy state, therefore by adding sample at high temperature with flux
Heat fusing, mixing can effectively eliminate mineral effect and grain effect.In addition, calibration can be better achieved by MTG YBCO bulk
The artificial preparation of sample, the present invention are prepared by the intersection between various criterion substance, effectively overcome existing standard sample number
The deficiency of amount.Therefore, the present invention carries out sample preparation using fuse piece method.
The selection of 2.2 flux and dilution ratio
According to the acidity index of Claisse（O/M）Concept, it is aobvious with silica and alundum (Al2O3) granite as main component
Acidity, therefore use basic solvent is beneficial to the abundant melting of sample, the present invention selects mass ratio for 12:22 lithium tetraborate
With lithium metaborate mixed flux.To the same sample, 3 are pressed respectively:1,5:1,8:1,10:1,20:1 flux and test specimen proportions into
Row melting prepares sheet glass.Experiment is found, when flux thinner ratio is less than 5:When 1, sample particle cannot be completely dissolved, and in cooling
Occur white cloud layer in the process, sheet glass is caused to crack；When flux thinner ratio is more than 8:When 1, sample can fully melt, and can be obtained
Uniformly, the smooth high quality sheet glass in surface.On the other hand, when thinner ratio increases, the fluorescence intensity of element to be measured will reduce.It is comprehensive
It closes and considers, select thinner ratio for 10:1.
The influence of 2.3 molten sample temperature
Melting prepares sheet glass at different temperatures, and melts sample by testing the fluorescence intensity change of each element in sheet glass and investigating
Influence of the temperature to element determination.Experiment is found, with the raising of melting temperature, sample fusing speed is accelerated, the stream of fusant
Dynamic property enhancing, the fluorescence intensity change of most elements is smaller, but the strength reduction of K, Zr, S element is more apparent（Table 3）, this is
Due to the raising with temperature, the evaporation rate of flux and sample is accelerated, and K, Zr, S belong to Volatile Elements, so as to cause most
The content of above three element is substantially reduced in whole print.Consider shadow of the molten sample temperature to molten sample time and Volatile Elements
It rings, sample temperature is melted in 1050 DEG C of conducts of final choice of the present invention.
Influence of 3 melting temperature of table to element determination intensity
2.4 basal image
The present invention eliminates the granularity effect and mineral effect of sample, but the absorption between element and enhancement effect using MTG YBCO bulk
It still has, the K electron such as the energy of Fe k α lines more than Cr combines energy, and Fe k α lines will inspire Cr k α, therefore need to carry out
Basal image.All calibration prints are measured according to determining measuring condition, by formula（1）It is returned, it is bent to find out calibration
Slope, intercept and the overlap of spectral lines correction coefficient of line carry out matrix effect school using the Theoretical Alpha Coefficient Method changed in instrument software
Just.From table 4, it can be seen that being had clear improvement to the standard deviation of the elements such as aluminium, iron, silicon, calcium using side reaction coefficient correction.
（1）
In formula: Ci、CjIt respectively measures element and influences the concentration of element;S, b is respectively the slope and intercept of calibration curve;
IiTo measure the x-ray fluorescence intensity of element; βikFor overlap of spectral lines correction coefficient; IkFor the intensity of Overlapped spectral line; αij For
Influence Theoretical Alpha of the element to measurement element.
The comparison of calibration curve standard deviation before and after 4 basal image of table
The detection limit of 2.5 methods
The detection limit of each element is related with the response condition of its analysis spectral line and background, and the inspection of each element is calculated according to formula 2
Rising limit, wherein background intensity are actual measured results, and background time of measuring is consistent with peak position time of measuring, the results are shown in Table 5.
（2）
In formula：M is the counting rate (cps) of unit content, i.e. content often changes the variation of x-ray fluorescence intensity caused by 1%；Ib
And tbThe respectively fluorescence intensity and time of measuring of background.
5 each component detection limit of table
2.6 precision
Melting 11 times is repeated to the same granite sample, and is measured the precision with preparation method respectively to fuse piece.From
6 result of table can be seen that the relative standard deviation of each component measurement result between 0.42% ~ 9.88%, method repeatability compared with
It is good.
6 Precision Experiment result of table
2.7 accuracy
Choose granite standard substance（GBW07111、GBW07103）It is verified, by comparing this method measurement result and mark
The sign value of quasi- substance investigates the accuracy of method.From 7 result of table as it can be seen that the measurement result of this method and sign value basic one
It causes, can meet test request.
7 accuracy experimental result of tablew/%
Embodiment 1
A kind of X-ray fluorescence spectra quickly measures primary and secondary in granite, the method for micro constitutent, includes the following steps：
1）Sample preparation：After mixing by sample and mixed flux, lithium nitrate solution is added, after pre-oxidation；It is with ammonium iodide
Releasing agent, heating melting；Fusant is poured into warmed-up mold, take out fuse piece after cooling and shaping, performed and mark and put
Enter to be measured in drier；
2）The selection of series of calibration sample：Choose granite, granodiorite, quartzy sandstone, shale, basalt, water system deposition
Object, soil, potassium feldspar, albite, siliceous sandstone, kaolinic certified reference material, and using these certified reference materials as base
Plinth mixes two of which or more than two standard substances in any proportion, increases the quantity of calibration sample, and makes each element
Content is distributed in certain gradient, to obtain being suitble to the series of calibration sample of granite inspection；By series of calibration sample according to
Step 1）Method sample preparation；
3）Using S8 Tiger types wavelength dispersion X-ray fluorescence spectrometers as detecting instrument, with step 2）Series of calibration after sample preparation
Sample is detection object, is optimized to the determination condition of each element in granite, determines the test condition of each element, and used
Absorption enhancement effect between the Theoretical Alpha Coefficient Method element correction of variation；
4）According to step 3）Determining test condition measures all calibration prints after sample preparation, and draws calibration curve；
5）In step 3）Under determining test condition, to step 1）Treated waits for that test sample is detected, and obtains result.
The foregoing is merely presently preferred embodiments of the present invention, all equivalent changes done according to scope of the present invention patent with
Modification should all belong to the covering scope of the present invention.
Claims (8)
1. a kind of X-ray fluorescence spectra quickly measures primary and secondary in granite, the method for micro constitutent, it is characterised in that：Including with
Lower step：
1）Sample preparation：After mixing by sample and mixed flux, lithium nitrate solution is added, after pre-oxidation；It is with ammonium iodide
Releasing agent, heating melting；Fusant is poured into warmed-up mold, take out fuse piece after cooling and shaping, performed and mark and put
Enter to be measured in drier；
2）The selection of series of calibration sample：Choose granite, granodiorite, quartzy sandstone, shale, basalt, water system deposition
Object, soil, potassium feldspar, albite, siliceous sandstone, kaolinic certified reference material, and using these certified reference materials as base
Plinth mixes two of which or more than two standard substances in any proportion, increases the quantity of calibration sample, and makes each element
Content is distributed in certain gradient, to obtain being suitble to the series of calibration sample of granite inspection；By series of calibration sample according to
Step 1）Method sample preparation；
3）Using S8 Tiger types wavelength dispersion X-ray fluorescence spectrometers as detecting instrument, with step 2）Series of calibration after sample preparation
Sample is detection object, is optimized to the determination condition of each element in granite, determines the test condition of each element, and used
Absorption enhancement effect between the Theoretical Alpha Coefficient Method element correction of variation；
4）According to step 3）Determining test condition measures all calibration prints after sample preparation, and draws calibration curve；
5）In step 3）Under determining test condition, to step 1）Treated waits for that test sample is detected, and obtains result.
2. X-ray fluorescence spectra according to claim 1 quickly measures primary and secondary in granite, the method for micro constitutent,
It is characterized in that：Step 1）Described in mixed flux be by lithium tetraborate and lithium metaborate in mass ratio 12:22 mixing, through 500
Manufactured flux after DEG C 4 h of calcination.
3. X-ray fluorescence spectra according to claim 1 quickly measures primary and secondary in granite, the method for micro constitutent,
It is characterized in that：Step 1）The mass ratio of middle sample and mixed flux is 1:10.
4. X-ray fluorescence spectra according to claim 1 quickly measures primary and secondary in granite, the method for micro constitutent,
It is characterized in that：Step 1）Described in lithium nitrate solution mass fraction be 22%, addition be 1 mL；The addition of ammonium iodide
For 0.05g.
5. X-ray fluorescence spectra according to claim 1 quickly measures primary and secondary in granite, the method for micro constitutent,
It is characterized in that：Step 1）The pre-oxidation is：700 DEG C of pre-oxidation 5min are warming up in high frequency fusion machine.
6. X-ray fluorescence spectra according to claim 1 quickly measures primary and secondary in granite, the method for micro constitutent,
It is characterized in that：Step 1）Described in heating melting be：Temperature is risen into 1050 DEG C of 4 min of melting, then waves 6 min of melting.
7. X-ray fluorescence spectra according to claim 1 quickly measures primary and secondary in granite, the method for micro constitutent,
It is characterized in that：Step 2）In, the constituent content of certified reference material directly uses certificate sign value, mixes the element of calibration sample
Content is directly calculated according to the actual ratio of each certified reference material.
8. X-ray fluorescence spectra according to claim 1 quickly measures primary and secondary in granite, the method for micro constitutent,
It is characterized in that：Step 3）The instrument of middle S8 Tiger type wavelength dispersion X-ray fluorescence spectrometers is characterized as：Rhodium target, maximum power
4KW, maximum working voltage 60KV, maximum operating currenbt 150mA.
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