CN103048346B - Check sample and fluorescent x-ray analyzer and fluorescent x-ray analysis method - Google Patents
Check sample and fluorescent x-ray analyzer and fluorescent x-ray analysis method Download PDFInfo
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- CN103048346B CN103048346B CN201210392351.2A CN201210392351A CN103048346B CN 103048346 B CN103048346 B CN 103048346B CN 201210392351 A CN201210392351 A CN 201210392351A CN 103048346 B CN103048346 B CN 103048346B
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Abstract
The problem of the present invention is to provide a kind of check sample and fluorescent x-ray analyzer and fluorescent x-ray analysis method, it is provided that the check sample etc. of the x-ray fluorescence analysis of liquor sample, its can life-time service, and correct offset correction can be carried out.The check sample of the present invention is the check sample of solid, this check sample is in the x-ray fluorescence analysis of liquor sample, the companion of the mensuration X-ray intensity of correction analysis object metallic element is over time, wherein, the metal level comprising analysis object metallic element is formed with the light element layer that thickness is more than 1mm with overlapping, in this light element layer, at least one light element in hydrogen, boron, carbon, nitrogen, oxygen and fluorine has maximum molfraction, in above-mentioned metal level, the opposite side surfaces of the side relative with light element layer is analysis face.
Description
Technical field
The check sample that the present invention relates to x-ray fluorescence analysis and the fluorescence X with it
Ray analysis device and the fluorescent x-ray analysis method using this device.
Background technology
In the past, measuring fluorescent X-ray sample being irradiated primary X-ray and produce
Intensity fluorescent x-ray analyzer in, carry out so-called offset correction termly,
Wherein, same sample is measured the adjoint time that X-ray intensity produces because of a variety of causes
And the situation of change (drift) is corrected.If carried out this offset correction, then for
Such as forming whole standard specimens of standard curve, measure X for each element correction
Transmitted intensity, then need many time and time whenever timing.Then, it is being used for
Check sample is previously set during offset correction, measures the X-ray intensity constituting benchmark,
When carrying out offset correction, only measure the check sample set, according to mensuration X now
Transmitted intensity and the mensuration X-ray intensity of composition said reference, obtain offset correction coefficient,
This offset correction coefficient is used for analyzing the mensuration X-ray intensity of object sample, carries out school
Just.
Thus, in x-ray fluorescence analysis, use various check sample.Such as, use
In the occasion that the sample forming metal film on a silicon substrate is analyzed, have and serve as a contrast at silicon
The check sample (patent documentation 1) of the metal film of Au, Pt, Co etc. is formed at the end.
It addition, have be loaded on thin film little power sample, be held in filter paper, poly-
The x-ray fluorescence analysis of micro solution sample on compound film, film sample etc. is used
Check sample.This check sample by polyimide film, be mixed with on this polyimide film
Analysis object elements polyimide film formed (patent documentation 2).As this check sample
Variation, people know have on metal forming, substrate formed be mixed with analysis object meta
The check sample of the polyimide film of element.
Additionally, in the mensuration of the concentration of the sulfur comprised in crude oil or petroleum product,
The concentration of sulfur is the occasion that known heavy oil is sealed in the standard specimen within container, by
Companion is produced over time, nothing in the concentration change caused because of liquid leakage or precipitation etc.
Method life-time service, therefore there is the simulation sample using solid as the method for standard specimen.
This simulation sample is formed by discoideus molybdenum main body and absorber, and this absorber is arranged at this
The primary X-ray of molybdenum main body irradiates on side, by polyethylene terephthalate, polyamides Asia
Amine constitutes (patent documentation 3).
Prior art literature
Patent documentation
Patent documentation 1: 2005 No. 156213 publications of Japanese Unexamined Patent Publication
Patent documentation 2: 2010 No. 204087 publications of Japanese Unexamined Patent Publication
Patent documentation 3: 7 No. 5127 publications of Japanese Unexamined Patent Publication
Summary of the invention
The problem that invention is to be solved
Check sample described in patent documentation 1 is for forming metal film on a silicon substrate
The analysis of sample, i.e. solid sample.It is used at the check sample described in patent documentation 2
The analysis of the solid sample of little power sample or film sample etc., and be used for being held in
The analysis of the micro solution sample on filter paper or polymeric film.Owing to this check sample is used for
The analysis of the micro sample of little power sample or micro solution sample etc., therefore tried by correction
The background that sample produces is constituted according to the least mode.
It is used only in crude oil or petroleum product at the simulation sample described in patent documentation 3
The mensuration of the concentration of the sulfur comprised, is not used in other element, other liquor sample.
This simulation sample is shone by discoideus molybdenum main body and the primary X-ray being arranged at this molybdenum main body
Penetrate side absorber formed, but, this absorber for decay by molybdenum main body produce glimmering
Light X-ray intensity, the background for being produced by sample does not has any consideration.Due to
In liquor sample, as in the water of solvent, organic solvent etc., comprise as main constituent
Hydrogen, carbon, the light element of oxygen etc., therefore produce scattered x-ray in large quantities, measured
X-ray in not only there is fluorescent X-ray, and comprise scattered x-ray in large quantities,
Big background is produced because of this scattered x-ray.But, in the past, it is contemplated that by liquid
The check sample of the solid of the background that sample produces the most does not occurs.
Like this, also there is no following check sample in the past, i.e. can correctly survey
Determine the correction of the companion (drift) over time of X-ray intensity, and can life-time service,
This mensuration X-ray intensity comprises the background produced by liquor sample.
The present invention be directed to the problem in above-mentioned past and propose, it is an object of the invention to
There is provided: can life-time service and liquor sample glimmering of correct offset correction can be carried out
The check sample of light X-ray analysis, there is its fluorescent x-ray analyzer, adopt
With the fluorescent x-ray analysis method of this device.
For solving the technical scheme of problem
To achieve these goals, the check sample of the present invention is the check sample of solid,
This check sample is in the x-ray fluorescence analysis of liquor sample, to analyzing object gold
The companion of the mensuration X-ray intensity belonging to element is corrected over time, wherein, and bag
The metal level including analysis object metallic element overlaps with the light element layer that thickness is more than 1mm
Ground is formed, in this light element layer, and at least one in hydrogen, boron, carbon, nitrogen, oxygen and fluorine
Light element has maximum molfraction, in above-mentioned metal level, with above-mentioned light element layer phase
To the opposite side surfaces of the side be analysis face.
Owing to the check sample of the present invention is solid, wherein, including analyzing object metal unit
The metal level of element is formed with the light element layer that thickness is more than 1mm with overlapping, this light element
In Ceng, at least one light element in hydrogen, boron, carbon, nitrogen, oxygen and fluorine has maximum and rubs
Your number, thus do not produce evaporation, precipitate, go bad etc. the companion caused over time,
Can life-time service.It addition, above-mentioned metal level is the analysis face irradiating primary X-ray,
The primary X-ray realizing transmission in this metal level injects light element layer, thus, light element
The light element of layer produces scattered x-ray (this with the fluent material same degree analyzing object
The end), so, correct offset correction can be carried out.
In the fluorescent x-ray analysis method of the present invention, use the check sample of the present invention
Carry out the x-ray fluorescence analysis of liquor sample.
According to the fluorescent x-ray analysis method of the present invention, owing to using the correction of the present invention
Sample, therefore the effect identical with the check sample of the present invention can be realized.
In the fluorescent x-ray analysis method of the present invention, the most also use background correction examination
Sample, this background correction sample is only formed by the above-mentioned light element layer of above-mentioned check sample,
For the companion of the background X-ray intensity of liquor sample is corrected over time.
In this occasion, owing to using the correction examination formed by above-mentioned metal level and above-mentioned light element layer
Sample and the 2 kinds of check samples of background correction sample only formed by above-mentioned light element layer,
Therefore more correct offset correction can be carried out.
The fluorescent x-ray analyzer of the present invention includes: the check sample of the present invention；Partially
Difference aligning gear, it is according to mensuration X analyzing object metallic element of above-mentioned check sample
Transmitted intensity, the companion that liquor sample measures X-ray intensity is carried out over time
Correction.
According to the fluorescent x-ray analyzer of the present invention, including: the correction examination of the present invention
Sample；Offset correction mechanism, it analyzes object metallic element according to above-mentioned check sample
Measure X-ray intensity, the adjoint time of the mensuration X-ray intensity of correction liquor sample
Change, therefore the effect identical with the check sample of the present invention can be realized.
Preferably, the fluorescent x-ray analyzer of the present invention also includes background correction sample,
This background correction sample is only formed by above-mentioned light element layer, for correcting liquor sample
Over time, above-mentioned offset correction mechanism is according to above-mentioned for the companion of background X-ray intensity
The mensuration X-ray intensity analyzing object metallic element of check sample and above-mentioned background correction
The mensuration X-ray intensity of sample, when measuring X-ray intensity adjoint to liquor sample
Between change be corrected.In this occasion, due to use by above-mentioned metal level and above-mentioned gently
Check sample that element layer is formed and the background correction that only formed by above-mentioned light element layer
2 kinds of check samples of sample, therefore more correct offset correction can be carried out.
Accompanying drawing explanation
Fig. 1 is the outward appearance of the fluorescent x-ray analyzer of the 1st embodiment of the present invention
Structure chart；
The side view of the check sample that Fig. 2 is had by this fluorescent x-ray analyzer；
Fig. 3 is the stream of the thickness of metal level and the light element layer representing and obtaining this check sample
The figure of journey；
Fig. 4 is the side sectional view of the version of this check sample；
Fig. 5 is the side view of another version of this check sample；
The fluorescent x-ray analyzer of the 2nd embodiment that Fig. 6 is the present invention is had
The axonometric chart of background correction sample.
Detailed description of the invention
Below the fluorescent x-ray analyzer of the 1st embodiment of the present invention is said
Bright.As shown in Figure 1, this fluorescent x-ray analyzer includes: sample bench 3,
Loading liquid sample S or check sample 20 on this sample bench 3；X-ray source 1, this X
Radiographic source 1 is for irradiate primary X-ray 2 such as to liquor sample S or check sample 20
Rhodium X-ray tube；Beam splitter 5, this beam splitter 5 is to by liquor sample S or correction
The secondary x rays 4 that sample 20 produces carries out light splitting；Detector 7, this detector 7 is examined
Survey the secondary x rays 6 by beam splitter 5 light splitting；Offset correction mechanism 9.Light splitting unit
Part 5 and detector 7 constitute testing agency 8.Offset correction mechanism 9 is according to check sample
The mensuration X-ray intensity analyzing object metallic element of 20, the mensuration to liquor sample S
The companion of X-ray intensity is corrected over time.Secondary x rays 4 and 6 includes
This fluorescent X-ray and scattered x-ray.
It is further preferred to, check sample 20 prior loading (is not shown in figure in sample switch
Go out) assigned position or be built-in with device.
Action to the fluorescent x-ray analyzer of the 1st embodiment, i.e. constitutes this
The fluorescent x-ray analysis method of a bright embodiment illustrates.If making fluorescence
X-ray analysis equipment action, then measure check sample 20, offset correction mechanism initially
9 using analyze object metallic element the mensuration X-ray intensity of secondary x rays 6 as base
Quasi-intensity ISAnd store.Hereafter, liquor sample S is in turn measured, at correction analysis pair
As measuring check sample 20 during the mensuration X-ray intensity of metallic element, obtain analysis object
The intensity I of the secondary x rays 6 of metallic elementM.If obtaining intensity IM, then according to partially
The I that difference aligning gear 9 is obtainedMThe reference intensity I formerly storedS, by following formula (1)
Calculate offset correction factor alpha.
α=IS/IM(1)
Additionally, offset correction mechanism 9 is by offset correction factor alpha and the liquid examination measured
Mensuration X-ray intensity I analyzing object metallic element of sample SnIt is multiplied, carries out deviation school
Just.
In the above example, by offset correction factor alpha and mensuration X-ray intensity InIt is multiplied,
Carry out offset correction, however, it is possible to by offset correction factor alpha and expression of first degree standard curve
Gradient constant a be multiplied, standard curve is corrected, carries out offset correction.
Below to the solid that the fluorescent x-ray analyzer of the 1st embodiment is had
Check sample 20 is specifically described.As shown in Figure 2, check sample 20 is pressed
Being formed according to following manner, which is: will include the metal level analyzing object metallic element
21 overlap with light element layer 22, this light element layer 22 make hydrogen, boron, carbon, nitrogen, oxygen and
At least one light element in fluorine is maximum molfraction, and thickness is more than 1mm, metal
Layer 21 is adhered on light element layer 22 by bonding agent.In above-mentioned metal level 21,
The opposite side surfaces of the side relative with light element layer 22 is analysis face 23.
Preferably, the correction being had at the fluorescent x-ray analyzer of the 1st embodiment
In sample 20, metal level 21 is formed according to the mode within following thickness 2 times, should
Thickness produces and is equivalent to: when the analysis object elements in liquor sample S is maximum level
The fluorescent X-ray intensity of the fluorescent X-ray intensity produced, light element layer 22 is according to product
Life is equal to the thickness of the background X-ray intensity of liquor sample S and is formed.
According to the flow process shown in Fig. 3, to as described above, it is suitable for liquor sample S's
The mode that solves of the thickness of metal level 21 and the thickness of light element layer 22 illustrates.
At the 1st stage S1, in order to obtain the thickness of metal level 21 and light element layer 22
Thickness, determines the fluorescent X-ray intensity (pure X-ray intensity) produced by metal level 21
Corresponding desired value with the background X-ray intensity produced by light element layer 22.Will be
Multiple standard specimens of the standard curve forming liquor sample S produce maximum fluorescence X
The fluorescent X-ray intensity (pure X-ray intensity) of the standard specimen of transmitted intensity is defined as gold
Belong to the desired value of layer 21.X-ray intensity using the intercept as established standard curve
Background X-ray intensity as the desired value of light element layer 22.
At the 2nd stage S2, use and determine as desired value in the 1st stage S1
The fluorescent X-ray intensity of metal level 21, by FP method (Fundamental parameter
Method) theoretical strength calculates, and calculating constitutes permitting of the desired value of this fluorescent X-ray intensity
The metal of X-ray intensity (such as, within desired value 100～200%) in the range of Xuing
The thickness of layer 21.
At the 3rd stage S3, it is formed at the metal level 21 of the thickness that the 2nd stage S2 calculates,
On the light element layer 22 of the arbitrary thickness that this metal level 21 is coincided with more than 1mm,
Form check sample 20.For established check sample 20, divided by fluorescent X-ray
Analysis apparatus measures fluorescent X-ray intensity and the background X of light element layer 22 of metal level 21
Transmitted intensity.It addition, overlap about by metal level 21 and light element layer 22 and form school
The mode of positive sample 20, will be described later.
At the 4th stage S4, it is judged that whether the fluorescent X-ray intensity of metal level 21 arrives
Intensity in the allowed band of the desired value determined in the 1st stage S1.If metal level
The fluorescent X-ray intensity of 21 arrives the intensity in the allowed band of desired value, then carry out the
5 stage S5.If judge the fluorescent X-ray intensity of metal level 21 at the 4th stage S4
It is less than in the 1st stage S1 the intensity in the allowed band of the desired value determined, then carries out
4A stage S4A.
At 4A stage S4A, arrive according to the fluorescent X-ray intensity of metal level 21
The mode of the intensity in the allowed band of the desired value determined in the 1st stage S1 changes metal
The thickness of layer 21, returns to the 3rd stage S3, at the 4th stage S4, is judging metal
The fluorescent X-ray intensity of layer 21 arrives the permission of the desired value determined in the 1st stage S1
In the range of intensity before, be repeated from 4A stage S4A to the 4th stage S4's
Flow process.
At the 5th stage S5, it is determined that whether the background X-ray intensity of light element layer 22 arrives
Reach the intensity in the allowed band of the desired value determined in the 1st stage S1.If it is determined that
The background X-ray intensity of light element layer 22 arrives the intensity in the allowed band of desired value,
Then carry out the 6th stage S6.If judge the background of light element layer 22 at the 5th stage S5
It is strong that X-ray intensity is less than in the allowed band of the desired value determined in the 1st stage S1
Degree, then carry out 5A stage S5A.
In 5A stage S5A, in order to make the background X-ray intensity of light element layer 22
Arrive the intensity in the allowed band of the desired value determined in the 1st stage S1, change light
The thickness of element layer 22, returns to the 3rd stage S3, is that the 5th stage S5 judges light
The fluorescent X-ray intensity of element layer 22 arrives the desired value determined in the 1st stage S1
Allowed band in intensity before, be repeated from 5A stage S5A to the 5th rank
The flow process of section S5.
At the 6th stage S6, determine metal level 21 and the thickness of light element layer 22.
As the version of check sample 20, to as in the liquor sample S of nickel plating bath
The check sample 20 of occasion that is analyzed of nickel illustrate.At this check sample 20
Occasion, as shown in Figure 4, such as, as the nickel foil 21 of thickness 10 μm
Metal level 21 is according to passing through ring-type solid with closely connected mode on the end face of light element layer 22
Locking member 50 and fix, this light element layer 22 is rectangular as such as thickness (highly) 10mm's
The acrylic resin 22 of body shape, the outer surface component analysis face 23 of this metal level 21.Long
The acrylic resin 22 of cube shape is constituted by as the carbon of light element, hydrogen, oxygen, and hydrogen has
Maximum molfraction.The size of rectangular-shaped acrylic resin 22 is the most horizontal
100mm, longitudinal 100mm, thickness (highly) 10mm.Liquid as this nickel plating bath tries
The metal level 21 of the check sample 20 of sample S and the thickness of light element layer 22 are by figure
Flow process shown in 3 and the value obtained.
Annular fixed pieces 50 is made up of annular plate 51 and fixing screw 52, fixing screw 52
With the screw thread on the top (part of stationary ring fixture 50) being formed at light element layer 22
Hole 25 screws togather, and metal level 21 is according to being held on the end face of light element layer 22 and ring-type fixing
Mode between the bottom surface (and the face faced by light element layer 22) of part 50 is fixed.It addition, it is golden
The fixing means belonging to layer 21 is not limited to annular fixed pieces 50 as described above, it is possible to by it
Its fixture and fix.
In the check sample 20 of Fig. 2, metal level 21 uses 1 thickness 100 μm
Nickel foil, however, it is possible to the most as shown in Figure 5, glues according to by bonding agent
The mode shape connecing the corresponding nickel foil in multiple nickel foil 21a, 21b, 21c and they overlapped
Become, also by the annular fixed pieces 50 shown in Fig. 4, multiple metal formings are fixed.It addition,
At the occasion of the check sample 20 for multiple analysis object metallic elements, metal level 21
Both can be formed according to by the mode that the different metal formings analyzing object metallic element overlaps,
Also can be formed by 1 metal forming with multiple analysis object metallic element.Additionally,
Metal level 21 also can not be metal forming, also can be according to passing through evaporation on light element layer 22
The thin film of the mode Overlap Analysis object metallic element of (PVD, CVD etc.), plating etc.
Mode is formed.Preferably, metal level 21 according to the flow process shown in Fig. 3, according to at liquid
The corresponding thickness of concentration analyzing object metallic element that comprises in sample S and formed,
As the concrete numerical value of thickness, such as, the thickest if high concentration, thickness is best
In the range of 10～300 μm, the most relatively thin if low concentration, thickness preferably 1～
In the range of 10 μm, if extremely low concentration the most preferably more than 0 less than the model of 10 μm
Enclose.
In the present embodiment, check sample 20 glues according on light element layer 22
Connect, the mode of the process of closely connected, evaporated metal layer 21 etc. is formed, but, also can be according to
There is between light element layer 22 and metal level 21 mode that the state in gap carries out overlapping
Formed.
Light element layer 22 uses acrylic resin, but, can be hydrogen, boron, carbon, nitrogen,
At least one light element in oxygen and fluorine have the thickness of molfraction of maximum be 1mm with
On material, can be also macromolecular organic compound (polypropylene, polyethylene, polyimides,
Fluororesin etc.), graphite, boron nitride, metal boron, quartz, glass etc..Field at graphite
Closing, carbon has the molfraction of maximum, is respectively provided with at the occasion of boron nitride, nitrogen and boron
Big molfraction.The light element layer of the check sample 20 shown in Fig. 2, Fig. 4, Fig. 5
22 can be according to the flow process shown in Fig. 3, according to the thickness corresponding with the kind of liquor sample S
Degree (highly) H and formed, the concrete numerical value of thickness H the most such as, 1～100mm
In the range of.The shape of light element layer 22 is not limited to rectangular-shaped, it is possible to for cylinder, many
Prisms etc., are also receivable in and are injected with inside the liquor sample container of liquor sample S.
Can be formed and the same degree of liquor sample S-phase by forming light element layer 22 like this
Background, with the liquid examination of the ratio measuring fluorescent X-ray intensity and scattered x-ray intensity
Sample S reaches identical degree, therefore can carry out correct offset correction.Use Fig. 2, Fig. 4,
Fig. 5, the check sample 20 having been described above constitutes an enforcement of the present invention respectively
Mode.
If according to the fluorescent x-ray analyzer of the 1st embodiment, this fluorescence X penetrates
The check sample 20 that line analysis device is had is following solid, i.e. metal level 21 by
Analyzing object metallic element to be formed, light element layer 22 is by hydrogen, boron, carbon, nitrogen, oxygen and fluorine
In at least one light element there is the thing that thickness is more than 1mm of molfraction of maximum
Matter is formed, and the light element of light element layer 22 produces with liquor sample S-phase with degree
Scattered x-ray (background), therefore can use chronically, and can correctly correction analysis pair
Deviation as the mensuration X-ray intensity of metallic element.
Below, the fluorescent x-ray analyzer to the 2nd embodiment as the present invention
Illustrate.The fluorescent x-ray analyzer of the 2nd embodiment is implemented with as the 1st
The difference of the fluorescent x-ray analyzer of mode is that the former includes the 1st embodiment
Check sample 20 and the background correction sample 40 (Fig. 6) that fluorescent x-ray analyzer has
The check sample of 2 kinds, this background correction sample 40 only light by check sample 20
Element layer 22 is formed, for the adjoint time of the background X-ray intensity to liquor sample S
Change be corrected, offset correction mechanism 9 is according to the analysis object of check sample 20 gold
The mensuration X-ray intensity belonging to element and the background correction sample 40 being loaded on sample bench 3
Mensuration X-ray intensity, liquor sample S is measured the adjoint time of X-ray intensity
Change be corrected.But owing to other structure is identical, therefore difference is clicked on
Line description.It addition, the fluorescence X of 2 kinds of check samples 20,40 and the 1st embodiment penetrates
Line analysis device is identical, preferably, prior loading in the assigned position of sample switch, or
It is built-in with device.
Action to the fluorescent x-ray analyzer of the 2nd embodiment, i.e. constitutes this
The fluorescent x-ray analysis method of a bright embodiment illustrates.If making fluorescence
X-ray analysis equipment action, the most initially measures background correction sample 40, offset correction machine
Structure 9 using background X-ray intensity as background reference intensity IBAnd store.Then, in school
During positive background X-ray intensity, measure background correction sample 40, obtain background X-ray strong
Degree IC.If obtaining background X-ray intensity IC, then offset correction mechanism 9 is according to asking
The intensity I gone outCThe reference intensity I formerly storedB, following formula (2) calculate background school
Positive coefficient β.
β=IB/IC(2)
Then, if the action phase of the fluorescent x-ray analyzer with the 1st embodiment
With measuring check sample 20, then offset correction mechanism 9 calculates offset correction factor alpha.Partially
Difference aligning gear 9 is by calculated offset correction factor alpha, background correction factor beta school
Gradient constant a of positive expression of first degree standard curve and intercept constant b, calibration standard curve.?
The liquor sample S measured after the correction of standard curve is quantitative according to the standard curve of correction.
Owing to the fluorescent x-ray analyzer of the 2nd embodiment includes and the 1st embodiment party
The check sample that check sample 20 that the fluorescent x-ray analyzer of formula is had is identical
20 with the background correction sample 40 only formed by light element layer 22, pass through high concentration region
2 kinds of the check sample 20 in territory and the background correction sample 40 of low concentration region
Check sample, is corrected gradient constant a and intercept constant b, calibration standard curve,
Therefore can more correctly calibration standard curve.Particularly, object metallic element is being analyzed
Measure the companion of X-ray intensity over time with adjoint time of background X-ray intensity
The different occasion of change, its effect is the biggest.
Shown in Fig. 2, Fig. 4, Fig. 5 that fluorescent x-ray analyzer described above has
Check sample 20 may be used without using the scattered x-ray that produced by check sample 20 as
Internal standard line and the scattered rays that measures monitors method (scattered rays internal reference method).Scattered rays monitors method
For being used for the analysis of liquor sample, organic compound that scattered x-ray occurs in a large number etc.,
By using the mensuration X-ray intensity and background (scattered x-ray) analyzing object metallic element
The ratio of X-ray intensity, compensate the impact of the coexistence elements in sample S is glimmering
Light X-ray analysis method.
Such as, line can be scattered and monitor that the multielement simultaneous type fluorescent X-ray of method divides
Analysis apparatus includes: measures and is analyzed the two of object metallic element by what liquor sample S produced
The mensuration passage of secondary X-ray (have the beam splitter being suitable for analyzing object metallic element and
X-ray detector)；Measure the background passage of the scattered x-ray produced by liquor sample S
(having beam splitter and the X-ray detector being suitable for background determination), making will be passed through
Measure X-ray intensity I that passage measuresaWith the X-ray intensity measured by background passage
IdRatio Ia/IdAs the longitudinal axis, by first for the analysis object metal of the liquor sample S measured
The concentration of element, as the standard curve of transverse axis, analyzes liquor sample S.
Initially, by measuring passage and background passage, simultaneously check sample 20 is carried out
Measure, calculate by measuring the reference intensity I as X-ray intensity that passage measurespWith
The reference intensity I as X-ray intensity measured by background passagegRatio Ip/Ig.?
During correcting determination X-ray intensity, by measuring passage and background passage simultaneously to correction
Sample 20 is measured, and calculates by measuring X-ray intensity I that passage measuresrWith pass through
X-ray intensity I that background passage measuresqRatio Ir/Iq.Use and calculated compare Ip/IgWith
Calculated compare Ir/IqRatio (Ip/Ig)/(Ir/Iq) calibration standard curve, carry out offset correction.
Check sample 20 can produce and analyze the liquor sample S-phase basis with degree of object
The end, due to ratio and the liquid analyzing object of fluorescent X-ray intensity and scattered x-ray intensity
The degree of body sample S is identical, therefore even for scattering supervision method, still can carry out correct
Offset correction.
The 1st, in the fluorescent x-ray analyzer of the 2nd embodiment, correction is tried
Sample 20 is for the correction of standard curve, but can also be used for evaluating x-ray fluorescence analysis dress
The sensitivity stability test of the sensitivity degree of stability put.Preferably, for fluorescent X-ray
The stability test sample of the sensitivity stability test of analytical equipment produces and liquor sample
S-phase, with the fluorescent X-ray of the intensity of degree, has with liquor sample S-phase with degree
Fluorescent X-ray and the ratio of scattered x-ray intensity, preferably, the such as thickness of metal level 21
Degree is 5 μm, and the thickness of light element layer 22 is 5mm.
1st, the fluorescent x-ray analyzer of the 2nd embodiment is as wavelength-dispersion type
Fluorescent x-ray analyzer and be illustrated, but, assembly of the invention be alternatively
Energy dispersion type fluorescent x-ray analyzer.
Label declaration
Label 1 represents x-ray source；
Label 2 represents primary X-ray；
Label 3 represents sample bench；
Label 4,6 represents secondary x rays；
Label 5 represents beam splitter；
Label 7 represents detector；
Label 8 represents testing agency；
Label 9 represents offset correction mechanism；
Label 20 represents check sample；
Label 21 represents metal level；
Label 22 represents light element layer；
Label 23 represents analysis face；
Label 40 represents background correction sample；
Symbol S represents liquor sample.
Claims (5)
1. a check sample, it is solid check sample, and this check sample is at liquid
In the x-ray fluorescence analysis of sample, metal level therein is formed with overlapping with light element layer,
At least one light element tool in this light element layer, in hydrogen, boron, carbon, nitrogen, oxygen and fluorine
There is maximum molfraction,
It is characterized in that, this check sample mensuration X-ray to analyzing object metallic element
The companion of intensity is corrected over time, and metal level is first for comprising analysis object metal
The metal level of element, light element layer thickness is more than 1mm, in above-mentioned metal level, with upper
The opposite side surfaces stating the relative side of light element layer is analysis face.
2. a fluorescent x-ray analysis method, it uses the correction described in claim 1
Sample carries out the analysis of liquor sample.
Fluorescent x-ray analysis method the most according to claim 2, it also uses this
End check sample, this background correction sample is only formed by above-mentioned light element layer, for right
The companion of the background X-ray intensity of liquor sample is corrected over time.
4. a fluorescent x-ray analyzer, this fluorescent x-ray analyzer includes:
Check sample described in claim 1；
Offset correction mechanism, it analyzes object metallic element according to above-mentioned check sample
Measure X-ray intensity, liquor sample is measured the change of the adjoint time of X-ray intensity
Change is corrected.
Fluorescent x-ray analyzer the most according to claim 4, also includes background
Check sample, this background correction sample is only formed by above-mentioned light element layer, for liquid
The companion of the background X-ray intensity of body sample is corrected over time,
Above-mentioned offset correction mechanism analyzes object metallic element according to above-mentioned check sample
Measure X-ray intensity and the mensuration X-ray intensity of above-mentioned background correction sample, to liquid
The companion of the mensuration X-ray intensity of sample is corrected over time.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2011-227624 | 2011-10-17 | ||
| JP2011227624A JP5938708B2 (en) | 2011-10-17 | 2011-10-17 | Calibration sample for fluorescent X-ray analysis, fluorescent X-ray analysis apparatus including the same, and fluorescent X-ray analysis method using the same |
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| CN103048346B true CN103048346B (en) | 2016-08-31 |
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| CN107290378A (en) * | 2017-07-05 | 2017-10-24 | 深圳市华唯计量技术开发有限公司 | Material adulterated method and its system are quickly judged based on X-fluorescence |
| CN116106347B (en) * | 2022-11-07 | 2023-06-20 | 成都物熙科技有限公司 | Second-order X-ray fluorometer and measuring method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2002090319A (en) * | 2000-09-20 | 2002-03-27 | Rigaku Industrial Co | Fluorescent x-ray analysis device |
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| JPS5917845U (en) * | 1982-07-27 | 1984-02-03 | 東京芝浦電気株式会社 | Standard sample for fluorescent X-rays |
| JPS61178651A (en) * | 1985-02-05 | 1986-08-11 | Daido Steel Co Ltd | Method for solidifying powdery specimen for fluorescent x-ray analysis |
| JPS62130345A (en) * | 1985-12-03 | 1987-06-12 | Seiko Instr & Electronics Ltd | Method for calibrating fluorescent x-ray liquid analyzer |
| JPH01257210A (en) * | 1988-04-06 | 1989-10-13 | Seiko Instr Inc | Fluorescent x-ray film thickness meter |
| JPH0257951A (en) * | 1988-08-23 | 1990-02-27 | Nippon Atom Ind Group Co Ltd | Standard specimen for fluorescent x rays and manufacture thereof |
| JPH02187689A (en) * | 1989-01-14 | 1990-07-23 | Toto Ltd | Method of calibrating energy dispersion type x-ray detector for light element |
| JPH07119716B2 (en) * | 1990-04-19 | 1995-12-20 | 株式会社島津製作所 | Surface analyzer |
| JPH075127A (en) * | 1993-06-14 | 1995-01-10 | Horiba Ltd | X-ray fluorescence analytic method for sulfur |
| JP2000065764A (en) * | 1998-08-20 | 2000-03-03 | Horiba Ltd | X-ray fluorescence analysis of liquid sample |
| RU2308024C2 (en) * | 2003-08-01 | 2007-10-10 | Ригаку Индастриал Корпорейшн | Device for fastening specimen for roentgen fluorescence analysis and method of roentgen fluorescence analysis |
| JP4296907B2 (en) * | 2003-11-21 | 2009-07-15 | 株式会社リガク | Calibration sample for fluorescent X-ray analysis and fluorescent X-ray analyzer provided with the same |
| JP5489098B2 (en) * | 2009-02-05 | 2014-05-14 | 株式会社リガク | Drift correction sample for fluorescent X-ray analysis, fluorescent X-ray analysis method using the same, and method for producing the same |
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| JP2013088216A (en) | 2013-05-13 |
| JP5938708B2 (en) | 2016-06-22 |
| CN103048346A (en) | 2013-04-17 |
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