CN103048346A - Calibration sample and fluorescence x-ray analytical device and method - Google Patents
Calibration sample and fluorescence x-ray analytical device and method Download PDFInfo
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- CN103048346A CN103048346A CN2012103923512A CN201210392351A CN103048346A CN 103048346 A CN103048346 A CN 103048346A CN 2012103923512 A CN2012103923512 A CN 2012103923512A CN 201210392351 A CN201210392351 A CN 201210392351A CN 103048346 A CN103048346 A CN 103048346A
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Abstract
The subject of the invention provides a calibration sample and a fluorescence X-ray analytical device and method, provides a calibration sample for analyzing fluorescence X-ray of a liquid sample, can be used for a long time and can perform accurate difference calibration. A calibration sample of the invention is a solid calibration sample which can be used for calibrating and analyzing change of measurement X-ray intensity of object metal elements as time goes, wherein metal layers of object metal elements and light element layers with thickness of more than 1mm are overlapped; in the light element layers, at least one light element selected from the group of hydrogen, boron, carbon, nitrogen, oxygen and fluorine possesses a largest Moore number; in the metal layers, a surface of an opposite side relative to the light element layers is an analytical layer.
Description
Technical field
The present invention relates to check sample and the fluorescent x-ray analyzer with it and the fluorescent x-ray analysis method that adopts this device that x-ray fluorescence analysis is used.
Background technology
In the past, in the fluorescent x-ray analyzer of the intensity of measuring the fluorescent X-ray that sample irradiation primary X-ray is produced, carry out termly so-called offset correction, wherein, the mensuration X ray intensity of same sample is proofreaied and correct because of the time situation of (drift) of changing of following that a variety of causes produces.If carry out this offset correction, then for such as the whole standard samples that are used to form typical curve, measure X ray intensity for each element correction, then whenever timing needs many time and time.So, when being used for offset correction, set in advance check sample, measure the X ray intensity that consists of benchmark, when carrying out offset correction, only measure the check sample of having set, according to the mensuration X ray intensity of this moment and the mensuration X ray intensity of formation said reference, obtain the offset correction coefficient, with the mensuration X ray intensity of this offset correction coefficient for the analytic target sample, proofread and correct.
Thus, in x-ray fluorescence analysis, adopt various check samples.Such as, the occasion for the sample that forms metal film at silicon substrate is analyzed has the check sample (patent documentation 1) that forms the metal film of Au, Pt, Co etc. at silicon substrate.
In addition, have the little power sample that is loaded on the film, remain in the check sample that the x-ray fluorescence analysis of micro solution sample on filter paper, the polymer film, film sample etc. adopts.This check sample forms (patent documentation 2) by polyimide film, the polyimide film that is mixed with the analytic target element on this polyimide film.As the variation of this check sample, people know the check sample that forms the polyimide film that is mixed with the analytic target element at metal forming, substrate.
In addition, in the mensuration of the concentration of the sulphur that in crude oil or petroleum product, comprises, concentration at sulphur is the occasion that known heavy oil is sealed in the standard sample of internal tank, because the concentration change that causes because of leak of liquid or precipitation etc. produces the companion over time, can't use for a long time, so have the simulation sample of employing solid as the method for standard sample.This simulation sample is formed by discoideus molybdenum main body and absorber, and this absorber is arranged on the primary X-ray irradiation side of this molybdenum main body, consists of (patent documentation 3) by polyethylene terephthalate, polyimide.
The prior art document
Patent documentation
Patent documentation 1: 2005-No. 156213 communiques of TOHKEMY
Patent documentation 2: 2010-No. 204087 communiques of TOHKEMY
Patent documentation 3: 7-No. 5127 communiques of Japanese kokai publication hei
Summary of the invention
The problem that invention will solve
The check sample of record is used for forming at silicon substrate the sample of metal film, the i.e. analysis of solid sample in the patent documentation 1.The check sample of record is used for the analysis of the solid sample of little power sample or film sample etc. in patent documentation 2, and is used for remaining in the analysis of the micro solution sample on filter paper or the polymer film.Because this check sample is used for the analysis of the micro sample of little power sample or micro solution sample etc., so the background that is produced by check sample consists of according to as much as possible little mode.
The simulation sample of record only is used for the mensuration of the concentration of the sulphur that crude oil or petroleum product comprise in patent documentation 3, is not used in other element, other liquor sample.This simulation sample is formed by the absorber of discoideus molybdenum main body with the primary X-ray irradiation side that is arranged at this molybdenum main body, and still, this absorber is used for the fluorescent X-ray intensity that decay is produced by the molybdenum main body, for by the background of sample generation without any consideration.Because in liquor sample, in as the water of solvent, organic solvent etc., the light element that comprises hydrogen as major component, carbon, oxygen etc., so produce in large quantities scattered x-ray, in the X ray of measuring, not only has fluorescent X-ray, and comprise in large quantities scattered x-ray, because this scattered x-ray produces large background.But, in the past, considered that the check sample of the solid of the background that produced by liquor sample does not also occur.
Like this, also do not have in the past following check sample, that is, can correctly measure the over time correction of (drift) of companion of X ray intensity, and can use for a long time, this mensuration X ray intensity comprises the background that is produced by liquor sample.
The problem that the present invention be directed to the above-mentioned past proposes, and the object of the present invention is to provide: can use for a long time and can carry out check sample, the fluorescent x-ray analyzer with it that the x-ray fluorescence analysis of the liquor sample of correct offset correction uses, the fluorescent x-ray analysis method that adopts this device.
Be used for solving the technical scheme of problem
To achieve these goals, check sample of the present invention is the check sample of solid, this check sample is used for the x-ray fluorescence analysis at liquor sample, companion to the mensuration X ray intensity of analytic target metallic element proofreaies and correct over time, wherein, the metal level that comprises the analytic target metallic element is that the above light element layer of 1mm forms with overlapping with thickness, in this light element layer, hydrogen, boron, carbon, nitrogen, at least a kind of light element in oxygen and the fluorine has maximum molfraction, in above-mentioned metal level, the opposite side surfaces of the side relative with above-mentioned light element layer is analysis face.
Because check sample of the present invention is solid, wherein, the metal level that comprises the analytic target metallic element is that the above light element layer of 1mm forms with overlapping with thickness, in this light element layer, at least a kind of light element in hydrogen, boron, carbon, nitrogen, oxygen and the fluorine has maximum molfraction, so the companion that do not produce evaporation, precipitation, go bad etc. caused over time, can use for a long time.In addition, above-mentioned metal level is the analysis face of irradiation primary X-ray, the primary X-ray of realizing transmission in this metal level is injected the light element layer, thus, the light element generation of light element layer and the scattered x-ray (background) of the fluent material same degree of analytic target, like this, can carry out correct offset correction.
In fluorescent x-ray analysis method of the present invention, adopt check sample of the present invention to carry out the x-ray fluorescence analysis of liquor sample.
According to fluorescent x-ray analysis method of the present invention, owing to adopt check sample of the present invention, so can realize the effect identical with check sample of the present invention.
In fluorescent x-ray analysis method of the present invention, preferably also adopt the background correction sample, this background correction sample is only formed by the above-mentioned light element layer of above-mentioned check sample, is used for the companion of the background X ray intensity of liquor sample is proofreaied and correct over time.In this occasion, owing to adopt the check sample that formed by above-mentioned metal level and above-mentioned light element layer, and 2 kinds of check samples of the background correction sample that only formed by above-mentioned light element layer, so can carry out more correct offset correction.
Fluorescent x-ray analyzer of the present invention comprises: check sample of the present invention; Offset correction mechanism, it is according to the mensuration X ray intensity of the analytic target metallic element of above-mentioned check sample, and the companion of the mensuration X ray intensity of liquor sample is proofreaied and correct over time.
According to fluorescent x-ray analyzer of the present invention, comprising: check sample of the present invention; Offset correction mechanism, it is according to the mensuration X ray intensity of the analytic target metallic element of above-mentioned check sample, proofread and correct liquor sample mensuration X ray intensity the companion over time, so can realize the effect identical with check sample of the present invention.
Best, fluorescent x-ray analyzer of the present invention also comprises the background correction sample, this background correction sample is only formed by above-mentioned light element layer, be used for to proofread and correct liquor sample background X ray intensity the companion over time, above-mentioned offset correction mechanism is according to the mensuration X ray intensity of the analytic target metallic element of above-mentioned check sample and the mensuration X ray intensity of above-mentioned background correction sample, and the companion of the mensuration X ray intensity of liquor sample is proofreaied and correct over time.In this occasion, owing to adopt the check sample that formed by above-mentioned metal level and above-mentioned light element layer, and 2 kinds of check samples of the background correction sample that only formed by above-mentioned light element layer, so can carry out more correct offset correction.
Description of drawings
Fig. 1 is the appearance assumption diagram of the fluorescent x-ray analyzer of the 1st embodiment of the present invention;
The side view of the check sample that Fig. 2 has for this fluorescent x-ray analyzer;
Fig. 3 obtains the figure of flow process of the thickness of the metal level of this check sample and light element layer for expression;
Fig. 4 is the side sectional view of the distortion example of this check sample;
Fig. 5 is the side view of another distortion example of this check sample;
Fig. 6 is the stereographic map of the background correction sample that has of the fluorescent x-ray analyzer of the 2nd embodiment of the present invention.
Embodiment
The below describes the fluorescent x-ray analyzer of the 1st embodiment of the present invention.As shown in Figure 1, this fluorescent x-ray analyzer comprises: sample bench 3, loading liquid sample S or check sample 20 on this sample bench 3; X-ray source 1, this x-ray source 1 be to liquor sample S or check sample 20 irradiation primary X-raies 2 such as the rhodium X-ray tube; Beam splitter 5,5 pairs of secondary x rays 4 that produced by liquor sample S or check sample 20 of this beam splitter carry out light splitting; Detecting device 7, the secondary x rays 6 that this detecting device 7 detects by beam splitter 5 light splitting; Offset correction mechanism 9.Beam splitter 5 and detecting device 7 consist of testing agency 8.Offset correction mechanism 9 is according to the mensuration X ray intensity of the analytic target metallic element of check sample 20, and the companion of the mensuration X ray intensity of liquor sample S is proofreaied and correct over time.Secondary x rays 4 and 6 comprises this fluorescent X-ray and scattered x-ray.
In addition, best, check sample 20 prior loadings are in the assigned position of sample switch (not shown) or be built-in with device.
To the action of the fluorescent x-ray analyzer of the 1st embodiment, the fluorescent x-ray analysis method that namely consists of an embodiment of the invention describes.If make fluorescent x-ray analyzer action, then at the initial check sample 20 of measuring, offset correction mechanism 9 with the mensuration X ray intensity of the secondary x rays 6 of analytic target metallic element as the benchmark intensity I
SAnd store.After this, in turn measure liquor sample S, when the mensuration X ray intensity of correction analysis object metallic element, measure check sample 20, obtain the intensity I of the secondary x rays 6 of analytic target metallic element
MIf obtain intensity I
M, the I that then obtains according to offset correction mechanism 9
MThe benchmark intensity I of formerly storing
S, by following formula (1) calculation deviation correction coefficient alpha.
α＝I
S/I
M(1)
In addition, offset correction mechanism 9 is with the mensuration X ray intensity I of offset correction factor alpha with the analytic target metallic element of the liquor sample S that measures
nMultiply each other, carry out offset correction.
In above-mentioned example, with offset correction factor alpha and mensuration X ray intensity I
nMultiply each other, carry out offset correction, still, also the gradient constant a of offset correction factor alpha and expression of first degree typical curve can be multiplied each other, typical curve is proofreaied and correct, carry out offset correction.
The below is specifically described the check sample 20 of the solid that the fluorescent x-ray analyzer of the 1st embodiment has.As shown in Figure 2, check sample 20 forms in the following manner, this mode is: will comprise that the metal level 21 of analytic target metallic element overlaps with light element layer 22, it is maximum molfraction that this light element layer 22 makes at least a kind of light element in hydrogen, boron, carbon, nitrogen, oxygen and the fluorine, thickness is more than the 1mm, and metal level 21 is adhered on the 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.
Best, in the check sample 20 that the fluorescent x-ray analyzer of the 1st embodiment has, metal level 21 forms in interior mode according to 2 times of following thickness, this thickness produces and is equivalent to: the fluorescent X-ray intensity of the fluorescent X-ray intensity that the analytic target element in liquor sample S produces when being maximum level, light element layer 22 be equal to according to generation liquor sample S background X ray intensity thickness and form.
According to flow process shown in Figure 3, to as described above, the mode of finding the solution that is suitable for the thickness of the thickness of metal level 21 of liquor sample S and light element layer 22 describes.
At the 1st stage S1, for the thickness of obtaining metal level 21 and the thickness of light element layer 22, determine the corresponding desired value of the fluorescent X-ray intensity (pure X ray intensity) that is produced by metal level 21 and the background X ray intensity that is produced by light element layer 22.The fluorescent X-ray intensity (pure X ray intensity) that will produce the standard sample of maximum fluorescence X ray intensity in a plurality of standard samples that the typical curve that forms liquor sample S is used is defined as the desired value of metal level 21.Will be as the background X ray intensity of the X ray intensity of the intercept of the established typical curve desired value as light element layer 22.
At the 2nd stage S2, employing in the 1st stage S1 as desired value and the fluorescent X-ray intensity of definite metal level 21, calculate by FP method (Fundamental parametermethod) theoretical strength, calculate to consist of in the allowed band of desired value of this fluorescent X-ray intensity (such as, in desired value 100～200%) the thickness of metal level 21 of X ray intensity.
At the 3rd stage S3, be formed on the metal level 21 of the thickness of the 2nd stage S2 calculating, this metal level 21 is coincided with on the light element layer 22 of the arbitrarily thickness more than the 1mm, form check sample 20.For established check sample 20, measure the fluorescent X-ray intensity of metal level 21 and the background X ray intensity of light element layer 22 by fluorescent x-ray analyzer.In addition, about metal level 21 and light element layer 22 are overlapped and the mode of formation check sample 20, will be described later.
At the 4th stage S4, whether the fluorescent X-ray intensity of judging metal level 21 arrives the intensity in the allowed band of the desired value of determining in the 1st stage S1.If the fluorescent X-ray intensity of metal level 21 arrives the interior intensity of allowed band of desired value, then carry out the 5th stage S5.If judge that at the 4th stage S4 the fluorescent X-ray intensity of metal level 21 is less than the intensity in the allowed band of the desired value of determining among the 1st stage S1, then carries out 4A stage S4A.
At 4A stage S4A, the mode that arrives the intensity in the allowed band of the desired value of determining according to the fluorescent X-ray intensity of metal level 21 in the 1st stage S1 changes the thickness of metal level 21, turn back to the 3rd stage S3, at the 4th stage S4, before the intensity in the fluorescent X-ray intensity of judging metal level 21 arrives the allowed band of the desired value of determining among the 1st stage S1, repeatedly carry out from the flow process of 4A stage S4A to the 4 stage S4.
At the 5th stage S5, whether the background X ray intensity of judging light element layer 22 arrives the intensity in the allowed band of the desired value of determining in the 1st stage S1.Arrive the interior intensity of allowed band of desired value if judge the background X ray intensity of light element layer 22, then carry out the 6th stage S6.If judge that at the 5th stage S5 the background X ray intensity of light element layer 22 is less than the intensity in the allowed band of the desired value of determining in the 1st stage S1, then carry out 5A stage S5A.
In 5A stage S5A, arrive the intensity in the allowed band of the desired value of in the 1st stage S1, determining for the background X ray intensity that makes light element layer 22, change the thickness of light element layer 22, turn back to the 3rd stage S3, be that the 5th stage S5 judges that the fluorescent X-ray intensity of light element layer 22 arrives before the intensity in the allowed band of the desired value of determining, carries out repeatedly from the flow process of 5A stage S5A to the 5 stage S5 in the 1st stage S1.
At the 6th stage S6, determine the thickness of metal level 21 and light element layer 22.
As the distortion example of check sample 20, the check sample 20 of the occasion analyzed as the nickel among the liquor sample S of nickel plating bath is described.Occasion at this check sample 20, as shown in Figure 4, such as, as the metal level 21 of the nickel foil 21 of thickness 10 μ m according to fixing by ring-type fixture 50 with closely connected mode on the end face of light element layer 22, this light element layer 22 is as the rectangular-shaped acryl resin 22 such as thickness (highly) 10mm, the outside surface component analysis face 23 of this metal level 21.Rectangular-shaped acryl resin 22 is made of carbon, hydrogen, the oxygen as light element, and hydrogen has maximum molfraction.Rectangular-shaped acryl resin 22 is of a size of such as horizontal 100mm, vertical 100mm, thickness (highly) 10mm.The metal level 21 of the check sample 20 of using as the liquor sample S of this nickel plating bath and the value of thickness for obtaining by flow process shown in Figure 3 of light element layer 22.
Ring-type fixture 50 is made of annular plate 51 and gib screw 52, gib screw 52 screws togather with threaded hole 25 on the top (the fixedly part of ring-type fixture 50) that is formed at light element layer 22, and metal level 21 is fixed according to the mode between the bottom surface of the end face that is held on light element layer 22 and ring-type fixture 50 (and light element layer 22 face face).In addition, the fixing means of metal level 21 is not limited to ring-type fixture 50 as described above, also can fix by other fixture.
In the check sample 20 of Fig. 2, metal level 21 adopts the nickel foil of 1 thickness 100 μ m, but, also comparable like shown in Figure 5, the mode that they is overlapped according to the corresponding nickel foil among bonding a plurality of nickel foil 21a, 21b, the 21c by bonding agent forms, and also can a plurality of metal formings be fixed by ring-type fixture 50 shown in Figure 4.In addition, occasion at the check sample 20 that is used for a plurality of analytic target metallic elements, the mode that metal level 21 both can overlap according to the metal forming with different analytic target metallic elements forms, and also can form by 1 metal forming with a plurality of analytic target metallic elements.In addition, metal level 21 can not be metal forming also, also can be according to forming in the mode of light element layer 22 by the film of the mode Overlap Analysis object metallic element of evaporation (PVD, CVD etc.), plating etc.Best, metal level 21 is according to flow process shown in Figure 3, according to the thickness of answering with the relative concentration of the analytic target metallic element that in liquor sample S, comprises and form, as the concrete numerical value of thickness, such as, if be high concentration then thicker, thickness is preferably in the scope of 10～300 μ m, if be low concentration then thinner, thickness is preferably in the scope of 1～10 μ m, if for extremely low concentration then be preferably in scope greater than 0 less than, 10 μ m.
In the present embodiment, check sample 20 is bonding, closely connected according to carrying out at light element layer 22, the mode of the processing of evaporated metal layer 21 etc. forms, but, also can form according to the mode that the gapped state of tool between light element layer 22 and metal level 21 overlaps.
Can be by forming like this light element layer 22, form the background with liquor sample S same degree, and measure the liquor sample S of fluorescent X-ray intensity with the ratio of scattered x-ray intensity and reach identical degree, so can carry out correct offset correction.Adopt Fig. 2, Fig. 4, Fig. 5, the check sample 20 that has illustrated in the above consists of an embodiment of the invention respectively.
If the fluorescent x-ray analyzer according to the 1st embodiment, the check sample 20 that this fluorescent x-ray analyzer has is following solid, be that metal level 21 is formed by the analytic target metallic element, light element layer 22 is by hydrogen, boron, carbon, nitrogen, the thickness that at least a kind of light element in oxygen and the fluorine has maximum molfraction is that the above material of 1mm forms, and the light element of light element layer 22 produces the scattered x-ray (background) with liquor sample S same degree, so can use chronically, and deviation of the mensuration X ray intensity of correction analysis object metallic element correctly.
Below, the fluorescent x-ray analyzer as the 2nd embodiment of the present invention is described.The fluorescent x-ray analyzer of the 2nd embodiment and difference as the fluorescent x-ray analyzer of the 1st embodiment are 2 kinds check sample of check sample 20 that the former comprises that the fluorescent x-ray analyzer of the 1st embodiment has and background correction sample 40 (Fig. 6), this background correction sample 40 is only formed by the light element layer 22 of check sample 20, be used for the companion of the background X ray intensity of liquor sample S is proofreaied and correct over time, offset correction mechanism 9 is according to the mensuration X ray intensity of the analytic target metallic element of check sample 20 and be loaded into the mensuration X ray intensity of the background correction sample 40 on the sample bench 3, and the companion of the mensuration X ray intensity of liquor sample S is proofreaied and correct over time.But because other structure is identical, so difference is described.In addition, 2 kinds of check samples 20,40 identical with the fluorescent x-ray analyzer of the 1st embodiment, best, prior loading is in the assigned position of sample switch, or is built-in with device.
To the action of the fluorescent x-ray analyzer of the 2nd embodiment, the fluorescent x-ray analysis method that namely consists of an embodiment of the invention describes.If make fluorescent x-ray analyzer action, then measure at first background correction sample 40, offset correction mechanism 9 with background X ray intensity as background benchmark intensity I
BAnd store.Then, at the bottom of the fair copy during X ray intensity, measure background correction sample 40, obtain background X ray intensity I
CIf obtain background X ray intensity I
C, then offset correction mechanism 9 is according to the intensity I of having obtained
CThe benchmark intensity I of formerly storing
B, by correction coefficient β at the bottom of following formula (2) calculating book.
β＝I
B/I
C(2)
Then, if with the action same measured check sample 20 of the fluorescent x-ray analyzer of the 1st embodiment, then offset correction mechanism 9 calculation deviation correction coefficient alpha.Offset correction mechanism 9 is by gradient constant a and the intercept constant b of calculated offset correction factor alpha, background correction factor beta correction expression of first degree typical curve, calibration standard curve.The liquor sample S that measures afterwards in the correction of typical curve according to the typical curve of proofreading and correct and quantitatively.
Since the fluorescent x-ray analyzer of the 2nd embodiment comprise the identical check sample 20 of the check sample 20 that has with the fluorescent x-ray analyzer of the 1st embodiment, with the background correction sample 40 that is only formed by light element layer 22,2 kinds check sample of the background correction sample 40 that the check sample 20 of using by area with high mercury and low concentration region are used, gradient constant a and intercept constant b are proofreaied and correct, the calibration standard curve is so calibration standard curve more correctly.Particularly, the companion of the mensuration X ray intensity of analytic target metallic element over time with the companion of background X ray intensity different occasion over time, its effect is very large.
Fig. 2 that fluorescent x-ray analyzer described above has, Fig. 4, check sample 20 shown in Figure 5 also can adopt and will monitor method (scattered ray internal reference method) by the scattered ray that the scattered x-ray that check sample 20 produces is measured as Internal standard line.Scattered ray supervision method is multiplex analysis in a large amount of liquor samples that occur of scattered x-ray, organic compound etc., the ratio of the mensuration X ray intensity by adopting the analytic target metallic element and the X ray intensity of background (scattered x-ray), the fluorescent x-ray analysis method that the impact of the coexistence elements among the sample S is compensated.
Such as, can carry out scattered ray and monitor in the multielement simultaneous type fluorescent x-ray analyzer of method and comprise: the mensuration passage (having the beam splitter and the X-ray detector that are suitable for the analytic target metallic element) of measuring the secondary x rays of the analytic target metallic element that is produced by liquor sample S; Mensuration is by the background passage (having the beam splitter and the X-ray detector that are suitable for background determination) of the scattered x-ray of liquor sample S generation, and making will be by measuring the X ray intensity I of passage mensuration
aWith the X ray intensity I of measuring by the background passage
dRatio I
a/ I
dAs the longitudinal axis, with the concentration of the analytic target metallic element of the liquor sample S that the measures typical curve as transverse axis, analyze liquor sample S.
At first, by measuring passage and background passage, side by side check sample 20 is measured, calculated the benchmark intensity I as X ray intensity of measuring by measuring passage
pWith the benchmark intensity I as X ray intensity of measuring by the background passage
gRatio I
p/ I
gWhen correcting determination X ray intensity, side by side check sample 20 is measured by measuring passage and background passage, calculate the X ray intensity I of measuring by measuring passage
rWith the X ray intensity I of measuring by the background passage
qRatio I
r/ I
qAdopt the calculated I that compares
p/ I
gWith the calculated I that compares
r/ I
qRatio (I
p/ I
g)/(I
r/ I
q) the calibration standard curve, carry out offset correction.
Check sample 20 can produce the background with the liquor sample S same degree of analytic target, because the degree of the ratio of fluorescent X-ray intensity and scattered x-ray intensity and the liquor sample S of analytic target is identical, even so monitor method for scattering, still can carry out correct offset correction.
In the fluorescent x-ray analyzer of the 1st, the 2nd embodiment, check sample 20 is used for the correction of typical curve, but also can be used for estimating the sensitivity stability test of the sensitivity degree of stability of fluorescent x-ray analyzer.Best, the stability test sample that is used for the sensitivity stability test of fluorescent x-ray analyzer produces the fluorescent X-ray with the intensity of liquor sample S same degree, have and the fluorescent X-ray of liquor sample S same degree and the ratio of scattered x-ray intensity, best, thickness such as metal level 21 is 5 μ m, and the thickness of light element layer 22 is 5mm.
1st, the fluorescent x-ray analyzer of the 2nd embodiment is illustrated as wavelength dispersion type fluorescent x-ray analyzer, and still, device of the present invention also can be the energy dispersion type fluorescent x-ray analyzer.
Label declaration
Label 1 expression x-ray source;
Label 2 expression primary X-raies;
Label 3 expression sample benchs;
Label 4,6 expression secondary x rays;
Label 5 expression beam splitters;
Label 7 expression detecting devices;
Label 8 expression testing agencies;
Label 9 expression offset correction mechanisms;
Label 40 expression background correction samples;
Symbol S express liquid sample.
Claims (5)
1. check sample, it is the solid check sample, this check sample is used for the x-ray fluorescence analysis at liquor sample, the companion of the mensuration X ray intensity of analytic target metallic element proofreaied and correct over time,
Wherein, the metal level that comprises the analytic target metallic element is that the above light element layer of 1mm forms with overlapping with thickness, and in this light element layer, at least a kind of light element in hydrogen, boron, carbon, nitrogen, oxygen and the fluorine has maximum molfraction,
In above-mentioned metal level, the opposite side surfaces of the side relative with above-mentioned light element layer is analysis face.
2. fluorescent x-ray analysis method, it adopts check sample claimed in claim 1 to carry out the analysis of liquor sample.
3. fluorescent x-ray analysis method according to claim 2, it also adopts the background correction sample, and this background correction sample is only formed by above-mentioned light element layer, is used for the companion of the background X ray intensity of liquor sample is proofreaied and correct over time.
4. fluorescent x-ray analyzer, this fluorescent x-ray analyzer comprises:
Check sample claimed in claim 1;
Offset correction mechanism, it is according to the mensuration X ray intensity of the analytic target metallic element of above-mentioned check sample, and the companion of the mensuration X ray intensity of liquor sample is proofreaied and correct over time.
5. fluorescent x-ray analyzer according to claim 4 also comprises the background correction sample, and this background correction sample is only formed by above-mentioned light element layer, be used for the companion of the background X ray intensity of liquor sample is proofreaied and correct over time,
Above-mentioned offset correction mechanism is according to the mensuration X ray intensity of the analytic target metallic element of above-mentioned check sample and the mensuration X ray intensity of above-mentioned background correction sample, and the companion of the mensuration X ray intensity of liquor sample is proofreaied and correct over time.
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| 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 |
| JP2011-227624 | 2011-10-17 |
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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 |
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| JP2010204087A (en) * | 2009-02-05 | 2010-09-16 | Rigaku Corp | Drift correction sample for fluorescent x-ray analysis, fluorescent x-ray analysis method using the same, and method of manufacturing the same |
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| JPH0257951A (en) * | 1988-08-23 | 1990-02-27 | Nippon Atom Ind Group Co Ltd | Standard specimen for fluorescent x rays and manufacture thereof |
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| CN1055998A (en) * | 1990-04-19 | 1991-11-06 | 株式会社岛津制作所 | Method and apparatus during sample surfaces is analyzed at the bottom of the fair copy |
| 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 |
| JP2002090319A (en) * | 2000-09-20 | 2002-03-27 | Rigaku Industrial Co | Fluorescent x-ray analysis device |
| CN1820195A (en) * | 2003-08-01 | 2006-08-16 | 理学电机工业株式会社 | Sample retainer for X-ray fluorescence analysis, X-ray fluorescence analyzing method using the same and X-ray fluorescence spectrometer therefor |
| JP2005156213A (en) * | 2003-11-21 | 2005-06-16 | Rigaku Industrial Co | Calibration sample for x-ray fluorescence analysis |
| JP2010204087A (en) * | 2009-02-05 | 2010-09-16 | Rigaku Corp | Drift correction sample for fluorescent x-ray analysis, fluorescent x-ray analysis method using the same, and method of manufacturing the same |
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| Publication number | Priority date | Publication date | Assignee | Title |
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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 |
Also Published As
| Publication number | Publication date |
|---|---|
| JP5938708B2 (en) | 2016-06-22 |
| CN103048346B (en) | 2016-08-31 |
| JP2013088216A (en) | 2013-05-13 |
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