CN103969274A - Energy dispersion type fluorescent X-ray analysis device - Google Patents
Energy dispersion type fluorescent X-ray analysis device Download PDFInfo
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- CN103969274A CN103969274A CN201410041223.2A CN201410041223A CN103969274A CN 103969274 A CN103969274 A CN 103969274A CN 201410041223 A CN201410041223 A CN 201410041223A CN 103969274 A CN103969274 A CN 103969274A
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Abstract
The invention provides an energy dispersion type fluorescent X-ray analysis device capable of measuring object elements accurately even a temperature changes. The energy dispersion type fluorescent X-ray analysis device comprises an X-ray source (1) irradiating exciting X rays (A) including characteristic X rays with energy E1 generated from a target, a filter (7) composed of an element that is identical to that consisting the target or has an anatomic number 1 larger than that of the target, a detector (4) that detects fluorescent X rays (B) from a sample while detecting the exciting X rays (A), a wave height analyzer (5) and a calculation portion (6). The calculation portion takes a low wave height side half part of the wave peak of the characteristic X rays with the energy E1 as being formed by overturning high wave height side half part with wave height value (H1) of the wave height top point as a folding axis, and works out a count value based on wave peaks of the characteristic X rays with energy Ex of the detected target element in the sample.
Description
Technical field
The present invention relates to a kind of energy dispersion type fluorescent x-ray analyzer.More particularly, change even if relate to one temperature, it also can be according to the crest of the characteristic X-ray obtaining from determination object element, the energy dispersion type fluorescent x-ray analyzer of accurate quantitative analysis determination object element.
Background technology
Fluorescent x-ray analyzer, is to utilize by sample is irradiated to the X ray excited fluorescent X-ray producing, and the determination object element in sample is identified or quantitative device.As long as contain the peculiar characteristic X-ray of determination object element in sample in fluorescent X-ray, can confirm to exist this determination object element, in addition, also can obtain from the count value of this characteristic X-ray the quantitative information of this determination object element.
In fluorescent x-ray analyzer, have Wavelength dispersion type and energy dispersion type, wherein, energy dispersion type fluorescent x-ray analyzer is owing to not needing beam splitting system, and miniaturization that can implement device is applied to the analysis of the carrying out to various samples.
All the time, use energy dispersion type fluorescent x-ray analyzer, be unable to do without strict temperature treatment (for example, patent documentation 1).This is because detecting device is especially easily subject to the impact of temperature, even the X ray of identical energy (wavelength), due to temperature variation, also can detect the crest of different wave height values.
In addition, research and propose in addition: the position deviation of surveying the wave height value of X ray excited scattered light, FEEDBACK CONTROL puts on the high tension voltage of detecting device etc., if the X ray of identical energy (wavelength),, without carrying out strict temperature treatment, can obtain the crest (patent documentation 2) of certain wave height value.
Prior art document
Patent documentation
Patent documentation 1: No. 3075377 communique of Jap.P. utility model patent
Patent documentation 2: Japanese patent laid-open 04-274745 communique
Summary of the invention
The problem that invention will solve
But, as Patent Document 1, if will carry out temperature treatment, be unable to do without the large scale system for temperature treatment.In addition, even if want to carry out strict temperature treatment, in the situations such as environment temperature significantly changes, cannot keep sometimes stationary temperature.While particularly using proportional counter as detecting device, it is acted upon by temperature changes larger, is analyzed and brings obstacle accurately sometimes.
In addition, as shown in patent documentation 2, even for fear of produce X ray excited scattered light wave height value position deviation and carry out FEEDBACK CONTROL, its effect also only limits to tackle the deviation of transverse axis (wave height value), cannot avoid count value (longitudinal axis) to be subject to the impact of temperature change.
The inventor is according to the count value of the characteristic X-ray of the target of x-ray source, and the count value (longitudinal axis) while attempting temperature change is revised.But, only depend on and revise simply count value (longitudinal axis), cannot carry out sample quantitative accurately.
The present invention In view of the foregoing does.The invention provides a kind of energy dispersion type fluorescent x-ray analyzer, even if temperature changes, it also can accurately obtain the count value of the crest of the characteristic X-ray obtaining from determination object element, accurate quantitative analysis determination object element.
For the scheme of dealing with problems
Even if the inventor carried out finding after further investigated with regard to transverse axis and the longitudinal axis all having been carried out to revise the reason that still cannot carry out accurate quantitative analysis, if temperature changes, except transverse axis and the longitudinal axis can move, the width of crest also can change.And then find, especially the bottom of the crest of the target based on x-ray source can be overlapping with determination object element, and its lap changes because of temperature variation, thereby produces quantitative error.
The present invention completes according to above-mentioned discovery, and it has adopted following structure.
The first scheme of the present invention is, a kind of energy dispersion type fluorescent x-ray analyzer, and it,, based on by sample is irradiated to X ray excited produced fluorescent X-ray, analyzes the determination object element in described sample, it is characterized in that,
It possesses:
X-ray source, characteristic X-ray X ray excited that its radiation comprises the energy E 1 producing from target,
Wave filter, it is made up of than the element of the element that forms described target large 1 element identical with the element that forms described target or atomic number, to filter the form setting of the X ray excited light beam from described x-ray source to described sample,
Detecting device, its detect described X ray excited in, detect the fluorescent X-ray producing from described sample,
Wave-height analyzer, its output by described detecting device is converted to the wave spectrum taking the wave height value of corresponding energy value as transverse axis, taking count value as the longitudinal axis,
Operational part, it tries to achieve the information of the determination object element in described sample according to the wave spectrum obtaining from this wave-height analyzer;
Wherein, described operational part, according to the count value of the crest of the characteristic X-ray based on energy E 1, count value to each wave height value is revised, simultaneously, by low wave height side half part on the crest summit of the crest of the characteristic X-ray based on energy E 1, high wave height side half part that is considered as overturning taking the wave height value H1 on crest summit as folding shaft forms, obtain the count value of the crest of the characteristic X-ray of the energy E x of the determination object element based in described sample, obtain the quantitative information of the determination object element in described sample.
Alternative plan of the present invention is that, according to the energy dispersion type fluorescent x-ray analyzer described in the first scheme, wherein, described detecting device is proportional counter.
Third party's case of the present invention is that, according to the energy dispersion type fluorescent x-ray analyzer described in the first scheme or alternative plan, wherein, the element that forms described target is titanium or scandium.
Cubic case of the present invention is that, according to the energy dispersion type fluorescent x-ray analyzer described in any one in the first scheme～third party case, wherein, the determination object element in described sample is sulphur.
The 5th scheme of the present invention is that, according to the energy dispersion type fluorescent x-ray analyzer described in any one in the cubic case of the first scheme～the, wherein, described sample is oil.
And the wave height value in the present invention not refers to the energy value of initial X ray itself, and refers to the energy value that detecting device identifies.
In addition, in this manual, " scattering " refers to the elastic scattering that energy (wavelength) does not change.
In addition, in this manual, " count value of crest " refers to the aggregate-value of the count value of this crest in principle, if but the crest obtaining when more sharp-pointed can be also the count value on crest summit.In addition, " aggregate-value of the count value of crest " can be both the aggregate-value apart from the count value within the scope of the crest summit certain width of this crest, can be also the aggregate-value of this crest whole body counting value.
Invention effect
According to energy dispersion type fluorescent x-ray analyzer of the present invention, even if temperature changes, it also can accurately obtain the count value of the crest of the characteristic X-ray obtaining from determination object element, accurate quantitative analysis determination object element.
Therefore, can omit or the temperature management system of simplification device, can analyze accurately with simple device.
Brief description of the drawings
Fig. 1 is the structural drawing of the energy dispersion type fluorescent x-ray analyzer of an embodiment of the invention;
Fig. 2 is an example of the light transmittance curve of the wave filter of Fig. 1;
Fig. 3 is the key diagram that modified chi ray arrives the light path of detecting device;
Fig. 4 is the key diagram of other being revised to body;
Fig. 5 is the energy dispersion type fluorescent x-ray analyzer by an embodiment of the invention, an example of wave spectrum when mensuration does not contain as the zero correction liquid of the sulphur of determination object element, and wherein, target and wave filter are titanium, correction body is aluminium;
Fig. 6 is the partial enlarged drawing of Fig. 5;
Fig. 7 is the energy dispersion type fluorescent x-ray analyzer by an embodiment of the invention, an example of the wave spectrum while measuring the measuring range adjustment solution of the sulphur as determination object element that contains known quantity, and wherein, target and wave filter are titanium, correction body is aluminium;
Fig. 8 is the key diagram of obtaining the method for the clean count value of sulphur crest;
Fig. 9 is the key diagram of obtaining the method for the clean count value of sulphur crest;
Figure 10 is the key diagram of obtaining the method for the clean count value of sulphur crest.
Symbol description
1 ... x-ray source
2 ... high-voltage power supply
3 ... flow cell
4 ... detecting device
5 ... wave-height analyzer
6 ... operational part
7 ... wave filter
8 ... revise body
A ... X ray excited
B ... fluorescent X-ray
C ... modified chi ray
Embodiment
Below the energy dispersion type fluorescent x-ray analyzer of an embodiment of the invention is described.As shown in Figure 1, the energy dispersion type fluorescent x-ray analyzer of present embodiment possesses: x-ray source 1, and it sends X ray excited A; High-voltage power supply 2, it applies high-tension electricity to x-ray source 1; Flow cell 3, it is for sample circulation; Detecting device 4, it is arranged at the light path by the X ray excited A of sample or flow cell 3 scatterings and the fluorescent X-ray B that sends from sample; Wave-height analyzer 5, it is transfused to the output of detecting device 4; Operational part 6, it tries to achieve the information of the determination object element in sample according to the wave spectrum being obtained by wave-height analyzer 5.
In addition, on the light path of the X ray excited A from x-ray source 1 to flow cell 3, be disposed with wave filter 7 and revise body 8.At the two ends of flow cell 3, be connected with respectively sample and import path 11 and sample drain passageway 12.The light path of X ray excited A from x-ray source 1 to flow cell 3, and X ray excited A from sample to detecting device 4 and the light path of fluorescent X-ray B, preferably under vacuum environment, or helium, nitrogen etc. do not hinder under the pure gas atmosphere through fluorescent X-ray B and form.
In x-ray source 1, possess not shown target in the enclosure interior that forms vacuum, by making high-velocity electrons collide this target, produce the characteristic X-ray of the peculiar energy E 1 of element that forms target, the X ray excited A of the characteristic X-ray that radiation comprises this energy E 1.High-voltage power supply 2 applies high voltage to x-ray source 1, to produce this high-velocity electrons.
Can use the solid target material such as Sc, Ti, Ag, Rh, Mo, Cu, Cr, W, Co, Fe as the element that forms target.Due to the energy E 1 of characteristic X-ray with forming the difference of element kind of target difference, therefore, according to suitably selection of the determination object element in sample.
The characteristic X-ray of energy E x that produces determination object element due to X ray excited A is as fluorescence, and energy E 1 must fully be greater than energy E x.Therefore, the element of formation target must be greater than determination object element.But, if energy E 1 is excessive compared with energy E x, also can produce the characteristic X-ray of the element that is greater than determination object element, reduce thereby cause measuring precision, therefore also not preferred.
For example, if the determination object element in sample is sulphur (K α=2.31keV), preferably use titanium (K α=4.51keV) or scandium (K α=4.09keV) as the element that forms target.
In flow cell 3, in a side of injecting from the X ray excited A of x-ray source 1, be provided with the window that can see through X ray.Conventionally use beryllium film as window.
Can adopt the known detecting devices such as proportional counter, semiconductor detector, scintillation counter, as detecting device 4.Wherein, because proportional counter is subject to the impact of temperature, therefore, can preferably it be applicable to the present invention.If can solve the problem of temperature impact, proportional counter can go out micro-X ray with higher output detections, therefore, is suitable for measuring micro-determination object element.The window of detecting device 4 also uses beryllium film conventionally.
Detecting device 4, being configured in can be in detecting the fluorescent X-ray B sending from sample, detects by the position of the X ray excited A of flow cell 3 scatterings and modified chi ray C described later.
Wave-height analyzer 5, is converted to the wave spectrum taking the wave height value of corresponding energy value as transverse axis, taking count value as the longitudinal axis by the output of detecting device 4.Specifically, be multiple (2048,4096 etc.) radio frequency channel by the Range-partition of wave height value that obtains wave spectrum, by calculate the X ray detecting in cut apart each radio frequency channel, obtain wave spectrum.
Wave filter 7, is arranged at the position of blocking X ray excited A, to filter the light beam of the X ray excited A from x-ray source 1 to flow cell 3.Wave filter 7 is made up of than the film of the element of the element that forms described target large 1 element or the atomic number identical with the element of target that forms x-ray source 1.For example, be titanium if form the element of target, can adopt titanium or vanadium as the element that forms wave filter 7.In addition, be scandium if form the element of target, can adopt scandium or titanium as the element that forms wave filter 7.
The X ray light transmission of wave filter 7, enough high in the energy E 1 of characteristic X-ray of element that forms target, along with the reduction gradually lower than energy E 1, can sharply reduce if exceed 1 of energy E.
For example, as shown in Figure 2, the transmittance of the wave filter being made up of titanium, taking 4.96keV as crest summit, along with reducing gradually lower than 4.96keV, can sharply reduce if exceed 1 of energy E.And the transmittance 1.0 in Fig. 2, refers to 100% printing opacity.
Therefore, if forming the element of target is titanium (K α=4.51keV) or scandium (K α=4.09keV), filter by the wave filter 7 to be formed by titanium, can, when the characteristic X-ray that makes the element that forms target fully sees through, reduce the white X-ray radiation in X ray excited A.In addition, also can elimination for example, because forming the element (, iron, nickel, cobalt) etc. of housing of x-ray source 1 characteristic X-ray that produces, form clutter.
Revise body 8, the characteristic X-ray by X ray excited A produce power E2 is as modified chi ray C.Energy E 2 is less than the energy E 1 of characteristic X-ray in X ray excited A certainly, and preferably it is also less than the energy E x of the characteristic X-ray of the element that forms the determination object element in sample.By making energy Ex between energy E 1 and energy E 2, can obtain more accurately and wave height value Hx corresponding to energy E x.
For example, if the determination object element in sample is sulphur (K α=2.31keV), can adopt aluminium (K α=1.49keV), silicon (K α=1.74keV), sodium (K α=1.04keV), magnesium (K α=1.25keV) as forming the element of revising body 8.Wherein, due to comparatively stable as monomer, preferably adopt aluminium and silicon; Owing to being easy to processing as pure material, especially preferably adopt aluminium.If adopt sodium or magnesium, should adopt the comparatively stable compounds such as its oxide.
As Fig. 3 is schematically shown, the correction body 8 of present embodiment is formed as possessing the structure of peristome 8a.Peristome 8a can be arranged to pin hole or slit etc., is preferably arranged to pin hole.By peristome 8a is arranged to pin hole, correction body 8 also can have the effect of the aperture of X ray excited A concurrently.For example, there is the correction body 8 of the pin hole of diameter 2mm left and right by near the position configuration of (1～5mm left and right) x-ray source 1, the segment beam of the X ray excited A irradiating to flow cell 3 from x-ray source 1 is corrected body 8 and blocks, and the core of light beam arrives flow cell 3 by pin hole (peristome 8a).
Although modified chi ray C produces from revising the body 8 all parts that X ray A is irradiated to that are excited, that detected by detecting device 4 is mainly the modified chi ray C producing in the marginal portion of peristome 8a.As shown in Fig. 3 (a), the part modified chi ray C producing in the marginal portion of peristome 8a is by arriving flow cell 3 with the roughly the same light path of X ray excited A, is scattered and by arriving detecting device 4 with the roughly the same light path of fluorescent X-ray B at this.In addition, as shown in Figure 3 (b), other parts directly arrive detecting device 4.And, detecting device 4 both can with only detect through the mode of modified chi ray C of the light path as shown in Fig. 3 (a) configure, also can with only detect through the mode of modified chi ray C of light path as shown in Figure 3 (b) configure.
As Fig. 4 is schematically shown, revising body 8 also can be by evaporation in the flow cell window of flow cell 3.In this case, revise body 8 and also have peristome 8a, peristome 8a becomes in fact flow cell window.The shape of peristome 8a can be arranged to pin hole or slit.In this case, modified chi ray C produces from revising the body 8 all parts that X ray A is irradiated to that are excited, and directly arrives detecting device 4 and is predicted.For example, can be centered by the center of flow cell window point, arrange in the form of a ring and revise body 8.
In addition, revise body 8 and also can not there is the structure of peristome in part, but by the local continuous of the circumference at flow cell window or intermittently evaporation form.For example, can be centered by the center of flow cell window point, be intermittently to arrange annularly and revise body 8.
As long as because modified chi ray C can confirm the wave height value H2 on crest summit, therefore, the count value being obtained by detecting device 4 is minimum also harmless.If the count value being obtained by detecting device 4 is excessive, the overlapping of the crest of the crest of modified chi ray C and the characteristic X-ray based on determination object element may cause error, so and not preferred.
Operational part 6, according to the wave spectrum obtaining from wave-height analyzer 5, tries to achieve the information of the determination object element in sample.
Below, with the energy dispersion type fluorescent x-ray analyzer by present embodiment (wherein, the target of x-ray source 1 and wave filter 7 are titanium, revise body 8 for aluminium) sulphur measured in oil is example, illustrate that operational part 6 is according to the wave spectrum obtaining from wave-height analyzer 5, qualification is as the sulphur of determination object element in sample, and then the step of acquisition quantitative information.
In addition, in the following description, so-called " count value of crest ", is the aggregate-value of the count value within the scope of the crest summit certain width of this crest of span.Consider from the viewpoint that obtains stability number, calculate with the number of channels of wave-height analyzer 5, certain width is preferably 5 more than radio frequency channel, more preferably 10 more than radio frequency channel.In addition, from reducing because considering with the viewpoint of the overlapping error causing of other crest, be preferably below the half breadth of each crest, more preferably below the half of half breadth.
Illustrate below.In this example, total number of channels of wave-height analyzer 5 is 2048 radio frequency channels, the aggregate-value of the count value of 21 radio frequency channels that form with its 10 of front and back radio frequency channel the count value of crest as the radio frequency channel by comprising crest summit.
(to the mensuration of zero correction liquid)
First, make the not zero correction liquid containing the sulphur as determination object element flow into flow cell 3.Can adopt such as whiteruss, naphthalane etc. as zero correction liquid.
Fig. 5 is an example of the wave spectrum that obtains at this moment, and Fig. 6 is its partial enlarged drawing.As shown in Figure 5, although the little degree to confirming in Fig. 5 of whole wave spectrum of the crest of aluminium, as shown in Figure 6, amplification can clearly be confirmed.
Based on energy E 1(K α=4.51keV) wave height value H1 and the energy E 2(K α=1.49keV on crest summit of titanium) the wave height value H2 on crest summit of aluminium, other wave height value also can be set up associated with energy value.
The corresponding energy E of wave height value H except wave height value H1, H2, can try to achieve by following formula.
E＝（E1－E2）×（H－H2）／（H1－H2）＋E2
In Fig. 5, Fig. 6, the wave height value H1 that sets the crest summit of titanium is energy E 1(K α=4.51keV), the wave height value H2 that sets the crest summit of aluminium is energy E 2(K α=1.49keV), set up the associated of all wave height values and energy value, completed the correction (transverse axis correction finishes) of the relation of energy value and wave height value.
(to the mensuration of measuring range adjustment solution)
Then, make the measuring range adjustment solution of the sulphur as determination object element that contains known quantity flow into flow cell 3.Can adopt and for example in whiteruss or naphthalane, dissolve the butyl sulfide of known quantity or the solution of dibutyl disulfide etc. as measuring range adjustment solution.
Fig. 7 is an example of the wave spectrum of the measuring range adjustment solution that obtains under temperature conditions different when measuring zero correction liquid." the original wave spectrum " of Fig. 7 is the former wave spectrum that does not add correction completely.The crest of titanium of " original wave spectrum " and the crest of the titanium of Fig. 5, appear at different wave height values with different sizes.In Fig. 7, cannot confirm the crest of aluminium, but after amplifying as shown in Figure 6, even if also can confirm the crest of aluminium in this " original wave spectrum ".
The crest that is sulphur at the crest occurring than the slightly high wavelength side of 2keV.
For this original wave spectrum, revise the relation of energy value and wave height value, be transverse axis correction wave spectrum.The correction of the relation of energy value and wave height value, identical with the explanation of doing in the mensuration of zero correction liquid, that is: the wave height value H1 on the crest summit of setting titanium is energy E 1(K α=4.51keV), the wave height value H2 on crest summit that sets aluminium is energy E 2(K α=1.49keV), set up the associated of all wave height values and energy value.
For example, the sulphur that contains higher concentration (about 500ppm) at measuring range adjustment solution, without carrying out transverse axis correction, can identify the crest of sulphur.In the device of present embodiment, by following formula, can obtain the energy E x(K α=2.31keV with the characteristic X-ray of sulphur) corresponding wave height value Hx, therefore, for example, even the crest of the sulphur of extremely low concentration (about 10ppm) also can be identified out.
Hx＝（H1－H2）×（Ex－E2）／（E1－E2）＋H2
Then, for this transverse axis correction wave spectrum, having revised count value (longitudinal axis correction), is longitudinal axis correction wave spectrum.Longitudinal axis correction is to carry out according to the count value of the crest of titanium.
Specifically, change the scale of the longitudinal axis, so that the count value of the crest of the titanium of transverse axis correction wave spectrum is identical with the count value of the crest of the titanium by measuring the acquisition of zero correction liquid.In the present embodiment, due to the serve as reasons aggregate-value of count value of the radio frequency channel that contains crest summit and 21 radio frequency channels that before and after it, 10 radio frequency channels form of the count value of crest, therefore, make the width area of 21 radio frequency channels that formed by 10 radio frequency channels before and after the radio frequency channel that contains 4.51keV and its, identical with the width area of the crest by measuring the titanium that zero correction liquid obtains.
And in longitudinal axis correction, and the count value of the nonessential crest taking the titanium by measuring the acquisition of zero correction liquid is as benchmark.For example, as the ratio of count value of the crest with respect to by measuring the titanium that measuring range adjustment solution obtains, also can show the count value by measuring other crest that measuring range adjustment solution obtains.
In the longitudinal axis correction wave spectrum obtaining, the bottom of the crest of sulphur and the crest of titanium is overlapping.Therefore,, in order to obtain the clean count value of crest of sulphur, must determine the position of the bottom of the crest of titanium.
Therefore, in the present embodiment, by low wave height side half part of the crest of the characteristic X-ray based on titanium, be considered as the wave height value H1(K α=4.51keV taking crest summit) as folding shaft high wave height side half part of overturning forms, obtain the count value of the crest of the characteristic X-ray based on energy E x.
High wave height side half part that why low wave height side half part can be considered as overturning taking the wave height value H1 on crest summit as folding shaft forms, because in the present embodiment, owing to having used titanium wave filter, elimination may stress with the high wave height of the crest of titanium the characteristic X-ray of folded iron (K α=1.94keV), cobalt (K α=1.79keV), nickel (K α=1.66keV) etc.Therefore, the high wave height side of the crest of titanium half part can be considered as to the crest shape based on clean titanium.And, be Gaussian distribution or the shape of copying Gaussian distribution because the crest of the X ray of single energy value (wavelength) is former, therefore, can be by low wave height side half part, high wave height side half part that is considered as overturning taking the wave height value H1 on crest summit as folding shaft forms.
Fig. 8 is by the wave height value H1(K α=4.51keV taking crest summit) be the overturn folding wave spectrum of high wave height side half part of folding shaft, be overlapped in the longitudinal axis correction wave spectrum that obtains in Fig. 7 and figure.
If at wave height value H1(K α=4.51keV) below, deduct folding wave spectrum from longitudinal axis correction wave spectrum, as shown in Figure 9, can obtain the clean crest of sulphur, therefore, can, according to the relation of the sulphur concentration of the count value of this clean crest and measuring range adjustment solution, carry out span calibration.
The low wave height side of the crest of titanium half part is considered as to the wave height value H1(K α=4.51keV taking crest summit) for the folding shaft high wave height side half of overturning partly forms, and obtain on this basis the method for the clean count value of the crest of sulphur, be not limited only to this.For example, if from longitudinal axis correction wave spectrum high wave height side half part of the crest of titanium, deduct high wave height side half part of the crest by measuring the titanium that zero correction liquid obtains, can obtain poor spectrum as shown in figure 10.
If from longitudinal axis correction wave spectrum, deduct α=4.51keV taking wave height value H1(K) compose the wave spectrum forming as folding shaft this difference of overturning, and then deduct again α=4.51keV at wave height value H1(K) below the wave spectrum that obtains by measuring zero correction liquid, can obtain the clean crest of sulphur, therefore, can, according to the relation of the sulphur concentration of the count value of this clean crest and measuring range adjustment solution, carry out span calibration.
(to the mensuration of sample)
Next, make the sample (oil) of the sulphur as determination object element that contains unknown quantity flow into flow cell 3.Wave spectrum processing in this situation, identical during with measuring range adjustment solution.
; the wave spectrum of the sample obtaining under temperature conditions different when measuring zero correction liquid or measuring range adjustment solution; if be " the original wave spectrum " that does not add correction completely; compared with the crest of the crest of titanium and the titanium of zero correction liquid or measuring range adjustment solution, can appear at different wave height values with different sizes.In addition, if be " original wave spectrum ", compared with the crest of the crest of sulphur and the sulphur of measuring range adjustment solution, there will be at different wave height values.Therefore, also use the crest of the aluminium that simultaneously detects, according to measuring range adjustment solution is explained to identical mode, carry out transverse axis correction.
In addition, according to measuring range adjustment solution explained to identical mode carry out longitudinal axis correction, obtain longitudinal axis correction wave spectrum.And then, by low wave height side half part of the crest of titanium in longitudinal axis correction wave spectrum, be considered as the wave height value H1(K α=4.51keV taking crest summit) as folding shaft high wave height side half part of overturning forms, obtain on this basis the clean count value of the crest of sulphur.The concrete method of obtaining clean count value is identical with the explanation that measuring range adjustment solution is done.By contrasting the clean count value of crest of sulphur in this count value and measuring range adjustment solution, can obtain the sulphur content in sample.
According to present embodiment, carry out transverse axis correction from the characteristic X-ray of the target of x-ray source 1 and characteristic X-ray two aspects that form the element of revising body, therefore, and even if temperature changes, the crest of the characteristic X-ray also can precise Identification obtaining from determination object element.
In addition, carry out longitudinal axis correction according to the characteristic X-ray of the target of x-ray source 1, and then, take the bottom of the crest of the characteristic X-ray based on target into account, obtain the clean count value of the crest of determination object element, therefore, can accurate quantitative analysis determination object element.
Therefore, can omit or the temperature management system of simplification device, can analyze accurately with simple device.
In addition, if adopt proportional counter as detecting device, can go out micro-X ray with higher output detections.All the time, because proportional counter is easily acted upon by temperature changes, and be difficult to obtain sharp-pointed crest, therefore, for micro-determination object element, even if obtained higher output, be also difficult to separate with the bottom zone of the characteristic X-ray of the target of x-ray source 1, accurately to obtain the count value of crest of clean determination object element, be difficult to micro-determination object element to implement to measure.According to present embodiment, without strict control temperature, can adopt proportional counter as detecting device, the determination object element of accurate quantitative analysis trace.
For example, in the time that the energy dispersion type fluorescent x-ray analyzer by present embodiment (wherein, the target of x-ray source 1 and wave filter 7 are titanium, and revising body 8 is aluminium) is measured the sulphur in oil, even the sulphur of the following extremely low concentration of 1ppm, also can be quantitative.
And, in the present invention, revise body nonessential.For example, if comprise determination object element in known sample, and while not comprising other element that the wavelength of characteristic X-ray and determination object element approach, needn't use correction body, crest that can particular assay object elements.In addition, by accurately obtain the count value of its specific crest according to the present invention, get final product accurate quantitative analysis.
Claims (5)
1. an energy dispersion type fluorescent x-ray analyzer, it,, based on by sample is irradiated to X ray excited produced fluorescent X-ray, analyzes the determination object element in described sample, it is characterized in that,
It possesses:
X-ray source, characteristic X-ray X ray excited that its radiation comprises the energy E 1 producing from target,
Wave filter, it is made up of than the element of the element that forms described target large 1 element identical with the element that forms described target or atomic number, to filter the form setting of the X ray excited light beam from described x-ray source to described sample;
Detecting device, its detect described X ray excited in, detect the fluorescent X-ray producing from described sample,
Wave-height analyzer, its output by described detecting device is converted to the wave spectrum taking the wave height value of corresponding energy value as transverse axis, taking count value as the longitudinal axis,
Operational part, it tries to achieve the information of the determination object element in described sample according to the wave spectrum obtaining from this wave-height analyzer;
Wherein, described operational part, according to the count value of the crest of the characteristic X-ray based on energy E 1, count value to each wave height value is revised, simultaneously, by low wave height side half part on the crest summit of the crest of the characteristic X-ray based on energy E 1, high wave height side half part that is considered as overturning taking the wave height value H1 on crest summit as folding shaft forms, obtain the count value of the crest of the characteristic X-ray of the energy E x of the determination object element based in described sample, obtain the quantitative information of the determination object element in described sample.
2. energy dispersion type fluorescent x-ray analyzer according to claim 1, wherein, described detecting device is proportional counter.
3. energy dispersion type fluorescent x-ray analyzer according to claim 1 and 2, wherein, the element that forms described target is titanium or scandium.
4. according to the energy dispersion type fluorescent x-ray analyzer described in any one in claim 1～3, wherein, the determination object element in described sample is sulphur.
5. according to the energy dispersion type fluorescent x-ray analyzer described in any one in claim 1～4, wherein, described sample is oil.
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| JP2013013174A JP5817750B2 (en) | 2013-01-28 | 2013-01-28 | Energy dispersive X-ray fluorescence analyzer |
| JP2013-013174 | 2013-01-28 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106053508A (en) * | 2016-08-16 | 2016-10-26 | 南京市产品质量监督检验院 | Method for energy chromatic dispersion X-ray fluorescence spectrum detection of sulfur trioxide in cement |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2018162984A (en) * | 2017-03-24 | 2018-10-18 | 株式会社日立ハイテクサイエンス | Radiation analyzer |
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Also Published As
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| CN103969274B (en) | 2018-05-15 |
| JP5817750B2 (en) | 2015-11-18 |
| JP2014145618A (en) | 2014-08-14 |
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