JP2006010603A - Element content determination method, program, device, and system - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an element content determination method, a program, a device, and a system capable of preventing erroneous determination when determining the presence of an assigned element in an analytical sample, and capable of obtaining highly reliable determination result easily. <P>SOLUTION: Verification work by other technique is able to be omitted, since a determination result is expressed clearly when a deterministic conclusion is drawn out from a data of a distributed spectral waveform SI obtained by a specified analytical technique in a measuring instrument 1. A forceful conclusion is not drawn out but that any problem is generated is indicated, when a problem is left, such as when the deterministic conclusion is not drawn out, or when a concentration is not settled although the content of the assigned element is determined, a method for coping therewith such as recommendation of using other measuring method is drawn out, and even a measuring person not skilled in a measuring technique can select the proper coping therewith, without generating an erroneous judgement. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an element content determination method, program, apparatus, and system for determining the presence or absence of a specified element in an analysis sample.

  Recently, in the industry, for example, to respond to "environmental legislation", it is desired to easily obtain information on the presence or absence of specific harmful heavy metal elements such as lead (Pb) in component raw materials. The demand is growing.

  As described above, examples of the method for analyzing the presence or absence of a specified element from a specific sample include a fluorescent X-ray analysis method and ICP-AES (Inductively Coupled Plasma-Atomic Emission Spectroscopy).

  Chemical analysis methods such as ICP-AES are advantageous in that measurement result information with much higher accuracy and reliability can be obtained as compared with fluorescent X-ray analysis methods. However, because it is a destructive analysis and sample preparation takes time, skill is required for the measurement operation, resulting in high costs, etc., it is refrained from the user's standpoint unless it is really necessary. The reality is what you want.

  On the other hand, the X-ray fluorescence analysis method can basically analyze non-destructively, so that almost no sample preparation is required. Moreover, since measurement can be performed in a short time and the operation is simple, the skill level of the measurer is not so much required, and as a result, the measurement cost can be kept low.

  Here, among commercially available X-ray fluorescence analyzers based on this X-ray fluorescence analysis method, a quantitative analysis device generally has a concentration value indicating how much a predetermined element is contained in a sample, and this calculated concentration. Is provided with a function for outputting as a quantitative result based on a value with a standard deviation indicating how much reliability there is.

  However, X-ray fluorescence analysis generally has a larger measurement error than chemical analysis. In addition, due to the presence of coexisting elements, the sensitivity of some of the elements to be measured to fluorescent X-ray types is reduced, or signals derived from other different elements having the same energy as this line type are mistaken for this line type. There is a problem that “false detection” may occur in which numerical values are output as if a considerable amount of a measurement target element that is processed in the X-ray fluorescence analyzer and does not actually exist is detected.

  Therefore, conventionally, the X-ray fluorescence analyzer industry has focused on how to improve the accuracy mainly in the “fluorescence X-ray analysis method”.

  For example, Patent Document 1 discloses a method of calculating the intensity of each spectral line more accurately when spectral lines of different elements are superimposed on the same peak.

  Patent Document 2 discloses an apparatus that performs function fitting under a predetermined condition to separate spectral lines.

  Further, Patent Document 3 discloses an apparatus including means for calculating a peak intensity so that a spectrum generated from each element in a sample is approximated by a function and the sum matches a spectrum of a measurement result.

Further, Non-Patent Document 1 discloses a fluorescent X-ray analysis system capable of performing a pass / fail determination with a single button for such an “environmental legislation purpose”.
Japanese Patent No. 3141803 Japanese Patent No. 2713120 Japanese Patent No. 3488918 "Energy dispersive X-ray fluorescence analysis system JSX-3202EV", [online], JEOL Ltd., [June 7, 2004 search], Internet <URL: http://www.jeol.co.jp/ products / product / jsx-3202ev / index.htm>

  However, the techniques disclosed in the above-mentioned Patent Documents 1 to 3 calculate how accurately the intensity of each spectral line is calculated from the information of the fluorescent X-ray spectrum that is delicate and difficult to judge. It is focused on whether to perform spectral separation, and it can be said that all of them are premised on deriving a final conclusion about the content from only the target fluorescent X-ray spectrum.

  However, in the first place, it is not easy to analyze a subtle spectrum where peaks are superimposed or function fitting is required, as assumed in the above document, from the viewpoint of content determination in the first place. Absent. Further, “false detection” derived from other elements can be prevented to some extent, but it is difficult to completely prevent them.

  Moreover, it is not particularly advantageous that the content accuracy or display reproducibility is good. This is because if the specific harmful heavy metal element is actually contained exceeding the reference value, it is necessary to take an improvement measure regardless of the excess amount.

  In addition, like the X-ray fluorescence analysis system disclosed in Non-Patent Document 1 described above, some X-ray fluorescence spectrometer manufacturers have accepted “pass / fail with a single button for the purpose of responding to environmental laws” at this time. Devices that have the characteristic that “determination can be performed” have also appeared.

  However, these pass / fail judgments are of a level that outputs pass / fail information depending on whether the quantitative calculation result by the conventional method exceeds the reference value, and in the case of `` false detection '' still originating from other elements, The problem remains that it cannot be determined accurately.

  As described above, according to the conventional technique, it is difficult to prevent erroneous determination and easily obtain a highly reliable determination result when determining whether or not the specified element is contained in the analysis sample.

  The present invention has been made in view of such problems, and its purpose is to prevent erroneous determination when determining the presence or absence of a specified element in an analysis sample, and to easily obtain a highly reliable determination result. An element content determination method, a program, an apparatus, and a system are provided.

  The element content determination method of the present invention calculates peak intensity for a predetermined peak of a specified element in a predetermined dispersion range, searches for the presence or absence of a desired peak waveform for a predetermined peak in a predetermined dispersion range, and performs this search. Based on the result, it is determined whether or not the peak intensity calculation result for the predetermined peak in the predetermined dispersion range is reliable. Here, when it is determined from the search result that the peak intensity calculation result is not reliable, it is preferable to derive a coping method based on the search result.

  The element content determination program of the present invention calculates a peak intensity for a predetermined peak of a specified element in a predetermined dispersion range, and searches for the presence or absence of a desired peak waveform for the predetermined peak in a predetermined dispersion range; And determining whether or not the peak intensity calculation result is reliable for a predetermined peak in a predetermined dispersion range based on the search result. Here, when it is determined from the search results that the peak intensity calculation result is not reliable, it is preferable to include a step of outputting at least one of the determined content and a coping method based thereon.

  The first element content determination apparatus according to the present invention includes an input means for inputting a dispersion spectrum waveform in an analysis sample, calculates a peak intensity for a predetermined peak of a specified element in a predetermined dispersion range, and determines a predetermined intensity in a predetermined dispersion range. Search means for searching for the presence or absence of a desired peak waveform for a given peak, and determining whether or not the peak intensity calculation result for a given peak in a given dispersion range is reliable based on the search result searched by the search means Determination means, and output means for outputting the content determined by the determination means. Here, when it is determined by the determining means that the peak intensity calculation result is not reliable, the output means preferably outputs at least one of the determined content and a coping method based thereon.

  The second element content determination apparatus of the present invention includes a measuring means for measuring a dispersion spectrum in an analysis sample, calculates a peak intensity for a predetermined peak of a specified element in a predetermined dispersion range, and a predetermined intensity in a predetermined dispersion range. Search means for searching for the presence or absence of a desired peak waveform for a peak, and determining whether or not the peak intensity calculation result for a predetermined peak in a predetermined dispersion range is reliable based on a search result searched by the search means It comprises a judging means and an output means for outputting the contents judged by the judging means. Here, when it is determined by the determining means that the peak intensity calculation result is not reliable, the output means preferably outputs at least one of the determined content and a coping method based thereon.

  In the element content determination system of the present invention, the measurement device includes a measurement unit that measures the dispersion spectrum waveform in the analysis sample, and the element content determination device inputs the dispersion spectrum waveform in the analysis sample measured by the measurement unit in the measurement device. An input means for calculating a peak intensity for a predetermined peak of a specified element in a predetermined dispersion range, a search means for searching for the presence or absence of a desired peak waveform for the predetermined peak in a predetermined dispersion range, and a search means A determination unit configured to determine whether or not the peak intensity calculation result for the predetermined peak in the predetermined dispersion range is reliable based on the searched search result; and an output unit configured to output the content determined by the determination unit. Is.

  In the element content determination method, program, apparatus, or system of the present invention, the peak intensity is calculated and the presence or absence of a desired peak waveform is searched for a predetermined peak of a specified element in a predetermined dispersion range. In addition, based on the search result, whether or not the peak intensity calculation result for the predetermined peak is reliable is determined. Thereby, the reliability of the peak intensity calculation result used when determining whether or not the designated element is contained is determined in advance. Here, when it is determined from this search result that the peak intensity calculation result is not reliable, a coping method based on the search result can be derived, and in that case, a specific coping method can be notified. Become.

  According to the element content determination method, program, apparatus, or system of the present invention, the peak intensity is calculated for the predetermined peak of the specified element in the predetermined dispersion range, and the presence or absence of a desired peak waveform is searched. Based on this, the reliability of the peak intensity calculation result for a given peak is judged. Therefore, when judging the presence or absence of the specified element in the analysis sample, it is possible to prevent misjudgment and to make the judgment highly reliable. The result can be easily obtained. In particular, when it is determined from this search result that the peak intensity calculation result is unreliable, the user can recognize the specific coping method when the coping method based on the search result is derived, This can be easily taken.

  Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.

[First Embodiment]
FIG. 1 shows an example of the entire configuration of the element content determination system according to the first embodiment of the present invention. The element content determination system includes a measuring device 1 that obtains dispersion spectrum waveform data from an analysis sample, and a specified element (for example, lead (Pb)) in the analysis sample from the dispersion spectrum waveform data obtained by the measurement device 1. ) Is included in the element content determination device 2 for determining the presence or absence of content.

  The measuring apparatus 1 includes an X-ray tube 11, a filter 12, a sample holder 13, an analysis sample 14, a detector (SSD; Solid State Detectors) 15, a liquid nitrogen dewar 16, a preamplifier 17, and a spectroscopy amplifier. (Amplifier) 18 and Multi Channel Analyzer (MCA) 19 are provided. On the other hand, the element content determination apparatus 2 includes a computer (PC: Personal Computer) 20 and an output unit 21.

  The X-ray tube 11 generates, for example, an irradiation X-ray X1 that irradiates the analysis sample 14 by accelerating an electron beam at a high voltage to collide with the counter cathode. The filter 12 adjusts the irradiation X-ray X1 generated by the X-ray tube 11 to a distribution only in a predetermined wavelength range.

  The sample holder 13 fixes the position of the analysis sample 14. The analysis sample 14 is a sample for determining whether or not the specified element is contained by the element content determination system. By irradiating the analysis sample 14 with the irradiated X-ray X1 that has passed through the filter 12, fluorescent X-ray X2 corresponding to the contained element is emitted.

  The detector 15 detects the fluorescent X-ray X2 emitted from the analysis sample 14, and is cooled by the liquid nitrogen dewar 16 at that time. The fluorescent X-ray X2 signal detected by the detector 15 is amplified by the preamplifier 17 and the spectroscopic amplifier 18. These fluorescent X-ray X2 signals are aggregated as a dispersed spectrum waveform SI by the multi-channel analyzer 19, and the data is output to the element content determination device 2.

  The computer 20 has a function of determining whether or not the specified element is contained in the analysis sample 14 from the data of the dispersion spectrum waveform SI obtained by the measuring apparatus 1 as described above. That is, the computer 20 is a part that plays a central role in the element content determination apparatus 2 and incorporates an element content determination program according to the present invention. In addition, the determination result and the waveform SI of the dispersion spectrum are output to the output unit 21 including, for example, the display 21A and the storage medium 21B as shown in the figure, and the user can recognize the result. It can be done.

  In addition, the component which the measuring apparatus 1 and the element content determination apparatus 2 have is not restricted to what was shown in FIG. 1, It may replace with (or in addition to) these, and may contain another component.

  FIG. 2 is a functional block diagram showing a schematic configuration of the element content determination apparatus 2 in FIG.

  The elemental analysis inclusion determination apparatus 2 includes an input unit 201, a search unit 202, a calculation unit 203, a determination unit 204, and the output unit 21 as functional blocks. Here, the input unit 201, the search unit 202, the calculation unit 203, and the determination unit 204 are configured so that the computer 20 has the functions.

  The input unit 201 inputs the dispersion spectrum waveform SI from the measurement device 1. Further, as will be described later, the input unit 201 performs a predetermined smoothing process and a background subtraction process on the input dispersed spectrum waveform SI to derive a peak intensity calculation spectrum. The peak intensity calculation spectrum derived in this way is output to the search unit 202 and the output unit 21.

  Based on the peak intensity calculation spectrum input from the input unit 201, the search unit 202 designates whether to determine whether or not it is contained in a predetermined dispersion range (for example, a predetermined energy range) set in advance. The peak intensity for each predetermined peak of the element (for example, in the case of the fluorescent X-ray spectroscopy method, the line type of the predetermined fluorescent X-ray) is calculated, and the presence or absence of a desired peak waveform is searched for this predetermined peak. The peak intensity for the predetermined peak calculated in this way is output to the calculation unit 203, and the search result of the desired peak waveform is output to the determination unit 204.

  The calculation unit 203 calculates the concentration of the designated element contained in the analysis sample 14 from the peak intensity for the predetermined peak input from the search unit 202. The concentration is calculated by a calibration curve method, for example. The concentration of the designated element calculated from each predetermined peak in this way is output to the determination unit 204.

The determination unit 204 has a function of determining the following three points when determining whether or not the specified element is contained in the analysis sample, and leading a coping method based on the determination results. These coping methods are output to the output unit 21 so that the user can recognize them as described above. Details of the processing for making these determinations will be described later.
(A) The reliability of the peak intensity calculation result for a predetermined peak is determined based on the search result of the desired peak waveform input from the search unit 202. (B) Calculation of the concentration of the designated element input from the calculation unit 203 According to the result, in the analysis sample 14, the probability that the designated element is contained exceeding the predetermined reference concentration is judged. When (C) and (B) are judged that the probability that the designated element is contained exceeding the reference concentration is high, Furthermore, in this predetermined peak, the probability that peak waveforms due to other different elements are superimposed is judged.

  In addition, the functional block with which element content determination apparatus 2 is provided is not restricted to what was shown in FIG. 2, You may comprise so that another functional block may be provided.

  Next, the operation of the element content determination system configured as described above will be described.

  FIG. 3 shows the entire process of the element content determination method according to the present embodiment. With reference to this figure, the flow of the whole process of the element content determination method will be described first.

  First, the measuring apparatus 1 measures the dispersion spectrum waveform SI in the analysis sample 14 (step S10), and outputs the data to the input unit 201 of the element content determination apparatus 2. Next, the input unit 201 performs predetermined smoothing processing and background subtraction processing on the dispersion spectrum waveform SI to derive a peak intensity calculation spectrum (step S11), and the search unit 202 and the output unit 21 search for the spectrum. Output to.

  Next, the search unit 202 calculates the peak intensity for the predetermined peak of the specified element in the predetermined dispersion range based on the peak intensity calculation spectrum, and searches for the presence or absence of a desired peak waveform. Then, the determination unit 204 determines the reliability of the peak intensity calculation result for a predetermined peak from the search result of the desired peak waveform input from the search unit 202 (step S12), and outputs a coping method based on the determination result. To the unit 21.

  Next, the calculation unit 203 calculates the concentration of the designated element contained in the analysis sample 14 from the peak intensity for the predetermined peak input from the search unit 202 (step S20), and determines the calculated concentration of the designated element. Output to the unit 204.

  Next, the determination unit 204 first determines the probability that the specified element contains in the analysis sample 14 in excess of a predetermined reference concentration based on the calculation result of the concentration of the specified element (step S21). If the determination unit 204 determines that the probability that the specified element is contained exceeding the reference concentration is high, the determination unit 204 determines the probability that peak waveforms due to other different elements are superimposed on the predetermined peak (step S22). . The coping method based on these determination results is also output to the output unit 21. As described above, the entire process of the element content determination method is completed.

  Next, details of each process will be described.

  First, FIG. 4 shows details of processing for deriving a peak intensity calculation spectrum in FIG. The details of the processing for deriving the peak intensity calculation spectrum will be described with reference to this figure.

  First, as described above, the input unit 201 inputs the dispersion spectrum waveform (raw data) SI from the measurement apparatus 1 (step S111). Then, the input unit 201 determines whether or not the user is set to perform a predetermined smoothing process (step S112). If it is set, a predetermined smoothing process is performed on the dispersion spectrum waveform SI (step S113). If it is not set, this process is skipped and the process proceeds to the next process.

  For the smoothing calculation, for example, the Savitzky-Golay method (A. Savitzky and M.J.E.Golay: Anal. Chem. 36, (1964) 1627., Numerical Recipes in C ++ Second Edition (2002) 655.) can be used. However, if the smoothing process can be performed without degrading the spectrum quality, it can be substituted, and is not necessarily limited to the Savitzky-Golay method. Data at the stage where smoothing processing has been performed as necessary (referred to as spectrum data A) is internally recorded, for example, in a memory (not shown) in the computer 20 (step S114).

  Next, the input unit 201 performs background spectrum extraction processing from the spectrum data A (step S115). The background spectrum is obtained by background estimation calculation that connects valleys of the spectrum signal. For example, the Sonneveld-Visser method (EJSonneveld and JWVisser: J. Appl. Cryst. 8, (1975)). 1. The Rigaku Journal Vol.2 / No.2 / 1985) can be used. However, any method that can obtain a reasonable background spectrum can be substituted, and the method is not necessarily limited to the Sonneveld-Visser method. Similarly, the background spectrum extracted from the spectrum data A (referred to as background spectrum B) is recorded internally in, for example, a memory (not shown) in the computer 20 (step S116).

  Note that the background spectrum B corresponds to noise corresponding to noise to be canceled without being included in the signal intensity. Therefore, next, the input unit 201 subtracts the background spectrum B corresponding to the same dispersion value (for example, energy) from the spectrum data A (step S117), and the peak intensity calculation spectrum corresponding to the net signal. Get C. Similarly, the peak intensity calculation spectrum C obtained by this subtraction is internally recorded, for example, in a memory (not shown) in the computer 20 (step S118).

  Then, the input unit 201 outputs the peak intensity calculation spectrum C to the search unit 202 and the output unit 21 (step S119), and the processing for deriving the peak intensity calculation spectrum ends.

  Next, FIG. 5 shows details of processing for determining the reliability of the peak intensity calculation result for the predetermined peak in FIG. With reference to this figure, the detail of the process which judges the reliability of the peak intensity calculation result is demonstrated.

  First, the search unit 202 inputs the peak intensity calculation spectrum C from the input unit 201 (step S121), and internally records it in, for example, a memory (not shown) inside the computer 20 (step S122).

  Next, when determining the reliability of the peak intensity calculation result for a predetermined peak, the input unit 201 searches for the presence or absence of a desired peak waveform for the predetermined peak. That is, the presence / absence of an appropriate peak waveform is searched in a predetermined dispersion range. Hereinafter, as an example of this search method, a method of comparing the peak intensities at the center and the end of the dispersion range in a predetermined dispersion range will be described.

  First, the search unit 202 extracts the signal intensity in the channel at the center of a predetermined dispersion range (that is, a part where a predetermined peak is estimated to exist) (step S123), and uses the intensity (set as intensity P). For example, it is internally recorded in a memory (not shown) inside the computer 20 (step S124). Similarly, the search unit 202 extracts signal intensities in the channels at the lower end and the upper end of the predetermined dispersion range (steps S125 and S127), and uses these intensities (intensities L and H) in the computer 20 for example. Internal recording is performed in a memory (not shown) (steps S126 and S128).

  Next, the determination unit 204 determines the reliability of the peak intensity calculation result by comparing these intensities P, L, and H. Specifically, determination is made based on whether (P> L) and (P> H) (whether there is a desired (upwardly convex) peak waveform in a predetermined dispersion range) (step S129).

  When the above conditions are satisfied, a desired peak waveform exists in a predetermined dispersion range, so that the peak intensity calculation result of the predetermined peak in this dispersion range is determined to be reliable, and peak intensity calculation is performed. The process for determining the reliability of the result ends.

  On the other hand, when the above conditions are not satisfied, the desired peak waveform does not exist in the predetermined dispersion range, and thus the peak intensity calculation result of the predetermined peak in this dispersion range can be said to be reliable. It is determined that there is not, and the fact is derived (step S130). Then, the output unit 21 outputs the contents set in advance to be output when the peak intensity calculation result is not sufficiently reliable in this way (step S131), and informs the user of the coping method and the like. In this case, the entire process of the element content determination method is completed, and the user will examine the coping method output to the output unit 21.

  Here, the method of comparing the peak intensities at the center and the end of the dispersion range in the predetermined dispersion range when searching for the presence or absence of a reasonable peak has been described, but of course it is not limited to this. Any method can be used as long as it can be confirmed that there is a reasonable peak (convex upward) with the central portion at the apex. For example, the differential value of this dispersion spectrum is calculated and the fact that the differential value becomes zero at the peak apex is used, or the curvature in this dispersion range is calculated and information on whether the curve is convex upward is used. It is also possible to do.

  FIG. 6 shows an example of the output contents based on the determination result by the process of FIG. 5, and shows the dispersion spectrum data obtained by the energy dispersion fluorescent X-ray analysis method. Specifically, a mode is shown in which the dispersion spectrum waveform 211 and the content 212 of the coping method based on the determination result are output on the screen of the output unit 21A (display) in the element content determination apparatus 2. Further, as shown in the figure, the upper and lower two waveforms are output as the dispersion spectrum waveform 211, and the lower waveform shows a part of the upper waveform (the region where the energy is 10 to 13 keV) is enlarged. Yes. In the dispersion spectrum waveform 211, the above-described spectrum data A (raw data) is indicated by a solid line, the background spectrum B is indicated by a broken line, and an actual peak intensity calculation spectrum C is obtained by subtracting B from A. is there. In this example, the analysis sample containing bismuth (Bi) represents the case where the presence or absence of the specified element as lead (Pb) is determined. Also, the output contents based on the determination result are not limited to those shown in this figure, and can be arbitrarily set according to the purpose and application of the user.

  The data of the dispersion spectrum waveform obtained by the fluorescent X-ray analysis method has a predetermined interval (for example, a set of data of energy and peak intensity corresponding to this energy over a predetermined range (for example, 0 to 40.96 keV)). For example, 0.02 keV) and a predetermined number of sets (for example, 2048 channels in this case) are arranged.

  Here, a predetermined peak in the dispersion spectrum waveform is used as two fluorescent X-ray line types of a PbLα ray (10.56 keV) and a PbLβ ray (12.62 keV). Centering on these predetermined peaks, the predetermined dispersion ranges for calculating the concentration of the designated element by the calibration curve method are, for example, (10.36 to 10.76 keV) and (12.42 to 12.2. 82 keV). In FIG. 6, these predetermined dispersion ranges 213A (for PbLα) and 213B (for PbLβ) are distinguished from other regions and are clearly shown.

  Here, Bi has an atomic number different from that of Pb, and the fluorescent X-ray signal also appears at an energy position close to Pb. Specifically, they are BiLα line (10.84 keV) and BiLβ line (13.02 keV), but since there is a peak width of about 0.4 keV, the conventional calibration curve method particularly calculates the intensity for PbLα line ( It is inevitable that the predetermined dispersion range affects 10.36 to 10.76 keV).

  Actually, when the dispersion spectrum waveform 211 shown in FIG. 6 is viewed, an appropriate peak waveform cannot be visually recognized at the positions of the PbLα line and the PbLβ line, but the difference between the solid line and the broken line corresponding to the peak intensity calculation spectrum C is Since there is a considerable degree in the predetermined dispersion range 213A used for calculating the intensity of the PbLα ray, the quantitative result of Pb by the calibration curve method has become a very large value of 5742.439 ppm. In such a case, of course, this quantitative value is not appropriate, and a definitive conclusion that “Pb is contained in the analysis sample” cannot be drawn from this number.

  On the other hand, the conclusion that “Pb of the reference concentration is not contained” cannot be guaranteed from this dispersion spectrum waveform. Therefore, the conclusion to be derived from this dispersion spectrum waveform is that “the line type in this analytical sample is not sufficiently reliable in the peak intensity calculation result”. Although it should be based on other measurement methods, such a conclusion cannot be drawn by looking only at the concentration calculated by the calibration curve method.

  Even in such a case, according to the element content determination method in the present embodiment, the difference between the solid line and the broken line corresponding to the peak intensity calculation spectrum C at the upper end (10.76 keV) in the predetermined dispersion range is Since the difference is larger than the difference in the central portion (10.56 keV), it is determined that there is no appropriate peak waveform as the line type, and “the concentration of the designated element is calculated for the line type in the analysis sample. It is possible to draw a conclusion that the peak intensity calculation result that is a prerequisite for this is not sufficiently reliable.

  Based on this, as shown in Fig. 6, "There is a high possibility that the tail of the peak signal of other elements is picked up" and "Please confirm the lead content by ICP-AES" A more specific coping method can be derived and the output unit 21 can recognize the user. The output content may be a flag representing a logical type (true or false).

  Thereby, for example, in the above case, even if there is an influence derived from Bi, it is possible to prevent the erroneous conclusion that “Pb is contained” from only the fluorescent X-ray analysis.

  FIG. 7 shows details of processing for calculating the concentration of the designated element in FIG. Details of the processing for calculating the concentration of the designated element will be described with reference to this figure. This process is based on the case where it is determined in step S129 of FIG. 5 that the peak intensity calculation result of a predetermined peak in a predetermined dispersion range is reliable.

  First, the calculation unit 203 inputs the peak intensity calculation spectrum C (step S201), and internally records it in, for example, a memory (not shown) inside the computer 20 (step S202). Next, the calculation unit 203 extracts a predetermined peak used for calculating the concentration of the designated element from the peak intensity calculation spectrum C. For example, the concentration of the designated element is determined by the first peak and the second peak. Is calculated (steps S203 and S205), and these (C1 and C2) are similarly recorded in, for example, a memory (not shown) in the computer 20 (steps S204 and S206). As described above, the processing for calculating the concentration of the designated element is completed. FIG. 7 shows an example in which the predetermined peak is composed of two peaks, the first peak and the second peak. However, the number of the predetermined peaks is not limited to this, and the user's purpose and It can be set arbitrarily according to the application. The same applies to the following description.

  FIG. 8 shows the details of the process of determining the probability that the specified element in FIG. 3 contains exceeding the reference concentration. With reference to this figure, the detail of the process which judges the probability that a designated element contains exceeding a standard concentration is demonstrated.

  First, the determination unit 204 determines whether or not the peak intensities of the predetermined peaks all exceed the reference concentration. That is, in the example of FIG. 7, whether or not both the concentration C1 of the designated element calculated by the first peak and the concentration C2 of the designated element calculated by the second peak exceed the reference concentration ( Whether (C1> reference density) and (C2> reference density) is determined (step S211).

  This is because the peak waveform is not necessarily generated only in one kind of element (that is, the designated element) in the predetermined dispersion range. For example, in the example shown in FIG. 6, in the Pb content determination, there is an element that produces a peak waveform that overlaps almost the same energy as the PbLα ray (10.56 keV), so only one dispersion range (energy range) is included. Attention has been paid to the fact that peak waveforms of other different elements are superposed, which may be mistaken.

  With respect to this problem, for example, in Patent Document 3 described above, a plurality of line types emitted from one designated element are focused, and the intensity spectrum is assumed to coincide with the theoretically derived intensity ratio. Since the concentration of the specified element is calculated so as to meet the above, the above misidentification can be avoided.

  However, as disclosed in the same document, there arises a problem that processing becomes complicated when simultaneous equations are solved by calculation or approximation by Gaussian function is required. This is because, as described above, an attempt is made to conclude an accurate content only from the fluorescent X-ray spectrum. In this case, the calculated concentration of the specified element alone can be used to determine whether a definitive conclusion has been clearly derived from the obtained spectrum data, or a spectrum that is difficult to analyze. It is not possible to obtain information such as

  Therefore, in the element content determination method according to the present embodiment, the probability that the specified element contains more than the reference concentration is determined depending on whether the peak intensities of the plurality of peaks all exceed the reference concentration as described above. .

  Returning to the description of FIG. 8, when the above condition is satisfied in step S211, the determination unit 204 determines that the probability that the specified element is contained exceeding a predetermined reference concentration is high, and derives that fact (step S212). . Then, the output unit 21 outputs the contents set in advance to be output when the probability that the specified element is contained exceeding the reference concentration is high (step S213), and informs the user of that fact. Thereby, the process which judges the probability that the designated element contains exceeding the reference concentration is completed.

  On the other hand, if the above condition is not satisfied in step S211, the determination unit 204 determines that the probability that the specified element is contained exceeding the predetermined reference concentration is not high, and derives that fact (step S211). S214). Then, the output unit 21 outputs contents set in advance to be output when the probability that the specified element is contained in excess of the reference concentration is not high (step S215). To inform. In this case, the entire process of the element content determination method is completed, and the user will examine the coping method output to the output unit 21.

  Note that the output content in steps S213 and S215 may be a flag indicating a logical type (true or false).

  In this way, when the specified element does not contain, if we focused only on the dispersion range where a certain predetermined peak exists, the peak waveform by another different element is superimposed, Even if there is a possibility that the concentration of an element may be calculated incorrectly, the determination is also made using the concentration calculated from other predetermined peaks, so it is possible not to erroneously derive a definitive conclusion. it can.

  Conversely, if the specified element clearly contains more than the reference concentration, a calculation result exceeding the reference concentration can be obtained in any dispersion range where the specified peak exists. It is possible to derive a correct conclusion that “the probability of containing the content exceeds that” is high.

  FIG. 9 shows details of processing for determining the probability that peak waveforms due to other different elements in FIG. 3 are superimposed. With reference to this figure, the detail of the process which judges the probability that the peak waveform by another different element has overlapped is demonstrated. This process is premised on the case where it is determined in step S211 of FIG. 8 that there is a high probability that the specified element is contained exceeding a predetermined reference concentration.

  First, the determination unit 204 compares a plurality of calculated densities with each other, and determines whether the ratio of these calculated densities exceeds a predetermined reference range. That is, in the example of FIG. 7, it is determined whether or not the ratio between the concentration C1 of the designated element calculated by the first peak and the concentration C2 of the designated element calculated by the second peak is equal to or greater than the reference range. Judgment is made (step S221).

  This is because in Steps S211 to S213, for all of the plurality of predetermined peaks, the calculated concentration of the designated element exceeds the predetermined reference value, so that “the specified element is contained exceeding the predetermined reference concentration. Although this conclusion itself is reasonable, the calculated concentration of the specified element is the standard because the peak waveforms of other different elements are superimposed on some of the peaks. This is because there is a probability that the concentration is exceeded.

  For example, if the calculated concentration ratio exceeds a predetermined reference range (for example, the concentration calculated from the PbLα line is about 600 ppm and the concentration calculated from the PbLβ line is 250 ppm), the position of the PbLα line It is considered that there is a high probability that peak waveforms due to other different elements are partially superimposed with an intensity corresponding to about 350 ppm.

  Therefore, in the element content determination method according to the present embodiment, in order to prevent unnecessary misunderstanding and confusion for the user because the ratio of the calculated concentration is large in such a case, the ratio of these calculated concentrations is predetermined. Determine whether the reference range is exceeded.

  Returning to the description of FIG. 8, when the ratio of the calculated concentrations does not exceed the predetermined reference range in step S221, the determination unit 204 determines that the probability that peak waveforms due to other different elements are superimposed is low. This completes the process of determining the probability that peak waveforms due to other different elements are superimposed, and the entire process of the element content determination method is also completed. As a result, the user can recognize that “the probability that the specified element is contained in the analysis sample is high and the peak waveform of other different elements is superimposed is low”.

  On the other hand, if the calculated concentration ratio exceeds the predetermined reference range in step S221, the determination unit 204 determines that there is a high probability that peak waveforms due to other different elements are superimposed, and derives that effect ( Step S222). Then, the output unit 21 overwrites or outputs in parallel the previously set contents to the output contents when there is a high probability that peak waveforms due to other different elements are superimposed (step S223). Let us know how to deal with it. In this case, the entire process of the element content determination method is completed, and the user examines the coping method output to the output unit 21.

  Thus, for example, “There is a high probability that peak waveforms due to other different elements are superimposed, but since it is certain that the specified element contains more than the reference concentration, verification by ICP-AES or the like is not necessary.” Or, it is certain that the specified element contains more than the standard concentration, but please verify with ICP-AES etc. to obtain an accurate concentration. It is possible to derive and output an appropriate coping method.

  In this way, a definitive conclusion can be drawn on the presence or absence of the specified element, and there is no other different element that causes a problem. Judgment and other verification techniques such as ICP-AES can be omitted. Further, when the output unit 21 outputs the contents, it can be shown to the user.

  Note that the output content in step S223 may be a flag indicating a logical type (true or false).

  As described above, according to the element content determination method, program, apparatus, and system of the present embodiment, the peak intensity is calculated and the presence or absence of a desired peak waveform is determined for a predetermined peak of a specified element in a predetermined dispersion range. Since the search is performed and the reliability of the peak intensity calculation result for the predetermined peak is determined based on the search result, an erroneous determination is made when determining the presence or absence of the specified element in the analysis sample. It is possible to easily obtain a determination result with high reliability. In addition, when it is determined from this search result that the peak intensity calculation result is not reliable, a coping method based on the search result is derived, so that the user can recognize the specific coping method and easily This can be taken.

  Thereby, for example, in a predetermined dispersion range (for example, energy range), the integrated value of the difference (peak intensity calculation spectrum C) between the dispersion spectrum waveform and the background is larger than the reference value, and the concentration of the designated element is true. Even if it is calculated to be larger than the concentration, it can be determined that “the peak intensity calculation result used to calculate the concentration is not sufficiently reliable”. Therefore, for example, in an analysis sample containing Bi but not containing Pb, even if there is an influence derived from Bi, an error such as “Pb is contained” immediately from the calculated concentration result. Judgment can be prevented.

  In addition, according to the element content determination method, program, apparatus, and system of the present embodiment, the presence or absence of a desired peak waveform is searched for each of a plurality of predetermined peaks, and an appropriate peak waveform is found from any of these search results. If it is determined, the concentration of the specified element for each peak is calculated from the peak intensities for the multiple peaks, and these multiple calculated concentrations are compared with the specified reference concentration, respectively. Since the probability that an element is contained in excess of the standard concentration is judged, there is a possibility that the concentration of the specified element may be erroneously calculated if focusing only on the dispersion range in which a certain predetermined peak exists However, since we decided to use the concentration calculated from other predetermined peaks, we should not accidentally draw a definitive conclusion. It can be.

  Conversely, if the specified element clearly contains more than the reference concentration, the calculation results exceeding the reference concentration can be obtained in any dispersion range where the specified peak exists. It is possible to derive a correct conclusion that “the probability of containing the content exceeds that” is high.

  In addition, with this configuration, for example, even a measurer who is not familiar with X-ray fluorescence analysis technology derives reliable judgment results without overlooking the possibility of false detection and making erroneous judgments. can do. In particular, for example, even when a large number of measurement results are processed together to create a result list, the content of the specified element is deterministic rather than simply using the calculated concentration as it is. Therefore, it is not necessary to transfer an analytical sample that can be used to derive a definitive conclusion to another analytical method such as the ICP-AES method. Can be reduced. On the other hand, for analytical samples for which a definitive conclusion could not be derived, if another definitive conclusion is made using another analytical method with excellent measurement accuracy, only subtle dispersion spectrum waveform data can be obtained. Based on the above, it is possible to eliminate the possibility of deriving an incorrect conclusion.

  In addition, according to the element content determination method, program, apparatus, and system of the present embodiment, when it is determined that there is a high probability that the specified element contains more than the reference concentration, a plurality of calculated concentrations are compared with each other, Depending on whether the ratio of these calculated concentrations exceeds the specified reference range, the probability that peak waveforms due to different elements are superimposed on the peak waveform determined to be reliable is determined. Even if it is clear that the element contains more than the reference value, if there is a possibility that the calculated concentration is partially affected by interfering elements, this will cause unnecessary misunderstanding and confusion to the user. It is possible to prevent such a situation and to take countermeasures as necessary. For example, a measurer who is not familiar with X-ray fluorescence analysis technology should be asked to turn to another analysis method so as not to take a false response only with the fact that it contains and the calculated concentration value. Also good.

  As described above, according to the element content determination method, program, apparatus, and system of the present embodiment, when a definitive conclusion can be drawn from the data of the dispersion spectrum waveform obtained by a specific analysis method, the determination result is clearly indicated. As a result, verification work by other methods can be omitted. In addition, when a problem remains, such as when a definitive conclusion cannot be made, or when the concentration of the specified element can be concluded but the concentration cannot be determined, it is not necessary to derive a conclusion, Even if a measurer who is not familiar with measurement technology does not make a wrong decision by deriving a countermeasure that indicates whether a problem has occurred and recommends the use of other measurement methods such as ICP-AES. It is possible to select an appropriate response.

[Second Embodiment]
In the element content determination method according to the first embodiment, the concentration is calculated for each of two or more peaks generated from the specified element, and the specified element is contained when both of the concentrations exceed a predetermined reference concentration. It was judged that there was a high probability of However, in the element content determination method according to the first embodiment, the user needs to calculate the concentration of each of the plurality of peaks individually. The element content determination method in the present embodiment reduces the burden on the user by omitting some of these operations, and calculates the concentration only for some of the peaks, and has almost the same reliability as the first embodiment. The probability that the specified element contains can be judged with the property. In order to simplify the description, the same parts as those in the first embodiment will be described below with the same reference numerals. In addition, the overall configuration of the element content determination system and the functional block diagram of the element content determination device in the present embodiment are the same as those shown in FIGS. 1 and 2 in the first embodiment, so the description thereof will be omitted. Omitted.

  FIG. 10 shows the entire process of the element content determination method according to the present embodiment. With reference to this figure, the flow of the whole process of the element content determination method will be described first. The overall processing flow of the element content determination method in the present embodiment is basically the same as that in FIG. 3 in the first embodiment, and a part of the description is omitted.

  First, the dispersion spectrum waveform SI is measured as in the first embodiment (step S10). Next, a predetermined smoothing process and background subtraction process are performed on the dispersion spectrum waveform SI to calculate peak intensity. A spectrum is derived (step S11).

  Next, similarly to the first embodiment, based on the peak intensity calculation spectrum, the peak intensity for the predetermined peak of the specified element in the predetermined dispersion range is calculated, and the desired peak waveform Search for existence. Then, the reliability of the peak intensity calculation result for the predetermined peak is determined from the search result of the desired peak waveform (step S12), and a countermeasure method based on the determination result is output.

  Next, the calculation unit 203 selects the specified element contained in the analysis sample 14 only for at least one of the peaks determined to be reliable from the peak intensity for the predetermined peak input from the search unit 202. The density is calculated (step S30). That is, the concentration is not calculated for the remaining peaks among the peaks determined to be reliable. In this manner, the calculation unit 203 outputs the concentration of the designated element calculated from only at least one peak and the peak intensity for other peaks to the determination unit 204.

  Next, the determination unit 204 first determines that the specified element in the analysis sample 14 has a predetermined reference based on the concentration of the specified element calculated from only at least one peak and the peak intensity of the other peak, as in the first embodiment. The probability of containing exceeding the concentration is judged (step S31). If the determination unit 204 further determines that the probability that the specified element is contained exceeding the reference concentration is high, the peak waveform of another predetermined element is superimposed on the predetermined peak as in the first embodiment. The probability of being present is determined (step S32). A coping method based on these determination results is output to the output unit 21. As described above, the entire process of the element content determination method is completed.

  Next, details of each process will be described. The details of step S11 (derivation of the peak intensity calculation spectrum) and step S12 (determining the reliability of the peak intensity calculation result for a predetermined peak) are the same as those in the first embodiment. Description is omitted.

  FIG. 11 shows details of processing for calculating the concentration of the designated element in FIG. Details of the processing for calculating the concentration of the designated element will be described with reference to this figure. Similar to the first embodiment, this process is based on the case where it is determined in step S129 in FIG. 5 that the peak intensity calculation result of a predetermined peak in a predetermined dispersion range is reliable.

  First, as in the first embodiment, the calculation unit 203 inputs the peak intensity calculation spectrum C (step S301), and internally records it in, for example, a memory (not shown) inside the computer 20 (step S302). Next, the calculation unit 203 extracts at least one peak used for calculating the concentration of the designated element from the peak intensity calculation spectrum C, and calculates the concentration of the designated element using, for example, the first peak. (Step S303).

  Here, in the element content determination method according to the present embodiment, the peak having the highest sensitivity under normal measurement conditions is selected from the predetermined peaks (for example, fluorescent X-ray line types) generated from the designated element. Is desirable. In this case, even when there is a probability that peak waveforms due to other different elements are superimposed on the same dispersion position (for example, energy position), this peak can be used. This is because if the concentration of the designated element calculated using this peak exceeds a predetermined reference value (step S32), the validity of this peak intensity (probability that peak waveforms of other different elements are superimposed) will be shown later. It is because it judges.

  On the other hand, when there is a possibility that the peak may be buried in the background due to the bottom of the peak waveform caused by another different element, it is desirable to avoid selecting this peak.

  For example, when Pb is a designated element as in the example shown in FIG. 6, the PbLα line and the PbLβ line have almost the same peak intensity, and both can be candidates in this respect, but for the following reasons, PbLα It is desirable to select a line.

  The first reason is that the energy in the PbLβ line depends on the measurement conditions of the apparatus used even when there is no peak waveform in the vicinity (for example, the case of the dispersive spectrum waveform of FIG. 16 described later). This is because the range has a higher background level than the energy range in the PbLα ray and may be buried.

  The second reason is that, for example, in the presence of bromine (Br) contained as a flame retardant in plastics, the peak waveform of the PbLβ line is that of the Br Kα line (11.92 keV) and Kβ line (13.30 keV). This is because the peak waveform of the PbLβ line may be buried even if the peak waveform of the PbLβ line appears because it falls between strong peak waveforms.

  When Pb is the designated element in this way, the concentration of the designated element is calculated using the PbLα ray (10.56 keV) (for example, calculated by the measurement line method), and the Pb concentration calculated from the PbLα ray is a predetermined standard. When the concentration is exceeded, the PbLβ ray (12.62 keV) is examined.

  Returning to the description of FIG. 11, in step S303, the concentration (designated as C1) of the designated element calculated from the first peak and the peak intensity (designated as P1) of this first peak are similarly set in the computer 20, for example. Internal recording is performed in a memory (not shown) (step S304). Next, the concentration of the designated element is not calculated from the second peak, and the second peak is extracted (step S305) and its intensity (P2) is stored in a memory (not shown) in the computer 20 for example. Recording is performed (step S306). As described above, the processing for calculating the concentration of the designated element is completed. FIG. 11 shows an example in which the predetermined peak is composed of two peaks, the first and second peaks. However, the number of the predetermined peaks is not limited to this, and the user's purpose and It can be set arbitrarily according to the application. The same applies to the following description.

  FIG. 12 shows the details of the process of determining the probability that the specified element in FIG. 10 contains exceeding the reference concentration. With reference to this figure, the detail of the process which judges the probability that a designated element contains exceeding a standard concentration is demonstrated.

  First, the determination unit 204 is estimated from a predetermined reference concentration, the concentration C1 of the designated element calculated from the first peak, the peak intensity P2 of the second peak, and the peak intensity P1 of the first peak. Using the value of the estimated peak intensity of the second peak, the probability that the specified element is contained exceeding the reference concentration is determined. Specifically, determination is made based on whether or not the conditions of (C1> reference concentration) and (P2> (estimated peak intensity of the second peak × reference concentration / C1)) are satisfied (step S311).

  If the above condition is satisfied in step S311, the determination unit 204 determines that there is a high probability that the specified element is contained in excess of a predetermined reference concentration, as in the first embodiment, and derives that effect (step S311). S312). Then, the output unit 21 outputs the contents set in advance to be output when the probability that the specified element is contained exceeding the reference concentration is high (step S313), and informs the user of that fact. Thereby, the process which judges the probability that the designated element contains exceeding the reference concentration is completed.

  On the other hand, if the above condition is not satisfied in step S311, the determination unit 204 cannot be said to have a high probability of containing the specified element exceeding the predetermined reference concentration, as in the first embodiment. Judgment is made and the fact is derived (step S314). Then, the output unit 21 outputs the contents set in advance to be output when the probability that the specified element is contained in excess of the reference concentration is not high (step S315), and the countermeasure method is given to the user. To inform. In this case, the entire process of the element content determination method is completed, and the user will examine the coping method output to the output unit 21.

  Note that the output content in steps S313 and S315 may be a flag indicating a logical type (true or false).

  In this way, it is possible to determine the probability that the designated element contains with almost the same reliability as that of the first embodiment, by calculating the concentration only for some of the peaks.

  Here, a specific determination method will be described with respect to an example in which it is determined that the probability that the specified element is contained exceeding the reference concentration is high. 6 shows an example in which the designated element is Pb as shown in FIG. 6. When an analysis sample containing only Pb is measured under this measurement condition, the PbLα line (10.56 keV) and the PbLβ line (12. The peak intensity ratio of 62 keV) is approximately 1: 1.

  In the measurement result of this analytical sample, for example, the Pb concentration calculated from the PbLα ray is about 600 ppm, and the peak intensity of the PbLβ ray is 5/12 times the peak intensity of the PbLα ray. The reference concentration is assumed to be 200 ppm. The determination method and result in this case are as follows.

  First, if the Pb concentration calculated from the PbLα ray is about 600 ppm and Pb is truly included in this concentration, the peak intensity of the PbLβ ray at this time should be almost the same as the peak intensity of the PbLα ray. Although there is actually, it is 5/12 times as described above. However, considering the value of (reference concentration / calculated designated element concentration) times this is (200 ppm (reference concentration) / 600 ppm (calculated designated element concentration)), the peak intensity of the PbLβ line is This is equivalent to 1/3 (= 4/12) times the peak intensity of the PbLα ray. Therefore, since the actual peak intensity of the PbLβ ray is 5/12 times as described above and exceeds 4/12 times, “the designated element (Pb) has a predetermined reference concentration (200 ppm). It is possible to derive a determination result that “the probability of containing the content is high”.

  In this case, however, the peak position due to different elements other than the true PbLα ray is superimposed on the dispersion position (energy position) of the PbLα ray, so that it becomes larger than the true value (intensity equivalent to 600 ppm). It is thought that. Thus, since the actual Pb concentration was 250 ppm, the peak intensity corresponding to 250/600 = 5/12 times was obtained at the dispersion position (energy position) of the PbLβ ray, but this intensity and (200 ppm (reference concentration ) / 600 ppm (calculated concentration of the specified element)) = 4/12 times the peak intensity calculated as equivalent to the peak intensity of the PbLβ line in the measurement result, so at least at the reference concentration It is possible to derive a judgment result that the content exceeds 200 ppm.

  FIG. 13 shows an example of output contents based on the determination result obtained by the process of FIG. As in the case of FIG. 6, an example in which the designated element is Pb is shown.

  In this example, the Pb concentration calculated from the PbLα ray outputs a result of 266.266 ppm. However, the existence of an appropriate peak waveform cannot be confirmed for the PbLβ ray, and as a result, the peak intensity for the PbLβ ray is determined. This means that the calculation result is not sufficiently reliable, and as a result, in this fluorescent X-ray analysis, it cannot be said that “the probability that the specified element is contained exceeding a predetermined reference concentration is high”. Therefore, as shown in the figure, “Please turn to ICP-AES analysis. It seems that other interfering elements are affecting the measurement results. The lead concentration calculated by the device exceeds 200 ppm, but the Pbβ The peak intensity at the position is very small or cannot be confirmed. Please measure the lead content by lead ICP-AES measurement and output it to encourage the user to respond appropriately. It is.

  FIG. 14 shows details of a process for determining the probability that peak waveforms due to other different elements in FIG. 10 are superimposed. With reference to this figure, the detail of the process which judges the probability that the peak waveform by another different element has overlapped is demonstrated. This process is premised on the case where it is determined in step S311 of FIG. 12 that the probability that the specified element is contained exceeding a predetermined reference concentration is high.

  First, the determination unit 204 compares the actual peak intensity with the estimated peak intensity for each peak not used for calculating the concentration of the designated element, and the ratio of these peak intensities exceeds a predetermined reference range. Depending on whether or not, the probability that peak waveforms due to other different elements are superimposed is judged. That is, in the example of FIG. 11, it is determined whether or not the ratio between the second peak intensity estimated from P1 and the actual peak intensity P2 of the second peak is greater than or equal to the reference range (step S321). .

  This is because, in the first embodiment, the concentration of the designated element is calculated from a plurality of predetermined peaks, and the ratio of these calculated concentrations is used as a judgment material, “probability that peak waveforms due to other different elements are superimposed”. However, in the present embodiment, the concentration of the designated element may be calculated from only one predetermined peak. In such a case as well, the case is the same as in the first embodiment. It is possible to make a judgment.

  Here, if the peak intensity ratio does not exceed the predetermined reference range in step S321, the determination unit 204 determines that the probability that peak waveforms of other different elements are superimposed is low. This completes the process of determining the probability that peak waveforms due to other different elements are superimposed, and the entire process of the element content determination method is also completed. As a result, the user can recognize that “the probability that the specified element is contained in the analysis sample is high and the peak waveform of other different elements is superimposed is low”.

  On the other hand, if the peak intensity ratio exceeds the predetermined reference range in step S321, the determination unit 204 determines that there is a high probability that peak waveforms of other different elements are superimposed, and derives that effect ( Step S322). Then, the output unit 21 overwrites the output contents so far or outputs in parallel the contents set in advance to output when there is a high probability that peak waveforms due to other different elements are superimposed (step S323). Let us know how to deal with it. In this case, the entire process of the element content determination method is completed, and the user will examine the coping method output to the output unit 21.

  Here, for example, taking the numerical values shown in the specific example in FIG. 12 as an example, the peak intensity estimated from the calculated concentration for the “peak not used for calculating the concentration of the designated element”, that is, for the PbLβ line, is Although it can be estimated that it is equivalent to the peak intensity of the PbLα ray, it is actually only about 5/12 times, so the peak intensity ratio is 12: 5. If the reference range is less than twice the peak intensity ratio, in this example, the difference is greater than the reference range. Therefore, it is judged that there is a high probability that peak waveforms from other different elements are superimposed. Accordingly, it is possible to derive that fact and prompt the user to take an appropriate action.

  FIG. 15 shows an example of output contents based on the determination result obtained by the process of FIG. As in the case of FIGS. 6 and 13, an example in which the designated element is Pb is shown.

  As shown in the figure, the peak intensity at the position of the PbLα line is 0.024, whereas the peak intensity at the position of the PbLβ line is 0.011. The Pb concentration calculated from the PbLα ray is 851.033 ppm. Here, if Pb corresponding to this concentration is truly contained, the peak intensity is expected to be about 0.0244 even at the position of the PbLβ line, but in reality there is not so much peak intensity. However, since the signal intensity (0.011) at the PbLβ position exceeds 0.024 × (200/851) = 0.0006, it can be determined that Pb is contained.

  The “peak intensity estimated from the calculated concentration” can be estimated to be equivalent to the peak signal intensity of the PbLα ray, but is actually only 0.011 / 0.024 times. Therefore, if the reference range is within twice the peak intensity ratio, a difference greater than the reference range is generated in this example, so “there is a high probability that peak waveforms due to other different elements are superimposed”. It is judged and it is derived.

Furthermore, even if it is clear that lead is contained above the reference value, as shown in the figure, “ICP-AES” is intended to consider a countermeasure after obtaining reliable values.
Please turn to analysis. Lead and other interfering elements may be mixed. The lead concentration calculated by the equipment exceeds 200 ppm, but the peak at the position of PbLβ is a little small if all contributes to lead. Check the content of lead by ICP-AES measurement and output a countermeasure method that prompts the user to take appropriate measures.

  FIG. 16 shows another example of output contents based on the determination result by the processing of FIG. Note that, as in the case of FIGS. 6, 13, and 15, an example in which the designated element is Pb is shown.

  As shown in the figure, the peak intensity at the position of the PbLα line is 0.0077, whereas the peak intensity at the position of the PbLβ line is 0.0075. The Pb concentration calculated from the PbLα ray is 308.462 ppm. Here, if Pb corresponding to this concentration is truly contained, the peak intensity at the position of the PbLβ line is expected to be about 0.0077, and the peak intensity at the position of the PbLβ line is actually 0.0075. Because there is, it is almost as expected. Moreover, since this value is over 0.0077 * (200/308) = 0.0055, it can be determined that Pb is contained.

  Further, the “peak intensity estimated from the calculated concentration” can be estimated to be equivalent to the peak signal intensity of the PbLα ray, and is actually 0.075 / 0.077 times, so that it is within the reference range of 2 times. Yes. Therefore, in this example, it can be determined that the probability that Pb contains is high and the probability that peak waveforms due to other different elements are superimposed is low.

  Therefore, as shown in the figure, “Pb can be confirmed. The lead concentration calculated by the device from the peak at the PbLα position exceeds 200 ppm. As can be seen from the graph, the peak corresponding to the position of PbLβ is also shown. Therefore, it can be determined that lead can be determined without performing ICP-AES analysis. "

  As described above, according to the element content determination method, program, apparatus, and system of the present embodiment, the presence or absence of a desired peak waveform is searched for each of a plurality of predetermined peaks, and any of these search results is appropriate. When it is determined that there is a peak, when the calculated concentration of the specified element calculated for at least one of the peaks exceeds the specified reference concentration, it is estimated from the actual peak intensity for the at least one other peak and the calculated concentration Since the probability that the specified element is contained in the analysis sample in excess of the reference concentration is determined depending on whether or not the estimated peak intensity to be satisfied satisfies a predetermined relationship, a plurality of similar to the first embodiment, By using the predetermined peak of the determination, it is possible not to erroneously derive a definitive conclusion.

  Further, according to the element content determination method, program, apparatus, and system of the present embodiment, when it is determined that there is a high probability that the specified element is contained in excess of the reference concentration as described above, the actual at least one other peak is actually measured. The peak intensity of other elements is superimposed on the peak waveform that is judged to be reliable depending on whether the ratio of these peak intensities exceeds a predetermined reference range. As in the first embodiment, even if it is clear that the specified element contains more than the reference value, the calculated concentration is partially influenced by the interfering element. If there is a possibility, it is possible to prevent the user from causing unnecessary misunderstandings and confusion by informing the fact and to take countermeasures as necessary.

  Furthermore, according to the element content determination method, program, apparatus, and system of the present embodiment, the specified element can be obtained with almost the same reliability as that of the first embodiment by calculating the concentration only for some of the peaks. Since it is configured to be able to determine the probability of containing it, in addition to the effects in the first embodiment, it is not necessary to individually calculate the concentration for all peaks, and the burden on the user can be reduced. Become.

  The present invention has been described with reference to the first and second embodiments. However, the present invention is not limited to this, and various modifications can be made.

  For example, in the specific examples in these embodiments, the measurement apparatus 1 has been described as an example of an energy dispersive X-ray analyzer using an X-ray analysis technique. Any other configuration may be used as long as it can be obtained.

  Moreover, in these embodiments, the element content determination system designates the analysis sample from the measurement device 1 that obtains the dispersion spectrum waveform data from the analysis sample and the dispersion spectrum waveform data obtained by the measurement device 1. Although an example in which the element content determination device 2 is configured to determine whether or not an element is contained has been described, for example, the element content determination device 2 may be configured to have the function of the measurement device 1.

  FIG. 17 illustrates an example of the overall configuration in the case where the element content determination device 2 has the function of the measurement device 1 in the element content determination system of FIG. In this way, by providing the element content determination device 2 with the measurement unit 22 corresponding to the measurement device 1 described so far, this device alone can obtain the effects described above. It becomes possible. FIG. 18 is a functional block diagram showing a schematic configuration of the element content determination apparatus 2 in FIG. 17, but is the same as FIG. 2 except that the measurement unit 22 is added. Description is omitted.

  Further, in these embodiments, the determination of the reliability of the calculation result of the peak intensity (step S12), the determination of the probability that the specified element is contained exceeding the reference concentration (steps S21 and S31), and other different elements The determination of the probability that the peak waveforms are superimposed (steps S22 and S32) is configured to perform the processing in order. However, these processings are performed in parallel, and the output contents are logical ( It is also possible to use a flag representing whether the flag is true or false, and to make a final determination using a logical expression based on these flags. In this case, since the processes are performed in parallel, it becomes possible to make a quicker determination.

It is a block diagram showing an example of the whole structure of the element content determination system which concerns on the 1st Embodiment of this invention. It is a functional block diagram showing schematic structure of the element content determination apparatus in FIG. It is a flowchart showing the whole process of the element content determination method which concerns on the 1st Embodiment of this invention. 4 is a flowchart showing details of processing for deriving a peak intensity calculation spectrum in FIG. 3. FIG. 4 is a flowchart showing details of processing for determining the reliability of a peak intensity calculation result for a predetermined peak in FIG. 3. It is a figure showing an example of the output content based on the judgment result by the process of FIG. FIG. 4 is a flowchart showing details of processing for calculating the concentration of a designated element in FIG. 3. It is a flowchart showing the detail of the process which judges the probability that the designated element contains in FIG. 3 exceeding reference | standard concentration. FIG. 4 is a flowchart showing details of processing for determining a probability that peak waveforms due to other different elements in FIG. 3 are superimposed. It is a flowchart showing the whole process of the element content determination method which concerns on the 2nd Embodiment of this invention. 11 is a flowchart showing details of processing for calculating the concentration of a designated element in FIG. 10. It is a flowchart showing the detail of the process which judges the probability that the designated element contains in FIG. 10 exceeding reference | standard concentration. It is a figure showing an example of the output content based on the judgment result by the process of FIG. FIG. 11 is a flowchart showing details of processing for determining a probability that peak waveforms due to other different elements are superimposed in FIG. 10. It is a figure showing an example of the output content based on the judgment result by the process of FIG. It is a figure showing the other example of the output content based on the judgment result by the process of FIG. It is a block diagram showing an example in case the element content determination apparatus has a function of a measuring device in the element content determination system of FIG. It is a functional block diagram showing schematic structure of the element containing determination apparatus in FIG.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Measuring apparatus, 11 ... X-ray tube, 12 ... Filter, 13 ... Sample holder, 14 ... Analysis sample, 15 ... Detector, 16 ... Liquid nitrogen dewar, 17 ... Preamplifier, 18 ... Spectroscopy amplifier, 19 ... Multichannel Analyzer, 2 ... Element content determination device, 20 ... Computer, 201 ... Input unit, 202 ... Search unit, 203 ... Calculation unit, 204 ... Judgment unit, 21 ... Output unit, 22 ... Measurement unit, X1 ... Irradiation X-ray, X2 ... X-ray fluorescence, SI ... dispersion spectrum waveform.

Claims (47)

An element content determination method for determining the presence or absence of a specified element in an analysis sample from a dispersion spectrum waveform obtained by a specific analysis method,
A peak intensity is calculated for a predetermined peak of the specified element in a predetermined dispersion range, and the presence / absence of a desired peak waveform for the predetermined peak in the predetermined dispersion range is searched. Based on the search result, An element content determination method comprising: determining whether or not the peak intensity calculation result for the predetermined peak in a predetermined dispersion range is reliable. The element content determination method according to claim 1, wherein when it is determined from the search result that the peak intensity calculation result is not reliable, a coping method based on the search result is derived. The element content determination method according to claim 1, wherein the specific analysis method is an X-ray analysis method. The element content determination method according to claim 1, wherein the search for the presence or absence of the desired peak waveform is performed by comparing signal intensities in end and center channels in the predetermined dispersion range. The element content determination method according to claim 1, wherein the search for the presence or absence of the desired peak waveform is performed by calculating a differential value of a spectrum waveform in the predetermined dispersion range. The element content determination method according to claim 1, wherein the search for the presence or absence of the desired peak waveform is performed by calculating a curvature of a spectrum waveform in the predetermined dispersion range. When searching for the presence or absence of a desired peak waveform for each of a plurality of predetermined peaks, and determining that there is a reasonable peak waveform from any of these search results,
By calculating the concentration of the designated element for each peak from the peak intensity for the plurality of peaks, and comparing each of the plurality of calculated concentrations with a predetermined reference concentration, the designated element is contained in the analysis sample. The element content determination method according to claim 1, wherein the probability of content exceeding the concentration is determined. As a result of comparing each of the plurality of calculated concentrations and the reference concentration, if at least one calculated concentration is lower than the reference concentration, it is determined that the probability that the specified element is contained exceeding the reference concentration is not high. Then, a coping method based on the comparison result is derived. The element content determination method according to claim 7. The element content determination method according to claim 7 or 8, wherein the concentration of the designated element is calculated by a calibration curve method. When it is determined that there is a high probability that the designated element contains more than the reference concentration,
The plurality of calculated concentrations are compared with each other, and depending on whether the ratio of these calculated concentrations exceeds a predetermined first reference range, a peak waveform due to another different element is included in the peak waveform determined to be reliable. The element content determination method according to claim 7, wherein the probability of overlapping is determined. As a result of comparing the plurality of calculated concentrations with each other, if the ratio of at least one calculated concentration exceeds the first reference range, it is determined that there is a high probability that peak waveforms due to other different elements are superimposed, and this comparison is performed. The coping method based on a result is guide | induced. The element content determination method of Claim 10 characterized by the above-mentioned. Search for the presence or absence of a desired peak waveform for each of a plurality of predetermined peaks, and if it is determined from these search results that there is an appropriate peak waveform, calculation of the specified element calculated for at least one of the peaks When the concentration exceeds the specified reference concentration,
Depending on whether or not the actual peak intensity of at least one other peak and the estimated peak intensity estimated from the calculated concentration satisfy the relationship of Equation 1, the designated element has the reference concentration in the analysis sample. The element content determination method according to claim 1, wherein the probability of content exceeding is determined.
(Equation 1)
(Actual peak intensity)> (estimated peak intensity) × (reference concentration / calculated concentration) When the actual peak intensity and the estimated intensity do not satisfy the relationship of Equation 1, it is determined that the probability that the specified element is contained exceeding the reference concentration is high, and a coping method based on the calculation result The element content determination method according to claim 12, wherein: The element content determination method according to claim 12 or 13, wherein the concentration of the designated element is calculated by a calibration curve method. When it is determined that there is a high probability that the designated element contains more than the reference concentration,
The actual peak intensity of the at least one other peak is compared with the estimated peak intensity, and the reliability is determined depending on whether the ratio of these peak intensities exceeds a predetermined second reference range. 13. The element content determination method according to claim 12, wherein the probability that a peak waveform of another different element is superimposed on the peak waveform determined as follows is determined. As a result of comparing the actual peak intensity with the estimated peak intensity for the at least one other peak, if the ratio of at least one peak intensity exceeds the second reference range, a peak waveform due to another different element is obtained. The element content determination method according to claim 15, wherein it is determined that the probability of overlapping is high, and a coping method based on the comparison result is derived. The element coping method according to claim 2, 8, 11, 13 or 16, wherein the coping method is based on another analysis method different from the specific analysis method. A program for determining the presence or absence of a specified element in an analysis sample from a dispersion spectrum waveform obtained by a specific analysis method,
Calculating a peak intensity for a predetermined peak of the specified element in a predetermined dispersion range, and searching for the presence or absence of a desired peak waveform for the predetermined peak in the predetermined dispersion range;
And a step of determining whether or not the peak intensity calculation result for the predetermined peak in the predetermined dispersion range is reliable based on the search result. 19. The element content determination according to claim 18, further comprising a step of outputting at least one of the determined content and a coping method based thereon when it is determined from the search result that the peak intensity calculation result is not reliable. program. The element content determination program according to claim 18, comprising a step of outputting only the presence or absence of reliability as the determination result of the presence or absence of reliability of the peak intensity calculation result. When searching for the presence or absence of a desired peak waveform for each of a plurality of predetermined peaks, and determining that there is a reasonable peak waveform from any of these search results,
Calculating a concentration of the designated element for each peak from peak intensities for the plurality of peaks;
And comparing the plurality of calculated concentrations with a predetermined reference concentration, respectively, to determine a probability that the specified element is contained in the analysis sample in excess of the reference concentration. 18. The element content determination program according to 18. Search for the presence or absence of a desired peak waveform for each of a plurality of predetermined peaks, and if it is determined from these search results that there is an appropriate peak waveform, the concentration of the specified element is calculated for at least one of the peaks And steps to
Whether or not the actual peak intensity of at least one other peak and the estimated peak intensity estimated from the calculated concentration satisfy the relationship of Formula 2 when the calculated concentration of the designated element exceeds a predetermined reference concentration 19. The element content determination program according to claim 18, further comprising: determining a probability that the specified element is contained in the analysis sample in excess of the reference concentration.
(Equation 2)
(Actual peak intensity)> (estimated peak intensity) × (reference concentration / calculated concentration) 23. A step of outputting at least one of the determined content and a coping method based on the determined content when the probability that the specified element is contained in the analysis sample in excess of the reference concentration is determined is included. Element content determination program described in 1. 23. The element content determination program according to claim 21, further comprising a step of outputting only the presence / absence of the probability as a determination result of the probability that the specified element is contained in the analysis sample in excess of the reference concentration. . When it is determined that there is a high probability that the designated element contains more than the reference concentration,
The plurality of calculated concentrations are compared with each other, and a peak waveform of another different element is superimposed on the peak determined to be reliable depending on whether the ratio of these calculated concentrations exceeds a predetermined first reference range. The element content determination program according to claim 21, further comprising a step of determining a probability of being performed. When it is determined that there is a high probability that the designated element contains more than the reference concentration,
The actual peak intensity of the at least one other peak is compared with the estimated peak intensity, and the reliability is determined depending on whether the ratio of these peak intensities exceeds a predetermined second reference range. 23. The element content determination program according to claim 22, comprising a step of determining a probability that a peak waveform of another different element is superimposed on the peak determined as. 27. The element according to claim 25, further comprising a step of outputting at least one of the determined content and a coping method based on the probability that peak waveforms due to the other different elements are superimposed. Content determination program. 27. The element content determination program according to claim 25 or 26, further comprising a step of outputting only the presence or absence of a probability as a determination result of the probability that the peak waveforms of the other different elements are superimposed. An element content determination device that receives the dispersion spectrum waveform from a measurement device that obtains a dispersion spectrum waveform by a specific analysis technique and determines the presence or absence of a specified element in an analysis sample,
Input means for inputting a dispersion spectrum waveform in the analysis sample;
Search means for calculating a peak intensity for a predetermined peak of the specified element in a predetermined dispersion range and searching for the presence or absence of a desired peak waveform for the predetermined peak in the predetermined dispersion range;
Determination means for determining whether or not the peak intensity calculation result for the predetermined peak in the predetermined dispersion range is reliable based on the search result searched by the search means;
An element content determination apparatus comprising: output means for outputting the content determined by the determination means. When it is determined by the determination means that the peak intensity calculation result is not reliable,
30. The element content determination apparatus according to claim 29, wherein the output means outputs at least one of the determined content and a coping method based on the determined content. 30. The element content determination apparatus according to claim 29, wherein the specific analysis method is an X-ray analysis method. A calculating means for calculating the concentration of the designated element from the peak intensity;
When the search means searches for the presence or absence of a desired peak waveform for each of a plurality of predetermined peaks, and the determination means determines that there is a reasonable peak waveform for any of these search results,
The calculation means calculates the concentration of the designated element for each peak from the peak intensity for the plurality of peaks,
The determination means determines the probability that the specified element is contained in the analysis sample in excess of the reference concentration by comparing each of the plurality of calculated concentrations with a predetermined reference concentration. Item 29. The element content determination apparatus according to Item 29. A calculating means for calculating the concentration of the designated element from the peak intensity;
When the search means searches for the presence or absence of a desired peak waveform for each of a plurality of predetermined peaks, and the determination means determines that there is a reasonable peak waveform for any of these search results,
The calculation means calculates the concentration of the designated element for at least one of the peaks determined to be appropriate,
When the calculated concentration of the designated element exceeds a predetermined reference concentration, the determining means has a relationship of an actual peak intensity of at least one other peak and an estimated peak intensity estimated from the calculated concentration of Equation 3: 30. The element content determination apparatus according to claim 29, wherein the probability that the specified element is contained in the analysis sample in excess of the reference concentration is determined depending on whether or not the condition is satisfied.
(Equation 3)
(Actual peak intensity)> (estimated peak intensity) × (reference concentration / calculated concentration) If the determination means determines the probability that the specified element is contained in the analysis sample in excess of the reference concentration,
34. The element content determination apparatus according to claim 32 or 33, wherein the output means outputs at least one of the determined content and a coping method based thereon. When it is determined that there is a high probability that the specified element contains more than the reference concentration,
The determination means compares the plurality of calculated concentrations with each other, and determines whether the peak determined to be reliable has another different element depending on whether the ratio of the calculated concentrations exceeds a predetermined first reference range. 33. The element content determination apparatus according to claim 32, wherein the probability that the peak waveform is superimposed is determined. When it is determined that there is a high probability that the specified element contains more than the reference concentration,
The determination means compares the actual peak intensity and the estimated peak intensity for the at least one other peak, and whether or not the ratio of these peak intensity exceeds a predetermined second reference range, 34. The element content determination apparatus according to claim 33, wherein a probability that a peak waveform of another different element is superimposed on the peak determined to be reliable is determined. When the determination means determines the probability that the peak waveforms due to the different elements are superimposed,
The element content determination device according to claim 35 or 36, wherein the output means outputs at least one of the determined content and a coping method based on the determined content. An element content determination device for determining the presence or absence of a specified element in an analysis sample,
Measuring means for measuring a dispersion spectrum waveform in the analysis sample;
Search means for calculating a peak intensity for a predetermined peak of the specified element in a predetermined dispersion range and searching for the presence or absence of a desired peak waveform for the predetermined peak in the predetermined dispersion range;
Determination means for determining whether or not the peak intensity calculation result for the predetermined peak in the predetermined dispersion range is reliable based on the search result searched by the search means;
An element content determination apparatus comprising: output means for outputting the content determined by the determination means. When it is determined by the determination means that the peak intensity calculation result is not reliable,
39. The element content determination apparatus according to claim 38, wherein the output means outputs at least one of the determined content and a coping method based thereon. The element content determination apparatus according to claim 38, wherein the measuring means is based on an X-ray analysis method. A calculating means for calculating the concentration of the designated element from the peak intensity;
When the search means searches for the presence or absence of a desired peak waveform for each of a plurality of predetermined peaks, and the determination means determines that there is a reasonable peak waveform for any of these search results,
The calculation means calculates the concentration of the designated element for each peak from the peak intensity for the plurality of peaks,
The determination means determines the probability that the specified element is contained in the analysis sample in excess of the reference concentration by comparing each of the plurality of calculated concentrations with a predetermined reference concentration. Item 38. The element content determination apparatus according to Item 38. A calculating means for calculating the concentration of the designated element from the peak intensity;
When the search means searches for the presence or absence of a desired peak waveform for each of a plurality of predetermined peaks, and the determination means determines that there is a reasonable peak waveform for any of these search results,
The calculation means calculates the concentration of the designated element for at least one of the peaks determined to be appropriate,
When the calculated concentration of the designated element exceeds a predetermined reference concentration, the determination means has a relationship of an actual peak intensity of at least one other peak and an estimated peak intensity estimated from the calculated concentration of Equation 4: 39. The element content determination apparatus according to claim 38, wherein the probability that the specified element is contained in the analysis sample in excess of the reference concentration is determined based on whether or not the condition is satisfied.
(Equation 4)
(Actual peak intensity)> (estimated peak intensity) × (reference concentration / calculated concentration) If the determination means determines the probability that the specified element is contained in the analysis sample in excess of the reference concentration,
43. The element content determination apparatus according to claim 41, wherein the output unit outputs at least one of the determined content and a coping method based thereon. When it is determined that there is a high probability that the specified element contains more than the reference concentration,
The determination means compares the plurality of calculated concentrations with each other, and determines whether the peak determined to be reliable has another different element depending on whether the ratio of the calculated concentrations exceeds a predetermined first reference range. 42. The element content determination device according to claim 41, wherein the probability that the peak waveform is superimposed is determined. When it is determined that there is a high probability that the specified element contains more than the reference concentration,
The determination means compares the actual peak intensity and the estimated peak intensity for the at least one other peak, and whether or not the ratio of these peak intensity exceeds a predetermined second reference range, 43. The element content determination apparatus according to claim 42, wherein a probability that a peak waveform of another different element is superimposed on the peak determined to be reliable is determined. When the determination means determines the probability that the peak waveforms due to the different elements are superimposed,
The element content determination apparatus according to claim 44 or 45, wherein the output means outputs at least one of the determined content and a coping method based on the determined content. An element content determination system comprising a measurement device and an element content determination device, for determining the presence or absence of a specified element in an analysis sample,
The measuring device is
Measuring means for measuring a dispersion spectrum waveform in the analysis sample,
The element content determination device includes:
Input means for inputting a dispersion spectrum waveform in the analysis sample measured by the measurement means in the measurement device;
Search means for calculating a peak intensity for a predetermined peak of the specified element in a predetermined dispersion range and searching for the presence or absence of a desired peak waveform for the predetermined peak in the predetermined dispersion range;
Determination means for determining whether or not the peak intensity calculation result for the predetermined peak in the predetermined dispersion range is reliable based on the search result searched by the search means;
An element content determination system comprising: output means for outputting the content determined by the determination means.

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