Emission analyzer

Abstract

To provide an analyzer that performs quick and exact emission analysis by multiple rounds of analysis.SOLUTION: An emission analyzer 1 comprises: a sample placement table 10 that forms in the inside a discharge chamber 11 where a gas is introduced to perform electrical discharge, and that includes an opening 12 formed adjacent to the discharge chamber so as to enable a sample S to be placed; a counter electrode 20 an edge of which is located in the discharge chamber and which generates electrical discharge upon voltage application between the sample and itself; a spectroscope 42 for spectrally separating light generated by electrical discharge; a plurality of detectors 43 for detecting light of each wavelength having been spectrally separated; and means for controlling the voltage applied between the sample and the counter electrode and processing measured data detected by the detectors to calculate the percentage contents of elements.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present disclosure relates to a luminescence analysis device.

Background Art

[0002] There are known a luminescence analysis method and device for performing compositional analysis of a solid sample by causing discharge between the solid sample and a counter electrode and analyzing the generated light (see, for example, Patent Document 1). The luminescence analysis method and device are used for process control in a factory that manufactures metal products.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

Summary of the Invention

Problems to be Solved by the Invention

[0004] In the manufacturing process of metal products, rapid and accurate compositional analysis of samples is required. In luminescence analysis, it is common to perform compositional analysis at multiple positions of the same sample and use the average value as a representative value. However, the compositional distribution in the sample is not always uniform, and the analysis values may be distributed depending on the analysis positions. Therefore, when calculating the representative value by performing the average value calculation process, it is preferable to select measurement values with relatively small differences after excluding outliers and calculate the average value thereof.

[0005] The inventor of the present invention has empirically grasped the important elements in the composition of the metal among a plurality of elements to be analyzed by a luminescence analyzer when performing composition analysis of metal products. First, focusing on the difference in the content rate of the important elements, the presence of singular points is judged by comparing the difference in the content rate of the important elements at two measurement points with the control width. Also, among the measurement results of the measurement points that are not singular points, a composition distribution is calculated from the measurement result of the measurement point with the smallest difference in the content rate of the important elements, and it has been found that results with little variation can be easily obtained.

[0006] Therefore, the luminescence analyzer according to the present invention aims to easily obtain results with little variation even for a measurer who has not used the luminescence analyzer by embodying in the apparatus the calculation method of the composition distribution that such an analyzer implicitly performs.

[0007] Also, when there are three or more measurement positions and two or more composition analysis values determined to be measurement normal (not singular values) are obtained by comparing a plurality of element content rates obtained from the emission spectroscopy results of each measurement position with the control width, it is desired to output as the composition analysis value of the sample the result with the smallest variation in the priority element.

Means for Solving the Problem

[0008] A first aspect of the present invention is a luminescence analyzer, a sample mounting table formed inside with a discharge chamber for introducing a gas to cause a discharge, and having an opening formed so that a sample can be placed in contact with the discharge chamber; a counter electrode having an end disposed in the discharge chamber and having a voltage applied between it and the sample to cause a discharge; a spectroscope for spectroscopically analyzing the light generated by the discharge; a plurality of detectors for detecting the light of each wavelength spectroscopically analyzed by the spectroscope; a control unit that controls the voltage applied between the sample and the counter electrode, processes the measurement data detected by the detector, and calculates the content rate of the element; and comprising the control unit Select one priority element from a plurality of elements to be analyzed for the components of the sample, and set a control range, which is the range of the content rate, for each of the plurality of elements to be analyzed for the components of the sample. Perform a plurality of measurements on a plurality of positions of the sample, and in each measurement, obtain the detection intensity for a plurality of elements, and calculate the content rate of each element from the detection intensity of each element. For the priority element, calculate the difference in the content rates between two of the plurality of measurements. When the difference is within the control range, For all the elements for which the control range is set, determine whether the difference in the content rates of each element between the two measurements is within the control range. For all the elements for which the control range is set, when the difference in the content rates of each element between the two measurements is within the control range of each element, Calculate the average value of the content rates of each element in the two measurements as the representative value and output it.

[0009] In the present disclosure, the difference in the content rates between two measurements means the absolute value and cannot take a negative value.

Advantages of the Invention

[0010] When calculating the representative analysis value of the sample, the emission analysis apparatus of the present disclosure can easily obtain a result with less variation by preferentially processing the measurement results of one selected element.

Brief Description of the Drawings

[0011]

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Embodiments for Carrying Out the Invention

[0012] <First Embodiment> (1) Configuration of the Luminescence Analyzer 1 As shown in FIG. 1, the luminescence analyzer 1 of this embodiment includes a sample stage 10, a counter electrode 20, a spectroscope 42, a plurality of detectors 43, and a control unit 50.

[0013] Inside the sample stage 10, a discharge chamber 11 is formed. An opening 12 is formed in the sample stage 10 facing the discharge chamber 11. The sample S is arranged so as to close the opening of the sample stage 10. A counter electrode 20 is attached to the sample stage 10 facing the sample S. The end of the counter electrode 20 is arranged inside the discharge chamber 11.

[0014] On the sample stage 10, a gas supply path 14 for supplying gas to the discharge chamber 11 and a gas discharge path 15 for discharging the gas in the discharge chamber 11 are formed. During analysis, an inert gas is introduced from the gas supply path 14 into the discharge chamber 11, overflows, and is discharged from the gas discharge path 15. By replacing the air in the discharge chamber with an inert gas in this way, it is possible to suppress the components in the air from affecting the analysis results. An example of the inert gas is argon.

[0015] Gas is introduced into the discharge chamber 11, and a voltage is applied between the sample and the counter electrode 20 to cause a discharge. The light generated by the discharge passes through the condenser lens 13 attached to the sample stage 10 and is guided to the measurement chamber 41.

[0016] In the measurement chamber 41, a spectroscope 42 and a plurality of detectors 43 are arranged. The spectroscope 42 is a concave diffraction grating. The light generated in the discharge chamber 11 is incident on the spectroscope 42 and dispersed, and is guided to the plurality of detectors 43 for each wavelength n of the emission line spectrum peculiar to each element. Each detector 43 detects the intensity of the emission line spectrum peculiar to each element at the wavelength n.

[0017] The control unit 50 is a computer. The control unit 50 includes a CPU 51, a memory 52, an operation unit 53, and a display unit 54. The control unit 50 controls the introduction of gas into the discharge chamber 11, the application of voltage between the sample S and the counter electrode 20, etc., and performs composition analysis of the sample S. Further, the control unit 50 receives measurement data from each detector 43 and performs data processing. The CPU 51 performs calculations. The CPU 51 executes programs. Also, the CPU 51 stores programs and data in the memory 52 and reads programs and data from the memory. Here, the memory 52 includes not only RAM (Random Access Memory) and ROM (Read Only Memory), but also external storage memories such as HDD (Hard Disk Drive). The CPU 51 outputs measurement programs, measurement data, calculation results, etc., and displays them on the display unit 54. The display unit 54 is a display. The operation unit 53 receives user input. According to the instructions input from the operation unit 53, the CPU 51 executes programs. The operation unit 53 is a keyboard, a mouse, a touch panel integrated with the display unit, etc.

[0018] The calibration curve data is stored in the memory 52. The calibration curve data is data showing the relationship between the detection intensity and the content rate (concentration) of each element for each wavelength n of the emission line spectrum specific to each element (exemplified in FIG. 3). At the time of analysis, the control unit 50 receives the detection intensity data from each detector 43 and calculates the content rate of the element from the calibration curve data stored in the memory 52. Further, the calculated content rate is displayed on the display unit 54.

[0019] In the composition analysis of the sample of the present disclosure, there are important elements depending on the sample to be measured, and the operator empirically focuses on the important components (in the present disclosure, the most important one element is called the priority element) for determining the variety from the contained elements. The analysis apparatus of the present disclosure is configured to utilize such findings.

[0020] For each sample of the same type, the control unit 50 selects a priority element from a plurality of elements to be measured and uses it for analysis. The priority element is input by the operator from the operation unit 53. The input priority element is stored in the memory 52. As a method for the operator to select a priority element, the operator may input a selection of a priority element from among a plurality of elements displayed on the display unit 54. The priority element is not limited to the element with the highest content rate. The priority element may be the element with the nth (n is an integer from 2 to 50) highest content. For example, in the case of carbon steel, carbon C, silicon Si, manganese Mn, etc. are important components for determining the type of carbon steel, and any of these elements may be selected as the priority element.

[0021] For the elements to be analyzed for the components of the sample, a management range is set. The management range is set for each element among all the elements to be analyzed for components including the priority element. Here, the management range is the allowable distribution range of the content rate.

[0022] Normally, for samples of the same type, a common priority element is selected and a common management range is set.

[0023] (2) Method for Analyzing Sample by Emission Analyzer 1 In the analysis of the sample of this embodiment, a plurality of measurements are performed on a plurality of positions of the sample. The control unit 50 acquires the detection intensity for a plurality of elements in each measurement cycle, and calculates the content rate of each element from the detection intensity of each element.

[0024] The sample S is shaped into a cylindrical shape and placed on the sample stage 10. The sample shape may be a rectangular parallelepiped, a mushroom shape, a coin shape, or other shapes. The analysis position on the sample S is changed for each analysis cycle. In FIG. 2, they are the first position 1A, the second position 2B, the third position 3C, and the fourth position 4D. This is to incorporate the variation in composition due to the position within the sample S into the measurement value. Also, accurate analysis cannot be performed if the discharge positions overlap.

[0025] A method for analyzing the composition of a sample using the luminescence analyzer 1 according to this embodiment will be described with reference to the flowcharts of FIGS. 4 to 10.

[0026] In the flowchart of FIG. 4, first, in step S100, one priority element is selected from a plurality of elements to be analyzed for the components of the sample. As the priority element, for the same type of measurement, an element that has been previously determined by the operator and stored in the memory 52 of the control unit 50 may be used. The priority element may be input by the operator during the measurement of a group of samples. Also, for one sample, an element input by the operator to the control unit 50 after the first or second measurement may be used.

[0027] In step S100, together with the selection of the priority element, for a plurality of elements to be analyzed for the components of the sample, a management width that is a range of the content rate is set for a predetermined element. The elements for which the management width is set here include the priority element and one or more other elements to be analyzed for the components of the sample.

[0028] In this embodiment, a plurality of measurements are performed on a plurality of positions of one sample, and in each measurement, detection intensities regarding a plurality of elements to be analyzed for the components of the sample are obtained, and the content rate of each element is calculated from the detection intensities of each element. It is determined whether the difference in the content rates between two measurement times is within the management width of each element for all the elements for which the management width is set. For all the elements for which the management width is set, when it is within the management width of each element, it is regarded that the two measurements have been successful. When the measurement is determined to be successful, the average value of the content rates of each element (all the measured elements, or a part of them as necessary) for the two measurement times is calculated as the representative value of the content rate of each element. Further, the calculated representative value is output. Outputting means, for example, outputting from the computer of the control unit 50 to the display unit 54. Outputting includes the case of storing in the memory 52. In the present disclosure, the difference in the content rates between two measurement times means the absolute value and is not a negative value.

[0029] In step S101, first, the sample S is set in the opening 12 of the sample stage 10. The control unit 50 performs the first measurement on the first position 1A of the sample S. That is, the control unit 50 introduces gas into the discharge chamber 11, applies a voltage between the first position 1A of the sample S and the counter electrode 20 to cause discharge. The emitted light is spectroscopically separated by the spectroscope 42 for each wavelength n of the emission line spectrum specific to each element, and detected by each detector 43. The data of the detection intensity detected by each detector 43 is acquired by the control unit 50.

[0030] From the detection intensity for each wavelength n of the emission line spectrum specific to each element (the detection intensity by the first analysis is referred to as the first detection intensity. The same applies to the second and subsequent times), the control unit 50 calculates the content rate (first content rate) of each element using the calibration curve data (illustrated in FIG. 3) stored in the memory 52 (S102). The content rate of each element (the content rate by the first analysis is referred to as the first content rate. The same applies to the second and subsequent times) is output from the CPU 51 to the display unit 54 and the memory 52. Thus, the first analysis is completed.

[0031] Similarly, the control unit performs the second analysis on the second position 2B of the sample S. That is, the second measurement is performed on the second position 2B of the sample S (S103), and from the obtained detection intensity (second detection intensity), the content rate (second content rate) of each element is calculated (S104). The content rate of each element (second content rate) is output from the CPU 51 to the display unit 54 and the memory 52.

[0032] Next, the control unit 50 calculates the difference (here, it means the absolute value of the difference) between the first content rate and the second content rate for the priority element. Then, it determines whether the difference in the content rate is less than or equal to a predetermined value (management width) (S105). When the difference in the content rate is less than or equal to the management width, it proceeds to step S106. When the difference in the content rate exceeds the management width, it proceeds to step S110 and further performs the third analysis (measurement).

[0033] On the other hand, in step S106, the control unit 50 determines, for each element for which a control range is set, excluding the priority element, among the plurality of elements contained in the sample, whether the difference between the first content rate and the second content rate is equal to or less than the control range. When the differences between the first content rates and the second content rates of all the elements for which the control range is set are equal to or less than the control range, it is determined that the first measurement (S101, S102) and the second measurement (S103, S104) have been successful.

[0034] Next, in step S107, the average value of the first content rate and the second content rate of each element is calculated. The calculated value is used as the representative value of the content rate of that element. The CPU 51 of the control unit 50 outputs the calculated representative value to the display unit 54. The display unit 54 displays the representative values of the respective elements output to the display unit 54. Then, the analysis of the sample is completed.

[0035] Next, in step S106, when the difference in the content rates between the two measurement times for one or more elements among all the elements for which the control range is set exceeds the control range of that element, the process proceeds to step S110, and a third analysis (measurement) is further performed.

[0036] The control unit 50 performs a third measurement on the third position 3C of the sample S (S110), and calculates the content rate (third content rate) of each element using a calibration curve from the obtained detection intensity (third detection intensity) (S111). The content rate (third content rate) of each element is displayed on the display unit 54.

[0037] Next, the control unit 50 calculates, in the same manner as in step S105, the difference between the first content rate and the third content rate, and the difference between the second content rate and the third content rate for the priority element. Then, a combination of measurement times with a smaller difference in content rates is selected. Then, it is determined whether the difference in the content rates of the two selected measurement times for the priority element is equal to or less than the control range (S112). When the difference in the content rates of the two selected measurement times is equal to or less than the control range, the process proceeds to step S113, and when the difference exceeds the control range, the process proceeds to the fourth measurement (S120).

[0038] In step S113, for all elements with a set control range other than the priority element, it is determined whether the difference in the content rates between the two selected measurement times is within the control range or not. When the difference in the content rates between the two selected measurement times is within the control range for all elements with a set control range other than the priority element, it is regarded that the two selected measurement times are successful, and the process proceeds to step S114. When the difference in the content rates between the two selected measurement times exceeds the control range for one or more elements among all elements with a set control range other than the priority element, the process proceeds to step S115.

[0039] In step S114, for the two selected measurement times, the average value of the content rate of each element is calculated. The CPU 51 of the control unit 50 outputs the calculated representative value to the display unit 54. The display unit 54 displays the output representative value of each element on the display unit 54. Then, the analysis of the sample is completed. Note that in step S114, the elements for which the representative value of the content rate is calculated may include not only the elements with a set control range but also the elements without a set control range.

[0040] Next, the case where the difference in the content rates between the two selected measurement times of the element exceeds the control range in step S112 or step S113 will be described. In this case, for the priority element, among the difference between the first content rate and the third content rate, and the difference between the second content rate and the third content rate, the combination of the measurement times with the larger difference in the content rate is selected. Then, for the priority element, it is determined whether the difference in the content rates between the two selected measurement times is within the control range or not (S115). When the difference in the content rates between the two selected measurement times is within the control range, the process proceeds to step S116, and when the difference exceeds the control range, the process proceeds to the fourth measurement (S120).

[0041] In step S116, for all elements with a set control range other than the priority element, it is determined whether the difference in the content rates between the two selected measurement times is equal to or less than the control range. When the difference in the content rates between the two selected measurement times is equal to or less than the control range for all elements with a set control range other than the priority element, it is considered that the two selected measurement times were successful, and the process proceeds to step S117. When the difference in the content rates between the two selected measurement times exceeds the control range for one or more elements among all elements with a set control range other than the priority element, the process proceeds to the fourth measurement (S120).

[0042] In step S117, for the two selected measurement times, the average value of the content rate of each element is calculated. The CPU 51 of the control unit 50 outputs the calculated representative value to the display unit 54. The display unit 54 displays the output representative value of each element on the display unit 54. Then, the analysis of the sample is completed. Note that in step S117, the elements for which the representative value of the content rate is calculated may include not only the elements with a set control range but also the elements without a set control range.

[0043] In step S120, a fourth analysis (measurement) is further performed. The control unit 50 performs a fourth measurement on the fourth position 4D of the sample S, and calculates the content rate (fourth content rate) of each element from the obtained detection intensity (fourth detection intensity). The content rate (fourth content rate) of each element is output from the CPU 51 to the display unit 54 and the memory 52 (S121).

[0044] Next, the control unit 50 calculates the difference between any one of the first to third content ratios and the fourth content ratio for one priority element selected from a plurality of elements. Then, it selects the combination of measurement times with the smallest difference between any one of the first to third content ratios and the fourth content ratio. Next, for the priority element, it determines whether the difference in the content ratios of the two selected measurement times is equal to or less than the control width (S122). When the difference in the content ratios of the two selected measurement times is equal to or less than the control width, it proceeds to step S123. When the difference exceeds the control width, it is considered unsuccessful and it proceeds to step S131. In step S131, as the output indicating that the measurement was unsuccessful, it outputs the content ratios of all elements as 0 (zero) and displays them on the display unit 54, and ends the measurement. Here, "unsuccessful" means that even in four measurements, the variation in the content ratios of the elements for which the control width was set did not fall within the desired control width range. Note that the output (S131) indicating that the measurement was unsuccessful may be any output as long as it can clearly determine that the measurement was unsuccessful, and is not limited to the above output mode.

[0045] In step S123, for all elements with a set control width other than the priority element, it determines whether the difference in the content ratios of the two selected measurement times is equal to or less than the control width. When the difference in the content ratios of the two selected measurement times is equal to or less than the control width for all elements with a set control width other than the priority element, it is considered that the two selected measurement times were successful, and it proceeds to step S124. When the difference in the content ratios of the two selected measurement times exceeds the control width for one or more elements among all elements with a set control width other than the priority element, it proceeds to step S125.

[0046] In step S124, for the two selected measurement times, it calculates the average value of the content ratios of each element. The CPU 51 of the control unit 50 outputs the calculated average value as a representative value to the display unit 54. The display unit 54 displays the output representative values of each element on the display unit 54. Then, it ends the analysis of the sample. Note that in step S124, the elements for which the representative value of the content ratio is calculated may include not only the elements for which the control width is set but also the elements for which the control width is not set. If the process proceeds to step S125, for the priority element calculated in step S122, the difference between any one of the first to third content rates and the fourth content rate is compared. Select the combination of measurement times that is the second smallest among the differences between any one of the first to third content rates and the fourth content rate. Next, for the priority element, it is determined whether the difference in the content rates of the two selected measurement times is within the control width or not. When the difference in the content rates of the two selected measurement times is within the control width, the process proceeds to step S126. When the difference exceeds the control width, it is considered unsuccessful and the process proceeds to step S132. In step S132, as an output indicating that the measurement is unsuccessful, the content rates of all elements are output as 0 (zero) and displayed on the display unit 54, and the measurement is terminated. Here, "unsuccessful" means that even in four measurements, the variation in the content rates of the elements for which the control width was set did not fall within the range of the desired control width. Note that the output (S132) indicating that the measurement is unsuccessful may be any output as long as it can clearly determine that the measurement is unsuccessful, and is not limited to the above output mode.

[0047] In step S126, for all elements with a set control width other than the priority element, it is determined whether the difference in the content rates of the two selected measurement times is within the control width or not. When the difference in the content rates of the two selected measurement times is within the control width for all elements with a set control width other than the priority element, the two selected measurement times are regarded as successful and the process proceeds to step S127. When the difference in the content rates of the two selected measurement times exceeds the control width for one or more elements among all elements with a set control width other than the priority element, the process proceeds to step S128.

[0048] In step S127, for the two selected measurement times, the average value of the content rate of each element is calculated. The CPU 51 of the control unit 50 outputs the calculated representative value to the display unit 54. The display unit 54 displays the representative value of each element output to the display unit 54. Then, the analysis of the sample is terminated. Note that in step S127, the elements for which the representative value of the content rate is calculated may include not only the elements for which the control width is set but also the elements for which the control width is not set.

[0049] When proceeding to step S128, for the priority element calculated in step S122, the differences between any one of the first to third content ratios and the fourth content ratio are compared. The combination of measurement times with the largest difference among the differences between any one of the first to third content ratios and the fourth content ratio is selected. Next, for the priority element, it is determined whether the difference in the content ratios of the two selected measurement times is within the control width or not. When the difference in the content ratios of the two selected measurement times is within the control width, proceed to step S129. When the difference exceeds the control width, assume it was unsuccessful and proceed to step S133. In step S133, as the output indicating measurement failure, the content ratios of all elements are output as 0 (zero) and displayed on the display unit 54, and the measurement is terminated. Here, "unsuccessful" means that even in the four measurements, the variation in the content ratios of the elements for which the control width was set did not fall within the desired control width range. Note that the output of measurement failure (S133) only needs to be an output that can clearly determine measurement failure and is not limited to the above output mode.

[0050] In step S129, for all elements with a set control range other than the priority element, it is determined whether the difference in the content rates between the two selected measurement times is within the control range or not. When the difference in the content rates between the two selected measurement times is within the control range for all elements with a set control range other than the priority element, the process proceeds to step S130. When the difference in the content rates between the two selected measurement times exceeds the control range for one or more of all elements with a set control range other than the priority element, it is considered unsuccessful, and the process proceeds to step S134. In step S134, as an output indicating that the measurement is unsuccessful, the content rates of all elements are output as 0 (zero) and displayed on the display unit 54, and the measurement is terminated. Here, "unsuccessful" means that even in four measurements, the variation in the content rates of the elements with a set control range did not fall within the desired control range. Note that the output (S134) indicating that the measurement is unsuccessful may be any output as long as it can clearly determine that the measurement is unsuccessful, and is not limited to the above output mode. Also, since the unsuccessful result in step S129 is due to the difference in the content rates of the elements with a set control range other than the priority element exceeding the control range, in order to clarify this, as the output in step S134, for the priority element, the average value of the content rates of the two selected measurement times in step S128 is calculated as the representative value, while the content rates of the other elements are output as 0 (zero) and displayed on the display unit 54.

[0051] In step S130, for the two selected measurement times, the average value of the content rate of each element is calculated. The CPU 51 of the control unit 50 outputs the calculated average value as the representative value to the display unit 54. The display unit 54 displays the output representative value of each element on the display unit 54. Then, the analysis of the sample is terminated. Note that in step S130, the elements for which the representative value of the content rate is calculated may include not only the elements with a set control range but also the elements without a set control range.

[0052] In the above embodiment, the case where the measurement is repeated up to four times has been described. Depending on the operation purpose, the maximum number of measurements may be three, five, or six or more.

[0053] (3) Features of the First Embodiment (3-1) In this embodiment, the control unit 50 preliminarily sets a management range, which is an allowable range of variation in the content rate, for important elements. Then, for all the elements for which the management range has been set, when the difference in the content rates between two measurement times is within the management range, those two measurement times are adopted. Then, the average value of the measurement results (content rates) at those two measurement times is calculated, and the average value is calculated as the representative value. By setting the management range for important elements and processing the measurement data, a highly reliable measurement result can be obtained simply.

[0054] (3-2) In this embodiment, the control unit 50 preliminarily designates the most important element as the priority element. Then, after measuring the content rates multiple times (twice or three times), first, it is determined whether the difference in the content rates obtained by two measurements for the priority element is within the management range. And when the average value of the content rate of the priority element exceeds the management range, the next measurement is performed. By making the determination by first paying attention to the priority element, in many cases, a primary determination regarding the validity of the measurement result can be made quickly. As a result, the measurement time can be shortened in the measurement of many samples.

[0055] (3-3) In this embodiment, after performing measurements three or more times, for the priority element, the difference between the content rate of the last measurement and the content rates of each of the previous measurement times is calculated, and it is checked whether all elements fall within the management range. First, for the priority element, among the differences in the content rates of two measurement times, first, the two measurement times with the smallest difference are selected. Then, it is determined whether the difference in the content rates of the two selected measurement times for the priority element is within the range of the management width. When the difference in the content rates of the two selected measurement times for the priority element is within the range of the management width, for all elements for which the management width is set, it is determined whether the difference in the content rates of the two selected measurement times is within the range of the management width. For all elements other than the priority element for which the management width is set, when the difference in the content rates of the two selected measurement times is less than or equal to the management width, the two selected measurement times are regarded as successful, and the representative value is calculated. When the difference in the content rates of the two selected measurement times exceeds the management width for one or more elements among all elements for which the management width is set, the measurement of the two measurement times with the smallest difference for the priority element is regarded as a failure. Then, for the priority element, the measurement of the two measurement times with the second smallest difference is selected, and the above operation is repeated.

[0056] As described above, when performing measurements three or more times, for the priority element, starting from the ones with smaller differences in the content rates of two measurement times, the variations of the priority element and the elements for which the management width is set other than the priority element are checked. Therefore, an appropriate measurement result can be obtained quickly with a small amount of calculation.

[0057] <Second Embodiment> (4) Analysis method of the sample by the emission analyzer 1 of the second embodiment In this embodiment, the same emission analyzer 1 as in the first embodiment is used, and the measurement (analysis) method for each time with respect to the sample S is also the same as in the first embodiment.

[0058] The difference between the analysis method of the second embodiment and the first embodiment is that in the second embodiment, four measurements (analyses) on the same sample are performed at once, whereas in the first embodiment, first, two measurements are performed, and the number of measurement times is increased one by one as necessary.

[0059] The analysis method of the sample of this embodiment will be described with reference to the flowcharts of FIGS. 11 and 12.

[0060] First, in step S200, similar to step 100 of the first embodiment, a priority element is selected, and for a specific element among the elements to be analyzed for the components of the sample, a control width that is a predetermined range of the content rate is set. The control width may be set for all of the elements to be analyzed for the components of the sample.

[0061] Next, in step S201, the sample S is set in the opening 12 of the sample mounting table 10, and the first measurement is performed on the first position 1A of the sample S. Subsequently, from the detection intensity obtained by this measurement, the content rate of each element is calculated. The details of the measurement are the same as those in steps S101 and S102 of the first embodiment. Subsequently, the second to fourth measurements are performed in the same manner as the second measurement (S103, S104) of the first embodiment to obtain data on the content rates of the second to fourth times for each element.

[0062] In step S202, for the priority element, the difference in the content rates between two measurement times is calculated. Regarding the combinations of two measurement times, calculations are performed for all cases of combining two measurement times from the four measurement times. That is, there are six combinations: the first and second times, the first and third times, the first and fourth times, the second and third times, the second and fourth times, and the third and fourth times.

[0063] In step S203, among the differences in the content rates of the six priority elements calculated in step S202, the one that is the nth (n = 1) smallest is selected.

[0064] Next, in step S204, for the priority element, it is determined whether the difference in the content rates between the two measurement times selected in step S203 is within the control width or not. When the difference in the content rates between the two selected measurement times is within the control width, the process proceeds to step S205. When the difference exceeds the control width, it is considered unsuccessful, and the process proceeds to step S207. In step S207, as an output indicating that the measurement is unsuccessful, the content rates of all elements are output as 0 (zero) and displayed on the display unit 54, and the measurement is terminated. Here, "unsuccessful" means that even in four measurements, the variation in the content rate of the element for which the control width was set did not fall within the desired control width range. Note that the output (S207) indicating that the measurement is unsuccessful may be any output as long as it can clearly determine that the measurement is unsuccessful, and is not limited to the above output mode.

[0065] In step S205, for all elements with a set control width other than the priority element, it is determined whether the difference in the content rates between the two selected measurement times is within the control width or not. When the difference in the content rates between the two selected measurement times is within the control width for all elements with a set control width other than the priority element, the two selected measurement times are considered successful, and the process proceeds to step S206. When the difference in the content rates between the two selected measurement times exceeds the control width for one or more elements among all elements with a set control width other than the priority element, the process returns to step S203.

[0066] When returning to step S203, for the difference in the content rate of the priority element, 1 is added to n, and the combination of the second smallest measurement times in terms of the difference is selected. Then, steps S204 and S205 are repeated. If necessary, the loop is repeated until n reaches 6. When n exceeds 6, the measurement is considered unsuccessful, and the process proceeds to step S207. In step S207, as an output indicating that the measurement is unsuccessful, the content rates of all elements are output as 0 (zero) and displayed on the display unit 54, and the process ends.

[0067] In step S206, for the two selected measurement times, the average value of the content rate of each element is calculated. The CPU 51 of the control unit 50 outputs the calculated representative value to the display unit 54. The display unit 54 displays the output representative value of each element on the display unit 54. Then, the analysis of the sample is completed. Note that in step S206, the elements for which the representative value of the content rate is calculated may include not only the elements for which the control width is set but also the elements for which the control width is not set.

[0068] In the above embodiment, the case where the measurement is performed four times has been described. Depending on the operation purpose, the maximum number of measurements may be three, five, or six or more.

[0069] The features of this embodiment are the same as the features of (3-1) to (3-3) of the first embodiment.

[0070] In this embodiment, since the measurement is performed a predetermined number of times (four times in this case) from the beginning, the third measurement and the fourth measurement, which may not be performed in the case of the first embodiment, are performed, which may increase the number of measurements. However, by making the predetermined number of measurements (four times) essential, it is possible to select a measurement result with a smaller difference in the content rate of the more priority elements from six combinations of measurement results, so there is a possibility of obtaining a highly accurate result.

[0071] As described above, an embodiment of the present disclosure has been described. However, the present disclosure is not limited to the above embodiment, and various modifications are possible without departing from the gist of the present disclosure. In particular, the embodiments described in this specification can be arbitrarily combined as needed.

[0072] (5) Aspect It is understood by those skilled in the art that the above-described plurality of exemplary embodiments are specific examples of the following aspects. (Item 1) A luminescence analysis apparatus according to one aspect is A sample mounting table having a discharge chamber formed therein for introducing a gas to cause a discharge, and having an opening formed so that a sample can be disposed in contact with the discharge chamber, An opposing electrode having an end disposed in the discharge chamber, across which a voltage is applied to the sample to generate a discharge; A spectroscope that spectroscopically analyzes the light generated by the discharge; A plurality of detectors that detect light of each wavelength spectroscopically analyzed by the spectroscope; A control unit that controls the voltage applied between the sample and the opposing electrode, processes the measurement data detected by the detector, and calculates the content ratio of the elements; Comprising; The control unit: Selects one priority element from a plurality of elements to be analyzed for the components of the sample, and sets a management range, which is a range of the content ratio, for each of the plurality of elements to be analyzed for the components of the sample; Performs a plurality of measurements on a plurality of positions of the sample, obtains the detection intensity for each of the plurality of elements in each measurement, and calculates the content ratio of each element from the detection intensity of each element; For the priority element, calculates the difference in the content ratio between two of the plurality of measurements, and when the difference is within the management range, Determines whether the difference in the content ratio between the two measurements for each element is within the management range for all the elements for which the management range has been set; For all the elements for which the management range has been set, when the difference in the content ratio between the two measurements for each element is within the management range of each element, Calculates and outputs the average value of the content ratio between the two measurements of each measured element as a representative value.

[0073] The emission analysis apparatus according to claim 1 sets one element among the elements to be measured as a priority element and processes the measurement data, so that measurement results with less variation can be easily obtained.

[0074] (Claim 2) In the emission analysis apparatus according to claim 1, The control unit performs three or more measurements on the sample; For the priority element, calculates the difference in the content ratio between two of the three or more measurements, preferentially selects the two measurements with the smallest difference, and when the difference between the two selected measurements is within the management range, For all elements with a set control range, determine whether the difference in the content rates of the selected two measurement times for each element is within the control range. For all elements with a set control range, when the difference in the content rates of the selected two measurement times for each element is within the control range of each element, Calculate the average value of the content rates of the selected two measurement times for each measured element as the representative value and output it.

[0075] When the luminescence analyzer according to claim 2 performs measurements three or more times, for the priority elements, the two measurement times with the smallest difference in the content rates of the two measurement times are preferentially selected for data processing, so that appropriate measurement results can be obtained quickly with a small amount of calculation.

[0076] (Claim 3) In the luminescence analyzer according to claim 1, The control unit performs two measurements on the sample, For the priority elements, calculate the difference in the content rates of the two measurement times, and when the difference is within the control range, For all elements with a set control range, determine whether the difference in the content rates of the two measurement times for each element is within the control range, For all elements with a set control range, when the difference in the content rates of the two measurement times for each element is within the control range of each element, Calculate the average value of the content rates of the two measurement times for each measured element as the representative value and output it.

[0077] The luminescence analyzer according to claim 3 can obtain highly reliable measurement data with only two measurements.

[0078] (Claim 4) In the luminescence analyzer according to claim 1, The control unit performs two measurements on the sample, For the priority elements, calculate the difference in the content rates of the two measurement times, and when the difference exceeds the control range, output that the two measurement results exceed the control range.

[0079] In the emission analysis apparatus according to the fourth aspect, since the determination of the control range is preferentially performed for the priority element, it is possible to quickly determine whether to perform additional measurements, which contributes to simple and rapid measurements.

[0080] (Item 5) In the emission analysis apparatus according to the fourth aspect, when the control unit performs the third measurement, the control unit determines whether the smaller of the difference between the content rate in the first measurement and the content rate in the third measurement and the difference between the content rate in the second measurement and the content rate in the third measurement for the priority element exceeds the control range. When it exceeds, the fourth measurement is performed on the sample. In the emission analysis apparatus according to the sixth aspect, since the determination of the control range is preferentially performed for the priority element, it is possible to quickly determine the fourth measurement, which contributes to simple and rapid measurements.

Explanation of Signs

[0081] 1 Emission analysis apparatus 10 Sample stage 11 Discharge chamber 12 Aperture 13 Condensing lens 14 Gas supply path 15 Gas discharge path 20 Counter electrode 41 Measurement chamber 42 Spectrometer 43 Detector 50 Control unit 51 CPU 52 Memory 53 Operation unit 54 Display unit

Claims

1. An emission analysis apparatus, comprising a sample stage formed with a discharge chamber for introducing a gas to cause a discharge therein and having an opening formed so that a sample can be placed in contact with the discharge chamber; a counter electrode having an end disposed in the discharge chamber and to which a voltage is applied between the sample to cause a discharge; a spectroscope for spectroscopically analyzing light generated by the discharge; a plurality of detectors for detecting light of each wavelength spectroscopically analyzed by the spectroscope; a control unit configured to control a voltage applied between the sample and the counter electrode, process measurement data detected by the detectors, and calculate a content ratio of an element; wherein: the control unit selects one priority element from a plurality of elements to be analyzed for the components of the sample, and sets a management range, which is a range of the content ratio, for each of the plurality of elements to be analyzed for the components of the sample; performs a plurality of measurements on a plurality of positions of the sample, obtains detection intensities for the plurality of elements in each measurement, and calculates a content ratio of each element from the detection intensities of each element; for the priority element, calculates a difference in the content ratio between two of the plurality of measurements, and when the difference is within the management range, determines, for all elements for which the management range is set, whether the difference in the content ratio between the two measurements of each element is within the management range of each element; for all elements for which the management range is set, when the difference in the content ratio between the two measurements of each element is within the management range of each element, calculates and outputs, as a representative value, an average value of the content ratios of the two measurements of each measured element; an emission analysis apparatus.

2. The emission spectroscopy apparatus according to claim 1, wherein the control unit performs three or more measurements on the sample, calculates a difference in the content ratio between two of the three or more measurements for the priority element, preferentially selects the two measurements with the smallest such difference, and when the difference is within the management range, determines, for all elements for which the management range is set, whether the difference in the content ratio between the two selected measurements of each element is within the management range of each element; for all elements for which the management range is set, when the difference in the content ratio between the two selected measurements of each element is within the management range of each element, calculates and outputs, as a representative value, an average value of the content ratios of the two selected measurements of each measured element; an emission analysis apparatus.

3. The emission spectroscopy apparatus according to claim 1, wherein the control unit performs two measurements on the sample, calculates a difference in the content ratio between the two measurements for the priority element, and when the difference is within the management range, For all elements with the control range set, determine whether the difference in the content ratios of the two measurement times for each element is within the control range. For all elements with the control range set, when the difference in the content ratios of the two measurement times for each element is within the control range of each element, calculate the average value of the content ratios of the two measurement times of each measured element as the representative value and output it. Emission analyzer.

4. The emission spectroscopy device according to claim 1, wherein the control unit performs two measurements on the sample, calculates the difference in the content ratios of the two measurement times for the priority elements, and when the difference exceeds the control range, outputs that the two measurement results exceed the control range. Emission analyzer.

5. The emission spectroscopy device according to claim 4, when the control unit performs the third measurement, the control unit determines whether the smaller of the difference between the content ratio of the first measurement time and the content ratio of the third measurement time and the difference between the content ratio of the second measurement time and the content ratio of the third measurement time for the priority elements exceeds the control range, and when it exceeds, performs a fourth measurement on the sample. Emission analyzer.

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