JP5169869B2 - Spark discharge emission spectroscopic analysis method and spectroscopic analysis system thereof - Google Patents

Description

  The present invention relates to a spark discharge emission spectroscopic analysis method for performing spectroscopic analysis of components contained in a sample according to a multi-analysis logic based on a spectrum generated by spark discharge emission for a plurality of measurement regions set on the surface of the sample, It relates to the spectroscopic analysis system.

  Conventionally, spark discharge optical emission spectrometry has been used to analyze components contained in a sample, and can analyze components in a short time. In particular, blast furnace hot metal, converter hot metal, converter steel, It is widely used for component composition management of steel materials made in steelmaking processes such as secondary refined steel and continuous cast steel.

  The sample used for this analysis is a cylindrical hot metal or steel taken from molten hot metal or steel and cooled and solidified. In order to perform elemental composition analysis using an analyzer based on spark discharge emission spectrometry, it is necessary to form a flat surface on the sample, and the surface of the sample is processed into a flat surface and then subjected to spectroscopic analysis. . Therefore, when the component analysis of a steel material is performed, the steel material to be analyzed is cut and then ground or polished to be finished in a flat shape. And the steel material in which the plane was formed is attached to the sample support stand of the emission spectrometer as a sample.

  In the spark discharge optical emission spectrometer, the flat surface of the steel material is one electrode, and a spark discharge electrode made of silver or tungsten is disposed opposite to the electrode. Therefore, a spark discharge is generated between the plane of the steel material and the spark discharge electrode, the spectrum line of the light emission generated on the plane is dispersed by a spectroscope, and the intensity of the spectrum line is measured (see JIS, G1235: 2002). ), The component of the steel material can be quantitatively analyzed based on the measured spectral line intensity (see, for example, Patent Documents 1 to 4).

  Here, with reference to FIG. 7, an outline of a generally known spark discharge optical emission spectrometer will be described below. The spark discharge optical emission spectrometer 1 includes a discharge chamber, a spectroscopic chamber, and a measurement control device. A spark discharge electrode 2 is disposed in the discharge chamber. On the discharge chamber wall facing the spark discharge electrode 2 at an appropriate distance, a circular window for specifying a measurement region is provided. In the example of FIG. Is placed. The inside of the discharge chamber is filled with Ar gas, and a spark discharge d is generated between the spark discharge electrode 2 and the sample A by a high voltage pulse supplied from the spark discharge generator 3 in the Ar gas atmosphere. Is generated.

  On the other hand, the inside of the spectroscopic chamber is maintained in a vacuum, and is separated from the discharge chamber by a condenser lens 4. The spectroscopic chamber is provided with an entrance slit 5, a diffraction grating 6, an exit slit 7, and a plurality of photomultiplier tubes 8. Here, the light due to the spark discharge d generated in the discharge chamber is taken out as a parallel light beam directed in a fixed direction by the condenser lens 4 and the entrance slit 5 and is split by the diffraction grating 6. The exit slit 7 is provided with slits at positions corresponding to the spectral wavelengths of a plurality of elements contained in the sample A, and the light dispersed by the diffraction grating 6 is light that has passed through the slit of the exit slit 7. Only the photomultiplier tube 8 is input.

  The measurement control device includes a measurement device 9 and a processing device 10. The measuring device 9 includes a single pulse integrator, has a function of integrating each output current from the plurality of photomultiplier tubes 8 in discharge units, and outputs each integrated value as a measured value corresponding to the spectral wavelength. . The processing device 10 includes a microcomputer, stores the measurement values measured by the measurement device 9 in a storage device for each spectral wavelength, and performs an analysis process on the elemental composition of the sample A based on each measurement value.

  By the way, as described above, when the sample for analysis is a molten hot metal or a steel material taken from steel, elemental composition analysis is performed on the sample by an analyzer using spark discharge emission spectrometry. However, in order to obtain a flat surface, a flat surface obtained by cutting or polishing is required. Of the flat surface of the sample obtained by cutting or polishing, a partial surface that does not have surface defects by visual inspection. Must be selected and analyzed for luminescence. This visual inspection and the subsequent work of selecting a defect-free partial surface and setting it in the analyzer depended on experienced workers.

  However, there is a problem in selecting a partial surface that does not have a surface defect by visual inspection, setting it in an analyzer, and analyzing it with an emission spectroscopic analyzer. For example, FIG. 8 shows an example of a sample surface obtained by cutting or polishing. The sample A shown in FIG. 8 has a circular shape with a diameter t. On the surface of the sample A after cutting or polishing, the spark discharge position of the spark discharge emission spectrometer, that is, the measurement region is indicated by Rd. The measurement region Rd is circular, and the center thereof is set at a position separated from the outer shape of the sample A by t / 4 (see, for example, Patent Document 5).

  By the way, although the surface of the sample A is flattened by cutting or polishing, as shown in FIG. 8, surface defects such as pinholes, cracks and uneven polishing are actually generated. . If this surface defect exists in the range to be selected in the measurement area, it must be selected as an abnormal surface that is inappropriate for measurement. In this way, it is difficult to make a quantitative standard for visual discrimination by hand, and it is inefficient. In addition, even if a good flat defect-free portion necessary for the component composition analysis of the sample is found by visual observation, it is necessary to confirm that it has a sufficiently large area as a measurement region required for analysis. I relied on.

JP 2000-9645 A JP-A-9-196850 JP 2006-266949 A JP 2001-83096 A JP-A-9-196850

  However, usually, spark discharge emission spectroscopic analysis is performed on two measurement areas on the sample surface, and the component values measured in the two measurement areas are simply averaged and used as representative components of the sample. Therefore, as described above, when the presence / absence of a surface defect is visually observed, the variation in the component value occurs due to the fact that the criterion for determining the flatness of the sample surface is not quantified. In some cases, the sample was judged to be unsuitable. In particular, in the steel type having a narrow target component value, there is a problem that the probability that this component is shifted increases. For this reason, it has been a problem to improve the analysis accuracy to improve the component ratio.

  In the spark discharge optical emission spectrometry, the surface of the sample is flattened, and then the surface roughness of the specified measurement region is inspected for the flatness. If the inspection does not pass, polishing is performed again as a sample failure. There was a need. Therefore, if the sample is defective, because of the re-polishing of the sample, the analysis waiting time of each process is increased by the time of the re-polishing, affecting the production plan of the steel material related to the sample, The temperature loss during the waiting time had a great influence on the steelmaking cost.

  Therefore, in the present invention, in spark discharge emission spectroscopic analysis, a plurality of measurement regions are inspected at the time of surface roughness inspection on a sample surface, and spark discharge emission is performed in which spectroscopic analysis of components contained in the sample is performed according to multiple analysis logic. It is an object of the present invention to provide a spectroscopic analysis method and a spectroscopic analysis system thereof.

In order to solve the above problems, in the present invention, a spark discharge emission spectroscopic analysis method for performing spectroscopic analysis of components contained in a sample based on a spectrum generated by spark discharge emission for a measurement region set on the surface of the sample A plurality of inspection ranges having a predetermined area are set apart from each other on the surface of the sample, a surface roughness inspection is performed for each of the plurality of inspection ranges, and a predetermined condition in the surface roughness inspection is set. Each of the inspection ranges satisfying the above is determined as a measurement region, and the measurement region located farthest from one of the measurement regions determined as the measurement region where the spark discharge light emission is performed is the measurement region where the spark discharge light emission is performed next. determined that sequentially performed to, determines the order of the spark discharge emission to the measurement region of the respective, said in order of spark discharge emission, before It was decided to carry out the spark discharge emission to the measurement region.

And each of the plurality of inspection ranges is set around a position shifted by a predetermined angle on a circumference of a half radius on the circular surface on the circular surface of the sample, and further, the inspection range settings, we decided to start from any angle position shifted from an arbitrary point on the circumference of one radius of 2 minutes in the circular surface.

The surface roughness inspection is performed every time the inspection range is set, and it is determined whether or not the inspection result satisfies the predetermined condition. When it is determined that the inspection range is satisfied, the inspection range is determined as the measurement region. We were decided.

  When the difference between the maximum value and the minimum value is less than or equal to the allowable value among the measured component values related to the respective measurement regions, the average value of the component values is used as the component value of the sample, or the measurement is performed. If the difference between the maximum value and the minimum value exceeds the allowable value among the component values related to each of the measured areas, the component values farthest from the average value of the component values are excluded, and the remaining component values Among these, when the difference between the maximum value and the minimum value is less than or equal to the allowable value, the average value of the remaining component values is determined as the component value of the sample.

  Among the measured component values for each of the measured areas, if the difference between the maximum value and the minimum value exceeds the allowable value, the component value farthest from the average value of the component values is excluded, and the remaining components If the difference between the maximum and minimum values exceeds the allowable value, the component value farthest from the average value of the remaining component values is excluded, and the maximum and minimum values among the remaining component values When the difference between the two values is equal to or less than the allowable value, the average value of the remaining component values is determined as the component value of the sample.

Further, the present invention provides a surface roughness inspection in a spark discharge emission spectroscopic analysis system that performs spectral analysis of components contained in a sample based on a spectrum generated by spark discharge emission for a measurement region set on the surface of the sample. A range setting means for setting a plurality of inspection ranges having a predetermined area on the surface of the sample placed in the apparatus, and a surface roughness inspection apparatus for each of the plurality of inspection ranges. Inspection determination means for determining whether the result of the executed surface roughness inspection satisfies a predetermined condition; a measurement area determination means for determining each of the inspection ranges determined to satisfy the predetermined condition; The measurement region located farthest from one of the measurement regions determined as the measurement region for performing the spark discharge light emission is then measured for performing the spark discharge light emission. Performed sequentially determining the area, and order determining means for determining the order of the spark discharge emission to the measurement region of the respective, relative to the spark discharge emission spectroscopic analysis apparatus wherein sample is placed, said spark discharge emission And instructing means for instructing the spark discharge emission according to the order.

Then, the range setting means sets each of the plurality of inspection ranges on the circular surface of the sample around a position shifted by a predetermined angle on a circumference of a half radius on the circular surface. Teisu was Rukoto.

  In addition, a processing unit that processes each component value related to each of the measurement regions measured in the spark discharge optical emission spectrometer is provided, and the processing unit includes the component values related to each of the measured measurement regions. In the case where the difference between the maximum value and the minimum value is less than or equal to the allowable value, the average value of the respective component values is set as the component value of the sample, and when the difference between the maximum value and the minimum value exceeds the allowable value, When the component value farthest from the average value is excluded and the difference between the maximum value and the minimum value is less than or equal to the allowable value among the remaining component values, the average value of the remaining component values is determined for the sample. The component values were used.

  As described above, according to the spark discharge optical emission spectrometry of the present invention, after performing a surface roughness inspection on each of a plurality of inspection ranges having a predetermined area set apart from each other on the surface of the sample. Since each of the inspection ranges satisfying the predetermined condition in the surface roughness inspection is determined as the measurement region, the maximum number of inspection ranges can be set within a range where the discharge traces on the sample surface do not interfere with each other. As a result of the surface roughness inspection, when the number of the inspection ranges satisfies the minimum emission analysis score, the sample can be normal, and when not, the sample can be defective.

  Therefore, if the minimum emission analysis score is set, the soundness of the sample can be easily evaluated, and the emission analysis score can be easily selected according to the purpose. In addition, since it is possible to easily determine whether a sample is normal or defective for spark discharge optical emission spectrometry, it is possible to improve work efficiency without requiring an expert.

  Further, since the surface roughness inspection is performed for the set inspection range, the determination of the flatness of the sample surface becomes clear, so that the occurrence of variations in the component values can be suppressed. In particular, even a steel type having a narrow target component value can reduce the probability that this component will be shifted, so that the component mid-value can be improved and the analysis accuracy can be improved.

  Further, for the sample determined to be normal, determine the order of the spark discharge emission for each of the measurement areas that are the analysis points specified on the sample surface, and according to the order of the spark discharge emission, Since the spark discharge emission can be performed on the sample surface, the analysis points to be subjected to the spark discharge emission can be dispersed on the sample surface, and the analysis points can be represented.

It is a flowchart explaining the procedure of the spectroscopic analysis method by spark discharge luminescence in this embodiment. It is a figure explaining the outline | summary of the spark discharge emission-spectral-analysis system by this embodiment. It is a flowchart explaining the detailed procedure which performs the surface roughness test | inspection for setting a some measurement area | region on a sample surface. It is a figure explaining the specific example which could set the some measurement area | region on the surface of a circular sample. It is a figure explaining the method of determining the order of the spark discharge light emission with respect to the several measurement area | region set on the surface of the circular sample. It is a flowchart explaining the procedure which calculates | requires a final analysis value from the measured value of the several measurement area | region obtained by discharge light emission according to the determined order. It is a figure explaining the outline | summary of a spark discharge emission-spectral-analysis apparatus. It is a figure explaining the setting method which concerns on the measurement area | region on the circular sample surface by a prior art.

  Next, an embodiment of a spark discharge emission spectroscopic analysis method according to the present invention will be described below with reference to FIGS.

  The flowchart of FIG. 1 shows the procedure of the spectroscopic analysis method by spark discharge emission in this embodiment, and FIG. 2 shows the outline of the system that can implement the procedure of the spark discharge emission spectroscopic analysis method by this embodiment. .

  A spark discharge emission spectroscopic analysis system 100 shown in FIG. 2 includes a spark discharge emission spectroscopic analysis apparatus (hereinafter referred to as an analysis apparatus) 1, a surface roughness inspection apparatus 101, a control apparatus 102, an input scanning apparatus 103, and a storage apparatus 104. The display device 105 is configured. As the analyzer 1, for example, the spark discharge emission spectroscopic analyzer 1 shown in FIG. 7 can be used. Further, for the surface roughness inspection apparatus 101, for example, a measurement sensor capable of detecting fine irregularities on the surface by irradiating laser light can be used.

  The control device 101 corresponds to the measurement control device including the measurement device 9 and the processing device 10 shown in FIG. 7, and further includes a range setting unit a, an inspection determination unit b, a measurement region determination unit c, and an order determination unit. d, instruction means e, and component value processing means f. The functions of these means are realized by a microcomputer according to a program. In addition, the display device 105 displays the setting state / evaluation result of the inspection range, the setting state / order determination state of the measurement region, the component analysis result of the sample, and the like as images.

  Next, the operation and processing of the analyzer of the present embodiment configured as described above will be described according to the flowchart shown in FIG. Here, it is assumed that one end surface of the sample to be subjected to spark discharge emission spectrometry is flattened.

  First, the sample is placed on the inspection table provided in the surface roughness inspection apparatus 101 with the polished surface facing the measurement sensor. The operator designates an arbitrary point on the sample surface using the input operation device 103. When an arbitrary point is designated, the range setting means a starts from the arbitrary point and sets a predetermined range, that is, a distance that does not overlap a range having a size corresponding to a spark discharge mark. The point at that distance is calculated and set as the center point of the inspection range, and stored in the storage device 104. By repeating this process, a plurality of inspection ranges are set on the surface of the sample (step S1). Details of this step will be described later.

  Next, the control device 102 reads the center point related to the inspection range set from the storage device 104, and the inspection table provided in the surface roughness inspection device 101 so that the center point matches the position of the measurement sensor. To control. Therefore, when the center point coincides with the position of the measurement sensor, the surface roughness inspection apparatus 101 is caused to execute the surface roughness inspection for the inspection range related to the center. This process is repeated for each set center point, and surface roughness inspection is performed for a plurality of set inspection ranges (step S2). Surface roughness inspection data relating to the inspection range corresponding to each center point is stored in the storage device 104.

  When the surface roughness inspection for a plurality of inspection ranges is completed, the inspection determination unit b of the control device 102 compares each surface roughness inspection data with a preset reference value, and the surface roughness for each inspection range. Inspection evaluation is executed (step S3).

  Here, if the surface roughness inspection data exceeds the reference value, it may be rejected as an object of emission spectroscopic analysis by spark discharge, and if it is within the reference value, it may be considered as acceptable. it can. Furthermore, for example, if there are two or more inspection ranges that are passed, the sample is subject to spectroscopic analysis as normal. In other cases, that is, if the passing inspection range is only one, the subject is spectroscopic analysis. The sample surface is re-polished.

  Next, the measurement region determination unit c determines a plurality of inspection ranges evaluated by the inspection determination unit b as being suitable for the emission spectroscopic analysis as measurement regions as the targets for the emission spectroscopic analysis, and measures them in the storage device 104. The position of the area is stored (step S4). Here, the sample for which a plurality of measurement areas have been determined is moved from the surface roughness inspection apparatus 101 to the analysis apparatus 1, and the measurement area on the sample surface faces the spark discharge electrode 2 in the discharge chamber of the analysis apparatus 1. Arranged.

  When the plurality of measurement regions are determined, the order determining unit d of the control device 102 determines the order of the spark discharge emission for the plurality of measurement regions, and stores the order in the storage device 104 (step S5). Here, in order to give representativeness to the analysis points on the sample surface and to disperse the light emission points, the light emission points should be separated as much as possible for a plurality of light emission points, so as not to be adjacent to each other. The order is determined. Details of this order determination will be described later.

  Next, when the order of the spark discharge light emission is determined, the instruction means e of the control device 102 faces the spark discharge electrode 2 in which the measurement region on the sample surface is in the discharge chamber of the analyzer 1 according to the determined order. In this manner, an instruction to move the sample is sent to the analyzer, and a spark discharge emission instruction is output every time the measurement region is moved, and the measurement value corresponding to the spectral wavelength acquired by the analyzer 1 is stored in the storage device 104. (Step S6).

  Here, the component value processing means f of the control device 102 executes an analysis process based on the measurement value corresponding to the spectral wavelength acquired by the analysis device 1, and the component composition of the element contained in the sample is measured. The measurement result is stored in the storage device 104 and can be displayed on the screen of the display device 105 according to an instruction from the input operation device 103 by the operator, if necessary.

  In the spark discharge optical emission spectrometry described above, the sample to be subjected to the spark discharge optical emission spectrometry is not limited to a cylindrical shape having a circular cross section, and may be any shape, for example, a square column, If the one end surface is flattened, it can be the target of this spark discharge emission spectroscopic analysis. When the sample has a cylindrical shape, it is arranged on a table that is driven to rotate. When the sample has an arbitrary shape, it is arranged on a table that can be driven by rotation or driven in the XY axis direction. Good.

  Next, the details of the processing procedure of steps S1 to S4 in the flowchart of FIG. 1 will be described below with reference to the flowchart of FIG.

  In the processing procedure shown in FIG. 1, a plurality of inspection ranges are set (step S1), surface roughness inspection of the inspection range (step S2), evaluation of the surface roughness inspection (step S3), and measurement area setting (step S4). Were sequentially processed to set a plurality of measurement areas on the sample surface. In this method, a plurality of inspection ranges are first set, and then a roughness inspection is performed. Therefore, if the inspection fails, the number of measurement areas set is reduced accordingly.

  Therefore, in the processing procedure according to the flowchart of FIG. 3, each time an inspection range is set on the surface of the sample A, a surface roughness inspection is performed, and each time the inspection range can be determined as a measurement region based on the inspection result. As much as possible, it was made possible to secure as many measurement areas as possible on the surface of the sample A.

  First, a cylindrical sample A having a diameter r is placed on the inspection table of the surface roughness inspection apparatus 101 (step S10). The range setting means a of the control device 102 determines an arbitrary point on the circumference of a half radius (r / 2) on the surface of the sample A (step S11). This arbitrary point becomes a reference for determining the position of the inspection range.

  Therefore, the range setting means a rotates the inspection table clockwise around the center point of the sample A with respect to the determined arbitrary point, for example, by 10 degrees. Then, a circular inspection range is determined centering on the rotation position on the circumference of the radius (step S12). Here, the inspection range is a region having a size in which a discharge mark having a diameter of 7 [mm] generated by the spark discharge is accommodated.

  Next, when the first inspection range is determined, the inspection determination unit b of the control device 102 causes the surface roughness inspection device 101 to perform a surface roughness inspection on the inspection range (step S13). And based on the measurement data acquired from the surface roughness inspection apparatus 101, the pass / fail determination of the surface roughness inspection in the said inspection range is performed (step S14).

  The inspection determination means b determines the inspection range as a measurement region when it is determined that the surface roughness inspection is acceptable (step S15). Thus, the first measurement area is determined. However, if the surface roughness inspection fails, the sample A is further rotated clockwise by 10 degrees without determining the inspection range as a measurement region, and the radius is rotated on the circumference. The inspection range is determined centering on the position (step S16).

  By the way, when the inspection range can be determined as the measurement region in step S15, the sample A is rotated clockwise by 10 degrees in order to determine the next inspection range in step S16. Rotate to a position that does not overlap with the inspection range, and determine that position as the next inspection range.

  Next, as in step S13, the inspection determination unit b of the control device 102 causes the surface roughness inspection device 101 to perform a surface roughness inspection for the next inspection range (step S17). And based on the measurement data acquired from the surface roughness inspection apparatus 101, the pass / fail determination of the surface roughness inspection in the next inspection range is performed (step S18).

  The inspection determination means b determines the next inspection range as a measurement region when it is determined that the surface roughness inspection is acceptable (step S19). Thus, the second measurement area is determined. However, if the surface roughness inspection fails, the sample A is further rotated clockwise by 10 degrees without determining the next inspection range as the measurement region, and the radius is on the circumference. The next inspection range is determined around the rotation position.

  Thereafter, the process from step S16 to step S19 is repeated while rotating the sample A by 10 degrees until it makes one round on the circumference of the radius of half (r / 2) (step S20). As described above, a plurality of measurement regions can be set on the surface of the sample A. Although the rotation direction of the sample A is clockwise, it may be counterclockwise. Although the rotation angle is set to 10 degrees, the present invention is not limited to this, and the rotation angle can be arbitrarily determined in consideration of the relationship between the size of the surface of the sample A and the size of the discharge mark.

  The details of the procedure for setting a plurality of measurement regions have been described above in the case of the columnar sample A. FIG. 4 shows a specific example in which a plurality of measurement regions are set according to the setting procedure. The state of this specific example was displayed in a diagram for convenience of explanation of the positional relationship, but actually, this positional relationship is stored as positional information in the storage device 104 and is displayed on the sample surface. It is not drawn. The display device 105 can create and display an image as shown on the basis of the position information.

  In the specific example of FIG. 4, a sample A is a cylindrical steel material having a diameter r of 30 [mm]. A circle having a half radius (r / 2) is indicated by a broken line, and six circular measurement regions Rd having a center on the circle and corresponding to a discharge mark having a diameter of 7 mm are set. ing. In this specific example, a circular window B provided in the discharge chamber of the analyzer 1 is also displayed, but this shows the relationship between the measurement region Rd and the circular window B for the sake of convenience. In this case, when the sample A is rotated, each of the measurement regions Rd sequentially faces one circular window B. The circular window B has a diameter of 12 [mm].

  According to the specific example shown in FIG. 4, in the case of the sample A having a diameter r of 30 [mm], if the measurement area setting procedure according to the flowchart of FIG. Thus, it has been shown that the six measurement regions Rd can be automatically set regardless of human hands.

  In the above, it has been described that a plurality of measurement regions are set on the surface of the sample A according to the measurement region setting procedure according to the flowchart of FIG. 3 described above. Next, the measurement regions in step S5 of the flowchart of FIG. Will be described with reference to FIGS. 5A to 5C.

  FIG. 5A shows a case where the maximum number of six measurement regions Rd11 to Rd16 is set on the surface of the sample A1, similarly to the specific example of FIG. Does not necessarily mean that six measurement areas can be set, and FIG. 5B shows a case where five measurement areas Rd21 to Rd25 can be set on the surface of the sample A2, and FIG. c) shows a case where four measurement regions Rd31 to Rd34 can be set on the surface of the sample A3.

  In order to determine the actual measurement order for multiple measurement areas set on the surface of the sample, the measurement positions are considered to be dispersed as much as possible. The components are analyzed in accordance with the order. The numbers in the circles corresponding to the measurement areas shown in FIGS. 5A to 5C indicate this order.

  In the case of FIG. 5A, each measurement region is measured in the order of Rd11, Rd14, Rd12, Rd15, Rd13, Rd16, and in the case of FIG. 5B, each measurement region is Rd21, Rd24. , Rd22, Rd25, Rd23, and in the case of FIG. 5C, each measurement region is measured in the order of Rd31, Rd22, Rd32, Rd34.

  As described above, the priorities of spectroscopic analysis are determined for a plurality of measurement regions set on the surface of the sample, so that the positions of emission spectroscopic analysis by spark discharge are dispersed. Based on the simple average value of the measured values obtained from the region, the representative component value of the sample can be obtained.

  As described above, according to the measurement region setting procedure according to the flowchart of FIG. 3, as many measurement regions as possible can be set on the surface of the sample A. However, since a plurality of measurement regions are set on the sample surface, a plurality of component values that are spectroscopic analysis results are also obtained, but these values may vary. Then, next, the procedure for determining the representative component value of the sample from the obtained plurality of component values will be described below with reference to FIG.

  First, in step S6 shown in the flowchart of FIG. 1 described above, each measurement region set on the sample surface moves in accordance with the determined order, and spark discharge emission spectroscopic analysis is performed for each movement, and control is performed. The component value processing means f of the apparatus 102 performs analysis processing based on the measured values, and obtains analysis values of elements contained in the sample from each of the plurality of measurement regions (step S100).

  Next, it is determined whether or not the difference between the maximum value and the minimum value included in the plurality of component values is within a preset allowable value range (step S101). Here, it is determined whether or not the plurality of analysis values vary greatly. If the difference is within the allowable value range (Y in step S101), an average value of the plurality of analysis values is obtained and Is the final analysis value of the sample (step S102).

  On the other hand, if the difference between the maximum value and the minimum value is not within the allowable range in step S101 (N in step S101), an average value of a plurality of analysis values is obtained, and the analysis value farthest from the average value is obtained. Exclude (step S103). Here, it is determined whether or not the difference between the maximum value and the minimum value included in the remaining plurality of component values excluding the farthest analysis value is within a preset allowable value range ( Step S104).

  If the difference is within the allowable value range (Y in step S104), the process proceeds to step S102, an average value of the remaining plurality of analysis values is obtained, and is used as the final analysis value of the sample. On the other hand, if the difference between the maximum value and the minimum value among the remaining analysis values is not within the allowable range in step S104 (N in step S104), an average value of the remaining plurality of analysis values is obtained. The analysis value farthest from the average value is excluded (step S105).

  Here, again, it is determined whether or not the difference between the maximum value and the minimum value included in the remaining plurality of component values from which the farthest analysis value is removed is within a preset allowable value range. (Step S106). If the difference is within the allowable value range (Y in step S106), the process proceeds to step S102, an average value of the remaining plurality of analysis values is obtained, and is used as the final analysis value of the sample. On the other hand, when the difference between the maximum value and the minimum value among the remaining analysis values is not within the allowable value range in step S106 (N in step S106), the sample is determined to be unqualified (step S107). ),finish.

  As described above, according to the spark discharge emission spectroscopic analysis method according to the present embodiment, the measurement region that is the analysis point set on the sample surface can be maximized, and the analysis for a plurality of set measurement regions is performed. Since the order can be determined and dispersed, and the component analysis of the sample can be performed according to the multi-analysis logic, the component analysis can be performed with high accuracy and the analysis process can be performed at high speed.

DESCRIPTION OF SYMBOLS 1 Spark discharge emission-spectral-analysis apparatus 2 Spark discharge electrode 3 Spark discharge generator 4 Condensing lens 5 Entrance slit 6 Diffraction grating 7 Exit slit 8 Photomultiplier tube 9 Measuring apparatus 10 Processing apparatus 100 Spark discharge emission-spectral-analysis system 101 Surface Roughness inspection apparatus 102 Control apparatus 103 Input operation means 104 Storage means 105 Display means A, A1 to A3 Sample Rd Measurement area

Claims (10)

In a spark discharge emission spectroscopic analysis method for performing spectroscopic analysis of components contained in a sample based on a spectrum generated by spark discharge emission for a measurement region set on the surface of the sample,
A plurality of inspection ranges having a predetermined area are set apart from each other on the surface of the sample,
Perform surface roughness inspection for each of the plurality of inspection ranges,
Each of the inspection ranges satisfying a predetermined condition in the surface roughness inspection is determined as a measurement region,
Each of the measurement areas is sequentially determined by sequentially determining a measurement area at a position farthest from one of the measurement areas determined as the measurement area where the spark discharge light emission is performed, as a measurement area where the spark discharge light emission is performed next. Determine the order of spark discharge emission for
A spark discharge emission spectroscopic analysis method, wherein the spark discharge emission is performed on the measurement region in the order of the spark discharge emission.   The plurality of inspection ranges are set on a circular surface of the sample with a position shifted by a predetermined angle on a circumference of a half radius on the circular surface. 2. The spark discharge emission spectroscopic analysis method according to 1.   3. The spark discharge emission spectroscopic analysis method according to claim 2, wherein the setting of the inspection range starts from a position shifted by an arbitrary angle from an arbitrary point on the circumference of a half radius on the circular surface.   The surface roughness inspection is performed every time the inspection range is set, and it is determined whether or not the inspection result satisfies the predetermined condition. When it is determined that the inspection range is satisfied, the inspection range is determined as the measurement region. The spark discharge emission spectroscopic analysis method according to claim 2 or 3, Among the measured component values for each of the measurement areas, when the difference between the maximum value and the minimum value is less than or equal to an allowable value, the average value of the component values is used as the component value of the sample. The spark discharge emission spectroscopic analysis method according to any one of claims 1 to 4 . Among the measured component values for each of the measured areas, if the difference between the maximum value and the minimum value exceeds the allowable value, the component value farthest from the average value of the component values is excluded, and the remaining components among the values, if the difference between the maximum value and the minimum value is equal to or less than the allowable value, any one of claims 1 to 4, characterized in that the component values of the sample average value of the component values of該残Ri The spark discharge emission spectroscopic analysis method according to one item. Among the measured component values for each of the measured areas, if the difference between the maximum value and the minimum value exceeds the allowable value, the component value farthest from the average value of the component values is excluded, and the remaining components If the difference between the maximum and minimum values exceeds the allowable value, the component value farthest from the average value of the remaining component values is excluded, and the maximum and minimum values among the remaining component values If the difference is equal to or less than the allowable value, the spark discharge emission spectroscopic analysis according to the average value of each component value of該残Ri to any one of claims 1 to 4, characterized in that the component values of the sample Method. In a spark discharge emission spectroscopic analysis system for performing spectroscopic analysis of components contained in a sample based on a spectrum generated by spark discharge emission for a measurement region set on the surface of the sample,
On the surface of the sample placed in the surface roughness inspection apparatus, a range setting means for setting a plurality of inspection ranges having a predetermined area apart from each other;
For each of the plurality of inspection ranges, inspection determination means for determining whether the result of the surface roughness inspection performed by the surface roughness inspection apparatus satisfies a predetermined condition;
A measurement region determining means for determining each of the inspection ranges determined to satisfy the predetermined condition as a measurement region;
Each of the measurement areas is sequentially determined by sequentially determining a measurement area at a position farthest from one of the measurement areas determined as the measurement area where the spark discharge light emission is performed, as a measurement area where the spark discharge light emission is performed next. Order determining means for determining the order of spark discharge emission with respect to
A spark discharge emission spectroscopic analysis system comprising: an instruction means for instructing the spark discharge emission in accordance with the order of the spark discharge emission to the spark discharge emission spectroscopic analysis apparatus on which the sample is placed . The range setting means sets each of the plurality of inspection ranges on a circular surface of the sample with a position shifted by a predetermined angle on a circumference of a half radius on the circular surface. The spark discharge emission spectroscopic analysis system according to claim 8 . A processing means for processing each component value relating to each of the measurement regions measured in the spark discharge optical emission spectrometer;
When the difference between the maximum value and the minimum value is less than or equal to an allowable value among the measured component values of the respective measurement regions, the processing means calculates the average value of the component values as the component value of the sample. If the difference between the maximum value and the minimum value exceeds the allowable value, the component value farthest from the average value of each component value is excluded, and the difference between the maximum value and the minimum value is the allowable value among the remaining component values. The spark discharge emission spectroscopic analysis system according to claim 8 or 9 , wherein an average value of the remaining component values is used as a component value of the sample in the case of the following.

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