JP4794848B2 - Analysis equipment - Google Patents

Description

  The present invention relates to an intelligent analyzer that can increase the productivity and reliability of analytical work in quantitative analysis of harmful elements contained in metallic materials and nonmetallic materials, and in particular, the types of coexisting elements. It is related with the apparatus which estimates the presence or absence of surface treatment, and the presence or absence of hexavalent chromium in a coating film.

  Conventionally, X-ray fluorescence analysis has been widely used for quality control and material research in material production as a means for specifying constituent elements of materials. Recently, regulations on hazardous substances in consumer products such as European RoHS regulations (Restriction of Hazardous Substances) and ELV (End of Life Vehicle) are being strengthened. Regarding products to be exported to Europe, As a means for checking whether or not a regulated element is contained in a part purchased from the outside, there are an increasing number of cases in which a large number of devices are introduced in parts specification departments and receiving departments in electrical manufacturers.

  In the determination of the presence or absence of harmful elements, it is necessary that the lower limit of quantification be sufficiently low in order to determine non-contained when the concentration is so small that it does not actually cause a problem. In addition, since an enormous number of parts constituting a product are to be investigated, it is necessary to check in a non-destructive manner and in a short time as much as possible. Since the energy dispersive X-ray fluorescence analysis method is suitable for such needs, energy dispersive X-ray fluorescence analyzers compliant with RoHS and ELV regulations are commercially available from analysis equipment manufacturers, such as Cd, Pb, etc. Development of a primary filter and a calibration curve program for facilitating detection of fluorescent X-rays of the elements subject to restriction is progressing and widely used.

  In addition, from the viewpoint of information processing related to analysis, analysis information that can be provided immediately when an analyst needs analysis information from reception and registration of analysis samples necessary for analysis work to creation of analysis result reports A unified management system has been proposed (for example, Patent Document 1). Furthermore, a database containing the entire contents of parts used in products and the contents of chemical substances contained in the parts, and the types and amounts of contained chemical substances are calculated using these databases. A management system has been proposed (for example, Patent Document 2).

  As an apparatus for inspecting a minute region nondestructively, an analyzer capable of element mapping using fluorescent X-rays excited by a minute beam is commercially available.

Phases in the vicinity of the sample surface obtained by secondary X-rays are analyzed by analyzing the distribution of parts (phases) having similar compositions by analysis means based on transmitted X-rays in addition to secondary X-rays such as fluorescent X-rays. In addition to the above, there has been proposed an X-ray analyzer capable of phase separation including a phase inside a sample obtained by transmission X-ray (for example, Patent Document 9). Furthermore, by synthesizing the stored second image data of the area instead of the first image data of the area, a partial image of the stored first image data is generated and displayed, There is provided a measurement result display method capable of easily recognizing the correspondence between an image obtained by imaging and an image obtained by X-ray measurement (for example, Patent Document 10).
JP-A-9-119933 JP 2003-256504 A Japanese Patent Publication No. 6-76977 JP 2001-281235 A Japanese Patent Publication No. 7-13302 JP-A-4-223210 JP-A-7-26385 JP 2001-296508 A JP 2004-93511 A JP 2001-233262 A

  Due to the technical improvements of analyzer manufacturers as described above, high-sensitivity energy dispersive X-ray fluorescence analyzers that can check the content of harmful elements have been put into practical use, but the presence or absence of harmful elements in purchased parts or materials is determined. In the analysis, there are unique problems as shown below, which are different from those of conventional material production management and material research.

  First, there are a wide variety of parts to be inspected, and each part is composed of many kinds of materials, and the number of analysis objects is enormous.

  Second, since the concentration calculation algorithm (calibration curve, primary filter, measurement time, tube voltage) differs for each material, the analyst determines the appropriate analysis conditions and calculation method for each material and regulated element in advance. It is necessary to keep. It is also necessary to determine the type of material. Furthermore, it is necessary to specify and input analysis conditions and algorithms for each target material.

  Third, it is difficult to analyze the fluorescent X-ray spectrum, for example, it is necessary to analyze the spectrum in consideration of the influence of the interference peak, which is a big problem with metal materials, and it is difficult to determine the presence or absence of a minute peak.

Fourthly, those who are involved in the analysis for determining the presence or absence of harmful elements are not necessarily experts in analysis and materials.
For the above reasons, the analysis of harmful element content in purchased parts has a problem that the productivity of the analysis work is low and misjudgment is likely to occur.

  Furthermore, with commercially available energy dispersive X-ray fluorescence spectrometers, it is impossible to measure the valence of an element, so the “hexavalent chromium” subject to regulation can only be detected as Cr (chromium). Yes, it is impossible to determine whether the valence is trivalent or hexavalent. Therefore, the sample in which Cr was detected had to be subjected to a separate dissolution test and quantified by colorimetry. However, in the elution test, hexavalent chromium in the sample was extracted into the solution and compared with the hexavalent chromium standard solution, and therefore, toxic substances had to be discharged by the elution test.

  In addition, the conventional energy dispersive X-ray fluorescence analyzer has been technically improved as a highly sensitive X-ray fluorescence analyzer capable of checking the content of harmful elements. In the determination of the presence or absence of lead in the solder material on the printed board unit in which a kind of solder material is used, there are the following problems.

  First, it is impossible to evaluate forbidden use or exclusion use for lead contained in specific parts of minute electronic components and parts of unit products.

  Secondly, trace amounts of lead can be detected due to problems such as differences in the intensity of fluorescent X-rays due to the distance between the sample and the detector that detects secondary X-rays, and the occurrence of missing images due to solid angles. Have difficulty.

  Third, since all types of solder materials such as mounting solder and component terminal plating are used on all components (printed board units) mounted on the printed board, fluorescent X-rays excited with a micro beam When all components are determined using an analyzer that can perform element mapping using, all areas where the components are mounted must be measured. Therefore, it took a lot of time and effort.

  Accordingly, an object of the present invention is to provide an intelligent analyzer that can increase the productivity and reliability of analysis work in quantitative analysis of harmful elements contained in metal-based materials and non-metal-based materials. It is.

In order to solve the above-mentioned problem, it is connectable with a fluorescent X-ray measuring apparatus, and supports detection of a specified element in a part or material using quantitative measurement based on the fluorescent X-ray analysis method by the fluorescent X-ray measuring apparatus. In the analyzer, a control unit for controlling processing in the analyzer and a result obtained by causing the X-ray fluorescence measurement device to perform quantitative measurement by the X-ray fluorescence analysis method according to a measurement condition instructed by the control unit Measurement result acquisition means for performing the measurement based on the fluorescent X-ray spectrum of the material based on the result of the material determination means and the result of the material determination means. A substance content determining means for causing the fluorescent X-ray measurement apparatus to perform quantitative measurement according to the measurement conditions specified in the above, and determining the presence or absence of the substance containing the designated element based on the quantitative measurement result; The material determining means determines whether or not the total value of the k ratio of each element detected from the component or material is greater than a predetermined value, so that the component or material is a metal-based material. It has a metal nonmetal determination means for determining whether it is a raw material or a material of a nonmetal material, and the substance content determination means is determined to be nonmetal by the metal nonmetal determination means, Cr presence / absence determination means for causing the fluorescent X-ray measurement means to perform quantitative measurement according to a predetermined measurement condition for determining the presence or absence of Cr with respect to a part or material, and for determining the presence or absence of Cr based on the quantitative result And when the Cr presence / absence determining means determines that Cr is contained, and none of the four elements Ba, Zn, Sr, and Pb coexists, it is determined that hexavalent chromium is not contained. Hexavalent Configured to have a beam-free determination means.

  In such an analyzer, the possibility of containing a designated substance (for example, a harmful substance) is verified by fluorescent X-ray analysis (for example, energy dispersive X-ray fluorescence analysis) without requiring specialized knowledge. Can do.

  As means for solving the above-described problems, the present invention may be an analysis method or a computer-executable program for causing a computer to execute processing in such an analysis apparatus.

  According to the present invention, by using an analysis device that realizes a processing flow based on a prior investigation by the inventor, the type of material is automatically determined based on the fluorescent X-ray analysis result, and the quantitative result of the designated element is displayed. It becomes possible. Therefore, even when a person other than an expert analyzes, the specified element contained in the metallic material and the nonmetallic material can be efficiently quantified without malfunction or misjudgment using the fluorescent X-ray analysis method.

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

  An analysis apparatus according to an embodiment of the present invention has a hardware configuration as shown in FIG. 1, for example. FIG. 1 is a diagram showing a hardware configuration of an analyzer according to an embodiment of the present invention.

  In FIG. 1, an analysis apparatus 100 is a terminal controlled by a computer, and includes a CPU (Central Processing Unit) 51, a memory unit 52, a display unit 53, an output unit 54, an input unit 55, and a communication unit. 56, a storage device 57, a driver 58 for accessing the storage medium 59, and an interface (I / F) for connecting to an X-ray fluorescence measuring instrument 62 for performing energy dispersive X-ray fluorescence analysis (EDXRF) ) 61 and connected to the system bus B.

  The CPU 51 controls the analyzer 100 according to a program stored in the memory unit 52. The memory unit 52 includes a RAM (Random Access Memory), a ROM (Read-Only Memory), and the like, and is obtained by a program executed by the CPU 51, data necessary for processing by the CPU 51, and processing by the CPU 51. Stored data. Further, a partial area of the memory unit 52 is allocated as a work area used for processing by the CPU 51.

  The display unit 53 displays various information required under the control of the CPU 51. The output unit 54 has a printer or the like and is used for outputting various types of information in accordance with instructions from a user such as an analyst. The input unit 55 includes a mouse, a keyboard, and the like, and is used by a user to input various information necessary for the analysis apparatus 100 to perform processing. The communication unit 56 is a device for controlling communication with the analysis apparatus 100 when the analysis apparatus 100 is connected to the analysis apparatus 100 via, for example, the Internet or a LAN (Local Area Network). The storage device 57 is composed of, for example, a hard disk unit, and stores data such as programs for executing various processes.

  The fluorescent X-ray measuring instrument 62 connected to the interface 61 is controlled by the CPU 51 and is made of a specified element (for example, a metal or non-metallic part and material by energy dispersive X-ray fluorescence analysis (EDXRF)). Quantitative measurement of harmful elements). A fluorescent X-ray spectrum obtained by irradiating a metallic or non-metallic component and material with primary X-rays is provided to the CPU 51.

Program for realizing processes performed by the analyzer 100, for example, is provided to the analyzer 100 by CD-ROM (Compact Disc Read- Only Memory) storing such medium 59. That is, when the storage medium 59 storing the program is set in the driver 58, the driver 58 reads the program from the storage medium 59, and the read program is installed in the storage device 57 via the system bus B. . When the program is activated, the CPU 51 starts its processing according to the program installed in the storage device 57. The medium for storing the program is not limited to a CD-ROM, and any medium that can be read by a computer may be used. The program for realizing the processing according to the present invention may be downloaded via the network by the communication unit 56 and installed in the storage device 57.

  Next, the analysis flow regarding Cd, Pb, Hg, Cr6 + subject to RoHS regulation and the processing flow for determining whether it is harmful and contained to some extent will be described.

  FIG. 2 is a flowchart for explaining the material determination process by the fluorescent X-ray analysis method. In FIG. 2, the worker executes a program according to the present invention, and performs a sampling process for specifying an article to be analyzed such as a purchased article, a part of the article, or a purchased material (step S11). In this sampling process, for example, when analyzing a part of an article, an object to be analyzed is specified by disassembling a purchased product as a sample and set in the fluorescent X-ray measuring device 62. Next, while confirming the setting state of the sample displayed on the display unit 53 from the CCD camera provided in the fluorescent X-ray measuring device 62 on the display unit 53, it is determined whether or not the sample area is sufficient. Setting is performed (step S12). The sample area determination process will be described later with reference to FIG.

  After confirming the setting, the operator operates the input unit 55 such as a mouse to execute quantitative analysis using the fundamental parameter method (FP method) by the fluorescent X-ray measuring device 62 (step S13). The operator causes the display unit 53 to display a screen for performing quantitative analysis provided by executing the program according to the present invention, and instructs execution of quantitative analysis according to the display on the screen. In accordance with an instruction from the CPU 51, the fluorescent X-ray measuring device 62 irradiates primary X-rays based on the instructed analysis conditions, and executes quantitative analysis.

  The measurement conditions here are, for example, that the tube current is automatic, the tube voltage is 50 kV, the primary filter is not used, and the measurement time is 60 seconds (LiveTime).

  The CPU 51 acquires a fluorescent X-ray spectrum as an analysis result from the fluorescent X-ray measuring device 62 via the interface 61, executes the removal of interference peak components and the presence / absence determination of a minute peak, and determines the peak of the fluorescent X-ray spectrum. To do. A method for removing the interfering peak component and a method for determining the presence or absence of a minute peak will be described later. After determining the peak, the contained elements are determined and quantified. The result is defined as a quantitative analysis result.

  It is determined from the quantitative analysis result whether or not the sample is a metal material, that is, whether or not the total k ratio of each element is larger than 0.65 (step S14). In the case of 0.65 or less, it is determined that the material is a non-metallic material, and the material of the non-metallic material is determined. Non-metallic materials are, for example, resin, paper, glass, ceramics, fats and oils, and the like.

  On the other hand, if it is determined in step S14 that the total k ratio of each element is greater than 0.65, it is determined that the material is a metal material, and the process proceeds to step S15. In step S15, the presence or absence of a coating film is determined. In other words, using the fluorescent X-ray spectrum acquired from the fluorescent X-ray measuring device 62, it is checked whether or not there is an organic substance on the surface from the amount of electromagnetic wave absorption in the infrared region. Judge that there is. The CPU 51 displays a message indicating that there is a coating film on the display unit 53, removing the coating film, and the like.

  In order to determine whether or not the coating film contains harmful substances, analysis / determination processing of the coating material is executed. On the other hand, in order to remove the coating film and expose the base material portion, the process proceeds to step S20. In step S20, in accordance with the message displayed on the display unit 53, the paint film is removed by the operator, and thereafter, the process proceeds to the metal substrate analysis / determination process to determine whether or not it contains a harmful substance. This metal substrate analysis / determination process will be described later with reference to FIG.

  When it is determined in step S15 that there is no coating film, a plating film presence / absence determination process and / or a chromate process presence / absence determination process is performed.

  First, the plating film presence / absence determination process will be described. A solder material determination process is executed (step S18). That is, it is determined whether Sn is detected and the metal surface is silver. As a method for detecting Sn, for example, when the quantification result of the FP method is Sn> 50 wt%, Pb is additionally designated and quantification is performed only with Sn and Pb. The gold / silver color determination process will be described later with reference to FIG.

  If Sn is detected and the metal surface is silver, it is determined that the material is a solder material, and the process proceeds to a solder material analysis / determination process to determine whether or not it contains a harmful substance. On the other hand, if Sn is detected and the metal surface is not silver, the presence or absence of a plating film is determined (step S19). Based on the quantitative results of the FP method, Zn is detected when it is greater than 50 wt%, Ni is detected when it is greater than 50 wt%, Cd is detected, Cr is detected when greater than 20 wt%, and detection of noble metals such as Au and Ag If at least one item is applicable, it is determined that there is a plating film, and the CPU 51 displays a message indicating that the display unit 53 has a plating film, peeling the plating film, and the like.

  In order to determine whether or not the base material portion and the plating film contain harmful substances, the plating film proceeds to the plating film analysis / determination process, and the base material portion is displayed on the display unit 53. According to the message, the plating film is peeled off by the operator and the base material is exposed (step S20), and then the process proceeds to the metal base material analysis / determination process. The metal substrate analysis / determination process will be described later with reference to FIG. 10, and the plating film analysis / determination process will be described later with reference to FIG.

  If it is determined in step S19 that there is no plating film, that is, if any one of the above detection conditions is not met, the analysis / determination process for the metal substrate is performed in order to determine whether or not a harmful substance is contained. Proceed with

  The chromate process presence / absence determination process will be described. When it is determined that there is no coating film in the determination process in step S15, the presence or absence of Cr is confirmed by measurement with increased sensitivity for detecting Cr (step S16). For example, the tube voltage is set to 40 kV, the primary filter is set to Cr, and the measurement time is set to 240 sec (LiveTime).

  Based on the quantitative results of the FP method, Zn is detected when it is greater than 50 wt%, Ni is detected when greater than 50 wt% and contains Cr (coexistence of Ni and Cr), Al is detected when greater than 50 wt% and contains Cr It is determined whether or not at least one item among the detection of Mg (greater than 50 wt%) and containing Cr (coexistence of Mg and Cr) is applicable (step S18-3). If at least one of the above detection conditions is met, it is determined that the chromate treatment is present, and the CPU 51 determines that the display unit 53 has been subjected to the chromate treatment. If a detailed analysis result is required, the hexavalent chromium elution is performed. Display a message indicating that the test should be submitted to an analytical specialist. In this case, the worker will perform a request procedure to an analysis specialist institution as necessary.

  On the other hand, if none of the items correspond to the above detection conditions, the CPU 51 displays a message indicating that the chromate process is not performed on the display unit 53 and ends the material determination process by the fluorescent X-ray analysis method.

  If it is determined in step S14 that the material is a non-metallic material, the presence or absence of Cr is confirmed by measuring the sensitivity for detecting Cr (step S16-5). The measurement conditions here are the same as in step S16 described above. It is determined whether or not Cr is contained (step S17-5). When it is determined that there is no Cr, the CPU 51 displays a message indicating that it is a non-metallic material not containing chromium on the display unit, and ends the material determination process by the fluorescent X-ray analysis method.

  On the other hand, if it is determined in step S17-5 that Cr is present, it is determined whether or not Ba, Sr, Zn, or Pb is contained based on the quantitative result of the FP method (step S18-5). ). That is, it is confirmed whether or not Cr and Ba, Sr, Zn, or Pb coexist. In the present invention, when Cr is present and at least one element of Ba, Sr, Zn, and Pb is contained, the possibility of containing hexavalent chromium is considered high. The elements of Ba, Sr, Zn, and Pb have been found by investigation and analysis by the inventors. Details will be described later.

  If it is not determined in step S18-5 that Ba, Sr, Zn, or Pb is contained, the CPU 51 is a chromium-containing nonmetallic material, but hexavalent chromium is not contained. A certain message is displayed on the display unit. In this case, the chromium contained may be trivalent chromium, but since the object of the harmful substance is hexavalent chromium, it does not contain any harmful substance.

  In the determination in step S18-5, when it is confirmed that Ba, Sr, Zn, or Pb is contained, the CPU 51 has a high possibility of containing hexavalent chromium, and if necessary, hexavalent chromium. A message indicating that a dissolution test is requested in order to confirm the content is displayed on the display unit 53.

  As described above, the analyzer according to the present invention can identify the material of the sample (which part of the product) and verify the possibility of containing harmful substances without requiring specialized knowledge from the operator. .

  The above is the outline of the material determination process by the fluorescent X-ray analysis method. Each analysis / determination process will be described in detail below.

  FIG. 3 is a flowchart for explaining the sample area determination process performed in step S12 of FIG. In FIG. 3, the sample area is determined from information such as an optical image obtained by a CCD camera or the like, or a transmitted X-ray image obtained by irradiation with transmitted X-rays (step S121). The sample area is compared with the primary X-ray irradiation area (step S122), and it is determined whether the sample area is equal to or larger than the primary X-ray irradiation area (step S123). If the sample area is not equal to or larger than the primary X-ray irradiation area, the CPU 51 displays a message such as “Replace the sample” on the display unit 53 (step S124), returns to step S12, and makes the sample setting again by the operator. The same processing as above is repeated. On the other hand, if the sample area is larger than the primary X-ray irradiation area, the process proceeds to step S13 in FIG. 2, and the sample area determination process is terminated.

  In step S124, after the message is displayed, the process may proceed to step S13 in FIG. 2 without performing the sample setting again. For example, on the message display screen, it may be possible to select whether to reset the worker or to continue the process.

  The interference peak component removal method performed in step S13 will be described in detail.

In the method of removing interfering peak components, for example, interfering peaks such as the sum peak of main components and diffraction lines in the fluorescent X-ray spectrum can be simultaneously added to separate and remove the peak of the detection element.
(1) Removal of sum peak In advance, the dependence of the sum peak of each element on the count amount is examined to create a database, and the energy of the sum peak is calculated from the energy value, X-ray intensity, and count amount of the main component peak obtained from the measured spectrum. The sum peak is removed by calculating the value and X-ray intensity and subtracting in addition to the peak separation component.
(2) Elimination of diffraction lines Estimate the type of substance (metal material) from the principal component information obtained from the measurement spectrum, and use the database of crystal structure and lattice plane type and spacing between each substance incorporated in advance. Bragg's formula
nλ = 2d ・ sinθ
(Λ: X-ray wavelength [Å], d: Lattice spacing [Å], θ: X-ray diffraction angle)
And E = h · λ
(E: X-ray energy [keV])
The following formula derived from
E [keV] = 12.399 / 2d · sinθ
Is used to calculate the energy value at which the diffraction line appears, consider the intensity ratio of the X-ray series of the detected element, determine whether the unidentified peak is a diffraction line, and if it is a diffraction line, The diffraction lines are removed by subtraction in addition to the separated components.

  As a method for confirming the diffraction line, when the half width of the peak is 1.2 times or more the fluorescent X-ray peak of an arbitrary element (preferably the main component element), it is determined to be a diffraction line. Taking a steel material as an example, the half width of the Fe-Kα line [6.4 keV] is 0.15 keV, the half width of the unidentified peak near 4.28 keV is 0.22 keV, and the Fe—Kα line There is about 1.4 times, and this peak is identified as a diffraction line.

  The method for determining the presence / absence of a minute peak performed in step S13 will be described in detail.

As a method for determining the presence or absence of an arbitrary trace component element, both the standard deviation σ converted into the concentration and the peak shape are used, and the quantitative result ≧ 3σ and the correlation coefficient of the peak shape to the Poisson distribution | r |> 0.2 Are simultaneously determined to be detected.
(1) Determination by Standard Deviation σ Converted to Concentration The peak of an arbitrary element obtained from a measurement spectrum can be defined as detection limit = σ and quantification lower limit = 3σ using standard deviation σ. At this time, measurement conditions (mainly measurement time) are determined so that a lower limit of quantification (3σ), preferably about 1/10, which is sufficiently smaller than the threshold value of the concentration of each regulatory element is obtained, and quantification is performed. If the result is ≧ 3σ, it is determined to be detected.
(2) Judgment by peak shape When the quantification result is 2σ or more, in order to judge by peak shape whether or not a peak actually exists, an energy range is set in advance for each element peak, and the background The degree of fitting to the Poisson distribution of the X-ray fluorescence spectrum of each element obtained by subtracting the above is examined using the correlation coefficient r, and when | r |> 0.2, there is a peak, that is, detection is determined. At this time, if necessary, a smoothed spectrum may be used.

  In addition, as a method for obtaining the background, a digitally converted spectrum of similar substances previously stored in a database is used. Various background removal methods may be used. The spectrum may be used with smoothing as necessary. In that case, the measured spectrum and the background spectrum are smoothed under the same conditions.

  FIG. 4 is a diagram for explaining the metal material determination process performed in step S14 of FIG. In FIG. 4 (A), a value (k ratio or k value) obtained by dividing the X-ray fluorescence spectrum obtained from the sample in step S13 by the intensity of 100% of the standard sample concentration of each element measured under the same conditions. If the sum of the ratios is greater than 0.65, the sum of the k ratio is obtained. ing. The determination result indicates that Sample 1 to Sample 3 are metallic materials, and Sample 4 and Sample 5 are non-metallic materials.

  A specific calculation example for sample 2 and sample 5 is shown in FIG. A value obtained by summing up the k ratio of each detection element for each sample is shown in the k ratio sum.

  FIG. 5 is a flowchart for explaining the coating film presence / absence determination process performed in step S15 of FIG. In FIG. 5, an electromagnetic wave having a wavelength of 0.75 μm to 1 mm (infrared rays) is irradiated, and the wavelength dependency of the reflectance is examined (step S151). By incorporating a function of irradiating a predetermined electromagnetic wave into the fluorescent X-ray measuring device 62, it is possible to automate by irradiating the electromagnetic wave according to the irradiation condition from the CPU 51.

  And CPU51 determines the presence or absence of a coating film by determining the presence or absence of a wavelength band with a reflectance of 50% based on the irradiation result of electromagnetic waves (step S152). When there is a wavelength band with a reflectance of 50%, a message indicating that there is a coating film, removing the coating film, etc. is displayed on the display unit 53, and the operator removes the coating film (step of FIG. 2). Go to S20). On the other hand, if there is no wavelength band with a reflectance of 50%, the process proceeds to a material determination process for a metal-based material.

  FIG. 6 is a flowchart for explaining the gold / silver color determination processing of the metal surface performed in step S18 of FIG. In FIG. 6, the reflectance of electromagnetic waves having wavelengths of 435 to 500 nm (blue) and wavelengths of 605 to 780 (red) is examined (step S181). By incorporating a function of irradiating a predetermined electromagnetic wave into the fluorescent X-ray measuring device 62, it is possible to automate by irradiating the electromagnetic wave according to the irradiation condition from the CPU 51.

  Then, the CPU 51 calculates the ratio of the red reflectance to the blue reflectance by dividing the red reflectance by the blue reflectance based on the electromagnetic wave irradiation result (step S182). As a result of the calculation, it is determined whether the ratio of the red reflectance to the blue reflectance is 1.5 or more (step S183). If the ratio is 1.5 or more, it is determined that the color is silver (step S184), and the gold / silver color determination process for the metal surface is terminated. On the other hand, if the ratio is less than 1.5, it is determined that the color is gold (step S185), and the gold / silver color determination process for the metal surface is terminated.

  A method for determining whether the detected element is a plating film component or a base material component when it is determined that there is a plating film in step S19 in FIG. 2 will be described. As a method for determining whether the detection element is a plating film component or a base material component, for example, the FP method quantification of the spectrum obtained by measuring the tube voltage for generating primary X-rays as 15 kV, 30 kV, and 50 kV is performed. Compare the results. Based on this comparison result, it is determined that an element having a high concentration is present on the surface when the tube voltage is low. As an example, the result of measuring a sample having a Ni plating / Fe structure is shown in FIG.

  FIG. 7 is a diagram showing the results of measuring a sample having a Ni plating / Fe structure. In FIG. 7, it can be seen that when a lower tube voltage is used, the concentration of Ni as the main component of the plating film is relatively increased. Therefore, CPU51 which acquired such a result judges that Ni is a plating film component.

  A method for determining whether or not the plating film has been completely removed after the worker peeled the plating film and removed the substrate in step S20 of FIG. 2 will be described. The CPU 51 compares the quantitative results obtained by performing the FP method quantitative analysis before and after polishing, and determines that the plating film still remains when the proportion of the plating film component is reduced, and polishes the worker again. Prompts the user to display a message on the display unit 53. After repeating such processing, if the CPU 51 determines that the quantitative value of the detected element is constant before and after polishing, the CPU 51 determines that the plating film has been completely removed, and displays a message to end polishing by the operator. 53 is displayed. An automatic polishing apparatus may be incorporated to automate the work.

  A method for quantitative analysis of trace elements contained in a plating film performed when it is determined that there is a plating film in step S19 in FIG. 2 will be described. CPU51 calculates the intensity | strength of the trace component element contained in a film | membrane on the basis of the intensity | strength sum total of the element of the main component of a plating film, and quantifies it using the calibration curve created from the calculation result. By such treatment, it is possible to quantify the regulated element contained in a trace amount in the plating film. For example, when Cd or Pb in a NiP plating film is quantified, a calibration curve of Cd or Pb intensity normalized with Ni-K peak intensity is prepared and quantified, so that Cd or Pb in NiP plating films having different thicknesses can be obtained. Accurate quantification is possible. The peak intensity and Ni-K peak intensity of trace elements such as Cd and Pb when creating a calibration curve are obtained from the measurement spectrum.

  FIG. 8 is a flowchart for explaining the analysis / determination processing of the metal substrate of FIG. In FIG. 8, based on the quantitative result obtained in step S13, the CPU 51 determines whether or not the main component corresponds to any one element of Mg, Al, Cu, Fe, and CuZn (step S801). . When none of Mg, Al, Cu, Fe, and Cu + Zn is a main component, the CPU 51 displays a message indicating that no harmful substance is contained in the display unit 53 (Step S802), The analysis / judgment process ends.

  On the other hand, if the main component corresponds to any one element of Mg, Al, Cu, Fe, and CuZn, the CPU 51 executes Cd presence / absence determination processing and / or Pb presence / absence determination processing.

  Since the peak of the Cd calibration curve and the peak of the CuZn (brass) calibration curve may overlap, the Cd presence / absence determination process is executed. The CPU 51 quantifies Cd by the Cd filter calibration curve method (step S811). Based on the quantitative result, it is determined whether Cd is 3σ or more based on the standard deviation and whether there is a peak (step S812). If Cd is less than 3σ or no peak, it is determined that Cd is less than the detection limit, and the CPU 51 causes the display unit 53 to display a message indicating that Cd is less than the detection limit (step S813). On the other hand, when Cd is 3σ or more and there is a peak, it is determined that Cd is detected, and the CPU 51 displays a message indicating that Cd as a harmful substance is detected on the display unit 53 (step S814).

  When the main component is Mg (Mg alloy), the CPU 51 quantifies Pb by the FP method in which Pb is additionally specified (step S821). Based on the quantitative result, it is determined whether Pb is 3σ or more based on the standard deviation and whether there is a peak (step S822). If Pb is less than 3σ or no peak, it is determined that Pb is less than the detection limit, and the CPU 51 causes the display unit 53 to display a message indicating that Pb is less than the detection limit (step S823). On the other hand, when Pb is 3σ or more and there is a peak, it is determined that Pb is detected, and the CPU 51 displays a message indicating that Pb as a harmful substance is detected on the display unit 53 (step S824).

  When the main component is Al (Al alloy), the CPU 51 quantifies Pb by the FP method in which Pb and Bi are additionally specified (step S831). Based on the quantitative result, it is determined whether Pb is 3σ or more based on the standard deviation and whether there is a peak (step S832). If Pb is less than 3σ or no peak, it is determined that Pb is less than the detection limit, and the CPU 51 causes the display unit 53 to display a message indicating that Pb is less than the detection limit (step S833). On the other hand, when Pb is 3σ or more and there is a peak, it is determined that Pb is detected, and the CPU 51 displays a message indicating that Pb as a harmful substance is detected on the display unit 53 (step S834).

  When the main component is Cu (Cu alloy), the CPU 51 quantifies Pb by the FP method in which Pb is additionally specified (step S841). Based on the quantitative result, it is determined whether Pb is 3σ or more based on the standard deviation and whether there is a peak (step S842). If Pb is less than 3σ or no peak, it is determined that Pb is less than the detection limit, and the CPU 51 causes the display unit 53 to display a message indicating that Pb is less than the detection limit (step S843). On the other hand, when Pb is 3σ or more and there is a peak, it is determined that Pb is detected, and the CPU 51 displays a message indicating that Pb as a harmful substance is detected on the display unit 53 (step S844).

  When the main component is Fe (Fe alloy), the CPU 51 quantifies Pb by the Pb filter calibration curve method because the peak of the Pb calibration curve and the peak of the Fe calibration curve may overlap each other (step) S851). Based on the quantitative result, it is determined whether Pb is 3σ or more based on the standard deviation and whether there is a peak (step S852). If Pb is less than 3σ or no peak, it is determined that Pb is less than the detection limit, and the CPU 51 displays a message indicating that Pb is less than the detection limit on the display unit 53 (step S853). On the other hand, when Pb is 3σ or more and there is a peak, it is determined that Pb is detected, and the CPU 51 displays a message indicating that Pb as a harmful substance is detected on the display unit 53 (step S854).

  FIG. 9 is a flowchart for explaining the analysis / determination processing of the plating film of FIG. In FIG. 9, the CPU 51 determines whether or not at least one item among the coexistence of Ni and P, the detection of Zn being greater than 50 wt%, and the detection of Cd is applicable based on the quantitative result (step S901). ). If none of the above detection conditions is satisfied, the CPU 51 determines that no harmful substance is contained, and displays a message indicating that the harmful substance is not contained in the display unit 53 (step S902). The analysis / determination process is terminated.

  If the corresponding item of the detection conditions in step S901 is the coexistence of Ni and P, the CPU 51 determines that the film is an electroless NiP plating film, and quantifies Cd by the Cd filter calibration curve method (step S911). ). Based on the quantitative result, it is determined whether Cd is 3σ or more based on the standard deviation and whether there is a peak (step S912). When Cd is 3σ or more and there is a peak, it is determined that Cd is detected, and the CPU 51 further determines whether or not Cd is contained in the base material (step S913). If not included in the base material, the CPU 51 causes the display unit 53 to display a message indicating that Cd has been detected as a harmful substance in the plating film (step S914), and the plating film analysis / determination process ends. On the other hand, when Cd is contained in the base material, the CPU 51 causes the display unit 53 to display a message indicating that only the NiP plating film is dissolved and Cd confirmation analysis is necessary (step S915), thereby analyzing the plating film.・ End the judgment process.

  In step S912, when Cd is less than 3σ or no peak, it is determined that Cd is less than the detection limit, and the CPU 51 further quantifies Pb by the Pb filter calibration curve method (step S916). Based on the quantitative result, it is determined whether Pb is 3σ or more based on the standard deviation and whether there is a peak (step S917). When Pb is 3σ or more and there is a peak, it is determined that Pb is detected, and the CPU 51 further determines whether or not Pb is contained in the base material (step S918). If not contained in the base material, the CPU 51 displays a message indicating that Pb has been detected as a harmful substance in the plating film on the display unit 53 (step S919), and the plating film analysis / determination process ends. On the other hand, when Pb is contained in the base material, the CPU 51 causes the display unit 53 to display a message indicating that only the NiP plating film is dissolved and Pb confirmation analysis is necessary (step S920), and analysis of the plating film is performed.・ End the judgment process.

  If Pb is less than 3σ or no peak in step S917, it is determined that Pb is less than the detection limit, and the CPU 51 displays a message indicating that Cd and Pb are less than the detection limit on the display unit 53. (Step S921), and the plating film analysis / determination process ends.

  Alternatively, if the relevant item of the detection conditions in step S901 is detection when Zn is greater than 50 wt%, the CPU 51 determines that the film is a Zn plating film, and quantifies Cd by the Cd filter calibration curve method. (Step S931). Based on the quantitative result, it is determined whether Cd is 3σ or more based on the standard deviation and whether there is a peak (step S932). When Cd is 3σ or more and there is a peak, it is determined that Cd is detected, and the CPU 51 displays a message indicating that Cd is detected as a harmful substance on the plating film on the display unit 53 (step S934), and the plating film The analysis / judgment process ends.

  If Cd is less than 3σ or no peak in step S932, it is determined that Cd is less than the detection limit, and the CPU 51 further quantifies Pb by the Pb filter calibration curve method (step S936). Based on the quantitative result, it is determined whether Pb is 3σ or more based on the standard deviation and whether there is a peak (step S937). When Pb is 3σ or more and there is a peak, it is determined that Pb is detected, and the CPU 51 further determines whether or not Pb is contained in the base material (step S938). If not included in the base material, the CPU 51 displays a message indicating that Pb is detected as a harmful substance in the plating film on the display unit 53 (step S939), and the plating film analysis / determination process ends. On the other hand, when Pb is contained in the base material, the CPU 51 causes the display unit 53 to display a message indicating that only the Zn plating film is dissolved and Pb confirmation analysis is necessary (step S940), and analysis of the plating film is performed.・ End the judgment process.

  In step S937, if Pb is less than 3σ or no peak, it is determined that Pb is less than the detection limit, and the CPU 51 displays a message indicating that Cd and Pb are less than the detection limit on the display unit 53. (Step S941), and the plating film analysis / determination process ends.

  When the corresponding item among the above detection conditions is Cd detection, the CPU 51 determines that it is Cd plating or AgCdO plating, and causes the display unit 53 to display a message indicating that Cd is detected as a harmful substance. (Step S951), the plating film analysis / determination process is terminated.

  In FIG. 9, a determination method in the case where the same harmful element is contained in both the base material and the plating film will be described. When the CPU 51 names the measurement file of the base material and the plating film of the same sample, the CPU 51 gives a name such as a number or a symbol that specifies the same sample, and also adds a name that specifies the site. For example, the base material 123S and the plating 123P are used. Compare the quantitative results of the measurement files with numbers or symbols that identify the same sample, and if both contain elements designated as harmful (hazardous elements), chemical analysis is required. Therefore, a message indicating that is displayed on the display unit.

  FIG. 10 is a flowchart for explaining the solder material analysis / determination process of FIG. In FIG. 10, the CPU 51 designates Sn and Pb and quantifies Pb by the FP method (step S1101). Based on the determination result, it is determined whether Pb is 3σ or more based on the standard deviation and whether there is a peak (step S1102). If Pb is less than 3σ or no peak, it is determined that Pb is less than the detection limit, and the CPU 51 displays a message indicating that Pb is less than the detection limit on the display unit 53 (step S1103). The solder material analysis / determination process ends.

  On the other hand, when Pb is 3σ or more and there is a peak, it is determined that Pb has been detected, and the CPU 51 displays a message indicating that Pb as a harmful substance has been detected on the display unit 53 (step, on the other hand, Pb is 3σ). If there is a peak and it is determined that Pb has been detected, the CPU 51 causes the display unit 53 to display a message indicating that Pb as a hazardous substance has been detected (step S1104), and solder material analysis / determination processing Exit.

  FIG. 11 is a diagram illustrating an example of sample setting. FIG. 11A shows a state where the setting state of the BGA solder balls is displayed on the display unit 53. FIG. 11B shows a state in which the setting state of the LSI lead is displayed on the display unit 53. FIG. 11C shows a state in which the setting state of the capacitor is displayed on the display unit 53. FIG. 11D shows a state in which the setting state of the mounted solder is displayed on the display unit 53.

  In FIG. 11 (A) to FIG. 11 (D), the operator confirms the setting state of the sample displayed on the display unit 53, and within the X-ray irradiation region (the range indicated by the elliptical line in the drawing) Set so that the ratio of the electrode portion is maximized. When there is an electrode inside the sample, the operator sets so that the ratio of the electrode portion inside the sample is maximized in the X-ray irradiation region without being disassembled.

  Next, an example of the determination result when the material determination process for the metal-based material is performed according to the flowchart described above will be described.

  FIG. 12 is a diagram illustrating an example of the result of the material determination process for the sample 1 illustrated in FIG. In FIG. 12, it can be determined that the sample 1 is provided with a NiP plating film.

  Next, an example of the result of removing the plating film and analyzing the base material will be described. FIG. 13 is a diagram illustrating a result example of the material determination process after the NiP plating film is removed. In FIG. 13, it can be seen that Sample 1 is obtained by applying a NiP plating film to the Fe material.

  Hereinafter, the material determination process for the nonmetallic material will be described in detail.

  In the present invention, the inventors specified that the factor that hexavalent chromium is present in the resin is the pigment, independently investigated and analyzed the commercially available pigment, and specialized in hexavalent chromium as the pigment. Coexisting elements were extracted. The presence of hexavalent chromium is determined by detecting the coexisting elements.

  Here, the coexisting element specialized in hexavalent chromium used in the determination is to investigate the composition of a pigment containing Cr that is widely used in general, and coexist when the form of Cr is hexavalent. An element that can be analyzed by X-ray. The only pigments that are commonly used are “lead chromate (yellow lead, reddish yellow lead, chromium green, chromium vermilion)”, “barium chromate”, “strontium chromate”, and “zinc chromate”. However, it has been investigated that it has a hexavalent chromium form, and other pigments have a trivalent chromium form. FIG. 14 shows the result of the investigation. From the investigation results shown in FIG. 14, the inventors have found that the coexisting elements are four elements of Zn, Sr, Ba, and Pb when the form of Cr is hexavalent.

Therefore, in the fluorescent X-ray analysis, Cr is quantified by a calibration curve method using a filter for detecting Cr, and at the same time, the FP method without a filter is also analyzed, and Pb L _α ray (10.55 keV), L _β ray (12.612 keV), Ba L _α ray (4.465 keV), L _β ray (4.827 keV), Sr K _α ray (14.140 keV), K _β ray (15.830 keV), Zn When the presence or absence of K _α ray (8.630 keV) and K _β ray (9.570 keV) is detected together with Cr, “hexavalent chromium content” is automatically Can be displayed.

  Further, if Cr is not detected, “hexavalent chromium-free” and Cr are detected, but if the coexisting element does not exist, “trivalent chromium-containing” can be displayed.

  In order for the CPU 51 to control the above processing, for example, a table as shown in FIG. 15 is stored in a predetermined storage area. Such a table can be realized by a program code.

  A comparison between the case where the material analysis processing of the nonmetallic material is performed without using the analysis device according to the present invention and the case where the material analysis processing of the nonmetallic material is performed using the analysis device according to the present invention is as follows. Shown in

  FIG. 16 and FIG. 17 are examples of results when a material analysis process of a non-metallic material is performed without using the analyzer according to the present invention and a fluorescent X-ray analysis of a hexavalent chromium-containing pigment is performed. Conventionally, it is possible to display only the presence / absence and concentration of Cr as described above. However, when the analyzer according to the present invention is used, Cr, Zn, Sr, Ba, and Pb are fixed as measurement target elements, and Cr in the first row is detected from the obtained detection results, and When each element in the second and subsequent rows does not become “no detection / nd”, as shown in FIG. 18, “hexavalent chromium content determination product” is displayed.

  Moreover, the result at the time of carrying out the fluorescent X ray analysis of the cable actually colored is shown in FIG. In the upper row, Cr and Pb are detected, and “hexavalent chromium content determination product” is displayed. In the lower row, Pb is detected but Cr is not detected, so “hexavalent chromium non-containing determination product” is displayed.

  Thus, when performing the material analysis processing of the non-metallic material using the analysis apparatus according to the present invention, the operator can check the result of the X-ray fluorescence analysis without checking the result of the X-ray fluorescence analysis, It is possible to easily know whether or not harmful substances are contained by displaying “determined product not containing hexavalent chromium”.

  In addition, the quantitative result of the nonmetallic material obtained in step S13 of FIG. 2 will be described. For example, when the sample is a resin, an operator can determine that the sample is a non-metallic material. Therefore, the analyzer 100 is set in advance to perform the XRF-FP quantitative analysis of the non-metallic material. May be. Alternatively, the XRF-FP method quantitative analysis of the nonmetallic material may be automatically performed when it is determined in step S14 that the material is a nonmetallic material. Alternatively, four elements of Zn, Sr, Ba, and Pb coexisting with Cr and Cr for specifying hexavalent chromium may be designated in advance in the XRF-FP method quantitative analysis in step S13.

  FIG. 20 is a diagram showing an example of the result of quantification of the nonmetallic material by the XRF-FP method. In FIG. 20 (A), the quantitative result of the hexavalent chromium content determination product by Pb coexistence is shown. FIG. 20 (B) shows the quantitative result of the hexavalent chromium non-contained determination product without detection of coexisting elements. As is clear from comparison of the quantitative results shown in FIG. 20A and FIG. 20B, when hexavalent chromium is contained, the mass% of Zn, Sr, Ba, and Pb that are coexistence designation elements. Is not “nd (not detected)” but a numerical value is shown.

  Thus, when the quantitative results of the non-metallic material by the XRF-FP method are shown, the quantitative results of these five elements are displayed without the operator specifying the four elements of Cr, Zn, Sr, Ba, and Pb. Is done.

  As described above, according to the present invention, it is possible to verify the presence of hexavalent chromium from only the result of fluorescent X-ray analysis, so that it may affect the environment in which a harmful substance is used as a comparative sample in order to verify the harmful substance. It is not necessary to perform a chemical analysis. Furthermore, it is possible to easily verify hazardous substances even if they are not specialists or specialist institutions capable of chemical analysis.

  Below, it is possible to evaluate the content of lead contained in specific parts of minute electronic parts and each part of the printed board unit by prohibited use and excluded use, and lead contained in solder materials, subject to RoHS regulation, etc. A method for quickly determining the presence / absence of non-destructive will be described.

  FIG. 21 is a flowchart for explaining a mapping measurement process for displaying an image of a part containing lead solder. In FIG. 21, the operator places a printed board unit as a sample on the sample stage of the fluorescent X-ray measuring device 62, and displays the whole image displayed by the CCD camera of the fluorescent X-ray measuring device 62 displayed on the display unit 53. While viewing, the height of the component (electronic component) on the set printed board unit that is considered to be the highest is set as the reference position, and for example, the whole image displayed on the display unit 53 A measurement area is designated by designating an area using a mouse or the like above (step S2001).

  At this time, in order to detect lead solder, at least Pb and Sn are included in the measurement conditions as designated elements. Alternatively, the operator only has to specify a preset measurement condition for lead solder from a menu or the like displayed on the display unit 53 under the control of the CPU 51.

  The CPU 51 causes the fluorescent X-ray measuring device 62 to perform X-ray measurement with the fluorescent X-rays excited by the X-ray probe according to the measurement conditions (step S2002), and uses the fluorescent X-ray measuring spectrum from the fluorescent X-ray measuring device 62 as a measurement result. Obtain (step S2003). By providing the fluorescent X-ray measuring device 62 with a CCD camera having an autofocus function whose relationship between the focus position and the height has been examined in advance, the CPU 51 causes the primary X-ray sample to be emitted each time the primary X-ray is irradiated. The primary X-ray generator measured with the upper irradiation position in focus and the measured height value up to the sample are acquired together with the fluorescent X-ray spectrum. The CPU 51 outputs information indicated by the measurement position and the acquired measurement height value to the memory unit 52 or the storage device 57 as two-dimensional information 70 of the measurement height. Further, the CPU 51 outputs information indicating the X-ray intensities of Pb and Sn from the acquired fluorescent X-ray spectrum to the Pb mapping image area 71 and the Sn mapping image area 72 of the memory unit 52 or the storage device 57, respectively. .

  Then, the CPU 51 moves the measurement position and repeats X-ray measurement (step S2004). That is, the CPU 51 determines whether or not the X-ray measurement has been completed up to the final measurement position in the measurement area set in step S2001. If not, the CPU 51 moves the measurement position to the next measurement position and proceeds to step S2002. Return to and repeat the above process.

  When the measurement has been completed, the CPU 51 determines the difference in the height of the sample by mounting the components at each measurement position based on the two-dimensional information 70 of the measurement height and the reference value of the height set in step S2001. The variation in the X-ray intensity indicated by the detection result is corrected (step S2005). The corrected X-ray intensity of Pb and Sn X-ray intensity are stored in the mapping image area 71 for Pb and the mapping image area 72 for Sn, respectively.

  The CPU 51 takes out the X-ray intensity of Pb and the X-ray intensity of Sn from the mapping image area 71 for Pb and the mapping image area 72 for Sn, and is contained when each is equal to or higher than each predetermined X-ray intensity. In response to the measurement position, information indicating the presence or absence of each Pb and Sn is generated as Pb detection position information 81 and Sn detection position information 82 in the memory unit 52 or the storage device 57 (step S2006).

  Next, the CPU 51 identifies a missing image portion that occurs because the detector has an inclination with respect to the optical axis of the primary X-ray beam, and corrects the Pb detection position information 81 and the Sn detection position information 82 (step S2007). ).

  The CPU 51 uses the corrected Pb detection position information 81 and the Sn detection position information 82 to generate information indicating that it is determined that lead solder is contained as the lead solder detection position information 83 (step S2008). Then, an image is generated based on the lead solder detection position information 83 and is displayed on the display unit 53 as a screen showing the distribution of lead solder (step S2009).

  In such mapping measurement processing, the missing image portion correction processing in step S2007 may be omitted. When verifying in more detail, it may be executed as an option.

  In this case, it is also possible to generate an image based on the Pb detection position information 81 in accordance with the operator's instruction and display a screen showing the distribution of Pb on the display unit 53. Similarly, an image can be generated based on the Sn detection position information 82 and a screen showing the distribution of Sn can be displayed on the display unit 53.

  Thus, the result of mapping about two or more elements Pb and Sn by mapping the measurement position of each element Pb and Sn for specifying lead solder and the possibility of inclusion based on the X-ray intensity at the time of detection As a result, the possibility of containing lead solder can be displayed in correspondence with the measurement position.

FIG. 22 is a diagram for explaining a method of extracting the X-ray intensity of each element in step S2003 in FIG. In FIG. 22, the CPU 51 acquires an X-ray spectrum as shown in FIG. 22A as a measurement result from the fluorescent X-ray measurement device 62. The X-ray spectrum received as a measurement result is captured in the energy range of 0 to 40 keV. Then, as shown in FIG. 22B, the CPU 51 obtains the integrated intensity in the energy range from 10.30 to 10.70 keV, takes the X-ray intensity of Pb-Lα as the peak intensity, and associates it with the measurement position. The X-ray intensity is stored in the mapping image area 71 for Pb.

Further, as shown in FIG. 22C, the CPU 51 obtains the integrated intensity in the energy range of 3.30 keV, takes the X-ray intensity of Sn-Lα as the peak intensity, and associates the X-ray with the measurement position. The intensity is stored in the Sn mapping image area 72.

  Next, X-ray intensity correction processing will be described with reference to FIGS. FIG. 23 is a flowchart for explaining the X-ray intensity correction processing in step S2005 shown in FIG. FIG. 24 is a diagram illustrating a method for determining the reference position.

  First, as shown in FIG. 24A, the fluorescent X-ray measuring instrument 62 uses the highest part 62e among the parts mounted on the printed board unit 62d in step S2001 of FIG. Is set. For example, the distance h0 from the irradiation port of the primary X-ray generator 62a to the component 62e is obtained by the focus of the CCD camera 62c provided adjacent to the primary X-ray generator 62a. Since the detector 62b is installed at a predetermined position away from the primary X-ray generator 62a, the reference distance L0 between the detector 62b and the component 62a can be calculated using the distance h0.

  In FIG. 23, the CPU 51 reads the measurement height value hi (i = 1, 2, 3,...) From the two-dimensional information 70 of the measurement height while sequentially shifting the measurement position (step S2021), and the read measurement. A distance Li (i = 1, 2, 3,...) Between the sample and the detector 62b at each measurement position is calculated from the height value hi (step S2022).

  The CPU 51 uses a predetermined relational expression based on the X-ray intensity Ii (i = 1, 2, 3...) Of each element at each measurement position of the sample and the distance Li between the detectors 62b, and uses a predetermined relational expression as a reference. The X-ray intensity I0 at the position is calculated, and the X-ray intensity is corrected (step S2023). Here, the predetermined relational expression is, for example,

I0: X-ray intensity measured at the reference position
Ii: X-ray intensity measured at each measurement position
L0: Reference distance from the detector to the reference position
Li: Distance from the detector to each measurement position.

  In this relational expression (1), the reference position is set to zero height, the X-ray intensity at the reference position is set to 100%, and the X-ray intensity obtained by measurement is calculated using the inverse square law. is there.

  The CPU 51 reads the X-ray intensity Ii of Pb from the Pb mapping image area 71 while sequentially shifting the measurement position in the process of step S2023, reads the X-ray intensity Ii of Pb, the distance Li calculated in step S2022, and the reference Substituting the distance L0 into the relational expression (1), the X-ray intensity I0 of Pb when converted to the reference position is calculated as a correction value. Then, by writing the calculated correction value into the Pb mapping image area 71, the X-ray intensity of Pb corrected in the entire measurement area is stored. Similarly, for the X-ray intensity of Sn, the X-ray intensity of Sn corrected using the Sn mapping image area 72 is stored in the Sn mapping image area 72.

  When the X-ray intensity of each element is corrected and stored in the respective storage areas, the CPU 51 ends the X-ray intensity correction process.

  By such an X-ray intensity correction process, different parts 62e and 62d are mounted on the printed board unit 62, for example, as shown in FIG. When the height of 62d is different, as shown in FIG. 24C showing a side view, when the height of the highest part 62e is used as a reference position, the parts 62e, 62f, and As the distance between the primary X-ray generator 62 and the measurement position when the primary X-ray is irradiated on each side surface of the printed board unit 62d changes to h0, h1, and h2, the detector 62b and the measurement position It can be seen that the distance changes to L0, L1, and L2.

  Even if there is a change in distance in this way, it is possible to convert to the X-ray intensity at the reference position by using the relational expression (1). can do.

  A method for generating an image showing the distribution of lead solder by synthesizing the mapping measurement of each element will be described with reference to FIGS. 25, 26, and 27. FIG. 25 is a diagram for explaining a method of synthesizing the mapping measurement of each element performed in steps S2006 to S2008 in FIG. In FIG. 25, in step S2006 of FIG. 21, it is determined that there is a possibility that Pb is contained when the X-ray intensity of Pb is equal to or higher than a predetermined X-ray intensity. Corresponding to the measurement position, the presence or absence of Pb is indicated by “0” or “1”.

  For example, eight consecutive measurement positions in the measurement area are mapped to addresses in a storage area in which the Pb detection position information 81 is stored, and the presence or absence of Pb at each measurement position is associated with a bit value. As shown in.

  Similarly, in step S2006 of FIG. 21, when the X-ray intensity of Sn is equal to or higher than the predetermined X-ray intensity, it is determined that there is a possibility that Sn is contained, for example, measurement such as Sn detection position information 81 Corresponding to the position, the presence or absence of Sn is indicated by “0” or “1”.

  In step S2007 of FIG. 21, for example, the CPU 51 compares the two-dimensional information 70 of the measurement height or the optical image captured by the CCD camera 62c with the Pb mapping image area 71 indicating the X-ray intensity value. The Pb detection position is detected by detecting the missing image portion, rotating the sample stage 180 degrees, partially measuring the region related to the missing image portion, and using the Pb missing image portion detection position information 81b that has determined the possibility of containing Pb. The Pb detection position information 81 corrected by rewriting the bit value corresponding to the missing image portion in the information 81 is acquired. The correction of the Pb detection position information 81 may be performed, for example, by ANDing the Pb missing image portion detection position information 81b and the bit value corresponding to the missing image portion in the Pb detection position information 81.

  In this case, there may be a plurality of missing image portions. If there are a plurality of Pb missing image portion detection position information 81b, a plurality of Pb missing image portion detection position information 81b is corrected by the plurality of Pb missing image portion detection position information 81b.

  Similarly, the CPU 51 detects the missing image portion by comparing the two-dimensional information 70 of the measurement height or the optical image captured by the CCD camera 62c with the Sn mapping image area 72 indicating the X-ray intensity value. The sample stage is rotated 180 degrees, the region related to the missing image portion is partially measured, and the missing image in the Sn detected position information 82 is detected using the Sn missing image portion detected position information 82b that is determined to contain Sn. The Sn detection position information 82 corrected by rewriting the bit value corresponding to the portion is acquired. The correction of the Sn detection position information 82 may be performed, for example, by ANDing the Sn missing portion detection position information 82b and the bit value corresponding to the missing image portion in the Sn detection position information 82.

  In this case, there may be a plurality of missing image portions. When there are a plurality of Sn missing image portion detection position information 82b, a plurality of Sn missing image portion detection position information 82b is generated, and the Sn detection position information 82 is corrected by the plurality of Sn missing image portion detection position information 82b.

  Furthermore, the CPU 51 generates a lead solder detection position information 83 by performing a logical product operation of the Pb detection position information 81 with the missing image portion corrected and the Sn detection position information 82.

  Based on the lead solder detection position information 83 generated in this way, an image showing the lead solder distribution is generated and displayed on the display unit 53. Further, an image showing the distribution of Pb may be generated and displayed on the display unit 53 based on the Pb detection position information 81 in which the missing image portion is corrected as necessary. Similarly, based on the Sn detection position information 82 in which the missing image portion is corrected, an image showing the distribution of Sn may be generated and displayed on the display unit 53.

  In the above description, the method of indicating presence / absence of a bit value has been described. However, a value corresponding to one byte is set for each measurement position, and the value is set when the intensity is equal to or higher than a predetermined X-ray intensity, or a predetermined level indicating a luminance level The level value may be set corresponding to the above. In this case, the larger value may be taken instead of the logical product operation.

  Examples of images processed based on a method for generating an image showing the distribution of lead solder by synthesizing mapping measurements of each element will be described with reference to FIGS. FIG. 26 is a diagram illustrating an optical image of the printed board unit photographed by the CCD camera. FIG. 27 is a diagram illustrating a distribution situation.

  In the printed board unit showing the optical image as shown in FIG. 26, for example, the Sn distribution as shown in FIG. 27A is shown in a bright color (white or yellow), and shown in FIG. 27B. Such a distribution of Pb is indicated by a bright color (white or yellow). Then, the Pb distribution and the Sn distribution are synthesized, and the lead solder distribution indicating a place where Pb and Sn coexist as shown in FIG. 27C is a bright color (white or yellow). Indicated by

  In this way, the possibility of containing harmful substances, which was difficult to understand simply by the presence or absence of specific elements, can be easily grasped visually.

  Next, the correction process of the missing image portion in step S2007 of FIG. 21 will be described with reference to FIGS. FIG. 28 is a flowchart for explaining the correction processing of the missing image portion in step S2007 of FIG.

  In FIG. 28, the CPU 51 extracts the position that is shaded by the solid angle of the mounted component from the comparison between the two-dimensional information 70 of the measurement height or the mapping image indicating the X-ray intensity and the optical image (step S2041). .

  As shown in FIG. 29, it is considered that a shaded portion occurs on the side surface side of the component 62e in the direction in which the detector 62b is directed. When the two-dimensional information 70 of the measurement height is used, the measurement position indicating the height from the height h0 to the reference position to the height h2 to the printed board unit 62d is specified from the two-dimensional information 70, and the shape is predicted. As a result, the shaded portion 62g of the printed board unit 62d on the side surface of the component in the direction in which the detector 62b is directed is extracted. On the other hand, when comparing the mapping image showing the X-ray intensity and the optical image, the X-ray intensity shown in the Pb mapping image area 71 is compared with the optical image, and the detector 62b is directed as described above. The position of the shaded portion 62g is extracted in the direction in which it is located.

  The CPU 51 identifies the position and size of the component where the missing image is generated, sets a partial measurement area (step S2042), rotates the sample stage 180 degrees with respect to the detector 62b, and identifies the identified component. Only, that is, only the partial measurement area set in step S2042 is measured again by the fluorescent X-ray measuring device 62 (step S2043).

  Then, similarly to the processing in step S2006 described with reference to FIG. 21, the CPU 51 determines that the re-measured X-ray spectrum contains when the intensity exceeds a predetermined X-ray intensity, and whether or not Pb and Sn are contained. Pb missing portion detection position information 81b and Sn missing portion detection position information 82b in a partial measurement area showing (step S2044), and the Pb detection position information 81 and the Sn detection position information 82 are corrected (step S2044). S2045).

  Examples of images processed based on such a method for correcting a missing image portion are shown in FIGS. In FIG. 30 to FIG. 32, in order to facilitate the explanation of the method for correcting the missing image portion, a description will be given with a printed board unit different from the printed board unit shown in FIG. 26, but the mapping measurement process is executed continuously. Because there is, it is essentially the same printed board unit. Here, the shadowed position is extracted from the comparison between the mapping image indicating the X-ray intensity and the optical image.

  FIG. 30 is a diagram showing an optical image and Sn distribution of the printed board unit. The CPU 51 compares the optical image of the printed board unit shown in FIG. 30A with the mapping image showing the Sn distribution shown in FIG. When specifying, it refers to the database regarding the shape of a part. In this case, a substantially square integrated circuit projected under the center is specified as a component with a missing image, and a measurement area is partially set.

  For example, the optical image in the set partial measurement area is as shown in FIG. 31A, and the optical image in the mapping image showing the distribution of Sn shown in FIG. A mapping image showing the distribution of Sn in the corresponding partial measurement area is an image portion as shown in FIG. A mapping image showing the distribution of Sn obtained by rotating this partial measurement area by 180 degrees with respect to the detector 62b is shown in FIG.

  The CPU 51 combines the mapping images shown in FIGS. 31B and 31C to create a mapping image of the entire printed board unit. Such a combined mapping image is an image as shown in FIG. Compared with the mapping image shown in FIG. 30B, it can be seen that Sn in the mapping image shown in FIG. 32 shows the distribution of Sn more clearly at the wiring portion at the bottom of the integrated circuit.

  In this way, by recognizing the shape of a part that is predicted to form a shadow without measuring the entire printed board unit rotated 180 degrees, it is only necessary to measure only that part again. A clear mapping image can be created.

  As an example of the method for correcting the missing image portion, the part is described above with reference to the database related to the shape of the part. However, by using such a database in the initial stage of the mapping measurement process, printing is performed. A method for reducing the amount of data generated by the fluorescent X-ray measurement of the plate unit and reducing the time required for the fluorescent X-ray measurement can be considered.

  Next, mapping measurement processing using such a database will be described. FIG. 33 is a flowchart for explaining another example of the mapping measurement process. In FIG. 33, the operator observes the appearance of the surface of the printed board unit, and first designates the entire area to be mapped while confirming the optical image displayed on the display unit 53, and then the actual fluorescence is displayed. A partial measurement area or the like on which a component for performing X-ray measurement is mounted is roughly specified (step S2101a).

  Alternatively, the operator refers to the X-ray transmission image displayed on the display unit 53 and designates the entire area to be mapped on the screen (step S2101b). The CPU 51 recognizes a metal portion from the designated entire area and sets a partial measurement area for performing fluorescent X-ray measurement.

  By designating the entire area to be mapped, each area where the fluorescent X-ray measurement is actually performed can be recognized at the relative position.

  The CPU 51 extracts a part portion in the partial measurement area using the image recognition function (step S2102), and determines the name and shape of each part by referring to the part database 90 (step S2103). The parts database 90 shows names and shapes for each part, measurement points for each form, and the like.

  The CPU 51 refers to the disassembly necessity table 92 based on the part name and determines whether the part can be analyzed without being disassembled (step S2104). If it is necessary to disassemble the CPU 51, the CPU 51 proceeds to step S2105.

  The CPU 51 displays a measurement method according to the part shape (step S2105), and the worker performs a predetermined process according to the instruction (step S2106). For example, the operator performs an operation such as peeling the component from the printed board unit and designates the measurement area. The CPU 51 proceeds to step S2108 in response to an input of work completion by the worker or an instruction to disclose fluorescent X-ray measurement.

  On the other hand, if it is not necessary to disassemble in step S2104, the CPU 51 sets a measurement area according to the identified part shape, and sets an element to be detected by referring to the disassembly necessity table 92 (step S2107). The fluorescent X-ray measurement is disclosed (step S2108). In response to an instruction from the CPU 51, the fluorescent X-ray measurement device 62 performs fluorescent X-ray measurement in a measurement area corresponding to the set part shape.

  In this case, the measurement area corresponding to the part shape is determined by referring to the part database 90, and the measurement area measured by the fluorescent X-ray measuring instrument 62 is not the whole part but according to the object of the shape. Only the area is divided equally. For example, if the shape of the component is substantially square, the area of a quarter portion on the predetermined position side when the component is divided into four equal parts becomes the measurement area. In the case of a substantially rectangular shape, an area of a half portion on the predetermined position side when divided in half is a measurement area. In this case, in consideration of the inclination of the detector 62b, a position where shadows hardly occur is selected.

  The CPU 51 takes in the measurement result from the fluorescent X-ray measuring device 62 (step S2109), and develops the mapping image area for each element. In this case, the mapping image area for each element is composed of one or more mapping image areas for each part, and this mapping image area for each part corresponds to the relative address for the entire area set in step S2101a or S2101b. To be deployed. Accordingly, since a mapping image area corresponding to the entire area is not required, the work area can be reduced (compressed). Further, the two-dimensional information of the measurement height for each part is developed in correspondence with the relative address with respect to the entire area. Also in this case, since the two-dimensional information of the measurement height corresponding to the entire area is not required, the work area can be reduced (compressed).

  The CPU 51 determines whether or not measurement has been completed for all measurement areas corresponding to the component shape of each component. If the measurement has not been completed, the CPU 51 moves the measurement position and causes the X-ray fluorescence measurement device 62 to measure fluorescence X-rays. (Step S2110).

  On the other hand, when the measurement is completed for all the parts, the CPU 51 corrects the X-ray intensity shown in the mapping image area for each element based on the two-dimensional information of the measurement height for each part (step S2111). Then, the CPU 51 determines whether each element has a predetermined X-ray intensity or more and determines the possibility of inclusion of the designated element (step S2112).

  The CPU 51 synthesizes detected position information based on the combination of coexisting elements for each component (step S2113). For example, a logical operation is performed on the detected position information of two elements.

  Next, the CPU 51 does not perform the process of correcting the missing image portion, but expands the detected position information based on the object property of the part shape (step S2114). In other words, if the shape of the component is substantially square, the detection position information corresponding to the area of the quarter portion on the predetermined position side is expanded four times according to the arrangement state of the component. If the shape of the component is substantially rectangular, the detection position information corresponding to the area of the half portion on the predetermined position side is expanded twice according to the arrangement state of the component.

  By such processing in step S2114, the fluorescent X-ray measurement of the component can be realized in a fraction of the processing time.

  Based on the relative address with respect to the entire area, the detection position information for each part indicating the possibility of containing harmful substances is arranged in the entire area to generate one detection position information, and the combined one detection position A mapping image is generated based on the information, and an image indicating the mapping image is displayed on the display unit 53 (step S2115). In this case, a mapping image may be selectively displayed for each element and for each part in accordance with an instruction from the operator.

  Furthermore, the CPU 51 refers to the disassembly necessity table 92, acquires display information based on the part name for each part, displays the display information on the display unit 53 as a determination result (step S2116), and ends the mapping measurement process.

  FIG. 34 is a diagram illustrating an example of a component database. In FIG. 34, the component database 90 includes items such as component type, component shape, symmetry, measurement area designation, and measurement area ratio. For example, the component type “QFP” is a chip whose shape is a square, has a four-fold symmetry, and, for example, the upper left quarter is designated as the measurement area with the center of symmetry as the axis. The ratio of the measurement area is designated so that the specified quarter of data is collected and displayed by quadrupling while rotating around the center of symmetry.

  In addition, the component type “BGA” is a chip having a square shape as in the case of QFP, has a four-fold symmetry, and a quarter of the center of symmetry is the measurement area. However, when measuring, the measurement area is displayed so that it is peeled off from the printed board and the quarter of the specified data is collected and rotated about the center of symmetry while being quadrupled. The percentage is specified.

  Furthermore, switching diodes, chip resistors, etc., have a slightly complicated part shape, and are symmetrical, exhibiting line symmetry, for example, the left half of the center axis is measured. The ratio of the measurement area is specified so that the half of the specified data is collected and displayed symmetrically with respect to the central axis.

  FIG. 35 is a diagram illustrating an example of a disassembly necessity table. In FIG. 35, the disassembly necessity table 92 categorizes the mounted components into those that do not require disassembly and those that require disassembly, and has items such as components and parts, harmful elements (materials), coexisting elements, and determination results, respectively.

  For example, in the case of mounting solder that does not require disassembly, Pb (solder material) is specified as a harmful element to be detected, and when detected, lead (Pb) and tin (Sn) are further overlapped and detected. When there is a portion to be displayed, it is specified to display on the display unit 53 that “eutectic solder subject to RoHS regulation (Pb / Sn solder) is used”.

  In addition, in the case of the fixed part of the coil / transformer winding, which requires disassembly, Pb (solder material) is designated as the harmful element to be detected. "Is displayed on the display unit 53.

  The disassembly necessity table 92 shown in FIG. 35 is a heading table indicating that there is a possibility that specific harmful substances Pb, Cd, and Cr may be contained in specific parts of the parts by the inventors' original investigation. is there.

  By causing the CPU 51 to perform processing using such a table based on the investigation, it is possible to indicate the possibility of containing harmful substances without requiring the worker to have specific knowledge about the harmful substances and parts.

  In this embodiment, the harmful element indicates an element that is considered harmful to the human body or the environment when the value is equal to or higher than a predetermined value, or an element that constitutes a harmful substance by the combination of elements. Such an element is automatically designated as an element to be detected when measured by the fluorescent X-ray measuring device 62. In addition to simply designating an element, processing that takes into account the characteristics of a fluorescent X-ray spectrum by fluorescent X-ray measurement of a substance (material) to be detected is executed to improve the detection accuracy of the designated element.

Regarding the above description, the following items are further disclosed.
(Appendix 1)
In an analyzer that can be connected to a fluorescent X-ray measuring device and supports detection of a specified element in a part or material using quantitative measurement based on a fluorescent X-ray analysis method by the fluorescent X-ray measuring device,
Control means for controlling processing in the analyzer;
Measurement result acquisition means for acquiring a result obtained by causing the fluorescent X-ray measurement apparatus to perform quantitative measurement by a type X-ray fluorescence analysis method according to a measurement condition instructed by the control means;
The control means further includes
Material determination means for determining the material of the part or material;
Based on the result of the material determination means, the fluorescent X-ray measurement apparatus is configured to perform quantitative measurement according to the measurement conditions specified based on the fluorescent X-ray spectrum of the material, and based on the quantitative measurement result, the designated element And a substance content determining means for determining the presence or absence of a substance containing.
(Appendix 2)
Setting state in which the display state of the setting state of the component or material is displayed so that the area of the component or material set in the fluorescent X-ray measurement apparatus is equal to or larger than the irradiation area of the primary X-rays irradiated to the component or material. The analyzer according to supplementary note 1, further comprising display means.
(Appendix 3)
The analyzer according to appendix 2, wherein the setting state display means displays an optical image or a transmitted X-ray image on a display unit.
(Appendix 4)
The material determination means includes
By determining whether or not the total value of the k ratio of each element detected from the part or material is greater than a predetermined value, the part or material is a metal-based material or a non-metallic material. The analyzer according to any one of appendices 1 to 3, further comprising a metal non-metal determination unit that determines whether the material is a material.
(Appendix 5)
The control means includes
It has an interference peak removing means for specifying an element to be a disturbing peak of a main component in a fluorescent X-ray spectrum, causing the fluorescent X-ray measuring means to perform quantitative measurement, and separating and removing a peak of a detected element. The analyzer according to appendix 1.
(Appendix 6)
The control means includes
The sum peak energy value and X-ray intensity are calculated from the energy value, X-ray intensity, and count amount of the main component peak obtained from the measurement spectrum, using a database that shows the dependency of the sum peak on each element. The analytical device according to appendix 5, wherein the sum peak is removed by subtraction in addition to the peak separation component.
(Appendix 7)
The control means includes
Estimate the type of component or material from the principal component information obtained from the measured spectrum, and use the database that shows the crystal structure and lattice plane type and spacing of each substance incorporated in advance, and the energy value at which diffraction lines appear Is calculated from the Bragg equation, and the X-ray series intensity ratio of the detected element is taken into account to determine whether the unidentified peak is a diffraction line. If it is a diffraction line, it is subtracted in addition to the peak separation component. 6. The analyzer according to appendix 5, wherein the diffraction line is removed.
(Appendix 8)
The control means includes
Additional remark 7 characterized in that, as a method of confirming that it is a diffraction line, it is determined as a diffraction line when the half width of the peak is 1.2 times or more of the fluorescent X-ray peak of the main component element. Analysis equipment.
(Appendix 9)
The control means includes
As a method for determining the presence or absence of an arbitrary trace component element, both the standard deviation σ converted into the concentration and the peak shape are used, and the quantitative result ≧ 3σ and the correlation coefficient of the peak shape to the Poisson distribution | r |> 0.2 The analyzer according to appendix 1, wherein it is determined that there is a detection when both of the above are satisfied simultaneously.
(Appendix 10)
The material determining means includes
As a result of quantification by the fundamental parameter method, when Zn> 50 wt%, Ni> 50 wt%, Cr> 20 wt%, when Cd or Au and Ag are detected, Sn is detected and the color is silver The analyzer according to appendix 1, further comprising plating film presence / absence determining means for determining the presence or absence of a plating film by determining that a plating film is attached to the surface of the component or material.
(Appendix 11)
The material determination means includes
As a result of quantification by the fundamental parameter method, when any of Mg, Al, Cu, Cu and Zn, Fe is the main component, the metal substrate is determined by determining that the metal substrate may contain harmful elements. The analyzer according to appendix 1, characterized by having a metal base material judging means for judging.
(Appendix 12)
The material determination means includes
As a result of quantification by the fundamental parameter method, when Sn> 50 wt%, the analysis according to appendix 1, characterized by having a solder material judging means for judging the solder material by additionally specifying Pb and quantifying only by Sn and Pb apparatus.
(Appendix 13)
The substance content determination means includes
When Ni and P coexist, the result of quantification by the fundamental parameter method, when Zn> 50 wt%, when Cd is detected, it is judged that there is a possibility that a plating film containing a harmful element is attached. The analyzer according to appendix 1, further comprising means for determining harmful elements for plating film.
(Appendix 14)
14. The analyzer according to appendix 13, wherein the quantitative analysis is performed using a calibration curve calculated from the strength of the trace component elements contained in the film, calculated based on the total strength of the main component elements of the plating film.
(Appendix 15)
15. The analyzer according to appendix 14, wherein the quantitative analysis of Cd or Pb in the NiP plating film is based on the Ni peak intensity of the fluorescent X-ray spectrum.
(Appendix 16)
15. The analyzer according to appendix 14, wherein the quantitative analysis of Cd or Pb in the Zn plating film is based on the Zn peak intensity of the fluorescent X-ray spectrum.
(Appendix 17)
The substance content determination means includes
As a result of quantitative determination by the fundamental parameter method, when Zn> 50 wt%, a trace amount of Cr is detected, and when Ni> 50 wt% or Al> 50 wt% or Mg> 50 wt%, the metal that may be chromated The analyzer according to appendix 1, wherein the analyzer is determined as a material.
(Appendix 18)
Using a tube voltage of 35 to 45 kV, measurement is performed at 200 to 600 sec using a primary X-ray obtained through a primary filter that cuts the primary X-ray spectrum intensity in the vicinity of Cr-K ray energy from 4.5 keV to 6.5 keV. 18. The analyzer according to appendix 17, wherein the presence or absence of a small amount of Cr is confirmed.
(Appendix 19)
The material determination means includes
By determining whether or not the total value of the k ratio of each element detected from the part or material is greater than a predetermined value, the part or material is a metal-based material or a non-metallic material. Metal non-metal determination means for determining whether it is a material,
The substance content determination means includes
When it is determined by the metal / non-metal determination means that it is non-metallic, the fluorescent X-ray measurement device is caused to perform quantitative measurement according to a predetermined measurement condition for determining the presence or absence of Cr with respect to the part or material. , Based on the quantitative result, Cr presence determination means for determining the presence or absence of Cr,
When it is determined that Cr is contained by the first determining means and none of the four elements Ba, Zn, Sr, and Pb coexists, it is determined that hexavalent chromium is not contained. The analyzer according to supplementary note 1, further comprising non-valent chromium content determination means.
(Appendix 20)
The control means includes quantitative measurement means for causing the fluorescent X-ray measurement apparatus to perform quantitative measurement according to predetermined measurement conditions designating four elements of Ba, Zn, Sr, and Pb,
The substance content determination means includes
A hexavalent chromium non-containing determination unit that determines that hexavalent chromium is not contained when none of the four elements of Ba, Zn, Sr, and Pb coexists with Cr based on a quantitative result by the quantitative measuring unit; The analyzer according to supplementary note 4, characterized by:
(Appendix 21)
In an analysis method for supporting detection of a specified element in a part or material using quantitative measurement by fluorescent X-ray analysis using an X-ray fluorescence measurement apparatus,
A control procedure for controlling processing in the computer;
A measurement result acquisition procedure for acquiring a result obtained by causing the fluorescent X-ray measurement apparatus to perform quantitative measurement by the fluorescent X-ray analysis method according to the measurement conditions instructed by the control procedure;
The control procedure further includes:
A material determination procedure for determining the material of the part or material;
Based on the result of the material determination procedure, the fluorescent X-ray measurement apparatus is configured to perform quantitative measurement according to the measurement conditions specified based on the fluorescent X-ray spectrum of the material, and based on the quantitative measurement result, the designated element A substance content determination procedure for determining the presence or absence of a substance containing
(Appendix 22)
In a computer-executable program for causing a computer to perform processing in an analysis method that supports detection of harmful elements in a part or material using quantitative measurement by energy dispersive X-ray fluorescence analysis,
A control procedure for controlling processing in the computer;
Performing a fluorescent X-ray measurement device to perform quantitative measurement by the energy dispersive X-ray fluorescence analysis method according to the measurement conditions instructed by the control procedure, and executing the fluorescent X-ray measurement procedure to obtain the result,
The control procedure further includes:
A material determination procedure for determining the material of the part or material;
Based on the result of the material determination procedure, the fluorescent X-ray measurement procedure performs quantitative measurement according to the measurement conditions specified based on the fluorescent X-ray spectrum of the material, and based on the quantitative measurement result, the harmful substance A computer-executable program for executing a harmful substance content determination procedure for determining the presence or absence of a toxic substance.
(Appendix 23)
In an analyzer that supports the detection of harmful elements in parts or materials using quantitative measurement by energy dispersive X-ray fluorescence analysis,
Control means for controlling processing in the analyzer;
Fluorescent X-ray measurement means for performing quantitative measurement by the energy dispersive X-ray fluorescence analysis method according to the measurement conditions instructed from the control means, and notifying the control means of the results,
The control means further includes
Material determination means for determining the material of the part or material;
Based on the result of the material determination means, the fluorescent X-ray measurement means is configured to perform quantitative measurement according to the measurement conditions specified based on the fluorescent X-ray spectrum of the material, and based on the quantitative measurement result, the harmful substance And an toxic substance content determining means for determining the presence or absence of a toxic substance.
(Appendix 24)
24. The analyzer according to claim 1, wherein the designated element is a harmful element.
(Appendix 25)
In an inspection method for inspecting the possibility of containing harmful elements in parts or materials using a fluorescent X-ray measurement device,
A control procedure for controlling processing in the analyzer;
According to the fluorescent X-ray measurement apparatus performed in accordance with distance information on the distance between the primary X-ray generator of the fluorescent X-ray measurement apparatus and the set irradiation position on the component or material, and according to an instruction by the control procedure A measurement result acquisition procedure for acquiring a measurement result;
The control procedure further includes:
A mapping data generation procedure for generating mapping data in which the X-ray intensity indicated by the measurement result corresponds to the positional information in the measurement area measured by the fluorescent X-ray measurement apparatus for each harmful element;
Based on the relationship between the detected X-ray intensity and the distance, an X-ray intensity correction procedure for correcting the X-ray intensity indicated by the mapping data for each harmful element using the distance information;
Based on the mapping data for each harmful element, the result of determining that there is a possibility of containing the harmful element at the irradiation position showing a predetermined X-ray intensity or more is detected position information indicating that the harmful element has been detected. A detection position information generation procedure to be generated;
Generate and display image data indicating the possibility of containing a specific hazardous substance by synthesizing the detection position information for each of the harmful elements generated in the detection position information procedure for two or more harmful elements. And a display procedure for displaying on the unit.
(Appendix 26)
The control procedure is:
A remeasurement procedure in which the part or material set in the X-ray fluorescence measurement apparatus is rotated at a predetermined angle with respect to the detector of the X-ray fluorescence measurement apparatus, and the measurement is performed again by the X-ray fluorescence measurement apparatus. Have
The remeasurement procedure is:
When the distance information on the distance between the primary X-ray generator and the set irradiation position on the part or material at the time of measurement by the remeasurement procedure and the measurement result are acquired by the measurement result acquisition procedure, the mapping data Combining the detection position information generated by executing the generation procedure, the X-ray correction procedure, and the detection position information generation procedure with the detection position information generated before rotating at the predetermined angle; The inspection method according to appendix 25, characterized by the above.
(Appendix 27)
The control procedure includes a measurement area setting procedure for setting a measurement area by referring to a database that manages the part or material in correspondence with one part that is equally divided using the symmetry of its shape. ,
The mapping data generation procedure generates the mapping data in the measurement area set by the measurement area setting procedure,
The display procedure is characterized in that the image data corresponding to the one part is synthesized by equalizing the image data according to the symmetry of the shape to generate image data corresponding to the shape. The inspection method described.

  The present invention is not limited to the specifically disclosed embodiments, and various modifications and changes can be made without departing from the scope of the claims.

It is a figure which shows the hardware constitutions of the analyzer which concerns on one Embodiment of this invention. It is a flowchart figure for demonstrating the material determination process by a fluorescent X ray analysis method. It is a flowchart for demonstrating the determination process of the sample area performed in step S12 of FIG. It is a figure for demonstrating the determination processing of the metal material performed in step S14 of FIG. It is a flowchart for demonstrating the presence-absence determination process of the coating film performed in step S15 of FIG. FIG. 3 is a flowchart for explaining a gold / silver color determination process for a metal surface performed in step S18 of FIG. It is a figure which shows the result of having measured the sample of Ni plating / Fe structure. It is a flowchart for demonstrating the analysis and determination process of the metal base material of FIG. It is a flowchart for demonstrating the analysis and determination process of the plating film of FIG. FIG. 3 is a flowchart for explaining solder material analysis / determination processing in FIG. 2; It is a figure which shows the example of a sample setting. It is a figure which shows the example of a result of the raw material determination process of the sample 1 shown by FIG. It is a figure which shows the example of a result of the raw material determination process after NiP plating film removal. It is a figure which shows a survey result. It is a figure which shows the table for specifying a hexavalent chromium containing product. It is a figure which shows the example of a result at the time of performing the raw material analysis process of a nonmetallic material, without using the analyzer which concerns on this invention. It is a figure which shows the example of a result at the time of performing the raw material analysis process of a nonmetallic material, without using the analyzer which concerns on this invention. It is a figure which shows the example by which the display of a hexavalent chromium content determination product is made. It is a figure which shows the result at the time of fluorescent X-ray analysis of the cable actually colored. It is a figure which shows the example of a fixed_quantity | quantitative_assay by the XRF-FP method of a nonmetallic material. It is a flowchart explaining the mapping measurement process which displays the site | part containing lead solder as an image. It is a figure for demonstrating the method of taking out the X-ray intensity of each element in step S2003 of FIG. FIG. 22 is a flowchart for explaining an X-ray intensity correction process in step S2005 shown in FIG. 21. It is a figure explaining the method of determining a reference position. It is a figure for demonstrating the method to synthesize | combine the mapping measurement of each element performed in step S2006 to S2008 of FIG. It is a figure which shows the optical image of the printed circuit board unit image | photographed with the CCD camera. It is a figure which shows a distribution condition. It is a flowchart for demonstrating the correction process of the missing-image part in FIG.21 S2007. It is a figure explaining the case where a shade is formed with the height of the components mounted in the printed circuit board unit. It is a figure which shows the optical image of a printed circuit board unit, and distribution of Sn. It is a figure which shows the partial measurement area at the time of measuring by rotating 180 degree | times. It is a figure which shows the mapping image which correct | amended the missing image part. It is a flowchart for demonstrating the other example of a mapping measurement process. It is a figure which shows the example of a components database. It is a figure which shows the example of a decomposition necessity table.

Explanation of symbols

51 CPU
52 Memory Unit 53 Display Unit 54 Output Unit 55 Input Unit 56 Communication Unit 57 Storage Device 58 Driver 59 Storage Medium 61 Interface (I / F)
62 X-ray fluorescence analyzer

Claims (3)

In an analyzer that can be connected to a fluorescent X-ray measuring device and supports detection of a specified element in a part or material using quantitative measurement based on a fluorescent X-ray analysis method by the fluorescent X-ray measuring device,
Control means for controlling processing in the analyzer;
Measurement result acquisition means for acquiring a result of causing the fluorescent X-ray measurement apparatus to perform quantitative measurement by the fluorescent X-ray analysis method in accordance with measurement conditions instructed by the control means;
The control means further includes
Material determination means for determining the material of the part or material;
Based on the result of the material determination means, the fluorescent X-ray measurement apparatus is configured to perform quantitative measurement according to the measurement conditions specified based on the fluorescent X-ray spectrum of the material, and based on the quantitative measurement result, the designated element A substance content determination means for determining the presence or absence of a substance containing
The material determining means includes
By determining whether or not the total value of the k ratio of each element detected from the part or material is larger than a predetermined value, the part or material is a metal-based material or a non-metallic material. Metal non-metal determination means for determining whether it is a material ,
The substance content determination means includes
When it is determined by the metal / non-metal determination means that it is non-metal, the fluorescent X-ray measurement means is caused to perform quantitative measurement according to a predetermined measurement condition for determining the presence or absence of Cr with respect to the part or material. , Based on the quantitative result, Cr presence determination means for determining the presence or absence of Cr,
When the Cr presence / absence determining means determines that Cr is contained, and none of the four elements Ba, Zn, Sr, and Pb coexists, the hexavalent is determined not to contain hexavalent chromium. An analysis apparatus comprising: a chromium non-containing determination unit . In an analyzer that can be connected to a fluorescent X-ray measuring device and supports detection of a specified element in a part or material using quantitative measurement based on a fluorescent X-ray analysis method by the fluorescent X-ray measuring device,
Control means for controlling processing in the analyzer;
Measurement result acquisition means for acquiring a result of causing the fluorescent X-ray measurement apparatus to perform quantitative measurement by the fluorescent X-ray analysis method in accordance with measurement conditions instructed by the control means;
The control means further includes
Material determination means for determining the material of the part or material;
Based on the result of the material determination means, the fluorescent X-ray measurement apparatus is configured to perform quantitative measurement according to the measurement conditions specified based on the fluorescent X-ray spectrum of the material, and based on the quantitative measurement result, the designated element A substance content determination means for determining the presence or absence of a substance containing
The material determination means includes
By determining whether or not the total value of the k ratio of each element detected from the part or material is larger than a predetermined value, the part or material is a metal-based material or a non-metallic material. Metal non-metal determination means for determining whether it is a material,
When the component or material is a metal-based material, and Sn is detected, the reflectance of electromagnetic waves having a wavelength of 435 nm to 500 nm (blue) and a wavelength of 605 nm to 780 nm (red) is examined.
Calculate the ratio of red reflectance to blue reflectance by dividing red reflectance by blue reflectance,
If the reflectance of the red is the ratio of 1.5 or more with respect to the reflectance of the blue, the metal surface was determined to be silver, analyzer material was characterized and this determines that solder material. In an analyzer that can be connected to a fluorescent X-ray measuring device and supports detection of a specified element in a part or material using quantitative measurement based on a fluorescent X-ray analysis method by the fluorescent X-ray measuring device,
Control means for controlling processing in the analyzer;
Measurement result acquisition means for acquiring a result of causing the fluorescent X-ray measurement apparatus to perform quantitative measurement by the fluorescent X-ray analysis method in accordance with measurement conditions instructed by the control means;
The control means further includes
Material determination means for determining the material of the part or material;
Based on the result of the material determination means, the fluorescent X-ray measurement apparatus is configured to perform quantitative measurement according to the measurement conditions specified based on the fluorescent X-ray spectrum of the material, and based on the quantitative measurement result, the designated element A substance content determination means for determining the presence or absence of a substance containing
The material determining means includes
By determining whether or not the total value of the k ratio of each element detected from the part or material is larger than a predetermined value, the part or material is a metal-based material or a non-metallic material. Metal non-metal determination means for determining whether it is a material,
When the material determining means determines that the part or material is a metal-based material and that there is a plated film, the substance content determining means is not included in the film based on the total strength of the main elements of the plated film. The analyzer according to claim 1, wherein the intensity of the trace component element contained is calculated, and quantification is performed using a calibration curve created from the calculation result.