JP3433178B2 - X-ray fluorescence analyzer - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an X-ray fluorescence analyzer which can automatically detect deterioration in performance. Here, the deterioration in performance means a failure such that the analysis is practically impossible even though the accuracy is insufficient, and the operation of each part of the device during the analysis that stops the automatic analysis. It is something that is milder than abnormal.

[0002]

2. Description of the Related Art Conventionally, some fluorescent X-ray analyzers have a function of automatically diagnosing a failure and a function of detecting an abnormal operation of each part of the apparatus under analysis.

[0003]

However, with these functions, it is not possible to find a deterioration in performance to the extent that the analysis accuracy is lowered, and it is possible for an ordinary operator to find a deterioration in performance. It wasn't easy. Further, it was not easy for the engineer (maintenance specialist) of the device manufacturer to investigate the cause of the deterioration in performance.

The present invention has been made in view of the above-mentioned conventional problems, and provides an X-ray fluorescence analyzer capable of automatically discovering a deterioration in performance to the extent that the accuracy of analysis is lowered, and facilitating the investigation of the cause. The purpose is to do.

[0005]

To achieve the above object, the present invention provides a secondary X-ray generated by irradiating a sample with a primary X-ray.
Fluorescence X that measures the intensity of the rays dispersed in the spectroscopic chamber with the detector
In the line analysis device, a performance diagnostic means for automatically diagnosing the presence or absence of various performance deterioration in the device according to an operator's selection, a display means for displaying a performance diagnostic result by the performance diagnostic means, and A storage unit that stores the performance diagnosis result as maintenance information together with detailed information regarding the state of the device at the time of performance diagnosis for investigating the cause of deterioration in performance.

Here, in the performance diagnosis by the performance diagnosing means, the secondary X-ray 2 is measured under a predetermined measurement condition for a predetermined sample.
The X-ray intensity diagnosis for measuring and diagnosing the θ scan profile, the noise diagnosis for measuring and diagnosing noise without irradiating primary X-rays, and the wave height distribution curve for a predetermined sample under predetermined measurement conditions For detector resolution diagnosis for diagnosing the energy resolution of the detector, or for reproducibility diagnosis for repeatedly measuring the intensity of secondary X-rays for a given sample under given measurement conditions and obtaining the accuracy of the measured intensity to diagnose reproducibility. Including at least one of them. In addition, the predetermined sample and the predetermined measurement condition are determined in advance for each diagnostic item. Also,
At least the peak waveform of the 2θ scan profile of the secondary X-ray, the waveform data of the pulse height distribution curve, the high voltage of the detector, the temperature inside the apparatus, or the vacuum degree of the spectroscopic chamber is included in the detailed information. Including one.

According to the X-ray fluorescence analyzer of the present invention, the performance diagnosing means automatically diagnoses the presence or absence of various performance deteriorations in the apparatus according to the operator's selection, and the performance diagnosis result is obtained. Since it is displayed on the display means, the deterioration in performance is automatically detected, and even a normal operator can easily detect the deterioration in performance. Further, the performance diagnosis result is stored in the storage means as the maintenance information together with the detailed information about the state of the apparatus at the time of performance diagnosis.By calling it, the engineer of the equipment manufacturer can also investigate the cause of the deterioration in performance. Will be easier.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION An X-ray fluorescence analyzer according to an embodiment of the present invention will be described below with reference to the drawings. First, the configuration of this device will be described. As shown in FIG. 1, this apparatus includes an X-ray tube 1 for generating X-rays, and an X-ray tube 1
Of the X-rays generated from the X-rays, X-rays having an increased attenuation rate of X-ray intensity in a predetermined wavelength range are passed as the primary X-rays 3 for irradiating the sample 4, and the fluorescence X generated from the sample 4 Diaphragm 6 which restricts the field of view of secondary X-rays 5 such as X-rays when viewed from the detector 10 side, and 2 which has passed through the diaphragm 6.
A divergence slit (solar slit) 7 that allows the next X-ray to pass in a limited direction, a spectroscopic element 8 that disperses the secondary X-ray that has passed through the divergence slit 7, and a secondary X-ray that is spectroscopically separated by the spectroscopic element 8. A light receiving slit (solar slit) 9 that passes in a limited direction, a detector 10 that measures the intensity of the secondary X-rays that have passed through the light receiving slit 9, a wave height analyzer 11, and a scaler 12 are provided. The sample 4 is placed on the sample table 14 via the sample holder 13 and exchanged by a sample exchange machine (not shown).

Here, the spectroscopic element 8, the light receiving slit 9 and the detector 10 are linked by a goniometer (not shown) so that the intensities of the secondary X-rays of various wavelengths can be measured. That is, this fluorescent X-ray analysis apparatus is a wavelength dispersion type and scanning type apparatus. Although only one filter 2, diaphragm 5, divergence slit 7, spectroscopic element 8, light-receiving slit 9 and detector 10 are shown in the drawing, in reality, a plurality of different types (performances) are provided. , An arbitrary one can be selected by an exchange (not shown). A sample chamber 15 in which the sample 4 is irradiated with the primary X-rays 3, and a spectroscopic chamber 16 in which the spectroscopic element 8 and the detector 10 are installed.
Is evacuated.

The signal from the scaler 12 is counted by the control computer 24 as an X-ray intensity via an I / O device (input / output device) (not shown) and transmitted to the personal computer 17. The calculation based on the count value and the operation of each part of the device are performed by the personal computer 17 included in the device. The personal computer 17 has input means such as a keyboard and a mouse (not shown), as well as the following performance diagnosis means 18, display means 19, storage means 20, failure diagnosis means 21 and file creation means 22. The performance diagnosing means 18 automatically diagnoses the presence or absence of various kinds of performance deterioration in the device according to the selection of the operator. Here, the performance diagnosis by the performance diagnosing means 18 is performed by X-ray intensity diagnosis, in which the 2θ scan profile of the secondary X-ray 5 is measured under a predetermined measurement condition with respect to a predetermined sample 4, and the primary X-ray 3 is irradiated. Noise diagnosis for measuring and diagnosing noise without doing so, detector resolution diagnosis for diagnosing the energy resolution of the detector 10 by measuring the wave height distribution curve of the predetermined sample 4 under predetermined measurement conditions, and the predetermined sample 4 Secondary X-ray 5
The reproducibility diagnosis for diagnosing the reproducibility by repeatedly measuring the intensity of the measurement and obtaining the accuracy of the measurement intensity is included. The predetermined sample 4 and the predetermined measurement conditions are determined in advance for each diagnostic item.

The display means 19 is a CRT, for example, and displays the performance diagnosis result by the performance diagnosis means 18. Storage means 2
0 is, for example, a hard disk, and the performance diagnosis result is
It is stored as maintenance information together with detailed information on the state of the device at the time of performance diagnosis for investigating the cause of deterioration in performance. Here, detailed information includes 2θ of the secondary X-ray 5.
Peak waveform of scan profile, waveform data of the wave height distribution curve, high voltage of the detector 10, temperature inside the apparatus (for example, inside the spectroscopic chamber 16), and the spectroscopic chamber 16
Includes the degree of vacuum.

Abnormality detection means 2 of the control computer 24
When an abnormality occurs in the device, 3 detects the abnormality of the device via an I / O device (not shown), and sends the contents of the abnormality and the state of each part of the device when the abnormality occurs to the personal computer 17. The failure diagnosis means 21 automatically diagnoses the presence or absence of various failures in the device according to the operator's selection. Here, the storage unit 20 stores the content of the abnormality detected by the abnormality detection unit 23, the state of the device at the time of the abnormality detection, the failure diagnosis result by the failure diagnosis unit 21, and the analysis management information that affects the analysis result. Is also stored as maintenance information. The file creating means 22 collects the maintenance information selected from the maintenance information stored in the storage means 20 and creates an electronic file.

Next, the operation of this device will be described.
When the operator uses the personal computer 17 to select an item of performance diagnosis displayed on the display unit 19 as necessary, the performance diagnosis unit 18 automatically performs the performance diagnosis of the selected item. For example, in the X-ray intensity diagnosis, the spectroscopic element 8,
For each combination of the detector 10, the slits 7, 9 and the like, a so-called 2θ scan profile before and after the peak of the designated fluorescent X-ray 5 is measured under predetermined measurement conditions for the predetermined sample 4, and the peak angle and the peak intensity are measured. The angular resolution (angle width at 50% of the peak intensity) is measured and compared with a predetermined reference value to make a pass / fail judgment. In the noise diagnosis (test), each detector 10 is counted by the scaler 12 without irradiating the primary X-ray 3 to measure the noise, and is compared with a predetermined reference value to make a pass / fail judgment. In detector resolution diagnostics,
For each detector 10, a wave height distribution curve is measured for a predetermined sample 4 under predetermined measurement conditions to calculate the energy resolution of the detector 10, and the energy resolution of the detector 10 is compared with a predetermined reference value to make a pass / fail judgment.

In the reproducibility diagnosis, the intensity of the secondary X-ray 5 is repeatedly measured on a predetermined sample 4 under predetermined measurement conditions, and X
The change (relative accuracy) of the line intensity is compared with a predetermined reference value to make a pass / fail judgment. The items of reproducibility to be diagnosed are further subdivided, simple reproducibility to repeat the measurement without operating the mechanical drive unit, reproducibility to repeat the measurement by moving the goniometer, and measurement by exchanging the spectroscopic element 8. Repeatability of spectroscopic element (dispersion crystal), repeatability of slit 7 and 9 to repeat measurement, repeatability of filter 2 to repeat measurement, diaphragm 6 to replace diaphragm 6 and repeat of measurement Reproducibility of sample loading / unloading (loading / ejection) in which the sample 4 is carried in and out of the sample chamber 15 and measurement is repeated, total reproducibility of performing measurement by exchanging all driving parts of each reproducibility, and long time There is long-term reproducibility in which measurement is repeated at regular intervals. The performance diagnosis result by the performance diagnosis means 18 described above is displayed on the display means 19 including the pass / fail of each item. An example is shown in Table 1 below.

[0015]

[Table 1]

As described above, according to the X-ray fluorescence analyzer of the present embodiment, the performance diagnosing means 18 automatically diagnoses the presence or absence of various performance deteriorations of the apparatus according to the operator's selection. Since the performance diagnosis result is displayed on the display means 19, the deterioration in performance is automatically found, and even a normal operator can easily find the deterioration in performance.

The storage means 20 stores the performance diagnosis result in
It is stored as maintenance information together with detailed information on the state of the device at the time of performance diagnosis for investigating the cause of deterioration in performance. Here, the detailed information includes the peak waveform of the 2θ scan profile of the secondary X-ray 5 in the X-ray intensity diagnosis, the waveform data of the wave height distribution curve in the detector resolution diagnosis, and the height of the detector 10 in the reproducibility diagnosis. Voltage,
The temperature inside the apparatus and the vacuum degree of the spectroscopic chamber 16 are included. The tilt of the spectroscopic element can be checked by examining the symmetry of the peak waveform. By checking the waveform data of the wave height distribution curve, it is possible to check noise and check deterioration of the detector 10 due to contamination of the core wire. Detector 1
When the high voltage of 0, the temperature in the apparatus, and the vacuum degree of the spectroscopic chamber 16 are examined, it can be seen whether or not their changes (unstable) caused the fluctuation of the X-ray intensity.

As described above, according to the fluorescent X-ray analysis apparatus of the present embodiment, the performance diagnosis result is stored in the storage means 20 as the maintenance information together with the detailed information regarding the state of the apparatus at the time of the performance diagnosis. By calling, it becomes easy for the engineer of the device manufacturer to investigate the cause of the deterioration in performance.

Further, in this apparatus, the abnormality detecting means 23
However, it detects an abnormal operation of the device under analysis, for example, the goniometer deviates from the movable range, or the spectroscopic element 8 cannot be replaced. Further, the failure diagnosis means 21 automatically diagnoses the presence or absence of various failures in the device according to the selection of the operator. Here, the items of the failure diagnosis include the drive time of each drive unit of the apparatus, the state of the X-ray tube 1 and the X-ray generator and the water supply device (not shown) connected to the X-ray tube 1, and the height of the detector 10. There are one for diagnosing the voltage and the like, one for diagnosing the ultimate vacuum degree and the stability of the vacuum degree in the vacuum exhaust system, and one for repeatedly operating each drive unit individually to diagnose the drive time. Then, the storage means 20 of this apparatus has a content of the abnormality detected by the abnormality detection means 23, a state of each part of the apparatus at the time of detecting the abnormality, a failure diagnosis result by the failure diagnosis means 21, and an analysis management which influences the analysis result. Information is also stored as maintenance information. Here, the analysis management information is
It is the information obtained every time PHA adjustment, drift correction, check analysis, etc. is performed, and is the record information of the result of adjustment and confirmation used for maintaining or managing the analysis accuracy (see Japanese Patent Application No. 11-374098). ).

More specifically, the analysis management information relating to PHA adjustment is the high voltage of the detector 10, the PH adjustment value for adjusting the gain of the detector 10 and the amplifier connected to the subsequent stage, or the detector 10. The PHA adjusted sample 4 having a known composition and a known composition can be obtained by performing measurement. The analysis management information regarding the drift correction is, for example, drift correction coefficients α and β, and corrects the deviation of the measurement value by the device over time. The analysis management information related to the check analysis includes the analysis value calculated by measuring the X-ray intensity of the check sample 4 having a known composition close to the sample to be analyzed 4 and the range width (difference between the maximum measurement value and the minimum measurement value). Is. This check analysis is performed prior to the analysis of the sample to be analyzed 4 and checks whether or not the measured analysis value deviates from the known content rate. The degree of long-term deterioration of the device and the maintenance timing can be read from the time-series changes in the results of these adjustments and confirmations.

Conventionally, the above maintenance information has not been stored in the device or stored separately, and thus cannot be appropriately used for investigating the cause of a failure or the like. On the other hand, in the apparatus of the present embodiment, for example, when an engineer of the apparatus manufacturer repairs the failure of the apparatus and selects an item of maintenance information displayed on the display unit 19 using the personal computer 17, a file is displayed. The creation unit 22 collects the maintenance information selected from the maintenance information stored in the storage unit 20 and creates an electronic file as a text file. Here, the text file is a file in which characters can be read by generalized software, and includes an HTML file and the like.

As described above, according to the fluorescent X-ray analysis apparatus of the present embodiment, the storage means 20 stores the maintenance information useful for investigating the cause of the failure or the deterioration in the performance, so that the technician of the apparatus manufacturer can individually Since it is possible to select and aggregate files that are considered to be related to the failure, etc., it becomes easy to investigate the cause of the failure by examining the contents. If it is a text file, it is easy to graph the data, etc., and it is easy to examine the contents. Note that a file can be created by a normal operator and transferred to a technician of the device manufacturer via a communication line such as a telephone line.

[0023]

As described in detail above, according to the fluorescent X-ray analysis apparatus of the present invention, the performance diagnostic means automatically determines the presence or absence of various performance deteriorations in the apparatus according to the operator's selection. Since the performance diagnosis result is displayed on the display means, the deterioration in performance is automatically detected, and even an ordinary operator can easily detect the deterioration in performance. Further, the performance diagnosis result is stored in the storage means as the maintenance information together with the detailed information about the state of the apparatus at the time of performance diagnosis.By calling it, the engineer of the equipment manufacturer can also investigate the cause of the deterioration in performance. Will be easier.

[Brief description of drawings]

FIG. 1 is a schematic view showing an X-ray fluorescence analyzer according to an embodiment of the present invention.

[Explanation of symbols]

3 ... Primary X-ray, 4 ... Sample, 5 ... Secondary X-ray, 10 ... Detector, 16 ... Spectroscopic chamber, 18 ... Performance diagnosis means, 19 ... Display means, 20 ... Storage means, 21 ... Failure diagnosis means, 22 ... File creating means, 23 ... Abnormality detecting means.

Continuation of front page (58) Fields surveyed (Int.Cl. ⁷ , DB name) G01N 23 / 00-23 / 227

Claims (2)

(57) [Claims] 1. A secondary X generated by irradiating a sample with a primary X-ray.
Fluorescence X that measures the intensity of the rays dispersed in the spectroscopic chamber with the detector
In the line analysis device, a performance diagnosing means for automatically diagnosing the presence or absence of various performance deterioration in the device according to an operator's selection, and a display means for displaying a performance diagnosing result by the performance diagnosing means, A storage means for storing the performance diagnosis result as maintenance information together with detailed information about the state of the device at the time of performance diagnosis for investigating the cause of deterioration in performance, and for the performance diagnosis by the performance diagnosis means, for a predetermined sample X-ray intensity diagnosis for measuring and diagnosing 2θ scan profile of secondary X-ray under predetermined measurement conditions, noise diagnosis for measuring and diagnosing noise without irradiating primary X-rays, predetermined measurement for a predetermined sample Detector resolution diagnosis for measuring the energy resolution of the detector by measuring the wave height distribution curve under the conditions, or secondary X-ray under a predetermined measurement condition for a predetermined sample The detailed information includes at least one of reproducibility diagnosis for diagnosing reproducibility by repeatedly measuring intensity and determining accuracy of the measured intensity, and the detailed information includes the peak waveform of the 2θ scan profile of the secondary X-ray and the wave height distribution. An X-ray fluorescence analysis apparatus comprising at least one of waveform data of a curve, high voltage of the detector, temperature inside the apparatus, or vacuum degree of the spectroscopic chamber. 2. The abnormality detecting means according to claim 1, which detects an abnormality in the operation of the device under analysis, and the failure diagnosing means for automatically diagnosing the presence or absence of various kinds of failures in the device in accordance with an operator's selection. The storage means, the content of the abnormality detected by the abnormality detection means and the state of the device at the time of the abnormality detection, failure diagnosis result by the failure diagnosis means, and analysis management information that affects the analysis result, Is also stored as maintenance information, and the fluorescent X-ray analysis apparatus is provided with a file creating unit that creates an electronic file by collecting selected maintenance information out of the maintenance information stored in the storage unit.