JP2002168812A - Fluorescence x-ray analyzer - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a fluorescence X-ray analyzer which enables automatic discovery of degrading in performance so much to lower the analysis accuracy for facilitating the investigation of the cause thereof. SOLUTION: A performance diagnosing means 18 automatically diagnoses the presence of degrading in various performances of the apparatus according to the selection of an operator and the results of the diagnosis of the performance is displayed on a display means 19.

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 performance degradation refers to a failure in which the analysis is possible while the accuracy is insufficient and the analysis is practically impossible, and an operation of each part of the apparatus during the analysis in which the automatic analysis is stopped. Lighter 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 during analysis.

[0003]

However, with these functions, it is impossible to find a deterioration in performance to the extent that the analysis accuracy is reduced, and it is difficult for an ordinary operator to find a deterioration in performance. It was not easy. Further, it has not been easy for a device manufacturer's engineer (maintenance expert) to find the cause of performance degradation.

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

[0005]

In order to achieve the above object, the present invention relates to a method for producing a secondary X-ray by irradiating a sample with primary X-rays.
X-ray fluorescence measured by a detector measuring the intensity of X-rays separated in the spectroscopic chamber
In the line analyzer, a performance diagnostic means for automatically diagnosing the presence or absence of various performance deteriorations in the apparatus according to an operator's selection, a display means for displaying a performance diagnostic result by the performance diagnostic means, Storage means for storing the performance diagnosis result as maintenance information together with detailed information on the state of the apparatus at the time of performance diagnosis for investigating the cause of performance degradation.

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

[0007] According to the X-ray fluorescence spectrometer of the present invention, the performance diagnosis means automatically diagnoses the presence or absence of various performance degradations in the apparatus according to the selection of the operator, and the performance diagnosis result is obtained. Since the information is displayed on the display means, the deterioration in performance is automatically detected, and even a normal operator can easily find the deterioration in performance. In addition, the performance diagnosis result is stored in the storage unit as maintenance information together with detailed information on the state of the device at the time of the performance diagnosis. By calling the result, even a technician of the device manufacturer can investigate the cause of the performance degradation. Becomes easier.

[0008]

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS An X-ray fluorescence analyzer according to one 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, the apparatus includes an X-ray tube 1 for generating X-rays,
A filter 2 that passes, as primary X-rays 3 irradiating a sample 4, X-rays having an increased attenuation rate of X-ray intensity in a predetermined wavelength range among X-rays generated from A diaphragm 6 that limits the field of view of the secondary X-rays 5 such as X-rays when viewed from the detector 10 side, and a diaphragm 6 that passes through the diaphragm 6
A divergent slit (solar slit) 7 for passing the secondary X-ray in a limited direction, a spectral element 8 for dispersing the secondary X-rays passing through the divergent slit 7, and a secondary X-ray split by the spectral element 8. The apparatus includes a light receiving slit (solar slit) 9 that allows light to pass in a limited direction, a detector 10 that measures the intensity of the secondary X-ray that has passed through the light receiving slit 9, a wave height analyzer 11, and a scaler 12. The sample 4 is placed on the sample stage 14 via the sample holder 13 and is replaced by a sample changer (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 intensity of secondary X-rays of various wavelengths can be measured. That is, this X-ray fluorescence analyzer is a wavelength-dispersion type and a scanning type. Although only one filter 2, diaphragm 5, divergence slit 7, spectral element 8, light receiving slit 9, and detector 10 are shown in the figure, a plurality of different types (performances) are provided in each case. , 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.

A signal from the scaler 12 is counted as X-ray intensity by a control computer 24 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 unit of the apparatus are performed by a personal computer 17 provided in the apparatus. The personal computer 17 has the following performance diagnosis means 18, display means 19, storage means 20, failure diagnosis means 21, and file creation means 22 in addition to input means such as a keyboard and a mouse (not shown). The performance diagnosing means 18 automatically diagnoses the presence or absence of various performance deteriorations in the apparatus according to the selection of the operator. Here, in the performance diagnosis by the performance diagnosis means 18, an X-ray intensity diagnosis for diagnosing the predetermined sample 4 by measuring a 2θ scan profile of the secondary X-ray 5 under predetermined measurement conditions, and irradiating the primary X-ray 3 are performed. Noise diagnosis for measuring and diagnosing noise without performing measurement, detector resolution diagnosis for measuring an energy resolution of the detector 10 by measuring a wave height distribution curve of a predetermined sample 4 under predetermined measurement conditions, and X-rays 5 under predetermined measurement conditions
Reproducibility diagnosis, in which repetition is measured by repeatedly measuring the intensity of the measured intensity to determine the accuracy of the measured intensity. Note that the predetermined sample 4 and the predetermined measurement conditions are determined in advance for each diagnostic item.

The display means 19 displays the result of performance diagnosis by the performance diagnosis means 18 on, for example, a CRT. 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 apparatus at the time of performance diagnosis for investigating the cause of performance degradation. Here, the detailed information includes 2θ of the secondary X-ray 5.
The peak waveform of the scan profile, the waveform data of the wave height distribution curve, the high voltage of the detector 10, the temperature in the apparatus (for example, in the spectroscopic chamber 16), and the spectroscopic chamber 16
Of vacuum.

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

Next, the operation of this device will be described.
When the operator uses the personal computer 17 to select a performance diagnosis item 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 spectral 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 a designated peak of the fluorescent X-ray 5 is measured under a predetermined measurement condition for a predetermined sample 4, and a peak angle and a peak intensity are measured. , The angular resolution (angle width at 50% of the peak intensity) is measured, and each is compared with a predetermined reference value to make a pass / fail judgment. In the noise diagnosis (test), the noise is measured by counting with the scaler 12 without irradiating the primary X-rays 3 for each detector 10, and the noise is measured, and is compared with a predetermined reference value to make a pass / fail judgment. In the detector resolution diagnosis,
For each of the detectors 10, a peak distribution curve is measured for a predetermined sample 4 under predetermined measurement conditions, the energy resolution of the detector 10 is calculated, and a pass / fail judgment is made by comparing the energy resolution with a predetermined reference value.

In the reproducibility diagnosis, the intensity of the secondary X-ray 5 is repeatedly measured on a predetermined sample 4 under predetermined measurement conditions,
The pass / fail judgment is made by comparing the fluctuation (the relative accuracy) of the line intensity with a predetermined reference value. The items of reproducibility to be diagnosed are further subdivided, simple repetition reproducibility to repeat the measurement without operating the mechanical driving unit, goniometer reproducibility to repeat the measurement by moving the goniometer, and measurement by replacing the spectroscopic element 8 Element (spectral crystal) reproducibility, measurement is repeated by exchanging slits 7 and 9, slit reproducibility is repeated by exchanging filter 2, filter reproducibility is repeated, and measurement is repeated by exchanging diaphragm 6 , Reproducibility of sample loading and unloading (injection / ejection) where sample 4 is carried in and out of sample chamber 15, total reproducibility of performing measurement by exchanging all drive units of each of the above reproducibility, and long time There is a long-term reproducibility that repeats the measurement at regular intervals over a long period of time. The results of the performance diagnosis by the performance diagnosis means 18 are 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 spectrometer of the present embodiment, the performance diagnosing means 18 automatically diagnoses the presence or absence of various performance deteriorations in the apparatus according to the selection of the operator. Since the performance diagnosis result is displayed on the display means 19, the performance deterioration is automatically detected, and even a normal operator can easily find the performance deterioration.

The storage means 20 stores the performance diagnosis result
It is stored as maintenance information together with detailed information on the state of the apparatus at the time of performance diagnosis for investigating the cause of performance degradation. 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 in the apparatus and the degree of vacuum in the spectroscopic chamber 16 are included. By checking the symmetry or the like of the peak waveform, the tilt of the spectral element can be checked. By examining 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
By examining the high voltage of 0, the temperature in the apparatus, and the degree of vacuum in the spectroscopic chamber 16, it can be determined whether or not the change (unstable) caused the fluctuation of the X-ray intensity.

As described above, according to the X-ray fluorescence analyzer of the present embodiment, the performance diagnosis result is stored in the storage means 20 as maintenance information together with detailed information on the state of the apparatus at the time of performance diagnosis. By calling, even the technician of the device manufacturer can easily find the cause of the performance degradation.

Further, in this device, the abnormality detecting means 23
However, it detects an abnormality in the operation of the apparatus under analysis, for example, when the goniometer has deviated from the movable range or when 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 driving time of each drive unit of the apparatus, the state of the X-ray tube 1, the state of 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 a method of diagnosing the voltage or the like, a method of diagnosing the ultimate vacuum degree and the stability of the vacuum degree in the evacuation system, and a method of diagnosing the driving time by operating each drive unit individually and repeatedly. The storage unit 20 of the apparatus stores the content of the abnormality detected by the abnormality detection unit 23, the state of each unit at the time of detection of the abnormality, the failure diagnosis result by the failure diagnosis unit 21, and the analysis management affecting the analysis result. The information is also stored as maintenance information. Here, the analysis management information is
It is information obtained every time PHA adjustment, drift correction, check analysis, etc. are performed, and refers to recorded information of adjustment and confirmation results used for maintaining or managing analysis accuracy (see Japanese Patent Application No. 11-374098). ).

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

Conventionally, the above-mentioned maintenance information has not been stored in the apparatus or has been stored separately, so that it has not been possible to appropriately use the information for investigating the cause of a failure or the like. On the other hand, in the apparatus according to the present embodiment, for example, when a technician of the apparatus maker repairs a failure of the apparatus, using the personal computer 17 to select an item of maintenance information displayed on the display unit 19, the file The creating unit 22 creates an electronic file as a text file by collecting the maintenance information selected from the maintenance information stored in the storage unit 20. Here, the text file is a file from which characters can be read by generalized software, and includes an HTML file and the like.

As described above, according to the X-ray fluorescence spectrometer 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, and the technician of the apparatus maker can individually perform the maintenance. Since it is possible to select items that are considered to be related to the failure or the like, collect them, and file them, by examining the contents, it becomes easy to find the cause of the failure or the like. If it is a text file, it is easy to make a graph of data and the like, and the contents can be easily examined. It should be noted that the file can be created by an ordinary operator and transferred to a technician of the device maker via a communication line such as a telephone line.

[0023]

As described above in detail, according to the X-ray fluorescence spectrometer of the present invention, the performance diagnosis means automatically determines whether or not there is any deterioration in the performance of the apparatus according to the selection of the operator. Since the result of the performance diagnosis is displayed on the display means, the performance deterioration is automatically detected, and even a normal operator can easily find the performance deterioration. In addition, the performance diagnosis result is stored in the storage unit as maintenance information together with detailed information on the state of the device at the time of the performance diagnosis. By calling the result, even a technician of the device manufacturer can investigate the cause of the performance degradation. Becomes easier.

[Brief description of the drawings]

FIG. 1 is a schematic diagram showing an X-ray fluorescence analyzer according to one 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 diagnostic means, 19: Display means, 20: Storage means, 21: Failure diagnostic means, 22: file creation means, 23: abnormality detection means.

Claims (2)

[Claims] 1. A secondary X-ray generated by irradiating a sample with a primary X-ray.
X-ray fluorescence measured by a detector measuring the intensity of X-rays separated in the spectroscopic chamber
In the line analyzer, a performance diagnostic means for automatically diagnosing the presence or absence of various performance degradations in the apparatus according to an operator's selection, a display means for displaying a performance diagnostic result by the performance diagnostic means, Storage means for storing the performance diagnosis result as maintenance information together with detailed information on the state of the apparatus at the time of performance diagnosis for investigating the cause of performance degradation, and for performance diagnosis by the performance diagnosis means, X-ray intensity diagnosis for measuring and diagnosing a 2θ scan profile of secondary X-rays 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 diagnosing the energy resolution of the detector by measuring the wave height distribution curve under the condition, or secondary X-ray under the predetermined measurement condition for a predetermined sample The detailed information includes at least one of reproducibility diagnostics for repeatedly measuring the intensity and determining the accuracy of the measured intensity to diagnose reproducibility. The detailed information includes a peak waveform of the 2θ scan profile of the secondary X-ray and the peak height distribution. An X-ray fluorescence analyzer comprising at least one of waveform data of a curve, a high voltage of the detector, a temperature in the apparatus, and a degree of vacuum in the spectroscopic chamber. 2. The fault detecting means according to claim 1, wherein said fault detecting means detects a fault in the operation of the apparatus under analysis, and the fault diagnosing means automatically diagnoses the presence or absence of various faults in the apparatus according to an operator's selection. The storage unit stores the content of the abnormality detected by the abnormality detection unit and the state of the device at the time of the abnormality detection, the failure diagnosis result by the failure diagnosis unit, and the analysis management information affecting the analysis result. An X-ray fluorescence spectrometer comprising: a storage unit configured to store maintenance information selected from among the maintenance information stored in the storage unit and to create an electronic file.