JPH06129963A - Method and device for producing glass bead for fluorescent x-ray analysis - Google Patents

Abstract

PURPOSE:To improve analysis accuracy and mass-producibility by grinding glass beads themselves if necessary so that their smoothness and flatness may be not more than a specified value. CONSTITUTION:Vibration is given to a container by a mixing section 11 to mix a sample and flux and a specified quantity of remover is put into the container. Next, the sample, flux, and remover put into the container are heated by a heating section 12 until they are dissolved, and the container is cooled by feeding cooling air through a cooling section 13 so as to peel off beads. Then, after the flatness and smoothness of the analysis face of the obtained beads are subject to total measurement by a measuring section 14, and it is judged based on the measured results whether or not they will satisfy the predetermined allowable value in compliance with target analysis accuracy and objective element for analysis. Further the analysis face of the beads which are judged to be defective is ground by a grinding section 15.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass bead manufacturing method and a glass bead manufacturing apparatus for fluorescent X-ray analysis suitable for fluorescent X-ray analysis of powdered oxides of ceramics, iron ore, cement and the like by the glass bead method.

[0002]

2. Description of the Related Art In order to obtain the content ratio of elements in powdered oxides such as ceramics, iron ore, cement, etc., a fluorescent X-ray analysis method utilizing the fact that the fluorescent X-ray intensity varies depending on the content ratio of the elements is generally widely used. Has been. Further, when performing the fluorescent X-ray analysis, it is necessary to adjust the sample (powder oxide) into a form suitable for the fluorescent X-ray analysis. The powder pressing method and the glass bead method are typical methods, but the glass bead method, which is superior in various points to the powder pressing method, is generally used.

In this glass bead method, as shown in FIG. 5, after a glass bead composition powder 2'is charged into a container 1, a melting and cooling process of the charged powder 2'is carried out, whereby the process shown in FIG. Vitrified glass beads 2 as shown in
To manufacture. The surface of the glass bead 2 corresponding to the bottom inner surface (diameter of about 30 mm) 1a of the container 1 becomes the analysis surface 2a in the fluorescent X-ray analysis.

The container 1 used in the glass bead method
Has no impurities mixed in the glass beads 2 obtained, and has good peelability when the glass beads 2 are cooled,
It is desirable that it is difficult to deform. As such a material,
Generally, an expensive precious metal such as an alloy of platinum and gold or an alloy of platinum, gold and rhodium is used. However,
Since the thermal expansion difference between the container 1 and the glass bead 2 is large, the bottom inner surface 1a of the container 1 is deformed as shown by the imaginary line in FIG. The analysis surface 2a is also deformed (flatness is 0.8 mm at maximum) as shown by the imaginary line in FIG. Therefore, when hundreds of glass beads 2 are manufactured in one container 1, the deformation is further increased and the analysis accuracy is lowered.

On the other hand, the Japanese Industrial Standard (JIS) does not specify the analysis surface 2a of the glass bead 2, and the container 1
Regarding the bottom inner surface 1a of the above, since it is merely defined as "to keep the bottom inner surface smooth in order to keep the bead releasability good", conventionally, even though there is an idea to smooth the bottom inner surface 1a, I had no idea to flatten it.

[0006]

However, with the recent technological innovation, high analysis accuracy is required, and when it is attempted to obtain the glass beads 2 satisfying the requirement, one container 1 is used in the conventional method. Only 10 pieces can be manufactured at most, which reduces the mass productivity. Further, if the casting is performed each time, the cost will increase.

Therefore, the present invention has been made in view of the above circumstances, and provides a glass bead manufacturing method and a glass bead manufacturing apparatus for fluorescent X-ray analysis, which can improve analysis accuracy and are excellent in mass productivity. It is an object.

[0008]

In order to achieve the above object, the manufacturing method according to the first aspect of the present invention is such that the composition powder of glass beads is charged into a container with a bottom having a smooth bottom inner surface, and then the glass bead is charged into the container. In a glass bead manufacturing method for fluorescent X-ray analysis, which obtains a glass bead having a surface in contact with the inner surface of the bottom as an analysis surface through a powder melting and cooling step, the smoothness and flatness of the analysis surface are not more than a predetermined value. As described above, the analysis surface is polished as required.

Further, the manufacturing method according to claim 2 is characterized in that the predetermined values of the smoothness and the flatness of the analysis surface differ depending on the element to be analyzed.

Further, in the manufacturing apparatus according to the third aspect of the invention, after the composition powder of the glass beads is charged into a bottomed container having a smooth bottom inner surface, the powder charged into the container is melted and cooled, and then the bottom part is subjected. In a glass bead manufacturing apparatus that obtains a glass bead having a surface in contact with an inner surface as an analysis surface, a measuring unit that measures the smoothness and flatness of the analysis surface, and the smoothness and flatness of the analysis surface become a predetermined value or less. Thus, it has a polishing part for polishing the analysis surface.

The manufacturing apparatus according to claim 4 is characterized in that the predetermined values of the smoothness and flatness of the analysis surface differ depending on the element to be analyzed.

[0012]

According to the manufacturing method of the first aspect, the smoothness and flatness of the inner surface of the bottom of the container are directly transferred to the analysis surface of the glass beads obtained through the melting and cooling steps. For this reason, a smooth analysis surface can be obtained by smoothing the inner surface of the bottom portion, but the analysis accuracy depends on the flatness rather than the smoothness of the analysis surface. Therefore, even if the container is deformed due to the melting and cooling processes and the smoothness and flatness are deteriorated, the glass bead itself is analyzed as necessary by polishing the glass bead itself so that the smoothness and flatness are below a predetermined value. Accuracy is improved and mass productivity is also improved.

According to the manufacturing method of the second aspect, by setting the predetermined values of the smoothness and the flatness according to the element to be analyzed, it is possible to improve the analysis accuracy according to the element to be analyzed.

According to the manufacturing apparatus of the third aspect, as in the first aspect, the smoothness and flatness of the inner surface of the bottom of the container are directly transferred to the analysis surface of the glass beads obtained through the melting and cooling steps. To be done. For this reason, a smooth analysis surface can be obtained by smoothing the inner surface of the bottom portion, but the analysis accuracy depends on the flatness rather than the smoothness of the analysis surface. Therefore, even if the container is deformed due to the melting and cooling steps and the smoothness and flatness are deteriorated, it is possible to measure the smoothness and flatness by the measurement unit and determine the quality, and the polishing unit determines that it is defective. By polishing so that the smoothness and flatness of the analysis surface of the glass bead are below a predetermined value,
Analysis accuracy is improved and mass productivity is also improved.

According to the manufacturing apparatus of the fourth aspect, similarly to the second aspect, by setting the predetermined values of the smoothness and the flatness according to the element to be analyzed, the analysis accuracy according to the element to be analyzed can be improved. Can be improved.

[0016]

Embodiments of the present invention will now be described in detail with reference to the drawings.

FIG. 2 is a schematic configuration diagram of a glass bead manufacturing apparatus according to the present invention.

The manufacturing apparatus 10 shown in the same figure has a container 1 similar to that shown in FIG. 5 for containing the composition powder (sample) 2 ′ of the glass bead 2, a sample placed in the container 1,
A mixing unit 11 that mixes the flux by vibration, a heating unit 12 that can heat the container 1 up to 1200 ° C. by high-frequency induction, and a cooling unit that cools the container 1 by sending cooling air to the container 1, for example. 13 and glass bead 2
Measuring unit 14 for measuring flatness and smoothness of the analysis surface 2a of
And a polishing section 15 for polishing the analysis surface 2a.

As the measuring unit 14, for example, a surface roughness meter generally used for measuring flatness and smoothness is applied. The term "smoothness" as used herein refers to JISB.
"Surface roughness" defined in 0601,
The center line average roughness (Ra) in the entire analysis surface 2a is shown. The "flatness" means "surface waviness" defined in JISB0610, and is shown as "maximum waviness" when the "reference length" is the diameter (about 30 mm) of the analysis surface 2a.

The polishing section 15 mechanically polishes the analysis surface 2a by a polishing means (not shown), so that the analysis surface 2a
The flatness is 10 μm or less and the smoothness is 5 μm or less. The polishing means is, for example, a polishing cloth, a whetstone, a polishing paper, etc.
A material coated with an abrasive such as 1 ₂ O ₃ ) or carborundum (SiC) is applied. If the desired analysis accuracy can be obtained even with a flatness of 50 μm or less and a smoothness of 5 μm or less, polishing by hand may be used.

Next, an embodiment of the glass bead manufacturing method of the present invention using the manufacturing apparatus 10 having the above-mentioned structure will be described with reference to the process chart shown in FIG.

First, a predetermined amount of sample 2'is put into the container 1 (step A). After this step A, a calcination step and a cooling step may be added. Next, a predetermined amount of the flux is put into the container 1 (step B), the container 1 is vibrated in the mixing section 11 to mix the sample 2'with the flux (step C), and a predetermined amount of the flux is added. A release agent is put into the container 1 (step D). Then, the heating unit 12
The sample 2 ′ charged in the container 1 is heated until the flux and the release agent are dissolved (step E), and cooling air is blown to the container 1 in the cooling unit 13 to cool the container 1 (step F), the bead 2 is peeled off (step G).

Then, the bead 2 thus obtained
All the flatness and smoothness of the analysis surface 2a are measured by the measuring unit 14 (process H). Based on the measurement result obtained in this step H, it is judged whether or not a predetermined allowable value (for example, flatness of 50 μm or less, smoothness of 5 μm or less) is satisfied depending on the target analysis accuracy, element to be analyzed and the like. (Step I). This determination may be automatic determination or human determination. The polishing unit 15 polishes the analysis surface 2a of the bead 2 which is determined to be defective in the process I (process J). As a result, the beads 2 whose flatness of the analysis surface 2a is 50 μm or less
Can be mass-produced. After that, the beads 2 are subjected to fluorescent X-ray analysis. In addition, after polishing all the beads 2, the flatness and the smoothness may be measured for the purpose of confirmation.

The effect of the manufacturing method of this embodiment for obtaining the bead 2 in this manner will be described with reference to FIGS.

FIG. 3 is a graph showing the relationship between the X-ray intensity and the flatness of zirconium (Zr). This figure shows that the X-ray intensity changes greatly depending on the flatness. As shown in the figure, according to the present embodiment, the flatness was 0.8 mm at the maximum in the prior art, but in the present embodiment, the flatness is all 50 μm or less. What varied from 7 to 47.7 kps
In this example, the variation was small at 46.10 to 46.13 kps, and high-precision analysis was possible.

Table 1 shows C of X-ray intensity before and after polishing.
It shows comparison of V values. The CV value is 100
Indicates α / X. (Α: standard deviation, X: average value) A / B ratio represents the molar ratio of Ba / (Ti + Zr), and n represents the number of samples (10).

[0027]

[Table 1]

As is clear from Table 1, the CV values before polishing were 0.05 for BaO, TiO ₂ and ZrO ₂ , respectively.
Those with 0.20 and 0.82 were after polishing (flatness 50
.mu.m or less) is 0.02, 0.08, and 0.14, respectively. Therefore, as with ZrO ₂ , BaO,
Even in TiO ₂ , variations in X-ray intensity are reduced,
High-precision analysis has become possible.

FIG. 4 is a graph showing the relationship between the relative intensity and the relative distance for each element. The relative intensity is based on the X-ray intensity of each element at a certain reference position.
The relative distance is indicated by minus in the direction approaching the X-ray tube from the reference position and by plus in the direction away from the X-ray tube.

As is clear from the figure, when the distance from the reference position changes, the X-ray intensity of each element also changes. Also,
The rate of change in X-ray intensity differs for each element. Further, even if the same element is used, different analyzers have different ways of changing. It depends on the optical conditions of the analyzer used, especially the black angle and the optical system. Therefore, by setting the target flatness depending on the element to be analyzed, it is possible to improve the analysis accuracy according to the element to be analyzed.

The present invention is not limited to the above embodiment, but can be modified in various ways.

[0032]

According to the invention described in claim 1 described above in detail, since the analysis surface is polished as necessary so that the smoothness and flatness of the analysis surface are not more than a predetermined value, the analysis is performed. It is possible to provide a method for producing a glass bead for fluorescent X-ray analysis, which can improve accuracy and is excellent in mass productivity.

According to the second aspect of the invention, by setting the predetermined values of the smoothness and the flatness according to the element to be analyzed, it is possible to improve the analysis accuracy according to the element to be analyzed.

According to the third aspect of the invention, the quality of the analysis surface can be determined by measuring the smoothness and flatness of the analysis surface, and the smoothness and flatness of the analysis surface of the glass bead determined to be defective. Since the analysis surface can be polished so as to be less than or equal to a predetermined value, it is possible to provide a glass bead manufacturing apparatus that can improve the analysis accuracy and that is excellent in mass productivity.

Further, according to the invention described in claim 4, as in the case of claim 2, it is possible to improve the analysis accuracy according to the element to be analyzed.

[Brief description of drawings]

FIG. 1 is a process drawing showing an embodiment of the glass bead manufacturing method of the present invention.

FIG. 2 is a schematic configuration diagram of a glass bead manufacturing apparatus according to the present invention.

FIG. 3 is a graph showing the relationship between X-ray intensity and flatness of zirconium (Zr).

FIG. 4 is a graph showing the relationship between relative intensity and relative distance for each element.

FIG. 5 is a cross-sectional view of a container and a view showing conventional problems.

FIG. 6 is a cross-sectional view of a glass bead and a view showing a conventional problem.

[Explanation of symbols]

 1 Container 1a Bottom Inner Surface 2 Glass Bead 2'Powder 2a Analysis Surface 10 Glass Bead Manufacturing Equipment 14 Measuring Section 15 Polishing Section

Front Page Continuation (72) Inventor Yutaro Yuzuhara 1-13-1 Nihonbashi, Chuo-ku, Tokyo Inside TDC Corporation

Claims (4)

[Claims] 1. A surface in contact with the bottom inner surface is used as an analysis surface after the glass bead composition powder is charged into a bottomed container having a smooth bottom inner surface, and the powder charged into the container is melted and cooled. In a method for producing a glass bead for fluorescent X-ray analysis for obtaining a glass bead, the fluorescent X-ray is polished as necessary so that the smoothness and flatness of the analytical surface are not more than a predetermined value. Method for manufacturing analytical glass beads. 2. The method for producing a glass bead for fluorescent X-ray analysis according to claim 1, wherein the predetermined values of the smoothness and flatness of the analysis surface differ depending on the element to be analyzed. 3. A surface in contact with the inner surface of the bottom is used as an analysis surface after the composition powder of the glass beads is put into a bottomed container having a smooth inner surface at the bottom, and the powder put into the container is melted and cooled. In a glass bead manufacturing apparatus for obtaining a glass bead, a measuring unit that measures the smoothness and flatness of the analysis surface, and a polishing unit that polishes the analysis surface so that the smoothness and flatness of the analysis surface becomes a predetermined value or less. An apparatus for manufacturing a glass bead, comprising: 4. The glass bead manufacturing apparatus according to claim 3, wherein the predetermined values of the smoothness and flatness of the analysis surface differ depending on the element to be analyzed.