JP2007285791A - Concave x-ray spectral element, method for manufacturing the same and x-ray analyzer using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for manufacturing a concave X-ray spectral element for a Johansson-type spectrometer, the curvature X-ray spectral element, and to provide an X-ray analyzer that uses it. <P>SOLUTION: The method for manufacturing a concave X-ray spectral element by pressurizing, heating and shaping polymer films has a step for forming a first laminate 13 by stacking polymer films; a step for forming a second laminate 14 and a third laminate 15 which are step-wise on the top face of the first laminate 13; a step for carbonizing the first laminate 13, the second laminate 14 and the third laminate 15, by subjecting them to thermal treatment at a thermal decomposition temperature of macromolecules or lower; and a step for pressurizing and shaping the first laminate 13, the second laminate 14 and the third laminate 15 with a concave shaping jig 11 and a cylindrical convex face 12 of a convex shaping jig at the thermal decomposition temperature of macromolecules or higher. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a method for manufacturing a curved X-ray spectroscopic element, a curved X-ray spectroscopic element, and an X-ray analyzer using the same.

Conventionally, a graphite crystal is used as an X-ray spectroscopic element, and a concentrated optical system or a parallel optical system is configured by using the crystal in a curved shape. Therefore, a method for producing graphite (Patent Document 1) suitable for curving graphite, a method for producing a curved graphite X-ray spectrometer (Patent Document 2), and an X using an X-ray spectrometer produced by these production methods. There is a technique of a beam irradiation device (Patent Document 3). In these techniques, a polymer film is pressure-molded while being heated in a temperature range below the polymer pyrolysis temperature, for example, 450 to 1600 ° C., to obtain a carbonized film (carbonaceous film). A plurality of the carbonized films obtained, for example, 50 sheets are stacked along a graphite press jig having a curved surface, and pressure-molded while heating at a temperature range exceeding the polymer thermal decomposition temperature, for example, 3000 ° C. A curved X-ray spectroscopic element as shown in FIG.
JP-A-4-202056 JP-A-2-83206 Japanese Patent Application Laid-Open No. 7-190962

  However, such a curved X-ray spectroscopic element is curved from a state in which a plurality of flat carbonized films are stacked, and the crystal lattice plane (network plane) of the graphite curved X-ray spectroscopic element coincides with the crystal reflecting surface ( Parallel) and always accompanied by aberrations. Also, it is difficult to bend from a state in which a plurality of flat carbonized films are stacked, and to cut the curvature radius of the curved spectral surface into a surface in which the crystal lattice plane and the crystal reflection surface do not coincide with each other. No graphite curved X-ray spectroscopic element has been produced.

  Conventionally, the Johann spectrometer shown in FIG. 6 and the Johanson spectrometer shown in FIG. 7 are known as curved X-ray spectrometers for X-ray analyzers. As shown in FIG. 6, in the Johann spectrometer 6, X-rays from the X-ray source 61 on the Roland circle 64 are condensed on the slit 62 which is a focal point by the spectroscopic element 63, but aberration occurs. On the other hand, in the Johansson type spectrometer 7 as shown in FIG. 7, the X-ray from the X-ray source 71 theoretically on the Roland circle 74 is condensed on the slit 72 which is the focal point by the spectroscopic element 73, and the aberration is reduced. Does not occur. It is a technique conventionally known in the art that a Johansson type spectrometer has no aberration, has a high reflection intensity, and has an excellent resolution.

  The curvature radius of the curved X-ray spectroscopic element of the Johansson type spectroscope is ½ of the curvature radius of the curved X-ray spectroscopic element of the Johann type spectroscope. It is curved from a state where a plurality of films are stacked, and it is difficult to cut the radius of curvature of a Johann curved spectroscopic element into a surface where the crystal lattice plane and the crystal reflecting surface do not coincide with each other. A functional graphite curved X-ray spectroscopic element has not been manufactured.

  The present invention has been made in view of the above-described conventional problems. In a method for manufacturing a curved graphite X-ray spectroscopic element, a curved X-ray spectroscopic element, and an X-ray analyzer using the same, a graphite curved X-ray spectrometer for a Johansson spectrometer is used. An object of the present invention is to provide an element manufacturing method, a curved X-ray spectroscopic element, and an X-ray analyzer using the same.

  In order to achieve the above object, a method for manufacturing a curved X-ray spectroscopic element according to a first configuration of the present invention is a method for manufacturing a curved X-ray spectroscopic element in which a polymer film is pressure-heat-molded, and has a predetermined radius. A step of preparing a concave molding jig having a cylindrical concave surface, a step of preparing a convex molding jig having a cylindrical convex surface of a predetermined radius, a plurality of polymer films are stacked on the concave surface of the concave molding jig, A step of forming one laminate, and a cylindrical convex surface of the convex molding jig is brought into contact with an upper surface of the first laminate, and a center line parallel to a cylindrical axis of the concave molding jig on the upper surface of the first laminate A plurality of polymer films are stacked on both sides with respect to the boundary, and the second laminated body and the second laminated body are stepped so that all the end faces on the center line side of the plurality of polymer films are in contact with the cylindrical convex surface Form with 3 laminates Performing a heat treatment at a temperature equal to or lower than a polymer pyrolysis temperature to carbonize the first laminate, the second laminate, and the third laminate, and the concave molding jig and the convex molding jig. And press-molding the first laminated body, the second laminated body, and the third laminated body at a temperature exceeding a polymer thermal decomposition temperature.

  According to the first configuration, a graphite curved X-ray spectroscopic element for a Johansson type spectroscope can be manufactured.

  In the first configuration, the polymer film is selected from polyimide, polyamide, polyoxadiazole, polyamideimide, polybenzimidazole, polybenzobisthiazole, and polyparaphenylene vinylene having a thickness of about 10 to 50 μm. Is preferably used. The radius of the cylindrical convex surface of the convex molding jig is preferably ½ of the predetermined radius of the cylindrical concave surface of the concave molding jig, and is preferably about 50 to 200 mm. The predetermined radius of the cylindrical concave surface of the concave forming jig is preferably about 100 to 400 mm. The first laminate is preferably stacked with about 5 to 30 polymer films.

  The second laminated body and the third laminated body preferably have about 10 to 100 polymer films stacked on both sides of the cylindrical convex surface of the convex molding jig. The number of polymer films of the second laminate and the third laminate may be the same or different. The heating temperature for carbonizing the first laminate, the second laminate, and the third laminate is preferably 2000 ° C. or less, and more preferably 1000 to 1600 ° C. The heating temperature when pressure-molding the first laminate, the second laminate, and the third laminate is preferably a temperature exceeding 2000 ° C., the molding pressure is preferably 392 kPa or more, and 392 to 4900 kPa. More preferred.

  The graphite curved X-ray spectroscopic element according to the second configuration of the present invention is manufactured using the manufacturing method of the first configuration.

  According to the second configuration, it is possible to provide a high-resolution X-ray spectrometer with less aberration and a high reflection intensity at a long wavelength.

  The X-ray analyzer according to the third configuration of the present invention includes the curved X-ray spectroscopic element having the second configuration.

  According to the third configuration, it is possible to provide an X-ray analyzer with a long wavelength and high sensitivity and high resolution, and it is possible to perform analysis with high sensitivity and high accuracy.

  Hereinafter, a method for manufacturing a graphite curved X-ray spectroscopic element according to the first embodiment of the present invention will be described. In this manufacturing method, the polymer film used as the raw material is, for example, polyimide having a thickness of 10 μm, and is pressure-heat molded using the molding part 1 of the ultra-high temperature pressure molding apparatus shown in FIG.

  As shown in FIG. 1, for example, on the concave surface of a concave molding tool 11 having a cylindrical surface with a radius of 200 mm, the short side of a polyimide film having a long side of 40 mm and a short side of 30 mm and a thickness of 10 μm is formed into the concave molding tool 11. 30 sheets are stacked so as to be parallel to the cylindrical axis of the first laminated body 13.

  For example, the cylindrical convex surface 12 of a convex molding jig having a cylindrical surface with a radius of 100 mm is lowered so as to be along the cylindrical concave surface 18 of the concave molding jig 11, and is brought into contact with the upper surface central portion 16 of the first laminate 13. For example, a long side of a polyimide film having a thickness of 30 μm and a short side of 20 mm and a thickness of 10 μm is in contact with the cylindrical convex surface 12 parallel to the cylindrical axis of the cylindrical convex surface 12 on both sides of the cylindrical convex surface 12 of the forming jig. Are placed on the upper surface of the first laminated body 13 to form the first layers of the second laminated body 14 and the third laminated body 15, and the second layer is shorter by 0.14 mm than the first layer only on the short side. Stacked on the first layer in the same manner as the one layer, sequentially stacked layers whose short sides are 0.14 mm shorter than the previous stage, and stacked 100 sheets on the upper surface of the first stacked body 13 to form a stepped second stacked body 14 and the third laminated body 15 are formed.

  For example, a slight vibration of 20 kHz is applied to the end surfaces of the second laminated body 14 and the third laminated body 15 opposite to the cylindrical convex surface side, and each of the 100 polyimide films is slid to end the cylindrical convex surface side of the polyimide film. Is reliably brought into contact with the cylindrical convex surface 12 of the convex forming jig.

  Next, the molding part 1 of the ultra-high pressure molding apparatus is heat-treated at a temperature equal to or lower than the polymer pyrolysis temperature. For example, the temperature is raised from room temperature to 1000 ° C. over 1 hour, and then kept at 1000 ° C. for 1 hour Then, the first stacked body 13, the second stacked body 14, and the third stacked body 15 are carbonized. Furthermore, the temperature of the molding part 1 of the ultra-high pressure molding apparatus is raised to a temperature exceeding the polymer thermal decomposition temperature, for example, 3000 ° C., and the cylindrical concave part 11 of the concave molding jig and the cylindrical convex surface 12 of the convex molding jig are respectively For example, when the first laminated body 13, the second laminated body 14 and the third laminated body 15 are pressure-molded for 1 hour at a pressure of 1960 kPa, for example, the graphite curved X-ray spectroscopic element 3 shown in FIG. 3 can be manufactured.

  In the first embodiment, the polymer film forming the first laminate is a rectangular film having a long side of 40 mm and a short side of 30 mm and a thickness of 10 μm, but the size of the curved X-ray spectroscopic element to be manufactured is large. It is sufficient to use a shape conforming to the above. The polymer film needs to have a thickness suitable for easy carbonization and a curved shape, and is preferably about 10 to 50 μm. The material is preferably polyamide, polyoxadiazole, polyamideimide, polybenzimidazole, polybenzobisthiazole, polyparaphenylene vinylene or the like.

  In the first embodiment, the concave molding jig has a cylindrical surface with a radius of 200 mm. However, a radius suitable for the curved X-ray spectroscopic element to be manufactured may be used, and is about 100 to 400 mm. preferable. The radius of the cylindrical surface of the convex forming jig is 100 mm, but it is preferably about 50 to 200 mm. The radius of the cylindrical convex surface of the convex molding jig and the radius of the cylindrical concave surface of the concave molding jig are in a ratio of 1: 2, that is, the radius of the cylindrical convex surface of the convex molding jig is R and the radius of the cylindrical concave surface of the concave molding jig is 2R. It is preferable that

  In the first embodiment, the first laminate is formed by stacking 30 10 μm polymer films. However, the present invention is not limited to this embodiment, and the thickness of the first laminate is preferably about 300 μm. It is preferable to stack about 5 to 30 sheets depending on the thickness of the film. Further, the second laminated body and the third laminated body are each formed by stacking 100 polymer films each having a thickness of 10 μm. However, the present invention is not limited to this embodiment. For example, as shown in FIG. The number of stacked layers of the second stacked body 19 and the third stacked body 20 may be different, such as 50 sheets and 100 third stacked bodies 20. In this way, the second laminated body 19 and the third laminated body 20 manufactured by different manufacturing methods have a curved X-ray spectroscopic element having an asymmetric reflecting surface 42 with respect to the cylindrical axis as shown in FIG. 4 The thickness of the second laminate and the third embodiment is preferably about 500 to 1000 μm, and about 10 to 100 are preferably stacked depending on the thickness of the polymer film.

  In the present embodiment, a 20 kHz vibration is applied to one end face of a polyimide film that is a stacked polymer film, and the polyimide films of the second laminate 14 and the third laminate 15 are slid one by one to obtain a polyimide film. The other end face is reliably brought into contact with the cylindrical convex surface 12 of the convex forming jig, but the vibration frequency to be vibrated is not limited to 20 kHz, and is preferably about 10 to 100 kHz. Instead of imparting vibration to the polymer film, wind may be blown and slid onto the end surface of the polymer film so as to be surely brought into contact with the cylindrical convex surface of the convex molding jig.

  In this embodiment, the heating temperature for carbonizing the first laminate, the second laminate, and the third laminate is preferably set according to the material of the polymer film to be used. If it is, it is preferable that it is 2000 degrees C or less, and it is more preferable that it is 1000-1600 degreeC. Further, the temperature and pressure for pressure heating molding are not limited to 3000 ° C. or 1960 kPa, but are determined by the material of the polymer film to be used, the radius of curvature to be molded, the laminated film thickness, etc. Is preferably a temperature exceeding 2000 ° C., more preferably 2500 to 3000 ° C., and the molding pressure is preferably 392 kPa or more, more preferably 392 to 4900 kPa. An appropriate time may be determined depending on the material of the polymer film to be used, the time of carbonization, the time of pressure heating molding, and the like, the radius of curvature to be molded, and the laminated film thickness.

  Next, a graphite curved X-ray spectroscopic element according to a second embodiment of the present invention will be described. The curved X-ray spectroscopic element of the present embodiment is manufactured by the manufacturing method of the first embodiment, and as shown in FIG. 3, the graphite curved X-ray spectroscopic element 3 has a curvature radius of 200 mm which is a reflective surface. The cylindrical concave surface 32, the cylindrical convex surface 31 with a radius of 100 mm, the thickness is 1 mm, and the length is 30 mm. The ratio of the radius of curvature of the cylindrical concave surface 32, which is the reflective surface, and the radius of curvature of the cylindrical convex surface 31 is 1: 2, and the crystal lattice plane and the crystal reflective surface do not coincide with each other. Used as a curved X-ray spectroscopic element for a spectroscope.

  The curved X-ray spectroscopic element of the present embodiment is not limited to the one manufactured by the manufacturing method of the first embodiment, and is manufactured by the preferable manufacturing method described in the first embodiment. The manufactured curved X-ray spectroscopic element is preferably a Johanson-type spectroscopic curved X-ray spectroscopic element in which the ratio of the radius of curvature of the cylindrical concave surface, which is the reflecting surface, and the radius of curvature of the cylindrical convex surface is 1: 2.

  Next, a fluorescent X-ray analyzer that is an X-ray analyzer according to a third embodiment of the present invention will be described. This fluorescent X-ray analyzer has the graphite curved X-ray spectroscopic element of the second embodiment. As shown in FIG. 5, the X-ray fluorescence analyzer 5 includes an X-ray source 51 that irradiates a sample 53 with primary X-rays 52, and fluorescent X-rays 54 generated from the sample 53 using the graphite curve X of the second embodiment. This analyzer has a counter 57 for detecting fluorescent X-rays 56 that are spectrally separated by a Johansson-type spectroscope 55 having a line spectroscopic element, and performs quantitative / qualitative analysis based on the detected X-ray intensity and energy. .

  The X-ray fluorescence analyzer of the present embodiment is not limited to the one having the curved X-ray spectroscopic element of the second embodiment, but may be any apparatus having the above-described preferable graphite curved X-ray spectroscopic element.

  According to the fluorescent X-ray analysis apparatus of this embodiment, the curved X-ray spectroscopic element does not coincide with the crystal lattice plane and the crystal reflection surface, and is used for a Johansson type spectroscope that is a concentrated optical system, and produces aberrations. In addition, the reflection intensity is strong and the resolution is excellent. In particular, microanalysis and microanalysis can be performed with high sensitivity and high accuracy. In addition, since the curved X-ray spectroscopic element of the X-ray fluorescence analyzer of the present embodiment is a graphite crystal, sulfur, phosphorus, chlorine, etc. are used using fluorescent X-rays such as S-Kα, P-Kα, Cl-Kα. Light elements can be analyzed with high sensitivity.

  In the present embodiment, the X-ray fluorescence analyzer is described as an X-ray analyzer. However, the X-ray analyzer is not limited to the X-ray fluorescence analyzer, and other X-ray analysis such as an X-ray diffractometer is possible. Including equipment.

It is a figure which shows the shaping | molding part of the ultra-high temperature press-molding apparatus in the manufacturing method of the curved X-ray spectroscopic element which is 1st Embodiment of this invention. It is a figure which shows the modification of the manufacturing method. It is a perspective view of the curved X-ray spectroscopic element which is 2nd Embodiment of this invention. It is a perspective view of the curved X-ray spectroscopic element which is a modification of the embodiment. It is the schematic which shows the fluorescent-X-ray-analysis apparatus which is 3rd Embodiment of this invention. It is an optical arrangement | positioning figure of a Johann type | mold spectrometer. It is an optical arrangement | positioning figure of a Johansson type | mold spectrometer. It is a perspective view of the conventional graphite crystal.

Explanation of symbols

1: Molding part 3, 4 of ultra high temperature pressure molding apparatus 4: Curved X-ray spectroscopic element 5: X-ray fluorescence analyzer 11: Concave molding jig 12: Cylindrical convex surface 13 of convex molding jig 13: First laminates 14 and 19 : Second laminated body 15, 20: third laminated body 18: cylindrical concave surface of concave surface forming jig

Claims (4)

A method for producing a curved X-ray spectroscopic device for pressure-heating a polymer film,
Providing a concave forming jig having a cylindrical concave surface of a predetermined radius;
Preparing a convex forming jig having a cylindrical convex surface of a predetermined radius;
Stacking a plurality of polymer films on the concave surface of the concave forming jig to form a first laminate;
The cylindrical convex surface of the convex molding jig is brought into contact with the upper surface of the first laminated body, and on each of both sides of the upper surface of the first laminated body with a center line parallel to the cylindrical axis of the concave molding jig as a boundary, Stacking a plurality of polymer films, and forming a second laminate and a third laminate in which all end faces on the center line side of the plurality of polymer films are stepped so as to contact the cylindrical convex surface; ,
Heat treating at a temperature equal to or lower than a polymer pyrolysis temperature, and carbonizing the first laminate, the second laminate, and the third laminate;
Pressure-molding the first laminated body, the second laminated body, and the third laminated body at a temperature exceeding a polymer pyrolysis temperature with the concave molding jig and the convex molding jig;
A method for manufacturing a curved X-ray spectroscopic element.   2. The method of manufacturing a curved X-ray spectroscopic element according to claim 1, wherein a radius of the cylindrical convex surface of the convex molding jig is ½ of a predetermined radius of the cylindrical concave surface of the concave molding jig.   A curved X-ray spectroscopic element manufactured by the manufacturing method according to claim 1.   An X-ray analyzer having the curved X-ray spectroscopic element according to claim 3.

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