JPH0862394A - Curved graphite monochromator and manufacturing method thereof - Google Patents

Abstract

(57) [Abstract] [PROBLEMS] To provide a curved graphite monochromator capable of utilizing a large amount of X-rays from an X-ray source and a manufacturing method thereof. [Structure] Polymer film at 400 ℃ or above and 10K
An isotropic graphite mold 2 in which a pressure of g / cm ² or less is applied intermittently or continuously, and a predetermined curved surface is processed into a part of the structure.
A curved graphite monochromator is obtained by thermocompression bonding to 6, 27.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a curved graphite monochromator having a curved surface such as a parabolic surface, a spherical surface, an aspherical surface or a toroidal curved surface which is used as an X-ray optical element, an X-ray monochromator, a neutron diffraction mirror and the like. And a method for manufacturing the same.

[0002]

2. Description of the Related Art X-rays are superior in quantitative intensity to measurement intensity as compared with electron beams and are widely used for quantitative structural analysis of substances, chemical analysis using fluorescent X-rays and the like. However, X
X-rays cannot be focused because there is no lens like rays. Therefore, if you want to extract information such as structure and strain from a very small area of the micron order, you can use a pinhole at the expense of strength to irradiate X-rays in a very small area and extract that information. This is the usual method. However, this method is accompanied by a marked decrease in strength, and in order to compensate for it, measures have been taken such as devising a counter so that the largest possible solid angle can be measured at one time. In addition, a method of collecting light using a toroidal mirror, which utilizes the phenomenon of total reflection when X-rays are made incident on a substance at a very low angle, is a radiation that has a very high intensity and good parallelism. Used in light etc. Such a method has an intensity of 1/1000 or less as compared with synchrotron radiation, and an ordinary X-ray encapsulation tube or a rotating anticathode tube type X-ray generator that can obtain only divergent light,
It cannot be used. The mirror used for synchrotron radiation is
There have been adopted methods such as a large crystal having a large radius of curvature and using CVD, or cutting into small pieces and sticking a flat crystal such as graphite to obtain a predetermined shape. These conventional methods cannot be used for ordinary X-ray encapsulation bulbs or rotating anticathode tube type X-ray generators. Further, since graphite has excellent heat resistance, chemical resistance, high conductivity, etc., it occupies an important position as an industrial material and is widely used as an electrode, a heating element, and a structural material. Above all,
Since single crystal graphite has excellent spectral and reflection characteristics for X-rays and neutron rays, it is widely used as a monochromator for X-rays and neutron rays, a filter or a dispersive crystal.

To obtain such single crystal graphite, it is easy to use a naturally occurring graphite,
The production amount of high-quality natural graphite is very limited, and since it is in the form of powder that is difficult to handle, or in the form of a very small block, its usable applications are limited.

Therefore, it has been considered to produce artificial graphite having properties equivalent to those of the above-mentioned natural single crystal graphite. The general method for producing artificial graphite can be classified into the following two methods.

[0005]

The first method is to use Fe,
This is a method for producing graphite by extruding from a Ni / C-based melt, classifying carbides such as Si and Al, or cooling the carbon melt under high temperature and high pressure. The graphite obtained by such a method is called quiche graphite and exhibits physical properties equivalent to those of natural graphite. However, in the above-mentioned method, only minute flaky graphite is obtained, and since the manufacturing process is complicated and the cost is high, it is hardly used industrially.

The second method is a method in which hydrocarbon gas is decomposed and deposited at high temperature in a vapor phase and hot working thereof, and graphite is obtained by a step of re-annealing at 3400 ° C. for a long time while applying pressure. Is manufactured. The graphite obtained in this way is called highly oriented pyrographite (HOPG), and its properties are almost the same as those of natural graphite. In this method, unlike the above-mentioned quiche graphite, it is possible to manufacture a considerably large size, but the manufacturing process is complicated, the yield is low, and not only the disadvantage that it is very expensive,
Only a single bent having a large curvature can be finally formed by post-processing, and it was impossible to obtain a double bent or other mirror having a curved surface from graphite.

By eliminating the drawbacks of these two manufacturing methods,
A manufacturing method that is easy to manufacture and inexpensive is devised, and a method of heating various organic substances or carbonaceous substances at 3000 ° C. or higher to graphitize them has been considered. However, with this method, it was not possible to obtain graphite having excellent properties equivalent to those of natural graphite and quiche graphite. For example, the most typical physical property of graphite, that is, the electric conductivity in the ab plane direction, is 1 to 2.5 × 10 ⁴ S / cm for natural graphite and quiche graphite, whereas that for the above method is generally 1-2 x 1
Only 0 ³ S / cm can be obtained. This indicates that graphitization does not proceed completely with the above method. In addition, the fact that the graphitization has not progressed completely indicates that it is difficult to obtain a uniformly graphitized product in units of planes.

In the case of the above method, a carbonaceous material such as coke and a binder such as coal tar are usually used as a starting material, but the structure of carbon produced by heating the coke or charcoal to about 3000 degrees. Is
There are various types, ranging from those relatively close to the graphite structure to those far from it. Among such carbon structures, carbon which is relatively easily converted into a graphitic structure by heat treatment is called graphitizable carbon, and carbon which is not such is called non-graphitizable carbon. The cause of such a structural difference is closely related to the mechanism of graphitization, and whether structural defects existing in the carbon precursor are easily removed by heat treatment at a higher temperature. Therefore, the microstructure of the carbon precursor plays an important role for graphitization.

In contrast to the above-mentioned method using coke as a starting material, some studies have been conducted on a method for producing a graphite film by using a polymer material and heat-treating it. The method seeks to control the microstructure of the carbon precursor by taking advantage of the molecular structure of the polymeric material.

The above method is a method in which a polymer is heat treated in a vacuum or in an inert gas, a carbonaceous material is changed through decomposition and polycondensation reaction, and the carbonaceous material is further graphitized. However, in the case of this method, even if it is used as an arbitrary polymer starting material, a graphite film having excellent properties is not obtained, and it is known that most polymer materials cannot be used for this purpose. .
For example, as a polymer for which heat treatment has been attempted for the purpose of graphitization as described above, there are phenol formaldehyde resin, polyparaphenylene, polyparaphenylene oxide, polyvinyl chloride, and the like. All of them belonged to non-graphitizable materials and did not have a high graphitization rate.

[0011]

[Means for Solving the Problems] The inventors of the present invention have conducted various studies to solve the problems of the method for producing graphite using a polymer as described above, and tried graphitization of many polymers. As a result, film-like polybenzothiazole (PBT), polyamide-imide (PA
I), polybenzobisimidazole (PBI), polybenzobisimidazole (PBBI), polyterephthalamide (PTA), polyphenylenevinylene (PPV),
Aromatic polyamide (PA), three kinds of polybenzobisthiazole (PBBT), polybenzoxazole (PB)
O), polybenzobisoxazole (PBBO), polythiazole (PT) aromatic polyimide (PI), etc. When heat-treated at a specific temperature, graphitized more easily than conventionally known polymer materials. Found.
The inventors of the present invention have filed patent applications based on these findings, and these patent applications are disclosed in JP-A-61-275114, JP-A-61-275115, and JP-A-61-2751.
No. 17, for example. According to this method, the polymer as described above is treated at 1800 ° C or higher, preferably 25
By heating at a temperature of 00 ° C. or higher, graphite having a high graphitization rate can be easily produced in a short time.

In order to express the degree of graphitization, parameters of X-ray analysis such as the lattice constant and the size of the crystallite in the C-axis direction, or the graphitization rate calculated from them are often used, and the electric conductivity value is also used. Is also often used. The lattice constant is calculated from the position of the (0002) diffraction line of X-ray and is 6.70 which is the lattice constant of natural single crystal graphite.
It is shown that the closer to 8A, the more the graphite structure is developed. The crystallite size in the CX axis direction is (000
2) It was calculated from the half-width of the diffraction line, and it was shown that the larger the crystallite value was, the better the planar structure of graphite was developed, and the crystallite size of natural single crystal graphite is 1000 A or more. The graphitization ratio is the crystal plane spacing (d
₀₂₂ ) (Reference: Carvone Vol. 1, 129)
Page, 1965 (see Les Carbons Vol.1 p129, 1965)). And, naturally, the graphitization rate of natural single crystal graphite is 100%. The electric conductivity is shown by the value in the ab plane direction of graphite, and the larger the conductivity value is, the closer it is to the graphite structure. It is 1 to 2.5 × 10 ⁴ S / cm for natural single crystal graphite.

Further, one of the X-ray diffraction parameters for evaluating the graphite structure is a rocking characteristic which shows how the ab planes overlap. This is called a diffraction intensity curve, and is a diffraction intensity curve obtained by rotating a crystal when a monochromatic and parallel X-ray flux is incident, and 2θ is fixed at an angle at which a (000 l) diffraction line appears, and θ Is measured by rotating. This value is evaluated by the full width at half maximum of absorption and is represented by the rotation angle (°). The smaller this value, the more clearly the ab planes overlap.

The curved graphite crystal of the present application is mainly intended to be used by attaching it to a normal X-ray generator that produces divergent X-rays, and a graphite crystal assembled and processed into a toroidal shape is used. Without significantly reducing the strength as when using a pinhole, X
Focuses the rays and enables quantitative X-ray diffraction from a minute area. Furthermore, this curved graphite monochromator does not utilize the incidence and reflection of X-rays at a low angle of about 0.1 degree, as in the case of using a toroidal mirror, but rather the use of graphite Single crystal (0
Since the diffraction (diffraction) from the (002) plane is used, it is possible to perform monochromaticization at the same time as condensing. Even in this respect alone, the curved graphite monochromator improves the measurement data and significantly improves the quantitativeness of strength as compared with the conventional method using a pinhole.

In addition, the above-mentioned method for producing graphite from a specific polymer film is a very excellent method because it is easy and inexpensive, and in particular,
It was found that in-plane homogeneous graphitization was performed.However, in order to manufacture curved graphite crystals such as curved surface, aspherical surface, and graphite curved surface, this method was subjected to various studies afterwards. , It became clear that there are some problems to be improved as follows.

The first problem is that not only is it impossible to produce thin toroidal graphite crystals by this method, but it is also possible to produce thick toroidal graphite crystals, that is, block-shaped toroidal graphite crystals. That is not possible. At first glance, the graphitization reaction seems to be independent of the thickness of the starting material film, but in reality, the graphitization reaction strongly depends on the thickness of the material. Regarding the film thickness and graphitization, the inventors have applied for a patent for the results of various experiments. Then, in the form of further developing the technology, we have been working on a method for producing a curved graphite crystal having a spherical surface, an aspherical surface, or a toroidal curved surface.

An object of the present invention is to improve the graphitization process in which the film is graphitized in the plane of parallel film, and to improve the process of graphitization, such as spherical surface, aspherical surface, toroidal curved surface (hereinafter collectively referred to as curved surface). A method for producing a curved graphite crystal, which solves the problem of graphitization along a curved isotropic graphite mold shape, and particularly solves the problem of remarkably strengthening the intensity of divergent X-rays using this method. It is.

Among the inventions for solving the above-mentioned problems, the invention according to claim 1 has a curved surface consisting of at least one predesigned shape and a divided part,
Each of the other individual pieces is a curved graphite monochromator having a shape that is part of the other design and combining them to form a parabolic surface, a spherical surface, an aspherical surface, a toroidal curved surface, or the like.

According to the second aspect of the invention, the polymer film is intermittently or continuously applied with a pressure of 400 ° C. or higher and a pressure of 10 kg / cm ² or higher, and a predetermined curved surface is processed into a part. It is a method for manufacturing a curved graphite monochromator, which obtains a curved graphite monochromator having a curved surface by heating and pressure bonding to an isotropic graphite mold.

The invention according to claim 3 is polybenzothiazole, polybenzobisthiazole, polybenzoxazole, polybenzobisoxazole, polyamideimide, polybenzimidazole, polybenzobisimidazole, polyterephthalamide, polyphenylenevinylene. , An aromatic polyimide, an aromatic polyamide, and a polyoxadiazole, a single or a plurality of polymer films having a thickness of 1 to 400 μm are heat-treated at 400 to 2000 ° C. to prepare a carbonaceous film. The carbonaceous film is used alone or in a plurality of layers, and a predetermined pressure is applied while intermittently or continuously applying a pressure of 20 Kg / cm ² or less in the temperature range of 2200 ° C. or less and 20 Kg / cm ² or more in the temperature range of 2200 ° C. or more. Of parabolic, spherical, aspherical and toroidal surfaces Parabolic surface, spherical surface, aspherical surface, toroidal curved surface, etc., characterized by being composed of at least one graphite crystal having a curved surface shape obtained by thermocompression bonding to an isotropic graphite mold Is a method for manufacturing a curved graphite monochromator.

The invention according to claim 4 is polybenzothiazole, polybenzobisthiazole, polybenzoxazole, polybenzobisoxazole, polyamideimide, polybenzimidazole, polybenzobisimidazole, polyterephthalamide, polyphenylenevinylene. , A heat-resistant polymer film having a thickness of 1 to 400 μm selected from aromatic polyimide, aromatic polyamide, and polyoxadiazole to prepare a carbonaceous film, and the obtained carbonaceous film may be used alone or in combination. Stack 10
400 ° C while intermittently applying a pressure of Kg / cm ² or more
As described above, it is composed of at least one graphite crystal having a curved surface shape obtained by thermocompression bonding a predetermined parabolic surface, spherical surface, aspherical surface, and toroidal curved surface to a mold processed into a part of the structure. Characteristic paraboloid, spherical surface, aspherical surface,
A method for manufacturing a curved graphite monochromator such as a toroidal curved surface.

Further, according to the invention of claim 5, in the state where the curved surfaces of the graphite molds of claim 2, claim 3, and claim 4 are sandwiched between the upper and lower molds, the force vector of the upper and lower molds is obtained. Is a curved graphite monochromator, which is manufactured by using a graphite mold designed so as to be only about approximately above and below.

[0023]

According to the invention as set forth in claim 1, the curved graphite crystal is preferably a divergent type X-ray which is preferably used for the purpose of collecting X-ray light in a desired region or extracting it as parallel light. The main purpose is to attach it to an ordinary X-ray generator that produces X-rays, and especially for a graphite crystal that has been assembled and processed into a toroidal shape of focus concentrating type, it can be used as a conventional slit or pinhole. As in the case of using, the X-ray is focused on a desired region without significantly lowering the intensity, and quantitative X-ray diffraction from a minute region is enabled. Furthermore, this curved graphite monochromator does not utilize the incidence and reflection of X-rays at a low angle of about 0.1 degree, as in the case of using a toroidal mirror, but rather the use of graphite Since the diffraction (diffraction) from the (0002) plane of the single crystal is used, it is possible to perform monochromaticization at the same time as condensing. Even in this respect alone, the curved graphite monochromator improves the measurement data and significantly improves the quantitativeness of strength as compared with the conventional method using a pinhole.

According to the second aspect of the present invention, a curved graphite monochromator obtained by graphitizing a polymer film is manufactured, and by heat-treating the specific polymer film, good quality is obtained. It is obtained by utilizing the graphite crystallization that can produce the carbonaceous film.

Further, according to the inventions of claims 3 and 4, when a plurality of carbonaceous films are stacked and thermocompression-bonded, predetermined paraboloids, spherical surfaces, aspherical surfaces, and toroidal curved surfaces are formed. By thermocompression bonding to a partially processed isotropic graphite mold and applying a pressure of 400 Kg or more and 10 Kg / cm ² or more continuously or intermittently, various properties such as rocking properties can be greatly improved. In addition to being excellent, it is possible to produce thick block-shaped graphite crystals that cannot be obtained with a single-layer film.

According to the fifth aspect of the present invention, the curved surfaces of the isotropic graphite mold are the upper and lower molds, and the force vectors of the upper and lower molds when sandwiched are about about the pressing direction, that is, the upper and lower molds. It is a method for manufacturing a curved surface characterized by being manufactured using an isotropic graphite mold designed so that only a curved graphite monochromator having excellent X-ray reflection characteristics and monochrome characteristics can be obtained. Is what you can get.

[0027]

【Example】

Example 1 First, in the present invention, a polymer film selected from aromatic polyimide, aromatic polyamide, and polyoxadiazole is used as a polymer film as a starting material. The various polyimides include polybenzothiazole, polybenzobisthiazole, polypentoxoxazole, polybenzobisoxazole, polyamideimide, polybenzimidazole, polybenzobisimidazole, polyterephthalamide, polyphenylenevinylene, and the following general formula (1 ) Is an aromatic polyimide.

[0028]

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[0029]

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[0030]

[Chemical 3]

Among the various polyamides, there are aromatic polyamides represented by the following general formula (2).

[0032]

[Chemical 4]

The specific material composition and blending of the polymer film are appropriately selected and carried out depending on the application and manufacturing conditions.
The thickness of the polymer film is 400 μm or less, preferably 1 to 400 μm. When the film thickness is more than 400 μm, only carbon precursor with disordered internal structure (that is, non-graphitizable carbon) can be formed due to gas generated in the process of carbonization and graphitization, and then part of the toroidal shape is formed. It is not possible to obtain good quality graphite even by performing thermocompression bonding to a mold having the above shape, that is, performing a hot pressing process. There is no particular limitation when the film thickness is thin. If it is thinner than 1 μm, it is economically disadvantageous because it is necessary to manufacture a larger number of carbonaceous films in order to manufacture a graphite block having the same thickness.

The heat treatment temperature for producing the carbonaceous film is in the range of 400 to 2000 ° C. 2000
Although the heat treatment can be performed in a temperature range of ℃ or more, the heat treatment in the above temperature range is performed in order to obtain the mirror or the monochromator shown in FIGS.
Divide into shapes such as (d), (e), and (f), and heat-press on a parabolic surface, a spherical surface, an aspherical surface, and a toroidal curved surface to an isotropic graphite mold that is partly processed. Hot pressing gives better results on the quality of the finally produced graphite. This step is a preliminary heat treatment step before hot pressing, but at this stage it is better to separately heat treat the polymer films without stacking them, especially 400 μm.
It is better not to stack on a thickness of m or more. This is because when the polymer films are heat-treated in a stacked state, gas generation from the polymer films is suppressed, and the same drawbacks as when using a thick film occur. After manufacturing the carbonaceous film through the preliminary heat treatment step as described above,
A plurality of carbonaceous films are superposed on each other, and a hot pressing process, which is a full-scale heating and pressure bonding process, is performed to promote graphitization of carbonaceous matter, and the mirror or the monochromator shown in FIGS. Curved graphite crystal obtained by thermocompression bonding to an isotropic graphite mold in which a parabolic surface, a spherical surface, an aspherical surface, and a toroidal curved surface are processed in order to obtain, that is, FIG. 3 (c), (d), (E) and (f) are divided, and in the case of 4 divisions, a toroidal curved surface graphite crystal monochromator 18 having a toroidal curved surface graphite crystal 19 is obtained, and in the case of 8 divisions, a toroidal curved surface graphite crystal 21 is obtained. It can be processed and manufactured in the shape of the toroidal curved surface graphite crystal monochromator 20 having. That is, the toroidal curved graphite crystal monochromator 14 having the toroidal curved graphite crystal 15 having the X-ray entrance 17 and the X-ray monochrome exit 16 can be manufactured. In this hot pressing process, the method of pressure application and temperature control are important. That is, in this hot pressing step, it is necessary to press-bond while removing wrinkles generated in the carbonaceous film during heat treatment. As a result of studying such a treatment condition, it is necessary that the pressure is 20 Kg / cm ² or less in the temperature range of 2200 ° C. or lower.
The carbonaceous film breaks. It should be noted that it is more effective in preventing cracking if the pressure is gradually applied without being applied suddenly. In the temperature range of 2200 ° C. or higher, a pressure of 20 Kg / cm ² or more is required to realize complete mounting, and pressure lower than that requires sufficient pressure bonding.

Through the above manufacturing steps, a parabolic surface, a spherical surface, or an aspherical surface having a predetermined block shape and a predetermined block shape having a thick block shape and significantly improved locking characteristics. ,
Curved graphite crystals can be manufactured that have been processed as part of the construction of a toroidal curved surface. For example, the POD film (thickness 4, 25, 10
(0,450 μm) is heat-treated at 100 ° C. to produce a carbonaceous film, and 10 films of each thickness are superposed on each other to carry out a hot pressing step. Hot pressing was performed with a heating process, until 2200 ° C. by applying a pressure of 4 Kg / cm ^2, becomes 2200 or more by applying a pressure of 20 Kg / cm ^2, a curved graph by performing a predetermined time processing at 3000 ° C. Produce a fight crystal.

Next, a manufacturing method which is partially different from the above method and which is similarly excellent in rocking characteristics and the like and which can manufacture a thick curved graphite crystal will be described.

Since the material of the polymer film and the heat treatment process for producing the carbonaceous film can be carried out in the same manner as the production process of the above-mentioned embodiment, detailed description thereof will be omitted. The manufacturing method of this embodiment is characterized by intermittently applying pressure in a temperature range of 400 ° C. or higher in the hot pressing step. As described above, in the hot pressing process of the carbonaceous film, it is important how well the wrinkles and distortions caused by the heat treatment are removed, and the parabolic surface, the spherical surface, the aspherical surface, and the toroidal curved surface are constituted. The shape and setting method of the isotropic graphite mold that is processed into the part are important. Based on this point, it is very effective to apply pressure intermittently. 1 and 2
In order to obtain the mirror or monochromator shown in FIG. 3, the parabolic surface, spherical surface, aspherical surface, and toroidal curved surface are subjected to thermocompression bonding to an isotropic graphite mold processed into a part of the structure to form a curved graphite. A crystal monochromator is manufactured.

As a method of continuously applying pressure, the maximum value of the pressure applied is kept relatively small in the low temperature region of the heat treatment process, and the maximum value of the pressure is increased in the high temperature region. , More effective. The maximum value of the applied pressure is most preferably 20 Kg / cm ² or less at 2200 ° C. or less, but is effective if it is 10 Kg / cm ² or more. 20Kg / c above 2200 ℃
It is desirable that the pressure is m ² , but the pressure may be 10 Kg / cm ² or more.

In each example, rocking characteristics were measured in order to evaluate the degree of graphitization, and the measurement conditions for these physical properties are as follows.

Rocking characteristic (○) Using a Rotaflex RU-200B type X-ray diffractometer manufactured by Rigaku Denki Co., Ltd., the rocking characteristic at the peak position of the graphite (0002) line was determined.

In the case of the spherical mirror monochromator 1 composed of the spherical graphite crystal 2 shown in FIG. 1, the strong X-ray 4 can be focused by providing the light source 3 and the focusing point 5 on the diameter surface. Also, a parabolic mirror monochromator 6,1 of the parabolic graphite crystal 7,12 shown in FIG.
In one case, the X-ray source 8 is installed at the focal point of the graphite crystal 7 parabolic mirror 6 by using two graphite crystal parabolic mirror monochromators, and the measurement object 10 is irradiated with X-rays 9, and after that, The sensor 13 provided at the focal point of the parabolic mirror monochromator 11 composed of the graphite crystals 12 installed opposite to each other is excellent in that analysis can be performed.

(Embodiment 2) The principle of a design method for obtaining a toroidal curved surface crystal, particularly the principle of a toroidal crystal monochromator will be described with reference to FIG.

FIG. 4 shows a light collecting principle of the toroidal crystal monochromator. In the figure, an X-ray target store, S is a sample, (AA′B′B) is a toroidal crystal monochromator main body, XX ′ is an X-ray main body, O and O ′ are the centers of focal circles on the paper, and arcs. FCS and FC'S are focal circles corresponding to these centers. Therefore, the distance FS
Is the distance between the X-ray target and the sample and depends on the diffractive device. Further, the radius OF (= rf) of the focal circle can be calculated from the following formula using the distance FS if the wavelength λ of the X-ray to be used is determined. First, from the Bragg diffraction condition, the scattering angle Θ is given by the following equation.

Θ = sin ⁻¹ (λ / 2d) (1) Here, d is the surface spacing of the (0002) plane of graphite, which is 3.354 Å. Therefore, r _f = FS / (2sin2Θ) (2) This gives the radius of the focal circle out of the horizontal plane of the toroidal crystal monochromator. Further, the radii CM and AN of the central portion and the entrance of the toroidal crystal monochromator are given by the following expressions using the length NN ′ of the toroidal crystal monochromator, the distance FS, and the scattering angle Θ.

CM = (FS / 2) tan Θ (3) AN = (1/2) (FS-NN ′) tan Θ (4) The X-rays diverging from the focus F form a focus circle so as to satisfy the Bragg condition. The diffracted beam, which is diffracted on the graphite crystal monochromator bent along and is monochromatic at another focal point S, is collected.

An actual toroidal curved surface crystal monochromator design will be described below using the example shown in FIG.

(1) As can be seen from the equation (2), the larger the scattering angle, the larger the curvature in the horizontal direction. Therefore, it is considered that when the characteristic X-ray having a short wavelength is targeted for design, the curvature becomes smaller and the molding becomes easier.

(2) The distance FS is a device-dependent constant as described above. That is, it is determined by the size of the tube shield holding the X-ray target and the radius of the goniometer. As can be seen from the equation (2), since the distance FS and the radius r _{f of the} focal circle are in a proportional relationship, the longer the FS, the smaller the horizontal curvature, which is easier for molding.

Specifically, an example is given in which an X-ray enclosing tube for molybdenum Kα rays is attached to an X-ray tube shield manufactured by Rigaku Denki Co., Ltd. and a goniometer manufactured by Rigaku Denki Co., Ltd. is used. The size of the toroidal curved crystal monochromator was actually calculated.

It is assumed that the X-ray tube used a 0.4 mm × 8 mm point focus. Distance FS = 182 mm (measured value) d (0002) = 3.354 Å From the formula (1), Θ = 6.082 °. Therefore, equation (2)
From r _f = 431.9 mm where the length of the toroidal curved surface crystal monochromator, N
When N ′ is 20 mm, the radius CM of the antinode portion of the toroidal curved-surface crystal monochromator is CM = 9.
70 mm. From the equation (4), the radius of the edge portion of the toroidal curved surface graphite crystal monochromator AN = 8.63 m
It became m.

FIG. 6 shows an X-ray optical path diagram and the toroidal curved surface graphite crystal monochromator 14 thus obtained.

The X-rays 25 from the X-ray source 23 are incident on the toroidal curved surface graphite crystal monochromator 14, and the condensed X-rays are condensed on the spot 24, and the monochromatic X-rays are magnified about 100 times. Was able to be collected. However, in order to make it completely monochrome,
In order to remove the X-rays that are directly focused from the light source, a beam stopper or, in the case of copper (Cu) Kα rays, a Ni foil is provided on the line connecting the toroidal shaped exit end face with a specific filter. Can be obtained. Similarly, the spherical graphite crystal monochromator of FIG. 1 and the parabolic graphite crystal monochromator of FIG. 2 having a light source and a condensing point determined by the wavelength of X-rays could be obtained.

(Example 3) POD and P having a thickness of 10 μm
Each polymer film of A and PI is sandwiched between graphite plates, heated to 1000 ° C. at a heating rate of 20 ° C./min in a nitrogen atmosphere, and then heat-treated by holding at 1000 ° C. for 1 hour to obtain a carbonaceous material. I got a film.

20 carbonaceous films made of the respective materials were stacked, and a hot pressing process was performed using an ultra-high temperature hot press manufactured by Chugai Furnace Industry Co., Ltd. to obtain a graphite block. The processing conditions of the hot pressing step are as follows: the temperature is raised at a heating rate of 10 ° C./min, and a predetermined pressure, that is, the mirror or the monochromator shown in FIGS. Or Figure 3
(C), (d), (e), (f) divided into toroidal curved surface is divided into isotropic graphite mold processed into a part of the structure by heat compression and pressure is gradually applied to the final 20K
Increased to g / cm ² . In the temperature range of 2800 ° C. or higher, the pressure was set to 40 Kg / cm ² , and pressing was performed at 3000 ° C. for 1 hour. At this time, physical properties differed depending on the formation of the isotropic graphite mold in which the toroidal curved surface was partly processed and the setting position design, and it was impossible to mold. The physical properties of the thus-obtained curved graphite crystals were as follows. When the graphite was actually produced under the above treatment conditions, the rocking characteristics were 0.6 ° (4 μm) and 0.8 ° (25 μm). 1.
5 ° (100 μm), 1.8 ° (450 μm),
A remarkable improvement in locking characteristics was observed.

(Embodiment 4) Next, an example in which the invention of the 8-segment toroidal graphite mold carried out by the method of Embodiment 3 is carried out by the isotropic graphite mold shown in FIGS. 7 and 8 will be described.

With the isotropic graphite upper mold 26 and the lower mold 27 shown in FIG. 7, no good product was obtained under any setting. It is considered that this is because slippage occurs in the directions of arrows 30 and 31 as the film sandwiched between the upper and lower design curved surfaces 28 and 29 is graphitized. This method often resulted in mold breakage. A good product could be obtained only by using the molds such as the upper mold 34 and the lower mold 35 of the isotropic graphite shown in FIG. This is because the upper and lower design curved surfaces 32 and 33 are designed such that the center of gravity of the curved surfaces is located at the center of the mold. That is, it is important that the upper and lower pressures are not distributed in other directions as much as possible.

[0057]

The curved graphite crystal manufacturing method and the curved graphite monochromator according to the present invention are capable of slitting X-rays of small size and high intensity, which biological researchers and physical property researchers have so far required. It is an unprecedented breakthrough that can be obtained at the spot.

This is obtained from an excellent process of obtaining highly crystalline graphite between films by stacking a specific polymer film, and specifically, polybenzothiazole and polybenzobisthiazole are obtained. Thickness selected from polybenzazoxazole, polybenzobisoxazole, polyamideimide, polybenzimidazole, polybenzobisimidazole, polyterephthalamide, polyphenylenevinylene, aromatic polyimide, aromatic polyamide, polyoxadiazole 1
~ 400 μm polymer film is heat-treated to produce a carbonaceous film, and the obtained carbonaceous film is used alone or
A plurality of layers are stacked and heated and pressure-bonded to a mold in which a predetermined parabolic surface, spherical surface, aspherical surface, and toroidal curved surface of 400 ° C. or higher are processed while applying a pressure of 10 kg / cm ² or more intermittently. It is something that can be obtained. This is an epoch-making manufacturing method in which a graphite monochromator having at least one curved surface shape thus obtained is obtained. In the case of a spherical graphite crystal mirror monochromator, a circle determined by the wavelength of X-rays. By providing the light source 3 and the condensing point 5 existing at the peripheral points, strong X-rays can be condensed. Further, in the case of a parabolic graphite crystal mirror monochromator, at least one or more graphite crystal parabolic mirror monochromator is used.
Is placed at the focal point of the graphite crystal 7 parabolic mirror 6,
The measurement object 10 is irradiated with X-rays 9 and, in the case of two, it can be analyzed by a sensor 13 installed at the focus of a graphite crystal 12 parabolic mirror monochromator 11 installed opposite to each other. That is an excellent thing. This makes it possible to obtain curved parallel X-ray light without using a slit. In particular, in the case of the toroidal curved surface graphite monochromator 14, it is possible to obtain an excellent effect that an X-ray slit or spot having a high intensity of about 100 times or more can be obtained only by inserting it into a conventional X-ray analyzer. it can. In addition, for molds that have a predetermined parabolic surface, spherical surface, aspherical surface, or toroidal curved surface that is required for manufacturing, part of the structure must be able to disperse the pressure in the pressure stress direction during pressure bonding to other directions. It was shown that by using a mold devised so that the pressure can be reduced with less pressure, damage to the pressure shaft at high temperatures and damage to the fired crystalline graphite can be prevented.

[Brief description of drawings]

FIG. 1 is a configuration diagram of a graphite crystal spherical mirror monochromator according to an embodiment of the present invention.

FIG. 2 is a configuration diagram of a graphite crystal parabolic mirror monochromator according to an embodiment of the present invention.

FIG. 3 (a) is a front view of the whole combination, (b) is a side view of the whole combination, and (c) is a four-divided toroidal curved surface monochromator of the present invention cut along two planes orthogonal to the axial direction of the optical path. Front view (d) is a side view of FIG. 3 (c) (e) is a front view of the toroidal curved surface monochromator of the present invention divided into eight parts (f) is a side view of FIG. 3 (e)

FIG. 4 is an explanatory diagram of the principle of a graphite crystal toroidal monochromator.

FIG. 5 is a configuration diagram in which an 8-division curved surface of the toroidal curved-surface monochromator of the present invention is assembled.

FIG. 6 Toroidal monochromator and X-ray optical path diagram

FIG. 7 (a) is a side view of an isotropic graphite mold which is an example of a bad type of isotropic graphite type for 8-segment toroidal curved surface. (B) is a bad mold of isotropic graphite type for 8-segment toroidal curved surface. Front view of isotropic graphite mold

FIG. 8 (a) is a side view of an isotropic graphite mold that is a good example of an isotropic graphite mold for 8-segment toroidal curved surface. (B) is a good mold of isotropic graphite mold for 8-segment toroidal curved surface. Front view of isotropic graphite mold

[Explanation of symbols]

1 Spherical mirror monochromator 6,11 Graphite crystal parabolic mirror Monochrome 14 Graphite crystal toroidal shape mirror Monochrome 22 8-segment graphite crystal toroidal shape mirror Monochrome 34 8 Isotropic graphite upper mold for 8-segment toroidal shape 35 8-segment toroidal shape etc. Isotropic graphite lower mold

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Naomi Nishiki, Inami 1006, Kadoma, Kadoma City, Osaka Prefecture, Matsushita Electric Industrial Co., Ltd. Giken Co., Ltd. (72) Inventor Eiichiro Matsubara 2nd Kume Mansion 4-16 1 Nishinosekicho, Takano-Sakyo-ku, Kyoto-shi, Kyoto

Claims (5)

[Claims] 1. A curved surface consisting of at least one or more pre-designed divided parts, each other piece having a shape that is part of the design, and combining them. A curved graphite monochromator formed by forming a parabolic surface, a spherical surface, an aspherical surface, a toroidal surface, and the like. 2. A polymer film at 400 ° C. or higher and 1
Apply a pressure of 0 Kg / cm ² or more intermittently or continuously,
A method for manufacturing a curved graphite monochromator, which obtains a curved graphite monochromator having a curved surface by thermocompression-bonding a predetermined curved surface to an isotropic graphite mold having a part thereof processed. 3. Polybenzothiazole and polybenzobis
Thiazole, polybenzoxazole, polybenzobis
Oxazole, polyamideimide, polybenzimidazo
, Polybenzobisimidazole, polyterephthala
Mido, polyphenylene vinylene, aromatic polyimide, aromatic
Selected from aromatic polyamide and polyoxadiazole
Single or multiple polymer films with a thickness of 1 to 400 μm
Carbonaceous film by heat treatment of Rum at 400-2000 ℃
And the obtained carbonaceous film alone or in a plurality.
20Kg / c in the temperature range below 2200 ℃
m ²20 kg / c in the temperature range of 2200 ° C or higher
m²While applying the above pressure intermittently or continuously,
Parabolic, spherical, aspherical, and toroidal curved surfaces are part of the composition
It is heat-pressed to a processed isotropic graphite mold to give a parabolic surface, spherical surface,
At least one song in an aspheric or toroidal surface
Characterized by obtaining a graphite crystal having a plane shape
Curved graphite monochromator manufacturing method. 4. Polybenzothiazole, polybenzobisthiazole, polybenzoxoxazole, polybenzobisoxazole, polyamideimide, polybenzimidazole, polybenzobisimidazole, polyterephthalamide, polyphenylenevinylene, aromatic polyimide, aromatic polyamide , A polymer film having a thickness of 1 to 400 μm selected from polyoxadiazoles is heat-treated to produce a carbonaceous film, and the obtained carbonaceous films are stacked singly or in a plurality of layers to obtain 10 kg / cm ² Specified paraboloid or sphere at 400 ℃ or higher while intermittently applying the above pressure
To obtain a graphite crystal having at least one of a parabolic surface, a spherical surface, an aspherical surface, and a toroidal curved surface by thermocompression bonding to a mold in which a surface, an aspherical surface, and a toroidal curved surface are partly processed. And a method for manufacturing a curved graphite monochromator. 5. The curved surface of the graphite mold is the upper and lower molds,
5. A graphite mold designed such that the force vectors of the upper and lower molds in the sandwiched state are only about about the upper and lower sides, and are manufactured by using the graphite mold. Method for manufacturing curved graphite monochromator.