Process for producing curved graphite articles

Abstract: Graphite blocks are produced by a process which comprises heat treating a 1 to 400 µm thick film of a polymer selected from the group consisting of aromatic polyimides, aromatic polyamides and polyoxadiazoles at a temperature sufficient to convert the film to a carbonaceous film, superposing a plurality of the carbonaceous films to hot pressing along a curved surface at a pressure of not higher than 20 kg/cm² in a temperature range of not higher than 2800°C and then at a pressure higher than 20 kg/cm² in a temperature range of higher than 2800°C for a time sufficient for graphitization.

Description: This invention relates to a process for producing curved graphite articles which have utility as radiation optical elements and the like. Graphite holds an important position as industrial materials because of its outstanding heat and chemical resistances, and high electric conductivity, and has been widely used as electrodes, heating elements and structural materials. Especially, single crystal graphite has good spectral and reflective characteristics and has been widely used as X-ray or neutron ray monochromators, filters or spectral crystal articles. Natural graphite may be used for such purposes. Natural graphite with high quality occurs in an extremely limited amount and is intractable because of its powder or block form. Therefore, efforts of producing artificial graphite having such characteristics as natural single crystal graphite have been made. The production of such artificial graphite can be broadly classified into the following two processes. In the first process, graphite is produced by separation from the melts of Fe, N/C system, decomposition of carbides of Si, Al and the like, or cooling of carbon melts under high temperature and high pressure. The graphite obtained by the process is called Kish graphite, and has the same properties as those of natural graphite. According to this process, however, only fine flakes of graphite are obtained. Therefore, together with the complexity of the manufacturing process and the expensive cost, this process has not been used in the industrial production. The second process is one in which graphite is produced by pyrogenic deposition in a gas phase and hot working of gaseous hydrocarbons wherein re-annealing is effected at a temperature of 3400°C for a long time under pressure. Graphite thus obtained is called highly oriented pyrographite (HOPG) and has almost the same properties as those of natural graphite. This process enables one to produce graphite of very large sizes, unlike Kish graphite. This process has, however, the disadvantage that the manufacturing process is complicated with a low yield and the cost is very high. In order to solve the problems involved in the above two processes and to produce graphite easily and inexpensively, graphitization of various organic matters or carbonaceous materials by heating at temperature not lower than 3000°C has been attempted. In this process, graphite having the same characteristics as those of natural graphite or Kish graphite cannot be obtained. Most of the polymeric materials cannot rather be used for this purpose. For example, the thermal treatment has been attempted to graphitize polymers such as phenolformaldehyde resins, polyparaphenylenes, polyparaphenylene oxides, polyvinyl chloride and the like. Since all of these polymers belong to a class of non-graphitizable materials, any product having a high degree of graphitization has not yet been obtained. For example, natural graphite and Kish graphite have an electric conductivity, which is the most typical property of graphite, of from 1 x 10 4 S/cm to 2.5 x 10 4 S/cm. In contrast, only the product having 1 x 10 3 S/cm to 2 x 10 3 S/cm can generally be obtained by this process. This indicates that graphitization does not well proceed in this process. We extensively made studies to solve the problems of the manufacturing process of graphite from such polymers as set out above wherein a number of polymers were used for graphitization. As a result, it was found that films of polymers such as an aromatic polyamide (PA), a polyoxadiazole (POD), an aromatic polyimide (PI), three polybenzobisthiazoles (PBBT), a polybenzooxazole (PBO), a polybenzobisoxazole (PBBO), a polythiazole and the like could be easily graphitized. Based on this finding, we proposed a graphitization process in European Patent Application No. 0 205 970. According to this process, graphite having a high degree of graphitization can be obtained easily within a short time by heating the polymers indicated above to temperatures not lower than 1800°C, preferably not lower than 2500°C. The degree of graphitization is often expressed by X-ray diffraction parameters such as a lattice constant and a crystallite size in the direction of c axis, or by a rate of graphitization calculated therefrom, along with electric conductivity. The lattice constant is calculated from the (002) refraction line of X-ray, and a value nearer to the lattice constant of natural single crystal graphite of 0,6708 nm (6.708 angstroms) indicates a more developed structure of graphite. The crystallite size in the direction of c axis is calculated from the half-width value of the (002) refraction line. A larger crystallite size indicates a more development of the plain structure of graphite. The crystallite size of natural single crystal graphite is 100 nm (1000 angstroms) or over. The degree or rate of graphitization is calculated from face spacing (d 022 ) (Les Carbons Vol. 1, p. 129, 1965). As a matter of course, the degree of graphitization of natural single crystal graphite is 100%. The electric conductivity is a value determined along the direction of ab plane of graphite wherein a larger electric conductivity shows a more resemblance to the graphite structure. Natural single crystal graphite has an electric conductivity of 1 x 10 4 to 2.5 x 10 4 S/cm. Another X-ray diffraction parameter used to evaluate the graphite structure is a rocking characteristic showing the manner of superposition of the ab planes. This is called a diffraction intensity curve which is obtained by rotating the crystal when monochromatic parallel X-ray fluxes are passed and measuring by fixing the value of 2 at the angle where the (002) diffraction line appears and rotating the angle, . This value is evaluated by the half-width value of the absorption and expressed by the angle of rotation (°). A smaller value shows more clearly superposed ab planes. The process of producing graphite from afore-described polymer films of the specific type is a very good process since it is simple and inexpensive. However, further studies revealed that this process had several drawbacks. The first problem is that thick graphite blocks cannot be produced according to the process. The graphitization reaction may be considered to be apparently irrespective of the thickness of the starting film. In fact, this reaction depends strongly on the thickness of starting film. This has not been known but we experimentally confirmed the above fact. For instance, Table 1 shows the results of a test where four films of a polyoxadiazole with different thicknesses were graphitized to determine the lattice constant, degree of graphitization and electric conductivity along the ab planes of the resultant graphite. Thickness of Starting POD Film (µm) Treating Temperature (°C) Lattice Constant Degree of Polymerization (%) Electric Conductivity (S/cm) (nm) [Å] 5 2600 0.6710 [6.710] 99 9800 25 2600 0.6713 [6.713] 97 7800 100 2600 0.6720 [6.720] 94 6100 450 2600 0.6731 [6.731] 87 4900 The above results demonstrate that the thickness of the POD film apparently influences how the graphitization reaction proceeds. For example, the degree of the graphitization varies from 99 to 87%, depending on the thickness of the film. This reveals that a thin film of graphite is obtained, but a thick graphite block is difficult to obtain. The second problem of the prior art process is that mere heating of polymer materials does not improve the rocking characteristic. The rocking characteristic is an important characteristic when graphite crystals are used as an X-ray optical element although the thickness and rocking characteristic of graphite crystal depend on the type of radiation optical element as will be described hereinafter. With the POD graphite indicated in Table 1, the rocking characteristic is 6.7° for the starting film thickness of 5 µm, 10.5° for the starting film thickness of 25 µm. 12° for the starting film thickness of 100 µm, and 17° for the thickness of 400 µm. Thus, the rocking characteristic is far from satisfactory. Thick radiation optical elements having a good rocking characteristic cannot be obtained by mere heating of polymer films for graphitization. It is considered that the cause for the poor rocking characteristic resides in a difficulty in orientation of the ab planes because a greater film thickness permit gases to generate in larger amount from the inside of the film undergoing the thermal treatment. EP-A-0203581 discloses a process for producing graphite, which comprises heat treating at least one polymer selected from the group consisting of a polyphenyleneoxadiazole, polybenzothiazoles, a polybenzobisthiazole, a polybenzoxazole, a polybenzobisoxazole and a polythiazole. A similar process is known from EP-A-0205970. In addition, from JP-A-63081300 graphite monochromators are known which comprise a lamination of a plurality of pyrolytic C films. It is an object of the invention to provide a process for producing curved graphite articles from polymer films which solves the problems of the prior art processes. It is another object of the invention to provide a process for producing curved graphite articles which are particularly suitable for use as radiation optical element and the like. It is a further object of the invention to provide a process for easily producing a radiation optical element made of a curved graphite crystal of the single or double bent type which has heretofore been very difficult to produce. Broadly, the above objects can be achieved according to the invention by a process for producing a curved graphite article, said process comprising: heat treating a 1 to 400 µm thick film of a polymer selected from the group consisting of aromatic polyimides, aromatic polyamides and polyoxadiazoles at a temperature, which is higher than the decomposition temperature of the polymer film and which is in the range of from 400 to 2000°C to convert the film to a carbonaceous film, superposing a plurality of the carbonaceous films and subjecting the plurality of the superposed carbonaceous films to hot pressing along a curved surface at a pressure of not higher than 1,962 MPa (20 kg/cm 2 ) in a temperature range of not higher than 2800°C for a time of several tens minutes to several hours and then at a pressure higher than 1,962 MPa (20 kg/cm 2 ), inclusive, in a temperature range of higher than 2800°C for a time sufficient for graphitization. Moreover, when a plurality of the carbonaceous films obtained by the above procedures are hot pressed against a curved surface at a temperature sufficient for graphitization at a pressure not lower than 0,3924 MPa (4 kg/cm 2 ), a curved graphite article is obtained for use as a radiation optical element. Moreover, when the starting polymer film or films are shaped in the form of a dome, thermally treated to form a carbonaceous shaped article and hot pressed in a dome-shaped mold, a double-bent graphite article can be obtained. For appropriate application as radiation optical elements, the graphite block should preferable have a certain thickness and a certain rocking characteristic depending on the type of optical element. When used as an X-ray monochromator, the graphite block should preferably have a thickness of not smaller than 0.1 mm and a rocking characteristic of not larger than 1°. For application as a neutron ray monochromator, the thickness should preferably be not smaller than 2 mm with a rocking characteristic of not larger than 1.5°. and for application as a neutron ray filter, the thickness should preferably be not smaller than 1 cm with a rocking characteristic of not larger than 4°. The graphite block having such a great thickness as indicated above with a good rocking characteristic can be obtained according to the process of the invention. Figs. 1a to 1c are, respectively, schematic sectional views of structures of carbonaceous films for comparison; Fig. 2 is a schematic perspective view of a radiation optical element made of a single-bent graphite article; and Fig. 3 is a schematic perspective view of a radiation optical element made of a double-bent graphite article. The broad aspect of the present invention is first described wherein a film of a certain polymer is thermally treated to provide a carbonaceous film, and a plurality of the carbonaceous films are superposed. The superposed films are hot pressed along a curved surface at a pressure not higher than 1,962 MPa (20 kg/cm 2 ) in a temperature range of not higher than 2800°C and then at a pressure higher than 1,962 MPa (20 kg/cm 2 ), inclusive, in a temperature range of higher than 2800°C for a time sufficient for graphitization. In the practice of the invention, starting films should be made of a polymer selected from aromatic polyimides. aromatic polyamides and polyoxadiazoles. Polyoxadiazoles useful in the present invention include, for example, poly(p-phenylene-1,3,4-oxadiazole) having recurring units of the following formula Polymers of other oxadiazole isomers are also usable including poly(m-phenylene-1,3,4-oxadiazole). poly(p-phenylene-1,2,4-oxadiazole), poly(m-phenylene-1,2,4-oxadiazole), poly(o-phenylene-1,3,4-oxadiazole), poly(o-phenylene-1,2,4-oxadiazole), and copolymers of these oxadiazole isomers. The aromatic polyimides are polymers which are obtained by reaction between dicarboxylic acid anhydrides and aromatic primary diamines and are represented by the following general formula Poly[N,N'-(p,p'-oxydiphenylene)pyromellitimide is typical of the aromatic polyamide of the above formula wherein R 1 is and R 2 is and is commercially available from Du Pont De Nemours under the designation of Kapton. In the above formula, R 1 may be and the like, and R 2 may be The aromatic polyamides used in the present invention are ones which have recurring units of the following formula wherein R 3 represents and R 4 represents The film of these polymers has a thickness of from 1 to 400 µm, preferably from 1 to 200 µm. If the film thickness is over 400 µm, gases are produced in the films during the course of carbonization and graphitization, and the resultant carbon precursor does not become homogeneous in the inner structure and is thus non-graphitizable carbon. If this precursor is subsequently hot pressed, graphite of good quality cannot be obtained. The lower limit of the film thickness is not critical, but if the thickness is less than 1 µm, a greater number of carbonaceous films have to be produced for the production of graphite blocks for the same thickness, thus being poor in economy. The thermal treatment of the polymer film or films is carried out at a temperature sufficient to provide a carbonaceous film. The temperature is in the range of from 400 to 2000°C. The thermal treatment is a preliminary step prior to the hot pressing. In the thermal treatment, the polymer films are treated separately. After the carbonaceous films have been produced through such a preliminary thermal treatment as described above, a plurality of the carbonaceous films are superposed and subjected to hot pressing which is a real heating and pressing procedure, so that graphitization of the carbonaceous films is caused to proceed thereby obtaining a graphite block. In the hot pressing step, the manner of application of the pressure and temperature control are important. More particularly, the hot pressing should be effected by pressing the films while removing wrinkles from the carbonaceous films which have been produced during the thermal treatment. For this purpose, the pressure of not higher than 1,962 MPa (20 kg/cm 2 ) is used in a temperature range of not higher than 2800°C. If a higher pressure is applied in the temperature range, the carbonaceous films are often apt to break. Preferably, gradual application of the pressure without abrupt application is effective in suppressing the breakage. At temperatures higher than 2800°C, a pressure higher than 1,962 MPa (20 kg/cm 2 ), inclusive, is necessary for attaining complete bonding of the films. At lower pressures, satisfactory press bonding is not obtained. The time of the hot pressing is not critical and is sufficient to allow satisfactory press bonding. The time is, for example, in the range of from several tens minutes to several hours. It will be noted that when polymer films are thermally treated and hot pressed, the thickness is reduced to about half the initial thickness. The thermal treatment and hot pressing are usually carried out in an inert gas atmosphere such as N 2 , Ar or the like. Through the above production process, there is obtained a thick curved graphite article which has a remarkably improved rocking characteristic. For example, when the POD films indicated in the Prior Art and having thicknesses of 4, 25, 100 and 450 µm, respectively, are each thermally treated at 1000°C to obtain carbonaceous films. Ten carbonaceous films of the respective thicknesses are superposed and hot pressed. The hot pressing is effected by applying a pressure of 0,3924 MPa (4 kg/cm 2 ) up to 2800°C and then a pressure of 1,962 MPa (20 kg/cm 2 ) over 2800°C, followed by keeping at 3000°C for a given time, thereby obtaining curved graphite articles. The curved graphite articles having a thickness of from 20 µm to 2.25 mm with a rocking characteristic of from 0.8 to 1.8° are obtained. This allows the curved graphite articles to be used as X-ray and neutron ray monochromators. As a matter of course, more thick articles may be likewise obtained. As will be seen from the above, the rocking characteristic is remarkably improved. It will be noted that when hot pressed, the thickness of the starting films is reduced to about 1/2. Examples of this embodiment are described. In the examples, the extent of graphitization was evaluated by measuring the lattice constant, rate of graphitization, electric conductivity and rocking characteristic according to the following procedures. (1) Lattice Constant (C o ) The X-ray diffraction line of sample is measured by the CuKα ray using a Philips Model PW-1051 X-ray diffractometer. The value of C o is calculated from the (002) diffraction line which appears in the neighbourhood of 2 equal to 26 to 27° by the use of the following Bragg's equation: nλ = 2dsin where 2d is equal to C o , n is equal to 2, and λ is the wavelength of X-ray. (2) Degree of Graphitization (%) Degree of graphitization is calculated from the value of face spacing (d) according to the following equation: d 002 = 3.354g + 3.44(1-g) where g represents the degree of graphitization, from the perfect graphite when g = 1 to the amorphous graphite where 9 = 0. (3) Electric Conductivity (S/cm) The sample is fitted with four-terminal electrodes by using silver paste and golden wires. The electric conductivity is determined by applying the electric current to the outer electrodes and measuring the voltage drop at the inner electrodes, and further determining the width, length and thickness of the sample through a microscope. (4) Rocking Characteristic (°) The rocking characteristic at the peak position of the (002) diffraction line of graphite is measured by the use of an Rotor Flex RU-200B X-ray diffraction apparatus, made by Rigaku Denki K.K. The rocking characteristic is determined as the half-value width of the obtained absorption. Reference is now made to Figs. 1a to 1c. Figs. 1a to 1c show the inner structure of a carbonaceous film 10 obtained after the heat treatment. Fig. 1a shows a thick polymer film which has been heat treated, in which molecules 11 are in disorder, as shown, with a gas 12 being left without removal. In order that good molecular orientation of the carbonaceous film is attained, it is important how to cause the thermal decomposition at the defined temperature. The polymer films 11 suffer a considerable degree of shrinkage along the film when heat treated. Heat treatment of a plurality of the films which are merely stacked will cause the films 11 to be deformed by the shrinkage as is particularly shown in Fig. 1b, showing the tendency toward the disorder of the inner structure. If the carbonaceous films 10 whose inner structure is in disorder are further graphitized at higher temperatures, the graphitization is attended with the internal strain. Graphite block with good characteristics cannot be expected. In order solve the above problem, the heat treatment of the polymer films should preferably be effected while pressing the films from opposite sides so that the films do not shrink along the film surface. The carbonaceous films obtained by the heat treatment is made, however, of hard carbon and suffer considerable shrinkage during the thermal decomposition. If the thermal treatment is effected under pressure, there is the possibility that the carbonaceous films 10 are broken as is shown in Fig. 1c. We found through a number of experiments on the pressure application that the thermal treatment under a pressure of from 0,0981 to 0,3924 MPa (1 to 4 kg/cm 2 ) produced good results on the molecular orientation in the carbonaceous film 10 with little cracks being produced. In addition, over 800°C, the pressure over 0,3924 MPa (4 kg/cm 2 ) may be applied without breakage of the films. Another approach for obtaining well oriented carbonaceous films 10 is a procedure wherein the heat treatment of the polymer films is carried out while inhibiting the films from expanding in the direction vertical to the film face, thereby preventing the disorder of the inner structure of the carbonaceous films 10. This is based on the fact that when thermally treated, the polymer films are significantly shrunk along the film face but suffer little shrinkage in the vertical direction. Accordingly, even though the shrinkage of the film in the direction parallel to the film face is allowed to take place but if the deformation or expansion of the film in the vertical direction is prevented, the disorder of the inner structure of the carbonaceous film 10 can be prevented. The process according to the invention wherein single or double-bent graphite articles for use as radiation optical elements are fabricated is described. In this process, starting polymer fims are those used as described before. It is preferred that starting films have a thickness of from 1 to 200 µm although thicker films having a thickness up to 400 µm may be used. Over 200 µm, it is rather difficult to attain a rocking characteristic of not higher than 0.5°. The starting polymer films are heat treated one by one. In this case, the heat treatment is carried out at a temperature higher than the thermal decomposition temperature of the aromatic polyamides, aromatic polyimides or polyoxadiazoles, i.e. at a temperature of from 400 to 2000°C. In this embodiment, it is necessary to make a bent-type graphite crystal article, so that the heat treatment temperature should be preferably not lower than 1000°C. This is because the carbonaceous film obtained by the heat treatment at temperatures lower than 1000°C is made of hard carbon and is not flexible with a difficulty in curving such a hard carbon film. Over 1000°C, the carbonaceous film becomes flexible is able to be easily curved as desired. In this case, a plurality of carbonaceous films have to be superposed for the hot pressing. As stated before, if a thick film is directly hot pressed, good characteristics cannot be obtained. The carbonaceous films are hot pressed after having been placed between a pair of press molds having a curved form, by which the films are converted into a curved graphite block. If the curved form is of a single bent type as shown in Fig. 2, the hot pressing can be relatively easily performed. If, however, the curved form is of the double bent type as shown in Fig. 3, the hot pressing may not necessarily be succeeded since the carbonaceous films are not so flexible. If double bent types of graphite crystal articles are obtained without a failure, starting polymer films should preferably be molded in a desired double bent shape such as the dome shape shown in Fig. 3. The double bent shape is readily obtained by casting a solution of polymer into a mold of such a shape. The double bent polymer films are likewise heat treated and hot pressed to obtain a graphite article of the desired shape. The graphite radiation optical element, whichever the single bent type or the double bent type, have ab planes of the graphite crystal clearly superposed and thus, have good characteristics including the rocking characteristic. It will be noted that since the bent-type graphite crystal is able not only to reflect, bus also to converge X-rays or neutron rays, more intense rays than those from flat crystals can be obtained. Example 1 A polyimide film having a thickness of 12.5 µm was sandwiched between quartz plates and heated up to 1000°C at a rate of 20°/minute in an atmosphere of nitrogen, followed by keeping at 1000°C for 1 hour. The thus heat treated films were sandwiched between graphite substrates, heated from room temperature at a rate of 10°C/minute and heat treated at 1600°C for 1 hour, followed by decreasing the temperature at a rate of 20°C/minute to obtain carbonaceous films. The heating furnace used was a carbon heating furnace. Fifty carbonaceous films thus obtained were hot pressed along a graphite press instrument having a single bent-type curved surface with a radius of curvature of 12.4 cm. The hot pressing apparatus used was a super-high temperature hot press. The hot pressing was effected at 3000°C at a pressure of 1,962 MPa (20 kg/cm 2 ) for 1 hour, thereby obtaining a 350 µm thick single bent-type graphite crystal as shown in Fig. 2. The rocking characteristic of the graphite crystal was 0.32°. The graphite crystal obtained in this manner was subjected to an X-ray spectroscope to determine characteristics against an X-ray. A CuKα ray was incident on the graphite crystal surface through a 1 mm opening of a Mo plate and an X-ray was measured on a photographic plate placed at the focal position. The image of th X-ray on the photographic plate had a length of 1 mm and a with of about 18 mm, thus the crystal having good converging properties. The intensity of the X-ray was as large as 2.8 times that of flat graphite crystal. Thus, the bent-type crystal was better in the intensity. Example 2 The aforementioned films having different thicknesses of 25, 50, 125, 200 and 400 µm were each heat treated in the same manner as in Example 1, thereby obtaining carbonaceous films of the respective thicknesses. 25, 13, 7, 4 and 2 carbonaceous films obtained from the respective thicknesses were, respectively, superposed and hot pressed in the same manner as in Example 1 to obtain single bent-type graphite crystals. These graphite crystals have, respectively, rocking characteristic values of 0.35, 0.41, 0.47, 0.61 and 0.95. The rocking characteristic of graphite crystal appropriately utilizable as a monochromator crystal for spectral analysis is 1° or below and better results are obtained when the rocking characteristic is 0.5° or below. Accordingly, the thickness of from 1 to 200 µm is preferred. Example 3 A polyimide material commercially supplied as a solution was applied onto a substrate by means of a doctor blade to form a 50 µm thick film, followed by heating to 160°C to evaporate part of the solvent. The polymer film having still sufficient flexibility was removed from the substrate and placed in a dome-shaped mold with an aperture of 50 mm by the use of a vacuum molding machine to obtain a dome-shaped molding. The thus obtained Polymer molding was heat treated in an electric furnace at 180°C for 2 hours and hardened, followed by heat treatment in the same manner as in Example 1 to obtain a dome-shaped carbonaceous film. The above procedure was repeated to obtain similar carbonaceous films. Twenty dome-shaped carbonaceous films were superposed and hot pressed by the use of a dome-shaped mold under the same conditions as in Example 1, thereby obtaining a double bent, dome-shaped graphite crystal articles as shown in Fig. 3. The rocking characteristic of the double bent, dome-shaped graphite article was 0.48°. The graphite article was subjected to measurement of characteristics against an X-ray. A CuKα ray was incident on the graphite crystal surface through a 1 mm opening of a Mo plate and a reflected X-ray was measured on a photographic plate placed at the focal position. The image of th X-ray on the photographic plate was a spot with an about 22 mm, thus the crystal having good converging properties. The intensity of the X-ray was about 15 times higher than that of a flat graphite crystal. Example 4 25 µm thick polyamide films and 25 µm thick polyoxadiazole films were each subjected to heat treatment and hot pressing in the same manner as in Example 1, thereby obtaining single bent-type graphite crystal articles. Forty carbonaceous films were used for the hot pressing. The rocking characteristic values of the graphite articles obtained from the polyamide and polyoxadiazole films were, respectively, 0.40° and 0.38°. Thus, these graphite articles were similar in the rocking characteristic to the graphite article obtained from the polyimide films as in Example 1. The converging properties against the CuKα ray were similar to those of the graphite article obtained in Example 1 and the intensity of the X-ray was as high as 2.5 times and 2.6 times that of a flat graphite crystal. As will be apparent from the above examples, substantially perfect single or double bent-type graphite articles as will be difficult to obtain by prior art processes can be produced. The radiation optical element made of the bent-type graphite article is better than known counterparts when used as an X-ray or neutron ray monochromator or filter. Especially with double bent-type graphite articles, preliminarily shaped polymer films are used and such articles can be readily obtained.

Claims: A process for producing a curved graphite article, said process comprising: heat-treating a 1 to 400 µm thick film of a polymer selected from the group consisting of aromatic polyimides, aromatic polyamides and polyoxadiazoles at a temperature, which is higher than the decomposition temperature of the polymer film and which is in the range of from 400 to 2000°C to convert the film to a carbonaceous film, superposing a plurality of the carbonaceous films and subjecting the plurality of the superposed carbonaceous films to hot pressing along a curved surface at a pressure of not higher than 1,962 MPa (20 kg/cm 2 ) in a temperature range of not higher than 2800°C for a time of several tens minutes to several hours and then at a pressure higher than 1,962 MPa (20 kg/cm 2 ), inclusive, in a temperature range of higher than 2800°C for a time sufficient for graphitization. A process according to claim 1, wherein the temperature of the heat treatment is not lower than 1000°C. A process according to claim 1, wherein the thickness of the films is in the range of 1 to 200 µm. A process according to claim 1, wherein the polymer film is in a dome-shaped form and heat treated and a plurality of the resulting dome-shaped carbonaceous films is hot pressed along a dome-shaped surface, thereby obtaining a double bent-type graphite article. A process according to claim 4, wherein the dome-shaped film is obtained by applying a solution of the polymer in a solvent on a substrate, evaporating part of the solvent and subjecting the resulting film to vacuum molding in a dome-shaped mold.

Inventors: MURAKAMI MATSUAKI, NAKAMURA KATSUYUKI, NISHIKI NAOMI, WATANABE KAZUHIRO, YOSHIMURA SUSUMU, MURAKAMI, MATSUAKI, NAKAMURA, KATSUYUKI, NISHIKI, NAOMI, WATANABE, KAZUHIRO, YOSHIMURA, SUSUMU
Applicants: MATSUSHITA ELECTRIC IND CO LTD, MATSUSHITA ELECTRIC INDUSTRIAL CO., LTD.
Application year: 1989
Main classification: C04B35
IPC codes: C04B35