TW201237889A - Method for manufacturing tape-shaped oxide superconductor wire and thermal processing device - Google Patents

Abstract

A thermal processing method is provided, which enhances the discharge efficiency of hydrogen fluoride gas to produce tape-shaped oxide superconductor wires with uniform and excellent superconducting properties in lengthwise direction. In the method, a cylindrical rotary body is rotatably disposed with respect to a furnace mandrel axis in an interior of a cylindrical thermal processing space of a furnace tube in a thermal processing device. In the rotary body, a tape-shaped wire with a superconductor precursor film formed is wound around a surface with many through holes formed thereon. A gas supply tube supplies an ambient gas to the tape-shaped wire wound around the rotary body. In the thermal processing space, a diaphragm is disposed in a residual space between two end parts of the rotary body and furnace flanges of the furnace tube such that gas reacted with a membrane surface, that is, waste gas, would not flow into the residual space.

Description

201237889 斗i4yipif VI. Description of the Invention: [Technical Field] The present invention relates to a strip-shaped oxide superconducting device, and in particular to a two-conductor == product (Metal-orgamc Deposition, M0D) A technique for forming a superconducting layer on an alignment metal substrate having an intermediate layer formed thereon.先前 [Prior Art] Conventionally, as a method for producing a YBaAOh (YBC0)-based ribbon-shaped oxide superconducting wire, it is known to form an intermediate layer by using an organic metal salt coating thermal decomposition (MOD: Metal-organic Deposition) method. A superconducting layer is formed on the alignment metal substrate (refer to Japanese Patent No. 44689-1, Japanese Patent Laid-Open No. 2009-48817, and Japanese Patent No. 4401992). In the MOD method, a strip-shaped substrate formed with an intermediate layer of an oxide is first immersed in a trifluoroacetate (TFA salt) containing each metal element constituting a superconductor at a predetermined molar ratio for silky meaning and acid observation (4) A mixed solution of a metal organic acid salt, that is, a superconducting raw material solution. The money is coated on the substrate by coating the substrate from the surface of the substrate with a superconducting material solution (dip coating method). Next, an oxide superconducting layer is formed by performing temporary sintering and formal sintering. The MOD method can form an oxide superconducting layer continuously on a long bond even in a non-clothing towel, so with pulsed laser deposition (pulse L followed by Deposition 'PLD) method or chemical vapor deposition ((3)(10)(6)丨v叩〇r Deposition Compared with gas phase methods such as CVD), the process is simple and can reduce the low cost of 201237889 4149lpif', which is of concern. A batch type heat treatment cleavage for heat-treating a substrate having a superconducting material solution adhered to its surface is disclosed in Japanese Patent Laid-Open No. Hei. No. Hei. No. Hei. No. 2009-48817. Compared with the roll-to-roll (red_t0_reen type heat treatment apparatus shown in Japanese Patent No. 4401992), the batch type heat treatment apparatus can easily control the furnace environment, and thus has an advantage that a stable superconducting layer can be formed. Compared with the roll-type heat treatment device, the batch type heat treatment device has the advantages of a small device and can complete the sintering in a short time. Incidentally, the roll-to-roll heat treatment device is in the tunnel-shaped furnace core tube. The wire output mechanism and the winding mechanism are provided at the end, and the wire is sintered by moving the wire into the furnace at a constant speed. The disclosure of Japanese Patent No. 4,446,901 and Japanese Patent Application Publication No. 2009-48817 is hereby incorporated by reference. A schematic configuration of a batch type heat treatment apparatus. As shown in Fig. ,, the heat treatment layer is wound around a substrate 2 on which a superconducting material is adhered on a drum-shaped rotating body 3. The soil material is wrapped in a cylindrical shape; The slewing body 3 is driven to rotate in the furnace tube 4 by a rotary drive mechanism, and the furnace core tube 4 is opened at the ends of the flange 4b _ in the tubular body portion 4a. Formed in. The U-holes not shown are formed ® rotating body 3. Level 2 is heated by the heater 5 provided in the surface direction of the substrate 2 at _ 3 _ wound on state. In addition,

The surface direction of St is sprayed to the substrate containing inert gas, oxygen and water (4) called the rolled body 6, and the ambient gas 6 and the superconducting material of the substrate 2 are 4 Μ after the reaction gas (exhaust gas), formed by rotating at 201237889 414yipif Ll 3 7 A heat treatment apparatus disclosed in Japanese Patent No. 44689-1, No. 2'-:8817, which is obtained by temporarily sintering a substrate coated with a mixed solution containing a chaotic acetate or the like. The superconducting precursor of (7) is formed on the intermediate layer, and then subjected to a method of forming a conventional YBCO film by sintering (TFA·Nafa), and the precursor atmosphere (reaction gas) is supplied with water vapor during the main sintering.

The YBCO generation reaction formula at this time is: l/2Y2Cu205+2BaF2+2Cu0+2H20->YBC0+4HF As described above, at the time of main sintering, since the precursor film is heat-treated using water vapor as an ambient gas, HF is generated. After the reaction, hydrogen fluoride (HF) gas was generated as a gas after the reaction. In the TFA-MOD method, the removal rate of fluorine in the decomposition of fluoride (BaF2) becomes the reaction rate limit of YBCO formation. Therefore, there is a problem that the superconducting property of the sintered YBCO film is lowered due to the influence of hydrogen fluoride (HF) gas (exhaust gas) generated after the reaction. In particular, in order to obtain a long strip-shaped wire having a characteristic of a critical current density (jc) of 2.0 or more and a critical current value (Ic) of 300 a or more, it is necessary to form a superconducting layer with a film thickness of 1.5 μm or more. When the film thickness is reached, the complete removal of hydrogen fluoride (HF) gas becomes more difficult. The above characteristics are not obtained. Therefore, in order to improve the superconducting property of the YBCO film, it is important to remove the fluorine contained in the precursor in the main sintering. 6 201237889 ^i4yipxf 佴走, in the heat treatment crack 1 shown in the figure "", in the furnace β = shape of the rotating body 3 and the flange (four) in the furnace tube 4: two, therefore, in the furnace tube 4 The gas is not discharged through the exhaust pipe 7 (the arrow in the figure is the remaining space R. Member b) 'and the stagnation is retained by the hydrogen fluoride generated by the precursor (formation - directional exhaust gas flow, and Helmet, _ b' can not gas you. If you can not completely remove the fluorine, then the problem of the superconductivity of the stored =., ..., the method is uniform [invention] The purpose of the present invention is to provide a strip oxide super (four) wire The manufacture of Yao and the heat treatment device, which improves the gas-like strip-shaped material-reducing super-feed wire after the reaction inside the furnace. The superconducting wire of W and Lai is the method of the present invention. The heat treatment device is provided with a furnace core tube, and the edge portion is formed by closing both ends of a cylindrical body portion having a heat treatment space, and a cylindrical rotating body is opposed to the inside of the heat treatment space. Core tube shaft Arranged in a rotating manner, and formed on a surface having a solid through-hole, a strip-shaped wire in which a film body of a superconducting precursor is formed: a gas supply pipe 'for supplying an ambient gas to the above-mentioned strip wire; and a gas discharge taste 'used to discharge ambient gas from the inside of the above-mentioned rotating body to the outside of the above-mentioned core tube, and to the film surface of the above-mentioned film body of the above-mentioned strip-shaped 201237889 wire wound on the above-mentioned rotating body, the gas separated from above The flange portion and the end portion of the rotating body are separated by a partition plate, and the ambient gas is supplied to a film surface of the film body wound around the rotating body: the strip wire. , ^, Ben, one of the schemes of the strip-shaped oxide superconducting wire, the 敎二^太二 has: a furnace core tube, which is formed by sealing the ends of the heat treatment space == with a flange portion; a cylindrical rotating body, In the above 3=;, with respect to the furnace core shaft of the furnace tube, it is rotatable, and is entangled in a surface formed with a plurality of through holes; a material for forming a right superconducting precursor; 3=The above strip wire on the rotating body In the above-mentioned "== body discharge position, the ambient gas is supplied to the film surface; and the gas after the gas is discharged from the inside of the rotating body; in the core tube, the following structure is adopted: the rotating shaft in the upper body of the distribution body The separator which is separated between the end portions of the direction Μ , , ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' ' 'In accordance with an embodiment of the present invention, an outline of a coffee deposit is described in detail with reference to the drawings. (10) A ribbon-shaped oxide superconducting wire having a superconducting layer guided by a method of using a superconducting layer (YBC0 Super 8 201237889 Conductance) Outline of the manufacturing method of the wire material. First, a GdaZi^O7 intermediate layer is formed as a template on a belt-shaped Ni alloy substrate (substrate) by a BAD method, and then a sputtering method is used thereon. Separating the Ce〇2 intermediate layer into a film, and then coating the Y-TFA salt (trifluoroacetate), Ba_TFA salt and the dip coating method on the obtained composite substrate by a coating process (refer to FIG. 5A) Cu ring acid To Y: Ba: Cu = l: 1.5: 3 proportion by dissolving a mixed solution (solution superconductive material) 8 obtained in an organic solvent. After the mixed solution 8 is applied, sintering is performed by a temporary sintering process (see Fig. 5B). The above-described coating process (see Fig. 5A) and the temporary sintering process (see Fig. 5B) are repeated a predetermined number of times, and a film body as a superconducting precursor is formed on the intermediate layer in the strip-shaped wire 2 turns. Thereafter, by a formal sintering process (see FIG. 5A, the crystallization heat treatment of the film body of the superconducting precursor in the strip wire 2G, that is, the heat treatment for generating the YBCO superconductor, is performed. Then, according to the manufacturing process (refer to the figure) 5D) An Ag stabilizing layer is formed on the generated YBC 〇 superconductor by a sputtering method, and then post-heat treatment is performed in accordance with a process (refer to FIG. 5E) to manufacture a YBC0 superconducting wire. The heat treatment apparatus according to the embodiment of the present invention is A crystallization heat treatment for a process (refer to Fig. 5C) which heat-treats the superconductor precursor formed in the strip-shaped wire to form a YBC 〇 superconductor. Further, the heat treatment apparatus can also be applied to the formation of the intermediate layer.

The Ni alloy substrate may be a substrate having biaxial alignment properties, or a substrate obtained by forming an intermediate layer having biaxial alignment properties on a metal substrate having no alignment. Moreover, one or more intermediate layers may be formed. 201237889 = The coating method 'In addition to the dip coating method described above, the method can be used, but basically, it is not limited to this example as long as it can be used in the composite membrane liquid. The number of times of the coating is 0 01 _~2·0, preferably 0.1 μm to 1·0 μΓη. The superconducting raw material solution used herein is a mixed solution obtained by dissolving a metal organic acid salt or an organometallic compound of a predetermined molar amount of ilY, Ba or Cu; an organic solvent. The molar number is a range of (10) Ba Mo Er di raw material solution using a < 2 when Y: Ba: a: 3. At this time, in order to obtain high values of Jc and Ic, it is preferred that the raw material 耝::, the Ba Mo Er ratio of six is in the range of losd. 8 'better than the Ba Mo Er ratio in the original liquid Within the scope. Thereby, the segregation of the Ba can be suppressed, and as a result, precipitation of Ba-based (e.g., Qifu) impurities in the grain boundary is suppressed. Therefore, it is possible to suppress the occurrence of cracks and the electrical bonding between the two crystal grains. By forming the ultra-electricity 2 by the mod method, it is possible to manufacture a uniform film thickness at a high speed and easily, and superconducting α, /' A tribute oxide superconductor. Further, as the metal organic acid salt, each of the above-mentioned salts of octanoate, orthosilicate, neodecanoate or trifluoroethyl is used, but as long as the above-mentioned salts of the above-mentioned species are uniformly dissolved in the gluten, The metal organic acid salt which can be applied to the composite substrate can be used. <Configuration of heat treatment device> The heat treatment device 100 shown in Figs. 2 and 3 is a mixed solution of a film coating of a superconducting precursor in a strip-shaped wire 20 (Fig. Sintering of the superconducting material solution 8) shown in Fig. 5A. The heat treatment apparatus 201237889 41491pif 100 includes a furnace tube 110 having a cylindrical heat treatment space 111, a cylindrical rotating body 120, a gas supply pipe 130, and a gas discharge pipe 140. And a partition plate (reflecting plate) 170. The furnace core tube 110 is formed in a hollow cylindrical shape. The furnace core tube 110 includes a cylindrical furnace core body portion (cylindrical body portion) 114, and the furnace core body portion 114 is closed, respectively. The furnace flange portion 116 and the furnace flange portion 118 having the openings at both ends. The furnace flange portion 116 and the furnace flange portion 118 constitute two end faces of the furnace core tube 110. The heat treatment space of the furnace core tube 110 111 is divided into a furnace core portion 114, a furnace flange portion 116, and a furnace flange portion 118. The heat treatment space 111 is composed of a furnace core portion 114, a furnace flange portion 116, and a furnace flange portion 118, so that It can maintain the decompression environment or vacuum in the furnace. The furnace tube 110 is around it. The heater 150 is placed and heated by the heater 150 as the inside of the heat treatment space 111. Inside the furnace tube 110, a rotating body 120 is disposed, and the rotating body 120 is centered on the furnace axis C which is the axis of the furnace tube 110. Further, in the furnace core tube 110, at least one of the furnace core flange portion 116 and the furnace core flange portion 118 is attached in a form detachably or freely opened and closed with respect to the furnace core portion 114. The rotating body 120 can be freely removed from the heat treatment space 111. In the furnace tube 110, the rotating body 120 is disposed at a position substantially separating the center of both the furnace flange portion 116 and the furnace flange portion 118, that is, A substantially central space of the heat treatment space 111 (referred to as a central space 111a). The rotating body 120 has a cylindrical body 121 having a belt of the 201237889-shaped wire 20 formed with a precursor on the surface 121a. Further, the strip-shaped wire 20' is as shown in the drawing. 5A, by applying a mixed solution (corresponding to the superconducting raw material solution 8 shown in Fig. 5a) and then performing temporary sintering, a YBCO superconducting product precursor is formed on the substrate. The strip wire 20 is exposed. package The film surface of the precursor of the mixed solution is spirally wound around the surface i21a of the cylindrical body 121 (the surface of the rotating body 120). As shown in Fig. 4, a plurality of through holes are formed in the cylindrical body 121 of the rotating body 120. 124. The inner diameter of the through hole 124 is preferably the same as the bandwidth of the strip wire 2〇. Further, the opening ratio thereof is 2G% to 95%, and particularly preferably 疋89% to 91% of the range is opened. The rotating body 12 is rotated at a constant speed during heat treatment by a rotating mechanism (not shown). The rotating body 12() is made of quartz glass, oxidized glass, or the like, and has a high temperature resistant and easily oxidizable material such as a Hasteldium alloy or an indond. The rotary body 120 is fixed to the gas discharge f just in the same manner as the furnace core shaft c which is the axis of the furnace core tube 11G, and is housed inside the cylindrical body 121 concentrically. Further, the gas discharge pipe 140 functions as a rotating shaft of the rotation |120. # - The space in the ^ other than the exported gas exhaust pipe i 4 G. In the tubular gas located in the internal space, the internal space connecting the rotating body 120 and the communication portion of the gas discharge pipe 12 201237889 41491pif are not shown. Further, as shown in Figs. 2 and 3, a plurality of gas supply pipes 13G are disposed in the central space ma in the processing space (1) of the furnace tube 11 from the surface (4) of the cylindrical body 121. The plurality of gas supply tubes i3 are arranged parallel to the furnace and are symmetric in the plane perpendicular to the furnace axis c. This morning in the furnace core tube 140, the four gas supply tubes 130 are symmetric with respect to the furnace axis C and The plurality of gas supply pipes 130__c are arranged in parallel with each other, and are arranged along a pitch. Each of the gas supply pipes 13G has a gas discharge hole 132 for discharging the ambient gas 6 to the rotating body (10). The gas ejection holes 132 in the tube 130 are at a certain interval in the longitudinal direction of the body portion of the m, and the same gas nozzle outlet holes m are _ holes, uniformly - the ambient gas 6. In order to uniformly discharge the ambient gas and further remove the fluorine gas, it is preferable that the flow rate of the supply of the soil gas is specifically in contact with the film surface of the film body wound around the rotating body. The flow rate is greater than or equal to 200 m/s and less than or equal to 500 m/s. When the flow rate is less than 200 m/s, it is not possible to uniformly supply the ambient gas to the superconducting precursor, and it is not possible to remove the exhaust gas (HF gas) remaining on the surface of the film surface of the film. Therefore, the superconducting characteristics of the desired/monthly are not obtained. On the other hand, when the flow rate exceeds 5 〇〇 m/s, the ambient gas can be uniformly discharged, but the crystallization reaction proceeds violently, so that it is difficult to control the epitaxial growth rate. Therefore, the desired superconducting characteristics cannot be obtained. 13 201237889 As shown in Fig. 2 and Fig. 3, the long-auger mm, ~ hole 132 is disposed so as to be ejected with respect to the cylindrical body 121 surface 5 S 13 = gas, and is supplied from the vertical direction to the circle === Ambient gas 6. <Surface 12ia In the furnace core tube 110, the gas supply pipe and the rotation = Table * 121, _ reach 1Qm just mm. When the right separation distance is in the above range, the peach gas can be uniformly sprayed to the superconducting precursor, so that the film having the smaller distance than the upper layer, the material (four) ring body and only the strip wire 20 on the 120 can be removed. A part of the film surface of the body is not able to obtain uniform superconducting properties in the longitudinal direction of the superconducting wire. Further, if the separation distance exceeds the upper rank, the amount of brain is increased, the production cost is increased, and the crystallization reaction proceeds rapidly, so that it is difficult to control the growth rate of the succeeding crystal. Therefore, the desired superconducting characteristics cannot be obtained. Therefore, in order to obtain a long strip-shaped wire superconducting layer having a film thickness of 15 μm or more, it is necessary to provide a film with a separation distance of the above range and an appropriate gas flow rate to the superconducting precursor (4). A superconducting wire having a characteristic of a thick critical current density (JC) of 2 大于 or more and a critical current value (Ic) of 300 A or more. The gas supply pipe 13 is supplied with the ambient gas 6 vertically from a position spaced apart from above on the film surface of the precursor wound in the strip-shaped wire 2 of the surface 121a of the cylindrical body 121. The diameter of the gas ejection hole 132 must be designed in such a manner that the gas pressure and the gas flow rate become uniform. '201237889 41491pif The ambient gas 6 is supplied via a connection pipe connected to the gas supply pipe ,, and is disposed outside the furnace tube 丨1〇. Incidentally, in the gas supply; ^; = 3 inert gas, oxygen or water vapor, etc. ^ = the official 130 sprays the ambient gas 6. The above-mentioned ambient gas-pore body 仏 仏 体 体 , , , , , , 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境 环境Fluorine (7) or the like, in the furnace, the length of the axial direction of the gas supply tube 13's E', and the body 12G is substantially the same, but the second t is longer than the length of the rotating body 12G. In other words, when the length between the gas 0titj holes 132 at both ends of the '# bit body supply pipe i3〇 is longer than the length of the rotating body (10), the banded wire 2缠绕 which is wound around the cylindrical rotating body 12〇 can be made. All are more efficient in performing a uniform reaction. The gas supply pipe is made of a material that is resistant to high temperatures and is not easily oxidized, such as quartz glass, oxidized material, or Hastelloy or a nickel-iron alloy. The gas discharge pipe 140 is inserted into the center of the furnace flange portion 116 and the furnace flange portion 118 at both ends extending outward from the lid body 122 and the lid body 123. The milk body discharge pipe 140 is rotatably supported by the furnace flange portion ι18 at both end portions 141 and 142 at the end portions 142. Further, both ends of the gas discharge s 140 are disposed outside the furnace tube ιι. Thereby, a state in which the inside of the rotating body 120 # communicates with the outside of the furnace anger tube 11 经由 via the gas discharge f 14 形成 is formed. The gas discharge pipe 140 is connected to the internal space of the cylindrical body 121, and 15 201237889 41491pjf

It is formed as a part of the rotation axis of the circular body 121. Here, the gas discharge pipe 140 is inserted into the inside of the cylindrical body 121, and the rotation of the cylindrical body 121 (corresponding to the furnace axis C) serves as a rotation of the shaft portion of the cylindrical body 121, that is, the rotation body 120. Formed by the shaft. In the gas discharge pipe 14A, a plurality of through holes (not shown) are formed on the outer periphery of the central portion disposed inside the cylindrical body 121. The inside of the cylindrical body 121, that is, the inside of the rotating body 12A and the inside of the gas discharge pipe 140 are in communication with each other via these through holes. Here, the gas discharge pipe 140 has a configuration in which the opening on the one end portion 141 side and the central portion disposed inside the cylindrical body 121 are closed, and only the opening of the other end portion side 142 and the inside of the cylindrical body 1·21 are closed. The connection is performed to discharge the HF gas from the opening on the other end portion 142 side. Further, the gas discharge pipe ι4 〇 may have a configuration in which the one end portion 141 is also connected to a portion inside the cylindrical body 121, whereby the HF gas is discharged from the openings at the both end portions 141 and the end portion 142 side. Further, the gas discharge pipe 140 may be designed in a separate form from the rotating shaft. Here, the gas discharge pipe 140 is inserted into the lid body 123 from the other end portion 142 side, and the gas after the reaction (herein referred to as HF gas) is discharged through a portion which is led out to the outside of the furnace tube 丨1〇. Thus, the gas discharge pipe 140 discharges the gas inside the cylindrical body 12 (the ambient gas 6 and the reacted gas) to the outside of the furnace core tube 110. Here, the gas discharge pipe 14 is formed on the cylindrical body ι21. Further, the gas discharge pipe 140 is made of a material such as quartz glass, alumina or the like, a material such as a Hastelloy-based alloy or a chrome-nickel alloy, which is resistant to high temperatures and is not easily oxidized. As described above, in the heat treatment space 1丨1 of the furnace tube 11〇, the gas supply pipe 13〇 and the spiral body are disposed outside the gas discharge pipe _HF gas core in the middle of the 201237889. The partition plate 170 is placed in the heat treatment L2 of the furnace core tube to separate the central space 111a. The two 111 partitions 170 are located perpendicular to the furnace core c, the core flange portion 116, the furnace flange, and the furnace.

The interval between the lid body 122 and the lid body 123). Here, m = is disposed in the space between the rotating body 120 and the furnace tube 11 凸 J: J = core 々 flange portion 118, so-called remaining space (1) remaining space R) l specifically, the partition No is separated by a smart body 12. The central space is called and the remaining space (10). In the morning, in the space between the core flange portion 116 and the shaft-end portion (the cover body 122) of the rotating body 12 (remaining * block partition 170. In addition, in the furnace " work 1 b) There are a plurality of partitions 17 that are disposed between the core flange portion 118 and the shaft of the rotating body 120 (the lid body 123). Both ends of the rotating body 120 in the axial direction (the position of the cover body If) are placed close to the end portions of the rotating body 120 (the positions of the lid body 122 and the outer surface of the lid body 123). . The position of the isn f ' spacer 1701 is closer to the side of the rotating body 12 than the heater portion longer than the rotating body 120, and is adjacent to and opposite to the end portions of the gas supply and the sigma. In the heat treatment space 111, the partition plate 170 reflects the reacted gas generated in the central space 111a in which the gas supply 17 201237889 ipif is supplied to the tube 130 and the rotating body 120, that is, the HF gas 6c' prevents the HF gas 6c from flowing into the remaining space mb. . That is, the partition Π0 prevents the HF gas generated in the central space iiia from flowing into the end portion of the rotating body 120 (the position of the lid body 122 and the outer surface of the lid body 123) to the furnace core flange portion 116 in the furnace tube 110, and the furnace. The space between the core flange portions 118. Further, the spacer 170 prevents the gas before the reaction, that is, the ambient gas 6 from flowing into the remaining space 111b, so that the ambient gas 6 can react more efficiently with the superconducting layer in the remaining space 111a. Further, it is preferable that a plurality of partition plates 170 are disposed in the remaining space mb. By arranging the plurality of partition plates 170, it is possible to further prevent the HF gas 6c from flowing into the remaining space mb, so that desired superconducting characteristics can be obtained. On these partition plates 170, a rotating shaft of the rotating body 12, that is, a gas discharge pipe 140 is inserted. Chasing the appropriate partition 170 is fixed to the gas discharge f (10). In other words, 'the plate mt is inserted into the rotating car with the shaft portion of the rotating body (10) (the (four) axis of the cylindrical body 121) and the shaft portion is fixed in the partition plate 170 and the rotating body 120 (the cylindrical body 121) The ends of the directions are aligned non-contactly and adjacently. Specifically, in the present embodiment, the partition plates 170 are respectively fixed to the respective core flanges 140 of the furnace tube boss 116, the furnace flange portion 118, and the rotating body m. 140 ^^^1Ub plate 170 When the rotating body 12G is removed from the rotating core 120 in the same manner as the rotating body 120, the gas discharge pipe 140 can be taken out from the furnace core tube 110 and rotated 201237889

Ceramics such as glass or alumina, Hastelloy-based alloys, and image material 20. In addition, the separator [0, etc., is composed of a material such as quartz glass or inconel, which is made of a material which is resistant to oxidation by the south temperature material. Although the separator 170 is fixed to the gas, it is formed, but The present invention is not limited to the configuration in which the partition plate 17G is fixed in the remaining space 111b in the furnace ride 11G. Further, 'the interval between the core flange portion m and the end portion (the cover 122) in the rotation axis direction of the rotary body 120, and the direction of the rotation axis in the furnace flange portion 118 and the rotary body 120 as long as the partition plate 17 is closed At least one of the intervals of the end portions (lids 123) may be provided in any manner as described above, and the heat treatment apparatus 100 is provided with a furnace core tube 110 which is a furnace core flange portion 116 and a furnace core flange portion 118 is formed by closing both ends of the furnace body portion 114 having the heat treatment space 111. Further, a cylindrical rotating body 120 is disposed inside the heat treatment space ill, and the rotating body is rotatably disposed with respect to the furnace core of the furnace tube 110, and is wound around a surface on which a square hole is formed to form a superconductance. A ribbon wire of a film body of a precursor. Further, the heat treatment apparatus 100 further includes a gas supply pipe 140 disposed in the heat treatment space U1 at a position spaced above the film surface of the film body of the strip-shaped wire wound around the rotating body 120. It supplies ambient gas to the membrane surface. Further, the heat treatment apparatus 100 further includes a gas discharge pipe 140'. The gas discharge pipe 140 discharges the reacted gas from the inside of the rotary body 120. A partition plate is disposed in the furnace tube 110. 201237889 p*f The distance between the furnace core flange portion H6 and the furnace flange portion 118 in the direction of the rotation axis of the human rotating body 12G is separated. In the upper processing weave (10), the circular-shaped rotating body i2G with the secret material Μ is rotated at a constant speed. Further, in the heat treatment (four) of the heating ring (4) by the heater 150, the ambient gas supplied from the secret supply device (not shown) is uniformly blown toward the strip through the plurality of gas ejection holes 132 of the gas supply pipe 13 The film surface of the wire 2 〇. The blown ambient gas 6 reacts with the membrane surface to generate HF gas, and enters the inside of the cylindrical body 121 through the plurality of through holes 124 of the cylindrical body 121 in the rotating body 12A. At this time, since a plurality of partition plates 170 are disposed in the furnace core tube 11 , the exhaust gas (specifically, HF gas) does not pass from the end portion of the rotating body 120 (the cylindrical body 121 ) (the cover body 122 and the lid body) 123) Flows to the core flange portion 116 of the furnace core tube uo and the furnace flange portion 118 side. Thereby, the exhaust gas does not stay in the remaining space 111b, but enters the cylindrical body 121 as indicated by an arrow 6c in Fig. 2 . Thereafter, the exhaust gas inside the cylindrical body 21 is discharged to the outside of the furnace via the gas discharge pipe 140 connected to the other end portion of the cylindrical body 121. In the manufacturing method using the heat treatment apparatus 1 described above, the end portion of the furnace flange portion 116, the furnace flange portion 118, and the rotating shaft 120 in the direction of the rotating shaft (core axis C) is partitioned by the partition plate 170. Interval. The film is supplied to the film surface of the superconducting precursor wound on the rotating body 120 while being spaced apart from the space, and the ambient gas is supplied from a position spaced apart from above. Further, the film body of the superconducting precursor is an intermediate layer formed on the substrate, and a mixed solution obtained by dissolving a metal organic acid salt or an organic metal compound containing a metal element in an organic solvent is applied to the intermediate layer, and then temporarily Film formed by sintering 201237889 41491pif. Further, the metal organic acid salt containing a metal element in the mixed solution contains one or more selected from the group consisting of an octanoate, a naphthenate, a neodecanoate or a trifluoroacetate. The produced oxide superconducting wire comprises: an intermediate layer formed on the substrate, a REBayCu3〇z-based superconducting layer formed on the intermediate layer, and a stabilizing layer formed on the superconducting layer, wherein RE comprises a selected from Y, Nd, Sm More than one element of Eu, Gd, and Ho. As described above, in the furnace core tube 110, when the membrane surface of the film body of the strip-shaped wire 20 wound around the rotary body 12 is supplied with the ambient gas 6 from a position spaced apart from above, it is separated by the partition no. In the central space 111a, the ambient gas 6 is supplied from a gas discharge hole 132 (see FIGS. 2 to 4) disposed in the gas supply pipe 13A extending over the entire length of the rotating body 120. Thereby, the atmosphere gas 6 can be favorably supplied to the entire strip-shaped wire 20 wound around the surface 121a of the cylindrical body 121 in the rotating body 120. Thereby, the discharge efficiency of the discharged gas, i.e., HF gas, is improved, and a strip-shaped oxide superconducting wire having uniform and excellent superconducting properties in the longitudinal direction can be produced. In the heat treatment apparatus 100, the gas supply pipe 130 is formed by a length of 2 m and an inner diameter of 20 m, and is further applied to the gas supply pipe 130 at a pitch of 30 mm in the longitudinal direction of the gas supply 130, 1. 〇mmcj) Each inner diameter (nozzle inner diameter) forms a gas discharge hole 132. At this time, the furnace pressure of the furnace tube 11〇, that is, the pressure in the heat treatment space 111 is raised from 50 torr to 2〇〇t〇rr, and the gas flow rate is raised from 250 L/min to 1〇〇〇L/min (normal temperature). , the conversion value under normal pressure). Further, the flow rate of the ambient gas which is ejected from the gas ejection hole 132 in the heat treatment apparatus 100 to supply the surface 121a of the rotary body 120 reaches 21 201237889, and the gas discharge hole 132 is disposed in the heat treatment apparatus 100. The surface 121& is separated by 80 faces. The above-mentioned film body of the strip-shaped wire 2 turns on the rotating body 120 is as follows: the film body to be used: on the belt-shaped Ni alloy substrate (substrate), using ibad /Gd2Zi*2〇7 The intermediate layer is formed as a template, and then the sputtering method is used thereon.

The Ce〇2 intermediate layer was formed into a film, and then Y_TF was coated by dip coating on the obtained composite substrate by a coating process.

Ba-ΤΡΛ ^ Y : Ba : cu^ " 5 examples of a mixed solution (superconducting raw material solution) obtained by dissolving in an organic solvent, followed by sintering by a temporary sintering process. The film body was heat-treated at a furnace temperature of 75 (rc) by a formal sintering process to obtain a 1.5 Mm superconducting layer. Further, three separators were provided on both ends of the rotating body 12〇. As an example, a configuration in which no separator is provided is used as Comparative Example 1. The characteristics of the superconducting wire rod produced by using the heat treatment apparatus of the above-described Example 1 are as follows: a hole of 2.2 and a k of 330 A, which was produced by Comparative Example 1. The characteristics of the superconducting wire rod were as follows: 1 and 5, 1 () was 225 A. The superconducting wire made of Example 1 was superior in superconducting wire characteristics as compared with the superconducting wire rod produced in Comparative Example 1. As described above, the method for producing a strip-shaped oxide superconducting wire using the heat treatment apparatus of the embodiment improves the discharge efficiency of HF gas (hydrogen fluoride gas) as compared with the method for producing a strip-shaped oxide superconducting wire using the heat treatment apparatus of the comparative example. It is possible to manufacture a strip-shaped oxide superconducting wire having uniform and excellent superconducting properties in the longitudinal direction. 22 201237889 41491pif Also, since batch sintering is performed, Compared with the case of sintering in the roll mode, it is easy to control the furnace environment, so that a stable superconducting layer can be formed, and the oxide superconducting wire can be manufactured in a short time. Further, the furnace tube 110 is made of a cylindrical furnace body. The portion 114 and the furnace flange portion 116 and the furnace flange portion 118 that respectively open the both ends of the furnace core portion 114 constitute at least one of the furnace core flange portion 116 and the furnace core flange portion U8. The core body portion 114 can be freely opened and closed or detached, but is not limited thereto. By simply detaching the inner rotating body 120, the winding and removing operation of the strip-shaped wire 2 can be performed in an easy manner. In the hollow cylindrical furnace tube 11〇, the furnace main body portion 114 may be divided into a semicircular shape. Further, the present invention can be variously modified without departing from the spirit of the invention. The invention of course includes the invention after the change. The disclosures of the descriptions, illustrations, and abstracts included in the application of the Japanese Patent Application No. 2011-022116, filed on February 3, 2011, are incorporated herein by reference. In summary, the method and the heat treatment device for the strip-shaped oxide superconducting wire rod according to the present invention improve the gas discharge efficiency after the reaction, and can be generally applied to form a uniform and excellent superconducting property in the longitudinal direction. The case of the strip oxide superconducting wire. [Simplified illustration of the drawing] Fig. 1 is a schematic cross-sectional view showing the main part of the conventional batch type heat treatment apparatus. 23 201237889 4i4yipif Fig. 2 Superconductance ^ (4) The present invention - Wei Fangyu's schematic diagram of the main part of the heat treatment device for the electrification of the strip oxide is shown in Fig. 2, which is the main part of the hot section of the county. A schematic view of a rotating body. Fig. 5A to Fig. 5B are schematic diagrams showing a method of manufacturing a YBCO superconducting wire material by the MOD method. [Description of main component symbols] 1. 1〇〇: Heat treatment device 2: Base material 3, 120: Rotating body 4' 110: Furnace tube 4a: Main body portion 4b: Flange portion 5, 150: Heater 6, 6a, 6c: ambient gas 7: exhaust pipe 8: mixed solution 20: strip wire 111: heat treatment space 111a: central space 111b: remaining space 114. core body portion (cylindrical body portion) 116, 118: furnace core flange Portion (flange portion) 24 201237889 41491pif 121 : cylindrical body 121a : surface 122 , 123 : cover body (end portion of the rotating body) 124 : through hole 130 : gas supply pipe 132 : gas ejection hole 140 : gas discharge pipe 141, 142: Ends 170, 170-1: Partition C: Furnace shaft R: Remaining space i 25

Claims (1)

201237889 414yipif VII. Patent application scope: A manufacturing method of a financial material super-material, in which a flange-shaped portion of a cylindrical body portion having a heat treatment space is used, and the inside of the heat treatment space is relatively The furnace core shaft is rotatably disposed, and a strip-shaped green material formed with a film body of the superconducting precursor is formed on the surface formed with =, 1, and the gas supply officer is configured to supply the ambient gas to the strip wire; And a gas discharge official for discharging the ambient gas from the inside of the rotating body to the outside of the furnace tube; wherein the manufacturing method is to use the heat treatment device to the above-mentioned strip-shaped wire wound around the red rotating body The membrane surface is supplied with the ambient gas at a position spaced apart from above, wherein 'the partition is separated from the end portion of the rotating body in the direction of the rotation axis by a partition plate' while being wound around the rotating body The ambient gas is supplied to the film surface of the film body of the strip wire. 2. The method for producing a strip-shaped oxide superconducting wire according to claim 1, wherein a plurality of the separators are disposed. 3. The method for producing a strip-shaped oxide superconducting wire according to the first or second aspect of the invention, wherein the film body of the superconducting precursor comprises an intermediate layer on a substrate and is coated on the intermediate layer. The cloth will contain a film body formed by temporary sintering after the mixed solution of the metal organic acid salt or the organometallic compound of the metal element of 26 201237889 41491pif dissolved in an organic solvent. 4. The method for producing a strip-shaped oxide superconducting wire according to claim 3, wherein the metal organic acid salt containing a metal element in the mixed solution is selected from the group consisting of octoate, naphthenic acid, and new More than one of a phosphonium salt or a trifluoroacetate salt. 5. The method for producing a strip-shaped oxide superconducting wire according to claim 1, wherein the oxide superconducting wire has an intermediate layer formed on the substrate; ... the REBayCuH formed on the intermediate layer, a superconducting layer; a stabilizing layer formed on the superconducting layer; wherein the RE comprises an element selected from the group consisting of Y, Nd, and Sm. One of the Eu, Gd, and Ho ===Oxide super (four) wire heat station at both ends = shape: the flange portion will have a cylindrical body portion of the heat treatment space ^ cylindrical rotating body, on the top, the core The furnace core shaft of the tube can be rotated: within 1:, the surface of the plurality of through holes is wound and shaped, and the wire material is formed; ^ The strip gas supply tube of the membrane body of the ultra-electric 'shovel body, u and the wire The upper strip-shaped membrane surface of the upper Wei upper surface is supplied with ambient gas; n; the upper separated position, the gas after the reaction is discharged from the inside of the above-mentioned rotating body to the above 27 201237889 41491pif ^«tube; In the direction of the rotation axis of the body, two = t are the convex strip-shaped oxide superconducting electrodes. Here, a plurality of the above-mentioned separators are arranged. 8. In the sixth or seventh hot-spinning section of the patent range, the (four)' of the above-mentioned turn f is inserted into the above-mentioned partition plate while being _ at the above-mentioned shaft portion. The end of the rotating shaft is non-contact: the rotation in the rotating body