SUPERCONDUCTIVE CERAMICS LAMINATES AND METHOD FOR PRODUCTION THEREOF

Abstract: A method for making superconductive ceramics laminates comprises forming a thick film (2) of a composite oxide comprising bismuth, strontium, calcium, copper and oxygen on a flat plane of a substrate (1), and orienting and crystallizing the thus formed film by heat treatment to cause the c-axis of composite oxide crystals to be substantially perpendicular to said flat plane of said substrate. An intermediate layer formed of a noble metal, MgO, SrTiO₃, yttria-stabilized zirconia or an oxide of a superconductive ceramics-­ constituting element may be interposed between the film and the substrate.

Description: A METHOD OF MAKING SUPERCONDUCTIVE CERAMICS LAMINATES This invention relates to a method of making a superconductive ceramics laminate comprising bismuth (Bi), strontium (Sr,) calcium (Ca), copper (Cu) and oxygen and, more particularly, a superconductive ceramics laminate based on Bi-Sr-Ca-Cu-O which is formed with a film of composite oxide crystals oriented in a specific direction. The invention also relates to a superconductive ceramics laminate made according to the method above. Superconductors are materials showing the property (superconduction) of reducing their electrical resistance to zero under such conditions as defined by values equal to or lower than critical values represented by the critical temperature Tc, critical magnetic field Hc and critical current density Jc. Known as oxide ceramics showing superconductivity at about 90K is a composite oxide based on Y-Ba-Cu-O. Recently, another superconductive ceramic based on Bi-Sr-Ca-Cu-O has been discovered as a composite oxide having a Tc of 80 to 110K. Such Bi-Sr-Ca-Cu-O systems are more stable and resistant to external environments such as moisture than the Y-Ba-Cu-O systems. Ordinarily, such composite oxide ceramics is obtained by sintering a compact of starting ceramics powders, under pressure or at an atmosphere. Nb-Ti or Nb₃Sn alloys have been known as the superconductive materials practically used in the form of wires, tapes and coils. However, these materials have to be cooled to the temperature of liquid helium at considerable expense. Various proposals have thus been made to put to practical use wires and tapes using high-temperature superconductors comprising composite oxides having high critical temperatures. In order to put superconductors to practical use, it is necessary that they can be formed into wires and tapes and that they have a large critical current density, Jc. Although not clarified, the crystal structure of the superconductive ceramics based on Bi-Sr-Ca-Cu-O, as proposed, is characterized in that, of the crystal axes, the c-axis is much longer in length, say, five times or more as long as the a- or b-axis, and the atoms are arranged and stratified on the ab-plane. In a superconductive state, therefore, it is theoretically considered that electrons migrate along the ab-plane (perpendicular to the c-axis), but hardly move along the c-axis. In wires and coils using conventional high-temperature superconductive ceramics, little attention is paid to such a crystal structure. Nor is any practically high current density obtained without providing means for passing large currents through wires and tapes in their longitudinal direction. Vapor-phase techniques such as vapor deposition, sputtering and CVD have been proposed as the processes for orienting crystals as mentioned above to pass large currents through wires and tapes in their lengthwise direction. However, problems with these techniques are that films are produced through complicated steps at low rates and very high costs, thus making it difficult to process them into continuous forms such as wires and tapes. An object of the present invention is to provide a method of making superconductive ceramics laminates of satisfactory crystal orientation in a simple and inexpensive manner. According to a first aspect of the present invention, there is provided a method of making superconductive ceramics laminates, comprising screen printing a thick film (2) of a composite oxide comprising bismuth, strontium, calcium, copper and oxygen having a thickness of the order of tens of µm to hundreds of µm, on a plane of a nickel alloy substrate (1) over a silver intermediate layer (3) a and heat-treating the thus formed film, wherein : said substrate is in the form of a tape; said composite oxide is oriented and crystallized by said heat treatment to cause its c-axis to be substantially perpendicular to a flat plane of said intermediate layer, and said intermediate layer serves to promote said orientation and has no adverse influence upon the superconductivity of the ceramics during said heat treatment, said heat treatment being carried out by heating said film to a temperature of 860° to 950°C in an oxygenous or non-oxygenous atmosphere to melt a part or the whole thereof, and then cooling the film at the cooling rate of between 500°C and 20°C per hour. Preferably, the heat treatment is carried out at a temperature of 870°C to 910°C. According to a second aspect of the invention, there is provided a superconductive ceramics laminate made by a method according to the first aspect of the invention. The invention will now be more particularly described, by way of example, with reference to the accompanying drawings, in which:- FIGS 1A and 1B are schematic perspective views showing two embodiments of a laminate made by a method according to this invention; FIG. 2 is a graph indicating the relationship between temperature and electrical resistivity of the composite oxide ceramics obtained in the Example; and FIG. 3 is a graph showing an X-ray analysis of the composite oxide ceramics obtained in the Example. Referring to Figures 1A and 1B, the laminate shown therein comprises a metal substrate 1 and a composite oxide ceramic film 2 provided on the plane of the substrate over an intermediate layer 3, in which the crystals have their c-axes substantially perpendicular to the flat plane of the intermediate layer. It is to be noted that this invention encompasses embodiments in which the a- and b- axes are or are not in agreement (as shown in Figure 1A or Figure 1B.) The substrate 1 is of a nickel alloy and is in the continuous form of a tape. The intermediate layer 3 is of silver and is formed on the substrate 1 by a vapour-phase process, such as plating, melt plating or vapour deposition. The silver intermediate layer 3 serves to promote the orientation of the ceramics and has no adverse influence upon the superconductivity of ceramics during heat treatment. The composite oxide film 2 is formed on the flat plane of the intermediate layer 3 by screen printing. The thickness of the composite oxide film can vary from tens of µm to hundreds of µm depending on the purpose. It is desirable that the types of starting compounds for ceramics be selected according to the intended purpose, while taking into consideration the film-forming methods applied. General methods for obtaining the starting powders for ceramics include, e.g. the dry-type methods wherein the powders of ceramics-constituting compounds are dried together and calcined and the wet-type methods wherein a mixed solution containing the constituents of the end ceramics is prepared, and a precipitant such as oxalic acid or potassium carbonate is added thereto in a single-or multi-stage manner to obtain co-precipitates, after which drying and calcination are carried out. The composite oxide is prepared as a paste by kneading the composite oxide powders obtained in a conventional manner with a binder such as an acrylic resin and adding to the kneaded product a solvent, a plasticizer or the like to regulate the viscosity of the paste. The paste is then coated on the flat plane of the intermediate layer 3. In order to regulate the sinterability and superconductivity of the superconductive ceramics in this invention, trace amounts of certain components can be added thereto. Examples of elements for such components are Pb, Ti, Sn, Mn, Al, Cs, Ce, V, Bi, Ir, Rh and Ga. Such components may be added in the form of their compounds such as hydroxides, oxychlorides, carbonates, bicarbonates, oxynitrates, sulfates, sulfites, nitrates, acetates, formates, oxalates, chlorides and fluorides. Such trace amounts of components can be contained in the starting or calcined composite oxide powders. Heat-Treatment of Films The composite oxide film formed on the flat plane of the intermediate layer is then heat-treated. According to this invention, the heat-treatment causes the c-axis of the composite oxide crystals to be oriented substantially perpendicular to the flat plane of the intermediate layer. Referring to the conditions for heat-treating the film, a suitable choice is made from the pre-treatments, heating rates, heating temperatures, heating atmospheres, heating periods of time, cooling rates and the like to achieve the c-axis orientation as mentioned above. The composite oxide film formed as a paste is dried at about 100°C and is then desirably pre-treated by annealing at about 400°C for 1 hour to evaporate off the binder such as a resin. The heating (firing) temperature is, e.g., 860 to 950°C, preferably 870 to 910°C, although it can be varied depending upon the compositions of composite oxides, etc. This is because at below 860°C, neither melting of the composite oxide film nor c-axial orientation of crystals takes place, and no melting of a part of ceramics grains in the film occurs so that the densification of the film does not proceed. At a temperature higher than 950°C, it is likely that the composite oxide may decompose thermally or a part thereof may evaporate off. The heating rate is determined depending upon the types and contents of composite oxide constituents, since it has a significant influence upon the microstructure and superconductive characteristics of ceramics. In this invention, heating is carried out in an oxygenous or non-oxygenous atmosphere. Besides oxygen, a nitrogen gas or an inert gas such as helium or argon can also be additionally provided. After heating, gradual cooling is applied for c-axial orientation and crystallization. For instance, the cooling rate applied is 500 to 20°C/hour, preferably 200 to 50°C/hour, more preferably about 100°C/hour. Composite Oxide Ceramics The superconductive ceramics laminate is a laminate in which a superconductive composite oxide ceramics film comprising bismuth, strontium, calcium, copper and oxygen is formed over a silver intermediate layer on a flat plane of a substrate in the form of a tape, said laminate being characterized in that composite oxide crystals in the film are oriented to cause the c-axis to be substantially perpendicular to the flat plane of the intermediate layer. The thus prepared ceramics can show superconductivity and be used as various superconductive materials. For a better understanding of this invention, reference will now be made specifically but not exclusively to the mechanism of the method of the ceramics produced according to this invention. In the method of this invention, the ceramic particles in the composite oxide film prior to treatment are randomly arranged and present in a mixed amorpohous/crystalline state. The heat treatment causes a part or the whole of the oxides in the film, to melt, and the film is then subjected to c-axial orientation and crystallization by gradual cooling. Silver is less reactive with superconductive phases and has good coherency with the Bi-Sr-Ca-Cu-O base ceramics in terms of the lattice constants so that the c-axial orientation of Bi-base ceramics can be easily promoted. By this invention, it is possible to obtain the following advantageous effects. (a) It is possible to simply and inexpensively make superconductive ceramics laminates of improved crystal orientation by making use of an easy-to-handle and inexpensive heat-treatment step. (b) By using a conductive tape as the substrate, it is possible to make up for the defect of ceramics which is that their processability is unsatisfactory and to make the laminates of this invention flexible. (c) Because of the orientation of the superconductive ceramics film, it is possible to obtain superconductive laminates having a critical current density practically high enough to pass a large current. A specific example of the invention will now be given. The silver intermediate layer was formed as a thick film on a Hastelloy tape (a heat-resistant Ni alloy) by plating. The tape was fired at 880°C for 1 hour to obtain a film thickness of 5 to 10 µm. Separately, 0.5 moles of Bi₂O₃, 1 mole of SrCO₃, 1 mole of CaCO₃ and 2 moles of CuO were dry-mixed together in a mortar, and the mixture was then calcinated at 800°C for 10 hours. The calcined powders were reduced in a mortar to a powder size of 280 mesh or less. Then, 3 parts by weight of an acrylic resin were added to 10 parts by weight of the calcined product, which step was followed by a 30-minute mixing with a kneader. For regulation of viscosity, drops of a solvent parapinole and a plasticizer dibutyl phthalate were added to and mixed well with the mixtures. The obtained composite oxide paste was formed as a thick film on the intermediate layer by screen printing. The film thickness varied from tens of um to hundreds of um, as measured prior to firing. The tape was dried at about 100°C, pre-treated at 400°C for 1 hour to evaporate off the binder, and heat-treated at 860°C for 5 minutes. After subsequent cooling at a cooling rate of 100°C/hour, a superconductive ceramics-laminated tape having a film thickness between 5 to 10µm and tens of µm was obtained. To test the superconductive characteristics of the obtained superconductive ceramics-laminated tape, a part of the tape was peeled off to determine the relationship between temperature and electrical resistivity by an ordinary four-terminal procedure. The results are shown in FIG 2, from which it was found that a Tc of 78K was obtained. The crystal orientation was examined by powder X-ray diffractometry. From FIG 3 showing the results, it was found that the peak of the (00n) plane is so high and intensive that the crystals are strikingly oriented along the c-axis.

Claims: A method of making superconductive ceramics laminates, comprising screen printing a thick film (2) of a composite oxide comprising bismuth, strontium, calcium, copper and oxygen having a thickness of the order of tens of µm to hundreds of µm, on a plane of a nickel alloy substrate (1) over a silver intermediate layer (3) and heat-treating the thus formed film, wherein: said substrate is in the form of a tape; said composite oxide is oriented and crystallized by said heat treatment to cause its c-axis to be substantially perpendicular to a flat plane of said intermediate layer, and said intermediate layer serves to promote said orientation and has no adverse influence upon the superconductivity of the ceramics during said heat treatment, said heat treatment being carried out by heating said film to a temperature of 860° to 950°C in an oxygenous or non-oxygenous atmosphere to melt a part or the whole thereof, and then cooling the film at the cooling rate of between 500°C and 20°C per hour. The method as claimed in claim 1, wherein the heat treatment is carried out at a temperature of 870°C to 910°C. A superconductive ceramics laminate made according to the method of claim 1 or claim 2.

Inventors: FUKUTOMI, MASAO, HOSHINO, KAZUTOMO, TAKAHARA, HIDEFUSA, YAMAZAKI, SHIGERU
Applicants: MITSUI KINZOKU KOGYO KABUSHIKI KAISHA, NATIONAL RESEARCH INSTITUTE FOR METALS, SCIENCE AND TECHNOLOGY AGENCY
Application year: 1989
Main classification: B32B18
IPC codes: B32B18, H01L39, C04B35