USH1683H - Superconducting material - Google Patents

Superconducting material Download PDF

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Publication number
USH1683H
USH1683H US08/474,797 US47479795A USH1683H US H1683 H USH1683 H US H1683H US 47479795 A US47479795 A US 47479795A US H1683 H USH1683 H US H1683H
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US
United States
Prior art keywords
superconducting
element selected
yttrium
copper
barium
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Abandoned
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US08/474,797
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English (en)
Inventor
Shunpei Yamazaki
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Semiconductor Energy Laboratory Co Ltd
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Semiconductor Energy Laboratory Co Ltd
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Priority to US08/474,797 priority Critical patent/USH1683H/en
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Publication of USH1683H publication Critical patent/USH1683H/en
Abandoned legal-status Critical Current

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10N60/00—Superconducting devices
    • H10N60/80—Constructional details
    • H10N60/85—Superconducting active materials
    • H10N60/855—Ceramic superconductors
    • H10N60/857—Ceramic superconductors comprising copper oxide
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B35/00—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
    • C04B35/01—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics
    • C04B35/45—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides
    • C04B35/4504—Shaped ceramic products characterised by their composition; Ceramics compositions; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products based on oxide ceramics based on copper oxide or solid solutions thereof with other oxides containing rare earth oxides

Definitions

  • the present invention relates to an oxide ceramic superconducting material, and more particularly to a composition wherein the temperature of a superconducting material at which electrical resistance becomes zero (which is referred to as Tco hereinafter) approaches a room temperature as much as possible.
  • a metallic composition including elements such as mercury and lead, alloys such as NbN, Nb 3 Ge, Nb 3 Ga, or three-element compounds such as Nb 3 (Al 0 .8 Ge 0 .2) are used as superconducting materials.
  • the onset of the superconducting critical temperature (which is referred to as Tc hereinafter) is as low as 25° K.
  • the inventor of the present invention has discovered, during efforts to improve the Tco and Tc of the superconducting ceramic materials, that these impurities collect at the boundaries of the ceramic particles and act as a barrier between the particles to which they adhere, so that they interfere with the electrical conductivity. In such conditions, it is not possible to increase the current density, and the Tco is lower than expected.
  • An object of the present invention is to provide, with due consideration to the drawbacks of such conventional materials, a superconducting material, utilizing new materials of high purity, which exhibits superconductivity at high temperatures, so that the Tc onset occurs between 80° K and 124° K.
  • a further object of the present invention is to provide a lower density of impurities contained throughout the superconducting ceramic material represented by the expression (A 1-x B x ) y Cu z O w .
  • a superconducting composition is provided to essentially consist of a superconducting material and no more than 0.2% by weight of Li(lithium), Na(sodium), and K(potassium) mixed into the superconducting material.
  • FIG. 1 is a graph showing the characteristics of the superconducting material made according to the present invention.
  • a ceramic superconducting material is made to essentially consist copper, oxygen and at least one element selected from the group of Groups 11a and 111a of the Periodic Table.
  • A is one element selected from the group of the yttrium group and other lanthanides.
  • the yttrium group is defined in "Physic and Chemistry Dictionary" (published Apr.
  • B is at least one element selected from the group of Ra(radium), Ba(barium), Sr(strontium), Ca(calcium), Mg(magnesium), and Be(beryllium).
  • composition of the present invention contains copper in a layered configuration, with one layer within one unit cell, or in a symmetric two-layer structure, and is based on a model in which superconductivity is obtained from the orbit of the furthest exterior nucleus electron.
  • raw materials of 99.99% (4N) purity or higher are used rather than the conventionally-used 99(2N) to 99. 95% purity as a starting material.
  • an oxygen atmosphere of a purity in excess of 4N is used rather than air for oxidation, and the material is fired in 5N oxygen and 5N argon, or under vacuum for reduction.
  • the crystalline grain size can be made larger, and in turn, a structure can be obtained to which the barrier at the crystal boundaries is caused to further disappear. As a result, an even higher Tco is obtained. In this case, ideally there would be a single crystalline structure in the nucleus with no defects.
  • the oxide or carbon oxides as the starting materials are mixed, compressed or compacted once, and an (A 1-x B x ) y Cu z O w type of structure is created from the oxide or carbon oxide.
  • this material is ground to form a fine powder, once again compressed or compacted into tablet form, and fired.
  • the new type of superconducting ceramic material of the present invention can be formed by an extremely simple process.
  • oxide or carbon oxide materials of 5N or 6N purity are used as the starting materials, finely ground in a ball mill, and mixed.
  • the respective values for x,y, z, and w in the expression (A 1-x B x ) y Cu z O w can be optionally varied and controlled stoichiometrically.
  • the present invention has made it possible to produce ceramic superconducting bodies which have been completely unattainable inthe past.
  • the respective starting material compounds are substantially the same as the final compound, specifically the compounds including the materials indicated by the expression (A 1-x B x ) y Cu z O w as a result of finely grinding the material after pre-firing.
  • a plurality of elements from Groups 11a and 111a of the Periodic Table are blended together in these end material compounds because the copper is more easily obtained in a layered configuration within the molecular configuration. In this way, the impurities which tend to segregate at the particle boundaries of the final compound are removed. In other materials, the respective particles tend to more easily fuse with the adjacent particles. Observation with an electron microscope ( ⁇ 40,000) shows that the spherical and granular particles are packed together in the third example with larger adjacent apertures. On the other hand, in the first example of the present invention, there is a sufficiently high degree of denseness in the packing and therefore only a few apertures are seen in the spheres.
  • the respective polycrystalline particles are clearly seen to be mutually adhering in a face to face relationship.
  • the Tc onset and Tco can be presumed to be at a higher temperature in the present invention because the alkali metal elements, halogen elements, carbon, and nitrogen have been removed.
  • the mechanism of the superconductivity of the superconducting ceramic materials which exhibit the molecular structure of the present invention is presumed to be related to the fact that the copper oxide material has a laminar structure, and this laminar structure has one layer or two layers in one unit cell. The superconductivity is obtained through carriers within this layer.
  • the present invention has succeeded for the first time in the world in enlarging the mutual surfaces of the particles and obtaining intimate contact between them by eliminating or reducing the alkali metal elements, halogen elements, carbon, and nitrogen.
  • the embodiments of the present invention are made in tablet form. However, it is possible to prepare a thin film superconducting ceramic material without the tablet step, dissolving the powder in a solvent after a pre-firing or full firing, coating a substrate or the like with that solution and firing the coated substrate in an oxidizing atmosphere, followed by firing in a reducing atmosphere.
  • A is one or more elements of Group IIIa of the Periodic Table, e.g., the rare earth elements
  • B is one or more elements of Group IIa of the Periodic Table, e.g., the alkaline earth metals including beryllium and magnesium
  • x 0 to 1
  • y 2.0 to 4.0, preferably
  • superconducting ceramics for use in accordance with the present invention may be prepared consistent with the stoichiometric formulae (A 1-x B x ) y Cu z O w , where A is one or more elements of Group Vb of the Periodic Table such as Bi, Sb, and As.
  • the Tconset and Tco of the composition Bi 4 Sr 4 Ca 2 Cu4O x are 110° K and 79° K, respectively.
  • the value of x in the above formulae is estimeated to be 6 to 10, for example about 8.1.
  • the stoichiometric formulae mentioned above can be determined for example by X-ray diffracton.
  • Example 1 of the present invention Y was used as A and Ba as B in the general expression.
  • This process is referred to as the pre-firing process.
  • this material was ground and blended in a mortar to an average particle radius of 10 ⁇ m or less.
  • This blended powder was sealingly inserted into a capsule and formed into tablets by compressing at a load of 50 kg/cm 2 .
  • the methods may also be adopted in a hot press system where the tablet is heated while it is being pressed, or in which an electric current is applied to the tablet, so that a light elecrtric current flows through the tablet while the tablet is being heated.
  • an oxidizing process was performed at between 500° C. and 1000° C., for example at 900° C., in an oxidizing atmosphere such as an atmosphere of highly purified oxygen, and full firing was carried out for 10 to 50 hours, for example, 15 hours.
  • this sample material was heated in a low oxygen O 2 -Ar mixture (with other impurities at 10 ppm or less) for 3 to 30 hours at 600° C. to 1100° C., for example, and for 20 hours at 800° C., for reduction, resulting in a new structure which was observed clearly.
  • O 2 -Ar mixture with other impurities at 10 ppm or less
  • the relationship between the specific resistance and temperature was determined.
  • the highest temperature obtained for the Tc onset was observed to be 114° K, while the Tco was observed to be 103° K.
  • the amount of impurities present was measured by means of a Secondary Ion Mass Spectrometer (SIMS).
  • SIMS Secondary Ion Mass Spectrometer
  • the amount of nitrogen and carbon dioxide were 0.1% or less by weight, specifically measured at only 0.01% by weight.
  • the halogen elements detected were 0.1% or less by weight, specifically detected at only 0.001% by weight.
  • the alkali metal elements were 0.2% or less by weight, specifically detected at only 0.001% by weight.
  • FIG. 1 shows the temperature versus specific resistance characteristics of the superconducting material of the present invention which was obtained n this example.
  • the Tc onset obtained was 119° K, and Tco 107° K in this example.
  • This example was made on the basis of a conventional method for comparison.
  • Example 1 the starting materials were 3N in purity.
  • the material was blended in the form of fine powders, but only a simple washing with city water being performed rather than ultrasonic washing with highly purified water. Other manufacturing conditions remained the same.
  • the Tc in this case was only 92° K and Tco only 74° K.
  • the results of analyses for impurities run on the formed tablets gave 0.3% by weight for sodium in the alkali metal elements, and 0.5% by weight for carbon and nitrogen.

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  • Engineering & Computer Science (AREA)
  • Chemical & Material Sciences (AREA)
  • Ceramic Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
US08/474,797 1987-03-27 1995-06-07 Superconducting material Abandoned USH1683H (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US08/474,797 USH1683H (en) 1987-03-27 1995-06-07 Superconducting material

Applications Claiming Priority (8)

Application Number Priority Date Filing Date Title
JP62-75201 1987-03-27
JP62075201A JP2630361B2 (ja) 1987-03-27 1987-03-27 超電導材料
US17442088A 1988-03-25 1988-03-25
US55079390A 1990-07-06 1990-07-06
US59365690A 1990-10-03 1990-10-03
US6071493A 1993-05-13 1993-05-13
US28691794A 1994-08-08 1994-08-08
US08/474,797 USH1683H (en) 1987-03-27 1995-06-07 Superconducting material

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US28691794A Continuation 1987-03-27 1994-08-08

Publications (1)

Publication Number Publication Date
USH1683H true USH1683H (en) 1997-10-07

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US08/474,797 Abandoned USH1683H (en) 1987-03-27 1995-06-07 Superconducting material

Country Status (6)

Country Link
US (1) USH1683H (de)
EP (1) EP0284438B1 (de)
JP (1) JP2630361B2 (de)
KR (1) KR950004294B1 (de)
CN (1) CN1032777C (de)
DE (1) DE3856473T2 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040077481A1 (en) * 2001-03-13 2004-04-22 Stefan Remke Method for producing multinary metal oxide powders in a pulsed reactor

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2597578B2 (ja) * 1987-05-11 1997-04-09 株式会社東芝 超電導体の製造方法
AU589068B2 (en) * 1987-08-10 1989-09-28 Furukawa Electric Co. Ltd., The Method of manufacturing oxide superconductor, and method of manufacturing composite oxide powder which is the precursor of the oxide superconductor
NZ228820A (en) * 1989-04-19 1992-07-28 Nz Scientific & Ind Res Superconducting metal oxide and its preparation
JP3217905B2 (ja) * 1992-06-26 2001-10-15 キヤノン株式会社 金属酸化物材料及びその製造方法
DE19603820A1 (de) * 1995-08-04 1997-02-06 Solvay Barium Strontium Gmbh Supraleitervormischung
CN110183473B (zh) * 2019-05-23 2021-09-14 深圳先进技术研究院 一种新型超导材料及其制备方法

Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4797510A (en) * 1987-10-13 1989-01-10 Amax, Inc. Device for joining superconducting wire
US4826808A (en) * 1987-03-27 1989-05-02 Massachusetts Institute Of Technology Preparation of superconducting oxides and oxide-metal composites
US4900715A (en) * 1988-02-29 1990-02-13 The United States Of America As Represented By The Secretary Of The Navy Method of preparing superconducting "orthorhomibic"-type compounds in bulk using C1 -C6 alkanoic acid salts
US4916116A (en) * 1987-05-06 1990-04-10 Semiconductor Energy Laboratory Co., Ltd. Method of adding a halogen element into oxide superconducting materials by ion injection
US4959345A (en) * 1987-05-06 1990-09-25 Semiconductor Energy Laboratory Co., Ltd. Method of adding oxygen into oxide superconducting materials by ion injection
US4971667A (en) * 1988-02-05 1990-11-20 Semiconductor Energy Laboratory Co., Ltd. Plasma processing method and apparatus

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS63230564A (ja) * 1987-03-18 1988-09-27 Semiconductor Energy Lab Co Ltd 超電導セラミツクス
JPS63230561A (ja) * 1987-03-18 1988-09-27 Semiconductor Energy Lab Co Ltd 超電導セラミツクス
JPS63230563A (ja) * 1987-03-18 1988-09-27 Semiconductor Energy Lab Co Ltd 超電導セラミツクス

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4826808A (en) * 1987-03-27 1989-05-02 Massachusetts Institute Of Technology Preparation of superconducting oxides and oxide-metal composites
US4916116A (en) * 1987-05-06 1990-04-10 Semiconductor Energy Laboratory Co., Ltd. Method of adding a halogen element into oxide superconducting materials by ion injection
US4959345A (en) * 1987-05-06 1990-09-25 Semiconductor Energy Laboratory Co., Ltd. Method of adding oxygen into oxide superconducting materials by ion injection
US4797510A (en) * 1987-10-13 1989-01-10 Amax, Inc. Device for joining superconducting wire
US4971667A (en) * 1988-02-05 1990-11-20 Semiconductor Energy Laboratory Co., Ltd. Plasma processing method and apparatus
US4900715A (en) * 1988-02-29 1990-02-13 The United States Of America As Represented By The Secretary Of The Navy Method of preparing superconducting "orthorhomibic"-type compounds in bulk using C1 -C6 alkanoic acid salts

Non-Patent Citations (23)

* Cited by examiner, † Cited by third party
Title
"Band Properties and Superconductivity in La2-y Xy CuO4 ", Mattheiss, Physical Review Letters, vol. 58, No. 10, Mar. 9, 1987, pp. 1028-1030.
"Evidence for Superconductivity above 40 K in the La-Ba-Cu-O Compound System", Chu et al., Physical Review Letters, vol. 58, No. 4, Jan. 26, 1987, pp. 405-407.
"High-Pressure Study of the New Y-Ba-Cu-O Superconducting Compound System", Hor et al., Physical Review Letters, vol. 58, No. 9, Mar. 2, 1987, pp. 911-912.
"Lattice Instability and High-T Superconductivity in La2-x Bax CuO4 ", Jorgansen et al., Physical Review Letters, vol. 58, No. 10, Mar. 9, 1987, pp. 1024-1027.
"Possible High Tc Superconductivity in the Ba-La-Cu-O System", Bednorz et al., Condensed Matter, 64, 1986, pp. 189-193.
"Preparation and Properties of the Compounds Ln2 CuO4 (Ln=La, Pr, Nd, Sm, Eu, Gd) and Some of Their Solid Solutions", Shaplygin et al., Russian Journal of Inorganic Chemistry, 24(6), 1979, pp. 820-824.
"Superconductivity above Liquid Nitrogen Temperature: Preparation and Properties of a Family of Perovskite-Based Superconductors", Engler et al., J. Am. Chem. Soc., 109, 1987, pp. 2848-2849.
"Superconductivity at 40K in La8 SiO2 CuO4 ", Politts et al., Condensed Matter, 66, 1987, pp. 141-144.
"Superconductivity at 52.5 K in the Lanthanum-Barium-Copper-Oxide System", Chu et al., Reports, Jan. 30, 1987, pp. 567-569.
Band Properties and Superconductivity in La 2 y X y CuO 4 , Mattheiss, Physical Review Letters, vol. 58, No. 10, Mar. 9, 1987, pp. 1028 1030. *
Chemical Abstracts, CA 109:161912, for BR 8,702,554 (Nov. 1987). *
Engler, E.M., et al., "Processing, Structure, and High-Temperature Superconductivity", Chemistry of High-Temperature Superconductors, ACS Symposium Series, 351 (1987), pp. 266-271.
Engler, E.M., et al., Processing, Structure, and High Temperature Superconductivity , Chemistry of High Temperature Superconductors, ACS Symposium Series, 351 (1987), pp. 266 271. *
Evidence for Superconductivity above 40 K in the La Ba Cu O Compound System , Chu et al., Physical Review Letters, vol. 58, No. 4, Jan. 26, 1987, pp. 405 407. *
High Pressure Study of the New Y Ba Cu O Superconducting Compound System , Hor et al., Physical Review Letters, vol. 58, No. 9, Mar. 2, 1987, pp. 911 912. *
Lattice Instability and High T Superconductivity in La 2 x Ba x CuO 4 , Jorgansen et al., Physical Review Letters, vol. 58, No. 10, Mar. 9, 1987, pp. 1024 1027. *
Possible High T c Superconductivity in the Ba La Cu O System , Bednorz et al., Condensed Matter, 64, 1986, pp. 189 193. *
Preparation and Properties of the Compounds Ln 2 CuO 4 (Ln La, Pr, Nd, Sm, Eu, Gd) and Some of Their Solid Solutions , Shaplygin et al., Russian Journal of Inorganic Chemistry, 24(6), 1979, pp. 820 824. *
Superconductivity above Liquid Nitrogen Temperature: Preparation and Properties of a Family of Perovskite Based Superconductors , Engler et al., J. Am. Chem. Soc., 109, 1987, pp. 2848 2849. *
Superconductivity at 40K in La 8 SiO 2 CuO 4 , Politts et al., Condensed Matter, 66, 1987, pp. 141 144. *
Superconductivity at 52.5 K in the Lanthanum Barium Copper Oxide System , Chu et al., Reports, Jan. 30, 1987, pp. 567 569. *
Tarascon, J.M., et al., "Oxygen and rare-earth doping of the 90-K superconducting perovskite YBa2 Cu3 O7-x ", Physical Review B, 36(1) (1 Jul. 1987), 226-234.
Tarascon, J.M., et al., Oxygen and rare earth doping of the 90 K superconducting perovskite YBa 2 Cu 3 O 7 x , Physical Review B, 36(1) (1 Jul. 1987), 226 234. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20040077481A1 (en) * 2001-03-13 2004-04-22 Stefan Remke Method for producing multinary metal oxide powders in a pulsed reactor
US7358212B2 (en) * 2001-03-13 2008-04-15 Merck Patent Gmbh Method for producing multinary metal oxide powders in a pulsed reactor

Also Published As

Publication number Publication date
EP0284438B1 (de) 2001-05-30
EP0284438A3 (de) 1990-10-31
DE3856473D1 (de) 2001-07-05
DE3856473T2 (de) 2001-09-13
JP2630361B2 (ja) 1997-07-16
EP0284438A2 (de) 1988-09-28
KR950004294B1 (ko) 1995-04-28
CN88101627A (zh) 1988-10-19
JPS63239110A (ja) 1988-10-05
CN1032777C (zh) 1996-09-11
KR880011831A (ko) 1988-10-31

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