Method of forming hollow metal oxide superconductors (MOS) and the like by polymer-metal-complex (PMC) techniques and novel hollow MOS structures produced thereby

• US 5,171,735 A
• Filed: 11/17/1989
• Issued: 12/15/1992
• Est. Priority Date: 11/17/1989
• Status: Expired due to Fees

• Current Assignee: Institute of Pharmacology and Toxicology Academy of Military Medical Sciences PLA China
• Original Assignee: Institute of Pharmacology and Toxicology Academy of Military Medical Sciences PLA China
• Inventors: Chien, James C. W.
• Primary Examiner(s): Silbaugh, Jan H.
• Assistant Examiner(s): Fiorilla, Christopher A.
• Application Number:
  US07/438,762
• Time in Patent Office: 1,124 Days
• Field of Search: 264/65, 264/313, 264/317, 264/59, 264/61, 505/1, 505/734, 505/737, 505/739, 505/740
• US Class Current: 505/430
• CPC Class Codes: H10N 60/0801 Processes peculiar to the manufacture or treatment of filaments or composite wires
• CPC Class Codes: Y10S 505/734 From organometallic precursors, e.g. acetylacetonates
• CPC Class Codes: Y10S 505/737 From inorganic salt precursors, e.g. nitrates
• CPC Class Codes: Y10S 505/74 To form wire or fiber

Abstract

A method for forming a high T_c metal oxide superconductor in the form of a hollow fiber. The method includes the steps of: forming a polymer-metal complex precursor; filling a decomposable hollow fiber mold with the precursor; and heating the filled mold to decompose the mold and convert the precursor to a metal oxide superconductor in the form of a hollow fiber. Ag-doped metal oxide superconductor structures can also be produced by the above method.

Claims

1. A method for forming a high T_c metal oxide superconductor in the form of a hollow fiber comprising:

(a) forming a polymer-metal complex precursor solution by homogeneously and uniformly complexing metal salt ions in desired stoichiometric ratio to a polymer solution;

(b) filling a hollow fiber mold of organic synthetic polymer with said polymer-metal complex precursor solution;

(c) thermalyzing the resulting product in N₂ whereby the hollow fiber mold is pyrolyzed and decomposed and the polymer-metal complex precursor is converted to intermediate intermetallic compounds; and

(d) calcining the intermediate intermetallic compounds under O₂ to convert said compounds to the desired high T_c metal oxide superconductor in the form of a hollow fiber, the hollow fiber form resulting from gravitation of the precursor toward the mold as the precursor is concentrated.

2. A method as claimed in claim 1 and in which said hollow fiber mold is non-porous such that metal oxide superconductor hollow fiber is non-porous.

3. A method as claimed in claim 1 and in which said hollow fiber mold is porous such that the metal oxide superconductor hollow fiber is porous.

4. A method as claimed in claim 1 and in which the said polymer solution is selected from the group consisting of poly(methacrylic acid), poly(vinyl acetate-comethacrylic acid), poly(itaconic acid-co-methacrylic acid) and polyamic acid and derivatives thereof.

5. A method as claimed in claim 1 and in which the metal oxide and ions are selected from the group consisting of combinations of at least two of Y, Ba, Cu, Ag, Au, Bi, Sr, Ca, Pb, Tl.

6. A method as claimed in claim 4 and in which the said superconducting metal oxide is YBa₂ Cu₃ O_x.

7. A method as claimed in claim 4 and in which the said superconducting metal oxide is Y₅ Ba₆ Cu₁₁ O_x.

8. A method as claimed in claim 5 and in which the said superconducting metal oxide is Bi₂ Sr₂ Ca₂ Cu₃ O_x.

9. A method as claimed in claim 5 and in which the said superconducting metal oxide is Pb_a Bi_b SrCaCu₂ O_x where a and b are greater than 0.1 and less than 0.9.

10. A method as claimed in claim 5 and in which the said superconducting metal oxides also contain doping metals as of Ag and Ag₂ O in amounts of from 1% to 90% of the combined weight of the other metals to control the morphological grain size.

11. A method as claimed in claim 10 and in which the Ag and Ag₂ O is present in the 10 to 40 weight percent range.

12. A method as claimed in claim 1 and in which the forming of the hollow fiber about the mold is also effected by nucleation on the mold walls.

13. A method as claimed in claim 1 in which a dopant metal or its oxide is added to the high T_c metal oxide superconductor.