KR970009737B1 - Method of manufacture for superconductor tape - Google Patents

Method of manufacture for superconductor tape Download PDF

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KR970009737B1
KR970009737B1 KR1019890008437A KR890008437A KR970009737B1 KR 970009737 B1 KR970009737 B1 KR 970009737B1 KR 1019890008437 A KR1019890008437 A KR 1019890008437A KR 890008437 A KR890008437 A KR 890008437A KR 970009737 B1 KR970009737 B1 KR 970009737B1
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South Korea
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plate
slurry
superconductor
cuo
tape
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KR1019890008437A
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Korean (ko)
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KR910002021A (en
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박종학
강원호
윤천
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삼성코닝 주식회사
한형수
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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
    • 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
    • H10N60/01—Manufacture or treatment

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

A fabrication method of a superconductor tape having constitutional formula of (BiPb)2Sr1, 7Ca2, 3Cu3, 6Oy is disclosed. The method comprises the steps of: mixing Bi2O3, PbO, SrCO3, and CaCO3 by adequate mole ratio; performing calcination the powder; forming a slurry by agitation of adequate solution; dipping a plate fabricated by metal plating of Cu to the slurry; and annealing the plate in oxygen atmosphere, thereby converting the Cu on the plate to the CuO.

Description

초전도 테이프의 제조방법Manufacturing method of superconducting tape

본 발명은 초전도 자석을 제조하기 위한 초전도 테이프의 제조방법에 관한 것이다.The present invention relates to a method of manufacturing a superconducting tape for producing a superconducting magnet.

초전도체를 에너지 응용분야에 이용하려면 초전도 자석을 만들어야 하는데 본 발명은 이러한 테이프의 제조방법에 관한 것이다.The use of superconductors in energy applications requires the creation of superconducting magnets and the present invention relates to a method of making such tapes.

종래에는 초전도체 중에 Nb3Sn, V3Ga등 A15 구조를 갖는 금속제 초전도체를 사용하여 고상 반응법에 유용한 브론즈(bronze) 공법에 의해 유연성이 있는 초전도 테이프를 제조하였다.Conventionally, a superconducting tape having flexibility has been manufactured by using a bronze method, which is useful for solid state reaction, using a metal superconductor having an A15 structure such as Nb 3 Sn and V 3 Ga in the superconductor.

또한, 고온 산화물 초전도체의 경우 일본 국립 금속 재료 기술연구소의 마에다(Maeda)등에 의해 Bi계 초전도체를 닥터 브레이트(doctor brade) 성형법에 의해 초전도체 테이프를 제조하였다. (Japanese Journel of Applied Physics, Vol 28, Nol. PP. 95~96)In the case of the high temperature oxide superconductor, a superconductor tape was manufactured by a doctor brade molding method for a Bi-based superconductor by Maeda et al. Of the Japan National Institute of Metals and Materials. (Japanese Journel of Applied Physics, Vol 28, Nol. PP. 95-96)

그러나, 상기 방법들은 제조공정이 복잡하고 반응조건 또한, 상당히 엄격함으로 초전도 테이프를 제조하는데 상당히 어려움이 존재하였다.However, the above methods have a considerable difficulty in producing a superconducting tape because the manufacturing process is complicated and the reaction conditions are also very strict.

따라서, 본 발명자는 상술한 문제점을 극복할 목적으로 다수의 실험과 연구를 거듭한 결과 표면 확산법(Surgace diffusion method)을 이용하고, Ag 시트에 Gu를 도금한 플레이트를 사용하는 것이 상당히 잇점이 있음을 인식하여 본 발명을 완성하게 된 것이다.Therefore, the present inventors have repeatedly conducted a number of experiments and studies for the purpose of overcoming the above-described problems. Therefore, the present inventors have found that using the surface diffusion method and using a plate plated with Gu on an Ag sheet has considerable advantages. Recognition has been made to complete the present invention.

본 발명은 Bi-Pb-Sr-Ca-Cu-O계의 고온 초전도 테이프를 제조하는데 있어서, Bi2O3, PbO, SrCO3및 CaCO3를 적절한 몰비로 혼합시켜 하소한후, 분쇄한 분말을 적절한 용매로 교반하여 슬러리로 제조한 다음, 이 슬러리에 Cu를 도금시킨 플레이트를 디핑(dipping) 한 후 산소분위기 하에서 열처리하여 플레이트상의 Cu를 CuO로 전환시키는 것을 특징으로 하는 초전도체의 제조방법에 관한 것이다.In the present invention, Bi-Pb-Sr-Ca-Cu-O-based high-temperature superconducting tape, Bi 2 O 3 , PbO, SrCO 3 and CaCO 3 by mixing in an appropriate molar ratio, calcined, and then pulverized powder The present invention relates to a method for producing a superconductor characterized by converting Cu on a plate into CuO by preparing a slurry by stirring with an appropriate solvent and then dipping the plate plated with Cu and then heat-treating it under an oxygen atmosphere. .

상기에서 적절한 몰비로는 (Bi+Pb) : Sr : Ca=2 : 2 : 2이나 휘발성분을 고려하여 Bi : Pb : Sr : Ca=1.5 : 0.5 : 1.7 : 2.3이 가장 양호한 몰비이다.Suitable molar ratios above are (Bi + Pb): Sr: Ca = 2: 2: 2, but Bi: Pb: Sr: Ca = 1.5: 0.5: 1.7: 2.3 is the best molar ratio in consideration of volatile components.

또한, 하소 조건으로는 예를 들면, 800도, 20시간 공기분위기 하에서 1회 또는 2회 하소시키는 것이 가장 적절하다.In addition, as the calcination conditions, it is most suitable to calcinate once or twice in an air atmosphere at 800 degrees for 20 hours, for example.

그리고, 상기 열처리 조건은 예를 들면, 845oC 까지 승온온도 200oC /hr로 승온시키고, 845oC 에서 유지시간을 120시간으로 하고, 냉각속도를 100oC /hr로 O2흐름 분위기하에서 처리하는 것이 가장 적절하다.In addition, the heat treatment conditions, for example, 845 o C and to an elevated temperature at a heating temperature of 200 o C / hr, 845 o the holding time in the C to 120 hours, and O and the cooling rate to 100 o C / hr 2 Flow Atmosphere It is most appropriate to process under.

본 발명에 있어서는 표면 확산법(Surface diffusion method) 즉, Cu 플레이트에 혼합분말의 슬러리를 디핑시킨후, 산소분위기 하에서 열처리함으로써 표면 Cu가 CuO로 산화되고, 상기 혼합분말에 CuO가 함유됨에 따라 (BiPb)2Sr1,7Ca2.3Cu3.6Oy의 구조식을 갖는 고온 초전도체 테이프가 제조 가능하게 된다.In the present invention, the surface diffusion is oxidized to CuO by dipping the slurry of the mixed powder into the Cu plate, and then heat-treating it under an oxygen atmosphere, so that the mixed powder contains CuO (BiPb). A high temperature superconductor tape having a structural formula of 2 Sr 1 , 7 Ca 2.3 Cu 3.6 Oy can be produced.

아울러, 상기에서 Cu를 도금시키는 대상으로 Ar 시트를 사용함으로써 테이프의 유연성(flexibility)은 향상 될 수가 있다.In addition, the flexibility of the tape can be improved by using an Ar sheet as a target for plating Cu.

본 발명의 제조방법에 따라 제조된 고온 초전도체는 상술한 표면 확산법에 의해 CuO를 도입함에 따라 제조방법이 간단하고, 초전도 까다롭지 않고, Cu를 도금시킨 Ag 플레이트를 사용함에 따라 산화물을 이용한 초전도 테이프에서 가장 필요로 하는 유연성을 대폭 향상시킬 수가 있다.The high temperature superconductor manufactured according to the manufacturing method of the present invention has a simple manufacturing method by introducing CuO by the surface diffusion method described above, and is not difficult to superconduct, and is used in a superconducting tape using an oxide by using an Ag plate coated with Cu. You can greatly improve the flexibility you need most.

이하, 실시예를 통해 본 발명의 제조방법 및 효과에 대하여 구체적으로 설명한다. 그러나 다음의 실시예가 본 발명의 범주를 한정하는 것은 아니다.Hereinafter, the production method and effects of the present invention will be described in detail through examples. However, the following examples do not limit the scope of the present invention.

실시예Example

Bi2O3, PbO, CaCO3및 SrCO3분말을 Bi : Pb : Sr : Ca=1.5 : 0.5 : 1.7 : 2.3의 몰비로 평량후 YZT볼을 사용하여 밀링(milling)한후 건조시켰다.Bi 2 O 3 , PbO, CaCO 3 and SrCO 3 powders were weighed in a molar ratio of Bi: Pb: Sr: Ca = 1.5: 0.5: 1.7: 2.3, and then dried using a YZT ball and then dried.

이때의 용매는 아세톤을 사용하였다. 건조된 분말을 전기로를 사용하여 800공기 분위기에서 20시간동안 2회 하소시킨후 분쇄시켰다.Acetone was used as the solvent at this time. The dried powder was calcined twice in an air atmosphere at 800 air for 20 hours and then pulverized.

테이프의 기질은 Ag 시트에 Cu를 도금한 플레이트를 사용하였다. 이 플레이트를 5cm×5cm로 자른후 알카리탈지역에서 5분간 탈지후 증류수에 세척시켜 건조한 후 사용하였다.As a substrate of the tape, a plate in which Cu was plated on an Ag sheet was used. The plate was cut into 5 cm × 5 cm, degreased in alkaline regions for 5 minutes, washed with distilled water, and dried.

Ag-Cu 플레이트에 하소분말의 코팅은 하소분말을 에틸알코올에 잘 분산시킨후, 에멀션 상태로 만든후 상기 플레트를 디핑법에 의해 코팅 시킨후 오븐에서 건조시켰다.The coating of the calcined powder on the Ag-Cu plate was well dispersed in the calcined powder in ethyl alcohol, and then made into an emulsion state, and then the plate was coated by dipping and dried in an oven.

건조시킨 플레이트는 알루미나 플레이트 위에 Pt선을 올려놓고 그위에 플레이트를 올려놓고 튜브로에 잡입시킨후 열처리하였다.The dried plate was placed on the alumina plate with a Pt wire, and the plate was placed thereon, mixed in a tube furnace, and heat treated.

이때의 열처리 온도 및 조건은 다음과 같다.The heat treatment temperature and conditions at this time are as follows.

온도 : 845oCTemperature: 845 o C

승온속도 : 200oC /hrTemperature increase rate: 200 o C / hr

유지시간 : 120시간Holding time: 120 hours

냉각속도 :100oC /hrCooling rate: 100 o C / hr

분위기 : O2흐름분위기Atmosphere: O 2 flow atmosphere

Claims (2)

(BiPb)2Sr1,7Ca2.3Cu3.6Oy 구조식을 갖고 고온 초전도체를 제조하는데 있어서, Bi2O3, PbO, SrCO3및 CaCO3를 적절한 몰비로 혼합시켜 하소한후 분쇄한 분말을 적절한 용매로 교반하여 슬러리를 제조한 다음, 이슬러리에 Cu를 도금시킨 플레이트를 디핑한 후 산소분위기하에서 열처리하여 플레이트상의 Cu를 CuO로 전환시키는 것을 특징으로 하는 초전도체의 제조방법.(BiPb) 2 Sr 1 , 7 Ca 2.3 Cu 3.6 Oy In the preparation of high temperature superconductor having a structural formula, Bi 2 O 3 , PbO, SrCO 3 and CaCO 3 were mixed and calcined in an appropriate molar ratio, and then the pulverized powder was prepared in an appropriate solvent. After preparing a slurry by stirring, and then dipped the plate plated with Cu on the dew slurry, and heat-treated under oxygen atmosphere to convert Cu on the plate into CuO. 제1항에 있어서, Cu를 도금시킨 플레이트의 기본시트로 Ag 시트가 사용되는 것을 특징으로 하는 초전도체의 제조방법.The method of manufacturing a superconductor according to claim 1, wherein an Ag sheet is used as a base sheet of the plate plated with Cu.
KR1019890008437A 1989-06-19 1989-06-19 Method of manufacture for superconductor tape KR970009737B1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100821209B1 (en) * 2006-10-31 2008-04-11 한국전력공사 Manufacturing method of high temperature superconductor thick films by using cu-free precursors on ni substrates

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100821209B1 (en) * 2006-10-31 2008-04-11 한국전력공사 Manufacturing method of high temperature superconductor thick films by using cu-free precursors on ni substrates

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