CN1044003A - Superconductor and preparation method thereof - Google Patents

Superconductor and preparation method thereof Download PDF

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Publication number
CN1044003A
CN1044003A CN90100388A CN90100388A CN1044003A CN 1044003 A CN1044003 A CN 1044003A CN 90100388 A CN90100388 A CN 90100388A CN 90100388 A CN90100388 A CN 90100388A CN 1044003 A CN1044003 A CN 1044003A
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China
Prior art keywords
temperature
superconductor
constant temperature
crucible
hour
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CN90100388A
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Chinese (zh)
Inventor
赵忠贤
陈立泉
杨乾声
黄玉珍
陈赓华
唐汝明
刘贵荣
崔长庚
陈烈
王连忠
郭树权
李山林
毕建清
车广灿
解思深
梁敬魁
张玉苓
俞育德
成向荣
李克胜
董�成
陈维
倪泳明
王昌庆
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Institute of Physics of CAS
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Institute of Physics of CAS
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Priority to CN90100388A priority Critical patent/CN1044003A/en
Publication of CN1044003A publication Critical patent/CN1044003A/en
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
    • Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment

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  • Inorganic Compounds Of Heavy Metals (AREA)
  • Compositions Of Oxide Ceramics (AREA)

Abstract

The high temperature superconducting materia of system of the present invention is by MxDzR 5-x-zA 5O 5 (3-Y)The expression formula of system represents that the quaternary oxide is formed, wherein
M＝Ca，Sr，Ba；
D＝Sc，Y，la，Th；
R＝Ce，Pr，Na，Pm，Sm，Eu，Ca，Tb，Dy，Ho，Er，Tm，Yb，Lu，Pb，Zr；
A＝Cu，Ag，Au；
X＝0.01-4.99；
Y＝0.01-4.99；
Z＝0.01-4.99；
High temperature superconducting materia of the present invention is made by direct sintering.Raw material is extensive, and technology is simple, is easy to promote, and broadens one's scope of mind for the research and the application of superconductor, gives a clue.

Description

Superconductor and preparation method thereof
The invention belongs to the superconductor field.
In February, 1987, we successfully prepared with MxR in the laboratory 5-xA 5O 5(3-Y)The superconductor of system, its initial transition temperature 110K, zero-resistance temperature 78.5K, mid point transition temperature 92.8K, the Ba.Y of width of transition 4K 5-xCu 5O 5(3-y)The liquid nitrogen temperature superconductor.As seen list of references (1) KEXVETONGBAO, VO1.32, NO.10(1987) 661-4; (2) number of patent application 87100997, March 2 87 year applying date.After this, reported that in the world the superconducting transition temperature that professor Zhu Jingwu of houston, u.s.a university makes superconductor is 98K.
The objective of the invention is to seek prepare have higher critical transition temperature, the better new superconductor of superconductivity.
High temperature superconducting materia of the present invention is by MxDzR 5-x-zA 5O 5(3-Y)The system that the quaternary oxide that expression formula is represented is formed, wherein
M＝Ca，Sr，Ba;
D＝Sc，Y，La，Th;
R＝Ce，Pr，Na，Pm，Sm，Em，Gd，Tb，Dy，Ho，Er，Tm，Yb，Lu，Pb，Zr;
A＝Cu，Ag，Au;
X＝0.01-4.99;
Y＝0.01-4.99;
Z＝0.01-4.99;
Superconductor of the present invention prepares with direct sintering.Selecting commercially available, general purity for use is 98.00%-99.999%.The oxide of respective element or the corresponding nitrate of these elements or carbonate raw material are (as Ba(NO 3) 2, BaCO 3) also have Th(OH) 4, press MxDzR 5-x-zA 5O 5(3-y)Body carries out combined ingredient arbitrarily, selected component is weighed up material, even with the abundant ground and mixed of agate mortar, powder is put into the metal die compaction moulding, put into the crucible of refractory material, as platinum, aluminium oxide, quartzy, also can not moldedly directly put into fire-clay crucible, the crucible that will assemble honest material more is put in the bigger refractory crucible and goes, and purpose is in order to make the sample environment temperature even, and controlled atmospher easily, next step this set crucible that assembles places tubular type or cabinet-type electric furnace, heat up with 10-400 ℃/hour heating rate, constant temperature is 2-24 hour when temperature reaches 900 ℃-1400 ℃, and sintering carries out solid-state reaction.Constant temperature is in order to make its sufficient reacting, make the furnace temperature cool to room temperature then, take out sample and carefully grind, again compaction moulding, reinstall fire-clay crucible and be built in and be warmed up to 900 ℃-1400 ℃ in the stove and heat-treated in constant temperature 1-10 hour, can obtain a kind of new superconductor.In sintering solid-state reaction or heat treatment process, can in air, carry out, also can in stove, fill with inert gas (N 2, Ar) or O 2, (flow velocity of inflation is 1-500ml/ minute) or in air, carry out under oxygen enrichment or the anoxic.
It is raw materials used extensively to prepare superconductor of the present invention, technology is simple, wherein the transition temperature of some liquid nitrogen temperature superconductor, critical current and critical magnetic field are higher than the Ba-Y-Cu-O superconductor, this just makes the kind of superconductor increase greatly, thereby for road has been opened up in the extensive use of superconductor, research and the searching room temperature superconductor for superconductivity theory provides more foundation simultaneously.
Embodiment one
Ba(NO with commercially available 99.99% 3) 20.0189 gram, Y 2O 30.2119 gram, Lu 2O 30.1867 gram, CuO 0.2485 gram is pressed Ba for raw material 0.5Y 3.0Lu 5-0.5-3.0Cu 5O 5(3-y)Proportioning, raw material is weighed up, put into agate mortar, put into platinum crucible again after fully grinding, in homemade tube furnace, be warmed up to 950 ℃, constant temperature 3 hours, make it carry out solid-state reaction, then with the stove cool to room temperature, after sample taken out again through grinding, again in mould, behind the compaction moulding, be placed on platinum crucible (or AI again after the grinding 2O 3In the crucible) anneal, can obtain high temperature superconducting materia.
Measurement result shows: the superconductor mid point transition temperature of preparation is 89.3K.
Embodiment two
Press Ba 0.5Y 4.2Dy5-0.5-4.2Cu 5O 5(3-Y)Proportioning is selected Ba(NO for use 3) 20.1633 gram, Y 2O 30.5932 gram, Dy 2O 30.0699d gram, CuO 0.4972 gram is raw material, and technical process is with example one, and the superconductor mid point transition temperature of preparation is 95.2K.
Embodiment three
Press Ba 0.5Dy 0.5Lu 5-0.5-0.5Cu 5O 5(3-Y)Proportioning is selected Ba(NO for use 3) 20.0819 gram, Dy 2O 30.0583 gram, Lu 2O 30.4974 gram CuO 0.2488 gram is raw material, technical process is with example one, and the superconductor mid point transition temperature of preparation is 89.5K.
Embodiment four
Press Ba 3YS cCu 5O 11+YProportioning is selected Ba(NO for use 3) 21.2689 gram, Y 2O 30.2259 gram, Sc 2O 30.1379 gram, Cu(NO 3) 23HO 2.4160 grams are raw material, and technical process is with example one, and when being heat treatment, temperature is 990 ℃ of constant temperature 6-8 hours, the superconductor initial transition temperature 100K of preparation, zero-resistance temperature 86.5K, magnetic measurement results 90.5K.
Embodiment five
Press Ba 3Th 5Pb 0.1Cu 5O 13+YProportioning is selected Ba(NO for use 3) 20.78402 gram, Th(OH) 40.49807 gram, Pb 3O 40.0246 gram, Cu(NO 3) 53HO 1.2080 grams are raw material, and technical process is with example one, and the superconductor initial transition temperature of preparation is 89.7K, and zero-resistance temperature is 79K, and magnetic measurement results is 81.4K.
Embodiment six
Press Ba 0.5Th 2Zr 0.1Cu 5O 10+YProportioning is selected Ba(NO for use 3) 20.13067 gram, Th(OH) 40.49807 gram, ZyO 20.012322 gram, Cu(NO 3) 23HO 1.208 grams are raw material, and technical process is with example one, and the superconductor magnetic measurement results of preparation is 71.4K.

Claims (2)

1, a kind of high temperature superconducting materia is characterized in that with M xD zR 5-xzA 5O 5 (3-y)The system that the quaternary oxide of expression is formed, wherein
M=Ca，Sr，Ba
D=Sc，Y，La，Th
R=Ce，Pr，Nd，Pm，Sm，Eu，Gd，Tb，Dy，Ho，Er，Tm，Yb，Lu，Pb，Zr
A=Cu，Ag，Au
X=0.01-4.99
Y=0.01-4.99
Z=0.01-4.99
2, a kind of preparation method by the described high temperature superconducting materia of claim 1 is characterized in that adopting direct sintering;
A, be element representative with M, D, R, A, with the various element corresponding oxide of commercially available 98.00%-99.999% purity, nitrate or carbonate compound are raw material, (as Ba(NO 3) 2, BaCO 3, Y 2O 3Or Tn(OH) 4, in the weighing of elemental constituent ratio, mixed grinding, compaction moulding is put into refractory crucible, (as platinum, quartz, aluminium oxide);
B, charged crucible placed in the tube furnace heat, heating rate is 35-200 ℃/hour, and when temperature reached 900 ℃-1400 ℃, constant temperature 2-24 hour, the constant temperature sintering carried out solid-state reaction, then, and the furnace temperature cool to room temperature;
C, take out sample and grind, compaction moulding is put into crucible again and is placed stove to heat again, carries out constant temperature heat treatment, during 900 ℃-1400 ℃ of heat treatment temperatures, and constant temperature 3-10 hour;
D, solid-state reaction and heat treatment can directly be carried out in air or under inert gas atmosphere, (as N 2, Ar or O 2) flow velocity of inflation is 1-500ml/ minute, or carries out under oxygen enrichment or the anoxic in air.
CN90100388A 1987-03-27 1987-03-27 Superconductor and preparation method thereof Pending CN1044003A (en)

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Application Number Priority Date Filing Date Title
CN90100388A CN1044003A (en) 1987-03-27 1987-03-27 Superconductor and preparation method thereof

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CN87102231 Division 1987-03-27

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CN1044003A true CN1044003A (en) 1990-07-18

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100389471C (en) * 2005-08-16 2008-05-21 孙万海 Diamagnetic superconductive materials with CuHz-H+P chlorine oxide and production thereof
CN105155178A (en) * 2015-07-31 2015-12-16 广东大众农业科技股份有限公司 Method for extracting printing and dyeing waste water heat with low cost

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN100389471C (en) * 2005-08-16 2008-05-21 孙万海 Diamagnetic superconductive materials with CuHz-H+P chlorine oxide and production thereof
CN105155178A (en) * 2015-07-31 2015-12-16 广东大众农业科技股份有限公司 Method for extracting printing and dyeing waste water heat with low cost

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