EP0441903A1 - Compositions d'oxyde metallique supraconducteur et procedes de fabrication et utilisation - Google Patents

Compositions d'oxyde metallique supraconducteur et procedes de fabrication et utilisation

Info

Publication number
EP0441903A1
EP0441903A1 EP19900903287 EP90903287A EP0441903A1 EP 0441903 A1 EP0441903 A1 EP 0441903A1 EP 19900903287 EP19900903287 EP 19900903287 EP 90903287 A EP90903287 A EP 90903287A EP 0441903 A1 EP0441903 A1 EP 0441903A1
Authority
EP
European Patent Office
Prior art keywords
temperature
composition
superconducting
heated
compositions
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP19900903287
Other languages
German (de)
English (en)
Other versions
EP0441903A4 (en
Inventor
Norman Herron
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
EIDP Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Publication of EP0441903A1 publication Critical patent/EP0441903A1/fr
Publication of EP0441903A4 publication Critical patent/EP0441903A4/en
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F1/00—Methods of preparing compounds of the metals beryllium, magnesium, aluminium, calcium, strontium, barium, radium, thorium, or the rare earths, in general
    • 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
    • C04B35/4512—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 thallium oxide
    • 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

Definitions

  • This invention relates to novel
  • superconducting phase has been identified as the composition La 1-x (Ba, Sr, Ca) x CuO 4-y with the tetragonal K 2 NiF 4 -type structure and with x typically about 0.15 and y indicating oxygen vacancies.
  • Bi-Sr-Cu-O system A pure phase was isolated for the composition Bi 2 Sr 2 Cu 2 O 7+ ⁇ .
  • the material made from ultrapure oxides has a superconducting transition with a midpoint of 22 K as determined from resistivity measurements and zero resistance below 14 K.
  • the material made from commercial grade oxides has a superconducting transition with a midpoint of 7 K.
  • Tl-Ba-Cu-O system in samples which have nominal compositions Tl 2 Ba 2 Cu 3 O 8 + x and TlBaCu 3 O 5 .5+x .
  • the samples were prepared by mixing and grinding appropriate amounts of BaCO 3 and CuO with an agate mortar and pestle. This mixture was heated in air at 925°C for more than 24 hours with several intermediate grindings to obtain a uniform black oxide Ba-Cu oxide powder which was mixed with an appropriate amount of Tl 2 O 3 , completely ground and pressed into a pellet with a diameter of 7 mm and a thickness of 1-2 mm.
  • the pellet was then put into a tube furnace which had been heated to 880-910°C and was heated for 2-5 minutes in flowing oxygen. As soon as it had slightly melted, the sample was taken from the furnace and quenched in air to room temperature. It was noted by visual inspection that Tl 2 O 3 had partially volatilized as black smoke, part had become a light yellow liquid, and part had reacted with Ba-Cu oxide forming a black, partially melted, porous material.
  • Tl-Ca-Ba-Cu-O system in samples which have nominal compositions Tl 2 Ca 2 BaCu 3 O 9+x with onset of superconductivity at 120 K.
  • Tl 2 Ba 2 Ca 2 Cu 3 O 10 and Tl 2 Ba 2 CaCu 2 O 8 both with onset of superconductivity near 120 K. C. C.
  • Torardi et al., Science 240, 631 (1988) disclose the preparation of Tl 2 Ba 2 Ca 2 Cu 3 O 10 with an onset of superconductivity of 125 K.
  • These compositions have an onset of superconductivity of at least 70 K.
  • Tl:Ca:Ba:Cu in the superconductor vary from
  • a is from about 2 to about 3
  • b is about 4
  • c is about 5
  • y is from about 1/2 to about 2.
  • the onset of superconductivity for these compositions is at a temperature of at least 130 K.
  • These superconducting compositions can be prepared by heating a mixture of the oxides of Tl, Ca and Cu and the peroxide of Ba or a
  • precursor oxide mixture prepared from these oxides the relative amounts of the oxides chosen so that the atomic ratio Tl:Ba:Ca:Cu is l:a:b:c, to a temperature of about 940°C to about 980°C, maintaining that temperature for about 5 minutes or more, said heating being carried out in a controlled atmosphere, e. g., in a sealed tube made of a non-reacting metal such as gold, which prevents any of the reactants including the metals and oxygen from escaping.
  • a controlled atmosphere e. g., in a sealed tube made of a non-reacting metal such as gold, which prevents any of the reactants including the metals and oxygen from escaping.
  • FIG. 1 shows a plot of the flux
  • composition of this invention excluded by a composition of this invention as a function of temperature.
  • the superconducting compositions of this invention can be prepared by the following process.
  • a is about 2 to about 4
  • b is from about 7/2 to about 5
  • c is from about 9/2 to about 7
  • x (a + b + c + y) where y is from about 1/2 to about 3.
  • a is about 2 to about 4
  • b is from about 7/2 to about 5
  • c is from about 9/2 to about 7
  • x (a + b + c + y) where y is from about 1/2 to about 3.
  • a is about 2 to about 4
  • b is from about 7/2 to about 5
  • the oxide mixture can be prepared directly by choosing quantities of the oxide reactants Tl 2 O 3 , CaO and CuO and the peroxide BaO 2 such that the atomic ratio Tl:Ba:Ca:Cu is l:a:b:c and mixing them, for example, by grinding them together in a mortar.
  • a precursor oxide mixture can be prepared by choosing quantities of the oxide reactants Tl 2 O 3 , CaO and CuO and the peroxide BaO 2 such that the atomic ratio
  • Tl:Ba:Ca:Cu is l:a:b:c.
  • the barium peroxide, calcium oxide and copper oxide are ground
  • this grey mixture is then heated in an alumina crucible in a muffle furnace in air, the temperature being increased from ambient temperature, about 20°C, to about 800°C in a period of about 2 hours. The temperature is held at about 800oC for 1 hour. The sample is then cooled and the black powder is recovered. This powder is re-ground and ground together with the thallium oxide to give the precursor oxide mixture.
  • the oxide mixture is then heated in a controlled atmosphere.
  • a controlled atmosphere is to place the oxide mixture in a tube made of a non-reacting metal such as gold and then sealing the tube by crimping or, preferably, by welding or fusing.
  • the precursor oxide mixture is less destructive of the gold tubes and is preferred for this reason.
  • the sealed tube is placed in a furnace and heated to a temperature of about 940°C to about 980oC and maintained at a
  • the black shiny platelets have proven to be single crystals of known materials, e. g., Tl-Ba-Ca-Cu compositions with Tl:Ba:Ca:Cu atomic ratios of 1:2:1:2 and 1:2:2:3 with lesser T c 's.
  • Resistivity measurements on the as prepared ingot shows onset at about 135 K and zero resistance at about 116 K.
  • the superconductivity arises from the bulk of the composition. Based on flux exclusion measurements at least 30% of each of the samples is superconducting. X-ray powder diffraction typically gives very weak lines.
  • the superconducting compositions of this invention can be used to conduct current extremely efficiently or to provide a magnetic field for magnetic imaging for medical purposes.
  • the composition in the form of a wire or bar can be used to conduct current extremely efficiently or to provide a magnetic field for magnetic imaging for medical purposes.
  • superconducting transition temperature (T c ) in a manner well known to those in this field, and initiating a flow of electrical current, one can obtain such flow without any electrical resistive losses.
  • the wire mentioned previously could be wound to form a coil which would be cooled to a temperature below the superconducting transition temperature before inducing any current into the coil.
  • Such fields can be used to levitate objects as large as railroad cars.
  • These superconducting compositions are also useful in Josephson devices such as SQUIDS (superconducting quantum interference devices) and in instruments that are based on the Josephson effect such as high speed sampling circuits and voltage standards.
  • Flux exclusion measurements showed the onset of superconductivity at about 130 K.
  • Example 2 0.456 g of Tl 2 O 3 , 1.020 g of BaO 2 , 0.448 g of CaO and 0.960 g of CuO, corresponding to a Tl:Ba:Ca:Cu atomic ratio of
  • Flux exclusion measurements showed the onset of superconductivity at about 130 K.
  • Examples 3 and 4 were carried out essentially as described for Example 2 except that in Example 3, 0.456 g of Tl 2 O 3 , 0.680 g of BaO 2 , 0.448 g of CaO and 0.960 g of CuO,
  • Tl:Ba:Ca:Cu atomic ratio of 1:2:4:6 were ground to form a fine grey powder and in Example 4, 0.456 g of Tl 2 O 3 , 1.020 g of BaO 2 , 0.448 g of CaO and 0.800 g of CuO,
  • Flux exclusion measurements showed the onset of superconductivity at about 130 K for Example 3 and at about 132 K for Example 4.
  • a precursor oxide mixture was prepared by grinding together 5.10 g of BaO 2 , 2.25 g of CaO and 4.00 g of CuO. This grey mixture was then heated in an alumina crucible in a muffle furnace in air from ambient temperature, about 20°C, to 800°C in a period of 2 hours. The temperature was held at 800°C for 1 hour and then reduced to ambient. The black powder product was recovered and re-ground. The powder contained the elements Ba:Ca:Cu in the atomic ratio 3:4:5.
  • this black powder was ground together with 0.456 g of Tl 2 O 3 to give a material with the atomic ratio of Tl:Ba:Ca:Cu of 1:3:4:5.
  • This powder was loaded into gold tube, about 3 inches long and 1/4 inch in diameter (7.6 cm long and 0 .64 cm in diamete r ) .
  • the tube was sealed at both ends by fusing and placed on an alumina boat which was placed in a horizontal quartz tube furnace.
  • Heating was ca r r i ed in the following manner.
  • the temperature was increased from room temperature to 700°C at a rate of about 3°C/min.
  • the temperature was then increased from 700°C to 977°C at a rate of about 18.5°C/min.
  • the sample cooled to 950°C over the next 5 minutes and was maintained at 950°C for 10 min.
  • the sample was then cooled in the furnace to 600°C at a rate of about 10°C/min.
  • the sample was then removed from the furnace and cooled to room temperature.
  • the recovered material is a shiny grey-black metallic ingot with a surface
  • Flux exclusion measurements showed the onset of superconductivity at about 132 K.
  • a precursor oxide mixture was prepared by grinding together 1.020 g of BaO 2 , 0.448 g of CaO and 0.800 g of CuO. This grey mixture was then heated in an alumina crucible in a muffle furnace in air from ambient temperature, about 20°C, to 800°C in a period of 2 hours. The temperature was held at 800oC for 1 hour and then reduced to ambient. The black powder product was recovered and re-ground. The powder contained the elements Ba:Ca:Cu in the atomic ratio 3:4:5.
  • the tube was sealed at both ends by fusing and placed on an alumina boat which was placed in a horizontal quartz tube furnace.
  • Heating was carried in the following manner. The temperature was increased from room temperature to 700°C at a rate of about 3oC/min. The temperature was then increased from 700°C to 968°C at a rate of about 25°C/min. The sample was maintained at 968°C for 15 min. The sample was then cooled in the furnace to 600oC at a rate of about 10oC/min. The sample was then removed from the furnace and cooled to room temperature.
  • the recovered material is a shiny grey-black metallic ingot with a surface
  • Flux exclusion measurements showed the onset of superconductivity at about 130 K.
  • Heating was carried in the following manner. The temperature was increased from room temperature to 700°C at a rate of about 3°C/min. The temperature was then increased from 700°C to 977°C at a rate of about 25°C/min. The sample was maintained at 977°C for 15 min. The sample was then cooled in the furnace to 600°C at a rate of about 10°C/min. The sample was then removed from the furnace and cooled to room temperature.
  • the recovered material is a shiny grey-black metallic ingot with a surface
  • Heating was carried in the following manner. The temperature was increased from room temperature to 700°C at a rate of about 3oC/min. The temperature was then increased from 700°C to a maximum temperature, T max , at a specified rate. The sample was maintained at T max for a specified time and was then cooled in the furnace to 600°C at a rate of 10°C/min except for Example 12 for which the rate was 50°C/min. The sample was then removed from the furnace and cooled to room temperature.
  • the recovered material is a shiny grey-black metallic ingot with a surface
  • the specified rate of heating from 700°C to T max , the temperature T max , the time for which the temperature was maintained at T max and the temperature of the onset of superconductivity are shown in Table II.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Ceramic Engineering (AREA)
  • Materials Engineering (AREA)
  • Structural Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Inorganic Chemistry (AREA)
  • Compositions Of Oxide Ceramics (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Oxygen, Ozone, And Oxides In General (AREA)

Abstract

Compositions ayant la formule nominale TlBaaCabCucOx, dans laquelle a est compris entre 2 et 4 environ, b est compris entre 7/2 et 5 environ, c est compris entre 9/2 et 7 environ, x = (a + b + c + y), où y est compris entre 1/2 et 3 environ, ces compositions étant supraconductrices. Des procédés de production de telles compositions et d'utilisation de ces compositions sont également décrits.
EP19900903287 1988-11-02 1989-10-16 Superconducting metal oxide compositions and processes for manufacture and use Withdrawn EP0441903A4 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US26618088A 1988-11-02 1988-11-02
US266180 1988-11-02

Publications (2)

Publication Number Publication Date
EP0441903A1 true EP0441903A1 (fr) 1991-08-21
EP0441903A4 EP0441903A4 (en) 1991-12-04

Family

ID=23013507

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19900903287 Withdrawn EP0441903A4 (en) 1988-11-02 1989-10-16 Superconducting metal oxide compositions and processes for manufacture and use

Country Status (8)

Country Link
EP (1) EP0441903A4 (fr)
JP (1) JPH04501553A (fr)
KR (1) KR900701659A (fr)
AU (1) AU5096990A (fr)
CA (1) CA2002022A1 (fr)
DK (1) DK72091A (fr)
NO (1) NO911667L (fr)
WO (1) WO1990005384A1 (fr)

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1990001461A1 (fr) * 1988-08-10 1990-02-22 E.I. Du Pont De Nemours And Company Compositions d'oxyde metallique supraconducteur et procedes de fabrication et d'utilisation
JPH07138019A (ja) * 1993-11-16 1995-05-30 Nec Corp タリウム系酸化物超伝導体の製造方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1168762A (fr) * 1981-06-22 1984-06-05 Osamu Michikami Methode de fabrication de jonctions tunnel josephson

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
NATURE vol. 334, August 11, 1988, LONDON, GB pages 510 - 511; H. IHARA ET AL.: 'A ne high-Tc TIBA2Ca3Cu4O11 superconductor with Tc >120K ' *
PHYSICA C vol. 159, no. 6, August 1, 1989, AMSTERDAM, NL pages 801 - 810; P.L. GAI ET AL.: 'Microstructure and microchem. of defects and interfaces in T12Ba2Ca3Cu4O12 , TIBa2Ca4Cu5O13 and (TI,Pb)Sr2Can-1CunO2n+3(n=2,3)oxide superconductors ' *
PROCEEDINGS OF THE INT. SYMPOSIUM ON SUPERCONDUCTIVITY August 29, 1988, TOKYO, JP pages 793 - 798; H. IHARA ET AL.: 'New T1-Ba-Ca-Cu-O (1234, 1245 and 2234) Superconductors with very high Tc ' *
See also references of WO9005384A1 *

Also Published As

Publication number Publication date
JPH04501553A (ja) 1992-03-19
NO911667D0 (no) 1991-04-26
KR900701659A (ko) 1990-12-04
DK72091D0 (da) 1991-04-19
DK72091A (da) 1991-04-19
NO911667L (no) 1991-04-26
WO1990005384A1 (fr) 1990-05-17
EP0441903A4 (en) 1991-12-04
AU5096990A (en) 1990-05-28
CA2002022A1 (fr) 1990-05-02

Similar Documents

Publication Publication Date Title
US4894361A (en) Superconducting metal oxide Tl-Pb-Ca-Sr-O compositions and processes for manufacture and use
US4929594A (en) Superconducting composition Tl2 Ba2 CuO6+x and process for manufacture
EP0432187B1 (fr) Compositions metal-oxyde supraconductrices
US5017554A (en) Superconducting metal oxide Tl-Pb-Ca-Sr-Cu-O compositions and processes for manufacture and use
US5264414A (en) Superconducting metal oxide (Tl,Bi)1 Sr2 Ca2 Cu3 O.sub.y
US6855670B1 (en) Superconducting bismuth-strontium-calcium-copper oxide compositions and process for manufacture
EP0489087B1 (fr) Compositions d'oxyde metallique supraconductrices et procedes de fabrication et d'utilisation de celles-ci
EP0441903A1 (fr) Compositions d'oxyde metallique supraconducteur et procedes de fabrication et utilisation
EP0441893B1 (fr) Compositions supraconductrices d'oxyde metallique, leurs procedes de fabrication et leur utilisation
EP0428630B1 (fr) Compositions d'oxyde metallique supraconducteur et procedes de fabrication et d'utilisation
US5219833A (en) Process for manufacturing single phase Tl2 Ba2 CuO6-x superconductors
US4835136A (en) Lanthanum: sodium copper superconducting metal oxide compositions and process for manufacture
Subramanian et al. Superconducting metal oxide (Tl, Bi) 1 Sr 2 Ca 2 Cu 3 O y
WO1991011391A1 (fr) Compositions d'oxydes metalliques supraconductrices

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 19910417

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT CH DE FR GB IT LI NL

RIN1 Information on inventor provided before grant (corrected)

Inventor name: HERRON, NORMAN

18W Application withdrawn

Withdrawal date: 19911001

A4 Supplementary search report drawn up and despatched

Effective date: 19911011

AK Designated contracting states

Kind code of ref document: A4

Designated state(s): AT CH DE FR GB IT LI NL

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

R18W Application withdrawn (corrected)

Effective date: 19911001