WO1989007086A1

WO1989007086A1 - SUPERCONDUCTING Bi-Sr-Ca-Cu OXIDE COMPOSITIONS AND PROCESS FOR MANUFACTURE

Info

Publication number: WO1989007086A1
Application number: PCT/US1989/000354
Authority: WO
Inventors: Jagannatha Gopalakrishnan; Arthur William Sleight; Munirpallam Appadorai Subramanian
Original assignee: E.I. Du Pont De Nemours And Company
Priority date: 1988-02-04
Filing date: 1989-02-03
Publication date: 1989-08-10
Also published as: DK177290A; KR900700389A; EP0398988A1; JPH03502445A; DK177290D0; US4835136A; HUT55319A; AU3184889A; HU891426D0

Abstract

Compositions containing a phase having the formula LA2-x?Nax?CuOz, wherein x is about 0.1 to about 0.3 and z is about 3.8 to about 4.2 are superconducting. Processes for manufacturing such compositions and for using them are disclosed.

Description

TITLE

SUPERCONDUCTING Bi-Sr-Ca-Cu OXIDE COMPOSITIONS AND PROCESS FOR MANUFACTURE

BACKGROUND OF THE INVENTION

Field of the Invention

This invention relates to novel sodium-containing lanthanum, copper oxide compositions which are superconducting and to a process for making them. References

Bednorz and Muller, Z. Phys. B64, 189 (1986), disclose a superconducting phase in the La-Ba-Cu-0 system with a superconducting transition temperature of about 35 K. This disclosure was subsequently confirmed by a number of investigators [see, for example, Rao and Ganguly, Current Science, 56, 47 (1987), Chu et al.. Science 235, 567 (1987), Chu et al., Phys. Rev. Lett. 58, 405 (1987), Cava et al., Phys. Rev. Lett. 58, 408 (1987), Bednorz et al. , Europhys. Lett. 3, 379 (1987)]. The superconducting phase has been identified as the composition La₁__χ (Ba,S ,Ca)_x0₄_ with the tetragonal K₂NiF₄-type structure and with x typically about 0.15 and y indicating oxygen vacancies.

Over 400 scientific papers have appeared covering various aspects of these materials. Only three papers discuss attempts to incorporate an alkali metal into the structure and all three have used potassium. Ogita et al., Japn. J. Appl. Phys. 26, L415 (1987) disclose the preparation of (La_{0 g5}K_{0 05})₂CuO₄_ by mixing prescribed amounts of La₂0₃, CuO and K₂C0₃ , preheating the mixture at 700°C in air for 12 hours and sintering at 1000°C in air for 2 hours. The (La₀ _ _g5K_{0 > 05} )₂Cu0₄ product was found to be of the orthorhombic K₂NiF₄ type structure and was a semiconductor and not a superconductor down to liquid helium temperature.

Fine et al., "Chemistry of High-Temperature Superconductors", ACS Symposium Series 351, Edited by D. L. Nelson, M. S. hittingham and T. F. George, American Chemical Society, Wash., D. C. (1987), Chapter 10, discuss the results of a study on the effect of nominal composition on superconductivity in La₂Cu0₄ . They mixed the oxides of La₂0₃ and CuO in appropriate amounts to form samples of the with nominal stoichiometries La₂Cu0₄_ and La_{χ g}Cu0₄_ respectively. Each mixture of starting materials was divided into three portions and 5% K₂ ^C0 ₃ ^anc 10% K₂C0₃ were added to the second and third portions of each mixture. A sample of nominal composition La_{χ 9}K_{Q j}CuO., was also prepared from appropriate amounts of La₂0₃ , CuO, and K₂C0₃. The x-ray powder diffraction data indicated that all compositions were single phase or nearly single phase and the authors suggested that either the K₂0 sublimed out of the sample or was present in a poorly crystalline form. The lattice parameters calculated for all seven samples were the same within two standard deviations and were consistent with the published values for the lattice p rarameters for La 2,CuO4.-y . The authors state that the implications are "that in all cases the bulk of the sample is stoichiometric, La₂Cu0₄ , and that a solid solution of the type La₂__χK_χCu0₄ did not form".

Fine et al., Phys. Rev. B 36, 5716 (1987), report on the same study discussed in their ACS Symposium Series 351 chapter along with data on an eighth sample of nominal composition La_{j^ 8}Cu0₄_ and state the same conclusions.

There is no disclosure that substitution of any alkali metal into La₂Cu0₄ will result in a single phase composition exhibiting superconductivity above liquid helium temperatures and no disclosure of a composition of the formula La₂__χA_χCu0₄_ where A is an alkali metal other than potassium.

SUMMARY OF THE INVENTION

This invention provides novel superconducting compositions having a phase with the formula La 2, - XNaXCuOz where x is from about 0.1 to about 0.3 and z is from about 3.8 to about 4.2; said composition having a superconducting transition temperature above 10 K.

This invention also provides a process for making these compositions, said process consisting essentially of heating a mixture of stoichiometric quantities of La₂0₃, Na₂0₂ and CuO in a sealed metal container at about 850°C to about 900°C for about 12 to about 24 hours. Preferred is the process in which the sealed metal container is subjected to external pressure, typically of the order of 3 kbar (100 MPa) since it results in compositions having superconducting transition temperatures of 20 K or higher.

DETAILED DESCRIPTION OF THE INVENTION

The superconducting phase of the composition of this invention has the nominal formula La, 2 - XNaXCuOz ,' wherein x is from about 0.1 to about 0.3, and wherein the phase has the tetragonal K₂NiF₄-type structure with the 14/mmm space group as determined by X-ray powder diffraction measurements.

The superconducting composition of the invention can be prepared by the following process: Stoichiometric quantities of La₂0₃, Na₂0₂ and CuO are mixed, for example, by grinding them together in a mortar and heating them in a controlled atmosphere. It has been found that the composition of this invention is produced only when the atmosphere in which the reactants are heated is carefully controlled. One way to accomplish this controlled atmosphere is to place the reactants in a tube made of a non-reacting metal such as gold and then sealing the tube by welding. The sealed tube is then placed in a furnace and heated at about 850°C to about 900°C for about 12 to 24 hours. The power to the furnace is then turned off and the tube is furnace-cooled to 100°C and then removed from the furnace and quenched to ambient temperature. The tube is then opened and the black powder product recovered. Compositions prepared in this manner have superconducting transition temperatures from about 10 K to about 15 K.

Preferred is the process in which the sealed container is subjected to external pressure, typically of the order of 3 kbar (100 MPa) before the heating commences and during the heating step. The compositions prepared in this manner have superconducting transition temperatures exceeding 15 K, typically in the range of about 20 K to about 30 K.

When the relative amounts of reactants are chosen consistent with the formula La 2,- XNaXCuOz ,' wherein x is from about 0.1 to about

0.3 and z is from about 3.8 to about 4.2, the product of the process of the invention is a single phase and is the composition of the invention. When the relative amounts of reactants are chosen such that x appreciably exceeds 0.3, e.g., such that x « 0.4, the product is not a single phase but is a mixture comprised of the composition of the invention and other phases.

Superconductivity can be confirmed by observing magnetic flux exclusion, i. e., the Meissner effect. This effect can be measured by the method described in an article by E. Polturak and B. Fisher in Physical Review B, 36, 5586(1987).

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. Thus, by cooling the composition in the form of a wire or bar to a temperature below the superconducting transition temperature, e.g., at or below about 30 K, preferably at or below about 10 K, by exposing the material to liquid helium 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. To provide exceptionally high magnetic fields with minimal power losses, the wire mentioned previously could be wound to form a coil which would be exposed to liquid helium before inducing any current into the coil.

EXAMPLES OF THE INVENTION

EXAMPLE 1 2.9323 g of La₂0₃ , 0.0780 g of Na₂0₂ and 0.7955 g CuO were ground together in an agate mortar for 30 min. inside a dry box. The resulting powder was loaded in a gold tube (3/8" dia and 5" length) and the tube was sealed by welding it. The tube was then heated to 850°C for 12 hours in a furnace. The tube was cooled to 100°C in the furnace, then removed from the furnace and quenched to room temperature. The tube was cut open and the black powder product was recovered. The results of an X-ray powder diffraction pattern of the product indicate that the L _{j 8}Na_{0 2}CuO_z product has tetragonal symmetry with a K₂NiF₄-type structure. No other phase was detected. The d-spacings, the relative intensities and the indices of the observed reflections are shown in Table I.

Meissner effect measurements showed that the compound is a superconductor with a transition temperature, T , of about 15 K.

hkl 101 004 103 110 006 105 114 200 116 107 211 008 204

213 EXAMPLE 2 2.7694 g of La₂0₃ , 0.1170 g of Na₂0₂ and 0.7955 g CuO were ground together in an agate mortar for 30 min. inside a dry box. The resulting powder was loaded in a gold tube (3/8" dia and 5" length) and the tube was sealed by welding it. The tube was then heated to 850°C for 12 hours in a furnace. The tube was cooled to 100°C in the furnace, then removed from the furnace and quenched to room temperature. The tube was cut open and the black powder product was recovered. The X-ray powder diffraction pattern of the product is essentially the same as that shown in Table I and indicates that the La_{χ 7}Na_{0 3} CuO_z product is a single phase and has tetragonal symmetry with the K₂NiF₄-type structure.

Meissner effect measurements of the powder showed a superconducting phase transition of about 12 K.

EXAMPLE 3 2.6065 g of La₂0₃, 0.1560 g of Na₂0₂ and 0.7955 g CuO were ground together in an agate mortar for 30 min. inside a dry box. The resulting powder was loaded in a gold tube (3/8" dia and 5" length) and the tube was sealed by welding it. The tube was then heated to 850°C for 12 hours in an autoclave. The tube was cooled in the autoclave to 100°C, then removed from the autoclave and quenched to room temperature. The tube was cut open and the black powder product was recovered. The results of an X-ray powder diffraction pattern of the product indicate that the product is a mixture of a tetragonal K₂NiF₄-type phase having essentially the same powder diffraction pattern as that shown in Table I and NaCu0₂.

EXAMPLE 4

2.7694 g of La₂0₃ , 0.1170 g of Na₂0₂ and 0.7955 g of CuO were ground together in an agate mortar for 30 min inside a dry box. The resulting powder was loaded in a gold tube (3/8" dia and 5" length) and the tube was sealed by welding it. The tube was subjected to an external pressure of 3 kbar (100 MPa) and heated to 900°C for 12 hours in an autoclave. The tube was cooled to 100°C in the autoclave, then removed from the autoclave and quenched to room temperature. The tube was cut open and the black powder product was recovered. The X-ray powder diffraction pattern of the product is essentially the same as that shown in Table I and indicates that the La. ,Na_n , CuO product is a single phase and has tetragonal symmetry with K₂NiF₄-type structure.

Meissner effect measurements showed the compound is a superconductor with a transition temperature, T_c , of about 30 K.

EXAMPLE 5 2.4436 g of La₂0₃ , 0.1950 g of Na₂0₂ and 0.7955 g of CuO were ground together in an agate mortar for 30 min inside a dry box. The resulting powder was loaded in a gold tube (3/8" dia and 5" length) and the tube was sealed by welding it. The tube was subjected to an external pressure of 3 kbar (100 MPa) and heated to 900°C for 12 hours in an autoclave. The tube was cooled to 100°C in the autoclave, then removed from the autoclave and quenched to room temperature. The tube was cut open and the black powder product was recovered. The X-ray powder diffraction pattern of the product indicates that the product is a mixture of a tetragonal K₂NiF₄-type phase having essentially the same powder diffraction pattern as that shown in Table I and NaCu0₂.

Meissner effect measurements of the powder showed a superconducting phase transition at about 30 K.

EXAMPLE 6 2.6065 g of La₂0₃ , 0.1560 g of Na₂0₂ and 0.7955 g CuO were ground together in an agate mortar for 30 min. inside a dry box. The resulting powder was loaded in a gold tube (3/8" dia and 5" length) and the tube was sealed by welding it. The tube was subjected to an external pressure of 3kbar (100 MPa) and heated to 900°C for 12 hours in an autoclave. The tube was cooled to 100°C in the autoclave, then removed from the autoclave and quenched to room temperature. The tube was cut open and the black powder product was recovered. The X-ray powder diffraction pattern of the product indicates that the product is a mixture of a tetragonal K₂NiF₄-type phase having essentially the same powder diffraction pattern as that shown in Table I and NaCu0₂.

Meissner effect measurements of the powder showed a superconducing phase transition at about 30 K.

EXAMPLE 7 2.9323 g of La₂0₃ , 0.0780 g of Na₂0₂ and 0.7955 g CuO were ground together in an agate mortar for 30 min. inside a dry box. The resulting powder was loaded in a gold tube (3/8" dia and 5" length) and the tube sealed by welding it. The tube was subjected to an external pressure of 3kbar (100 MPa) and heated to 900°C for 12 hours in an autoclave. The tube was cooled to 100°C in the autoclave, then removed from the autoclave and quenched to room temperature. The tube was cut open and the black powder product was recovered. The X-ray powder diffraction pattern of the product is essentilly the same as that shown in Table I and indicates that the La_{χ 8}Na_{0 2}CuO_z product is a single phase and has tetragonal symmetry with the K₂NiF₄-type structure.

Meissner effect showed the compound is a superconductor with a transition temperature of about 20 K.

Claims

CLAIMSThe Invention Being Claimed Is;

1. A superconducting composition containing a metal oxide phase of the formula La₂__χNa_χCuO_z wherein x is a value from about 0.1 to about 0.3; z is a value from about 3.8 to about 4.2; and said phase has the tetragonal K₂NiF₄-type structure containing the 14/mmm space group as determined by X-ray powder diffraction measurements, said composition having a superconducting transition temperature above 10K.

2. A superconducting composition as in Claim 1 wherein z has a value of about 4.

3. A process for making superconducting compositions consisting essentially of mixing stoichiometric quantities of La₂0₃ , Na₂0₂ and Cu; heating said mixture in a sealed container at about 850°C to about 900°C for about 12 to about 24 hours to form an oxide composition; furnance-cooling said composition to about 100°C; and thereafter quenching said composition at ambient temperature.

4. A process as in Claim 3 wherein said sealed container while being heated is subjected to an external pressure of about 3 kbar.

5. A method for conducting an electrical current within a conductor material without electrical resistive losses comprising the steps of: cooling a conductor material composed of a composition containing a metal oxide phase of the formula La₂__xNa_χCuO_z wherein x is a value from about 0.1 to about 0.3; z is a value from about 3.8 to about 4.2; and said phase has the tetragonal K₂NiF₄-type structure containing the 14/mmm space group as determined by X-ray powder diffractive measurements, to a temperature at or below about 10K; initiating a flow of electrical current within said conductor material while maintaining said material at or below 10K at which said material becomes superconductive.

6. A method as in Claim 5 wherein said conductor material is cooled to a temperature at or below about 30 K.

7. A method as in Claim 5 wherein said conductor material is in the form of a coiled wire.