Method for in-situ prevention of stable barium carbonate formation in high T.sub.c ceramic superconductor including the use of iodine or an iodine containing compound

Abstract

Description

h iodine, because of its high solubility in alcohols and other organic solvents.

The hydrolysis reaction step may use any suitable quantity of water. In general, excellent results are obtained with from about two to ten (2-10) equivalents of water.

The concentrated viscous mass or dry resin mass of pre-ceramic material, which results from concentration after the addition of the iodine solution, may be redissolved in any suitable non-polar solvent. Typical solvents include binary mixtures of isopropanol and benzene, xylene, toluene, hexane, cyclohexane, pentane, isopentane or octane. Generally, a weight ratio of isopropanol to the non-polar solvent of about one to six (1:6) to one to thirty (1:30) may be used. The solvent quantity is adjusted to provide the desired fiber drawing or film forming characteristics, or to provide desired characteristics for other methods of producing a shaped product.

Any suitable method may be used for the conversion of the pre-ceramic shapes into superconductors. Initially, the pre-ceramic resin is heated to a temperature that is sufficient to form gamma copper iodide. Preferably, the resin is heated for about two to sixteen (2-16) hours at a temperature from about 100.degree. to 200.degree. C. Then, the temperature is increased to gradually decompose the copper iodide to copper oxide. Preferably, the resin is heated to about 250.degree. to 450.degree. C. for about two to twenty-four (2-24) hours. The resin material is then heated to a much higher temperature to convert it to the superconducting ceramic, preferably to about 800.degree. to 900.degree. C. for about two to ten (2-10) hours. Finally, the material is sintered, preferably at about 920.degree. to 1,000.degree. C. for about two to thirty (2-30) hours, to improve product physical characteristics. In order to maximize oxygen content, the product is then preferably annealed at a temperature of about 360.degree. to 500.degree. C. for a few hours.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Details of the present invention will be further understood upon reference to the following examples, which disclose preferred embodiments of this invention. All parts and percentages are by weight, unless otherwise indicated.

EXAMPLE I

Initially, the required starting materials are prepared. An about three tenths molar (0.3M) solution of yttrium isopropoxide solution in isopropanol is prepared by reacting yttrium metal chips in dry isopropanol with a small amount of mercuric chloride and refluxing for about three (3) days at about 82.degree. C., followed by filtering to obtain clear solution. An about three tenths molar (0.3M) solution of barium isopropoxide in isopropanol is prepared by adding barium metal to dry isopropanol and filtering the solution. Copper ethylhexanoate is mixed in dry isopropanol to produce an about three tenths molar (0.3M) solution. An iodine/isopropanol solution is prepared by dissolving iodine crystal flakes into dry isopropanol. These solutions are stored under dry nitrogen until used.

Stoichiometric amounts of the barium isopropoxide/isopropanol solution and the yttrium isopropoxide/isopropanol are calculated to give a final ceramic composition of YBa.sub.2 Cu.sub.3 O.sub.y. Those amounts are pipetted into a round bottom flask. The solution is refluxed at its boiling point under nitrogen for about one (1) hour. The stoichiometric amount of copper ethylhexanoate/isopropanol solution is then added. A green precipitate forms and is kept at the boiling temperature for an additional eight (8) hours under dry nitrogen. The temperature of the precipitated solution is then reduced to about 60.degree. C. A water/isopropanol solution is prepared using four (4) equivalents of water per mole of yttrium isopropoxide. This solution is added to the flask, gradually dissolving the precipitate and forming a dark green homogeneous solution. This solution is stirred for about four (4) hours at about 60.degree. C. To this solution is then added a quantity of the iodine starting solution sufficient to provide about one and a half (1.5) mole of iodine per mole of yttrium. This solution is immediately concentrated on a rotary concentrator. A brownish highly viscous liquid is obtained. This viscous liquid is further concentrated in a vacuum oven to a tenacious resin mass.

The resin mass is redissolved in sufficient benzene/isopropanol mixture to produce a solution which is about two (2) wt % isopropanol, about eighty-five (85) wt % resin and the balance benzene to total one hundred (100) wt %. Fibers are drawn by hand dipping a glass rod and drawing the viscous solution. The resulting pre-ceramic fibers are found to have sufficient green strength to resist breaking on gentle handling.

The pre-ceramic fibers are calcined in an oxygen atmosphere at about 150.degree. C. for about sixteen (16) hours to form gamma copper iodide, then heat treated at about 400.degree. C. for about twenty-four (24) hours, during which the gamma copper iodide gradually decomposes to copper oxide. No barium carbonate is observed in this material. The fibers are then converted to yttrium barium cuprate superconducting fibers by heat treating in dry oxygen at about 910.degree. C. for about ten (10) hours and then sintered at about 970.degree. C. for up to twenty-four (24) hours followed by annealing at about 400.degree. C. for about eighteen (18) hours to maximize the oxygen content. Fibers having excellent strength and superconducting properties with no observable barium carbonate result.

EXAMPLE II

The experiment of Example I is repeated, except that the step of adding the iodine starting solution to the dark green hydrolized solution is omitted. Stable barium carbonate is found to have formed in the material during the pyrolysis steps. The transport current density of the superconducting fiber product is found to have been adversely affected.

EXAMPLE III

Initially, the required starting materials are prepared. An about one tenth molar (0.1M) solution of erbium isopropoxide solution in isopropanol is prepared by reacting erbium metal chips in dry isopropanol with a small amount of mercuric chloride and refluxing for about three (3) days, followed by filtering to obtain a clear solution. An about one tenth molar (0.1M) solution of barium isopropoxide in isopropanol is prepared by adding barium metal to dry isopropanol and filtering the solution. Copper ethylhexanoate is mixed in dry isopropanol to produce an about one tenth molar (0.1M) solution. An iodine/isopropanol solution is prepared by dissolving iodine crystal flakes into dry isopropanol. These solutions are stored under dry nitrogen until used.

Stoichiometric amounts of the barium isopropoxide/isopropanol solution and the erbium isopropoxide/isopropanol are calculated to give a final ceramic composition of ErBa.sub.2 Cu.sub.3 O.sub.y. Those amounts are pipetted into a round bottom flask. The solution is refluxed at its boiling point under nitrogen for about one (1) hour. The stoichiometric amount of copper ethylhexanoate/isopropanol solution is then added. A green precipitate forms and is kept at the boiling temperature for an additional two (2) hours under dry nitrogen. The temperature of the precipitated solution is reduced to about 50.degree. C. A water/isopropanol solution is prepared using five (5) equivalents of water per mole of erbium isopropoxide. This solution is added to the flask, gradually dissolving the precipitate and forming a dark green homogeneous solution. This solution is stirred for about five (5) hours at about 50.degree. C. To this solution is then added a quantity of the iodine starting solution sufficient to provide about one (1) mole of iodine per mole of erbium. This solution is immediately concentrated on a rotary concentrator. A highly viscous liquid is obtained. This viscous liquid is further concentrated in a vacuum oven to a tenacious resin mass.

The resin mass is redissolved in sufficient toluene/isopropanol mixture to produce a solution which is about two (2) wt % isopropanol, about eighty-five (85) wt % resin and the balance toluene to total one hundred (100) wt %. Fibers are drawn by hand dipping a glass rod and drawing the viscous solution. The resulting pre-ceramic fibers are found to have sufficient green strength to resist breaking on gentle handling.

The pre-ceramic fibers are calcined in an oxygen atmosphere at about 150.degree. C. for about four (4) hours to form gamma copper iodide, then heat treated at about 300.degree. C. for about four (4) hours, during which the gamma copper iodide gradually decomposes to copper oxide. No barium carbonate is observed in the material. The fibers are then converted to erbium barium cuprate superconducting fibers by heat treating in dry oxygen at about 800.degree. C. for about six (6) hours and then sintered at about 920.degree. C. for about twenty (20) hours, then annealed at about 450.degree. C. for about eighteen (18) hours to maximize the oxygen content. Fibers having excellent strength and superconducting properties with no observable barium carbonate result.

EXAMPLE IV

The experiment of Example III is repeated, except that the iodine starting solution is not added to the dark green hydrolized solution. Stable barium carbonate is found to have formed in the material during the pyrolysis steps.

Various specific materials, quantities and conditions have been detailed in the above examples of preferred embodiments. These may be varied, where suitable, with similar results. For example, various additives may be added at appropriate points in the method to cause desired modifications in the final product. Also, shapes other than fibers, such as films, tapes or other structures, may be produced if desired.

Other applications, ramifications and modifications of the above-described method and products will occur to those skilled in the art upon reading this disclosure. Those are intended to be included within the scope of this invention, as defined in the appended claims.

Claims

1. A method of making a pre-ceramic resinous material capable of being converted into a ceramic semiconductor material substantially free from stable barium carbonate and having the general composition RR'.sub.2 Cu.sub.3 O.sub.7-x where R is a rare earth meta, R' is an alkaline earth metal, and x is from 0 to 0.5, the method comprising:

refluxing stoichiometric amounts of a first solution comprising a rare earth isopropoxide and an alkaline earth isopropoxide in isopropanol;

adding to said first solution a stoichiometric amount of a second solution comprising copper ethylhexanoate in isopropanol;

refluxing said first and second solutions to obtain a precipitate;

hydrolyzing said precipitate in a quantity of a first solvent comprising water and isopropanol sufficient to substantially dissolve said precipitate into a precipitate solution;

adding a third solution comprising an iodine compound in an alcohol to said precipitate solution to form a precursor solution having at least about 1 mole of iodine per mole of rare earth metal;

concentrating said precursor solution by removing a sufficient amount of solvents to produce the pre-ceramic resinous material; and

adding a second solvent comprising a nonpolar solvent to the pre-ceramic resinous material to obtain a desired viscosity of the material.

2. The method according to claim 1 wherein said iodine compound is selected from a group consisting of iodine crystals, diiodine pentoxide, silver iodate, silver iodide, and mixtures thereof.

3. The method according to claim 1 wherein said rare earth metal is selected from the group consisting of yttrium, erbium, europium, gadolinium, holmium, lutetium, neodymium, samarium, dysprosium and mixtures thereof.

4. The method according to claim 3 wherein said rare earth metal is yttrium.

5. The method according to claim 1 wherein said alkaline earth metal is barium.

6. A method for making a ceramic superconductor material substantially free from stable barium carbonate and having the general composition RR'.sub.2 Cu.sub.3 O.sub.7-x is a rare earth metal, R' is an alkaline earth metal, and x is from 0 to 0.5, the method comprising:

refluxing stoichiometric amounts of a first solution comprising a rare earth isopropoxide and an alkaline earth isopropoxide in isopropanol;

adding to said first solution a stoichiometric amount of a second solution comprising copper ethylhexanoate in isopropanol;

refluxing said first and second solutions to obtain a precipitate;

hydrolyzing said precipitate in a quantity of a first solvent comprising water and isopropanol sufficient to substantially dissolve said precipitate into a precipitate solution;

adding a third solution comprising an iodine compound in an alcohol to said precipitate solution to form a precursor solution having at least about 1 mole of iodine per mole of rare earth metal;

concentrating said precursor solution by removing a sufficient amount of solvents to produce the pre-ceramic resinous material;

adding a second solvent comprising ak nonpolar solvent to the pre-ceramic resinous material to obtain a desired viscosity of the material;

forming the viscous pre-ceramic resinous material into a desired product shape;

heating the product shape in an oxygen atmosphere to a first temperature for a sufficient time to form gamma copper iodide in said pre-ceramic resinous material;

heating the product shape in an oxygen atmosphere to a second temperature higher than said first temperature for a sufficient time to decompose said gamma copper iodide in said pre-ceramic resinous material to copper oxide;

heating said product shape in dry oxygen at a temperature of from about 800.degree. to 900.degree. C. for from about 2 to 10 hours to convert said pre-ceramic material to said ceramic superconductor material;

sintering said product shape at about 920.degree. to 1,000.degree. C. for about 2 to 24 hours; and

annealing said product shape at a temperature of about 360.degree. to 500.degree. C. for about 4 to 48 hours whereby a final superconducting article ready for use results.

7. The method according to claim 6 wherein said shapes are heated to form said gamma copper iodide at said first temperature of from about 100.degree. to 200.degree. C. for from about 2 to 16 hours.

8. The method according to claim 6 wherein said shapes are heated to decompose said gamma copper iodide to copper oxide at said second temperature of from about 250.degree. to 450.degree. C. for from about 2 to 24 hours.

9. The method according to claim 6 wherein said iodine solution comprises iodine in the form of iodine crystals, diiodine pentoxide, silver iodate, silver iodide, and mixtures thereof.

10. The method according to claim 6 wherein said rare earth metal is selected from the group consisting of yttrium, erbium, europium, gadolinium, holmium, lutetium, neodymium, samarium, dysprosium and mixtures thereof.

11. The method according to claim 10 wherein said rare earth metal is yttrium.

12. The method according to claim 6 wherein said alkaline earth metal is barium.

13. The method according to claim 6 wherein R is yttrium and R' is barium.