CA1339692C - Melt-produced high temperature superconductor and processes for making same - Google Patents
Melt-produced high temperature superconductor and processes for making sameInfo
- Publication number
- CA1339692C CA1339692C CA000573616A CA573616A CA1339692C CA 1339692 C CA1339692 C CA 1339692C CA 000573616 A CA000573616 A CA 000573616A CA 573616 A CA573616 A CA 573616A CA 1339692 C CA1339692 C CA 1339692C
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- 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
- C04B35/622—Forming processes; Processing powders of inorganic compounds preparatory to the manufacturing of ceramic products
- C04B35/653—Processes involving a melting step
-
- 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
- C04B35/4504—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 rare earth oxides
-
- 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
- H10N60/0268—Manufacture or treatment of devices comprising copper oxide
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S505/00—Superconductor technology: apparatus, material, process
- Y10S505/80—Material per se process of making same
- Y10S505/801—Composition
- Y10S505/809—Ceramic
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S505/00—Superconductor technology: apparatus, material, process
- Y10S505/80—Material per se process of making same
- Y10S505/81—Compound
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S505/00—Superconductor technology: apparatus, material, process
- Y10S505/80—Material per se process of making same
- Y10S505/815—Process of making per se
-
- 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
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S505/00—Superconductor technology: apparatus, material, process
- Y10S505/80—Material per se process of making same
- Y10S505/815—Process of making per se
- Y10S505/822—Shaping
Abstract
A class of melt-produced, high temperature superconductors and processes of making same are provided. The superconductor has a preferred composition of R-Ba-Cu-O wherein R is chosen from the group of rare earth metals excluding: Praseodyium;
Cerium; and Terbium. The process is carried out at a relatively low temperature of about 950°C, and the process allows fabrication of melt-produced high temperature superconductors of arbitrary shape.
Cerium; and Terbium. The process is carried out at a relatively low temperature of about 950°C, and the process allows fabrication of melt-produced high temperature superconductors of arbitrary shape.
Description
13~9~
S P E C I F I C A T I O N
"MELT-PRODUCED HIGH TEMPERATURE SUPERCONDUCTOR
AND PROCESSES FOR MAKING SAME"
The present invention relates generally to high temperature superconductors. More specifically, the present invention relates to a melt-produced, high temperature superconductor and processes for making same.
Recently, there has been much work done on the utilization of ternary oxides containing copper, barium, and rare earth elements for superconductivity at temperatures above 90~K with the belief that superconductivity at or above room temperature is possible. Some of this work has centered on the utilization of a yttrium (Y)-barium tBa)-copper (Cu)-oxygen (O) system.
Current developments of the Y-Ba-Cu-O class of ceramic superconductors have yielded optimistic results. These systems are typically created utilizing bulk materials which are powders or very small granule substances. These powders must be compressed to facilitate measurements and are relatively intractable.
As can be appreciated, the structure of these substances is not conducive to the manufacturing of components from these ceramic superconductors.
A melt-produced, high temperature superconductor would be desirable for many reasons.
Melt-produced superconductors would: (1) allow the growth of large bulk single crystals--this is important because it could facilitate the discovery of the correct theory on superconductivity; (2) provide low cost processing and manufacturability; (3) allow components to be cast in any shape; (4) allow the addition of other components to the melt-produced hi~h temperature superconductors--this would allow one to 2 1~396~2 create an extrudeable composition allowing the superconductor to be useful in the manufacture of superconducting wires, magnets, etc.; and (5) the inventors believe, allow for high critical currents in the high temperature superconductor allowing the generation of large currents therethrough.
Accordingly, there is a need for melt-produced high temperature superconductors and processes for making same.
The present invention provides melt-produced high temperature superconductors and processes for making same that are unique to date among high temperature superconductors.
The present invention preferably comprises a composition having the following formula:
R-Ba-Cu-0 wherein:
R is chosen from the group of rare earth metals excluding: Praseodymium (Pr); Cerium (Ce); and Terbium (Tb).
Preferably, R is chosen from the group of rare earth metals that include: Yttrium (Y);
Gadolinium (Gd); Erbium (Er); Holmium (Ho); Neodymium (Nd); Samarium (Sm); Europium (Eu); Ytterbium (Yb);
Dysprosium (Dy); Thulium (Tm); and Lutetium (Lu). In a preferred embodiment, R is Yttrium.
In a preferred embodiment, the melt-produced superconductor has the following nominal stoichiometry:
Rsa2Cu3O6 5 wherein:
R is a rare earth metal not including: Pr;
Tb; or Ce. Preferably, R is chosen from the group of rare earth metals that include: Yttrium (Y);
Gadolinium (Gd); Erbium (Er); Holmium (Ho); Neodymium 13 3 9 b ~ 2 (Nd); Samarium (Sm); Europium (Eu); Ytterbium (Yb);
Dysprosium (Dy); Thulium (Tm); and Lutetium (Lu).
In a preferred embodiment, the melt-produced superconductor has the following nominal stoichlometry:
YBa2Cu306 5.
A method of making the melt-produced, high temperature superconductors is also provided. The method is based on reaction between molten Ba-Cu oxides and solid rare earth oxides, rare earth barium oxides, rare earth copper oxides, or rare earth-Ba-Cu oxides.
The method allows melt-producing to be carried out at a relatively low temperature of approximately 950~C. The method further allows the use of precursor materials for the superconductor in the form of pellets, powders, or pellets and powders.
The method comprises the steps of: mixing and grinding BaC03 and CuO with nominal compositions of Ba2Cu305, BaCu304, BaCu405, BaCu607, and BaCu12013;
pressing the resultant mixture into a pellet, if necessary; placing the pellet or powder on a pellet or powder chosen from the group consisting of R203, or R-Ba-oxides (e.g. RBaO2 5), R-Cu-oxides, or R-Ba-Cu-g. R1.2BaO.8CuO3 6) wherein R is chosen fromthe group of rare earth metals excluding: Tb, Pr, and Ce; heating the pellets and/or powders to a temperature of approximately 950~C; and removing a melt-produced superconductor from the remaining pellet or powder at the bottom.
In an embodiment of the method, a mixture of BaC03 and CuO with nominal composition of BaCu304 is ground and heated to approximately 900~C in air for about 12 hours. The heated mixture is reground and pressed into pellets. A mixture of Y203, BaC03, and CuO with nominal composition of Y1 2Ba8 8CuO3 6 is ground and heated at approximately 950 C in air for 133~2 about 12 hours. The resultant material is reground.
The black BaCu3O4 pellet (of arbitrary shape) is placed (g ) Yl.2BaO.8CuO3.6 powder, and is heated in flowing ~2 at about 950 C for 12 hours, then at 650~C
for 4 hours, then cooled down to 200~C in about 1-2 hours, then removed from the furnace. A black melt-produced superconductor is formed which is embedded in the (green) Yl 2BaO 8CuO3 6 powder and separated from it (the recovered Y1 2BaO 8CuO3 6 powder may be reused if desired).
Accordingly, an advantage of the present invention is to provide a melt-produced, high temperature superconductor and method of making same.
A further advantage of the present invention is to provide a method that affords the ability to grow large single crystals of this superconductor.
A still further advantage of the present invention is that it provides a melt-produced, high temperature superconductor that is easily formable and manufacturable allowing it to be utilized in commercial applications.
Furthermore, an advantage of the present invention is that it provides a melt-produced, high temperature superconductor to which other components can be added to make, for example, wire-type high temperature superconductors.
Still another advantage of the present invention is that it provides a high temperature superconductor having high critical currents.
Moreover, an advantage of the present invention is that it provides a high temperature superconductor that can be used to carry high currents without energy loss.
A further advantage of the present invention is that it provides a method for making melt-produced, 133~92 high temperature superconductors at relatively low temperatures of about 950~C.
A still further advantage of the present invention is that it provides a superconductor that can be utilized to levitate vehicles, store energy in magnetic fields, and produce more intense magnetic fields than heretofore possible.
Additional advantages and features of the present invention are described in, and will be apparent from, the detailed description of the presently preferred embodiments.
The figure illustrates the resistance of a sample of a superconductor made by the method of the present invention as a function of temperature.
The present invention provides a melt-produced, high temperature superconductor and process for making same. As used herein, the term "high temperature" refers to a temperature above the boiling temperature of nitrogen.
It has been found that the melt-produced, high temperature superconductor of the present invention upon reaction of the molten and solid constituents is superconducting with a critical temperature of at least 90 K.
The melt-produced, high temperature superconductor composition of the present invention preferably has the formula:
R-Ba-Cu-O
wherein:
R is chosen from the group of rare earth metals excluding: Praseodymium (Pr); Terbium (Tb); and Cerium (Ce).
Preferably, R is a rare earth metal chosen from the group consisting of: Yttrium (Y); Gadolinium (Gd); Erbium (Er); ~olmium (Ho); Neodymium (Nd);
6 I~.~969~
Samarium (Sm); Europium (Eu); Ytterbium (Yb);
Dysoprosium (Dy): Thulium (Tm); and Lutetium (Lu).
In a preferred embodiment, R is Yttrium.
Preferably, the melt-produced, high temperature superconductor has the following nominal stoichiometry:
RBa2Cu306 5 wherein:
R is a rare earth metal excluding: Tb; Pr;
and Ce and preferably: Y; Gd; Er; ~o; Nd; Sm; Eu; Yb;
Dy; Tm; and Lu.
In a preferred embodiment, the melt-produced, high temperature superconductor has the following nominal stoichiometry:
YBa2Cu306 5.
The present invention provides methods for making melt-produced high temperature superconductors at temperatures as low as 950~C.
By way of example, and not limitation, examples of the methods of making the melt-produced, high temperature superconductors will now be given.
EXAMPLE 1:
A. Y203, BaC03, and CuO with nominal 2Cu3~5 and Yl 2BaO 8Cu~3 6 were mixed and ground in an agate mortar. The powders were heated to approximately 900~C in air for approximately 12 to about 24 hours.
B. The heated mixtures were then reground.
The resultant Ba2Cu305 powder was then pressed into a pellet. The Ba2Cu305 pellet was then placed on the Yl 2BaO 8CuO3 6 powder. The pellet and powder were then heated at approximately 950 C in flowing oxygen, for approximately 24 hours in a tube furnace. The tube furnace was then cooled to approximately 650~C and remained at that temperature for approximately 2 to 133~b92 about 4 hours. The tube furnace was then cooled to approximately 200~C before the pellet and powder were removed from the furnace.
C. During the heating process, part of the Ba2Cu305 pellet melted into the Yl 2BaO 8CuO3 6 powder.
This melt-produced material was black in color and was superconductive.
The figure illustrates resistance (as a function of temperature) of the melt-produced superconductor embedded in the powder. It is seen that the superconductor has a high transition temperature.
Specifically, the midpoint transition temperature is 93K and the transition width is about 2K.
The superconductive material had a high density of approximately 6.4 grams per cm . X-ray diffraction showed that the superconductor consisted of YBa2Cu306 5 (nominal composition) with very little CuO
as an impurity. The melt-produced, superconductor demonstrated a strong Meissner effect and levitated in a magnetic field of 8 kiloGauss.
EXAMPLE N0. 2 An experiment was performed to find a Ba-Cu-oxide system with a low melt point. It should be noted that in the previous example, at 950~C, more than half of Ba2Cu305 did not melt. In order to search for a Ba-Cu-oxide system with a lower melting point, the following experiment was performed.
A. CuO or mixtures of BaC03 and CuO with nominal compositions of Ba3Cu205, Ba2Cu305, BaCu304, 4 5 6~7' BaCu12013, and BaCU48~4 were weighed and ground in an agate mortar.
B. The resultant powders were heated in air at 950~C for approximately 8 hours.
The experiment demonstrated that BaCu304 and BaCu405 are the Ba-Cu-oxides with the lowest melting 8 13~39b92 points. To this end, these powders were essentially completely melted at 950~C.
EXAMPLE N0. 3 A. A mixture of BaC03 and CuO with a nominal composition of BaCu304 was ground in an agate mortar, and pressed into a pellet.
B. The resultant pellet was put on a powder consisting of Yl 2BaO 8CuO3 6 (nominal composition) that had been heated at approximately 950~C. The pellet and powder were then heated at approximately 950~C in flowing ~2 for approximately 24 hours in a tube furnace. The furnace was then cooled to approximately 650~C and remained at 650~C for about 2 to about 4 hours. The furnace was then turned off, and, when the furnace temperature was below 200~C, the pellet and powder were removed from the furnace.
After removing the heated materials from the furnace it was noted that the BaCu304 pellet had almost completely melted into the powder. A black chunk of superconductor material was formed, embedded in the g 1.2 0.8 3.6 P t t as g een i color. This superconductor had properties similar to those of Example No. 1.
EXAMPLE N0. 4 A. A mixture of BaC03 and CuO with a nominal composition of BaCu304 was ground in an agate mortar. The resultant powder was then pressed into a pellet.
B. A mixture of Y203 and CuO with a nominal composition YBaO2 5 was also ground.
C. The BaCu304 pellet was put on the resultant YBaO2 5 powder of Step B and heated at 950 C
in flowing ~2 for approximately 24 hours in a tube furnace. The temperature of the furnace was then reduced to 650~C and the pellet and powder were left in 133~69~
the furnace at this temperature for approximately 2 to about 4 hours. The furnace was then cooled to approximately 200~C before the pellet and powder were removed from the furnace.
The BaCu304 pellet was almost completely melted into the powder. This resulted in a black chunk of superconductor being formed, that was embedded in the remainin~ white YBaO2 5 powder- This superconductor had properties similar to those of Example No. 1.
EXAMPLE N0. 5 A. A Ba2Cu305 pellet was put on a powder that consisted of Y203. The pellet and powder were heated at 950~C in flowing ~2 for approximately 12 to 15 about 24 hours in a tube furnace. The temperature of the furnace was reduced to 650~C and the pellet and powder remained therein for approximately 2 to about 4 hours. The furnace was then cooled to 200~C before the pellet and powder were removed from the furnace.
A part of the pellet was melted. The interface between the Ba2Cu305 pellet and Y203 powder contained a black piece of melt-produced material. The material was found to have superconductive properties.
EXAMPLE N0. 6 A. A Ba2Cu305 pellet was placed on YBa2Cu304 5F4 powder which had been heated to approximately 950~C. The pellet and powder were heated to approximately 950~C in flowing ~2 for approximately 24 hours in a tube furnace. The furnace was cooled to 30 650~C and the pellet and powder remained therein for approximately 2 to about 4 hours. The furnace was cooled to 200~C before the pellet and powder were removed from the furnace.
A part of the Ba2Cu305 pellet was melted into 35 the powder. A black piece of superconductor was formed 13 3~ ~g2 in the interface of the pellet and the powder. This superconductor had properties similar to those of Example No. 1.
EXAMPLE N0. 7 In this example, superconductors were created from a Ba2Cu305 pellet melted into a powder with nominal composition Rl 2BaO 8CuO3 6 wherein R is a rare earth chosen from the group consisting of: Nd; Sm; Eu;
and Dy.
A. BaC03 and CuO with a nominal composition of Ba2Cu305 were ground and heated in air at approximately 900~C for 12 hours. The mixture was then reground and pressed into pellets.
B. R203 (wherein R is chosen from the group consisting of: Nd; Sm; Eu; and Dy), BaC03 and CuO with a nominal composition of R1.2BaO.8CuO3O6 g and heated in air at approximately 950 C for 12 hours and then cooled down to less than 200~C, and reground.
C. A Ba2Cu305 pellet was put on the Rl.2BaO 8CuO3.6 powder, and heated in ~2 at approximately 950 C for approximately 15 hours in a tube furnace. The furnace was then cooled to approximately 650~C and the pellet and powder were heated therein for approximately 2 hours. The furnace was then cooled down to 200~C and the pellet and powder removed.
The Ba2Cu305 pellet was partly melted, and a black chunk of melt-produced superconductor was formed, which embedded in the remaining Rl 2BaO 8CuO3 6 powder.
The formed superconductor exhibited properties similar to those exhibited by the superconductors produced in Example No. 1. The superconductors had the following nominal stoichiometry: RBa2Cu306 5, wherein R= Nd; Sm;
Eu; or Dy.
The inventors believe that R= Gd, Ho, Er, Tm, Yb, and Lu would also work to create a superconductor followin~ the steps of the above example.
EXAMPLE N0. 8 A. R2O3 (wherein R is chosen from the group consisting of: Gd; Ho; Er; and Yb) and BaC03 with nominal composition of RBaO2 5 were ground and heated in air at approximately 950~C for approximately 6 hours and reground.
B. BaC03 and CuO with a nominal composition of BaCu3O4 were ground and pressed into pellets.
C. A BaCu304 pellet was put on an RBaO2 5 powder and heated in ~2 at approximately 950~C for approximately 5 hours. The tube furnace was then cooled down to less than 200~C before the materials were removed from the furnace.
The BaCu3O4 pellet was almost completely melted, and a black chunk was formed, which was embedded in the remaining RBaO2 5 powder. The superconductor had properties similar to the superconductors produced in Example No. 1.
The inventors believe a melt-produced superconductor can also be produced if R= Nd, Sm, Eu, Dy, Tm and Lu and the above steps are followed.
EXAMPLE N0. 9 A. Ho203 and BaC03 with nominal composition of HoBa203 5 were ground and heated in air at approximately 950~C for approximately 6 hours. The mixture was then reground.
B. BaC03 and CuO with a nominal composition of BaCu3O4 were ground and pressed into pellets.
C. The resultant BaCu304 pellet was put on HoBa2O3 5 powder, heated in ~2 at approximately 950 C
for approximately 5 hours in a tube furnace. The 1 ~ 3 ~ b ~ 2 furnace was cooled down to less than 200 C before the materials were removed from the furnace.
The BaCu304 pellet had almost completely melted, and a black chunk was formed, which was embedded in the remaining HoBa203 5 powder. The black chunk had superconductive properties similar to those of the previous examples.
EXAMPLE NO. 10 A. Ho203 and SrC03 with nominal composition of HoSrO2 5 were ground and heated in air at 950~C for 6 hours and reground.
B. BaC03 and CuO with a nominal composition of BaCu304 were ground and pressed into pellets.
C. The resultant BaCu304 pellet was put on HoSrO2 5 powder, heated in ~2 at approximately 950~C
for approximately 5 hours in a tube furnace. The furnace was then cooled down to less than 200~ before the pellet and powder were moved out of the furnace.
The BaCu304 pellet was almost completely melted, and a black chunk was formed, which was embedded in the remaining HoSrO2 5 powder. The black chunk had superconductive properties similar to those of the previous examples.
EXAMPLE NO. 11 The present example deals with the fabrication of arbitrarily-shaped components made from melt-produced superconductors. The example given is for a ring shape.
A. BaC03 and CuO with nominal composition of BaCu304 were mixed and ground, and then heated in air at 900~C for 12 hours. The resultant black material was reground and pressed into pellets (hereafter called Ba-Cu pellets).
B. Y203, BaC03, and CuO were mixed to a nominal composition of Y1 2BaO.8CuO3.6 g 13 ~3 ~ 6g2 then heated in air at 950~C for 12 hours. The resultant (green) material was then powdered (hereafter called Y 2 powder).
1.
C. The Y1 2 powder was packed into a crucible and the surface leveled. Ba-Cu pellets were then placed one-by-one onto the Y1 2 powder to form a ring shape.
D. The crucible and its contents were then heated in a tube furnace in flowing ~2 at 950~C for about 12 hours, then held at 650~C for 4 hours, and then cooled down to below 200~C, at which point they were removed from the furnace and cooled to room temperature.
E. A black melt-produced superconductive ring was formed, embedded in the Y1 2 (green) powder.
The ring was removed from the powder. If desired, the powder could then be reground and used again in similar fashion.
EXAMPLE N0. 12 The present example deals with the fabrication of arbitrarily-shaped components made from melt-produced superconductors.
A. BaC03 and CuO with nominal composition of BaCu304 were mixed and ground, and then heated in 2S air at 900~C for 12 hours. The resultant black material was reground.
B. Y203, BaC03, and CuO were mixed to a nominal composition of Yl 2BaO,8CuO3,6 g then heated in air at 950~C for 12 hours. The resultant (green) material was then powdered (hereafter called Y1 2 powder).
C. The Y1 2 powder was packed into a crucible and the surface leveled. BaCu3O4 powder was then placed onto the Y1 2 powder.
133~2 D. The crucible and its contents were then heated in a tube furnace in flowing ~2 at 950~C for about 12 hours, then held at 650~C for 4 hours, and then cooled down to below 200~C, at which point they S were removed from the furnace and cooled to room temperature.
E. A black melt-produced superconductive compound was formed, embedded in the Yl 2 (green) powder. The compound was removed from the powder. The powder could then be reground and used again in similar fashion.
EXAMPLE N0. 13 The present example deals with the fabrication of arbitrarily-shaped components made from lS melt-produced superconductors. The example given is for a ring shape.
A. 8aC03 and CuO with nominal composition of BaCu304 were mixed and ground, and then heated in air at 900~C for 12 hours. The resultant black material was reground and pressed into a ring (hereafter called BaCu304 ring).
B. Y203, BaC03, and CuO were mixed to a nominal composition of Y1 2BaO.8CuO3.6 a g then heated in air at 9S0 C for 12 hours. The resultant (green) material was then powdered (hereafter called Y1 2 powder).
C. The Yl 2 powder was packed into a crucible and the surface leveled. The BaCu304 ring was then placed onto the Yl 2 powder.
D. The crucible and its contents were then heated in a tube furnace in flowing ~2 at 950~C for about 12 hours, then held at 650 C for 4 hours, and then cooled down to below 200~C, at which point they were removed from the furnace and cooled to room temperature.
1~3~92 E. A black melt-produced superconductive ring was formed, embedded in the Y1 2 (green) powder.
The ring was removed from the powder. The powder could then be reground and used again in similar fashion.
It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present invention and without diminishing its attendant advantages. It is therefore intended that such changes and modifications be covered by the appended claims.
S P E C I F I C A T I O N
"MELT-PRODUCED HIGH TEMPERATURE SUPERCONDUCTOR
AND PROCESSES FOR MAKING SAME"
The present invention relates generally to high temperature superconductors. More specifically, the present invention relates to a melt-produced, high temperature superconductor and processes for making same.
Recently, there has been much work done on the utilization of ternary oxides containing copper, barium, and rare earth elements for superconductivity at temperatures above 90~K with the belief that superconductivity at or above room temperature is possible. Some of this work has centered on the utilization of a yttrium (Y)-barium tBa)-copper (Cu)-oxygen (O) system.
Current developments of the Y-Ba-Cu-O class of ceramic superconductors have yielded optimistic results. These systems are typically created utilizing bulk materials which are powders or very small granule substances. These powders must be compressed to facilitate measurements and are relatively intractable.
As can be appreciated, the structure of these substances is not conducive to the manufacturing of components from these ceramic superconductors.
A melt-produced, high temperature superconductor would be desirable for many reasons.
Melt-produced superconductors would: (1) allow the growth of large bulk single crystals--this is important because it could facilitate the discovery of the correct theory on superconductivity; (2) provide low cost processing and manufacturability; (3) allow components to be cast in any shape; (4) allow the addition of other components to the melt-produced hi~h temperature superconductors--this would allow one to 2 1~396~2 create an extrudeable composition allowing the superconductor to be useful in the manufacture of superconducting wires, magnets, etc.; and (5) the inventors believe, allow for high critical currents in the high temperature superconductor allowing the generation of large currents therethrough.
Accordingly, there is a need for melt-produced high temperature superconductors and processes for making same.
The present invention provides melt-produced high temperature superconductors and processes for making same that are unique to date among high temperature superconductors.
The present invention preferably comprises a composition having the following formula:
R-Ba-Cu-0 wherein:
R is chosen from the group of rare earth metals excluding: Praseodymium (Pr); Cerium (Ce); and Terbium (Tb).
Preferably, R is chosen from the group of rare earth metals that include: Yttrium (Y);
Gadolinium (Gd); Erbium (Er); Holmium (Ho); Neodymium (Nd); Samarium (Sm); Europium (Eu); Ytterbium (Yb);
Dysprosium (Dy); Thulium (Tm); and Lutetium (Lu). In a preferred embodiment, R is Yttrium.
In a preferred embodiment, the melt-produced superconductor has the following nominal stoichiometry:
Rsa2Cu3O6 5 wherein:
R is a rare earth metal not including: Pr;
Tb; or Ce. Preferably, R is chosen from the group of rare earth metals that include: Yttrium (Y);
Gadolinium (Gd); Erbium (Er); Holmium (Ho); Neodymium 13 3 9 b ~ 2 (Nd); Samarium (Sm); Europium (Eu); Ytterbium (Yb);
Dysprosium (Dy); Thulium (Tm); and Lutetium (Lu).
In a preferred embodiment, the melt-produced superconductor has the following nominal stoichlometry:
YBa2Cu306 5.
A method of making the melt-produced, high temperature superconductors is also provided. The method is based on reaction between molten Ba-Cu oxides and solid rare earth oxides, rare earth barium oxides, rare earth copper oxides, or rare earth-Ba-Cu oxides.
The method allows melt-producing to be carried out at a relatively low temperature of approximately 950~C. The method further allows the use of precursor materials for the superconductor in the form of pellets, powders, or pellets and powders.
The method comprises the steps of: mixing and grinding BaC03 and CuO with nominal compositions of Ba2Cu305, BaCu304, BaCu405, BaCu607, and BaCu12013;
pressing the resultant mixture into a pellet, if necessary; placing the pellet or powder on a pellet or powder chosen from the group consisting of R203, or R-Ba-oxides (e.g. RBaO2 5), R-Cu-oxides, or R-Ba-Cu-g. R1.2BaO.8CuO3 6) wherein R is chosen fromthe group of rare earth metals excluding: Tb, Pr, and Ce; heating the pellets and/or powders to a temperature of approximately 950~C; and removing a melt-produced superconductor from the remaining pellet or powder at the bottom.
In an embodiment of the method, a mixture of BaC03 and CuO with nominal composition of BaCu304 is ground and heated to approximately 900~C in air for about 12 hours. The heated mixture is reground and pressed into pellets. A mixture of Y203, BaC03, and CuO with nominal composition of Y1 2Ba8 8CuO3 6 is ground and heated at approximately 950 C in air for 133~2 about 12 hours. The resultant material is reground.
The black BaCu3O4 pellet (of arbitrary shape) is placed (g ) Yl.2BaO.8CuO3.6 powder, and is heated in flowing ~2 at about 950 C for 12 hours, then at 650~C
for 4 hours, then cooled down to 200~C in about 1-2 hours, then removed from the furnace. A black melt-produced superconductor is formed which is embedded in the (green) Yl 2BaO 8CuO3 6 powder and separated from it (the recovered Y1 2BaO 8CuO3 6 powder may be reused if desired).
Accordingly, an advantage of the present invention is to provide a melt-produced, high temperature superconductor and method of making same.
A further advantage of the present invention is to provide a method that affords the ability to grow large single crystals of this superconductor.
A still further advantage of the present invention is that it provides a melt-produced, high temperature superconductor that is easily formable and manufacturable allowing it to be utilized in commercial applications.
Furthermore, an advantage of the present invention is that it provides a melt-produced, high temperature superconductor to which other components can be added to make, for example, wire-type high temperature superconductors.
Still another advantage of the present invention is that it provides a high temperature superconductor having high critical currents.
Moreover, an advantage of the present invention is that it provides a high temperature superconductor that can be used to carry high currents without energy loss.
A further advantage of the present invention is that it provides a method for making melt-produced, 133~92 high temperature superconductors at relatively low temperatures of about 950~C.
A still further advantage of the present invention is that it provides a superconductor that can be utilized to levitate vehicles, store energy in magnetic fields, and produce more intense magnetic fields than heretofore possible.
Additional advantages and features of the present invention are described in, and will be apparent from, the detailed description of the presently preferred embodiments.
The figure illustrates the resistance of a sample of a superconductor made by the method of the present invention as a function of temperature.
The present invention provides a melt-produced, high temperature superconductor and process for making same. As used herein, the term "high temperature" refers to a temperature above the boiling temperature of nitrogen.
It has been found that the melt-produced, high temperature superconductor of the present invention upon reaction of the molten and solid constituents is superconducting with a critical temperature of at least 90 K.
The melt-produced, high temperature superconductor composition of the present invention preferably has the formula:
R-Ba-Cu-O
wherein:
R is chosen from the group of rare earth metals excluding: Praseodymium (Pr); Terbium (Tb); and Cerium (Ce).
Preferably, R is a rare earth metal chosen from the group consisting of: Yttrium (Y); Gadolinium (Gd); Erbium (Er); ~olmium (Ho); Neodymium (Nd);
6 I~.~969~
Samarium (Sm); Europium (Eu); Ytterbium (Yb);
Dysoprosium (Dy): Thulium (Tm); and Lutetium (Lu).
In a preferred embodiment, R is Yttrium.
Preferably, the melt-produced, high temperature superconductor has the following nominal stoichiometry:
RBa2Cu306 5 wherein:
R is a rare earth metal excluding: Tb; Pr;
and Ce and preferably: Y; Gd; Er; ~o; Nd; Sm; Eu; Yb;
Dy; Tm; and Lu.
In a preferred embodiment, the melt-produced, high temperature superconductor has the following nominal stoichiometry:
YBa2Cu306 5.
The present invention provides methods for making melt-produced high temperature superconductors at temperatures as low as 950~C.
By way of example, and not limitation, examples of the methods of making the melt-produced, high temperature superconductors will now be given.
EXAMPLE 1:
A. Y203, BaC03, and CuO with nominal 2Cu3~5 and Yl 2BaO 8Cu~3 6 were mixed and ground in an agate mortar. The powders were heated to approximately 900~C in air for approximately 12 to about 24 hours.
B. The heated mixtures were then reground.
The resultant Ba2Cu305 powder was then pressed into a pellet. The Ba2Cu305 pellet was then placed on the Yl 2BaO 8CuO3 6 powder. The pellet and powder were then heated at approximately 950 C in flowing oxygen, for approximately 24 hours in a tube furnace. The tube furnace was then cooled to approximately 650~C and remained at that temperature for approximately 2 to 133~b92 about 4 hours. The tube furnace was then cooled to approximately 200~C before the pellet and powder were removed from the furnace.
C. During the heating process, part of the Ba2Cu305 pellet melted into the Yl 2BaO 8CuO3 6 powder.
This melt-produced material was black in color and was superconductive.
The figure illustrates resistance (as a function of temperature) of the melt-produced superconductor embedded in the powder. It is seen that the superconductor has a high transition temperature.
Specifically, the midpoint transition temperature is 93K and the transition width is about 2K.
The superconductive material had a high density of approximately 6.4 grams per cm . X-ray diffraction showed that the superconductor consisted of YBa2Cu306 5 (nominal composition) with very little CuO
as an impurity. The melt-produced, superconductor demonstrated a strong Meissner effect and levitated in a magnetic field of 8 kiloGauss.
EXAMPLE N0. 2 An experiment was performed to find a Ba-Cu-oxide system with a low melt point. It should be noted that in the previous example, at 950~C, more than half of Ba2Cu305 did not melt. In order to search for a Ba-Cu-oxide system with a lower melting point, the following experiment was performed.
A. CuO or mixtures of BaC03 and CuO with nominal compositions of Ba3Cu205, Ba2Cu305, BaCu304, 4 5 6~7' BaCu12013, and BaCU48~4 were weighed and ground in an agate mortar.
B. The resultant powders were heated in air at 950~C for approximately 8 hours.
The experiment demonstrated that BaCu304 and BaCu405 are the Ba-Cu-oxides with the lowest melting 8 13~39b92 points. To this end, these powders were essentially completely melted at 950~C.
EXAMPLE N0. 3 A. A mixture of BaC03 and CuO with a nominal composition of BaCu304 was ground in an agate mortar, and pressed into a pellet.
B. The resultant pellet was put on a powder consisting of Yl 2BaO 8CuO3 6 (nominal composition) that had been heated at approximately 950~C. The pellet and powder were then heated at approximately 950~C in flowing ~2 for approximately 24 hours in a tube furnace. The furnace was then cooled to approximately 650~C and remained at 650~C for about 2 to about 4 hours. The furnace was then turned off, and, when the furnace temperature was below 200~C, the pellet and powder were removed from the furnace.
After removing the heated materials from the furnace it was noted that the BaCu304 pellet had almost completely melted into the powder. A black chunk of superconductor material was formed, embedded in the g 1.2 0.8 3.6 P t t as g een i color. This superconductor had properties similar to those of Example No. 1.
EXAMPLE N0. 4 A. A mixture of BaC03 and CuO with a nominal composition of BaCu304 was ground in an agate mortar. The resultant powder was then pressed into a pellet.
B. A mixture of Y203 and CuO with a nominal composition YBaO2 5 was also ground.
C. The BaCu304 pellet was put on the resultant YBaO2 5 powder of Step B and heated at 950 C
in flowing ~2 for approximately 24 hours in a tube furnace. The temperature of the furnace was then reduced to 650~C and the pellet and powder were left in 133~69~
the furnace at this temperature for approximately 2 to about 4 hours. The furnace was then cooled to approximately 200~C before the pellet and powder were removed from the furnace.
The BaCu304 pellet was almost completely melted into the powder. This resulted in a black chunk of superconductor being formed, that was embedded in the remainin~ white YBaO2 5 powder- This superconductor had properties similar to those of Example No. 1.
EXAMPLE N0. 5 A. A Ba2Cu305 pellet was put on a powder that consisted of Y203. The pellet and powder were heated at 950~C in flowing ~2 for approximately 12 to 15 about 24 hours in a tube furnace. The temperature of the furnace was reduced to 650~C and the pellet and powder remained therein for approximately 2 to about 4 hours. The furnace was then cooled to 200~C before the pellet and powder were removed from the furnace.
A part of the pellet was melted. The interface between the Ba2Cu305 pellet and Y203 powder contained a black piece of melt-produced material. The material was found to have superconductive properties.
EXAMPLE N0. 6 A. A Ba2Cu305 pellet was placed on YBa2Cu304 5F4 powder which had been heated to approximately 950~C. The pellet and powder were heated to approximately 950~C in flowing ~2 for approximately 24 hours in a tube furnace. The furnace was cooled to 30 650~C and the pellet and powder remained therein for approximately 2 to about 4 hours. The furnace was cooled to 200~C before the pellet and powder were removed from the furnace.
A part of the Ba2Cu305 pellet was melted into 35 the powder. A black piece of superconductor was formed 13 3~ ~g2 in the interface of the pellet and the powder. This superconductor had properties similar to those of Example No. 1.
EXAMPLE N0. 7 In this example, superconductors were created from a Ba2Cu305 pellet melted into a powder with nominal composition Rl 2BaO 8CuO3 6 wherein R is a rare earth chosen from the group consisting of: Nd; Sm; Eu;
and Dy.
A. BaC03 and CuO with a nominal composition of Ba2Cu305 were ground and heated in air at approximately 900~C for 12 hours. The mixture was then reground and pressed into pellets.
B. R203 (wherein R is chosen from the group consisting of: Nd; Sm; Eu; and Dy), BaC03 and CuO with a nominal composition of R1.2BaO.8CuO3O6 g and heated in air at approximately 950 C for 12 hours and then cooled down to less than 200~C, and reground.
C. A Ba2Cu305 pellet was put on the Rl.2BaO 8CuO3.6 powder, and heated in ~2 at approximately 950 C for approximately 15 hours in a tube furnace. The furnace was then cooled to approximately 650~C and the pellet and powder were heated therein for approximately 2 hours. The furnace was then cooled down to 200~C and the pellet and powder removed.
The Ba2Cu305 pellet was partly melted, and a black chunk of melt-produced superconductor was formed, which embedded in the remaining Rl 2BaO 8CuO3 6 powder.
The formed superconductor exhibited properties similar to those exhibited by the superconductors produced in Example No. 1. The superconductors had the following nominal stoichiometry: RBa2Cu306 5, wherein R= Nd; Sm;
Eu; or Dy.
The inventors believe that R= Gd, Ho, Er, Tm, Yb, and Lu would also work to create a superconductor followin~ the steps of the above example.
EXAMPLE N0. 8 A. R2O3 (wherein R is chosen from the group consisting of: Gd; Ho; Er; and Yb) and BaC03 with nominal composition of RBaO2 5 were ground and heated in air at approximately 950~C for approximately 6 hours and reground.
B. BaC03 and CuO with a nominal composition of BaCu3O4 were ground and pressed into pellets.
C. A BaCu304 pellet was put on an RBaO2 5 powder and heated in ~2 at approximately 950~C for approximately 5 hours. The tube furnace was then cooled down to less than 200~C before the materials were removed from the furnace.
The BaCu3O4 pellet was almost completely melted, and a black chunk was formed, which was embedded in the remaining RBaO2 5 powder. The superconductor had properties similar to the superconductors produced in Example No. 1.
The inventors believe a melt-produced superconductor can also be produced if R= Nd, Sm, Eu, Dy, Tm and Lu and the above steps are followed.
EXAMPLE N0. 9 A. Ho203 and BaC03 with nominal composition of HoBa203 5 were ground and heated in air at approximately 950~C for approximately 6 hours. The mixture was then reground.
B. BaC03 and CuO with a nominal composition of BaCu3O4 were ground and pressed into pellets.
C. The resultant BaCu304 pellet was put on HoBa2O3 5 powder, heated in ~2 at approximately 950 C
for approximately 5 hours in a tube furnace. The 1 ~ 3 ~ b ~ 2 furnace was cooled down to less than 200 C before the materials were removed from the furnace.
The BaCu304 pellet had almost completely melted, and a black chunk was formed, which was embedded in the remaining HoBa203 5 powder. The black chunk had superconductive properties similar to those of the previous examples.
EXAMPLE NO. 10 A. Ho203 and SrC03 with nominal composition of HoSrO2 5 were ground and heated in air at 950~C for 6 hours and reground.
B. BaC03 and CuO with a nominal composition of BaCu304 were ground and pressed into pellets.
C. The resultant BaCu304 pellet was put on HoSrO2 5 powder, heated in ~2 at approximately 950~C
for approximately 5 hours in a tube furnace. The furnace was then cooled down to less than 200~ before the pellet and powder were moved out of the furnace.
The BaCu304 pellet was almost completely melted, and a black chunk was formed, which was embedded in the remaining HoSrO2 5 powder. The black chunk had superconductive properties similar to those of the previous examples.
EXAMPLE NO. 11 The present example deals with the fabrication of arbitrarily-shaped components made from melt-produced superconductors. The example given is for a ring shape.
A. BaC03 and CuO with nominal composition of BaCu304 were mixed and ground, and then heated in air at 900~C for 12 hours. The resultant black material was reground and pressed into pellets (hereafter called Ba-Cu pellets).
B. Y203, BaC03, and CuO were mixed to a nominal composition of Y1 2BaO.8CuO3.6 g 13 ~3 ~ 6g2 then heated in air at 950~C for 12 hours. The resultant (green) material was then powdered (hereafter called Y 2 powder).
1.
C. The Y1 2 powder was packed into a crucible and the surface leveled. Ba-Cu pellets were then placed one-by-one onto the Y1 2 powder to form a ring shape.
D. The crucible and its contents were then heated in a tube furnace in flowing ~2 at 950~C for about 12 hours, then held at 650~C for 4 hours, and then cooled down to below 200~C, at which point they were removed from the furnace and cooled to room temperature.
E. A black melt-produced superconductive ring was formed, embedded in the Y1 2 (green) powder.
The ring was removed from the powder. If desired, the powder could then be reground and used again in similar fashion.
EXAMPLE N0. 12 The present example deals with the fabrication of arbitrarily-shaped components made from melt-produced superconductors.
A. BaC03 and CuO with nominal composition of BaCu304 were mixed and ground, and then heated in 2S air at 900~C for 12 hours. The resultant black material was reground.
B. Y203, BaC03, and CuO were mixed to a nominal composition of Yl 2BaO,8CuO3,6 g then heated in air at 950~C for 12 hours. The resultant (green) material was then powdered (hereafter called Y1 2 powder).
C. The Y1 2 powder was packed into a crucible and the surface leveled. BaCu3O4 powder was then placed onto the Y1 2 powder.
133~2 D. The crucible and its contents were then heated in a tube furnace in flowing ~2 at 950~C for about 12 hours, then held at 650~C for 4 hours, and then cooled down to below 200~C, at which point they S were removed from the furnace and cooled to room temperature.
E. A black melt-produced superconductive compound was formed, embedded in the Yl 2 (green) powder. The compound was removed from the powder. The powder could then be reground and used again in similar fashion.
EXAMPLE N0. 13 The present example deals with the fabrication of arbitrarily-shaped components made from lS melt-produced superconductors. The example given is for a ring shape.
A. 8aC03 and CuO with nominal composition of BaCu304 were mixed and ground, and then heated in air at 900~C for 12 hours. The resultant black material was reground and pressed into a ring (hereafter called BaCu304 ring).
B. Y203, BaC03, and CuO were mixed to a nominal composition of Y1 2BaO.8CuO3.6 a g then heated in air at 9S0 C for 12 hours. The resultant (green) material was then powdered (hereafter called Y1 2 powder).
C. The Yl 2 powder was packed into a crucible and the surface leveled. The BaCu304 ring was then placed onto the Yl 2 powder.
D. The crucible and its contents were then heated in a tube furnace in flowing ~2 at 950~C for about 12 hours, then held at 650 C for 4 hours, and then cooled down to below 200~C, at which point they were removed from the furnace and cooled to room temperature.
1~3~92 E. A black melt-produced superconductive ring was formed, embedded in the Y1 2 (green) powder.
The ring was removed from the powder. The powder could then be reground and used again in similar fashion.
It should be understood that various changes and modifications to the presently preferred embodiments described herein will be apparent to those skilled in the art. Such changes and modifications can be made without departing from the spirit and scope of the present invention and without diminishing its attendant advantages. It is therefore intended that such changes and modifications be covered by the appended claims.
Claims (29)
1. A method for making a melt-produced high temperature superconductor comprising the steps of:
mixing and grinding BaCO3 and CuO with nominal compositions of at least one compound chosen from the group consisting of Ba2Cu3O5, BaCu3O4, BaCu4O5, BaCu6O7, and BaCu12O13 pressing the resultant mixture into a pellet;
placing the pellet on a powder comprising at least one compound chosen from the group consisting of R1.2Ba0.8CuO3.6, RBa2Cu3O4.5F4, RBa2O3.6, RBa2O2.5, or R2O3 wherein R is chosen from the group of rare earth metals excluding: Tb, Pr, and Ce;
heating the pellet and the powder in a furnace to a temperature of greater than or equal to 950°C and less than or equal to 1000°C to form a melt at a pellet: powder interface; and removing the melt-produced superconductor from the powder in which the superconductor is embedded.
mixing and grinding BaCO3 and CuO with nominal compositions of at least one compound chosen from the group consisting of Ba2Cu3O5, BaCu3O4, BaCu4O5, BaCu6O7, and BaCu12O13 pressing the resultant mixture into a pellet;
placing the pellet on a powder comprising at least one compound chosen from the group consisting of R1.2Ba0.8CuO3.6, RBa2Cu3O4.5F4, RBa2O3.6, RBa2O2.5, or R2O3 wherein R is chosen from the group of rare earth metals excluding: Tb, Pr, and Ce;
heating the pellet and the powder in a furnace to a temperature of greater than or equal to 950°C and less than or equal to 1000°C to form a melt at a pellet: powder interface; and removing the melt-produced superconductor from the powder in which the superconductor is embedded.
2. The method of Claim 1 wherein R is chosen from the group of rare earth metals consisting of: Y, Gd, Er, Ho, Nd, Sm, Eu, Yb, Dy, Tm, and Lu.
3. The method of Claim 1 wherein after the mixing and grinding step of Ba-Cu oxide, the resultant mixture is heated to approximately 850-920°C.
4. The method of Claim 1 wherein the powder on which the Ba-Cu-oxide pellet is placed has been previously heated to approximately 900-1000°C.
5. The method of Claim 1 wherein after the pellet and powder are heated to 940-1000°C for a predetermined time in the furnace, the temperature of the furnace is lowered to approximately 650°C and the pellet and mixture remain therein for a predetermined time.
6. The method of Claim 5 including the step of cooling the furnace to 200°C or less before removing the pellet and powder therefrom.
7. The method of Claim 1 wherein the oxide chosen is BaCu3O4.
8. The method of Claim 1 wherein the oxide chosen is BaCu4O5.
9. The method of Claim 1 wherein the oxide chosen is Ba2Cu3O5.
10. The method of Claim 1 wherein the pellet and powder are heated in the furnace at a temperature between 940°C
to about 1000°C for approximately 12 to about 24 hours.
to about 1000°C for approximately 12 to about 24 hours.
11. A method for making a superconductor comprising the steps of:
mixing and grinding BaCO3 and CuO with nominal compositions of at least one compound chosen from the group consisting of Ba2Cu3O5, BaCu3O4, BaCu4O5, BaCu6O7, and BaCu12O13;
heating the resultant mixture;
pressing the resultant mixture into a pellet;
placing the pellet on a preheated powder comprising RBa2Cu3O4.5F4 wherein R is chosen from the group consisting of: Gd, Ho, Er, Yb, Nd, Sm, Eu, Dy, Tm, and Lu;
heating the pellet and the powder in a furnace to approximately 940° to about 1000°C to form a melt at a powder:powder interface; and removing a melted interface between the pellet and powder.
mixing and grinding BaCO3 and CuO with nominal compositions of at least one compound chosen from the group consisting of Ba2Cu3O5, BaCu3O4, BaCu4O5, BaCu6O7, and BaCu12O13;
heating the resultant mixture;
pressing the resultant mixture into a pellet;
placing the pellet on a preheated powder comprising RBa2Cu3O4.5F4 wherein R is chosen from the group consisting of: Gd, Ho, Er, Yb, Nd, Sm, Eu, Dy, Tm, and Lu;
heating the pellet and the powder in a furnace to approximately 940° to about 1000°C to form a melt at a powder:powder interface; and removing a melted interface between the pellet and powder.
12. A method for making a superconductor comprising the steps of:
mixing and grinding BaCO3 and CuO with nominal compositions of at least one compound chosen from the group consisting of Ba2Cu3O5, BaCu3O4, BaCu4O5, BaCu6O7, or BaCu12O13;
heating the resultant mixture;
pressing the resultant mixture into a pellet;
placing the pellet on a powder that has previously been heated comprising R1.2Ba0.8CuO3.6 wherein R is chosen from the group consisting of: Y, Gd, Er, Ho, Nd, Sm, Eu, Yb, Dy, Tm, and Lu;
heating the pellet and the powder in a furnace to a temperature of greater than or equal to 950°C and less than or equal to 1000°C to form a melt at a pellet:powder interface; and removing the melt-produced superconductor from the powder in which the superconductor is embedded.
mixing and grinding BaCO3 and CuO with nominal compositions of at least one compound chosen from the group consisting of Ba2Cu3O5, BaCu3O4, BaCu4O5, BaCu6O7, or BaCu12O13;
heating the resultant mixture;
pressing the resultant mixture into a pellet;
placing the pellet on a powder that has previously been heated comprising R1.2Ba0.8CuO3.6 wherein R is chosen from the group consisting of: Y, Gd, Er, Ho, Nd, Sm, Eu, Yb, Dy, Tm, and Lu;
heating the pellet and the powder in a furnace to a temperature of greater than or equal to 950°C and less than or equal to 1000°C to form a melt at a pellet:powder interface; and removing the melt-produced superconductor from the powder in which the superconductor is embedded.
13. The method of Claim 12 wherein after the mixing and grinding step, the resultant mixture is heated to approximately 850-920°C.
14. The method of Claim 12 wherein the powder the pellet is placed on has been previously heated to approximately 900-1000°C.
15. The method of Claim 12 wherein after the pellet and powder are heated to 940-1000°C for a predetermined time in the furnace, the temperature of the furnace is lowered to approximately 650°C and the pellet and mixture remain therein for a predetermined time.
16. The method of Claim 12 wherein the pellet and powder are heated in the furnace at a temperature between 940°C
to about 1000°C for approximately 12 to about 24 hours.
to about 1000°C for approximately 12 to about 24 hours.
17. A method for making a superconductor comprising the steps of:
mixing and grinding BaCO3 and CuO with nominal compositions of at least one compound chosen from the group consisting of BaCu3O5, Ba2Cu3O4, BaCu4O5, BaCu6O7, or BaCu12O13;
heating the resultant mixture to a temperature of approximately 900°C;
pressing the resultant mixture into a pellet;
placing the pellet on a preheated powder comprising Y1.2Ba0.8CuO3.6;
heating the pellet and the powder in a furnace to a temperature greater than or equal to 940°C and less than or equal to 1000°C for approximately 12 to about 24 hours to form a melt at a pellet:powder interface;
cooling the furnace to approximately 650°C and heating the pellet and powder therein;
cooling the furnace to at least equal to approximately 200°C; and removing a melted interface between the pellet and powder.
mixing and grinding BaCO3 and CuO with nominal compositions of at least one compound chosen from the group consisting of BaCu3O5, Ba2Cu3O4, BaCu4O5, BaCu6O7, or BaCu12O13;
heating the resultant mixture to a temperature of approximately 900°C;
pressing the resultant mixture into a pellet;
placing the pellet on a preheated powder comprising Y1.2Ba0.8CuO3.6;
heating the pellet and the powder in a furnace to a temperature greater than or equal to 940°C and less than or equal to 1000°C for approximately 12 to about 24 hours to form a melt at a pellet:powder interface;
cooling the furnace to approximately 650°C and heating the pellet and powder therein;
cooling the furnace to at least equal to approximately 200°C; and removing a melted interface between the pellet and powder.
18. A method for making a superconductor comprising the steps of:
placing a pellet consisting of a compound chosen from the group consisting of Ba2Cu3O5, BaCu3O4, and BaCu4O5 on a powder consisting of a compound chosen from the group consisting of RBa2Cu3O4.5F4, R1.2Ba0.8CuO3.6, R2O3, and RBa2O3.5 wherein R is chosen from the group of rare earth metals excluding Tb, Pr, and Ce;
heating the pellet and powder to approximately 950°C to about 1000°C for 12 to 24 hours to form a melt at a pellet:powder interface; and removing the melted interface between the pellet and powder.
placing a pellet consisting of a compound chosen from the group consisting of Ba2Cu3O5, BaCu3O4, and BaCu4O5 on a powder consisting of a compound chosen from the group consisting of RBa2Cu3O4.5F4, R1.2Ba0.8CuO3.6, R2O3, and RBa2O3.5 wherein R is chosen from the group of rare earth metals excluding Tb, Pr, and Ce;
heating the pellet and powder to approximately 950°C to about 1000°C for 12 to 24 hours to form a melt at a pellet:powder interface; and removing the melted interface between the pellet and powder.
19. The method of Claim 18 wherein R is chosen from the group of rare earth metals consisting of: Y, Gd, Er, Ho, Nd, Sm, Eu, Yb, Dy, Tm, and Lu.
20. The method of Claim 18 wherein R is Y.
21 21. The method of Claim 18 wherein after the pellet and powder are heated to 950-1000°C for a predetermined time in the furnace, the temperature of the furnace is lowered to approximately 650°C and the pellet and the mixture remain therein for a predetermined time.
22. The method of Claim 18 including the step of cooling the furnace to 200°C or less before removing the pellet and powder therefrom.
23. The method of Claim 18 wherein the pellet and powder are heated in the furnace at a temperature between 950°C
to about 1000°C for approximately 12 to about 24 hours.
to about 1000°C for approximately 12 to about 24 hours.
24. The method of Claim 18 wherein the powder the pellet is placed on has been previously heated to approximately 900-1000°C.
25. A method of making a superconductor comprising the steps of:
placing a pellet consisting of BaCu3O4 on a powder consisting of HoBa2O3.5;
heating the pellet and powder for approximately 940°C
to 1000°C to form a melt at a pellet:powder interface; and removing the melted interface between the pellet and powder.
placing a pellet consisting of BaCu3O4 on a powder consisting of HoBa2O3.5;
heating the pellet and powder for approximately 940°C
to 1000°C to form a melt at a pellet:powder interface; and removing the melted interface between the pellet and powder.
26. A method of making a superconductor comprising the steps of:
placing a pellet consisting of BaCu3O4 on a powder consisting of HoSrO2.5;
heating the pellet and powder to approximately 950°C to 1000°C to form a melt at a pellet:powder interface; and removing the melted interface between the pellet and powder.
placing a pellet consisting of BaCu3O4 on a powder consisting of HoSrO2.5;
heating the pellet and powder to approximately 950°C to 1000°C to form a melt at a pellet:powder interface; and removing the melted interface between the pellet and powder.
27. A process of making melt-produced superconductor components of arbitrary shape comprising the steps of:
mixing and grinding BaCO3 and CuO in nominal composition of BaCu3O4;
heating the mixture in air at about 900°C for about 12 hours, and cooling it and grinding it;
mixing and grinding Y2O3, BaCO3, and CuO in a nominal composition of Y1.2Ba0.8CuO3.6;
heating the mixture in air at about 950°C for about 12 hours, then cooling it and grinding it;
placing resultant BaCu3O4 powder into an arbitrary shape and onto the Y1.2Ba0.8CuO3.6 powder;
heating the BaCu3O4 and Y1.2Ba0.8CuO3.6 in a furnace in flowing O2 at about 950°C for about 12 hours to form a melt at a shape:powder interface;
holding the furnace at 650°C for about 4 hours;
cooling the furnace to less than 200°C and removing from the furnace the heated materials to bring to room temperature;
separating the black melt-produced superconductor from the remaining Y1.2Ba0.8CuO3.6 powder in which the superconductor is embedded; and recovering the excess Y1.2Ba0.8CuO3.6 powder for re-use after regrinding.
mixing and grinding BaCO3 and CuO in nominal composition of BaCu3O4;
heating the mixture in air at about 900°C for about 12 hours, and cooling it and grinding it;
mixing and grinding Y2O3, BaCO3, and CuO in a nominal composition of Y1.2Ba0.8CuO3.6;
heating the mixture in air at about 950°C for about 12 hours, then cooling it and grinding it;
placing resultant BaCu3O4 powder into an arbitrary shape and onto the Y1.2Ba0.8CuO3.6 powder;
heating the BaCu3O4 and Y1.2Ba0.8CuO3.6 in a furnace in flowing O2 at about 950°C for about 12 hours to form a melt at a shape:powder interface;
holding the furnace at 650°C for about 4 hours;
cooling the furnace to less than 200°C and removing from the furnace the heated materials to bring to room temperature;
separating the black melt-produced superconductor from the remaining Y1.2Ba0.8CuO3.6 powder in which the superconductor is embedded; and recovering the excess Y1.2Ba0.8CuO3.6 powder for re-use after regrinding.
28. The process of Claim 27 wherein the BaCu3O4 powder is replaced by pellets.
29. The process of Claim 27 wherein the BaCu3O4 powder is replaced by pressed BaCu3O4 of an arbitrary shape.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/089,067 US4857504A (en) | 1987-08-25 | 1987-08-25 | Melt-produced high temperature rare earth barium copper oxide superconductor and processes for making same |
| US089,067 | 1987-08-25 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1339692C true CA1339692C (en) | 1998-03-03 |
Family
ID=22215504
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000573616A Expired - Fee Related CA1339692C (en) | 1987-08-25 | 1988-08-02 | Melt-produced high temperature superconductor and processes for making same |
Country Status (5)
| Country | Link |
|---|---|
| US (1) | US4857504A (en) |
| EP (1) | EP0305179A1 (en) |
| JP (1) | JPH0764627B2 (en) |
| AU (1) | AU604362B2 (en) |
| CA (1) | CA1339692C (en) |
Families Citing this family (20)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5648320A (en) * | 1985-05-31 | 1997-07-15 | Jacobs; Richard L. | Method of manufacturing ceramic superconductor circuit board |
| US5504138A (en) * | 1985-05-31 | 1996-04-02 | Jacobs; Richard | Circuit board devices with superconducting bonds and lines |
| US5032570A (en) * | 1987-08-04 | 1991-07-16 | Hitachi Metals, Ltd. | Method for producing ceramic superconducting material using intermediate products |
| AU600156B2 (en) * | 1987-08-06 | 1990-08-02 | University Of Arkansas, The | Meltable high temperature superconductor |
| JPH0764628B2 (en) * | 1988-08-12 | 1995-07-12 | 日本碍子株式会社 | Yttrium-barium-copper oxide powder and method for producing yttrium-barium-copper oxide superconducting sintered body |
| US5217943A (en) * | 1989-01-25 | 1993-06-08 | The University Of Arkansas | Process for making composite ceramic superconducting wires |
| US5356868A (en) * | 1989-07-03 | 1994-10-18 | Gte Laboratories Incorporated | Highly oriented superconductor oxide ceramic platelets and process for the production thereof |
| EP0436723B1 (en) * | 1989-07-07 | 1995-06-21 | Mitsubishi Materials Corporation | Oxide superconductor and method of producing the same |
| WO1991019029A1 (en) * | 1990-06-07 | 1991-12-12 | Nippon Steel Corporation | Oxide superconductor and production thereof |
| FR2668500B1 (en) * | 1990-10-29 | 1992-12-24 | Alsthom Cge Alcatel | PROCESS FOR THE PREPARATION OF A MICROCRYSTALLINE STRUCTURE OF RBA2CU3OY OR R DESIGNATES A LANTHANIDE. |
| KR930002960B1 (en) * | 1990-12-15 | 1993-04-16 | 재단법인 한국표준연구소 | PROCESS FOR MANUFACTURING YBa2Cu3Ox |
| CH682358A5 (en) * | 1991-02-22 | 1993-08-31 | Asea Brown Boveri | Ceramic high temp. superconductor prodn. - by pouring starting material into mould, heating, cooling, thermally treating in oxygen@ and cooling, for shield magnetic fields in switching elements |
| US5193349A (en) * | 1991-08-05 | 1993-03-16 | Chicago Bridge & Iron Technical Services Company | Method and apparatus for cooling high temperature superconductors with neon-nitrogen mixtures |
| US5455223A (en) * | 1993-02-24 | 1995-10-03 | American Superconductor Corporation | Coated precursor powder for oxide superdonductors |
| JP4794145B2 (en) * | 2004-07-26 | 2011-10-19 | 新日本製鐵株式会社 | Method for producing RE-Ba-Cu-O oxide superconductor |
| JP4925639B2 (en) * | 2005-03-31 | 2012-05-09 | 財団法人国際超電導産業技術研究センター | RE123 oxide superconductor and manufacturing method thereof |
| CN102586876B (en) * | 2012-02-08 | 2015-07-15 | 上海交通大学 | Preparation method of Russian export blend crude oil (REBCO) high-temperature superconducting block materials |
| US8946830B2 (en) | 2012-04-04 | 2015-02-03 | Asm Ip Holdings B.V. | Metal oxide protective layer for a semiconductor device |
| US9556516B2 (en) | 2013-10-09 | 2017-01-31 | ASM IP Holding B.V | Method for forming Ti-containing film by PEALD using TDMAT or TDEAT |
| US9478415B2 (en) | 2015-02-13 | 2016-10-25 | Asm Ip Holding B.V. | Method for forming film having low resistance and shallow junction depth |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| AU600156B2 (en) * | 1987-08-06 | 1990-08-02 | University Of Arkansas, The | Meltable high temperature superconductor |
-
1987
- 1987-08-25 US US07/089,067 patent/US4857504A/en not_active Expired - Lifetime
-
1988
- 1988-08-02 AU AU20313/88A patent/AU604362B2/en not_active Ceased
- 1988-08-02 CA CA000573616A patent/CA1339692C/en not_active Expired - Fee Related
- 1988-08-05 JP JP63195941A patent/JPH0764627B2/en not_active Expired - Lifetime
- 1988-08-25 EP EP88307875A patent/EP0305179A1/en not_active Withdrawn
Also Published As
| Publication number | Publication date |
|---|---|
| AU604362B2 (en) | 1990-12-13 |
| AU2031388A (en) | 1989-03-02 |
| EP0305179A1 (en) | 1989-03-01 |
| US4857504A (en) | 1989-08-15 |
| JPH01138168A (en) | 1989-05-31 |
| JPH0764627B2 (en) | 1995-07-12 |
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