US3294529A - Superconductive alloys - Google Patents
Superconductive alloys Download PDFInfo
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- US3294529A US3294529A US312309A US31230963A US3294529A US 3294529 A US3294529 A US 3294529A US 312309 A US312309 A US 312309A US 31230963 A US31230963 A US 31230963A US 3294529 A US3294529 A US 3294529A
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- 229910045601 alloy Inorganic materials 0.000 title description 15
- 239000000956 alloy Substances 0.000 title description 15
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical class [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 32
- 239000001257 hydrogen Substances 0.000 claims description 32
- 229910052739 hydrogen Inorganic materials 0.000 claims description 32
- 239000002887 superconductor Substances 0.000 claims description 8
- 229910001257 Nb alloy Inorganic materials 0.000 claims description 7
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 7
- GFUGMBIZUXZOAF-UHFFFAOYSA-N niobium zirconium Chemical compound [Zr].[Nb] GFUGMBIZUXZOAF-UHFFFAOYSA-N 0.000 claims description 7
- 229910052726 zirconium Inorganic materials 0.000 claims description 7
- 239000000463 material Substances 0.000 description 33
- 238000000034 method Methods 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 10
- 239000010955 niobium Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 229910052758 niobium Inorganic materials 0.000 description 5
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052718 tin Inorganic materials 0.000 description 3
- ZSLUVFAKFWKJRC-IGMARMGPSA-N 232Th Chemical compound [232Th] ZSLUVFAKFWKJRC-IGMARMGPSA-N 0.000 description 2
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229910052776 Thorium Inorganic materials 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 229910052770 Uranium Inorganic materials 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 239000000470 constituent Substances 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 229910052733 gallium Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 229910052500 inorganic mineral Inorganic materials 0.000 description 2
- 229910052746 lanthanum Inorganic materials 0.000 description 2
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 229910052753 mercury Inorganic materials 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 239000011707 mineral Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 229910052715 tantalum Inorganic materials 0.000 description 2
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 2
- 229910052716 thallium Inorganic materials 0.000 description 2
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- DNYWZCXLKNTFFI-UHFFFAOYSA-N uranium Chemical compound [U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U][U] DNYWZCXLKNTFFI-UHFFFAOYSA-N 0.000 description 2
- 229910052720 vanadium Inorganic materials 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- 238000000137 annealing Methods 0.000 description 1
- 239000002801 charged material Substances 0.000 description 1
- 238000005097 cold rolling Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 238000005096 rolling process Methods 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 238000005482 strain hardening Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N—ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
- H10N60/00—Superconducting devices
- H10N60/80—Constructional details
- H10N60/85—Superconducting active materials
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C14/00—Alloys based on titanium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C16/00—Alloys based on zirconium
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C27/00—Alloys based on rhenium or a refractory metal not mentioned in groups C22C14/00 or C22C16/00
- C22C27/02—Alloys based on vanadium, niobium, or tantalum
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C32/00—Non-ferrous alloys containing at least 5% by weight but less than 50% by weight of oxides, carbides, borides, nitrides, silicides or other metal compounds, e.g. oxynitrides, sulfides, whether added as such or formed in situ
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
-
- 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
-
- 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
- Y10S420/00—Alloys or metallic compositions
- Y10S420/901—Superconductive
-
- 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
- Y10S505/805—Alloy or metallic
-
- 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
- Y10S505/805—Alloy or metallic
- Y10S505/806—Niobium base, Nb
-
- 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
Definitions
- This invention relates to the preparation of superconductive alloys and in particular comprises a method to improve cryogenic properties of superconductive alloys as well as to provide novel superconductive alloys.
- a further object of the invention is to provide a method in accordance with the foregoing object in which fabrication problems are not complicated and there result superconductive materials having improved cryogenic properties.
- Another object of the invention is to provide new superconductive materials.
- the invention can be practiced with superconductive alloys and compounds generally.
- This includes alloys and compounds of superconducting, exothermic, hydrogen occluding elements. These elements are in two groups.
- the first group includes titanium, vanadium, niobium, zirconium, lanthanum, tantalum, thorium and uranium, while the second group includes aluminum, zinc, gallium, cadmium, indium, tin, mercury, thallium and lead.
- the compounds and alloys can be composed of 1) any two or more elements of the first group, or (2) one or more elements of the first group with any one or more elements of the second group.
- the preferred superconductive materials with which the invention can be practiced are the zirconium-niobium alloys in which zirconium may range from about to 65, and preferably to 50, weight percent, and the bimetallic compound of niobium and tin,
- hydrogen is added to superconductive material by electrolytically liberating it on the superconductor while the latter is a cathode in an electrolytic system. Accordingly, an electrolyte that liberates hydrogen upon electrolysis is required.
- Any hydrogen liberating electrolyte is operative in the invention, but it is preferred to use aqueous mineral acid solutions of, for example, hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid and mixtures thereof.
- an aqueous electrolyte having an acid concentration within the range of about 5 to 25 weight percent is used.
- the usual parameters in electrolysis such as the electrolyte constitution and concentration, current density and the like, vary the effectiveness of the hydrogen charging process and are not independently critical.
- cathodic charging is limited by embrittlement of the superconductive cathode from hydrogen occlusion. That, of course, is a practical limitation rather than a limitation affecting operability.
- cathodic charging is conducted sufficiently to cause a volume increase in the superconductor being treated of about 5 to 15 percent or more, based on the original volume. It is to be noted that the volume change adds considerably to the plastic deformation of the matrix. While reference 'has been made above to the hydrogen addition as being an occlusion phenomenon, it should be understood that this has been done for purposes of discussion and our invention is not to be limited by any theory regarding the, nature of the hydrogen retention. Whatever the manner by which the hydrogen is held, there result new superconductive materials composed of hydrogen and the two metals. These materials are stable at ordinary conditions and it is expected that stability will be retained for a number of years.
- An 0.010 inch diameter cold drawn Wire having a composition, by weight, of 25 percent zirconium and the remainder niobium was used.
- This Wire was connected as a cathode to a DC. power source and placed in an electrolyte formed from a concentrated acid mixture of, by weight, 1 part of hydrofluoric acid, 3 parts of nitric acid and 5 parts of sulfuric acid, the acid mixture having been diluted with Water to a 10 weight percent solution.
- a platinum electrode was :used as the anode.
- the cathode was then hydrogen charged in accordance with this invention by passing current through the cell at a current density, measured at the cathode, of 1 ampereper square centimeter.
- a method of improving the cryogenic properties of superconductive materials comprising electrolytically liberating hydrogen on said superconductive material while said material is disposed as a cathode in a hydrogen liberating electrolyte, the said superconductive material being composed of at least one member selected from the group consisting of titanium, vanadium, niobium, zirconium, lanthanum, tantalum, thorium and uranium and one diflerent member of the group consisting of each of the members of the foregoing group and aluminum, zinc, gallium, cadmium, indium, tin, mercury, thallium and lead, and recovering the resulting hydrogen occluding superconductive material.
- a method of improving the cryogenic properties of superconductive materials comprising electrolytically liberating hydrogen on said superconductive material while said material is disposed as a cathode in a hydrogen liberating electrolyte, said superconductive material comprising an alloy of 10 to weight percent zirconium and the remainder niobium, and recovering the resulting hydrogen occluding superconductive alloy.
- a new superconductor comprising hydrogen and a zirconium-niobium alloy in which the zirconium is present to an amount of 15 to 60 weight percent of the alloy, the hydrogen being present in an amount sutficient to provide a volume in the superconductor of about 5 to 15 percent greater than that of the Zirconium-niobium alloy free from the hydrogen.
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Superconductors And Manufacturing Methods Therefor (AREA)
- Superconductor Devices And Manufacturing Methods Thereof (AREA)
- Electrolytic Production Of Metals (AREA)
Description
United States Patent M 3,294,529 SUPERCONDUCTIVE ALLOYS Robert C. Haverstraw, Willoughby, Ohio, and Malcolm J.
Fraser, Penn Hills, Pittsburgh, Pa., assignors to Westinghouse Electric Corporation, East Pittsburgh, Pa., a corporation of Pennsylvania No Drawing. Filed Sept. 30, 1963, Ser. No. 312,309 5 Claims. (Cl. 75-134) This invention relates to the preparation of superconductive alloys and in particular comprises a method to improve cryogenic properties of superconductive alloys as well as to provide novel superconductive alloys.
A major goal in research in superconductive alloys is the improvement of the critical current density at high magnetic fields. Changes in alloy content as Well as the use of different alloying constituents are ways in which improved critical current densities have been obtained. However, upon making such changes, production problems are changed and may create insurmountable obstacles to the use of an otherwise promising material. Accordingly, it is highly desirable to find ways of improving cryogenic properties in superconductive alloys that are known to be fabricable or to provide improved cryogenic properties in ways such that fabrication problems are not encountered.
It is therefore a primary object of the present invention to provide a method whereby the cryogenic properties of superconductive alloys can be improved by an easily practiced procedure that does not deleteriously affect the mechanical properties of the materials.
A further object of the invention is to provide a method in accordance with the foregoing object in which fabrication problems are not complicated and there result superconductive materials having improved cryogenic properties.
Another object of the invention is to provide new superconductive materials.
Other objects and advantages of the invention will appear from the following detaileddescription and discusmen.
It has now been discovered, and it is on this discovery that the invention is in large part predicated, that upon introducing hydrogen into superconductive materials, as described more particularly hereinafter, there results a superconductive material comprising the metal constituents and hydrogen having an increased volume. Upon determining, for example, the critical current density of the superconductive material before and after the hydrogen addition, it is found that a surprising increase therein results. Moreover, since the introduction of hydrogen can be practiced on the superconductive material after it has been worked to the desired state, it is evident that loss, if any, in mechanical properties need not prevent use of the improved superconductive material.
The invention can be practiced with superconductive alloys and compounds generally. This includes alloys and compounds of superconducting, exothermic, hydrogen occluding elements. These elements are in two groups. The first group includes titanium, vanadium, niobium, zirconium, lanthanum, tantalum, thorium and uranium, while the second group includes aluminum, zinc, gallium, cadmium, indium, tin, mercury, thallium and lead. The compounds and alloys can be composed of 1) any two or more elements of the first group, or (2) one or more elements of the first group with any one or more elements of the second group. The preferred superconductive materials with which the invention can be practiced are the zirconium-niobium alloys in which zirconium may range from about to 65, and preferably to 50, weight percent, and the bimetallic compound of niobium and tin,
3,294,529 Patented Dec. 27, 1966 Nb Sn, since the former of these can be fabricated to fine Wire or other shape readily and the latter has the highest known critical current density attained prior to the present invention. These materials may be used in the invention in the conventional forms now used in superconducing applications, with thin wires on the order of 0.015 inch and smaller down to about 0.001 inch in diameter being preferred. The shapes can be formed in the usual manner of alloying the metals, preferably in a purity of at least 99 weight percent, and then working the resulting material to final size and shape by practices presently known, for example, hot and cold working at light passes, the latter suitably using intermediate annealing steps.
In the invention hydrogen is added to superconductive material by electrolytically liberating it on the superconductor while the latter is a cathode in an electrolytic system. Accordingly, an electrolyte that liberates hydrogen upon electrolysis is required. Any hydrogen liberating electrolyte is operative in the invention, but it is preferred to use aqueous mineral acid solutions of, for example, hydrofluoric acid, hydrochloric acid, nitric acid, sulfuric acid and mixtures thereof. Preferably, an aqueous electrolyte having an acid concentration within the range of about 5 to 25 weight percent is used. The usual parameters in electrolysis, such as the electrolyte constitution and concentration, current density and the like, vary the effectiveness of the hydrogen charging process and are not independently critical. Generally a current density on the order of 0.1 to 5 amperes per square centimeter of cathode is used. As will be apparent to the artisan, the best conditions of operation as well as electrolyte constitution will be largely dictated by the specific application and materials involved in any given process. Platinum and stainless steel are the preferred materials for the anode in these cells, but other materials can be used as well.
The amount of cathodic charging that can be practiced in thi sinvention is limited by embrittlement of the superconductive cathode from hydrogen occlusion. That, of course, is a practical limitation rather than a limitation affecting operability. Generally cathodic charging is conducted sufficiently to cause a volume increase in the superconductor being treated of about 5 to 15 percent or more, based on the original volume. It is to be noted that the volume change adds considerably to the plastic deformation of the matrix. While reference 'has been made above to the hydrogen addition as being an occlusion phenomenon, it should be understood that this has been done for purposes of discussion and our invention is not to be limited by any theory regarding the, nature of the hydrogen retention. Whatever the manner by which the hydrogen is held, there result new superconductive materials composed of hydrogen and the two metals. These materials are stable at ordinary conditions and it is expected that stability will be retained for a number of years.
The invention will be described further in conjunction with the following examples in which the details are given by way of illustration and not by way of limitation.
An 0.010 inch diameter cold drawn Wire having a composition, by weight, of 25 percent zirconium and the remainder niobium was used. This Wire was connected as a cathode to a DC. power source and placed in an electrolyte formed from a concentrated acid mixture of, by weight, 1 part of hydrofluoric acid, 3 parts of nitric acid and 5 parts of sulfuric acid, the acid mixture having been diluted with Water to a 10 weight percent solution. A platinum electrode was :used as the anode. The cathode was then hydrogen charged in accordance with this invention by passing current through the cell at a current density, measured at the cathode, of 1 ampereper square centimeter.
The foregoing procedure was carried out on several samples. A first sample was charged for a total of 3 minutes under the above conditions. In another run a sample was charged for a period of 6 minutes. In addition, another sample was changed for two 3-minute cycles. The critical current density (in amperes) at fields of 5 to 20 kilogauss was determined on each sample before and after each charging cycle. The data obtained are:
It should be noted that these tests were of a qualitative rather than of a quantitative nature and no attempts were made to produce the highest possible current density. The above data demonstrate markedly that cathodic charging with hydrogen produce a significant increase in the critical current density at each of the fields tested. At the 20 kilogauss field and with 6 minutes of the cathodic charging, an increase in the critical current density of as high as 30 percent occurred. It is thus apparent that the invention can produce significant improvements in the critical current density of these materials.
To determine whether or not hydrogen charging destroyed the mechanical properties of the material, ductility tests were conducted on the sample charged for the 6-minute cycle. It was found that it could be bent to a radius at least as small as 0.005 inch without breakage. This sample was then cold reduced by rolling it to a ribbon 0.0025 inch thick and 0.025 inch wide. The critical current (in amperes) was again determined at fields of 5 to 20 kilogauss. In addition, a sample of the same 0.010 inch diameter wire that had not been charged was similarly cold reduced and its critical current (amperes) determined. The data obtained are:
Though the cold rolling was conducted to see if the charged material could be further worked, we were surprised to find further marked improvements in the critical current as shown by the above data. The values transverse to the rolled surface should be compared with those under sample 2 in Table I. Thus the invention provides an additional Way by which superconductive materials with improved critical current density can be obtained.
The hydrogen charging of the other superconductive materials is carried out in the same general fashion but with suitable variations of electrolyte composition to avoid unnecessary attack on the superconductive cathode. It is to be noted that even Nb Sn, the material with the highest known critical current density, can be improved in accordance with our discoveries, that is by cathodically charging it with hydrogen in aqueous mineral acid electrolyte.
From the foregoing discussion and description, it is manifest that a markedly simple and effective procedure is provided by which the critical current density of a superconductive material can be improved.
While the invention has been described with regard to detailed specific embodiments, it will be understood that variations, substitutions, changes and the like can be made without departing from its scope.
We claim:
1. A method of improving the cryogenic properties of superconductive materials comprising electrolytically liberating hydrogen on said superconductive material while said material is disposed as a cathode in a hydrogen liberating electrolyte, the said superconductive material being composed of at least one member selected from the group consisting of titanium, vanadium, niobium, zirconium, lanthanum, tantalum, thorium and uranium and one diflerent member of the group consisting of each of the members of the foregoing group and aluminum, zinc, gallium, cadmium, indium, tin, mercury, thallium and lead, and recovering the resulting hydrogen occluding superconductive material.
2. A method of improving the cryogenic properties of superconductive materials comprising electrolytically liberating hydrogen on said superconductive material while said material is disposed as a cathode in a hydrogen liberating electrolyte, said superconductive material comprising an alloy of 10 to weight percent zirconium and the remainder niobium, and recovering the resulting hydrogen occluding superconductive alloy.
3. A method in accordance with claim 2 in which the zirconium-niobium alloy superconductor is in wire form and is hydrogen charged until its volume increases up to about 15 percent.
4. A process in accordance with claim 3 in which the charged zirconium-niobium alloy superconductor is then cold worked to further increase the cryogenic properties.
5. A new superconductor comprising hydrogen and a zirconium-niobium alloy in which the zirconium is present to an amount of 15 to 60 weight percent of the alloy, the hydrogen being present in an amount sutficient to provide a volume in the superconductor of about 5 to 15 percent greater than that of the Zirconium-niobium alloy free from the hydrogen.
References Cited by the Examiner UNITED STATES PATENTS 1/1957 Brown 204- OTHER REFERENCES DAVID L. RECK, Primary Examiner.
W. C. TOWNSEND, Examiner. v C. N. LQVELL, Assistant Examiner.
Claims (1)
- 5. A NEW SUPERCONDUCTOR COMPRISING HYDROGEN AND A ZIRCONIUM-NIOBIUM ALLOY IN WHICH THE ZIRCONIUM IS PRESENT TO AN AMOUNT OF 15 TO 60 WEIGHT PERCENT OF THE ALLOY, THE HYDROGEN BEING PRESENT IN AN AMOUNT SUFFICIENT TO PROVIDE A VOLUME IN THE SUPERCONDUCTOR OF ABOUT 5 TO 15 PERCENT GREATER THAN THAT OF THE ZIRCONIUM-NIOBIUM ALLOY FREE FROM THE HYDROGEN.
Priority Applications (8)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US312309A US3294529A (en) | 1963-09-30 | 1963-09-30 | Superconductive alloys |
GB32679/64A GB1034546A (en) | 1963-09-30 | 1964-08-11 | Superconductive alloys |
DEW37495A DE1279331B (en) | 1963-09-30 | 1964-09-01 | Process for improving the superconducting properties of superconducting materials |
CH1171064A CH413019A (en) | 1963-09-30 | 1964-09-08 | Process for improving the superconducting properties of superconducting material |
ES0303961A ES303961A1 (en) | 1963-09-30 | 1964-09-11 | Method for improving the cryogenic properties of superconductor materials. (Machine-translation by Google Translate, not legally binding) |
BE653466A BE653466A (en) | 1963-09-30 | 1964-09-23 | |
FR989887A FR1410065A (en) | 1963-09-30 | 1964-09-30 | Superconducting alloys |
JP39055285A JPS5116756B1 (en) | 1963-09-30 | 1964-09-30 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US312309A US3294529A (en) | 1963-09-30 | 1963-09-30 | Superconductive alloys |
Publications (1)
Publication Number | Publication Date |
---|---|
US3294529A true US3294529A (en) | 1966-12-27 |
Family
ID=23210862
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
US312309A Expired - Lifetime US3294529A (en) | 1963-09-30 | 1963-09-30 | Superconductive alloys |
Country Status (7)
Country | Link |
---|---|
US (1) | US3294529A (en) |
JP (1) | JPS5116756B1 (en) |
BE (1) | BE653466A (en) |
CH (1) | CH413019A (en) |
DE (1) | DE1279331B (en) |
ES (1) | ES303961A1 (en) |
GB (1) | GB1034546A (en) |
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4943559A (en) * | 1988-03-07 | 1990-07-24 | U.S. Philips Corporation | Device comprising a temperature sensor |
US5122334A (en) * | 1991-02-25 | 1992-06-16 | Sandvik Special Metals Corporation | Zirconium-gallium alloy and structural components made thereof for use in nuclear reactors |
DE19526822A1 (en) * | 1995-07-15 | 1997-01-16 | Euromat Gmbh | Alloy, in particular solder alloy, method for connecting workpieces by soldering using a solder alloy and use of an alloy for soldering |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5424945U (en) * | 1977-07-19 | 1979-02-19 | ||
DE3002177C2 (en) * | 1980-01-22 | 1985-10-24 | Siemens AG, 1000 Berlin und 8000 München | Method for producing a superconductor with an intermetallic compound |
DE3035220A1 (en) * | 1980-09-18 | 1982-04-29 | Kernforschungszentrum Karlsruhe Gmbh, 7500 Karlsruhe | SUPER-CONDUCTIVE WIRE BASED ON BRONZE-NB (DOWN ARROW) 3 (DOWN ARROW) SN AND METHOD FOR THE PRODUCTION THEREOF |
Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2778725A (en) * | 1952-07-18 | 1957-01-22 | Union Carbide & Carbon Corp | Method for making powdered vanadium metal |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR1301289A (en) * | 1960-06-09 | 1962-08-17 | Gen Dynamics Corp | Process for hydrogenating zirconium and its alloys |
-
1963
- 1963-09-30 US US312309A patent/US3294529A/en not_active Expired - Lifetime
-
1964
- 1964-08-11 GB GB32679/64A patent/GB1034546A/en not_active Expired
- 1964-09-01 DE DEW37495A patent/DE1279331B/en active Pending
- 1964-09-08 CH CH1171064A patent/CH413019A/en unknown
- 1964-09-11 ES ES0303961A patent/ES303961A1/en not_active Expired
- 1964-09-23 BE BE653466A patent/BE653466A/xx unknown
- 1964-09-30 JP JP39055285A patent/JPS5116756B1/ja active Pending
Patent Citations (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US2778725A (en) * | 1952-07-18 | 1957-01-22 | Union Carbide & Carbon Corp | Method for making powdered vanadium metal |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4943559A (en) * | 1988-03-07 | 1990-07-24 | U.S. Philips Corporation | Device comprising a temperature sensor |
US5122334A (en) * | 1991-02-25 | 1992-06-16 | Sandvik Special Metals Corporation | Zirconium-gallium alloy and structural components made thereof for use in nuclear reactors |
DE19526822A1 (en) * | 1995-07-15 | 1997-01-16 | Euromat Gmbh | Alloy, in particular solder alloy, method for connecting workpieces by soldering using a solder alloy and use of an alloy for soldering |
DE19526822C2 (en) * | 1995-07-15 | 1998-07-02 | Euromat Gmbh | Solder alloy, use of the solder alloy and method for joining workpieces by soldering |
Also Published As
Publication number | Publication date |
---|---|
JPS5116756B1 (en) | 1976-05-27 |
GB1034546A (en) | 1966-06-29 |
DE1279331B (en) | 1968-10-03 |
BE653466A (en) | 1965-01-18 |
ES303961A1 (en) | 1965-03-16 |
CH413019A (en) | 1966-05-15 |
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