CN104851513A - Superconductive wire rod and preparation method thereof - Google Patents
Superconductive wire rod and preparation method thereof Download PDFInfo
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- CN104851513A CN104851513A CN201510247202.0A CN201510247202A CN104851513A CN 104851513 A CN104851513 A CN 104851513A CN 201510247202 A CN201510247202 A CN 201510247202A CN 104851513 A CN104851513 A CN 104851513A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000010949 copper Substances 0.000 claims abstract description 78
- 238000003466 welding Methods 0.000 claims abstract description 76
- 230000003064 anti-oxidating effect Effects 0.000 claims abstract description 57
- 239000000758 substrate Substances 0.000 claims abstract description 21
- 238000007747 plating Methods 0.000 claims description 19
- 239000000463 material Substances 0.000 claims description 17
- 239000003963 antioxidant agent Substances 0.000 claims description 16
- 230000003078 antioxidant effect Effects 0.000 claims description 16
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 0.000 claims description 16
- 229940043237 diethanolamine Drugs 0.000 claims description 16
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 14
- 229910052802 copper Inorganic materials 0.000 claims description 13
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 11
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 10
- -1 alcohol compound Chemical class 0.000 claims description 10
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 9
- 150000001875 compounds Chemical class 0.000 claims description 6
- 238000007598 dipping method Methods 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 5
- 150000002148 esters Chemical class 0.000 claims description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- 239000010410 layer Substances 0.000 abstract description 187
- 238000000034 method Methods 0.000 abstract description 32
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 abstract description 11
- 239000007788 liquid Substances 0.000 abstract description 7
- 238000003860 storage Methods 0.000 abstract description 3
- 239000007787 solid Substances 0.000 abstract description 2
- 239000011229 interlayer Substances 0.000 abstract 2
- 239000005751 Copper oxide Substances 0.000 abstract 1
- 230000015556 catabolic process Effects 0.000 abstract 1
- 229910000431 copper oxide Inorganic materials 0.000 abstract 1
- 238000006731 degradation reaction Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 31
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 20
- 238000011056 performance test Methods 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 12
- 238000004544 sputter deposition Methods 0.000 description 9
- 239000002887 superconductor Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 239000004094 surface-active agent Substances 0.000 description 6
- 239000002202 Polyethylene glycol Substances 0.000 description 5
- 239000011248 coating agent Substances 0.000 description 5
- 238000000576 coating method Methods 0.000 description 5
- 229960004643 cupric oxide Drugs 0.000 description 5
- 230000006866 deterioration Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 229920001223 polyethylene glycol Polymers 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 4
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical compound OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 description 4
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 4
- 239000003945 anionic surfactant Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000009713 electroplating Methods 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 229910002328 LaMnO3 Inorganic materials 0.000 description 3
- 229910000990 Ni alloy Inorganic materials 0.000 description 3
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 229910052788 barium Inorganic materials 0.000 description 3
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 3
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 3
- 229910000366 copper(II) sulfate Inorganic materials 0.000 description 3
- 229910052593 corundum Inorganic materials 0.000 description 3
- 238000000354 decomposition reaction Methods 0.000 description 3
- 238000004821 distillation Methods 0.000 description 3
- 238000007735 ion beam assisted deposition Methods 0.000 description 3
- 238000005554 pickling Methods 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- 229910001845 yogo sapphire Inorganic materials 0.000 description 3
- 229910052688 Gadolinium Inorganic materials 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 229910052772 Samarium Inorganic materials 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 229910000856 hastalloy Inorganic materials 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 229920001451 polypropylene glycol Polymers 0.000 description 2
- 239000001103 potassium chloride Substances 0.000 description 2
- 235000011164 potassium chloride Nutrition 0.000 description 2
- 230000006641 stabilisation Effects 0.000 description 2
- 238000011105 stabilization Methods 0.000 description 2
- BDHFUVZGWQCTTF-UHFFFAOYSA-M sulfonate Chemical compound [O-]S(=O)=O BDHFUVZGWQCTTF-UHFFFAOYSA-M 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052727 yttrium Inorganic materials 0.000 description 2
- AGIJRRREJXSQJR-UHFFFAOYSA-N 2h-thiazine Chemical compound N1SC=CC=C1 AGIJRRREJXSQJR-UHFFFAOYSA-N 0.000 description 1
- LRBQNJMCXXYXIU-PPKXGCFTSA-N Chinese gallotannin Chemical compound OC1=C(O)C(O)=CC(C(=O)OC=2C(=C(O)C=C(C=2)C(=O)OC[C@@H]2[C@H]([C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)[C@H](OC(=O)C=3C=C(OC(=O)C=4C=C(O)C(O)=C(O)C=4)C(O)=C(O)C=3)O2)OC(=O)C=2C=C(OC(=O)C=3C=C(O)C(O)=C(O)C=3)C(O)=C(O)C=2)O)=C1 LRBQNJMCXXYXIU-PPKXGCFTSA-N 0.000 description 1
- 229910052692 Dysprosium Inorganic materials 0.000 description 1
- 229910052691 Erbium Inorganic materials 0.000 description 1
- 229910052693 Europium Inorganic materials 0.000 description 1
- 229910052689 Holmium Inorganic materials 0.000 description 1
- 241001272567 Hominoidea Species 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910052779 Neodymium Inorganic materials 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 1
- 229910052771 Terbium Inorganic materials 0.000 description 1
- 229910052775 Thulium Inorganic materials 0.000 description 1
- 229910052769 Ytterbium Inorganic materials 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 150000007942 carboxylates Chemical class 0.000 description 1
- 238000005229 chemical vapour deposition Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 239000000975 dye Substances 0.000 description 1
- 238000000313 electron-beam-induced deposition Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000002346 layers by function Substances 0.000 description 1
- 150000007522 mineralic acids Chemical class 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920000136 polysorbate Polymers 0.000 description 1
- 229950008882 polysorbate Drugs 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
Classifications
-
- 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
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
- Y02E40/60—Superconducting electric elements or equipment; Power systems integrating superconducting elements or equipment
Abstract
Provided in the invention is a superconductive wire rod comprising a substrate, an interlayer formed on the substrate, a superconductive layer formed on the interlayer, a Ag layer formed on the superconductive layer, a Cu layer formed on the Ag layer, and an anti-oxidation layer formed on the Cu layer. The anti-oxidation layer is in a liquid or solid state under a normal temperature and is converted into a gaseous state under a welding temperature. In addition, the invention also provides a preparation method of the superconductive wire rod. Under a normal temperature, the Cu of the wire rod is protected by the anti-oxidation layer; and the Cu layer is not oxidized and no copper oxide is generated during the long-time transport and storage process. When the superconductive wire rod and an electrode is welded, the anti-oxidation layer on the Cu layer is converted into one in a gaseous state under a welding temperature and thus the Cu layer is exposed, thereby realizing welding of the Cu and the electrode. Therefore, the welding intensity is not reduced; the welding part resistance is not increased; and the degradation of the superconductive wire rod is not influenced.
Description
Technical field
The invention belongs to superconducting wire technical field, particularly relate to a kind of superconducting wire and preparation method thereof.
Background technology
Superconductor has under certain cryogenic conditions, to present resistance to equal zero the material of character, is widely used in making magnet, making power cable etc.
Along with the development of superconductor, two generation superconducting wire occur thereupon, its typical structure is made up of substrate, resilient coating, superconducting layer and stabilization layer, and wherein, substrate is the supporter of whole superconducting wire; Resilient coating is named intermediate layer again, and effect is that the growth for superconducting layer provides texture etc.; Superconducting layer is formed by superconductor, is the carrier of electric current; Stabilization layer is stabilized zone again, and effect is to protect superconducting layer, and it is generally Ag layer.In addition, prior art is generally electroplated on superconducting wire surface, forms stable Cu layer.But Cu also can be oxidized generation cupric oxide gradually, particularly when carrying out superconducting wire taking care of for a long time or transporting for a long time, the generation highly significant of cupric oxide.If under the state that cupric oxide is contained on surface, welded with electrode by superconducting wire, weld strength not only can be caused to reduce, and the contact resistance of welding position can be made to increase.
Summary of the invention
The object of the present invention is to provide a kind of superconducting wire and preparation method thereof, when superconducting wire provided by the invention welds with electrode, the contact resistance of welding position is less.
The invention provides a kind of superconducting wire, comprising:
Substrate;
Form intermediate layer on the substrate;
Be formed in the superconducting layer on described intermediate layer;
Be formed in the Ag layer on described superconducting layer;
Be formed in the Cu layer on described Ag layer;
Be formed in the anti oxidation layer on described Cu layer.
Preferably, described anti oxidation layer is formed by the material being converted into gaseous products under welding temperature.
Preferably, described anti oxidation layer is formed by one or more in ester type compound, aminated compounds, alcohol compound and organic acid compound.
Preferably, described anti oxidation layer is formed by diethanol amine or glycerine.
Present invention also offers a kind of preparation method of superconducting wire, comprising: be formed at the step intermediate layer on substrate being formed superconducting layer; Described superconducting layer is formed the step of silver-colored stabilized zone; After silver-colored stabilized zone is formed, electroplating by immersing copper sulfate solution, described silver layer being formed the copper plating treatment step of copper stabilized zone, is also included in step copper stabilized zone being formed anti oxidation layer by the material being converted into gaseous state under welding temperature.
Preferably, the temperature of described dipping is less than 30 DEG C, and the time of described dipping is 0.5min ~ 3min.
Preferably, described antioxidant is diethanol amine or glycerine.
Preferably, the concentration of described antioxidant solution is 0.5mL/L ~ 2mL/L.
Compared with prior art, superconducting wire provided by the invention comprises substrate, forms intermediate layer on the substrate, the superconducting layer be formed on described intermediate layer, the Ag layer be formed on described superconducting layer, the Cu layer be formed on described Ag layer, the anti oxidation layer be formed on described Cu layer, and described anti oxidation layer is formed by the material being converted into gaseous products under welding temperature.The present invention is converted into gaseous products material under adopting welding temperature obtains superconducting wire at superconducting wire Cu layer outside formation anti oxidation layer, at normal temperatures, the Cu of this superconducting wire is protected by anti oxidation layer, in long transport and storage process, Cu layer can not be oxidized, can not generate cupric oxide; And when superconducting wire is welded with electrode, antioxidant on Cu layer is converted into gaseous state by modes such as volatilization, distillation or decomposition under welding temperature, thus expose Cu layer, realize welding of Cu and electrode, thus weld strength not only can not be caused to reduce, the resistance of welding position can not be made to increase, also can not affect the deterioration of superconducting wire performance.Experimental result shows, superconducting wire provided by the invention through with electrode welding after, its welding kesistance is at 0.5 below μ Ω.
Accompanying drawing explanation
The structural representation of the superconducting wire that Fig. 1 provides for the embodiment of the present invention;
The Cu layer central portion of the superconducting wire that Fig. 2 provides for the embodiment of the present invention and the structural representation of edge part.
Embodiment
The invention provides a kind of superconducting wire, comprising:
Substrate;
Form intermediate layer on the substrate;
Be formed in the superconducting layer on described intermediate layer;
Be formed in the Ag layer on described superconducting layer;
Be formed in the Cu layer on described Ag layer;
Be formed in the anti oxidation layer on described Cu layer, described anti oxidation layer is formed by the material being converted into gaseous products under welding temperature.
See Fig. 1, the structural representation of the superconducting wire that Fig. 1 provides for the embodiment of the present invention, wherein, 1 is substrate, 2 for forming intermediate layer on substrate 1, and 3 for being formed in the superconducting layer on intermediate layer 2, and 4 for being formed in the Ag layer on superconducting layer, 5 for being formed in the Cu layer on Ag layer, and 6 for being formed in the anti oxidation layer on Cu layer.
First, superconducting wire provided by the invention comprises substrate, and described substrate, as the supporter of whole superconducting wire, can be nickel alloy plate, as Hastelloy nickel alloy plate etc.
After forming intermediate layer on the substrate, then form superconducting layer on the intermediate layer.The growth that described intermediate layer is superconducting layer provides texture, can for Al2O3 layer, Y2O3 layer, MgO layer, LaMnO3 layer, CeO2 layer, stabilized with yttrium oxide zirconia layer, comprise the multilayer such as yittrium oxide and zirconic GdZrO layer form, such as, the five-layer structure forming Al2O3 layer, Y2O3 layer, MgO layer, LaMnO3 layer and CeO2 layer is successively preferably.At least one method that intermediate layer can be passed through in sputtering, laser grinding, electron beam deposition (IBAD) is formed, and wherein, preferably adopts sputtering method to form Al2O3 layer, Y2O3 layer, LaMnO3 layer and CeO2 layer, adopts IBAD method to form MgO layer.
The superconducting layer that described intermediate layer is formed is the functional layer of superconducting wire, can adopt REBaCuO series superconducting material, and wherein, RE is one or more in Y, Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm and Yb.Such as, this superconducting layer can be the superconductor comprising Ho, Ba, Cu and O; Or comprise the superconductor of Y, Ba, Cu and O; Or comprise the superconductor of Gd, Ba, Cu and O; Or comprise the superconductor of Sm, Ba, Cu and O.At least one method that superconducting layer can pass through in sputtering, laser grinding, metal organic deposition (MOD) and metal organic chemical vapor deposition (MOCVD) is formed, and preferably adopts MOD method to be formed.
In superconducting wire provided by the invention, described superconducting layer is also formed with Ag layer, the effect of Ag layer is to protect superconducting layer, and its thickness is preferably 5 μm ~ 50 μm, when its thickness is greater than 50 μm, and cost is higher and can affect the mechanical strength of superconducting wire; When thickness is less than 5 μm, inadequate to the protection of superconducting layer.In the present invention, Ag layer can be formed by sputtering method.
Thereafter, for improve Cu layer and Ag layer in conjunction with tightness degree, the present invention uses acid solution to process the wire rod with Ag Rotating fields.Described acid solution is inorganic acid, and such as, watery hydrochloric acid, dilute sulfuric acid etc., be preferably dilute sulfuric acid.The concentration of described dilute sulfuric acid is preferably 3ml/L ~ 10ml/L.When concentration exceeds above-mentioned scope, the wire rod with Ag Rotating fields, from the impact of edge part by dilute sulfuric acid, causes the superconductivity of wire rod to reduce.During lower than above-mentioned scope, peel strength is caused to reduce owing to can not get clean effect.
The temperature of the described pickling processes adopting acid solution to carry out is preferably less than 30 DEG C; The time of described pickling processes is preferably 5s ~ 30s.Described acid solution process, uses acid solution to clean specifically.When exceeding above-mentioned scope, the wire rod with Ag Rotating fields, from the impact of edge part by dilute sulfuric acid, causes the superconductivity of wire rod to reduce.During lower than above-mentioned scope, peel strength is caused to reduce owing to can not get clean effect.
After using acid solution to process superconducting wire, copper plating treatment can be carried out on Ag layer.Concrete grammar is as follows: to have the wire rod of Ag Rotating fields as negative electrode, be anode, in copper sulfate bath, carry out electroplating processes, Ag layer is formed Cu layer with electrode.
In addition, before carrying out copper facing, neutrality process cleaning can also be carried out to the wire rod with Ag Rotating fields, namely adopt water or alkaline solution to clean superconducting wire, make superconducting wire keep neutral.Preferred use water carries out middle process.
Can carry out electroplating processes to the wire rod with Ag Rotating fields after washing, Ag layer is formed Cu layer Ag layer to defencive function, the thickness of Cu layer is preferably 10 μm ~ 50 μm, is more preferably 10 μm ~ 40 μm.Except Ag layer, Cu layer also may be formed in the another side of substrate.When adopting galvanoplastic to form Cu layer, electroplate again after preferably successively pickling and washing being carried out to Ag layer, thus improve Ag layer and Cu layer in conjunction with tightness degree.In addition, the present invention carries out copper plating treatment to wire rod in copper sulfate bath, and the main component of described copper sulfate bath is cupric sulfate pentahydrate, sulfuric acid and chloride ion, can also comprise the additives known such as brightener, leveling agent.Wherein, the concentration of cupric sulfate pentahydrate is preferably 180g/L ~ 240g/L, and sulfuric acid concentration is preferably 60g/L ~ 90g/L, and the concentration of chloride ion is preferably 30ppm ~ 800ppm, and chloride ion can be provided by the chloride such as potassium chloride, sodium chloride.Brightener can be sodium polydithio-dipropyl sulfonate, and its concentration is preferably 0.4g/L ~ 0.8g/L; Leveling agent can be thiazin dyes, and its concentration can be 0.2g/L ~ 0.4g/L.Even in order to make at the Cu layer thickness of Ag layer surface formation, preferably also comprise non-ionic surface active agent and anion surfactant in described copper sulfate bath.Wherein, non-ionic surface active agent comprises polyoxyethylene surfactant, as APES, octyl phenyl polyoxyethylene ether, AEO etc.; Or polyol surfactant, as the copolymer etc. of polyethylene glycol, polypropylene glycol, polysorbate, pentaerythrite, polyethylene glycol and polypropylene glycol, is preferably polyethylene glycol.The concentration of described polyethylene glycol in copper sulfate solution is preferably 0.05g/L ~ 15g/L, is more preferably 0.1g/L ~ 10g/L.Exceed above-mentioned scope, can make superconducting layer that deterioration occurs, cause superconductivity to decline; Lower than above-mentioned scope, meeting as described below makes the thickness of central portion 51 and the uneven thickness of edge part 52.
Described anion surfactant comprises sulfonate, sulfuric acid, carboxylate etc., as neopelex, lauryl sodium sulfate, dodecyl sodium sulfate etc., is preferably lauryl sodium sulfate.The concentration of described lauryl sodium sulfate in copper sulfate bath is preferably 0.05g/L ~ 1.5g/L, is more preferably 0.1g/L ~ 1g/L.Exceed above-mentioned scope, can make superconducting layer that deterioration occurs, cause superconductivity to decline; Lower than above-mentioned scope, meeting as described below makes the thickness of central portion 51 and the uneven thickness of edge part 52.The mass ratio of described anion surfactant and non-ionic surface active agent is preferably 0.1 ~ 0.9:1, is more preferably 0.2 ~ 0.8:1.In above-mentioned scope, the thickness of central portion 51 and the thickness of edge part 52 comparatively homogeneous, substantially identical.
The Cu layer central portion of superconducting wire provided for the embodiment of the present invention see Fig. 2, Fig. 2 and the structural representation of edge part, 51 is central portion, and 52 is edge part; When adopting common copper-bath to electroplate it, the thickness of central portion 51 is less than the thickness of edge part 52, add non-ionic surface active agent and anion surfactant in copper-bath after simultaneously, the thickness of central portion 51 and the thickness of edge part 52 comparatively homogeneous, substantially identical.
When electroplating, the current density of plated surface is not higher than 10A/dm
2, be preferably 1A/dm
2~ 5A/dm
2; The temperature of plating solution is preferably less than 40 DEG C; The time of plating is preferably 10min ~ 30min.
In superconducting wire provided by the invention, also on Cu layer, form anti oxidation layer.Described anti oxidation layer by under normal temperature for liquid or the solid-state and material being converted into gaseous state under welding temperature is formed, the present invention claims this material to be antioxidant.In the present invention, described antioxidant is liquid or solid-state at normal temperatures, and wherein, normal temperature refers to 10 DEG C ~ 40 DEG C, and it can be attached to Cu layer surface protection Cu layer for liquid or solid-state this material that makes at normal temperatures, avoids Cu to be oxidized; Meanwhile, described antioxidant can be converted into gaseous state under welding temperature, wherein, welding temperature refers to temperature when being welded with electrode by superconducting wire, general more than 130 DEG C, be preferably 140 DEG C ~ 250 DEG C, can make superconducting wire that deterioration occurs higher than above-mentioned scope.Be converted into gaseous state to refer to and be converted into gas by evaporation, distillation or the physics such as decomposition or chemical method.That is, described antioxidant under welding temperature can from liquid or solid state transformed be gaseous state, thus with Cu pull-up from, expose Cu layer, ensure that Cu makes Cu layer smoothly and electrode welding while not oxidized, thus obtain higher weld strength, and make the contact resistance of welding position less.
In the present invention, described anti oxidation layer can by under normal temperature for the liquid and material volatilized under welding temperature is formed; Or, described anti oxidation layer by under normal temperature for the liquid and material being decomposed into gaseous products under welding temperature is formed; Or, described anti oxidation layer by under normal temperature for solid-state and material that is that distil under welding temperature is formed.This type of material include but not limited in ester type compound, aminated compounds, alcohol compound and organic acid compound one or more, be preferably diethanol amine or glycerine.
The present invention is converted into gaseous state material under adopting welding temperature obtains superconducting wire at superconducting wire Cu layer outside formation anti oxidation layer, at normal temperatures, the Cu of this superconducting wire is protected by anti oxidation layer, in long transport and storage process, Cu layer can not be oxidized, can not generate cupric oxide; And when superconducting wire is welded with electrode, antioxidant on Cu layer is converted into gaseous state by modes such as volatilization, distillation or decomposition under welding temperature, thus expose Cu layer, realize welding of Cu and electrode, thus weld strength not only can not be caused to reduce, the resistance of welding position can not be made to increase, also can not affect the deterioration of superconducting wire performance.
Above-mentioned antioxidant solution is directly coated on the Cu layer of superconducting wire by the present invention, can obtain anti oxidation layer; Or superconducting wire can be flooded in antioxidant solution, after taking-up, also can form anti oxidation layer on Cu layer; Or the method for spraying can be adopted to be sprayed on superconducting wire by antioxidant solution, Cu layer forms anti oxidation layer.In the present invention, antioxidant solution is preferably the aqueous solution of antioxidant; The concentration of antioxidant solution is preferably 0.5mL/L ~ 2mL/L.In the present invention, the temperature of described coating is preferably less than 30 DEG C, and the time of described coating is preferably 0.5min ~ 3min; The temperature of described dipping is preferably less than 30 DEG C, and the time of described dipping is preferably 0.5min ~ 3min; The temperature of the solution of described spraying is preferably less than 30 DEG C, and the time of described spraying is preferably 0.5min ~ 3min.
Experimental result shows, superconducting wire provided by the invention through with electrode welding after, its welding kesistance is at 0.5 below μ Ω.
In order to further illustrate the present invention, be described superconducting wire provided by the invention and preparation method thereof below in conjunction with embodiment, protection scope of the present invention is not limited by the following examples.
Embodiment 1
Ni alloy substrate (Hastelloy (registered trade mark) band) use successively sputtering method form Al
2o
3layer, sputtering method form Y
2o
3layer, IBAD method form MgO layer, sputtering method forms LaMnO
3layer and sputtering method form CeO
2layer; At CeO
2layer use MOD method form YBaCuO superconducting layer; Use sputtering method to form Ag layer, form the superconducting wire with Ag Rotating fields.
By described wire rod 20 DEG C, flood 10s in the sulfuric acid solution of 5mL/L, then wash 10s; Superconducting wire after washing is electroplated in copper sulfate solution as negative electrode, the Cu layer that formation 15 μm is thick on Ag layer, copper sulfate solution comprises the lauryl sodium sulfate of the cupric sulfate pentahydrate of 200g/L, the sulfuric acid of 80g/L, the potassium chloride of 300ppm, the polyethylene glycol of 0.3g/L and 0.05g/L, the temperature of copper sulfate solution is 20 DEG C, plating 20min, current density is 3A/dm
2; By superconducting wire after plating Cu temperature be 20 DEG C, concentration is flood 2min in the diethanolamine solution of 1ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Embodiment 2
The method adopting embodiment 1 to prepare is prepared superconducting wire, difference be by superconducting wire after plating Cu temperature be 20 DEG C, concentration is flood 2min in the glycerite of 1ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Embodiment 3
The method adopting embodiment 1 to prepare is prepared superconducting wire, difference be by superconducting wire after plating Cu temperature be 20 DEG C, concentration is flood 2min in the diethanolamine solution of 0.5ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Embodiment 4
The method adopting embodiment 1 to prepare is prepared superconducting wire, difference be by superconducting wire after plating Cu temperature be 20 DEG C, concentration is flood 2min in the diethanolamine solution of 2ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Embodiment 5
The method adopting embodiment 1 to prepare is prepared superconducting wire, difference be by superconducting wire after plating Cu temperature be 30 DEG C, concentration is flood 2min in the diethanolamine solution of 1ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Embodiment 6
The method adopting embodiment 1 to prepare is prepared superconducting wire, difference be by superconducting wire after plating Cu temperature be 20 DEG C, concentration is flood 0.5min in the diethanolamine solution of 1ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Embodiment 7
The method adopting embodiment 1 to prepare is prepared superconducting wire, difference be by superconducting wire after plating Cu temperature be 20 DEG C, concentration is flood 3min in the diethanolamine solution of 1ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Comparative example 1
The method adopting embodiment 1 to prepare is prepared superconducting wire, and difference is not carry out anti oxidation layer coating on superconducting wire surface.
By the described superconducting wire without anti oxidation layer and electrode welding, measure the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Comparative example 2
The method adopting embodiment 1 to prepare is prepared superconducting wire, difference be by superconducting wire after plating Cu temperature be 20 DEG C, concentration is flood 2min in the diethanolamine solution of 0.1ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Comparative example 3
The method adopting embodiment 1 to prepare is prepared superconducting wire, difference be by superconducting wire after plating Cu temperature be 20 DEG C, concentration is flood 2min in the diethanolamine solution of 3ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Comparative example 4
The method adopting embodiment 1 to prepare is prepared superconducting wire, difference be by superconducting wire after plating Cu temperature be 40 DEG C, concentration is flood 2min in the diethanolamine solution of 1ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Comparative example 5
The method adopting embodiment 1 to prepare is prepared superconducting wire, difference be by superconducting wire after plating Cu temperature be 20 DEG C, concentration is flood 0.1min in the diethanolamine solution of 1ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Comparative example 6
The method adopting embodiment 1 to prepare is prepared superconducting wire, difference be by superconducting wire after plating Cu temperature be 20 DEG C, concentration is flood 4min in the diethanolamine solution of 1ml/L to carry out being coated in superconducting wire surface and form anti oxidation layer.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part and weld strength, result see table 1, the performance test results after the superconducting wire welding that table 1 provides for the embodiment of the present invention.
Weld strength test is carried out and welding kesistance measures, in the superconducting wire performance test table that table 1 embodiment of the present invention provides after embodiment and the superconducting wire compared and tab welding.
The superconducting wire performance test table that table 1 embodiment of the present invention provides
| Welding kesistance (μ Ω) | Weld strength | |
| Embodiment 1 | 0.45 | By force |
| Embodiment 2 | 0.45 | By force |
| Embodiment 3 | 0.50 | By force |
| Embodiment 4 | 0.49 | By force |
| Embodiment 5 | 0.48 | By force |
| Embodiment 6 | 0.51 | By force |
| Embodiment 7 | 0.49 | By force |
| Comparative example 1 | 9.51 | Weak |
| Comparative example 2 | 1.92 | Weak |
| Comparative example 3 | 1.15 | Stronger |
| Comparative example 4 | 1.43 | Weak |
| Comparative example 5 | 1.68 | Weak |
| Comparative example 6 | 1.45 | Stronger |
The above is only the preferred embodiment of the present invention; it should be pointed out that for those skilled in the art, under the premise without departing from the principles of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (8)
1. a superconducting wire, comprising:
Substrate;
Form intermediate layer on the substrate;
Be formed in the superconducting layer on described intermediate layer;
Be formed in the Ag layer on described superconducting layer;
Be formed in the Cu layer on described Ag layer;
Be formed in the anti oxidation layer on described Cu layer.
2. superconducting wire according to claim 1, is characterized in that, described anti oxidation layer is formed by the material being converted into gaseous products under welding temperature.
3. superconducting wire according to claim 2, is characterized in that, described anti oxidation layer is formed by one or more in ester type compound, aminated compounds, alcohol compound and organic acid compound.
4. superconducting wire according to claim 3, is characterized in that, described anti oxidation layer is formed by diethanol amine or glycerine.
5. a preparation method for superconducting wire, comprising: be formed at the step intermediate layer on substrate being formed superconducting layer; Described superconducting layer is formed the step of silver-colored stabilized zone; After silver-colored stabilized zone is formed, electroplate by immersing copper sulfate solution, described silver layer is formed the copper plating treatment step of copper stabilized zone, it is characterized in that, be also included in step copper stabilized zone being formed anti oxidation layer by the material being converted into gaseous state under welding temperature.
6. preparation method according to claim 5, is characterized in that, the temperature of described dipping is less than 30 DEG C, and the time of described dipping is 0.5min ~ 3min.
7. preparation method according to claim 6, is characterized in that, described antioxidant is diethanol amine or glycerine.
8. preparation method according to claim 7, is characterized in that, the concentration of described antioxidant solution is 0.5mL/L ~ 2mL/L.
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| CN115274211A (en) * | 2022-08-15 | 2022-11-01 | 中国科学院上海微系统与信息技术研究所 | Iron-based superconducting transmission line for trans-temperature-zone microwave signal transmission and preparation method thereof |
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