CN104916772A - Preparation method of superconducting wire rod - Google Patents

Preparation method of superconducting wire rod Download PDF

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Publication number
CN104916772A
CN104916772A CN201510247473.6A CN201510247473A CN104916772A CN 104916772 A CN104916772 A CN 104916772A CN 201510247473 A CN201510247473 A CN 201510247473A CN 104916772 A CN104916772 A CN 104916772A
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China
Prior art keywords
layer
superconducting wire
superconducting
copper
thickness
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Chinese (zh)
Inventor
王醒东
青木裕治
长谷川隆代
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Fortis Group (tianjin) Superconductor Technology Application Co Ltd
Futong Group Co Ltd
SWCC Showa Cable Systems Co Ltd
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Fortis Group (tianjin) Superconductor Technology Application Co Ltd
Futong Group Co Ltd
SWCC Showa Cable Systems Co Ltd
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Priority to CN201510247473.6A priority Critical patent/CN104916772A/en
Publication of CN104916772A publication Critical patent/CN104916772A/en
Pending legal-status Critical Current

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Abstract

The invention provides a preparation method of a superconducting wire rod. The method includes the following steps that: an intermediate layer is formed on a substrate; a superconducting layer is formed on the intermediate layer; a silver stabilization layer is formed on the superconducting layer; and copper plating processing is performed: after the silver stabilization layer is formed, the substrate is impregnated by a copper sulfate aqueous solution, so that a copper stabilization layer can be formed on the silver stabilization layer through electroplating, wherein the copper sulfate aqueous solution contains blue vitriol, sulfuric acid, chloride ions, a nonionic surfactant and an anionic surfactant. According to the preparation method of the invention, the nonionic surfactant and the anionic surfactant are added in the copper plating solution, so that the Cu layer can be obtained on the Ag layer, the thickness of the Cu layer along the width direction of the Cu layer is uniform, and the thickness of the center and edge of the Cu layer is uniform, and therefore, the contact resistance of welding portions of the superconducting wire rod and an electrode when the superconducting wire rod and the electrode are welded to each other will not be affected, and the superconducting performance of the superconducting wire rod will not be affected.

Description

A kind of preparation method of superconducting wire
Technical field
The invention belongs to superconducting wire technical field, particularly relate to a kind of preparation method of superconducting wire.
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 the Cu layer that plating is formed is in uneven thickness on substrate width direction, and namely the thickness of the Thickness Ratio central portion of edge part is large, as shown in Figure 1, the Cu layer central portion of the superconducting wire that Fig. 1 provides for the embodiment of the present invention and the structural representation of edge part, 51 is central portion, and 52 is edge part.When Cu layer central portion 51 and edge part 21 meeting in uneven thickness make the superconducting wire that obtains and electrode welding, the contact resistance of weld part increases, and affects the superconductivity of superconducting wire.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of superconducting wire, preparation method provided by the invention can prepare the comparatively uniform Cu layer of thickness, and the superconducting wire obtained has good superconductivity.
The invention provides a kind of preparation method of superconducting wire, comprising:
Substrate is formed the step in intermediate layer; Described intermediate layer is formed the step of superconducting layer; Described superconducting layer is formed the step of silver-colored stabilized zone; The copper plating treatment step being formed copper stabilized zone in copper sulfate solution by plating on described silver-colored stabilized zone is impregnated into after forming described silver-colored stabilized zone, it is characterized in that, in described copper sulfate solution, comprise cupric sulfate pentahydrate, sulfuric acid, chloride ion, non-ionic surface active agent and anion surfactant.
Preferably, described non-ionic surface active agent is the one in polyoxyethylene surfactant and polyol surfactant; Described anion surfactant is the one in sulfonate, sulfuric acid and carboxylate.
Preferably, described non-ionic surface active agent is the one in the copolymer of APES, octyl phenyl polyoxyethylene ether, AEO, polyethylene glycol, polypropylene glycol, polysorbate, pentaerythrite, polyethylene glycol and polypropylene glycol; Described anion surfactant is the one in neopelex, lauryl sodium sulfate, dodecyl sodium sulfate.
Preferably, the concentration of described non-ionic surface active agent in copper sulfate solution is 0.05g/L ~ 15g/L; The concentration of described anion surfactant in copper sulfate solution is 0.05g/L ~ 1.5g/L.
Preferably, the mass ratio of described anion surfactant and non-ionic surface active agent is 0.1 ~ 0.9:1.
Compared with prior art, the preparation method of superconducting wire provided by the invention comprises the following steps: the step forming intermediate layer on substrate; Described intermediate layer is formed the step of superconducting layer; Described superconducting layer is formed the step of silver-colored stabilized zone; The copper plating treatment step being formed copper stabilized zone in copper sulfate solution by plating on described silver-colored stabilized zone is impregnated into after forming described silver-colored stabilized zone, wherein, cupric sulfate pentahydrate, sulfuric acid, chloride ion, non-ionic surface active agent and anion surfactant is comprised in described copper sulfate solution.The present invention adds non-ionic surface active agent and anion surfactant in copper plating bath, make the Cu layer broad ways thickness that obtains on Ag layer even, especially the thickness of central portion and edge part is homogeneous, thus the contact resistance of weld part when can not affect the superconducting wire and electrode welding that obtain, the superconductivity of superconducting wire can not be affected.
Accompanying drawing explanation
The Cu layer central portion of the superconducting wire that Fig. 1 provides for the embodiment of the present invention and the structural representation of edge part;
The structural representation of the superconducting wire that Fig. 2 provides for the embodiment of the present invention.
Embodiment
The invention provides a kind of preparation method of superconducting wire, comprising:
Substrate is formed the step in intermediate layer; Described intermediate layer is formed the step of superconducting layer; Described superconducting layer is formed the step of silver-colored stabilized zone; The copper plating treatment step being formed copper stabilized zone in copper sulfate solution by plating on described silver-colored stabilized zone is impregnated into after forming described silver-colored stabilized zone, it is characterized in that, in described copper sulfate solution, comprise cupric sulfate pentahydrate, sulfuric acid, chloride ion, non-ionic surface active agent and anion surfactant.。
See Fig. 2, the structural representation of the superconducting wire that Fig. 2 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. 1, Fig. 1 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.
The present invention adds non-ionic surface active agent and anion surfactant in copper plating bath, make the Cu layer broad ways thickness that obtains on Ag layer even, especially the thickness of central portion and edge part is homogeneous, thus the contact resistance of weld part when can not affect the superconducting wire and electrode welding that obtain, the superconductivity of superconducting wire can not be affected.
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;
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 2
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 20 DEG C, flood 10s in the hydrochloric acid solution of 5mL/L, then wash 10s.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 3
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 20 DEG C, flood 10s in the sulfuric acid solution of 5mL/L, then directly electroplate.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 4
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 20 DEG C, flood 10s in the sulfuric acid solution of 3mL/L, then wash 10s.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 5
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 20 DEG C, flood 10s in the sulfuric acid solution of 10mL/L, then wash 10s.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 6
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 20 DEG C, flood 10s in the sulfuric acid solution of 15mL/L, then wash 10s.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 7
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 20 DEG C, flood 10s in the sulfuric acid solution of 1mL/L, then wash 10s.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 8
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 20 DEG C, flood 30s in the sulfuric acid solution of 5mL/L, then wash 10s.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 9
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 20 DEG C, flood 5s in the sulfuric acid solution of 5mL/L, then wash 10s.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 10
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 20 DEG C, flood 2s in the sulfuric acid solution of 5mL/L, then wash 10s.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 11
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 20 DEG C, flood 60s in the sulfuric acid solution of 5mL/L, then wash 10s.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 12
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 30 DEG C, flood 30s in the sulfuric acid solution of 5mL/L, then wash 10s.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Embodiment 13
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference be by the superconducting wire of formation Ag layer 50 DEG C, flood 30s in the sulfuric acid solution of 5mL/L, then wash 10s.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Comparative example 1
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference is to form the superconducting wire of Ag layer without pickling and washing, direct copper plating.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Comparative example 2
Adopt the method identical with embodiment 1 to prepare superconducting wire, when difference is to electroplate, in copper sulfate solution, do not comprise polyethylene glycol and lauryl sodium sulfate.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result;
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
Comparative example 3
Adopt the method identical with embodiment 1 to prepare superconducting wire, difference is to form the superconducting wire of Ag layer without pickling and washing, direct copper plating, and when electroplating, does not comprise polyethylene glycol and lauryl sodium sulfate in copper sulfate solution.
After copper coating, measure the peel strength of superconducting wire and Ic value, result see table 1, the peel strength of the superconducting wire that table 1 provides for the embodiment of the present invention and Ic value test result.
The peel strength of embodiment and comparative example pastes clava on superconducting wire, uses the vertical pull-up clava of cupping machine, measured by pulling force when peeling off as peel strength [MPa].
The peel strength of the superconducting wire that table 1 embodiment of the present invention provides and Ic value test result
Peel strength (MPa) Ic value (A)
Embodiment 1 80 410
Embodiment 2 50 400
Embodiment 3 60 400
Embodiment 4 50 400
Embodiment 5 70 380
Embodiment 6 70 90
Embodiment 7 30 150
Embodiment 8 60 390
Embodiment 9 50 400
Embodiment 10 30 140
Embodiment 11 60 80
Embodiment 12 60 400
Embodiment 13 30 80
Comparative example 1 20 400
Comparative example 2 70 410
Comparative example 3 20 400
After copper coating, measure the thickness of superconducting wire Cu layer central portion and the thickness of edge part, result is see table 2, and the superconducting wire surface C u tunic that table 2 provides for the embodiment of the present invention is thick.
The superconducting wire surface C u tunic that table 2 embodiment of the present invention provides is thick
Central portion thickness (μm) Edge part thickness (μm)
Embodiment 1 15 15
Embodiment 2 15 15
Embodiment 3 15 15
Embodiment 4 15 15
Embodiment 5 15 15
Embodiment 6 15 15
Embodiment 7 15 15
Embodiment 8 15 15
Embodiment 9 15 15
Embodiment 10 15 15
Embodiment 11 15 15
Embodiment 12 15 15
Embodiment 13 15 15
Comparative example 1 15 15
Comparative example 2 15 22
Comparative example 3 15 23
Embodiment 14
Superconducting wire after plated surface Cu embodiment 1 prepared is the diethanolamine solution dipping 1.5min of 1ml/L, temperature 20 DEG C in concentration, forms anti oxidation layer on superconducting wire surface.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the welding kesistance value of weld part, result see table 3, the performance test results after the superconducting wire welding that table 3 provides for the embodiment of the present invention.
Embodiment 15
Superconducting wire after plated surface Cu embodiment 1 prepared is the glycerite dipping 2min of 1.5ml/L, temperature 20 DEG C in concentration, forms anti oxidation layer on superconducting wire surface.
Described surface is formed with superconducting wire and the electrode welding of anti oxidation layer, measures the weld strength of weld part, welding kesistance and Ic value, result see table 3, table 3 for superconducting wire that the embodiment of the present invention provides weld after the performance test results.
The performance test results after the superconducting wire welding that table 3 embodiment of the present invention provides
Welding kesistance (μ Ω)
Embodiment 1 1.0
Embodiment 14 0.4
Embodiment 15 0.4
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 (5)

1. a preparation method for superconducting wire, comprising:
Substrate is formed the step in intermediate layer; Described intermediate layer is formed the step of superconducting layer; Described superconducting layer is formed the step of silver-colored stabilized zone; The copper plating treatment step being formed copper stabilized zone in copper sulfate solution by plating on described silver-colored stabilized zone is impregnated into after forming described silver-colored stabilized zone, it is characterized in that, in described copper sulfate solution, comprise cupric sulfate pentahydrate, sulfuric acid, chloride ion, non-ionic surface active agent and anion surfactant.
2. preparation method according to claim 1, is characterized in that, described non-ionic surface active agent is the one in polyoxyethylene surfactant and polyol surfactant; Described anion surfactant is the one in sulfonate, sulfuric acid and carboxylate.
3. preparation method according to claim 2, it is characterized in that, described non-ionic surface active agent is the one in the copolymer of APES, octyl phenyl polyoxyethylene ether, AEO, polyethylene glycol, polypropylene glycol, polysorbate, pentaerythrite, polyethylene glycol and polypropylene glycol; Described anion surfactant is the one in neopelex, lauryl sodium sulfate, dodecyl sodium sulfate.
4. preparation method according to claim 1, is characterized in that, the concentration of described non-ionic surface active agent in copper sulfate solution is 0.05g/L ~ 15g/L; The concentration of described anion surfactant in copper sulfate solution is 0.05g/L ~ 1.5g/L.
5. preparation method according to claim 1, is characterized in that, the mass ratio of described anion surfactant and non-ionic surface active agent is 0.1 ~ 0.9:1.
CN201510247473.6A 2015-05-15 2015-05-15 Preparation method of superconducting wire rod Pending CN104916772A (en)

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CN101421860A (en) * 2006-06-29 2009-04-29 泽奈基电力公司 Method for applying a metallic covering layer to a high-temperature superconductor
CN101490861A (en) * 2006-07-14 2009-07-22 美国超能公司 Method of forming a multifilament AC tolerant conductor withstriated stabilizer, articles related to the same, and devices incorporating the same
CN101831675A (en) * 2010-05-21 2010-09-15 南通市申海特种镀饰有限责任公司 Nickel plating process for superconducting materials
CN102222761A (en) * 2011-04-12 2011-10-19 西南交通大学 Preparation method of high temperature superconductive coating conductor La2Zr2O7 buffer layer film

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CN1714412A (en) * 2002-11-01 2005-12-28 牛津超导技术公司 Method for increasing the copper to superconductor ratio in a superconductor wire
CN101421860A (en) * 2006-06-29 2009-04-29 泽奈基电力公司 Method for applying a metallic covering layer to a high-temperature superconductor
CN101490861A (en) * 2006-07-14 2009-07-22 美国超能公司 Method of forming a multifilament AC tolerant conductor withstriated stabilizer, articles related to the same, and devices incorporating the same
CN101831675A (en) * 2010-05-21 2010-09-15 南通市申海特种镀饰有限责任公司 Nickel plating process for superconducting materials
CN102222761A (en) * 2011-04-12 2011-10-19 西南交通大学 Preparation method of high temperature superconductive coating conductor La2Zr2O7 buffer layer film

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109972182A (en) * 2019-05-16 2019-07-05 苏州新材料研究所有限公司 The roll-to-roll continuous surface treatment process of superconducting tape and equipment

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