CN104953022A - Production method of superconducting wire - Google Patents

Production method of superconducting wire Download PDF

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Publication number
CN104953022A
CN104953022A CN201510251018.3A CN201510251018A CN104953022A CN 104953022 A CN104953022 A CN 104953022A CN 201510251018 A CN201510251018 A CN 201510251018A CN 104953022 A CN104953022 A CN 104953022A
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China
Prior art keywords
layer
superconducting wire
superconducting
copper
silver
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CN201510251018.3A
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Chinese (zh)
Inventor
王醒东
叶新羽
林中山
雷俊玲
张恩
郭慧
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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Application filed by Fortis Group (tianjin) Superconductor Technology Application Co Ltd, Futong Group Co Ltd, SWCC Showa Cable Systems Co Ltd filed Critical Fortis Group (tianjin) Superconductor Technology Application Co Ltd
Priority to CN201510251018.3A priority Critical patent/CN104953022A/en
Publication of CN104953022A publication Critical patent/CN104953022A/en
Pending legal-status Critical Current

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Abstract

The invention provides a production method of a superconducting wire. The production method includes the steps of forming a superconducting layer on an intermediate layer formed on a substrate; forming a silver stable layer on the superconducting layer; after the silver stable layer forms, performing immersing with copper sulfate solution for copper plating so as to form a copper stable layer on the silver stable layer; before forming of the copper stable layer, using acid solution to pickle the surface of the silver stable layer. During copper plating of the Ag layer, the Ag layer is subjected to acid treatment first to remove dirt, impurity, silver oxide and the like on the surface of the Ag layer; connection tightness of the Ag layer and the Cu layer is improved without lowering the superconductivity of the superconducting wire; the peel strength of the superconducting wire is higher. Experiments show that the peel strength of the superconducting wire produced by the production method reaches above 50 MPa.

Description

The preparation method of superconducting wire
Technical field
The invention belongs to superconducting wire technical field, particularly relate to a kind of preparation of superconducting wire.
Background technology
Superconductor has the material presenting the null character of resistance under certain cryogenic conditions, 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 if just merely form Cu layer on Ag layer, poor in conjunction with tightness degree because of between Cu layer and Ag layer, can reduce the Cu layer of superconducting wire and the peel strength of Ag layer.
Summary of the invention
The object of the present invention is to provide a kind of preparation method of superconducting wire, the superconducting wire that preparation method provided by the invention obtains when not making superconductivity that deterioration occurs, can improve peel strength.
The invention provides 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, 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, before formation copper stabilized zone step, also comprise the solution using and be made up of acid solution carries out pickling processes step to silver-colored stabilized zone surface.
Preferably, described acid solution is dilute sulfuric acid.
Preferably, the concentration of described dilute sulfuric acid is 3ml/L ~ 10ml/L.
Preferably, the temperature of described pickling processes step is less than 30 DEG C, and the time of described pickling processes step is 5s ~ 30s.
Preferably, also comprise between described pickling processes step and described copper plating treatment step, the neutral step processed is carried out to the superconducting wire that pickling processes step process is crossed.
Preferably, described neutrality is treated to washing.
Preferably, also comprise:
Described copper stabilized zone is formed the step of anti oxidation layer, and described anti oxidation layer is formed by the material being converted into gaseous state under welding temperature.
Preferably, described material is diethanol amine or glycerine.
Preferably, the copper plating bath that copper plating treatment step adopts comprises: cupric sulfate pentahydrate, sulfuric acid, chloride ion, non-ionic surface active agent and anion surfactant.
Preferably, described non-ionic surface active agent is polyethylene glycol; Described anion surfactant is lauryl sodium sulfate.
The present invention is when carrying out copper plating treatment to Ag layer, first acid treatment is carried out to Ag layer, remove the dirt on Ag surface, impurity and silver oxide etc., improve when not making the superconductivity of superconducting wire that deterioration occurs Ag layer and Cu layer in conjunction with tightness degree, make the superconducting wire obtained have higher peel strength.Experimental result shows, the peel strength of the superconducting wire that method provided by the invention prepares is at more than 50MPa.
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:
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, and on described silver layer, form the copper plating treatment step of copper stabilized zone, before formation copper stabilized zone step, also comprise the solution using and be made up of acid solution carries out pickling processes step to silver-colored stabilized zone surface.
In the present invention, to described superconducting layer, form the step of silver-colored stabilized zone, prepare in accordance with the following methods.
The structural representation of the superconducting wire that Fig. 2 provides for the embodiment of the present invention.Wherein, 1 is substrate, and 2 is form 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, and 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.Described substrate is the supporter of whole superconducting wire, can be nickel alloy plate, as Hastelloy nickel alloy plate etc.
Form intermediate layer on the substrate, and then form superconducting layer on the intermediate layer.The growth that described intermediate layer is superconducting layer provides texture, can be by Al 2o 3layer, Y 2o 3layer, MgO layer, LaMnO 3layer, CeO 2the sandwich construction of the formation such as zirconia layer, GdZrO layer of layer, stabilized with yttrium oxide.Such as, preferably Al is formed successively 2o 3layer, Y 2o 3layer, MgO layer, LaMnO 3layer and CeO 2the five-layer structure of layer.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 Al 2o 3layer, Y 2o 3layer, LaMnO 3layer and CeO 2layer, adopts IBAD method to form MgO layer.
The superconducting layer formed on the substrate is the functional layer of superconducting wire, adopts 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.
In order to improve between Cu layer and Ag layer in conjunction with tightness degree, the wire rod with Ag Rotating fields is carried out pickling processes by the present invention in by the solution that acid solution is formed.Wherein, described acid solution can be inorganic acid fluid, as watery hydrochloric acid, dilute sulfuric acid etc., is preferably dilute sulfuric acid.The concentration of described dilute sulfuric acid is preferably 3ml/L ~ 10ml/L, higher than above-mentioned concentration, dilute sulfuric acid can be caused to form deterioration from the edge part with Ag Rotating fields wire rod to superconducting layer, and reduce superconductivity.Lower than above-mentioned concentration, because clean effect cannot be obtained, and reduce peel strength.
When adopting acid solution to carry out described pickling processes step, the temperature of process is preferably less than 30 DEG C; The time of described pickling processes step is preferably 5s ~ 30s.Specifically, described carry out in acid solution process can for adopt acid solution wash.Higher than above-mentioned scope, dilute sulfuric acid can be caused to form deterioration from the edge part of the superconducting wire with Ag Rotating fields to superconducting layer and reduce superconductivity; Lower than above-mentioned scope, because clean effect cannot be obtained, and reduce peel strength.
After adopting acid solution to process superconducting wire, copper plating treatment can be carried out on Ag layer.Concrete grammar is, using having the wire rod of Ag Rotating fields as negative electrode, taking electrode as anode, electroplating in copper sulfate bath, Ag layer is formed Cu layer.
Before electroplating, neutrality process can also be carried out to the wire rod with Ag Rotating fields, namely adopt water or alkaline solution to clean to Ag layer, make it keep neutral.Preferred use water carries out neutrality process.
Wash complete after, electroplating processes can be carried out to the wire rod with Ag Rotating fields obtained, Ag layer is formed the Cu layer of protection Ag layer function.Its thickness is preferably 10 μm ~ 50 μm, is more preferably 10 μm ~ 40 μm.Cu is formed on Ag layer by galvanoplastic.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 the present invention, 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 includes but not limited to 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, be preferably polyethylene glycol, the concentration of described polyethylene glycol in copper sulfate solution, be preferably 0.05g/L ~ 15g/L, be more preferably 0.1g/L ~ 10g/L.Higher than above-mentioned scope, superconducting layer deterioration can be caused and reduce superconductivity; Lower than above-mentioned scope, the thickness of central portion 51 as described below and the uneven thickness of edge part 52 can be caused.
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.Higher than above-mentioned scope, superconducting layer deterioration can be caused and reduce superconductivity; Lower than above-mentioned scope, the thickness of central portion 51 as described below and the uneven thickness of edge part 52 can be caused.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 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 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 the present invention, form Cu layer after plating, in order to prevent Cu layer to be oxidized, the present invention preferably can also form anti oxidation layer on Cu layer.Described anti oxidation layer is formed by the material being converted into gaseous state under welding temperature.In the present invention, described material 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 material can be converted into gaseous state under welding temperature, and wherein, welding temperature refers to temperature when being welded with electrode by superconducting wire, generally more than 200 DEG C; 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 anti oxidation layer can be gaseous state from solid-state or liquid conversion under welding temperature, 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 by under normal temperature for the liquid and material distilled 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 in diethanol amine, glycerine one or more.
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; When antioxidant is liquid, the concentration of antioxidant is preferably 0.5ml/L ~ 2ml/L.Higher than above-mentioned scope, diethanol amine or glycerine can be caused to form deterioration from the edge part of superconducting wire to superconducting layer and reduce superconductivity; Lower than above-mentioned scope, because obtaining Cu antioxidant effect, the cupric oxide of formation reduces weld strength, welding kesistance is raised.
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.Higher than above-mentioned scope, diethanol amine or glycerine can be caused to form deterioration from the edge part of superconducting wire to superconducting layer and reduce superconductivity; Lower than above-mentioned scope, because obtaining Cu antioxidant effect, the cupric oxide of formation reduces weld strength, welding kesistance is raised.
Formed after anti oxidation layer at Cu layer, the superconducting wire can obtain having shape superconducting layer on the intermediate layer that formed on substrate, forming Cu layer again after this superconducting layer uplink layer Ag layer, form anti oxidation layer structure on this Cu layer.
The present invention is when carrying out copper plating treatment to Ag layer, first acid treatment is carried out to Ag layer, remove the dirt on Ag surface, impurity and silver oxide etc., improve when not making the superconductivity of superconducting wire that deterioration occurs Ag layer and Cu layer in conjunction with tightness degree, make the superconducting wire obtained have higher peel strength.Experimental result shows, the peel strength of the superconducting wire that method provided by the invention prepares is at more than 50MPa.
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 (10)

1. 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, before formation copper stabilized zone step, also comprise the solution using and be made up of acid solution carries out pickling processes step to silver-colored stabilized zone surface.
2. preparation method according to claim 1, is characterized in that, described acid solution is dilute sulfuric acid.
3. preparation method according to claim 2, is characterized in that, the concentration of described dilute sulfuric acid is 3ml/L ~ 10ml/L.
4. preparation method according to claim 3, is characterized in that, the temperature of described pickling processes step is less than 30 DEG C, and the time of described pickling processes step is 5s ~ 30s.
5. preparation method according to claim 1, is characterized in that, also comprises between described pickling processes step and described copper plating treatment step, carries out the neutral step processed to the superconducting wire that pickling processes step process is crossed.
6. preparation method according to claim 5, is characterized in that, described neutrality is treated to washing.
7. preparation method according to claim 1, is characterized in that, also comprises:
Described copper stabilized zone is formed the step of anti oxidation layer, and described anti oxidation layer is formed by the material being converted into gaseous state under welding temperature.
8. preparation method according to claim 7, is characterized in that, described material is diethanol amine or glycerine.
9. the preparation method according to claim 1 ~ 8 any one, is characterized in that, the copper plating bath that copper plating treatment step adopts comprises: cupric sulfate pentahydrate, sulfuric acid, chloride ion, non-ionic surface active agent and anion surfactant.
10. preparation method according to claim 9, is characterized in that, described non-ionic surface active agent is polyethylene glycol; Described anion surfactant is lauryl sodium sulfate.
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