CN101250705A - Method for manufacturing nickel-cuprum metallic baseband layer of highly oriented double-shaft texture - Google Patents
Method for manufacturing nickel-cuprum metallic baseband layer of highly oriented double-shaft texture Download PDFInfo
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- CN101250705A CN101250705A CNA2008100445014A CN200810044501A CN101250705A CN 101250705 A CN101250705 A CN 101250705A CN A2008100445014 A CNA2008100445014 A CN A2008100445014A CN 200810044501 A CN200810044501 A CN 200810044501A CN 101250705 A CN101250705 A CN 101250705A
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Abstract
The invention relates to a method for preparing a nickel-copper metal substrate layer of strong oriented biaxial texture, which concretely comprises following steps: firstly, annealing, arranging a copper sheet in a tube furnace, inputting mixed gas of hydrogen and argon, heating to 590-610DEG C, preserving heat for about 2 hours, naturally cooling, secondly, polishing, mixing polishing slurry according to chromium trioxide 18-23g/L, phosphoric acid 85% 940-960ml/L and sulphuric acid 95-98% 40-60ml/L, taking the copper sheet which is annealed in the polishing slurry as an anode, taking an aluminium sheet as a cathode, polishing for 2-5 minutes with current flow of 200-400mA, thirdly, electroplating, preparing electroplating solution of deionized water solution according to nickel sulfate 95-110g/L, nickel chloride 8-15g/L and boric acid 25-30g/L, taking the copper sheet which is polished as the cathode, and taking a nickel sheet as the anode to electroplate for 5-15 minutes, wherein the current flow is 10-50mA. The method has simple manufacturing process, simple equipment, low cost, easy operation and control, the thickness and the phase orientation of a plating layer can be extremely easily controlled, the method is easy in large scale preparation production, the method is environmental friendly and does not generate contaminant which is harmful to environment, and the method is energy-saving.
Description
Technical field
The present invention relates to a kind of preparation method of metallic baseband layer of biaxial texture preferred orientation.
Background technology
S-generation high-temperature superconductor--yttrium barium copper oxide (YBCO) superconducting coating conductor becomes the focus of present various countries research and development.The superconducting coating conductor is made of metallic baseband layer, transition layer (transition layer or buffer layer), superconducting layer.Wherein, metallic baseband layer is the substrate of superconducting coating conductor, on (200) direction that requires the orientation of its crystalline structure mainly to concentrate on, the biaxial texture that also promptly has extremely strong orientation, with the transition layer of the biaxial texture of can growing thereon, and then on transition layer sediment-filled phase with the superconducting layer of biaxial texture.Therefore, the baseband layer to biaxial texture is taken in preparation by force, is the key of preparation superconducting coating conductor.
Except having biaxial texture, baseband layer as high temperature superconducting materia also has following the requirement: one, high-temperature superconducting thin film is 500-900 ℃ of preparation, therefore require the lattice parameter of baseband layer to be complementary, can lead in the middle of the epitaxy with high-temperature superconducting thin film.Two,, require not have between baseband layer and superconducting thin film or seldom diffusion in the pyroprocess of the preparation and the aftertreatment of high-temperature superconducting thin film.High-temperature superconducting thin film produces slight crack during three, for fear of cooling, requires the thermal expansivity of baseband layer and high-temperature superconductor material approaching.
The metallic baseband layer that can satisfy above requirement at present mainly contains: pure nickel, nickelalloy series: Ni-Cr, Ni-V, Ni-W, Ni-Cu, Ha Site nickel-base alloy (Hastelloy); Silver, silver alloys, SrTiO
3, LaAlO
3Deng monocrystalline.
The preparation of metallic baseband layer is mainly by physical method, as rolling auxiliary biaxial texture base band technology (RABiTS technology) etc.Its preparation process is similar to traditional rolling thermal treatment process, and it is the spindle with the Ni of vacuum melting or powder metallurgy preparation or Ni base alloy, and through after the pre-treatment, it is rolling to carry out aximal deformation value, then 1000～1400 ℃ of anneal.The baseband layer for preparing, its inside is cubic texture, is oriented to (001).Its major advantage is to generate by rolling deformation and thermal treatment to take by force to texture, make various oxide compound transition layers and YBCO superconducting film can by this take by force to the texture metallic baseband layer, induce, epitaxy.But also there is significant disadvantages in it simultaneously: the rolling equipment that rolling technology is numerous and diverse, needs are special-purpose, and equipment drops into huge, the cost height; The thermal treatment temp height, energy consumption is higher; Be unfavorable for large-scale industrialization production.
Summary of the invention
Purpose of the present invention just provides a kind of preparation method of metallic baseband layer of biaxial texture preferred orientation, and this method manufacture craft is simple, and equipment is simple, and cost is low; Operation control easily, and the thickness of very easily controlling coating is orientated mutually with thing; Be easy to mass preparation production; Environmental protection does not produce the pollutent of hostile environment, and is energy-conservation.
The present invention realizes its goal of the invention, and the technical scheme that is adopted is:
A kind of preparation method who takes by force to the nickel-cuprum metallic baseband layer of biaxial texture, its concrete practice is:
A, annealing: copper sheet is put into tube furnace, and to feed bulk specific gravity be the hydrogen-argon-mixed body that 5% hydrogen, 95% argon gas are formed, rise to 590-610 ℃, be incubated about 2 hours, then naturally cooling by the temperature rise rate of 100-200 ℃/h.
B, polishing: press chromium trioxide 18-23g/L, 85% phosphatase 79 40-960ml/L, 95-98% sulfuric acid 40-60ml/L mixes, and is mixed with polishing fluid; Copper sheet after handling with a step in polishing fluid again is an anode, and other active preferred metal such as metals such as aluminium, copper are negative electrode, carries out electrochemical etching, polishing time 2-5 minute with the electric current of 200-400mA.
C, plating: press single nickel salt 95-110g/L, nickelous chloride 8-15g/L, the ratio of boric acid 25-30g/L is mixed with deionized water solution, forms electroplate liquid; The copper sheet that b goes on foot after the polished finish is made negative electrode, and the nickel sheet is electroplated as anode, and electroplating time 5-15 minute, electric current 10-50mA.
Compared with prior art, the invention has the beneficial effects as follows:
Adopt annealing, polishing, galvanized electrochemical production metallic baseband layer, do not need expensive complex apparatus in the preparation, cost is low.Preparation technology is simple, and in the electroplating process, parameters such as electroplate liquid and electroplating current are easy to control, and the thickness of plating layer that can accurately control generation is orientated mutually with thing, makes the metallic baseband layer performance of preparing be easy to control.Temperature is low in the preparation process, save energy.Polishing fluid and electroplate liquid in the preparation once are equipped with, and can be repeatedly used, and whole process of preparation has good reproducibility and repeatability, and have further reduced cost; And polishing fluid and electroplate liquid are reused, and externally do not discharge hazardous and noxious substances, help environmental protection.
Before carrying out above-mentioned a step annealing, copper sheet is put into acetone in elder generation or dehydrated alcohol carries out ultrasonic cleaning in 0.5-1 hour.Like this, can remove the impurity such as greasy dirt on copper sheet surface, make the anneal better effects if of copper sheet.
Behind a step annealing of only stating, elder generation carries out the b polished finish in step to copper sheet after copper sheet is put into the dilute hydrochloric acid cleaning of 3%-8% again.
Like this, in the time of can removing high temperature annealing, the small amounts impurity in that the copper sheet surface forms is easier to carrying out smoothly of electrochemical etching.
Below in conjunction with the drawings and specific embodiments the present invention is further described.
Description of drawings
Fig. 1 is the X ray diffracting spectrum of the copper sheet raw material of the inventive method use.
Fig. 2 is the X ray diffracting spectrum with the copper sheet after the inventive method annealing, the polished finish.
Fig. 3 is the X ray collection of illustrative plates with the copper-nickel metallic baseband layer of the inventive method preparation.
Fig. 4 is 5000 times of scanning electronic microscope (SEM) photo with the copper-nickel metallic baseband layer of the inventive method preparation.
Among Fig. 1-3, ordinate zou is diffracted intensity (Intensity), arbitrary unit (a.u.), and X-coordinate is diffraction angle 2 θ, unit is degree (deg.).
Embodiment
Embodiment one
A kind of embodiment of the present invention is:
Copper sheet is put into acetone in elder generation or dehydrated alcohol carries out ultrasonic cleaning in 45 minutes.
A, annealing: the copper sheet after a step cleaned is put into tube furnace, and to feed bulk specific gravity be the hydrogen-argon-mixed body that 5% hydrogen, 95% argon gas are formed, and rises to 600 ℃ by the temperature rise rate of 190 ℃/h, is incubated 2 hours, then naturally cooling.
After the annealing, the copper sheet after the polishing is put into 5% dilute hydrochloric acid clean, to remove the oxide impurity on surface.
B, polishing: press chromium trioxide 20g/L, 85% phosphatase 79 50ml/L, 97% sulfuric acid 50ml/L mixes, and is mixed with polishing fluid; Be anode with the copper sheet after the anneal in polishing fluid again, aluminium flake is a negative electrode, carries out electrochemical etching with the electric current of 300mA, polishes 4 minutes.
C, plating: press single nickel salt 105g/L, nickelous chloride 10g/L, the ratio of boric acid 28g/L is mixed with deionized water solution, forms electroplate liquid; Copper sheet after the polished and cleaned is made negative electrode, electroplate as anode with the nickel sheet, electroplated 10 minutes, electric current 20mA can form the thick nickel coating of about 2.7 μ m on the surface of substrate copper sheet.
Embodiment two
This example and embodiment one are basic identical, different only be:
30 minutes ultrasonic cleaning time; Speed with 100 ℃/h during annealing is warming up to 590 ℃, is incubated 1.5 hours; Copper sheet being put into 3% dilute hydrochloric acid cleans; Press chromium trioxide 18g/L, 85% phosphatase 79 40ml/L, the ratio of 95% sulfuric acid 40ml/L is joined polishing fluid, polishing electric current 200mA; Polishing time 2 minutes; By single nickel salt is 95g/L, and nickelous chloride is 8g/L, and boric acid is 25g/L, dissolve in to form solution in the deionized water, and the configuration electroplate liquid, electroplating time 5 minutes, electric current 10mA can form the thick nickel coating of about 1 μ m on the surface of substrate copper sheet.
Embodiment three
This example and embodiment one are basic identical, different only be:
60 minutes ultrasonic cleaning time; Speed with 200 ℃/h during annealing is warming up to 610 ℃, is incubated 2.5 hours; Copper sheet being put into 8% dilute hydrochloric acid cleans; Press chromium trioxide 23g/L, 85% phosphatase 79 60ml/L, the ratio of 98% sulfuric acid 60ml/L is joined polishing fluid, polishing electric current 400mA; Polishing time 5 minutes; By single nickel salt is 110g/L, and nickelous chloride is 15g/L, and boric acid is 30g/L, dissolve in and dispose electroplate liquid in the deionized water, and electroplating time 15 minutes, electric current 50mA can form the thick nickel coating of about 10.3 μ m on the surface of substrate copper sheet.
Embodiment four
A kind of preparation method who takes by force to the nickel-cuprum metallic baseband layer of biaxial texture, its concrete practice is:
A, annealing: copper sheet is put into tube furnace, and to feed bulk specific gravity be the hydrogen-argon-mixed body that 5% hydrogen, 95% argon gas are formed, rise to 600 ℃, be incubated 2 hours, then naturally cooling by the temperature rise rate of 180 ℃/h.
B, polishing: press chromium trioxide 20g/L, 85% phosphatase 79 50ml/L, 97% sulfuric acid 50ml/L mixes, and is mixed with polishing fluid; Be anode with the copper sheet after the annealing in polishing fluid again, aluminium flake is a negative electrode, carries out electrochemical etching, polishing time 4 minutes with the electric current of 300mA.
C, plating: press single nickel salt 100g/L, nickelous chloride 10g/L, the ratio of boric acid 28g/L is mixed with deionized water solution, forms electroplate liquid; The copper sheet that b goes on foot after the polished finish is made negative electrode, and the nickel sheet is electroplated as anode, electroplating time 10 minutes, and electric current 25mA can form the thick nickel coating of about 3.4 μ m on the surface of substrate copper sheet.
Fig. 1 illustrates, and obviously there is (220) orientation in the copper in the copper sheet raw material before being untreated, and copper (200) orientation relatively a little less than, also promptly the copper sheet of this moment do not have take by force to biaxial texture; Fig. 2 illustrates, annealing, after the polished finish, (220) orientation in the copper sheet obviously weakens, (200) orientation strengthens greatly, the copper sheet of this moment had take by force to biaxial texture; Fig. 3 illustrates, and nickel plating forms copper-nickel metallic baseband layer on copper sheet, and this baseband layer also has extremely strong (200) orientation, and other orientation is very weak.As seen, with the metallic baseband layer that present method is made, has extremely strong (200) orientation, it is diaxial orientation, (200) Qu Xiang relative intensity obtains tangible extension and raising, has good epitaxy characteristic, is suitable for the metallic baseband layer as s-generation superconducting material.
Claims (3)
1. preparation method who takes by force to the nickel-cuprum metallic baseband layer of biaxial texture, its concrete practice is:
A, annealing: copper sheet is put into tube furnace, and to feed bulk specific gravity be the hydrogen-argon-mixed body that 5% hydrogen, 95% argon gas are formed, rise to 590-610 ℃, be incubated about 2 hours, then naturally cooling by the temperature rise rate of 100-200 ℃/h;
B, polishing: press chromium trioxide 18-23g/L, 85% phosphatase 79 40-960ml/L, 95-98% sulfuric acid 40-60ml/L mixes, and is mixed with polishing fluid; Copper sheet after handling with a step in polishing fluid again is an anode, and other active preferred metal such as metals such as aluminium, copper are negative electrode, carries out electrochemical etching, polishing time 2-5 minute with the electric current of 200-400mA;
C, plating: press single nickel salt 95-110g/L, nickelous chloride 8-15g/L, the ratio of boric acid 25-30g/L is mixed with deionized water solution, forms electroplate liquid; The copper sheet that b goes on foot after the polished finish is made negative electrode, and the nickel sheet is electroplated as anode, and electroplating time 5-15 minute, electric current 10-50mA.
2. a kind of preparation method who takes by force to the nickel-cuprum metallic baseband layer of biaxial texture according to claim 1 is characterized in that: before carrying out described a step annealing, copper sheet is put into acetone in elder generation or dehydrated alcohol carries out ultrasonic cleaning in 0.5-1 hour.
3. a kind of preparation method who takes by force to the nickel-cuprum metallic baseband layer of biaxial texture according to claim 1, it is characterized in that: after carrying out described a step annealing, after earlier copper sheet being put into the dilute hydrochloric acid cleaning of 3%-8%, again copper sheet is carried out the b polished finish in step.
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| CN2008100445014A CN101250705B (en) | 2008-04-01 | 2008-04-01 | Method for manufacturing nickel-cuprum metallic baseband layer of highly oriented double-shaft texture |
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| CN2008100445014A CN101250705B (en) | 2008-04-01 | 2008-04-01 | Method for manufacturing nickel-cuprum metallic baseband layer of highly oriented double-shaft texture |
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| CN101250705A true CN101250705A (en) | 2008-08-27 |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892511A (en) * | 2010-07-08 | 2010-11-24 | 北京七星华创电子股份有限公司 | Electropolishing method for austenitic stainless steel orifice |
| CN102146559A (en) * | 2011-03-09 | 2011-08-10 | 西北有色金属研究院 | Vulcanization method for NiW alloy baseband surface used for coating conductor |
| CN103071640A (en) * | 2013-01-11 | 2013-05-01 | 东南大学 | Cleaning method for fine-texture metal surface for electric discharge machining |
| CN108342757A (en) * | 2018-02-05 | 2018-07-31 | 苏州新材料研究所有限公司 | A kind of method that electro-coppering prepares high-temperature superconductor band protective layer |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004530584A (en) * | 2001-06-28 | 2004-10-07 | エナージーニアス，インコーポレイテッド | Method for producing nickel-coated copper substrate and thin film composite including the substrate |
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2008
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101892511A (en) * | 2010-07-08 | 2010-11-24 | 北京七星华创电子股份有限公司 | Electropolishing method for austenitic stainless steel orifice |
| CN101892511B (en) * | 2010-07-08 | 2011-08-31 | 北京七星华创电子股份有限公司 | Electropolishing method for austenitic stainless steel orifice |
| CN102146559A (en) * | 2011-03-09 | 2011-08-10 | 西北有色金属研究院 | Vulcanization method for NiW alloy baseband surface used for coating conductor |
| CN102146559B (en) * | 2011-03-09 | 2012-05-30 | 西北有色金属研究院 | Vulcanization method for NiW alloy baseband surface used for coating conductor |
| CN103071640A (en) * | 2013-01-11 | 2013-05-01 | 东南大学 | Cleaning method for fine-texture metal surface for electric discharge machining |
| CN103071640B (en) * | 2013-01-11 | 2015-07-15 | 东南大学 | Cleaning method for fine-texture metal surface for electric discharge machining |
| CN108342757A (en) * | 2018-02-05 | 2018-07-31 | 苏州新材料研究所有限公司 | A kind of method that electro-coppering prepares high-temperature superconductor band protective layer |
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| CN101250705B (en) | 2010-10-06 |
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