CN114974725B - Polishing method of batched superconducting base bands and superconducting base bands - Google Patents
Polishing method of batched superconducting base bands and superconducting base bands Download PDFInfo
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- CN114974725B CN114974725B CN202210563859.8A CN202210563859A CN114974725B CN 114974725 B CN114974725 B CN 114974725B CN 202210563859 A CN202210563859 A CN 202210563859A CN 114974725 B CN114974725 B CN 114974725B
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B12/00—Superconductive or hyperconductive conductors, cables, or transmission lines
- H01B12/02—Superconductive or hyperconductive conductors, cables, or transmission lines characterised by their form
- H01B12/06—Films or wires on bases or cores
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/16—Polishing
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E40/00—Technologies for an efficient electrical power generation, transmission or distribution
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Abstract
The invention provides a polishing method of a batch superconducting base band and the superconducting base band, wherein one surface of the superconducting base band which is not subjected to electrochemical polishing is selected for film pasting; mechanically polishing the other side of the superconducting base band which is not pasted with the film; and removing the film attached to the superconducting base band. Compared with the traditional electrochemical polishing process, the invention greatly improves the production efficiency. The superconducting base band prepared by the invention has no material trace, and the final superconducting strip current is consistent with the length direction along the width direction, so that the superconducting base band can be used as a Roeble cable. The invention realizes single-side electro-polishing, saves more than half of consumables and prolongs the service life of the electro-polishing solution by 2-10 times. The superconducting base band prepared by the method has consistent relative thickness, and the volume turns of the pancake coil are easy to control in the subsequent coil application.
Description
Technical Field
The invention relates to the field of superconducting materials, in particular to a polishing method of a batch superconducting baseband and the superconducting baseband.
Background
Since the first discovery of superconducting phenomena in laboratories by professor ondansi in 1911 at Leiden (Leiden), superconducting materials and their applications have been one of the most active leading research fields of contemporary science and technology. During the last decades, the research on high-temperature superconducting power and magnet equipment represented by the second-generation high-temperature superconducting tape has been rapidly developed, and remarkable results are achieved in the fields of superconducting energy storage, superconducting motors, superconducting cables, superconducting current limiters, superconducting transformers, superconducting magnetic levitation, nuclear magnetic resonance and the like.
The second generation superconducting tapes made of REBCO (RE is a rare earth element) are also called as coated conductors, and have wider and better application prospects in various fields such as medical treatment, military, energy and the like because of higher current carrying capacity, higher magnetic field performance and lower material cost compared with bismuth-based tapes. Second generation superconducting tapes, which are also referred to as coated conductors, are generally produced by a process of applying a multilayer coating film on a nickel-based alloy substrate because REBCO, which is a superconducting current-carrying core, is inherently hard and brittle. The second generation superconducting tapes generally consist of a base tape, a buffer layer (transition layer), a superconducting layer, and a protective layer. The role of the metal substrate is to provide the strip with excellent mechanical properties. The transition layer has the functions of preventing the mutual diffusion of elements between the superconducting layer and the metal substrate, and providing a good template for the epitaxial growth of the superconducting layer to improve the REBCO crystal grain arrangement quality. Coated conductors with excellent superconducting properties are produced, requiring a superconducting layer with a consistent biaxial texture. Biaxial texture means that the grains are nearly uniformly aligned in both the a/b axis and the c axis (the c axis is perpendicular to the a/b plane). The alignment degree (in-plane texture) of the REBCO film in the a/b axis direction is relatively difficult to realize, and the poor in-plane texture can seriously reduce the superconducting performance. It is therefore desirable to grow epitaxially a REBCO superconducting film on a transition layer that already has a biaxial texture and a matched lattice. Two main technical routes for realizing the biaxial texture are provided, one is a rolling auxiliary biaxial texture base band technology, and the other is an ion beam auxiliary deposition technology. The common techniques for preparing the REBCO superconducting layer are divided into various techniques, such as pulsed laser deposition, metal organic chemical vapor deposition, reactive co-evaporation and the like.
The protective layer is mainly used for protecting the superconducting film layer, generally, a silver layer with the thickness of 0.5-5 μm is plated on the front surface and the back surface of the superconducting strip by magnetron sputtering or evaporation, in order to pursue lower material cost, the silver layer on the superconducting surface is generally set to be 1-2 μm, and the silver layer on the non-superconducting surface is generally set to be 0.5-1 μm. And then, according to the requirement of specific application on the width of the strip, cutting the strip of 10-12 mm into strips of 2-8 mm. And finally, carrying out copper plating or subsequent packaging reinforcement treatment. The thickness of the copper plated on the strip material for subsequent packaging can be 1-10 mu m. The copper plating of the copper plating reinforced strip material is performed with the thickness of copper plating on one surface of 10-30 mu m and the thickness of copper plating on the two surfaces of 20-60 mu m.
Because the crystal grains of the superconducting layer need to be arranged regularly to form better critical current performance, certain requirements are made on the texture formed by the buffer layer. The quality of the MgO film with biaxial texture prepared by the IBAD process is directly related to the root mean square surface Roughness (RMS) of the front surface. Therefore, specific requirements are required for rough plating of the hastelloy surface of the base band.
The current mass production superconductive stabilization process has the requirement of 0.6-0.8nm (the scanning area of an atomic force microscope is 1 multiplied by 1 square micron) on the surface roughness of the hastelloy base band. The surface roughness of the high-specification metal base band sold in the market at present is about 50 nanometers due to the limitations of the precision of a rolling mill, the finish degree of a roller and the cleanliness of a rolling environment. The industry typically requires electrochemical polishing to handle.
At present, the second generation high temperature superconducting tape is already in the mass production stage, and one production line can produce hundreds of kilometers of superconducting tape every year. However, these amounts are far from sufficient in the face of the demands of the applications. For example, a compact fusion intermediate prototype requires tens of thousands of kilometers of material, and the pressure on the yield expansion of the material end is gradually developed. The increase of the production capacity by orders of magnitude has to be considered, and the optimization of the raw material processing mode is needed.
The hastelloy base band is limited by rolling level, the surface roughness after rough rolling is about 200 nanometers generally, and the surface roughness after finish rolling is about 30-50 nanometers generally. The cost of finish rolling is much higher than the cost of rough rolling.
There are two main ways of polishing: continuous mechanical polishing and continuous electrochemical polishing.
The benefit of continuous mechanical polishing is that the acceptable range of raw material surface roughness is large, typically from 20 to 500 nm. The weaknesses of continuous mechanical polishing are that: 1. the polishing speed is slow, and the speed is 1 order of magnitude lower than the production speed of the superconducting tape; 2. the possibility of secondary deformation is provided after mechanical polishing; 3. the ultimate roughness of the casting can be 1-2nm, and the requirement of the production of the superconducting strip on the hastelloy can not be met.
The continuous electrochemical polishing has the advantage that the limit roughness of the continuous electrochemical polishing can reach 0.2-0.5 nanometer, and the requirement of the superconducting strip production on the Hastelloy is met. Bad in continuous electrochemical polishing: 1. 2, the electrode needs to be replaced more frequently, and the consumed platinum is plated again; 3. the process needs to be readjusted every time the replacement is carried out; 4. the polishing capacity can change along with the old and new of the polishing solution; 5. because the electric field is unbalanced, the section of the electrically-thrown strip is not strictly rectangular, and a great problem is caused in the subsequent application of the superconducting strip wound magnet.
The composition of the electrolyte is related to the chemical composition of the metal part being polished, and extensive experimentation is required to find the desired polishing parameters and the appropriate electrolyte. In addition, the use of electrochemical polishing also places certain requirements on the original surface roughness of the metal substrate. The method of electrochemical polishing is described in US7,169,286. Practice has shown that the surface roughness of the original metal substrate must be less than 50 nm to effectively obtain a metal substrate having an RMS < 1 nm.
As described above, in the conventional process for treating the surface roughness of the superconducting base tape for the coated conductor, or the process treatment time is long, the productivity per unit time is low, and the preparation requirement of the subsequent superconducting material cannot be met; or the stability of the process is poor, the precision of the process cannot be guaranteed, the preparation yield of the superconducting material is influenced, and the method is a key factor influencing the batch production of the high-temperature superconducting baseband.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a polishing method for batch-wise superconducting base bands and the superconducting base bands.
The invention provides a polishing method of a batch superconducting baseband, which comprises the following steps:
s1, selecting one surface of a superconducting base band which is not subjected to electrochemical polishing to carry out film pasting;
s3, performing electrochemical polishing on the other surface of the superconducting base band which is not coated with the film;
and S4, removing the film attached to the superconducting base band.
Preferably, between step S1 and step S3, further comprising:
and S2, mechanically polishing the other surface of the superconducting base band without the film until the roughness reaches 5nm @50 multiplied by 50 microns.
Preferably, the step S2 further includes cutting the mechanically polished superconducting base tape.
Preferably, the slitting mode is non-cushion slitting, the slitting speed is 50-500m/h, the blade is made of high-speed steel, and the hardness reaches Rockwell hardness HRC62-66.
Preferably, the electrochemical polishing is from a roughness of 0.8-5nm @50 × 50 μm to a roughness of 0.4-0.7nm @1 × 1 μm.
Preferably, the electrochemical polishing solution comprises the following components:
10 to 30 percent of 98 percent concentrated sulfuric acid
85% concentrated phosphoric acid 70-90%
0.5 to 3 percent of citric acid
0.5 to 3 percent of glycerin.
Preferably, the working temperature of the electro-polishing solution for the electrochemical polishing is 30-80 ℃, the superconducting base band is used as a cathode, a shielding plate is arranged between the anode and the non-film-coated surface of the superconducting base band, and the shielding plate is shielded between the end part of the superconducting base band and the anode;
the area ratio of the cathode to the anode is (1-3): 1, the distance between the cathode and the front surface of the anode is 8-36mm, the distance between the shielding plate and the superconducting base band is 0-8mm, and the shielding plate vertically projects to the superconducting strip to cover the end part of the superconducting strip by 1-4mm.
Preferably, the electrochemical polishing apparatus is a roll-to-roll electrochemical polishing device, and the polishing process includes: discharging, washing the strip material before, polishing the strip material electrochemically, washing the strip material after, drying, detecting the thickness and the defect of the strip material on line and receiving the material.
Preferably, the apparatus for removing the film attached to the superconducting tape includes:
receiving agencies, drop feed mechanism, location guide pulley group and dyestripping mechanism, the location guide pulley group sets up receiving agencies with between the drop feed mechanism, dyestripping mechanism set up in location guide pulley group below.
According to the superconducting base band provided by the invention, the polishing method of the batched superconducting base band is adopted for preparation.
The superconducting tape provided by the invention comprises the superconducting base tape, and a buffer layer, a superconducting layer and a protective layer are sequentially prepared on the superconducting base tape.
Compared with the prior art, the invention has the following beneficial effects:
1. compared with the traditional electrochemical polishing process, the invention greatly improves the production efficiency.
2. The superconducting base band prepared by the invention has no material trace, and the final superconducting strip current is consistent with the length direction along the width direction, so that the superconducting base band can be used as a Roeble cable.
3. The invention realizes single-side electro-polishing, saves more than half of consumables and prolongs the service life of the electro-polishing solution by 2-10 times.
4. The superconducting base band prepared by the method has consistent relative thickness, and the volume turns of the pancake coil are easy to control in the subsequent coil application.
Drawings
Other features, objects and advantages of the invention will become more apparent upon reading of the detailed description of non-limiting embodiments with reference to the following drawings:
FIG. 1 is a flow chart of the operation of the present invention;
FIG. 2 is a schematic of the electrochemical polishing of the present invention;
FIG. 3 is a schematic diagram of stripping of the present invention.
Detailed Description
The present invention will be described in detail with reference to specific examples. The following examples will aid those skilled in the art in further understanding the present invention, but are not intended to limit the invention in any manner. It should be noted that variations and modifications can be made by persons skilled in the art without departing from the concept of the invention. All falling within the scope of the present invention.
Example 1
As shown in fig. 1, the present embodiment provides a batch polishing method of superconducting tapes, comprising the steps of:
s1: and (3) sticking a film on the surface with less surface problems of the base band which is not subjected to electrochemical polishing to form a double-layer structure. The film is made of acid-resistant material, such as PE and PP, and has a surface with adhesive and a thickness of 20-120um.
S2: the base tape which has not been electrochemically polished and to which the film has been attached is mechanically polished to further reduce the surface roughness to within 5nm @50 × 50 μm. Meanwhile, the base belt is pasted with the film, so that the bending and wrinkling phenomena caused by the rotation of the polishing equipment in the mechanical polishing process of the base belt can be avoided. In the rolling process of mechanical polishing, the film-pasting surface of the superconducting base band rolls on the inner side of the roll, the friction force between the base bands is increased through the pasted film, and the condition that the receiving is unstable and manual intervention is needed is avoided.
S3: and cutting the base band with the film after the machine polishing in a mode without a rubber mat. The cutting mode is no cushion cutting, the cutting speed is 50-500m/h, the blade is made of high-speed steel, and the hardness reaches Rockwell hardness HRC62-66.
S4: the slit tape with the adhesive film was subjected to single-side electrochemical polishing by an electropolishing apparatus from a roughness of 0.8-5nm @50 × 50 μm to a roughness of 0.4-0.7nm @1 × 1 μm (conventionally from a roughness of 20-80nm @1 × 1 μm to a roughness of 0.4-0.7nm @1 × 1 μm). After electrochemical polishing, the difference between the thickness of the edge parts at both sides and the thickness of the middle part in the width direction of the strip material is less than 5 percent.
The electrochemical polishing equipment is a roll-to-roll electrochemical polishing device, and the polishing process comprises the following steps: discharging, washing the strip material before, polishing the strip material electrochemically, washing the strip material after, drying, detecting the thickness and the defect of the strip material on line and receiving the material.
The working temperature of the electro-polishing solution for electro-chemical polishing is 30-80 ℃, as shown in fig. 2, the superconducting base band is used as a cathode, a shielding plate is arranged between the non-film-coated surface of the superconducting base band and the anode, and the shielding plate is shielded between the end part of the superconducting base band and the anode. The area ratio of the cathode to the anode is (1-3): 1, the distance between the cathode and the front surface of the anode is 8-36mm, the distance between the shielding plate and the superconducting base band is 0-8mm, and the shielding plate vertically projects to the superconducting strip to cover the end part of the superconducting strip by 1-4mm. The shielding function is to avoid the bone shape at the two ends of the Korea base band, so that the base band is integrally flat and the end parts are kept square.
The current of the electrochemical polishing is 45-135A, and the components of the electrochemical polishing solution are as follows:
98% concentrated sulfuric acid 10-30%
85% of concentrated phosphoric acid 70-90%
0.5 to 3 percent of citric acid
0.5 to 3 percent of glycerin.
Because the superconducting base band is subjected to single-side electrochemical polishing, two superconducting base bands can be arranged in parallel at the same time for electrochemical polishing (the surfaces of the films of the two superconducting base bands are opposite), and the tape moving speed is 80-180m/h. The strip material is washed before being soaked and then sprayed, wherein an ultrasonic device is used in the soaking process, the ultrasonic frequency is 40KHz, the strip material stays for 30-90s, the water temperature is controlled at 40-50 ℃, and the front and back washing water is ultrapure water, so that the surface dirt of the base strip is basically removed completely. The tail ends of the front washing tank, the working tank (electrochemical polishing tank) and the rear washing tank are all blown by clean compressed air with the pressure of 0.85-1Mpa and the drying temperature of 100-500 ℃.
S5: and tearing off the adhesive film on the back surface of the strip material after the single-side electrochemical polishing by adopting corresponding film removing equipment. As shown in fig. 3, the apparatus includes:
the film tearing device comprises a receiving mechanism, a discharging mechanism, a positioning guide wheel set and a film tearing mechanism, wherein the positioning guide wheel set is arranged between the receiving mechanism and the discharging mechanism, and the film tearing mechanism is arranged below the positioning guide wheel set. Receiving agencies, drop feed mechanism and dyestripping mechanism are the form realization of rod in this embodiment. Receive the material rod and the blowing rod normal receipts blowing of receiving, and the film on the superconductive baseband is collected to the dyestripping rod below location guide pulley group, and the rotational speed of dyestripping rod is the same with the rotational speed of receiving and blowing rod.
Example 2
This embodiment provides the superconducting tape, which is prepared by the batch polishing method of the superconducting tape described in embodiment 1.
In the description of the present application, it is to be understood that the terms "upper", "lower", "front", "rear", "left", "right", "vertical", "horizontal", "top", "bottom", "inner", "outer", and the like indicate orientations or positional relationships based on those shown in the drawings, and are only for convenience in describing the present application and simplifying the description, but do not indicate or imply that the referred device or element must have a specific orientation, be constructed in a specific orientation, and be operated, and thus, should not be construed as limiting the present application.
The foregoing description has described specific embodiments of the present invention. It is to be understood that the present invention is not limited to the specific embodiments described above, and that various changes or modifications may be made by one skilled in the art within the scope of the appended claims without departing from the spirit of the invention. The embodiments and features of the embodiments of the present application may be combined with each other arbitrarily without conflict.
Claims (10)
1. A polishing method of a batch superconducting baseband is characterized by comprising the following steps:
s1, selecting one surface of a superconducting base band which is not subjected to electrochemical polishing to carry out film pasting;
s3, performing electrochemical polishing on the other surface of the superconducting base band which is not coated with the film;
s4, removing the film attached to the superconducting base band;
the working temperature of the electro-polishing solution for electrochemical polishing is 30-80 ℃, the superconducting base band is used as a cathode, a shielding plate is arranged between the surface, which is not pasted with the film, of the superconducting base band and the anode, and the shielding plate is shielded between the end part of the superconducting base band and the anode;
the area ratio of the cathode to the anode is (1-3): 1, the distance between the cathode and the front surface of the anode is 8-36mm, the distance between the shielding plate and the superconducting base band is 0-8mm, and the shielding plate vertically projects to the superconducting strip to cover the end part of the superconducting strip by 1-4mm.
2. The method for polishing batched superconducting tapes according to claim 1, further comprising, between step S1 and step S3:
and S2, mechanically polishing the other surface of the superconducting base band without the film until the roughness reaches 5nm @50 multiplied by 50 microns.
3. The method for polishing batched superconducting base tapes according to claim 2, wherein the step S2 further comprises cutting the mechanically polished superconducting base tapes.
4. The method for polishing batched superconducting tapes according to claim 3, wherein the slitting is performed in a non-rubber-pad slitting mode, the slitting speed is 50-500m/h, the blade is made of high-speed steel, and the hardness is HRC62-66 in Rockwell hardness.
5. The method for polishing batched superconducting tapes according to claim 1, wherein the electrochemical polishing is performed from a roughness of 0.8-5nm @50 x 50 μm to a roughness of 0.4-0.7nm @1 x 1 μm.
6. The batched superconducting baseband polishing method according to claim 1, wherein the electrochemical polishing electropolishing solution comprises the following components:
10 to 30 percent of 98 percent concentrated sulfuric acid
85% concentrated phosphoric acid 70-90%
0.5 to 3 percent of citric acid
0.5 to 3 percent of glycerin.
7. The batched superconducting tape polishing method according to claim 1, wherein the electrochemical polishing device is a roll-to-roll electrochemical polishing apparatus, and the polishing process comprises: discharging, washing the strip material before, polishing the strip material electrochemically, washing the strip material after, drying, detecting the thickness and the defect of the strip material on line and receiving the material.
8. The method for polishing batched superconducting tapes according to claim 1, wherein the apparatus for removing the film attached to the superconducting tape comprises:
receiving agencies, drop feed mechanism, location guide pulley group and dyestripping mechanism, the location guide pulley group sets up receiving agencies with between the drop feed mechanism, dyestripping mechanism set up in location guide pulley group below.
9. A superconducting base tape, characterized in that it is prepared by the method of polishing a bulk superconducting base tape according to any one of claims 1 to 8.
10. A superconducting tape comprising the superconducting tape of claim 9, on which a buffer layer, a superconducting layer and a protective layer are sequentially formed.
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Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2008200773A (en) * | 2007-02-16 | 2008-09-04 | Nihon Micro Coating Co Ltd | Method for manufacturing tape substrate for superconductor, and tape substrate |
CN106992112A (en) * | 2016-01-21 | 2017-07-28 | 苏州新美光纳米科技有限公司 | The polishing method of ultra thin wafer |
CN107059108A (en) * | 2017-01-20 | 2017-08-18 | 上海材料研究所 | A kind of composite surface treatment method of hts band timber-used Hastelloy base band |
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Patent Citations (3)
Publication number | Priority date | Publication date | Assignee | Title |
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JP2008200773A (en) * | 2007-02-16 | 2008-09-04 | Nihon Micro Coating Co Ltd | Method for manufacturing tape substrate for superconductor, and tape substrate |
CN106992112A (en) * | 2016-01-21 | 2017-07-28 | 苏州新美光纳米科技有限公司 | The polishing method of ultra thin wafer |
CN107059108A (en) * | 2017-01-20 | 2017-08-18 | 上海材料研究所 | A kind of composite surface treatment method of hts band timber-used Hastelloy base band |
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