Treatment process and treatment system for defective superconducting tape

Abstract

The invention discloses a treatment process and a treatment system for a superconductive strip defective product, and the treatment process comprises the following steps: carrying out the first pickling treatment, the first cleaning treatment, the first alkali washing treatment, the second cleaning treatment, the second pickling treatment and the third cleaning treatment on the superconductive strip defective product containing a metal oxide film on the surface in sequence, and obtaining the superconductive strip with the surface metal oxide film removed. The technical problem that a large number of unqualified products are generated in the production process of the second-generation high-temperature superconducting tape is solved, the green, economical, environment-friendly and sustainable treatment method is provided, and the method and the equipment are relatively simple to operate and can be used for large-scale industrialization.

Description

Technical Field

[0001] The present invention relates to the technical field of superconducting tapes, and in particular to a processing technology and a processing system for defective superconducting tapes. Background Art

[0002] The production process of the second-generation high-temperature superconducting tape is mainly divided into four steps: the first step is electrochemical polishing, which uses the electrochemical principle to polish the surface roughness of the original base tape to the required degree; the second step is the growth of the intermediate transition layer, that is, under high vacuum conditions, a ceramic oxide film is grown on the surface of the polished base tape by magnetron sputtering to serve as a transition layer (buffer layer) for the subsequent growth of the functional layer (superconducting layer); the third step is the epitaxial growth of the functional layer, which uses chemical vapor deposition to grow a rare earth barium copper oxide (REBCO) superconducting layer in the intermediate transition layer; the fourth step is to encapsulate and protect the functional layer with superior growth performance.

[0003] In the production process of the second-generation high-temperature superconducting tapes, a large number of unqualified products will be produced, mainly concentrated in the growth of the intermediate transition layer and the epitaxial growth process of the functional layer. At the same time, a large number of traction tapes need to be provided during the production process. The main problem of these defective products is that a dense metal oxide ceramic film is formed on the surface of the tape. For these defective products, the traditional treatment method is: direct scrapping, but direct scrapping causes waste of resources and also generates a large amount of solid waste, which in turn causes a significant increase in manufacturing costs, which is not conducive to subsequent industrialization; mechanical grinding, the mechanical grinding process is not easy to control, and mechanical external forces can easily cause irreparable damage to the surface of the tape. There will be more and more defects in the tape repair process, and the surface roughness is high due to incomplete grinding, which cannot meet the conditions for secondary use.

[0004] Therefore, it is crucial to adopt green, economical, environmentally friendly and sustainable methods to deal with the large number of unqualified products generated during the production process of second-generation high-temperature superconducting tapes for the later application of superconducting tapes. Summary of the invention

[0005] In order to solve the above technical problems, the purpose of the present invention is to provide a process for processing defective superconducting tapes.

[0006] Another object of the present invention is to provide a system for processing defective superconducting tapes.

[0007] The above object of the present invention is achieved through the following technical solutions:

[0008] The present invention provides a process for treating defective superconducting tapes, comprising the following steps:

[0009] The defective superconducting tape with a metal oxide film on the surface is sequentially subjected to a primary pickling treatment, a primary cleaning treatment, a primary alkali cleaning treatment, a secondary cleaning treatment, a secondary pickling treatment and a tertiary cleaning treatment to obtain a superconducting tape with the metal oxide film on the surface removed; the primary pickling treatment uses phosphoric acid and / or sulfuric acid with a concentration of 10% to 50%, the primary alkali cleaning treatment uses one or more of ammonia water, triethylamine and ethylenediamine with a concentration of 10% to 25%, and the secondary pickling treatment uses nitric acid with a concentration of 10% to 50%.

[0010] The surfaces of defective superconducting tapes before and after treatment were observed, tested, analyzed and compared, verifying that the superconducting tapes with the metal oxide film on the surface removed after treatment can be recycled.

[0011] Furthermore, the superconducting tape is Hastelloy, such as C276.

[0012] Furthermore, the defective superconducting tapes include defective traction tapes, defective intermediate transition layer superconducting tapes and defective semi-finished superconducting tapes.

[0013] Furthermore, the defective superconducting tape may have a width of 1 to 12 mm and a thickness of 30 to 80 μm.

[0014] Furthermore, the first pickling treatment, the first alkali washing treatment and the second pickling treatment also include a heat treatment step.

[0015] Furthermore, the temperature of the heat treatment is 25-40°C.

[0016] Furthermore, the time of the pickling treatment is 0.1 to 2 minutes, preferably 1 to 2 minutes.

[0017] Furthermore, the time of the alkali washing treatment is 0.1 to 2 minutes, preferably 1 to 2 minutes.

[0018] Furthermore, the secondary pickling treatment lasts for 0.1 to 2 minutes.

[0019] Furthermore, the three cleaning processes also include a drying step.

[0020] Furthermore, the temperature of the drying treatment is 100-120°C.

[0021] The present invention also provides a processing system for defective superconducting tapes, which is sequentially arranged to include a pay-off drum, an acid tank A, a cleaning tank A, an alkali tank, a cleaning tank B, an acid tank B, a cleaning tank C, a drying device, and a take-up drum.

[0022] Furthermore, the acid solution A in the acid tank A is phosphoric acid and / or sulfuric acid with a concentration of 10% to 50%, the alkali solution in the alkali tank is one or more of ammonia water, triethylamine and ethylenediamine with a concentration of 10% to 25%, and the acid solution B in the acid tank B is nitric acid with a concentration of 10% to 50%.

[0023] Furthermore, the length of the acid tank A is 0.5 to 15 meters, the length of the cleaning tank A is 0.5 to 15 meters, the length of the alkali tank is 0.5 to 15 meters, the length of the cleaning tank B is 0.5 to 15 meters, the length of the acid tank B is 0.5 to 15 meters, and the length of the cleaning tank C is 0.5 to 15 meters.

[0024] In a specific embodiment, a process for treating defective superconducting tapes in combination with a treatment system includes the following steps:

[0025] (1) Loading defective superconducting tapes into a pay-off reel for processing;

[0026] (2) adding corresponding acid and alkali solutions into acid tank A, alkali tank and acid tank B, and heat treating the corresponding acid and alkali solutions;

[0027] (3) The defective superconducting tape is drawn out from the pay-off reel, tension is applied to make it taut, and the tape passes through the acid tank A, the cleaning tank A, the alkali tank, the cleaning tank B, the acid tank B, the cleaning tank C, and the drying device in sequence, and finally connected to the take-up reel to obtain the superconducting tape with the surface metal oxide film removed.

[0028] Furthermore, the speed at which the defective superconducting tape passes through the circulation processing system is 1 to 8 m / min.

[0029] Beneficial effects of the present invention:

[0030] The present invention solves the technical problem of a large number of unqualified products being produced in the production process of second-generation high-temperature superconducting tapes, and provides a green, economical, environmentally friendly and sustainable treatment method. The method, equipment and operation are relatively simple and can be used for large-scale industrialization. BRIEF DESCRIPTION OF THE DRAWINGS

[0031] Figure 1 This is an appearance diagram of a defective traction belt before being processed in Example 1.

[0032] Figure 2 This is the appearance of the traction belt obtained after the treatment of Example 1.

[0033] Figure 3 This is a test result diagram of laser online testing of the microscopic surface of the traction belt obtained after the treatment of Example 1.

[0034] Figure 4 This is an appearance diagram of a defective intermediate transition layer superconducting tape before being processed in Example 2.

[0035] Figure 5 This is the appearance of the intermediate transition layer superconducting tape obtained after the treatment of Example 2.

[0036] Figure 6 This is a test result diagram of laser online testing of the microscopic surface of the intermediate transition layer superconducting tape obtained after the treatment of Example 2.

[0037] Figure 7 This is an appearance diagram of a defective semi-finished superconducting tape before being processed in Example 3.

[0038] Figure 8 This is the appearance of the semi-finished superconducting tape obtained after the treatment of Example 3.

[0039] Fig. 9 This is a test result diagram of laser online testing of the microscopic surface of the semi-finished superconducting tape obtained after the treatment of Example 3. DETAILED DESCRIPTION

[0040] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those generally understood by those skilled in the art of the present invention. The terms used herein in the specification of the present invention are only for the purpose of describing specific embodiments and are not intended to limit the present invention. The term "and / or" used herein includes any and all combinations of one or more related listed items.

[0041] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments so that those skilled in the art can better understand the present invention and implement it, but the embodiments are not intended to limit the present invention.

[0042] Unless otherwise specified, the experimental methods used in the following examples are all conventional methods, and the materials, reagents, etc. used are all available from commercial sources unless otherwise specified.

[0043] Example 1

[0044] A process for processing defective traction belts comprises the following steps:

[0045] (1) Use electric welding to connect the defective traction belts with a length of about 550 meters and a metal oxide film on the surface of C276 and load them into the pay-off drum for subsequent processing.

[0046] (2) Add 50% phosphoric acid into the PP material acid tank A, add 25% ammonia water into the PP material alkali tank, add 40% nitric acid into the PP material acid tank B, and heat treat the corresponding acid and alkali solutions at 40°C.

[0047] (3) Turn on the power supply, turn on the ultrasonic cleaning device of the cleaning tank, and turn on the heating and drying device. When the drying temperature reaches 120°C and the drying temperature remains basically unchanged, turn on the processing system, lead the defective traction belt from the pay-off reel, add tension to make it taut, and pass it through the acid tank A (about 1 meter), cleaning tank A (about 0.5 meters), alkali tank (about 1.5 meters), cleaning tank B (about 0.5 meters), acid tank B (about 0.5 meters), cleaning tank C (about 0.5 meters), and drying device in sequence. The speed of passing through the circulation processing system is 5m / min, and finally connect the take-up reel to obtain the traction belt with the surface metal oxide film removed.

[0048] Figure 1 This is the appearance of the defective traction belt before treatment in Example 1. Figure 1 It can be seen that the appearance of the defective traction belt before treatment is colored and not shiny.

[0049] Figure 2 This is the appearance of the traction belt obtained after the treatment of Example 1. Figure 2 It can be seen that its appearance is the original color of C276, which is bright gray.

[0050] The microscopic surface of the traction belt obtained after the treatment in Example 1 was subjected to quality test analysis, mainly observing defects and the surface roughness of the treated belt (laser online test). The belt used in this process is the original belt, and the surface roughness of the treated belt (laser online test) is above 10nm. The test results are as follows: Figure 3 shown.

[0051] Example 2

[0052] A process for treating defective intermediate transition layer superconducting tapes comprises the following steps:

[0053] (1) Defective intermediate transition layer superconducting tapes with a length of about 1000 meters and a metal oxide film layer on the surface of C276 are connected by electric welding and loaded into a pay-off reel for subsequent processing.

[0054] (2) Add 30% sulfuric acid and phosphoric acid into the PP material acid tank A, add 60% triethylamine into the PP material alkali tank, add 40% nitric acid into the PP material acid tank B, and heat treat the corresponding acid and alkali solutions at 25°C.

[0055] (3) Turn on the power supply, turn on the ultrasonic cleaning device of the cleaning tank, and turn on the heating and drying device. When the drying temperature reaches 100°C and the drying temperature remains basically unchanged, turn on the processing system, lead the defective intermediate transition layer superconducting tape from the pay-off reel, apply tension to make it taut, and pass through the acid tank A (about 1 meter), cleaning tank A (about 0.5 meters), alkali tank (about 1.5 meters), cleaning tank B (about 0.5 meters), acid tank B (about 0.5 meters), cleaning tank C (about 0.5 meters), and drying device in sequence. The speed of passing through the circulation processing system is 4m / min. Finally, connect the take-up reel to obtain the intermediate transition layer superconducting tape with the surface metal oxide film removed.

[0056] During the production process, the surface of the intermediate transition layer superconducting tape usually has irreparable defects, such as inconsistent sputtering coating thickness, no coating on the edge, weak bonding strength of the tape after coating, etc., resulting in defective intermediate transition layer superconducting tapes with appearance like Figure 4 shown.

[0057] The intermediate transition layer superconducting tape obtained after the treatment in Example 2 is a C276 base tape polishing tape, and its appearance is the original color of C276, that is, bright gray. Figure 5 shown.

[0058] The microscopic surface of the intermediate transition layer superconducting tape obtained after the treatment in Example 2 was subjected to quality test and analysis, mainly observing defects and the surface roughness of the tape after treatment (laser online test) was less than 10nm. The test results are as follows: Figure 6 shown.

[0059] Example 3

[0060] A process for treating defective semi-finished superconducting tapes comprises the following steps:

[0061] (1) Using electric welding, the defective semi-finished superconducting tape with a length of about 900 meters and a metal oxide film layer on the surface of C276 is loaded into the wire reel for subsequent processing.

[0062] (2) Add 40% sulfuric acid into the PP material acid tank A, add 60% ethylenediamine into the PP material alkali tank, add 40% nitric acid into the PP material acid tank B, and heat treat the corresponding acid and alkali solutions at 35°C.

[0063] (3) Turn on the power supply, turn on the ultrasonic cleaning device of the cleaning tank, and turn on the heating and drying device. When the drying temperature reaches 100° C. and the drying temperature remains basically unchanged, turn on the processing system, lead the defective semi-finished superconducting tape from the pay-off reel, apply tension to make it taut, and pass through the acid tank A (about 1 meter), cleaning tank A (about 0.5 meter), alkali tank (about 1.5 meters), cleaning tank B (about 0.5 meter), acid tank B (about 0.5 meter), cleaning tank C (about 0.5 meter), and drying device in sequence. The speed of passing through the circulation processing system is 1 m / min. Finally, the take-up reel is connected to obtain the semi-finished superconducting tape with the surface metal oxide film removed.

[0064] During the production process, the surface of semi-finished superconducting tapes usually has irreparable defects, such as inconsistent thickness uniformity of the chemical vapor deposition coating, no coating on the edge, weak bonding strength of the strip after coating, etc., resulting in defective semi-finished superconducting tapes with appearance like Figure 7 shown.

[0065] The semi-finished superconducting tape obtained after the treatment in Example 3 is a C276 base tape polishing tape, and its appearance is the original color of C276, that is, bright gray. Figure 8 shown.

[0066] The microscopic surface of the semi-finished superconducting tape obtained after the treatment in Example 3 was subjected to quality test and analysis, mainly observing defects and the surface roughness of the tape after treatment (laser online test) was less than 10nm. The test results are as follows: Fig. 9 shown.

[0067] Example 4

[0068] A process for treating defective semi-finished superconducting tapes is basically the same as that of Example 3, except that in step (2), the corresponding acid and alkali solution is not heat treated.

[0069] The appearance of the defective semi-finished superconducting tape after treatment is not as bright as the appearance of the semi-finished superconducting tape obtained after treatment in Example 3.

[0070] Comparative Example 1

[0071] A treatment process for defective traction belts is basically the same as Example 1, except that: in step (2), 50% phosphoric acid is added to the PP material acid tank A, 25% sodium hydroxide is added to the PP material alkali tank, 40% nitric acid is added to the PP material acid tank B, and the corresponding acid and alkali solutions are heat treated at 40°C.

[0072] The appearance of the treated traction belt is not as bright as the traction belt obtained after the treatment in Example 1.

[0073] Comparative Example 2

[0074] A treatment process for defective intermediate transition layer superconducting tape is basically the same as Example 2, except that: in step (2), 30% sulfuric acid and phosphoric acid are added to the PP material acid tank A, 60% triethylamine is added to the PP material alkali tank, 30% nitric acid and 10% hydrofluoric acid are added to the PP material acid tank B, and the corresponding acid and alkali solutions are heat treated at 25°C.

[0075] The appearance of the treated intermediate transition layer superconducting tape is not as bright as the appearance of the intermediate transition layer superconducting tape obtained after the treatment in Example 2.

[0076] Comparative Example 3

[0077] A process for treating defective semi-finished superconducting tapes is basically the same as Example 3, except that: in step (2), sulfuric acid with a concentration of 40% is added to the PP material acid tank A, potassium hydroxide with a concentration of 60% is added to the PP material alkali tank, nitric acid with a concentration of 40% is added to the PP material acid tank B, and the corresponding acid and alkali solutions are heat treated at 35°C.

[0078] The appearance of the treated semi-finished superconducting tape is not as bright as the appearance of the semi-finished superconducting tape obtained after the treatment in Example 3.

[0079] Comparative Example 4

[0080] A process for treating defective semi-finished superconducting tapes is basically the same as Example 3, except that: in step (2), sulfuric acid with a concentration of 40% is added to the PP material acid tank A, ethylenediamine with a concentration of 60% is added to the PP material alkali tank, sulfuric acid with a concentration of 20% and phosphoric acid with a concentration of 20% are added to the PP material acid tank B, and the corresponding acid and alkali solutions are heat treated at 35°C.

[0081] The appearance of the treated semi-finished superconducting tape is not as bright as the appearance of the semi-finished superconducting tape obtained after the treatment in Example 3.

[0082] Obviously, the above embodiments of the present invention are only examples for clearly illustrating the present invention, and are not intended to limit the embodiments of the present invention. Those skilled in the art should understand that other different forms of changes or modifications can be made based on the above description. It is not necessary and impossible to list all the embodiments here. Any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should be included in the protection scope of the claims of the present invention.

Claims

1. A process for treating defective superconducting tapes, characterized in that: The following steps are involved: The defective superconducting tape with a metal oxide film on the surface is sequentially subjected to a primary pickling treatment, a primary cleaning treatment, a primary alkali cleaning treatment, a secondary cleaning treatment, a secondary pickling treatment and a tertiary cleaning treatment to obtain a superconducting tape with the metal oxide film on the surface removed; the primary pickling treatment uses phosphoric acid and / or sulfuric acid with a concentration of 10% to 50%, the primary alkali cleaning treatment uses one or more of ammonia water, triethylamine and ethylenediamine with a concentration of 10% to 25%, and the secondary pickling treatment uses nitric acid with a concentration of 10% to 50%.

2. The treatment process according to claim 1, characterized in that: The superconducting tape is made of Hastelloy.

3. The treatment process according to claim 1, characterized in that: The defective superconducting tapes include defective traction tapes, defective intermediate transition layer superconducting tapes and defective semi-finished superconducting tapes.

4. The treatment process according to claim 1, characterized in that: The first pickling treatment, the first alkali washing treatment and the second pickling treatment also include a heat treatment step.

5. The treatment process according to claim 4, characterized in that: The temperature of the heat treatment is 25-40°C.

6. The treatment process according to claim 1, characterized in that: The time of the pickling treatment is 0.1 to 2 minutes.

7. The treatment process according to claim 1, characterized in that: The time of the alkali washing treatment is 0.1 to 2 minutes.

8. The treatment process according to claim 1, characterized in that: The step of drying is also included after the three cleaning processes.

9. A system for processing defective superconducting tapes, characterized in that: The processing system is sequentially arranged to include a wire pay-off reel, an acid tank A, a cleaning tank A, an alkali tank, a cleaning tank B, an acid tank B, a cleaning tank C, a drying device, and a wire take-up reel.

10. The processing system according to claim 9, characterized in that The running speed of the defective superconducting tape in the processing system is 1-8 m / min.

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