KR100485886B1 - Method and apparatus for manufacturing both sides coated superconductors and product thereof - Google Patents

Abstract

The present invention is to form a superconducting layer on both sides of the Ag substrate, the first deposition portion in which the superconducting raw material injection means is located on one side of the heating portion, and the second deposition portion in which the superconducting raw material injection means is located on the other side of the heating portion Providing in the reactor at a predetermined distance; And transferring wires of the Ag or Ag alloy substrate so as to sequentially pass between the heating units of the both deposition units and the superconducting material injection means, while heating the substrate and spraying the superconducting material onto both sides of the substrate to perform the deposition process. A high temperature superconductor manufacturing method is disclosed.

Description

Method, apparatus for manufacturing both sides coated superconductors and product

The present invention relates to a method, an apparatus, and a product for manufacturing a double-sided deposition high temperature superconductor, and more particularly, to forming a superconducting layer on both sides of an Ag substrate by using chemical vapor deposition (CVD). It relates to a method and an apparatus and a preparation thereof.

Current methods for forming superconducting layers such as YBa ₂ Cu ₃ O _7-X (0 <X <0.5) on metal substrates include electron beam evaporation and pulsed laser ablasion. PLD) method, sputtering method, chemical vapor deposition method, etc. are mentioned.

Among them, the chemical vapor deposition method has an advantage of increasing the productivity because the process is performed under low vacuum compared to other methods.

On the other hand, as an example of configuring a superconducting layer on a metal substrate through the above method as shown in Figure 1 Ni or Ni alloy substrate 10 (hereinafter referred to collectively as Ni substrate), the buffer layer 11 and The structure containing the superconducting layer 12 is mentioned.

Herein, the Ni substrate 10 is manufactured to have an aggregate structure, and a well-known RABiTS (Rolling Assisted Biaxially Textured Substrate) method is widely used.

When the superconducting layer is directly formed on the Ni substrate 10, not only the lattice constants are inconsistent with each other but also a problem in which nickel is diffused into the superconducting layer occurs, thereby degrading the superconducting property. ), A buffer layer 11 including Ag, CeO ₂ , MgO ₂ , Y ₂ O ₃ , SrTiO ₃ , LaAlO ₂ , Al ₂ O _3, etc. is formed, and then a superconducting layer 12 is formed on the buffer layer 11. Epitaxially deposited to form a superconductor.

Therefore, the superconductor having such a structure should include a deposition process using pulsed laser ablasion-PLD, sputtering, chemical vapor deposition, or the like to form the buffer layer 11. As a result, the manufacturing process is complicated and productivity is low.

Another example of a superconductor having a superconducting layer formed on a metal substrate is a superconducting layer 21 formed on an upper surface of an Ag or Ag alloy substrate 20 (hereinafter, collectively referred to as Ag substrate) as shown in FIG. 2. The structure can be mentioned.

As is well known, the Ag or Ag alloy substrate does not require the diffusion of the Ag component into the superconducting layer 21, and there is no problem of lattice constant mismatch with the superconducting layer 21, thus eliminating the need for the buffer layer 11. There is an advantage.

However, in the related art, a method of forming a superconducting layer 21 by depositing a superconducting material on only one surface of the Ag substrate 20 was used, and it was a fact that the utilization efficiency of the Ag substrate was low, and the superconducting layer ( In case of increasing the deposition thickness of 21), there was a problem that current density decreased due to misalignment of the Ag substrate 20 (Low Cost Y-Ba-Cu-O Coated Conductors such as MW Rupich, IEEE). TRANSACTIONS ON APPLIED SUPERCONDUCTIVITY, VOL. 11.NO. 1, MARCH 2001).

The present invention has been made in consideration of the above problems, and an object thereof is to provide a method and apparatus for producing a double-sided high temperature superconductor in which a superconducting layer is formed on both sides of an Ag substrate, and an article thereof.

In order to achieve the above object, the method for manufacturing double-sided deposition high temperature superconductor according to the present invention includes a first deposition unit in which a superconducting raw material injection means is located on one side of the heating unit, and a superconducting raw material injection means in the other side of the heating unit. A first step of providing a second deposition unit in the reactor at a predetermined distance; And transferring wires of the Ag or Ag alloy substrate so as to sequentially pass between the heating units of the both deposition units and the superconducting material injection means, while heating the substrate and spraying the superconducting material onto both sides of the substrate to perform the deposition process. It includes; a second step.

Preferably, a mixture of Y (THD), Ba (THD) and Cu (THD) is used as the superconducting material, and oxygen is maintained in the substrate while the temperature of the substrate is maintained at a temperature relatively lower than the heating temperature. Supplying a third step; may be further included.

The third step is preferably performed in a state in which the wire of the Ag or Ag alloy substrate which has been deposited is retransmitted in the opposite direction and the temperature of the heating unit is set relatively low.

According to another aspect of the present invention, there is formed a receiving space therein, the reaction furnace is coupled to the pumping means for maintaining the vacuum of the receiving space; A first deposition part installed in the reactor and including a heating part and a superconducting material injection means positioned on one side of the heating part; A second deposition unit comprising a heating unit and a superconducting raw material spraying unit positioned on the other side of the heating unit and spaced apart from the first deposition unit by a predetermined distance; And a transfer means for sequentially transferring the wire rod of the Ag or Ag alloy substrate so as to pass between the heating part and the superconducting material injection means of each deposition unit in a high temperature superconductor manufacturing apparatus.

The transfer means, the first bobbin is wound around the wire rod of Ag or Ag alloy substrate; And a second bobbin disposed on the other side of the first bobbin with the first deposition unit and the second deposition unit interposed therebetween to wind up the substrate wire rod supplied from the first bobbin.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings.

3 is a view schematically showing the configuration of a double-sided deposition high temperature superconductor manufacturing apparatus according to a preferred embodiment of the present invention. Referring to the drawings, the present invention is a reactor 100 having a receiving space, the first deposition portion (A) and the second deposition portion (B) accommodated in the reactor 100, Ag substrate wire (1) It includes a conveying means for conveying.

The reactor 100 corresponds to a chamber for deposition processing on the Ag substrate wire 1, and preferably made of a metal material having excellent corrosion resistance, such as stainless steel.

The reactor 100 is coupled to the pumping means for maintaining the vacuum of the inner receiving space. As the technical configuration of this pumping means, various forms of well-known techniques can be employed.

Preferably, the pumping means includes a diffusion pump 170 and a rotary pump 180 connected to the reactor 100, the first valve provided between the diffusion pump 170 and the reactor 100 ( 165, a second valve 175 provided between the rotary pump 180 and the reactor 100, and a third valve 185 interposed between the diffusion pump 170 and the rotary pump 180. It may be configured to include.

The reactor 100 is coupled to the supply pipe 105 for supplying a superconducting material. In this case, a mixture of Y (THD), Ba (THD) and Cu (THD) is preferably used as the superconducting material, but not limited thereto, and various kinds of known superconducting materials may be used. The superconducting material is transferred by an inert gas such as argon (Ar) or nitrogen (N ₂ ) in the supply pipe 105, and thus, the first deposition unit A and the second deposition unit B inside the reactor 100. Is supplied.

The first deposition unit A is a deposition process for one surface of the Ag substrate wire 1 supplied from the outside, and the heating unit 115 with the heating unit 115 and the Ag substrate wire 1 therebetween. The superconducting raw material injection means 110 is located on one side.

The heating unit 115 preferably consists of two parts, which are divided into a preheating unit 115a and a high temperature heating unit 115b. Here, the preheating unit 115a preheats the transferred Ag substrate wire 1 to, for example, 600 to 750 ° C., and the high temperature heating unit 115b is installed to face the superconducting material injection means 110. The Ag substrate wire 1 transferred in the preheated state through the preheating unit 115a is heated to a deposition temperature corresponding to, for example, 700 to 1000 ° C.

The superconducting raw material injection means 110 includes an injection nozzle 110b for injecting the superconducting material supplied from the supply pipe 105 to the surface of the Ag substrate wire 1, and between the supply pipe 105 and the injection nozzle 110b. It includes a gas flow rate control unit 110a interposed to control the injection amount of the superconducting material. Since the injection nozzle 110b and the gas flow rate adjusting unit 110a may be known in the art, a detailed description thereof will be omitted.

The second deposition unit B is installed in the reactor 100 at a distance of, for example, several tens of centimeters from the first deposition unit A, while the Ag substrate wire is opposite to the first deposition unit A. The superconducting material is deposited on the other surface of (1).

To this end, the second deposition unit B is installed on the other side of the heating unit 125 with the heating unit 125 for heating the transferred Ag substrate wire 1 and the Ag substrate wire 1 therebetween. Superconducting raw material injection means 120 is included.

The heating part 125 is composed of two parts of the preheating part 125a and the high temperature heating part 125b, and the superconducting material injection means 120 includes an injection nozzle 120b and a gas flow control part 120a. do. Since the heating unit 125 and the superconducting material injection means 120 are the same as the detailed configuration of the first deposition unit A described above, the detailed description thereof will be omitted.

In addition, the present invention is provided with a tube-shaped protective tube 130 to surround the first deposition portion (A) and the second deposition portion (B), the injection nozzle 110b of the first deposition portion (A) ) And the injection nozzles 120b of the second deposition portion B penetrate the protective tube 130, respectively, so that the superconducting material sprayed on the Ag substrate wire 1 does not scatter and stays around the substrate. It is desirable to sustain the reaction time.

The conveying means continuously supplies the Ag substrate wire 1 so that the Ag substrate wire 1 passes between the heating part 115 of the first deposition part A and the superconducting raw material injection means 110, and then 2 is passed through the heating section 125 and the superconducting raw material injection means 120 of the deposition unit (B). Here, the transfer direction of the Ag substrate wire (1) may be set to pass through the second deposition portion (B) first, in any case the first deposition portion (A) and the second deposition portion ( Through B), superconducting materials are deposited on both sides of the Ag substrate wire 1.

Preferably, the conveying means has a first bobbin 135 on which the Ag substrate wire 1 is wound, and the first bobbin (B) between the first deposition unit (A) and the second deposition unit (B). The second bobbin 145 is installed at the other side of the 135 and winds up the substrate wire rod which is unwound from the first bobbin 135 and supplied.

The first bobbin 135 and the second bobbin 145 are provided with driving units 140 and 150, each of which includes a power unit such as a motor, to control a rotation operation for supplying and winding the Ag substrate wire 1.

It is preferable to configure the rotary pump 160 having the fourth valve 155 in the transfer means as described above to maintain the vacuum state.

Then, the process of manufacturing the double-sided deposition high temperature superconductor through the present invention as described above will be described.

In the present invention, as the Ag substrate wire rod 1, a wire rod having a biaxial aggregate structure is preferably used. Thus, a substrate of Ag or Ag alloy having a {110} <110> aggregate structure is used. do. In this case, the length of the substrate may be variously set, for example, from 1 m to 1 km, and the width and thickness may be formed to 1 m or less and 1 cm or less, respectively.

The Ag substrate wire 1 is wound around the first bobbin 135, and a predetermined length is set in a state in which the Ag substrate wire 1 is wound around the second bobbin 145 via the first deposition unit A and the second deposition unit B. do.

First, in order to maintain the inside of the reactor 1 in a vacuum state, the second valve 175 and the fourth valve 155 are opened to perform the exhaust operation by the rotary pumps 160 and 180, and reach a constant vacuum state. When the second valve 175 is closed, the first valve 165 is opened to exhaust the gas through the diffusion pump 170, and the third valve 185 is opened to exhaust gas and air. It is to be discharged by the rotary pump 180. Here, it is preferable that the vacuum degree inside the reactor 1 after the diffusion pump 170 is operated is 1 Torr or less.

After the vacuum setting of the reactor 1 is completed, the heating units 115 and 125 are driven to heat the Ag substrate wire 1. At this time, the heating unit (115, 125) preheats the Ag substrate wire (1) at a temperature of 600 ~ 750 ℃ and then heated to 700 ~ 1000 ℃ to perform the deposition treatment, the heating rate is preferably 1 ~ 100 ℃ / It is set to min.

Next, the first bobbin 135 and the second bobbin 145 are driven by the driving units 140 and 150 so that the Ag substrate wire 1 is unwound from the first bobbin 135 and wound around the second bobbin 145. The continuous feeding operation is performed in such a way. At this time, the transfer speed of the Ag substrate wire 1 is preferably set in the range of 0.1 ~ 10m / hr in consideration of the deposition temperature and the appropriate deposition thickness for the optimal superconductivity.

As the superconducting raw material, preferably Y (THD), Ba (THD) and Cu (THD) is mixed and supplied into the reactor 1 through the supply pipe 105, wherein the flow rate of the superconducting raw material is a gas flow control unit ( 110a, 120a) is set to approximately 1 ~ 500 sccm.

When the superconducting raw material is supplied into the reaction furnace 1 together with the transport gas, the vacuum degree inside the reaction furnace 1 is about 0.1 to 100 Torr.

The superconducting raw material supplied to the superconducting raw material spraying means 110 and 120 connected to the supply pipe 105 is sprayed onto the upper and lower surfaces of the Ag substrate wire 1 by the spray nozzles 110b and 120b to be deposited. At this time, the deposition rate has a value of about 0.1 ~ 10 ㎛ / hr.

Ag substrate wire (1) to be transported while being released from the first bobbin 135 is wound on the second bobbin 145 after the double-sided deposition is continuously performed through the above process.

4 illustrates a cross section of a structure in which a first superconducting layer 31 is formed on one surface of the substrate unit 30 and a second superconducting layer 32 is formed on the other surface of the substrate 30 through the deposition process as described above.

On the other hand, when a mixture of Y (THD), Ba (THD) and Cu (THD) is used as the superconducting material as is well known, oxygen (A) before the deposited Ag substrate wire 1 is wound on the second bobbin 145, O ₂ ) through the implantation process to form a more stable superconducting phase.

This process is performed in a state in which the Ag substrate wire 1, which has been formed on both sides, is cooled and maintained at about 450 to 600 ° C., which is a relatively low heat treatment temperature compared to the heating temperature.

More preferably, the oxygen injection process causes the Ag substrate wire 1 subjected to the deposition process to be immediately wound on the second bobbin 145 and then, when all the Ag substrate wire 1 of the first bobbin 135 is loosened. The first bobbin 135 is wound again to transfer the Ag substrate wire 1 in the reverse direction.

The Ag substrate wire 1 conveyed in the reverse direction is maintained at 450 to 600 ° C. by the heating parts 115 and 125, and is preferably supplied with oxygen (O ₂ ) through the supply pipe 105. The flow rate of the supplied oxygen is controlled by the gas flow rate control unit (110a, 120a) is maintained at approximately 1 ~ 500 sccm, wherein the vacuum degree of the reactor (1) is preferably maintained at a value of 0.1 ~ 100 Torr.

When the Ag substrate wire 1 is transferred at a speed of about 0.1 to 10 m / hr under the above conditions, YBa ₂ Cu ₃ O _7-X (0 <X <0.5) having high temperature superconductivity of 77k or more above the critical temperature is produced. do.

Then, a more specific experimental example of the double-sided high temperature superconductor manufacturing method provided according to the present invention will be described.

In this embodiment, the Ag substrate wire 1 has a length of 30 m, a width of 10 cm, and a thickness of 1 mm having a {110} <110> texture, and a vacuum degree of the reactor 1 is maintained at 0.5 Torr. In one state, the temperature of the preheating units 115a and 125a is set to 700 ° C., and the temperature of the high temperature heating units 115b and 125b is set to 900 ° C., and the feeding speed of the Ag substrate wire 1 is 1 m / hr. Set.

As a superconducting material, a mixture of Y (THD), Ba (THD), and Cu (THD) was used, and argon (Ar) was used as the feed gas, and was supplied into the reactor 100 through the supply pipe 105.

In addition, by adjusting the gas flow rate control unit (110a, 120a), the supply flow rate was set to 50 sccm, while maintaining the degree of vacuum in the reactor (1) at 1 Torr to the Ag substrate surface at a rate of 5㎛ / hr Deposition was performed.

After all the Ag substrate wires 1 of the first bobbin 135 were released and the deposition process was completed, the first bobbin 135 was wound again to transfer the Ag substrate wires 1 in the reverse direction to supply oxygen. At this time, the vacuum degree of the reactor 1 was set to 5 Torr, and the feed rate of the Ag substrate wire 1 was maintained at 1 m / hr.

Under these conditions, the temperature of the heating parts 115 and 125 is set to 550 ° C. for heat treatment, and the gas flow rate adjusting parts 110a and 120a are adjusted to supply oxygen (O ₂ ) at a flow rate of 200 sccm from the supply pipe 105. As a result, a 300 탆 YBa ₂ Cu ₃ O _{7 -X} (0 <X <0.5) layer is formed on both sides of the Ag substrate.

In the above, preferred embodiments of the present invention have been described with reference to the accompanying drawings. Herein, the terms or words used in the present specification and claims should not be interpreted as being limited to the ordinary or dictionary meanings, and the inventors properly define the concept of terms in order to explain their own invention in the best way. It should be interpreted as meaning and concept corresponding to the technical idea of the present invention based on the principle that it can. Therefore, the embodiments described in the specification and the drawings shown in the drawings are only the most preferred embodiment of the present invention and do not represent all of the technical idea of the present invention, various modifications that can be replaced at the time of the present application It should be understood that there may be equivalents and variations.

According to the present invention, since the high temperature superconducting layer is formed epitaxially on both sides of the Ag substrate, there is an effect of doubling the current transfer capability compared to the single-layer deposition superconductor of the same thickness.

In addition, the present invention has the advantage of providing high productivity because both sides of the substrate is deposited at the same time in accordance with the transfer of the substrate wire.

The following drawings attached to this specification are illustrative of preferred embodiments of the present invention, and together with the detailed description of the invention to serve to further understand the technical spirit of the present invention, the present invention is a matter described in such drawings It should not be construed as limited to

1 is a cross-sectional view showing a structure in which a superconducting layer is deposited on a Ni (nickel) substrate according to the related art.

2 is a cross-sectional view showing a structure in which a superconducting layer is deposited on an Ag (silver) substrate according to the related art.

Figure 3 is a schematic view showing the configuration of a double-sided deposition high temperature superconductor manufacturing apparatus according to a preferred embodiment of the present invention.

Figure 4 is a cross-sectional view showing a structure in which a superconducting layer is deposited on both sides of the Ag substrate in accordance with the present invention.

<Description of main reference numerals in the drawings>

30 ... substrate 31 ... first superconducting layer

32 second superconducting layer 100 ... reactor

105.Supply pipe 110,120 ... Superconducting raw material injection means

115,125 Heater 130 ... Protector

135 ... First Bobbin 145 ... Second Bobbin

160,180 Rotary pump 170Diffusion pump

Claims (7)

A first step of providing a first deposition part in which the superconducting material injection means is located on one side of the heating part and a second deposition part in which the superconducting material injection means is located on the other side of the heating part at a predetermined distance from the reaction furnace; And While transferring the wire of the Ag or Ag alloy substrate to sequentially pass between the heating unit and the superconducting raw material injection means of the both sides of the deposition unit, while heating the substrate and spraying the superconducting raw material on both sides of the substrate to perform the deposition process A high temperature superconductor manufacturing method comprising a second step. The method of claim 1, In the second step, the high speed superconductor manufacturing method characterized in that the feed rate of the substrate wire is set to 0.1 ~ 10m / hr. The method of claim 1, As the superconducting material, a mixture of Y (THD), Ba (THD) and Cu (THD) is employed. And a third step of supplying oxygen to the substrate while maintaining the temperature of the substrate at a temperature relatively lower than the heating temperature. The method of claim 3, wherein The third step, the high temperature superconductor manufacturing method characterized in that the re-transfer the wire of the Ag or Ag alloy substrate is completed in the opposite direction and the temperature of the heating unit is set relatively low. A reactor having an accommodation space formed therein and having a pumping means coupled to maintain the vacuum of the accommodation space; A first deposition part installed in the reactor and including a heating part and a superconducting material injection means positioned on one side of the heating part; A second deposition unit comprising a heating unit and a superconducting raw material spraying unit positioned on the other side of the heating unit and spaced apart from the first deposition unit by a predetermined distance; And High temperature superconductor manufacturing apparatus comprising a; transfer means for sequentially transferring the wire of the Ag or Ag alloy substrate so as to pass between the heating portion and the superconducting raw material injection means of each deposition unit. The method of claim 5, The conveying means, A first bobbin in which a wire rod of Ag or Ag alloy substrate is wound; And A second bobbin installed on the other side of the first bobbin with the first deposition part and the second deposition part interposed therebetween to wind the substrate wire supplied from the first bobbin and supplied; . A substrate portion made of Ag or Ag alloy; A first superconducting layer formed on one surface of the substrate portion; And And a second superconducting layer formed on the other surface of the substrate portion.