WO2019098417A1

WO2019098417A1 - Ceramic wire manufacturing method and manufacturing equipment therefor

Info

Publication number: WO2019098417A1
Application number: PCT/KR2017/013036
Authority: WO
Inventors: 문승현; 이헌주; 이재훈; 김태훈; 이유리
Original assignee: 주식회사 서남
Priority date: 2017-11-16
Filing date: 2017-11-16
Publication date: 2019-05-23

Abstract

A ceramic wire manufacturing method and manufacturing equipment therefor are disclosed. The method comprises the steps of forming a superconductive layer on a substrate and forming a protective layer on the superconductive layer, wherein the step of forming a superconductive layer comprises the steps of: depositing the superconductive layer by evaporating a plurality of metal sources through a co-evaporation method; detecting the surface color of the superconductive layer; and determining the component ratio of the metal sources of the superconductive layer according to the surface color.

Description

METHOD AND APPARATUS FOR MANUFACTURING CERAMIC WIRE

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of manufacturing a ceramic wire using surface color and an apparatus for manufacturing the same.

Generally, a superconducting body is able to flow a large amount of electric current due to its electric resistance approaching zero at a low temperature. In recent years, studies have been actively made on a thin buffer layer having biaxially oriented texture or a second generation high temperature superconducting wire forming a superconducting layer on a metal substrate. The second-generation high-temperature superconducting wire has far superior current carrying capacity per unit area than a general metal wire. Second-generation high-temperature superconducting wires can be used in fields such as power fields with low power loss, MRI, superconducting magnetic levitation trains, and superconducting propulsion vessels. Second generation high-temperature superconducting wires are referred to as ceramic wires because they contain metal oxides. However, in the conventional method of manufacturing a ceramic wire rod, it is difficult to control a quantitative ratio of metal components.

It is an object of the present invention to provide a method of manufacturing a ceramic wire rod capable of quantitatively controlling a composition ratio of metal sources of a superconducting layer and an apparatus for manufacturing the same.

A method of manufacturing a ceramic wire according to an embodiment of the present invention includes: forming a superconducting layer on a substrate; And forming a protective layer on the superconducting layer. Wherein forming the superconducting layer comprises: evaporating a plurality of metal sources by a reactive co-evaporation method to deposit the superconducting layer; Detecting a surface color of the superconducting layer; And determining a component ratio of the metal sources in the superconducting layer according to the surface color.

According to one embodiment of the present invention, the metal sources may comprise a rare-earth metal source, a barium source, and a copper source. The rare earth metal source may comprise gadolinium. The step of determining the composition ratio may include determining the composition ratio of gadolinium, barium and copper to be 1: 1: 4 when the surface color is blue with a wavelength of 500 nm. The superconducting layer may have a thickness of 1.5 micrometers to 2 micrometers. The forming of the superconducting layer may further include adjusting a composition ratio of the metal sources when the surface color of the superconducting layer is not blue. The step of adjusting the composition of the metal sources may include relatively adjusting the copper source relative to the source of the metal source and the source of the alkaline earth metal. The step of forming the superconducting layer may include: determining intensity of the surface color; And adjusting the component ratio of the plurality of metal sources when the intensity of the surface color is different from a reference value. The step of adjusting the composition ratio of the metal sources may include relatively adjusting the copper source to the source of the metal source and the source of the alkaline earth metal. The substrate may include the buffer layer. The buffer layer may be formed by a sputtering method, an i-beam deposition method, or an ion beam assisted deposition method. And heat treating the superconducting layer.

According to another embodiment of the present invention, there is provided a production facility for a ceramic wire rod, comprising: a first roll-to-roll apparatus for providing a substrate; An evaporator for forming a superconducting layer by simultaneous evaporation of a plurality of metal sources on the substrate in the first roll-to-roll apparatus; A camera for detecting an image of the superconducting layer deposited in the evaporator; And a controller for detecting a surface color of the superconducting layer from the image detected by the camera and adjusting a composition ratio of the metal sources according to the surface color.

According to one embodiment of the present invention, the evaporator comprises: a cruiser capable of providing the metal sources; A second roll-to-roll apparatus for providing the substrate on the crucible; And an ion gun disposed adjacent to the crucible and providing an ion beam to the metal sources in the crucible. The controller may control the power of the ion beam according to the surface color.

According to the embodiment of the present invention, a method of manufacturing a ceramic wire rod can detect the surface color of the superconducting layer and quantitatively adjust the composition ratio of the metal sources according to the surface color.

1 is a cross-sectional view schematically showing a ceramic wire of the present invention.

2 is a flow chart showing a method of manufacturing a ceramic wire according to an embodiment of the present invention.

3 is a view showing an apparatus for forming a superconducting layer in Fig.

4 is a graph showing surface color values in a three-dimensional color coordinate system.

BRIEF DESCRIPTION OF THE DRAWINGS The advantages and features of the present invention, and how to accomplish them, will become apparent by reference to the embodiments described in detail below with reference to the accompanying drawings. The present invention may, however, be embodied in many different forms and should not be construed as being limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete, and will fully convey the concept of the invention to those skilled in the art. Is provided to fully convey the scope of the invention to those skilled in the art, and the invention is only defined by the scope of the claims. Like reference numerals refer to like elements throughout the specification.

The terminology used herein is for the purpose of illustrating embodiments and is not intended to be limiting of the present invention. In the present specification, the singular form includes plural forms unless otherwise specified in the specification. It is to be understood that the phrase "comprises" and / or "comprising" used in the specification excludes the presence or addition of one or more other elements, steps, operations and / or layers, I never do that.

In addition, the embodiments described herein will be described with reference to cross-sectional views and / or plan views, which are ideal illustrations of the present invention. In the drawings, the thicknesses of the films and regions are exaggerated for an effective description of the technical content. Thus, the shape of the illustrations may be modified by manufacturing techniques and / or tolerances.

1 schematically shows a ceramic wire rod 50 of the present invention. The ceramic wire rod 50 may include a substrate 10, a buffer layer 20, a superconducting layer 30, and a protective layer 40. The substrate 10 may comprise a metal such as stainless steel or Hastelloy. The buffer layer 20 may be disposed between the substrate 10 and the superconducting layer 30. For example, the buffer layer 20 may include a diffusion barrier layer 21, a seed layer 22, an IBO (Ion Beam-Assisted Deposition) MgO layer 23, an Epi MgO layer 24, and a LaMnO ₃ (25) Layer. Alternatively, the substrate 10 may comprise a C-axis oriented crystallized (RaBit) substrate, including a buffer layer 20. The superconducting layer 30 may include a multi-component metal oxide such as ReBCO (ReBaCuO). Here, Re may include a hetradium metal such as gadolinium. The protective layer 40 may include at least one of gold, silver, Al, Cu, and Pb.

A method of manufacturing the ceramic wire material 50 having the above-described structure will be described below.

2 shows a method of manufacturing the ceramic wire 50 according to the embodiment of the present invention.

First, a substrate 10 is provided (S10). For example, a buffer layer 20 may be formed on the substrate 10. The buffer layer 20 may be formed by a sputtering method, an i-beam deposition method, or an ion beam assisted deposition method. Alternatively, the substrate 10 may be a C-axis oriented crystallized (RaBit) substrate.

Next, a superconducting layer 30 is formed on the buffer layer 20 (S20). According to one example, the superconducting layer 30 may be formed to a thickness of about 1.2 탆 to about 2 탆 by a reactive simultaneous evaporation method.

3 shows an apparatus 100 for forming a superconducting layer 30 for implementing a reactive simultaneous evaporation method. The apparatus 100 for forming a superconducting layer 30 includes a first roll feed apparatus 110, a deposition apparatus 120, a heat treatment apparatus 130, a camera 140, a light source 142, 150).

The first roll feed apparatus 110 may provide the substrate 10 on the evaporator 120. For example, the first roll-to-roll apparatus 110 may include a first release reel 112 and a first winding reel 114.

The evaporator 120 may form a superconducting layer 30 on the substrate 10. The evaporator 120 may be disposed between the first release reel 112 and the first winding reel 114. According to one example, the deposition apparatus 120 may include a second roll feed apparatus 122, a crucible 124, an ion gun 126, and a Quartz crystal microbalance 128.

A second roll turrol device 122 may provide the substrate 10 on the crucible 124. The second roll-to-roll apparatus 122 may multi-turn the substrate 10 in the transverse direction. The second roll-to-roll device 122 may include a second release reel 121 and a second winding reel 123.

The cruivel 124 may have a plurality of boats 125 that contain metal sources 160. Metal sources 160 may include a source of helium metal 162, an alkaline earth source 164, and a source of copper 166. The source metal source 162 may include gadolinium (Gd) or iridium (Yi). The alkaline earth metal source 164 may comprise barium. The arrangement order of the metal sources 160 may be variously changed.

The ion gun 126 may provide an ion beam 127 within the boats 125. The ion beam 127 can vaporize the metal sources 160. According to one example, the ion gun 126 may provide an ion beam 127 at a frequency of about 60 Hz to each of the metal sources 160. The amount of evaporation of the metal sources 160 may be adjusted according to the power of the ion beam 127. As the power of the ion beam 127 increases, the amount of evaporation of the metal sources 160 can be increased. The superconducting layer 30 may be formed from metal sources 160. For example, the superconducting layer 30 may comprise GdBCO (GdBaCuO).

The quartz crystal microbalance 128 may be disposed adjacent to the substrate 10 between the second release reel 121 and the second winding reel 123. The quartz crystal microbalance 128 may sense the metal sources 160 on the crucible 124.

The heat treatment apparatus 130 can heat-treat the superconducting layer 30. The heat treatment apparatus 130 can melt and crystallize the superconducting layer 30 at a high temperature of about 700 ° C to about 1100 ° C. The heat treatment apparatus 130 may provide oxygen to the superconducting layer 30. According to one example, the heat treatment apparatus 130 may have a low-pressure oxygen region 132 and a high-pressure oxygen region 134. For example, low-pressure oxygen region 132 is about 1X10 ^- may provide an oxygen pressure of ³ Torr ^- ⁵ Torr to about 1X10. Hyperbaric region 134 is about 1X10 ^- may provide an oxygen pressure of ² Torr ^- ³ Torr to about 1X10.

The camera 140 may be disposed between the heat treatment apparatus 130 and the first winding reel 114. The camera 140 may detect an image of the superconducting layer 30. [ For example, the camera 140 may include a CCD or CMOS sensor.

The light source 142 may be disposed adjacent to the camera 140. The light source 142 may provide white light to the superconducting layer 30. The camera 140 can detect the reflected light of the white light. The reflected light may have various colors depending on the surface state of the superconducting layer 30. [ The surface color of the superconducting layer 30 will be described later.

The control unit 150 can control the power of the ion beam 127 for each of the metal scales 160. The power of the ion beam 127 may be adjusted based on the quartz crystal microbalance 128 and the output signal of the camera 140.

The control unit 150 may monitor the deposition rate of the metal sources 160 according to the sensing signal of the Quartz crystal microbalance 128. The deposition rate of the metal sources 160 and the composition ratio of the superconducting layer 30 may be different from each other. The deposition rates of the metal sources 160 may be differently determined depending on the location of the quartz crystal microbalance 128. Because the quartz crystal microbalance 128 can not simultaneously sense the entire metal sources 160 between the crucible 124 and the substrate 10.

The control unit 150 may adjust the composition ratio of the metal sources 160 in the superconducting layer 30 according to the color of the image of the camera 140. [ Here, the color of the image may be the surface color of the superconducting layer 30. The control unit 150 can determine the composition ratio of the metal sources 160 according to the surface color. According to one example, the controller 150 may control the evaporator 120 to form the superconducting layer 30 based on FIG.

First, the controller 150 controls the ion beam 127 to evaporate the metal sources 160 to deposit the superconducting layer 30 on the buffer layer 20 (S22). For example, an ion beam 127 of about 50% power is provided to gadolinium, an ion beam 127 of about 20% power is provided to barium, and an ion beam 127 of about 30% power is provided to copper .

Thereafter, the control unit 150 can control the heat treatment apparatus 130 to heat the superconducting layer 30 (S24). For example, the heat treatment apparatus 130 may heat the substrate 10 to about 800 ° C. to heat the superconducting layer 30.

Next, the control unit 150 can detect the surface color of the superconducting layer 30 from the image of the camera 140 (S26). The control unit 150 can detect the wavelength band of the surface color. Gadolinium has a red hue of about 625 nm to about 740 nm, barium has a yellow hue of about 565 nm to about 590 nm, and copper has a blue hue of about 440 nm to about 450 nm. The surface color may vary depending on the composition ratio of the metal sources 160 in the superconducting layer 30. If gadolinium is present in the superconducting layer 30 relative to barium and copper, the image may have a red color. If barium is relatively large compared to gadolinium and copper, the image may have green or yellow color. If the copper is relatively large compared to gadolinium and barium, the image may have a blue color.

The control unit 150 can discriminate the surface color (S28). The control unit 150 can determine whether the color of the predetermined wavelength band is a color. The controller 150 can determine the composition ratio of the metal sources 160 in the superconducting layer 30 according to the surface color in the color coordinate system of FIG.

FIG. 4 shows surface color values in the three-dimensional color coordinates of RGB. When the gadolinium, barium, and copper in the superconducting layer 30 each have a composition ratio of about 1: 1: 1 (80), the superconducting layer 30 of about 1.5 탆 to about 2 탆 in thickness has a critical current Lt; / RTI > The surface color of the superconducting layer 30 having a 1: 1: 1 component ratio may appear white.

When gadolinium, barium, and copper each have a composition ratio of about 1: 1: 4 (90), the superconducting layer 30 can pass a critical current of about 700 A or more. Copper can have a relatively high composition ratio relative to gadolinium and barium. The superconducting layer 30 having a 1: 1: 4 component ratio can have superior superconducting properties to the superconducting layer 30 having the 1: 1: 1 component ratio. The surface color of the superconducting layer 30 having a 1: 1: 4 component ratio may appear blue.

Table 1 shows the wavelengths of the reflected light according to the composition ratios of gadolinium, barium, and copper in the superconducting layer 30.

성분 비Ingredient ratio	1 : 1.5 : 3.51: 1.5: 3.5	1.5 : 1.5 : 3.51.5: 1.5: 3.5	1 : 1 : 41: 1: 4
파장(nm)Wavelength (nm)	600600	700700	500500

Referring to Table 1, when the gadolinium, barium, and copper have a 1: 1: 4 component ratio, the superconducting layer 30 may have the surface color of blue with a wavelength of 500 nm. When the gadolinium, barium, and copper have a 1: 1.5: 3.5 component ratio, the superconducting layer 30 may have the surface color of yellow at a wavelength of 600 nm. When the gadolinium, barium, and copper have a component ratio of 1.5: 1.5: 3, the superconducting layer 30 may have the surface color of red at a wavelength of 700 nm.

Referring to FIGS. 2 and 3, the controller 150 can determine the composition ratio of the metal sources 160 to the surface color of the superconducting layer 30 (S28). The control unit 150 may control the power of the ion beam 127 according to the color of the surface of the superconducting layer 30. [ The composition ratio of the metal sources 160 in the superconducting layer 30 can be quantitatively controlled by the power of the ion beam 127. [

If the color of the image is not blue, the controller 150 may adjust the component ratio of the metal sources by adjusting the power of the ion beam 127 relative to the metal sources 160 until the surface color is blue S30). For example, the controller 150 may increase the power of the ion beam 127 relative to the copper source 166.

Next, when the surface color is blue, the controller 150 can determine the intensity of the surface color (S32). If the image does not have a predetermined intensity of blue, the controller 150 adjusts the power of the ion beam 127 (S30). The copper source 166 may be adjusted relative to the source of rare earth metal 162 and the source of alkaline earth metal 164. When the blue color becomes dark and the intensity becomes high, the power of the ion beam 127 provided to the copper source 166 can be reduced. Alternatively, the power of the ion beam 127 of the copper source 166 may be increased when the blue light is weaker in intensity. The control unit 150 may finely adjust the composition ratio of the metal sources 160 using the intensity of the surface color of the superconducting layer 30. [

If the intensity of the surface color is appropriate, the controller 150 can maintain the power of the ion beam 127 constant until the step S20 of forming the superconducting layer 30 is completed.

Finally, a protective layer 40 is formed on the superconducting layer 30 (S40)

While the present invention has been described in connection with what is presently considered to be practical exemplary embodiments, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, It will be understood. It is therefore to be understood that the above-described embodiments are illustrative and not restrictive in every respect.

Claims

Forming a superconducting layer on the substrate; And

And forming a protective layer on the superconducting layer,

Wherein forming the superconducting layer comprises:

Depositing the superconducting layer by evaporating a plurality of metal sources using a reactive co-evaporation method;

Detecting a surface color of the superconducting layer; And

And determining the composition ratio of the metal sources in the superconducting layer according to the surface color.
The method according to claim 1,

Wherein the metal sources comprise a rare earth metal source, a barium source, and a copper source, wherein the rare earth metal source comprises gadolinium.
3. The method of claim 2,

The step of determining the component ratio

Barium and copper in a ratio of 1: 1: 4 when the color of the surface is blue with a wavelength of 500 nm.
The method of claim 3,

Wherein the superconducting layer has a thickness of 1.5 micrometers to 2 micrometers.
The method of claim 3,

Wherein the step of forming the superconducting layer further comprises the step of adjusting a composition ratio of the metal sources when the surface color of the superconducting layer is not blue.
6. The method of claim 5,

Wherein adjusting the ratio of the metal sources comprises relatively adjusting the copper source relative to the source of the lead metal and the source of the alkaline earth metal.
The method according to claim 1,

The step of forming the superconducting layer

Determining an intensity of the surface color; And

Further comprising adjusting the composition ratio of the plurality of metal sources when the intensity of the surface color is different from a reference value.
8. The method of claim 7,

Wherein adjusting the ratio of the metal sources comprises adjusting the copper source relative to the source of the lead metal and the source of the alkaline earth metal.
The method according to claim 1,

Wherein the substrate comprises the buffer layer,

Wherein the buffer layer is formed by a sputtering method, an i-beam deposition method, or an ion beam assist deposition method.
The method according to claim 1,

And heat treating the superconducting layer.
A first roll-to-roll apparatus for providing a substrate;

An evaporator for forming a superconducting layer by simultaneous evaporation of a plurality of metal sources on the substrate in the first roll-to-roll apparatus;

A camera for detecting an image of the superconducting layer deposited in the evaporator; And

And a controller for detecting a surface color of the superconducting layer from the image detected by the camera and adjusting a composition ratio of the metal sources according to the surface color.
12. The method of claim 11,

The evaporator comprises:

A crucible for providing the metal sources;

A second roll-to-roll apparatus for providing the substrate on the crucible; And

An ion gun disposed adjacent the crucible and providing an ion beam to the metal sources in the crucible,

Wherein the control unit controls the power of the ion beam according to the surface color.
13. The method of claim 12,

The metal sources include a rare-earth metal source, a barium source, and a copper source,

Wherein the control unit controls the rare earth metal source, the barium source, and the copper source in the superconducting layer to a ratio of 1: 1: 4.
14. The method of claim 13,

The superconducting layer

Wherein the rare earth metal source comprises red gadolinium, the one barium source has a green or yellow hue, the copper source has a blue hue,

Wherein the control unit controls the power of the ion beam so that the superconducting layer has the blue surface color at a thickness of 1.5 micrometers to 2 micrometers.
13. The method of claim 12,

Further comprising a heat treatment device disposed between the second roll roll device and the camera, for heat treating the superconducting layer on the substrate,

The heat treatment apparatus comprises:

A low pressure oxygen region for providing oxygen to the substrate; And

And a high-pressure oxygen region that provides the oxygen higher than the pressure of the low-pressure oxygen region.
12. The method of claim 11,

Further comprising a light source disposed adjacent to the camera and providing white light on the superconducting layer.