JP5113430B2 - Metal plating composite substrate - Google Patents

Description

  The present invention relates to a metal-plated composite base material used for an orientation substrate for forming a tape such as an oxide superconducting tape, a thin film superconductor, or a bulk superconductor.

FIG. 7 shows the basic structure of the REBa ₂ Cu ₃ O _7-δ- based wire. The REBa ₂ Cu ₃ O _7-δ- based wire is largely composed of a metal substrate tape wire 5, a buffer layer 6, a superconducting layer 7, and a stabilizing metal layer 8. In an oxide superconductor, the symmetry of the cooper pair is d-wave-like and there is a node every 90 °, so that there is a problem that the critical current density cannot be increased unless the in-plane orientation fluctuation is suppressed low. . In order to keep the in-plane orientation fluctuation of the superconductor film low, the in-plane orientation fluctuation of the underlying buffer layer of the superconducting layer must be small.

The in-plane orientation control technology of the underlying buffer layer on the metal tape wire is the key to realizing the REBa ₂ Cu ₃ O _7-δ type wire. As an in-plane orientation control technique, there are known an IBAD method, an ISD method, and the like for constructing an in-plane orientation with a base buffer layer material on a non-oriented substrate tape.

The IBAD method is a technique for growing an alignment film on a non-aligned substrate by performing YSZ (Yttrium Stabilized Zirconia) film deposition while irradiating ions from a specific angle. Here, the incident angle of ions corresponds exactly to the <111> direction.
The ISD method is a technique for achieving in-plane orientation by making a constituent element incident at a certain angle on a substrate surface. An ISD-YSZ film is formed by a laser deposition (PLD) method, and a REBa ₂ Cu ₃ O _7-δ film is grown thereon.

  As the base material used in the IBAD method and ISD method, Hastelloy is often used from the viewpoint of strength.

  The RABiTS method is intended to obtain a biaxially oriented base material by strong rolling, and the base material used in the RABiTS method is a Ni-base containing several percent of W or Cr. The crystal grain size is kept small by the Cr and W impurities, and the strength of the tape wire is gained.

  However, when a large amount of impurities is added, the biaxial orientation by rolling is lost. Moreover, the pure Ni base material by the RABiTS method has a problem with respect to strength and magnetism in practical use. As a solution, Ni alloy material is used as a clad material, and Ni is vapor-deposited and rolled thereon to obtain an alignment substrate. Yes. However, in this system, as described above, when a large amount of additive is added to the Ni alloy, the Ni alloy is not oriented by rolling, and the orientation of Ni on the top is dragged by the orientation of the underlying Ni alloy, thereby providing strong biaxial orientation. There is a problem of not becoming. Therefore, the additive is limited to 15 at% or less.

  Patent Document 1 discloses a noble metal as a base material used for an oxide superconductor formed with an oxide superconducting thin film by a known means such as a plating method on the surface of a heat-resistant Ni alloy such as hastelloy having high strength. A base material is disclosed in which at least a portion on which an oxide superconducting thin film is formed is oriented in the direction of the (100) plane on the outer surface of the coating layer by strong rolling and subsequent heat treatment. .

Patent Document 2 discloses a heat-resistant Ni alloy such as Hastelloy having high strength as a base material used for an oxide superconductor formed by forming an oxide superconducting thin film, and heat-resistant Ni such as Hastelloy having high strength. Apart from the alloy, a base material is disclosed in which a Ni alloy is bonded to an alloy oriented in the [100] direction in a direction perpendicular to the Ni surface formed by strong rolling and subsequent heat treatment.
Japanese Patent Laid-Open No. 4-21597 JP 2006-127847 A

  The method of Patent Document 1 requires strong rolling for orientation and subsequent heat treatment for forming after plating, which complicates the process. Moreover, since it is strong rolling from the surface direction, the plated metal crystal grains do not extend long in one direction.

  In the method of the above-mentioned patent document 2, the process is complicated because an alloy oriented in the [100] direction is bonded to a direction perpendicular to the surface, which is produced by strong rolling and subsequent heat treatment. Moreover, since it is strong rolling from the surface direction, the plated metal crystal grains do not extend long in one direction.

  Therefore, the present invention provides a heat-resistant and oxidation-resistant material in which the plated metal crystal grains are elongated in one direction and are oriented in the direction of the (100) plane in a direction perpendicular to the surface of the heat-resistant and oxidation-resistant metal substrate. The metal-metal plating composite base material and its manufacturing method are provided.

The metal plating composite substrate of the present invention is provided with a metal plating layer on the surface of the heat and oxidation resistant metal substrate, and the crystal grains of the metal plating layer are in the longitudinal direction of the heat and oxidation resistant metal substrate, and It extends in one direction and is oriented in the [ 100] direction in a direction perpendicular to the surface of the heat-resistant and oxidation-resistant metal substrate (claim 1).

  The heat-resistant and oxidation-resistant metal substrate is made of an alloy based on any of Ni, Co, Fe, Cu, Ag, W, Cr, Mo, Mn, and V, and includes Mo, W, Cr, V, Mn, and AL. Any one or two or more of these are added (Claim 2).

The metal plating layer is made of Ni (claim 3).

The heat-resistant and oxidation-resistant metal underlying the metal plating layer is formed with depressions and / or bulges that are long in the longitudinal direction of the heat-resistant and oxidation-resistant metal (claim 4 ).

One or more elements of Ni, Co, Fe, Cu, Ag, W, Cr, Mo, Mn, V, and Ta, which are different from the metal of the metal plating layer, are a heat-resistant and oxidation-resistant metal substrate. And a metal plating layer (Claim 5 ).

The method for producing a metal-plated composite base material of the present invention comprises providing a metal strike plating layer on the surface of a heat-resistant and oxidation-resistant metal base material, and further comprising nickel sulfate, nickel chloride and boric acid as main components on the metal strike plating layer. With the nickel plating bath, the crystal grains are elongated in the longitudinal direction and in one direction of the heat-resistant and oxidation-resistant metal substrate, and the (100) plane orientation is perpendicular to the surface of the heat-resistant and oxidation-resistant metal substrate. A metal plating layer formed is formed (claim 6).

A stripe composed of a plurality of irregularities is formed on the surface of the heat-resistant and oxidation-resistant metal substrate along the longitudinal direction of the conductor (claim 7 ).

  In the present invention, as the heat-resistant oxidation-resistant metal base material, Hastelloy B {Ni-28Mo-5Fe-1.5Co}, Hastelloy C {Ni-16Mo-15.5Cr-5Fe-3W-1Co}, Hastelloy X {Ni Alloys such as -9Mo-22Cr-18.5Fe-1.5Co} and Hastelloy G {Ni-6.5Mo-22Cr-19.5Fe-2Cu-1W-1Co} can be used.

  In the present invention, for example, an organic material having acid resistance is applied onto non-oriented Hastelloy c-276, which is a Ni alloy containing a high concentration additive, and a part of the organic material is coated with a plurality of parts along the longitudinal direction of Hastelloy c-276. The organic material is removed so as to form a stripe. By etching Hastelloy c-276 patterned in this stripe shape, a stripe composed of a plurality of irregularities is formed along the longitudinal direction of Hastelloy c-276. A pure nickel film is electrodeposited on the surface of Hastelloy c-276 having stripes by electrochemical deposition in a watt bath having a pH of, for example, 4.5. Here, a heat-resistant oxidation-resistant material having a lattice constant different from that of Ni may be inserted between the patterned substrate and the nickel film. With this pattern, the grown [100] oriented nickel film has crystal grains extending in one direction. Thereby, an in-plane oriented nickel film is achieved. In the present invention, it is designed such that at least a nickel film is deposited on a heat and oxidation resistant metal substrate, for example, a Hastelloy substrate containing an additive not less than 15%.

  In the present invention, the strike nickel plating that improves the adhesion between the heat-resistant and oxidation-resistant metal substrate and the nickel plating is performed, for example, by adding hydrogen chloride to nickel chloride to increase the hydrogen ion concentration of the bath from the cathode during plating. Plating is performed while generating a large amount of hydrogen gas and reducing the oxide on the surface of the object to be metal by reducing the cathode surface to a reducing atmosphere.

The nickel plating using the Watt bath is performed with the most practical and general nickel plating bath mainly composed of nickel sulfate, nickel chloride and boric acid.

  Further, in the present invention, a stripe composed of a plurality of projections and depressions along the longitudinal direction of the conductor is formed by applying a surfactant to the surface of a metal substrate such as Hastelloy and then spin-coating a photoresist film, , Exposure, development, and etching to form uneven stripes.

After cleaning the formed metal substrate with stripes, a buffer layer is deposited by sputtering, and then subjected to nickel plating in a nickel plating bath mainly composed of strike plating, nickel sulfate, nickel chloride and boric acid .

  In the present invention, the nickel plating layer allows the crystal grains to extend long in one direction and be oriented in the [100] direction in a direction perpendicular to the surface of the metal substrate. In addition, the orientation can be controlled by changing the plating conditions, and the strong rolling for the orientation and the subsequent heat treatment can be omitted.

  By forming uneven stripes, a (100) -oriented nickel plating film with crystal grains elongated in the direction of the stripes can be obtained.

  Examples of the present invention will be described.

  FIG. 1 is a diagram for explaining a first embodiment of the present invention, wherein 1 is a heat-resistant and oxidation-resistant metal substrate, and 2 is nickel that is strongly oriented in the [100] direction. The manufacturing method of the metal plating composite base material by this Example is based on the following procedures.

(1) The surface oxide layer is removed and washed on a heat-resistant and oxidation-resistant metal substrate (Hastelloy c-276) having a flat surface. Specifically, NaOH 80 g / L is heated to 90 ° C. or more with a burner, in which oil and fat are washed for 5 minutes, and washed with running water immediately after oil and fat washing. Thereafter, reverse electrolysis (+50 mA / cm ^{2 at} 40 ° C. for 30 seconds) in Ni solution (NiCl ₂ 240 g / L HCl 80 g / L) is performed to remove the remaining dirt.

(2) Immediately, strike plating is performed in (NiCl ₂ 240 g / L HCl 80 g / L) (solution temperature is 40 ° C. for 3 minutes). Wash with running water immediately after strike plating.

(3) Nickel plating bath whose main components are nickel sulfate, nickel chloride and boric acid with a pH of 4.5, for example, NiSO ₄ .6H ₂ O 250 g / L, NiCl ₂ .6H ₂ O 50 g / L, Boric acid 30 g / L, an appropriate amount of NaOH is added, and the temperature of the solution is adjusted to 40 degrees and pH 4.5).

(4) Plating is performed from the end portion of the heat-resistant and oxidation-resistant metal substrate in the produced nickel plating bath. Wash with running water after plating.

(5) When the surface of the plated nickel film is rough, the surface is polished (chemical physical polishing).

  Thus, the heat-resistant and oxidation-resistant metal-metal plating composite base material shown in FIG. 1 is completed.

In FIG. 1, since the nickel plating film starts plating from the end on the heat-resistant oxidation-resistant metal 1, crystal grains gradually grow from the end toward the portion that enters the nickel plating bath. Therefore, since the plated nickel crystal grains are elongated in one direction and the pH of the nickel plating bath is 2 to 7 (4.5 in Example 1), it is almost in the direction perpendicular to the surface of the heat-resistant and oxidation-resistant metal substrate. A (100) face-oriented heat-resistant oxidation-resistant metal-metal plating composite base material was obtained.

  Here, strike plating is used to remove the surface oxide layer of the heat-resistant and oxidation-resistant metal substrate. However, the surface of the metal substrate is oxidized by preparing the heat-resistant and oxidation-resistant metal substrate in an oxygen-free atmosphere. Needless to say, when there is no physical layer, the strike plating step is unnecessary.

  FIG. 2 is a diagram for explaining a second embodiment of the present invention. In the first embodiment, a buffer layer 3 is deposited on the entire surface of the substrate between the nickel film 2 and the heat-resistant oxidation-resistant metal substrate 1. Only a different structure. The effect is that when the lattice constants of the heat-resistant and oxidation-resistant metal substrate and the nickel film are close to each other, the orientation of the nickel film becomes random due to being dragged by the orientation of the heat-resistant and oxidation-resistant metal substrate. The buffer layer 3 for preventing the problem can be added to solve the problem. Next, the actual creation method is shown.

(1) The surface oxide layer of the heat-resistant oxidation-resistant metal substrate (Hastelloy c-276) having a flat surface is removed and washed (NaOH 80 g / L is heated to 90 ° C. or more with a burner for 5 minutes) The oil and fat is washed, washed with water in a beaker immediately after the oil and fat washing, and washed with running water, and then reverse electrolysis (+50 mA / cm ² 40 ° C.) in a Ni solution (NiCl ₂ 240 g / L HCl 80 g / L). For 30 seconds) to remove residual dirt.)

(2) Any of Co, Fe, Cu, Ag, W, Cr, Mo, Mn, V, and Ta having a lattice constant different from that of the metal of the metal plating layer (here, nickel) on the heat-resistant oxidation-resistant metal substrate A buffer layer 3 made of one element or a plurality of elements is deposited.

(3) Strike plating (solution temperature at 40 ° C. for 3 minutes) in NiCl ₂ 240 g / L HCl 80 g / L). Wash with running water immediately after strike plating.

(4) Next , a nickel plating bath mainly composed of nickel sulfate, nickel chloride and boric acid having a pH of, for example, 4.5 (for example, NiSO ₄ .6H ₂ O 250 g / L, NiCl ₂ .6H ₂ O 50 g / L L, boric acid 30 g / L, and a suitable amount of NaOH are added, and the temperature of the solution is adjusted to 40 ° C. and pH 4.5), and plating is performed from the end of the heat and oxidation resistant metal substrate.

(5) When the surface of the plated nickel film is rough, the surface is polished (chemical physical polishing).

  Thus, the heat-resistant and oxidation-resistant metal-metal plating composite substrate shown in FIG. 2 is completed.

  FIG. 2 is the same as the embodiment of FIG. 1 except that there is a lattice mismatch metal buffer film between the heat-resistant oxidation-resistant metal 1 and the nickel plating film 2. The presence of the lattice-mismatched metal buffer film prevents nickel crystals from being dragged in the orientation of the underlying metal substrate, and the nickel crystal grains extend longer in the longitudinal direction than in the width direction of the metal substrate, and are resistant to heat and oxidation. There is an effect that the nickel film thickness required to become a heat-resistant and oxidation-resistant metal-metal plating composite base material oriented substantially (100) in the direction perpendicular to the surface of the metal base material can be reduced.

  FIG. 3 is a diagram for explaining a third embodiment of the present invention, wherein 1 is a heat-resistant and oxidation-resistant metal substrate, 2 is nickel strongly oriented in the (100) direction, and 4 is a heat-resistant and oxidation-resistant metal substrate. Material 1 Striped depressions or bulges, and patterns of both. The manufacturing method of the device according to this embodiment is as follows.

(1) The surface oxide layer is removed and washed on a heat-resistant and oxidation-resistant metal substrate (Hastelloy c-276) having a flat surface. Specifically, NaOH 80 g / L is heated to 90 ° C. or more with a burner, in which oil and fat are washed for 5 minutes, and washed with running water immediately after fat and oil washing. Thereafter, reverse electrolysis (+50 mA / cm ^{2 at} 40 ° C. for 30 seconds) in Ni solution (NiCl ₂ 240 g / L HCl 80 g / L) is performed to remove the remaining dirt.

(2) The surface of a metal substrate such as Hastelloy is coated with a surfactant (HMDS) and then coated with a photoresist film, then masked, exposed and developed to form uneven stripes.

(3) Etching is performed for 2 minutes in a cerium ammonium nitrate solution. After etching, the substrate is washed with running water.

(4) After washing the resist with acetone or the like, NaOH 80 g / L is heated to 90 ° C. or more with a burner, in which oil and fat are washed for 5 minutes, and washed with running water immediately after oil and fat washing. Thereafter, reverse electrolysis (+50 mA / cm ^{2 at} 40 ° C. for 30 seconds) in Ni solution (NiCl ₂ 240 g / L HCl 80 g / L) is performed to remove the remaining dirt.

(5) Immediately, strike plating (solution temperature at 40 ° C. for 3 minutes) in (NiCl ₂ 240 g / L HCl 80 g / L) is performed. Wash with running water immediately after strike plating.

(6) Next , a nickel plating bath mainly composed of nickel sulfate, nickel chloride and boric acid having a pH of 4.5, for example, NiSO ₄ .6H ₂ O 250 g / L, NiCl ₂ .6H ₂ O 50 g / L L, boric acid 30 g / L, and a suitable amount of NaOH are added, and the temperature of the solution is adjusted to 40 ° C. and pH 4.5), and plating is performed from the end of the heat and oxidation resistant metal substrate.

(7) When the surface of the plated nickel film is rough, the surface is polished (chemical physical polishing).

  Thus, the heat-resistant and oxidation-resistant metal-metal plating composite substrate shown in FIG. 3 is completed.

  FIG. 3 is exactly the same as the embodiment of FIG. 1 except that the surface of the heat-resistant oxidation-resistant metal 1 has stripe-shaped depressions or bulges, and patterns of both. The stripe-shaped depressions or bulges and the pattern of both have the effect that the unidirectional orientation of the nickel plating film is greatly emphasized and the aspect ratio between the width direction and the longitudinal direction becomes very large.

  In addition, here, the method of creating a stripe pattern by photoresist and photolithography was described, but a paint that protects the etching solution was applied, and the dried paint was one-way with many sharpened needles such as Kenzan. It goes without saying that the same effect can be obtained even if the metal surface is scratched.

  FIG. 4 is a diagram for explaining a fourth embodiment of the present invention. In the third embodiment, a buffer layer 3 is deposited on the entire surface of the substrate between the nickel film 2 and the heat-resistant oxidation-resistant metal base material 1. Only a different structure. The effect is that when the lattice constants of the heat-resistant and oxidation-resistant metal substrate and the nickel film are close to each other, the orientation of the nickel film becomes random due to being dragged by the orientation of the heat-resistant and oxidation-resistant metal substrate. The buffer layer 3 for preventing the problem can be added to solve the problem. As in Example 2, Co, Fe, Cu, Ag, W having a lattice constant different from that of the metal of the metal plating layer (here, nickel) between the nickel plating film and the heat-resistant oxidation-resistant metal substrate. Needless to say, when the buffer layer 3 made of one element or a plurality of elements of any one of Cr, Mo, Mn, V, and Ta is deposited, the orientation is further improved.

  FIG. 5 is an X-ray diffraction pattern diagram for explaining the orientation of the nickel plating film produced according to Example 3 of the present invention, and a very strong 200 peak is observed.

  FIG. 6 is an electron beam diffraction pattern diagram for explaining the in-plane orientation of the nickel plating film produced according to Example 3 of the present invention, in which crystal grains having a uniform orientation along the produced stripe are observed.

It is a figure explaining the 1st Example of this invention. It is a figure explaining the 2nd Example of this invention. It is a figure explaining the 3rd Example of the present invention. It is a figure explaining the 4th Example of this invention. It is a figure explaining orientation of the nickel plating film produced by the 3rd example of the present invention. It is a figure explaining the nickel crystal grain of the nickel plating film produced by the 3rd example of the present invention. It is a diagram illustrating the basic structure of REBa ₂ Cu ₃ O _7-δ type wire.

Explanation of symbols

1: Heat-resistant and oxidation-resistant metal substrate 2: Nickel plating layer 3: Buffer layer 4: Indentation or swelling
5: Metal substrate tape wire 6: Buffer layer 7: Superconducting layer 8: Stabilized metal layer

Claims (7)

  A metal plating layer is provided on the surface of the heat-resistant and oxidation-resistant metal substrate, and the crystal grains of the metal plating layer extend in the longitudinal direction and in one direction of the heat-resistant and oxidation-resistant metal substrate and are heat-resistant and oxidation-resistant. A metal-plated composite substrate characterized by being oriented in the [100] direction in a direction perpendicular to the surface of the conductive metal substrate.   The heat-resistant and oxidation-resistant metal substrate is made of an alloy based on any of Ni, Co, Fe, Cu, Ag, W, Cr, Mo, Mn, and V, and Mo, W, Cr, V, Mn, or AL The metal plating composite base material according to claim 1, wherein one or more of any of the above are added.   The metal plating composite substrate according to claim 1, wherein the metal plating layer is made of Ni.   A recess and / or a bulge having a long pattern with respect to the longitudinal direction of the heat-resistant and oxidation-resistant metal substrate is formed on the surface of the heat-resistant and oxidation-resistant metal substrate underlying the metal plating layer. Item 4. The metal-plated composite substrate according to any one of Items 1 to 3.   One or more elements of Ni, Co, Fe, Cu, Ag, W, Cr, Mo, Mn, V, and Ta, which are different from the metal of the metal plating layer, are a heat-resistant and oxidation-resistant substrate. The metal-plated composite base material according to claim 1, wherein the metal-plated composite base material exists between the metal-plated layer and the metal-plated layer. On the surface of the heat-resistant and oxidation-resistant metal base material, on the metal strike plating layer, a nickel plating bath mainly composed of nickel sulfate, nickel chloride and boric acid makes the crystal grains longer than the heat-resistant and oxidation-resistant metal base material. A method for producing a metal-plated composite base material, comprising: forming a metal plating layer extending in one direction and extending in one direction and having a (100) orientation in a direction perpendicular to the surface of the heat-resistant and oxidation-resistant metal base material.   The metal-plated composite base material according to claim 6, wherein a stripe composed of a plurality of irregularities is formed on the surface of the heat-resistant and oxidation-resistant metal base material along a longitudinal direction of the heat-resistant and oxidation-resistant metal base material. Production method.