KR101776151B1 - Bonding method for cemented carbide material using metal coating layer with exothermic and amorphous characteristics - Google Patents

Bonding method for cemented carbide material using metal coating layer with exothermic and amorphous characteristics Download PDF

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KR101776151B1
KR101776151B1 KR1020150108652A KR20150108652A KR101776151B1 KR 101776151 B1 KR101776151 B1 KR 101776151B1 KR 1020150108652 A KR1020150108652 A KR 1020150108652A KR 20150108652 A KR20150108652 A KR 20150108652A KR 101776151 B1 KR101776151 B1 KR 101776151B1
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South Korea
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metal
cemented carbide
plating
bonding
acid
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KR1020150108652A
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Korean (ko)
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KR20170014777A (en
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정재필
이준형
정도현
임동욱
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덕산하이메탈(주)
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Priority to PCT/KR2016/008065 priority patent/WO2017022991A1/en
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/001—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by extrusion or drawing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/002—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating specially adapted for particular articles or work
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/02—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a press ; Diffusion bonding
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/04—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating by means of a rolling mill
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K20/00—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating
    • B23K20/16—Non-electric welding by applying impact or other pressure, with or without the application of heat, e.g. cladding or plating with interposition of special material to facilitate connection of the parts, e.g. material for absorbing or producing gas
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/02—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape
    • B23K35/0222—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting characterised by mechanical features, e.g. shape for use in soldering, brazing
    • B23K35/0233—Sheets, foils
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
    • B23K—SOLDERING OR UNSOLDERING; WELDING; CLADDING OR PLATING BY SOLDERING OR WELDING; CUTTING BY APPLYING HEAT LOCALLY, e.g. FLAME CUTTING; WORKING BY LASER BEAM
    • B23K35/00—Rods, electrodes, materials, or media, for use in soldering, welding, or cutting
    • B23K35/40—Making wire or rods for soldering or welding
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D21/00—Processes for servicing or operating cells for electrolytic coating
    • C25D21/12—Process control or regulation
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/04—Electroplating: Baths therefor from solutions of chromium
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/06—Wires; Strips; Foils
    • C25D7/0614—Strips or foils

Abstract

The present invention provides a method of manufacturing an electrolytic plating circuit, comprising the steps of preparing an aqueous alloy plating solution containing two or more metal salts including a first metal salt and a second metal salt, forming an electrolytic plating circuit by immersing the electrode in the aqueous alloy plating solution, A control voltage is applied to the control electrode in the range of +2 V to -4.5 V or a corresponding current value based on a 25 DEG C standard hydrogen electrode according to the reduction potential of the metal salt to be plated to apply a reduced potential or current to the electrode , One side of the first cemented carbide material or the second cemented carbide material or one side of both the first cemented carbide material and the second cemented carbide material by the standard reduction potential difference of the metal salts, On both sides of the core metal to be disposed therebetween, at least two or more layers Forming a multilayer amorphous metal plating film and arranging the first and second carbide materials in such a manner that the multilayer amorphous metal plating film is disposed between and facing the first and second carbide materials, Is placed between the first and second cemented carbide materials, and the first and second cemented materials are pressurized and bonded to each other while heating to a melting temperature range so that the exothermic characteristics of the multilayered amorphous metal plating film can be exhibited And a joining step of joining the cemented carbide material.
According to the present invention, it is possible to form a bonding portion exhibiting excellent bonding strength even at a relatively low bonding temperature by forming a metal plating film between the cemented materials to bond the cemented carbide material and the tool steel, There is an effect that can be done.

Description

BACKGROUND OF THE INVENTION 1. Field of the Invention [0001] The present invention relates to a bonding method of a carbide material using a metal plating film having amorphous and heat-

The present invention relates to a method of bonding a hard metal material using a metal plating film having amorphous and heat-generating properties, and a metal plating film having amorphous and heat-generating properties is formed on a surface of a low melting point core metal in the form of a foil, The present invention relates to a method of joining a cemented carbide by an easy method which can form an excellent joint even at a relatively low joining temperature by joining a cemented carbide material and a tool steel.

Generally, there are many parts of equipment such as buildings, automobiles, ships, airplanes, trains, transportation equipment, various pipes and pipes that require bonding between metals or alloys. A high-temperature fusion welding method is used.

However, the fusion bonding (or welding) process has a problem in that the working temperature is so high as to change the texture of the surrounding base material such as coarsening of particles and formation of heat affected part, Resulting in material defects such as stress corrosion cracking due to stress formation. Therefore, in recent years, studies have been actively made on a low temperature and high-temperature bonding technique capable of imparting sufficient tensile strength, adhesive strength, and excellent leakage preventing property between metals and alloys of such structural parts.

FIG. 1 is a schematic view showing a bonding process of a tool steel and a cemented carbide in the prior art.

1, Japanese Unexamined Patent Publication (Kokai) No. 60-250872 discloses a technique for bonding a cemented carbide 12 and a tool steel 11 to a powder metal insert 13 made of Ni and Co And the central part of the bonding interface is uneven. However, this method inconveniences that the tool steel 11 should be machined separately. In addition, it is important to provide an appropriate roughness to the bonding surface in order to improve the bonding strength by eliminating defects in the bonding portion. However, there is a problem in that the surface polishing is difficult due to the uneven processing and proper surface roughness can not be given. In addition, since the tool steel has a large thermal expansion coefficient, and the cemented carbide has a small thermal expansion coefficient, there is a problem that cracks are likely to occur in the cemented carbide due to the stress due to the difference in brazing.

FIG. 2 is a schematic view showing a conventional joining process of joining tool steel and cemented carbide using a nickel-based metal.

2, a technique 20 (domestic patent application 1999-0033635) 20 for bonding a tool steel and a cemented carbide using a nickel-based metal is a method of polishing a tool steel 21 and a cemented carbide 22 The joining of the tool steel having excellent bonding strength is carried out by appropriately adjusting the coagulation width and the size of the reaction layer by inserting the foil-like Ni-based metal 23 as a bonding medium between the tool steel 21 and the cemented carbide 22, to provide. Specifically, the cemented carbide 22 and the tool steel 21 are fixed through the jigs 25a, 25b, 25c, and 25d fixed by the fixtures 26a and 26b so as to face the polished surfaces, The Ni-based metal 23 is inserted to form a laminate and the flow preventive agent 24 of the foil-based Ni-based metal 23 is applied to the contact area between the tool steel 21 and the cemented carbide 22. Thereafter, such a laminate is heated to a temperature 20 to 100 DEG C higher than the melting point of the Ni-based insertion metal 23 in a vacuum furnace to be bonded.

However, in the case of this technique, a separate specimen fixing device is required, and there is an inconvenience to apply the flow inhibiting agent of the insertion metal. In addition, the melting point of Ni, which is an intercalation metal, is very high at 1455 ° C, which causes a high junction energy consumption and can cause thermal damage to the base metal.

As described above, in the case of bonding using a conventional bulk bonding medium, since the bonding is performed at a temperature higher than the melting temperature of the bonding medium, the energy consumption cost due to heating is large, and sometimes thermal damage is caused to the base material There is also concern.

Accordingly, in the case of using a bonding medium in powder form, the melting point is lower than that in the case of using a bulk type bonding medium so as to solve the problem of using such a bulk type bonding medium , And can be bonded at a relatively low temperature.

However, such a powdery bonding medium has the following problems.

First, the powder tends to be oxidized, and there is an inconvenience that the surface of the powder must be covered with a chemical to prevent this.

Second, there is a great risk of explosion or fire due to the rapid oxidation of the powder itself.

Third, Ag and Au powder, which are noble metals that are difficult to oxidize at present, have been put to practical use, but materials that are easily oxidized, such as Cu and Sn, are difficult to be put to practical use.

Fourth, the process is complicated because various chemicals must be coated on powder surface or mixed with powder to prevent oxidation.

Fifth, it is difficult to keep powder or paste, and it is difficult to manage such as prevention of oxidation during manufacturing.

Sixth, powder or paste is expensive.

Seventh, the powder is harmful because it is easy to penetrate the human body.

Eighth, the powder paste is applied on curves or vertical surfaces and is difficult to use, so its applicability is limited.

Therefore, there is a need for a joining method capable of joining with excellent bonding strength even at a low temperature and easily joining without causing the above problems.

Japanese Patent Application Laid-Open No. 60-250872 Domestic patent application 1999-0033635

SUMMARY OF THE INVENTION An object of the present invention is to solve the problems of the prior art as described above, and to provide an excellent bonding property between a tool steel and a cemented carbide. The present invention also relates to a bonding method of a cemented carbide and a tool steel which is safe by an exothermic reaction due to a change from an amorphous to a crystalline state, and can provide bonding strength and bonding reliability which are excellent even at low temperatures.

According to an aspect of the present invention, there is provided a method of manufacturing an electrolytic plating circuit, comprising: preparing an aqueous alloy plating solution containing two or more metal salts including a first metal salt and a second metal salt; A voltage between +2 V and -4.5 V or a corresponding current value based on a 25 DEG C standard hydrogen electrode is input to a control unit for controlling the electrolytic plating circuit according to the reduction potential value of the metal salt to be plated Applying a reduction potential or current to the electrode, applying one of the first surface of the first or second hard material or the first surface of the first and second hard materials according to the standard reduction potential difference of the metal salts, At least two or more layers on both surfaces of the core metal to be disposed between the first and second hard materials Forming a multilayer amorphous metal plating film and arranging the first and second carbide materials in such a manner that the multilayer amorphous metal plating film is disposed between and facing the first and second carbide materials, Is placed between the first and second cemented carbide materials, and the first and second cemented materials are pressurized and bonded to each other while heating to a melting temperature range so that the exothermic characteristics of the multilayered amorphous metal plating film can be exhibited And a bonding step.

The range of the reduction potential of the metal salt may be a voltage between +1.83 V and -1.67 V or a corresponding current value based on a standard hydrogen electrode at 25 캜.

The water-based alloy plating solution may include a first metal salt, a second metal salt, an acid and a base, and an additive in a water-based plating solution.

The first and second metal salts include Sn, Cu, Zn, Ni, Al, Ti, V, Cr, Mn, Fe, Co, Ga, Ge, As, Zr, Nb, Mo, Ru, Rh, Pd, And at least one metal salt selected from the group consisting of In, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb and Bi.

The first and second metal salts may be selected from two or more metal salts of the elements showing the difference in the standard reduction potential.

The acid may be selected from sulfuric acid, hydrochloric acid, methanesulfonic acid (MSA), nitric acid, boric acid, acetic acid, organic sulfuric acid, citric acid, formic acid, ascorbic acid, hydrofluoric acid, phosphoric acid, amino acid and hypochlorous acid.

The additive may be selected from among polyoxyethylene lauryl ether (POELE), a plating flatting agent (smoothing agent), an accelerator, an inhibitor, a defoaming agent, a polishing agent and an oxidation inhibitor.

The step of applying the reducing potential or the current to the electrode may alternately cause a first voltage section in which the first metal and the second metal are simultaneously coated and a second voltage section in which the second metal is plated alternately.

The metallic plating film may be formed by mixing a powder with a liquid in the form of a multi-layered plated film, a multi-layered foil sheet, a multi-layered foil sheet, And a metal particle type in which a multi-layered plated thin film is formed on the surface.

The metal plating layer may be a multilayer thin film having a structure in which at least two thin film layers containing different metal elements are alternately stacked.

The metal plating film may be a multilayer thin film having a structure in which at least six thin film layers are laminated.

When the metal plating film is laminated on two films, the sum of the two film thicknesses can be realized in a thickness ranging from 0.1 nm to 5 占 퐉.

The metal plating film may have a total thickness ranging from 0.6 nm to 300 탆.

The melting temperature range of the metal plating film may be a melting point of an element having a low melting point among the elements included in each of the thin film layers constituting the metal plating film or a temperature lower than a melting point of the entire bulk composition constituting the metal plating film.

The first cemented carbide material may be a metal material, and the second cemented carbide material may be a material selected from the group consisting of a metal material, a ceramic material, and a plastic material different from the first carbide material.

The first cemented carbide material may be a tool steel, and the second cemented carbide material may be a hard metal.

According to the present invention, by forming a multilayer amorphous metal plating film between the cemented carbide materials to bond the cemented carbide materials, it is possible to form a junction exhibiting excellent bonding strength even at a relatively low junction temperature, It is possible to provide an excellent bonding strength and bonding reliability even when bonded at a low temperature by the reaction.

FIG. 1 is a schematic view showing a bonding process of a tool steel and a cemented carbide in the prior art.
2 is a schematic view showing a conventional joining process of joining a tool steel and a cemented carbide using a nickel-based metal.
FIG. 3 is a schematic view illustrating a state in which a tool steel and a cemented carbide are joined together according to an embodiment of the present invention.
4 is a schematic view illustrating a process of bonding a tool steel and a cemented carbide according to an embodiment of the present invention.
FIG. 5 is a graph showing melting points according to particle size of the multi-layer thin film joint in the process of bonding the tool steel and the cemented carbide according to an embodiment of the present invention.
6 is a graph showing the results of differential thermal analysis (DTA) of a Cu-Ni multilayer thin film junction in the process of bonding tool steel and cemented carbide according to an embodiment of the present invention.
7 is a graph showing differential scanning calorimetry (DSC) results of a Sn-Cu multilayer thin-film joint in a process of bonding a tool steel and a cemented carbide according to an embodiment of the present invention.
8 is a graph showing the results of differential thermal analysis (DTA) of a Cu-Ag multilayer thin film junction in the process of bonding tool steel and cemented carbide according to an embodiment of the present invention.
9 is a table showing the formation of a metal plating film according to the content ratio of the metal salt and the difference in reduction potential in the plating solution according to the present invention.
FIGS. 10A to 10H are cross-sectional photographs of a metal plating film when the conditions of the first metal salt, the second metal salt and the reduction potential are different in the plating solution according to the present invention.
11 is a range graph showing the formation of a metal plating film according to the content ratio of the metal salt and the difference in reduction potential in the plating solution according to the present invention.
12 is a table of various core metal alloy compositions used in the present invention.
13 is a photograph showing a core metal alloy based on Cu-Ag and Cu-Zn produced by using an induction furnace.
FIG. 14 is a photograph of a core metal surface nanocomposite plating based on Cu-Ag or Cu-Zn after being processed by a rolling mill.
15A to 15B are photographs of a joint between a tool steel and a cemented carbide using a Cu-Ag and Cu-Zn based core metal alloy according to the present invention.
16 is a block diagram showing a bonding process of a tool steel and a cemented carbide using a core metal in the present invention.
17 is a scanning electron microscope (SEM) photograph showing an actual cross-section of a Ni-Cu multilayer thin-film joint before joining in the process of bonding tool steel and cemented carbide according to an embodiment of the present invention.
18 is a photograph of a Ni-Cu multilayer thin film joint formed on the surface of a tool steel without using a core alloy in the process of bonding the tool steel and the cemented carbide according to an embodiment of the present invention.
19 is an actual photograph of a cemented carbide and a tool steel bonded together without using a core alloy in a process of bonding a tool steel and a cemented carbide according to an embodiment of the present invention.
FIG. 20 is a graph showing the relationship between the first and second plated metal layers (left) as plated before heating of the Sn-Cu metal plating film produced in the present invention and the It is a photograph.
FIG. 21 is a photograph (right) of the first and second plating layers (left) as plated before heating of the Ni-Cu metal plating film produced in the present invention and the disappearance of the first and second plating layers by diffusion after heating to be.
22 is a graph showing the amorphous characteristics (left) as a result of XRD analysis of the metal plating film in the plated state before heating of the Sn-Cu metal plating film prepared in the present invention, and FIG. (XRD) analysis result shows that the crystalline characteristic (right) appears.
23 is an electron micrograph (SEM) photograph showing a cross section of a metal plating film produced by thickening the sum of the thicknesses of the two plating layers to 5 占 퐉.
24 is a heating graph in which a metal plating film is manufactured by thickening the sum of the thicknesses of the two plating layers to 5 占 퐉 and measuring thermal characteristics using a differential scanning calorimeter (DSC).
Fig. 25 is an optical microscope photograph showing a real section after bonding of a joint where the sum of the thicknesses of the two plated layers is made thick to 5 占 퐉.
Fig. 26 is an optical microscope photograph showing the copper electrode cross section made by laminating six layers of the metal plating film at a low temperature.
Fig. 27 is an optical microscope photograph showing an end face portion of a Sn-Cu-based metal plating thin film produced by lengthening the plating time of the metal plating film to a total plating thickness of 300 m.

The terms or words used in the present specification and claims are intended to mean that the inventive concept of the present invention is in accordance with the technical idea of the present invention based on the principle that the inventor can appropriately define the concept of the term in order to explain its invention in the best way Should be interpreted as a concept.

Throughout the specification, when an element is referred to as "comprising ", it means that it can include other elements as well, without excluding other elements unless specifically stated otherwise.

The method for joining a cemented carbide material according to the present invention comprises the steps of preparing an aqueous alloy plating solution containing at least two metal salts including a first metal salt and a second metal salt; immersing the electrode in the aqueous alloy plating solution to constitute an electrolytic plating circuit A voltage between +2 V and -4.5 V or a corresponding current value based on a standard hydrogen electrode at 25 DEG C is input to a control unit for controlling the electroplating circuit according to the reduction potential value of the metal salt to be plated, Applying a reduction potential or current to the one surface of the first carbide material or the second carbide material or a surface of both the first carbide material and the second carbide material by the standard reduction potential difference of the metal salts, At least two or more layers on both surfaces of the core metal to be disposed between the material or the second hard material Forming a multilayer amorphous metal plating film and arranging the first and second carbide materials in such a manner that the multilayer amorphous metal plating film is disposed between and facing the first and second carbide materials, Is placed between the first and second cemented carbide materials, and the first and second cemented materials are pressurized and bonded to each other while heating to a melting temperature range so that the exothermic characteristics of the multilayered amorphous metal plating film can be exhibited And a bonding step.

In the present invention, the metal salt in the plating solution is ionized, and in order to deposit on the cathode using electric current, a voltage higher than the reduction potential of each element must be applied. In the case of a plating solution in which two or more metal salts are present, there is a difference in standard reduction potential between the two elements, and a voltage range in which the type of metal to be precipitated varies. When these voltage sections are alternately applied, metal layers of different kinds are alternately deposited. The voltage section may be represented by a first section in which both the first metal and the second metal are plated and a second section in which only the second metal is plated.

As described above, in the present invention, the alternately deposited plating layers have a laminated structure in which thin films having a wide surface are piled up in a regular order. At this time, if the thickness of the individual metal layer in the multi-layered plating layer is reduced to the nanometer scale, the characteristics are significantly different from those of the bulk metal. Specifically, each of the plated layers laminated at a nanometer level has an amorphous characteristic and becomes unstable due to an increase in the surface area between the respective metal layers, and each of the plated layers laminated easily shows an exothermic reaction when it is heated at a low temperature. This allows the alloy to be easily melted to form an alloy even at a temperature lower than the melting point in the bulk material state. Therefore, it is generally possible to perform the bonding process performed at a high temperature at a low temperature.

Here, an apparatus for implementing the method of forming a metal plating film having amorphous and exothermic characteristics using the plating method of the present invention may include a container, a reference electrode, a cathode, a cathode, a magnet for stirring, and a PC as a control unit.

The container may be formed in the form of a plating bath in which an opened upper end is closed with a cap and an agitating magnet is installed on an inner bottom.

As the reference electrode, a saturated calomel electrode may be used. A platinum (Pt) electrode of 10 mm x 10 mm may be used as the anode electrode, and a copper (Cu) electrode of 10 mm x 10 mm may be used as the cathode electrode. Different types of conductive metals can be used for the anode and cathode depending on the plating conditions and the size can be adjusted. The power supply can use both a constant current and a constant voltage.

Wherein the magnet for stirring is disposed on the bottom surface of the container and stirs the plating liquid stored in the container, and when the driving motor having the driving magnet on the driving shaft is driven at the lower end of the container, And the stirring magnet disposed on the surface can be operated using the principle of interlocking.

As the control unit, the PC is provided with software such as a power supply capable of adjusting voltage and current waveforms and a waveform adjustment program, and it is possible to control voltage and current waveforms through input and operation. The PC is provided with a positive electrode of a power source to be electrically connected to the positive electrode through a wire, a reference electrode of a power source to be electrically connected to the reference electrode through a wire, and a power source A cathode may be installed.

The step of preparing the electrode and the aqueous alloy plating solution is a step of preparing and preparing an electrode and an aqueous alloy plating solution, respectively. At this time, the electrode may include a reference electrode, an anode, and a cathode. The plating solution includes a first metal salt and a second metal salt, and may include an acid and an additive.

The first and second metal salts may be at least one selected from the group consisting of Sn, Cu, Zn, Ni, Al, Ti, V, Cr, Mn, Fe, Co, Gallium, Ge, As, Zr, Nb, Mo, (Rh), Pd, Ag, Cd, In, Sb, Tell, Hf, Ta, W, Metals such as rhenium (Re), osmium (Os), iridium (Ir), platinum (Pt), gold (Au), thallium (Tl), lead (Pb) and bismuth (Bi) Two or more metal salts of the elements that differ in the range of the reduction potential of 0.029 V to 1.0496 V may be selected and used. The concentration ratio of the first and second metal salts in the plating solution is preferably selected in the range of 2: 1 to 100: 1. In this embodiment, Cu, Sn, Bi, Ag, Ni, and Zn, which have the highest utilization, are selected and multilayer plating is performed.

In the case of acid, it is ionized and electricity such as hydrochloric acid, sulfuric acid, methanesulfonic acid (MSA), nitric acid, boric acid, acetic acid, organic sulfuric acid, citric acid, formic acid, ascorbic acid, hydrofluoric acid, phosphoric acid, amino acid, hypochlorous acid Sulfuric acid, which is easy to obtain at low cost, is used in the examples.

In the case of additives, the surface of the plated film is made uniform, and a leveling agent (smoothing agent), an accelerator and an inhibitor may be added. In addition, various additives such as a defoaming agent, a polishing agent, a particle refining agent and the like may be used in some cases. In the examples, polyoxyethylene lauryl ether (POELE) was used as an additive in the flattening agent, but it is possible to form a multilayer film without using it.

In the step of forming the electrolytic plating circuit, a reference electrode, an anode and a cathode are immersed in an aqueous alloy plating solution, and the power is connected to the electrolytic plating circuit. That is, the electron movement sequence of the circuit in the electrolytic plating circuit forming step is performed in a process of moving through the anode, the power source, and the cathode.

The reduction potential or current application step is a step of inputting and applying a reduced potential (voltage) or current through software of a PC as a control unit.

In this case, the pulse voltage and the current may be represented by a first period in which both the first metal and the second metal are plated, and a second period in which only the second metal is plated.

The input of the thickness condition of the plated thin film is performed by inputting the voltage corresponding to the plating thickness having the desired heat generating characteristic for each metal plating layer or the corresponding current, time and number of cycles through the software of the PC.

That is, the input of the thickness condition of the plated thin film may be performed by adjusting the voltage between +2 V and -4.5 V or the corresponding current and time based on the standard hydrogen electrode at 25 ° C according to the thickness condition, The plating thickness can be adjusted. Preferably, in the present invention, the thickness of the plating layer having the exothermic characteristics of the first and second regions can be controlled by adjusting the voltage or the corresponding current and time between + 1.83V and -1.67V with respect to the standard hydrogen electrode.

More preferably, the plating can be performed by adjusting the voltage between + 1.83V and -1.67V or the corresponding current and time based on the standard hydrogen electrode. When the reduction potential is lower than -1.67 V (for example, Li, Na, Ca, etc.), it is difficult to produce by the plating method of the present invention, and it is difficult to manufacture. When the potential is + 1.83 V or more, .

The multi-layer plating of the metal plating film is a step of obtaining a metal plating film having amorphous and exothermic characteristics through sequential plating of respective plating layers such as a first plating layer and a second plating layer. The metal salt in the plating solution is ionized, and in order to be reduced and deposited on the cathode, a voltage higher than the reduction potential of each element should be applied. By using this principle, a layer in which one metal precipitates and a layer in which two or all of the metals are precipitated alternately appear. The number of alternating plating layers is unstable because the surface area between the plating layers is wider as the number of layers is increased. However, the current density at plating should not exceed the limit current density.

On the other hand, the metal plating film having amorphous and exothermic characteristics is formed such that the sum of the thicknesses of the first and second plating layers is in the range of 0.1 nm to 5 μm so that the first metal layer and the second metal layer may exhibit heat- .

In addition, it is preferable that the amorphous and heat-generating metal plating films have a structure in which at least six amorphous metal plating films such as the first and second plating layers are stacked. When each of these amorphous metal plating films is less than 6 layers, the endothermic reaction occurs more than the exothermic reaction at the time of bonding, and the crystalline phase of the amorphous bonding material is not changed to the crystalline state, so that the bonding strength of the bonding portion is lowered and the bonding reliability is lowered It is not preferable.

On the other hand, the metal plating film having the amorphous and exothermic characteristics can easily form a laminate up to a nanometer thickness so as to have a heat generating characteristic, and the number of laminations can be increased to several tens of thousands or more.

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, a bonding method of a cemented carbide according to the present invention will be described in detail with reference to the drawings.

FIG. 3 is a schematic view showing a state in which a tool steel and a cemented carbide are bonded together according to an embodiment of the present invention. FIG. 4 is a schematic view showing a bonding process of a tool steel and a cemented carbide according to an embodiment of the present invention, FIG. 5 is a graph showing a melting point according to a particle size of a multi-layer thin film joint in a process of bonding a tool steel and a cemented carbide according to an embodiment of the present invention.

FIG. 6 is a graph showing a differential thermal analyzer (DTA) result of a Cu-Ni multi-layer thin-film joint in a process of bonding a tool steel and a cemented carbide according to an embodiment of the present invention. FIG. 8 is a graph showing the results of differential scanning calorimetry (DSC) of a Sn-Cu multilayer thin-film joint in the process of bonding a tool steel and a cemented carbide according to an embodiment of the present invention. FIG. 0.0 > (DTA) < / RTI > of Ag multilayer thin film junctions.

Referring to these drawings, the tool steel and cemented carbide bonding method of the present invention includes the steps of forming a metal coating layer 121 on one side of a first cemented carbide material 110 and a second cemented carbide material 120, A step of forming a metal plating film 130 on the surface of the first and second cemented carbide materials 110 and 120 by disposing a metal plating film 130 between the first and second cemented carbide materials 110 and 120, And pressing and bonding the first and second cemented carbide materials 110 and 120 while heating the film 130 to the melting temperature range.

The core metal 140 may use an alloy having a low melting point to increase the amount of the molten metal, and a metal plating film 130 is formed on the surface of the core metal 140.

The noble metal (140) alloy is preferably a tractive solid solution alloy that does not form an intermetallic compound, and the alloy melting point is preferably 700 ° C or less for low temperature bonding. Further, it is preferable to have flexible properties that are easy to process in the form of a foil.

Cu, Sn, and the like, which are not easily oxidized, are formed on the bonding surfaces of the first and second cemented carbide materials 110 and 120 by the metal plating film 130, Ag, and Au may be formed on the surface of the metal coating layer 121.

The metal plating film 130 serves as a bonding medium between the materials, and may be formed in the form of a multilayer plating film using a metal element.

Specifically, the metal plating film 130 may be formed in the form of a multilayer plating film having a nanometer thickness level by using a reduction potential difference of a metal salt on a bonding surface of a material, or a foil made by peeling the plating film, As shown in FIG. The metal plating film 130 is a multi-layered thin film structure made of different elements, which is unstable due to its large surface area between the films and high surface energy. Therefore, diffusion is easy even if it is heated a little, and heat is generated in this process.

That is, the metal element has a property of being amorphous when it is in the form of a thin film plating layer, and since the amorphous is unstable, even when heated slightly from the outside, it is crystallized and exothermic. .

Such a metal plating film 130 has a phenomenon in which the melting point of the multilayer thin film structure is lowered compared with a normal bulk, similarly to the powder state of the material. That is, as the particle size of the powder of the material becomes smaller, the melting point is gradually lowered. For example, the powder of the metal particles has a melting point (T M (d)) lower than the melting point (T MB ) of the lump metal according to the particle diameter (d), such as Gibbs Thomson equation below. Therefore, the lower the diameter d of the particles, the lower the melting point thereof.

[Gibbs Thomson Equation]

Figure 112015074586268-pat00001

As can be seen from Fig. 5, it can be observed that the melting point of the metal plating film becomes smaller and the melting point of the metal plating film gradually decreases. When the particle size becomes 3 nm or less, the melting point thereof is remarkably decreased.

Therefore, it is possible to perform the bonding process between the materials which are generally performed at a high temperature at a relatively low temperature, and the characteristic of the multilayer thin film structure in which the melting point is raised again after the melting and the coagulation, Can be obtained.

The metal plating film 130 may be disposed between the first and second cemented carbide materials 110 and 120 in various forms. For example, the surface of the cemented carbide material or the core metal may be plated with a plated multi- A multilayer thin film foil sheet, a multilayer thin foil sheet, a multilayer thin foil sheet, a multilayer thin foil sheet, a multilayer thin foil sheet, and a multilayer thin film foil sheet, , And the like.

In the paste form prepared by mixing the pulverized particles of the multilayer foil sheet with a liquid, the liquid may contain, for example, alcohols, phenols, ethers, acetone, aliphatic hydrocarbons having 5 to 18 carbon atoms, kerosene, diesel, toluene, Aromatic hydrocarbons such as xylene, silicone oil, and the like. Of these, alcohols, ethers, or acetone having a certain degree of solubility in water can be preferably used.

The formation of the multilayered plated film on the surface of the first or second cemented carbide material may be performed, for example, by an electrolytic plating method. In this case, a plating solution, a metal salt, an additive, an electrode, a conductive substrate, A waveform-adjustable power supply, and a waveform control program.

The advantages of forming a metal plating film by the plating method are as follows.

First, there is no danger of explosion compared with the case of forming a multilayered thin film using a powdery bonding medium such as a nano powder, and since it is plated in a plating solution,

Secondly, since it can be applied regardless of a curved surface or a vertical surface, it is possible to compensate for the disadvantages of a solder paste type bonding medium which is difficult to use because it is applied to a curved surface or a vertical surface of a bonding material such as an electrode.

Third, when the plated multi-layered thin film is peeled off and used in foil form, it can be handled independently of the material to be bonded, and can be used as a low-temperature bonding material.

Fourth, since precious metals as well as common metals (eg, various metals such as copper, tin, zinc, and nickel) can be plated and formed into a multilayered thin film, the cost of the bonding medium is much lower than that of the powdery bonding medium.

Fifth, the powdered bonding medium has a risk of explosion or fire due to rapid oxidation and heat generation, while the multi-layered thin film is easy to handle and safe.

Sixth, compared with physical vapor deposition (PVD) such as sputtering in vacuum, the method of forming a multilayered plated film is simple and mass-producible.

Seventh, the thickness of the multi-layered plated thin film can be arbitrarily adjusted by adjusting plating conditions such as voltage and plating time.

Eighth, the junction temperature can be lowered significantly compared to the conventional junction method, which can save a great deal of energy cost. Specifically, the Sn-3.5 wt% Ag bonding medium used in the electronics industry has a melting point of about 221 캜, and usually the bonding material should be bonded at a temperature of about 250 캜. On the other hand, when a multilayered thin film having a structure in which thin film layers including metal elements such as Sn and Ag are alternately laminated is used, the plated bonded material has an advantage that it can be bonded at a temperature of about 160 캜 or less. In addition, if the thickness of the thin layer is made thinner, bonding can be performed even at a lower temperature, and if the thickness of the thin layer is further reduced to the nano level, bonding of the materials can be performed at almost room temperature.

The structure of the multilayer thin film of the metal plating film 130 is not particularly limited and preferably a multilayer thin film having a structure in which at least six thin film layers are laminated or at least two thin film layers made of different elements are alternately stacked Layered thin film having a structure in which a layer is formed.

The metal plating film 130 having a structure in which six or more thin film layers are laminated exhibits high electrical conductivity and bonding strength due to diffusion of the multilayered plating layer at the time of bonding the first and second cemented materials 110 and 120 . The multilayer thin film having a structure in which at least two thin film layers made of different elements are alternately stacked is formed at a temperature lower than the bonding temperature of a general metal at the time of bonding the first and second hard materials 110 and 120 Even when bonding is performed, diffusion due to the mutual concentration difference of the thin film layers occurs, and at the same time, an exothermic reaction is exhibited, and a stable and stable bonding can be achieved.

In addition, the multi-layer thin film structure has an excellent property that the bonding temperature is lower than the bonding temperature of a general metal, but the melting point is increased to the melting point of a common metal after melting and solidification at the time of bonding.

Each of the thin film layers constituting the metal plating layer 130 may be formed of at least one selected from the group consisting of Sn, Cu, Zn, Ni, Ti, V, Cr, Mn, Fe, Co, Ga, Ge, As, Al, Zr, At least one metal element selected from the group consisting of Rh, Pd, Ag, Cd, In, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb, Can be used.

The multilayer thin film made of such a metal element may be formed by alternately laminating thin films made of elements such as Sn-Cu, Sn-Ag, Cu-Zn, Cu-Ni and Al- .

When the metal plating film 130 is laminated on two films, the sum of the two film thicknesses is preferably in the range of 0.1 nm to 5 μm, Lt; RTI ID = 0.0 > um. ≪ / RTI >

When the thickness of the metal plating layer 130 is less than 0.6 nm, it can be bonded even at a temperature significantly lower than the bonding temperature of a metal electrode. However, it is difficult to form a thin film layer, have. If the thickness of the metal plating film is more than 300 mu m, the bonding temperature may increase, and the bonding strength and bonding reliability may be lowered.

The melting temperature range of the metal plating film 130 is set to a temperature range lower than a melting point of an element having a low melting point among the elements included in each of the thin film layers constituting the metal plating film or a melting point of the entire bulk composition constituting the metal plating film .

For example, the melting temperature range of the metal plating film 130 may be in the range of 0.5% to 80% of the melting point of the low melting point element or the melting point of the alloy of the elements contained in the respective thin film layers constituting the metal plating film, Lt; / RTI >

Specifically, the bonding temperature range of the metal plating film 130 is preferably a melting point of an element having a lower melting point among the elements included in each thin film layer constituting the metal plating film at a peak temperature or more at which the exothermic characteristic appears, It may be set at a temperature lower than the melting point of the alloy or at a temperature lower than the melting point of the material to be bonded.

In the bonding technique of metal materials such as the conventional tool steel, a bonding medium is disposed between the materials to be bonded and heated at a temperature higher than the melting point of the bonding medium to heat the bonding portions of the materials. For example, when brazing using a Cu-Ni alloy or a Ni alloy as a bonding medium, the bonding temperature is higher than their melting point (the melting point of copper is 1083 ° C), and the normal brazing junction temperature is about 1150-1200 / RTI > Further, in the case of a bonding medium composed of Ni-based elements, the bonding temperature reaches 1455 占 폚.

However, when a metal plating film according to the present invention is formed as a Ni-based element and used as a bonding medium, bonding can be performed at a bonding temperature of 900 ° C and a temperature of about 550 ° C. In other words, bonding can be performed at 38.1% of the junction temperature when using a conventional bonding medium. Therefore, the junction temperature consumption energy of the multilayer thin film junction according to the present invention is only about 38% of the conventional junction temperature, which is very economical. Further, when the thickness of the thin film layer constituting the multilayer thin film in the metal plating film is further reduced, bonding at a lower temperature is possible.

This can reduce the cost of consumed energy and decrease the strength of the joint due to high-temperature heating (decrease in strength due to grain growth) and growth of the intermetallic compound at the joint due to high-temperature heating.

The metal plating film 130 is characterized in that thin film layers including elements other than Sn and Cu such as Sn-Ag, Cu-Zn, Cu-Ni and Al-Ni are alternately stacked Similar results can be obtained for multilayer thin film junctions. The excellent performance as a bonding medium of the multilayer thin film bonding portion 130 is realized by the principle that when the thin film layers are heated and pressed, an exothermic reaction occurs in the diffusion process due to mutual concentration differences and the bonding is easily performed even at a low temperature.

The theory of the activation process during heating during bonding of the materials of the metal plating film 130 is summarized as follows.

First, the thin film layer of the metal plating film 130 is liable to decrease in surface energy due to an increase in surface area due to a decrease in thickness, and is very unstable. Further, it is desired that the reaction proceeds in the direction in which the interfacial interface of the thin film layer exists and the interface energy is reduced. Reduced interfacial energy means that the area of the interface is reduced, which means that junctions occur at both interfaces. For example, nano metal particles are unstable and may be bonded together at temperatures below the melting point of the bulk metal, or even at room temperature.

Since the thin film layer of the metal plating film 130 is formed by alternately stacking the different materials, the dissimilar materials forming such a stacked structure have a shorter diffusion distance as the interlayer spacing becomes shorter , Which causes the concentration gradient to become severe, which leads to active diffusion. For example, if the A and B thin film metal layers are alternately stacked, the A atom diffuses to the B layer and the B atom diffuses to the A layer. This diffusion can be seen by the diffusion 1 rule of Fick's below that the diffusion flux J is inversely proportional to the distance.

[The law of diffusion of the fix]

Figure 112015074586268-pat00002

J B : Number of B atoms passing through the unit area per unit time (Flux)

D B : diffusion coefficient of B atom

C: Concentration of B atom

x: spreading distance

dC B / dx: rate of change of B concentration in x direction

Therefore, the diffusion of the material and the metal plating film is activated by the diffusion due to the concentration difference, and the bonding is achieved through the diffusion.

Third, the thin film layer of the metal plating film 130 is unstable, and an exothermic reaction occurs during heating.

For example, the first cemented carbide material may be a metal material, and the second cemented carbide material may be a metal material other than the first carbide material, a ceramic material such as ceramics And a plastic material. Preferably, the first cemented carbide material is a tool steel, and the second cemented carbide material is a hard metal.

Here, the cemented carbide may be a WC-Co cemented carbide mainly composed of tungsten carbide (WC) and cobalt (Co). The cemented carbide and tool steel are characterized in that the interface stress is large due to a large difference in thermal expansion coefficient, However, excellent bonding strength and bonding reliability can be obtained when the present invention is bonded using a metal plating film.

FIGS. 15A to 15B show a bonding image of a tool steel and a cemented carbide using a Cu-Ag and Cu-Zn based core metal alloy according to the present invention. FIG. 17 is a scanning electron microscope (SEM) photograph showing the actual cross-section of the Ni-Cu multilayer thin film bonding portion before the bonding in the process of bonding the tool steel and the cemented carbide according to an embodiment of the present invention. .

FIG. 18 is a photograph showing a Ni-Cu multilayer thin film bonding portion formed on the surface of a tool steel sample without using a core alloy in the process of bonding the tool steel and the cemented carbide according to an embodiment of the present invention. Actual photographs of cemented carbide and tool steel bonded without using a core alloy in the process of bonding tool steel and cemented carbide according to one embodiment are disclosed.

Referring to these drawings, a configuration required for bonding a tool steel and a hard metal material includes a foil sheet of a low melting point core metal alloy for forming a multilayer thin film according to the present invention, A plating apparatus for forming a thin film junction, a heating apparatus for bonding, a vacuum heating apparatus as the case may be, a non-oxidizing atmosphere heating apparatus, a cleaning liquid for cleaning the surface of the nano-plated layer, .

The pretreatment for joining the tool steel and the hard metal material is performed by, for example, in order to remove contaminants or oxides on the surface on which the multilayer thin film joint is formed, the surface of the multilayer thin film joint is immersed in a diluted acid solution such as 5 vol% For about 1 minute, followed by rinsing with distilled water. Where the aqueous acid solution removes the metal oxide, which further facilitates bonding.

The junction can be bonded without a flux when bonding in a vacuum or non-oxidizing atmosphere. If the materials are to be bonded in the atmosphere, a low temperature flux can be used to remove the oxide layer on the surface of the multilayer thin film junction.

The tool steel can be prepared by using, for example, a hard metal such as stainless steel, carbon steel, alloy tool steel and WC. Since hard cemented carbide such as WC is difficult to bond normally with tool steel substrate such as stainless steel, it can be bonded with tool steel by coating the surface with metal by pretreatment to metallize the surface of cemented carbide.

In order to form a multi-layer thin film of the core metal alloy, the core metal alloy is rolled and processed to facilitate joining. In order to form an easy multi-layer thin-film joint of the processed core metal alloy, the core metal alloy may be polished and then the multilayer thin-film joint may be formed by electrolytic plating.

Hereinafter, with reference to these drawings, a specific embodiment of low-temperature bonding of a cemented carbide material and a tool steel using the metal plating film of the present invention will be described.

For example, the process of forming the metal plating film of the present invention and the low temperature bonding of the cemented carbide material and the tool steel will be described as follows.

[Example 1] Measurement of low melting point characteristics of a metal plating film

The metal plating film developed in the present invention has a low melting point because heat is generated due to diffusion at a low temperature between the laminated plating layers. To confirm this, the thermal properties were measured with DSC and DTA.

In this embodiment, the thermal characteristics of a multilayered thin film including Sn, Cu, Ni, and Ag, which are considered to be frequently used among various elements used as a bonding medium for bonding thermoelectric elements, were measured.

Generally, when a Ni-Cu alloy (bulk material) is used as a bonding medium, the melting point increases as Ni increases. Therefore, the lowest melting temperature is 1083 (melting point of substantially Cu) at 100% Cu- / RTI > On the other hand, the Cu-Ni multi-layered thin film used in the bonding method of the present invention showed a peak at 567 ° C, which is lower than that of a general bulk alloy, and a Ni-Cu The multilayered thin film was melted. The thermal characteristics of the Ni-Cu multilayered thin film at this time were measured by DTA and are shown in Fig. The peak in Fig. 6 corresponds to about 51.8% of the lowest melting point of the Cu-Ni-based alloy at 1083 캜.

In addition, the Sn-Cu multilayered thin film developed in the present invention diffuses at a low temperature and generates heat. When measured by DSC, a peak appears at 144 ° C, and the Sn-Cu multilayered thin film is melted. The thermal properties at this time are measured by DSC and are shown in Fig. The peak in Fig. 7 corresponds to about 63.4% of the lowest melting point (eutectic temperature) of 227 캜 of the Sn-Cu based alloy.

In another embodiment, the Cu-Ag multilayer nanotubes were prepared by the method of the present invention, and the thermal characteristics at this time were measured by DTA and are shown in FIG. At this time, a peak appears at 678.54 ° C, which corresponds to about 87.1% of the lowest melting point (eutectic temperature, Cu-40% Ag) of Cu-Ag bulk alloy at 779 ° C.

[Example 2] Manufacturing range of metal plating film

In this embodiment, the plating was performed by dissolving the first metal salt and the second metal salt in a molar ratio of 1: 1 to 200: 1 in the alloy plating solution. 9 and 10A to 10H, when the ratio of the first metal salt to the second metal salt is less than 2: 1, for example, when the ratio of 6: 4 and 5: 5 is satisfied, The difference in the concentration of the second metal is reduced, so that the multilayered thin film is not formed. If the ratio of the first metal salt to the second metal salt exceeds 100: 1, for example, when the ratio of the first metal salt to the second metal salt is in the range of 200: 1, the second metal salt is easily consumed during plating and the concentration of the second metal salt becomes thin, Instead, the hydrogen ions in the plating liquid are reduced to generate hydrogen bubbles. This makes it difficult to form a multilayered thin film.

Further, in order to determine the first and second metal salts forming the multilayered plated thin film, a metal salt of an element having a standard reduction potential of 0.004 V or more and 1.5614 V or less was selected to perform multilayer plating (Fig. 9, Figs. 10 10h). When the reduction potential difference of the first and second metal salts is reduced to less than 0.029 V, the first and second metal salts are reduced when the first and second plating layers are formed, and the boundary between the plating layers disappears and the multilayered thin film is not formed. In addition, when the reduction potential difference of the first and second metal salts exceeds 1.0496 V, the second metal interferes with the plating of the first metal, so that the boundary between the plating layers also disappears and the multilayered thin film is not formed.

10A to 10H show cross-sectional views of the multi-layered plated thin films corresponding to the respective conditions of FIG. 9, and it is possible to confirm by photographs whether multi-layered plated thin films are formed according to the plating conditions. The numbers in Figs. 10A to 10H correspond to the numbers in Fig. For example, a photograph of the condition 2-3 'in FIG. 9 shows a photograph 2-3' in FIGS. 10A to 10H.

FIG. 11 is a graph showing a range of conditions under which the multilayer plating is formed as a result of FIG.

As a result, in order to produce a multilayered thin film in the manufacturing method according to the present invention, a metal salt having a reduction potential difference of 0.029 V or more and 1.0496 V or less in the first metal salt and the second metal salt in the plating solution is used, 2 metal salt is preferably in the range of 2: 1 to 100: 1.

[Example 3] Production of core metal alloy

In this embodiment, a core metal alloy containing Cu, Zn, Ag, Si, or the like, which is considered to be used frequently among various elements used as a bonding medium, is manufactured and rolled for low temperature bonding of tool steel and cemented carbide, The core metal surface was alloy plated.

Generally, when an Al-based core metal alloy and a Cu-Ni multi-layered plating alloy are jointed, an Al-Ni intermetallic compound is produced, and the joint portion exhibits brittle characteristics. In this case, since the bonding reliability is deteriorated, it is preferable that the alloying element is a turbulent solid solution alloy in which the two elements do not form an intermetallic compound. Figure 12 shows various alloy candidate groups used for the production of core metal alloys.

For the low-temperature bonding of the tool steel, the melting point of the core metal alloy is preferably 700 캜 or less, and the workability for the core metal surface nanocomposite plating should be excellent.

13 shows a Cu-Ag and Cu-Zn core metal alloy prepared by using an induction furnace and having a vacuum furnace and an induction heating furnace.

For alloy plating on the surface of the core metal, it is desirable to produce the core metal in the form of a thin foil, and the thickness of the alloy foil after rolling is preferably about 0.1 mm to 0.2 mm. FIG. 14 shows a Cu-Ag core metal alloy after rolling.

[Example 4] Cemented carbide tool steel joint test

In this embodiment, for the low-temperature bonding of tool steel and cemented carbide, a core metal containing Cu, Zn, and Ag among various elements used as a bonding medium was manufactured. Using a multilayered thin film, the tool steel and the cemented carbide were bonded using a vacuum furnace at a temperature about 15-50 ° C higher than the core metal melting temperature. 15A shows a tool steel joint using a Cu-Ag based core metal, and FIG. 15B shows a tool steel bonded using a Cu-Zn based core metal alloy. In the case of bonding using Cu-Ag and Cu-Zn alloy, it can be confirmed that the bonding core metal melts and diffuses and good bonding is achieved. The joining process at this time is shown in FIG. 16 as a process of joining the tool steel and the cemented carbide using the core metal. 17 is a scanning electron microscope (SEM) photograph showing the actual cross-sectional area of the Ni-Cu multilayer thin film formed on the core metal of the present invention. It can be confirmed that the nano-scale metal multilayer thin film is uniformly plated.

The core metal used in this joining helps to produce a uniform multi-layered thin film and helps to obtain a good joint surface. However, multilayer thin films can be formed without core metal, and low temperature bonding is possible. FIG. 18 is a photograph showing a Ni-Cu multilayer thin-film joint formed on the surface of a tool steel sample without using a core alloy in the process of bonding the tool steel and the cemented carbide according to the embodiment of the present invention. , Actual photographs of the cemented carbide and tool steel bonded together without using the core alloy are shown in the process of bonding the tool steel and the cemented carbide according to the present invention.

FIG. 20 is a graph showing the relationship between the first and second plated metal layers (left) and the first and second plated metal layers (left) and the second plated metal layers A photograph is disclosed.

21 shows photographs of the Ni-Cu metal plating films prepared in the present invention, in which the first and second plating layers (left) were plated before heating and the first and second plating layers were dissipated FIG. 22 is a graph showing the amorphous characteristics (left) of a Sn-Cu metal plating film produced by the present invention as a result of XRD analysis of a metal plating film in a plated state before heating, 1 and the second plating layer are extinguished is analyzed by XRD. As a result, a graph showing a crystalline characteristic (right) appears.

FIG. 23 shows an electron microscope (SEM) photograph showing a metal plating film in which the sum of the thicknesses of the two plating layers is 5 μm and the cross section is shown. FIG. 24 shows a metal plating film in which the sum of the thicknesses of the two plating layers is 5 μm (DSC), and FIG. 25 shows a heating graph in which a metal plating film is formed in such a manner that the sum of the thicknesses of the two plating layers is 5 μm thick, An optical microscope photograph showing an actual cross section is disclosed.

Fig. 26 shows an optical microscope photograph showing a copper electrode cross section made by laminating six layers of a metal plating film at a low temperature. Fig. 27 shows a photomicrograph of the end portion of a copper electrode obtained by laminating a metal plating film in six layers, An Sn-Cu-based metal-plated thin film formed on the surface of the Sn-Cu-based metal-plated thin film.

[Example 4]

When the metal plating film of the present invention is used as a bonding medium for low-temperature bonding, the first and second plating layers of the metal plating films having heat and amorphous characteristics when they are heated, And is easily melted to crystallize as a joint. A Sn-Cu-based multi-layered nano-thin film layer having a heat generation characteristic was formed and heated at 160 ° C to confirm that the multi-layered nano-film layer was extinguished. FIG. 20 shows the first and second plating layers before the heating of the metal plating film having the Sn-Cu heating and amorphous characteristics at this time, and the first and second plating layers disappearing after the heating and diffusion.

In addition, a metal plating film having Ni-Cu exothermic and amorphous characteristics was formed and heated at 650 ° C to confirm that the multi-layered nano thin film layer disappeared. FIG. 21 shows a state in which the first and second plating layers of the Ni-Cu based multi-layered nano thin film layer at this time and the first and second plating layers disappear due to diffusion after heating.

In addition, the phase was analyzed by XRD in order to confirm the amorphous phase characteristics of the metal plating film having heat and amorphous characteristics. The X-ray diffraction (XRD) analysis of the metal plating film having the exothermic and amorphous characteristics as the plated state before the heating of the metal plating film having the Sn-Cu thermal and amorphous characteristics produced by the metal plating film according to the present invention showed amorphous characteristics ) And a state in which the first and second plating layers disappear due to diffusion after heating are analyzed by XRD to show a crystalline characteristic (right) as shown in Fig.

[Comparative Example 1] A metal plating film having no exothermic reaction

When the thickness of each layer of the multilayered metal plating film becomes thicker or the number of the plating layers decreases, the area of the interface in the multilayered metal plating film becomes smaller. If the thickness of the entire plating layer is increased to 300 占 퐉 or more, the proportion of defects in the plating layer becomes high and the exothermic reaction does not occur. In this comparative example, a Sn-Cu-based bonding material having a thickness of 5 μm and a thickness of two layers was prepared so as not to generate an exothermic reaction. The cross-section of the Sn-Cu multi-layer material manufactured to a total thickness of 5 占 퐉 of the two layers at this time was confirmed by an electron microscope and is shown in Fig. The thermal characteristics of the multi-layer material were measured by DTA and are shown in Fig. As a result, the DSC measurement did not show a low-temperature exothermic peak, and an endothermic peak appeared at 228 ° C at which the tin, which is an element constituting the plating, melts at a high temperature. That is, an exothermic peak at 144 ° C, which was exhibited in a Sn-Cu-based bonding material prepared by thinning the thickness of the two layers to 40 nm, was not found in the thick-made 5 μm thick material.

In order to avoid the exothermic reaction at this time, the semiconductor was heated to a copper electrode at a temperature of 170 ° C using a material in which each plating layer was made thick. The junction between the semiconductor and the electrode at this time was observed by an optical microscope and was not bonded. The results are shown in Fig. The bonding material in which each of the plated layers is made thick can be judged not to be bonded because only the endothermic peak is shown by the thermal analysis and the endothermic quantity is larger than the calorific value.

In addition, a Sn-Cu multilayered metal plating thin film having 6 layers of plating layers was prepared, and the copper electrode was bonded at 160 占 폚 at low temperature. FIG. 26 shows a cross section at this time. The joints at this time were partially bonded. This is because the amount of the plated layer was insufficient and the amount of molten metal was not sufficient.

In addition, the plating time was elongated, and a Sn-Cu-based multilayered metal plating thin film having a total plating thickness of 300 탆 was produced. The multilayered metal thin film produced by the present invention may cause defects on the surface of the plating layer as the plating progresses. When the defects grow continuously to the vertical plane and the plating layer is formed to a thickness of 300 탆 or more, the proportion of defects in the multilayered plating layer increases, The plating layer is not well formed, the amorphous and exothermic characteristics are not exhibited, and the low temperature bonding is not achieved.

While the invention has been shown and described with reference to certain preferred embodiments thereof, it will be understood by those of ordinary skill in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims. This is possible.

Therefore, the scope of the present invention should not be limited by the described embodiments, but should be determined by the equivalents of the appended claims, as well as the appended claims.

110: First carbide material
120: Second carbide material
130: metal plating layer

Claims (16)

Preparing an aqueous alloy plating solution containing two or more metal salts including a first metal salt and a second metal salt;
Immersing the electrode in the aqueous alloy plating solution to form an electrolytic plating circuit;
A voltage between +2 V and -4.5 V or a corresponding current value based on a 25 DEG C standard hydrogen electrode is input to a control unit for controlling the electrolytic plating circuit according to the reduction potential value of the metal salt to be plated, Applying a potential or current;
The one side of the first cemented carbide material or the second cemented carbide material or one side of both the first cemented carbide material and the second cemented carbide material or between the first cemented carbide material and the second cemented carbide material And a second metal material different from the first metal material, the amorphous material having a thickness of 0.1 nm to 300 mu m and being made of amorphous material, the first metal material having a thickness of 0.1 to 300 mu m, Forming at least two or more multilayer amorphous metal plating films including a plating layer and a second plating layer showing an interlayer boundary; And
Wherein the multilayered amorphous metal plating film is disposed between the first and second cemented carbide materials so that the first and second cemented carbide materials are opposed to each other, The first and second plating layers are heated and melted at a temperature lower than the eutectic temperature of the alloy of the first metal material and the second metal material, A joining step of joining the first and second cemented carbide materials to the multilayered amorphous metal plating film as a bonding material;
And a second step of bonding the cemented carbide material.
The method according to claim 1,
Wherein the range of the reduction potential of the metal salt is a voltage between +1.83 V and -1.67 V or a current value corresponding thereto at a standard hydrogen electrode of 25 캜.
The method according to claim 1,
Wherein said aqueous alloy plating solution comprises a first metal salt, a second metal salt, an acid and an additive in a plating solution based on water.
The method of claim 3,
The first and second metal salts include Sn, Cu, Zn, Ni, Al, Ti, V, Cr, Mn, Fe, Co, Ga, Ge, As, Zr, Nb, Mo, Ru, Rh, Pd, And at least one metal salt selected from the group consisting of In, Sb, Te, Hf, Ta, W, Re, Os, Ir, Pt, Au, Tl, Pb and Bi metal salts.
5. The method of claim 4,
Wherein the first and second metal salts are selected from two or more metal salts of elements showing a difference in standard reduction potential.
The method of claim 3,
The acid is selected from the group consisting of sulfuric acid, hydrochloric acid, methanesulfonic acid (MSA), nitric acid, boric acid, acetic acid, organic sulfuric acid, citric acid, formic acid, ascorbic acid, hydrofluoric acid, phosphoric acid, lactic acid, amino acid and hypochlorous acid. Bonding method.
The method of claim 3,
Wherein the additive is selected from the group consisting of polyoxyethylene lauryl ether (POELE), a plating flatting agent (smoothing agent), an accelerator, an inhibitor, a defoamer, a polishing agent and an oxidation inhibitor.
The method according to claim 1,
Wherein the step of applying a reducing potential or current to the electrode includes a step of forming a first voltage section in which the first metal and the second metal are simultaneously plated and a second voltage section in which only the second metal is plated, Bonding method.
The method according to claim 1,
The metallic plating film may be formed by mixing a powder with a liquid in the form of a multi-layered plated film, a multi-layered foil sheet, a multi-layered foil sheet, And a metal particle type in which a multi-layered plated thin film is formed on the surface.
The method according to claim 1,
Wherein the metal plating film is a multilayer thin film having a structure in which at least two thin film layers containing different metal elements are alternately stacked.
The method according to claim 1,
Wherein the metal plating film is a multilayer thin film having a structure in which at least six thin film layers are laminated.
The method according to claim 1,
Wherein the metal plating film is formed with a thickness in the range of 0.1 nm to 5 占 퐉 in the sum of the two film thicknesses when the metal plating film is laminated on two films.
The method according to claim 1,
Wherein the metal plating film is formed to a thickness ranging from 0.6 nm to 300 占 퐉.
The method according to claim 1,
Wherein the melting temperature range of the metal plating film is a temperature range lower than a melting point of an element having a lower melting point among the elements contained in each of the thin film layers constituting the metal plating film or a melting point of the entire bulk composition constituting the metal plating film .
The method according to claim 1,
Wherein the first cemented carbide material is a metal material and the second cemented carbide material is a material selected from the group consisting of a metal material, a ceramic material, and a plastic material different from the first carbide material.
The method according to claim 1,
Wherein the first cemented carbide material is a tool steel and the second cemented carbide material is a hard metal.
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