CN104040035B - Plated Article And Manufacturing Method Therefor - Google Patents
Plated Article And Manufacturing Method Therefor Download PDFInfo
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- CN104040035B CN104040035B CN201280063675.XA CN201280063675A CN104040035B CN 104040035 B CN104040035 B CN 104040035B CN 201280063675 A CN201280063675 A CN 201280063675A CN 104040035 B CN104040035 B CN 104040035B
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- Prior art keywords
- coating
- plating
- multicoating
- porous
- thickness
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/10—Electroplating with more than one layer of the same or of different metals
- C25D5/12—Electroplating with more than one layer of the same or of different metals at least one layer being of nickel or chromium
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/623—Porosity of the layers
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- 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
- C25D3/12—Electroplating: Baths therefor from solutions of nickel or cobalt
-
- 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
- C25D3/38—Electroplating: Baths therefor from solutions of copper
-
- 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
- C25D3/46—Electroplating: Baths therefor from solutions of silver
-
- 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
- C25D3/48—Electroplating: Baths therefor from solutions of gold
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/34—Pretreatment of metallic surfaces to be electroplated
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/60—Electroplating characterised by the structure or texture of the layers
- C25D5/605—Surface topography of the layers, e.g. rough, dendritic or nodular layers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/04—Co-operating contacts of different material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
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- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K3/00—Apparatus or processes for manufacturing printed circuits
- H05K3/22—Secondary treatment of printed circuits
- H05K3/24—Reinforcing the conductive pattern
- H05K3/244—Finish plating of conductors, especially of copper conductors, e.g. for pads or lands
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01R—ELECTRICALLY-CONDUCTIVE CONNECTIONS; STRUCTURAL ASSOCIATIONS OF A PLURALITY OF MUTUALLY-INSULATED ELECTRICAL CONNECTING ELEMENTS; COUPLING DEVICES; CURRENT COLLECTORS
- H01R13/00—Details of coupling devices of the kinds covered by groups H01R12/70 or H01R24/00 - H01R33/00
- H01R13/02—Contact members
- H01R13/03—Contact members characterised by the material, e.g. plating, or coating materials
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05K—PRINTED CIRCUITS; CASINGS OR CONSTRUCTIONAL DETAILS OF ELECTRIC APPARATUS; MANUFACTURE OF ASSEMBLAGES OF ELECTRICAL COMPONENTS
- H05K2201/00—Indexing scheme relating to printed circuits covered by H05K1/00
- H05K2201/03—Conductive materials
- H05K2201/0332—Structure of the conductor
- H05K2201/0335—Layered conductors or foils
- H05K2201/0338—Layered conductor, e.g. layered metal substrate, layered finish layer, layered thin film adhesion layer
Abstract
A plated article comprising a multi-layer plating film formed on top of a conductive-metal substrate. Said plated article is characterized by having the following on top of the aforementioned substrate, in this order: a porous plating layer consisting primarily of nickel or copper; and a surface plating layer consisting primarily of gold or silver. This plated article is further characterized in that a large number of holes are formed in the surface of the multi-layer plating film. The plated article preferably also has an oxide layer comprising a nickel oxide or a copper oxide between the porous plating layer and the surface plating layer. It is also preferable that the surface plating layer is thinner where the aforementioned holes are than where bumps are. This makes it possible to provide a low-cost, highly corrosion-resistant plated article.
Description
Technical field
The present invention relates to be formed with the plating product of multicoating on the base material being made up of conductive metal.In addition, of the invention
It is related to the manufacture method and purposes of such plating product.
Background technology
At present, the plating product that applying plating is obtained on the base material being made up of conductive metal are used in various fields.Pass through
Apply plating on base material, electricity, machinery, the chemical characteristics such as contact resistance attenuating, abrasion performance improve, corrosion resistance improves can be made
Improve.Wherein, lower from contact resistance from the viewpoint of improving with corrosion resistance, the coating of the noble metal such as Au, Ag is electric zero
It is widely adopted in contact of part etc..For example, in the contact portion of connector, usually in the base material being made up of conductive metal
Surface, after the bottom coating such as Ni, Cu are formed, thinly forms thereon the overlay coating of the noble metals such as Au (with reference to patent
Document 1).
However, it is known that there is electrolytic corrosion by potential difference when contacting with the metal low-priceder than its in the noble metal such as Au, Ag.Cause
This, from from the viewpoint of corrosion resistance, it is necessary to avoid the pinprick in the overlay coating of noble metal from producing.For this purpose, attempting or thickening
The thickness of overlay coating or the method for forming overlay coating homogeneous, but the manufacturing cost of any method is all inevitably
Rise.Therefore, the consumption that the noble metal for reducing expensive is sought strongly and the electroplating method that electrical characteristics and chemical characteristic can be improved.
Prior art literature
Patent document
Patent document 1：Japanese Unexamined Patent Publication 2007-173224 publications
The content of the invention
Invent problem to be solved
The present invention makes to solve above-mentioned problem, it is therefore intended that provide with excellent corrosion resistance and it is low into
This plating product.In addition, purpose also resides in the manufacture method and purposes for providing such plating product.
Method for solving problem
Above-mentioned problem is solved by providing a kind of following plating product of feature：The shape on the base material being made up of conductive metal
Into there is multicoating, on above-mentioned base material, it is with the Porous coating with Ni or Cu as main component and with Au or Ag successively
The overlay coating of main component, on the surface of above-mentioned multicoating substantial amounts of hole is formed with.Now, the average diameter in above-mentioned hole,
In terms of area loading mean value, preferably 0.2～20 μm.The thickness of further preferably above-mentioned Porous coating be 0.1～20 μm and on
The thickness for stating overlay coating is 0.001～3 μm.Have by oxygen further preferably between above-mentioned Porous coating and above-mentioned overlay coating
Change the oxide skin(coating) that Ni or oxidation Cu are constituted.Overlay coating thickness of thin of the overlay coating thickness in further preferably above-mentioned hole than convex portion.
It is also preferable between base material and Porous coating, be also formed with the Porous coating identical metal
For the bottom coating of main component.Now, the thickness of above-mentioned bottom coating is preferably 0.1～20 μm.
Above-mentioned problem is also provided by the manufacture method of above-mentioned plating product to solve, and the feature of the manufacture method of the plating product exists
In, possess the first plating operation that Porous coating is formed in the plating bath containing Ni ions or Cu ions and containing Au ions or
The second plating operation of overlay coating is formed in the plating bath of Ag ions.
Now, preferably between the above-mentioned first plating operation and above-mentioned second plating operation, it is also equipped with to Porous coating surface
Carry out the operation of oxidation processes.Further preferably above-mentioned first plating operation after, Porous coating surface is carried out oxidation processes it
Afterwards, activation is carried out to the surface.Further preferably after the above-mentioned second plating operation, the surface of multicoating is carried out at oxidation
Reason.
Above-mentioned problem is also provided by the electric parts that is made up of above-mentioned plating product to solve, and the feature of the electric parts exists
In the part for being formed with above-mentioned multicoating is electric terminal.Now, preferably above-mentioned electric parts is with contact portion and terminal
The connector terminal or switch terminal in portion, forms above-mentioned multicoating in the contact portion.It is also preferable to above-mentioned electric
Part is printed substrate.
The effect of invention
By means of the invention it is possible to provide with excellent anticorrosive and low cost plating product.In addition, using the teaching of the invention it is possible to provide such
The manufacture method and purposes of plating product.
Description of the drawings
Fig. 1 is the scanning ion microscope image of the Porous Ni coating sections in embodiment 1.
Fig. 2 is the secondary electron image on the surface of the plating product of embodiment 1.
Fig. 3 is the friction wear result of the test of the plating product of embodiment 1.
Fig. 4 is the secondary electron image after the friction wear test of the plating product of embodiment 1.
Fig. 5 is the secondary electron image on the surface of the plating product of comparative example 1.
Fig. 6 is the friction wear result of the test of the plating product of comparative example 1.
Fig. 7 is the secondary electron image after the friction wear test of the plating product of comparative example 1.
Fig. 8 is the secondary electron image on the surface of the plating product of embodiment 7.
Specific embodiment
The present invention relates to be formed with the plating product of multicoating on the base material being made up of conductive metal.Here, it is important
It is that there is successively the Porous coating with Ni or Cu as main component and the plated surface with Au or Ag as main component on base material
Layer, on the surface of multicoating substantial amounts of hole is formed with.By forming such Rotating fields, using the teaching of the invention it is possible to provide with excellent corrosion resistant
The plating product of corrosion and low cost.
As long as the base material that the base material for being used in the present invention is made up of conductive metal, its material is without special
Limit.Wherein, from viewpoints such as electric conductivities, the suitably alloy using copper or with copper as main component.Here, " based on
Want composition " refer to containing more than 50 weight %.
Porous coating in the present invention is the coating with Ni or Cu as main component.Here, " being main component " is
Refer to containing more than 50 weight %.The content of Ni or Cu from contact resistance aspect, Porous coating is more preferably 60 weights
It is more than amount more than %, more preferably 80 weight %.In addition, in the present invention, " Porous " are referred to be had greatly on the surface of coating
The hole of amount, surface area is big.More specifically, refer to and have to enter for concave a large amount of recesses towards base material low-lying area.
In the present invention, the thickness of Porous coating is preferably 0.1～20 μm.The thickness of Porous coating is less than 0.1 μm
When, there is the worry that corrosion resistance, wear characteristic are reduced.The thickness of Porous coating is more preferably more than 0.2 μm, is more preferably
More than 0.5 μm.When the thickness of Porous coating is more than 20 μm, there is the worry for causing manufacturing cost to rise.The thickness of Porous coating
More preferably less than 10 μm, more preferably less than 5 μm of degree.Here, the thickness of Porous coating is referred to and forms many on base material
Thickness during the matter coating of hole from the substrate surface to the convex portion of Porous coating.
In the plating product of the present invention, the overlay coating with Au or Ag as main component is formed on above-mentioned Porous coating.
Here, " being main component " is referred to containing more than 50 weight %.From contact resistance aspect, the Au or Ag in overlay coating contains
Amount is more preferably more than 55 weight %, is more preferably more than 70 weight %.
In the present invention, the thickness of overlay coating is preferably 0.001～3 μm.The thickness of overlay coating is less than 0.001 μm
When, having can not obtain the worry of desired contact resistance in the plating product of the present invention used in electric terminal.Overlay coating
Thickness is more preferably more than 0.005 μm, is more preferably more than 0.01 μm.On the other hand, when the thickness of overlay coating is thick, manufacture
Cost uprises.The thickness of overlay coating is more preferably less than 1 μm.Multicoating in the present invention, even if the thickness of overlay coating
Than it is generally thin when, corrosion resistance is also excellent.From from the viewpoint of the usage amount for reducing noble metal, particularly overlay coating is with Au
Thickness during main component is more preferably less than 0.1 μm, is more preferably less than 0.04 μm, particularly preferably less than 0.025 μm.
Now, the thickness of overlay coating refers to the thickness that will be calculated divided by proportion and plating area with the adhesion weight of Au or Ag.Here,
Plating area does not consider the concavo-convex of surface.
In addition, in the present invention, it is preferred to the overlay coating thickness in hole than convex portion overlay coating thickness of thin.So, pass through
Thickening contributes to the most overlay coating thickness of coefficient of friction, contact resistance or corrosion resistance, reduces can not performance
Reduce the consumption of Au or Ag in ground.Especially because Au high costs, therefore, its interests is big.The overlay coating thickness in more preferably hole is
Less than 0.8 times of the overlay coating thickness of convex portion.
By forming overlay coating on Porous coating, plated surface is formed in the concavo-convex mode along Porous coating
Layer, also forms hole in overlay coating.Overlay coating is easily formed in the convex portion of Porous coating surface, Porous plating is being formed at
The bottom surface and side in the hole of layer surface is difficult to form overlay coating.As a result, producing the part and surface for not forming overlay coating
The thin part of thickness of coating.In the present invention, this point is important, it is known that due to the plated surface with Au or Ag as main component
Layer is uneven, is prevented from causing the corrosion current of electrolytic corrosion to concentrate, and corrosion resistance is improved.In the past, extensively carried out or added
Thick overlay coating carries out homogenizing the trial for improving corrosion resistance, but current it is especially surprising that by making corrosion current
Topical Dispersion, improves on the contrary corrosion resistance.Due to making noble metal dosage reduce and can effectively improve corrosion resistance,
Therefore, from from the viewpoint of save resources, cost degradation, meaning is also big.
In terms of area loading mean value, the average diameter for being formed at the hole on multicoating surface is preferably 0.2～20 μm.It is flat
When diameter is less than 0.2 μm, there is the worry that can not be made corrosion current dispersion, excellent corrosion resistance can not be obtained.Hole it is average
Diameter is more preferably more than 0.5 μm, is more preferably more than 1 μm.When the average diameter in hole is more than 20 μm, by the plating product of the present invention
When using as electric terminal, there is the worry that contact resistance value increase, electrical conductivity decline.The average diameter in hole is more preferably 10
Below μm, it is more preferably less than 5 μm.Here, the average diameter in hole is shone by the scanning electron microscope from plating product surface
Multiple holes are selected in piece (secondary electron image), measuring the diameter of this some holes carries out area loading averagely to obtain.Hole is not round
During shape, with equivalent to diameter of a circle as diameter.
The specific surface area of the multicoating of the present invention preferably do not formed more than 1.2 times of specific surface area of the plated film in hole,
More preferably more than 1.4 times.Big by specific surface area, corrosion current is disperseed, and can obtain excellent corrosion resistance.
In the present invention, it is preferred between base material and Porous coating, further be formed with identical with the Porous coating
Metal for main component bottom coating.When the hole of Porous coating is from surface insertion in the substrate, by forming bottom
Coating, is prevented from exposing for base material.In addition, by making Porous coating with bottom coating with same metal as main component,
The potential difference of Porous coating and bottom coating is eliminated, the electrolytic corrosion caused by potential difference is prevented from.
The thickness of bottom coating is preferably 0.1～20 μm.When the thickness of bottom coating is less than 0.1 μm, has and abundant can not obtain
To the worry of the effect for preventing base material from exposing.The thickness of bottom coating be more preferably more than 0.2 μm, be more preferably 0.5 μm with
On.When thickness is more than 20 μm, manufacturing cost is uprised.The thickness of bottom coating be more preferably less than 10 μm, be more preferably 5 μm with
Under.
The multicoating of the present invention, further has by oxidation Ni or oxygen preferably between Porous coating and overlay coating
Change the oxide skin(coating) that Cu is constituted.By having the oxide skin(coating) between Porous coating and overlay coating, the corrosion-resistant of product is plated
Property is more improved.That is, by having the oxide skin(coating) as insulating barrier, Porous plating between Porous coating and overlay coating
Layer and overlay coating are not directly contacted with, and can suppress the generation of corrosion current.
The suitable manufacture method of the plating product of the present invention, possesses and forms porous in the plating bath containing Ni ions or Cu ions
The first of matter coating is plated operation and the second plating operation of overlay coating is formed in the plating bath containing Au ions or Ag ions.
First, as the first plating operation, to ungrease treatment as needed, water in the plating bath containing Ni ions or Cu ions
Washed base material applies plating, forms the Porous coating with Ni or Cu as main component.As long as forming Porous coating, plating
Method is not particularly limited.Can be illustrated in containing Ni ions or Cu ions and be added with the water-soluble season with hydrophobicity base
Electric plating method etc. in the plating bath of ammonium salt.Here, as hydrophobicity base, it is suitable that carbon number is more than 6 alkyl.This
When, quaternary ammonium salt can add in known Ni electroplating baths and Cu electroplating baths.The suitable addition of quaternary ammonium salt be 0.001～
0.5mol/L.As known electroplating bath, for example, can illustrate watt bath, Wood bath, sulfamic acid Ni baths, organic acid Ni baths,
Cyaniding Cu baths, sulfuric acid Cu baths, pyrophosphoric acid Cu baths etc..When being electroplated, appropriate setting electric current density and time so that Porous
Coating is desired thickness.
Then, as the second plating operation, in the plating bath containing Au ions or Ag ions, on Porous coating table is formed
Face coating.Plating bath species containing Au ions or Ag ions is not particularly limited, can be electric using known Au electroplating baths and Ag
Plating bath.For example, as Au plating bath, cyaniding Au baths (acid bath, neutral bath, alkalescence bath), non-cyaniding bath (sulfurous acid can be illustrated
Bath), as Ag plating bath, cyaniding Ag baths can be illustrated.Overlay coating can be formed by electroless plating, it is also possible to and with electroless
Plating and plating.In addition, the condition of plating, appropriate setting electric current density and time so that overlay coating be desired thickness i.e.
Can.
In addition, in the manufacture method of the plating product of the present invention, preferably between the first plating operation and the second plating operation, to many
The surface of hole matter coating carries out oxidation processes.The method of oxidation processes is not particularly limited, as long as can be in Porous coating
The method that surface forms oxide film thereon.For example, can be set forth in the method for heated porous matter coating under oxygen-containing atmosphere, make it is many
Hole matter coating is immersed in method in hot water, various medicines etc., is not particularly limited.In heated porous matter coating, heating temperature
Spend according to the appropriate setting such as oxygen concentration of atmosphere, usually 80～350 DEG C.In addition, as long as above-mentioned oxidation processes can be more
Hole matter coating surface imports the oxidation processes of oxygen atom, comprising the process for forming hydroxy.Therefore, in Porous coating
Surface, not only can form the oxide envelope of oxidation Ni etc., and can also form the hydroxide envelope of hydroxide Ni etc..
Then, oxidation-treated Porous coating surface is implemented to above-mentioned, in the second plating operation plated surface is formed
Layer.Now, preferably after the oxidising treat-ment, formed before overlay coating, activation process is carried out to the surface of Porous coating.Thus,
The surface of oxide film thereon is moderately etched, and forming overlay coating in the second plating operation becomes easy.In addition, overlay coating is attached
Put forth effort also to improve.As the liquid that can be used in activation process, as long as Porous coating surface institute shape can be etched in
Into oxide envelope surface liquid, be not particularly limited, acidic aqueous solution, alkaline aqueous solution, reduction can be used
The agent aqueous solution, complexant aqueous solution etc..As acidic aqueous solution, can illustrate containing hydrochloric acid, nitric acid, sulfuric acid, fluoric acid, fluorination
The aqueous solution of ammonium, phosphoric acid, citric acid etc..As alkaline aqueous solution, can illustrate containing NaOH, potassium hydroxide, hydroxide
The aqueous solution of lithium, ammonia etc..As reducing agent aqueous solution, can illustrate containing ortho phosphorous acid, hydrazine, dimethylamine borane, trimethylamine boron
The aqueous solution of alkane, ascorbic acid, sodium borohydride, potassium borohydride etc..In addition, as the complexant aqueous solution, can illustrate containing lemon
The polybasic carboxylic acid of lemon acid, oxalic acid, butanedioic acid, tartaric acid, maleic acid, ascorbic acid, fumaric acid etc.；Ethylenediamine, ethylenediamine tetrem
The polyamine of sour (EDTA) etc.；The aqueous solution of the amino acid of glycine, aspartic acid etc. etc..Wherein, from etch capabilities and cost
Aspect is set out, and preferably uses acidic aqueous solution.
Due to the present invention Porous coating surface have it is concavo-convex, therefore, be difficult to be etched in hole, convex portion is easily eclipsed
Carve.Also, easily form overlay coating at the position of etching.Therefore, plated surface thickness of the overlay coating thickness in hole than convex portion
It is easy that degree is thin.Therefore, from funds effect aspect is saved, it is also have to carry out activation process to the surface of Porous coating
Profit.
It is also preferable to carry out oxidation processes to the surface of multicoating after the second plating operation.That is, preferably table is being formed
Oxidation processes are carried out after the coating of face.By so operation, overlay coating is not formed and exposes the part and surface of Porous coating
The surface of the Porous coating of the thin part of coating thickness is oxidized and processes, therefore, it is possible to effectively improve corrosion resistance.This
When oxidation treatment method can adopt between the first plating operation and the second plating operation the oxidation treatment method that carries out it is identical
Condition, it is also possible to unlike this.
In addition, the present invention plating product manufacture method in, can also further add to be formed with Porous coating phase
Same metal is the operation of the bottom coating of main component.That is, before the first plating operation for forming Porous coating, base material is applied
Plus plating, formed with the bottom coating with Porous coating identical metal as main component.Form plating bath during bottom coating
It is not particularly limited, it is possible to use the plating bath from used in the above-mentioned first plating operation removes plating bath of quaternary ammonium salt etc..In addition, with regard to
The condition of plating, appropriate setting electric current density and time so that bottom coating is desired thickness.
In addition, the multicoating of the present invention, as long as in the scope for not damaging effect of the present invention, it is also possible to comprising plated surface
Coating beyond layer, oxide skin(coating), Porous coating, bottom coating.For example, between base material and bottom coating, Porous plating
Between layer and overlay coating, other coating can be gripped with.Wherein, it is preferably sandwiched between Porous coating and overlay coating
There is the intermediate deposit of the intermediate potential of the current potential for showing Porous coating current potential and overlay coating.By so operation, can contract
Potential difference between the coating of little directly contact, therefore, it is possible to suppress the generation of corrosion current, can further improve corrosion-resistant
Property.As such intermediate deposit, the coating with Pd as main component and the coating with Sn as main component can be enumerated.This
In, " being main component " is referred to containing more than 50 weight %.As the intermediate deposit with Pd as main component, can illustrate only by
The coating of Pd compositions, the coating being made up of Pd-Ni alloys, Pd-P alloys.As the intermediate deposit with Sn as main component, can be with
Illustrate the coating being only made up of Sn, the coating being made up of Sn-Ni alloys.In addition, overlay coating is the plating with Au as main component
During layer, as intermediate deposit it is also preferred that using the coating with Ag as main component.Here, " being main component " is referred to containing 50 weights
Amount more than %.As the intermediate deposit with Ag as main component, can illustrate only be made up of Ag coating, by Ag-Sn alloy structures
Into coating.
From preventing from the viewpoint of corrosion, can be surface-treated with the enforcement on the surface of multicoating.Overlay coating with
When Au is main component, sealing pores etc. can be illustrated, when overlay coating is with Ag as main component, can illustrate prevents sulfuration
Process (preventing discoloration from processing) etc..In addition, from the viewpoint of improving from lubricity, it is also possible in the table of the multicoating of the present invention
Face application of lubricating.In addition, in order that the water-repellancy of the multicoating of the present invention is improved, it is also possible to which surface is implemented at drying
Reason.
The purposes of the plating product of the present invention is not particularly limited.Can using low contact resistance and excellent corrosion resistance,
Sliding, uses in a variety of applications where.Wherein, it is suitable that the part for being formed with above-mentioned multicoating is the electric parts of electric terminal
The embodiment of conjunction.The electric terminal of the electrical characteristic and excellent in te pins of durability for remaining required can be provided.More specifically, should
Electric parts is connector or switch terminal with contact portion and portion of terminal, and in the contact portion above-mentioned multilayer plating is formed with
Film, is suitable embodiment.Contact portion is contacted with other connectors etc., the part of circulating current, and portion of terminal is and cable
Deng the part of connection.The connector terminal of the present invention, even if plugging repeatedly, electrical characteristic is not easy to decline, so it is preferred that.Separately
Outward, it is also suitable embodiment that the electric parts being made up of the plating product of the present invention is printed substrate.
Embodiment
Hereinafter, the present invention is illustrated in greater detail using embodiment, but the present invention is not limited by these embodiments.The present embodiment
In test method carry out as follows.
(1) section observation
Using the focused ion Shu Jiagong finder " FB- of Co., Ltd.'s Hitachi High-Technologies productions
2100 ", the scanning ion microscope figure after FIB (Focused Ion Beam, the focused ion beam) processing of plating product section is obtained
Picture.
(2) surface observation
Using the electric field radioactive SEM of Co., Ltd.'s Hitachi High-Technologies productions
(FE-SEM) " S-4800 ", the surface to plating product is photographed, and obtains secondary electron image.
(3) specific surface area
The resolution in laser microscope (X-Y) direction in length and breadth is set as into 0.001 μm, the resolution in height (Z) direction sets
It is set to 0.001 μm, determines the surface area of plating product.Then, with above-mentioned surface area relative to 1664 μm2Measure at viewed in plan face
The ratio of product is specific surface area.Laser microscope is the colored 3D laser microscopes " VK-9700 " of Co., Ltd. KEYENCE productions.
(4) friction wear test
The friction wear testing machine (form SSWT) produced using Shen Gangzao machines Co., Ltd., is surveyed with following experimental condition
The skin-friction coefficient of fixed resulting plating product.Then, it is to come and go slip number of times, figure of the longitudinal axis as coefficient of friction to obtain with transverse axis
Table.Coefficient of friction per 20 circulations is obtained according to resulting chart, average friction coefficient is calculated.
Ball：Φ 9.8mm, brass (after 1 μm of Ni bottoms, Au0.4 μm of plating)
Test temperature：22℃
Testing load：500mN
Stroke：4.00mm
Frequency：2.00Hz
Round slip number of times：3600 circulations
(5-1) corrosion resistance test (gas attack test)
Tested according to described sulfur dioxide gas in JIS H8502, tested with following condition.Then,
The corrosion default occurred on plating product surface is evaluated with classification numeral.Here, it is the erosional surface shared by the test face that represents to be classified numeral
The scoring of product rate (%) ratio, is divided into 10～0.With corrode completely without situation as 10, it is however generally that, be classified digital 9 with
On be chosen as it is good.
Device：The mixed gas corrosion testing machine " GPL-91-C " of Jing Ji research institutes of Yamazaki Co. Ltd. production
Sulfur dioxide concentration：10ppm
Test temperature：40℃
Relative humidity：80%
Test period：96 hours
(5-2) corrosion resistance test (salt spraytest)
Using following described device, in plating product surface spray salt solution, plating product surface is observed after 48 hrs.Then,
The corrosion default occurred on plating product surface is evaluated with classification numeral.It is same as described above with regard to the metewand of classification numeral.
Device：The salt spray tester " CAP-90 " of Suga Test Instruments Co., Ltd. production
Experimental liquid：47% salt solution
Test temperature：35℃
Test period：48 hours
(6) contact resistance test
The electric terminal simulator " CRS-113-AU types " produced using Jing Ji research institutes of Yamazaki Co. Ltd., by four ends
Sub- method determines the contact resistance of plating product with following condition.Specifically, measure is that slowly pin pressurizes from no load condition, is applied
Plus the loading of maximum 1.0N.Then, determining makes loading slowly decline, the change of contact resistance when being finally returned to no load condition
Change.The measurement of contact resistance, when loading when determining pressurization (past) respectively is 0.5N, as maximum loading 1.0N when, reduce pressure
Resistance value when loading when (returning) is 0.5N.
Probe：R025-K-18 types (radius 0.1mm shapes)
Probe material：K18(Φ1mm)
Apply electric current：10mA
(7) chemical composition analysis of plated film
The chemical composition analysis of plating product envelope are carried out using the following device that determines.Specifically, resulting plating is carried out
The hole of product and the analysis of the chemical composition of convex portion.
Determine device：Scanning electron microscope (FE-SEM/EDX)
FE-SEM portions：" S-4800 " of Co., Ltd.'s Hitachi High-Technologies productions
EDX portions：" SX-350 " of Horiba Ltd's production
Condition determination：Accelerating potential 10kV, operating distance (W.D.) 15mm, 10000 times of multiplying power
Embodiment 1
(electrolytic degreasing process)
First, as base material, prepare the copper coin of 30mm × 40mm × 0.3mm, with the copper coin as negative electrode, be immersed in 60g/
L is dissolved with 50 DEG C of aqueous solution of the electrolytic degreasing agent " PAKUNA THE-210 " of YUKEN Industrial Co., Ltd production, with negative electrode
Current density 4A/dm2Carry out ungrease treatment 60 seconds.Washed after the base material 3 times of ungrease treatment with ion exchange water,
In room temperature immersion 60 seconds in the aqueous sulfuric acid of 2vol%, pickling is carried out net.Then, then wash 3 times.
(formation of bottom Ni coating)
The sample that electrolytic degreasing was processed is immersed in the aqueous solution of following compositions of the pH4.4 of 50 DEG C of insulations.Then,
While air stirring is carried out, while with cathode-current density 3A/dm2Carry out electrolysis plating Ni to process 190 seconds, form the bottom of 1 μm of thickness
Layer Ni coating.Hereafter, sample 3 times is cleaned with ion exchange water.
Nickel sulfamic acid [Ni (SO3NH2)2·4H2O]：396g/L
Nickel chloride [NiCl2·6H2O]：30g/L
Boric acid [H3BO3]：30g/L
(formation of Porous Ni coating)
The sample for being formed with bottom Ni coating is immersed in the aqueous solution of following compositions of the pH4.2 of 50 DEG C of insulations.So
Afterwards, while carrying out air stirring, while with cathode-current density 3A/dm2Carry out electrolysis plating Ni to process 80 seconds, on bottom Ni coating
Form the Porous Ni coating of 1 μm of thickness.Hereafter, after with the clean sample of ion exchange water 3 times, 1 is impregnated in ion exchange water
Minute, ultrasonic cleansing.
Nickel sulfamic acid [Ni (SO3NH2)2·4H2O]：396g/L
Nickel chloride [NiCl2·6H2O]：30g/L
Boric acid [H3BO3]：30g/L
DTAC：0.02mol/L
Sample after being formed to the Porous Ni coating in embodiment 1 by FIB (Focused Ion Beam) carries out adding
Work, observes section.The scanning ion microscope image of section is represented in FIG.As shown in Figure 1, it is known that Porous Ni electrodeposited coatings
Sample after formation, with entering for concave multiple recesses towards base material low-lying area from surface.
(formation of surface A u electrodeposited coating)
The sample for being formed with Porous Ni coating is immersed in the Japanese high-purity chemical strain formula meeting of the pH4.2 of 60 DEG C of insulations
In the Au plating solutions " BAR7 " (Au contents are 5g/L) of society's production.Then, while being stirred with magnetic stirring apparatus, while with cathode current
Density 3A/dm2Carry out electrolysis plating Au to process 8 seconds, the Au coating of 0.05 μm of thickness is formed on Porous Ni electrodeposited coatings.This
Afterwards, sample 3 times is cleaned with ion exchange water, is impregnated 60 seconds in 60 DEG C of ion exchange water, done after ultrasonic cleansing
It is dry, thus obtain the plating product of embodiment 1.
The secondary electron image on the plating product surface of embodiment 1 is represented in fig. 2.As shown in Fig. 2 confirming in embodiment 1
Plating product surface has hole, is formed with the coating of Porous.In addition, the secondary electron figure of the plating product of the embodiment 1 for representing in fig. 2
As in, multiple holes are selected at random, area is obtained respectively.Now, when hole is not circle, with equivalent to circular diameter as diameter.So
Afterwards, the average diameter in hole is obtained with area loading mean value, as a result average diameter is for about 3.5 μm.
The result of the friction wear test of the plating product of embodiment 1 is represented in figure 3.As shown in figure 3, without true in measure
Recognize the obvious rising of coefficient of friction.In addition, the secondary electricity after in the diagram the friction wear of the plating product of expression embodiment 1 is tested
Subgraph.As shown in Figure 4, it is known that, even if also maintaining that there is fine concave porous structure after friction wear test.Separately
Outward, for the plating product of embodiment 1, specific surface area, average friction coefficient, corrosion resistance are evaluated according to above-mentioned test method and is connect
Get an electric shock and hinder.Result is collected into expression in table 2.
Embodiment 2
Embodiment 2 is the example that the plating product surface to obtaining in embodiment 1 implements sealing pores.While by embodiment 1
Plating product 45 DEG C insulation Co., Ltd. TETRA production plating Au hole sealing processing agents " TETRA No.4 " the aqueous solution
(200mL/L) apply ultrasonic wave side in impregnate 10 seconds.Then, the aqueous solution in surface attachment is removed with air knife, is implemented
The plating product of example 2.In addition, for the plating product of embodiment 2, also evaluating average friction coefficient, corrosion resistance according to above-mentioned test method
And contact resistance.Result is collected into expression in table 2.
Embodiment 3
While be stirred with magnetic stirring apparatus, while with cathode-current density 3A/dm2Carry out electrolysis plating Au to process 5 seconds,
The Au coating of 0.03 μm of thickness is formed on Porous Ni electrodeposited coatings, in addition, is plated in method similarly to Example 1
Product.In addition, for the plating product of embodiment 3, also evaluating corrosion resistance and contact resistance according to above-mentioned test method.By result in table
Collect expression in 2.
Embodiment 4
Embodiment 4 is the example that the plating product surface to obtaining in embodiment 3 implements sealing pores.The side of sealing pores
Method is same as Example 2.In addition, for the plating product of embodiment 4, also evaluating corrosion resistance and contact according to above-mentioned test method
Resistance.Result is collected into expression in table 2.
Embodiment 5
While be stirred with magnetic stirring apparatus, while with cathode-current density 3A/dm2Carry out electrolysis plating Au to process 3 seconds,
The Au coating of 0.02 μm of thickness is formed on Porous Ni electrodeposited coatings, in addition, is plated in method similarly to Example 1
Product.In addition, for the plating product of embodiment 5, also evaluating corrosion resistance and contact resistance according to above-mentioned test method.By result in table
Collect expression in 2.
Embodiment 6
Embodiment 6 is the example that the plating product surface to obtaining in embodiment 5 implements sealing pores.The side of sealing pores
Method is same as Example 2.In addition, for the plating product of embodiment 6, also evaluating corrosion resistance and contact according to above-mentioned test method
Resistance.Result is collected into expression in table 2.
Embodiment 7
Embodiment 7 is defined in embodiment 1 after Porous Ni coating, is carried out with acidic aqueous solution after the oxidising treat-ment
Process, form the example of surface A u coating.After the washing of the sample of Porous Ni coating, drying will be formed with, 260 DEG C are being warmed to
Thermostat in place 10 minutes after, from thermostat take out.The sample that so operation has carried out oxidation processes is existed in room temperature
After impregnating 1 minute in the hydrochloric acid of 5vol%, washed.Hereafter, operate similarly to Example 1, carry out the shape of surface A u coating
Into.
The secondary electron image on the plating product surface of embodiment 7 is represented in fig. 8.As shown in figure 8, confirming the plating of embodiment 7
Product have hole on its surface, are formed with the coating of Porous.In addition, for the plating product of embodiment 7, according to above-mentioned test side
Method, evaluates average friction coefficient, corrosion resistance and contact resistance.Result is collected into expression in table 2.In the plating product of embodiment 7
In, also carry out the elementary analysis in the hole (spectrum 1) and convex portion (spectrum 2) represented in Fig. 8.Result is represented in table 1.
[table 1]
Embodiment 8
Embodiment 8 is to be formed after surface A u electrodeposited coating in embodiment 1, has carried out the example of oxidation processes.Oxidation processes
Method it is same as Example 7.According to above-mentioned test method, average friction coefficient, corrosion resistance and contact resistance are evaluated.Will
As a result expression is collected in table 2.
Embodiment 9
Embodiment 9 is that instead of the surface A u coating in embodiment 1, forms the example of surface A g coating.That is, embodiment 9
Plating product, sequentially form bottom Ni coating, Porous Ni coating and surface A g coating on base material.Carry out the work of electrolytic degreasing process
Sequence, the operation for forming bottom Ni coating, the operation of formation Porous Ni coating are same as Example 1.Form surface A g coating
Operation is as described below.
(formation of surface A g coating)
Dipping is formed with the sample of Porous Ni coating in the aqueous solution of following compositions of room temperature.Then, with negative electrode electricity
Current density 2A/dm2Carry out striking plating Ag to process 10 seconds.Hereafter, sample 3 times is cleaned with ion exchange water.
Silver cyanide [AgCN]：3g/L
Potassium cyanide [KCN]：160g/L
Potassium carbonate [K2CO3]：100g/L
The electricity of following compositions is added in " S-900 " 2L of Metalor Technologies Japan Co., Ltd. production
Dipping is formed with the sample of Ag striking coating in plating solution.In 55 DEG C of insulations, with cathode-current density 5A/dm2Carry out plating the Ag15 seconds
Clock.Hereafter, sample 3 times is cleaned with ion exchange water, carries out ultrasonic cleansing, thus form thickness on Porous Ni coating
0.4 μm of surface A g coating.
Silver potassium cyanide [KAg (CN)2]：150g/L
Potassium cyanide [KCN]：2.5g/L
Further implement to prevent discoloration from processing on the plating product surface for obtaining.Specifically, by resulting plating product at 55 DEG C
Dipping 5 seconds in the aqueous solution (200mL/L) of the anti-blushing agent " CE-9700W " of the ChemicalDensi Co., Ltds production of insulation
Clock.Then, cleaned 3 times with ion exchange water, be dried.For the plating product of embodiment 9, according to above-mentioned test method, evaluate resistance to
Corrosivity and contact resistance.Result is collected into expression in table 2.
Comparative example 1
Comparative example 1 is the example of the formation for not carrying out Porous Ni coating in embodiment 1.Specifically, comparative example 1
Plating product, sequentially form bottom Ni coating and surface A u coating on base material.The base material of ungrease treatment is immersed in into 50 DEG C of insulations
PH4.4 plating bath in.Then, when air stirring is carried out with 3A/dm2Current density carry out electrolysis plating Ni processs, formation
The Ni coating of 2 μm of thickness.Hereafter, sample 3 times is cleaned with ion exchange water, is impregnated 60 seconds in 60 DEG C of ion exchange water,
Ultrasonic cleansing.The composition of plating bath is identical with the composition of the plating bath in embodiment 1 during formation bottom Ni coating.
Then, the surface A u coating of 0.05 μm of thickness is formed in the specimen surface for being formed with bottom Ni coating, is compared
The plating product of example 1.Condition when forming surface A u coating is identical with the condition illustrated in embodiment 1.
The secondary electron image on the surface of the plating product of comparative example 1 is represented in Figure 5.As shown in figure 5, not having in plating layer surface
Confirm hole.
The result of the friction wear test of the plating product of comparative example 1 is represented in figure 6.As shown in fig. 6, in determining, due to rubbing
Wipe coefficient to rise rapidly and stop test.In addition, secondary after the friction wear test of the plating product of expression comparative example 1 in the figure 7
Electronic image.As shown in Figure 7, it is known that after friction wear test, plated film is shaved.In addition, for the plating product of comparative example 1, according to
Above-mentioned test method, evaluates average friction coefficient, corrosion resistance and contact resistance.Result is collected into expression in table 2.
Comparative example 2
Comparative example 2 is the example that the plating product surface to obtaining in comparative example 1 implements sealing pores.The condition of sealing pores
It is same as Example 1.In addition, for the plating product of comparative example 2, according to above-mentioned test method, average friction coefficient, corrosion-resistant is evaluated
Property and contact resistance.Result is collected into expression in table 2.
As shown in table 2, it is thus identified that relative to the specific surface area of the plating product of comparative example 1 be 1.0043, the plating product of embodiment 1
Specific surface area is 1.5112, increases to about 1.5 times.By the comparison of embodiment and comparative example, it is thus identified that by having on surface
Hole, corrosion resistance is increased substantially, meanwhile, average friction coefficient declines.Even if in addition, the surface of multicoating have hole,
Also not confirming contact resistance value has big change.Knowable to the result of embodiment 1～6, even if making the thickness of overlay coating
It is thinning, also maintain corrosion resistance and contact resistance value.In addition, by the comparison of embodiment 1 and embodiment 7, by many
Also there is oxidation Ni layers, corrosion resistance is further improved between hole matter coating and overlay coating.By embodiment 1 and embodiment 8
Comparison understand that oxidation processes are carried out to surface after overlay coating is defined, and corrosion resistance is also further improved.Therefore, may be used
Know and meet the plating product that the present invention is constituted, be able to maintain that electrical characteristics and obtain excellent corrosion resistance and abrasion performance.
Claims (14)
1. a kind of electric parts, it is characterised in that：
It is made up of the product of plating,
The plating product are formed with multicoating on the base material being made up of conductive metal,
The base material is copper or the alloy with copper as main component,
On the substrate, successively with the Porous coating with Ni or Cu as main component and with Au or Ag as main component
Overlay coating,
It is formed with by entering the substantial amounts of hole that constitutes for concave recess towards base material low-lying area on the surface of the multicoating,
The part for being formed with the multicoating is electric terminal,
The electric parts is connector terminal or switch terminal with contact portion and portion of terminal, the shape in the contact portion
Into there is the multicoating.
2. a kind of electric parts, it is characterised in that：
It is made up of the product of plating,
The plating product are formed with multicoating on the base material being made up of conductive metal,
The base material is copper or the alloy with copper as main component,
On the substrate, successively with the Porous coating with Ni or Cu as main component and with Au or Ag as main component
Overlay coating,
It is formed with by entering the substantial amounts of hole that constitutes for concave recess towards base material low-lying area on the surface of the multicoating,
The part for being formed with the multicoating is electric terminal,
The electric parts is printed substrate.
3. electric parts as claimed in claim 1 or 2, it is characterised in that：
In terms of area loading mean value, the average diameter in the hole is 0.2～20 μm.
4. electric parts as claimed in claim 1 or 2, it is characterised in that：
The thickness of the Porous coating is 0.1～20 μm, and the thickness of the overlay coating is 0.001～3 μm.
5. electric parts as claimed in claim 1 or 2, it is characterised in that：
Also there is the oxide skin(coating) being made up of oxidation Ni or oxidation Cu between the Porous coating and the overlay coating.
6. electric parts as claimed in claim 1 or 2, it is characterised in that：
Overlay coating thickness of thin of the overlay coating thickness in the hole of the multicoating than the convex portion of multicoating.
7. electric parts as claimed in claim 1 or 2, it is characterised in that：
Between base material and Porous coating, be also formed with the bottom of the Porous coating identical metal as main component
Coating.
8. electric parts as claimed in claim 7, it is characterised in that：
The thickness of the bottom coating is 0.1～20 μm.
9. a kind of plating product, it is characterised in that：
Multicoating is formed with the base material being made up of conductive metal,
The base material is copper or the alloy with copper as main component,
On the substrate, successively with the Porous coating with Ni or Cu as main component and with Au or Ag as main component
Overlay coating,
It is formed with by entering the substantial amounts of hole that constitutes for concave recess towards base material low-lying area on the surface of the multicoating,
Also there is the oxide skin(coating) being made up of oxidation Ni or oxidation Cu between the Porous coating and the overlay coating.
It is 10. as claimed in claim 9 to plate product, it is characterised in that：
In terms of area loading mean value, the average diameter in the hole is 0.2～20 μm.
The 11. plating product as described in claim 9 or 10, it is characterised in that：
The thickness of the Porous coating is 0.1～20 μm, and the thickness of the overlay coating is 0.001～3 μm.
The 12. plating product as described in claim 9 or 10, it is characterised in that：
Overlay coating thickness of thin of the overlay coating thickness in the hole of the multicoating than the convex portion of multicoating.
The 13. plating product as described in claim 9 or 10, it is characterised in that：
Between base material and Porous coating, be also formed with the bottom of the Porous coating identical metal as main component
Coating.
14. plating product as claimed in claim 13, it is characterised in that：
The thickness of the bottom coating is 0.1～20 μm.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JP2011-282348 | 2011-12-22 | ||
| JP2011282348 | 2011-12-22 | ||
| PCT/JP2012/083371 WO2013094766A1 (en) | 2011-12-22 | 2012-12-22 | Plated article and manufacturing method therefor |
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| CN104040035B true CN104040035B (en) | 2017-05-03 |
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| JP5851232B2 (en) * | 2011-12-22 | 2016-02-03 | 日本圧着端子製造株式会社 | parts |
| JP5851231B2 (en) * | 2011-12-22 | 2016-02-03 | 日本圧着端子製造株式会社 | parts |
| JP5975351B2 (en) * | 2013-05-27 | 2016-08-23 | スガ試験機株式会社 | Corrosion promotion tester and corrosion promotion test method |
| US9783902B2 (en) | 2013-10-25 | 2017-10-10 | Om Sangyo Co., Ltd. | Method for producing plated article |
| JP6978262B2 (en) * | 2017-09-22 | 2021-12-08 | セーレン株式会社 | Breathable waterproof metal leaf |
| JP7352939B2 (en) * | 2019-05-09 | 2023-09-29 | ナミックス株式会社 | composite copper parts |
| JP7456579B2 (en) * | 2019-05-09 | 2024-03-27 | ナミックス株式会社 | Method for manufacturing a metal member having a metal layer |
| JP2022100002A (en) | 2020-12-23 | 2022-07-05 | Ｄｏｗａメタルテック株式会社 | Ag PLATING MATERIAL, PRODUCTION METHOD OF Ag PLATING MATERIAL, AND ELECTRICAL COMPONENT |
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| GB593763A (en) * | 1944-04-24 | 1947-10-24 | Galvanostegie Almeta Sa De | Improvements in or relating to processes for covering the surfaces of aluminium or aluminium alloy articles with adherent and protective metallic coatings |
| JPH03257193A (en) * | 1990-03-08 | 1991-11-15 | Ebara Yuujiraito Kk | Nickel plating method rendering high corrosion resistance |
| EP1260609A1 (en) * | 2000-02-24 | 2002-11-27 | Ibiden Co., Ltd. | Nickel-gold plating exhibiting high resistance to corrosion |
| CN101824617A (en) * | 2010-04-30 | 2010-09-08 | 西南交通大学 | Process method for realizing porousness of surface of iron and steel material |
| CN103518006A (en) * | 2011-05-09 | 2014-01-15 | 泰科电子公司 | Corrosion resistant electrical conductor |
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| Publication number | Publication date |
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| JP6089341B2 (en) | 2017-03-08 |
| JPWO2013094766A1 (en) | 2015-04-27 |
| CN104040035A (en) | 2014-09-10 |
| WO2013094766A1 (en) | 2013-06-27 |
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