CN105392928A - Noble metal-coated member and method for manufacturing same - Google Patents
Noble metal-coated member and method for manufacturing same Download PDFInfo
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- CN105392928A CN105392928A CN201480031587.0A CN201480031587A CN105392928A CN 105392928 A CN105392928 A CN 105392928A CN 201480031587 A CN201480031587 A CN 201480031587A CN 105392928 A CN105392928 A CN 105392928A
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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
- C25D7/00—Electroplating characterised by the article coated
-
- 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
- C25D5/611—Smooth layers
-
- 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
-
- 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
- C25D3/00—Electroplating: Baths therefor
- C25D3/02—Electroplating: Baths therefor from solutions
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/562—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of iron or nickel or cobalt
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Electroplating Methods And Accessories (AREA)
- Electroplating And Plating Baths Therefor (AREA)
Abstract
Provided is a noble metal-coated member having further improved corrosion resistance. The noble metal-coated member is characterized by comprising a member, a nickel-cobalt alloy layer containing cobalt in an amount of 0.5 to 99 mass% and a noble metal layer, wherein the nickel-cobalt alloy layer and the noble metal layer are laminated in this order on the surface of the member.
Description
Technical field
The present invention relates to the precious metal that a kind of erosion resistance improves and be coated to component.
Background technology
The precious metal being provided with the layer of precious metal such as gold in component surface is coated to component because being coated with precious metal, and is used in ornament.In addition, precious metal is stablized in recent years, particularly whisker resistance, wear resistance, excellent corrosion resistance, and then because having low contact resistance, so its contact or the terminal etc. such as interval connector, switch, rly. of being used in industry instrument are coating.
But, when precious metal is used in coating, require thinning because precious metal is expensive, but substrate plating layer is corroded because thin layer of precious metal has the existence of a lot of pin hole, and then has the shortcoming becoming even starting material and be also easily corroded.In addition, when the nickel layer for substrate plating layer contains the sulphur used as gloss-imparting agent etc. in the past, more hold corrosion-prone problem in addition.For this reason, be required that being coated to component to precious metal gives erosion resistance.
In order to correspondence precious metal so is coated to corrosion (erosion resistance) problem of component, report has the technology (patent documentation 1) such as being formed the layer of precious metal such as layer of nickel-phosphorous, nickel-tin layers, palladium-nickel dam or cobalt-tin layers etc., gold by plating on the surface of the component be made up of copper based material successively.
Prior art document
Patent documentation
Patent documentation 1: Japanese Unexamined Patent Publication 2004-307954 publication
Summary of the invention
But in the technology described in patent documentation 1, although avoid how much promoting erosion resistance containing sulphur by nickel dam, surface roughness becomes large, reduces plug property, has the problem that corrosion occurs from scar (plug trace).Therefore, component is coated to by problem of the present invention for providing a kind of precious metal improving erosion resistance further.
The present inventors are in order to solve found that of above-mentioned problem further investigation, before layer of precious metal is set in component surface, first the nickel-cobalt alloy layer containing cobalt is set with specific content, even if layer of precious metal is thin situation or the situation containing sulphur at nickel dam, also can be coated to component to precious metal and give erosion resistance, and complete the present invention.
That is, the present invention is that a kind of precious metal is coated to component, it is characterized in that, in component surface sequentially laminated with the nickel-cobalt alloy layer containing 0.5 ~ 99 quality % cobalt and layer of precious metal.
In addition, the present invention is the manufacture method that a kind of precious metal is coated to component, it is characterized in that, stacks gradually nickel-cobalt alloy layer containing 0.5 ~ 99 quality % cobalt and layer of precious metal in component surface.
And then the present invention is the erosion resistance method for improving that a kind of precious metal is coated to component, it is characterized in that, stack gradually nickel-cobalt alloy layer containing 0.5 ~ 99 quality % cobalt and layer of precious metal in component surface.
The effect of invention
According to the present invention, component can be coated to precious metal and give erosion resistance.Specifically, even if due to the reduced thickness by be coated to layer of precious metal, also not easily cause because of the caused problem such as pin hole, so can erosion resistance be promoted.In addition, also can not impact erosion resistance even if contain sulphur at nickel dam, therefore can maintain the plug that the nickel plating bath in the past containing gloss-imparting agent has.
Accompanying drawing explanation
Fig. 1 represents that precious metal of the present invention is coated to the diagram of an example of the formation of component.
Fig. 2 represents that precious metal of the present invention is coated to the diagram of another example of the formation of component.
Embodiment
The component being coated to component for precious metal of the present invention is not particularly limited, and is formed as long as such as its surface is the metal or alloy such as copper, copper alloy, nickel, nickelalloy, stainless steel.In addition, the inside starting material of component or the shape of component are not particularly limited.
In above-mentioned component surface, the nickel-cobalt alloy layer containing 0.5 ~ 99 quality % (as follows referred to as " % "), preferably 1 ~ 80% cobalt is set.This nickel-cobalt alloy layer is formed by known formation method, such as, can use the plating of nickel-cobalt plating solution, be formed using nickel-cobalt alloy as the mode of the sputtering of sputtering source, evaporation etc.In addition, the thickness of this nickel-cobalt alloy layer is not particularly limited, such as, be 0.01 ~ 100 μm, is preferably 0.5 ~ 5 μm.
In addition, can also containing sulphur etc. in above-mentioned nickel-cobalt alloy layer.The content of sulphur etc. is not particularly limited, such as, be 0.001 ~ 1%, is preferably 0.001 ~ 0.25%.In order to make to contain sulphur etc. in nickel-cobalt alloy layer, sulphur or sulfocompound etc. can be contained in above-mentioned plating solution or sputtering source.Become fine containing separating out during sulphur, surface also becomes level and smooth.
Then, layer of precious metal is set on nickel-cobalt alloy layer.Such as Au Ag Pt Pd, rhodium, iridium, ruthenium, osmium can be enumerated, preferred gold and silver, palladium in these precious metals as precious metal.This layer of precious metal is formed by known formation method, such as can with precious metal plating, using precious metal as formation such as the sputtering of sputtering source, evaporations.Further, the thickness of this layer of precious metal is not particularly limited, such as, be more than 0.01 μm, is preferably 0.01 ~ 10 μm, is more preferably 0.05 ~ 2 μm.
In addition, this layer of precious metal can also containing cobalt etc.The content of cobalt etc. is not particularly limited, such as, be 0.1 ~ 8%, is preferably 0.2 ~ 0.4%.In order to make to contain cobalt etc. in layer gold, cobalt or cobalt compound etc. can also be contained in above-mentioned plating solution or sputtering source.Become fine containing separating out during cobalt, and the hardness of epithelium can uprise.
Be coated in component at precious metal of the present invention, between nickel-cobalt alloy layer and layer of precious metal, the one kind or two or more middle layer be selected from nickel-tin layers, palladium layers and palladium-nickel dam can also be set, the middle layer of 2 kinds can be preferably set (wherein, when using palladium formed layer of precious metal situation or when arranging palladium layers individually as middle layer, the layer as the layer of precious metal side in middle layer of more than two kinds can get rid of palladium layers).Erosion resistance can be promoted further by arranging these middle layers.
In above-mentioned middle layer, nickel-tin layers is formed by known formation method, such as can nickel-Xi plating, using nickel-tin alloy as formation such as the sputtering of sputtering source, evaporations.In addition, the stanniferous content of nickel-tin layers is not particularly limited, such as, be 40% ~ 70%.In addition, the thickness of nickel-tin layers is not particularly limited, such as, be 0.001 ~ 10 μm, is preferably 0.05 ~ 1 μm.
In addition, palladium layers is formed by known formation method, such as can with palladium plating, using formation such as the sputtering of the palladium as sputtering source, evaporations.In addition, the thickness of palladium layers is not particularly limited, such as, be 0.001 ~ 10 μm, is preferably 0.05 ~ 2 μm.
Palladium-nickel dam can also be formed by known formation method, such as can palladium-nickel plating, using palladium-nickelalloy as formation such as the sputtering of sputtering source, evaporations.In addition, the nickeliferous content of palladium-nickel dam is not particularly limited, such as, be 10 ~ 50%, is preferably 15 ~ 20%.In addition, the thickness of palladium-nickel dam is not particularly limited, such as, be 0.001 ~ 10 μm, is preferably 0.05 ~ 2 μm.
Precious metal of the present invention is coated in component the sealing pores oxidant layer that can also arrange and promote for plug property.This sealing pores oxidant layer can be formed with commercially available hole sealing processing agent.In addition, this sealing pores oxidant layer is preferably disposed on layer of precious metal.
Enumerate the example forming each layer with plating solution, the optimal way being coated to component for the formation of precious metal of the present invention is expressed as follows.
(1) after the known factures such as dipping such as the component formed with copper, copper alloy, nickel, nickelalloy, stainless steel etc. skimming treatment, electrolytic degreasing process, acid activity process being given pre-treatment, impregnated in the nickel-cobalt plating solution of following composition with following condition, and with above-mentioned thickness, nickel-cobalt alloy layer is set in component surface.
< nickel-cobalt plating solution composition >
(watt bath)
Single nickel salt: 200 ~ 400g/l, is preferably 250 ~ 300g/l
Nickelous chloride: 30 ~ 60g/l, is preferably 40 ~ 50g/l
Boric acid: 30 ~ 50g/l, is preferably 30 ~ 40g/l
Rose vitriol: 0.4 ~ 70g/l, is preferably 0.4 ~ 40g/l
Soluble saccharin: 0.5 ~ 8g/l, is preferably 1 ~ 3g/l
(sulfanilamide (SN) acid bath)
Sulfanilic acid nickel: 300 ~ 800g/l, is preferably 300 ~ 600g/l
Nickelous chloride: 5 ~ 15g/l, is preferably 5 ~ 10g/l
Boric acid: 30 ~ 60g/l, is preferably 30 ~ 40g/l
Rose vitriol: 0.4 ~ 70g/l, is preferably 30 ~ 40g/l
Soluble saccharin: 0.5 ~ 8g/l, is preferably 1 ~ 3g/l
< nickel-cobalt plating condition >
Bath temperature: 45 ~ 60 DEG C, is preferably 50 ~ 55 DEG C
PH:3.0 ~ 4.5, are preferably 3.5 ~ 4.0
Current density: 2 ~ 20A/dm
2, be preferably 4 ~ 10A/dm
2
(2) in the nickel-cobalt alloy layer component being provided with above-mentioned (1), optionally the one kind or two or more middle layer be selected from nickel-tin layers, palladium layers and palladium-nickel dam can be set with above-mentioned thickness.In addition for the composition of the plating solution of the formation in these middle layers and the condition of plating as follows.
< nickel-Xi plating solution composition >
Tin chloride (II): 20 ~ 40g/l, is preferably 25 ~ 30g/l
Nickelous chloride: 15 ~ 45g/l, is preferably 20 ~ 40g/l
Potassium pyrophosphate: 100 ~ 300g/l, is preferably 150 ~ 250g/l
Glycine: 10 ~ 30g/l, is preferably 10 ~ 25g/l
Ammoniacal liquor (28%): 5ml/l
< nickel-Xi plating condition >
Bath temperature: 40 ~ 60 DEG C, is preferably 40 ~ 50 DEG C
PH:7.5 ~ 8.5, are preferably 7.5 ~ 8
Current density: 1 ~ 10A/dm
2, be preferably 2 ~ 5A/dm
2
< palladium plating solution composition >
Diamino sulfurous acid palladium salt: 10 ~ 30g/l, is preferably 10 ~ 15g/l
Ammonium chloride: 5 ~ 140g/l, is preferably 80 ~ 120g/l
Boric acid: 5 ~ 50g/l, is preferably 10 ~ 20g/l
3-pyridine-sulfonic acid: 1 ~ 10g/l, is preferably 3 ~ 5g/l
Potassium selenite: 0.01 ~ 0.1g/l, is preferably 0.03 ~ 0.05g/l
< palladium plating condition >
Bath temperature: 40 ~ 60 DEG C, is preferably 45 ~ 55 DEG C
PH:7 ~ 9, are preferably 8 ~ 9
Current density: 0.5 ~ 5A/dm
2, be preferably 1 ~ 3A/dm
2
< palladium-nickel plating bath composition >
Dichloro two ammino palladium: 20 ~ 100g/l, is preferably 20 ~ 50g/l
Nickel sulfate hexahydrate compound: 50 ~ 400g/l, is preferably 100 ~ 200g/l
Ammonium sulfate: 10 ~ 70g/l, is preferably 30 ~ 50g/l
3-pyridine-sulfonic acid: 1 ~ 10g/l, is preferably 3 ~ 5g/l
< palladium-nickel plating condition >
Bath temperature: 40 ~ 60 DEG C, is preferably 45 ~ 55 DEG C
PH:7 ~ 9, are preferably 8 ~ 9
Current density: 0.5 ~ 5A/dm
2, be preferably 1 ~ 3A/dm
2
(3) be provided with above-mentioned (1) nickel-cobalt alloy layer component or in the nickel-cobalt alloy layer component being provided with above-mentioned (2), optionally, in the component being provided with the one kind or two or more middle layer be selected from nickel-tin layers, palladium layers and palladium-nickel dam, layer of precious metal can be set with above-mentioned thickness.In addition, the composition of precious metal plating solution and the condition of plating as follows.
< gold plating solution composition >
Potassium auric cyanide: gold concentration 4 ~ 16g/l, is preferably 8 ~ 12g/l
Rose vitriol: 0.25 ~ 25g/l, is preferably 0.5 ~ 10g/l
Citric acid: 10 ~ 150g/l, is preferably 50 ~ 100g/l
< gold plating condition >
Bath temperature: 20 ~ 55 DEG C, is preferably 30 ~ 50 DEG C
PH:3 ~ 5, are preferably 3.5 ~ 4.5
Current density: 0.4 ~ 40A/dm
2, be preferably 5A/dm
2
Precious metal of the present invention is coated to the preferred mode of component, and as shown in Figure 1, component (2) is disposed with in the mode of nickel-cobalt alloy layer (3), layer of precious metal (4), layer of precious metal is layer gold.In addition, precious metal of the present invention is coated to other preferred modes of component, as shown in Figure 2, component (2) is disposed with in the mode of nickel-cobalt alloy layer (3), middle layer (5), layer of precious metal (4), middle layer is nickel-tin layers and/or palladium layers, and layer of precious metal is layer gold.
The precious metal of the present invention of acquisition like this is coated to component and has erosion resistance.
In addition, have erosion resistance herein and refer to, such as, after carrying out salt spray testing (JISC60068-2-11) or nitric acid aeration test (according to JISH8620), erodable section is overall less than 30%, is preferably less than 10%.
Above-mentioned precious metal of the present invention is coated to component because having erosion resistance as above, contact or the terminal etc. such as interval connector, switch, rly. of suitable industry instrument.
[embodiment]
As follows, enumerate embodiment and explain the present invention, but the present invention is not limited to these embodiments.
Embodiment 1
The formation of the coating component of gold:
(1) formation of nickel-cobalt alloy layer
After the junctor formation component thickness formed with copper alloy being about 0.10mm carries out degreasing, at bath temperature 55 DEG C, current density 10A/dm
2condition under impregnated in the nickel-cobalt plating solution of following composition, make it form the nickel-cobalt alloy layer of 1.5 μm in component surface.In addition, the content of the cobalt of this nickel-cobalt alloy layer is 20%.
< nickel-cobalt plating solution composition >
Single nickel salt: 300g/l
Nickelous chloride: 40g/l
Boric acid: 30g/l
SB-10B (trade(brand)name: JUCCORPORATION system)
* 1: 40ml/l
SB-10D (trade(brand)name: JUCCORPORATION system)
* 2: 25ml/l
* 1: containing the cobalt additive of cobalt
* 2: the gloss-imparting agent of sulfur-bearing
(2) formation of layer gold
After the component obtained in above-mentioned (1) is washed, at bath temperature 45 DEG C, current density 2A/dm
2condition under impregnated in the golden plating solution of following composition, make it form the layer gold of 0.1 μm in component surface, obtain the coating component of gold.In addition, the content of the cobalt of this layer gold is 0.2 ~ 0.4%.
< gold plating solution composition >
Potassium auric cyanide: gold concentration 8g/l
Rose vitriol: 0.75g/l
Citric acid: 75g/l
Embodiment 2
The formation of the coating component of gold:
Implement in the same manner as (1) and (2) of embodiment 1, and after making its layer gold forming the nickel-cobalt alloy layer of 1.5 μm and 0.1 μm in component surface, heat-treat in the baking oven of 260 DEG C and within 2 minutes, obtain the coating component of gold.In addition, even if thermal treatment is in order to confirm that heating erosion resistance whether can deterioration and implementing.
Embodiment 3
The formation of the coating component of gold:
The component of nickel-cobalt alloy layer of 1.5 μm will be formed with in component surface, at bath temperature 55 DEG C, current density 2A/dm in the same manner as (1) of embodiment 1
2condition under impregnated in the nickel-Xi plating solution of following composition, make it form the nickel-tin layers of 0.3 μm in component surface.Then, make it form the layer gold of 0.1 μm in component surface in the same manner as (2) of embodiment 1, obtain the coating component of gold.In addition, the content of the tin of nickel-tin layers is 60%.
< nickel-Xi plating solution composition >
SB-20MU (trade(brand)name: JUCCORPORATION system)
* 3: 500ml/l
* 3: nickel-Xi plating solution
Embodiment 4
The formation of the coating component of gold:
Make it similarly to Example 3 after component surface forms the layer gold of 0.1 μm, heat-treat in the baking oven of 260 DEG C and within 2 minutes, obtain the coating component of gold.
Embodiment 5
The formation of the coating component of gold:
The component of nickel-cobalt alloy layer of 1.5 μm will be formed with in component surface, at bath temperature 55 DEG C, current density 2A/dm in the same manner as (1) of embodiment 1
2condition under impregnated in the palladium plating solution of following composition, make it form the palladium layers of 0.05 μm in component surface.Then, make it form the layer gold of 0.1 μm in component surface in the same manner as (2) of embodiment 1, obtain the coating component of gold.
< palladium plating solution composition >
Diamino sulfurous acid palladium salt: 15g/l
Ammonium chloride: 100g/l
Boric acid: 10g/l
3-pyridine-sulfonic acid: 5g/l
Potassium selenite: 0.05g/l
Embodiment 6
The formation of the coating component of gold:
After making it form the layer gold of 0.1 μm similarly to Example 5 in component surface, heat-treat in the baking oven of 260 DEG C and within 2 minutes, obtain the coating component of gold.
Embodiment 7
The formation of the coating component of gold:
The sample of the nickel-cobalt alloy layer being formed with 1.5 μm in the same manner as (1) of embodiment 1 in component surface is being bathed temperature 55 DEG C, current density 2A/dm
2condition under impregnated in the nickel-Xi plating solution of the composition recorded in embodiment 3, and make it form the nickel-tin layers of 0.3 μm in component surface.Then, at bath temperature 55 DEG C, current density 2A/dm
2condition under impregnated in embodiment 5 record composition palladium plating solution in, make it form the palladium layers of 0.05 μm in component surface.Finally, make it form the layer gold of 0.1 μm in component surface in the same manner as (2) of embodiment 1, obtain the coating component of gold.
Embodiment 8
The formation of the coating component of gold:
Make it similarly to Example 7 after specimen surface forms the layer gold of 0.1 μm, heat-treat in the baking oven of 260 DEG C and within 2 minutes, obtain the coating component of gold.
Embodiment 9
The formation of the coating component of gold:
Be that except the nickel-cobalt plating solution of following composition, all the other are implemented similarly to Example 1 and obtain the coating component of gold except making the nickel-cobalt plating solution used in embodiment 1.
< nickel-cobalt plating solution composition >
SB-10A (trade(brand)name: JUCCORPORATION system)
* 4: 300ml/l
SB-10B (trade(brand)name: JUCCORPORATION system)
* 1: 40ml/l
SB-10C (trade(brand)name: JUCCORPORATION system)
* 5: 120ml/l
SB-10D (trade(brand)name: JUCCORPORATION system)
* 2: 25ml/l
Nickelous chloride: 25g/l
* 4: nickeliferous additive
* 5: containing the additive of pH buffer reagent
Embodiment 10
The formation of the coating component of gold:
Except making the composition of the nickel-cobalt plating solution of use in embodiment 2 for record in embodiment 9, all the other are implemented similarly to Example 2 and obtain the coating component of gold.
Embodiment 11
The formation of the coating component of gold:
Except making the composition of the nickel-cobalt plating solution of use in embodiment 3 for record in embodiment 9, all the other are implemented similarly to Example 3 and obtain the coating component of gold.
Embodiment 12
The formation of the coating component of gold:
Except making the composition of the nickel-cobalt plating solution of use in embodiment 4 for record in embodiment 9, all the other implement to obtain the coating component of gold similarly to Example 4.
Embodiment 13
The formation of the coating component of gold:
Except making the composition of the nickel-cobalt plating solution of use in embodiment 5 for record in embodiment 9, all the other are implemented similarly to Example 5 and obtain the coating component of gold.
Embodiment 14
The formation of the coating component of gold:
Except making the composition of the nickel-cobalt plating solution of use in embodiment 6 for record in embodiment 9, all the other are implemented similarly to Example 6 and obtain the coating component of gold.
Embodiment 15
The formation of the coating component of gold:
Except making the composition of the nickel-cobalt plating solution of use in embodiment 7 for record in embodiment 9, all the other are implemented similarly to Example 7 and obtain the coating component of gold.
Embodiment 16
The formation of the coating component of gold:
Except making the composition of the nickel-cobalt plating solution of use in embodiment 8 for record in embodiment 9, all the other are implemented similarly to Example 8 and obtain the coating component of gold.
Comparative example 1 ~ 8
The formation of the coating component of gold:
Be that except the nickel plating bath of following composition, all the other implement and obtain the coating component of gold in the same manner as embodiment 1 ~ 8 except making the nickel-cobalt plating solution used in embodiment 1 ~ 8.
< nickel plating bath composition >
Single nickel salt: 300g/l
Nickelous chloride: 40g/l
Boric acid: 30g/l
Soluble saccharin: 2g/l
Comparative example 9 ~ 16
The formation of the coating component of gold:
Be that except the nickel plating bath of following composition, all the other implement and obtain the coating component of gold in the same manner as embodiment 9 ~ 16 except making the nickel-cobalt plating solution used in embodiment 9 ~ 16.
< nickel plating bath composition >
SB-10A (trade(brand)name: JUCCORPORATION system)
* 4: 300ml/l
SB-10C (trade(brand)name: JUCCORPORATION system)
* 5: 120ml/l
SB-10D (trade(brand)name: JUCCORPORATION system)
* 2: 25ml/l
Nickelous chloride: 25g/l
Comparative example 17 ~ 20
The formation of the coating component of gold:
Be that except the nickel plating bath of following composition, all the other implement and obtain the coating component of gold in the same manner as embodiment 1,2,7,8 except making the nickel-cobalt plating solution used in embodiment 1,2,7,8.
< nickel plating bath composition >
Single nickel salt: 300g/l
Nickelous chloride: 40g/l
Boric acid: 30g/l
SB-10D (trade(brand)name: JUCCORPORATION system)
* 2: 25ml/l
Comparative example 21 ~ 24
The formation of the coating component of gold:
Be that except the nickel plating bath of following composition, all the other implement and obtain the coating component of gold in the same manner as embodiment 9,10,15,16 except making the nickel-cobalt plating solution used in embodiment 9,10,15,16.
< nickel plating bath composition >
SB-10A (trade(brand)name: JUCCORPORATION system)
* 4: 300ml/l
SB-10C (trade(brand)name: JUCCORPORATION system)
* 5: 120ml/l
SB-10D (trade(brand)name: JUCCORPORATION system)
* 2: 25ml/l
Nickelous chloride: 25g/l
Test example 1
Corrosion resistance test:
Use the gold obtained in embodiment 1 ~ 16 and comparative example 1 ~ 24 to be coated to component, carry out following salt spray testing and nitric acid aeration test with regard to these components.After these tests, based on following metewand with the degree of the corrosion of the coating component of visual valuation gold.These results are shown in table 1.
< salt spray testing method (according to JISH8502) >
Test temperature: 35 ± 2 DEG C
Brines: 5 ± 1% sodium chloride solutions
Test period: 24 hours
< nitric acid aeration test method (according to JISH8620) >
(1) make it dry after using ethanol, sherwood oil, gasoline equal solvent to remove the dirt of test film.
(2) after appropriate nitric acid is inserted in the bottom of moisture eliminator, test film is carried in magnetic making sheet, cover lid.
(3) place 1 hour at about 23 DEG C.
(4) self-desiccation device takes out test film, gives drying quietly after washing.
The judgment standard > of the degree of < corrosion
Evaluate (content)
◎: erodable section is overall less than 10%
Zero: erodable section is more than overall 10% and be less than 30%
△: erodable section is more than overall 30% and be less than 50%
×: erodable section is more than overall 50% and be less than 80%
××: erodable section is more than overall 80%
[table 1]
| Salt spray testing | Nitric acid aeration test | |
| Embodiment 1 | ○ | ○ |
| Embodiment 2 | ○ | ○ |
| Embodiment 3 | ○ | ○ |
| Embodiment 4 | ○ | ○ |
| Embodiment 5 | ◎ | ◎ |
| Embodiment 6 | ◎ | ◎ |
| Embodiment 7 | ◎ | ◎ |
| Embodiment 8 | ◎ | ◎ |
| Embodiment 9 | ○ | ○ |
| Embodiment 10 | ○ | ○ |
| Embodiment 11 | ○ | ○ |
| Embodiment 12 | ○ | ○ |
| Embodiment 13 | ◎ | ◎ |
| Embodiment 14 | ◎ | ◎ |
| Embodiment 15 | ◎ | ◎ |
| Embodiment 16 | ◎ | ◎ |
| Comparative example 1 | ×× | ×× |
| Comparative example 2 | ×× | ×× |
| Comparative example 3 | × | × |
| Comparative example 4 | × | × |
| Comparative example 5 | △ | △ |
| Comparative example 6 | △ | △ |
| Comparative example 7 | △ | △ |
| Comparative example 8 | △ | △ |
| Comparative example 9 | ×× | ×× |
| Comparative example 10 | ×× | ×× |
| Comparative example 11 | × | × |
| Comparative example 12 | × | × |
| Comparative example 13 | △ | △ |
| Comparative example 14 | △ | △ |
| Comparative example 15 | △ | △ |
| Comparative example 16 | △ | △ |
| Comparative example 17 | ○ | ○ |
| Comparative example 18 | ○ | ○ |
| Comparative example 19 | ◎ | ◎ |
| Comparative example 20 | ◎ | ◎ |
| Comparative example 21 | ○ | ○ |
| Comparative example 22 | ○ | ○ |
| Comparative example 23 | ◎ | ◎ |
| Comparative example 24 | ◎ | ◎ |
Known from above result, as shown in the Examples, can erosion resistance be obtained by the nickel layer (sulfur-bearing) formed successively containing cobalt with layer gold.In addition we know, when being provided with the situation in middle layer, erosion resistance can promote.On the other hand known, as shown in comparative example, not containing cobalt nickel coating (sulfur-bearing) even if in form middle layer, layer gold successively, only can obtain the low component of erosion resistance.
Test example 2
Traumatic resistance is tested:
Use in embodiment 1 ~ 16 and comparative example 1 ~ 24 and obtain the coating component of gold, carry out following scratch test with regard to these components.Be coated to the degree of the damage of component with visual valuation gold based on following metewand after this test.In addition, in order to evaluate the corrodibility from the position scraping damage after scratch test, implementing in the same manner as test example 1 and carrying out nitric acid aeration test, evaluating the degree of corrosion.These results are shown in table 2.
< scratch test >
Use and increase the weight of superficiality measuring machine (Xin Dong science Co., Ltd. system: TORAIBOGIATYPE:22H) continuously, certain loading (500gf) is applied to the front end fixture that is zirconia ball and the surface being coated to component at gold scrapes scar.
The judgment standard > of the degree of < scar
Evaluate (content)
◎: be quite not easy to scrape scar
Zero: be not easy to scrape scar
△: a little not easily scrape scar
×: easily scrape scar
××: quite easily scrape scar
[table 2]
| Scratch test | Nitric acid aeration test | |
| Embodiment 1 | △ | △ |
| Embodiment 2 | △ | △ |
| Embodiment 3 | ○ | ○ |
| Embodiment 4 | ○ | ○ |
| Embodiment 5 | ○ | ○ |
| Embodiment 6 | ○ | ○ |
| Embodiment 7 | ◎ | ◎ |
| Embodiment 8 | ◎ | ◎ |
| Embodiment 9 | △ | △ |
| Embodiment 10 | △ | △ |
| Embodiment 11 | ○ | ○ |
| Embodiment 12 | ○ | ○ |
| Embodiment 13 | ○ | ○ |
| Embodiment 14 | ○ | ○ |
| Embodiment 15 | ◎ | ◎ |
| Embodiment 16 | ◎ | ◎ |
| Comparative example 1 | × | × |
| Comparative example 2 | × | × |
| Comparative example 3 | △ | △ |
| Comparative example 4 | △ | △ |
| Comparative example 5 | △ | △ |
| Comparative example 6 | △ | △ |
| Comparative example 7 | ○ | ○ |
| Comparative example 8 | ○ | ○ |
| Comparative example 9 | × | × |
| Comparative example 10 | × | × |
| Comparative example 11 | △ | △ |
| Comparative example 12 | △ | △ |
| Comparative example 13 | △ | △ |
| Comparative example 14 | △ | △ |
| Comparative example 15 | ○ | ○ |
| Comparative example 16 | ○ | ○ |
| Comparative example 17 | ×× | ×× |
| Comparative example 18 | ×× | ×× |
| Comparative example 19 | × | × |
| Comparative example 20 | × | × |
| Comparative example 21 | ×× | ×× |
| Comparative example 22 | ×× | ×× |
| Comparative example 23 | × | × |
| Comparative example 24 | × | × |
Known from above result, as shown in the Examples, can traumatic resistance be obtained by the nickel layer (sulfur-bearing) formed successively containing cobalt with layer gold.In addition we know, when being provided with the situation in middle layer, traumatic resistance can promote, and when being particularly provided with the situation in 2 kinds of middle layers, traumatic resistance significantly promotes.Known on the other hand, as shown in comparative example, not containing the nickel layer (sulfur-bearing) of cobalt even if form middle layer or layer gold successively, only can obtain the low component of traumatic resistance.
Embodiment 17
The relation of the cobalt contents in nickel-cobalt alloy layer and erosion resistance and traumatic resistance:
In order to check the relation of cobalt contents in nickel-cobalt alloy layer and erosion resistance and traumatic resistance, except the nickel concentration in adjustment plating solution and cobalt concentration, and formed change nickel, cobalt determination of total precipitated quantities the nickel-cobalt alloy layer of 1.5 μm beyond, all the other implement to form nickel-tin layers, palladium layers, layer gold similarly to Example 15, obtain the coating component of gold.About the coating component of these gold, implementation evaluation erosion resistance and traumatic resistance in the same manner as test example 1 and 2.These results are shown in table 3.
[table 3]
During the situation of the cobalt amount in nickel alloy layer more than 0.5%, known erosion resistance or traumatic resistance can promote.
[utilizing possibility in industry]
It is high because of erosion resistance that precious metal of the present invention is coated to component, is applicable to the coating of the contact of the interval connector of industry instrument, switch, rly. etc. or terminal etc.
1,6 precious metals are coated to component
2 components
3 nickel-cobalt alloy layer
4 layer of precious metal
5 middle layers
Claims (8)
1. precious metal is coated to a component, it is characterized in that, in component surface sequentially laminated with the nickel-cobalt alloy layer containing 0.5 ~ 99 quality % cobalt and layer of precious metal.
2. precious metal according to claim 1 is coated to component, and wherein, the thickness of layer of precious metal is 0.01 ~ 10 μm.
3. precious metal according to claim 1 and 2 is coated to component, and wherein, the surface of component is formed with metal.
4. the precious metal according to any one of claims 1 to 3 is coated to component, wherein, is provided with the one kind or two or more middle layer be selected from nickel-tin layers, palladium layers and palladium-nickel dam between nickel-cobalt alloy layer and layer of precious metal.
5. the precious metal according to any one of Claims 1 to 4 is coated to component, and wherein, the nickel-cobalt alloy layer containing 0.5 ~ 99 quality % cobalt is also containing sulphur.
6. the precious metal according to any one of Claims 1 to 5 is coated to component, and wherein, described component forms each layer with plating.
7. precious metal is coated to a manufacture method for component, it is characterized in that, stacks gradually nickel-cobalt alloy layer containing 0.5 ~ 99 quality % cobalt and layer of precious metal in component surface.
8. precious metal is coated to an erosion resistance method for improving for component, it is characterized in that, stacks gradually nickel-cobalt alloy layer containing 0.5 ~ 99 quality % cobalt and layer of precious metal in component surface.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2013120525 | 2013-06-07 | ||
| JP2013-120525 | 2013-06-07 | ||
| PCT/JP2014/062006 WO2014196291A1 (en) | 2013-06-07 | 2014-04-30 | Noble metal-coated member and method for manufacturing same |
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| CN105392928A true CN105392928A (en) | 2016-03-09 |
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| JP (1) | JPWO2014196291A1 (en) |
| CN (1) | CN105392928A (en) |
| TW (1) | TW201509643A (en) |
| WO (1) | WO2014196291A1 (en) |
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| JP6823363B2 (en) * | 2015-07-24 | 2021-02-03 | 住友金属鉱山株式会社 | Conductive substrate, manufacturing method of conductive substrate |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59180908A (en) * | 1983-03-30 | 1984-10-15 | 古河電気工業株式会社 | Silver-coated conductor and method of producing same |
| US4767508A (en) * | 1986-02-27 | 1988-08-30 | Nippon Mining Co., Ltd. | Strike plating solution useful in applying primer plating to electronic parts |
| JP2006117983A (en) * | 2004-10-20 | 2006-05-11 | Matsushita Electric Works Ltd | Stainless steel with plated film |
| CN101681729A (en) * | 2007-03-27 | 2010-03-24 | 古河电气工业株式会社 | Silver-coated material for movable contact component and method for manufacturing such silver-coated material |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS6013078B2 (en) * | 1978-09-05 | 1985-04-04 | 日本特殊陶業株式会社 | Gold-plated electronic components and their manufacturing method |
| JPS62199794A (en) * | 1986-02-27 | 1987-09-03 | Nippon Mining Co Ltd | Parts for electronic and electric appliances |
| JPS62199795A (en) * | 1986-02-27 | 1987-09-03 | Nippon Mining Co Ltd | Parts for electronic and electrical appliances |
| JPS6383291A (en) * | 1986-09-25 | 1988-04-13 | Kyocera Corp | Electronic parts having electrically conductive gold layer |
| JP2001003194A (en) * | 1999-06-21 | 2001-01-09 | Nippon Mining & Metals Co Ltd | Heat resistant and corrosion resistant silver plating material |
| JP2004307954A (en) * | 2003-04-08 | 2004-11-04 | Matsushita Electric Works Ltd | Plating forming member |
| JP2008196010A (en) * | 2007-02-13 | 2008-08-28 | Hitachi Cable Ltd | Plating material for connector terminal |
| JP4834022B2 (en) * | 2007-03-27 | 2011-12-07 | 古河電気工業株式会社 | Silver coating material for movable contact parts and manufacturing method thereof |
-
2014
- 2014-04-30 WO PCT/JP2014/062006 patent/WO2014196291A1/en active Application Filing
- 2014-04-30 JP JP2015521344A patent/JPWO2014196291A1/en active Pending
- 2014-04-30 CN CN201480031587.0A patent/CN105392928A/en active Pending
- 2014-05-29 TW TW103118808A patent/TW201509643A/en unknown
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS59180908A (en) * | 1983-03-30 | 1984-10-15 | 古河電気工業株式会社 | Silver-coated conductor and method of producing same |
| US4767508A (en) * | 1986-02-27 | 1988-08-30 | Nippon Mining Co., Ltd. | Strike plating solution useful in applying primer plating to electronic parts |
| JP2006117983A (en) * | 2004-10-20 | 2006-05-11 | Matsushita Electric Works Ltd | Stainless steel with plated film |
| CN101681729A (en) * | 2007-03-27 | 2010-03-24 | 古河电气工业株式会社 | Silver-coated material for movable contact component and method for manufacturing such silver-coated material |
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| Publication number | Publication date |
|---|---|
| WO2014196291A1 (en) | 2014-12-11 |
| TW201509643A (en) | 2015-03-16 |
| JPWO2014196291A1 (en) | 2017-02-23 |
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