CN104080606B - Coating goods, electrodeposition bath and related system - Google Patents
Coating goods, electrodeposition bath and related system Download PDFInfo
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- CN104080606B CN104080606B CN201280055952.2A CN201280055952A CN104080606B CN 104080606 B CN104080606 B CN 104080606B CN 201280055952 A CN201280055952 A CN 201280055952A CN 104080606 B CN104080606 B CN 104080606B
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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
- C25D3/56—Electroplating: Baths therefor from solutions of alloys
- C25D3/64—Electroplating: Baths therefor from solutions of alloys containing more than 50% by weight of silver
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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
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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
- C25D5/48—After-treatment of electroplated surfaces
-
- 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
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/617—Crystalline 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
- 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
- C25D5/615—Microstructure of the layers, e.g. mixed structure
- C25D5/619—Amorphous 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
- 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
- C25D5/00—Electroplating characterised by the process; Pretreatment or after-treatment of workpieces
- C25D5/627—Electroplating characterised by the visual appearance of the layers, e.g. colour, brightness or mat appearance
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D21/00—Processes for servicing or operating cells for electrolytic coating
- C25D21/12—Process control or regulation
- C25D21/14—Controlled addition of electrolyte components
-
- 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
- C25D5/18—Electroplating using modulated, pulsed or reversing current
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Crystallography & Structural Chemistry (AREA)
- Electroplating And Plating Baths Therefor (AREA)
- Electroplating Methods And Accessories (AREA)
Abstract
Coating goods described herein, electrodeposition bath and related system.Described goods can include base material and the coating comprising silver being formed on.In some embodiments, described coating comprises silver-base alloy, such as silver tungsten.Described coating can present desirable character and feature, such as durability (such as, abrasion), hardness, corrosion resistance and high conductivity, and this can be useful in such as electricity application and/or electronic application.In some cases, described coating can make Means of Electrodeposition apply.
Description
Technical field
In short, the present invention relates to coat goods, electrodeposition bath and related system.Implement at some
In scheme, coating is metallic and electro-deposition forms.
Background technology
Permitted eurypalynous coating can put on base material.Electro-deposition is the common technique depositing this type coating.
Electro-deposition is usually directed to apply voltage to the base material that is placed in electrodeposition bath, in order to make metal in bath from
Sub-material reduces and is deposited on base material with the form of metal or metal alloy coating.Voltage can make electricity consumption
Source applies between the anode and the cathode.At least one in male or female can be as base material to be coated.
In some electro-deposition methods, voltage can apply as composite wave-shape, such as in pulsed deposition, exchange
In electro-deposition or reverse impulse deposition.
Noble metal and precious metal alloys coating can use the method depositions such as such as electro-deposition.Apply at some
In, coating at least partly can be worn and torn owing to repeating friction surface.Described effect is probably undesirable,
Especially when at least partly applying coating to improve electric conductivity, because this effect can increase coating
Resistance.
Summary of the invention
The present invention provides coating goods, electrodeposition bath and goods.
In an aspect, it is provided that bath.Bath comprise silver ion material, tungsten and/or molybdenum ion material and
Sodium hydroxide, wherein, bath is suitable for electro-deposition method.
In one aspect of the method, it is provided that bath.Bath comprise silver ion material, tungsten and/or molybdenum ion material with
And selected from 2,2-bipyridyl and the brightener of 3-formoxyl-1-(3-sulfonate radical propyl group) pyridine.
In an aspect, it is provided that electro-deposition system.Electro-deposition system includes comprising the anode of silver, the moon
Pole, bath and power supply, wherein, bath comprises tungsten and/or molybdenum ion material and at least one chelating agent, its
In, bath is connected with anode and negative electrode, and wherein, power supply is connected at least one in anode and negative electrode,
And wherein, the surface area of anode is at least five times of surface area of negative electrode.
In an aspect, it is provided that goods.Goods include base material and the coating formed on base material, are coated with
Layer comprises silver-base alloy, and silver-base alloy comprises tungsten and/or molybdenum further, and silver-base alloy has less than about 100
The granularity of nm, wherein, after being exposed to the temperature at least 1000 hours of at least 125 DEG C, granularity changes
It is not more than 30nm.
In one aspect of the method, it is provided that goods.Goods include base material；The coating formed on base material,
Coating comprises silver-base alloy, and silver-base alloy comprises tungsten and/or molybdenum, wherein, tungsten in silver-base alloy further
And/or the concentration of molybdenum is at least 1.5 atomic percents, and silver-base alloy has putting down less than 1 micron
All granularities；And in coating formed lubricating layer.
In another aspect, it is provided that goods.Goods include base material；The coating formed on base material,
Coating comprises silver-base alloy, and silver-base alloy comprises tungsten and/or molybdenum further；And in coating formed profit
Slip layer, wherein, the hardness of goods is greater than about 1GPa and coefficient of friction is less than about 0.3.
In a further aspect, it is provided that goods.Goods include base material and the coating formed on base material,
Coating comprises silver-base alloy, and silver-base alloy comprises tungsten and/or the molybdenum of at least 1.5 atomic percents further,
Wherein, coating has the porosity of at least 10%.
When considered in conjunction with the accompanying drawings, from the other side of the present invention described further below, embodiment and
Feature will become clear from.Accompanying drawing is schematic and is not intended to be drawn to scale.For succinctly
Purpose, the most each assembly marks out in each figure, and in graphic extension for affiliated
Field artisans understand that the present invention non-vital in the case of, and each reality of non-invention
The each assembly executing scheme shows that.All patent application cases incorporated herein by reference and specially
The full text of profit is all incorporated by reference.If contradiction occurs, then it is as the criterion with this specification (including definition).
Brief Description Of Drawings
Fig. 1 shows the electro-deposition system according to embodiment.
Fig. 2 shows the goods according to embodiment.
Fig. 3 A-3B shows the image of the goods standing endurancing according to some embodiments: A) do not have
Have lubricating layer, and B) there is lubricating layer.
Fig. 4 A-4C show comprise A according to some embodiment electro-deposition) 2.3wt% tungsten, B) 4.5
Wt% tungsten and C) scanning electron micrograph of cross section of silver alloy coating of 8.7wt% tungsten.
Fig. 4 D shows the porosity of the silver-tungsten alloy according to some the embodiment electro-deposition wt% to tungsten
Figure.
Fig. 5 A shows the granularity weight hundred to tungsten of the silver-tungsten alloy according to some embodiment electro-deposition
The figure of proportion by subtraction.
Fig. 5 B shows the silver-tungsten being heated to 125 DEG C of holdings electro-deposition of 1000 hours according to embodiment
The contact resistance of alloy is to executing loaded figure.
Fig. 6 shows that comprising different anodes according to some embodiments sinks to the electricity of cathodic surface area ratio
The silver concentration of the long-pending bath figure to the time.
Fig. 7 shows that the W content of the silver-tungsten alloy according to some embodiment electro-deposition is to electric current density
Figure.
Fig. 8 shows that the pH according to some embodiment electrodeposition bath is to observing precipitation in electrodeposition bath
The figure of experienced natural law.
Detailed description of the invention
Coating goods described herein, electrodeposition bath and related system.Goods can include base material and thereon
The coating comprising silver formed.In some embodiments, coating comprises silver-base alloy, such as silver-tungsten
Alloy.In some cases, coating can include at least two-layer.Such as, coating can include comprising money base
The ground floor of alloy and comprise the second layer of noble metal.Coating can present desirable character and feature, example
Such as durability (such as, abrasion), hardness, corrosion resistance and high conductivity, this such as electricity application and/
Or electronic application can be useful.In some cases, coating can make Means of Electrodeposition apply.
Fig. 1 shows the electro-deposition system 10 according to embodiment.System 10 includes electrodeposition bath 12.
As described further below, bath includes the source metal for forming coating and one or more interpolations
Agent.Anode 14 and negative electrode 16 are provided in bath.Power supply 18 is connected to anode and negative electrode.In validity period
Between, power supply generates the waveform producing voltage difference between the anode and the cathode.Voltage difference makes the gold in bath
Belonging to ionic species reduction and be deposited on negative electrode with coating form, in this embodiment, negative electrode is also
As substrate.
Should be understood that illustrated system is not intended to restrictive, but art can be included
Multiple amendment known to the skilled person.
Electrodeposition bath comprises the fluid vehicle of source metal and additive.In some embodiments, fluid
Supporting agent is water (that is, bath is aqueous solution).However, it should be understood that and be used as other fluid vehicle, example
As fuse salt, low-temperature solvent, alcohol are bathed and other.In some embodiments, fluid vehicle is water
Mixture (that is, water bath can contain at least some organic solvent) with at least one organic solvent.Belonging to
The technical staff in field can select the fluid vehicle being suitable for.
Bath includes the source metal being suitable for so that deposition has the coating of desirable composition.Should be understood that when heavy
During long-pending metal alloy, all metal ingredients in alloy all have source in bath.Source metal is the most molten
Solution ionic species in fluid vehicle.As described further below, during electro-deposition method, from
Sub-material forms coating so that the form of metal or metal alloy deposits.Generally, any being suitable for can be used
Ionic species.Ionic species can be provided by slaine.Such as, when deposition comprises the coating of silver,
Silver nitrate, silver sulfate, sulfamic acid silver can be used to provide silver ion material；When deposition comprises tungsten
During coating, sodium tungstate, ammonium tungstate, wolframic acid etc. can be used to provide tungsten ion material.In certain situation
Under, ionic species can comprise molybdenum.When deposition comprises the coating of molybdenum, can use sodium molybdate, ammonium molybdate,
Molybdenum oxides etc. provide molybdenum ion material.Should be understood that these ionic species provide as an example and
Other sources many are feasible.The metallics of any applicable concentration, and art can be used
Technical staff can by normal experiment select be suitable for concentration.In some embodiments, in bath
Ionic species can have between 0.1g/L and 100g/L, between 5g/L and 50g/L
Or the concentration between 1g/L and 20g/L.
As described herein, electrodeposition bath can include one or more can improve electrodeposition technology and/
Or the additive of coating quality.Such as, electrodeposition bath can comprise at least one chelating agent (that is, chelating agent
Or the mixture of chelating agent).Chelating agent refers to can be with any material of ion coordination of containing in solution.
In some embodiments, the mixture tolerable at least two elemental co-deposition of chelating agent or chelating agent.
Such as, mixture tolerable silver and the tungsten of chelating agent or chelating agent co-deposits.
Chelating agent can be organic substance, such as citrate ion, comprise hydantoin compound,
Acid imide functional group or the pyridine compounds being substituted.Chelating agent can be inorganic substances, such as ammonium ion.
In some cases, chelating agent is neutral substance.In some cases, chelating agent is charged thing
Matter (such as, electronegative ion, positively charged ion).The example of chelating agent include citrate,
Gluconate, tartrate and other alkyl hydroxy carboxylic acid；Cyanide；Hydantoins (such as, 5,5-
Dimethyl hydantoin), butanimide class (such as, butanimide) and other comprise acid imide official
The compound of energy base；And the pyridine compounds (such as, nicotiamide) being substituted.
Generally, the mixture of chelating agent or chelating agent can with the concentration in the range of 0.1-200g/L and
Under certain situation, the concentration in the range of 40-80g/L is included in electrodeposition bath.In one embodiment,
The mixture of chelating agent comprises 5,5-dimethyl hydantoin, citric acid and nicotiamide.When chelating agent is
When comprising the compound of acid imide functional group, the concentration of chelating agent can be at 30-70g/L or 40-60g/L
In the range of.When chelating agent is alkyl hydroxy carboxylic acid, in some cases, the concentration of chelating agent can
In the range of 1-20g/L or 5-15g/L.When chelating agent is the pyridine compounds being substituted,
Under certain situation, the concentration of chelating agent can be in the range of 0.5-20g/L or 0.5-5g/L.Work as complexation
When agent is hydantoin, in some cases, the concentration of chelating agent can be in the range of 50-70g/L.
It is usable in the concentration beyond these scopes, and those skilled in the art will be easily by often
Rule experiment determines applicable concentration.
In some embodiments, ammonium ion can be included in electrolyte bath as chelating agent and in order to adjust
The pH of whole solution.Such as, in the range of electrodeposition bath can comprise 1-50g/L and 10-30g/L scope
Interior ammonium ion.Other concentration range is alternatively applicable.
In some cases, bath can include at least one wetting agent.It is heavy that wetting agent refers to reduce electricity
Any material of the ability that the surface tension of long-pending bath and/or increase bubble surface from bath depart from.Such as,
Substrate can comprise hydrophilic surface, and wetting agent can strengthen bathe relative to substrate the compatibility (such as,
Wettability).In some cases, the quantity of defect in wetting agent also can reduce produced metal coating.
Wetting agent can comprise organic substance, inorganic substances, organic metal material or combinations thereof.At some
In embodiment, wetting agent can be chosen and presents the compatibility with electrodeposition bath and component thereof (such as,
Dissolubility).Such as, wetting agent can be chosen and includes one or more hydroaropic substances, including
Amine, mercaptan, alcohol, carboxylic acid and carboxylate, sulfate, phosphate, Polyethylene Glycol (PEG) or poly-second two
The derivant of alcohol, in order to strengthen the water solublity of wetting agent.In some embodiments, wetting agent can wrap
Fluorine-containing surfactant.In some embodiments, wetting agent can includeFSJ(Dupont)、
CaptsoneTMOr Triton (Dupont)TMQS-15(Dow)。
The wetting agent of any applicable concentration can be used.Such as, the concentration of wetting agent can be between 10 microlitres
Between/L and 2000 microlitres/L, between 20 microlitres/L and 1000 microlitres/L or between 50 microlitres
Between/L and 500 microlitres/L.Other concentration range is alternatively applicable.
In some embodiments, bath can include at least one brightener.Brightener can be when being included in
Brightness and/or any thing of smoothness of produced electrodeposited coating is improved time in bath specifically described herein
Matter.In some cases, brightener is neutral substance.In some cases, brightener comprises charged
The material (such as, positively charged ion, electronegative ion) of lotus.In a set of embodiment,
Brightener can comprise at least one pyridine ring or at least one pyridine ring.In some embodiments,
Brightener comprises the bipyridyl being optionally substituted.
The brightener of any applicable concentration can be used.Such as, the concentration of brightener can be between 0.01g/L
And between 50g/L, between 0.01g/L and 10g/L, between 0.1g/L and 5g/L or
Between 0.1g/L and 1g/L.Other concentration range is alternatively applicable.
In some embodiments, brightener is 2,2-bipyridyl or 3-formoxyl-1-(3-sulfonate radical propyl group)
Pyridine.In bath 2, the concentration of 2-bipyridyl can between about 0.1g/L and about 5g/L, or between
Between 0.1g/L and about 1g/L, or between about 0.1g/L and about 0.8g/L.In concrete enforcement
In scheme, brightener is 2,2-bipyridyl, and its concentration is between about 0.2g/L and about 0.6g/L.?
In specific embodiment, brightener is 3-formoxyl-1-(3-sulfonate radical propyl group) pyridine, and its concentration is
About 2g/L.In one embodiment, electrodeposition bath comprises 2, and 2-bipyridyl is as brightener and wraps
Containing TritonTMQS-15 (Dow) is as wetting agent.
Those skilled in the art can select ionic species, the profit being suitably applicable to specifically apply
Humectant, chelating agent and/or the combination of other additive (such as, brightener).Generally, the interpolation in bath
Agent is compatible with electrodeposition technology, i.e. bath may be adapted to electro-deposition method.Those skilled in the art's energy
Enough identification is suitable to the bath of electro-deposition method.Equally, those skilled in the art is capable of identify that when adding
Make time in bath to bathe the additive being unsuitable for electro-deposition method.
In certain aspects, various technology can be used to monitor the content of electrodeposition bath.Such as, described
Technology can measure one or more additives in bath (such as brightener, wetting agent, chelating agent etc.)
Concentration.If the concentration of additive is below or above desirable concentration, then the composition of adjustable bath,
So that concentration is in desirable scope.
The pH of electrodeposition bath can be about 2.0 to 12.0.In some cases, electrodeposition bath can have about
7.0 to 9.0 or the most about 7.6 to 8.4 or the most about 7.9 to 8.1
pH.However, it should be understood that pH can be outside the above range.Those skilled in the art can be used
Any applicable reagent known adjusts the pH of bath.In some embodiments, alkali (such as hydroxide is used
Salt, such as potassium hydroxide) adjust the pH bathed.In some embodiments, acid (such as, nitric acid) is used
Adjust the pH of bath.
In some embodiments, electrodeposition bath comprises hydroxide salt.In particular embodiments,
Hydroxide salt is sodium hydroxide.In some cases, hydroxide salt is not potassium hydroxide.Do not wish
Prestige is limited to theory, and using sodium hydroxide in electrodeposition bath can be favourable compared with using potassium hydroxide
, because it can reduce and/or prevent to be formed in solution precipitation.Such as, in one embodiment,
When using the electrodeposition bath comprising potassium hydroxide, it was observed that tungsten oxide precipitates, and using hydrogen-oxygen
Change sodium substantially similar under conditions of do not observe precipitation.In some cases, when using hydroxide
During sodium, electrodeposition bath can have the pH of greater than about 6.5 to 9.0.In some cases, pH is between about
Between 6.5 and about 9.5, between about 6.5 and about 8.5, between about 7.0 and about 8.5, or
Between about between 6.5 and 8.0.In some cases, pH is less than 9.0, less than 8.5 or less than 8.0.
In one embodiment, electrodeposition bath comprises about 8g/L to about 9g/L silver ion material, about
27g/L tungsten ion material, and have less than about 8, greater than about 6.5 or between about between 6.5 and 8
PH.In another embodiment, electrodeposition bath comprise about 4g/L to about 5g/L silver ion material,
About 60g/L tungsten ion material, and have less than about 8.5, greater than about 6.5 or between about 6.5 and 8.5
Between pH.
In some cases, the opereating specification of electrodeposition bath specifically described herein be 5-100 DEG C, 10-70 DEG C,
10-30 DEG C, 25-80 DEG C, or in some cases, 40-70 DEG C.In some cases, temperature is less than
80℃.However, it should be understood that what other temperature range was likely to be suitable for.
Generally, electrodeposition bath can use in conjunction with any electro-deposition method.Electro-deposition is usually directed to by making
Substrate contacts with electrodeposition bath and makes between (that is, due to the electric potential difference between two electrodes) two electrodes
Coating is deposited on substrate by electric current flowing by electrodeposition bath.Such as, method specifically described herein
Can relate to provide anode, negative electrode, the electrodeposition bath of be connected with anode and negative electrode (such as, contact) and company
Receive the power supply of anode and negative electrode.In some cases, power supply can be driven to generate for producing coating
Waveform, as described more detail below.In some embodiments, at least one electrode can conduct
Substrate to be coated.
In some embodiments, electro-deposition system include anode, negative electrode, bathe and be connected to anode and
The power supply of at least one in negative electrode.In some cases, anode comprises silver (such as, wherein, anode
Silver ion material is provided to bath), and bathe and comprise tungsten and/or molybdenum ion material and optionally at least a kind of network
Mixture and/or other additive.In these embodiments, the anticathode surface area of surface area of anode
Ratio can be chosen and to bath provide proper amount of silver ion material.It is not intended to be limited to theory,
In the embodiment that the ratio of the anticathode surface area of surface area of anode is too small, anode can be passivated and
Silver ion material in solution will not be supplemented.In some cases, the table of anode (such as comprising silver)
Area is at least about 5 times, at least about 6 times, at least about 7 times of the surface area of negative electrode, at least about 8
Again, at least about 9 times or at least about 10 times.In particular embodiments, the surface area of anode is cloudy
At least about 5 times of the surface area of pole.
The anode comprising silver can substantially by silver is formed (such as, more than 95% silver medal, more than 97% silver medal, greatly
In 98% silver medal, more than 99% silver medal, more than 99.5% silver medal, more than 99.9% silver medal), or be not substantially
Formed by silver.In some cases, the anode comprising silver can be included in substrate (such as, conductive substrates)
The silver of upper formation.In some cases, the anode comprising silver also can comprise the metal that at least one is additional
(such as, tungsten), wherein, each additional metal may or may not provide metal ion species (example to bath
As, tungsten ion material).
Generally, during electro-deposition method, substrate to be coated can exist electromotive force, and apply
The change of voltage, electric current or electric current density may result in the change of electromotive force on substrate.In some cases,
Electro-deposition method can include using the waveform comprising one or more sections, wherein, each sheet
Section relates to one group of specific electrodeposition condition (such as, electric current density, current duration, electrodeposition bath
Temperature etc.).Waveform can have any shape, including square wave, the non-square wave etc. of arbitrary shape.One
In a little methods, such as, when forming the coating with different piece, waveform can have for forming difference
The different fragments of part.However, it should be understood that and not all method all uses the ripple with different fragments
Shape.
In some embodiments, unidirectional current (DC) deposition can be used to come electrodeposited coating or one part.
Such as, steady current can be made to pass through electrodeposition bath to produce coating or one part on substrate.?
In some embodiments, apply electromotive force in-between the electrodes (such as, electromotive force controls or Control of Voltage) and/
Or allow electric current or electric current density (such as, electric current or the electric current density control) alterable of flowing.Such as,
Pulse, vibration and/or other voltage, electromotive force, electric current and/or electric current can be included in during electro-deposition method
The change of density.In some embodiments, the pulse of controlled voltage can be close with controlled current flow or electric current
The pulse of degree is alternately.In some embodiments, coating can use pulse current electro-deposition, reverse arteries and veins
Rush electric current electro-deposition or a combination thereof and form (such as, electro-deposition).
In some cases, bipolar waveform, described waveform can be used to comprise at least one direct impulse
And at least one reverse impulse, i.e. " reverse impulse sequence ".As described above, specifically described herein
Electrodeposition bath is particularly suited for using composite wave-shape (such as reverse impulse sequence) deposition coating.Implement at some
In scheme, after at least one reverse impulse is next at least one direct impulse.Some embodiment party
In case, after at least one direct impulse is next at least one reverse impulse.In some cases,
Bipolar waveform includes multiple direct impulse and reverse impulse.Some embodiments can include comprising multiple
Direct impulse and the bipolar waveform of reverse impulse, each pulse has specific electric current density and continues
Time.In some cases, use bidirectional pulse train tolerable regulate produced coating composition and/
Or granularity.
Means of Electrodeposition can be made so that lacking 0.001A/cm2, at least 0.01A/cm2Or at least 0.02
A/cm2Electric current density applying coating.Can be used on the electric current density beyond these scopes.At some
In the case of, use and there is greater than about 10mA/cm2, greater than about 15mA/cm2, greater than about 20mA/cm2、
Greater than about 30mA/cm2Or greater than about 50mA/cm2The unidirectional current of unidirectional current density.Real at some
Executing in scheme, unidirectional current density is greater than about 15mA/cm2, and close at the electric current less than this level
Under degree, only silver is deposited.
For the electric current applied with pulse, frequency can be that any applicable frequency is (such as, between 0.1 hertz
Hereby and between about 100 hertz).Similarly, voltage can be any applicable voltage (such as, Jie Yuyue
Between 0.1V and about 1V).
The sedimentation rate of coating can be controlled.In some cases, sedimentation rate can be at least 0.1 micron/
Minute, at least 0.3 [mu, at least 1 [mu or at least 3 [mu.It is used as
Sedimentation rate beyond these scopes.
Those skilled in the art will realize that electro-deposition method specifically described herein can be different from master
Want or use chemical reducing agent deposition coating completely rather than execute alive without method for electrically.Institute herein
The electrodeposition bath stated can be substantially upper without such as there is not the chemistry applying to deposit coating under voltage
Reducing agent.
Electro-deposition system/method may utilize entitled " Method for Producing Alloy Deposits
and Controlling the Nanostructure Thereof using Negative Current Pulsing
Electro-deposition, and Articles Incorporating Such Deposits " United States Patent (USP) open
Some aspect of method/system described in case the 2006/02722949th, the full text of described case
Incorporated herein by reference.The aspect of other electro-deposition method/system is the most applicable, including the U.S.
Patent publication the 2006/0154084th and U. S. application case the 11/985,569th are (entitled
“Methods for Tailoring the Surface Topography of a Nanocrystalline or
Amorphous Metal or Alloy and Articles Formed by Such Methods ", in
11/15/07 files an application)；United States Patent (USP) publication the 20090286103rd and U.S. patent application case
No. 12/120,564 (filing an application on May 14th, 2008)；U. S. application case the 12/723,020th
Number (entitled " Electrodeposition Baths and Systems ", file an application in 03/12/10)；And
U. S. application case the 12/723rd, 044 (entitled " Coated Articles and Methods ", in
03/12/10 files an application) described in those, being incorporated by reference in its entirety herein of described case.
Fig. 2 shows the goods 20 according to embodiment.Goods have the coating formed on base material 24
22.In some embodiments, coating includes multiple layer.In some embodiments, coating can be wrapped
Include the ground floor 26 formed on base material and the second layer 28 formed on the first layer.Each layer can use suitable
The method coating closed, as described in greater detail below.Should be understood that coating can include more than two-layer.Also
Should be understood that coating can only include one layer.But, in some embodiments, coating can only include two
Layer, as shown.In some cases, coating can substrate surface at least some of on formed.?
In the case of other, coating covers whole substrate surface.
In some embodiments, coating comprises one or more metals.Such as, coating can be wrapped
Metal-containing alloy.In some cases, the alloy (that is, silver-base alloy) comprising silver is preferred.This type of alloy
Also tungsten and/or molybdenum can be comprised.In some cases, silver-tungsten alloy can be preferred.Some embodiment party
In case, silver-molybdenum alloy is also feasible.In some cases, tungsten and/or the atomic percent of molybdenum in alloy
Ratio can be between 0.1 atomic percent and 50 atomic percents；Further, in some cases, it is situated between
Between 0.1 atomic percent and 20 atomic percents.In some embodiments, in alloy tungsten and/
Or the atomic percent of molybdenum can be at least 0.1 atomic percent, at least 1 atomic percent, at least 1.5
Atomic percent, at least 5 atomic percents, at least 10 atomic percents or at least 20 atomic percent
Ratio.Can be used on other atomic percent beyond this scope.
In some embodiments, silver-base alloy can form the ground floor 26 of coating.Some embodiment party
In case, the second layer 28 comprising one or more noble metals can form the second layer of coating.In some feelings
Under condition, the ground floor comprising silver alloy is formed on base material, and comprises one or more noble metals
The second layer is formed on the first layer.The example of noble metal being suitable for include Ru, Os, Rh, Re, Ir,
Pd, Pt, Ag, Au or their any combination.In some embodiments, Jin Kewei is preferred.
In some embodiments, layer is substantially made up of a kind of noble metal.In some embodiments, layer (example
Such as, the second layer) the most stanniferous be preferred.In other cases, layer can comprise alloy, described alloy
Including at least one noble metal and at least one other element.Described element be especially selected from Ni, W,
Fe, B, S, Co, Mo, Cu, Cr, Zn and Sn.Such as, layer can comprise Ni-Pd alloy, Au-Co
Alloy and/or Au-Ni alloy.
In some embodiments, coating can include the layer (such as nickel alloy, such as nickel-tungsten) comprising nickel.
In some cases, the layer comprising nickel can be disposed between base material and silver-base alloy layer.An enforcement
In scheme, coating include the ground floor comprising nickel, the second layer comprising silver-base alloy and comprise one or
The third layer of multiple noble metal, wherein, ground floor is formed on base material, second layer shape on the first layer
Become, and third layer is formed on the second layer.
The layer of coating can have any applicable thickness.In some embodiments, layer is relatively thin so that example
Can be favourable as saved material cost.In some embodiments, layer (such as, silver-base alloy layer)
Thickness be smaller than about 1000 microinch (such as, between about 1 microinch and about 1000 microinch,
Between about 1 microinch and about 750 microinch, between about 1 microinch and about 500 microinch it
Between, between about 1 microinch and about 100 microinch, between about 1 microinch and 50 microinch it
Between).The thickness of layer is smaller than about 500 microinch or less than 250 microinch (such as, between about 1 microinch
Between very little and 250 microinch).In some cases, the thickness of layer can be the thinnest.Such as, the thickness of layer
Degree is smaller than 30 microinch (such as, between about 1 microinch and about 30 microinch；In some feelings
Under condition, between about 5 microinch and about 30 microinch)；In some cases, the thickness of layer can
Less than 20 microinch (such as, between about 1 microinch and about 20 microinch；In some cases,
Between about 5 microinch and about 20 microinch)；Further, in some cases, the thickness of layer can
Less than 10 microinch (such as, between about 1 microinch and about 10 microinch；In some cases,
Between about 5 microinch and about 10 microinch).In some embodiments, the thickness of layer is selected
So that layer substantial transparent from the teeth outwards.Should be understood that what other layer thickness was alternatively suitable for.
The second layer can cover whole ground floor.However, it should be understood that in other embodiments, second
Layer only covers a part for ground floor.In some cases, the second layer covers the surface area of ground floor
At least 50%；In other cases, at least the 75% of the surface area of ground floor.In some cases,
Element from ground floor can be included in the second layer and/or can include ground floor in from the element of the second layer
In.
In some embodiments, ground floor is directly formed on base material can be preferred.These are implemented
It can be preferred that scheme utilizes the prior art of the layer between ground floor and base material to construct compared to some
, because there is not this type of intermediate layer can save total material cost.However, it is understood that it is real at other
Execute in scheme, one or more layers can be formed between ground floor and base material.Such as, at some
In embodiment, barrier layer can be formed between base material and ground floor.Barrier layer can comprise metal.?
In some embodiments, barrier layer comprises nickel.In some cases, barrier layer comprises nickel-tungsten or amino
Nickel sulphonic acid.
In some embodiments, lubricating layer can be formed as the upper part of coating.Lubricating layer can wrap
Containing such as organic material, self-assembled monolayer, CNT etc..In some cases, with substantially class
Like but do not include that the coating of lubricating layer is compared, the existence of lubricating layer reduces the coefficient of friction of coating.Lubrication
Layer can be formed by any applicable material, the most halogen-containing organic lubricant, organic profit containing polyphenyl
Lubrication prescription or the lubricant containing polyethers.In one embodiment, lubricating layer is by halogen-containing organic lubrication
Agent is formed.The concrete limiting examples of lubricant includes EvabriteTM(Enthone)、Au lube
(AMP)、570H(Nye Lubricants)、FS-5(Gabriel Performance
Products), S-30 (Gabriel Performance Products) and MS-383H
(Miller-Stephenson).In some cases, lubricating layer comprises the list formed on the surface of the coating
Layer.
Those skilled in the art forms the appropriate methodology of lubricating layer in coating by knowing.Such as,
In some embodiments, can make to include that the goods of coating are exposed to (such as, being immersed into wherein) lubricant
(such as, optionally in solution form), and goods can be subsequently dried, thus at the upper part of coating
Upper formation lubricating layer.
In some embodiments, the system of the lubricating layer that (such as, on base material) is formed it is included in coating
Product with do not include lubricating layer substantially like the coefficient of friction can compared with goods with reduction.At some
In the case of, the coefficient of friction of the goods with lubricating layer is the coefficient of friction of the goods without lubricating layer
At most 1/2nd, at most 1/3rd, at most 1/4th, at most 1/5th or at most ten
/ mono-.
In some cases, there are the goods of lubricating layer with do not have lubricating layer substantially like goods
Compare and can have preferable wear durability.Those skilled in the art will know applicable mensuration material
(such as, ball grinds the method for the wear durability of material at flat board mo(u)ld top half (ball-on-plate-type) reciprocating friction
Corrosion test, wherein, ball and flat board both of which are coated with alloy-layer and optionally lubricating layer).Such as, exist
In some embodiments, for including the goods of silver-base alloy and lubricating layer, under 100g applies load,
Through 50 circulations, 100 circulations, 250 circulations, 500 circulations or 1000 circulation observables
To the most worn out or do not observe worn out, wherein, do not include can showing substantially like goods of lubricating layer
Show serious or the most worn out.
In some cases, coating (such as, ground floor and/or the second layer) can have specific micro structure.
Such as, coating can have nanocrystalline microstructure at least partially.As used herein, " nanometer
Crystallization " structure refers to the quantity average-size of the crystal grain structure less than 1 micron.The average chi of quantity of crystal grain
The very little statistical weight equal for the offer of each crystal grain, and it is calculated as in the representative volume of main body all
The summation of the ball equivalent diameter of crystal grain is divided by total number of die.In some embodiments, the quantity of crystal grain
Average-size is smaller than 100nm.In some cases, silver-base alloy has less than silver-base alloy layer
The number average particle size of the 50% of thickness.In some cases, number average particle size is smaller than money base conjunction
The 10% of the thickness of layer gold.In some embodiments, coating can have at least partially amorphous
Structure.As known in the art, impalpable structure is to be characterised by not having on a large scale at atom site
Symmetrical non-crystalline structure.The example of impalpable structure includes glass or vitreous texture.Some are implemented
Scheme may be provided in the coating in the most whole coating with nanocrystalline structures.Some embodiments
May be provided in the coating in the most whole coating with impalpable structure.
In some embodiments, coating can be the crystalline solid with face-centred cubic structure.Real at some
Executing in scheme, coating can be solid solution, wherein, constitutes the metal of coating basically as single former
Son dispersion.This class formation can make Means of Electrodeposition produce.Solid solution can be different from and such as use nothing
The alternative structure that method for electrically is formed, in alternative structure, is constituted containing the first metallics (that is, tungsten
And/or molybdenum) the granule of the first phase be scattered in the second phase constituted containing the second metallics (that is, silver)
Coating in, the second phase has different compositions and/or crystal structure from the first phase.In some cases,
Solid solution can be substantially free of oxygen.
In some embodiments, coating can comprise multiple part with different micro structure.Such as,
Ground floor can have different micro structures from the second layer.Coating can include such as one or more tools
Have the part of nanocrystalline structures and one or more there is the part of impalpable structure.A set of
In embodiment, coating comprises nanocrystal and other presents the part of impalpable structure.In some feelings
Under condition, coating or one part (such as a, part for ground floor, a part for the second layer or ground floor
And the part both the second layer) part with crystal grain can be comprised, major part crystal grain has diameter and is more than
The granularity of 1 micron.In some embodiments, coating can include other structure or phase, individually or with receive
Rice crystalline portion or pars amorpha subassembly.Those skilled in the art can select to be suitable for this
Other structure of summary of the invention or phase.
Advantageously, coating (that is, ground floor, the second layer or ground floor and the second layer both) can the most not
Containing having high toxicity or the element of other shortcoming or compound.In some cases, additionally advantageously, it is coated with
Layer is substantially free of element or the compound using the electrodeposition substance with high toxicity or other shortcoming.Example
As, in some cases, coating is without chromium ion material (such as, the Cr generally using toxicity6+) deposition
Chromium (such as, chromated oxide).In some cases, coating can be sunk by the electricity being substantially free of cyanide
Long-pending bath deposition forms.This type coating can provide multiple and be better than some first process of Front-coating mirror, health and ring
Border advantage.
In some embodiments, the coating (such as, alloy) of electro-deposition can be porous.At some
In the case of, coating has at least 5%, at least 10%, at least 15%, at least 20%, at least 25%,
The porosity of at least 30% or at least 50%.In some cases, coating have between about 5% with about
Porosity between 30% or between about 10% and about 25%.In some cases, for comprising
Tungsten and/or the silver-base alloy of molybdenum, can percentage ratio based on the tungsten contained in alloy change and/or control hole
Rate.In particular embodiments, the silver of the tungsten and/or molybdenum for comprising at least 1.5 atomic percents
Base alloy, coating has at least about 10% or porosity between about 10% and about 25%.
Those skilled in the art will know the method for the porosity measuring coating (such as, alloy), bag
Include but be not limited by optics and/or density method directly measures porosity.In some cases, can make
Optically measure porosity, wherein, by obtaining the image of the cross section of coating and calculating hole (example
As, in some cases, can observe as black speck) area to measure porosity.Assuming that hole is whole
Individual coating is uniform, the volume fraction in hole can be calculated.
In some embodiments, can include in coating metal, nonmetal and/or metalloid material,
Salt etc. (such as, phosphate, or redox mediators, the such as potassium ferricyanide, or its fragment).
The composition of coating or its part or layer can use applicable technology as known in the art to characterize, example
Such as Auger electron spectroscopy (AES), x-ray photoelectron power spectrum (XPS) etc..Such as, can use AES and
/ or XPS characterize the chemical composition on surface of coating.
Coating can have any thickness being suitable for for application-specific.Such as, the thickness of coating can be more than
About 1 microinch (such as, between about 1 microinch and about 1000 microinch, between about 1 microinch
Between very little and about 750 microinch, between about 1 microinch and about 500 microinch, between about 1
Between microinch and about 100 microinch, between about 1 microinch and 50 microinch)；At some
In the case of, greater than about 5 microinch are (such as, between about 5 microinch and about 100 microinch, Jie
Between about 5 microinch and 50 microinch)；Greater than about 25 microinch are (such as, between about 25 microinch
Between very little and about 100 microinch, between about 1 microinch and 50 microinch).Should be understood that it
Its thickness is alternatively applicable.In some embodiments, select the thickness of coating so that coating
Substantial transparent from the teeth outwards.Thickness can be measured by technology known to those skilled in the art.
Base material 30 can be coated to form coating goods, as described above.In some cases, base material
Conductive material, such as metal, metal alloy, intermetallic material etc. can be comprised.The base material being suitable for includes
Steel, copper, aluminum, pyrite, bronze, nickel, have conductive surface and/or surface treated polymer,
Transparent conductive oxide and other.In some embodiments, Copper base material is preferred.
Goods can use in numerous applications, including electricity application, such as electric connector (such as, plug-in type).
In some embodiments, the coating on electric connector includes the ground floor comprising silver alloy, ground floor
It is arranged on base material；And comprising the second layer of noble metal, the second layer is arranged on ground floor.Coating can
Give the feature that goods are desirable, such as durability, hardness, corrosion resistance, heat stability and reduction
Resistivity.These character are especially advantageous for the goods for electricity application (such as electric connector), these systems
Product be connected to circuit and/or from circuit disconnect after can experience friction or abrasion stress and can damage or reduce
The electrical conductivity of the conductive layer on goods.The limiting examples of electric connector include infrared connector,
USB connector, battery charger, battery contact, automobile electric connector etc..Some embodiment party
In case, the existence of the ground floor of coating can be that coating provides at least some durability and corrosion resistance.?
In some embodiments, coating can give decoration character, the such as blue and variable color that weakens.It addition,
The thickness of the existence tolerable second layer of ground floor reduces, thus significantly reduces the amount of noble metal in goods.
Coating specifically described herein can give the character that goods (such as electric connector) are favourable.Implement at some
In scheme, the layer of coating or coating can have low-resistivity.Such as, resistivity be smaller than 100 micro-ohms-
Centimetre, less than 50 microohm-cm, less than 10 microohm-cm or less than 2 microohm-cm.
The layer of coating or coating can have at least 1GPa, at least 1.5GPa, at least 2GPa, at least
2.5GPa or at least 3GPa or the hardness between about 2.0GPa and about 3.0GPa.Affiliated neck
The technical staff in territory can be easily determined by these character.In some cases, comprise silver-base alloy and
The coating of lubricating layer can have at least 1GPa, at least 1.5GPa, at least 2GPa, at least 2.5GPa
Or the hardness of at least 3GPa and less than about 1.0, less than about 0.75, less than about 0.5, less than about 0.4,
Less than about 0.3, less than about 0.2 or the coefficient of friction of less than about 0.1.In some embodiments, firmly
Degree is between about 2.0GPa and about 3.0GPa, and coefficient of friction is less than about 0.3, or between about
Between 0.3 and about 0.1.
The layer of coating or coating can be heat-staple.In some cases, tungsten and/or molybdenum are comprised further
And the coating comprising silver-base alloy with the granularity of less than about 100nm is being exposed to the temperature of raising
Present the change of less granularity after long period or do not present granularity change.In some cases, cruelly
Being exposed to the temperature of at least 125 DEG C after at least 1000 hours, the granularity change of coating is not greater than about 30nm,
It is not greater than about 20nm, no more than about 15nm, no more than about 10nm or no more than about 5nm.?
Under certain situation, after being exposed to the temperature at least about 1000 hours of about 125 DEG C, granularity change is little
In about 30nm, no more than about 20nm, no more than about 15nm, no more than about 10nm or be not more than
About 5nm.Heat stability can measure, such as, at about 150 DEG C at least under conditions of other is suitable for
About 24 hours, at about 200 DEG C at least about 24 hours, at about 250 DEG C at least about 24 hours,
Or at about 200 DEG C at least about 120 hours.It addition, in the temperature at least about 1000 being exposed to about 125 DEG C
After hour, the contact resistance alterable of coating is less than about 25%, and less than about 20%, less than about 15%,
Less than about 10%, or less than about 5%.
Those skilled in the art will know the appropriate methodology of the heat stability measuring material.At some
In the case of, heat stability can be by observing during beat exposure and/or the micro structure of before and afterwards material
Change (such as, grain growth, phase in version etc.) measures.Heat stability can use differential scanning calorimetry
(DSC) or differential thermal analysis (DTA) measures, wherein, heating material under controlled conditions.For measuring
The change of granularity and/or phase in version, can implement x-ray experiment in situ during heating process.
As described above, coating 20 can make Means of Electrodeposition be formed.In some cases, coating
Each layer can use single electrodeposition bath to coat.In some cases, can couple together by single goods,
So that they can be exposed to single electrodeposition bath in order, such as in reel-to-reel (reel-to-reel) method
In.Such as, goods can be connected to common conductive substrates (such as, band).In some embodiments
In, each electrodeposition bath can be connected with single anode, and the independent goods interconnected are usual
May be connected to negative electrode.
In some embodiments, present invention offer can be in one or more potential corrosive environments
Opposing is corroded and/or protects following backing material to avoid the coating goods of corrosion.This type of corrosive environment
Example includes but not limited to aqueous solution, acid solution, alkali or alkaline solution or combinations thereof.Such as,
Coating goods specifically described herein can being exposed to (such as, be in contact with it, be immersed in it medium) corrosion ring
Corrosion is resisted in border (such as, corrosive liquids, steam or wet environment) afterwards.
Corrosion resistance can use such as ASTM B845 (entitled " Standard Guide for Mixed
Flowing Gas (MFG) Tests for Electrical Contacts ") etc. test follow IIa class scheme and carry out
Evaluate it can also be used to evaluate the corrosion resistance of coating goods.These test general introductions make the substrate of coating try
Sample is exposed to aggressive atmosphere (that is, NO2、H2S、Cl2And SO2Mixture) program.Flowing gas
The mixture of body can comprise 200+/-50ppb NO2、10+/-5ppb H2S、10+/-3ppb Cl2And
100+/-20ppb SO2.Also temperature controllable and relative humidity.Such as, temperature can be 30+/-1 DEG C,
And relative humidity can be 70+/-2%.
Can according to the one in above-mentioned test, being exposed to before corrosive environment sets the time period and/or
Measure the low-level contact resistance of sample afterwards.In some embodiments, low-level contact resistance can
Test procedure 23 according to specification EIA364 measures.Generally, the contact resistivity of sample can be by making
Sample under given load and electric current with there is that define and sample contacts cross-sectional area mensuration probe
Contact measures.Such as, low-level contact resistance can be in 25g, 50g, 150g, 200g even load
Lower mensuration.Generally, low-level contact resistance increases with load and reduces.
In some embodiments, coating goods have the low-level contact resistance of reduction.That reduces is low
Flat contact resistance can be useful for the goods in electricity application (such as electric connector).At some
In the case of, goods can have less than about 100mOhm, the least under the load of 25g
In about 10mOhm, it is less than about 5mOhm and in some cases less than about 1 in some cases
The low-level contact resistance of mOhm.Should be understood that goods also can have the low water beyond this scope
Flat contact resistance.Should also be understood that the contact cross-sectional area measuring probe can affect measured low-level
The value of contact resistance.
Following example are not construed as restrictive, but illustrate some feature of the present invention.
Embodiment
Embodiment 1
This embodiment show reach with multiple sample coating layer thickness, W content, granularity, coating hardness
And contact resistance.
Means of Electrodeposition is made to make coating electro-deposition in aqueous electrodeposition bath on base material.Electrodeposition bath
Containing silver ion material, tungsten ion material and chelating agent.Coating is made directly to be formed on base material substrate.
It addition, for sample 28-35, make nickel dam before electro-deposition silver-base alloy electro-deposition on substrate.
Table 1 and table 2 show the result that these coatings obtain.
Thickness, W content, granularity and the hardness of the various sample of table 1..N.D.=undetermined.
Substrate, W content and the contact resistance of the various sample of table 2..N.D.=undetermined.
Embodiment 2
This embodiment shows the coating abrasion durability of the material comprising lubricating layer.
Make the electro-deposition as described in Example 1 of silver-tungsten alloy in two spherical surfaces and two flat boards
On surface.Alloy comprises about 5wt% tungsten, and the thickness of coating is about 80 microinch.Coating hard
Degree is about 2.0-2.5GPa.After electro-deposition, simple dip-coating method as known in the art is used to exist
Lubricating layer is formed on one spherical surface and a planar surface.In this embodiment, lubricant is
EvabriteTM.Following wear durability of implementing is studied: by the flat board table of the spherical surface of coating with coating
Face contact is placed；Subsequently, planar surface is made to be ground toward each other by linear reciprocal movement with spherical surface
Damage.As shown in Figure 3, do not include that goods (Fig. 3 A) display after 25 circulations of lubricating layer is obvious
Worn out, and include that the goods (Fig. 3 B) of lubricating layer even the most do not show mill after 100 circulations
Wear.The coefficient of friction of the goods without lubricating layer is about 1.0, and includes the friction of the goods of lubricating layer
Coefficient is about 0.2.
Embodiment 3
This embodiment shows the electrodeposited coating of the silver alloy comprising the tungsten with Different Weight percentage ratio
The change of porosity.
Fig. 4 A-4C show comprise A according to the method electro-deposition described in embodiment 1) 2.3wt% tungsten,
B) 4.5wt% tungsten and C) scanning electron micrograph of cross section of silver-tungsten alloy of 8.7wt% tungsten.Figure
4D shows the porosity of the silver-tungsten alloy according to some the embodiment electro-deposition figure to the wt% of tungsten.
Embodiment 4
This embodiment shows the use electrodeposition bath containing at least one brightener.
According to the method Electrodeposited Silver-tungsten alloy described in embodiment 1.In the first scenario, bath contains
There is the 2,2-bipyridyl brightener of about 0.2g/L to 0.5g/L concentration.2,2-bipyridyl is dissolved in second two
In alcohol, subsequently this brightener is added in bath.In another case, bath is containing about 2g/L concentration
3-formoxyl-1-(3-sulfonate radical propyl group) pyridine brightener.In both cases, close at all electric currents
Under degree, coating is bright.
Embodiment 5
This embodiment shows the heat stability of silver-tungsten alloy.
By the most electric for silver-tungsten alloy coating of comprising the tungsten of multiple percentage by weight
It is deposited on base material.The temperature making goods be exposed to raising reaches the selected time period.Fig. 5 A shows alloy
The granularity (nm) figure to tungsten percentage by weight.Fig. 5 B shows and is coated with EvabriteTMThe silver of lubricant
The contact resistance of-tungsten coating the figure to applying load, is heated to 125 DEG C by described coating, keeps 1000
Hour.
Embodiment 6
This embodiment shows the cathodic surface area change to the ratio of anode surface area.
By the electro-deposition as described in Example 1 of silver-tungsten alloy coating on base material, wherein, from certainly
Consumption silver anode provides silver ion material to bath.In this embodiment, the surface area of anode is the table of negative electrode
3.5 times of area or 5 times.At anode: the surface area ratio of negative electrode is under 3.5:1, anodic passivity, and
And the silver ion material in solution can not be supplemented.At anode: the surface area ratio of negative electrode is under 5:1,
Silver concentration generally remains constant (see Fig. 6).
Embodiment 7
This embodiment show the pH of electrodeposition bath change and with the relation of the W content in alloy.
By the electro-deposition as described in Example 1 of silver-tungsten alloy coating on base material.Use hydroxide
Sodium adjusts the pH of electrodeposition bath.The figure of electric current density is shown in Fig. 7 by W content.
Embodiment 8
This embodiment shows the change of the additive in order to the pH adjusting electrodeposition bath.
By silver-tungsten alloy coating as described in Example 1 from multiple bath electro-deposition in base material.Make
The pH of electrodeposition bath is adjusted with sodium hydroxide, sodium carbonate, potassium hydroxide or potassium carbonate.For containing hydrogen
Sodium oxide or the bath of sodium carbonate, do not observe precipitation (such as, tungsten oxide).By contrast, containing
The bath of potassium hydroxide or potassium carbonate is observed precipitation (see Fig. 8).
Claims (49)
1. goods, comprising:
Base material；And
The coating formed on the substrate, described coating comprises silver-base alloy, and described silver-base alloy enters
One step comprises tungsten and/or molybdenum, and described silver-base alloy has the granularity less than 100nm, wherein, cruelly
Being exposed to the temperature of at least 125 DEG C after at least 1000 hours, the change of described granularity is not more than 30nm,
It is characterized in that, described silver-base alloy is solid solution.
Goods the most according to claim 1, wherein, described goods are electric components.
Goods the most according to claim 2, wherein, described base material is conductive base.
Goods the most according to claim 1, wherein, described silver-base alloy contains 0.1 atom hundred
Proportion by subtraction is to the tungsten of 50 atomic percents and/or molybdenum.
Goods the most according to claim 1, wherein, described coating has more than 5 microinch
Thickness.
Goods the most according to claim 1, wherein, the change of described granularity is not more than 20nm.
Goods the most according to claim 1, wherein, described coating makes Means of Electrodeposition be formed.
Goods the most according to claim 1, wherein, described coating is formed in bath.
Goods the most according to claim 1, wherein, described base material comprises copper.
Goods the most according to claim 1, wherein, described coating farther includes to comprise nickel
Layer.
11. goods according to claim 1, wherein, described coating farther include to comprise Ru,
Os, Rh, Re, Ir, Pd, Pt, Ag, Au or the layer of combinations thereof.
12. 1 kinds of goods, comprising:
Base material；
The coating formed on the substrate, described coating comprises silver-base alloy, and described silver-base alloy enters
One step comprises tungsten and/or molybdenum, and wherein, in described silver-base alloy, the concentration of tungsten and/or molybdenum is at least 1.5 former
Sub-percentage ratio, and described silver-base alloy has the particle mean size less than 1 micron；And
The lubricating layer formed in described coating,
It is characterized in that, described silver-base alloy is solid solution.
13. goods according to claim 12, wherein, described goods are electric components.
14. goods according to claim 13, wherein, described base material is conductive base.
15. goods according to claim 12, wherein, described silver-base alloy contains 1.5 atoms
Percentage ratio is to the tungsten of 50 atomic percents and/or molybdenum.
16. goods according to claim 12, wherein, described coating has more than 5 microinch
Thickness.
17. goods according to claim 12, wherein, described lubricating layer is halogen-containing lubrication
Agent, the lubricant containing polyphenyl or the lubricant containing polyethers.
18. goods according to claim 12, wherein, described coating makes Means of Electrodeposition shape
Become.
19. goods according to claim 12, wherein, described coating is formed in bath.
20. goods according to claim 12, wherein, described base material comprises copper.
21. goods according to claim 12, wherein, described coating farther includes to comprise nickel
Layer.
22. goods according to claim 12, wherein, described coating farther include to comprise Ru,
Os, Rh, Re, Ir, Pd, Pt, Ag, Au or the layer of combinations thereof.
23. goods according to claim 12, wherein, the coefficient of friction of described goods is not wrap
Include the goods of described lubricating layer coefficient of friction at most 1/2nd.
24. goods according to claim 12, wherein, the coefficient of friction of described goods is not wrap
Include the goods of described lubricating layer coefficient of friction at most 1/3rd.
25. 1 kinds of goods, comprising:
Base material；
The coating formed on the substrate, described coating comprises silver-base alloy, and described silver-base alloy enters
One step comprises tungsten and/or molybdenum；And
The lubricating layer formed in described coating,
Wherein, the hardness of described goods is more than 1Gpa, and coefficient of friction is less than 0.3,
It is characterized in that, described silver-base alloy is solid solution.
26. goods according to claim 25, wherein, described goods are electric components.
27. goods according to claim 26, wherein, described base material is conductive base.
28. goods according to claim 25, wherein, described silver-base alloy contains 0.1 atom
Percentage ratio is to the tungsten of 50 atomic percents and/or molybdenum.
29. goods according to claim 25, wherein, described coating has more than 5 microinch
Thickness.
30. goods according to claim 25, wherein, the described hardness of described alloy is between 1.5
Between Gpa and 3.0Gpa.
31. goods according to claim 25, wherein, described coating makes Means of Electrodeposition shape
Become.
32. goods according to claim 25, wherein, described coating is formed in bath.
33. goods according to claim 25, wherein, described base material comprises copper.
34. goods according to claim 25, wherein, described coating farther includes to comprise nickel
Layer.
35. goods according to claim 25, wherein, described coating farther include to comprise Ru,
Os, Rh, Re, Ir, Pd, Pt, Ag, Au or the layer of combinations thereof.
36. goods according to claim 25, wherein, the coefficient of friction of described goods is not wrap
Include the goods of described lubricating layer coefficient of friction at most 1/2nd.
37. goods according to claim 25, wherein, the coefficient of friction of described goods is not wrap
Include the goods of described lubricating layer coefficient of friction at most 1/3rd.
38. 1 kinds of goods, comprising:
Base material；And
The coating formed on the substrate, described coating comprises silver-base alloy, and described silver-base alloy enters
One step comprises tungsten and/or the molybdenum of at least 1.5 atomic percents,
Wherein, described coating has the porosity of at least 10%,
It is characterized in that, described silver-base alloy is solid solution.
39. according to the goods described in claim 38, and wherein, described coating has 10% to 25%
Porosity.
40. according to the goods described in claim 38, and wherein, described goods are electric components.
41. goods according to claim 40, wherein, described base material is conductive base.
42. according to the goods described in claim 38, and wherein, described silver-base alloy contains 0.1 atom
Percentage ratio is to the tungsten of 50 atomic percents and/or molybdenum.
43. according to the goods described in claim 38, and wherein, described coating has more than 5 microinch
Thickness.
44. according to the goods described in claim 38, and wherein, described silver-base alloy has face-centered cubic
Structure.
45. according to the goods described in claim 38, and wherein, described coating makes Means of Electrodeposition shape
Become.
46. according to the goods described in claim 38, and wherein, described coating is formed in bath.
47. according to the goods described in claim 38, and wherein, described base material comprises copper.
48. according to the goods described in claim 38, and wherein, described coating farther includes to comprise nickel
Layer.
49. according to the goods described in claim 38, wherein, described coating farther include to comprise Ru,
Os, Rh, Re, Ir, Pd, Pt, Ag, Au or the layer of combinations thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201611001346.9A CN106947986B (en) | 2011-09-14 | 2012-09-14 | Coat product, electrodeposition bath and related system |
Applications Claiming Priority (5)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US13/232,261 US20120118755A1 (en) | 2010-03-12 | 2011-09-14 | Coated articles, electrodeposition baths, and related systems |
| US13/232,261 | 2011-09-14 | ||
| US13/232,291 US20120121925A1 (en) | 2010-03-12 | 2011-09-14 | Coated articles, electrodeposition baths, and related systems |
| US13/232,291 | 2011-09-14 | ||
| PCT/US2012/055495 WO2013040400A1 (en) | 2011-09-14 | 2012-09-14 | Coated articles, electrodeposition baths, and related systems |
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| CN201611001346.9A Division CN106947986B (en) | 2011-09-14 | 2012-09-14 | Coat product, electrodeposition bath and related system |
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| EP (1) | EP2755819B1 (en) |
| JP (1) | JP6159726B2 (en) |
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| WO (1) | WO2013040400A1 (en) |
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| JP6159726B2 (en) * | 2011-09-14 | 2017-07-05 | エクスタリック コーポレイションＸｔａｌｉｃ Ｃｏｒｐｏｒａｔｉｏｎ | Coated products, electrodeposition baths, and related systems |
| JP2015014019A (en) * | 2013-07-03 | 2015-01-22 | パナソニック株式会社 | Surface treatment method of electrical contact, electrical contact member, connector and contact treatment agent |
| CN107250430A (en) * | 2016-02-16 | 2017-10-13 | 思力柯集团 | Product and method including laminated coating |
| CN106521284A (en) * | 2016-11-24 | 2017-03-22 | 苏州华意铭铄激光科技有限公司 | Composite resistance strain material for high-performance electrical equipment |
| KR101913568B1 (en) * | 2017-04-26 | 2018-10-31 | 재단법인대구경북과학기술원 | Porous acupuncture-needle plated noble metal-nanoparticles and Manufacturing method thereof |
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| US3762882A (en) * | 1971-06-23 | 1973-10-02 | Di Coat Corp | Wear resistant diamond coating and method of application |
| GB1418108A (en) * | 1972-09-12 | 1975-12-17 | Siemens Ag | Preparation of a catalytic material |
| SU1035655A1 (en) * | 1980-12-12 | 1983-08-15 | Предприятие П/Я А-1955 | Electrochemical controllable resistor |
| JPS61248314A (en) * | 1985-04-24 | 1986-11-05 | 松下電工株式会社 | Making of contact material |
| US5225253A (en) * | 1992-04-17 | 1993-07-06 | General Motors Corporation | Method of forming silver/molybdenum surface coating material |
| US5525206A (en) * | 1995-02-01 | 1996-06-11 | Enthone-Omi, Inc. | Brightening additive for tungsten alloy electroplate |
| JPH10302866A (en) * | 1997-04-28 | 1998-11-13 | Harness Sogo Gijutsu Kenkyusho:Kk | Connection terminal of fitting type |
| JP2003183882A (en) * | 2001-12-11 | 2003-07-03 | Kobe Steel Ltd | Tinned electronic material |
| SG121757A1 (en) * | 2003-02-11 | 2006-05-26 | Agency Science Tech & Res | Thin film magnetic recording media |
| JP2005062624A (en) * | 2003-08-18 | 2005-03-10 | Seiko Epson Corp | Reflective film and its manufacturing method, color filter and its manufacturing method, and substrate for electrooptical device, electrooptical device, and electronic equipment |
| US7320832B2 (en) * | 2004-12-17 | 2008-01-22 | Integran Technologies Inc. | Fine-grained metallic coatings having the coefficient of thermal expansion matched to the one of the substrate |
| JP4176081B2 (en) * | 2005-01-19 | 2008-11-05 | 日本航空電子工業株式会社 | Contact manufacturing method |
| WO2006100917A1 (en) * | 2005-03-22 | 2006-09-28 | Tanaka Kikinzoku Kogyo K.K. | Light emitting element reflector, manufacturing method thereof, and light emitting device using the reflector |
| US7695808B2 (en) * | 2005-11-07 | 2010-04-13 | 3M Innovative Properties Company | Thermal transfer coating |
| JP5144302B2 (en) * | 2007-02-20 | 2013-02-13 | 株式会社神戸製鋼所 | Reflective film laminate |
| US9005420B2 (en) * | 2007-12-20 | 2015-04-14 | Integran Technologies Inc. | Variable property electrodepositing of metallic structures |
| JP2012508322A (en) * | 2008-11-07 | 2012-04-05 | エクスタリック コーポレイション | Electrodeposition bath, electrodeposition system, and electrodeposition method |
| US8652649B2 (en) * | 2009-07-10 | 2014-02-18 | Xtalic Corporation | Coated articles and methods |
| JP5719179B2 (en) * | 2010-01-25 | 2015-05-13 | 株式会社神戸製鋼所 | Reflective film laminate |
| KR20130006658A (en) * | 2010-03-12 | 2013-01-17 | 엑스탤릭 코포레이션 | Coated articles and methods |
| US9694562B2 (en) * | 2010-03-12 | 2017-07-04 | Xtalic Corporation | Coated articles and methods |
| JP6159726B2 (en) * | 2011-09-14 | 2017-07-05 | エクスタリック コーポレイションＸｔａｌｉｃ Ｃｏｒｐｏｒａｔｉｏｎ | Coated products, electrodeposition baths, and related systems |
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| CN106947986B (en) | 2019-07-19 |
| JP2014526615A (en) | 2014-10-06 |
| EP2755819A4 (en) | 2015-04-15 |
| JP6159726B2 (en) | 2017-07-05 |
| CN106947986A (en) | 2017-07-14 |
| WO2013040400A1 (en) | 2013-03-21 |
| EP2755819A1 (en) | 2014-07-23 |
| CN104080606A (en) | 2014-10-01 |
| EP2755819B1 (en) | 2016-09-14 |
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