CN106947986A - Coat product, electrodeposition bath and related system - Google Patents
Coat product, electrodeposition bath and related system Download PDFInfo
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- CN106947986A CN106947986A CN201611001346.9A CN201611001346A CN106947986A CN 106947986 A CN106947986 A CN 106947986A CN 201611001346 A CN201611001346 A CN 201611001346A CN 106947986 A CN106947986 A CN 106947986A
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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 product, electrodeposition bath and related system is described herein.The coating for including silver that the product may include base material and be formed on.In some embodiments, the coating includes silver-base alloy, such as silver tungsten.Desirable property and feature, such as durability (for example, abrasion), hardness, corrosion resistance and high conductivity can be presented in the coating, and this can be beneficial in such as electricity application and/or electronic application.In some cases, electro-deposition method can be used to apply for the coating.
Description
Technical field
In short, the present invention relates to coating product, electrodeposition bath and related system.In some embodiments, coating
It is metallicity and electro-deposition is formed.
Background technology
The coating of many types can be put on base material.Electro-deposition is the common technique for depositing this type coating.Electro-deposition is led to
Often be related to the base material that is placed in electrodeposition bath and apply voltage, so as to reduce the metal ion species in bath and with metal or gold
The form of category alloy coat is deposited on base material.Power supply can be used to apply between the anode and the cathode for voltage.In male or female
At least one can be used as base material to be coated.In some electro-deposition methods, voltage can apply as composite wave-shape, for example, exist
In pulsed deposition, AC electrodeposition or reverse impulse deposition.
The method such as electro-deposition can be used to deposit for noble metal and precious metal alloys coating.In some applications, coating meeting
At least partly worn and torn due to repeating friction surface.The effect is probably undesirable, especially when at least part applies coating
To improve during electric conductivity, because this effect can increase the resistance of coating.
The content of the invention
The present invention provides coating product, electrodeposition bath and product.
There is provided bath in an aspect.Bath includes silver ion material, tungsten and/or molybdenum ion material and NaOH, its
In, bath is suitable for electro-deposition method.
There is provided bath in another aspect.Bath is comprising silver ion material, tungsten and/or molybdenum ion material and selected from 2,2-
The brightener of bipyridyl and 3- formoxyls -1- (3- sulfonate radicals propyl group) pyridine.
There is provided electro-deposition system in an aspect.Electro-deposition system includes anode, negative electrode, bath and the power supply for including silver,
Wherein, bath includes tungsten and/or molybdenum ion material and at least one complexing agent, wherein, bath is connected with anode and negative electrode, wherein,
Power supply is connected at least one of anode and negative electrode, and wherein, the surface area of anode is at least the five of the surface area of negative electrode
Times.
There is provided product in an aspect.Product includes base material and the coating formed on base material, and coating is closed comprising silver-based
Gold, silver-base alloy further includes tungsten and/or molybdenum, and silver-base alloy has the granularity less than about 100nm, wherein, exposed to extremely
Few 125 DEG C temperature is after at least 1000 hours, and granularity change is not more than 30nm.
There is provided product in another aspect.Product includes base material；The coating formed on base material, coating includes silver-based
Alloy, silver-base alloy further includes tungsten and/or molybdenum, wherein, the concentration of tungsten and/or molybdenum is at least 1.5 atoms in silver-base alloy
Percentage, and silver-base alloy has the particle mean size less than 1 micron；And the lubricating layer formed on coating.
There is provided product in another aspect.Product includes base material；The coating formed on base material, coating includes silver-based
Alloy, silver-base alloy further includes tungsten and/or molybdenum；And the lubricating layer formed on coating, wherein, the hardness of product is greater than about
1GPa and coefficient of friction are less than about 0.3.
There is provided product in a further aspect.Product includes base material and the coating formed on base material, and coating includes silver-based
Alloy, silver-base alloy further includes the tungsten and/or molybdenum of at least 1.5 atomic percents, wherein, coating has at least 10% hole
Gap rate.
When considered in conjunction with the accompanying drawings, it will become from other side of the invention described further below, embodiment and feature
Obviously.Accompanying drawing is schematical and is not intended to be drawn to scale.For purposes of brevity, not each component is every
Mark out and in individual figure, and understand the present invention and non-vital feelings for those skilled in the art illustrating
Under condition, and each component of each embodiment of non-invention is showd that.All patents incorporated herein by reference
The full text of applications and patent is all incorporated by reference.If there is contradiction, then it is defined by this specification (including definition).
Brief Description Of Drawings
Fig. 1 shows the electro-deposition system according to embodiment.
Fig. 2 shows the product according to embodiment.
Fig. 3 A-3B show the image for the product that endurancing is subjected to according to some embodiments：A) without lubricating layer, and
B) there is lubricating layer.
Fig. 4 A-4C, which is shown, include A according to some embodiment electro-deposition) 2.3wt% tungsten, B) 4.5wt% tungsten and C)
The scanning electron micrograph of the cross section of the silver alloy coating of 8.7wt% tungsten.
Fig. 4 D show the figure to the wt% of tungsten according to the porosity of silver-tungsten alloy of some embodiment electro-deposition.
Fig. 5 A show the figure to the percentage by weight of tungsten according to the granularity of silver-tungsten alloy of some embodiment electro-deposition.
Fig. 5 B show the contact for silver-tungsten alloy that 125 DEG C of electro-deposition for being kept for 1000 hours are heated to according to embodiment
Resistance is to applying loaded figure.
Fig. 6 is shown according to some embodiments comprising different anodes to the silver-colored dense of the electrodeposition bath of cathodic surface area ratio
Spend the figure to the time.
Fig. 7 shows the figure to current density according to the W content of silver-tungsten alloy of some embodiment electro-deposition.
Fig. 8 shows the pH according to some embodiment electrodeposition baths to observing that precipitation undergoes number of days in electrodeposition bath
Figure.
Embodiment
Coating product, electrodeposition bath and related system is described herein.Product may include base material and including of being formed on
The coating of silver.In some embodiments, coating includes silver-base alloy, such as silver-tungsten alloy.In some cases, coating can
Including at least two layers.For example, coating may include the first layer comprising silver-base alloy and the second layer comprising noble metal.Coating can be in
Existing desirable property and feature, such as durability (for example, abrasion), hardness, corrosion resistance and high conductivity, this should in such as electricity
With and/or electronic application in can be beneficial.In some cases, electro-deposition method can be used to apply for coating.
Fig. 1 shows the electro-deposition system 10 according to embodiment.System 10 includes electrodeposition bath 12.Following article is further retouched
State, bath includes source metal and the one or more additive for being used to form coating.Anode 14 and negative electrode 16 are provided in bath.
Power supply 18 is connected to anode and negative electrode.During use, power supply generation produces the waveform of voltage difference between the anode and the cathode.Electricity
Pressure difference make it that the metal ion species in bath are reduced and are deposited on coating form on negative electrode, in this embodiment, negative electrode
Also as substrate.
It should be understood that illustrated system is not intended to restricted, but it may include those skilled in the art
The a variety of modifications known.
Fluid vehicle of the electrodeposition bath comprising source metal and additive.In some embodiments, fluid vehicle is water
(that is, bath is aqueous solution).However, it should be understood that other fluid vehicles can also be used, for example fuse salt, low-temperature solvent, alcohol bath with
And it is other.In some embodiments, fluid vehicle is water and (that is, water bath can contain the mixture of at least one organic solvent
There are at least some organic solvents).Those skilled in the art can select suitable fluid vehicle.
Bath includes suitable source metal to deposit the coating with desirable composition.It should be understood that working as deposit metal alloy
When, all metal ingredients in alloy have source in bath.Source metal is usually the ionic species being dissolved in fluid vehicle.
As described further below, during electro-deposition method, ionic species are deposited in the form of metal or metal alloy and form painting
Layer.Generally, any suitable ionic species can be used.Ionic species can be provided by metal salt.For example, when deposition includes the painting of silver
During layer, silver nitrate, silver sulfate, sulfamic acid silver can be used to provide silver ion material；When deposition includes the coating of tungsten, it can make
Tungsten ion material is provided with sodium tungstate, ammonium tungstate, wolframic acid etc..In some cases, ionic species can include molybdenum.When deposition bag
During coating containing molybdenum, sodium molybdate, ammonium molybdate, molybdenum oxide etc. can be used to provide molybdenum ion material.It should be understood that these ion things
Matter is provided as example and many other sources are feasible.The metallics of any suitable concentration can be used, and it is affiliated
The technical staff in field can select suitable concentration by normal experiment.In some embodiments, the ionic species in bath
There can be the concentration between 0.1g/L and 100g/L, between 5g/L and 50g/L or between 1g/L and 20g/L.
As described herein, electrodeposition bath may include that one or more can improve electrodeposition technology and/or coating matter
The additive of amount.For example, electrodeposition bath can include at least one complexing agent (that is, the mixture of complexing agent or complexing agent).Complexing
Agent refers to any material that can be with the ion coordination contained in solution.In some embodiments, complexing agent or complexing agent is mixed
Compound may be allowed at least two elemental co-depositions.For example, the tolerable silver of the mixture of complexing agent or complexing agent and tungsten are co-deposited.
Complexing agent can be organic substance, such as citrate ion, the compound comprising hydantoins, acid imide functional group
Or the pyridine compounds being substituted.Complexing agent can be inorganic substances, such as ammonium ion.In some cases, complexing agent is neutral
Material.In some cases, complexing agent is electrically charged material (for example, negatively charged ion, positively charged ion).Network
The example of mixture includes citrate, gluconate, tartrate and other alkyl hydroxy carboxylic acids；Cyanide；Hydantoins
(for example, 5,5- dimethyl hydantoins), succinimide class (for example, succinimide) and it is other include acid imide functional group
Compound；And the pyridine compounds (for example, niacinamide) being substituted.
Generally, the mixture of complexing agent or complexing agent can with the concentration in the range of 0.1-200g/L and in some cases
Concentration in the range of 40-80g/L is included in electrodeposition bath.In one embodiment, the mixture of complexing agent includes 5,5-
Dimethyl hydantoin, citric acid and niacinamide.When complexing agent be comprising acid imide functional group compound when, complexing agent it is dense
Degree can be in the range of 30-70g/L or 40-60g/L.When complexing agent is alkyl hydroxy carboxylic acid, in some cases, complexing agent
Concentration can be in the range of 1-20g/L or 5-15g/L.When complexing agent is the pyridine compounds being substituted, in certain situation
Under, the concentration of complexing agent can be in the range of 0.5-20g/L or 0.5-5g/L.When complexing agent is hydantoins, in some feelings
Under condition, the concentration of complexing agent can be in the range of 50-70g/L.It may be used at the concentration beyond these scopes, and art
Technical staff will easily pass through normal experiment and determine suitable concentration.
In some embodiments, ammonium ion can be included in electrolyte bath as complexing agent and to adjust solution
pH.For example, electrodeposition bath can include the ammonium ion in the range of 1-50g/L and in the range of 10-30g/L.Other concentration ranges
Can be what is be adapted to.
In some cases, bath may include at least one wetting agent.Wetting agent is to refer to reduce the surface of electrodeposition bath
Any material for the ability that tension force and/or increase bubble depart from from the surface in bath.For example, substrate can include hydrophilic surface,
And wetting agent can strengthen compatibility (for example, wettable) of the bath relative to substrate.In some cases, wetting agent can also be reduced
The quantity of defect in produced metal coating.Wetting agent can comprising organic substance, inorganic substances, organic metal material or they
Combination.In some embodiments, wetting agent can be chosen and present with the compatibility of electrodeposition bath and its component (for example,
Dissolubility).For example, wetting agent can be chosen and including one or more kinds of hydroaropic substances, including amine, mercaptan, alcohol, carboxylic acid
And carboxylate, sulfate, phosphate, the derivative of polyethylene glycol (PEG) or polyethylene glycol, to strengthen the water-soluble of wetting agent
Property.In some embodiments, wetting agent can include fluorine surfactant.In some embodiments, wetting agent may includeFSJ(Dupont)、CaptsoneTMOr Triton (Dupont)TMQS-15(Dow)。
The wetting agent of any suitable concentration can be used.For example, the concentration of wetting agent can be micro- between 10 microlitres/L and 2000
Between liter/L, between 20 microlitres/L and 1000 microlitre/L or between 50 microlitres/L and 500 microlitre/L.Other concentration models
Enclose and be alternatively what is be adapted to.
In some embodiments, bath may include at least one brightener.Brightener can be specifically described herein when being included in
Bath in when improve produced by electrodeposited coating brightness and/or any material of smoothness.In some cases, brightener
It is neutral substance.In some cases, brightener comprising electrically charged material (for example, positively charged ion, negatively charged
Ion).In a set of embodiment, brightener can include at least one pyridine ring or at least one pyridine ring.In some realities
Apply in scheme, brightener includes the bipyridyl being optionally substituted.
The brightener of any suitable concentration can be used.For example, the concentration of brightener can between 0.01g/L and 50g/L it
Between, between 0.01g/L and 10g/L, between 0.1g/L and 5g/L or between 0.1g/L and 1g/L.Other concentration
Scope is alternatively suitable.
In some embodiments, brightener is 2,2- bipyridyls or 3- formoxyls -1- (3- sulfonate radicals propyl group) pyridine.
The concentration of 2,2- bipyridyls can be between about 0.1g/L and about 5g/L, or between 0.1g/L and about 1g/L in bath, or is situated between
Between about 0.1g/L and about 0.8g/L.In specific embodiments, brightener is 2,2- bipyridyls, and its concentration is between about
Between 0.2g/L and about 0.6g/L.In specific embodiments, brightener is 3- formoxyls -1- (3- sulfonate radicals propyl group) pyridine
, its concentration is about 2g/L.In one embodiment, electrodeposition bath comprising 2,2- bipyridyls as brightener and comprising
TritonTMQS-15 (Dow) is used as wetting agent.
Those skilled in the art can select suitable ionic species, wetting agent, complexing suitable for concrete application
Agent and/or the combination of other additives (for example, brightener).Generally, the additive in bath is compatible with electrodeposition technology, i.e. bath
It may be adapted to electro-deposition method.Those skilled in the art can recognize the bath suitable for electro-deposition method.Equally, art
Technical staff can be recognized when being added in bath so that bathing the additive for being unsuitable for electro-deposition method.
In certain aspects, various technologies can be used to monitor the content of electrodeposition bath.For example, the technology can determine bath
The concentration of middle one or more kinds of additives (such as brightener, wetting agent, complexing agent).If the concentration of additive is less than
Or higher than 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
About 7.6 to 8.4 or in some cases about 7.9 to 8.1 pH in some cases.However, it should be understood that pH can be in above-mentioned model
Outside enclosing.The pH of any suitable reagent adjustment bath known to those skilled in the art can be used.In some embodiments,
The pH of bath is adjusted using alkali (such as hydroxide salt, such as potassium hydroxide).In some embodiments, using acid (for example, nitre
Acid) adjust the pH bathed.
In some embodiments, electrodeposition bath includes hydroxide salt.In specific embodiments, hydroxide salt
It is NaOH.In some cases, hydroxide salt is not potassium hydroxide.Theory is not intended to be limited to, in electrodeposition bath
, compared to that can be favourable, be precipitated using NaOH with using potassium hydroxide because it can reduce and/or prevent to be formed in solution.
For example, in one embodiment, when using the electrodeposition bath comprising potassium hydroxide, it was observed that tungsten oxide is precipitated, and
Using NaOH it is substantially similar under conditions of do not observe precipitation.In some cases, when sodium hydroxide is used, it is electric
Deposition bath can have greater than about 6.5 to 9.0 pH.In some cases, pH is between about 6.5 and about 9.5, between about 6.5
Between about 8.5, between about 7.0 and about 8.5, or between about 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 includes about 8g/L to about 9g/L silver ions material, about 27g/L tungsten ion things
Matter, and with less than about 8, greater than about the 6.5 or pH between about 6.5 and 8.In another embodiment, electro-deposition
Bath includes about 4g/L to about 5g/L silver ions material, about 60g/L tungsten ion materials, and with less than about 8.5, greater than about 6.5
Or the pH between about 6.5 and 8.5.
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 DEG C.However, it should be understood that other temperature
What scope may also be adapted to.
Generally, electrodeposition bath can be used with reference to any electro-deposition method.Electro-deposition is usually directed to is sunk by making substrate with electricity
Product bath contacts and makes the electric current flowing between (that is, due to the electrical potential difference between two electrodes) two electrodes by electrodeposition bath
Coating is deposited on substrate.For example, method specifically described herein can relate to provide anode, negative electrode, be connected with anode and negative electrode
The electrodeposition bath of (for example, contact) and the power supply for being connected to anode and negative electrode.In some cases, can driving power supply to generate
Waveform for producing coating, following article is more fully described.In some embodiments, at least one electrode can be as to be coated
The substrate covered.
In some embodiments, electro-deposition system include anode, negative electrode, bathe and be connected to anode and negative electrode at least
The power supply of one.In some cases, anode includes silver (for example, wherein, anode provides silver ion material to bath), and bathes bag
Tungstenic and/or molybdenum ion material and optionally at least a kind of complexing agent and/or other additives.In these embodiments, sun
The ratio of the anticathode surface area of surface area of pole can be chosen and provide proper amount of silver ion material to bath.It is not intended to be limited
In theory, in the too small embodiment of the ratio of the anticathode surface area of surface area of anode, anode can be passivated and solution
In silver ion material will not be supplemented.In some cases, the surface area of anode (such as comprising silver) is the surface of negative electrode
Long-pending at least about 5 times, at least about 6 times, at least about 7 times, at least about 8 times, at least about 9 times or at least about 10 times.Specific real
Apply in scheme, the surface area of anode is at least about 5 times of the surface area of negative electrode.
Comprising silver anode can substantially by silver is formed (for example, more than 95% silver medal, more than 97% silver medal, more than 98% silver medal, greatly
In 99% silver medal, more than 99.5% silver medal, more than 99.9% silver medal), or be not substantially to be formed by silver.In some cases, comprising
The anode of silver can be included in the silver formed on substrate (for example, conductive substrates).In some cases, the anode comprising silver can also be wrapped
Containing at least one additional metal (for example, tungsten), wherein, each additional metal may or may not provide metal ion thing to bath
Matter (for example, tungsten ion material).
Generally, during electro-deposition method, may be present potential on substrate to be coated, and apply voltage, electric current or
The change of current density can cause the change of potential on substrate.In some cases, electro-deposition method may include to use comprising one
Individual or more than one section waveform, wherein, each fragment be related to one group of specific electrodeposition condition (for example, current density,
Current duration, temperature of electrodeposition bath etc.).Waveform can have any shape, include the non-square wave of square wave, arbitrary shape
Deng.In certain methods, such as when forming the coating with different piece, waveform, which can have, to be used to form different piece not
Same fragment.However, it should be understood that simultaneously not all method is all using the waveform with different fragments.
In some embodiments, direct current (DC) deposition can be used to come electrodeposited coating or one part.For example, can make
Steady current is by electrodeposition bath so as to generation coating or one part on substrate.In some embodiments, it is applied to electricity
Between pole potential (for example, potential control or voltage control) and/or allow flowing electric current or current density (for example, electric current
Or current density control) alterable.For example, can be included during electro-deposition method pulse, vibration and/or other voltages, potential,
The change of electric current and/or current density.In some embodiments, the pulse of controlled voltage can be with controlled current flow or current density
Pulse alternating.In some embodiments, pulse current electro-deposition, reverse pulse current electro-deposition or its group can be used in coating
Close and formed (for example, electro-deposition).
In some cases, can be used bipolar waveform, the waveform comprising at least one direct impulse and at least one
Reverse impulse, i.e. " reverse impulse sequence ".As described above, electrodeposition bath specifically described herein is particularly suited for using complex wave
Shape (such as reverse impulse sequence) depositing coating.In some embodiments, at least one reverse impulse is next at least one
After direct impulse.In some embodiments, at least one direct impulse is next to after at least one reverse impulse.One
In the case of a little, bipolar waveform includes multiple direct impulses and reverse impulse.Some embodiments may include to include multiple forward directions
Pulse and the bipolar waveform of reverse impulse, each pulse have specific current density and duration.In some cases,
Use the composition and/or granularity of coating produced by the tolerable regulation of bidirectional pulse train.
Electro-deposition method can be used with least 0.001A/cm2, at least 0.01A/cm2Or at least 0.02A/cm2Electric current it is close
Spend applying coating.The current density that can be used on beyond these scopes.In some cases, using with greater than about 10mA/
cm2, greater than about 15mA/cm2, greater than about 20mA/cm2, greater than about 30mA/cm2Or greater than about 50mA/cm2Direct current density
Direct current.In some embodiments, direct current density is greater than about 15mA/cm2, and in the current density less than this level
Under, only silver is deposited.
For the electric current applied with pulse, frequency can be any suitable frequency (for example, between 0.1 hertz and about 100 hertz
Between hereby).Similarly, voltage can be any suitable voltage (for example, between about 0.1V and about 1V).
The sedimentation rate of controllable coating.In some cases, sedimentation rate can be at least 0.1 [mu, at least
0.3 [mu, at least 1 [mu or at least 3 [mus.The sedimentation rate that can be used on beyond these scopes.
Mainly or entirely make those skilled in the art will realize that electro-deposition method specifically described herein can be different from
With chemical reducing agent depositing coating rather than apply alive without method for electrically.Electrodeposition bath specifically described herein can substantially on not
Containing meeting for example in the chemical reducing agent in the absence of depositing coating under applying voltage.
Electro-deposition system/method can utilize entitled " Method for Producing Alloy Deposits and
Controlling the Nanostructure Thereof using Negative Current Pulsing Electro-
Deposition, and Articles Incorporating Such Deposits " U.S. Patent Publication case the 2006/th
Some aspects of method/system described in No. 02722949, being incorporated by reference in its entirety for the case is herein.Its
The aspect of its electro-deposition method/system is also applicable, including U.S. Patent Publication case the 2006/0154084th and U. S. application
(entitled " the Methods for Tailoring the Surface Topography of a of case the 11/985,569th
Nanocrystalline or Amorphous Metal or Alloy and Articles Formed by Such
Methods ", is filed an application in 11/15/07)；U.S. Patent Publication case the 20090286103rd and U.S. Patent Application No.
No. 12/120,564 (being filed an application on May 14th, 2008)；U. S. application case the 12/723,020th is (entitled
" Electrodeposition Baths and Systems ", filed an application in 03/12/10)；And U. S. application case the 12/th
That described in 723, No. 044 (entitled " Coated Articles and Methods ", filed an application in 03/12/10)
A bit, the case be incorporated by reference in its entirety herein.
Fig. 2 shows the product 20 according to embodiment.Product has the coating 22 formed on base material 24.In some implementations
In scheme, coating includes multiple layers.In some embodiments, coating may include the first layer 26 formed on base material and
One layer of upper second layer 28 formed.Suitable method coating can be used in each layer, as described in greater detail below.It should be understood that coating
It may include to be more than two layers.It should also be understood that coating can only include one layer.However, in some embodiments, coating can only include two
Layer, as shown.In some cases, coating can be formed at least a portion of substrate surface.In other cases, coating covers
Cover whole substrate surface.
In some embodiments, coating includes one or more kinds of metals.For example, coating can include metal alloy.
In some cases, the alloy (that is, silver-base alloy) comprising silver is preferably.Such alloy can also include tungsten and/or molybdenum.In some feelings
Under condition, silver-tungsten alloy can be preferred.In some embodiments, silver-molybdenum alloy is also feasible.In some cases, close
The atomic percent of tungsten and/or molybdenum can be between 0.1 atomic percent and 50 atomic percents in gold；Also, in some feelings
Under condition, between 0.1 atomic percent and 20 atomic percents.In some embodiments, in alloy tungsten and/or molybdenum original
Sub- percentage can be at least 0.1 atomic percent, at least 1 atomic percent, at least at least 1.5 atomic percents, 5 atomic percents
Than, at least 10 atomic percents or at least 20 atomic percents.The other atomic percents that can be used on beyond this scope.
In some embodiments, silver-base alloy can form the first layer 26 of coating.In some embodiments, comprising one
Plant or the second layer 28 of a variety of noble metals can form the second layer of coating.In some cases, the first layer comprising silver alloy exists
Formed on base material, and the second layer comprising one or more noble metals is formed on the first layer.The example of suitable noble metal
Including Ru, Os, Rh, Re, Ir, Pd, Pt, Ag, Au or any combination of them.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 (for example, second layer) is no
Stanniferous is preferred.In other cases, layer can include alloy, and the alloy includes at least one noble metal and at least one
Other elements.The element especially may be selected from Ni, W, Fe, B, S, Co, Mo, Cu, Cr, Zn and Sn.For example, layer can include Ni-Pd
Alloy, Au-Co alloys and/or Au-Ni alloys.
In some embodiments, coating may include the layer (such as nickel alloy, such as nickel-tungsten) for including nickel.In some feelings
Under condition, the layer comprising nickel can be disposed between base material and silver-base alloy layer.In one embodiment, coating includes including nickel
First layer, the second layer comprising silver-base alloy and the third layer for including one or more noble metals, wherein, first layer is on base material
Formed, the second layer is formed on the first layer, and third layer is formed on the second layer.
The layer of coating can have any suitable thickness.In some embodiments, layer is relatively thin for example to save material
Cost can be favourable.In some embodiments, the thickness of layer (for example, silver-base alloy layer) is smaller than about 1000 microinch
(for example, between about 1 microinch and about 1000 microinch, between about 1 microinch and about 750 microinch, between about 1
Between microinch and about 500 microinch, between about 1 microinch and about 100 microinch, between about 1 microinch and 50 microinch
Between very little).The thickness of layer is smaller than about 500 microinch or less than 250 microinch (for example, between about 1 microinch and 250 microinch
Between very little).In some cases, the thickness of layer can be very thin.For example, the thickness of layer is smaller than 30 microinch (for example, between about
Between 1 microinch and about 30 microinch；In some cases, between about 5 microinch and about 30 microinch)；In some feelings
Under condition, the thickness of layer is smaller than 20 microinch (for example, between about 1 microinch and about 20 microinch；In some cases,
Between about 5 microinch and about 20 microinch)；Also, in some cases, the thickness of layer be smaller than 10 microinch (for example,
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 on the surface.It should be understood that other thickness degree also may be used
For what is be adapted to.
The second layer can cover whole first layer.However, it should be understood that in other embodiments, the second layer only covers first
A part for layer.In some cases, at least the 50% of the surface area of second layer covering first layer；In other cases, first
At least the 75% of the surface area of layer.In some cases, the element from first layer can be included in the second layer and/or from second
The element of layer can be included in first layer.
In some embodiments, it can be preferred that first layer is formed directly on base material.These embodiments compared to
The prior art construction of some layers using between first layer and base material can be preferably as can in the absence of such intermediate layer
Save total material cost.However, it is understood that in other embodiments, one or one can be formed between first layer and base material
It is individual with upper strata.For example, in some embodiments, barrier layer can be formed between base material and first layer.Barrier layer can include gold
Category.In some embodiments, barrier layer includes nickel.In some cases, barrier layer includes nickel-tungsten or nickel sulfamic acid.
In some embodiments, lubricating layer can partly be formed as above coating.Lubricating layer can include for example organic
Material, self-assembled monolayer, CNT etc..In some cases, compared with substantially similar but not including the coating of lubricating layer,
The presence of lubricating layer reduces the coefficient of friction of coating.Lubricating layer can be formed by any suitable material, such as halogen-containing organic
Lubricant, the organic lubricant containing polyphenyl or the lubricant containing polyethers.In one embodiment, lubricating layer is had by halogen-containing
Machine lubricant is formed.The specific non-limiting examples of lubricant include 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, which is included in, applies
The individual layer formed on the surface of layer.
Those skilled in the art will know the appropriate methodology of the formation lubricating layer on coating.For example, in some implementations
In scheme, the product for including coating can be made exposed to (for example, being immersed into wherein) lubricant (for example, being optionally in solution shape
Formula), and product can be subsequently dried, thus forming lubricating layer on part above coating.
In some embodiments, it is included on coating the product of lubricating layer of (for example, on base material) formation with not wrapping
Include lubricating layer compares the coefficient of friction can with reduction substantially like product.In some cases, the system with lubricating layer
The coefficient of friction of product is at most 1/2nd, at most 1/3rd, at most the four of the coefficient of friction of the product without lubricating layer
/ mono-, at most 1/5th or at most 1/10th.
In some cases, the product with lubricating layer with without lubricating layer substantially like product compared with can have
Preferable wear durability.Those skilled in the art will know the method (example of the wear durability of suitable measure material
Such as, ball is in flat board mo(u)ld top half (ball-on-plate-type) reciprocating friction abrasion test, wherein, both ball and flat board are coated with
Alloy-layer and optionally lubricating layer).For example, in some embodiments, the product for including silver-base alloy and lubricating layer,
100g applies under load, and pole can be observed through 50 circulations, 100 circulations, 250 circulations, 500 circulations or 1000 circulations
It is few worn out or do not observe it is worn out, wherein, can not show serious or completely worn out substantially like product including lubricating layer.
In some cases, coating (for example, first layer and/or second layer) can have specific micro-structural.For example, coating
At least a portion can have nanocrystalline microstructure.As used herein, " nanocrystal " structure refers to the quantity of crystal grain
Average-size is less than 1 micron of structure.The quantity average-size of crystal grain provides equal statistical weight for each crystal grain, and calculates
For the summation divided by total number of die of the ball equivalent diameter of all crystal grains in the representative volume of main body.In some embodiments
In, the quantity average-size of crystal grain is smaller than 100nm.In some cases, silver-base alloy has the thickness less than silver-base alloy layer
50% number average particle size of degree.In some cases, number average particle size is smaller than the 10% of the thickness of silver-base alloy layer.
In some embodiments, at least a portion of coating can have impalpable structure.As known in the art, impalpable structure is
It is characterised by atom site without a wide range of symmetrical non-crystalline structure.The example of impalpable structure includes glass or glass
Shape structure.Some embodiments may be provided on substantially whole coating the coating with nanocrystalline structures.Some embodiment party
Case may be provided on substantially whole coating the coating with impalpable structure.
In some embodiments, coating can be the crystalline solid with face-centred cubic structure.In some embodiments, apply
Layer can be solid solution, wherein, the metal for constituting coating is scattered basically as single atom.Electro-deposition can be used in this class formation
Method is produced.Solid solution can be different from for example using the alternative structure formed without method for electrically, and in alternative structure, composition contains
The particle of first phase of the first metallics (that is, tungsten and/or molybdenum) is scattered in composition containing second of metallics (that is, silver-colored)
The second phase coating in, second from first mutually have different composition and/or crystal structure.In some cases, solid
Solution can be substantially free of oxygen.
In some embodiments, coating can include multiple parts with different micro-structurals.For example, first layer and second
Layer can have different micro-structurals.Coating may include such as one or more parts with nanocrystalline structures and one
Or more than one has the part of impalpable structure.In a set of embodiment, coating includes nanocrystal and other presentation nothings
The part of amorphous configuration.In some cases, coating or one part are (for example, a part for first layer, a part for the second layer
Or a part for both first layer and the second layer) part with crystal grain can be included, most of crystal grain has with diameter greater than 1 micron
Granularity.In some embodiments, coating may include other structures or phase, individually or with nanocrystalline fraction or pars amorpha
Subassembly.Those skilled in the art can select to be suitable for the other structures or phase of present invention.
Advantageously, coating (that is, first layer, the second layer or both first layer and the second layer) can be substantially free of with high poison
The element or compound of property or other shortcomings.In some cases, additionally advantageously, coating is substantially free of using with high toxicity
Or the element or compound of the electrodeposition substance of other shortcomings.For example, in some cases, coating is free of the chromium usually using toxicity
Ionic species are (for example, Cr6+) deposition chromium (for example, chromated oxide).In some cases, coating can be by being substantially free of cyaniding
The electrodeposition bath deposition of thing is formed.This type coating can provide multiple better than the handling of some first Front-coating mirrors, health and environmental advantage.
In some embodiments, the coating (for example, alloy) of electro-deposition can be porous.In some cases, apply
Layer has at least 5%, at least 10%, at least 15%, at least 20%, at least 25%, at least 30% or at least 50% porosity.
In some cases, coating has the porosity between about 5% and about 30% or between about 10% and about 25%.
Under certain situation, the silver-base alloy for including tungsten and/or molybdenum, can based on the tungsten contained in alloy percentage change and/or
Control porosity.In specific embodiments, for including the silver-base alloy of at least tungsten of 1.5 atomic percents and/or molybdenum,
Coating has at least about 10% or the porosity between about 10% and about 25%.
Those skilled in the art will know the method for determining the porosity of coating (for example, alloy), including but not limit
In directly determining porosity by optics and/or density method.In some cases, optical method measuring porosity can be used,
Wherein, by the image of the cross section for obtaining coating and hole (for example, in some cases, can be observed as blackspot) is calculated
Area determines porosity.It is assumed that hole is uniform in whole coating, the volume fraction in hole can be calculated.
In some embodiments, metal can be included into coating, nonmetallic and/or metalloid material, salt etc. (for example,
Phosphate, or redox mediators, such as potassium ferricyanide, or its fragment).
Suitable technology as known in the art can be used to characterize for the composition of coating or part thereof or layer, such as auger electrons
Power spectrum (AES), x-ray photoelectron power spectrum (XPS) etc..For example, the chemistry on the surface that AES and/or XPS can be used to characterize coating
Composition.
Coating can have any thickness being adapted to for application-specific.For example, the thickness of coating can be greater than about 1 microinch
(for example, between about 1 microinch and about 1000 microinch, between about 1 microinch and about 750 microinch, between about 1
Between microinch and about 500 microinch, between about 1 microinch and about 100 microinch, between about 1 microinch and 50 microinch
Between very little)；In some cases, greater than about 5 microinch are (for example, between about 5 microinch and about 100 microinch, between about
Between 5 microinch and 50 microinch)；Greater than about 25 microinch are (for example, between about 25 microinch and about 100 microinch, be situated between
Between about 1 microinch and 50 microinch).It should be understood that other thickness be alternatively it is suitable.In some embodiments, select
The thickness of coating is so that coating substantial transparent on the surface.Thickness can pass through skill known to those skilled in the art
Art is determined.
Base material 30 can be coated to form coating product, as described above.In some cases, base material can include conduction material
Material, such as metal, metal alloy, intermetallic material.Suitable base material include steel, copper, aluminium, brass, bronze, nickel, with leading
Ammeter face and/or surface treated polymer, transparent conductive oxide and other.In some embodiments, it is copper-based
Material is preferred.
Product can be used in numerous applications, including electricity application, such as electric connector (for example, plug-in type).In some realities
Apply in scheme, the coating on electric connector includes the first layer comprising silver alloy, first layer is arranged on base material；And your gold included
The second layer of category, the second layer is arranged on first layer.Coating can assign product desirable feature, for example durability, hardness, corrosion resistant
Corrosion, heat endurance and the resistivity of reduction.These properties especially have for applying the product of (such as electric connector) for electricity
Profit, these products can damage or reduce system being connected to circuit and/or can undergo friction or abrasion stress after circuit disconnection
The electrical conductivity of conductive layer on product.The non-limiting examples of electric connector include infrared connector, USB connector, battery
Charger, battery contact, automobile electric connector etc..In some embodiments, the presence of the first layer of coating can carry for coating
For at least some durability and corrosion resistance.In some embodiments, coating can assign decoration property, such as blueness and decrease
Discoloration.In addition, the presence of first layer may be allowed the thickness reduction of the second layer, so as to significantly reduce the amount of noble metal in product.
Coating specifically described herein can assign product (such as electric connector) favourable property.In some embodiments,
The layer of coating or coating can have low-resistivity.For example, resistivity is smaller than 100 microohm-cms, it is small less than 50 microohm-cms
In 10 microohm-cms or less than 2 microohm-cms.
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.These can be easily determined in those skilled in the art
Property.In some cases, coating comprising silver-base alloy and lubricating layer can have at least 1GPa, at least 1.5GPa, at least
2GPa, at least 2.5GPa or at least 3GPa hardness and less than about 1.0, less than about 0.75, less than about 0.5, less than about 0.4, it is small
In the about 0.3, coefficient of friction less than about 0.2 or less than about 0.1.In some embodiments, hardness between about 2.0GPa with about
Between 3.0GPa, and coefficient of friction is less than about 0.3, or between about 0.3 and about 0.1.
The layer of coating or coating can be heat-staple.In some cases, further comprising tungsten and/or molybdenum and with small
Less granularity is presented after the temperature long period exposed to raising in the coating comprising silver-base alloy of about 100nm granularity
Granularity change is not presented in change.In some cases, after at least 125 DEG C of temperature at least 1000 hours, coating
Granularity change be not greater than about 30nm, no more than about no more than about 20nm, 15nm, no more than about 10nm or no more than about 5nm.
Under certain situation, after about 125 DEG C of temperature at least about 1000 hours, granularity change is not greater than about 30nm, is not more than
About 20nm, no more than about 15nm, no more than about no more than about 10nm or 5nm.Heat endurance can be surveyed under conditions of other be adapted to
It is fixed, for example, at least about 24 hours at about 150 DEG C, at least about 24 hours at about 200 DEG C, at least about 24 is small at about 250 DEG C
When, or at least about 120 hours at about 200 DEG C.In addition, after about 125 DEG C of temperature at least about 1000 hours, coating
Contact resistance alterable be less than about 25%, less than about 20%, less than about 15%, less than about 10%, or less than about 5%.
Those skilled in the art will know to determine the appropriate methodology of the heat endurance of material.In some cases, it is hot
Stability can be by during observing heat exposure and/or before and the change of the micro-structural of material afterwards is (for example, grain growth, phase
Transformation etc.) determine.Differential scanning calorimetry (DSC) or differential thermal analysis (DTA) can be used to determine for heat endurance, wherein,
Heating material under controlled conditions.To determine change and/or the phase in version of granularity, original position x can be implemented during heating process and penetrated
Line is tested.
As described above, electro-deposition method can be used to be formed for coating 20.In some cases, each layer of coating can be used single
Only electrodeposition bath coating.In some cases, can single product connect so that they can be in order exposed to independent
Electrodeposition bath, such as in reel-to-reel (reel-to-reel) method.For example, product can be connected to common conductive substrates
(for example, band).In some embodiments, each electrodeposition bath can be connected with single anode, and interconnect it is only
Vertical product may be generally coupled to negative electrode.
In some embodiments, the present invention, which is provided, to resist corrosion in one or more potential corrosive environments
And/or the following backing material of protection is from the coating product of corrosion.The example of such corrosive environment is including but not limited to aqueous
Solution, acid solution, alkali or alkaline solution or combinations thereof.For example, coating product specifically described herein can be exposed to (example
Such as, it is in contact with it, to be immersed in its medium) corrosive environment (for example, corrosive liquids, steam or wet environment) resists corrosion afterwards.
Such as ASTM B845 (entitled " Standard Guide for Mixed Flowing can be used in corrosion resistance
Gas (MFG) Tests for Electrical Contacts ") etc. experiment follow IIa class schemes and evaluated, it can also be used to comment
Valency coats the corrosion resistance of product.These experiment general introductions make the sample substrate of coating be exposed to aggressive atmosphere (that is, NO2、H2S、
Cl2And SO2Mixture) program.The mixture of flowing gas can include 200+/- 50ppb NO2、10+/-5ppb H2S、10
+/-3ppb Cl2And 100+/- 20ppb SO2.Also temperature controllable and relative humidity.For example, temperature can be 30+/- 1 DEG C, and
Relative humidity can be 70+/- 2%.
It can determine before corrosive environment setting time section and/or afterwards according to one of above-mentioned experiment
The low-level contact resistance of sample.In some embodiments, low-level contact resistance can be according to specification EIA 364 experiment journey
Sequence 23 is determined.Generally, the contact resistivity of sample can be by making the sample under given load and electric current with having define and examination
The measure probe of the cross-sectional area of sample contact contacts to determine.For example, low-level contact resistance can be in 25g, 50g, 150g, 200g
Determined under even load.Generally, low-level contact resistance increases and reduced with load.
In some embodiments, coating product has the low-level contact resistance of reduction.The low-level contact electricity of reduction
Hinder for that can be useful for the product in electricity application (such as electric connector).In some cases, load of the product in 25g
Under can have less than about 100mOhm, be less than about 10mOhm in some cases, be less than about 5mOhm and one in some cases
It is less than about 1mOhm low-level contact resistance in the case of a little.It should be understood that product can also have the low-level beyond this scope
Contact resistance.It should also be understood that the value of determined low-level contact resistance can be influenceed by determining the contact cross-sectional area of probe.
Following examples are not construed as restricted, but some features of the invention are illustrated.
Embodiment
Embodiment 1
Coating layer thickness, W content, granularity, coating hardness and contact resistance that the displaying of this embodiment is reached with a variety of samples.
Make coating electro-deposition in aqueous electrodeposition bath on base material using electro-deposition method.Electrodeposition bath contains silver ion
Material, tungsten ion material and complexing agent.Coating is set directly to be formed on base material substrate.In addition, for sample 28-35, making nickel dam
Electro-deposition is on substrate before Electrodeposited Silver based alloy.
Table 1 and table 2 show the result that these coatings are obtained.
Thickness, W content, granularity and the hardness of the various samples of table 1..N.D.=undetermineds.
Substrate, W content and the contact resistance of the various samples of table 2..N.D.=undetermineds.
Embodiment 2
The coating abrasion durability of material of this embodiment displaying comprising lubricating layer.
Make silver-tungsten alloy as described in Example 1 electro-deposition on two spherical surfaces and two planar surfaces.Close
Gold includes about 5wt% tungsten, and the thickness of coating is about 80 microinch.The hardness of coating is about 2.0-2.5GPa.In electro-deposition
Afterwards, lubricating layer is formed on a spherical surface and a planar surface using simple dip-coating method as known in the art.
In this embodiment, lubricant is EvabriteTM.Wear durability research is implemented as follows：By the spherical surface of coating and painting
The planar surface contact covered is placed；Then, planar surface is made to be worn and torn toward each other by linear reciprocal movement with spherical surface.Such as
Shown in Fig. 3, product (Fig. 3 A) not including lubricating layer shows obvious worn out after 25 circulations, and the system including lubricating layer
Product (Fig. 3 B) in addition 100 circulate after do not show worn out substantially yet.The coefficient of friction of product without lubricating layer is about
1.0, and the coefficient of friction of the product including lubricating layer is about 0.2.
Embodiment 3
The porosity of the electrodeposited coating of silver alloy of this embodiment displaying comprising the tungsten with Different Weight percentage
Change.
Fig. 4 A-4C show the method electro-deposition according to embodiment 1 include A) 2.3wt% tungsten, B) 4.5wt% tungsten
And C) 8.7wt% tungsten silver-tungsten alloy cross section scanning electron micrograph.Fig. 4 D are shown according to some embodiments electricity
Figure of the porosity of silver-tungsten alloy of deposition to the wt% of tungsten.
Embodiment 4
The displaying of this embodiment uses the electrodeposition bath containing at least one brightener.
Method Electrodeposited Silver-tungsten alloy according to embodiment 1.In the first scenario, bath contains about 0.2g/L
To the 2,2- bipyridyl brighteners of 0.5g/L concentration.2,2- bipyridyls are dissolved in ethylene glycol, then the brightener are added
Into bath.In another case, 3- formoxyls -1- (3- sulfonate radicals propyl group) the pyridine blast of bath containing about 2g/L concentration
Agent.In both cases, under all current densities, coating is bright.
Embodiment 5
This embodiment shows the heat endurance of silver-tungsten alloy.
By silver-tungsten alloy coating of the tungsten comprising multiple percentage by weights as described in Example 1 electro-deposition in base
On material.Product is set to reach the selected period exposed to the temperature improved.Fig. 5 A show the granularity (nm) of alloy to tungsten weight percent
The figure of ratio.Fig. 5 B, which are shown, is coated with EvabriteTMThe contact resistance of silver-tungsten coating of lubricant to apply load figure, by institute
State coating and be heated to 125 DEG C, kept for 1000 hours.
Embodiment 6
This embodiment shows change of the cathodic surface area to the ratio of anode surface area.
By silver-tungsten alloy coating as described in Example 1 electro-deposition on base material, wherein, given from consumable silver anode
Bath provides silver ion material.In this embodiment, the surface area of anode is 3.5 times or 5 times of the surface area of negative electrode.In anode:
The surface area ratio of negative electrode is 3.5:Under 1, the silver ion material in anodic passivity, and solution can not be supplemented.In anode:
The surface area ratio of negative electrode is 5:Under 1, silver concentration is generally remained constant (see Fig. 6).
Embodiment 7
The pH of this embodiment displaying electrodeposition bath change and its relation with the W content in alloy.
By silver-tungsten alloy coating as described in Example 1 electro-deposition on base material.It is heavy using NaOH adjustment electricity
The pH of product bath.W content is shown in Fig. 7 to the figure of current density.
Embodiment 8
This embodiment shows the change of the additive of the pH to adjust electrodeposition bath.
By silver-tungsten alloy coating as described in Example 1 from a variety of bath electro-deposition on base material.Use hydroxide
Sodium, sodium carbonate, potassium hydroxide or potassium carbonate adjust the pH of electrodeposition bath.For the bath containing NaOH or sodium carbonate, do not see
Observe precipitation (for example, tungsten oxide).By contrast, observe precipitation (see figure in the bath containing potassium hydroxide or potassium carbonate
8)。
Claims (9)
1. one kind bath, it is included：
Silver ion material；
Tungsten and/or molybdenum ion material；And
NaOH, wherein, the bath is suitable for electro-deposition method.
2. bath according to claim 50, wherein, the pH of the bath is less than about 8.0.
3. bath according to claim 50, wherein, the pH of the bath is between about 6.5 and about 8.5.
4. bath according to claim 50, it further includes complexing agent.
5. bath according to claim 53, wherein, at least one complexing agent allows to be co-deposited silver and tungsten.
6. bath according to claim 53, wherein, the complexing agent is 2,2- dimethyl hydantoins.
7. bath according to claim 50, wherein, the bath is aqueous solution.
8. bath according to claim 50, wherein, the bath further includes wetting agent.
9. bath according to claim 50, wherein, the bath further includes brightener.
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 | 2011-09-14 | ||
| US13/232,291 US20120121925A1 (en) | 2010-03-12 | 2011-09-14 | Coated articles, electrodeposition baths, and related systems |
| CN201280055952.2A CN104080606B (en) | 2011-09-14 | 2012-09-14 | Coating goods, electrodeposition bath and related system |
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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 |
| US20170253008A1 (en) * | 2016-02-16 | 2017-09-07 | Xtalic Corporation | Articles including a multi-layer coating and methods |
| 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 |
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| Publication number | Publication date |
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| EP2755819B1 (en) | 2016-09-14 |
| EP2755819A1 (en) | 2014-07-23 |
| EP2755819A4 (en) | 2015-04-15 |
| CN106947986B (en) | 2019-07-19 |
| WO2013040400A1 (en) | 2013-03-21 |
| JP2014526615A (en) | 2014-10-06 |
| CN104080606A (en) | 2014-10-01 |
| JP6159726B2 (en) | 2017-07-05 |
| CN104080606B (en) | 2016-12-07 |
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