CN104103432A - Switch contact comprising molybdenum alloy coating and production method thereof - Google Patents
Switch contact comprising molybdenum alloy coating and production method thereof Download PDFInfo
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- CN104103432A CN104103432A CN201410348996.5A CN201410348996A CN104103432A CN 104103432 A CN104103432 A CN 104103432A CN 201410348996 A CN201410348996 A CN 201410348996A CN 104103432 A CN104103432 A CN 104103432A
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- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C18/00—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating
- C23C18/16—Chemical coating by decomposition of either liquid compounds or solutions of the coating forming compounds, without leaving reaction products of surface material in the coating; Contact plating by reduction or substitution, e.g. electroless plating
- C23C18/48—Coating with alloys
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/021—Composite material
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H11/00—Apparatus or processes specially adapted for the manufacture of electric switches
- H01H11/04—Apparatus or processes specially adapted for the manufacture of electric switches of switch contacts
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Abstract
The invention discloses a switch contact comprising a molybdenum alloy coating and a production method thereof. The switch contact comprises three layers of structures; the first layer is a hydrophobic rubber layer; the second layer is a sheet metal layer; the third layer is a molybdenum alloy chemical sediment layer; a plating solution adopted in the chemical sediment layer comprises 20 to 125 grams per liter of soluble molybdenum compounds; the molybdenum alloy coating is selectively deposited on the metal surface when the chemical deposition is performed on layered composites of the hydrophobic rubber layer and the sheet metal layer through the plating solution. According to the switch contact comprising the molybdenum alloy coating and the production method thereof, the switch contact is good in metal color, low in contact resistance, high in switching arc erosion resistance, long in service life and suitable for hot vulcanization bonding and forming with rubber.
Description
Technical field
Can be by being in contact with one another parts (namely electrical contact or contact) that the stream of can powering passes through and preparation method thereof thereby the present invention is specifically related in switch in a kind of electric power or electronic product or circuit between two conductors.
Background technology
Thereby electrical contact or contact are the important spare parts passing through by being in contact with one another the stream of can powering between two conductors in switch or circuit, bear the function of connection, carrying and disjunction normal current and fault current, are directly determining quality and the useful life of whole switch or circuit in its quality and useful life.Electrical contact or contact are mainly used in relay, contactor, air switch, current limiting switch, motor protecter, microswitch, instrument and meter, computor-keyboard, hand-held set, household electrical appliance, car electrics (on-load switch such as car window switch, switch for rear-vision mirror, lamp switch, actuating motor), earth leakage circuit-breaker etc.Electric contact or contact to prepare material a lot, mainly contain silver, silver-colored nickel, silver copper oxide, Agcdo, siller tin oxide, silver-tin oxide or indium oxide, Ag-ZnO, red copper, brass, phosphor-copper, bronze, tin copper, beryllium copper, copper nickel, packfong, stainless steel etc.
In the equipment such as car electrics, household electrical appliance, computor-keyboard and hand-held set, its switch block is usually the printed circuit board (PCB) (PCB) that is provided with contact and the combination that is provided with the rubber key of contact.Circular contact on PCB, is divided into the two halves of not conducting by straight line or curve (as S type curve).Contact on button is the circle that need not cut apart.With the circular contact of a same diameter on button, do aspectant contact with a circular contact on PCB, just can connect a circuit on PCB.Slider material on button is conductive rubber or metal.Contact resistance when conductive rubber contact contacts with PCB contact is larger, and conductive rubber contact is not suitable for the PCB circuit of large (for example electric current is greater than 50 milliamperes) of making current.Contact resistance when hard contact contacts with PCB contact is less, and hard contact both can be for the less PCB circuit of making current, also can be for the larger PCB circuit of making current.Thereby make the problems such as its application is restricted but metal current contact exists that chemicals-resistant burn into arc ablation resistance performance is undesirable, cost of manufacture is high.
In atmosphere, switch element produces electric spark or electric arc often at connection circuit or minute deenergizing.The existence of switching arc phenomenon, will make contact be oxidized and ablation, thereby and may make airborne organic carbonization produce carbon distribution, make the contact resistance of switch increase even and open circuit gradually.
The number of applying for a patent is that the patent document of 201220499100.X discloses " a kind of three-layered composite electric contact ", this contact is on the contact-making surface of copper base contact bodies, to plate one deck silver, make the electric conductivity of contact better, and will save production cost than adopting silver to make completely.Although conductivity and the conductivity of heat of silver are all the highest in all metals, the atmospheric corrosion resistance of silver is poor, salt spray resistance is poor.Hydrogen sulfide (the H of silver easily and in atmosphere
2s) reaction generates the silver sulfide of black.Silver is used as some contact, although initial surface resistance is little, be also restricted its useful life in atmosphere.Although silver-plated cost compare is low, silver is also one of noble metal.In addition, in such electric contact, there is no rubber layer, therefore, thereby this electric contact is unsuitable for carrying out with rubber, heat cure is bonding makes with heat cure moulding the rubber key that contains electric contact.The contact of only containing rubber layer, or the contact all being formed by conductive rubber, thereby just may be smoothly carry out the bonding and heat cure moulding of heat cure with other rubber, make the rubber key that contains contact, and can be in heat cure do not produce the quality problems such as excessive glue, Poor cohesion in bonding and heat cure forming process.
United States Patent (USP) 7169215 discloses the materials and methods of chemical deposition copper molybdenum alloy, the copper molybdenum alloy resistance of resulting alkali-free metal ion and alkaline-earth metal ions lower than 30 microhms/centimetre.This alloy deposition is on single silicon wafer, on silicon thermal oxidation layer, on copper and cobalt thin film on silicon substrate.This copper molybdenum alloy can be used as the barrier layer of metal interlevel and the interconnection material on chip.Although this copper molybdenum alloy can replace copper in these application, resistivity is higher than copper.In this invention, disclose palladium solution activation for base material, then allowed copper molybdenum on base material, carry out chemical deposition.
Japan Patent JP2001003179 discloses molybdenum compound has been joined to the method for preparing palladium molybdenum alloy in the chemical plating fluid of palladium, and prepared palladium molybdenum alloy coating has outstanding adhesive property and weldability.Japan Patent JP62060878 discloses the chemical plating fluid of a kind of nickel-molybdenum alloy that the aqueous solution of several compounds is formed together.
United States Patent (USP) 4019910 discloses the chemical plating fluid of preparing a kind of polymetallic nickel alloy.In this nickel alloy, except containing boron or phosphorus, also contain one or more metal as tin, tungsten, molybdenum or copper.The ester complexes that contains inorganic acid and polyacid or polyol reaction gained in this chemical plating fluid, as two boron esters, wolframic acid ester or the molybdates esters of glucoheptonic acid.This nickel alloy is mainly comprised of nickel, nickel content conventionally about 60% to about 95%(weight ratio) scope in.This alloy has good mechanical performance and decay resistance, and wherein some alloy, as phosphorous nickel alloy, particularly nickel-phosphorus-tin-copper alloy, has non magnetic or nonferromagnetic.Boron or phosphorus that the disclosed polymetallic nickel alloy of this invention contains larger content, as used as slider material, the boron of larger content or the existence of phosphorus, by the initial resistance of influencing contactor.Our test shows, the nickel alloy that pure nickel, nickel alloy (as monel or monel metal, nichrome etc.) that nickel content is large, nickeliferous stainless steel or the nickel obtaining by chemical plating are chief component, if as the contact of switch, all there is poor arc resistance energy and lower switch useful life.
The invention that the patentee's the number of applying for a patent is 201110193369.5 provides a kind of " pitted skin metal and rubber combined conductive particle ", is bonded, or cuts and form after bonding by metal faced with rubber matrix.Metal faced is pitted skin, has pit, salient point or both all have; Pit or salient point all have on metal faced outer surface, inner surface or two surfaces.The degree of depth of pit is less than metal faced thickness, and the height of salient point is not less than 1/10th of metal faced thickness.Metal faced material is metal or alloy, and outer surface can plate gold, silver, copper or nickel etc.; Rubber matrix is silicon rubber or polyurethane rubber etc.; Between metal faced and rubber matrix, can have adhesive linkage, adhesive linkage is heat vulcanizate stick, silane coupling agent or is the material identical with rubber matrix.Metal faced inner surface can scribble the auxiliary agents such as coupling agent.Metal faced intensity of the present invention is high, stable conductivity, and adhesive linkage intensity is high, rubber matrix elasticity foot.This invention does not have to propose how on metal faced outer surface, to obtain the concrete grammar of one or more layers coating.On the pitted skin of this invention, gold-plated silver waits noble metal, and because surface area is large, noble metal dosage is many, and cost is high.
As everyone knows, tungsten and molybdenum are the most frequently used refractory metals.Although tungsten has higher fusing point, lower vapour pressure and evaporation rate, in simple metal, after the conductivity of molybdenum comes silver, copper, gold, aluminium, also less than the resistivity of tungsten, zinc, nickel, cadmium, palladium, iron, platinum, tin, lead, antimony, titanium, mercury.Molybdenum is conducive to reduce the contact resistance of contact during as slider material.In addition, the hardness of molybdenum and molybdenum alloy is generally low than tungsten and tungsten alloy hardness.Lower hardness, is not only conducive to carry out roll extrusion and Punching Technology, and while being conducive to contact with another contact as contact, contact more closely, more reliable, dust fastness is better, thereby improves reliability of contact.The density of molybdenum is 10.23g/cm, is about half (density 19.36g/cm of tungsten) of tungsten, obtains identical thickness of coating, and molybdenum used is fewer.
The price of molybdenum is also low than tungsten, and correspondingly, the price of preparing the required soluble molybdenum compound of molybdenum alloy is also low than soluble tungsten compound.Therefore, prepare the cost of molybdenum alloy lower.
In present patent application, will disclose molybdenum alloy contact of arc ablation resistance and preparation method thereof, this contact is owing to comprising rubber layer, thereby thereby can carry out with rubber the rubber key of the bonding and contact that heat cure moulding preparation comprises arc ablation resistance of heat cure.
Summary of the invention
The first goal of the invention: overcome gold-plated, the money base of tradition or the silver-plated defect that switch contact cost is higher, arc resistance is not too high, although although or overcome copper base, tinbase, Ni-based or stainless steel contact cost compared with shortcoming low but that arc resistance is poor, overcome tungsten alloy contact arc ablation resistance better but the shortcoming that hardness is large, manufacturing cost is higher, provide that a kind of low cost of manufacture, On current are large, the switch contact of the plating molybdenum alloy of arc ablation resistance.
The first technical scheme: a kind of switch contact that contains molybdenum alloy coating provided by the invention, switch contact is the layered composite with three layers of layer structure, ground floor is the hydrophobic rubber layer that 0.1mm to 10mm is thick, and the second layer is the layer of metal foil that 0.01mm to 1.0mm is thick, and the 3rd layer is 2*10
-5the molybdenum alloy coating that-0.02mm is thick; Wherein, the complex that the 3rd layer of molybdenum alloy coating is ground floor and the second layer is immersed in the chemical plating fluid that contains soluble molybdenum compound, the surface that by the method for chemical deposition, the coating of molybdenum alloy is deposited on to the second layer in the complex of ground floor and the second layer forms, in molybdenum alloy coating, contain weight ratio and be not less than 30% molybdenum element, contain transition metal elemental nickel, cobalt, copper or major element tin, antimony, lead or bismuth etc. that weight ratio is 0-70%, allow to contain a small amount of phosphorus or boron.
The ion that adds the transition metals such as nickel, cobalt, copper, manganese in the plating solution of molybdenum alloy, is in order to make coating and metal base bonding firmly, and in order to accelerate the speed of chemical deposition.In plating solution, can also add the ion of the elements such as tin, antimony, lead or bismuth, so that coating obtains specific performance.Such as, in plating solution, add a small amount of stannous ion, or add stannous ion, antimony ion and lead ion simultaneously, can make the hardness of coating decline.Owing to having used the reducing agent of phosphorous or boracic, a small amount of phosphorus also may be deposited in coating.But because the content of phosphorus in coating and boron is high, will make the initial surface resistance of coating increase, therefore, should take to control the measures such as the concentration of reducing agent in plating solution and bath temperature, control the content of phosphorus and boron in coating.
Adopting molybdenum alloy to do outermost layer reason is: metal molybdenum is stable chemical nature in atmosphere, is refractory metal, although fusing point is lower than tungsten, but in the circuit of reduced-current, as contact, use, its life-span is also very long, and, compare with tungsten, the hardness of molybdenum alloy is also lower, and the resistivity of metal molybdenum is also more smaller than tungsten, therefore, during as slider material, being conducive to reduce the contact resistance of contact, is good slider material.
The cost ratio tungsten of molybdenum is low, and correspondingly, the price of preparing the required soluble molybdenum compound of molybdenum alloy is also low than soluble tungsten compound.Therefore, prepare the cost of molybdenum alloy lower.
The compound that can add nickel, cobalt, copper other soluble transition metal element in addition in plating solution, and the compound of solubility major element is as tin compound, antimonial, bismuth compound and lead compound, but should note the optionally impact on deposited base material on chemical plating of these compounds.In addition also to note, physiology toxicity, environmental toxicity and the danger of these compounds.Such as, should use less maybe need not be to human body and the harmful soluble lead compound of environment as far as possible.Although silver is element conventional in electrical contact or contact, do not advise adding the silver soluble compounds such as silver nitrate in molybdenum alloy plating solution.Because we find in experiment, in molybdenum alloy plating solution, add after a certain amount of silver nitrate (as 5g/L), when the layered composite of the layer of metal foil of the hydrophobic rubber layer of ground floor and the second layer is carried out to chemical plating, the chemical deposition occurring, to not occur over just in the layer of metal foil that the second layer is, also occur on the hydrophobic rubber layer of ground floor, chemical deposition has not just had selectivity to base material like this.When sedimentation time long enough, with the naked eye just can be clear that on hydrophobic rubber layer He in layer of metal foil and have grey black or argenteous sedimentary deposit.Use X-ray fluorescence spectra analysis, a large amount of silver is all contained on the discovery surface of layer of metal foil and the surface of hydrophobic rubber layer.Use same formula to cancel after adding of silver nitrate,, in the process of chemical plating, chemical deposition layer is only created on the metal covering of layer of metal foil.
In general, the hydrophobicity of elastomeric material used is stronger, is more conducive to molybdenum alloy and uses in the present invention on the metal covering in rubber-metal stratiform compound and deposit, and on the surface of elastomeric material, do not deposit.Hydrophily rubber, the elastomeric material that contains surfactant or antistatic agent, the elastomeric material that contains a large amount of hydrophilies or water absorption filler, water-expansible rubber material, should not be used in the present invention.If use these elastomeric materials, when carrying out chemical plating, will make molybdenum alloy also be deposited on these elastomeric materials.
As optimization: described hydrophobic rubber layer is because carboxyl, hydroxyl, carbonyl, amino, amide groups, itrile group, nitro, halogen, sulfydryl, sulfonate radical and benzene sulfonic acid radical content on rubber molecular chain are low, thereby the elastomeric material that makes the water contact angle of rubber surface be greater than 65o forms; Or, described hydrophobic rubber layer be due in rubber not containing or contain a small amount of hydrophilic filler or additive, thereby the elastomeric material that makes the water contact angle of rubber surface be greater than 65o forms.Elastomeric material is thermosetting or thermoplasticity.
As optimization: described hydrophobic rubber layer is prepared from by ethylene propylene diene rubber, methyl vinyl silicone rubber or methyl ethylene phenyl siloxane rubber.Ethylene propylene diene rubber, methyl vinyl silicone rubber and methyl ethylene phenyl siloxane rubber are non-polar rubbers, hydrophobicity is strong, and their good weatherability can keep for a long time good elasticity in atmosphere simultaneously, therefore, they are materials of the preferential use of described hydrophobic rubber layer.The acrylonitrile-butadiene rubber of high nitrile group content and hydrogenated nitrile-butadiene rubber, carboxyl end of the liquid acrylonitrile-butadiene rubber, chlorosulfonated polyethylene rubber, epichlorohydrin rubber, acrylate rubber, polyurethane rubber isopolarity rubber, and the polarity of the material such as the rubber of hydrophiling (as hydrophily silicon rubber) and water-expansible rubber is large or contain a large amount of hydroaropic substances, these material surface hydrophobicitys are not strong.These materials are in containing the chemical plating fluid of soluble molybdenum compound, and molybdenum alloy coating will be deposited on the surface of these materials.
Hydrophobic rubber in hydrophobic rubber layer has repulsion ability to glassware for drinking water, and water can not come at hydrophobic rubber surface spreading.In order to obtain the selective chemical deposition of molybdenum alloy on metal material, the hydrophobicity of the quality of rubber materials in the complex by ground floor hydrophobic rubber layer and second layer metal thin slice is more high better.When carrying out chemical deposition with plating solution, for the alloy that makes to be deposited on ground floor hydrophobic rubber layer is negligiblely few, the water contact angle of rubber substrate need be greater than 65o.Here so-called selective chemical deposition, refers to molybdenum alloy coating, is optionally deposited on metal material, and is not deposited on quality of rubber materials.Carboxyl, hydroxyl, carbonyl, amino, amide groups, itrile group, nitro, halogen, sulfydryl, sulfonate radical and benzene sulfonic acid root on rubber molecular chain, will increase polarity and the hydrophily of rubber.Particularly carboxyl, hydroxyl, sulfonate radical and benzene sulfonic acid root, will increase polarity and the hydrophily of rubber greatly.If what use in the complex of rubber and metal is the carboxylic rubber that hydrophily is strong, chemical deposition will both can occur in metal surface, also occurred in quality of rubber materials surface simultaneously.If there is the sedimentary deposit of molybdenum alloy on quality of rubber materials, the plating solution of chemical plating will not only be wasted, and the heat cure that is unfavorable for quality of rubber materials and other quality of rubber materials is bonding or thermoplastic bonded, and this heat cure is bonding or thermoplastic bonded is necessary in following process.The existence of ground floor hydrophobic rubber layer, exactly for ground floor hydrophobic rubber layer and other rubber carry out the bonding or thermoplastic bonded of heat cure, thus the rubber key that preparation comprises contact.
Therefore, must limit the content of these polar groups in rubber substrate, to obtain the good molybdenum alloy chemical deposition of selectivity.In order to obtain the chemical deposition of selectivity the best, in rubber substrate, can not contain these groups.Same reason, quality of rubber materials body or surface do not contain or contain on a small quantity filler, additive or the surfactant that hydrophily is strong, are also conducive to obtain optionally chemical deposition.
Ethylene propylene diene rubber, methyl vinyl silicone rubber, methyl ethylene silicon phenyl rubber are the elastomeric materials that polarity is more weak, hydrophobicity is more intense, are suitable for carrying out compound preparation layered composite with sheet metal.When the chemical plating fluid of stating before use carries out chemical plating, chemical deposition does not occur on rubber layer.
As optimization: the layer of metal foil of the described second layer is the metal sheet with salient point or concave point, have convex line bar or concave bar metal sheet, have convex surface or concave surface metal sheet, there is area and be less than 1mm
2metal sheet, the order number of the aperture wire netting, metal foam or the metallic fiber sintered felt that are greater than 100 so that larger with the contact footprint pressure on PCB, conduction is better; Metal material is magnesium, aluminium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin or the alloy that contains these elements; The sheet metal of the second layer be single metal material or different metal materials stratiform compound; The metal or alloy that preferably conductivity is higher and price comparison is low.
As optimization: the sheet metal of the described second layer consists of the thick stainless steel of 0.01mm to 1.0mm, copper or copper alloy, nickel or nickel alloy thin slice, at the one or both sides of stainless steel, copper or copper alloy, nickel or nickel alloy thin slice, be coated with pure-nickel-layer or the nickel alloy layer of 0.1 micron to 10 microns; Nickel alloy layer on stainless steel, copper or copper alloy, nickel or nickel alloy thin slice is to be prepared by the method for vacuum coating, plating or chemical plating.On stainless steel, copper or copper alloy, nickel or nickel alloy thin slice, plate one deck pure-nickel-layer or nickel alloy layer, can improve the bonding strength of sheet metal and molybdenum alloy coating, avoid molybdenum alloy coating to come off in the use procedure of contact.Particularly copper and copper alloy thin slice should plate skim pure-nickel-layer or nickel alloy, to improve the resistance to oxidation of copper and copper alloy, the performance of resistance to chemical attack before chemical deposition molybdenum alloy coating on copper and copper alloy thin slice.
Thereby stainless steel is the special stainless steel of the corrosion of common stainless steel, acid resisting steel or the atmospheric corrosion resistance that improves, the particularly atmosphere of resistance to chloride that has added molybdenum element.
The thickness of sheet metal should not be excessively thin.If the sheet metal thickness of the second layer, lower than 0.01mm, just can not support the molybdenum alloy coating of the 3rd layer well, with rubber combined before, among or in processing afterwards, easily break.If the sheet metal of the second layer is too thick, will increase the integral hardness of contact, waste metal material simultaneously.So the thickness of sheet metal, should not be greater than 1.0mm.
In advance the hydrophobic rubber layer of ground floor and the sheet metal of the second layer being made to layered composite, is using layered composite as contact application in preparing rubber key for convenient.Hydrophobic rubber in layered composite, can be directly and other rubber carry out the bonding or thermoplastic bonded of heat cure and form rubber key.If will have the sheet metal oneself of rubber layer and other rubber to carry out the bonding or thermoplastic bonded of heat cure, do not form rubber key, excessive glue phenomenon will occur in moulding process.The so-called glue phenomenon of overflowing, refers in moulding process, rubber overflows to the front of contact, thus the electric conductivity of influencing contactor.On contact, having excessive glue phenomenon, is unacceptable to the quality of contact.
The second goal of the invention: a kind of preparation method that the above-mentioned switch contact that contains molybdenum alloy coating is provided.
The second technical scheme: a kind of preparation method of the switch contact that contains molybdenum alloy coating, comprises the steps:
(1) processing of sheet metal: sheet metal is stainless steel, copper or copper alloy, nickel or the nickel alloy thin slice that 0.01mm to 1.0mm is thick; With cleaning agent and organic solvent, sheet metal is carried out to oil removing, cleaning; Or by sandblast, polishing, sheet metal is carried out to surperficial mechanical roughening treatment; Or process to process out by chemical etching pit or the salient point that diameter is less than 1mm; Or at the one or both sides of sheet metal, with electroplating or the method for chemical plating is coated with pure-nickel-layer or the nickel alloy layer of 0.1 micron to 10 microns; Then with cleaning agent and organic solvent, resulting sheet metal is carried out to oil removing, cleaning;
(2) adhesion process of hydrophobic rubber and sheet metal: hydrophobic rubber, by heat cure moulding, is bonded on the sheet metal that scribbles silane coupling agent or adhesion promotor, the composite sheet of formation stratiform; Or will there is tack hydrophobic rubber, by heat cure moulding, be bonded in the layer of metal foil that scribbles silane coupling agent or there is no silane coupling agent, form the composite sheet of stratiform;
(3) cutting process: the composite sheet in above-mentioned steps cut apart or be die-cut into the cylinder that diameter is 2-10mm, cleaning approximately 5 minutes with alkaline cleaning fluid, washing, then uses 5% hydrochloric acid cleaning 3 minutes, then cleans up with deionized water, is filtered dry; The object of the hydrochloric acid cleaning with 5%, is the oxide for remove portion metallic substrate surface, makes metallic substrate surface activation, strengthens the bond strength between metal base and molybdenum alloy coating.Using other to clean and acid solution activation method, is also feasible.
(4) preparation of molybdenum alloy coating: by above-mentioned cylinder, be immersed in the chemical plating fluid that contains soluble molybdenum compound, stir, form molybdenum alloy coating by the method for chemical plating; Or, above-mentioned cylinder is put into the cylinder of the chemical plating fluid that contains soluble molybdenum compound, allow cylinder rotate, in the metal surface of small cylinder, form molybdenum alloy coating;
The soluble molybdenum compound that contains 20-125g/L in plating solution, the transition metal iron of the solubility of 0-60g/L, nickel, cobalt, the compound of copper or manganese or the combination in any of these compounds, the tin of the solubility of 0-30g/L, antimony, the combination in any of lead or bismuth compound or these compounds, the reducing agent of 20-100g/L, the complexing agent of 30-150g/L, the pH value conditioning agent of 20-100g/L, the stabilizer of 0.1-1g/L, the surfactant of 0.1-1g/L, the brightener of 0-50 g/L or roughness conditioning agent, also can in plating solution, add other auxiliary agent, as chemical plating accelerator.Accelerator can be selected sodium fluoride.Sodium fluoride can be used as accelerator, also can increase the brightness of coating simultaneously;
Preferably select inferior sodium phosphate as reducing agent.When using inferior sodium phosphate as reducing agent, the temperature of molybdenum alloy chemical plating that coating adopts is 65-90 ℃, and the time is 30-300 minute, and the pH value of plating solution is 8.5-9.5.
(5) clean, dry: take out plated body, by distilled water or rinsed with deionized water, drain, cold wind dries up or be placed in the constant temperature oven of 70 ℃ and dry, and obtains being coated with the switch contact of molybdenum alloy.
In the present invention, described soluble molybdenum compound be sodium molybdate, potassium molybdate, ammonium molybdate, phosphomolybdic acid, ammonium phosphomolybdate, molybdic acid, molybdenum trioxide.When use is slightly soluble in the molybdic acid of water or water-fast molybdenum trioxide as molybdenum source, can first with sodium hydroxide solution, it be dissolved, then with it, prepare chemical plating fluid.
The compound of described soluble transition metal nickel, cobalt, copper is one or more in nickelous sulfate, nickel chloride, nickel nitrate, ammonium nickel sulfate, basic nickel carbonate, nickel sulfamic acid, nickel acetate, nickelous hypophosphite, cobaltous sulfate, cobalt chloride, cobalt nitrate, ammonium cobaltous sulfate, basic cobaltous carbonate, sulfamic acid cobalt, cobalt acetate, cobalt oxalate, copper sulphate, copper chloride, copper nitrate, hydration basic copper carbonate, copper acetate.We find during molybdenum alloy in plating, but in chemical plating fluid the precursor of nickel use nickelous sulfate and basic nickel carbonate composite, can make to plate molybdenum alloy layer there is brighter silvery white, the sheet resistance of gained Mo-Ni alloy coating is lower.
Described reducing agent is one or more in inferior sodium phosphate, sodium borohydride, alkylamine borine, hydrazine.If take boron hydride or amino borane during as reducing agent, will contain a small amount of boron (mass fraction can reach 7%) in molybdenum alloy coating.With hydrazine, make reducing agent, the content of nonmetal in resulting coating (phosphorus or boron) is almost nil, and tenor can reach more than 99%.While selecting inferior sodium phosphate to be reducing agent, owing to there being phosphorus to separate out, there is the codeposition of phosphorus and metal, in coating, apart from metal molybdenum, cobalt, nickel, also contain the phosphorus (mass fraction can reach l5%) of small part outward.Phosphorus is harmful to the conductivity of contact, and may injure the decay resistance of molybdenum alloy, therefore, and the essential phosphorus content of controlling in molybdenum alloy.By controlling the concentration of inferior sodium phosphate, the measures such as the concentration of complexing agent, pH value can be controlled the phosphorus content in coating.Control the molybdenum alloy coating that phosphorus content can obtain densification, atresia.The inferior sodium phosphate that in the present invention, preferential use price is lower and toxicity is lower.Select inferior sodium phosphate as reducing agent, contact resistance between our resulting molybdenum alloy coating and molybdenum alloy coating, less than 99.5% pure nickel and the contact resistance between 99.5% pure nickel, resulting coating can significantly reduce nickel alloy base material and stainless steel substrate initial contact resistance, improve its resistance to switching arc performance.
Described complexing agent is one or more in natrium citricum, ammonium citrate, sodium tartrate, sodium potassium tartrate tetrahydrate, disodium EDTA, tetrasodium salt of EDTA.The effect of complexing agent is to control to improve bath stability for the concentration of the free metal ion reacting, and extends bath life, improves quality of coating.Complexing agent all has impact to deposition rate, phosphorus content and corrosion resistance etc.
As preferably, when adopting inferior sodium phosphate as reducing agent, the pH value of plating solution is 8.5-9.5.Described pH adjusting agent is one or more in NaOH, potassium hydroxide, sodium carbonate, ammoniacal liquor, sodium pyrophosphate.The preferential pH value of using ammoniacal liquor or sodium hydroxide solution to regulate plating solution.Can obtain like this adhesion more by force, more stable, the better molybdenum alloy coating of quality of coating.The time of chemical plating is longer, and the molybdenum alloy coating being deposited on metal base will be thicker.Thicker molybdenum alloy coating is conducive to the resistance to switching arc performance of contact.But the time of chemical plating is not that the longer the better.The overlong time of chemical plating, not only production efficiency is low, and with alkaline chemical plating fluid, may injure the hydrophobic rubber layer of ground floor and the bonding strength between the layer of metal foil of the second layer, even causes delamination.PH value can not be greater than 12, although because too high pH accelerates deposition velocity, make the adhesive force variation between coating or sedimentary deposit and metal base, makes darkening of coating or sedimentary deposit, even becomes black.In plating solution, can add strong acid weak base salt or strong base-weak acid salt, as the pH buffer of plating solution.
As optimization: when not considering color, gloss, described stabilizer is KI, Potassiumiodate, benzotriazole, 4,5-bis-sulfo-octane-1, the mixture of one or more in 8-disulfonate, 3-sulfydryl-1-propane sulfonic acid salt, sodium thiosulfate, thiocarbamide.When considering color, gloss, described stabilizer is preferably sodium thiosulfate, thiocarbamide or both mixtures, makes molybdenum alloy coating have good metallic luster simultaneously.Thereby the effect of stabilizer is the self-catalyzed reaction that suppresses to occur in chemical plating process stablizes plating solution, prevents fierce self-catalyzed reaction, prevent from generating a large amount of phosphorous ferrous metal powder.But stabilizer is the poisonous agent of chemical plating, i.e. anticaltalysis reaction, so can not excessively use, needs to control its consumption in plating solution, in order to avoid affect chemical plating efficiency.
Described surfactant is: the surfactant of one or more in dodecyl benzene sulfonate, lauryl sulfate, n-octyl sodium sulphate; Be preferably: lauryl sodium sulfate or neopelex.Add a little surfactants to contribute to overflowing of plating piece surface gas, reduce the porosity of coating, make coating fine and close, thereby increase the arc resistance energy of coating.
As optimization: in the plating solution that described chemical plating adopts, the chemical plating brightener that contains 0.05-50g/L; Described chemical plating brightener is butynediols, propilolic alcohol, 1-diethylin third-2-alkynes, ethoxyquin propilolic alcohol, benzoic sulfimide sodium (saccharin sodium), sodium vinyl sulfonate, propine sodium sulfonate, pyridine-2-hydroxy-propanesulfonic acid inner salt, APES (such as the APES of commodity OP-10 by name) or the commercial chemical plating brightener such as commercially available.
The time of chemical plating selected, requires relevant with performance requirement or the useful life of the arc ablation resistance of switch product.The time of chemical plating is longer, and the molybdenum alloy coating being deposited on metal base will be thicker.Thicker molybdenum alloy coating is conducive to the resistance to switching arc performance of contact.But the time of chemical plating is not that the longer the better.The overlong time of chemical plating, not only production efficiency is low, and the chemical plating fluid of meta-alkalescence, may injure the hydrophobic rubber layer of ground floor and the bonding strength between the layer of metal foil of the second layer, even causes delamination.As preferably, if required, under the On current of 500mA, on-off times can be more than 10,000 times, and the time of described molybdenum alloy chemical plating that coating adopts is 200 minutes.The temperature of rising chemical plating fluid, can make the speed of chemical deposition accelerate, but too high bath temperature (higher than 90 ℃), will the darkening of chemical deposit, coating be declined to the adhesive force of metal base.
In the present invention, use the complex of hydrophobic rubber layer and layer of metal foil, with above-mentioned plating solution, carry out chemical plating, can make molybdenum alloy coating be deposited on metallic surface.We detect the molybdenum element content of metal surface with Xray fluorescence spectrometer (XRF), can find, in same plating solution, along with the prolongation of chemical plating time, the molybdenum signal detecting in metal surface is more and more stronger.Molybdenum signal is more and more stronger, means that molybdenum alloy coating is more and more thicker along with the chemical plating time.Even but chemical plating is for up to 300 minutes, the molybdenum signal detecting on hydrophobic rubber surface is almost nil.
Beneficial effect:
The present invention's method with chemical plating in the layered composite of hydrophobic rubber layer and sheet metal optionally plates one deck containing the alloy of molybdenum on sheet metal, can effectively improve conductivity and the resistance to switching arc ablation property of sheet metal.The contact that is coated with molybdenum alloy layer being made by stainless steel substrates (as SS304 stainless steel substrates), nickel sheet (as N6 nickel sheet), nickel alloy sheet (as NCu30 monel), contact with the gold plated contact on printed circuit board (PCB) (PCB), contact resistance between contact, less than the similar contact and the contact resistance between the gold plated contact on printed circuit board (PCB) (PCB) that do not plate molybdenum alloy, there is good conduction property.By not plating the stainless steel substrates of molybdenum alloy or contact that nickel sheet makes and PCB gold plated contact by the direct current of 300 milliamperes, under room temperature continuously after about 2000-4000 time of switch, arc erosion owing to there is switch, contact resistance between sequin and PCB gold plated contact just obviously raise (being increased to more than 100 ohm not even conducting by approximately 1 ohm); And under same circuit condition, by the present invention, being coated with the similar contact of molybdenum alloy and PCB contact by the direct current of 300 milliamperes, after switch approximately 8000 times, the contact resistance between contact and PCB contact, still below 1 ohm.
This contact that is coated with molybdenum alloy, with the switch contact comparison that is coated with gold, platinum or silver, can by or bear larger electric current, there is good arc ablation resistance performance.And the price of metal molybdenum is not higher than gold, platinum or silver, also low than tungsten.
Regulate the formula of plating solution to form and time and the temperature of chemical plating, can there be the appearance effect such as color, gloss that are similar to yellow gold, silver, silver, steel or some titanium nitride the contact of gained.Especially, use the molybdenum alloy plating solution in the present invention, can be relatively easy to obtain close to argenteous molybdenum alloy.Product of the present invention is applicable to various high-grade places, is particularly suitable for making in the electric appliance and electronic equipment such as automobile, electric tool, game machine, needs to be greater than the switch contact that 50mA electric current passes through under button.
Hydrophobic rubber layer is contained in molybdenum alloy contact in the present invention, thereby have, is easy to carry out the bonding and moulding of heat cure with rubber and makes the characteristic containing the rubber key product of contact.
Accompanying drawing explanation
Fig. 1 is a kind of cross-sectional view of the present invention; In figure: 1, rubber layer; 2, layer of metal foil; 3, molybdenum alloy coating.
Fig. 2 is a kind of process chart in preparation method of the present invention.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1:
Plating solution forms: Sodium Molybdate Dihydrate 50g ∕ L, nickel sulfate hexahydrate 20g/L, a waterside sodium phosphite 40g ∕ L, sodium acetate 25g/L, natrium citricum 50g/L, sodium fluoride 2g/L, ammonium sulfate 20g/L, thiocarbamide 0.2g/L, sodium potassium tartrate tetrahydrate 30g ∕ L, sodium pyrophosphate 24g ∕ L, Potassiumiodate 40mg ∕ L, lauryl sodium sulfate 0.5g/L.Ammoniacal liquor adds in right amount, and the pH value of plating solution is maintained between 8.5 to 9.5.
Process route:
As shown in Figure 1, by the one side of the thick smooth stainless steel substrates (stainless steel model 304) of 0.1mm, carry out mechanical roughening treatment (sandblast or sand papering), then carry out alkaline degreasing, with deionized water, clean up again, air-dry, stainless steel is carried out to primary coat processing through the one side of sandblast alligatoring with a kind of rubber to metal adhesive Chemlok CH238, then, this one side that primary coat was processed, with the elastomeric compound of ethylene propylene diene rubber (EPDM) carries out the bonding and heat cure moulding of heat cure, form the thick stainless steel-EPDM composite sheet of 1.0mm.Wherein, stainless steel substrates is made layer of metal foil 2, and EPDM is rubber layer 1, the formula of EPDM elastomeric compound is: DPDM(trade mark Keltan 514) 100(weight portion, lower same), zinc oxide 5, sulphur 1.5, stearic acid 1.0, Fumed silica 45, paraffin oil 15, accelerant B Z 2.0, altax 1.0, acceterator TE TD 0.4, Vulcanization accelerator TMTD 0.4, TM monex TM 1.0.
Stainless steel-EPDM composite sheet of gained is die-cut into the small cylinder that diameter is 2-10mm, this roundlet grain is cleaned approximately 5 minutes with alkaline cleaning fluid, washing, then uses 5% salt acid soak 3 minutes, then with deionized water, cleans up, and is filtered dry, and cold wind dries up.
By 500 such sequins, put into the above-mentioned 300ml plating solution of 70 ℃, stir, after 200 minutes, take out, by distilled water or rinsed with deionized water, drain, cold wind dries up or be placed in the constant temperature oven of 70 ℃ and dry, and obtains the metal faced little round shaped grain that is coated with molybdenum alloy coating 3.In the process of chemical plating, should constantly note the pH value situation of change of solution, add in time the pH value that ammoniacal liquor or sodium hydroxide solution are controlled solution, make pH value again between 8.5 to 9.0.The time that the thickness of the molybdenum alloy that plates is placed in plating solution with little round shaped grain is relevant.The time of placing is longer, and the thickness of Mo-Ni alloy coating is thicker.Mo-Ni alloy is the deposition of the stainless steel surfaces in little round shaped grain only, not the deposition of the rubber surface in little round shaped grain.
This little round shaped grain that is coated with molybdenum alloy, (it is bonding that the rubber face in little round shaped grain and other rubber carry out heat cure to carry out the bonding and heat cure moulding of heat cure with above-mentioned EPDM elastomeric compound, be coated with the one side of molybdenum alloy outwardly), make the rubber key that contains molybdenum alloy contact.As the contact that is used as contactor in rubber key, this contact contacts with the gold plated contact of printed circuit board (PCB) (PCB), the contact resistance of contact is lower than the little round shaped grain and the contact resistance between the gold plated contact of PCB that are directly made by stainless steel substrates, and this little round shaped grain that is coated with molybdenum alloy has better conducting stability: the little round shaped grain being made by the stainless steel that there is no molybdenum alloy coating and PCB gold plated contact are by the direct current of 300 milliamperes, after switch approximately 3000 times, because existence is opened, arc erosion during pass, contact resistance between little round shaped grain and PCB gold plated contact just obviously raises and (by approximately 1 ohm, is increased to more than 100 ohm, during test of many times, even can there is the situation of not conducting), and under same circuit condition, this little round shaped grain that is coated with Mo-Ni alloy and PCB gold plated contact be by the direct current of 300 milliamperes, after switch approximately 8000 times, the contact resistance between this sequin and PCB gold plated contact, still below 1 ohm.
Embodiment 2
Plating solution forms: Sodium Molybdate Dihydrate 60g ∕ L, nickel sulfate hexahydrate 10g/L, four water basic nickel carbonate 10/L, hydrazine 100/L, sodium pyrophosphate 15g/L, sodium potassium tartrate tetrahydrate 20g ∕ L, lauryl sodium sulfate 0.5g/L.Ammoniacal liquor adds in right amount, and the pH value of plating solution is maintained between 8.5 to 9.5.
Process route
By the one side of the thick smooth stainless steel substrates (model 304) of 0.075mm, with the ferric trichloride etching solution of acidifying, etching equally distributed diameter is the aperture that 0.25mm, the degree of depth are 0.03-0.04mm, and aperture pitch is 0.25mm.Then this stainless steel substrates is carried out to alkaline degreasing, with deionized water, clean up again, air-dry, the rubber to metal adhesive Megum W 2535 of the water-based that the smooth one side of stainless steel is produced with a kind of U.S. Rhom and Hass carries out primary coat processing, then by be coated with this one side processed and the silicon rubber KE 751U of the Japan XINYUE's production that contains 1% cumyl peroxide (DCP) carry out heat cure bonding with heat cure moulding, form the thick stainless steel-silicon rubber composite sheet of 1.0mm, wherein stainless steel is layer of metal foil 2, and silicon rubber is rubber layer 1.Stainless steel-silicon rubber composite sheet of gained is die-cut into the small cylinder that diameter is 2-10mm, this roundlet grain is cleaned approximately 5 minutes with alkaline cleaning fluid, washing, then uses 5% salt acid soak 3 minutes, then with deionized water, cleans up, and is filtered dry.
By 500 such sequins, put into the above-mentioned 500mL plating solution of 90 ℃, stir, controlling pH value takes out after 200 minutes in 9.0 left and right, by distilled water or rinsed with deionized water, drain, then cold wind dries up, obtain the metal faced little round shaped grain that is coated with molybdenum alloy coating 3, this is namely coated with the contact of molybdenum alloy.
The contact that is coated with molybdenum alloy of gained, have close to argenteous metal appearance, and the useful life (on-off times) of this contact under 300 milliamperes of electric currents, be more than doubled, by the corresponding contact 3000 times of not plating molybdenum alloy, brought up to more than 10000 times.
Embodiment 3:
The 400 object stainless steel plain weave nets (stainless steel model is 304) of take replace the stainless steel substrates in embodiment 1, adopt technique and the chemical plating fluid implemented in 1, and prepared contact also has lower contact resistance and good arc ablation resistance performance.
400 object stainless (steel) wire mesh are very little, and when with silicon rubber moulded, silicon rubber can not penetrate the mesh of stainless (steel) wire.If select the stainless (steel) wire that order number is little, as the stainless (steel) wire below 80 orders, when mold pressing, will produce the technological problems that silicon rubber penetrates stainless steel mesh.Therefore, need to adopt the stainless (steel) wire of larger order number to prepare coated switch contact.
For those skilled in the art, under the premise without departing from the principles of the invention, can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (10)
1. a switch contact that contains molybdenum alloy coating, is characterized in that: switch contact is the layered composite with three layers of layer structure; Ground floor is the hydrophobic rubber layer that 0.1-10mm is thick, and the second layer is the layer of metal foil containing magnesium, aluminium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, niobium, molybdenum, silver or tin that 0.01-2.0mm is thick, and the 3rd layer is 2*10
-5the molybdenum alloy coating that-0.02mm is thick; Wherein, the complex that the 3rd layer of molybdenum alloy coating is ground floor and the second layer is immersed in the chemical plating fluid that contains soluble molybdenum compound, and the surface that by the method for chemical deposition, molybdenum alloy is deposited on to the second layer in the complex of ground floor and the second layer forms; In the 3rd layer of molybdenum alloy coating, contain weight ratio and be not less than 30% molybdenum element.
2. the switch contact that contains molybdenum alloy coating according to claim 1, it is characterized in that: described hydrophobic rubber layer is because carboxyl, hydroxyl, carbonyl, amino, amide groups, itrile group, nitro, halogen, sulfydryl, sulfonate radical and benzene sulfonic acid radical content on rubber molecular chain are low, thereby the elastomeric material that makes the water contact angle of rubber surface be greater than 65o forms; Or, described hydrophobic rubber layer be due in rubber not containing or contain a small amount of hydrophilic filler or additive, thereby the elastomeric material that makes the water contact angle of rubber surface be greater than 65o forms.
3. the switch contact that contains molybdenum alloy coating according to claim 1 and 2, is characterized in that: the rubber of described hydrophobic rubber layer a little less than by nonpolar or polarity is prepared from; Preferentially select ethylene propylene diene rubber, methyl vinyl silicone rubber or methyl ethylene phenyl siloxane rubber.
4. according to the switch contact that contains molybdenum alloy coating described in claim 1 or 3, it is characterized in that: described layer of metal foil is metal sheet, the metal sheet with convex line bar or concave bar, the metal sheet with convex surface or concave surface with salient point or concave point, have area is less than 1mm
2metal sheet, wire netting, metal foam or the metallic fiber sintered felt of aperture; Metal material is magnesium, aluminium, titanium, chromium, manganese, iron, cobalt, nickel, copper, zinc, tin or the alloy that contains these elements; Described layer of metal foil is that the stratiform of single metal material or different metal material is compounded to form.
5. according to the switch contact that contains molybdenum alloy coating described in claim 1 or 4, it is characterized in that: the sheet metal of described layer of metal foil consists of the thick stainless steel of 0.01-1.0mm, copper or copper alloy, nickel or nickel alloy thin slice, at the one or both sides of stainless steel, copper or copper alloy, nickel or nickel alloy thin slice, be coated with pure-nickel-layer or nickel alloy layer, pure cobalt layer or the cobalt alloy layer of 0.01-10 micron; Pure-nickel-layer on stainless steel, copper or copper alloy, nickel or nickel alloy thin slice or nickel alloy layer, pure cobalt layer or cobalt alloy layer are to be prepared by the method for vacuum coating, plating or chemical plating.
6. a preparation method who contains the switch contact of molybdenum alloy coating, is characterized in that: the preparation of switch contact comprises the steps:
(1) processing of sheet metal: sheet metal is stainless steel, copper or copper alloy, nickel or the nickel alloy thin slice that 0.01mm to 1.0mm is thick; With cleaning agent and organic solvent, sheet metal is carried out to oil removing, cleaning; Or by sandblast, polishing, sheet metal is carried out to surperficial mechanical roughening treatment; Or process to process out by chemical etching pit or the salient point that diameter is less than 1mm; Or at the one or both sides of sheet metal, with electroplating or the method for chemical plating is coated with pure-nickel-layer or the nickel alloy layer of 0.1 micron to 10 microns; Then with cleaning agent and organic solvent, resulting sheet metal is carried out to oil removing, cleaning;
(2) adhesion process of hydrophobic rubber and sheet metal: hydrophobic rubber, by heat cure moulding, is bonded on the sheet metal that scribbles silane coupling agent or adhesion promotor, the composite sheet of formation stratiform; Or by thering is the hydrophobic rubber of tack, by heat cure moulding, be bonded on the sheet metal that scribbles silane coupling agent or there is no silane coupling agent, form the composite sheet of stratiform;
(3) cutting process: the composite sheet in above-mentioned steps is cut apart or be die-cut into and include the cylinder that the diameter of hydrophobic rubber layer and layer of metal foil is 2-10mm, or the composite sheet in above-mentioned steps is cut apart or be die-cut into cross section for ellipse, polygon, cross, star, crescent or their object of combination in any; With alkaline cleaning fluid, clean approximately 5 minutes, washing, then uses 5% hydrochloric acid cleaning 3 minutes, then with deionized water, cleans up, and is filtered dry;
(4) preparation of molybdenum alloy coating: by above-mentioned cylinder or object, be immersed in the chemical plating fluid that contains soluble molybdenum compound, stir, form molybdenum alloy coating by the method for chemical plating in the metal surface of cylinder or object; Or, above-mentioned cylinder is put into the cylinder of the chemical plating fluid that contains soluble molybdenum compound, allow cylinder rotate, by the method for chemical plating, in the metal surface of cylinder or object, form molybdenum alloy coating;
The soluble molybdenum compound that contains 20-125g/L in plating solution, the transition metal iron of the solubility of 0-60g/L, nickel, cobalt, the compound of copper or manganese or the combination in any of these compounds, the tin of the solubility of 0-30g/L, antimony, the combination in any of lead or bismuth compound or these compounds, the reducing agent of 20-100g/L, the complexing agent of 30-150g/L, the pH value conditioning agent of 20-100g/L, the stabilizer of 0.1-1g/L, the surfactant of 0.1-1g/L, the brightener of 0-50 g/L or roughness conditioning agent,
Described soluble molybdenum compound is sodium molybdate, potassium molybdate, ammonium molybdate, phosphomolybdic acid, ammonium phosphomolybdate, molybdic acid, molybdenum trioxide;
When use is slightly soluble in the molybdic acid of water or water-fast molybdenum trioxide as molybdenum source, can first with sodium hydroxide solution, it be dissolved, then with it, prepare chemical plating fluid; Preferably inferior sodium phosphate is the reducing agent in plating solution; While adopting inferior sodium phosphate to be reducing agent, the temperature of molybdenum alloy chemical plating that coating adopts is 60-90 ℃, and the time is 30-300 minute, and the pH value of plating solution is 8.0-10.0;
(5) clean, cold wind dries up: after taking-up by distilled water or rinsed with deionized water, drain, cold wind dries up or be placed in the constant temperature oven of 70 ℃ and dry, and obtains the metal faced switch contact that is coated with molybdenum alloy.
7. the preparation method of the switch contact that contains molybdenum alloy coating according to claim 6, is characterized in that: while selecting inferior sodium phosphate as reducing agent in plating solution, the temperature of plating solution is 70-85 ℃, and the time of chemical plating is 150-200 minute; The pH value of plating solution is controlled between 8.5 to 9.0, in plating solution, contain there is the strong base-weak acid salt of pH buffer capacity or strong acid weak base salt and pH adjusting agent NaOH, one or more in potassium hydroxide, sodium carbonate, sodium acetate, ammoniacal liquor, sodium pyrophosphate, potassium pyrophosphate.
8. the preparation method of the switch contact that contains molybdenum alloy coating according to claim 6, it is characterized in that: described stabilizer is KI, Potassiumiodate, benzotriazole, 4,5-bis-sulfo-octane-1, the mixture of one or more in 8-disulfonate, 3-sulfydryl-1-propane sulfonic acid salt, sodium thiosulfate, thiocarbamide, is preferably sodium thiosulfate, thiocarbamide or both mixtures.
9. the preparation method of the switch contact that contains molybdenum alloy coating according to claim 6, it is characterized in that: in the plating solution that described chemical plating adopts, contain one or more in reducing agent inferior sodium phosphate, sodium borohydride, alkylamine borine, hydrazine or titanium trichloride, preferentially select inferior sodium phosphate.
10. the preparation method of the switch contact that contains molybdenum alloy coating according to claim 6, it is characterized in that: in the plating solution that described transition metal alloy coating, low tungsten alloy layer and tungsten alloy layer chemical plating adopt, the chemical plating brightener that contains 0.05-50g/L; Described chemical plating brightener is butynediols, propilolic alcohol, 1-diethylin third-2-alkynes, ethoxyquin propilolic alcohol, benzoic sulfimide sodium, sodium vinyl sulfonate, propine sodium sulfonate, pyridine-2-hydroxy-propanesulfonic acid inner salt, APES or commercially available commercial chemical plating brightener.
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| CN201410348996.5A CN104103432B (en) | 2014-07-21 | 2014-07-21 | Switch contact containing molybdenum alloy coating and preparation method thereof |
| PCT/CN2015/084166 WO2016011910A1 (en) | 2014-07-21 | 2015-07-15 | Switch contact with molybdenum alloy plating and preparation method for same |
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| CN108517516A (en) * | 2018-05-29 | 2018-09-11 | 电子科技大学 | A kind of chemical plating liquid and preparation method thereof |
| CN110541150A (en) * | 2019-08-22 | 2019-12-06 | 沈阳科友真空技术有限公司 | Multilayer film structure for reed switch relay contact and preparation method thereof |
| CN110541150B (en) * | 2019-08-22 | 2024-05-03 | 沈阳科友真空技术有限公司 | Multilayer film structure for reed switch relay contact and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| WO2016011910A1 (en) | 2016-01-28 |
| CN104103432B (en) | 2015-11-18 |
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