CN105489420A - Composite of foamed rubber and metal and preparation method of composite - Google Patents
Composite of foamed rubber and metal and preparation method of composite Download PDFInfo
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- CN105489420A CN105489420A CN201511008697.8A CN201511008697A CN105489420A CN 105489420 A CN105489420 A CN 105489420A CN 201511008697 A CN201511008697 A CN 201511008697A CN 105489420 A CN105489420 A CN 105489420A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01H—ELECTRIC SWITCHES; RELAYS; SELECTORS; EMERGENCY PROTECTIVE DEVICES
- H01H1/00—Contacts
- H01H1/02—Contacts characterised by the material thereof
- H01H1/04—Co-operating contacts of different material
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/2006—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30
- C23C18/2046—Pretreatment of the material to be coated of organic surfaces, e.g. resins by other methods than those of C23C18/22 - C23C18/30 by chemical pretreatment
- C23C18/2073—Multistep pretreatment
- C23C18/2086—Multistep pretreatment with use of organic or inorganic compounds other than metals, first
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/22—Roughening, e.g. by etching
- C23C18/24—Roughening, e.g. by etching using acid aqueous solutions
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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
- C23C18/18—Pretreatment of the material to be coated
- C23C18/20—Pretreatment of the material to be coated of organic surfaces, e.g. resins
- C23C18/28—Sensitising or activating
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/22—Conductive material dispersed in non-conductive organic material the conductive material comprising metals or alloys
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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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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Metallurgy (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
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- Mechanical Engineering (AREA)
- Organic Chemistry (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Dispersion Chemistry (AREA)
- Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
Abstract
The invention discloses a composite of foamed rubber and metal and a preparation method of the composite. A continuous metal network is formed by carrying out chemical plating and electroplating on the inner wall surface of holes of opened foamed rubber or opened and closed hybrid foamed rubber, so that the composite of the foamed rubber and the metal in which the rubber and the metal are tightly combined is obtained. The material for preparing the composite is wide in selection, the composite has the flexibility of the rubber and also has the conductivity of the metal, the contact resistance can be lower to be below 1 ohm, the conductive performance is excellent, and the composite can be used as a conductive material or an electromagnetic shielding material. Since the composite contains the rubber, the composite is easy to bond with a rubber material in a heat vulcanization way, and is particularly and suitably used for preparing a contact material in a rubber key.
Description
Technical field
The invention belongs to electric conducting material field, be specifically related to a kind of foam rubber and metal form compound method by chemical plating and plating.
Background technology
As everyone knows, General Purpose Rubber is insulator.Being filled in elastomeric material by the carbon class material (as conductive black, carbon fiber, graphite, carbon nano-tube and Graphene) of conduction and metal material (as metal dust, metallic fiber etc.), is the main method preparing conductive rubber.Like this with conductive rubber prepared by the method for filled conductive filler, be widely used.But because added conductive filler is dispersion, such conductive rubber, specific insulation and surface resistivity are still large than common metal electric conducting material, and the ability of conducting larger current seems not enough in some occasion.Such conductive rubber is as switch contact material, and also can only be applied in the circuit of electric current less (being such as less than 200 milliamperes), guarantee switch contact has suitable useful life.
Application number be 201010592410.1 patent documentation " composite conducting strip " disclose by macromolecule matrix and be compounded in the composite conducting strip that metal forming wherein forms.Here metal forming refers to that, containing pertusate nickel foil, Copper Foil, aluminium foil, stainless steel foil, goldleaf, silver foil or mesh grid, macromolecule matrix refers to silicon rubber, nitrile rubber, ethylene-propylene rubber, natural rubber, rubber-plastics material, thermoplastics, thermoset plastics or fibre reinforced plastics etc.Application number be 201010609386.8 patent documentation " a kind of conductive rubber and application thereof " disclose, with mold pressing or injection system, rubber and metallic fiber sintered felt (or metal nonwoven fabrics) compound obtained conductive rubber, this metallic fiber sintered felt has hole, and this hole is at least partly by rubber filling.Application number be 201010609385.3 patent documentation " method for producing conductive particles for key " disclose a kind of by shaping for metal embedded part heat cure together with the rubber production method preparing the conductive particle of button.Application number be 200680015484.0 patent documentation " electrically conducting contact and manufacture method thereof " disclose and to be permeated by elastomeric material at least in part by metal sponge thus the method for obtained conductive contact element.That is, which disclose a kind of by ready-made metal sponge (or metal foam) and the rubber combined a kind of method preparing conducting element.
In the metal to rubber compound described in these patent documentations above, after metal material has been all forming in advance, then carry out compound with rubber.
Application number is the patent documentation " rubber conductive particle and preparation method thereof " of 201110027418.8, discloses and carries out metal coating on the surface of rubber substrate and prepare the method for rubber conductive particle.Rubber substrate used in the method is solid, and metal coating is plated in the surface of rubber substrate.
Application number is respectively the patent documentation " a kind of Highly-conductive elastomer and production method thereof " of 201310142541.3 and 201310142978.7, disclose the sponge matrix of being bored a hole by up/down perforation, and sponge matrix is electroplated and gluing or dipping process, more required high electroconductive rubber elastomer can be obtained through pressing process.This patent documentation is for the sponge matrix such as material such as polyester, polyethers, polyolefin of foaming, sponge also needs to carry out gluing or dipping process after plating, its rubberised layer can affect electric conductivity and cause adhesion problem, increase the unsteadiness of properties of product, clear and definite defining is not made to electro-plating method yet, operability is not high, and in fact sponge directly cannot realize plating.
Application number be 200680015484.0 patent documentation and relevant U.S. Patent Application No. be the patent documentation " ElectricallyConductingContactandMethodforProductionthere of " of 20090068857A1, disclosed in be by ready-made foam metal and rubber combinedly prepare conductive contact material.But the kind of foam metal, specification and commercial availability are very limited.The preparation of metal foam, than the preparation of rubbery foam, difficulty is much older.The particularly foam metal of open cell type, kind is less.Therefore, prepare the compound of foam metal and rubber, on Material selec-tion, be limited by very large.But any rubber all can foam, frothing percentage and foaming type control than being easier to.A variety of metal and alloy, can be prepared by current chemical plating and electroplating technology.In the present invention, we will break through the restriction on material, provide and are carried out compound by ready-made foam rubber and metal by chemical plating and plating and prepared the method for electric conducting material, conductive contact material and electromagnetic shielding material.
Summary of the invention
Goal of the invention: the invention discloses a kind of by compound obtaining foam rubber and metal and preparation method thereof in foam rubber hole inner wall surface chemical plating and plating, solve prior art when preparing rubber-metal compound, the problem be restricted on raw material are selected, thus obtain a kind of electric conducting material, conductive contact material and electromagnetic shielding material.
The invention discloses compound of a kind of foam rubber and metal and preparation method thereof.Described compound is combined closely by matrix and filler wherein and is formed, described matrix is foam rubber, the continuous print metalolic network that described filler is formed for metal, hole in described foam rubber is partially or completely interconnected, and having hole to expose to the surface of foam rubber, the mean value in aperture is not more than 5mm; Described metalolic network carries out chemical plating in described foam rubber hole inner wall surface, or first carry out chemical plating and carry out electroplating again being formed.Hole in foam rubber can be in irregular shape, also can be that shape is identical, and such as, hole can be the hollow cylinder of diameter 0.5mm, or the hollow prism body of cross section to be the foursquare length of side be 0.5mm.Hole in foam rubber should partially or completely be interconnected, and has hole to expose to the surface of foam rubber, various treatment fluid, water and plating solution can be made like this to pass through from foam rubber, and have an effect.
The material of foam rubber of the present invention can be selected from the natural rubber commercially produced and synthetic rubber.Described elastomeric material is silicon rubber, fluorubber, fluorosioloxane rubber, ethylene-propylene rubber, ethylene propylene diene rubber, butadiene-styrene rubber, butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, neoprene, chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber, acrylate rubber, polysulfide rubber, polyurethane rubber, or the blend of these rubber and modified product.
Described foam rubber contains one or several in pulverous inorganic filler calcium carbonate (or lime stone, calcite), calcium sulfate or gypsum, zinc oxide, zinc sulphide, Firebrake ZB, magnesium oxide, potter's clay, talcum, zeolite, feldspar, asbestos, mica, kaolin, bentonite, wollastonite, attapulgite, silica-alumina carbon black, pulverized coal ash, sepiolite, titanium dioxide, glass, quartz, silicon dioxide, barium sulfate, and described inorganic filler can be crossed by coupling agent treatment.
Inorganic fibrous fillers, as inorganic filler, also may be used in foam rubber.Described foam rubber can containing one or several in inorganic fibrous fillers glass fibre, quartz glass fibre, brucite fiber, gypsum fiber, sepiolite fibre, fiber asbestos, fibrous wollastonite, boron fibre, ceramic fibre and metallic fiber; Described inorganic fibrous fillers can be crossed by coupling agent treatment.Long inorfil and short inorfil can use.In order to convenient with compounding rubber, can use short fiber, if precursor diameter is 6 μm, average length is the non-alkali ultra-fine fibre glass of 22 μm.
The rubber that the overwhelming majority is commercially produced is hydrophobicity.The hydrophily of these inorganic powdered filler or bat wool is better than rubber.Before chemical plating in pretreated coarsening process, these fillers partly can be etched immersion erosion and dissolve, and form the surface of micro-rough, thus improve the adhesion between coating and rubber.
The alloy that in foam rubber of the present invention and metal composite, metalolic network carries out electroless copper, nickel, tin, lead, cobalt, iron, silver or these elements by the hole inner wall surface at foam rubber is formed, or first carry out the alloy of electroless copper, nickel, tin, lead, cobalt, iron, tungsten, silver or these elements, more further chemical plating or electrosilvering, gold, ruthenium, rhodium, palladium, platinum are formed; Preferred chemical plating copper and mickel.Copper, nickel, tin, lead, cobalt, iron, tungsten are base metals, can as the bottom of chemical deposit, on these bottoms, and can chemical plating or the plating conductive better noble metal such as silver-colored, golden.First plate base metal and plate noble metal again, can noble metal be saved and reach almost good equally electric conductivity.
Foam rubber is normally undertaken foaming obtain by adding chemical foaming agent or physical blowing agent in rubber compounding, and the open-celled foam rubber obtained thus or mixing pass foam rubber, can as the base material preparing foam rubber and metal composite.Preferably select open-celled foam rubber.
The preparation method of the compound of foam rubber of the present invention and metal comprises the steps:
(1) preparation of base material foam rubber: by using the method for physical blowing agent or chemical foaming agent, or by the method for machinery, the method for laser engraving, or these methods of conbined usage, preparation has several holes running through entirety to be exposed to the open cell type of foam rubber surface or the foam rubber of mixing pass;
(2) chemical plating and plating: form continuous print metalolic network through hole in foam rubber hole inner wall surface by chemical plating and plating, can comprise as steps such as cleaning, alligatoring, neutralization, sensitization, activation, reduction or dispergation, chemical plating, plating; The compound of chemical plating and the foam rubber obtained after electroplating and metal, porosity is between 0-90%.
When chemical plating and plating, plating solution can be allowed constantly to flow through from foam rubber hole, allow in the flow process of plating solution in foam rubber hole and metal deposition occurs.
Except using the foam rubber obtained by foaming agent foam, the foam rubber in the present invention also can be prepared by the method for machinery:
(1) when rubber heat cure is shaping, by stretching for the ganoid wire of some circumscribed circle diameter 0.08-2mm and be embedded in heat cure die cavity, be parallel or uneven between wire, contact with each other between at least part of wire; After rubber heat cure in die cavity is shaping, wire is transferred to, namely obtains a kind of foam rubber; Or
(2) be that the metal column of 0.25-2mm is fixed in die cavity by some circumscribed circle diameters; Between metal column be parallel or uneven, contact with each other or do not contact with each other, mutually through or mutually do not pass; After heat cure, during rubber stripper, metal column is still fixed in die cavity, thus in rubber, forms hole because of sloughing of metal column; Or
(3) when rubber heat cure is shaping, the wire that can remove after simultaneously using heat cure shaping and metal column;
The material of wire and metal column is steel, stainless steel or other metal material.For the ease of the rubber stripper after making heat cure shaping, wire and metal column should be smooth.Smooth wire and metal column, be easy to pull out from rubber.
Prepared by the foam rubber of the present invention method that also available laser is carved: by a crosslinked solid block rubber, open cell type block rubber, or obturator-type block rubber or mixing pass block rubber, going out with laser engraving the linear pattern hole that some diameters are 0.1-2mm, is parallel, uneven or crossing between hole; Hole can show through block rubber.Use the laser engraving machine of numerical control, can greatly improve the efficiency manufacturing hole in rubber.
The various method preparing foam rubber above, can conbined usage.Method with machinery or the method with laser engraving, can prepare hole size consistent, hole distribution is uniform and hole is the straight foam rubber run through.
Carrying out in the preliminary treatment before chemical plating to foam rubber, the step of swelling treatment can carried out foam rubber organic solvent; Carrying out swelling treatment solvent used is have swelling action to rubber and the swelling ratio of rubber is greater than the single organic solvent of 5% or the mixture of organic solvent; This step was carried out before roughening step; The optional organic solvent being used for carrying out swelling treatment has: the mixture etc. of the equal-volume ratio of ethyl acetate, ethyl acetate and dimethylbenzene, ethyl acetate and isopropyl alcohol.Our test finds, swelling treatment is conducive to realizing chemical plating, is conducive to increasing the adhesive force between coating and rubber.This may be because swelling treatment has carried out a solvent clean to foam rubber inwall on the one hand, the lower-molecular substance such as residue, plasticizer, fat, aliphatic acid, paraffin after the crosslinking agent decomposition of foam rubber hole inner wall surface can be removed, on the other hand, due to swelling to rubber of solvent, also impact is had to the microscopic pattern of foam rubber hole inwall, thus chemical plating is had an impact.
Carrying out in the preliminary treatment before chemical plating to foam rubber, chemical modification can carried out to foam rubber hole inner wall surface.The method of chemical modification comprises chlorination, bromination, sulfonation, chlorosulfonation, epoxidation, carboxylated, oxidation and hydrolysis etc.; This step was carried out before or after roughening step; Or replace roughening step by this step.
Described chlorination utilizes the organic solution of chlorinating agent trichlorine cyanic acid at room temperature to process foam rubber, and the processing time is 2 hours or longer time.The object of chlorination is to introduce chlorine atom in the rubber molecular chain of foam rubber hole inner wall surface, to increase polarity and the hydrophily of hole inwall rubber.
Described bromination utilizes bromide to make acidic aqueous solution to carry out immersion treatment to foam rubber material, and the object of bromination is polarity in order to increase foam rubber hole inwall rubber and hydrophily equally.
Described sulfonation carries out impregnation process with sulfurous acid or sulfuric acid solution to foam rubber; By the method for sulfiting, be applicable to the foam rubber containing double bond on strand.The strand of foam rubber hole inwall rubber introduces sulfonate radical, will significantly increase polarity and the hydrophily of hole inwall rubber.
Described chlorosulfonation processes with chlorosulfonic acid or with the mixture of chlorine and sulfur dioxide foam rubber, to increase polarity and the hydrophily of foam rubber hole inwall rubber.
Described epoxidation processes the foam rubber containing double bond on strand with organic acid peroxide or hydrogen peroxide and organic acid.
Described oxidation uses the acid with strong oxidizing property concentrated sulfuric acid, red fuming nitric acid (RFNA) and chloroazotic acid to process foam rubber, the carbon-carbon bond of the upper rubber molecular chain of hole inner wall surface is opened, carbon atom oxidation generates carbonyl, hydroxyl and carboxyl isopolarity group, thus making hole inwall rubber surface polarity, surface free energy improves.But need hyperoxidation be avoided, because over oxidation can make rubber surface form trickle slight crack.
Described carboxylated be respectively with sodium hydride process butyl rubber and maleic anhydride and cinnamic acid process foam rubber.This is also a kind of raising rubber surface polarity and hydrophilic a kind of effective ways.
Described hydrolysis processes the foam rubber having silicon rubber or polyurethane rubber to obtain with acid solution or alkaline solution.This Measures compare is simple, but must prevent excessive hydrolysis, because hydrolytic process is also the degradation process of rubber molecular chain, excessively hydrolysis has a negative impact to the mechanical property of rubber.
In a word, rubber being carried out to the object of these chemical modifications, is in order to the realization of chemical plating creates conditions, in order to increase the adhesive force of chemical plating coating to rubber further, to ensure to combine closely between the coat of metal and rubber.
The compound of foam rubber of the present invention and metal, can be used to for further processing.Because they contain rubber substrate, it is shaping that this compound is easy to carry out heat cure with other rubber, thus form combination closely with other rubber.Such as, the compound of foam silicone rubber and metal, can as electric contact material, and silicon rubber to carry out heat cure shaping, the silastic press key of preparation containing electric contact.
Beneficial effect: in the present invention, can select various material such as copper, nickel, tin, cobalt, tungsten, gold, silver, ruthenium, rhodium, palladium, platinum etc. to prepare the compound of foam rubber and metal as metal component.This compound had both had the flexibility of rubber, had again the conductivity of metal, and the contact resistance of the gold-plated electric contact on itself and PCB can be low to moderate at 1 below Ω, and electric conductivity is excellent, can be used as electric conducting material, contact material and electromagnetic shielding material.Owing to containing rubber in this compound, this compound is easy to carry out heat cure bonding with elastomeric material, is particularly useful for making the slider material in rubber key.
Embodiment
Below in conjunction with specific embodiment, the invention will be further described.
Embodiment 1
The present embodiment Mechanical Method prepares foam rubber, then prepares the compound of foam rubber and metal.Be square 304 stainless steel wires in light face of 0.5mm by the length of side, stretching and be clouded in rubber heat cure mould.The arrangement mode of stainless steel wire is: all arranged in parallel in X-axis, Y-axis and Z-direction, and the distance between stainless steel wire axle center arranged in parallel is 0.75mm.Stainless steel wire on three-dimensional contacts with each other.Y direction (short transverse) can the length of side be 0.5mm square metal post replace stainless steel wire, the height of metal column is the height of mould cavity.
One silicon rubber gross rubber (containing Dow Corning Corporation silicon rubber SE-4705U100 part, peroxide vulcanizing agent DCP1 part) is put into die cavity, and at 175 DEG C, press cure obtains silicon rubber vulcanization glue in 10 minutes.Stainless steel wire is taken out from silicon rubber vulcanization glue, namely obtains a kind of foam silicone rubber.At 200 DEG C, post vulcanization is carried out 2 hours to this foam silicone rubber.
This foam silicone rubber is cleaned, swelling, alligatoring, neutralization, sensitization, activation, reduction, and chemical nickel plating.Adopt alkaline cleaner and ethanolic solution cleaning in the present invention, adopt the equal-volume mixed solvent of ethyl acetate and isopropyl alcohol to carry out swelling to foam silicone rubber, then dry; The chromium type high coarsening solution of sulfur acid and chromic anhydride is adopted to carry out alligatoring, 10% ammonia spirit is adopted to neutralize, the sensitizing solution containing titanium trichloride and hydrochloric acid is adopted to carry out sensitization, palladium bichloride activating solution is adopted to activate, adopt the reducing solution containing inferior sodium phosphate to reduce, then carry out chemical nickel plating.The electroplate liquid formulation of chemical nickel plating is: nickelous sulfate 25g/L, natrium citricum 12g/L, ammonium chloride 30g/L, inferior sodium phosphate 35g/L.Chemical plating be maintain bath temperature at 50 DEG C, with ammoniacal liquor adjustment pH between 9.0 to 9.5.Chemical plating fluid is allowed constantly to flow through from the hole of foam silicone rubber during chemical plating.When flow velocity is very slow, foam silicone rubber is taken out from plating solution, dry and be reentered in plating solution.Electroless plating time is 150 minutes.After chemical plating completes, spend the foam silicone rubber of deionized water chemical nickel plating, after drying, namely obtain the compound of a kind of foam rubber and metal, namely the compound of foam silicone rubber and nickel.This compound is machined to diameter is 7.5mm, thickness is the sequin of 1mm, as electric contact and silicon rubber heat cure shaping, make the silastic press key containing electric contact.When this electric contact and gold-plated PCB contact, contact resistance between the two only has 0.3 Ω, much smaller than 1 Ω, meets some key switch to the low-resistance requirement of electric contact.
Embodiment 2
As embodiment 1, but the time of chemical nickel plating be 50 minutes, then carry out the electronickelling of 10 minutes.The foam rubber obtained and the compound of nickel, also have very low contact resistance.
Embodiment 3
As embodiment 1, the compound of obtained foam silicone rubber and nickel, and obtained diameter be 7.5mm, thickness is the sequin of 1mm.This sequin is carried out chemical gilding process, and the average thickness of Gold plated Layer is 0.1 μm.Gold plated Layer is only deposited on the surface of nickel in sequin, can not deposit Gold plated Layer at silastic surface.The sequin of gained, as electric contact material, keeps in touch the on-off times of resistance 1 below Ω under the electric current of 200mA, than the on-off times of not gold-plated sequin as electric contact material, and at least many 20%.
Or, as embodiment 1, the compound of obtained foam silicone rubber and nickel, and the obtained length of side be 75mm, thickness is the square sheets of 1mm, carries out electrogilding process to sheet material.Then die-cutly the sequin that diameter is 7.5mm is rushed.This gold-plated sequin, also has good electric conductivity.
Embodiment 4
By the foam silicone rubber obtained after post vulcanization in embodiment 1, at 80 DEG C, 1 hour is processed with 5% sodium hydroxide solution, to increase the quantity of the hydroxyl isopolarity group of foam silicone rubber hole inwall silastic surface, increase the hydrophily of foam silicone rubber hole inwall.After being disposed, chemical plating can be carried out according to the method described in embodiment 1.
Embodiment 5
Polydiene, as natural rubber, butadiene-styrene rubber, butadiene rubber, nitrile rubber and the silicon rubber containing vinyl, carries out halogenation treatment before chemical plating.Foam acrylonitrile-butadiene rubber by sulfuration, is immersed in the solution containing KBr 50-100g/L, potassium permanganate 75-125g/L, sulfuric acid 100-200g/L, or allows this solution constantly by the hole 1-2 hour of foam acrylonitrile-butadiene rubber at 50-85 DEG C.Then by washed with de-ionized water, dry, namely obtain hole inner wall surface by bromated foam acrylonitrile-butadiene rubber.This foam rubber is carried out chemical plating and plating by the step shown in embodiment 1.The bromination of acrylonitrile-butadiene rubber, can improve the adhesive force between acrylonitrile-butadiene rubber and coating.Natural rubber, butadiene-styrene rubber, butadiene rubber, before chemical plating, also can do similar bromination process.
Embodiment 6
The formula of foam rubber is: 100 parts, silicon rubber (SE-4705U), blowing agent H (N, N '-dinitrosopentamethlyene tetramine) 5 parts, brucite fiber 7.5 parts, crosslinking agent paste BP(50%) 1.5 parts.The particle diameter of brucite fiber used is between 1-5 μm, and length is between 1-20 μm.The main component of brucite fiber is magnesian hydrate, be a kind of safe, there is no pathogenic natural inorganic mineral material.In coarsening process, the weakly alkaline brucite fiber in foam rubber by by the coarsening solution etch of acidity, thus increases the asperity of foam rubber hole inwall, increases coating to the adhesive force of rubber.
At 130 DEG C, carry out one step cure 10 minutes to the silicon rubber gross rubber of above-mentioned formula on vulcanizing press, then at 200 DEG C, carry out post vulcanization 2 hours with baking oven, the obtained length of side is 150mm, and thickness is the square foam silicone rubber sheet of 1mm.
By this foam silicone rubber sheet laser in a thickness direction ablation go out the hole that some diameters are 0.25mm, hole is planar uniformly distributed, and the pitch of holes of any adjacent holes is 1mm, to increase the porosity of foam silicone rubber further.
This foam silicone rubber is carried out chemical plating as described in Example 1, the compound of foam silicone rubber and nickel can be obtained.
Claims (10)
1. the compound of a foam rubber and metal, it is characterized in that: described compound is combined closely by matrix and filler wherein and formed, described matrix is foam rubber, the continuous print metalolic network that described filler is formed for metal, hole in described foam rubber is partially or completely interconnected, and having the hole through foam rubber to expose to the surface of foam rubber, the mean value in aperture is not more than 5mm; Described metalolic network carries out chemical plating in described foam rubber hole inner wall surface, or first carry out chemical plating and carry out electroplating again being formed.
2. the compound of foam rubber according to claim 1 and metal, is characterized in that: the material of described foam rubber is natural rubber or synthetic rubber; Described elastomeric material is silicon rubber, fluorubber, fluorosioloxane rubber, ethylene-propylene rubber, ethylene propylene diene rubber, butadiene-styrene rubber, butadiene rubber, isoprene rubber, acrylonitrile-butadiene rubber, neoprene, chlorinated polyethylene rubber, chlorosulfonated polyethylene rubber, acrylate rubber, polysulfide rubber, polyurethane rubber, or the blend of these rubber and modified product; Described foam rubber has open cell type structure, or has the mixing pass structure of perforate and closed pore.
3. the compound of foam rubber according to claim 1 and metal, is characterized in that: described foam rubber contains one or several in pulverous inorganic filler calcium carbonate, calcium sulfate or gypsum, zinc oxide, zinc sulphide, Firebrake ZB, magnesium oxide, potter's clay, talcum, zeolite, feldspar, asbestos, mica, kaolin, bentonite, wollastonite, attapulgite, silica-alumina carbon black, pulverized coal ash, sepiolite, titanium dioxide, glass, quartz, white carbon, barium sulfate.
4. the compound of foam rubber according to claim 1 and metal, is characterized in that: described foam rubber contains one or several in inorganic fibrous fillers glass fibre, quartz glass fibre, brucite fiber, gypsum fiber, sepiolite fibre, fiber asbestos, fibrous wollastonite, boron fibre, ceramic fibre and metallic fiber.
5. the compound of foam rubber according to claim 1 and metal, it is characterized in that: the alloy that metalolic network carries out electroless copper, nickel, tin, lead, cobalt, iron, silver or these elements by the hole inner wall surface at foam rubber is formed, or first carry out the alloy of electroless copper, nickel, tin, lead, cobalt, iron, tungsten, silver or these elements, more further chemical plating or electrosilvering, gold, ruthenium, rhodium, palladium, platinum are formed.
6. the preparation method of the compound of foam rubber according to claim 1 and metal, is characterized in that: comprise the steps:
(1) preparation of foam rubber: by using the method for physical blowing agent or chemical foaming agent, or by the method for machinery, the method for laser engraving, or these methods of conbined usage, preparation has several holes running through entirety to be exposed to the open cell type of foam rubber surface or the foam rubber of perforate and closed pore mixing pass;
(2) chemical plating and plating: form continuous print metalolic network through hole by chemical plating and plating in foam rubber hole inner wall surface, comprises cleaning, swelling, alligatoring, neutralization, sensitization, activation, reduction or dispergation, chemical plating and plating step; The compound of chemical plating and the foam rubber obtained after electroplating and metal, porosity is between 0-90%.
7. a preparation method for the compound of foam rubber according to claim 6 and metal, is characterized in that: described foam rubber prepares by the method for following machinery:
(1) when rubber heat cure is shaping, by stretching for the ganoid wire of some circumscribed circle diameter 0.08-2mm and be embedded in the die cavity of heat cure mould, be parallel or uneven between wire, contact with each other between at least part of wire; After rubber heat cure in die cavity is shaping, wire is transferred to, namely obtains a kind of foam rubber; Or
(2) be that the metal column of 0.25-2mm is fixed in die cavity by some circumscribed circle diameters; Parallel or uneven between metal column, contact with each other or do not contact with each other, mutually through or mutually do not pass; After heat cure, during rubber stripper, metal column is still fixed in die cavity, thus in rubber, forms hole because of sloughing of metal column;
(3) when rubber heat cure is shaping, the wire that can remove after simultaneously using heat cure shaping and metal column;
Described wire and metal column are steel or stainless steel.
8. the preparation method of the compound of a foam rubber according to claim 6 and metal, it is characterized in that: described foam rubber prepares by the method for laser engraving: by a crosslinked solid block rubber, open cell type block rubber, or obturator-type block rubber or mixing pass block rubber, going out with laser engraving the linear pattern hole that some diameters are 0.1-2mm, is parallel, uneven or crossing between hole; Hole can show through block rubber.
9. the preparation method of the foam rubber according to claim 1 and 6 and the compound of metal, is characterized in that: also comprise the step of foam rubber being carried out to swelling treatment; Carrying out swelling treatment solvent used is have swelling action to rubber and the swelling ratio of rubber is greater than the single organic solvent of 5% or the mixture of organic solvent; This step was carried out before roughening step.
10. the preparation method of the foam rubber according to claim 1 and 6 and the compound of metal, is characterized in that: also comprise the step that foam rubber hole inner wall surface carries out chemical modification; The method of described chemical modification comprises chlorination, bromination, sulfonation, chlorosulfonation, epoxidation, carboxylated, oxidation and hydrolysis; This step was carried out before or after roughening step; Or replace roughening step by this step;
Described chlorination utilizes the organic solution of chlorinating agent trichlorine cyanic acid at room temperature to process foam rubber, and the processing time is 2 hours or longer time;
Described bromination utilizes bromide to make acidic aqueous solution to carry out immersion treatment to foam rubber material;
Described sulfonation carries out impregnation process with sulfurous acid or sulfuric acid solution to foam rubber; By the method for sulfiting, be applicable to the foam rubber containing double bond on strand;
Described chlorosulfonation processes with chlorosulfonic acid or with the mixture of chlorine and sulfur dioxide foam rubber;
Described epoxidation processes the foam rubber containing double bond on strand with organic acid peroxide or hydrogen peroxide and organic acid;
Described oxidation uses the acid with strong oxidizing property concentrated sulfuric acid, red fuming nitric acid (RFNA) and chloroazotic acid to process foam rubber;
Described carboxylated be respectively with sodium hydride process butyl rubber and maleic anhydride and cinnamic acid process foam rubber;
Described hydrolysis processes the foam rubber having silicon rubber or polyurethane rubber to obtain with acid solution or alkaline solution.
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