CN102002694A - Method for preparing uniform silver conducting layer on surface of metal or nonmetal material - Google Patents
Method for preparing uniform silver conducting layer on surface of metal or nonmetal material Download PDFInfo
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- CN102002694A CN102002694A CN 201010586488 CN201010586488A CN102002694A CN 102002694 A CN102002694 A CN 102002694A CN 201010586488 CN201010586488 CN 201010586488 CN 201010586488 A CN201010586488 A CN 201010586488A CN 102002694 A CN102002694 A CN 102002694A
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Abstract
The invention relates to a method for preparing a uniform silver conducting layer on the surface of a metal or nonmetal material, relating to a method plating a continuous and uniform silver conducting layer on the surface of the metal or nonmetal material. The method comprises the following steps of: firstly preplating a small amount of metal silver or nickel on the surface of the metal or nonmetal material through a preplating processing process; then reducing the silver by using hydrogen in a silver-containing aqueous ammonia solution through a plating process; plating the silver on the surface of the metal or nonmetal material; and then carrying out filtering, washing and drying processes to obtain a metal or nonmetal material product with the surface plated with the continuous and uniform silver conducting layer. The invention firstly forms uniform metal silver and nickel nanoparticles on the surface of the powdery or fibriform metal or nonmetal material by adopting a preplating method and can enable the silver plating layer to uniformly wrap the surface of the metal or nonmetal material during plating to form a continuous plating layer, thereby reducing the thickness of the plating layer and the using amount of the metal silver; in addition, the invention has simple operation process, high applicability and little needed equipment, greatly reduces the using sorts and the using amount of chemical reagents and reduces the pollution of a plating solution on environments.
Description
Technical field
A kind of metal or non-metal material surface prepare the method for even silver conductive layer, belong to electro-conductive material and composite metal powder preparing technical field.Relate at powder or fibrous metal or the continuously uniform silver conductive layer of non-metal material surface plating one deck.
Technical background
The conducting metal composite powder material is widely used in making solar cell, chip multilayer ceramic capacitor, electronic printing circuit, electric contact material, conductive filler material, electrically conducting coating, electromagnetic shielding material, absorbing material, invisible coating, friction materials, ceramic composite, special alloy etc., various in style, complicated component.Just comprise that as conductive powder filler only metal is that powder filler, carbon are powder filler, burning system powder filler and composite powder filler etc.; Wherein metal is that powder filler mainly is divided into silver powder, nickel powder and copper powder etc., carbon is that the powder filler has graphite, carbon black etc., metal oxide filler then comprises stannic oxide, zinc oxide, Indium sesquioxide etc., and compounded mix has granulated glass sphere, hollow glass micropearl, copper powder, silver bag talcum powder and Yin Bao mica powder and nickel bag carbon black, nickel bag graphite etc. multiple; The shape of conductive powder filler is according to preparation technology's difference, and multiple shapes such as spherical, sheet, needle-like and fibrous powder are arranged.
Conducting metal composite powder material general requirement conducts electricity very well, oxidation-resistance is strong, composition is even.Silver is that conductivity is best in all metals, and silver powder has advantages such as good conductivity, resistance of oxidation are strong, stable chemical performance, but because of costing an arm and a leg, has limited its widespread use.The silver-plated consumption of saving silver of material surface if surperficial silver-colored cladding ratio is more complete, can replace silver powder under a stable condition.For example, silver powder is to use the widest conductive filler material in the electric slurry, but relative base metal, price is much higher, and copper powder then price is low, electric heating property is only second to silver, but the oxidation easily of copper powder surface generates cupric oxide, Red copper oxide, forms one deck insulating oxide film, make the stability and the reliability deficiency of copper powder, reduced the range of application of copper powder.Silver-coated copper powder is to coat one deck silver particulate or silver layer on the copper powder surface, has improved the antioxidative stabilizer and the electroconductibility of copper powder, can reduce material cost significantly.Silver-coated copper powder has been used in electronic circuit, electrode materials, conductive resin, polymer paste, and electric slurries such as electrically conducting coating, electromagnetic shielding, non-conductive material surface modification prepare the aspect.And for example, silver bag graphite composite material combines silver and graphite excellent properties separately, has been widely used in extraordinary brush, radar slip ring and to electric signal requirement ten minutes sensitive slip electrical contact material.Along with the continuous development of aerospace and electronic industry, more and more higher to the performance requriements of this material, demand is also increasing.Therefore, produce various goods, both can improve the conductivity of goods, can reduce the consumption of argent again, reduce production costs, save precious metal silver resource with the metal or the non-metallic material replacement fine silver powder of silver-colored plating.
The silver plated method of material surface has plating, electroless plating, vapour deposition process, magnetron sputtering etc. multiple.Electroplate wherein that only to be suitable for electro-conductive material silver-plated; And vapour deposition process, magnetron sputtering required equipment complexity, investment are big, to also being had higher requirements by plating material geometrical shape; Electroless plating method is obtaining evenly, is having bigger advantage aspect the dispersive metal plating, electroless plating method almost can be silver-plated on the material of any matrix and geometrical shape, especially silver-plated on powder, inorganic materials and polymer surface, thereby chemical silvering becomes most widely used silver-coating method.
Pre-treatment before the chemical silvering comprises steps such as surface cleaning, electrochemical deoiling, alligatoring, sensitization, activation.Most of materials have adsorbed oily matter when preparation or surface treatment, remove with the electrochemical deoiling method.Sensitization is the process of the material surface absorption last layer reducing substances after alligatoring, generally uses the mixing solutions of stannous chloride solution or itself and hydrochloric acid; After the sensitization by activation, powder surface form one deck continuously, uniform distribution and metallic particles with catalytic activity, bring out the chemical silvering reaction as catalytic center.Non-metallic powder itself does not have catalytic activity, must make its surface active could cause the electroless plating reaction.Activation method mainly contains the palladium method of soaking, silver-colored slurry method, molybdenum manganese method, vapour deposition process, dielectric layer electric discharge, photochemical method etc., and commonly used is the palladium activation method.Though have catalytic activity in some metal-powders, can electroless plating reaction take place on its surface, in order to obtain good coating, electroless plating often also will activate in the past.It is disposable that the plating bath of chemical silvering all belongs to basically, is spontaneous decomposition and can not continue to use after the use.
The chemical plating liquid complicated component generally comprises main salt and complexing agent, reductive agent, stablizer, brightening agent, tensio-active agent, buffer reagent and other auxiliary agents etc.Chemical plating liquid is very unstable, often with main salt of silver and separately preparation of reductive agent, just mixes before bringing into use.Generally all use AgNO
3As main salt, complexing agent is an ammoniacal liquor etc.; Reductive agent comprise formaldehyde, Nulomoline (D-glucose, fructose), tartrate and tartrate (Seignette salt), hydrazine class compound (hydrazonium sulfate, hydrazine hydrate), Citrate trianion (Triammonium citrate, trisodium citrate), inferior sodium phosphate, oxalic dialdehyde, hydroborate (POTASSIUM BOROHYDRIDE), dimethyamine borane, aldolactol, trolamine, glycerol and N-methyl p-aminophenol sulfate etc.; For preventing that muddy the decomposition from appearring in plating bath, the stablizer that adds has polyoxyethylene glycol, ethanol, gelatin, iodide, or the inorganic salt of copper, nickel, cobalt, lead, mercury etc., the sulfocompound stablizer has thiocarbamide, thiosulphate, sulfydryl propane sulfonate, Gelucystine, halfcystine, Methyl disulfide carbamate, dodecyl ammonium acetate, diiodotyrosine etc.In order further to improve quality of coating, except will adding above-mentioned a few class material, also to add some auxiliary agents, comprise sodium hydroxide etc., when being reductive agent, prevent oxymethylene polymerization and the stopper (alcohols) that adds with formaldehyde.A large amount of uses of various chemical reagent make the chemical silvering system become very complicated, and influence factor is many, the production control difficulty, contain the plating of various chemical reagent after solution also will produce detrimentally affect to environment, wherein many reagent toxicities are strong, as formaldehyde etc.
As mentioned above, from the production actual analysis of chemical plating liquid, present related very many of chemical silvering by the material category of plating, the silver plating solution complicated component, and also employed amount of reagent is many, and solution preparation and silver-plated operation are many.When chemical silvering, the material surface of also being everlasting forms silver-colored particle, rather than uniform silvering, influences the covered effect of argent, has reduced the antioxidant property of product, has increased the consumption and the cost of argent.Will form continuously uniform silverskin or silver layer on the surface of material, it is bigger to adopt the chemical silvering legal system to be equipped with technology difficulty, and control condition is harsh, and influence factor is more.Each when silver-plated, it is very slow that reductive agent adds speed, otherwise easily form big silver powder particles on by plated product, adsorb not closely, and quality product is descended, and production efficiency is limited, and needs increase contracted payment amount, has increased the products production cost.
Along with the increase of silver-plated conducting metal composite powder material consumption and the raising that quality product is required, silver-coating method is also had higher requirement.
The problem that exists in the chemical silvering process at above-mentioned conducting metal composite powder material, the present invention at a lower temperature with hydrogen atmosphere in to being carried out the pre-plated surface modification by metallizing or non-metallic material, to be joined in the argentiferous ammonia aqueous solution by the plating material then, in reactor, feed hydrogen as reductive agent, to be plated on after the argent reduction by on the plating material, form the continuously uniform silver conductive layer of one deck, improve by the electroconductibility and the oxidation-resistance of plating material, make the product properties that comprises by the plating material stable, satisfy the service requirements under the different situations.
Summary of the invention
The objective of the invention is: a kind of coating surface is provided one deck continuously uniformly composite conductive powder of silver conductive layer or the preparation method of filamentary material, this method Technology is simple, adaptability is strong, can be silver-plated on the complicated powder of pattern or fibrous metal or nonmetallic surface, improve electroconductibility, oxidation-resistance and the stability of conducting metal composite powder material; The requirement of field material preparations such as solar cell, chip multilayer ceramic capacitor, electronic printing circuit, electric contact material, conductive filler material, electrically conducting coating, electromagnetic shielding material, absorbing material, invisible coating, friction materials, ceramic composite, special alloy can be satisfied in the silver-plated conducting metal composite powder material surface that is produced.This method required equipment is less, and operation easier is low, reduces chemical reagent usage quantity and kind significantly, reduces the argent consumption, reduces the environmental pollution of plating back solution.
The objective of the invention is to be achieved through the following technical solutions, may further comprise the steps:
(1) powder or fibrous metal or non-metal material surface plating are continuously uniformly during silver conductive layer, earlier through the pre-plating treatment process, at material surface elder generation's pre-plating little metal silver or nickel, pass through plating process then, in the argentiferous ammonia aqueous solution, use hydrogen reducing silver, silver is plated on metal or non-metal material surface, more after filtration, washing, drying process, and the obtained coating surface metal or the non-metallic material product of silver conductive layer uniformly continuously.
(2) detailed process comprises: will need to be mixed with Silver Nitrate or nickel nitrate solution by the powder of silver-colored plating or fibrous metal or non-metallic material, stirred 2～30 minutes, then solution and metal or non-metallic material filtering separation, the metal or the non-metallic material that are adsorbed with Silver Nitrate or nickel nitrate solution are put into the baking oven inner drying, dried metal or non-metallic material are put into airtight process furnace, and the thermal treatment pre-plating is 0.5～5 hour in the atmosphere of 150～450 ℃ of following hydrogen; After thermal treatment pre-plating and cooling, metal or non-metallic material are joined in the argentiferous ammonia solution mix, join in the reactor together, the mixture of metal or non-metallic material and argentiferous ammonia solution in the reactor heating, when temperature reaches 70～150 ℃, feed hydrogen, reacted 10～60 minutes, argent is plated on metal or non-metal material surface, behind the cooling mixture solution, in reactor, emit, after filtration, washing, drying, obtain the surface by plating the evenly metal or the non-metallic material of metallic silver layer continuously.
(3) comprise in the pre-plating treatment process and soak pre-treatment and thermal treatment pre-plating; When soaking pre-treatment powder or fibrous metal or non-metallic material are mixed with Silver Nitrate or nickel nitrate solution, the concentration of Silver Nitrate or nickel nitrate solution is 0.1～1mol/L, wherein, and adding glycerol 1.0～5.0g/L, 15～70 ℃ of solution temperatures; Stirred 2～30 minutes, metal or non-metallic material after the filtering separation are not washed, and have adsorbed Silver Nitrate or nickelous nitrate, 60～105 ℃ of oven dry; When adsorptive capacity is not enough, can directly Silver Nitrate or nickel nitrate solution dropping on the metal or non-metallic material 50～70 ℃ of heat, continued oven dry at 60～105 ℃ again after the oven dry.
(4) during the thermal treatment pre-plating, after having adsorbed the metal or non-metallic material oven dry of Silver Nitrate or nickelous nitrate, under 150～450 ℃ of temperature, handle, 0.5～5 hour treatment time, feed the mixed gas of hydrogen or hydrogen and nitrogen, the mixed gas hydrogen 50～90% of hydrogen and nitrogen wherein obtains powder or the fibrous metal or the non-metallic material of a small amount of nanometer metallic silver of pre-plating or nickel.
When (5) argentiferous ammonia solution is prepared, the silver material that contains that adopts is Silver Nitrate or Sulfuric acid disilver salt, concentration of silver ions is 5～50g/L in the argentiferous ammonia solution, and adding in complexing agent ammoniacal liquor, quadrol, triethylene tetramine, diethylenetriamine, tetraethylene pentamine or the polyethylene polyamine one or both, add-on is 1～5.5 by the ratio of complexing agent total mol concentration and the volumetric molar concentration of silver ions.
When (6) argentiferous ammonia solution is prepared, add additive sulfur sodium thiosulfate 10～40g/L, polyoxyethylene glycol 3～25g/L, polyethylene pyrrole iron alkane ketone 0.05～0.5g/L, gelatine 0.05～1g/L.
(7) metal after the pre-plating or non-metallic material are joined in the argentiferous ammonia solution, join in the reactor together, the mixture of metal or non-metallic material and argentiferous ammonia solution in the reactor heating, when temperature reaches 75～150 ℃, feed hydrogen, hydrogen pressure 0.8～3.5MPa reacted 10～60 minutes, and argent is plated on metal or non-metal material surface.
(8) after plating is finished, cooling mixture solution, in reactor, emit, washing after filtration,, drying, obtain the surface by plating the evenly metal or the non-metallic material of metallic silver layer continuously, silver content 5～70%, promptly the argent weight of plating account for argent with by the percentage ratio of the metal of plating or non-metallic material gross weight, argent with also be the weight of product after the plate silver by the gross weight of the metal of plating or non-metallic material.When needs increase the plate silver amount, can be behind plating of argentiferous ammonia solution, the metal or the non-metallic material of metallic silver layer of having isolated plating are no longer passed through pre-plating, mix with new argentiferous ammonia solution, carry out the secondary plating in solution.
(9) existed with powder or fibrous pattern by the metal of plating or non-metallic material, powder diameter is 0.1～1000 μ m, and the fibrous material diameter is that 0.5～80 μ m, length are 5～9000 μ m; Wherein metallic substance is meant non-ferrous metal, rare earth metal, ferrous metal and alloy thereof, includes but not limited to copper, lead, zinc, tin, antimony, cadmium, aluminium, nickel, cobalt, iron, manganese, chromium, tungsten, molybdenum, indium, titanium, zirconium, vanadium, rare earth and alloy thereof; Non-metallic material are meant non-metal simple-substance, metal oxide, nonmetal oxide, rare-earth oxide, complex metal oxides, metal carbonate, metal hydroxides, oxide ceramics, nitride ceramics, carbide ceramics, boride ceramics, conductivity ceramics, sintering metal and glass include but not limited to boron, powdered carbon, graphite, stannic oxide, Indium sesquioxide, bismuth oxide, titanium dioxide, zirconium white, chromium sesquioxide, ytterbium oxide, yttrium oxide, cerium oxide, tungstic oxide, silicon-dioxide, lime carbonate, barium carbonate, norbide, titanium carbide, silicon nitride, boron nitride, titanium nitride, aluminium nitride, four boron monoxides, silicon carbide, titanium carbide, zirconium carbide, wolfram varbide, zirconium diboride, TiB2, spinel, mullite, Pb-based lanthanumdoped zirconate titanates.
Advantage of the present invention and positively effect are compared with prior art, mainly be: the method that adopts pre-plating forms even metal silver, nano nickel particles at powder or fibrous metal or non-metal material surface, when plating, can make silvering evenly be coated on the surface of metal or non-metallic material, form continuous coating layer, reduce coating layer thickness, the usage quantity of argent when reducing plating.Adopt the hydrogen reducing plating, by changing hydrogen pressure, the solubleness of regulating hydrogen in the argentiferous ammonia solution control the plating speed of response, and hydrogen dissolution profiles in solution is even, easily obtains continuous, uniform silver-colored coating layer.Compare with electroless plating, Technology requires low, and operating process is simple, and suitability is strong, and required equipment is few, has reduced the use kind and the usage quantity of chemical reagent significantly, has reduced environmental pollution; Improved speed of response and productivity, caused the generation of silver powder particles because of adding the reductive agent excessive velocities when having avoided electroless plating, thereby cause the phenomenon of the discontinuous densification of silvering; Some materials are arranged because sensitization, activation effect is not good and can't plating or form uneven silver-colored coating layer when having overcome electroless plating.The hydrogen reducing agent is to environment and body harmless, and the tail washings amount is few behind the plating, and composition is simple, is easy to handle.Compare with other silver-coating methods such as vapour deposition process, magnetron sputterings, the required equipment less investment, cost is low, and treatment scale is big, is more suitable at nature difference very big powder or fibrous differing materials electroplate.
Embodiment
Embodiment 1
Copper powder coating surface silver.Measure the silver nitrate solution 1L of concentration 0.3mol/L, pour in the glass beaker that volume is 2L, add glycerol 1.5g again, take by weighing the copper powder 200g of median size 30 μ m, join in the beaker, mix with silver nitrate solution; Stir after 3 minutes, copper powder is separated with silver nitrate solution, the wet copper powder that is adsorbed with silver nitrate solution is packed in the alumina boat, sprawl evenly, in baking oven, dried 3 hours down for 90 ℃, take out alumina boat then, put it into the middle part of the heating tube in the tube furnace, fixedly the sealing cover at heating tube two ends; Open the air valve on the heating tube sealed end, continue to feed nitrogen, open the tube furnace heating power supply, rising heating tube temperature when temperature rises to 150 ℃, is turn-offed the nitrogen intake valve, open the hydrogen intake valve, hydrogen is entered in the heating tube, and flow out, continue elevated temperature to 320 ℃ from the air outlet, be incubated 1 hour, turn-off the hydrogen intake valve, feed nitrogen again, take out the cooling back.The copper powder of pre-plating silver in the alumina boat is poured in the 5L glass beaker that fills 3L argentiferous ammonia solution, mix, wherein argentiferous ammonia solution is prepared with ammoniacal liquor and Silver Nitrate, concentration of silver ions 20.3g/L, quadrol is 3.3 with the ratio of the volumetric molar concentration of silver ions, Sulfothiorine 15g/L, polyoxyethylene glycol concentration 15g/L, the polyethylene pyrrole irons alkane ketone 0.1g/L, gelatine 0.15g/L.Copper powder and argentiferous ammonia solution mixture are joined in the closed reactor, under constantly stirring, the mixture of copper powder and argentiferous ammonia solution in the reactor heating, when temperature is elevated to 110 ℃, feed hydrogen, hydrogen pressure keeps 1.6MPa, continues the rising reactor temperature, when temperature reaches 125 ℃, turn-off heating power supply; When hydrogen pressure drops to 1.0MPa in the reactor, feed hydrogen once more, improve hydrogen pressure to 1.6MPa, so repeat to feed hydrogen; When treating that hydrogen pressure no longer descends, refrigeration cycle water pipe in reactor feeds cold water, make the temperature of mixture in the reactor drop to 70 ℃, emit mixture aqueous solution, with the copper powder filtering separation after the plate silver, with 30～50 ℃ hot washes three times, the 65 ℃ of dryings 4 hours in baking oven of the copper powder after the plate silver, obtain silver-plated copper powder (silver-coated copper powder) product, be silvery white in color.Through chemical composition analysis, silver-plated copper powder argentiferous 22.31% is used the microscopic examination silver-plated copper powder, and its surfacing is smooth.
Embodiment 2
Flake graphite in powder coating surface silver.Measure the nickel nitrate solution 2L of concentration 0.4mol/L, pouring volume into is in the 5L glass beaker, adds glycerol 2.5g, takes by weighing the flake graphite in powder 50g of particle diameter 60～80 μ m, joins in the beaker, mixes with nickel nitrate solution; Stir after 15 minutes, flake graphite in powder is separated with nickel nitrate solution, the flake graphite in powder that is adsorbed with nickel nitrate solution is packed in the stainless steel boat, be uniformly dispersed, in baking oven, dried 4 hours down for 100 ℃, take out the stainless steel boat that flake graphite in powder is housed then, put into the middle part of tube furnace heating tube, fixedly the sealing cover at heating tube two ends; Open the air valve on the heating tube sealed end, continue to feed nitrogen, open the tube furnace heating power supply, rising heating tube temperature when temperature rises to 300 ℃, is turn-offed the nitrogen intake valve, open the hydrogen breather valve, hydrogen is entered in the heating tube, and flow out, continue elevated temperature to 360 ℃ from the air outlet, insulation is 1.5 hours under feeding hydrogen, turn-off the hydrogen intake valve then, feed nitrogen again, take out the cooling back.The flake graphite in powder of pre-plating nickel in the stainless steel boat is poured in the 5L glass beaker that fills 3.5L argentiferous ammonia solution, mixes.Wherein argentiferous ammonia solution prepares with ammoniacal liquor and Sulfuric acid disilver salt, concentration of silver ions 9.5g/L, and ammonia is 3.2 with the ratio of the volumetric molar concentration of silver ions, Sulfothiorine 20g/L, polyoxyethylene glycol concentration 10g/L, polyethylene pyrrole iron alkane ketone 0.1g/L, gelatine 0.1g/L.The flake graphite in powder of pre-plating nickel and the mixture of argentiferous ammonia solution are joined in the closed reactor, mixture under constantly stirring in the reactor heating, when temperature is elevated to 90 ℃, feed hydrogen, hydrogen pressure keeps 2.1MPa, continue the rising reactor temperature, when temperature reaches 120 ℃, turn-off heating power supply; When hydrogen pressure drops to 1.0MPa in the reactor, feed hydrogen once more, improve hydrogen pressure to 2.1MPa, so repeat to feed hydrogen; When treating that hydrogen pressure no longer descends, refrigeration cycle water pipe in reactor feeds cold water, make the temperature of mixture in the reactor drop to 70 ℃, emit mixture aqueous solution, with the flake graphite in powder filtering separation after the plate silver, flake graphite in powder after the acquisition plate silver first time, plating tail washings otherwise processed.
Flake graphite in powder after the plate silver for the first time without washing, carries out plating second time, repeats above-mentioned plating process, and the flake graphite in powder that is about to after the plate silver first time is poured in the 5L glass beaker that fills 4L argentiferous ammonia solution once more, mixes.Wherein argentiferous ammonia solution prepares with ammoniacal liquor and Silver Nitrate, concentration of silver ions 9.5g/L, and ammonia is 3 with the ratio of the volumetric molar concentration of silver ions, polyoxyethylene glycol concentration 10g/L, polyethylene pyrrole iron alkane ketone 0.1g/L, gelatine 0.1g/L.Flake graphite in powder and argentiferous ammonia solution mixture after the first time plate silver are joined in the closed reactor, under constantly stirring, the mixture of flake graphite in powder and argentiferous ammonia solution in the reactor heating, when temperature is elevated to 90 ℃, feed hydrogen, hydrogen pressure keeps 2.1MPa, continues the rising reactor temperature, when temperature reaches 120 ℃, turn-off heating power supply; When hydrogen pressure drops to 1.0MPa in the reactor, feed hydrogen once more, improve hydrogen pressure to 2.1MPa, so repeat to feed hydrogen; When treating that hydrogen pressure no longer descends, refrigeration cycle water pipe in reactor feeds cold water, make the temperature of mixture in the reactor drop to 70 ℃, emit mixture aqueous solution, with the flake graphite in powder filtering separation after the plate silver, with 30～50 ℃ hot washes three times, the flake graphite in powder after the plate silver in baking oven 80 ℃ dry 3 hours down, obtain the flake graphite in powder after the plate silver for the second time; The appearance of flake graphite in powder product changes silvery white into by black.Through chemical composition analysis, silver-plated flake graphite in powder argentiferous 57.92% is used microscopic examination, and its coating surface silver layer is even, and plating is complete.
Embodiment 3
Glass microballon coating surface silver.Measure the silver nitrate solution 1L of concentration 0.5mol/L, pour in the glass beaker that volume is 2L, add glycerol 3.0g, take by weighing the glass microballon 300g of particle diameter 30～60 μ m, join in the beaker, mix with silver nitrate solution; Stir after 5 minutes, glass microballon is separated with silver nitrate solution, the glass microballon that is adsorbed with silver nitrate solution is packed in the alumina boat, disperse to sprawl evenly, in baking oven, dried 2 hours down for 90 ℃, take out alumina boat, on glass microballon, drip the silver nitrate solution 15ml of 0.5mol/L while hot, mix with the glass microballon in the alumina boat, continue oven dry 0.5 hour, take out alumina boat then, put it into the middle part of the heating tube in the tube furnace, fixedly the sealing cover at heating tube two ends; Open the air valve on the heating tube sealed end, continue to feed nitrogen, open the tube furnace heating power supply, rising heating tube temperature when temperature rises to 180 ℃, is turn-offed the nitrogen intake valve, open the hydrogen breather valve, hydrogen is entered in the heating tube, and flow out, continue elevated temperature to 280 ℃ from the air outlet, be incubated 1.5 hours, turn-off the hydrogen intake valve, feed nitrogen again, take out the cooling back.The glass microballon of pre-plating silver in the alumina boat is poured in the 5L glass beaker that fills 4L argentiferous ammonia solution, mix, wherein argentiferous ammonia solution is prepared with triethylene tetramine and Silver Nitrate, concentration of silver ions 15g/L, triethylene tetramine is 3.6 with the ratio of the volumetric molar concentration of silver ions, Sulfothiorine 12g/L, polyoxyethylene glycol 10g/L, the polyethylene pyrrole irons alkane ketone 0.15g/L, gelatine 0.2g/L.The glass microballon and the argentiferous ammonia solution mixture of pre-plating silver are joined in the closed reactor, under constantly stirring, the mixture of glass microballon and argentiferous ammonia solution in the reactor heating, when temperature is elevated to 90 ℃, feed hydrogen, hydrogen pressure keeps 2MPa, continues the rising reactor temperature, when temperature reaches 120 ℃, turn-off heating power supply; When hydrogen pressure drops to 1.0MPa in the reactor, feed hydrogen once more, improve hydrogen pressure to 2MPa, so repeat to feed hydrogen; When treating that hydrogen pressure no longer descends, refrigeration cycle water pipe in reactor feeds cold water, the temperature of mixture in the reactor is dropped to 60 ℃, emit mixture aqueous solution, with the glass microballon filtering separation after the plate silver, with 30～40 ℃ hot washes three times, the 70 ℃ of dryings 3 hours in baking oven of the glass microballon after the plate silver obtain the glass microballon product of plate silver.Through chemical composition analysis, silvered glass microballon argentiferous 15.72%, with microscopic examination silvered glass microballon, its surface is more level and smooth.
Embodiment 4
Ytterbium oxide coating surface silver.Measure the silver nitrate solution 1L of concentration 0.3mol/L, pouring volume into is in the 2L glass beaker, adds glycerol 3.2g, takes by weighing the rare-earth oxidation ytterbium 180g of particle diameter 15～30 μ m, joins in the beaker, mixes with silver nitrate solution; Stir after 3 minutes, ytterbium oxide is separated with silver nitrate solution, the wet oxidation ytterbium that is adsorbed with silver nitrate solution is packed in the alumina boat, sprawl evenly, in baking oven, dried 4 hours down for 80 ℃, take out alumina boat then, put it into the middle part of the heating tube in the tube furnace, fixedly the sealing cover at heating tube two ends; Open the air valve on the heating tube sealed end, continue to feed nitrogen, open the tube furnace heating power supply, rising heating tube temperature when temperature rises to 200 ℃, is turn-offed the nitrogen intake valve, open the hydrogen breather valve, hydrogen is entered in the heating tube, and flow out, continue elevated temperature to 400 ℃ from the air outlet, be incubated 2 hours, turn-off the hydrogen intake valve, feed nitrogen again, take out the cooling back.The ytterbium oxide of pre-plating silver in the alumina boat is poured in the 5L glass beaker that fills 3.5L argentiferous ammonia solution, mix, wherein argentiferous ammonia solution is prepared with quadrol, ammonia and Sulfuric acid disilver salt, concentration of silver ions 36g/L, the total mol concentration of quadrol and ammonia is 3.8 with the ratio of the volumetric molar concentration of silver ions, Sulfothiorine 25g/L, polyoxyethylene glycol concentration 8g/L, the polyethylene pyrrole irons alkane ketone 0.08g/L, gelatine 0.1g/L.The ytterbium oxide and the argentiferous ammonia solution mixture of pre-plating silver are joined in the closed reactor, under constantly stirring, the mixture of ytterbium oxide and argentiferous ammonia solution in the reactor heating, when temperature is elevated to 105 ℃, feed hydrogen, hydrogen pressure keeps 1.8MPa, continues the rising reactor temperature, when temperature reaches 135 ℃, turn-off heating power supply; When hydrogen pressure drops to 1.0MPa in the reactor, feed hydrogen once more, improve hydrogen pressure to 1.8MPa, so repeat to feed hydrogen; When treating that hydrogen pressure no longer descends, refrigeration cycle water pipe in reactor feeds cold water, the temperature of mixture in the reactor is dropped to 70 ℃, emit mixture aqueous solution, with the ytterbium oxide filtering separation after the plate silver, with 30～50 ℃ hot washes three times, the 65 ℃ of dryings 4 hours in baking oven of the ytterbium oxide after the plate silver obtain contracted payment ytterbium oxide product.Through chemical composition analysis, silver-plated ytterbium oxide argentiferous 40.59%, with the silver-plated ytterbium oxide of microscopic examination, its surperficial silver-colored coating layer is smooth.
Embodiment 5
The carbon fiber surface plate silver.Measure the silver nitrate solution 1L of concentration 0.3mol/L, pouring volume into is in the 2L glass beaker, adds glycerol 4.1g, takes by weighing the carbon fiber 40g of mean diameter 7 μ m, long 5000～6000 μ m, joins in the beaker, mixes with silver nitrate solution; Stir after 3 minutes, carbon fiber is separated with silver nitrate solution, the wet carbon fiber that is adsorbed with silver nitrate solution is packed in the alumina boat, sprawl evenly, in baking oven, dried 2 hours down for 100 ℃, take out alumina boat then, put it into the middle part of the heating tube in the tube furnace, fixedly the sealing cover at heating tube two ends; Open the air valve on the heating tube sealed end, continue to feed nitrogen, open the tube furnace heating power supply, rising heating tube temperature when temperature rises to 160 ℃, reduces the nitrogen air input, open the hydrogen breather valve, hydrogen is entered in the heating tube, hydrogen mixes with nitrogen, wherein hydrogen is controlled at 75～80% (percent by volumes), and flows out from the air outlet, continues elevated temperature to 310 ℃, be incubated 2 hours, turn-off the hydrogen intake valve, feed nitrogen again, take out the cooling back.The carbon fiber of pre-plating silver in the alumina boat is poured in the 5L glass beaker that fills 4L argentiferous ammonia solution, mix, wherein argentiferous ammonia solution is prepared with diethylenetriamine, ammonia and Silver Nitrate, concentration of silver ions 15g/L, the total mol concentration of diethylenetriamine and ammonia is 3.9 with the ratio of the volumetric molar concentration of silver ions, Sulfothiorine 20g/L, polyoxyethylene glycol concentration 12g/L, the polyethylene pyrrole irons alkane ketone 0.12g/L, gelatine 0.5g/L.The carbon fiber and the argentiferous ammonia solution mixture of pre-plating silver are joined in the closed reactor, under constantly stirring, the carbon fiber of pre-plating silver and the mixture of argentiferous ammonia solution in the reactor heating, when temperature is elevated to 115 ℃, feed hydrogen, hydrogen pressure keeps 2MPa, continues the rising reactor temperature, when temperature reaches 130 ℃, turn-off heating power supply; When hydrogen pressure drops to 1.0MPa in the reactor, feed hydrogen once more, improve hydrogen pressure to 2MPa, so repeat to feed hydrogen; When treating that hydrogen pressure no longer descends, refrigeration cycle water pipe in reactor feeds cold water, the temperature of mixture in the reactor is dropped to 70 ℃, emit mixture aqueous solution, with the carbon fiber filtering separation after the plate silver, with 30～50 ℃ hot washes three times, the 65 ℃ of dryings 4 hours in baking oven of the carbon fiber after the plate silver obtain silver-plated carbon fiber product.Through chemical composition analysis, silver-plated carbon fiber argentiferous 58.64%, with the silver-plated carbon fiber of microscopic examination, its surperficial silver-colored coating layer is smooth.
The above only is specific embodiments of the invention, enforcement of the present invention is not limited thereto, anyly be familiar with those skilled in the art according to the foregoing description, the specific requirement that provides by technical solution of the present invention, through suitably changing or replacing, all can be at powder or fibrous metal or non-metal material surface plating silver conductive layer uniformly continuously, wherein should be noted that it is the quality of pre-plating silver or nickel on metal or non-metal material surface especially.
Claims (6)
1. metal or non-metal material surface prepare the method for even silver conductive layer, at powder or fibrous metal or non-metal material surface plating continuously uniformly during silver conductive layer, earlier through the pre-plating treatment process, at material surface elder generation's a small amount of nanometer metallic silver of pre-plating or nickel, pass through plating process then, in the argentiferous ammonia aqueous solution, use hydrogen reducing silver, silver is plated on metal or non-metal material surface, washing more after filtration,, drying process, the obtained coating surface metal or the non-metallic material product of silver conductive layer uniformly continuously is characterized in that:
Need are mixed with Silver Nitrate or nickel nitrate solution by the powder of silver-colored plating or fibrous metal or non-metallic material, stir after 2～30 minutes, solution and metal or non-metallic material filtering separation, the metal or the non-metallic material that are adsorbed with Silver Nitrate or nickel nitrate solution are put into the baking oven inner drying, dried metal or non-metallic material are put into airtight process furnace, and the thermal treatment pre-plating is 0.5～5 hour in the atmosphere of 150～450 ℃ of following hydrogen; After thermal treatment pre-plating and cooling, metal after the pre-plating or non-metallic material are joined in the argentiferous ammonia solution mix, and mixture is joined in the reactor heated mixt, when temperature reaches 70～150 ℃, feed hydrogen, reacted 10～60 minutes, argent is plated on metal or non-metal material surface, behind the cooling mixture, in reactor, emit, after filtration, washing, drying, obtain the surface by plating the evenly metal or the non-metallic material of metallic silver layer continuously.
2. the method that is prepared even silver conductive layer by described a kind of metal of claim 1 or non-metal material surface is characterized in that comprising in the pre-plating treatment process and soaks pre-treatment and thermal treatment pre-plating, wherein:
When (1) soaking pre-treatment powder or fibrous metal or non-metallic material are mixed with the solution of Silver Nitrate or nickelous nitrate, the concentration of Silver Nitrate or nickel nitrate solution is 0.1～1mol/L, wherein, and adding glycerol 1.0～5.0g/L, 15～70 ℃ of solution temperatures; Stirred 2～30 minutes, metal or non-metallic material after the filtering separation are not washed, and have adsorbed Silver Nitrate or nickelous nitrate, 60～105 ℃ of oven dry; When adsorptive capacity is not enough, can directly Silver Nitrate or nickel nitrate solution dropping on the metal or non-metallic material 50～70 ℃ of heat, continued oven dry at 60～105 ℃ again after the oven dry;
(2) during the thermal treatment pre-plating, after having adsorbed the metal or non-metallic material oven dry of Silver Nitrate or nickelous nitrate, thermal treatment pre-plating under 150～450 ℃ of temperature, 0.5～5 hour treatment time, feed the mixed gas of hydrogen or hydrogen and nitrogen, the mixed gas hydrogen 50～90% of hydrogen and nitrogen wherein obtains powder or the fibrous metal or the non-metallic material of a small amount of nanometer metallic silver of pre-plating or nickel.
3. the method for preparing even silver conductive layer by described a kind of metal of claim 1 or non-metal material surface, when it is characterized in that argentiferous ammonia solution is prepared, the silver material that contains that adopts is Silver Nitrate or Sulfuric acid disilver salt, concentration of silver ions is 5～50g/L in the argentiferous ammonia solution, and adding in complexing agent ammoniacal liquor, quadrol, triethylene tetramine, diethylenetriamine, tetraethylene pentamine or the polyethylene polyamine one or both, add-on is 1～5.5 by the ratio of complexing agent total mol concentration and the volumetric molar concentration of silver ions; Also add additive sulfur sodium thiosulfate 10～40g/L, polyoxyethylene glycol 3～25g/L in the argentiferous ammonia solution, the polyethylene pyrrole irons alkane ketone 0.05～0.5g/L, gelatine 0.05～1g/L.
4. the method for preparing even silver conductive layer by claim 1,2,3 described a kind of metals or non-metal material surface, it is characterized in that the metal after the pre-plating or non-metallic material are joined in the argentiferous ammonia solution and mix, and mixture joined in the reactor, the mixture of metal or non-metallic material and argentiferous ammonia solution in the reactor heating, when temperature reaches 75～150 ℃, feed hydrogen, hydrogen pressure 0.8～3.5MPa, reacted 10～60 minutes, argent is plated on metal or non-metal material surface.
5. the method for preparing even silver conductive layer by claim 1,4 described a kind of metals or non-metal material surface, after it is characterized in that plate silver, by plating the metal or the non-metallic material silver content 5～70% of metallic silver layer, be the argent weight of plating account for argent with by the percentage ratio of the metal of plating or non-metallic material gross weight, argent and the weight that by the gross weight of the metal of plating or non-metallic material also is product after the plate silver; When needs increase the plate silver amount, can be behind plating of argentiferous ammonia solution, the metal or the non-metallic material of metallic silver layer of having isolated plating are no longer passed through pre-plating, directly and new argentiferous ammonia solution mix, in solution, carry out the secondary plating.
6. the method for preparing even silver conductive layer by described a kind of metal of claim 1 or non-metal material surface, it is characterized in that being existed with powder or fibrous pattern by the metal of plating or non-metallic material, powder diameter is 0.1～1000 μ m, fibrous material diameter 0.5～80 μ m, length 5～9000 μ m; Wherein metallic substance is meant non-ferrous metal, rare earth metal, ferrous metal and alloy thereof; Non-metallic material are meant non-metal simple-substance, metal oxide, nonmetal oxide, rare-earth oxide, complex metal oxides, metal carbonate, metal hydroxides, oxide ceramics, nitride ceramics, carbide ceramics, boride ceramics, conductivity ceramics, sintering metal and glass.
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