CN1158774A - Method and apparatus for making sintered porous metal plate - Google Patents
Method and apparatus for making sintered porous metal plate Download PDFInfo
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- CN1158774A CN1158774A CN 96123492 CN96123492A CN1158774A CN 1158774 A CN1158774 A CN 1158774A CN 96123492 CN96123492 CN 96123492 CN 96123492 A CN96123492 A CN 96123492A CN 1158774 A CN1158774 A CN 1158774A
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Abstract
A method for making a sintered porous metal plate comprises the steps of: a slurry preparation step for preparing a foamable slurry containing metal powder; a shaping step for shaping the foamable slurry into a plate article; a foaming the plate article; and a drying step for drying the plate article after foaming. Further, an apparatus for making a sintered porous metal plate comprises a slurry preparation section for preparing a foamable slurry containing at least metal powder, a foaming agent and a liquid medium; a shaping section for shaping the foamable slurry fed from the slurry preparation section into a plate article; a foaming section for foaming the plate article of the foamable slurry; and a drying section for drying the cellular article; and these section are integrated in series by a transfer section.
Description
The present invention relates to make the method and apparatus of the sintered porous metal plate that is used for filter, electrode for secondary battery substrate etc.
Comprise three-dimensional netted framework and have highly porous expanded metal and be used to the electrode of battery, various filter and catalyst carrier.
The art methods of making this class expanded metal comprises: the method for firing behind the polyurethane foam of plating conduction (Japanese unexamined patent publication No. 4-2759); Metal dust is sticked on the urethane foam that scribbles bonding agent, and with its method of firing (Japanese unexamined patent publication No. 3-188203); And low-melting metal sprayed in the container that contains thin crystal powder that can be water-soluble with pressure, wash the method (Japanese unexamined patent publication No. 59-1651) of the crystal powder of removing water soluble then after metal-cured with water.
But, among the above-mentioned Japanese unexamined patent publication No. 4-2759, restricted based on the method for plating to metal component, so its purposes is limited.And then, in two kinds of methods of first and second correlation technique, form empty skeleton because burning resin, cause the minimizing of effective spatial volume.In addition, in Japanese unexamined patent publication No. 59-1651 disclosed method, almost can not obtain the loose structure of hole dimension less than 100 μ m, therefore, resulting porous article has only less specific area.
The purpose of this invention is to provide a kind of manufacturing metal component is had selection freedom largely and the method and apparatus that has than the sintered porous metal plate of bigger serface.
Another object of the present invention provides a kind of manufacturing as the intermediate product of sintered porous metal plate, the method and apparatus of unsintered metal foam.
According to first target of the present invention, make the included step of method of sintered porous metal plate: preparation contains the slurry manufacturing step of the foamable slurry of metal dust; Make the slurry that to foam form the forming step of plate-shaped products; Make the foaming step of plate-shaped products foaming; And make the drying steps of the plate-shaped products drying after the foaming.
The slurry that can foam can comprise the resinite bonding agent and the surfactant of metal dust, blowing agent, water soluble.
Preferably this method also comprises the step of firing of the greasy dirt of removing the dry plate-shaped products behind the drying steps.
This fires the step that step can comprise the sintering plate-shaped products.Being preferably in the forming step is shaped the foaming slurry with the scraping blade method.This scraping blade method is used two with predetermined space doctor spaced apart from each other.
Be better, in slurry preparation step, preparation contains second aqueous solution of the resinite binding agent of first aqueous solution of resinite binding agent of blowing agent, surfactant and water soluble and metal-containing powders and water soluble respectively, and with first and second aqueous solution, so that before forming step, just make the foaming slurry.
In foaming step, contained blowing agent foams under high humility in the foaming slurry.Best this high humility is 65% or higher.
Drying steps is a kind of drying steps of far-infrared radiation.
Be that forming step is finished the shaping of the plate-shaped products that can foam better on carrier plate.
Before this forming step, on carrier plate, be formed in advance and fire the disengaging film that to burn in the step.Say exactly, break away from film and contain polyurethane resin.
According to second target of the present invention, the equipment of making sintered porous metal plate comprises and prepares the pulp preparation device of the foamed slurry of metal-containing powders, blowing agent and liquid medium at least; Make for the building mortion that forms plate-shaped products from the foamed slurry of pulp preparation device; Make the foam device of the plate-shaped products foaming of the slurry that can foam; And make the drying device of born of the same parents' shape product dried; Wherein these devices are connected into an integral body by conveying device.
Be that conveying device comprises a continuous carrier plate better.
Be better, a degreaser that dry plate-shaped products is deoiled is set behind drying device, preferably degreaser has carrier plate.
Suitable sintering equipment can be arranged on after the deoiler, for the plate-shaped products of sintering de-oiling.
Be that building mortion comprises the doctor device better.The doctor device comprises two scrapers.
Be better, the pulp preparation device comprises the first aqueous solution device that mixes first aqueous solution contain blowing agent, surfactant and moisture resinite binding agent and mixes metal-containing powders and the second aqueous solution device second aqueous solution of moisture resinite binding agent and that separate with the first aqueous solution device, and first and second aqueous solution just are mixed with the 3rd mixing arrangement of the slurry that can foam before forming step.
Preferably foam device comprises that one keeps 65% or the device of high humility atmosphere more.
Building mortion comprises that a short time deposits the slurry container of defeated foamed slurry from the pulp preparation device and one prevent from the to foam liquid medium sprayer unit of pulp surface drying.
Foam device comprises a baker, it has around the entrance and exit of the transfer passage of conveying device, is located in the baker, have the water receiver of thermostat, in baker, be provided with, the heater of heating molded article and be located at anti-condensation water heater on the baker inwall along transfer passage.
Drying device comprises a far-infrared radiation device.
The release agent coating unit is located at before the shaped device, so that form the film of release agent on conveying device.The release agent coating unit comprises a doctor machine and release agent drying machine.
Suitable sintering equipment comprises that plate shape goods that a tunnel cave and one will remove greasy dirt continuously transport to the bearing part of its outlet from the inlet of kiln; And bearing part comprises and a plurality ofly transports roller by what carriage direction rotated at least a portion of tunnel cave.Control is transported roller so that transmission speed reduces gradually along carriage direction.
Will be further understood that other characteristic of the present invention and advantage from conjunction with the accompanying drawings statement hereinafter, wherein:
Fig. 1 is a profile of making the equipment of non sintered metal foam, and this metal foam is as the intermediate product of the sintered porous metal plate of first embodiment of the invention;
Fig. 2 is the non sintered metal foam process is made in explanation by first embodiment a flow chart;
Fig. 3 is the profile of the major part of the doctor that two scrapers are arranged shown in Fig. 1;
Fig. 4 is the profile of the doctor running shown in the key diagram 3;
Fig. 5 A-5E is the simple profile that schematically illustrates foamed state under high humidity;
Fig. 6 A-6E is the simple profile that schematically illustrates foamed state under the low humidity condition;
Fig. 7 is the profile of the major part of foaming machine of the present invention;
Fig. 8 is the profile of the major part of drying machine of the present invention;
Fig. 9 A-9D is the simple profile that schematically illustrates the cell structure of the sintered porous metal that obtains by the inventive method;
Figure 10 is the simple profile that explanation the present invention makes the equipment of the foamed slurry of second embodiment and the composite that the present invention makes the 4th embodiment;
Figure 11 is the profile that schematically illustrates the slurry cabin structure of four embodiment of the invention;
Figure 12 is the flow chart that explanation the present invention makes the sintered porous metal plate method of the 5th embodiment;
Figure 13 is that the present invention shown in explanation Figure 12 is used to finish the equipment profile that the 5th embodiment is made the sintered porous metal plate method.
Produce sintered porous metal plate according to the present invention, also produce non sintered metal foam as the intermediate product of sintered porous metal plate.First embodiment
By first embodiment of the invention, explain the production of non sintered metal foam as the intermediate product of sintered porous metal plate (or not sintered plate).Fig. 1 is the equipment profile of the manufacturing non sintered metal foam of first embodiment of the invention, and Fig. 2 is the flow chart of the production technology of the explanation first embodiment non sintered metal foam.
As shown in Figure 1, the equipment of making unsintered metal foam comprises preparation and drying nest, foaming pulp preparation part, foaming part, drying nest and the cutting part of release agent film.The non sintered metal foam is pressed the illustrated method production of Fig. 2 flow chart.That is, the non sintered metal foam is by release agent film preparation step, release agent drying steps, the slurry preparation step that can foam, forming step, foaming step, drying steps and cutting step production.
The equipment of manufacturing non sintered metal foam shown in Figure 1 is according to method operation shown in Figure 2.This equipment is equipped with first roller 20 and second roller 21, is provided with carrier plate 10 between them.This carrier plate 10 just plays conveyer belt by moving between first roller 20 and second roller 21.To second roller 21, this equipment is provided with release agent reservoir 80, release agent drying machine 100, slurry reservoir 30, the high temperature humidifier 40 that is used to foam and drying machine 50 from first roller 20.Release agent reservoir 80 is cuboids, and it plays and the effect that contacts above near the carrier plate 10 of first roller 20.On the right wall of release agent reservoir 80, doctor 90 is arranged.Doctor 90 is set, and to make the gap of 10 of itself and carrier plates be adjustable.In this way, release agent reservoir 80 and doctor 90 have just constituted solutioning machine 11.
Explain each step of method shown in Figure 2 with reference to the each several part of equipment shown in Figure 1.The preparation of release agent film and drying
When release agent reservoir 80 is equipped with when moving with the disengaging coating material u of urethane resin preparation and carrier plate 100, breaks away from coating material u and just be extruded out, so that form the coated film 2 of given thickness from the gap of 10 of doctor 90 and carrier plates.This coated film 2 moves to following release agent drying machine with carrier plate 10, so that coating material is dry and curing.The thickness of release agent film 2 can be by the gap adjustment of 10 of doctor 90 and carrier plates.
Release agent drying machine 100 makes release agent the film 2 dry and curing that are formed on the carrier plate 10.The preferred example of release agent drying machine comprises air drier and far infrared drying machine.Release agent film 2 helps sintered plate is not peeled from carrier plate.Release agent film 2 is removed by firing in the sintering step of sintered plate not.Also have, release agent film 2 also can be used as the not carrier belt of sintered plate.
As mentioned below, dry not sintered plate 1C can handle at an easy rate by the formation of release agent film 2.Therefore, for the present invention, just always do not need the preparation process and the drying steps of urethane coating film.The pulp preparation that can foam and forming step
In the slurry preparation step that can foam, preparation contains the slurry of metal dust, water soluble resinite binding agent, blowing agent, surfactant, water etc.
In forming step, the foamed slurry of gained is shaped as plate.Manufacturing process is hereinafter with reference to Fig. 3 and the detailed doctor method of explaining of Fig. 4 preferably.
Though consider that the preparation of the slurry that can foam and the forming step of following are whole steps, hereinafter still be described with step independent of each other.A. the preparation process of slurry can foam
The slurry reservoir 30 of a cuboid form is set, so that contact with the top of carrier plate in release agent drying machine 100 the place aheads.Above slurry reservoir 30, be provided with the slurry blender 110 that to foam, for preparing the foamed slurry S that will send in the slurry reservoir 30.The slurry blender 110 that can foam is provided with and is used to mediate the kneader of failing from the raw material of a plurality of feed bins 111, and is used for the blowing agent mixing apparatus 113 of mixed foaming agent.The slurry blender 110 that can foam will mix with mixed blowing agent in blowing agent mixing apparatus 113 by the raw material that kneader 112 is mediated, to prepare the slurry S that can foam.Pulp components is divided into two kinds of liquid owing to can foam, and just before this mixture is sent into doctor 60 these two kinds of liquid is mixed, so prevented the volatilization of blowing agent.
The wall of the slurry reservoir 30 of the downstream part of the carriage direction of carrier plate has doctor 60.Regulate the gap between doctor 60 and the carrier plate 10, with the desirable not sintered plate of preparation thickness 1A.In material reservoir 30 the slurry S that can foam is housed, when carrier plate was moved, the slurry S that can foam just was extruded from the gap location between doctor 60 and the carrier plate 10, so that form the plate-shaped products with given thickness.The plate-shaped products 1A humidifier towards the back on carrier plate 10 that is shaped moves, and heats for foaming.
Because below, the slurry reservoir preferably is provided with the lip-deep mechanism of slurry S that the liquid medium atomizing is sprayed on storage.When the slurry S that can foam sent in the reservoir, air bubble B and original pulp surface Ssu were brought into the inside of this slurry as shown in Figure 4.The shaping plate-shaped products of slurry comprises this air bubble if can foam, and then will form the undesirable cavity based on air bubble in expanded metal.Since different by the hole that air bubble forms with the hole dimension that forms by blowing agent, so expanded metal just has uneven cell structure.Because raise in the viscosity on surface, so air bubble is extremely difficult discharges, so just bring air bubble in a large number into when the dry tack free of the slurry S in the reservoir.On the contrary, when on the surface that liquid medium is sprayed on as shown in Figure 11 slurry, the surface in reservoir is then moist, thereby has prevented the inhomogeneous cell structure in this expanded metal.Can be continuously or jetting liquid medium discontinuously, as long as prevent the pulp surface drying.
Can suitably select according to the purpose of final products for the metal dust that forms the non sintered metal foam in the present invention.When this metal foam was used for electrode, the example of this metal dust comprised such as the sintering metal of Ni, Cu, Fe, stainless steel, Cr, Co, Au and Ag or the powder of alloy.The particle mean size of metal dust better is 500 μ m or littler, and is more preferably 0.5-100 μ m.When particle mean size is 0.5 μ m or more hour, void ratio is too small.On the other hand, when particle mean size be 500 μ m or when bigger, the sintered porous metal plate that obtains by sintering non sintered metal foam will not have enough intensity.The content range of metal dust is that (weight % Hereinafter the same), is more preferably 30-80% to 5-80% in slurry.
The keep dry shape of the porous article after the step of water soluble resinite binding agent.Water soluble resinite adhesive also plays the slurry viscosity conditioning agent.The example of the resinite binding agent of this water soluble comprises: methylcellulose, hydroxypropyl methylcellulose, hydroxyethylcellulose, carboxymethyl cellulose ammonium, ethyl cellulose and polyvinyl alcohol.The content of water-soluble resin matter binding agent better is in the scope of 0.5-20%, is more preferably in the scope of 2-10%.When this content is 0.5% or more hour, the undercapacity of dry metallic article is with through being subject to processing.On the other hand, when this content is 20% or when higher, the too high formed article that can not get of viscosity.
Any owing to discharge the blowing agent that gas can form hole, all can use as compound and the volatile organic solvent that discharges gas owing to decomposition under predetermined temperature.The example of volatile organic solvent includes the hydrocarbon organic solvent of 5-8 carbon atom.These organic solvents are liquid in room temperature, and form capsule when surfactant exists in slurry.These organic solvents at room temperature evaporate by heating and form tiny bubble in slurries.There is the example of the hydrocarbon organic solvent of 5-8 carbon atom to comprise: pentane, neopentane, hexane, isohexane, heptane, isoheptane, benzene, octane and toluene.The content range of blowing agent is preferably 0.05-10%, and 0.5-5% more preferably.Content can not form the bubble that presents in an amount at least sufficient to reach predetermined porosity less than 0.05%.On the other hand, content forms large-sized capsule greater than 5%, thereby forms bigger bubble, causes the intensity of molded article and sintered foam to descend.The slurry that can foam can pass through mist forcefully, replaces blowing agent as air and prepares.
Surfactant makes foaming attitude stabilisation, and forms the capsule of blowing agent.The example of surfactant comprises anion surfactant, as the salt of alkylbenzenesulfonate, alpha-alefinically sulfonic acid, alkyl sulfate, the salt and the paraffin sulfonate of alkyl ether sulphate; With non-ionic surface active agent, as the derivative of polyethyleneglycol derivative and polyalcohol.The content range of surfactant is 0.05-5%, better is 0.5-3%.Less than 0.05% o'clock, capsule formed instability in amount, thereby was difficult to the bubble that keeps tiny in slurry.On the other hand, content surpasses 5%, does not improve above-mentioned effect.
Slurry also plasticizer-containing, combustible etc. except that above-mentioned solvent but the present invention can foam.
Adding plasticizer can make unsintered porous metals spare that plasticity is arranged.The example of plasticizer comprises polyalcohol, as ethylene glycol, polyethylene glycol and glycerine; Oils is as sardine oil, rape seed oil and olive oil; Ethers is as benzinum; And the ester class, as diethyl phthalate, n-butyl phthalate, phthalic acid diethylhexyl ester, dioctyl phthalate, sorbitan-oleate, sorbitan trioleate, dehydrated sorbitol palmitate and sorbitan stearate.The plasticizer loading scope is preferably 0.1-15%, is more preferably 2-10%.Content less than 0.1% can not cause enough plasticization effects, otherwise the content above 15% makes formed article not have gratifying intensity.Preferred plasticizer is polyalcohol and glycerine.These plasticizer can improve the porosity of molded article.
Combustible is by the formation that burning during the step promotes the hole of firing at the molded article of doing.Any powder and fibrous combustible all can use.In detail, adopt powder and the long 200 μ m or littler of about 0.1-200 μ m, the fiber of preferably long 30-120 μ m.The example of combustible comprises: paper pulp, cotton, useless fine fibre, beautiful material starch, carboxymethyl cellulose, water-insoluble cellulose fibre, polyethylene butyral resin, polyvinyl resin and polyvinyl resin.
By being mixed, said components can obtain the slurry that foams of the present invention.Though the order of mixing is unrestricted, preferably adds blowing agent at last, to reduce the formation of bubble in blend step.After slurry bubbles, its mobile decline, thereby cause bad forming characteristic.But, can control by the kind of blowing agent and the temperature of consumption and slurry until the time of foaming beginning behind the interpolation blowing agent.Therefore, by preferred these parameters, can in still having time of fluidity, slurry make it be formed with the not sintered porous metal spare of reservation shape.The viscosity of slurry is preferably 20000-70000cps, and 30000-55000cps more preferably.When this viscosity is lower than 20000cps when temperature is 20 ℃, then cell structure will be in dry run variation.On the other hand, when viscosity was higher than 70000cps, then forming characteristic can be because of the high viscosity variation.B. forming step
The slurry for preparing in the above-mentioned steps is shaped as plate.A kind of suitable manufacturing process is the doctor method.
Fig. 3 and 4 is embodiment of the present invention, and the profile of major part of the doctor of two scrapers is arranged.
The doctor unit is provided with first roller 20 of being with the carrier plate 10 that twines and the 2nd roller 21 (not showing this roller at Fig. 3 and 4) that is used for straining carrier plate 10.Doctor 60 is located at the carriage direction downstream of this carrier plate, and on the right wall of slurry reservoir 30, and an adjustable gap is between doctor 60 and carrier plate 10.Thickness with the gap adjustment molded article between it.When slurry 30 is loaded into the slurries that can foam, when carrier plate 10 was moved, the slurry S that can foam was then extruded from gap location, thereby was formed with the plate-shaped products 1A of predetermined thickness.Foaming district 40 below this plate-shaped products 1A moves on carrier plate 10.
As shown in Fig. 3 and 4, by with two scraper 60A and 60B as doctor, then emit big bubble from the gap between scraper 60A and the 60B.Therefore the plate-shaped products 1A that releases from the gap location between the second scraper 60B and the carrier plate 10 does not contain big bubble, thereby regardless of the amount of the slurry S that can foam, the thickness of plate-shaped products 1A can be uniform.Clearance G 1 between the first scraper 60A and the carrier plate 10 suits greater than the clearance G 2 between the second scraper 60B and the carrier plate 10.Preferably the distance D between the first scraper 60A and the second scraper 60B is about 5-20mm.Clearance G 2 between the second scraper 60B and the carrier plate 10 is preferably 0.2-2mm.Foaming step
Molded article is fully foamed.For production non sintered metal foam of the present invention, always do not need foaming step.But when making molded article dry after forming step immediately, its surface is at first dry and form one deck skin, is suppressed at the inside of molded article with water evaporates thereby will foam.Therefore, for reaching even foaming, preferably between forming step and drying steps, foaming step is set.
When the shaping goods are dry in foaming process, form crackle easily in its surface.Therefore, preferably in the environment of high humility, foam, to prevent the molded article drying.Such as, when the viscosity of slurry is 35000cps or when higher, humidity is at least 65%, is more preferably at least 80%.Can on the molded article surface, form crackle in humidity less than 65% o'clock.The blowing temperature scope is preferably 15-65 ℃, more preferably 28-40 ℃.For foaming needs a lot of time under 15 ℃ the temperature being lower than, such as 2 hours.When temperature surpassed 65 ℃, molded article bubbled egregiously, thereby causes breaking of molded article sometimes.Foaming generally will be carried out 10-45 minute.
Fig. 5 A-5E schematically illustrates the foaming situation under high humility.Be shaped as reservation shape at the slurry that can foam, plate for example, as (Fig. 5 A) after the molded article 1A, the blowing agent in the slurry is just emitted gas and is formed bubble 3 (Fig. 5 B-5C) in molded article in this foaming step.In the high humidity foaming step, slurry viscosity is uniformly in whole molded article 1A, and bubble is evenly growth in molded article, thereby molded article just becomes the born of the same parents' shape goods 1B with uniform cell structure.And then the high humidity foaming step does not cause crackle and other defective on the surface of born of the same parents' shape goods 1B.
Fig. 6 A-6E schematically illustrates when the slurry that can foam after being shaped is dried, or under low humidity the foaming situation during foaming.When a kind of like this low humidity foams, be shaped as reservation shape at the slurry that can foam, as (Fig. 6 A) behind the molded article 1A, the blowing agent in the slurry is emitted gas in foaming step, thereby, in molded article 1A, form bubble 3 (Fig. 6 B-6C) as in the high humility foaming step.But the surface of molded article 1A is at first dry, and the slurry viscosity of goods 1A is owing to the low humidity condition becomes inhomogeneous.Therefore, bubble 3 is growth unevenly in molded article, causes having born of the same parents' shape goods 1B (Fig. 6 D) of inhomogeneous cell structure.And then, easily on the surface of born of the same parents' shape goods 1B, form crackle and other defective (Fig. 6 E).
Foaming is to carry out in the foaming district with the high temperature humidifier 40 that is used for foaming.
Fig. 7 is the profile of the embodiment of the high temperature humidifier 40 that is used to foam.Be preferably, the high temperature humidifier 40 that is used to foam comprises a baker 46, and it surrounds the passage that transports as the carrier plate of conveying device, and is provided with inlet 47 and outlet 48; One is located in the stove, has the cistern of thermostat; One is used for heating at the heater 44 of stove along the molded article that transports the passage supply; And anti-condensation water heater 42 that is located on the furnace wall.Baker 46 surround carrier plates 10 transport passage and at upper and lower formation space 49A, the 49B of this carrier plate 10.The inlet 47 of carrier plate 10 is located at the middle part (the first roller side) of the head bay wall of baker 46, and exports 48 middle parts (the second roller side) that are located at the downstream wall of baker 46.The lower space that is formed at carrier plate 10 belows plays a part water receptacle, and it is equipped with the water 45 of specified rate.Variable heater 43 is located at the bottom than low spatial 49A, so that by making water 45 evaporation make atmosphere in the baking keep given humidity better, be provided with agitator among the lower space 49A, so that even water temperature.In baker 46 carrier plate 10 transport above the passage on plate heater 42 is set on the wall among the 49A of space.The anti-sealings of plate heater 42 condense on the wall and help the operation of variable heater.Plate heater 44 just under carrier plate 10 along transporting the passage setting, so that promote foaming by the shaping pulp product 1A of heating on carrier plate 10.Plate heater 42 and 44 example comprise the carbon plate heater, and the example of variable heater comprises armouring Ni-Cr alloy silk heater.Drying steps
Born of the same parents' shape goods 1B is transported to dry section 50 from the foaming district.Bubble is owing to existing moisture film to keep before dry, and slurry condenses part and then forms skeleton structure (cell structure) on the interface of bubble.When moisture film broke under this state, the slurry that forms skeleton flowed, and has destroyed skeleton structure.Therefore, by only otherwise the drying of destroying skeleton structure just can obtain this cell structure.The rapid draing that skeleton structure wherein is not destroyed is a kind of in these class methods.For this purpose, far infrared drying suits.Be that the composition of slurry has such characteristics preferably: evaporate a bit when water is firm, viscosity just raises rapidly.
Condition in the drying steps comprises: such as, temperature 120-180 ℃, atmosphere temperature 40-80 °, drying time the 20-120 branch.Obtain not sintered plate 1C after the drying, its thickness is generally 3-8 times of G2 height shown in Figure 3.Sintered plate is not by delivery and carrier plate is bent downwardly and separates with carrier plate 10.
The example of this drying means comprises radiant heat method, as hot-air drying, FAR INFRARED HEATING method and microwave heating method.Wherein the rate of drying of microwave heating method is the highest, then is the FAR INFRARED HEATING method.Because the rate of drying of radiant heat method is more much smaller than the speed of other two methods, so born of the same parents' shape goods are inhomogeneously dry between surface and inside.Therefore, for quick removal water, far infrared collimation method or microwave method all are effective.But because with the foaming slurry in metal-containing powders because metal dust burning and can not use microwave.So, the most handy far infrared method.But drying machine 50 is not limited to the far infrared drying machine.Such as, air drier and FAR INFRARED HEATING and heat conduction also can be used for the present invention as the combination of heated-air drying.
Fig. 8 is the profile of the far infrared drying machine structure of explanation embodiment of the present invention.Far infrared drying machine 50 surrounds the passage that transports of carrier plate 10, and has baker 10 so that form the space of a sealing above carrier plate 10.The wall of baker 51 upstreams (the first roller side) is provided with the inlet 56 of carrier plate 10, and the wall of baker 51 downstreams (the second roller side) is provided with outlet 57.The inside of baker 51 uses the partition wall 53A, the 53B that link to each other with top and the side wall of baker 51 inside to be divided into three cabin 54A, 54B and 54C along carriage direction.Between partition wall 53A, 53B and carrier plate 10, leave suitable space 58A, 58B, so that the cell structure goods 1B on carrier plate 10 passes through towards next cabin through space 58A, 58B.Be provided with a plurality of far infra-red heaters 52 transporting among cabin 54A, 54B above the passage and the 54C of carrier plate 10.Exhaust blower 55A, 55B, 55C are located on the roof of three cabin 54A, 54B, 54C, so that extract the gas atmosphere of the humidity in these cabins out.Preferably, the interior wall among this cabin 54A, 54B, the 54C has reflecting properties, so that carry out effective dry with far infrared.Number to the cabin does not limit in the present invention.Alternative is not as above-mentioned embodiment, will not be divided into a plurality of cabins by baker.And then, a plurality of independently far infrared drying machine arows can be arranged.
Be listed as for obtaining to have the not sintered plate of the cell structure that meets the requirements and don't skeleton structure being broken, preferably the water of a little just can make the viscosity of paste compound improve rapidly in the slurry by only evaporating.
With far infrared drying machine 50, to do quick-fried the drying time that the environment temperature and the 20-120 of 120-180 ℃ heter temperature, 40-80 ℃ divides.In this step, obtain dry plate-shaped products or sintered plate 1C not.Not the thickness of sintered plate 1C be the G2 among Fig. 3 height 3-8 doubly.Cutting step
To not with cutter 70, sintered plate is cut into predetermined length.The not sintered plate of cutting, such as, on demand, be sent to and fire step.
In the equipment of the manufacturing sintered porous metal plate of embodiment of the present invention shown in Figure 1, sintered plate 1C does not make its crooked being separated when carrier plate 10 is moved.With cutter 70 not sintered plate 1C be cut into predetermined length, and transport next step (this is not shown in the figures) to.
In above statement, shaping, foaming and dry order are carried out.Alternative is that these are handled available its equipment separately and carry out.
The continuous technology of making unsintered metal foam of equipment of the expanded metal of sintering is made in explanation now with the present invention.
1. after forming disengaging film 2 on the surface of carrier plate 10, the slurry S that can foam charges in the slurry reservoir 30, so that with doctor slurry S is shaped as plate.In detail, will extrude the space of release coating u between doctor 90 and the carrier plate 10 that moves of sending in the release agent reservoir 80, thereby be formed with the paint film 2 of given thickness.To solidify by the paint film 2 of carrier plate 10 deliveries with release agent drying machine 100.
2. the plate-shaped products 1A of the slurry S that can foam is shaped on the release agent film 2 that obtains.Carrier plate 10 plays a part the conveyer belt of plate-shaped products 1A.With extruding the space of foamed slurry S between doctor 60 and carrier plate 10 that is transported in the slurry reservoir 30, be shaped as the plate-shaped products 1A of predetermined thickness then.Plate-shaped products moves to the high temperature humidifier 40 that foams with carrier plate 10.
3. in the high temperature humidifier 40 that foams, foam and before plate-shaped products 1A drying, thoroughly finish, dry in foaming process to prevent plate-shaped products.
4. born of the same parents' shape goods 1B is sent in the dry section of drying machine 50 in the high temperature humidifier for foaming, obtains not sintered plate 1C after the drying.
5. unsintered plate 1C is bent downwardly when carrier plate 10 is moved and is separated, and is cut into predetermined length with cutter 70 then.The not sintered plate of cutting is transported to next step, such as firing the step (not shown).Embodiment 1-1
Referring now to embodiment the present invention is described.
Prepare foamable slurry by mixing based on the metal dust of the listed prescription of table 1 (weight %), resinite binding agent, blowing agent and surfactant that can be water-soluble.With equipment shown in Figure 3 the every kind of slurry that can foam is shaped as plate-shaped products, the open height of the first scraper 60A wherein shown in Figure 3 is that the open height of 0.8mm, the second scraper 60B is 0.6mm, and the translational speed of carrier plate 10 is the 20cm/ branch.
As shown in table 2, with molded article 1A foaming in setting to fixed temperature, humidity, the warm and humid device 40 of preset time.Is 160 ℃ far infrared drying machine 50 dryings with formed article 1B with the setting heter temperature, with the sintered plate 1C that must arrive.Sintered plate is not on graphite cake for the general, and de-oiling fat is 30 minutes in 450 ℃ air.Will be not sintered plate sintering under the conditions shown in Table 2, to obtain the expanded metal of sintering.Behind the sintering, the length of expanded metal ratio not sintered plate has dwindled 20%.
The part of the expanded metal of each sintering is dipped in the resin, then with its cross section polishing.Survey pore-size and the porosity that polishes part with image analyzer, and survey its specific area with the BET method.The results are shown in table 2.
As a comparison case, prepare the expanded metal of sintering as follows: the Ni that evaporation 0.5 μ m is thick on commercially available poly-hydrogen base Ethyl formate foam interior surface immerses this foam in the nickel sulfate solution with after making it to have electric conductivity; With 1A/dm
2Current density the foam as negative electrode is electroplated, be the Ni coating of 75 μ m on the surface of the opening loculus of foam, to form average thickness; The foam of electroplating was kept 0.5 hour in Oxygen Flow under 1100 ℃, to remove poly-hydrogen base Ethyl formate foam.The sintered porous metal plate diameter 50mm of gained, length 100mm.The hole dimension of the expanded metal of this sintering, porosity and BET specific area resemble to be measured the embodiment 1.The results are shown in table 2.
Table 1
| Composition | Embodiment 1-1 | Embodiment 1-2 | |
| Metal dust | Pure nickel (particle mean size: 10 μ m) | ????60 | ????- |
| Stainless steel (particle mean size: 12 μ m) | ????- | ????60 | |
| Blowing agent | The n-hexane | ????1.8 | ????1.8 |
| Water soluble resinite binding agent | HPMC | ????6.5 | ????6.5 |
| ?MC | ????3.5 | ????3.5 | |
| Surfactant | DBS | ????2.0 | ????2.0 |
| Plasticizer | Glycerine | ????2.5 | ????2.5 |
| Water | Surplus | Surplus |
HPMC: hydroxypropyl methylcellulose
MC: methylcellulose
DBS: 12 carbon benzene sulfonic acid sodium salts
Table 2
| Embodiment 1-1 | Embodiment 1-2 | Comparative Examples | ||
| Foaming condition | Humidity (%) | ????95 | ????90 | ???- |
| Temperature (℃) | ????35 | ????30 | ???- | |
| Retention time (branch) | ????15 | ????30 | ???- | |
| Sintering condition | Atmosphere | ??N 2-5％H2 | ????H 2 | ??H 2 |
| Temperature (℃) | ????1150 | ????1200 | ??1100 | |
| Retention time (hour) | ????3 | ????1 | ??0.5 | |
| Sintered article | Thickness (mm) | ????1.8 | ????2.0 | ???- |
| Average cell size (μ m) | ????250 | ????300 | ??290 | |
| Porosity (%) | ????95.9 | ????96.5 | ??95 | |
| Specific area (cm 2/cm 3) | ????750 | ????810 | ??41 |
Can prepare sintered porous metal plate by this way with three-dimensional framework structure and bigger serface.The sintered porous metal plate of gained has the following different cell structure shown in Fig. 9 A-9D, this difference depends on pulp preparation, foaming, dry and fire condition obtains the open skeleton structure of skeleton structure and the surface shown in Fig. 9 D of the surface sealing shown in the multilayer sealing born of the same parents structure shown in the unit cell shape layer structure shown in Fig. 9 A, Fig. 9 B, Fig. 9 C.
Because skeleton is made by sintering metal powder, so the three-dimensional framework structure of the expanded metal of sintering of the present invention itself also is a porous.Therefore the expanded metal of sintering has very big specific area, such as 300-1500cm
2/ cm
3The BET specific area.Also have, be easy to form minimum, such as 100 μ m or littler born of the same parents.The average cell size of the sintering metal powder of gained is 60-600 μ m, and porosity is 90-98% (volume).
The unsintered metal foam that obtains by embodiment of the present invention can be used as secondary alkaline cccumulator electrode, the active material carrier of hydrolysis electrode, the sprayer unit of oil heater, the magnetic screen outer cover, the gas expansion cushion in the air cushion is used in blast, acoustic material, the hydrolysed filtrate device of water purifier, the electrostatic filter of air purifier, the oil mist filter of oil waste gas, the deodorizing catalyst and the analog thereof of oil heater, the dust filter unit of high-temperature dust is under high pressure filled out the expanded metal of the final sintering of the matrix of composite of aluminium and industrial catalyst and carrier in the hole.The modification of previous embodiments
In the present invention, except that aforesaid embodiment, also can finish various modification.
Such as, can be used on firing of sintered plate 1C not resin molding that disappear in the step and that do not influence the performance of sintering metal foam and replace disengaging film 2 in the previous embodiments.Be preferably, this resin molding does not tear off in the foaming of the slurry that can foam and drying steps, and is firing the back complete obiteration.Also have, be preferably, resin molding easily separates with carrier plate 10.The example of this resin comprises urethane resin, epoxy resin, thermosetting polyester resin, heat-resisting thermoplastic, acrylic resin, acrylic resin and vinyl-vinyl acetate resins.After details will be illustrated in.
Except that doctor 60, the example of available film-forming method comprises: brushing, sponge roll-in and extruding.Also has usable resins film and need not to make the film step.Such as, with being tied with the roller of resin molding, can on the resin molding that breaks away from this roller, form the foaming slurry.
Dry not sintered plate 1C can be used as one long and do not fire with not cutting, and this embodiment with aforesaid unsintered plate 1C usefulness cutter cuts is different.In the case, form crackle easily owing to the big contraction of dry not sintered plate 1C.Therefore, basis as follows not the contraction of sintered plate can to make it be basic moving on the carrier plate easily: be coated with lubricating oil on the surface at vehicle to reduce the not contact resistance between the sintered plate and vehicle; Constitute vehicles to reduce not contact area between the sintered plate and vehicle with a plurality of rollers; Or vehicle is tilted by outlet is set at the position that is higher than inlet.
As mentioned above, by this embodiment be easy to get the very much metal component of high selectivity and the non sintered metal foam of bigger serface.Second embodiment
Now explain preferred embodiment as another foaming slurry of second embodiment.
Because of using the aqueous slurry solution contain blowing agent in the present invention, thus before being shaped in the slurry blowing agent bubble sometimes, so the characteristic of this foaming metal is a rather unstable.In second embodiment, such problem is improved.
When preparation can be foamed slurry, the component in the slurry is divided into two kinds of aqueous solution, before shaping, they are mixed then.
Figure 10 be similar to equipment shown in Figure 1 carry out can foam pulp preparation, shaping and dry equipment schematic cross sectional view continuously.This equipment comprises the slurry manufacturing equipment 102 that can foam, vehicle equipment 300, breaks away from membrane producing device 11, former 5, foaming machine 40 and drying equipment 50.
The slurry manufacturing equipment 102 that can foam comprises first blender 113 of mixed aqueous solution (A), second blender 112 of mixed aqueous solution (B) and the 3rd blender 110.The 3rd blender will be failed water-soluble device (A) and (B) mixing from first and second blender, and the foamed slurry S with gained after the mixing delivers to former 5.Second blender 112 has the dispenser 111 of two automatic transport aqueous solution (B) component.
The formation thing of the aqueous solution (A) transported to make with predetermined amount sneak in first blender 113, with given flow, 113a transports to the 3rd blender 110 through pipe with the aqueous solution (A) (among Figure 10 with Aq (A) expression) after the mixing.Similarly, the formation thing of the aqueous solution (B) transported to make with predetermined amount sneak into second blender 112, after the mixing aqueous solution (B) (in Figure 10 with Aq (B) expression) is sent to the 3rd blender with given flow through managing 112a.The aqueous solution (A) and (B) mix in the 3rd blender with the preparation slurry S that can foam is delivered to foaming machine 5 through the pipe 110a slurry S that will foam then.
The slurry S that can foam is the same with first embodiment, also metal-containing powders, water soluble resinite adhesive, blowing agent, surfactant and water.Metal dust surrounds the thin liquid wall of minute bubbles and draws close in the slurry that can foam, and metal dust and water soluble resinite adhesive solidify, so that keep the shape of bubble.Remove this binding agent by firing, sintering metal powder again is to make the sintered porous metal plate of three-dimensional net structure.
But the example that is used for the metal of metal dust comprises the metal of all powder process and sintering.Therefore, this metal components is highly selectable, promptly can obtain the composition of the multiple combination of a variety of metals and different kinds of metals.Also have and since sintering metal, skeleton itself also has loose structure.Therefore, the porous metals of this sintering have great specific area.
In this embodiment, foamable slurry formation thing is divided into two kinds of solution.Just before being transported to forming machine, by these two kinds of solution are mixed the volatilization that reduces blowing agent.
The example of the formation thing of solution (A) comprises blowing agent, surfactant, water soluble resinite adhesive.The example of the formation thing in the solution (B) comprises the resinite adhesive of metal dust and water soluble.
In second embodiment, also use the blowing agent identical with first embodiment.Blowing agent is added in the aqueous solution (A), so that the content of the blowing agent in the slurry is 0.05-10% (weight), 0.5-5% (weight) more preferably.This content is during less than 0.05% (weight), and then bubble forms deficiency or porosity descends.Then form bigger capsule when on the other hand, this content surpasses 10% (weight).As a result, the intensity of the unsintered plate of gained and the goods that burn till descends because of forming bigger bubble.
The also available surfactant identical with first embodiment makes the foam state stabilisation and impels capsule to form.In the aqueous solution (A), add surfactant so that its content in slurry is 0.05-5% (weight), is more preferably 0.5-3% (weight).This content is less than 0.05 (weight), and then capsule forms instability and can not keep tiny bubble.On the other hand, this content then no longer improves effect above 5% (weight).Surfactant can be added in the aqueous solution (A) and (B) in the two.
Add water soluble resinite adhesive in order that the viscosity that in the slurry drying process, keeps the cell structure shape of products and regulate slurry.The available water soluble resinite adhesive identical in second embodiment with first embodiment.Be that the amount of the water soluble resinite adhesive in the aqueous solution (A) is regulated preferably, be 0.5-20% (weight) so that it mixes the concentration of back in the slurry that can foam with solution (B), and be more preferably 2-10% (weight).This amount causes that less than 0.5% (weight) gratifying processing intensity is low excessively.On the other hand, this measures greater than 20% (weight), because viscosity excessively increases and makes the forming characteristic variation.
Each components contents is as follows in the solution (A):
Blowing agent: 0.05-10% (weight), especially 0.5-5% (weight),
Surfactant: 0.05-5% (weight), especially 0.5-3% (weight),
Water soluble resinite binding agent: 5-20% (weight), especially 2-10% (weight).
The viscosity of aqueous solution during room temperature (A) with 5000-80000cps for well, 100000-40000cps more preferably.
Prepare the aqueous solution (A) by above-mentioned each component being mixed with first blender 113.Blender such as blade mixer, static mixer all can be used as first blender 113.
The another kind of aqueous solution (B) comprises aforesaid metal dust, water soluble binding agent etc.Available metal is not limited to, but can comprise all sintering metals and alloys thereof such as nickel, copper, iron, stainless steel, chromium, cobalt, gold, silver.The particle mean size of metal dust is 500 μ m or littler, and is more preferably 0.5-100 μ m.When particle mean size during, can not get desired porosity less than 0.5 μ m.On the other hand, particle mean size surpasses 500 μ m, and the intensity of sintered porous metal plate is low excessively.Adding metal dust in solution (B), is 5-80% (weight) so that mix its content in the slurry that can foam of back with solution (A).Be more preferably 30-80% (weight).
Above-mentioned any water soluble resinite binding agent is all available.Add water soluble resinite adhesive,, be preferably 25000-50000cps so that the viscosity of the aqueous solution (B) is 20000-200000cps under the room temperature.Each components contents is as follows in the aqueous solution (B):
Metal dust: 5-80% (weight), especially 50-70% (weight)
Water soluble resinite binding agent: 0.5-20% (weight), especially 2-10% (weight).
Because the viscosity height of the aqueous solution (B), so general blade mixer and kneading device can be used as second blender 112.
Foamed slurry in second embodiment also can comprise plasticizer, promote the combustible material that the hole forms except that above-mentioned solvent.Though these additives can add to the aqueous solution (A) or (B) in, preferably be added in the aqueous solution (B).
Plasticizer makes molded article have plasticity, also can be used for second embodiment with plasticizer identical in first embodiment.Add plasticizer at the aqueous solution (A) or (B), so that its concentration in the slurry that can foam is 0.1-15% (weight), 2-10% (weight) more preferably.When its content is less than 0.1% (weight) in the slurry that can foam, the plasticity deficiency.On the other hand, when this content surpasses 15% (weight), the undercapacity of molded article.
For the combustible material that impels the hole to form promotes the formation in hole by disappearing in the step firing of dry forming goods.Any have such as powder and fiber shape, and the material that disappears in firing step all can use.This class examples of material comprises powder and the long 200 μ m or shorter of 0.1-200 μ m, and is more preferably the fiber of 30-120 μ m.
Can be by with the aqueous solution (A) and (B) mixing the foamed slurry prepare in the 2nd embodiment.The aqueous solution (A) is 0.5/9.5-3/7 with the scope of (B) weight ratio (A)/(B), and 0.9/8-1.8/7.5 more preferably.
The example of the 3rd blender 110 comprises blender and the interior blender that rotates spiral or Z-shaped blade.The foamed slurry of gained is 20000-70000cps in the scope of 20 ℃ viscosity, and 30000-50000cps more preferably.Viscosity is during less than 20000cps, and cell structure can break in drying steps.On the other hand, viscosity almost can not be shaped above the 70000cps slurry.
In the equipment of above-mentioned second embodiment, be transported to foaming machine 5 by in the 3rd blender, mixing the foamed slurry for preparing.Like this, being mixed into the time that slurry is transported to foaming step from blowing agent the slurry that can foam can shorten dramatically.The 3rd embodiment
Make the dry forming plate-shaped products of the slurry that can foam stand sintering step, to form the expanded metal of sintering.Dry plate-shaped products as intermediate product is frangible, so it is difficult to transportation or preservation.
By the 3rd embodiment, it is a kind of as intermediate product that its purpose is to provide, the composite that can make dry plate-shaped products be easy to process; The method of this composite of preparation is provided; And provide the method for making sintered porous metal plate with this composite.
Figure 10 also is the equipment that is used to make the 3rd embodiment composite.Separate to allay now and be used to prepare parts and the operation thereof that to foam outside the parts of slurry by reference Figure 10.All the other are identical with first embodiment except that producing composite for this technology.
In the 3rd embodiment, sintered plate is not produced by making the same the moving continuously of its similar conveyer belt with the composite that resin molding constitutes.
Transport equipment 300 usefulness driven rollers 332,333 carrier plate 331 as conveyer belt is moved along the direction of arrow, these rollers are not by drive force (being shown among the figure).To terminal, as first embodiment, this material stands to break away from film preparation step, forming step, foaming step, drying steps and cutting step from the top of carrier plate 331.
Can foam and extrude the gap of slurry S between scraper 60 and resin molding R, to be shaped as the plate of predetermined thickness.
Along in the disengaging film preparation step as shown in the profile (A) of A-A line, resin molding R forms on carrier plate 331 in as Figure 10.The slurry that can foam is shaped on resin molding R.Doctor 90 is used as disengaging film preparation machine 11.With uncured polyurethane solution, such as, with doctor 90, be coated on the carrier plate with the thickness of 0.05-0.2mm, and in drying machine 100, solidify, break away from film R so that on carrier plate 331, form.Replace breaking away from the film preparation step, the slurry that can foam can be shaped with breaking away from the film formed roller of resin.
In forming step, making foamable slurry S be shaped as thickness on resin molding R with the doctor 60 with two scrapers is 0.1-15mm, more preferably the thin plate of 0.2-2mm.
Foamed slurry on carrier plate 331 enters foaming machine 40, so that the slurry that can foam foams fully.Add heater-type though foaming machine 40 can be the humidifier shown in Fig. 7, the machine that adds heater-type without humidifier also can reach the condition of high humility, high-temperature.The slurry that can foam foamed 10-45 minute in foaming machine 40.
In drying machine 50 as shown in Figure 8, make the slurry drying that has foamed, so that obtain the composite that constitutes by dry plate-shaped products or unsintered plate G and resin molding R.Suitable drying machine is the far infrared drying machine, and drying condition is identical with first or second embodiment, that is, and and the atmosphere temperature of 120-180 ℃ heter temperature, 40-80 ℃ and the drying time of 20-120 branch.Preparation laminates dry tabular not sintered plate G on resin molding R described in Figure 10 (B) by this way.The 3-8 that is generally firm thickness after forming around the thickness of plate G of knot is not doubly.As along shown in the profile (B) of the B-B line among Figure 10, the composite 1 that comprises dry not sintered plate G and resin molding R forms on carrier plate.
Then, composite 1 and carrier plate 331 are separated.At last, with cutter 70 composite 1 is pressed the given length cutting.
Can improve the processing of frangible not sintered plate G with the composite 1 that has resin molding R.Available resin molding R can not eliminate in the sintering step of sintered plate G in drying, and does not influence the film of the characteristic of sintered porous metal plate.Be preferably, this resin does not shrink in the foaming of the slurry that can foam and drying steps, and eliminates fully in sintering step.In addition, preferably, this resin easily separates with carrier plate 331.The preferred example of this resin is a urethane resin.The example of the resin that other is available comprises epoxy resin, thermosetting polyester, heat-resisting thermoplastic resin, as polyvinyl resin, butyral resin and acrylic resin.
In the equipment shown in Figure 10, when being moved down, carrier plate 331, resin molding R and carrier plate 331 are separated by being wound on the roller 332.The composite 1 usefulness cutter 70 that comprises dry not sintered plate G and resin molding R as shown in the figure is by predetermined length cutting and stacking.Can foam slurry can be on carrier plate 331 direct forming, and without resin molding.
In the de-oiling step, resin molding is eliminated.Since deoil and sintering process in volume reduce 20% approximately, so be preferably in a slidably plate, as deoiling on the graphite cake and sintering.Its thickness can wait and control by the surface rolling behind the sintering (Skin path rolling).
As mentioned above, the composite of the 3rd embodiment prepares by shaping of foamed slurry and the drying that makes metal-containing powders on this resin molding.Composite can make frangible not sintered plate be easy to processing, transportation and store.Behind sintering, can prepare the expanded metal of sintering by the burning-off resin molding.Can use prefabricated resin molding.Alternatively, the slurry that can foam can be shaped on resin molding, and resin molding just forms in the preparation process at film before can foaming material shaped step.The resin molding material is seldom to shrink in the drying steps of slurry that can foam preferably, has good maintenance shape performance and the polyurethane resin that can eliminate in sintering step.
According to the 3rd embodiment, can produce and be easy to process, not the composite of sintered plate.Therefore, can high yield obtain sintered porous metal plate at last.Embodiment 1-2
To be similar to the mode of embodiment 1-1, prepare the composite that comprises dry not sintered plate G and resin molding R but increase the resin molding preparation process.
In the resin molding preparation process, among resin molding R such as Figure 10 along forming on the profile (A) of the A-A line institute carrier plate that is shown in 331.With uncured poly-hydrogen base Ethyl formate solution u, such as, make to break away from film maker 11 with doctor 90 and be coated on the carrier plate 331, and in drying machine 100, solidify with thickness such as 0.05-0.3mm, break away from film so that on carrier plate 331, form.
Then shaping, foaming, drying and cutting step are identical with embodiment 1-1.The 4th embodiment
When the foaming slurry foamed simultaneously and be dry, the surface of sintered plate was at first dry, therefore uneven foaming can take place or can form some crackles on the surface of sintered plate not.
In the 4th embodiment, its objective is provides the method and apparatus that makes the inner even foaming of foaming slurry.
Based on following reason, a kind of liquid medium is sprayed on the surface as the foamed slurry in the opening cabin of slurry reservoir.Though the opening cabin is effectively for resulting from that bubble in the slurry that can foam discharges into the atmosphere, the surface of the slurry that can foam simultaneously is dry in the opening cabin.Therefore, when the slurry that can foam infeeded in the opening cabin, the interface Ssu of slurry inside along former slurry produced air bubble foaming.Comprising this bubble if can foam in the plate-shaped products of shaping of slurry, be basic nonconforming hole with the air bubble that forms in expanded metal then.Because the size in the hole that is formed by air bubble is with different with the size in the formed hole of blowing agent, so expanded metal has uneven cell structure.When being sprayed at liquid medium on the pulp surface, surperficial moist in reservoir, thus can prevent inhomogeneous cell structure in expanded metal.
The 4th embodiment is characterised in that and sprays a kind of liquid medium on the pulp surface that can foam.The remodeling of the 4th embodiment
Be equipped with according to the slurry reservoir of the 4th embodiment or opening cabin and be the humidifier 69 on the surperficial Ssu that liquid medium M is sprayed at slurry S.Can prevent the surperficial Ssu drying of the slurry S in the slurry reservoir 30 by humidifier spraying liquid medium on slurry from then on.And, in slurry, do not produce air bubble.This spraying operation can carry out continuously or discontinuously.
Scraper 60A, 60B shown in Fig. 3 and 4 can be used as the doctor 60 in this embodiment.Embodiment 2
The fluorocarbon resin dispersion is coated on the steel band in the equipment shown in Fig. 1 and 10 as release agent (R).
In the blender 110 of slurry mixer 102,, the aqueous solution (A) and the aqueous solution (B) prepares the slurry (3) that to foam by being mixed, wherein the aqueous solution (A) contains hydroxypropyl methylcellulose, 30.8% (weight) glycerine of 1.5% (weight), hexane, 4% (weight) neopelex of 30.8% (weight) and the water of surplus, and the aqueous solution (B) contains 62.0% (weight), the hydroxypropyl methylcellulose of the pure nickel powder, 2.4% (weight) of particle mean size 10 μ m and the water of surplus.Each of born of the same parents' shape goods 1-9 prepares by following program: be coated on the steel band 1 with the height of the doctor shown in the table 3 60 slurry (S) that can foam; Under the conditions shown in Table 3, the temperature by the heater in the humidifier 40 of accommodation zone heater 42,43,44 makes slurry (S) foaming of can foaming; Then under the conditions shown in Table 3, make the slurry drying that foams with far infrared drying machine 50.
Regulate the retention time of slurry in humidifier 40 by the translational speed that changes steel band.Born of the same parents' shape goods degreasing of gained is fallen, and presintering 30 minutes in 850 ℃ the nitrogen atmosphere that contains 5% nitrogen, then 1250 ℃ of sintering 15 minutes, so that obtain metal foam No.1-9.Weight and size by each metal foam of gained are calculated its voidage.Determine the size in hole by the optical microscope photograph graphical analysis, 10 times are taken, amplified to photo in 10 places.The results are shown in table 4.
In order to contrast,, but foam and the metal foam 11-14 shown in the preparation table 4 at 20 ℃ room temperature and 55% humidity, inoperative high temperature humidifier with identical shaping and sintering condition.Determine porosity and hole dimension with same method.
Table 3 and table 4 prove in this embodiment clearly, adopts the high temperature humidifier, by under predetermined condition, promptly 35-65 ℃ temperature and 70% or higher humidity under can easily prepare 97% or higher highly porous foam metal with the short time.
By this embodiment, there is not uniform cell structure sintered plate inside.Therefore, there is highly selection can easily and surely make with the sintered porous metal plate of high-specific surface area freely to metal component.
Table 3
| Sample | Foaming condition | |||||||
| Scraper height mm | High temperature humidifier (foaming condition) | The far infrared drying machine | ||||||
| Temperature (℃) | Humidity % | Retention time (branch) | Heter temperature ℃ | Atmosphere temperature ℃ | ||||
| Use high temperature humidifier of the present invention | ??1 | ??0.10 | ??35 | ??95 | ????15 | ????140 | ????40 | |
| ??2 | ??0.10 | ??50 | ??75 | ????15 | ????140 | ????40 | ||
| ??3 | ??0.30 | ??65 | ??80 | ????5 | ????160 | ????45 | ||
| ??4 | ??0.30 | ??40 | ??95 | ????20 | ????140 | ????40 | ||
| ??5 | ??0.50 | ??35 | ??90 | ????30 | ????140 | ????40 | ||
| ??6 | ??0.50 | ??50 | ??70 | ????15 | ????160 | ????45 | ||
| ??7 | ??0.10 | ??25 | ??65 | ????10 | ????140 | ????40 | ||
| ??8 | ??0.30 | ??30 | ??60 | ????20 | ????140 | ????40 | ||
| ??9 | ??0.50 | ??30 | ??65 | ????15 | ????160 | ????45 | ||
| Do not use | ??11 | ??0.10 | ??20 | ??55 | ????5 | ????140 | ????40 | |
| ??12 | ??0.30 | ??20 | ??55 | ????15 | ????140 | ????40 | ||
| ??13 | ??0.30 | ??20 | ??55 | ????30 | ????160 | ????45 | ||
| ??14 | ??0.50 | ??20 | ??55 | ????60 | ????160 | ????45 | ||
Table 4
The 5th embodiment
| Sample | The metal foam characteristic | |||
| Porosity % | Hole dimension μ m | |||
| Use high temperature humidifier of the present invention | ??1 | ??97.5 | ?????206 | |
| ??2 | ??97.7 | ?????210 | ||
| ??3 | ??97.1 | ?????180 | ||
| ??4 | ??98.4 | ?????225 | ||
| ??5 | ??98.7 | ?????262 | ||
| ??6 | ??97.4 | ?????214 | ||
| ??7 | ??95.5 | ?????255 | ||
| ??8 | ??96.3 | ?????218 | ||
| ??9 | ??96.1 | ?????216 | ||
| Do not use | ??11 | ??92.5 | ?????265 | |
| ??12 | ??94.6 | ?????286 | ||
| ??13 | ??95.5 | ?????314 | ||
| ??14 | ??96.0 | ?????328 | ||
The 5th embodiment comprises unsintered metal foam degreasing and the method and apparatus of SINTERING PRODUCTION sintered porous metal plate and the sintered porous metal plate that obtains that is shaped in the first embodiment by making.
Figure 12 is that the explanation fifth embodiment of the invention is produced the flow chart of sintered porous metal plate method.
Sintered porous metal plate is the unsintered metal foam for preparing by through the disengaging film preparation shown in Fig. 2, disengaging film drying, shaping, foaming and drying steps, makes through degreasing shown in Figure 12 and sintering step.
Figure 13 is used to carry out technology shown in Figure 12, is the profile of the equipment of producing sintered porous metal plate.Equipment among Figure 13 is identical with equipment among Fig. 1, but it also comprises the machine that is used for degreasing and sintering step.This method, equipment and operation and first embodiment of producing the non sintered metal foam is basic identical.
This degreasing step refers to a kind of presintering step, because it is a kind of baking procedure, so normal sintering step just is called as final sintering step.The degreasing step
In the degreasing step, toast unsintered born of the same parents' shape goods so that organic material 300-700 ℃ temperature, as binding agent, in air or reducing atmosphere, as volatilization in hydrogen 10-60 minute.Normal sintering step
Normally firing in the step, born of the same parents' shape goods that baking is deoiled, so that under 800-1400 ℃ temperature, according to the characteristic of used metal, in the ammonia atmosphere that decomposes, in the reducing atmosphere such as hydrogen, in a vacuum or in atmosphere with metal powder sintered 20-120 minute.Since deoil and sintering process in, that its volume is reduced is about 20% because of contraction, carries out on the plate so these steps are preferably in slidably.The thickness of sintered article can be controlled by methods such as surface rollings.Equipment in the 5th embodiment
Comprise as by the make-up machine part 201 shown in Fig. 1 first embodiment equipment by the 5th embodiment equipment as shown in figure 13, and in the 5th embodiment, increase fire part 202.Figure in Figure 13 also comprises delivery system.
Forming machine part 201 is identical with the forming machine of the unsintered metal foam of production among Fig. 1.This forming machine comprises that from first roller, 153 side to the second rollers, 154 sides the doctor 60 that breaks away from film coating machine 11, air drier 100, slurry reservoir 30, makes the slurry shaping, the high temperature humidifier 40 that is used to foam reach to obtaining the drying machine 50 of non sintered metal foam.
Forming machine part 201 has first roller 153 (being equivalent to the roller 20 among Fig. 1) and second roller 154 (being equivalent to the roller 21 among Fig. 1), with carrying steel carrier plate 151.The carrier plate 151 that is carried between first and second rollers 153,154 plays conveyer belt (conveying device).
Be similar to first embodiment, release agent coating machine 11 has release agent reservoir 80 and is used to apply the doctor 90 of release agent.Release agent reservoir 80 is a cuboid, and is set near first roller 153 the loading plate 151, and doctor 90 is arranged on the wall in downstream of release agent reservoir 80, thereby keeps predetermined gap with carrier plate 151.The film thickness of release agent u can be adjusted by the gap between doctor 90 and the carrier plate 151.When release agent reservoir 80 was stated from the carrier plate, with release agent u, such as the fluorine carbon dispersion, when being fed to wherein, release agent u just extruded from the gap of 151 of doctor 90 and carrier plates, so that form the film of predetermined thickness.The film that applies moves to next release agent drying machine 100 along carrier plate 151.
Drying machine all can be used as release agent drying machine 100 as air drier and far infrared drying machine, so that the curing of coating of this release agent, this and first embodiment are similar.The release agent film that obtains is used as the carrier belt of sintered porous metal plate, removes by burning in sintering step then.Carry out the formation of release agent film, in order that be convenient to the not sintered plate of ground as mentioned below processing fragile.
Similar to first embodiment, slurry reservoir (cabin) 30 is the cuboids on the carrier plate 151 that places release agent drying machine 100 downstream parts.The upstream wall of slurry reservoir 30 is provided with and 151 of carrier plates have the doctor 60 of predetermined gap.The thickness of molded article 1A is adjusted by the gap between doctor 60 and the carrier plate 151.When the slurry that can foam when carrier plate 151 is moved is sent in the slurry reservoir 30, extrude the gap of slurry between doctor 60 and carrier plate 151 of can foaming, so that be shaped as the plate-shaped products 1A of predetermined thickness.Above slurry reservoir 30, be provided with the foamed slurry blender that is used for preparing the foamed slurry of sending into slurry reservoir 30.This slurry blender that can foam be provided with the solution reservoir 113 that contains blowing agent, metal-containing powders solution reservoir 112, be used for defeated material from these two reservoirs is mixed the kneader 110 for preparing the slurry S that can foam.Component by the slurry that can foam is divided into two kinds of solution, just its mixing can be prevented effectively the volatilization of blowing agent then before slurry is delivered to doctor.
Can the mode identical prepare the slurry that to foam with first or second embodiment.
High temperature humidifier 40 is identical with humidifier among the Fig. 7 that meets first embodiment.High temperature humidifier 40 among Figure 13 has a passage that transports that surrounds carrier plate 151, and is formed in the rectangle baker 46 of the upper and lower enclosure space of carrier plate 151.In the upstream wall (first roller, 153 sides) of baker 46, be provided with the inlet of carrier plate 151.On the other hand, the downstream wall (second roller, 154 sides) at baker 46 is provided with the outlet of carrier plate 151.Carrier plate 151 belows play a part cistern than low spatial, it is equipped with the water 45 as the specified rate of moisture source.Other structure and operation are identical with the diagram among Fig. 7.
Identical among drying machine 50 and Fig. 8.Identical in drying condition and first embodiment.In the embodiment of Figure 13, unsintered plate or dry plate-shaped products are by being carried to second roller 154 and being bent downwardly simultaneously and open with carrier plate 151.
With drying not sintered plate 1C send into and fire part 202.Preferably, the metal foam sintering that carries out in firing part 202 comprises two steps,, removes organic component that is, as second step or the normal sintering step of the first step of binding agent or deoil step and sintering metal powder.By sequentially carrying out these steps, just shortened the time that plate-shaped products is in very easily broken state at same plate.Therefore, the sintered article steady quality of gained.
Deoil and the presintering step can be at air, blanket of nitrogen or at reducing atmosphere for the preparation expanded metal,, under the temperature of 300-900 ℃ or 700-900 ℃, carried out 10-60 minute as (can be nitrogenous) in the hydrogen atmosphere if need.Normal sintering step is preferably in reducing atmosphere, as the ammonia that decomposes or hydrogen, in a vacuum, in air or in nitrogen, under 800-1400 ℃ or 1000-1300 ℃ of temperature, carried out 20-120 minute, this depends on the metal that is used to prepare porous metals.
In Figure 13, firing part has deoiling/pre-burning freezing of a furnace 170 and normal sintering furnace 180 along the delivery direction.Deoil/pre-burning freezing of a furnace 170 has by first roller 172 that has driver element and second roller 173 and drives, and play the carrier plate 174 of the steel band that conveyer belt (conveying arrangement) acts on.Deoil/the pre-burning freezing of a furnace is the continuous tunnel furnace that forms the cuboid of an enclosure space above carrier plate 174.The inlet 175 of carrier plate 174 is located on the upstream side wall of first roller 172 in this stove, is located on the downstream side wall of second roller 173 in this stove and export 176.
This deoils/and pre-burning freezing of a furnace 170 can use nichrome wire heater, Mo heater, SiC heater or the heating of W heater, and this depends on the metal that is sintered.
Lubricant application machine 161 is located under first roller 172 and contacts with carrier plate 174, so that lubricant is not coated on the surface of carrier plate 174 before the sintered plate 1C in the delivery drying.
Deoil/the presintering step is for vaporing away the organic component among the sintered plate 1C not, as binding agent.Owing to not a little contraction of sintered plate in this step, occurs, cause carrier plate 174 and the dry not slip between the sintered plate 1C effectively so be coated in carrier plate 174 lip-deep lubricants, therefore alleviated because of shrinking the not distortion of sintered plate.The example of available lubricant comprises graphite, pitch prill, the silicon of liquid and solid, the nitride and the carborundum of boron.
Though make carrier plate with steel band in this embodiment, a lot of heat-resisting metals also can use as stainless steel, Refractoloy, molybdenum alloy.
Make drying not sintered plate 1C deoiling/deoiling in the pre-burning freezing of a furnace 170 and presintering with the formation plate 1D that deoils.Separate with the carrier plate that moves at the second roller 173 plate 1D that deoils, be admitted to normal sintering furnace 180 then.Normal sintering
Normal sintering furnace is the continuous tunnel furnace of a cuboid, it with deoil/the presintering kiln 170 the same spaces that also form a sealing.The inlet of plate 1D of deoiling is located at the side wall place, upstream of normal stove 180, is located at its side wall place, downstream and export 186.In normal stove 180,185 sequentially be provided with a plurality of carry rollers 182 to outlet 186, to form roll-type furnace bottom 183 as the continuous sintering siege from entering the mouth.Each carry roller 182 is rotated along the delivery direction.This roll-type furnace bottom 183 is to deoiling/extend near second roller 173 of pre-burning freezing of a furnace 170, and reaches the outside of outlet 186.Deoil plate 1D with transport roller 182 and contact on a plurality of carry rollers 182 that rotate along carriage direction, move.
Spacing between the carry roller 182 of roll-type furnace bottom 183 is determined at thickness and porosity, sintering state etc. according to the plate 1D that deoils.Because big interval is not enough to support the plate that deoils, so essential definite suitable distance.Such as, the scope of this spacing is about 25-70mm.Inlet 185 and near, need be provided with short interval and transport roller.
Different carry rollers can adopt with a contact and support a plurality of spherical or axiolitic of the plate 1D that deoils as conveying arrangement.This line or some contact device only can be used on the part that causes the big contraction of plate 1D of deoiling, and can be with any conventional conveyer, as banded transporter in other parts.This line or some contact device can be used to deoil/conveyer in the pre-burning freezing of a furnace 170.
When nickel foam when 1200 ℃ of quilts are fired, metallic plate shrinks about 20% because of sintering at most.When adopting conventional band oven, obtain the sintered porous metal plate that length mostly is tens of centimetres most.Otherwise, in this embodiment, can obtain long sintered porous metal plate 1E by above-mentioned conveying device.In detail, because born of the same parents' shape goods move on the roll of a plurality of lines with it or some contact, so the contact resistance between these born of the same parents' shape goods and conveying device is very little, thereby born of the same parents' shape goods slide on roll easily, and the contraction of born of the same parents' shape goods can be easy to realize like this.Because because of the distortion of shrinking is alleviated, so can prevent crackle because of shrinking.
Be that the velocity of rotation of each rolling member 182 is regulated according to amount of contraction preferably.Such as, just can easily there be the contraction of distortion less than the rolling speed of inlet by the rolling speed of setting outlet.
Normal sintering furnace 180 can be divided into several little, especially be divided into three, therein, be these born of the same parents' shape goods of sintering progressively, these temperature of little are raise along carriage direction.In this normal sintering furnace 180, can prevent crackle by the Fast Heating generation, therefore can stably carry out sintering.
Firing rate scope at carriage direction in normal sintering furnace 180 is preferably 2-50 ℃/minute, more preferably 3-30 ℃/minute.
Be located at heater in the normal sintering furnace 180 and be not limited to be similar to and deoil/heater in the pre-burning freezing of a furnace 170, such as can from nichrome heater, Mo heater, SiC heater and W heater, suitably selecting.
The sintered metal plates 1E of gained is sent from normal sintering furnace 180, then as a continuous roller winding 192 on wrapping machine 191.
If need, can be by the thickness of control sintered metal plates 1E such as surface rolling.The mill speed V of milling train
2Be expressed from the next:
V
2=V
1* (100-S)/100 wherein S represents the final contraction speed of sintering metal, and V
1The translational speed of the carrier plate in the machine is fired in expression.
Can prepare the sintered porous metal plate that three-dimensional framework structure and bigger serface are arranged by this way.The sintered porous metal plate of gained has the different cell structures shown in following Fig. 9 A-9D, depends on pulp preparation, foaming condition, drying condition and fires condition; Unit cell layer structure shown in Fig. 9 A, the multilayer sealing cell structure shown in Fig. 9 B, the surface sealing skeleton structure shown in Fig. 9 C, the skeleton structure of the surface opening shown in Fig. 9 D.
Because three-dimensional framework is made by sintering metal powder, so the three-dimensional framework of sintered porous metal plate of the present invention itself also is a porous.Therefore sintered porous metal plate has sizable specific area, such as 300-1500cm is arranged
2/ cm
3The BET specific area.Therefore, be easy to form minimum, as, 100 μ m or littler born of the same parents.The average cell size of the sintered metal plates of gained is 60-600 μ m, and porosity is 90-98% (volume).
As a comparison case, prepare the expanded metal of sintering in the following manner:, foam is dipped in the nickel sulfate solution for improving electric conductivity behind the nickel of the thick 0.5 μ m of inner face evaporation of commercially available polyurethane; This foam is stood 1A/dm as negative pole
2The plating of current density is so that form the nickel coating of average thick 75 μ m on the opening born of the same parents' of this foam surface; The foam that plated in hydrogen stream, was kept 0.5 hour in 1100 ℃, to remove polyurethane foam.The diameter of the sintered porous metal plate of gained is 50mm, and long is 100mm.Determine hole dimension, porosity and the BET specific area of this sintered porous metal plate with the method identical with embodiment 1-1.The results are shown in the table 2.
The sintered porous metal plate that obtains by this embodiment of the present invention can be used for the atomization unit, magnetic screen packing, the gas expansion cushion that is used for the explosion air cushion, acoustic material, the hydrolysed filtrate device of aqueous cleaner, the electrostatic filter of air cleaner of active material carrier, the oil heater of electrode, the hydrolysis electrode of alkaline secondary cell, the deodorizing catalyst of the oil mist filter of waste gas, oil heater etc., the dust filter unit of high-temperature dust, under high pressure matrix and the industrial catalyst and the carrier of the composite of filling aluminum in its hole.
The invention is not restricted to above-mentioned embodiment, and can change within the scope of the invention.
In the 5th embodiment, the machine of firing comprises and is used to deoil/two stoves of presintering step and normal sintering step.But these two steps also can be finished in a stove with two cabins that separate with wall.In addition, can from fire machine, remove the step of deoiling.
Second to the 4th embodiment also can be adapted to the 5th embodiment.
Except that producing sintered porous metal plate, the sintering method in the 5th embodiment also is suitable for the production method of the continuous band of closed metal plate and metal forming.In addition, this sintering method also is suitable for producing the long sintered body of uniform cross-section, as the method for rod or pipe.In addition, this sintering method also is suitable for producing the method for long sintered ceramic product.
According to the 5th embodiment, can make things convenient for and stably obtain the sintered porous metal plate of freely selecting that metal is formed by bigger serface and height.In addition, can easily obtain long sintered article with powder metallurgic method etc.
Claims (29)
1. method of making sintered porous metal plate, the step that it comprises is:
The slurry preparation step of the foamed slurry of preparation metal-containing powders;
Make the described slurry that foams form the forming step of plate-shaped products;
Make the foaming step of described plate-shaped products foaming; With
Make the drying steps of described plate-shaped products drying after the foaming.
2. the method for the manufacturing sintered porous metal plate of claim 1, the resinite binding agent and the surfactant of wherein said foam pulp bales metal-containing powders, blowing agent, water soluble.
3. the method for the manufacturing sintered porous metal plate of claim 1, wherein said method also comprise makes the step of firing that described plate-shaped products deoils behind the drying steps.
4. the method for the manufacturing sintered porous metal plate of claim 3 is wherein saidly fired the step that step comprises the described plate-shaped products of sintering.
5. the method for the manufacturing sintered porous metal plate of claim 1, the wherein said slurry that foams is shaped with the doctor method in described forming step.
6. the method for the manufacturing sintered porous metal plate of claim 5, wherein said doctor method adopts several pieces with predetermined space doctor spaced apart from each other.
7. the method for the manufacturing sintered porous metal plate of claim 1, wherein, in described slurry preparation step, preparation contains second aqueous solution of the resinite binding agent of first aqueous solution of resinite binding agent of blowing agent, surfactant and water soluble and metal-containing powders and water soluble respectively, and just before described forming step with first aqueous solution and second aqueous solution, to prepare the described slurry that foams.
8. the method for the manufacturing sintered porous metal plate of claim 1, wherein, in described foaming step, the blowing agent that is contained in the described slurry that foams foams under high humility.
9. the method for the manufacturing sintered porous metal plate of claim 8, wherein said high humility is 65% or higher.
10. the method for the manufacturing sintered porous metal plate of claim 1, wherein said drying steps is a kind of drying steps of far-infrared radiation.
The shaping of plate-shaped products 11. the method for the manufacturing sintered porous metal plate of claim 1, wherein said forming step carry out foaming on carrier plate.
12. the method for the manufacturing sintered porous metal plate of claim 1 wherein before described forming step, is provided with the disengaging film that can burn in advance in firing step on described carrier plate.
13. the method for the manufacturing sintered porous metal plate of claim 12, wherein said release agent film comprises polyurethane resin.
14. an equipment of making sintered porous metal plate, it comprises:
Preparation contains the pulp preparation device of the foamed slurry of metal dust, blowing agent and liquid medium at least;
Make for the building mortion that forms plate-shaped products from the foamed slurry of described pulp preparation device;
Make the foam device of foaming of the plate-shaped products of the slurry that can foam; And
Make the drying device of described porous article drying;
Wherein these devices conspire to create an integral body by a conveying device.
15. the equipment of the manufacturing sintered porous metal plate of claim 15, wherein said conveying device comprises continuous carrier plate.
16. the equipment of the manufacturing sintered porous metal plate of claim 15 wherein is provided with the degreaser for dry plate-shaped products is deoiled behind described drying device.
17. the equipment of the manufacturing sintered porous metal plate of claim 16, wherein said degreaser has carrier plate.
18. the equipment of the manufacturing sintered porous metal plate of claim 16 wherein is provided with the normal sintering equipment of this plate-shaped products that deoils for sintering behind described degreaser.
19. the equipment of the manufacturing sintered porous metal plate of claim 14, wherein said building mortion comprises a plurality of doctors.
20. the equipment of the manufacturing sintered porous metal plate of claim 19, wherein said doctor device comprises two doctors.
21. the equipment of the manufacturing sintered porous metal plate of claim 14, wherein said pulp preparation device comprises that being used for mixing contains blowing agent, the first aqueous solution device of first aqueous solution of the resinite adhesive of surfactant and water soluble, with the second aqueous solution device of second aqueous solution that is used to mix metal-containing powders and moisture resinite binding agent, this device is what to separate with the first aqueous solution device; And be used for by just before carrying out described forming step, mixing the 3rd mixing arrangement that first aqueous solution and second aqueous solution prepare the described slurry that foams.
22. comprising, the equipment of the manufacturing sintered porous metal plate of claim 14, wherein said foam device maintains 65% or the device of high humility atmosphere more.
23. the equipment of the manufacturing sintered porous metal plate of claim 19, wherein said building mortion comprises that the short time deposits for from the slurry reservoir of the foamed slurry of described pulp preparation device with prevent the sprayer unit of the liquid medium of the described pulp surface drying that foams.
24. the equipment of the manufacturing sintered porous metal plate of claim 14.
Wherein said foam device comprises having entrance and exit, is trapped among the parameatal stove of transporting of described conveying device;
Be located in this stove, have the cistern of thermostat;
The heater that is used to heat molded article of passage setting is transported on the edge in described stove;
Be located at the heater of the anti-freezing water on the furnace sidewall.
25. the equipment of the manufacturing sintered porous metal plate of claim 14, wherein said drying equipment comprises the far-infrared radiation device.
26. the equipment of the manufacturing sintered porous metal plate of claim 14 is before the release agent film coating unit that wherein is used on described conveying device forming the release agent film is located at described shaped device.
27. the equipment of the manufacturing sintered porous metal plate of claim 26, wherein said release agent coating unit comprises doctor machine and release agent drying machine.
28. comprising continuous tunnel furnace and continuously will the described plate-shaped products that deoils transport outlet to from the inlet of described continuous tunnel furnace, the equipment of the manufacturing sintered porous metal plate of claim 18, wherein said normal sintering equipment delivers part; Described delivery part comprises a plurality of carry rollers that roll along the delivery direction at least a portion of described continuous tunnel furnace.
29. the equipment of the manufacturing sintered porous metal plate of claim 28 is wherein controlled described carry roller so that its rolling speed progressively reduces along the dynamic load direction.
Applications Claiming Priority (12)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP30140495 | 1995-11-20 | ||
| JP301404/95 | 1995-11-20 | ||
| JP301404/1995 | 1995-11-20 | ||
| JP124285/1996 | 1996-05-20 | ||
| JP124324/96 | 1996-05-20 | ||
| JP124284/1996 | 1996-05-20 | ||
| JP124285/96 | 1996-05-20 | ||
| JP12428596A JP3377019B2 (en) | 1996-05-20 | 1996-05-20 | Continuous firing method and firing apparatus for long molded body |
| JP12432496A JP3282497B2 (en) | 1996-05-20 | 1996-05-20 | Method and apparatus for producing dry molded body for porous sintered body |
| JP124284/96 | 1996-05-20 | ||
| JP124324/1996 | 1996-05-20 | ||
| JP12428496A JPH09202904A (en) | 1995-11-20 | 1996-05-20 | Device for producing porous sintered metallic sheet |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1158774A true CN1158774A (en) | 1997-09-10 |
| CN1213826C CN1213826C (en) | 2005-08-10 |
Family
ID=27471021
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 96123492 Expired - Fee Related CN1213826C (en) | 1995-11-20 | 1996-11-20 | Method and apparatus for making sintered porous metal plate |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN1213826C (en) |
Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1292890C (en) * | 2000-12-11 | 2007-01-03 | 布鲁内尔大学 | Material processing method |
| CN101920230A (en) * | 2009-06-15 | 2010-12-22 | 三菱电机株式会社 | Electrostatic atomizer and air conditioner |
| CN101528955B (en) * | 2006-10-23 | 2011-03-09 | 三菱麻铁里亚尔株式会社 | Apparatus for producing porous body and method for producing porous body |
| CN101537496B (en) * | 2008-03-17 | 2013-03-20 | 大阳日酸株式会社 | Process for producing porous metal body |
| CN103586469A (en) * | 2013-11-11 | 2014-02-19 | 广州有色金属研究院 | Preparation method of foamed porous metal plate |
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- 1996-11-20 CN CN 96123492 patent/CN1213826C/en not_active Expired - Fee Related
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1292890C (en) * | 2000-12-11 | 2007-01-03 | 布鲁内尔大学 | Material processing method |
| CN101528955B (en) * | 2006-10-23 | 2011-03-09 | 三菱麻铁里亚尔株式会社 | Apparatus for producing porous body and method for producing porous body |
| CN101537496B (en) * | 2008-03-17 | 2013-03-20 | 大阳日酸株式会社 | Process for producing porous metal body |
| CN101920230A (en) * | 2009-06-15 | 2010-12-22 | 三菱电机株式会社 | Electrostatic atomizer and air conditioner |
| CN101920230B (en) * | 2009-06-15 | 2015-06-17 | 三菱电机株式会社 | Electrostatic atomizer and air conditioner |
| US9132439B2 (en) | 2009-06-15 | 2015-09-15 | Mitsubishi Electric Corporation | Electrostatic atomizer and air conditioner |
| CN103586469A (en) * | 2013-11-11 | 2014-02-19 | 广州有色金属研究院 | Preparation method of foamed porous metal plate |
| CN106903972A (en) * | 2015-10-29 | 2017-06-30 | 精工爱普生株式会社 | The manufacture method and its manufacture device of three-dimensional structure |
| US20170120331A1 (en) | 2015-10-29 | 2017-05-04 | Seiko Epson Corporation | Manufacturing method for three-dimensional structure, manufacturing apparatus for three-dimensional structure, and control program for manufacturing apparatus |
| CN112743100A (en) * | 2015-10-29 | 2021-05-04 | 精工爱普生株式会社 | Method and apparatus for manufacturing three-dimensional structure |
| US11185922B2 (en) | 2015-10-29 | 2021-11-30 | Seiko Epson Corporation | Manufacturing method for three-dimensional structure, manufacturing apparatus for three-dimensional structure, and control program for manufacturing apparatus |
| CN108602118A (en) * | 2015-11-10 | 2018-09-28 | 爱德曼技术欧洲公司 | The increasing material manufacturing of metal object |
| CN109844994A (en) * | 2016-10-05 | 2019-06-04 | 江森自控汽车电池有限责任公司 | Conductive structure and its manufacturing method |
| CN109205806A (en) * | 2018-08-07 | 2019-01-15 | 厦门建霖健康家居股份有限公司 | A kind of environment-friendly type non-phosphorus scale foamed alloy cluster and preparation method thereof |
| CN109201416A (en) * | 2018-10-09 | 2019-01-15 | 爱美（浙江）纺织品有限公司 | A kind of Curtain cloth foam coating equipment |
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| CN1213826C (en) | 2005-08-10 |
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