CN1480542A - Porous body of composite metal and its preparing method - Google Patents
Porous body of composite metal and its preparing method Download PDFInfo
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Abstract
A process for preparing the composite porous metallic body by hot-dip aluminizing includes using a foam material as core film, depositing one or more metals on the core film to obtain porous metal or alloy as skeleton, and hot-dip aluminizing on said skeleton. Its advantages are high porosity (more than 90%) etc.
Description
Technical field
What the present invention relates to is a kind of porous body of composite metal and preparation method thereof, especially adopts the method for hot dipping metal to prepare porous body of composite metal and preparation method thereof.
Background technology
Metal porous body is little with its density, porosity is high, specific surface area is big and have tridimensional network and be widely used in aspects such as filtration, shielding, sound-absorbing and secondary cell and carrier.The preparation method of metal porous body can adopt powder metallurgy, galvanic deposit (electroforming), vapour deposition and methods such as Metal Melting casting (seepage flow) and metal foaming to be prepared.Existing widely used metal porous body has: nickel foam (copper), titanium foam (alloy) and foamed aluminium etc.
The preparation method of nickel foam adopts the method for galvanic deposit (electroforming) to be prepared, its technology at first is the preparation conductive layer, after being about to the coated electrically conducting coating of urethane foam (or processing such as electroless plating, vapor deposited metal), make non-conductive urethane foam have electroconductibility; Adopt method metal refining nickel on porous plastics of galvanic deposit (electroforming) afterwards, remove organism by thermal treatment at last and improve metallicity to prepare nickel foam.Nickel foam is mainly used in secondary battery electrode substrate and carrier.
The preparation method of titanium foam (alloy) adopts powder metallurgy method to be prepared, and promptly selects the metal or metal alloy powder of certain particle diameter for use, carries out sintering processes after the repressed moulding.Titanium foam (alloy) is mainly used in filtration.
What metal porous aluminium (foamed aluminium) preparation method mainly adopted at present is Metal Melting casting (seepage flow) method and metal foaming method.Metal Melting casting (seepage flow) method mainly be will fusing aluminium (aluminium alloy) melt liquid casting (seepage flow) and be equipped with in the container of nonmetal ball, make aluminium liquid enter into the gap of nonmetal ball, treat to remove nonmetal ball again after metallic aluminium (aluminium alloy) cooled and solidified, thereby prepare metal porous aluminium.The metal foaming method places whipping agent in aluminium (aluminium alloy) melt or exactly by extraneous gas (as nitrogen etc.), by controlled temperature and stirring velocity whipping agent is decomposed producing gas, thus the metal porous aluminium of aluminium (aluminium alloy) foaming becoming.Metal porous aluminium (foamed aluminium) is mainly used in shielding and sound-absorbing.
The preparation method of above-mentioned metal porous body is the main method of preparation metal porous body, can adopt diverse ways to be prepared metal porous body at different purposes.
Summary of the invention
The purpose of this invention is to provide the high porous body of composite metal of a kind of porosity, particularly composition metal aluminium (aluminium alloy) porous insert.
Another object of the present invention provides a kind of porous body of composite metal, the particularly preparation method of composition metal aluminium (aluminium alloy) porous insert, and its production technique is simple and be easy to industrialization.
For achieving the above object, the present invention takes following technical scheme:
A kind of porous body of composite metal is to be that skeleton carries out the porous body of composite metal that the hot dipping metal or alloy is made with foamed metal or foamed alloy, wherein, component content 40～95 (wt) % of foamed metal or foamed alloy, surplus is the metal or alloy of hot dipping.
In porous body of composite metal, the aperture of described porous body of composite metal is 0.2～10.0mm, and porosity is not less than 90%, and thickness is at 1.5～10.0mm.
In porous body of composite metal, to the metal in the foamed metal, the alloy in the foamed alloy does not limit, and wherein, preferably: described foamed metal is metals such as nickel, iron, copper, lead, zinc; Foamed alloy is Ni-Fe or alloys such as copper-iron or nickel-copper.Wherein, binary alloy can, the above alloy of ternary is also passable.
In porous body of composite metal, described hot dipping metal comprises: any one in the metals such as aluminium, tin, zinc and lead.Wherein, preferable alloy is an aluminium.
In porous body of composite metal, described hot dipping alloy comprises: alloys such as aluminium-zinc or lead-Xi.Wherein, preferred alloy is an aluminum-zinc alloy.
A kind of method for preparing porous body of composite metal, this method comprises the steps:
At first be the core film with the foam materials, on this core film the deposition a kind of or more than two kinds or two kinds metal prepare porous metal or porous alloy;
Be skeleton with porous metal or porous alloy more afterwards, on this skeleton, adopt the hot dipping method to carry out the hot dipping metal or alloy.
The inventive point of the inventive method is: galvanic deposit (electroforming) and hot-dip process are combined the preparation porous body of composite metal.Promptly be the core film with the foam materials, metal refining prepares porous metal or porous alloy on this core film, is skeleton with it again, adopts the hot dipping method to carry out the hot dipping metal or alloy on this skeleton, can prepare porous body of composite metal.
In aforesaid method, in preparation porous metal or porous alloy step, described foam materials is urethane foam, weaving or adhesive-bonded cloth, fibrefelt etc.
In aforesaid method, on above-mentioned core film, deposit a kind of or metal more than two kinds or two kinds, the sedimentary metal of institute is not limited, wherein, preferably: described metal is any one metal or the metal more than two kinds or two kinds in nickel, iron, copper, lead, the zinc etc.,, then heat-treats more than two kinds or two kinds during metal in deposition, alloying by thermal treatment realization metal becomes Ni-Fe or alloys such as copper-iron or nickel-copper.
In aforesaid method, described hot dipping metal comprises: any one in the metals such as aluminium, tin, zinc and lead, wherein, preferable alloy is an aluminium.Described hot dipping alloy comprises: alloys such as aluminium-zinc or lead-Xi, wherein, preferred alloy is an aluminum-zinc alloy.
In aforesaid method, described hot dipping method is to carry out in air, or carries out under non-oxidizing atmosphere, or carries out under vacuum condition.
In aforesaid method, described hot dipping method comprises that employing is cast or the mode of seepage flow is carried out.
In aforesaid method, described foamed metal or foamed alloy are prepared foamed metal or foamed alloy for adopting methods such as powder metallurgy, galvanic deposit (electroforming) or vapour deposition.
Advantage of the present invention is: the porous body of composite metal that this method is prepared, particularly composition metal aluminium (aluminium alloy) porous insert is a tridimensional network, porosity height (〉=90%), the aperture is 0.2～10.0mm, compare with the preparation technology of foamed aluminium, have that production technique is simple, preparation cost is low and be easy to industrialization.
Embodiment
The preparation porous body of composite metal, prepare porous metal or porous alloy earlier, at first: make it have electroconductibility the foam materials processing, its step can be: (1) carries out oxide treatment with foam materials containing in the solution of oxygenant, again foam materials is reduced afterwards, purpose is exactly to improve the wettability and the wetting ability of foam materials, improves percentage of open area; (2) make non-conductive foam materials have electroconductibility by the electroless plating or the methods such as electrocondution slurry, vapour deposition, spraying plating, vacuum plating that are coated with.Or directly adopt the method for (2) to prepare conductive layer foam materials.Secondly: adopt the method for galvanic deposit (electroforming) to deposit metal on the foam materials, by the isoparametric adjusting of electric current, depositing time and strength of solution with control metal deposition amount.The 3rd: the foam materials that will deposit metal can be prepared foamed metal by thermal treatment (burning separate and reduce processing).
Foamed metal can be at first prepared in the preparation of foamed alloy as stated above, and a kind of or two kinds or other two or more metals are gone up in galvanic deposit more afterwards (electroforming); Also can after above-mentioned second step, carry out another kind of or other the two or more metal of galvanic deposit (electroforming) after a kind of metal of i.e. galvanic deposit (electroforming) again, then heat-treat.By the alloying of thermal treatment realization metal, improve its performance.The composition of foamed alloy ratio is on request adjusted.
Porous metal or porous alloy hot dipping metal or alloy, preferably hot aluminizing or aluminium alloy.In hot aluminizing or aluminium alloy process, in the container that the aluminum or aluminum alloy melt is housed, porous metal or porous alloy are flooded wherein exactly, by the deposition of parameters such as period and temperature with the decision aluminum or aluminum alloy.In order to improve the performance of porous aluminum, in the process of hot aluminizing, can add some additives.
The method of hot aluminizing can also adopt casting or seepage flow mode to carry out, aluminium (aluminium alloy) liquid that is about to melt casts on the foamed metal or makes aluminium (aluminium alloy) liquid by foamed metal under certain pressure, thereby forms the metal porous body of composition metal aluminium (aluminium alloy).
It is suitable equally that the present invention carries out hot dipping aluminum or aluminum alloy and other metals of hot dipping and alloy to the porous metal that adopt methods such as powder metallurgy, galvanic deposit (electroforming), vapour deposition and prepare or porous alloy.
Below by for example porous body of composite metal of the present invention and preparation method thereof being described further.
Embodiment 1
At a kind of iron-nickel foam alloy is to carry out hot aluminizing on the skeleton.
The preparation method is as follows: getting thickness is the urethane foam that 2.0mm, aperture are not less than 0.5mm, size 11.0cm * 9.0cm.At first in the acidic solution of potassium permanganate, soak 0.5～5min, in oxalic acid solution, reduce 0.5～5min again; Next prepares conductive layer, and the porous plastics that washs drying is dipped in 2～5min in the carbonaceous electrically conducting coating, squeezes clean remaining coating and oven dry.The 3rd step was carried out galvanic deposit iron, and at the ferrous 150～350g/l of sulfur acid, ammonium sulfate 80～200g/l, pH value are 2.0～5.5,15～60 ℃ of temperature, current density 3～8A/dm
2Condition under carry out galvanic deposit iron; The 4th goes on foot in Watts bath with current density 3～8A/dm
2, 40～45 ℃ of temperature are carried out electric deposition nickel, and nickel is coated on the iron; The 5th step was promptly carried out the thermolysis plastic core film that defoams at 300～500 ℃ by thermal treatment in air, reduce 10～30min at 850～1000 ℃ in reducing atmosphere and form nickel-ferro alloy; The 6th step had been equipped with in the crucible of fine aluminium in 720～900 ℃, with foam nickel-ferro alloy dipping 1～3min wherein, was the metal porous body of novel composition metal aluminium after the taking-up.
This preparation technology compares with the preparation technology of present porous aluminum, and it is low to have a cost, and technology is simple and be easy to characteristics such as large-scale production; The porous aluminum porosity height of preparing (〉=90%).
Embodiment 2
With a kind of copper-nickel foam alloy is that skeleton carries out hot aluminizing.Its preparation method is similar to embodiment 1, get the urethane foam that thickness 2.0mm, aperture are not less than 0.8mm, at first prepare conductive layer (this step is identical with embodiment 1), containing copper sulfate 100～250g/l then, sulfuric acid 100～400g/l carries out acid copper 30min in the 8A electric current under the condition that temperature is 15～50 ℃, afterwards in Watts bath in electric current 10A, carry out electric deposition nickel 15min under the condition that temperature is 40～45 ℃, thermal treatment again after the clean oven dry.In air, be heated to 300～500 ℃ the insulation 15～20min, again in reducing atmosphere in 700～950 ℃ the insulation 10～30min, prepare the foam nickel-copper alloy thus.The foam nickel-copper alloy is placed 1～5min in 700～800 ℃ of aluminiferous crucibles, take out the metal porous body that promptly gets composition metal aluminium.
Embodiment 3
With a kind of nickel foam is that skeleton carries out hot aluminizing.Its preparation method is similar substantially to embodiment 1, gets the urethane foam that thickness 5.0mm, aperture are not less than 1.0mm, at first prepares conductive layer (this step is identical with embodiment 1), is carrying out electric deposition nickel then in Watts bath, hot aluminizing after thermal treatment; Add the additive (additive is metals such as silicon and rare earth) of 1～10 (wt) % when hot aluminizing in the aluminium liquid of fusing, the aluminium liquid with fusing in the time of 680～730 ℃ casts on the nickel foam, takes out the metal porous body that is composition metal aluminium after cooling.
Embodiment 4
With a kind of nickel foam is that skeleton carries out hot aluminizing-zinc.Its preparation method is similar substantially to embodiment 3, get the urethane foam that thickness 5.0mm, aperture are not less than 1.5mm, at first prepare conductive layer (this step is identical with embodiment 1), in Watts bath, carrying out electric deposition nickel then, hot aluminizing-zinc after thermal treatment; The additive that adds 1～10 (wt) % when hot aluminizing-zinc in the aluminium-zinc liquid of 450～730 ℃ of fusings, dipping 2～15min takes out the metal porous body that is composition metal aluminium-zinc.
Embodiment 5
With a kind of nickel foam is that skeleton carries out tinning.Its preparation method is similar substantially to embodiment 3, get the urethane foam that thickness 3.0mm, aperture are not less than 1.0mm, at first prepare conductive layer (this step is identical with embodiment 1), in Watts bath, carrying out electric deposition nickel then, prepare nickel foam through thermal treatment, carry out tinning afterwards; Nickel foam be impregnated in 0.5～5min in the tin liquor of 250～300 ℃ of fusings, take out the metal porous body that after cooling, is composition metal tin.
Embodiment 6
With a kind of nickel foam is that skeleton carries out galvanizing.Its preparation method is similar substantially to embodiment 3, get the urethane foam that thickness 4.0mm, aperture are not less than 0.8mm, at first prepare conductive layer (this step is identical with embodiment 1), in Watts bath, carrying out electric deposition nickel then, prepare nickel foam through thermal treatment, carry out galvanizing afterwards; Nickel foam be impregnated in 0.5～5min in the zinc liquid of 440～480 ℃ of fusings, take out the metal porous body that after cooling, is composition metal zinc.
Claims (11)
1, a kind of porous body of composite metal, it is characterized in that: be to be that skeleton carries out the porous body of composite metal that the hot dipping metal or alloy is made with foamed metal or foamed alloy, wherein, component content 40～95 (wt) % of foamed metal or foamed alloy, surplus is the metal or alloy of hot dipping.
2, porous body of composite metal according to claim 1 is characterized in that: the aperture of described porous body of composite metal is 0.2～10.0mm, and porosity is not less than 90%, and thickness is at 1.5～10.0mm.
3, porous body of composite metal according to claim 1 and 2, it is characterized in that: described foamed metal is any one metal in the metals such as nickel, iron, copper, lead, zinc; Foamed alloy is Ni-Fe or alloys such as copper-iron or nickel-copper alloy.
4, porous body of composite metal according to claim 3 is characterized in that: described hot dipping metal comprises: any one metal in the metals such as aluminium, tin, zinc and lead; Described hot dipping alloy comprises: alloys such as aluminium-zinc or Lead-tin alloy.
5, a kind of method for preparing the described porous body of composite metal of claim 1, it is characterized in that: this method comprises the steps:
At first be the core film with the foam materials, on this core film the deposition a kind of or more than two kinds or two kinds metal prepare porous metal or porous alloy;
Be skeleton with porous metal or porous alloy more afterwards, on this skeleton, adopt the hot dipping method to carry out the hot dipping metal or alloy, can prepare porous body of composite metal.
6, method according to claim 5 is characterized in that: in preparation porous metal or porous alloy step, described foam materials is urethane foam or weaving or adhesive-bonded cloth or fibrefelt.
7, according to claim 5 or 6 described methods, it is characterized in that: in preparation porous metal or porous alloy step, described metal is any one metal or the metal more than two kinds or two kinds in the metals such as nickel, iron, copper, lead, zinc.
8, method according to claim 7, it is characterized in that: carry out in the hot dipping metal or alloy step in the hot dipping method, described hot dipping metal comprises: any one metal in the metals such as aluminium, tin, zinc and lead, described hot dipping alloy comprises: alloys such as aluminium-zinc or lead-Xi.
9, method according to claim 8 is characterized in that: described hot dipping metal or alloy method is to carry out in air, or carries out under non-oxidizing atmosphere, or carries out under vacuum condition.
10, according to claim 5 or 6 described methods, it is characterized in that: described hot dipping metal or alloy method comprises that employing is cast or the mode of seepage flow is carried out.
11, according to claim 5 or 6 described methods, it is characterized in that: in preparation porous metal or porous alloy step, described foamed metal or foamed alloy are prepared foamed metal or foamed alloy for adopting powder metallurgy or methods such as galvanic deposit (electroforming) or vapour deposition.
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| CN100427623C (en) * | 2006-10-20 | 2008-10-22 | 西安理工大学 | Method for preparing polymer/foam zinc-aluminium alloy composite material |
| CN101050903B (en) * | 2006-04-05 | 2010-06-16 | Lg电子株式会社 | Noise reduction device and air conditioner having the same |
| CN1921971B (en) * | 2004-03-19 | 2010-09-29 | 维尔国际有限公司 | A metal foam body having an open-porous structure as well as a method for the production thereof |
| CN102492966A (en) * | 2011-12-22 | 2012-06-13 | 菏泽天宇科技开发有限责任公司 | Foam nickel with ultra-low surface density and high aperture ratio and manufacturing method thereof |
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- 2002-09-02 CN CN02129612.XA patent/CN1244710C/en not_active Expired - Lifetime
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| CN103249850A (en) * | 2010-12-08 | 2013-08-14 | 住友电气工业株式会社 | Metallic porous body having high corrosion resistance and method for manufacturing same |
| CN103249850B (en) * | 2010-12-08 | 2015-09-02 | 住友电气工业株式会社 | There is metal porous body and the manufacture method thereof of high corrosion resistance |
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