EP1960138A1 - Mousse metallique biporeuse de grande porosite - Google Patents

Mousse metallique biporeuse de grande porosite

Info

Publication number
EP1960138A1
EP1960138A1 EP06775110A EP06775110A EP1960138A1 EP 1960138 A1 EP1960138 A1 EP 1960138A1 EP 06775110 A EP06775110 A EP 06775110A EP 06775110 A EP06775110 A EP 06775110A EP 1960138 A1 EP1960138 A1 EP 1960138A1
Authority
EP
European Patent Office
Prior art keywords
foam
metal
process according
powder
biporous
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP06775110A
Other languages
German (de)
English (en)
Other versions
EP1960138A4 (fr
Inventor
Douglas Kenneth Charles
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Vale Canada Ltd
Original Assignee
Vale Canada Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Vale Canada Ltd filed Critical Vale Canada Ltd
Publication of EP1960138A1 publication Critical patent/EP1960138A1/fr
Publication of EP1960138A4 publication Critical patent/EP1960138A4/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F3/00—Manufacture of workpieces or articles from metallic powder characterised by the manner of compacting or sintering; Apparatus specially adapted therefor ; Presses and furnaces
    • B22F3/10—Sintering only
    • B22F3/11—Making porous workpieces or articles
    • B22F3/1121—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers
    • B22F3/1125—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers involving a foaming process
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01D—SEPARATION
    • B01D39/00—Filtering material for liquid or gaseous fluids
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
    • B22F5/10—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product of articles with cavities or holes, not otherwise provided for in the preceding subgroups
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B22—CASTING; POWDER METALLURGY
    • B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
    • B22F2998/00—Supplementary information concerning processes or compositions relating to powder metallurgy
    • B22F2998/10—Processes characterised by the sequence of their steps

Definitions

  • the present invention relates to porous foams in general and to porous metal foams in particular
  • Porous metal foams are used in many industrial and consumer applications Examples include filters, strong and lightweight supports, internal combustion engine exhaust collectors, pollution controls, fuel cells, catalysts, cushioning and absorbing material, electrodes for primary and secondary batteries, etc Demand for finer porosity, greater surface area, varying metal content and other physical and chemical parameters is driving increased research and development of improved porous metal foams and methods for producing them
  • porous metal foams act as electrodes Typically pasted and activated with the appropriate materials, the foams are both electrodes and conduits for the electrolytes Depending on the physical nature of the foam, the substrates engender chemical activity, mass transport, electrical conductivity and fluid flow
  • open celled foams are those wherein a significant portion of each wall between the cells or bubbles has been destroyed leaving only struts or ligaments at the former intersections of the bubbles These discontinuities result in windows between the cells creating a continuous path, in all directions, between the larger cells Open celled foams tend to be used as frameworks or skeletons for holding other materials or as filters The value of these structures in such applications is such that processes have been developed to modify traditional open cell metal foams by coating additional metal or ceramic onto the struts and ligaments of the metal foams to enhance the surface area prior to treating them with the desired material
  • a variation of the open cell structure results when the metal forming the struts or ligaments (both terms may be used interchangeably) around the initial bubbles of gas is not derived from molten metal but from metal particles gently fused or sintered together
  • the struts rather than being closed and impervious are largely, in contrast, porous
  • the foam is comprised of less than 100% metal, sometimes much less, and extensive void space
  • U S patent 5,848,351 to Hoshino, et al claims struts having porosity as high as 60%, i e a metal content of only 40% Foams of this sort may be referred to as metal biporous foams since they possess both macro porosity resulting from the gas bubbles forming the joined cells and micro porosity resulting from the void space within the struts
  • the overall or bulk porosity of these foams is the average of the two levels of porosity in the foam Therefore, altering either the micro or strut porosity or the macro or bubble poros
  • the small pores through the struts may simply trap contaminants contained in the fluid as they become lodged in the small pores without reducing the flow of the fluid through the body of the structure. Liquid contaminants in a gas would coalesce in and around the struts and drain away under gravity. In all of these cases, the porous struts play an integral role in the function of the structure.
  • metal biporous foams include:
  • U.S. 5,976,454 to Sterzel et al. discloses the use of dissolved gas, CO 2 or water (steam) to generate the foam but adds high temperature to speed evaporation to thicken the foam matrix to arrest the foaming process.
  • U.S. 5,848,351 to Hoshino et al. discloses the use of volatile organic solvents that evaporate upon heating forming the foam. They sinter only partially and leave the micro porosity intact. The organics present a fire and environmental issue. Moreover, there is no control over bubble size.
  • U.S. 4,569,821 to Duperray et al. discloses the use of a water- activated polymer to stabilize the foam after adding the metal powder on the foam. This process requires the use of a gelling agent to prevent the destruction of the foam when the metal powder is added. Adding the metal as dry powder draws water from the foam structure causing it to collapse. The original character of the foam is altered greatly by the addition of metal powder in this way. It also incorporates into the mixture a pocket of air surrounding each particle or agglomeration of particles which later contributes to the microstructure of the foam to an uncontrolled extent.
  • U.S. 5,213,612 to Minnear et al. discloses a method of forming a porous body of molybdenum, tungsten, and their respective alloys by mixing metal powder and a foaming agent dissolved in an organic solvent and sintered. There are fire and environmental issues caused by this process.
  • U.S. 6,087,024 to Whinnery et al. discloses a siloxane based foaming process. Volatization of the combined hydroxide functional siloxene and the hydride functional siloxane leads to environmental concerns.
  • U.S. 6,660,224 B2 to Lefebvre et al. discloses a foaming process that utilizes organic solvents.
  • a method for producing metal biporous foams by utilizing a solution of filamentary metal powders.
  • a thickened cellulose based foam precursor and the wet metal powder mixture solution are mixed together. Foaming of the precursor is caused to occur. Once completed the resultant foam is moderately dried to form a green cake. The green cake is sintered in a reducing atmosphere.
  • Figure 1 is a photograph of an embodiment of the invention.
  • Figure 2 is a photomicrograph of an embodiment of the invention.
  • Figure 3 is a photomicrograph of an embodiment of the invention.
  • Figure 4 is a photomicrograph of an embodiment of the invention.
  • Figure 5 is a photomicrograph of an embodiment of the invention.
  • Figure 6 is a photomicrograph of foam made in accordance with the invention attached to a copper pipe.
  • the present method is an environmentally friendly process for making high porosity metal biporous foam using GRAS materials or their derivatives (which i inn the latter case may not all be GRAS members).
  • struts Using traditional methods and traditional atomized metal particles, commercially available struts have a porosity of about 10% - 60% or a metal content only as low as 40%. In contrast, the present process of using filamentary carbonyl derived metal powders results in struts having about 85% - 95% porosity or a metal density of about 5% - 15%.
  • filamentary means, a characteristic three-dimensional chain-like network of fine or extra fine particles exhibited, for non-limiting example, by Inco® T255 nickel powder.
  • the assignee of the present invention produces and sells a series of ultra fine and exceedingly pure filamentary metal powders derived from the dissolution of metal carbonyl compounds via the extraordinar Mond process.
  • the present process preferably uses such filamentary metal powders to provide the significantly enhanced product, metal powders produced by other methods may be employed to good advantage as well.
  • Foams can be generated by any of several methods as known to those skilled in the art. Some of the processes are described below:
  • Foam can also be created continuously by mechanical means such as those used in the fire fighting and foam insulation fields.
  • methylcellulose (MC) or hydroxypropyl methylcellulose (HPMC) as the major foam starter component of foam only requires raising the temperature to the thermal gelation temperature of the aqueous solution to solidify the structure. It is not necessary to completely drive off the water for this purpose The remaining water is removed during sintering. The gelled structure does need to be at least partially dried to prevent it from returning to its slurry state upon cooling.
  • the nickel powder is combined with it.
  • adding dry metal powder degrades the foam.
  • This debilitating issue is addressed and overcome by the present invention in the following manner.
  • the nickel powder is first wetted with a solution of water and a wetting agent, for example a surfactant such as household dish washing liquid, to displace the air from around the particles or agglomerates of particles before mixing with the foam.
  • the wet nickel solution mixture and the foam starter are added together with gentle mixing in order not to degrade the structure of either the foam or the nickel.
  • the character of the final product can be controlled at this point by controlling the density of the foam while the nickel additions are combined with it.
  • a foam density of about 0.5 g/cc results in a good product.
  • the wet foam is then dried or baked to stabilize or harden the structure while the water is driven out.
  • the foam will stabilize once it has been heated to above the thermal gelation temperature. Since the foam is initially a closed cell structure, changes in temperature will result in changes in the size of the bubbles. As water is driven out of the foam, the cell walls dry and the structure changes from closed to open cell allowing the liberation of the entrained gas and the free evaporation of the entrained water. Thus, the foam will stretch beyond its stabilized dimension while in the closed cell state but revert to its stabilized dimension after later changing to an open cell. The result is a dried green cake.
  • the porosity of the struts is normally at least about 80% rather than the lower 60% porosity when using non-filamentary powders, and less than about 20% nickel in the struts as metal compared with 40% for the prior art such as U.S. 5,868,351 as above. Indeed, the present process results in an overall porosity that is very high, up to about 95% or less than about 5% nickel.
  • Such a high porosity metal biporous foam has a great ability to filter solids from fluids and liquids from gases.
  • the metal structure can be made magnetic (if appropriate) by the application of a magnetic field and thus filters metal cuttings and filings from cutting fluids and releases them, when cleaning the filter, upon removal of the magnetic field.
  • the present method preferably uses the following ingredients:
  • D Other benign agents such as glycerin, readily accessible to the general public and also GRAS.
  • dish washing solution typically SUNLIGHT® dish washing liquid in water
  • the foam is transferred to a mold or pan for drying [0056] 10.
  • the wet foam is dried in a humid oven at 250 0 F (121 0 C) for two hours. A hotter oven results in much expansion of the air bubbles in the foam causing the foam to collapse after about 30 minutes into the drying process.
  • the resulting nickel biporous foam is mechanically robust and has a porosity of about 95% or a density of about 5% nickel, distributed throughout in a biporous structure.
  • the variation in macro pore size of the final product is determined by the uniformity of the original foam and therefore, any other suitable method for making the foam can be applied in order to achieve the desired texture in the final product.
  • the nickel biporous foam can be shaped at various stages in the process including wet foam, green foam or the final sintered foam.
  • Figure 1 is a sintered metal biporous foam as produced in accordance with the above example. Scales along the putative x and y axis provide a physical sense of the product.
  • Figures 2 and 3 demonstrate the macroporosity of the foam at two selected magnifications.
  • Figure 4 demonstrates the microporosity of a strut.
  • Figure 5 demonstrates the microporosity of the foam at high magnification.
  • the wet metal biporous foam of the present invention was applied to the interior surface of a short length of copper pipe and then dried.
  • the metal slurry is made into foam with different foam densities.
  • different types of gases dissolved in the slurry such as air, carbon dioxide, nitrogen, nitrous oxide, etc. may result in different foam textures and other physical and chemical properties since they affect the foam.
  • the foam starter, MC, MC derivatives, molecular weights, GRAS binders, starch, surfactants and other concentrations the size of the bubbles and the foam's composition may be modified.
  • the invention is not limited to only one metal. Other metal powders such as copper, iron, nickel-based alloys, copper-base alloys, iron-base alloys etc. may be utilized singly instead or be mixed with the nickel powder or other metal powders that preferably display similar filamentary structures to those of the nickel particles.

Abstract

L’invention concerne un procédé écologique de fabrication d’une mousse métallique biporeuse utilisant des poudres métalliques filamenteuses telles que du nickel ou du cuivre. Les poudres métalliques filamenteuses sont initialement humides lors de leur mélange avec un agent moussant approprié tel que la méthylcellulose. La poudre métallique filamenteuse étant humide, elle n’extrait pas l’eau de la structure mousseuse, permettant ainsi d’obtenir une mousse métallique de grande porosité présentant à la fois une grande macroporosité et une grande microporosité.
EP06775110A 2005-10-07 2006-08-15 Mousse metallique biporeuse de grande porosite Withdrawn EP1960138A4 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US11/245,660 US20070081911A1 (en) 2005-10-07 2005-10-07 High porosity metal biporous foam
PCT/CA2006/001335 WO2007041827A1 (fr) 2005-10-07 2006-08-15 Mousse metallique biporeuse de grande porosite

Publications (2)

Publication Number Publication Date
EP1960138A1 true EP1960138A1 (fr) 2008-08-27
EP1960138A4 EP1960138A4 (fr) 2009-08-19

Family

ID=37911218

Family Applications (1)

Application Number Title Priority Date Filing Date
EP06775110A Withdrawn EP1960138A4 (fr) 2005-10-07 2006-08-15 Mousse metallique biporeuse de grande porosite

Country Status (8)

Country Link
US (1) US20070081911A1 (fr)
EP (1) EP1960138A4 (fr)
JP (1) JP2009510266A (fr)
KR (1) KR20080044344A (fr)
CN (1) CN101300095A (fr)
CA (1) CA2624715A1 (fr)
TW (1) TW200730277A (fr)
WO (1) WO2007041827A1 (fr)

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JP4986259B2 (ja) * 2006-10-24 2012-07-25 三菱マテリアル株式会社 発泡速度の速い多孔質金属焼結体製造用混合原料
EP2349360B1 (fr) 2008-10-29 2018-12-12 Smith & Nephew, Inc. Couches de surface poreuses présentant une rugosité de surface accrue et implants les incorporant
TWI471424B (zh) * 2009-03-30 2015-02-01 Mitsubishi Materials Corp 鋁多孔質燒結體的製造方法及鋁多孔質燒結體
JP5402380B2 (ja) 2009-03-30 2014-01-29 三菱マテリアル株式会社 アルミニウム多孔質焼結体の製造方法
CN102598376A (zh) * 2009-09-04 2012-07-18 G4协同学公司 用于形成发泡的电极结构的方法
CN102549814A (zh) * 2009-09-22 2012-07-04 G4协同学公司 高性能电极
US20110239890A1 (en) * 2010-04-06 2011-10-06 Spritzer Michael H Thermite-Metal Foam
CN102554241A (zh) * 2012-01-12 2012-07-11 昆山德泰新材料科技有限公司 泡沫团化铜粉制备方法
US9827530B2 (en) * 2015-01-30 2017-11-28 Hamilton Sundstrand Corporation Enhanced device for separation of oxygen and nitrogen
KR20180041343A (ko) 2016-10-14 2018-04-24 주식회사 엘지화학 금속합금폼의 제조 방법
KR101891405B1 (ko) * 2016-11-08 2018-08-23 부경대학교 산학협력단 금속 발포체 및 이의 제조 방법
KR102218856B1 (ko) 2016-11-30 2021-02-23 주식회사 엘지화학 금속폼의 제조 방법

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Also Published As

Publication number Publication date
TW200730277A (en) 2007-08-16
US20070081911A1 (en) 2007-04-12
JP2009510266A (ja) 2009-03-12
WO2007041827A1 (fr) 2007-04-19
KR20080044344A (ko) 2008-05-20
EP1960138A4 (fr) 2009-08-19
CA2624715A1 (fr) 2007-04-19
CN101300095A (zh) 2008-11-05

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