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US20040074338A1 - Method for producing metal foams and furnace for producing same - Google Patents

Method for producing metal foams and furnace for producing same Download PDF

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Publication number
US20040074338A1
US20040074338A1 US10/466,975 US46697503A US2004074338A1 US 20040074338 A1 US20040074338 A1 US 20040074338A1 US 46697503 A US46697503 A US 46697503A US 2004074338 A1 US2004074338 A1 US 2004074338A1
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United States
Prior art keywords
metal
polymer substrate
coated polymer
hot zone
zone
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US10/466,975
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English (en)
Inventor
Marc Kuhn
Damien Duncan
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Efoam SA
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Efoam SA
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Assigned to EFOAM S.A. reassignment EFOAM S.A. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: KUHN, MARC, MICHEL, DAMIEN
Publication of US20040074338A1 publication Critical patent/US20040074338A1/en
Abandoned legal-status Critical Current

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    • 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
    • B22F3/1137—Making porous workpieces or articles by using decomposable, meltable or sublimatable fillers by coating porous removable preforms
    • 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
    • B22F3/1017—Multiple heating or additional steps
    • B22F3/1021—Removal of binder or filler
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D1/00—Electroforming
    • C25D1/08—Perforated or foraminous objects, e.g. sieves
    • 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
    • B22F2999/00—Aspects linked to processes or compositions used in powder metallurgy
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • F27B9/04—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity adapted for treating the charge in vacuum or special atmosphere
    • F27B9/045—Furnaces with controlled atmosphere
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • F27B9/14—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment
    • F27B9/147—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity characterised by the path of the charge during treatment; characterised by the means by which the charge is moved during treatment the charge moving on an inclined floor
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27B—FURNACES, KILNS, OVENS OR RETORTS IN GENERAL; OPEN SINTERING OR LIKE APPARATUS
    • F27B9/00—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity
    • F27B9/28—Furnaces through which the charge is moved mechanically, e.g. of tunnel type; Similar furnaces in which the charge moves by gravity for treating continuous lengths of work
    • F—MECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F27—FURNACES; KILNS; OVENS; RETORTS
    • F27D—DETAILS OR ACCESSORIES OF FURNACES, KILNS, OVENS OR RETORTS, IN SO FAR AS THEY ARE OF KINDS OCCURRING IN MORE THAN ONE KIND OF FURNACE
    • F27D99/00—Subject matter not provided for in other groups of this subclass
    • F27D99/007—Partitions
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/02—Electrodes composed of, or comprising, active material
    • H01M4/64—Carriers or collectors
    • H01M4/70—Carriers or collectors characterised by shape or form
    • H01M4/80—Porous plates, e.g. sintered carriers
    • H01M4/808—Foamed, spongy materials
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries

Definitions

  • the present invention generally relates to a method for producing metal foams from metal-coated polymer structures and to a furnace for producing metal foams.
  • nickel foam is produced by firstly depositing nickel on a polymer foam substrate, e.g. polyurethane foam, and then, subjecting the nickel-coated polymer substrate to a thermal treatment.
  • a thermal treatment is generally carried out in a continuous belt furnace with three zones.
  • the nickel-coated polymer substrate, laid on the conveyor belt firstly travels through an oxidizing zone in which it is exposed to a high temperature and to free oxygen, whereby the polymer is burned.
  • the polymer substrate is thus removed, leaving an oxidized nickel foam structure.
  • a reducing and annealing zone in which the oxidized nickel foam structure is exposed to a reducing atmosphere, generally pure hydrogen, and to high temperatures.
  • Treating the oxidized nickel foam structure in this reducing and annealing zone causes the nickel oxides formed in the first zone to return to a metallic state, the annealing step enhances the mechanical properties i.a. the ductility of the nickel foam structure.
  • the ductile nickel foam structure enters a cooling zone, in which it is cooled down in a controlled atmosphere of nitrogen and hydrogen.
  • Such a thermal treatment has many drawbacks. Firstly, burning the polymer in free oxygen allows the removal of the polymer substrate, but it unfortunately also causes oxidation of the metallic nickel. The oxidized nickel structure must then be reduced in a reducing atmosphere after the polymer removal, which complicates the treatment; Furthermore, the oxidized nickel structure is very brittle and fragile. Therefore the brittle, oxidized nickel structure has to be supported on a conveyor belt in the furnace. These conveyor belts are very heavy as compared to the nickel structure and are generally made of special refractory steel. Because of the repeated heating and cooling cycles, the conveyor belts need to be replaced frequently.
  • the conveyor belt has a negative influence on the energy balance of the process since not only the comparatively light nickel structure needs to be heated and cooled but also the comparatively heavy conveyor belt structure.
  • Another drawback of this process is the use of pure hydrogen, which increases the production costs and which is dangerous to handle.
  • JP 10 064268-A discloses a method for producing a porous Ni—Cr alloy.
  • a slurry containing Ni and Cr metallic powders is coated onto a foamed resin.
  • the coated product is heated at a temperature between 700 and 900° C. in a reducing gas atmosphere containing water vapour or carbon dioxide gas, whereby the foam is thermally degraded and the carbon content is removed.
  • the resulting product is then sintered by heating in at a temperature between 1100 and 1300° C. to yield a porous Ni—Cr alloy.
  • the water vapour or carbon dioxide content is in the range of 2.5 to 30 vol. %; an amount higher than 30 vol. % resulting in an over oxidation of the metal.
  • the reducing gas is hydrogen or ammonia decomposition gas.
  • U.S. Pat. No. 3,695,869 describes a method for producing fibrous metal materials, wherein a conductive carbon skeleton is prepared and a metal or alloy is deposited on the carbon skeleton by chemical or electrolytic method. The resulting product is then subjected to an oxidation operation at high temperature for eliminating the skeleton either in a hydrogen atmosphere containing a suitable proportion of water vapour or in air.
  • the object of the present invention is to provide a simpler method for producing a metal structure from metal-coated polymer substrates. This is achieved by a method as claimed in claim 1.
  • a method for producing a metal structure in accordance with the invention proposes to treat a metal-coated polymer structure in a hot zone, in which a temperature of at least 600° C. prevails as well as an atmosphere essentially composed of water vapor.
  • the water vapor is injected and maintained.
  • the polymer substrate is thermally decomposed and reacts with the water vapor.
  • the oxidation reaction intervening is an endothermic reaction known as “water gas” reaction, noted C+H 2 O CO+H 2 .
  • water gas noted C+H 2 O CO+H 2
  • the oxidizer employed to remove the polymer is water vapor and the metal-coated polymer substrate is not exposed to free oxygen.
  • the hot zone contains at least 80 to 85 vol. % of water vapor, more preferably about 90 vol. % and most preferably about 100 vol. %.
  • a metal structure remains. It shall be noted that the water vapor is, under the conditions employed, only oxidizing to carbon and the metal is not oxidized. As the metal is not oxidized during removal of the polymer, no specific reducing treatment is needed. In particular, the metal structure is not exposed to an atmosphere containing high concentrations of hydrogen. This means that the conventional reducing step in pure or highly concentrated hydrogen is not required any more. In fact, in the method according to the present invention the use of hydrogen is not required at all. The manufacturing costs are thus reduced and the risks involved with the use of pure or highly concentrated hydrogen are eliminated.
  • the metal structure is cooled down under controlled conditions in a cooling zone, preferably having a non-oxidizing atmosphere.
  • a cooling zone preferably having a non-oxidizing atmosphere.
  • hydrogen may be used at very low concentrations in the cooling zone to compensate for air leaks.
  • the treatment of the metal-coated polymer substrate in the hot zone allows for the removal of the polymer substrate without oxidizing the metal initially supported thereon.
  • the high temperature prevailing in the hot zone has the effect of a thermal or annealing treatment on the metal structure. It increases the strength of the metal structure and confers a good ductility to the latter.
  • a further advantage of the method is that since the metal is not oxidized, it does not become brittle.
  • the metal foam structure formed in the hot zone is self-supporting and is easier to handle.
  • the method of the invention is thus a simpler method for producing a metal structure from a metal-coated polymer structure.
  • the metal coating may consist of a variety of metals such as e.g. nickel, copper, iron, chromium, zinc, aluminum, lead, tin, gold, platinum or other metals belonging to the platinumgroup, and their alloys, as well as other metals and alloys, which are sufficiently noble to resist oxidation in water vapor at elevated temperatures.
  • the method is particularly suitable for the production of copper foam structures from copper-coated polymer substrates or nickel foam structures from nickel-coated polymer substrates.
  • the method proves economical and easy to implement, as the gases employed are cheaper and less dangerous.
  • the method of the invention permits to obtain a ductile metal structure by means of water vapor in one step.
  • the present method does not require a reducing step in a hydrogen atmosphere to reduce the metal structure, since in the present method the metal is not oxidized during polymer decomposition.
  • the method of the invention is advantageously performed in a furnace assembly configured in such a way as to allow the metal-coated polymer substrate, respectively the metal structure, to be continuously guided through the hot zone and through the cooling zone.
  • the temperature in the hot zone is of at least 650° C., more preferably of about 750 to 950° C. and most preferably from about 900 to 950° C.
  • the annealing temperature is chosen as a function of the ductility of the metal structure to be obtained.
  • an inert or slightly reducing atmosphere in the cooling zone prevents oxidation of the metal structure during cooling.
  • a suitable inert gas is nitrogen.
  • an atmosphere essentially composed of nitrogen and hydrogen is preferably maintained in the cooling zone.
  • the hydrogen content is not above 5 per cent in volume. Such hydrogen content allows to obtain a protective, slightly reducing atmosphere and is not problematic with regard to safety.
  • the metal-coated polymer substrate can be treated in coiled form. Moreover, as the obtained metal structure is ductile, it can be unrolled after cooling.
  • the metal-coated polymer substrate in strip form is made to slide on a sliding surface extending through the hot zone and through the cooling zone.
  • the metal-coated polymer substrate can for example be submitted to a slight traction effort without causing any damage to the metal structure.
  • the latter is advantageously inclined towards the cooling zone.
  • conveying means may be employed, if desired, to support the metal-coated polymer substrate, for example when treating metal-coated polymer substrates having low mass surface density.
  • Such conveying means may be a conveyor belt, as in conventional methods.
  • a preferred alternative conveying means is a metal foil. Since the metal foil is much lighter than a conveyor belt, its thermal inertia is much lower and the metal foil is heated much quicker. The heating loss is thus reduced.
  • copper foam is produced from copper-coated polymer structure, the latter is preferably supported on a copper foil, which appears to be a by-product of conventional copper foil production.
  • Such a supporting copper foil can be recycled at low cost after a single or multiple passages through the furnace.
  • a furnace for producing a metal structure from a metal-coated polymer substrate comprises:
  • a surface extending through the hot zone and the cooling zone for moving the metal-coated polymer substrate, respectively the metal structure, through the hot zone and the cooling zone.
  • the hot zone comprises heating means to heat the hot zone to a temperature of at least 600° C., injecting means to inject water vapor into the hot zone in such a way as to maintain a water vapor concentration of at least 80 vol. %, and extraction means to extract gas from the hot zone.
  • the cooling zone comprises injecting means to inject neutral and/or reducing gases into the cooling zone and at least part of the gases contained in the cooling zone are transferred to the hot zone and extracted from the hot zone through the extracting means.
  • the furnace may further comprise guiding means, for guiding the metal-coated polymer substrate, respectively the metal structure, through the hot zone and the cooling zone.
  • Such a furnace allows the production of metal foams from metal-coated polymer substrates in only two zones, and is thus more compact than conventional furnaces with three zones, respectively oxidizing, reducing/annealing, and cooling.
  • the present furnace is much safer than the conventional three-zone furnace, where a zone containing free oxygen lies next to a zone containing pure hydrogen. Indeed, in the present furnace, the gases of the two atmospheres may mix together without risk of explosion. This also simplifies the furnace construction and in particular the structure of the separation between the hot zone and the cooling zone, since a gas tight separation is not required.
  • An advantageous separation between hot zone and cooling zone is provided by baffle means, which allow to control the gas flow from one zone to the other.
  • the present furnace is thus a simpler, safer and more compact furnace allowing the manufacture of metal foam from metal-coated polymer structures.
  • the metal coating may be nickel, copper, and their alloys, or other metallic alloys resisting oxidation in water vapor at elevated temperatures.
  • the present furnace is particularly suited for the production of copper foams from copper-coated polymer substrates.
  • the guiding means will be of different type.
  • the metal structure obtained in the hot zone of the furnace is ductile and self-supporting. Therefore, the metal-coated polymer substrate does not need to be supported on a conveyor belt, which simplifies the structure of the furnace.
  • the furnace comprises a sliding surface extending through the hot zone and the cooling zone, on which the metal-coated polymer substrate is made to slide.
  • Guiding means installed outside and/or inside the furnace may e.g. comprise a first roll arranged before the hot zone and a second roll arranged about the exit of the cooling zone. As the rolls rotate, the metal-coated polymer substrate progresses in the furnace by sliding on the sliding surface.
  • the sliding surface may be formed by the upper surface of a sliding plate extending through the hot zone and the cooling zone. Th sliding plate is pref rably perforated to allow for an easy access of the water vapor to the strip, and for efficient evacuation of the reaction products.
  • the furnace is configured in such a way that the hot zone is at a higher level than the cooling zone, so that a part of the gases from the cooling zone flow to the hot zone where they are extracted with the gases from the hot zone.
  • the extracted gases mainly contain water vapor, but also small quantities of carbon oxides and hydrogen formed in situ as a result of the foam oxidation, nitrogen and possibly hydrogen from the cooling zone, as well as thermal decomposition products of the organic foam. These gases may be burned for heating purposes, or evacuated through a propane flare tip.
  • FIG. 1 is a schematic diagram of a two-zone-controlled-atmosphere furnace, in which a first embodiment of the method of the invention is implemented.
  • FIG. 2 is a schematic diagram of a two-zone-controlled-atmosphere furnace, in which a second embodiment of the method of the invention is implemented.
  • the present method relies on the heating of a metal-coated polymer structure by exposing it to a high temperature in a controlled water vapor atmosphere so as to remove the polymer substrate and produce a ductile metal foam structure.
  • the metal-coated polymer structure from which the metal foam is produced is generally obtained by electroplating a metal on a conductive polymer foam.
  • metals such as e.g. nickel, copper, iron, chromium, zinc, aluminum, lead, tin, gold, platinum or other metals belonging to the platinum group and their alloys, can be electroplated on such polymer foams as films, superposition of films or as blend of phases or structures in order to treat them according to the present method to obtain the corresponding metal foam.
  • the present method is particularly adapted for the production of ductile copper, respectively nickel, foam structures from copper-coated, respectively nickel-coated, polymer structures.
  • the polymer substrate may consist of a reticulated open cell foam structure, closed cell foam structure, felt, woven or non woven structures or similar structures or any combination thereof.
  • Acceptable polymer substrates include: polyester, polyurethane, polystyrene, polyvinylchloride, polyethylene, polyisocyanurates, polyphenols and polypropylene, paper or other cellulosic materials (carbon based natural or synthetic polymers). These polymers all thermally decompose and react with the water vapor in the hot zone to be oxidized.
  • Particularly preferred foams are e.g. reticulated foams for industrial use that are available e.g. in strip form from companies of the British Vita Group (based in the United Kingdom) such as Caligen Europe B.V. (The Netherlands) and Crest Foam Inc. (USA) or from Recticel International (headquartered in Belgium).
  • the weight of the foams are expressed herein with reference to their “surface mass density”. This term is herein understood as the mass of the apparent surface of the strip of foam. For example, if a foam has a surface mass density of 600 g/m 2 it means that a piece of foam having apparent external dimensions of 1 m ⁇ 2 m will have a mass of 1 200 g.
  • the real surface (including the surface of the pores) of the foam depends on its porosity.
  • a strip of foam having an apparent area of 1 m 2 (i.e. having external dimensions of 1 m ⁇ 1 m) and a porosity of 90 pores per inch will have a specific surface of about 200 to 300 m 2 .
  • the measure of the porosity is linear; it corresponds to the number of pores that are counted along a line of one inch in length.
  • Foams that are to be used to form the metal-coated polymer structures to be treated according to the present method will preferably have a porosity of 30 to 120 pores per inch, or even higher.
  • the thickness of the foams should preferably be in the range between 0.2 and 2 mm.
  • foams of about 1.6 mm in thickness will be used for secondary alkaline batteries, whereas thinner foams will be used for Li-Ion batteries.
  • foams of about 1.6 mm in thickness will be used for manufacturing metal-coated polymer structures to be used as charge collectors in secondary alkaline batteries, whereas thinner foams will typically be used for Li-ion batteries.
  • the surface of a strip of foam is made electrically conductive by: firstly deposing on the strip of foam a monomer that is electrically conductive in a polymerized form, and then polymerizing the monomer into an electrically conductive polymer.
  • a monomer may be pyrrole, which can be polymerized by oxidation-doping into electrically conductive polypyrrole.
  • vacuum deposition also called “Physical Vapor Deposition” (PVD)
  • PVD Physical Vapor Deposition
  • Vacuum deposition allows to form a coherent, thin metal pre-coating at the surface of the strip of foam.
  • Actual vacuum deposition techniques allow to form, on a strip of foam, a thin metal pre-coating that has an improved conductivity; and the obtained composite strip has a better tear resistance than a strip of foam rendered conductive by chemical treatment.
  • the strip of foam shall preferably be precoated with a very thin layer, of e.g. 1 to 10 g/m 2 , preferably not more than 5 g/m 2 , of copper deposited by vacuum deposition from heated crucibles containing liquid copper.
  • a copper-coated polymer structure is employed so as to produce copper foam.
  • the copper-coated polymer structure may have a mass surface density ranging typically from 100 to 2500 g/m 2 . Higher or lower coating weights can also be obtained on particular foam substrates.
  • the thickness of the copper plating on the polymer foam structure it shall preferably have a thickness in the range of 1 to 50 ⁇ m, more preferably between 2 and 15 ⁇ m, and most preferably above 8 ⁇ m.
  • a two-zone-atmosphere-controlled furnace 10 is schematically shown.
  • the furnace 10 comprises a hot zone 12 and an adjacent cooling zone 14 .
  • the hot zone 12 is provided with heating means (not shown) that are adapted to create a temperature of at least 600° C. therein.
  • the atmosphere of the hot zone 12 is composed of at least 80 vol. % of water vapor and may be mixed with a neutral gas such as nitrogen.
  • the atmosphere in the hot zone is composed of about 90 vol. % of water vapour and more preferably of about 100 vol. %.
  • the water vapor or the mixture is introduced through injecting means schematically represented by arrow 18 .
  • the atmosphere in the cooling zone 14 is also controlled, and advantageously consists of a gaseous mixture of N 2 with a maximum of 5 vol. % of H 2 .
  • This gaseous mixture is introduced in the furnace through injecting means schematically represented by arrow 20 .
  • injecting means schematically represented by arrow 20 .
  • the hot zone 12 and the cooling zone 14 are separated from each other by means of a series of baffles 16 . They provide a convenient separation, which allows to control the flow of gas between the two zones. Indeed, it shall be noted that the gases of the two zones 12 and 14 can mix with each other without danger, so that a gas tight separation is not needed.
  • the latter are preferably operated at a slight overpressure.
  • recirculation of water vapor into the cooling zone can be prevented by increasing the pressure in the cooling zone and/or by favoring a “chimney effect” in the hot zone in the case where the furnace is tilted with the hot zone placed at a higher level than the cooling zone.
  • Reference sign 22 indicates a copper-coated polymer substrate in strip form to be treated in the furnace 10 .
  • the copper-coated polymer substrate 22 is introduced into the hot zone 12 and is then continuously guided through the furnace 10 so as to travel through both zones.
  • the polymer substrate is thermally decomposed due to the high temperature which is preferably of about 900 to 950° C. and the presence of water vapor.
  • the carbon from the polymer reacts with the water vapor to form carbon oxides and hydrogen.
  • the polymer removal is carried out in an atmosphere which is basically free of molecular oxygen.
  • the polymer is thus removed and a polymer-free copper structure 23 is obtained.
  • the water vapor in the hot zone is not oxidizing to the copper, which thus remains in its metallic state. It will be appreciated that the use of a 100% water vapor atmosphere is particularly preferred for treating copper-coated polymer structures.
  • the high temperature has an annealing effect on the metal, thereby inducing recristallisation and improving its ductility.
  • a polymer-free, ductile copper foam structure is obtained at the end of the hot zone 12 .
  • the copper structure 23 then enters the cooling zone 14 , in which it is cooled down to a temperature between 20 and 75° C. in a controlled manner.
  • the temperature in the cooling zone 14 approaches that in the hot zone 12 , and at the end of the cooling zone 14 the temperature is of about 50° C.
  • the slightly reducing atmosphere maintained in the cooling zone 14 permits to avoid oxidation of the copper structure 23 and causes the reduction of any trace of copper oxide.
  • the copper-coated polymer substrate 22 is not necessarily supported on a conveyor belt in furnace 10 . This is possible since in the present method, copper is not oxidized and thus remains self-supporting, as already explained.
  • the copper-coated polymer substrate 22 is made to slide on a sliding surface 24 of the furnace 10 , which is formed by the furnace floor.
  • the furnace 10 may have a generally cylindrical inner shape and the furnace floor may be formed by a perforated plate placed at half height within the cylindrical furnace. In order to reduce frictional forces of the copper-coated polymer substrate 22 on the sliding surface 24 , the furnace floor should be relatively smooth.
  • the copper-coated polymer substrate 22 can easily be made to slide.
  • two rolls 26 and 28 are provided for guiding the copper-coated polymer substrate 22 through the furnace 10 .
  • the first roll 26 supports the copper-coated polymer substrate 22 before its entry into the hot zone 12 and the second roll 28 is arranged about the exit of the cooling zone 14 in order to collect the produced copper foam structure.
  • The, rotation of the two rolls is synchronized in such a way that—depending on the slope of the furnace—either the first roll 26 or the second roll 28 exerts a slight traction effort on the copper-coated polymer substrate 22 .
  • the copper-coated polymer substrate 22 progresses in the furnace 10 without damage.
  • the metallic foam may shrink by up to 30% in all three dimensions, and this phenomenon shall advantageously be taken into consideration for synchronizing the upper, first roll 26 and the lower, second roll 28 .
  • the furnace 10 is advantageously inclined in such a way that the hot zone 12 is at a higher level than the cooling zone 14 .
  • the sliding surface 24 thus defines a descending slope towards the cooling zone 14 , which facilitates the progress of the copper-coated polymer substrate 22 in the furnace 10 .
  • the copper-coated polymer substrate slides through the furnace under the effect of gravity.
  • the first roll 26 will be used to control the speed of the copper-coated polymer substrate 22 traveling through the furnace.
  • This configuration also has an impact on the gas flow within the furnace.
  • the gaseous mixture of N 2 and H 2 is introduced into the furnace 10 in the end part of the cooling zone 12 .
  • This gaseous mixture then travels through the cooling zone, in opposed direction to the copper-coated polymer substrate 22 , thereby ensuring the cooling of the latter.
  • the separation baffles 16 are arranged between the hot zone and the cooling zone in such a way as to allow at least part of the gaseous mixture from the cooling zone 14 to flow to the hot zone 12 .
  • the gases from the hot zone 12 i.e.
  • FIG. 2 a furnace 110 equivalent to that of FIG. 1 is shown. Similarly, it comprises a hot zone 112 in which a temperature of 900 to 950° C. prevails and in which an atmosphere essentially composed of water vapor is maintained. Water vapor is introduced into the hot zone at the level of arrow 118 . Adjacent to the hot zone 112 is a cooling zone 114 with a controlled atmosphere essentially consisting of nitrogen with 5 vol. % of hydrogen. This gaseous mixture of nitrogen and hydrogen is introduced in the furnace 110 at the level of arrow 120 . The two zones 112 and 114 are separated by means of baffles 116 . As in FIG. 1, the furnace 110 is inclined towards the cooling zone 114 and a part of the gases from the cooling zone 114 flows to the hot zone 112 , where they are extracted together with the other gases at the level of arrow 121 to be burned in a propane flare tip.
  • Reference sign 122 indicates a copper-coated polymer substrate 122 , which is to be treated in furnace 110 .
  • the copper-coated polymer substrate 122 is supported in the furnace 110 on a copper foil 124 .
  • the use of a supporting copper foil 124 is particularly suitable when treating fragile, low weight copper-coated polymer substrates 122 , e.g. having a mass surface density below 450 g/m 2 , typically between 100 and 300 g/m 2 .
  • the copper foil 124 stored on a supply roll 126 , is lead to an assembly roll 128 .
  • the copper-coated polymer substrate 122 is also guided to the assembly roll, in such a way as to be placed on top of the copper foil 124 .
  • the copper-coated polymer substrate 122 then enters the furnace 110 on the copper foil 124 .
  • the polymer substrate is removed and the obtained copper structure 123 is cooled.
  • the copper structure 123 supported on the copper foil 124 is collected on a separation roll 130 , on which they are separated.
  • the copper-coated polymer substrate 122 progresses in the furnace 110 due to the rotation of the two rolls 128 and 130 .
  • the traction effort is not exerted on the copper-coated polymer substrate 122 but on the copper foil 124 .
  • the copper-coated polymer substrate 122 is not in contact with the furnace floor, as it lies on the copper foil 124 . The copper-coated polymer substrate 122 is thus protected from any damage, tearing or deformation during its travel in the furnace 110 .
  • a copper foil is more interesting than a conveyor belt.
  • a conveyor belt typically has a surface mass density of 10 to 15 kg/m 2 whereas the surface mass density of suitable copper foils may be typically between 100-200 g/m 2 .
  • the copper thus has a much lower thermal in rtia than a conveyor belt and is heated much quicker, whereby heating loss is reduced.
  • the copper foil can be recycled after use in th production of the metal-coated polymer substrate.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Electrochemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Manufacture Of Porous Articles, And Recovery And Treatment Of Waste Products (AREA)
  • Superconductors And Manufacturing Methods Therefor (AREA)
  • Physical Vapour Deposition (AREA)
US10/466,975 2001-01-25 2002-01-24 Method for producing metal foams and furnace for producing same Abandoned US20040074338A1 (en)

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LU90721A LU90721B1 (en) 2001-01-25 2001-01-25 Method for producing metal foams and furnace for producing same
LU90721 2001-01-25
PCT/EP2002/000714 WO2002059396A1 (en) 2001-01-25 2002-01-24 Method for producing metal foams and furnace for producing same

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EP (1) EP1356137B1 (de)
JP (1) JP4334224B2 (de)
CN (1) CN1237209C (de)
AT (1) ATE278824T1 (de)
DE (1) DE60201499T2 (de)
LU (1) LU90721B1 (de)
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Cited By (17)

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US20060029736A1 (en) * 1996-04-22 2006-02-09 Micron Technology, Inc. Method to reduce fixed charge in CVD ozone deposited films
US20070098587A1 (en) * 2004-08-10 2007-05-03 Pan-Ting Hsueh Sintered porous frame and its producing method
US20150014172A1 (en) * 2013-07-12 2015-01-15 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method of synthesizing a metal foam, metal foam, uses thereof and device comprising such a metal foam
US9093778B2 (en) 2010-07-16 2015-07-28 Amc Electrical connection device having improved conductance
CN104903972A (zh) * 2012-10-03 2015-09-09 Amc控股公司 改善电连接导电性的粉末与糊剂
US9679706B2 (en) 2012-11-05 2017-06-13 Amc Etec Device for disconnecting an electrical supply line with a high-intensity current
EP3549699A4 (de) * 2016-11-30 2019-10-16 LG Chem, Ltd. Verfahren zur herstellung eines metallschaumstoffes
US11355779B2 (en) 2013-10-07 2022-06-07 Quantumscape Battery, Inc. Garnet materials for Li secondary batteries and methods of making and using garnet materials
US11391514B2 (en) 2015-04-16 2022-07-19 Quantumscape Battery, Inc. Lithium stuffed garnet setter plates for solid electrolyte fabrication
US11489193B2 (en) 2017-06-23 2022-11-01 Quantumscape Battery, Inc. Lithium-stuffed garnet electrolytes with secondary phase inclusions
US11581576B2 (en) 2016-01-27 2023-02-14 Quantumscape Battery, Inc. Annealed garnet electrolyte separators
US11600850B2 (en) 2017-11-06 2023-03-07 Quantumscape Battery, Inc. Lithium-stuffed garnet thin films and pellets having an oxyfluorinated and/or fluorinated surface and methods of making and using the thin films and pellets
US11876208B2 (en) 2013-01-07 2024-01-16 Quantumscape Battery, Inc. Thin film lithium conducting powder material deposition from flux
US11916200B2 (en) 2016-10-21 2024-02-27 Quantumscape Battery, Inc. Lithium-stuffed garnet electrolytes with a reduced surface defect density and methods of making and using the same
US12084387B2 (en) 2015-07-21 2024-09-10 Quantumscape Battery, Inc. Processes and materials for casting and sintering green garnet thin films
US12142727B2 (en) 2016-08-05 2024-11-12 Quantumscape Battery, Inc. Translucent and transparent separators
US12469876B2 (en) 2020-01-15 2025-11-11 Quantumscape Battery, Inc. High green density ceramics for battery

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US7458991B2 (en) 2002-02-08 2008-12-02 Howmedica Osteonics Corp. Porous metallic scaffold for tissue ingrowth
FR2847391A1 (fr) * 2002-11-20 2004-05-21 A M C Dispositif de contact pour ameliorer la duree de vie des connexions electriques
CN100372808C (zh) * 2006-04-18 2008-03-05 中国建筑材料科学研究院大石桥镁砖厂 含锆镁砖制造方法
DE102008027767B4 (de) 2008-06-11 2015-05-21 Süd-Chemie Ip Gmbh & Co. Kg Radial durchströmter monolithischer Katalysator aus beschichtetem Nickelschaum und dessen Verwendung
FR2952377B1 (fr) * 2009-11-09 2012-05-04 Amc Holding Dispositif de contact pour ameliorer la dissipation thermique des appareils generateurs de chaleur
JP5029974B2 (ja) * 2010-01-21 2012-09-19 富山住友電工株式会社 金属多孔体及びそれを用いた電池用電極、並びに金属多孔体の製造方法
JP5641016B2 (ja) * 2012-06-08 2014-12-17 トヨタ自動車株式会社 熱処理方法、及び熱処理炉
CN102864321A (zh) * 2012-09-04 2013-01-09 太原科技大学 粉末冶金法泡沫铝合金的连续发泡装置

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Cited By (37)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060029736A1 (en) * 1996-04-22 2006-02-09 Micron Technology, Inc. Method to reduce fixed charge in CVD ozone deposited films
US7763327B2 (en) 1996-04-22 2010-07-27 Micron Technology, Inc. Methods using ozone for CVD deposited films
US20100285238A1 (en) * 1996-04-22 2010-11-11 Sandhu Gurtej S Methods of forming glass on a substrate
US8420170B2 (en) 1996-04-22 2013-04-16 Micron Technology, Inc. Methods of forming glass on a substrate
US20070098587A1 (en) * 2004-08-10 2007-05-03 Pan-Ting Hsueh Sintered porous frame and its producing method
US9093778B2 (en) 2010-07-16 2015-07-28 Amc Electrical connection device having improved conductance
US9748014B2 (en) 2012-10-03 2017-08-29 Amc Powder and paste for improving the conductivity of electrical connections
CN104903972A (zh) * 2012-10-03 2015-09-09 Amc控股公司 改善电连接导电性的粉末与糊剂
US9679706B2 (en) 2012-11-05 2017-06-13 Amc Etec Device for disconnecting an electrical supply line with a high-intensity current
US11876208B2 (en) 2013-01-07 2024-01-16 Quantumscape Battery, Inc. Thin film lithium conducting powder material deposition from flux
US20150014172A1 (en) * 2013-07-12 2015-01-15 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method of synthesizing a metal foam, metal foam, uses thereof and device comprising such a metal foam
US10400345B2 (en) 2013-07-12 2019-09-03 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method of synthesizing a metal foam, metal foam, uses thereof and device comprising such a metal foam
US9512528B2 (en) * 2013-07-12 2016-12-06 Commissariat A L'energie Atomique Et Aux Energies Alternatives Method of synthesizing a metal foam, metal foam, uses thereof and device comprising such a metal foam
US11575153B2 (en) 2013-10-07 2023-02-07 Quantumscape Battery, Inc. Garnet materials for Li secondary batteries and methods of making and using garnet materials
US11367896B2 (en) 2013-10-07 2022-06-21 Quantumscape Battery, Inc. Garnet materials for Li secondary batteries and methods of making and using garnet materials
US11355779B2 (en) 2013-10-07 2022-06-07 Quantumscape Battery, Inc. Garnet materials for Li secondary batteries and methods of making and using garnet materials
US12095031B2 (en) 2013-10-07 2024-09-17 Quantumscape Battery, Inc. Garnet materials for Li secondary batteries and methods of making and using garnet materials
US11600857B2 (en) 2013-10-07 2023-03-07 Quantumscape Battery, Inc. Garnet materials for Li secondary batteries and methods of making and using garnet materials
US11658338B2 (en) 2013-10-07 2023-05-23 Quantumscape Battery, Inc. Garnet materials for li secondary batteries and methods of making and using garnet materials
US11391514B2 (en) 2015-04-16 2022-07-19 Quantumscape Battery, Inc. Lithium stuffed garnet setter plates for solid electrolyte fabrication
US12111109B2 (en) 2015-04-16 2024-10-08 Quantumscape Battery, Inc. Lithium stuffed garnet setter plates for solid electrolyte fabrication
US11592237B2 (en) 2015-04-16 2023-02-28 Quantumscape Battery, Inc. Lithium stuffed garnet setter plates for solid electrolyte fabrication
US12479771B2 (en) 2015-07-21 2025-11-25 Quantumscape Battery, Inc. Processes and materials for casting and sintering green garnet thin films
US12084387B2 (en) 2015-07-21 2024-09-10 Quantumscape Battery, Inc. Processes and materials for casting and sintering green garnet thin films
US11581576B2 (en) 2016-01-27 2023-02-14 Quantumscape Battery, Inc. Annealed garnet electrolyte separators
US12119444B2 (en) 2016-01-27 2024-10-15 Quantumscape Battery, Inc. Annealed garnet electrolyte separators
US12142727B2 (en) 2016-08-05 2024-11-12 Quantumscape Battery, Inc. Translucent and transparent separators
US11916200B2 (en) 2016-10-21 2024-02-27 Quantumscape Battery, Inc. Lithium-stuffed garnet electrolytes with a reduced surface defect density and methods of making and using the same
US12237475B2 (en) 2016-10-21 2025-02-25 Quantumscape Battery, Inc. Lithium-stuffed garnet electrolytes with a reduced surface defect density and methods of making and using the same
US11980942B2 (en) 2016-11-30 2024-05-14 Lg Chem, Ltd. Method for manufacturing metal foam
EP3549699A4 (de) * 2016-11-30 2019-10-16 LG Chem, Ltd. Verfahren zur herstellung eines metallschaumstoffes
US11901506B2 (en) 2017-06-23 2024-02-13 Quantumscape Battery, Inc. Lithium-stuffed garnet electrolytes with secondary phase inclusions
US12074281B2 (en) 2017-06-23 2024-08-27 Quantumscape Battery, Inc. Lithium-stuffed garnet electrolytes with secondary phase inclusions
US11489193B2 (en) 2017-06-23 2022-11-01 Quantumscape Battery, Inc. Lithium-stuffed garnet electrolytes with secondary phase inclusions
US11817551B2 (en) 2017-11-06 2023-11-14 Quantumscape Battery, Inc. Lithium-stuffed garnet thin films and pellets having an oxyfluorinated and/or fluorinated surface and methods of making and using the thin films and pellets
US11600850B2 (en) 2017-11-06 2023-03-07 Quantumscape Battery, Inc. Lithium-stuffed garnet thin films and pellets having an oxyfluorinated and/or fluorinated surface and methods of making and using the thin films and pellets
US12469876B2 (en) 2020-01-15 2025-11-11 Quantumscape Battery, Inc. High green density ceramics for battery

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WO2002059396A1 (en) 2002-08-01
ATE278824T1 (de) 2004-10-15
DE60201499T2 (de) 2006-02-02
LU90721B1 (en) 2002-07-26
DE60201499D1 (de) 2004-11-11
EP1356137B1 (de) 2004-10-06
CN1488011A (zh) 2004-04-07
JP2004523651A (ja) 2004-08-05
CN1237209C (zh) 2006-01-18
EP1356137A1 (de) 2003-10-29
JP4334224B2 (ja) 2009-09-30
TW555889B (en) 2003-10-01

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