EP2207915B1 - Verfahren zur herstellung einer geordneten porösen struktur aus einem aluminiumsubstrat - Google Patents

Verfahren zur herstellung einer geordneten porösen struktur aus einem aluminiumsubstrat Download PDF

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Publication number
EP2207915B1
EP2207915B1 EP08844577A EP08844577A EP2207915B1 EP 2207915 B1 EP2207915 B1 EP 2207915B1 EP 08844577 A EP08844577 A EP 08844577A EP 08844577 A EP08844577 A EP 08844577A EP 2207915 B1 EP2207915 B1 EP 2207915B1
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Prior art keywords
porous structure
thickness
anodization
carried out
abrasion
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French (fr)
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EP2207915A2 (de
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Laurent Arurault
François LE COZ
René BES
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Centre National de la Recherche Scientifique CNRS
Universite Toulouse III Paul Sabatier
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Centre National de la Recherche Scientifique CNRS
Universite Toulouse III Paul Sabatier
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    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
    • C25D11/02—Anodisation
    • C25D11/04—Anodisation of aluminium or alloys based thereon
    • C25D11/18—After-treatment, e.g. pore-sealing

Definitions

  • the invention relates to a method of manufacturing an ordered porous structure from an aluminum substrate.
  • a porous structure is said to be "ordered” when it has pores, in the form of rectilinear channels, of the same cross section (shape and dimensions), parallel and adjacent in a radial plane, and uniformly distributed in the radial plane.
  • the aluminum part and the anode structures resulting from the anodizing of said aluminum part are oriented according to their two opposite faces, a first face, referred to as the outer face, in contact with the electrolyte solution. and a second face, said substrate face, which is not in contact with the electrolytic solution.
  • alumina refers to the general term covering oxidized forms of aluminum, namely aluminum oxides, aluminum hydroxides and aluminum oxy-hydroxides.
  • porous structures For this purpose, it is known to produce, by anodizing aluminum metal substrates, ordered porous structures, based on the aluminum chemical element, the surface of which extends over several ⁇ m 2 .
  • porous structures also called porous anodic films
  • These porous structures can be used as support or as matrix for original applications such as nanofiltration or the realization of nanoscale functional elements such as nanoscreens, nanowires and nanotubes.
  • the improvement of the technical performances of these materials, whose ultrastructures are of meso- or nanometric dimension, follows directly from the technological advances allowing the realization of porous anodic films, of big dimension and controlled thickness.
  • this document describes a reference process for the manufacture of an aluminum-based porous structure, by means of several successive treatments that are all chemical or electrochemical.
  • This document presents the surface state of the substrate face of the porous structure, after removal of the residual substrate and the barrier layer. It does not describe the state of the porous structure within its thickness, especially at the outer face.
  • an ordered porous structure by anodizing an aluminum substrate having, on its outer surface, a plurality of concavities, of the same shape, and regularly distributed.
  • Such a print can be obtained by nanoindentation of the aluminum substrate, for example, by applying and pressing on the aluminum substrate, a hard matrix, in particular of silicon carbide having a plurality of convexities.
  • this nanoindentation step is technologically very difficult to implement because of the technical difficulties to achieve, on the meso- and nanometric scales, the silicon carbide matrix having a plurality of convexities. This step of producing a matrix is, consequently, an expensive step.
  • Double anodizing Another known method for obtaining a plurality of concavities, of the same shape, and regularly distributed on the surface of the aluminum or aluminum alloy substrate, is called “double anodizing".
  • a first anodizing step makes it possible to form a plurality of concavities at the interface of the initially smooth aluminum substrate and the porous structure resulting from this anodization.
  • the complete dissolution, by chemical means, of the porous structure resulting from the anodization then reveals the plurality of underlying concavities.
  • These concave impressions then serve as a guide for the growth, during a second anodizing step, of an ordered porous structure.
  • This process of "double anodizing” is slow to implement because of the duplication of the anodizing step.
  • This process also requires a step of chemical dissolution of the porous structure resulting from the first anodization, which is difficult to implement, and is therefore, little or not compatible with industrial scale operation. .
  • this The process requires the implementation, during the dissolution step, of toxic chemicals, such as chromium derivatives, in particular chromium VI.
  • the porous structure thickness, produced at the end of the initial anodizing treatment of the aluminum substrate, then dissolved by chemical treatment is not valued.
  • EP 1715085 proposes a method in which the chemical dissolution treatment is replaced by an electrochemical treatment, leading to the separation of the residual aluminum substrate and the entire structure resulting from the first anodization.
  • this process is time-consuming, relatively complex, expensive and not very compatible with commercial scale operation.
  • the invention aims to overcome all these drawbacks by proposing a method of manufacturing, by anodizing an aluminum or smooth aluminum alloy substrate, an ordered porous structure, which avoids the use of double anodization, and which does not require the achievement of a prior step of mechanical nanoindentation of the aluminum substrate or aluminum alloy.
  • the object of the invention is more particularly to provide a process for the production, by anodization, of an ordered porous structure which is simple, fast, inexpensive, environmentally friendly, and which is compatible with a exploitation on an industrial scale.
  • the object of the invention is more particularly to provide a method for obtaining an ordered porous structure of high quality, homogeneous throughout its thickness, and in which the shape, the pore diameter and the pore ordering are perfectly controlled.
  • the invention aims more particularly to provide a method for obtaining an ordered porous structure that can have a large thickness, especially greater than 50 microns.
  • the invention also aims at providing a method of manufacturing an ordered porous structure that does not require the use of toxic chemical compounds such as chromium derivatives, in particular chromium VI.
  • the porous structure obtained by simple anodization of a smooth aluminum substrate has, on its outer face side, a porous structure of imperfectly ordered thickness, that is to say which does not have pores in the form of straight channels, of the same cross section (shape and dimensions), parallel and adjacent in a radial plane, and uniformly distributed in the radial plane. But, if the anodization time is sufficiently long, the porous structure also has, underlying this imperfectly ordered porous structure, a porous structure, perfectly ordered, that is to say having pores in the form of rectilinear channels , of the same cross section (shape and dimensions), parallel and adjacent in a radial plane, and uniformly distributed in the radial plane.
  • the only fact of directly producing anodization on a smooth aluminum substrate that is to say, having an arithmetic roughness of less than 5 nm and therefore not having a plurality of concavities resulting from a prior anodization, -proceded by double anodizing-, or a mechanical nanoindentation step, allows, in fact, if the duration of anodization is long enough, to obtain an ordered porous structure thickness, below one imperfectly ordered porous layer extending to the surface.
  • the thickness corresponding to this imperfectly ordered layer is removed by mechanical machining so as to open the pores of the ordered porous structure on the surface.
  • an anodizing treatment is carried out from a substrate made of aluminum alloy of the 1XXX series, for example the aluminum alloy 1050A, or else aluminum refined, in particular chosen from the group consisting of 4N aluminum and 5N aluminum.
  • the outer surface layer comprising at least one porous structure thickness
  • the outer surface layer is obtained after an anodizing time which depends on the growth rate of said outer surface layer.
  • the growth rate of the outer surface layer depends on the operating conditions chosen for the realization of the physical properties of the porous structure.
  • the process according to the invention makes it possible to carry out quickly and simply in a single anodization and without requiring either a subsequent chemical treatment of selective dissolution or separation.
  • electrochemical a porous structure having a non-zero thickness of an ordered porous structure.
  • This ordered porous structure has an open porosity, at least on one of its faces, said outer face, and an ordered porous structure thickness on a micrometer scale.
  • the outer surface layer comprises a plurality of thicknesses of superimposed ordered porous structures.
  • These different thicknesses are obtained in particular by an anodizing treatment comprising a plurality of successive anodizing steps, none of said steps of the anodization treatment being followed by a treatment by selective chemical dissolution or electrochemical separation of part of the thickness of the layer formed by anodization.
  • the various steps of the anodization treatment are carried out under anodizing conditions in which at least one of the anodizing parameters selected in the method is modified between two successive anodizing steps. group consisting of the anodizing voltage, the temperature of the anodization solution, the chemical composition of the anodizing solution, the density of the anodizing current.
  • a process according to the invention it is possible to use any known process for removing material by mechanical machining to effect the removal of a part of the thickness of said layer formed by anodization, this part of thickness being extending from the outer surface of said layer, retaining at least one non-zero thickness of an ordered porous structure and such that the ordered porous structure forms the free outer surface of the residual layer.
  • mechanical machining is understood to mean any suitable method for superficial removal of particles of material.
  • these particles of material removed by mechanical machining are particles in the solid state.
  • the particles of material removed by machining mechanical may be in the gaseous state.
  • a process according to the invention it is possible to use any known method for removing material by mechanical machining, excluding chemical etching treatments, in particular chemical treatments of the layer formed by anodizing with a solution, capable of penetrating by capillarity in the pores of said porous layer and change the shape and size of the pores of the porous structure.
  • Such mechanical machining can be carried out in a single step, or on the contrary by a plurality of successive steps. It is also possible to perform such mechanical machining with only one mechanical machining technique implemented during the different machining steps, or conversely by implementing a plurality of mechanical machining techniques during steps of machining. successive mechanical machining.
  • Such a mechanical machining according to the invention may in particular be carried out by ionic polishing using an ion flux, in particular a Precision Ion Polishing System (PIPS), or by using the broad and energetic primary beam of a Secondary Ions Mass Spectrometry (SIMS).
  • PIPS Precision Ion Polishing System
  • SIMS Secondary Ions Mass Spectrometry
  • said thickness portion is removed by mechanical abrasion, that is to say by solid / solid dynamic friction, by means of a mobile abrasive solid tool, which is applied to the surface outer of the porous layer formed by anodizing, and exerting pressure on said movable abrasive solid tool.
  • this mechanical abrasion is performed so as to obtain an ordered porous structure whose outer surface is flat.
  • said thickness portion is removed by a mechanical machining treatment, in particular by mechanical abrasion, which only affects the outer surface of the porous layer formed by anodizing, and which does not affect, in the thickness of the porous structure, the pore diameter of the ordered porous structure and the shape of said pores revealed during the abrasive treatment.
  • This mechanical abrasion treatment is distinguished from a chemical dissolution treatment which necessarily affects not only the thickness of the porous layer formed by anodization, but also the shape and pore diameter of said layer.
  • the mechanical abrasion is carried out by means of a piece of fabric, in particular a piece of felt-, impregnated with a suspension, called an abrasive suspension, of a powder in an aqueous phase.
  • said powder comprising at least one mineral selected from the group of abrasive minerals, consisting of diamond and ceramics, in particular corundum.
  • the choice of the abrasive mineral also makes it possible to select the hardness of said mineral, so as to control the abrasion speed of the porous structure.
  • the hardness of the abrasive mineral contained in the abrasive suspension is greater than the hardness of the porous layer whose composition is based on alumina, in particular oxidized, hydroxylated and / or oxy-hydroxylated derivatives of the aluminum.
  • the mechanical abrasion is carried out in a single step, or on the contrary, by a plurality of successive stages of abrasion, each of said successive abrasion stages being carried out by means of an abrasive suspension.
  • the abrasive suspensions of each of the successive abrasion stages being chosen so as to have a decreasing particle size from one step to another.
  • the mechanical abrasion is carried out by a succession of abrasion steps ranging from a less fine and faster abrasion to a finer and slower abrasion.
  • the choice of the particle size of the mineral powder makes it possible to control both the abrasion speed of the porous structure and the quality of the finish of the surface of the porous structure.
  • the succession of abrasion steps carried out by means of abrasive suspensions of decreasing particle size makes it possible moreover to reduce the abrasion time while conferring on the surface of the porous structure a low roughness and an excellent finish.
  • each of the plurality of successive stages of abrasion is carried out by means of a piece of fabric impregnated with an abrasive suspension, said piece of fabric being applied to the surface of the abrasion.
  • a rigid support selected from the group consisting of a vibrating support and a rotatable support.
  • each of the plurality of successive abrasion steps is carried out by means of a piece of fabric impregnated with an abrasive suspension, said piece of fabric being applied to the surface of a rigid support chosen from the group consisting of a vibrating support and a rotatable support, the smallest dimension of the piece of fabric and the rigid support being greater than the largest dimension of the outer surface layer.
  • each abrasion step of the plurality of successive stages of abrasion is carried out by means of a rotary support having a rotation speed of less than 30 rad / s, in particular included between 2 rad / s and 20 rad / s.
  • the pressure applied to the surface of the porous layer during mechanical abrasion is in particular between 1 kPa and 50 kPa.
  • the mechanical abrasion is carried out by a first abrasion step by means of a piece of felt impregnated with a diamond suspension whose average particle size is between 0.8 ⁇ m and 1.5 ⁇ m. ⁇ m, in particular of the order of 1 ⁇ m, and by a second abrasion step by means of a piece of felt impregnated with a diamond suspension whose average particle size is between 0.2 ⁇ m and 0.4 ⁇ m. , in particular of the order of 0.25 microns.
  • the total duration of the mechanical abrasion is less than 30 min, in particular between 10 min and 20 min. This time makes it possible in practice to eliminate the entire thickness of the unordered porous layer formed on the outer surface during the anodization.
  • abrasion step is carried out by means of a piece of felt impregnated with a diamond suspension whose average particle size is close to 1 ⁇ m, and then the second stage by means of a piece of felt impregnated with a suspension diamond whose average particle size is close to 0.25 microns, and finally the third step by means of a piece of felt impregnated with a diamond suspension whose average particle size is close to 0.10 microns.
  • the invention removes a thickness of the outer surface layer between 15 microns and 25 microns, in particular of the order of 17 microns to 20 microns.
  • This thickness is at least the thickness of the imperfectly ordered porous structure extending from the outer surface of the anodized layer.
  • an anodizing treatment is carried out on a smooth aluminum substrate, with a duration adapted to obtain an outer surface layer formed by anodizing having a total thickness of between 25 ⁇ m and 300 ⁇ m, especially between 100 ⁇ m and 200 ⁇ m.
  • a single anodizing treatment is carried out on a smooth aluminum substrate, said treatment having a duration of between 1 h and 12 h, in particular of the order of 4 h.
  • a method according to the invention consists in carrying out a single anodizing treatment, comprising at least one anodizing step, then a step of removing the thickness portion of the outer surface layer whose porous structure is imperfectly ordered.
  • the anodizing step marking the end of the anodization treatment is immediately followed by a mechanical machining treatment, in particular by mechanical abrasion.
  • a single anodizing treatment is carried out on a smooth aluminum substrate for a period of time adapted so that the thickness of the ordered porous structure formed by anodization is between 1 ⁇ m and 150 ⁇ m, in particular between 50 ⁇ m and 150 ⁇ m.
  • anodization is carried out in an aqueous electrolyte solution chosen from the group consisting of aqueous solutions of acids, in particular sulfuric acid, a mixture of sulfuric acid and boric acid, oxalic acid, phosphoric acid, malonic acid, tartaric acid and citric acid.
  • acids in particular sulfuric acid, a mixture of sulfuric acid and boric acid, oxalic acid, phosphoric acid, malonic acid, tartaric acid and citric acid.
  • anodizing in an aqueous electrolyte solution whose composition is adapted to provide an ordered porous structure whose pores have a diameter of between 10 nm and 500 nm, in particular between 100 nm and 200 nm.
  • anodization is carried out at a temperature of between -2 ° C. and + 2 ° C., in particular of the order of -1.5 ° C.
  • anodization is carried out under a voltage of between 19 V and 240 V, in particular between 125 V and 195 V with an aqueous solution comprising phosphoric acid as the electrolyte.
  • At least one anodization is carried out in a single step, or in a set of immediately successive anodizing steps, and then a mechanical abrasion treatment.
  • a porous structure is obtained comprising at least one ordered porous structure thickness.
  • the non-oxidized aluminum substrate and a portion of non-porous thickness of said layer are removed in order to retain only the ordered porous structure.
  • a chemical treatment of the ordered porous structure adapted to increase the pore diameter of said porous structure is then carried out.
  • Such a chemical treatment is particularly suitable for partially dissolving the pore wall, from the face of said partition which faces the pore and towards the internal part of the partition.
  • the inventor has observed that the chemical composition of the layer of material constituting said partition varies along the radial axis of the pores.
  • the chemical composition of the face of the layer of material constituting the partition, which is opposite the pore, is a mixture based on oxidized aluminum, hydroxylated and / or oxyhydroxylated, and comprising up to 20% of compounds derived from the electrolytic solution used for anodization.
  • the inner part of said partition is composed essentially of oxides, hydroxides and / or aluminum oxy-hydroxides.
  • the invention also relates to a method of manufacturing a porous structure characterized in combination by all or some of the characteristics mentioned above or below.
  • the figure 1a represents a piece 1 of aluminum or aluminum alloy serving as substrate for the treatment 24 by anodization and to obtain an ordered porous structure 7 according to the invention.
  • This piece 1 of aluminum has at least one face, called the outer face 2, subjected to a set of physical or chemical treatments of the part 1 as indicated below.
  • the aluminum substrate used may for example be made of aluminum alloy of the 1XXX series, for example alloy 1050A, or refined aluminum type 4N (99.99% pure) or type 5N (99.999% pure).
  • Pretreatment 18 of the piece 1 is carried out in order to prepare it for its anodization 24.
  • This pretreatment 18 has the objective of promoting the obtaining of an ordered porous structure thickness. It allows on the one hand to increase the wettability of the piece 1 in aqueous solution, and on the other hand to reduce or eliminate pre-existing defects on the surface of the part 1.
  • the pretreatment 18 contributes to the establishment of a contact a regular between the piece 1 and the anodizing solution 24.
  • This pretreatment 18 of the part 1 comprises a succession of four treatments 19, 20, 21, 22.
  • the first treatment 19 is a degreasing of the part 1 by means of organic or aqueous chemical solvents. This first treatment can be carried out by dipping the part 1 in a hydroalcoholic solution which makes it possible to dissolve and then rinse off the dirt, grease, oils or lubricants originating from the previous methods of shaping said part 1, for example rolling. Piece 1 is then rinsed with distilled water.
  • the second treatment 20 is a mechanical polishing to reduce the roughness of the surface of the workpiece 1 and thus to obtain a smooth substrate.
  • the inventor has shown that it is, on the contrary, preferable to perform anodizing from an outer surface as smooth and even as possible. Indeed, structural defects of the substrate, which are known to be irregularly distributed on the outer face 2 of the substrate, are at the origin of the formation of irregular pores, and the growth of imperfectly ordered porous structures.
  • abrasive discs of finer and finer, rotating or vibrating nature are used, followed by pieces of fabric. particularly of felt, impregnated with abrasive suspensions.
  • a sheet impregnated with a suspension of diamond powder, the average diamond grain size of which is of the order of 1 ⁇ m makes it possible to obtain a finish suitable for carrying out the process according to the invention.
  • the piece 1 is rinsed with distilled water.
  • the third treatment 21 consists of a heat treatment of the part 1 to release the internal stresses and to increase the size of the aluminum grains.
  • this thermal treatment is preferably carried out under a non-oxidizing atmosphere, typically in a neutral or even reducing atmosphere, namely under an inert gas atmosphere, typically under a nitrogen atmosphere or under partial vacuum.
  • the part 1 is heated, in an oven, at a temperature between 350 ° C and 600 ° C, preferably at 450 ° C.
  • the heat treatment lasts between 0.1 h and 8 h, in particular between 0.5 h and 5 h, preferably for 1 h at an effective temperature of 450 ° C under a nitrogen atmosphere.
  • the fourth treatment is an electropolishing 22 of the piece 1. It aims to improve the surface condition of the outer face 2 of the part 1 which, as indicated above, must be as smooth as possible.
  • the piece 1 is subjected, for a period of between 1 min and 1 h, to electrolysis at a voltage of between 25 V and 26 V in a cell containing a controlled bath at a temperature of between 20 ° C. and 30 ° C.
  • Said bath may be an alkaline bath or an acid bath.
  • This is, for example, a Jacquet bath.
  • the Jacquet bath consists of the 33% by volume mixture of perchloric acid and 66% by volume of glacial acetic acid, the piece 1 constituting the anode of the electrolysis.
  • an electropolishing 22 according to the invention is obtained by treating, for 2 min, the part 1, by electrolysis under 25 V, in a Jacquet bath thermoregulated at 20 ° C. Piece 1 is then rinsed with distilled water and subjected, immediately after rinsing, to treatment 24 by anodization.
  • a part 1 is obtained whose external face 2 has a low and regular arithmetic roughness, in particular of arithmetic roughness of less than 5 nm.
  • This piece 1 is used to prepare a porous structure 7 ordered by a treatment 23 comprising anodization 24 followed by an abrasion 25.
  • the piece 1 is subjected to a single anodization 24, in which the piece 1 constitutes the anode.
  • single anodization 24 is meant a treatment comprising either a single anodizing step or successive anodizing steps, without intermediate chemical or electrochemical treatment step of the porous structure.
  • the anodizing conditions are preferably of the "hard anodising" type as described, for example, in the publication Lee W., Ji, R., Gösele, U. and Nielsch K., (2006), Nature Mat., 5; 9, 741-747 "Fast manufacture of long-range controlled porous alumina membranes by hard anodization" .
  • the oxidation rate of the aluminum is advantageously greater than the dissolution rate, by the electrolyte, of the alumina formed.
  • Anodization 24 leads to the formation of an anode structure comprising a layer 3 of outer surface, supported by a layer 4 of residual aluminum.
  • the anodization 24 may be carried out in an electrolyte chosen from sulfuric acid, the mixture of sulfuric acid and boric acid, oxalic acid, phosphoric acid, malonic acid, tartaric acid or citric acid.
  • the use as electrolyte of a mixture of sulfuric acid and boric acid provides a structural thickness of up to 300 microns. Such anodic structure thickness, however, does not have an ordered porous structure over its entire thickness.
  • an aqueous solution of phosphoric acid with a mass concentration of between 1% and 8%, preferably 8%, is employed in a cell whose temperature is regulated between -2 ° C and +2 ° C, preferably at -1.5 ° C.
  • the solution is homogenized, continuously, by stirring.
  • the voltage applied to the aluminum piece 1 is typically between 125 V and 195 V.
  • the anodizing treatment 24 is carried out for a sufficient time so that the outer surface layer 3 has a sufficient thickness and the outer surface layer 3 has, over a part of its thickness, an ordered porous structure thickness.
  • anodizing time for example, a layer 3 of outer surface 130 ⁇ m thick for an anodizing time of 4 hours.
  • the anodic structure is schematized on the figure 1b .
  • the figure 1b is only schematic and illustrative, and the scales are not respected. It comprises a layer 4 of residual aluminum, unoxidized, supporting a layer 3 of outer surface.
  • the outer surface layer 3 consists of a barrier layer, non-porous, also called a compact layer, defining on its inner face 6 the interface between the residual aluminum layer 4 and the outer surface layer 3 and on its outer face, the non-emergent end of the pores 8.
  • the outer surface layer 3 comprises on its outer face an unordered porous layer 11 extending from the outer face of the outer surface layer 3 to the ordered / unordered interface 14 with the ordered porous structure 7.
  • the ordered porous structure 7 has a regular juxtaposition of pores 8 empty of material, in the form of linear tubular channels, of constant diameter, extending axially in a main direction, corresponding to the direction of anodization, orthogonal to the outer face 2 of the anodic structure, and partitions 9, separating the pores 8.
  • the partitions 9 have, in addition, a constant thickness over the entire thickness of the porous structure.
  • the average distance joining the centers of two adjacent pores varies from 50 nm to 600 nm and the mean diameter of said pores varies from 10 nm to 500 nm.
  • the unordered porous layer 11 is formed by an irregular juxtaposition of empty pores of material, shapes, orientations, and variable dimensions, separated by partitions, also of varying shapes, orientations and dimensions of thickness on the wall. set of the unordered porous layer 11.
  • unordered porous layer 11 superimposed on the ordered porous structure 7 obscures and partially obstructs the outer surface of said ordered porous structure.
  • the unordered porous layer 11 is then removed from the anode structure so as to reveal at least one ordered porous structure thickness.
  • the unordered porous layer 11 is removed by removal of material, in particular by at least one mechanical abrasion treatment.
  • a solid tool 12 is applied to the outer face of the outer surface layer 3, such as a discoidal, rigid, plane rotary device, and on the surface of which a piece 13 of fabric is fixed. , in particular felt, previously impregnated with an abrasive suspension.
  • the abrasive suspension consists of an aqueous dispersion of particles, insoluble in water, characterized by their hardness as well as by their size.
  • the solid particles of the abrasive suspensions are selected from the group consisting of solid and abrasive materials, for example diamond and ceramics, especially corundum.
  • a first portion of the unordered porous layer 11 is removed by abrasion from the outer face of the outer surface layer 3 for a few minutes, for example 10 minutes, with an abrasive suspension formed of a suspension of diamond, the average diameter of said particles being close to 1 ⁇ m.
  • the surface of the porous layer is rinsed with distilled water.
  • a second portion of the unordered porous layer 11 is removed by fine abrasion from the outer face of the anode structure for a few minutes, for example 10 minutes, with an abrasive suspension formed of an aqueous suspension of diamond particles, the average diameter of said particles being close to 0.25 microns.
  • the part 15, resulting from the abrasion 25 of the outer face of the outer surface layer 3, by elimination of the unordered porous layer 11, is shown schematically on the figure 1c .
  • This part 15 comprises an anodized layer 36, supported on a layer 4 of residual aluminum, said layer 36 having a through porosity, but non-emerging because of the presence of a barrier layer and the aluminum layer 4.
  • Removal of the unordered porous layer 11 by surface mechanical abrasion allows the radial distribution of the pores 8 to be retained intact at the outer surface 16 of the ordered porous structure 7.
  • the removal of the unordered porous layer 11 by mechanical surface abrasion makes it possible to keep the value of the pore diameter 8 unchanged at a value equal to that which it had at the end of the anodizing. .
  • Exhibit 15 schematized on the figure 1c has on its outer surface 16 a uniform distribution of tubular pores 8 of circular cross section, organized in a hexagonal network, that is to say in a configuration of "honeycomb".
  • the pores 8 have a circular cross section and have, for example, a diameter of the order of 250 nm.
  • this part 15 can be used without further modification, with the barrier layer and the residual aluminum layer 4. In other applications, this part is subjected to at least one of the subsequent treatments 26, 30 for adjusting the functional properties of the part 15.
  • the residual aluminum layer 4 is removed by electrochemical separation of the anodized layer 36 and the residual aluminum layer 4.
  • This separation 31 is carried out in a stirred solution of phosphoric acid at a mass concentration of between 5% and 20%, typically 16%, and at a temperature between 25 ° C and 35 ° C, typically 30 ° C under tension. alternative of 30 volts for 30 min.
  • this treatment 30 leads simultaneously to the removal of the barrier layer and to the opening of the pores 8, in particular on the inner face of the porous structure 33.
  • the piece 34 obtained has a through-porosity and opens on both faces, outer surface 16 and inner surface 17 of the ordered porous structure 7, and is schematized on the figure 1e .
  • a treatment 32 by chemical dissolution, leading to the enlargement of the pores 8 of the ordered porous structure 7.
  • the piece 34 is immersed in a solution of phosphoric acid at a mass concentration of between 5% and 16%, typically 16%.
  • the duration of the treatment 32, and the mass concentration of phosphoric acid are chosen to increase the diameter of the pores 8, until reaching a value of diameter which is, for example, of the same order of magnitude as the distance separating the center. two pores adjacent in the ordered porous structure 7.
  • a succession of three treatments 27, 28, 29 is obtained from the part obtained at the end of the mechanical abrasion 25 by selective dissolution of the constituents of the part 15: a first treatment 27 for controlled opening of the pores 8, a second treatment 28 for the chemical / redox dissolution of the residual aluminum layer 4, then a third treatment 29 for the chemical dissolution of the barrier layer.
  • the first treatment 27 consists of a partial chemical dissolution of the partitions 9 and makes it possible to increase the diameter of the pores 8 to a value which depends on the reaction time and the mass concentration of the acid used.
  • This first treatment 27 perfectly controls not only the diameter but also the geometry of the transverse cross section of the pores 8, from a circular section to a hexagonal section.
  • This first treatment 27 also makes it possible to modify the diameter of the pores 8, without however affecting the barrier layer or the residual aluminum layer 4.
  • This first treatment 27 is carried out by immersing the part 15 in a solution of phosphoric acid at a mass concentration of between 5 and 16%, at a controlled temperature, especially between 25 and 35 ° C. Typically, the concentration of the phosphoric acid solution is 16% and the temperature is 30 ° C.
  • the duration of the treatment varies according to the desired surface geometry 16 of the anodized layer 36.
  • a treatment time of 65 min results in an ordered porous structure 7 in which the pores 8 are hexagonally ordered and have a hexagonal cross section, a diameter of the order of 400 nm, in a "wasp nest" configuration.
  • Intermediate processing times lead to intermediate configurations between the "honeycomb” configuration and the "nest of wasps" configuration, in which the pore diameter varies between 250 nm and 400 nm.
  • the second treatment 28 by chemical dissolution or redox of the aluminum layer 4 makes it possible to specifically eliminate the layer 4 residual aluminum.
  • the part 15 is immersed in an oxidizing solution at room temperature.
  • This oxidizing solution may be a mixture of CuCl or else CuCl 2 at a concentration of 0.1 mol / L and hydrochloric acid at a mass concentration of 18%. This immersion simultaneously causes the oxidation of metallic aluminum and the reduction of copper cations.
  • Other redox couples having a large difference in redox potential with the Al 3+ / Al pair may advantageously be used, in particular the Hg 2+ / Hg pair.
  • amalgam is made of a liquid metal at room temperature, in particular gallium or mercury, with the aluminum of the residual aluminum layer 4. Extraction of the amalgam thus makes it possible to eliminate the aluminum from the support.
  • This second treatment 28 leads to a piece 33 having a through porosity, without aluminum substrate, but not open due to the presence of the barrier layer.
  • the third treatment 29 consists of the chemical dissolution of the barrier layer by immersion of the piece 33 in a solution of phosphoric acid at a mass concentration of between 5% and 20%, for example of the order of 16%, the temperature of said solution being regulated between 25 ° C and 35 ° C, especially at 30 ° C.
  • the piece 34 whose hardness is low, in particular of the order of 150 Hv, is then heat treated in order to increase its hardness, in particular up to a value of 2000 Hv.
  • a piece 1 of refined aluminum of 4N quality, of disc shape, 10 -2 m in diameter, and 10 -3 m thick, is subjected to mechanical polishing, by means of a polisher, and abrasive discs and a fabric impregnated with a suspension of diamond particles whose average size decreases to 1 ⁇ m.
  • the total duration of abrasion is approximately 20 minutes to 30 minutes.
  • the aluminum piece 1 is then rinsed with distilled water and placed in an oven, under a nitrogen atmosphere, at 450 ° C. for 2 hours.
  • the piece 1 of aluminum is subjected to a treatment 22 by electropolishing in a Jacquet bath, whose volume composition is 33% perchloric acid and 66% glacial acetic acid, regulated at 20 ° C. for 2 minutes under a voltage of 25 V.
  • the piece 1 of aluminum is placed in an anodizing tank containing an aqueous bath of 8% phosphoric acid (mass), homogenized by rotary stirring at a speed of 37 rad / s and regulated at a temperature of -1.5 ° C.
  • the voltage is fixed at 180 V and the duration of the anodization is 4 h.
  • FIG. figure 5 The analysis, by field-effect electron microscopy, of the outer face 2 of the outer surface layer 3 obtained after anodizing 24 and before polishing 25 is represented on FIG. figure 5 .
  • This image shows a plurality of pores, irregularly distributed over the entire surface, and of heterogeneous cross section in size and shape. It is noted, moreover, that a minority of these pores has an open porosity.
  • a piece 1 of aluminum is prepared as described in Example 1, and subjected to anodization at a voltage of 185 V for 4 h.
  • the outer surface of the anode structure is removed by abrasion 25 by means of a piece of felt impregnated with a suspension of diamond particles having an average diameter of 1 ⁇ m for 10 minutes. then by means of a piece of felt impregnated with a suspension of diamond particles whose average diameter is 0.25 microns, for another 10 min.
  • the aluminum part 1 supporting the porous structure is then treated with a solution of phosphoric acid at a mass concentration of 16%, regulated at a temperature of 30 ° C., homogenized by stirring. rotational at a speed of 37 rad / s, for 1 h.
  • the aluminum part 1 supporting the porous structure is treated with a solution of CuCl and HCl at a temperature of 20 ° C. until the residual aluminum thickness is completely dissolved.
  • FIG. figure 3 The electron field-effect microscopy analysis of the longitudinal section of the ordered porous structure 7 obtained is shown in FIG. figure 3 .
  • FIG. figure 3 There is a juxtaposition of sections of linear tubes, elongated in the direction of growth of the porous structure, whose average width is 360 nm.
  • a piece 1 of aluminum is prepared as described in Example 1, then anodized at a voltage of 185 V for 4 h and finally subjected to mechanical abrasion as described in Example 2.
  • the ordered porous structure is immersed in a solution of CuCl and HCl, regulated at a temperature of 20 ° C, until complete dissolution of the residual aluminum thickness. There is obtained a piece 33, without layer 4 of residual metallic aluminum, with through porosity and non-emerging with a barrier layer.
  • FIG. figure 4 The electron field effect microscopy analysis of the surface of the barrier layer of the workpiece 33 is shown in FIG. figure 4 .
  • FIG. figure 4 There is a juxtaposition of hexagonal hexagonal hexagonal non-emergent hexagons, regularly ordered in a centered hexagonal arrangement, whose average diameter of the circle describing this hexagon is 460 nm.
  • FIG. figure 6 the analysis, by field-effect electron microscopy, of the polished outer face 2 of the part 33 is represented on FIG. figure 6 .
  • a piece 1 of aluminum is prepared as described in Example 1, then is anodized at a voltage of 180 V for 4 hours and finally subjected to mechanical abrasion as described in Example 2.
  • the porous structure is treated by electrochemistry at a voltage of 30 V / 50 Hz in a solution of phosphoric acid at a mass concentration of 16%, regulated at a temperature of 30 ° C., homogenized by stirring. rotating at a speed of 37 rad / s, for 45 min.
  • a piece 33, without layer 4 of residual aluminum, porosity through, open, without barrier layer, and the diameter of the pores 8 has been enlarged.
  • FIG. figure 7 The electron field effect microscopy analysis of the outer surface of the ordered porous structure 7 thus obtained is shown on FIG. figure 7 .
  • a piece 1 of aluminum is prepared as described in Example 1, then anodized at a voltage of 210 V for 15 h and finally subjected to mechanical abrasion as described in Example 2.
  • the structure is electrochemically treated, as described in Example 4, at 35 V / 50 Hz for 65 min. There is obtained a piece 33, without layer 4 of metallic aluminum, with porosity through, without barrier layer, and opening on both sides of the ordered porous structure 7.
  • FIG. figure 8 The electron field effect microscopy analysis of the outer surface of the ordered porous structure 7 thus obtained is shown on FIG. figure 8 .
  • pores 8 of hexagonal section regularly ordered in a centered hexagonal arrangement of the "wasp nest" type, and whose average pore diameter is 240 nm.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing Of Magnetic Record Carriers (AREA)
  • Porous Artificial Stone Or Porous Ceramic Products (AREA)
  • Finish Polishing, Edge Sharpening, And Grinding By Specific Grinding Devices (AREA)
  • Chemical Vapour Deposition (AREA)
  • Compounds Of Alkaline-Earth Elements, Aluminum Or Rare-Earth Metals (AREA)
  • ing And Chemical Polishing (AREA)

Claims (16)

  1. Verfahren zur Herstellung einer porösen Struktur (15, 33, 34), bei dem durch Eloxieren (24) ein Aluminiumsubstrat (1) produziert wird, wobei eine äußere Oberflächenschicht (3) eine poröse Struktur (7) umfasst, dadurch gekennzeichnet, dass:
    - eine Eloxierbehandlung (24) auf einem glatten Aluminiumsubstrat (1) mit einer ausreichenden Dauer durchgeführt wird, um den Erhalt wenigstens einer geordneten, porösen Strukturdicke (7) zu ermöglichen,
    - anschließend per mechanischer Bearbeitung ein Teil der Dicke der genannten Schicht (3) entfernt wird, die durch Eloxieren (24) gebildet wurde, wobei sich dieser Dickenteil ab der äußeren Oberfläche der genannten Schicht (3) erstreckt, die per Eloxieren (24) gebildet wird, indem wenigstens eine Dicke mit einer geordneten porösen Struktur ungleich Null (7) und derart beibehalten wird, dass diese geordnete poröse Struktur (7) die freie äußere Oberfläche (16) der restlichen Schicht bildet.
  2. Verfahren gemäß Anspruch 1, dadurch gekennzeichnet, dass der genannte Dickenteil per mechanischem Abrief (25) entfernt wird.
  3. Verfahren gemäß Anspruch 2, dadurch gekennzeichnet, dass der mechanische Abrieb (25) mittels eines Stücks (13) Stoff realisiert wird, dass mit einer Suspension imprägniert ist, bezeichnet als abrasive Suspension, einem Pulver in einer wässerigen Phase, wobei das genannte Pulver wenigstens ein Mineral umfasst, das aus der Gruppe der abrasiven Mineralien ausgewählt ist.
  4. Verfahren gemäß Anspruch 2 bis 3, dadurch gekennzeichnet, dass der mechanische Abrieb (25) durch eine Vielzahl von sukzessiven Abriebstufen realisiert wird, wobei jede der genannten sukzessiven Abriebstufen mittels einer abrasiven Suspension realisiert wird, wobei die abrasiven Suspensionen jeder sukzessiven Stufe derart ausgewählt werden, dass sie eine von einer Stufe zur anderen absteigende Granulometrie aufweisen,
  5. Verfahren gemäß Anspruch 4, dadurch gekennzeichnet, dass jede Abriebstufe der Vielzahl von sukzessiven Abriebstufen mittels eines Stücks Stoff realisiert wird, das mit einer abrasiven Suspension imprägniert wird, wobei das genannte Stück Stoff auf der Oberfläche eines steifen Trägers angewendet wird, der aus der Gruppe ausgewählt ist, die aus einem vibrierenden Träger und einem rotierenden Träger ausgewählt ist.
  6. Verfahren gemäß Anspruch 2 bis 5, dadurch gekennzeichnet, dass der mechanische Abrieb (25) durch eine erste Abriebstufe mittels eines Stücks Wollfilz realisiert wird, das mit einer Diamantsuspension imprägniert ist, deren durchschnittliche Granulometrie zwischen 0,8 µm und 1,5 µm, insbesondere in der Größenordnung von 1 µm inbegriffen ist, dann durch eine zweite Abriebstufe mittels eines Stücks Wollfilz, das mit einer Diamantsuspension imprägniert ist, deren durchschnittliche Granulometrie zwischen 0,2 µm und 0,4 µm, insbesondere in der Größenordnung von 0,25 µm inbegriffen ist.
  7. Verfahren gemäß Anspruch 1 bis 6, dadurch gekennzeichnet, dass ein Teil der Dicke der äußeren Oberflächenschicht (3) entfernt wird, wobei die Dicke des genannten Teils der Dicke der äußeren Oberflächenschicht (3) zwischen 15 µm und 25 µm, insbesondere in der Größenordnung von 17 µm bis 20 µm, inbegriffen ist.
  8. Verfahren gemäß Anspruch 1 bis 7, dadurch gekennzeichnet, dass eine Eloxierbehandlung (24) au einem glatten Aluminiumsubstrat (1) mit einer geeigneten Dauer realisiert wird, um eine äußere Oberflächenschicht (3) mit einer Dicke zu erreichen, die zwischen 25 µm und 300 µm, insbesondere zwischen 100 µm und 200 µm inbegriffen ist.
  9. Verfahren gemäß Anspruch 1 bis 8, dadurch gekennzeichnet, dass eine einzige Eloxierbehandlung (24) auf einem glatten Aluminiumsubstrat (1) realisiert wird, wobei die genannte Behandlung eine Dauer hat, die zwischen 1 Std. und 12 Std., insbesondere in der Größenordnung von 4 Std., inbegriffen ist.
  10. Verfahren gemäß Anspruch 1 bis 9, dadurch gekennzeichnet, dass eine einzige Oberflächenbehandlung (24) auf einem glatten Aluminiumsubstrat (1) während einer geeigneten Dauer realisiert wird, damit die Dicke der geordneten porösen Struktur (7), die per Eloxieren (24) gebildet wird, zwischen 1 µm und 150 µm inbegriffen ist.
  11. Verfahren gemäß Anspruch 1 bis 10, dadurch gekennzeichnet, dass das Eloxieren (24) in einer wässerigen Elektrolytlösung realisiert wird, die aus einer Gruppe ausgewählt ist, die aus wässerigen Lösungen aus oxidierenden Säuren gebildet wird, insbesondere Schwefelsäure, der Mischung aus Schwefelsäure und Borsäure, Xylylsäure, Phosphorsäure, Malonsäure, Weinsäure und Zitronensäure.
  12. Verfahren gemäß Anspruch 1 bis 11, dadurch gekennzeichnet, dass das Eloxieren (24) in einer wässerigen Elektrolytlösung realisiert wird, deren Zusammensetzung geeignet ist, um eine geordnete, poröse Struktur zu liefern, deren Poren einen Durchmesser aufweisen, der zwischen 10 nm und 500 nm, insbesondere zwischen 100 nm und 200 nm inbegriffen ist.
  13. Verfahren gemäß Anspruch 1 bis 12, dadurch gekennzeichnet, dass das Eloxieren (24) bei einer Temperatur realisiert wird, die zwischen -2°C und +2°C - insbesondere in der Größenordnung von -1,5°C - inbegriffen ist.
  14. Verfahren gemäß Anspruch 1 bis 13, dadurch gekennzeichnet, dass das Eloxieren (24) unter einer Spannung realisiert wird, die zwischen 19 V und 240 V - insbesondere zwischen 125 V und 195 V - mit einer wässerigen Lösung realisiert wird, die als Elektrolyt Phosphorsäure umfasst.
  15. Verfahren gemäß Anspruch 1 bis 14, dadurch gekennzeichnet, dass unmittelbar nach dem Entfernen des genannten Dickenteils das nicht oxidierte Aluminiumsubstrat (4) und ein nicht poröser Dickenteil (5) der genannten Schicht entfernt werden, um nur die geordnete poröse Struktur (7) zu behalten.
  16. Verfahren gemäß Anspruch 1 bis 15, dadurch gekennzeichnet, dass anschließend eines chemische Behandlung der geordneten porösen Struktur (7) realisiert wird, die geeignet ist, um den Durchmesser der Poren der genannten porösen Struktur (7) zu erhöhen.
EP08844577A 2007-10-26 2008-10-23 Verfahren zur herstellung einer geordneten porösen struktur aus einem aluminiumsubstrat Not-in-force EP2207915B1 (de)

Applications Claiming Priority (2)

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FR0707540A FR2922899B1 (fr) 2007-10-26 2007-10-26 Procede de fabrication d'une structure poreuse ordonnee a partir d'un substrat d'aluminium
PCT/FR2008/051921 WO2009056744A2 (fr) 2007-10-26 2008-10-23 Procédé de fabrication d'une structure poreuse ordonnée à partir d'un substrat d'aluminium

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Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
NL2003250C2 (en) * 2009-07-20 2011-01-24 Metal Membranes Com B V Method for producing a membrane and such membrane.
EP2433659A3 (de) * 2010-08-13 2014-09-03 Biotronik AG Implantat und Verfahren zur Herstellung desselben
TWI442014B (zh) * 2010-11-24 2014-06-21 Ind Tech Res Inst 散熱元件及散熱元件的處理方法
KR101701314B1 (ko) * 2015-07-02 2017-02-02 고려대학교 산학협력단 양극산화된 금속산화물 나노다공성 템플레이트 제작방법
KR102443973B1 (ko) * 2017-12-11 2022-09-16 (주)코미코 내부식성 및 절연특성이 우수한 양극산화된 알루미늄 또는 알루미늄 합금 부재의 제조방법 및 표면처리된 반도체 장치
JP6584604B1 (ja) * 2018-07-31 2019-10-02 株式会社Uacj アルミニウム部材及びその製造方法
US11230786B2 (en) * 2019-06-17 2022-01-25 Nanopec, Inc. Nano-porous anodic aluminum oxide membrane for healthcare and biotechnology
US20220355265A1 (en) * 2021-05-04 2022-11-10 Nanopec, Inc. Controlled pore ceramics chips for high throughput solid state oligonucleotide synthesis
CN114369402B (zh) * 2021-12-18 2022-10-11 佛山市顺德区固得丽涂料有限公司 一种铝合金涂层材料

Family Cites Families (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4225399A (en) * 1979-04-25 1980-09-30 Setsuo Tomita High speed aluminum anodizing
JPS5671821A (en) * 1979-11-14 1981-06-15 Hitachi Ltd Substrate for magnetic disc and its manufacture
GB2142043B (en) * 1983-06-10 1986-12-10 Nippon Light Metal Co Magnetic recording media
JPS60177198A (ja) * 1984-02-22 1985-09-11 Nippon Sheet Glass Co Ltd 薄膜状Ａｌ↓２Ｏ↓３多孔質体の製造方法
JPS60231921A (ja) * 1984-05-01 1985-11-18 Kobe Steel Ltd 磁気デイスク用基盤の表面処理方法
JPS61101946A (ja) * 1984-10-23 1986-05-20 Kao Corp メツシユの製造方法
JPS62149029A (ja) * 1985-09-04 1987-07-03 Furukawa Alum Co Ltd アルマイト磁気デイスク基板とその製造方法
JPS63166993A (ja) * 1986-12-27 1988-07-11 Nippon Light Metal Co Ltd 磁気デイスク用基板の製造方法
JP2645022B2 (ja) * 1987-08-21 1997-08-25 株式会社東芝 加入者回路
US5240590A (en) * 1989-07-19 1993-08-31 Seagate Technology, Inc. Process for forming a bearing surface for aluminum alloy
US5691256A (en) * 1995-12-28 1997-11-25 Yamamura Glass Co., Ltd. Glass composition for magnetic disk substrates and magnetic disk substrate
JP3559920B2 (ja) * 1996-07-29 2004-09-02 東京エレクトロン株式会社 プラズマ処理装置
US6359288B1 (en) * 1997-04-24 2002-03-19 Massachusetts Institute Of Technology Nanowire arrays
US6804081B2 (en) * 2001-05-11 2004-10-12 Canon Kabushiki Kaisha Structure having pores and its manufacturing method
US6709929B2 (en) * 2001-06-25 2004-03-23 North Carolina State University Methods of forming nano-scale electronic and optoelectronic devices using non-photolithographically defined nano-channel templates
US20050159087A1 (en) * 2002-10-31 2005-07-21 Hans-Joachim Bartz Method for the creation of highly lustrous surfaceson aluminum workpieces
US20040221959A1 (en) * 2003-05-09 2004-11-11 Applied Materials, Inc. Anodized substrate support
JP4603402B2 (ja) * 2005-03-31 2010-12-22 富士フイルム株式会社 微細構造体およびその製造方法
US20060234396A1 (en) * 2005-04-18 2006-10-19 Fuji Photo Film Co., Ltd. Method for producing structure
JP4813925B2 (ja) * 2006-02-28 2011-11-09 富士フイルム株式会社 微細構造体の製造方法および微細構造体
JP4768478B2 (ja) * 2006-03-17 2011-09-07 富士フイルム株式会社 微細構造体の製造方法および微細構造体
US7811180B2 (en) * 2006-09-25 2010-10-12 Cobra Golf, Inc. Multi-metal golf clubs

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FR2922899B1 (fr) 2010-11-26
JP2011500969A (ja) 2011-01-06
US20100258445A1 (en) 2010-10-14
EP2207915A2 (de) 2010-07-21
ATE522640T1 (de) 2011-09-15
FR2922899A1 (fr) 2009-05-01
JP5199376B2 (ja) 2013-05-15
ES2372790T3 (es) 2012-01-26
WO2009056744A3 (fr) 2009-07-30
WO2009056744A2 (fr) 2009-05-07

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