EP2824219A1 - Syntheseverfahren eines Metallschaums, Metallschaum, seine Anwendungen und Vorrichtung, die einen solchen Metallschaum umfasst - Google Patents

Syntheseverfahren eines Metallschaums, Metallschaum, seine Anwendungen und Vorrichtung, die einen solchen Metallschaum umfasst Download PDF

Info

Publication number
EP2824219A1
EP2824219A1 EP14176382.1A EP14176382A EP2824219A1 EP 2824219 A1 EP2824219 A1 EP 2824219A1 EP 14176382 A EP14176382 A EP 14176382A EP 2824219 A1 EP2824219 A1 EP 2824219A1
Authority
EP
European Patent Office
Prior art keywords
metal
cathode
electrolyte
electrolytic
electrolytic solution
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP14176382.1A
Other languages
English (en)
French (fr)
Other versions
EP2824219B1 (de
Inventor
Ronan Botrel
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Original Assignee
Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Commissariat a lEnergie Atomique et aux Energies Alternatives CEA filed Critical Commissariat a lEnergie Atomique et aux Energies Alternatives CEA
Publication of EP2824219A1 publication Critical patent/EP2824219A1/de
Application granted granted Critical
Publication of EP2824219B1 publication Critical patent/EP2824219B1/de
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • 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
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D3/00—Electroplating: Baths therefor
    • C25D3/02—Electroplating: Baths therefor from solutions
    • C25D3/38—Electroplating: Baths therefor from solutions of copper
    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
    • C25D7/00—Electroplating characterised by the article coated
    • C25D7/005—Jewels; Clockworks; Coins

Definitions

  • micrometric structure is understood to mean a structure whose constituent elements, namely the strands, have a dimension, or length, between 0.1 ⁇ m and 100 ⁇ m, or even between 0.01 ⁇ m. and 100 ⁇ m.
  • the invention also relates to a porous metal foam and whose strands have a dimension, or length, included in these same intervals, this metal foam being capable of being obtained by this method of synthesis.
  • the invention also relates to the use of such a metal foam, especially in the field of catalysis and electronics.
  • the invention relates to a device comprising such a metal foam, such a device may in particular be constituted by a microelectrode or a micro-sensor.
  • low density metal foam means a metal foam whose bulk density is less than or equal to 10% of the theoretical density of the corresponding metal.
  • Such metal foams consist of metallic materials which have a micrometric, even nanometric, three-dimensional and porous structure. It is specified that by the expression “nanometric structure” or by the term “nanostructure” is meant a structure whose constituent elements, namely the strands, have a dimension, or length, of between 1 nm and 100 ⁇ m. nm.
  • these metal foams Because of their micrometric structure, these metal foams have a large specific surface area, which gives them many advantages, among them that of offering a very fast electrochemical response capacity. It is thus possible to envisage using these metal foams to manufacture gas micro-sensors as well as microelectrodes, such microelectrodes being particularly suitable for use in the electronics industry.
  • the electrolytic reduction of the water produces, on the surface of the cathode, a gas evolution formed of a multitude of hydrogen bubbles which will serve as a matrix for the formation of the interstices or pores of the metal foam.
  • the deposition of the reduced metal M in the form of a metal foam is thus observed on the surface of the cathode. Indeed, this deposit has a porous structure, the formation of pores being provided by the hydrogen bubbles resulting from the reduction of the water present in the electrolyte.
  • the pores of the metal foam as obtained by this electrolytic reduction method with a high current density, do not They do not have a uniform and regular size, this size increasing in particular with the thickness of the metal foam due to a phenomenon of coalescence of the evolved hydrogen bubbles.
  • this metal foam deposited on the surface of the cathode is limited to a few hundred micrometers, also because of this phenomenon of coalescence of the evolved hydrogen bubbles. It can be seen, moreover, that this metal foam is very fragile and that it can not be manipulated and even less shaped.
  • Electrolysis by glow discharge contact is a process that has been experiencing a renewed interest in several fields of research in recent years.
  • nanoparticles are described as being able to reach particle sizes ranging from a few tens of nanometers to a few nanometers.
  • nanoparticles of nickel having a particle size of between a few nanometers and about 50 nm have been synthesized as well as copper nanoparticles having a particle size of between 5 nm and about 30 nm.
  • the publication [3] does not describe the synthesis of nanomaterials and even less metal foams. Indeed, to control the size of the nanoparticles and avoid the formation of a metal deposit at the cathode, this publication [3] teaches the use of a rotating disc electrode to ensure the production of a colloidal solution. of nanoparticles.
  • an observation of the cathode surface by means of a scanning electron microscope shows the presence of relatively dispersed nanospheres having a size of a few hundred nanometers.
  • the publication [1] proposes the implementation of the method of electrolysis by glow discharge contact for the synthesis, not of colloidal metal nanoparticles, but of porous metal nanomaterials. More specifically, the publication [1] describes the synthesis of a composite material comprising the deposition of a nanoporous platinum foam, by such a method conducted at room temperature, on a nickel foam substrate. The tests conducted in the publication [1] show that the higher the Pt 4+ platinum cation concentration in the electrolytic solution, the more the surface of the nickel foam is covered with nanoporous platinum foam and the lower the average pore diameter decreases. to reach a value of about 100 nm.
  • the object of the invention is, therefore, to overcome the drawbacks of the prior art and to propose a method for synthesizing a low density metal foam, which has a porous, even nanometric porous micrometric three-dimensional structure. structure is also regular and homogeneous throughout its thickness, unlike the foam obtained with the electrolysis process with high current density.
  • This method must also make it possible to obtain a metal foam having a certain thickness, such a thickness being advantageously at least 0.1 mm, such a metal foam being moreover sufficiently solid to allow its handling, or even a step complementary shaping, including machining, to give it a shape that is, for example, compatible with a potential use of such a metal foam.
  • this method comprises a step of electrolysis by glow discharge contact, this electrolysis consisting of an electrolytic plasma reduction conducted in an electrolytic solution in which are immersed an anode and a cathode connected to a continuous power supply, the electrolytic solution comprising at least a first electrolyte in a solvent, the first electrolyte being said at least one metal M in cationic form, the electrolyte solution further comprising gelatin.
  • the method of electrolysis by glow discharge discharge (in English, “Contact Glow Discharge Electrolysis” and abbreviated “CGDE”), also called “electrolytic plasma” electrolysis process, is a particular electrolytic process in which a plasma called “ electrolytic plasma "is located between a polarized electrode and the electrolytic solution in which the electrodes are immersed.
  • This electrolytic plasma is formed from an electrical voltage called “critical electrical voltage”, following the ionization of the gas surrounding the polarized electrode and which has itself been formed during the electrolytic reduction, or electrolytic oxidation, solvent and some of the compounds that are found to be ionized in the electrolytic solution.
  • the electrolytic plasma which is in the form of a gaseous envelope, is formed on the surface of the cathode.
  • the presence of gelatin in the electrolytic solution combined with the application of a direct current, makes it possible to maintain and contain, around the cathode, this gaseous envelope and, consequently, the electrolytic plasma.
  • the gelatin promotes the growth of the metal foam from the metal M present in cationic form, M n + , in the electrolytic solution.
  • the metal foam synthesized by the process according to the invention consists of strands, these strands being obtained by germination then growth of reduced metal ions. These strands correspond, in fact, to the imprints left by the electric micro-arcs formed during electrolysis by glow discharge contact. These electric micro-arcs ensure the reduction, by electronic transfer, of the metal cation M n + metal M when these micro-electric arcs come into contact with the electrolytic solution.
  • gelatin by keeping the gaseous envelope around the cathode, makes it possible to maintain the formation of said electric micro-arcs in the space formed by this gaseous envelope, ie in the volume between the cathode and the electrolytic solution.
  • micro-electric arcs which leave the surface of the cathode, propagate at the end of each metal strand progressively formed, thus leading to an expansion of the metal foam synthesized that continues as long as the gaseous envelope is maintained.
  • This propagation of the electric micro-arcs at the ends of the metal strands formed makes it possible to ensure a synthesis of metal foam with a particularly homogeneous density and, throughout its thickness, by preventing any densification at the core of the metal foam.
  • a metal foam which is characterized by a very low bulk density, typically less than or equal to 10%, or even less than or equal to 0.5%, and or by a specific surface area, measured according to the BET method, which is particularly high, typically greater than or equal to 250 m 2 / g.
  • bulk density means the percentage represented by the density of the metal foam considered relative to the density of the corresponding metal M.
  • relative density expresses the ratio between the density of the metal foam and the density of the same metal M.
  • the metal foam synthesized by the process according to the invention remains, moreover, perfectly handled.
  • the method according to the invention makes it possible to obtain a significant metal foam thickness, this thickness being at least equal to 0.1 mm and, preferably, greater than or equal to 0.5 mm.
  • the method according to the invention makes it possible, in fact, to reach thicknesses of metal foam up to a few centimeters.
  • the synthesis method according to the invention makes it possible to form a metal foam directly on the surface of the cathode, and not necessarily on a nickel foam substrate, as is the case with the synthesis method described in the description. publication [1]. It is thus conceivable to directly obtain a metal foam of at least one metal M, without the need to resort to a complementary step of separation from a metal foam substrate, for example a nickel foam substrate as taught by the publication [1].
  • metal foams may be formed of the same metal M or at least two different metals M 1 and M 2 .
  • continuous power supply means a power supply that delivers a direct current, that is to say a current flowing continuously and therefore not interrupted during the electrolysis process. glow discharge as opposed to alternating or pulsed current.
  • the maintenance of the electrolytic plasma also makes it possible to maintain substantially constant electrolytic reduction conditions which favor the production of a metal foam having a uniform and uniform structure throughout its thickness.
  • colloidal gold nanoparticles with a size of 10 nm were in fact synthesized by a plasma solution method, implemented under an applied electrical voltage of 2500 V and under a width of 2 ⁇ s pulse, from an electrolyte solution comprising an aqueous solution of HAuCl 4 as electrolyte and KCl and gelatin as additives.
  • the plasma solution method described in this publication [5] is not comparable with the method of electrolysis by glow discharge contact implemented in the method according to the invention.
  • the application of a high voltage of 2500 V combined with an electrolysis time of 2 ⁇ s does not allow the gaseous envelope, and therefore the electrolytic plasma, to form and especially to maintain and localized containment around the single cathode, unlike what occurs in the synthesis method of the invention wherein is implemented a direct current.
  • the process according to the invention can be carried out at room temperature. But we can also consider implementing it at other temperatures, lower or higher than this ambient temperature.
  • the method according to the invention therefore makes it possible to synthesize, in a single step and in a relatively easy manner, the metal foam formed of the metal M, from the cations of the metal M present in the electrolytic solution.
  • a second complementary collection step makes it possible to isolate the metal foam thus formed on the surface of the cathode.
  • the determination of the critical electrical voltage, noted U c , for a given electrolytic solution is done by establishing the curve of the intensity, denoted I (in A), measured as a function of the applied electrical voltage, denoted U ( in V), as detailed below, in particular in the chapters entitled “Demonstration of electrolysis process by electrolytic plasma " and " Effects of gelatin on the curve of the intensity as a function of the electrical voltage” applied ", in relation to figures 2 and 13 , respectively.
  • the applied electrical voltage is located in a range of electrical voltages in which the intensity is substantially constant as a function of this voltage.
  • the electrolytic plasma is integrally formed around the cathode.
  • the cathode is removed from the electrolytic solution before switching off the electrical voltage.
  • the method according to the invention may further comprise at least one or more complementary steps, taken alone or in combination.
  • the stirring of the electrolytic solution allows a homogeneous mixing of the ionic species present in said electrolytic solution, thus making it possible to maintain the presence of M n + metal cations in the immediate vicinity of the gaseous envelope and, consequently, the reduction of these cations in the form of of strands.
  • This agitation may in particular be carried out by means of a magnetized rod in rotation, the rotation being for example provided by a magnetic stirrer or a magnetic bar.
  • the rotation of the cathode can in particular be ensured by fixing said cathode to a rotary motor.
  • the rotation of the cathode, during the application and then the maintenance of the electrical voltage, makes it possible to form a metal foam of perfectly homogeneous and regular thickness on the surface of said cathode, but also to vary the shape as well as the apparent density, or relative density, of the metal foam.
  • the rotation of the cathode makes it possible to further reduce the apparent density of the metal foam to apparent density values which may be of the order of 0.2%, the remaining metallic foam being elsewhere, perfectly manageable.
  • the cathode can be rotated up to an angular speed of 5000 rpm, without risk of degradation of the synthesized metal foam, the latter being in a way protected by the gaseous envelope which environ.
  • the voltage value applied to the electrodes is between 10 V and 100 V, advantageously between 15 V and 50 V and, preferably, between 20 V and 30 V.
  • the voltage value applied to the electrodes is maintained for a period of between 5 s and 5 min, advantageously between 10 s and 2 min, and preferably between 20 s and 60 s .
  • the metal foam synthesis method further comprises a shaping step of the collected metal foam.
  • This shaping step may in particular be a machining of the metal foam as collected at the end of the synthesis process according to the invention.
  • this shaping step consists of electroforming.
  • the growth of the metal foam is carried out on a cathode which has a shape corresponding to the shape that is desired to give to said metal foam.
  • the electrolyte solution comprises gelatin.
  • this gelatin concentration in the electrolytic solution is less than or equal to 200 g / l, advantageously between 1 g / l and 100 g / l, preferably between 5 g / l and 50 g / l, and even more preferably, between 10 g / l and 25 g / l.
  • gelatin concentration in the electrolytic solution is meant the concentration of the gelatin in solution in the electrolytic solution and this, before the implementation of electrolysis by glow discharge contact.
  • the first electrolyte present in the electrolytic solution is a metal salt in which the metal M, in cation form, combines with at least one anion and, where appropriate, with one or several cations to form, for example, double or triple metal salts.
  • this metal salt comprises at least one element chosen from an SO 4 2- sulfate, a nitrate NO 3 - , a halide X - (such as Cl - , Br - or I - ), a cyanide CN - and an OH hydroxide - metal M.
  • the concentration of the first electrolyte in the electrolytic solution is less than or equal to the solubility of said first electrolyte in the solvent.
  • the first electrolyte is completely in solution in the electrolytic solution.
  • the concentration of this first electrolyte in solution in the electrolytic solution As previously for the gelatin concentration, by concentration of the first electrolyte in the electrolytic solution, the concentration of this first electrolyte in solution in the electrolytic solution and this, before the implementation of electrolysis by glow discharge contact.
  • this concentration of first electrolyte is between 0.1 mol / l and 2 mol / l and preferably between 0.2 mol / l and 1 mol / l.
  • the solvent of the electrolytic solution is water and, preferably, deionized water.
  • organic solvents such as alcohols, ethers, hydrocarbons, especially aromatic hydrocarbons such as benzene or toluene.
  • the electrolytic solution further comprises at least one second electrolyte.
  • This second electrolyte is chosen so that it is capable of improving the electrical conductivity of the electrolytic solution.
  • the second electrolyte is a strong electrolyte, which has the advantage of dissociating or ionizing totally or substantially totally in the solvent of the electrolytic solution.
  • This second electrolyte present in the electrolytic solution is advantageously chosen from a salt, an acid or a base.
  • salts there may be mentioned sodium chloride NaCl or potassium chloride KCl.
  • the concentration of the second electrolyte in the electrolytic solution is less than or equal to the solubility of said second electrolyte in the solvent.
  • the second electrolyte is found to be completely in solution in the electrolytic solution.
  • the second electrolyte concentration in the electrolytic solution is understood to mean the concentration of this second electrolyte in solution in the electrolytic solution and this before the electrolysis by glow discharge of contact is carried out.
  • this concentration of second electrolyte is between 0.1 mol / l and 18 mol / l and preferably between 0.5 mol / l and 10 mol / l.
  • the cathode is made of a material having a high melting temperature of at least 1500 ° C.
  • a cathode made of stainless steel, tantalum or tungsten it is possible to envisage the use of a cathode made of stainless steel, tantalum or tungsten.
  • the cathode is rotatable, in particular when electroforming shaping of the metal foam is envisaged.
  • the anode is made of an inert metal.
  • the anode seat of the oxidation reactions that occur with some of the compounds present in the electrolytic solution, does not dissolve during the electrolytic plasma electrolysis process.
  • Such anode may in particular be made of platinum.
  • the anode is made in the metal M. This is called a “soluble anode” because it is consumed during the CGDE process.
  • this electrolytic solution which also comprises already available metal cations M n + immediately available from the dissociation of the first electrolyte, is enriched in M n + metal cations, according to the following electrolytic oxidation reaction (3): M ⁇ M n + + ne - (3)
  • the metal M is obviously chosen so that it can be reduced by electrolysis in the electrolytic solution used.
  • the metal M comprises at least one element chosen from transition metals and poor metals.
  • the metal M can consist of a single metal, whether it is transition metal or poor metal, but it can also comprise two or more metals, and thus form a metal alloy.
  • transition metals such as nickel, palladium, platinum, copper, silver and gold.
  • the metal M comprises at least one element chosen from nickel, copper, silver, tin, platinum and gold.
  • copper foam For the synthesis of copper foam, it may be envisaged in particular to use copper sulphate, for example copper sulphate hydrate CuSO 4 , 5H 2 O, as the first electrolyte. It is also possible to envisage using a double metal salt such as Cu (CN) 2 K potassium cuprocyanide. For the synthesis of gold foam, it is possible to envisage using the HAuCl 4 compound, as described in the publication [ 5].
  • copper sulphate for example copper sulphate hydrate CuSO 4 , 5H 2 O
  • a double metal salt such as Cu (CN) 2 K potassium cuprocyanide.
  • gold foam it is possible to envisage using the HAuCl 4 compound, as described in the publication [ 5].
  • the process according to the invention makes it possible to obtain a copper foam with an apparent density p of less than or equal to 1 g / cm 3 , advantageously of between 0.10 g / cm 3. and 0.80 g / cm 3 and, preferably, between 0.15 g / cm 3 and 0.50 g / cm 3 .
  • the invention relates, secondly, to a metal foam of at least one metal M having a porous micrometric structure, that is to say a porous structure and whose constituent elements, in this case the strands, have a dimension, or length, between 0.1 ⁇ m and 100 ⁇ m, or even between 0.01 ⁇ m and 100 ⁇ m.
  • this metal foam is capable of being obtained by the implementation of the synthesis method which has just been defined above.
  • this metal foam is obtainable by the process comprising a contact glow discharge electrolysis step, this electrolysis consisting of an electrolytic plasma reduction carried out in an electrolytic solution in which an anode and a cathode are immersed. connected to a continuous power supply, the electrolyte solution comprising at least a first electrolyte in a solvent, the first electrolyte being said at least one metal M in cationic form, the electrolyte solution further comprising gelatin.
  • Such a metal foam according to the invention differs structurally from the nanoporous platinum deposition obtained by the method described in the publication [1]. Indeed, as indicated in the publication [1], the nanoporous platinum deposition is formed by a stack of platinum nanoparticles resulting from the reduction of Pt 4+ cations and having a particle size distribution that is uniform. This stack, moreover observable on the plates of this same publication [1], results in a nanoporous network characterized by a structure which is very clearly distinguished from the structure of the metal foam according to the invention, a structure which consists of strands.
  • the metal foam according to the invention is characterized by a very low bulk density, typically less than or equal to 10%, or even less than or equal to 0.5%, and / or a specific surface, measured according to the BET method, particularly high, typically greater than or equal to 250 m 2 / g.
  • the invention relates, thirdly, to the use of the metal foam of at least one metal M having a porous micrometric structure as defined above.
  • this metal foam is advantageously used in the field of catalysis, jewelery, absorbents, batteries, new energies or electronics.
  • jewelery made of metal foam (for example, gold jewelery, in particular 24 carats) or to make a veneer on the jewels to increase its resistance to wear.
  • metal foam for example, gold jewelery, in particular 24 carats
  • the invention relates, fourthly, to a device comprising a metal foam of at least one metal M having a porous micrometric structure as defined above.
  • this device may in particular be a microelectrode, a micro-sensor, in particular a gas micro-sensor, a battery or a storage device, in particular a gas storage device.
  • the process for synthesizing copper foam which is detailed below is of course applicable to the synthesis of a foam of one or more metals other than copper.
  • This experimental device 10 comprises a beaker 12 with a capacity of 500 ml placed on a magnetic stirrer 14.
  • This beaker 12 comprises an electrolytic solution 16 in which two electrodes plunge, namely an anode 18 and a cathode 20.
  • the anode 18 and the cathode 20 are respectively connected to the positive and negative poles of a DC power supply 22 which makes it possible to apply an electrical voltage of up to 35 volts.
  • a coulometer (not shown) is also arranged in series between the anode 18 and the cathode 20. This coulometer makes it possible to measure the quantity of electric charges involved during electrolysis by glow discharge of contact.
  • a DCC camera (not shown), which comprises a charge-coupled device (CCD) and which is equipped with an objective arranged inside the beaker 12, makes it possible to visualize in FIG. real time the formation of the metal foam on the cathode 20.
  • CCD charge-coupled device
  • the anode 18 is formed by a copper strip 10 cm long, 5 cm wide and 0.2 mm thick, while the cathode 20 is constituted by a tungsten wire whose diameter is between 0.4 and 1 mm.
  • the electrolytic solution 16 comprises at least a first electrolyte in a solvent, the first electrolyte being the metal M in cationic form M n + .
  • the electrolytic solution 16 further comprises a second electrolyte consisting of a strong electrolyte.
  • the electrolytic solution 16 also comprises gelatin, in this case gelatin (CAS 9000708), the concentration of which varies between 0 g / l (this solution then corresponds to a reference electrolytic solution) and 25 g / l.
  • Copper sulphate is the salt generating Cu 2+ copper cations which will be reduced at cathode 20, as will be seen below.
  • This copper sulphate is totally ionized in the electrolytic solution 16, thanks in particular to the presence of the second strong electrolyte, in this case sulfuric acid. The presence of this sulfuric acid thus ensures good electrical conductivity of the electrolytic solution 16 and further promotes the corrosion of the copper anode 18.
  • Stirring of the electrolytic solution 16 may, where appropriate, be provided by a magnetic bar 26 disposed inside the beaker 12.
  • the rotation of the cathode 20 may, where appropriate, be provided by means of a rotary motor 28 to which the cathode 20 is fixed.
  • electrolysis by glow discharge contact also called “electrolytic plasma” electrolysis process
  • electrolytic plasma a plasma located between a polarized electrode and the electrolytic solution wherein the electrodes are immersed.
  • This electrolytic plasma is formed from an electrical voltage called "critical electrical voltage” and denoted U c , following the ionization of the gas surrounding the polarized electrode and which has itself been formed during the reduction or the electrolytic oxidation of the solvent and some of the ionized compounds in the electrolytic solution.
  • the electrolytic plasma which is located between the cathode 20 and the electrolytic solution 16, is formed following the ionization of the hydrogen H 2 which surrounds the cathode 20, this dihydrogen being itself formed during the electrolytic reduction of the H + protons present in the electrolytic solution 16.
  • the figure 2 illustrates the curve of the intensity I in ampere (A) measured as a function of the voltage U in volt (V) applied to the cathode 20, as obtained experimentally with the device 10 described above with the electrolytic solution 16 formed by the aqueous solution of copper sulfate above, at a temperature of 25 ° C, and in the absence of gelatin, this solution corresponding to the electrolyte solution A, as will be seen later.
  • the first part of the curve, designated I corresponds to a conventional electrolysis process (in this case, a cathodic reduction), that is to say to a purely electrolytic process corresponding to Ohm's law, in which intensity increases as a function of the applied electrical voltage and up to a value of electrical voltage, called "critical electrical voltage” and noted U c , 25 V.
  • critical electrical voltage a value of electrical voltage
  • U c 25 V.
  • This reduction reaction of the copper (4) is accompanied, for the highest electrical voltages, of the water-reducing reaction (5) with evolution of hydrogen, in the form of bubbles which coalesce in the vicinity of the critical electrical voltage.
  • the intensity decreases sharply as a function of the applied electrical voltage up to a voltage value of 30 V, the value from which the intensity is stabilized.
  • This range of electrical voltages corresponds to the second part of the curve, designated II.
  • This drop in intensity as a function of the applied electrical voltage is the consequence of the formation then growth, around the cathode 20, of the gaseous envelope, also called "electrolytic plasma".
  • electrolytic plasma the gaseous envelope
  • the process of electrolysis by glow discharge of contact begins to be established.
  • the electrical conductivity of this gas envelope being lower than that of the electrolytic solution 16, the intensity drops.
  • thermocouple 20 was replaced by a metal thermocouple at the tip of which was formed the electrolytic plasma. Temperature measurements taken by the thermocouple, when applying a voltage varying from 10 V to 35 V, are plotted on the curve shown in FIG. figure 5 . It is specified that the measurements are made with an uncertainty of +/- 10 ° C.
  • the temperature measured by the thermocouple which therefore corresponds to the temperature of the surface of the cathode 20, increases suddenly from an applied voltage of 30 V.
  • This temperature corresponds to the temperature at which the gas envelope, or "electrolytic plasma” is totally formed.
  • the measured temperature reaches 180 ° C.
  • this temperature of 180 ° C is called “normal temperature” for this type of electrolytic plasma, also called “cold plasma”.
  • solutions A to E are aqueous solutions prepared with deionized water as the solvent.
  • the gelatin used bearing the registration number CAS 9000708, is introduced as a powder into the mixture. This mixture is heated, at a temperature of 60 ° C, so as to allow the complete dissolution of the gelatin in each of the electrolyte solutions B to E.
  • Table 1 Electrolytic solution AT B VS D E Copper sulphate (g / l) 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 64 Sulfuric acid (ml / l) 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 80 Gelatin (g / l) 0 1 5 10 25
  • Figures 6A to 6D schematically illustrate the successive steps of the operating protocol that has been followed to synthesize copper foams.
  • the anode 18 and cathode 20 of the experimental device 10 are immersed in the electrolytic solution 16.
  • the anode 18 is connected to the positive pole of the power supply 22 and the cathode 20 is, in turn, connected to the negative pole of this power supply 22.
  • the power supply 22 is then set to an electrical voltage of between 25 V and 35 V and then switched on, to ensure the formation and growth of the electrolytic plasma 24 ( Figure 6B ).
  • the electrolytic plasma 24 is formed and then increases around the cathode 20. Electrical micro-arcs are formed and evolve from the surface of the cathode 20 to the interface between the plasma electrolytic 24 and the electrolytic solution 16. These electric micro-arcs being composed of negative charges, Cu 2+ copper cations present in the electrolytic solution 16 are reduced at the end of each electric micro-arc, in accordance with the reduction reaction electrolytic (4) mentioned above.
  • This reduction of the Cu 2+ copper cations creates, on the surface of the cathode 20, a copper foam 30 consisting of an entanglement of a multitude of copper strands, these strands representing the "negative" of the micro-arcs formed during the electrolysis method by glow discharge contact (CGDE) or electrolytic plasma.
  • CGDE glow discharge contact
  • FIGS. Figures 6B and 6C The growth of this metal foam 30 continues as long as the electrolytic plasma 24 is maintained.
  • the cathode 20 is removed from the electrolytic solution 16 (in this case the electrolytic solution A), while remaining under the applied voltage of 25 V.
  • the electrolytic solution 16 in this case the electrolytic solution A
  • electrolytic solution 16 as shown in FIG. Figure 6D .
  • the metal foam 30 formed on the surface of the cathode 20 is completely dry. Although it is relatively fragile, this copper foam 30 nevertheless has sufficient mechanical strength that allows it to detach from the cathode 20, by pushing it with a brush.
  • FIG. 8A is a snapshot resulting from an observation with a binocular magnifying glass
  • Figure 8B is a snapshot resulting from an observation using a scanning electron microscope (SEM). It can be seen that the copper strands are very thin, with a size of the order of a micrometer, and that they have an unusual melt-like appearance of the structures that are obtained with the implementation of a conventional electrolysis process, such as that illustrated in FIG. figure 3 .
  • the metal foam obtained with the electrolytic solution A has a micrometric porous and homogeneous structure throughout its thickness.
  • the metal foam synthesized with the electrolytic solution A has a general shape which is systematically irregular.
  • metal foams synthesized from electrolytic solutions B to E have, for their part, not only these same characteristics of micrometric porous structure and homogeneous throughout their thickness, but also a particularly regular overall shape.
  • Figures 10A and 10B correspond to copper foil plates such as obtained on the surface of a cathode after the implementation of an electrolytic plasma electrolysis process under identical operating conditions, namely under a voltage of 25 V maintained for 5 seconds. More precisely, the cliché of the figure 10A corresponds to the copper foam obtained with the implementation of the electrolyte solution A while the cliche of the figure 10B corresponds to the copper foam obtained with use of the electrolytic solution E.
  • the metal foam synthesized from the electrolytic solution A is relatively fragile. Although it can be detached by gently proceeding with a brush, the cathode on the surface of which it was formed, it is absolutely not possible to subject this metal foam to a subsequent step of formatting, for example, by machining. This fragility is particularly related to its irregular general form as it clearly appears on the cliche of the figure 10A .
  • This irregularity of shape which characterizes the metallic foam obtained with the implementation of the electrolytic solution A is caused by the deformation of the gaseous envelope (or electrolytic plasma) during the electrolysis process by glow discharge of contact and, more particularly, during the growth of the metal foam.
  • the observation, by means of the DCC camera, of the phenomena occurring at the level of the cathode 20 during the electrolysis by glow discharge of contact shows that the formation of the metal foam occurs rapidly, in a dozen of seconds, and quite violently: the gaseous envelope does not seem to have sufficient strength to resist the forces generated by the growth of this metal foam and therefore can not maintain a regular shape around the cathode 20. It is even observed that beyond 15 seconds, this gaseous envelope breaks, thus causing the interruption of the electrolytic plasma and the total destruction of the formed metal foam.
  • an electrolytic solution comprising gelatin makes it possible to obtain a gaseous envelope which, as shown by the images of the CCD camera, remains uniform around the cathode during the growth of the metallic foam and this , for a duration that is clearly greater than 15 seconds.
  • the figure 11 clearly illustrates this phenomenon. On this figure 11 the times after which the rupture of the gaseous envelope, which is formed during the electrolytic plasma electrolysis process generated under an electrical voltage of 25 V, is reported as a function of the gelatin concentration of the electrolytic solutions. A to E implemented.
  • this electrolytic plasma can be maintained for a period of two minutes with a concentration of only 1 g / 1 g of gelatin in the electrolyte solution B, or even reach 4 minutes with concentrations of 10 g / l and 25 g / l of gelatin (electrolyte solutions D and E).
  • metal foams take a more irregular general shape, as shown in the picture of the figure 12B .
  • the Figures 12A and 12B correspond to copper foam plates as obtained on the surface of the cathode after the implementation of the electrolytic solution E in the process according to the invention.
  • the electrolytic plasma generated at an electrical voltage of 25 V, was maintained for 45 seconds in the case of the figure 12A , and for 60 seconds in the case of the figure 12B .
  • This figure 13 represents the curve of the intensity, denoted I (in A), measured as a function of the applied electrical voltage, denoted U (in V), as obtained with the implementation of the electrolytic solutions A to E, at a temperature of 25 ° C, in the electrolytic plasma electrolysis process.
  • the electrolysis by contact glow discharge stabilizes when the gaseous envelope is completely formed around the cathode, such stabilization occurring when the value of applied voltage is located in a range of electrical voltages in which the intensity is substantially constant as a function of this voltage.
  • this electrolysis by glow discharge contact is stabilized at a lower voltage value when the electrolyte solution comprises gelatin and, in particular, from a value of 25 V with the implementation electrolytic solutions C, D and E.
  • the gelatin would better contain, on the surface of the cathode, the gaseous envelope formed by the release of dihydrogen resulting from the electrolytic reduction of the protons contained in the electrolytic solution, by decreasing the solubility of this gaseous envelope in this electrolytic solution.
  • the electrolytic solution comprises gelatin
  • the gaseous envelope is found to be totally created at a lower electrical voltage than when the electrolytic solution does not contain it and thus allows ionization of the gas and thus the complete formation of the electrolytic plasma at a lower voltage.
  • This cathodic efficiency R was calculated for each of the metal foams obtained after the implementation of an electrolytic plasma electrolysis process carried out under an applied electrical voltage of 30 V, for a duration of 10 s, with each of the electrolytic solutions B to E.
  • the determination of the total quantity of electric charges involved in the electrolytic plasma electrolysis process which corresponds to the quantity of electricity denoted Q, was performed by coulometric measurement using an EGG type coulometer. PARK.
  • the figure 14 appended represents the curve corresponding to the cathodic efficiency R thus calculated as a function of the concentration of gelatin, denoted by [gelatin], of these electrolytic solutions B to E.
  • the shape of the curve of the figure 14 shows that the increase in cathodic efficiency R as a function of this gelatin concentration is directly related to an increase in the electrical density in the gaseous envelope or electrolytic plasma.
  • the metal foam obtained with the electrolytic solution B comprising 1 g / l of gelatin is formed of copper strands having a size of between 500 nm and 1000 nm while the metal foam obtained with the Electrolyte solution E comprising 25 g / l of gelatin is formed of copper strands whose size is only about 100 nm.
  • the increase in the concentration of gelatin in the electrolytic solution causes the increase in the number of metal strands and the decrease in the size of the interstices between the metal strands.
  • the x-ray magnification at x 70 000 shows that the metal strands of the foams obtained with the electrolytic solutions B to D have small nodules which have a structure similar to that of the copper deposits obtained with the conventional electrolysis process. . It is important to note, however, that the presence of such nodules decreases as the concentration of gelatin in the electrolyte solution increases to completely disappear at a concentration of 25 g / l (electrolyte solution E). This observation also confirms that the higher the gelatin concentration in the electrolytic solution, the faster the electrolytic reduction reaction of Cu 2+ cations, which occurs at the interface between the gaseous envelope and the electrolytic solution, is rapid. and intense, presumably because of an increasingly energetic electrolytic plasma.
  • the metal foam obtained with the implementation of the Electrolytic solution E in the electrolytic plasma electrolysis process under an applied electrical voltage of 25 V, for a period of 10 s was analyzed by means of an energy dispersive analyzer.
  • -ray spectrometry and abbreviated EDX) ESM reference LMTPCMEB001 was analyzed by means of an energy dispersive analyzer.
  • two metal foams have been synthesized from the implementation of this electrolytic solution E in the electrolytic plasma electrolysis process, for a period of time. of 10 s, under two separate applied voltages, one of 25 V and the other of 30 V.
  • Measurements to determine the mass (denoted m and expressed in ⁇ g) and the apparent volume (denoted V and expressed in cm 3 ) were carried out in order to make it possible to calculate the bulk density (denoted p and expressed in g / cm 3 ) of three copper foams MM1, MM2 and MM3 synthesized successively from the electrolytic solution E, according to the synthesis method according to the invention conducted under an applied electrical voltage of 25 V and for a duration of 15 s, in the absence agitation of the electrolyte solution E and in the absence of rotation of the cathode.
  • Table 4 also shows the apparent density values p calculated as a percentage, based on the theoretical density of the copper, which is 8.92 g / cm 3 at 20 ° C.
  • the values of the percentages of apparent density as calculated and reported in Table 4 give an order of magnitude of the apparent densities of metal foams that can be obtained with the method according to the invention.
  • the electrolytic solution E is kept under agitation at an angular speed of 220 rpm while the cathode is kept in rotation at an angular speed of 300 rpm, while the whole synthesis.
  • the cliché of the figure 19 corresponds to the MM5 metal foam.
  • the metal foam MM5 could easily be detached from the cathode, machined in the form of a cylinder and manipulated by means of a micro-nozzle in the absence of any degradation thereof. ci, as illustrated on the picture of the figure 20 .

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Electrodes For Compound Or Non-Metal Manufacture (AREA)
  • Cell Electrode Carriers And Collectors (AREA)
EP14176382.1A 2013-07-12 2014-07-09 Syntheseverfahren eines Metallschaums, Metallschaum, seine Anwendungen und Vorrichtung, die einen solchen Metallschaum umfasst Active EP2824219B1 (de)

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
FR1356875A FR3008429A1 (fr) 2013-07-12 2013-07-12 Procede de synthese d'une mousse metallique, mousse metallique, ses utilisations et dispositif comprenant une telle mousse metallique

Publications (2)

Publication Number Publication Date
EP2824219A1 true EP2824219A1 (de) 2015-01-14
EP2824219B1 EP2824219B1 (de) 2015-12-02

Family

ID=49212929

Family Applications (1)

Application Number Title Priority Date Filing Date
EP14176382.1A Active EP2824219B1 (de) 2013-07-12 2014-07-09 Syntheseverfahren eines Metallschaums, Metallschaum, seine Anwendungen und Vorrichtung, die einen solchen Metallschaum umfasst

Country Status (8)

Country Link
US (2) US9512528B2 (de)
EP (1) EP2824219B1 (de)
JP (1) JP6526392B2 (de)
CN (1) CN104278296B (de)
DK (1) DK2824219T3 (de)
ES (1) ES2564413T3 (de)
FR (1) FR3008429A1 (de)
RU (1) RU2014128541A (de)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105004709B (zh) * 2015-04-13 2018-06-15 中国地质大学（武汉） 一种液体放电微等离子体激发源装置及等离子体激发方法
CN106006758B (zh) * 2016-05-20 2017-07-18 西北师范大学 一种利用废铁丝制备纳米Fe3O4的方法
FR3052183B1 (fr) 2016-06-02 2020-03-06 Safran Aircraft Engines Aube de turbine comprenant une portion d'admission d'air de refroidissement incluant un element helicoidal pour faire tourbillonner l'air de refroidissement
CN107217279B (zh) * 2017-05-31 2018-10-02 东北大学 一种电解法制备金属纳米颗粒的方法
US10301233B2 (en) * 2017-07-03 2019-05-28 Chevron U.S.A. Inc. Natural gas liquid upgrading by ionic liquid catalyzed alkylation
WO2019152918A1 (en) * 2018-02-02 2019-08-08 Santeri Holdings LLC Identifiable physical form, sales instruments, and information marketplace for commodity trades
CN111111662A (zh) * 2020-01-03 2020-05-08 中国重型机械研究院股份公司 一种负载型针铁矿的泡沫金属催化剂及其制备方法
CN116043256B (zh) * 2022-11-11 2024-05-07 石河子大学 一种溶液等离子体原位合成羟基氧化物的制备方法

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060204741A1 (en) * 2003-06-13 2006-09-14 Peter Rehbein Contact surfaces for electrical contacts and method for producing the same
WO2006111837A2 (fr) * 2005-04-21 2006-10-26 Pillet, Michel Procede de fabrication de mousse de metal

Family Cites Families (25)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3620813A (en) 1968-11-12 1971-11-16 Udylite Corp Method of treating workpieces in a treating fluid
CH555752A (de) 1972-06-02 1974-11-15 Montblanc Simplo Gmbh Kugelschreiberminenspitze.
DE2543599A1 (de) 1975-09-30 1977-04-07 Herbert Fruehschuetz Vorrichtung zur elektrochemischen oberflaechenbehandlung von kleinteilen
US4053371A (en) * 1976-06-01 1977-10-11 The Dow Chemical Company Cellular metal by electrolysis
US4316786A (en) 1980-09-19 1982-02-23 The United States Of America As Represented By The United States Department Of Energy Apparatus for electroplating particles of small dimension
JPS5881990A (ja) 1981-11-11 1983-05-17 Fujitsu Ltd 電気めつき処理方法
US4758272A (en) * 1987-05-27 1988-07-19 Corning Glass Works Porous metal bodies
US4801947A (en) * 1987-06-25 1989-01-31 Burlington Industries, Inc. Electrodeposition-produced orifice plate of amorphous metal
JP3481020B2 (ja) * 1995-09-07 2003-12-22 ディップソール株式会社 Ｓｎ−Ｂｉ系合金めっき浴
CN1058057C (zh) * 1996-10-10 2000-11-01 中国科学院固体物理研究所 泡沫金属铝及其合金的制备方法
US6419981B1 (en) * 1998-03-03 2002-07-16 Ppg Industries Ohio, Inc. Impregnated glass fiber strands and products including the same
AUPR129900A0 (en) * 2000-11-08 2000-11-30 Chang, Chak Man Thomas Plasma electroplating
LU90721B1 (en) * 2001-01-25 2002-07-26 Circuit Foil Luxembourg Trading Sarl Method for producing metal foams and furnace for producing same
FR2883889B1 (fr) 2005-04-04 2007-06-08 Commissariat Energie Atomique Electrode de reduction pour depot de metal par oxydoreduction.
CN1887418A (zh) * 2006-07-17 2007-01-03 山东大学 一种纳米多孔金属催化剂及其制备方法
CN100553733C (zh) * 2007-02-14 2009-10-28 中国科学院金属研究所 一种网状Cu抗菌过滤金属材料的制备方法
CN100503862C (zh) * 2007-09-30 2009-06-24 北京师范大学 一种新型多孔泡沫钨及其制备方法
US8529749B2 (en) * 2009-08-13 2013-09-10 Case Western Reserve University Electrochemical cell including a plasma source and method of operating the electrochemical cell
WO2011067957A1 (ja) * 2009-12-04 2011-06-09 三井金属鉱業株式会社 多孔質金属箔およびその製造方法
US9562296B2 (en) * 2010-11-02 2017-02-07 I'msep Co., Ltd. Production method for silicon nanoparticles
KR101199004B1 (ko) * 2011-01-06 2012-11-07 성균관대학교산학협력단 슈퍼커패시터용 나노다공성 전극 및 이의 제조방법
US9634168B2 (en) * 2011-08-04 2017-04-25 Beijing Apollo Ding Rong Solar Technology Co., Ltd. Attachment structures for building integrable photovoltaic modules
CN103255467A (zh) * 2012-10-25 2013-08-21 北京太禹天工科技有限公司 一种新型材料表面改性的方法和装置
CN103147100B (zh) * 2013-04-02 2016-06-01 中南大学 一种混杂多孔金属材料的制备方法
EP3092349A4 (de) * 2014-01-07 2017-09-06 Nama Development LLC 3d-wabenschaumstruktur

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20060204741A1 (en) * 2003-06-13 2006-09-14 Peter Rehbein Contact surfaces for electrical contacts and method for producing the same
WO2006111837A2 (fr) * 2005-04-21 2006-10-26 Pillet, Michel Procede de fabrication de mousse de metal

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
0. TAKAI, PURE APPL. CHEM., vol. 80, no. 9, 2008, pages 2003 - 2011
0. TAKAI: "Solution plasma processing (SPP)", PURE APPL. CHEM., vol. 80, no. 9, 2008, pages 2003 - 2011
C. ZHOU ET AL., ELECTROCHEMISTRY COMMUNICATIONS, vol. 18, 2012, pages 33 - 36
C. ZHOU ET AL.: "Nanoporous platinum grown on nickel foam by facile plasma reduction with enhanced electro-catalytic performance", ELECTROCHEMISTRY COMMUNICATIONS, vol. 18, 2012, pages 33 - 36, XP028479940, DOI: doi:10.1016/j.elecom.2012.01.029
CHUNMEI ZHOU ET AL: "Nanoporous platinum grown on nickel foam by facile plasma reduction with enhanced electro-catalytic performance", ELECTROCHEMISTRY COMMUNICATIONS, ELSEVIER, AMSTERDAM, NL, vol. 18, 10 February 2012 (2012-02-10), pages 33 - 36, XP028479940, ISSN: 1388-2481, [retrieved on 20120210], DOI: 10.1016/J.ELECOM.2012.01.029 *
K. AZUMI ET AL., ELECTROCHIMICA ACTA, vol. 52, 2007, pages 4463 - 4470
K. AZUMI ET AL.: "Removal ofoxide layeron SUS304 using high-voltage discharging polarization", ELECTROCHIMICA ACTA, vol. 52, 2007, pages 4463 - 4470
KIM J H ET AL: "Preparation of copper foam with 3-dimensionally interconnected spherical pore network by electrodeposition", ELECTROCHEMISTRY COMMUNICATIONS, ELSEVIER, AMSTERDAM, NL, vol. 10, no. 8, 27 May 2008 (2008-05-27), pages 1148 - 1151, XP023183066, ISSN: 1388-2481, [retrieved on 20080527], DOI: 10.1016/J.ELECOM.2008.05.035 *
R. WÜTHRICH ET AL., ELECTROCHIMICA ACTA, vol. 55, 2010, pages 8189 - 8196
R. WÜTHRICH ET AL.: "Building micro and nanosystems with electrochemical discharges", ELECTROCHIMICA ACTA, vol. 55, 2010, pages 8189 - 8196, XP027428442, DOI: doi:10.1016/j.electacta.2010.01.096
T.A. KAREEM ET AL., LONICS, vol. 18, 2012, pages 315 - 327
T.A. KAREEM ET AL.: "Glow discharge plasma electrolysis for nanoparticles synthesis", LONICS, vol. 18, 2012, pages 315 - 327
WUTHRICH R ET AL: "Building micro and nanosystems with electrochemical discharges", ELECTROCHIMICA ACTA, ELSEVIER SCIENCE PUBLISHERS, BARKING, GB, vol. 55, no. 27, 2 February 2010 (2010-02-02), pages 8189 - 8196, XP027428442, ISSN: 0013-4686, [retrieved on 20100202], DOI: 10.1016/J.ELECTACTA.2010.01.096 *

Also Published As

Publication number Publication date
CN104278296A (zh) 2015-01-14
US9512528B2 (en) 2016-12-06
ES2564413T3 (es) 2016-03-22
CN104278296B (zh) 2018-02-16
US10400345B2 (en) 2019-09-03
RU2014128541A (ru) 2016-02-10
DK2824219T3 (en) 2016-03-07
JP6526392B2 (ja) 2019-06-05
US20170051420A1 (en) 2017-02-23
FR3008429A1 (fr) 2015-01-16
US20150014172A1 (en) 2015-01-15
JP2015038242A (ja) 2015-02-26
EP2824219B1 (de) 2015-12-02

Similar Documents

Publication Publication Date Title
EP2824219B1 (de) Syntheseverfahren eines Metallschaums, Metallschaum, seine Anwendungen und Vorrichtung, die einen solchen Metallschaum umfasst
EP2823524B1 (de) Vollfestkörper-dünnschichtbatterien und verfahren zur herstellung von vollfestkörper-dünnschichtbatterien
CA1247047A (fr) Procede pour la production electrolytique d'hydrogene sur une cathode
CN104677715B (zh) 一种用于原位记录观察镁合金微观组织腐蚀行为的方法
JP2012500896A (ja) ポリオキソメタレートを含む方法および組成物
BE1005928A5 (fr) Materiau structurel pour electrode insoluble.
EP3263744B1 (de) Elektrochemisches rückgewinnungsverfahren von platin mithilfe eines materials, in dem es enthalten ist
WO2015114168A1 (fr) DEPOT METALLIQUE PROFOND DANS UNE MATRICE POREUSE PAR PULVERISATION MAGNETRON PULSEE HAUTE PUISSANCE HiPIMS, SUBSTRATS POREUX IMPREGNES DE CATALYSEUR METALLIQUE ET LEURS UTILISATIONS
Bromberg et al. Synthesis of ultrathin and continuous layers of nanoporous Au on glassy carbon substrates
EP0274329B1 (de) Verfahren zur Dekontamination einer mit Tritium kontaminierten metallischen Oberfläche und Vorrichtung zur Verwendung desselben
Shigihara et al. Dissolution and Consequent Morphological Evolution of Electrodeposited Pt− Cu Nanoparticles under Potential Cycling in 0.5 M H2SO4 Solution
FR2461023A1 (fr) Procede de preparation de substrats conducteurs et d'electrodes pour l'electrolyse d'une saumure, et l'electrode a faible surtension ainsi obtenue
WO2019217805A1 (en) Biofouling-resistant nanoporous alloys
EP2702190B1 (de) Verfahren zum wachstum von metallischen partikeln mittels galvanisieren mit in situ inhibitionsphase
Yanagishita et al. Preparation of multilayered porous alumina hollow spheres by anodization of Al particles
EP1866462A2 (de) Oberflächenbehandlungselektrode
EP1838903A2 (de) Verfahren zur galvanischen abscheidung eines metalls zur herstellung von zellen mit elektroden-polymerfestelektrolyt
FR2918214A1 (fr) Dispersion de materiaux composites, notamment pour des piles a combustible
EP0497675B1 (de) Verfahren zur Herstellung eines feinen dendritischen Pulvers und nach diesem Verfahren erzeugtes Pulver
CA3043427A1 (fr) Procede electrolytique pour extraire de l'etain et/ou du plomb compris dans un melange electriquement conducteur
EP3452637A1 (de) Magnesiumbasierte legierung und verwendung davon bei der herstellung von elektroden und der elektrochemischen synthese von struvit
EP2555897A1 (de) Verfahren und vorrichtung zur herstellung eines zylinders mit mikrometerdurchmesser
FR2821627A1 (fr) Procede et dispositif d'elaboration par voie electrolytique d'un depot selectif epais de nickel sur une piece
CA1080204A (fr) Procede d'obtention de catalyseurs electrochimiques pour la reduction de l'oxygene________________________________________________________
WO2023088601A1 (fr) Fil électrode

Legal Events

Date Code Title Description
17P Request for examination filed

Effective date: 20140709

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

AX Request for extension of the european patent

Extension state: BA ME

PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

R17P Request for examination filed (corrected)

Effective date: 20150212

RBV Designated contracting states (corrected)

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

RIC1 Information provided on ipc code assigned before grant

Ipc: C25D 1/08 20060101AFI20150320BHEP

Ipc: C25D 3/38 20060101ALI20150320BHEP

Ipc: C25D 7/00 20060101ALN20150320BHEP

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150612

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

Free format text: NOT ENGLISH

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 763677

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151215

Ref country code: CH

Ref legal event code: NV

Representative=s name: BOVARD AG, CH

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

Free format text: LANGUAGE OF EP DOCUMENT: FRENCH

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602014000514

Country of ref document: DE

REG Reference to a national code

Ref country code: DK

Ref legal event code: T3

Effective date: 20160301

REG Reference to a national code

Ref country code: NL

Ref legal event code: FP

REG Reference to a national code

Ref country code: SE

Ref legal event code: TRGR

REG Reference to a national code

Ref country code: NO

Ref legal event code: T2

Effective date: 20151202

REG Reference to a national code

Ref country code: ES

Ref legal event code: FG2A

Ref document number: 2564413

Country of ref document: ES

Kind code of ref document: T3

Effective date: 20160322

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 763677

Country of ref document: AT

Kind code of ref document: T

Effective date: 20151202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160303

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 3

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160404

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20160402

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602014000514

Country of ref document: DE

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed

Effective date: 20160905

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 4

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20140709

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

Ref country code: MT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

REG Reference to a national code

Ref country code: FR

Ref legal event code: PLFP

Year of fee payment: 5

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: TR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20151202

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20230517

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NO

Payment date: 20230720

Year of fee payment: 10

Ref country code: IT

Payment date: 20230731

Year of fee payment: 10

Ref country code: ES

Payment date: 20230821

Year of fee payment: 10

Ref country code: CH

Payment date: 20230801

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 20230724

Year of fee payment: 10

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 20240722

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 20240726

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FI

Payment date: 20240719

Year of fee payment: 11

Ref country code: DE

Payment date: 20240719

Year of fee payment: 11

Ref country code: IE

Payment date: 20240726

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DK

Payment date: 20240722

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 20240722

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 20240726

Year of fee payment: 11

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20240723

Year of fee payment: 11