[go: up one dir, main page]

EP2179071B1 - Procédé de dépôt de nanoparticules sur un support - Google Patents

Procédé de dépôt de nanoparticules sur un support Download PDF

Info

Publication number
EP2179071B1
EP2179071B1 EP08787216.4A EP08787216A EP2179071B1 EP 2179071 B1 EP2179071 B1 EP 2179071B1 EP 08787216 A EP08787216 A EP 08787216A EP 2179071 B1 EP2179071 B1 EP 2179071B1
Authority
EP
European Patent Office
Prior art keywords
nanoparticles
support
plasma
atmospheric plasma
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.)
Not-in-force
Application number
EP08787216.4A
Other languages
German (de)
English (en)
French (fr)
Other versions
EP2179071A1 (fr
Inventor
François RENIERS
Frédéric Demoisson
Jean-Jacques Pireaux
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.)
Facultes Universitaires Notre Dame de la Paix
Universite Libre de Bruxelles ULB
Original Assignee
Facultes Universitaires Notre Dame de la Paix
Universite Libre de Bruxelles ULB
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
Priority claimed from EP08151463A external-priority patent/EP2093305A1/fr
Application filed by Facultes Universitaires Notre Dame de la Paix, Universite Libre de Bruxelles ULB filed Critical Facultes Universitaires Notre Dame de la Paix
Priority to EP08787216.4A priority Critical patent/EP2179071B1/fr
Publication of EP2179071A1 publication Critical patent/EP2179071A1/fr
Application granted granted Critical
Publication of EP2179071B1 publication Critical patent/EP2179071B1/fr
Not-in-force legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/02—Pretreatment of the material to be coated, e.g. for coating on selected surface areas
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C24/00—Coating starting from inorganic powder
    • C23C24/02—Coating starting from inorganic powder by application of pressure only
    • C23C24/04—Impact or kinetic deposition of particles
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/06—Metallic material
    • C23C4/08—Metallic material containing only metal elements
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/04—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the coating material
    • C23C4/10—Oxides, borides, carbides, nitrides or silicides; Mixtures thereof
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/134—Plasma spraying
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C4/00—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge
    • C23C4/12—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying
    • C23C4/14—Coating by spraying the coating material in the molten state, e.g. by flame, plasma or electric discharge characterised by the method of spraying for coating elongate material
    • C23C4/16—Wires; Tubes

Definitions

  • the present invention relates to a method for depositing and fixing nanoparticles on any support.
  • nanoparticle describes an aggregate of small molecules, or an assembly of a few tens to a few thousand atoms, forming a particle whose dimensions are of the order of one nanometer, that is to say say less than 1000nm (1 ⁇ ), preferably less than 100 nm. Because of their size, these particles possess particular physical, electrical, chemical and magnetic properties and give the supports to which they are applied new physical, electrical, chemical, magnetic and mechanical properties.
  • Nanoparticles are of growing interest because of their involvement in the development of many devices used in very different fields, such as the detection of biological or chemical compounds, the detection of chemical gases or vapors, the elaboration of batteries. fuel or hydrogen storage devices, the production of electronic or optical nanostructures, new chemical catalysts, biosensors, or so-called intelligent coatings, such as self-cleaning coatings or which have a particular biological activity, antibacterial for example.
  • the document WO2007 / 122256 describes the deposition of nanoporous layers by spraying a colloidal solution in a jet of thermal plasma, a plasma whose neutral species, ionized species and electrons have the same temperature.
  • the particles of the colloidal solution are at least partially melted in order to adhere to the substrate.
  • the plasma jet described has a gas temperature of between 5000 ° K and 15000 ° K. A not insignificant thermal effect will therefore be noted on both the substrate and the soil particles.
  • the document FR 2,877,015 discloses a method comprising injecting a colloidal sol of nanoparticles into a plasma jet that projects them onto a surface.
  • This type of plasma is a hot plasma, generally working at a temperature above the melting point of the colloidal particles.
  • the present invention provides a method for depositing nanoparticles on a support which does not have the drawbacks of the state of the art.
  • the present invention provides a fast, inexpensive process and easy implementation.
  • the present invention also proposes to minimize the thermal stresses both on the substrate and on the nanoparticles.
  • the present invention also provides a deposition method which improves the homogeneity of the deposit, and, more particularly, the dispersion of the nanoparticles on the substrate.
  • the present invention discloses a method using a colloidal solution (or suspension) of nanoparticles for the deposition of nanoparticles on a support, and using an atmospheric plasma for the deposition of nanoparticles on a support.
  • nanoparticle means an aggregate of small molecules, or an assembly of a few hundred to a few thousand atoms, forming a particle whose dimensions are of the order of one nanometer, generally less than 100 nm.
  • colloidal solution is intended to mean a homogeneous suspension of particles in which the solvent is a liquid and the solute a solid that is homogeneously dispersed in the form of very fine particles.
  • Colloidal solutions can take various forms, liquid, gel or paste. Colloidal solutions are intermediate between suspensions, which are heterogeneous media comprising microscopic particles dispersed in a liquid, and true solutions, in which the solute or solutes are in the state of molecular division in the solvent. In liquid form, colloidal solutions are sometimes also called "soil”.
  • the atmospheric plasma is an atmospheric non-thermal plasma.
  • non-thermal plasma or "cold plasma” means a partially or totally ionized gas that includes electrons, ions (molecular or atomic), atoms or molecules, and radicals, out of thermodynamic equilibrium. , whose electron temperature (temperature of several thousands or tens of thousands of Kelvin) is significantly higher than that of ions and neutrons (temperature close to room temperature up to a few hundred Kelvin).
  • Atmospheric plasma or “atmospheric non-thermal plasma” or “atmospheric cold plasma” means a partially or totally ionized gas that comprises electrons, ions (molecular or atomic), atoms or molecules, and radicals, out of thermodynamic equilibrium, whose electron temperature is significantly higher than that of ions and neutrons (the temperatures are similar to those described for a "cold plasma"), and whose pressure is between about 1 mbar and about 1200 mbar, preferably between about 800 and about 1200 mbar.
  • the colloidal solution comprises a surfactant.
  • surfactant means a compound modifying the surface tension between two surfaces.
  • the surfactant compounds are amphiphilic molecules, that is to say that they have two parts of different polarity, one lipophilic and apolar, and the other, hydrophilic and polar. This type of molecule helps stabilize colloids.
  • cationic surfactants anionic, amphoteric or nonionic.
  • An example of such a surfactant is sodium citrate.
  • the present invention also discloses the use of a colloidal solution of nanoparticles for depositing nanoparticles on a support using an atmospheric plasma.
  • the present invention also describes the use of an atmospheric plasma for the deposition of nanoparticles on a support, said nanoparticles being in the form of a colloidal solution of nanoparticles, and said colloidal solution being nebulized on the surface of said support in the said atmospheric plasma.
  • the figure 1 represents the size distribution of the gold particles of a colloidal solution.
  • the figure 2 represents an image obtained by transmission electron microscopy (TEM) of a colloidal solution of gold particles.
  • TEM transmission electron microscopy
  • the figure 3 schematically represents an atmospheric plasma torch.
  • the figure 4 represents X-ray photoelectron spectroscopy (XPS) spectra of the HOPG graphite surface after plasma gold nanoparticle deposition according to the method of the present invention.
  • XPS X-ray photoelectron spectroscopy
  • the figure 5 represents atomic force microscopy (AFM) images of a HOPG graphite sample a) before, and b) after deposition of gold nanoparticles according to the method of the present invention.
  • AFM atomic force microscopy
  • the figure 6 represents high-resolution electron microscopy images of secondary electrons (FEG-SEM) of a HOPG graphite sample a) before, b) and c) after deposition of gold nanoparticles according to the method of the present invention.
  • FEG-SEM secondary electrons
  • magnification x 2000 magnification x 2000
  • magnification x 25000 magnification x 80000.
  • EDS Energy dispersive analysis
  • the figure 7 represents the comparison of the experimental XPS spectrum of Au 4f level presented in Figure 4 (b) and spectrum modeled using a Volmer-Weber growth model.
  • the figure 8 represents an X-ray photoelectron spectroscopy spectrum (XPS) of the surface of HOPG graphite after deposition of gold nanoparticles without the use of plasma (comparative).
  • XPS X-ray photoelectron spectroscopy spectrum
  • the figure 9 represents a high-resolution electron microscopy image of secondary electrons (FEG-SEM) of a HOPG graphite sample after the deposition of gold nanoparticles without the use of plasma (comparative).
  • FEG-SEM secondary electrons
  • the figure 10 represents an image (magnification x 100000) obtained by high resolution electron microscopy of secondary electrons (FEG-SEM) of a steel sample after deposition of gold nanoparticles according to the method of the present invention.
  • the figure 11 represents an image (magnification x 3000) obtained by high resolution electron microscopy of secondary electrons (FEG-SEM) of a glass sample after deposition of gold nanoparticles according to the method of the present invention.
  • the figure 12 represents an image (magnification x 50000) obtained by high resolution electron microscopy of secondary electrons (FEG-SEM) of a sample of PVC polymer after deposition of gold nanoparticles according to the method of the present invention.
  • the figure 13 represents an image (magnification ⁇ 10000) obtained by high resolution electron microscopy of secondary electrons (FEG-SEM) of a sample of HDPE polymer after deposition of gold nanoparticles according to the method of the present invention.
  • the figure 14 represents an image (magnification ⁇ 10000) obtained by high-resolution electron microscopy of secondary electrons (FEG-SEM) of a steel sample after deposition of gold nanoparticles, in the absence of plasma (comparative).
  • the figure 15 represents an image obtained by transmission electron microscopy (TEM) of a sample of carbon nanotubes before (a) and after deposition of gold nanoparticles according to the method of the present invention (b).
  • TEM transmission electron microscopy
  • the figure 16 represents an X-ray photoelectron spectroscopy spectrum (XPS) of the surface of the carbon nanotubes after deposition of gold nanoparticles according to the method of the present invention.
  • XPS X-ray photoelectron spectroscopy spectrum
  • the figure 17 represents an image obtained by transmission electron microscopy (TEM) of a sample of carbon nanotubes after deposit of platinum nanoparticles according to the process of the present invention.
  • TEM transmission electron microscopy
  • the figure 18 represents an X-ray photoelectron spectroscopy spectrum (XPS) of the surface of the carbon nanotubes after deposition of platinum nanoparticles according to the method of the present invention.
  • XPS X-ray photoelectron spectroscopy spectrum
  • the figure 19 represents an image (magnification x 120000) of high-resolution electron microscopy of secondary electrons (FEG-SEM) of a HOPG graphite sample after the deposition of rhodium nanoparticles according to the method of the present invention.
  • the figure 20 represents an X-ray photoelectron spectroscopy spectrum (XPS) of the HOPG graphite surface after deposition of rhodium nanoparticles according to the method of the present invention.
  • XPS X-ray photoelectron spectroscopy spectrum
  • the figure 21 represents an image (magnification x 100000) of secondary electron electron microscopy (FEG-SEM) of a steel sample after the deposition of platinum nanoparticles according to the method of the present invention.
  • FEG-SEM secondary electron electron microscopy
  • the figure 22 represents an image (magnification x 100000) of secondary electron electron microscopy (FEG-SEM) of a PVC sample after the deposition of rhodium nanoparticles according to the method of the present invention.
  • FEG-SEM secondary electron electron microscopy
  • the figure 23 represents an image (magnification x 100000) of secondary electron electron microscopy (FEG-SEM) of a sample of HDPE after the deposition of rhodium nanoparticles according to the method of the present invention.
  • FEG-SEM secondary electron electron microscopy
  • the method for deposition of nanoparticles according to the invention involves a colloidal solution or suspension of nanoparticles which is deposited on any support with the aid of an atmospheric plasma, said atmospheric plasma being able to be generated by any suitable device making use of of an atmospheric plasma.
  • the deposition of nanoparticles according to the invention uses only a low energy consumption.
  • the deposition of nanoparticles is rapid because the activation of the support and the nebulization of the nanoparticles, and possibly also the prior cleaning of the support, are carried out in the atmospheric plasma, or in the flow of the atmospheric plasma, in a single step or one continuous process.
  • the process according to the invention allows a strong adhesion of the nanoparticles to the support.
  • This technique makes it possible to control the properties of the interface and to adjust the deposition of the nanoparticles on the support.
  • this method does not require expensive installations and is easily implemented industrially.
  • the colloidal solution of nanoparticles can be prepared by any technique and / or any suitable means.
  • the support on which the colloidal solution of nanoparticles is deposited is any suitable material that can be coated with nanoparticles, any material whatever its nature and / or its shape.
  • he it is a solid support, a gel or a nano-structured material.
  • the plasma is any suitable atmospheric plasma. It is a plasma generated at a pressure of between about 1 mbar and about 1200 mbar, preferably between 800 and 1200 mbar. Preferably, it is an atmospheric plasma whose macroscopic temperature of the gas can vary for example between room temperature and about 400 ° C. Preferably, the plasma is generated by an atmospheric plasma torch.
  • An atmospheric plasma does not use vacuum, which makes it inexpensive and easy to maintain.
  • the atmospheric plasma makes it possible to clean and activate the surface of the support, either by functionalizing it, for example by creating oxygen, nitrogen, sulfur, and / or hydrogenated groups, or by creating surface defects, for example gaps, steps, and / or stings.
  • These surface groups can for example comprise very reactive radicals and having a short life.
  • nanoparticles themselves can be activated by plasma, either directly by radical formation from the water of hydration, or by reactions with a surfactant attached to the surface of the nanoparticle.
  • the activation of the support and the nebulization of the colloidal solution are concomitant, namely in the plasma, or in the plasma flow, generated by a device making use of an atmospheric plasma.
  • the nebulization of the colloidal solution occurs at the same time, or immediately after, the activation of the support by the atmospheric plasma.
  • the nebulization of the colloidal solution can be done either in the discharge zone or in the post-discharge zone of the atmospheric plasma.
  • the nebulization of the colloidal solution is in the post-discharge area of the plasma because, in some cases, this may have additional advantages. This may not contaminate the device generating the plasma. This may make it possible to facilitate the treatment of polymeric supports, to avoid the degradation of the support to be coated, and also, for example, not to cause melting, oxidation, degradation and / or aggregation of the nanoparticles.
  • the nebulization of the colloidal solution is any nebulization adequate and can be done in any direction (orientation) relative to the surface of the support.
  • the nebulization is in a direction substantially parallel to the support, but it can also be done for example at an angle of about 45 °, or for example at an angle of about 75 ° relative to the surface of the support treat.
  • Gold nanoparticles were deposited on highly oriented pyrolytic graphite (HOPG), a support that has chemical properties similar to those of multiwall carbon nanotubes (MWCNTs).
  • HOPG highly oriented pyrolytic graphite
  • HOPG Highly Oriented Pyrolytic Graphite
  • HOPG Highly Oriented Pyrolytic Graphite
  • this graphite with a size of 10 mm x 10 mm x 1 mm, has an angle called "mosaic spread angle" of 0.8 ° ⁇ 0.2 ° and a lateral grit size. greater than 1 mm. Few layers of The surface of the graphite is previously detached with adhesive tape, before the graphite sample is immersed in an ethanol solution for 5 minutes, under ultrasonication.
  • the colloidal suspension is prepared for example according to the thermal reduction method of citrate as described in the article. Turkevich et al. J. Faraday Discuss. Chem. Soc. (1951), 11 page 55 , according to the following reaction: 6 HAuCl 4 + K 3 C 6 H 5 O 7 + 5 H 2 O ⁇ 6 Au + 6 CO 2 + 21 HCl + 3 KCl wherein the citrate acts as a reducing agent and as a stabilizer.
  • a gold solution is prepared by adding 95 ml of a 134 mM aqueous solution of tetrachloroauric acid (HAuCl 4 , 3H 2 O, Merck) and 5 ml of a 34 mM aqueous solution of trisodium citrate ( C 6 H 8 O 7 Na 3 , 2H 2 O, Merck) with 900 mL of distilled water. The solution thus obtained is then boiled for 15 minutes. In a pale yellow color, the gold solution then changes to a red color in the space of one to three minutes.
  • HuCl 4 tetrachloroauric acid
  • trisodium citrate C 6 H 8 O 7 Na 3 , 2H 2 O, Merck
  • This method of thermal reduction of the citrate makes it possible to obtain a stable dispersion of gold particles, whose gold concentration is 134 mM, and whose particles have an average diameter of approximately 10 nm and approximately 10% of polydispersity ( Figure 1 ).
  • the diffuser of the plasma torch comprises two perforated aluminum electrodes, 33 mm in diameter, and separated by a gap of 1.6 mm wide.
  • the diffuser is placed inside an airtight chamber, under argon atmosphere at room temperature.
  • the upper electrode 1 of the plasma source is connected to a radio frequency generator, for example 13.56 MHz, while the lower electrode 2 is grounded.
  • the plasma torch operates at 80 W and the plasma 3 is formed by feeding the torch upstream of the electrodes with argon 4 at a rate of 30 L / min.
  • the space between the sample of graphite HOPG resting on a sample holder 7 and the lower electrode 2 is 6 ⁇ 1 mm. This space is under atmospheric pressure.
  • the graphite support Before the deposition of the nanoparticles, the graphite support is subjected to the plasma flow of the plasma torch, for for example about 2 minutes, which allows cleaning and activating the support.
  • 3 to 5 ml of colloidal suspension is nebulized, in the post-discharge area of the plasma torch and in a direction 6 substantially parallel to the sample ( Figure 3 ).
  • the colloidal suspension is injected for about 5 minutes, by periodic pulsations of about one second, spaced about 15 seconds apart.
  • the samples are then washed in ethanol solution under ultrasonication for about 5 minutes.
  • XPS X-ray photoelectron spectroscopy
  • the charge effects on the measured binding energy positions were corrected by setting the binding energy of the carbon spectral envelope, C (1s), to 284.6 eV, a generally accepted value for contamination. accidental carbon surface.
  • the carbon, oxygen and gold spectra were deconvolved using a Shirley baseline model and a Gaussian-Lorentzian model.
  • FIG. figure 4 The XPS spectra of the surface of HOPG graphite coated with nanoparticles are represented in FIG. figure 4 .
  • the figure 4a shows the presence of carbon at a percentage of 77.8%, oxygen at a percentage of 14.9%, potassium at a percentage of 3.2% and gold at a percentage of 1.0%. Traces of silica were also detected; these are impurities incorporated in the HOPG graphite samples. This analysis indicates a high gold adhesion to HOPG graphite although the samples were washed in an ethanol solution under ultrasonication. It should be noted that with or without the ultrasonic ethanol cleaning step, the amount of gold deposited on the HOPG graphite is similar.
  • the surface morphology of HOPG graphite coated with nanoparticles was studied by performing Atomic Force Microscopy (AFM) images recorded using a PicoSPM® LE instrument with a functioning Nanoscope IIIa (Digital Instruments, Veeco) controller. under ambient conditions.
  • the microscope is equipped with a 25 ⁇ m analyzer and operates in contact mode.
  • the cantilever used is a Nanosensors NC-AFM Pointprobe® low-frequency silica probe (Wetzlar-Blankenfeld, Germany) having an integrated pyramidal end with a radius of curvature of 110 nm.
  • the spring constant of the cantilever is between 30 and 70 N m -1 and its free resonance frequency measurement is 163.1 kHz.
  • the images were recorded at scan rates of 0.5 to 1 line per second.
  • FIG. figure 5 Atomic force microscopy images (1 ⁇ m x 1 ⁇ m) before and after the deposition of the nanoparticles by plasma treatment are represented in FIG. figure 5 .
  • the graphite is covered with clusters, or islands, of gold that are either isolated, and have a diameter greater than 0.01 ⁇ m (10 nm), or branched. These islands are dispersed homogeneously with a recovery rate of about 12%.
  • the graphite samples are first deposited on a copper strip of a sample holder before being introduced into the analysis chamber under a pressure of approximately 10 -8 mbar.
  • the growth mode is of the Volmer-Weber type (3D structure in islands)
  • Table 1 Samples Height of islands of gold h (nm) Percentage of recovery (%) Thickness of carbon (contamination layer) (nm) AT 10.6 9.9 1.0 B 11.1 15.0 0.6 VS 9.2 6.0 0.2
  • the height of the islands of gold varies between 9.2 and 10.6 nm, values substantially identical to the average diameter of the nanoparticles of the colloidal suspension ( Figure 1 ).
  • the surface of the support is covered with islands of gold of about 10 nm.
  • a gold coverage percentage of about 10% is in agreement with the recovery rate determined by atomic force microscopy and scanning electron microscopy.
  • a deposit of gold nanoparticles on HOPG according to the method of Example 1 is carried out, with the exception of the step of nanoparticle deposition which is carried out without the use of an atmospheric plasma ( Figures 8 and 9 ). After the deposition of the nanoparticles and before analysis, the samples obtained are washed with ethanol for about 5 minutes with ultrasound.
  • a deposit of gold nanoparticles on steel according to the method of Example 1 is carried out, with the exception of the nanoparticle deposition step which is carried out without the use of an atmospheric plasma. After the deposition of the nanoparticles and before analysis, the samples obtained are washed with ethanol for about 5 minutes with ultrasound. We notice at the figure 14 the absence of nanoparticles on the surface of the steel.
  • Gold nanoparticles were deposited on a steel support according to the method described in Example 1, with ultrasonic cleaning. We notice at the figure 10 the presence of nanoparticles.
  • Gold nanoparticles were deposited on a glass support according to the process described in Example 1. It can be seen from the figure 11 the presence of nanoparticles after ultrasonic cleaning.
  • Gold nanoparticles were deposited on a PVC support according to the method described in Example 1, with ultrasonic cleaning.
  • the microscopy image of the figure 12 was obtained after covering the sample with a metal layer. We notice at the figure 12 the presence of nanoparticles.
  • Gold nanoparticles have been deposited on an HDPE support ( Figure 13 ) according to the method described in Example 1, with ultrasonic cleaning.
  • the microscopy image of the figure 13 was obtained after covering the sample with a metal layer. We notice at the figure 13 the presence of nanoparticles.
  • Gold nanoparticles were deposited on a carbon nanotube support according to the method described in Example 1, with ultrasonic cleaning. We notice at the figure 15 the presence of spherical nanoparticles of about 10 nm after ultrasonic cleaning. This presence of gold is confirmed by the XPS spectrum at the figure 16 .
  • Platinum nanoparticles were deposited on a carbon nanotube support according to the method described in US Pat. example 1. We notice at the figure 17 the presence of spherical nanoparticles of about 10 nm. This presence of platinum is confirmed by the XPS spectrum at the figure 18 .
  • Rhodium nanoparticles were deposited on a HOPG carbon support according to the method described in Example 1. It can be seen from FIG. figure 19 the presence of spherical nanoparticles of about 10 nm after ultrasonic cleaning. This presence of rhodium is confirmed by the XPS spectrum at the figure 20 .
  • Rhodium nanoparticles were deposited on a PVC support according to the method described in Example 1, with ultrasonic cleaning.
  • the microscopy image of the figure 22 was obtained after covering the sample with a metal layer. We notice at the figure 22 the presence of nanoparticles.
  • Gold nanoparticles were deposited on an HDPE support according to the method described in Example 1, with ultrasonic cleaning.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Plasma & Fusion (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Physics & Mathematics (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Metal Powder And Suspensions Thereof (AREA)
  • Powder Metallurgy (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
  • Carbon And Carbon Compounds (AREA)
EP08787216.4A 2007-08-14 2008-08-14 Procédé de dépôt de nanoparticules sur un support Not-in-force EP2179071B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08787216.4A EP2179071B1 (fr) 2007-08-14 2008-08-14 Procédé de dépôt de nanoparticules sur un support

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP07114344 2007-08-14
EP08151463A EP2093305A1 (fr) 2008-02-14 2008-02-14 Procédé de dépôt de nanoparticules sur un support
PCT/EP2008/060676 WO2009021988A1 (fr) 2007-08-14 2008-08-14 Procédé de dépôt de nanoparticules sur un support
EP08787216.4A EP2179071B1 (fr) 2007-08-14 2008-08-14 Procédé de dépôt de nanoparticules sur un support

Publications (2)

Publication Number Publication Date
EP2179071A1 EP2179071A1 (fr) 2010-04-28
EP2179071B1 true EP2179071B1 (fr) 2016-04-13

Family

ID=39800555

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08787216.4A Not-in-force EP2179071B1 (fr) 2007-08-14 2008-08-14 Procédé de dépôt de nanoparticules sur un support

Country Status (7)

Country Link
US (1) US20120003397A1 (zh)
EP (1) EP2179071B1 (zh)
JP (1) JP2010535624A (zh)
KR (1) KR20100072184A (zh)
CN (1) CN101821421A (zh)
CA (1) CA2696081A1 (zh)
WO (1) WO2009021988A1 (zh)

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100983224B1 (ko) * 2008-04-10 2010-09-20 김선휘 흑연의 미세입자 및 흑연 콜로이드 제조방법
KR101127121B1 (ko) * 2009-06-12 2012-03-20 한국과학기술원 공기 분사를 이용하여 목표 기판에 금속 나노입자층을 형성시키는 방법
DE102009037846A1 (de) * 2009-08-18 2011-02-24 Siemens Aktiengesellschaft Partikelgefüllte Beschichtungen, Verfahren zur Herstellung und Verwendungen dazu
CN101840852A (zh) * 2010-04-02 2010-09-22 中国科学院半导体研究所 在图形化的半导体衬底上制作有序半导体纳米结构的方法
EP2611948A2 (en) * 2010-09-01 2013-07-10 Facultés Universitaires Notre-Dame de la Paix Method for depositing nanoparticles on substrates
CN102258921A (zh) * 2011-05-27 2011-11-30 安徽南风环境工程技术有限公司 一种油烟吸附过滤网及其制备方法
JP6142362B2 (ja) * 2011-07-26 2017-06-07 ワンディー マテリアル エルエルシー ナノ構造化電池活性物質およびその生成方法
US9963345B2 (en) * 2013-03-15 2018-05-08 The United States Of America As Represented By The Administrator Of Nasa Nanoparticle hybrid composites by RF plasma spray deposition
JP6278368B2 (ja) * 2013-08-01 2018-02-14 エルジー・ケム・リミテッド 炭素担体−金属ナノ粒子複合体の製造方法およびこれにより製造された炭素担体−金属ナノ粒子複合体
EP2937890B1 (en) * 2014-04-22 2020-06-03 Europlasma nv Plasma coating apparatus with a plasma diffuser and method preventing discolouration of a substrate
KR102254644B1 (ko) * 2014-12-19 2021-05-21 (주)바이오니아 바인더 결합형 탄소나노구조체 나노다공막 및 그의 제조방법
CN104711568B (zh) * 2015-02-27 2017-11-14 南京邮电大学 一种在金属丝上包裹碳纳米材料的制备方法及其装置
US20180248199A1 (en) * 2015-08-27 2018-08-30 Osaka University Method for manufacturing metal nanoparticles, method for manufacturing metal nanoparticle-loaded carrier, and metal nanoparticle-loaded carrier
CN105369180A (zh) * 2015-12-02 2016-03-02 广州有色金属研究院 一种致密氧离子-电子混合导体氧化物涂层的制备方法
JP7155104B2 (ja) 2016-07-15 2022-10-18 ワンディー マテリアル、 インコーポレイテッド 電池における使用のために炭素系粉末上にシリコンナノワイヤを作るための製造装置および方法
KR101957234B1 (ko) * 2017-03-10 2019-06-19 경북대학교 산학협력단 플라즈마 발생장치
WO2020086825A1 (en) * 2018-10-24 2020-04-30 Atmospheric Plasma Solutions, Inc. Plasma source and method for preparing and coating surfaces using atmospheric plasma pressure waves

Family Cites Families (20)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5141017B2 (zh) * 1972-12-26 1976-11-08
JPH0941251A (ja) * 1995-07-28 1997-02-10 Kyodo Kumiai Zou Shudan 撥水布に合成樹脂立体模様の形成付着方法
JP3511128B2 (ja) * 1998-03-02 2004-03-29 日立造船株式会社 金属微粒子の製造方法および同微粒子の多孔質担体への担持方法
JP3256741B2 (ja) * 1998-07-24 2002-02-12 独立行政法人産業技術総合研究所 超微粒子成膜法
JP2002237480A (ja) * 2000-07-28 2002-08-23 Sekisui Chem Co Ltd 放電プラズマ処理方法
JP2002121024A (ja) * 2000-10-12 2002-04-23 Seiko Epson Corp 酸化チタン膜の製造方法、酸化チタン膜および太陽電池
JP2003007497A (ja) * 2001-06-19 2003-01-10 Pearl Kogyo Kk 大気圧プラズマ処理装置
DE10211701A1 (de) * 2002-03-16 2003-09-25 Studiengesellschaft Kohle Mbh Verfahren zur in situ Immobilisierung von wasserlöslichen nanodispergierten Metalloxid-Kolloiden
GB0208263D0 (en) * 2002-04-10 2002-05-22 Dow Corning Protective coating composition
US20050031876A1 (en) * 2003-07-18 2005-02-10 Songwei Lu Nanostructured coatings and related methods
WO2004035496A2 (en) * 2002-07-19 2004-04-29 Ppg Industries Ohio, Inc. Article having nano-scaled structures and a process for making such article
CA2513327A1 (en) * 2003-01-31 2004-08-12 Dow Corning Ireland Limited Plasma generating electrode assembly
JP2004356558A (ja) * 2003-05-30 2004-12-16 Toshio Goto コーティング装置およびコーティング方法
CH696811A5 (de) * 2003-09-26 2007-12-14 Michael Dvorak Dr Ing Dipl Phy Verfahren zur Beschichtung einer Substratoberfläche unter Verwendung eines Plasmastrahles.
JP2005163117A (ja) * 2003-12-03 2005-06-23 Ainobekkusu Kk 金属コロイドの製造方法及びこの方法によって製造された金属コロイド
JP4177244B2 (ja) * 2003-12-15 2008-11-05 日信工業株式会社 多孔質複合金属材料の製造方法
JP4300105B2 (ja) * 2003-12-19 2009-07-22 株式会社コーセー 抗酸化剤
FR2877015B1 (fr) * 2004-10-21 2007-10-26 Commissariat Energie Atomique Revetement nanostructure et procede de revetement.
EA010940B1 (ru) * 2004-11-05 2008-12-30 Дау Корнинг Айэлэнд Лимитед Плазменная система
DE102006005775A1 (de) * 2006-02-07 2007-08-09 Forschungszentrum Jülich GmbH Thermisches Spritzverfahren mit kolloidaler Suspension

Also Published As

Publication number Publication date
JP2010535624A (ja) 2010-11-25
WO2009021988A1 (fr) 2009-02-19
CA2696081A1 (en) 2009-02-19
US20120003397A1 (en) 2012-01-05
KR20100072184A (ko) 2010-06-30
EP2179071A1 (fr) 2010-04-28
CN101821421A (zh) 2010-09-01

Similar Documents

Publication Publication Date Title
EP2179071B1 (fr) Procédé de dépôt de nanoparticules sur un support
CN107313046B (zh) 一种sers基底及其制备方法
Zoval et al. Electrochemical deposition of silver nanocrystallites on the atomically smooth graphite basal plane
Biggs et al. Study of anion adsorption at the gold-aqueous solution interface by atomic force microscopy
Luo et al. Catalytic activation of core-shell assembled gold nanoparticles as catalyst for methanol electrooxidation
US6656339B2 (en) Method of forming a nano-supported catalyst on a substrate for nanotube growth
EP1802783B1 (fr) Procede de revêtement
Ahmad et al. Self-assembly and wetting properties of gold nanorod–CTAB molecules on HOPG
Pron'kin et al. Nanoparticles of Pt hydrosol immobilised on Au support: An approach to the study of structural effects in electrocatalysis
Twardowski et al. Chemically mediated grain growth in nanotextured Au, Au/Cu thin films: Novel substrates for the formation of self-assembled monolayers
Chen et al. Sonochemical and mechanical stirring synthesis of liquid metal nanograss structures for low‐cost SERS substrates
Saito et al. Fabrication of silver probes for localized plasmon excitation in near-field Raman spectroscopy
Bao et al. Nanoscale chemical characterization of materials and interfaces by tip-enhanced Raman spectroscopy
EP2093305A1 (fr) Procédé de dépôt de nanoparticules sur un support
EP3180810A1 (fr) Procédé de synthèse de nanocomposites a base de tio2 et de nanostructures carbonées
Su et al. Pt monolayer deposition onto carbon nanotube mattes with high electrochemical activity
EP2850223B1 (fr) Procede de fabrication d'un materiau composite
Dieluweit et al. Monodisperse gold nanoparticles formed on bacterial crystalline surface layers (S-layers) by electroless deposition
Rao et al. Reversal and control the tip-enhanced Raman scattering efficiency of rough plasmonic probes fabricated using UV-ozone and hydrazine
US20190217382A1 (en) Methods for synthesizing silver nanowires
Tabet-Aoul et al. Rhodium thin film-carbon nanotube nanostructures: Synthesis, characterization and electron transfer properties
EP2162938A2 (fr) Dispersion de materiaux composites, notamment pour des piles a combustible
Yoshida et al. The patterned Au oxide layer formation on Au surfaces by F2 laser irradiation under the atmospheric conditions
Borodinova et al. Growth of Gold Nanostructures on the MoS2 Surface Modified with Polyvinylpyrrolidone
Yoshimoto et al. Spontaneous electrodeposition of gold and platinum complexes through a coronene adlayer on Au (111)

Legal Events

Date Code Title Description
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

17P Request for examination filed

Effective date: 20100219

AK Designated contracting states

Kind code of ref document: A1

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

AX Request for extension of the european patent

Extension state: AL BA MK RS

RIN1 Information on inventor provided before grant (corrected)

Inventor name: RENIERS, FRANCOIS

Inventor name: DEMOISSON, FREDERIC

Inventor name: PIREAUX, JEAN-JACQUES

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20121206

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: UNIVERSITE DE NAMUR

Owner name: UNIVERSITE LIBRE DE BRUXELLES

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20150721

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

GRAJ Information related to disapproval of communication of intention to grant by the applicant or resumption of examination proceedings by the epo deleted

Free format text: ORIGINAL CODE: EPIDOSDIGR1

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

INTG Intention to grant announced

Effective date: 20151117

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): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MT NL NO PL PT RO SE SI SK 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: 790246

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160415

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: 602008043564

Country of ref document: DE

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: 790246

Country of ref document: AT

Kind code of ref document: T

Effective date: 20160413

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20160413

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

Ref country code: NL

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: 20160413

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: 20160413

Ref country code: FI

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: 20160413

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: 20160413

Ref country code: NO

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: 20160713

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

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: 20160413

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: 20160816

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: 20160714

Ref country code: ES

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: 20160413

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: 20160413

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: 20160413

Ref country code: SE

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: 20160413

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

Ref country code: IT

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: 20160413

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160831

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602008043564

Country of ref document: DE

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: 20160413

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: 20160413

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: 20160413

Ref country code: DK

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: 20160413

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: 20160413

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: 20170116

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: 20160413

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20160814

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

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160831

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160831

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

Effective date: 20170428

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: 20160413

REG Reference to a national code

Ref country code: IE

Ref legal event code: MM4A

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

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160814

Ref country code: FR

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160831

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160814

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

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20160814

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: 20080814

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: 20160413

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: 20160413

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: 20160413

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: 20160413

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: 20160413

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

Ref country code: DE

Payment date: 20190722

Year of fee payment: 12

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602008043564

Country of ref document: DE

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

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20210302