EP2179071B1 - Method of depositing nanoparticles on a support - Google Patents

Method of depositing nanoparticles on a 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)
French (fr)
Other versions
EP2179071A1 (en
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.)
Universite Libre de Bruxelles ULB
Universite de Namur
Original Assignee
Universite Libre de Bruxelles ULB
Universite de Namur
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/en
Application filed by Universite Libre de Bruxelles ULB, Universite de Namur filed Critical Universite Libre de Bruxelles ULB
Priority to EP08787216.4A priority Critical patent/EP2179071B1/en
Publication of EP2179071A1 publication Critical patent/EP2179071A1/en
Application granted granted Critical
Publication of EP2179071B1 publication Critical patent/EP2179071B1/en
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.

Description

Objet de l'inventionObject of the invention

La présente invention se rapporte à un procédé de dépôt et de fixation de nanoparticules sur un support quelconque.The present invention relates to a method for depositing and fixing nanoparticles on any support.

Etat de la techniqueState of the art

Il est généralement admis que le terme « nanoparticule » décrit un agrégat de petites molécules, ou un assemblage de quelques dizaines à quelques milliers d'atomes, formant une particule dont les dimensions sont de l'ordre du nanomètre, c'est-à-dire inférieures à 1000nm (1µ), de préférence inférieures à 100 nm. De par leur taille, ces particules possèdent des propriétés physiques, électriques, chimiques et magnétiques particulières et confèrent aux supports sur lesquels elles sont appliquées de nouvelles propriétés physiques, électriques, chimiques, magnétiques et mécaniques.It is generally accepted that the term "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 (1μ), 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.

Les nanoparticules présentent un intérêt grandissant du fait de leur implication dans le développement de nombreux dispositifs utilisés dans des domaines très différents, comme par exemple la détection de composés biologiques ou chimiques, la détection de gaz ou de vapeurs chimiques, l'élaboration de piles à combustible ou de dispositifs de stockage d'hydrogène, la réalisation de nanostructures électroniques ou optiques, de nouveaux catalyseurs chimiques, de bio-senseurs, ou de revêtements dits intelligents, tels des revêtements autonettoyants ou qui possèdent une activité biologique particulière, antibactérienne par exemple.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.

Il existe de nombreuses techniques permettant le dépôt de nanoparticules de différente nature, sur divers supports. Il existe des procédés de chimie en solution comme décrits par exemple dans l'article « Deposition of PbS particles from a nonaqueous chemical bath at room temperature » de T. Chaudhuri et al. Materials Letters (2005), 59 (17) pp 2191-2193 , et l'article « Deposition of gold nanoparticles on silica spheres by electroless metal plating technique » de Y. Kobayashi et al., Journal of Colloid and Interface Science (2005), 283 (2) pp 601-604 .There are many techniques allowing the deposition of nanoparticles of different nature, on various supports. There are methods of chemistry in solution as described for example in the article "Deposition of PbS particles from a nonaqueous chemical bath at room temperature" by T. Chaudhuri et al. Materials Letters (2005), 59 (17) pp 2191-2193 , and the article "Deposition of gold nanoparticles on silica spheres by electroless metal plating technique" by Y. Kobayashi et al., Journal of Colloid and Interface Science (2005), 283 (2) pp. 601-604 .

Il existe également des procédés d'électrochimie comme décrit par exemple dans l'article « Deposition of clusters and nanoparticles onto boron-doped diamond electrodes for electrocatalysis » de G. Sine et al., Journal of Applied Electrochemistry, (2006) 36 (8) pp 847-862 , et dans l'article « Deposition of platinum nanoparticles on organic functionalized carbon nanotubes grown in situ on carbon paper for fuel cell » de M. Waje et al., Nanotechnology (2005), 16 (7) pp 395-400 .There are also electrochemical methods as described for example in the article "Deposition of clusters and nanoparticles on boron-doped diamond electrodes for electrocatalysis" by G. Sine et al., Journal of Applied Electrochemistry, (2006) 36 (8) pp 847-862 and in the article "Deposition of platinum nanoparticles on organic functionalized carbon nanotubes grown in situ on carbon paper for fuel cell" by M. Waje et al., Nanotechnology (2005), 16 (7) pp 395-400 .

Il peut s'agir également de techniques de dépôt sous vide faisant intervenir un plasma comme décrit en particulier dans l'article « Platinum nanoparticles interaction with chemically modified highly oriented pyrolytic graphite surfaces » de D. Yang et al., Chemistry of materials (2006) 18 (7) pp 1811-1816 , et dans l'article « Au nanoparticles supported on HOPG: An XPS characterization », de D. Barreca et al. Surface Science Spectra (2005) 10 pp 164-169 .It may also be vacuum deposition techniques involving a plasma as described in particular in the article "Platinum nanoparticles interaction with chemically modified highly oriented pyrolytic graphite surfaces" by D. Yang et al., Chemistry of Materials (2006) 18 (7) pp 1811-1816 and in the article "Nanoparticles supported on HOPG: An XPS characterization" by D. Barreca et al. Surface Science Spectra (2005) 10 pp 164-169 .

Ces techniques présentent de nombreux inconvénients, qui peuvent être par exemple des problèmes liés à la reproductibilité du procédé utilisé, des problèmes de distribution, d'homogénéité et de régularité du dépôt de nanoparticules. Ces techniques sont également d'une mise en oeuvre complexe. Elles sont, d'une manière générale, onéreuses, du fait, entre autre, de la nécessité de générer un vide même partiel, et sont difficilement applicables à une échelle industrielle. De plus, le dépôt de nanoparticules comprend habituellement une étape d'activation du support, qui, dans les techniques décrites précédemment, requiert un traitement préalable qui est bien souvent complexe et qui peut prendre plusieurs heures, voire des jours.These techniques have many disadvantages, which can be for example problems related to the reproducibility of the process used, problems of distribution, homogeneity and regularity of the deposition of nanoparticles. These techniques are also of a complex implementation. They are, in a way generally, expensive, because, among other things, the need to generate even a partial vacuum, and are difficult to apply on an industrial scale. In addition, the deposition of nanoparticles usually comprises a step of activation of the support, which, in the techniques described above, requires a pretreatment which is often complex and may take several hours or even days.

En outre, toutes ces techniques posent des problèmes environnementaux, pour la chimie en solution ainsi que l'électrochimie, du fait notamment de l'utilisation de solvants et de réactifs chimiques polluant, et des problèmes de forte consommation d'énergie, pour ce qui concerne les techniques sous vide utilisant un plasma.In addition, all these techniques pose environmental problems for solution chemistry and electrochemistry, in particular because of the use of pollutant solvents and chemical reagents, and problems of high energy consumption, for example. relates to vacuum techniques using a plasma.

En particulier, le document WO2007/122256 décrit le dépôt de couches nanoporeuses par projection d'une solution colloïdale dans un jet de plasma thermique, un plasma dont les espèces neutres, les espèces ionisées et les électrons présentent une même température. Dans ce document, il est précisé que les particules de la solution colloïdale sont au moins partiellement fondues pour pouvoir adhérer au substrat. En particulier, le jet plasma décrit présente une température de gaz comprise entre 5000°K à 15000°K. On notera donc un effet thermique non négligeable tant sur le substrat que sur les particules du sol.In particular, 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. In this document, it is specified that the particles of the colloidal solution are at least partially melted in order to adhere to the substrate. In particular, 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.

Le document FR 2 877 015 décrit un procédé comprenant une injection d'un sol colloïdal de nanoparticules dans un jet de plasma qui les projette sur une surface. Ce type de plasma est un plasma chaud, travaillant généralement à une température supérieure au point de fusion des particules colloïdales.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.

Buts de l'inventionGoals of the invention

La présente invention propose un procédé de dépôt de nanoparticules sur un support qui ne présente pas les inconvénients de l'état de la technique.The present invention provides a method for depositing nanoparticles on a support which does not have the drawbacks of the state of the art.

La présente invention propose un procédé rapide, peu onéreux et d'une mise en oeuvre facilitée.The present invention provides a fast, inexpensive process and easy implementation.

La présente invention propose aussi de minimiser les contraintes thermiques tant sur le substrat que sur les nanoparticules.The present invention also proposes to minimize the thermal stresses both on the substrate and on the nanoparticles.

La présente invention propose également un procédé de dépôt qui améliore l'homogénéité du dépôt, et, plus particulièrement, la dispersion des nanoparticules sur le substrat.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.

Résumé de l'inventionSummary of the invention

La présente invention divulgue un procédé utilisant une solution (ou une suspension) colloïdale de nanoparticules pour le dépôt de nanoparticules sur un support, et utilisant un plasma atmosphérique pour le dépôt de nanoparticules sur un support.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.

La présente invention concerne un procédé de dépôt de nanoparticules sur un support comprenant les étapes suivantes :

  • prendre une solution (ou une suspension) colloïdale de nanoparticules et,
  • nébuliser ladite solution (ou une suspension) colloïdale de nanoparticules sur une surface dudit support dans un plasma atmosphérique.
The present invention relates to a method for depositing nanoparticles on a support comprising the following steps:
  • take a colloidal solution (or suspension) of nanoparticles and,
  • nebulizing said colloidal solution (or suspension) of nanoparticles on a surface of said support in an atmospheric plasma.

On entend par « nanoparticule » un agrégat de petites molécules, ou un assemblage de quelques centaines à quelques milliers d'atomes, formant une particule dont les dimensions sont de l'ordre du nanomètre, généralement inférieures à 100nm.The term "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.

On entend par « solution colloïdale » une suspension homogène de particules dans laquelle le solvant est un liquide et le soluté un solide disséminé de manière homogène sous forme de très fines particules. Les solutions colloïdales peuvent prendre des formes diverses, liquide, gel ou pâte. Les solutions colloïdales sont intermédiaires entre les suspensions, qui sont des milieux hétérogènes comprenant des particules microscopiques dispersées dans un liquide, et les solutions vraies, dans lesquelles le ou les solutés sont à l'état de division moléculaire dans le solvant. Sous forme liquide, les solutions colloïdales sont parfois aussi appelées des « sol ».The term "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".

Dans une forme préférée de réalisation de la présente invention, le plasma atmosphérique est un plasma non-thermique atmosphérique.In a preferred embodiment of the present invention, the atmospheric plasma is an atmospheric non-thermal plasma.

On entend par « plasma non-thermique », ou « plasma froid », un gaz partiellement ou totalement ionisé qui comprend des électrons, des ions (moléculaires ou atomiques), des atomes ou molécules, et des radicaux, hors de l'équilibre thermodynamique, dont la température des électrons (température de plusieurs milliers ou plusieurs dizaines de milliers de Kelvin) est significativement supérieure à celle des ions et des neutres (température proche de la température ambiante jusqu'à quelques centaines de Kelvin).The term "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).

On entend par « plasma atmosphérique » ou, « plasma non-thermique atmosphérique » ou encore « plasma froid atmosphérique », un gaz partiellement ou totalement ionisé qui comprend des électrons, des ions (moléculaires ou atomiques), des atomes ou molécules, et des radicaux, hors de l'équilibre thermodynamique, dont la température des électrons est significativement supérieure à celle des ions et des neutres (les températures sont similaires à celles décrites pour un « plasma froid »), et dont la pression est comprise entre environ 1 mbar et environ 1200 mbar, de préférence entre environ 800 et environ 1200 mbar.The term "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.

Selon une forme particulière de réalisation de l'invention, le procédé comporte l'une ou plusieurs des caractéristiques suivantes :

  • le plasma comprend un gaz plasmagène et que la température macroscopique dudit gaz plasmagène dans ledit plasma peut varier entre environ -20°C et environ 600°C, de préférence entre -10°C et environ 400°C et de préférence entre la température ambiante et environ 400°C;
  • le procédé comprend en outre une étape d'activation de la surface du support en soumettant ladite surface dudit support au plasma atmosphérique ;
  • l'activation de la surface du support et la nébulisation de la solution colloïdale sont concomitantes ;
  • l'activation de la surface du support est précédée par une étape de nettoyage de ladite surface dudit support ;
  • la nébulisation de la solution colloïdale de nanoparticules se fait dans la zone décharge ou dans la zone post-décharge du plasma atmosphérique ;
  • le plasma est généré par une torche à plasma atmosphérique ;
  • la nébulisation de la solution colloïdale de nanoparticules se fait dans une direction sensiblement parallèle à la surface du support ;
  • les nanoparticules sont des nanoparticules d'un métal, d'un oxyde métallique, d'un alliage métallique ou de leur mélange ;
  • les nanoparticules sont des nanoparticules d'au moins un métal de transition, de son oxyde correspondant, d'un alliage de métaux de transition ou de leur mélange ;
  • les nanoparticules sont choisies dans le groupe formé par le magnésium (Mg), le strontium (Sr), le titane (Ti), le zirconium (Zr), le lanthane (La), le vanadium (V), le niobium (Nb), le tantale (Ta), le chrome (Cr), le molybdène (Mo), le tungstène (W), le manganèse (Mn), le rhénium (Re), le fer (Fe), le ruthénium (Ru), l'osmium (Os), le cobalt (Co), le rhodium (Rh), l'iridium (Ir), le nickel (Ni), le palladium (Pd), le platine (Pt), le cuivre (Cu), l'argent (Ag), l'or (Au), le zinc (Zn), le cadmium (Cd), l'aluminium (Al), l'iridium (In), l'étain (Sn), le plomb (Pb), leurs oxydes correspondants, ou un alliage de ces métaux ;
  • les nanoparticules sont choisies dans le groupe formé par le dioxyde de titane (titane (TiO2)), l'oxyde de cuivre (CuO), l'oxyde ferreux (FeO), l'oxyde ferrique (Fe2O3), l'oxyde de fer (Fe3O4), le dioxyde d'iridium (IrO2), de dioxyde de zirconium (ZrO2), l'oxyde d'aluminium (Al2O3) ;
  • les nanoparticules sont choisies dans le groupe formé par un alliage or/platine (AuPt), platine/ruthénium (PtRu), cadmium/soufre (CdS), ou plomb/souffre (PbS) ;
  • le support est un support solide, un gel ou un matériau nano-structuré ;
  • le support est choisi parmi le groupe formé par un support carboné, des nanotubes de carbone, un métal, un alliage métallique, un oxyde métallique, une zéolite, un semi-conducteur, un polymère, du verre et/ou de la céramique ;
  • le support est de la silice, du carbone, du titane, de l'alumine, ou des nanotubes de carbone multi-parois ;
  • le plasma atmosphérique est généré à partir d'un gaz plasmagène choisi parmi le groupe formé par l'argon, l'hélium, l'azote, l'hydrogène, l'oxygène, du dioxyde de carbone, de l'air ou leur mélange ;
According to a particular embodiment of the invention, the method comprises one or more of the following characteristics:
  • the plasma comprises a plasma gas and the macroscopic temperature of said plasma gas in said plasma can range from about -20 ° C to about 600 ° C, preferably from -10 ° C to about 400 ° C and preferably from room temperature to about 400 ° C;
  • the method further comprises a step of activating the surface of the support by subjecting said surface of said support to atmospheric plasma;
  • the activation of the surface of the support and the nebulization of the colloidal solution are concomitant;
  • the activation of the surface of the support is preceded by a step of cleaning said surface of said support;
  • the nebulization of the colloidal solution of nanoparticles is done in the discharge zone or in the post-discharge zone of the atmospheric plasma;
  • the plasma is generated by an atmospheric plasma torch;
  • the nebulization of the colloidal solution of nanoparticles is in a direction substantially parallel to the surface of the support;
  • the nanoparticles are nanoparticles of a metal, a metal oxide, a metal alloy or their mixture;
  • the nanoparticles are nanoparticles of at least one transition metal, its corresponding oxide, a transition metal alloy or their mixture;
  • the nanoparticles are chosen from the group formed by magnesium (Mg), strontium (Sr), titanium (Ti), zirconium (Zr), lanthanum (La), vanadium (V), niobium (Nb) , tantalum (Ta), chromium (Cr), molybdenum (Mo), tungsten (W), manganese (Mn), rhenium (Re), iron (Fe), ruthenium (Ru), l osmium (Os), cobalt (Co), rhodium (Rh), iridium (Ir), nickel (Ni), palladium (Pd), platinum (Pt), copper (Cu), silver (Ag), gold (Au), zinc (Zn), cadmium (Cd), aluminum (Al), iridium (In), tin (Sn), lead (Pb), their corresponding oxides, or an alloy of these metals;
  • the nanoparticles are chosen from the group formed by titanium dioxide (titanium (TiO 2 )), copper oxide (CuO), ferrous oxide (FeO), ferric oxide (Fe 2 O 3 ), l iron oxide (Fe 3 O 4 ), iridium dioxide (IrO 2 ), zirconium dioxide (ZrO 2 ), aluminum oxide (Al 2 O 3 );
  • the nanoparticles are chosen from the group formed by a gold / platinum (AuPt), platinum / ruthenium (PtRu), cadmium / sulfur (CdS) or lead / sulfur (PbS) alloy;
  • the support is a solid support, a gel or a nano-structured material;
  • the support is selected from the group consisting of a carbon support, carbon nanotubes, a metal, a metal alloy, a metal oxide, a zeolite, a semiconductor, a polymer, glass and / or ceramic;
  • the support is silica, carbon, titanium, alumina, or multi-walled carbon nanotubes;
  • the atmospheric plasma is generated from a plasma gas selected from the group consisting of argon, helium, nitrogen, hydrogen, oxygen, carbon dioxide, air or their mixture ;

Dans une forme préférée de réalisation de la présente invention, la solution colloïdale comprend un surfactant.In a preferred embodiment of the present invention, the colloidal solution comprises a surfactant.

On entend par « surfactant », « tensioactif » ou « agent de surface », un composé modifiant la tension superficielle entre deux surfaces. Les composés tensioactifs sont des molécules amphiphiles, c'est-à-dire qu'elles présentent deux parties de polarité différente, l'une lipophile et apolaire, et, l'autre, hydrophile et polaire. Ce type de molécules permet de stabiliser les colloïdes. Il existe des tensioactifs cationiques, anioniques, amphotères ou non ioniques. Un exemple de tel tensioactif est le citrate de sodium.The term "surfactant", "surfactant" or "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. There are cationic surfactants, anionic, amphoteric or nonionic. An example of such a surfactant is sodium citrate.

La présente invention divulgue par ailleurs l'utilisation d'une solution colloïdale de nanoparticules pour le dépôt de nanoparticules sur un support à l'aide d'un plasma atmosphérique.The present invention also discloses the use of a colloidal solution of nanoparticles for depositing nanoparticles on a support using an atmospheric plasma.

Selon des formes particulières de réalisation, l'utilisation de la solution colloïdale de nanoparticule comporte l'une ou plusieurs des caractéristiques suivantes :

  • la solution colloïdale est nébulisée dans la zone décharge ou post-décharge du plasma atmosphérique ;
  • le plasma atmosphérique est généré par une torche à plasma atmosphérique.
According to particular embodiments, the use of the colloidal nanoparticle solution comprises one or more of the following characteristics:
  • the colloidal solution is nebulized in the discharge or post-discharge zone of the atmospheric plasma;
  • the atmospheric plasma is generated by an atmospheric plasma torch.

La présente invention décrit également l'utilisation d'un plasma atmosphérique pour le dépôt de nanoparticules sur un support, lesdites nanoparticules étant sous la forme d'une solution colloïdale de nanoparticules, et ladite solution colloïdale étant nébulisée à la surface dudit support dans la ledit plasma atmosphérique.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.

Brève description des figuresBrief description of the figures

La figure 1 représente la distribution en taille des particules d'or d'une solution colloïdale.The figure 1 represents the size distribution of the gold particles of a colloidal solution.

La figure 2 représente une image obtenue par microscopie électronique à transmission (MET) d'une solution colloïdale des particules d'or.The figure 2 represents an image obtained by transmission electron microscopy (TEM) of a colloidal solution of gold particles.

La figure 3 représente schématiquement une torche à plasma atmosphérique.The figure 3 schematically represents an atmospheric plasma torch.

La figure 4 représente des spectres de spectroscopie de photoélectrons X (XPS) de la surface du graphite HOPGaprès dépôt de nanoparticules d'or par plasma selon le procédé de la présente invention. (a) spectre global, (b) spectre déconvolué du niveau Au 4f, (c) spectre déconvolué du niveau O 1s, (d) spectre déconvolué du niveau C 1s.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. (a) spectrum global, (b) Deconvolved spectrum of the Au 4f level, (c) deconvolved spectrum of the O 1s level, (d) deconvolved spectrum of the C 1s level.

La figure 5 représente des images de microscopie à force atomique (AFM) d'un échantillon de graphite HOPG a)avant, et b) après dépôt de nanoparticules d'or selon le procédé de la présente invention.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.

La figure 6 représente des images de microscopie électronique à haute résolution des électrons secondaires (FEG-SEM) d'un échantillon de graphite HOPG a)avant, b) et c) après dépôt de nanoparticules d'or selon le procédé de la présente invention. (a) grossissement x 2000, (b) grossissement x 25000, (c) grossissement x 80000. L'analyse par dispersion d'énergie (EDS) est collectée sur des nanoparticules.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. (a) magnification x 2000, (b) magnification x 25000, (c) magnification x 80000. Energy dispersive analysis (EDS) is collected on nanoparticles.

La figure 7 représente la comparaison du spectre XPS expérimental du niveau Au 4f présenté en figure 4(b) et du spectre modélisé en utilisant un modèle de croissance de type Volmer-Weber.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.

La figure 8 représente un spectre de spectroscopie de photoélectrons X (XPS) de la surface du graphite HOPG après dépôt de nanoparticules d'or sans l'utilisation d'un plasma (comparatif).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).

La figure 9 représente une image de microscopie électronique à haute résolution des électrons secondaires (FEG-SEM) d'un échantillon de graphite HOPG après le dépôt de nanoparticules d'or sans l'utilisation d'un plasma (comparatif).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).

La figure 10 représente une image (grossissement x 100000) obtenue par microscopie électronique à haute résolution des électrons secondaires (FEG-SEM) d'un échantillon d'acier après dépôt de nanoparticules d'or selon le procédé de la présente invention.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.

La figure 11 représente une image (grossissement x 3000) obtenue par microscopie électronique à haute résolution des électrons secondaires (FEG-SEM) d'un échantillon de verre après dépôt de nanoparticules d'or selon le procédé de la présente 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.

La figure 12 représente une image (grossissement x 50000) obtenue par microscopie électronique à haute résolution des électrons secondaires (FEG-SEM) d'un échantillon de polymère PVC après dépôt de nanoparticules d'or selon le procédé de la présente 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.

La figure 13 représente une image (grossissement x 10000) obtenue par microscopie électronique à haute résolution des électrons secondaires (FEG-SEM) d'un échantillon de polymère HDPE après dépôt de nanoparticules d'or selon le procédé de la présente 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.

La figure 14 représente une image (grossissement x 10000) obtenue par microscopie électronique à haute résolution des électrons secondaires (FEG-SEM) d'un échantillon d'acier après dépôt de nanoparticules d'or, en absence de plasma (comparatif).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).

La figure 15 représente une image obtenue par microscopie électronique à transmission (TEM) d'un échantillon de nanotubes de carbones avant (a) et après dépôt de nanoparticules d'or selon le procédé de la présente invention (b).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).

La figure 16 représente un spectre de spectroscopie de photoélectrons X (XPS) de la surface des nanotubes de carbones après dépôt de nanoparticules d'or selon le procédé de la présente invention.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.

La figure 17 représente une image obtenue par microscopie électronique à transmission (TEM) d'un échantillon de nanotubes de carbones après dépôt de nanoparticules de platine selon le procédé de la présente invention.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.

La figure 18 représente un spectre de spectroscopie de photoélectrons X (XPS) de la surface des nanotubes de carbones après dépôt de nanoparticules de platine selon le procédé de la présente invention.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.

La figure 19 représente une image (grossissement x 120000) de microscopie électronique à haute résolution des électrons secondaires (FEG-SEM) d'un échantillon de graphite HOPG après le dépôt de nanoparticules de rhodium selon le procédé de la présente invention.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.

La figure 20 représente un spectre de spectroscopie de photoélectrons X (XPS) de la surface de graphite HOPG après dépôt de nanoparticules de rhodium selon le procédé de la présente 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.

La figure 21 représente une image (grossissement x 100000) de microscopie électronique des électrons secondaires (FEG-SEM) d'un échantillon d'acier après le dépôt de nanoparticules de platine selon le procédé de la présente invention.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.

La figure 22 représente une image (grossissement x 100000) de microscopie électronique des électrons secondaires (FEG-SEM) d'un échantillon de PVC après le dépôt de nanoparticules de rhodium selon le procédé de la présente invention.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.

La figure 23 représente une image (grossissement x 100000) de microscopie électronique des électrons secondaires (FEG-SEM) d'un échantillon de HDPE après le dépôt de nanoparticules de rhodium selon le procédé de la présente invention.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.

Description détaillée de plusieurs formes d'exécution de l'inventionDetailed description of several embodiments of the invention

Le procédé de dépôt de nanoparticules selon l'invention fait intervenir une solution, ou suspension, colloïdale de nanoparticules qui est déposée sur un support quelconque à l'aide d'un plasma atmosphérique, ledit plasma atmosphérique pouvant être généré par tout dispositif adéquat faisant usage d'un plasma atmosphérique.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.

Ce procédé présente de nombreux avantages. Par exemple, il permet d'effectuer un dépôt dit «propre», c'est-à-dire sans utilisation de solvants dits «polluant». Avantageusement, le dépôt de nanoparticules selon l'invention ne fait appel qu'à une faible consommation d'énergie. De manière surprenante, le dépôt de nanoparticules est rapide car l'activation du support et la nébulisation des nanoparticules, éventuellement également le nettoyage préalable du support, sont réalisés dans le plasma atmosphérique, ou dans le flux du plasma atmosphérique, en une seule étape ou un seul processus continu.This method has many advantages. For example, it allows a so-called "clean" deposit, that is to say without the use of solvents called "pollutant". Advantageously, the deposition of nanoparticles according to the invention uses only a low energy consumption. Surprisingly, 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.

De manière surprenante, le procédé selon l'invention permet une forte adhésion des nanoparticules au support. Cette technique permet de contrôler les propriétés de l'interface et d'ajuster le dépôt des nanoparticules sur le support. De plus, ce procédé ne requiert pas d'installations onéreuses et il est facilement mis en oeuvre industriellement.Surprisingly, 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. In addition, this method does not require expensive installations and is easily implemented industrially.

La solution colloïdale de nanoparticules peut être préparée par toute technique et/ou tout moyen adéquat.The colloidal solution of nanoparticles can be prepared by any technique and / or any suitable means.

Dans le procédé selon l'invention, le support, sur lequel la solution colloïdale de nanoparticules est déposée, est tout matériau adéquat pouvant être recouvert de nanoparticules, tout matériau quel que soit sa nature et/ou sa forme. De préférence, il s'agit d'un support solide, d'un gel ou d'un matériau nano-structuré.In the process according to the invention, 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. Preferably, he it is a solid support, a gel or a nano-structured material.

Dans le procédé selon l'invention, le plasma est tout plasma atmosphérique adéquat. Il s'agit d'un plasma généré à une pression comprise entre environ 1 mbar et environ 1200 mbar, de préférence entre 800 et 1200 mbar. De préférence, il s'agit d'un plasma atmosphérique dont la température macroscopique du gaz peut varier par exemple entre la température ambiante et environ 400°C. De préférence, le plasma est généré par une torche à plasma atmosphérique.In the process according to the invention, 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.

Un plasma atmosphérique ne fait pas appel au vide, ce qui permet d'être peu onéreux et d'un entretien facilité. Le plasma atmosphérique permet de nettoyer et d'activer la surface du support, soit en la fonctionnalisant, en créant par exemple des groupements oxygénés, azotés, soufrés, et/ou hydrogénés, soit en créant des défauts en surface, par exemple des lacunes, des marches, et/ou des piqûres. Ces groupements de surfaces peuvent par exemple comprendre des radicaux très réactifs et ayant une courte durée de vie.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.

Ces groupements réactifs à la surface du substrat peuvent alors réagir avec la surface des nanoparticules, ou, avec les surfactants présents à leurs surfaces. Les nanoparticules elles même peuvent être activées par le plasma, soit directement par formation de radicaux à partir de l'eau d'hydratation, soit par réactions avec un surfactant fixé à la surface de la nanoparticule.These reactive groups on the surface of the substrate can then react with the surface of the nanoparticles, or with the surfactants present on their surfaces. The 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.

De préférence, dans le procédé selon l'invention, l'activation du support et la nébulisation de la solution colloïdale se font de manière concomitante, à savoir dans le plasma, ou dans le flux du plasma, généré par un dispositif faisant usage d'un plasma atmosphérique. Ainsi la nébulisation de la solution colloïdale se produit en même temps, ou bien immédiatement après, l'activation du support par le plasma atmosphérique.Preferably, in the method according to the invention, 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. Thus the nebulization of the colloidal solution occurs at the same time, or immediately after, the activation of the support by the atmospheric plasma.

La nébulisation de la solution colloïdale peut se faire soit dans la zone décharge ou dans la zone post décharge du plasma atmosphérique. De préférence, la nébulisation de la solution colloïdale se fait dans la zone post décharge du plasma car, dans certains cas, cela peut présenter des avantages supplémentaires. Cela peut permettre de ne pas contaminer le dispositif générant le plasma. Cela peut permettre de faciliter le traitement de supports polymériques, d'éviter la dégradation du support à recouvrir, et aussi, par exemple, ne pas causer la fusion, l'oxydation, la dégradation et/ou l'agrégation des nanoparticules.The nebulization of the colloidal solution can be done either in the discharge zone or in the post-discharge zone of the atmospheric plasma. Preferably, 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.

La nébulisation de la solution colloïdale est toute nébulisation adéquate et peut se faire sous n'importe quelle direction (orientation) par rapport à la surface du support. De préférence, la nébulisation se fait dans une direction sensiblement parallèle au support, mais elle peut également se faire par exemple sous un angle d'environ 45°, ou par exemple sous un angle d'environ 75°par rapport à la surface du support à traiter.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. Preferably, 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.

Exemple 1 :Example 1

Des nanoparticules d'or ont été déposées sur du graphite pyrolytique hautement orienté (HOPG), un support qui présente des propriétés chimiques similaires à celles des nanotubes de carbone multiparois(MWCNTs).Gold nanoparticles were deposited on highly oriented pyrolytic graphite (HOPG), a support that has chemical properties similar to those of multiwall carbon nanotubes (MWCNTs).

Le graphite pyrolytique hautement orienté (HOPG) est commercialement disponible (MikroMasch - Axesstech, France). D'une qualité ZYB, ce graphite, d'une taille de 10 mm x 10 mm x 1 mm, présente un angle appelé « mosaic spread angle » de 0,8°±0,2° et une taille de « lateral grain » supérieur à 1 mm. Quelques couches de surface du graphite sont préalablement détachées à l'aide de ruban adhésif, avant que l'échantillon de graphite ne soit immergé dans une solution d'éthanol pendant 5 minutes, sous ultrasonication.Highly Oriented Pyrolytic Graphite (HOPG) is commercially available (MikroMasch - Axesstech, France). With a ZYB quality, 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.

La suspension colloïdale est préparée par exemple selon la méthode de réduction thermique du citrate comme décrite dans l'article de Turkevich et al. J. Faraday Discuss. Chem. Soc. (1951), 11 page 55 , d'après la réaction suivante :

        6 HAuCl4 + K3C6H5O7 + 5 H2O → 6 Au + 6 CO2 + 21 HCl + 3 KCl,

dans laquelle le citrate agissant comme réducteur et comme stabilisant. Classiquement, une solution d'or est préparée en additionnant 95 mL d'une solution aqueuse à 134 mM d'acide tetrachloroaurique (HAuCl4, 3H2O, Merck) et 5 mL d'une solution aqueuse à 34 mM de citrate trisodique (C6H8O7Na3, 2H2O, Merck) avec 900 mL d'eau distillée. La solution ainsi obtenue est alors portée à ébullition pendant 15 minutes. D'une couleur jaune pâle, la solution d'or passe alors à une couleur rouge en l'espace d'une à trois minutes.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. Conventionally, 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.

Cette méthode de réduction thermique du citrate permet d'obtenir une dispersion stable de particules d'or, dont la concentration en or est de 134mM, et dont les particules ont un diamètre moyen d'environ 10 nm et environ 10 % de polydispersité (Figure 1).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 ).

Le dépôt de la suspension colloïdale d'or sur le graphite pyrolytique hautement orienté s'effectue à l'aide d'une source plasma AtomfloTM-250 (Surfx Technologies LLC). Comme décrit à la figure 3, le diffuseur de la torche à plasma comprend deux électrodes perforées en aluminium, de 33 mm de diamètre, et séparées par un espace de 1,6 mm de large. Dans cet exemple précis, le diffuseur est placé à l'intérieur d'une chambre hermétique, sous atmosphère d'argon, à température ambiante. L'électrode supérieure 1 de la source plasma est connectée à un générateur de radiofréquence, par exemple de 13,56MHz, alors que l'électrode inférieure 2 est mise à la terre.Deposition of the gold colloidal suspension on the highly oriented pyrolytic graphite is carried out using an AtomfloTM-250 plasma source (Surfx Technologies LLC). As described in figure 3 , 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. In this specific example, 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.

La torche à plasma fonctionne à 80 W et le plasma 3 est formé en alimentant la torche en amont des électrodes avec de l'argon 4 à un débit de 30 L/min. L'espace entre l'échantillon 5 de graphite HOPG reposant sur un porte échantillon 7 et l'électrode inférieure 2 est de 6 ± 1 mm. Cet espace est sous pression atmosphérique.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.

Avant le dépôt des nanoparticules, le support graphite est soumis au flux de plasma de la torche à plasma, pendant par exemple environ 2 minutes, ce qui permet de nettoyer et d'activer le support. 3 à 5 ml de suspension colloïdale, est nébulisée, dans la zone post-décharge de la torche à plasma et dans une direction 6 sensiblement parallèlement à l'échantillon (Figure 3). La suspension colloïdale est injectée pendant environ 5 minutes, par pulsations périodiques d'environ une seconde, espacées d'environ 15 secondes. Les échantillons 5 sont ensuite lavés dans une solution d'éthanol sous ultrasonication pendant environ 5 minutes.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.

Une analyse par spectroscopie de photoélectrons X (XPS) de la surface du graphite HOPG recouvert de nanoparticules a été réalisée sur un appareil ThermoVG Microlab 350, avec une chambre analytique à une pression de 10-9 mbar et une source de rayons-X Al Kα (hγ =1486.6 eV) fonctionnant à 300 W. Les spectres ont été mesurés avec un angle d'enregistrement de 90° et ont été enregistrés avec une énergie de passage dans l'analyseur de 100 eV et une taille de faisceau de rayons-X de 2 mm x 5 mm. La détermination de l'état chimique a été faite, quant à elle, avec une énergie de passage dans l'analyseur de 20 eV. Les effets de charge sur les positions de l'énergie de liaison mesurées ont été corrigés en fixant l'énergie de liaison de l'enveloppe spectrale du carbone, C(1s), à 284,6 eV, une valeur généralement admise pour une contamination accidentelle de la surface du carbone. Les spectres du carbone, de l'oxygène et de l'or ont été déconvolués en utilisant un modèle de ligne de base de Shirley et un modèle Gaussien-Lorentzien.An X-ray photoelectron spectroscopy (XPS) analysis of the surface of nanoparticle-coated HOPG graphite was performed on a ThermoVG Microlab 350, with an analytical chamber at a pressure of 10 -9 mbar and an Al Kα X-ray source. (hγ = 1486.6 eV) operating at 300 W. The spectra were measured at a recording angle of 90 ° and were recorded with 100 eV analyzer pass energy and X-ray beam size 2 mm x 5 mm. The determination of the chemical state was made, with a passing energy in the analyzer of 20 eV. 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.

Les spectres XPS de la surface du graphite HOPG recouvert de nanoparticules sont représentés à la figure 4. La figure 4a) montre la présence de carbone à un pourcentage de 77,8%, d'oxygène à un pourcentage de 14,9%, de potassium à un pourcentage de 3,2% et d'or à un pourcentage de 1,0%. Des traces de silice ont été également détectées ; il s'agit d'impuretés incorporées aux échantillons de graphite HOPG. Cette analyse indique une forte adhésion de l'or sur le graphite HOPG bien que les échantillons aient été lavés dans une solution d'éthanol sous ultrasonication. Il est à noter qu'avec ou sans l'étape de nettoyage à l'éthanol par ultrasons, la quantité d'or déposée sur le graphite HOPG est similaire.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.

Le spectre de l'or, Au(4f) (Figure 4b), a été déconvolué par rapport aux doublets spin-orbite Au4f5/2- Au4f7/2 avec un rapport d'intensité fixe de 0,75:1 et avec une énergie de séparation de 3,7 eV. La composante unique Au4f7/2 est localisée à 83,7 eV, ce qui permet de l'attribuer sans ambigüité à de l'or métallique. Cela signifie que les amas d'or n'ont pas été significativement oxydés durant le traitement avec le plasma.The spectrum of gold, Au (4f) ( Figure 4b ), was deconvolved relative to Au4f5 / 2- Au4f7 / 2 spin-orbit doublets with a fixed intensity ratio of 0.75: 1 and with a separation energy of 3.7 eV. The unique Au4f7 / 2 component is located at 83.7 eV, allowing unambiguous attribution to metallic gold. This means that the gold clusters have not been significantly oxidized during plasma treatment.

Le spectre du carbone, C(1s), représenté à la Figure 4d) comprend un pic principal à 283,7 eV qui est attribué à une liaison carbone-carbone (sp2). Les pics localisés à 284,6 eV, 285,8 eV et 288,6 eV peuvent être attribués respectivement aux liaisons C-C (sp3), C-O, et O-C=O. La présence de liaisons C-O et O-C=O observées provient probablement, soit de la brève exposition des échantillons à l'oxygène ambiant durant leur manipulation, soit de la présence d'une faible quantité d'oxygène durant le traitement plasma comme le suggère la caractérisation post-décharge par spectrométrie optique d'émission (données non représentées). Cette explication est en accord avec le spectre de l'oxygène, O(1s qui montre la présence de liaisons O-C (533,5 eV) et O=C (531,9 eV).The carbon spectrum, C (1s), represented at Figure 4d ) comprises a main peak at 283.7 eV which is attributed to a carbon-carbon bond (sp2). Peaks at 284.6 eV, 285.8 eV and 288.6 eV can be attributed to the CC (sp3), CO, and OC = O bonds, respectively. The presence of observed CO and OC = O bonds is probably due either to the brief exposure of the samples to ambient oxygen during handling, or to the presence of a small amount of oxygen during the plasma treatment as suggested by the characterization post-discharge by optical emission spectrometry (data not shown). This explanation is in agreement with the oxygen spectrum, O (1s which shows the presence of OC bonds (533.5 eV) and O = C (531.9 eV).

La morphologie de la surface du graphite HOPG recouvert de nanoparticules a été étudiée en réalisant des images de microscopie à force atomique (AFM) enregistrées à l'aide d'un appareil PicoSPM® LE avec un contrôleur Nanoscope IIIa (Digital Instruments, Veeco) fonctionnant dans les conditions du milieu ambiant. Le microscope est équipé d'un analyseur de 25 µm et fonctionne en mode contact. Le cantilever utilisé est une sonde silice basse fréquence NC-AFM Pointprobe® de Nanosensors (Wetzlar-Blankenfeld, Germany) ayant une extrémité pyramidale intégrée avec un rayon de courbure de 110 nm. La constante de ressort du cantilever se situe entre 30 et 70 N m-1 et sa mesure de fréquence de résonnance libre est de 163,1 kHz. Les images ont été enregistrées à des fréquences de balayage de 0,5 à 1 ligne par seconde.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 μm 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.

Les images de microscopie à force atomique (1µm x 1µm) avant et après le dépôt des nanoparticules par traitement plasma sont représentées en figure 5. Comme le montre la figure 5b), le graphite est recouvert d'amas, ou d'ilots, d'or qui sont soit isolés, et qui ont un diamètre supérieur à 0,01µm (10 nm), soit ramifiés. Ces îlots sont dispersés de façon homogène avec un taux de recouvrement d'environ 12%.Atomic force microscopy images (1 μm x 1 μm) before and after the deposition of the nanoparticles by plasma treatment are represented in FIG. figure 5 . As shown in figure 5b ), the graphite is covered with clusters, or islands, of gold that are either isolated, and have a diameter greater than 0.01μm (10 nm), or branched. These islands are dispersed homogeneously with a recovery rate of about 12%.

Afin de confirmer la nature des ilots et afin d'en obtenir des images à fort grossissement, des images de microscopie électronique à balayage couplée à un spectromètre rayons-X à dispersion d'énergie (EDS) ont été réalisées grâce à un appareil JEOL JSM-7000F équipé d'un spectromètre (EDS, JED-2300F). Cet instrument, en fonctionnant à une tension d'accélération de 15kV et avec un grossissement de 80000 fois, permet non seulement d'analyser la morphologie des structures de surface, qui peuvent être ainsi observées avec un contraste optimal, mais aussi de déterminer la distribution de la taille des ilots. L'analyse par spectrométrie rayons-X à dispersion d'énergie (EDS) permet, quant à elle, d'appréhender leur composition chimique.In order to confirm the nature of the islands and to obtain high magnification images, images of Scanning electron microscopy coupled to an energy dispersive X-ray spectrometer (EDS) were performed using a JEOL JSM-7000F instrument equipped with a spectrometer (EDS, JED-2300F). This instrument, operating at an acceleration voltage of 15kV and with a magnification of 80000 times, not only allows to analyze the morphology of the surface structures, which can thus be observed with an optimal contrast, but also to determine the distribution the size of the islands. Analysis by energy dispersive X-ray spectrometry (EDS) makes it possible to understand their chemical composition.

Avant leur analyse, les échantillons de graphite sont préalablement déposés sur une bande de cuivre d'un porte échantillon avant d'être introduits dans la chambre d'analyse sous une pression d'environ 10-8 mbar.Before their analysis, 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.

Comme le montre la figure 6a, à l'état initial, plusieurs marches sont observables à un grossissement de 20000 fois. De plus, comme le montre la figure 6b) de nombreux amas, représentés par des points brillants, et ayant une distribution homogène, sont présents à la surface du graphite après le dépôt de nanoparticules selon le procédé de l'invention. A un grossissement plus important (80000 fois, Figure 6c)) il est facile d'apercevoir des agrégats et des nanoparticules isolées d'un diamètre d'environ 10 nm. Une analyse par spectrométrie rayons-X à dispersion d'énergie (Figure 6d)) confirme que les points brillants sont des nanoparticules d'or. Il est également important de noter que les agrégats sont organisés en paquet de grappes de nanoparticules d'or qui ont le même diamètre de particule que celles de la suspension colloïdale initiale (Figure 1).As shown in figure 6a in the initial state, several steps are observable at a magnification of 20000 times. In addition, as shown in figure 6b ) many clusters, represented by bright spots, and having a homogeneous distribution, are present on the surface of the graphite after the deposition of nanoparticles according to the method of the invention. At a higher magnification (80000 times, Figure 6c )) it is easy to see isolated aggregates and nanoparticles with a diameter of about 10 nm. Energy dispersive X-ray spectrometry analysis (Figure 6d) ) confirms that the bright dots are gold nanoparticles. It is also important to note that the aggregates are organized into clusters of gold nanoparticles that have the same particle diameter as those of the original colloidal suspension ( Figure 1 ).

La morphologie du dépôt, à une résolution de profondeur de l'ordre du nanomètre, a également été quantifiée par l'analyse du signal du pic Au 4f (Figure 7), une méthode proposée par Tougaard et collaborateurs dans un article de J. Vac. Sci. Technol (1996) 14 page 1415 .The morphology of the deposit, at a depth resolution of about one nanometer, was also quantified by Au 4f peak signal analysis ( Figure 7 ), a method proposed by Tougaard et al. in an article by J. Vac. Sci. Technol (1996) 14 page 1415 .

Le tableau 1 résume les caractéristiques de la structure des ilots d'or sur le graphite HOPG résultant de l'analyse de trois spectres Au4f par le logiciel QUASES-Tougaard, qui s'expriment en taux de recouvrement (t = épaisseur de la couche de C de contamination) et hauteur des ilots d'or (h). Le mode de croissance est de type Volmer-Weber (structure 3D en ilots) Tableau 1 : Echantillons Hauteur des ilots d'or h (nm) Pourcentage de recouvrement (%) Epaisseur de carbone (couche de contamination) (nm) A 10,6 9,9 1,0 B 11,1 15,0 0,6 C 9,2 6,0 0,2 Table 1 summarizes the characteristics of the structure of the islands of gold on the HOPG graphite resulting from the analysis of three Au4f spectra by the QUASES-Tougaard software, which express themselves in recovery rate (t = thickness of the layer of C of contamination) and height of the islands of gold (h). 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

De façon surprenante, la hauteur des ilots d'or (h) varie entre 9,2 et 10,6 nm, des valeurs sensiblement identiques au diamètre moyen des nanoparticules de la suspension colloïdale (Figure 1). De plus, il apparaît qu'environ 12 % de la surface du support est recouvert avec des ilots d'or d'environ 10nm. Il convient de noter qu'un pourcentage de couverture en or d'environ 10% est en accord avec le taux de recouvrement déterminé par microscopie à force atomique et par microscopie électronique à balayage. Ainsi, l'analyse de la courbe spectrale Au 4f par le logiciel QUASES met en évidence une bonne corrélation entre données expérimentales et théoriques.Surprisingly, the height of the islands of gold (h) varies between 9.2 and 10.6 nm, values substantially identical to the average diameter of the nanoparticles of the colloidal suspension ( Figure 1 ). In addition, it appears that about 12% of the surface of the support is covered with islands of gold of about 10 nm. It should be noted that a gold coverage percentage of about 10% is in agreement with the recovery rate determined by atomic force microscopy and scanning electron microscopy. Thus, the analysis of the Au 4f spectral curve by the QUASES software shows a good correlation between experimental and theoretical data.

Exemple 2 (comparatif) :Example 2 (comparative):

Un dépôt de nanoparticules d'or sur HOPG selon le procédé de l'exemple 1 est effectué, à l'exception de l'étape de dépôt de nanoparticule qui s'effectue sans l'utilisation d'un plasma atmosphérique (Figures 8 et 9). Après le dépôt des nanoparticules et avant analyse, les échantillons obtenus sont lavés à l'éthanol pendant environ 5 minutes aux ultrasons.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.

Comme le montre la figure 8, comparée à la figure 4a, le spectre XPS de l'échantillon obtenu après la nébulisation de la solution colloïdale d'or sans l'utilisation d'un plasma atmosphérique, démontre la présence de carbone et d'oxygène, et l'absence d'or ; ce qui est confirmé par l'image de microscopie à force atomique (AFM) de l'échantillon en question (figure 9 comparée aux figures 5b ou 6b).As shown in figure 8 , compared to the figure 4a the XPS spectrum of the sample obtained after nebulization of the colloidal gold solution without the use of an atmospheric plasma, demonstrates the presence of carbon and oxygen, and the absence of gold; which is confirmed by the Atomic Force Microscopy (AFM) image of the sample in question ( figure 9 compared to figures 5b or 6b ).

Exemple 3 (comparatif) :Example 3 (comparative):

Un dépôt de nanoparticules d'or sur de l'acier selon le procédé de l'exemple 1 est effectué, à l'exception de l'étape de dépôt de nanoparticule qui s'effectue sans l'utilisation d'un plasma atmosphérique. Après le dépôt des nanoparticules et avant analyse, les échantillons obtenus sont lavés à l'éthanol pendant environ 5 minutes aux ultrasons. On remarque à la figure 14 l'absence de nanoparticules à la surface de l'acier.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.

Dans les exemples qui suivent, le procédé utilisé est celui décrit à l'exemple 1, seul les supports (substrats) utilisés et la nature des solutions colloïdales sont différents.In the examples which follow, the method used is that described in Example 1, only the supports (substrates) used and the nature of the colloidal solutions are different.

Exemple 4 :Example 4

Des nanoparticules d'or ont été déposées sur un support en acier selon la méthode décrite à l'exemple 1, avec nettoyage aux ultrasons. On remarque à la figure 10 la présence de nanoparticules.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.

Exemple 5 :Example 5

Des nanoparticules d'or ont été déposées sur un support en verre selon le procédé décrit à l'exemple 1. On remarque à la figure 11 la présence de nanoparticules après nettoyage aux ultrasons.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.

Exemple 6 :Example 6

Des nanoparticules d'or ont été déposées sur un support en PVC selon le procédé décrit à l'exemple 1, avec nettoyage aux ultrasons. L'image de microscopie de la figure 12 a été obtenue après avoir recouvert l'échantillon d'une couche métallique. On remarque à la figure 12 la présence de nanoparticules.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.

Exemple 7 :Example 7

Des nanoparticules d'or ont été déposées sur un support en HDPE (Figure 13) selon le procédé décrit à l'exemple 1, avec nettoyage aux ultrasons. L'image de microscopie de la figure 13 a été obtenue après avoir recouvert l'échantillon d'une couche métallique. On remarque à la figure 13 la présence de nanoparticules.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.

Exemple 8 :Example 8

Des nanoparticules d'or ont été déposées sur un support en nanotubes de carbone selon le procédé décrit à l'exemple 1, avec nettoyage aux ultrasons. On remarque à la figure 15 la présence de nanoparticules sphériques d'environs 10nm après nettoyage aux ultrasons. Cette présence d'or est confirmée par le spectre XPS à la figure 16.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 .

Dans les exemples qui suivent, des solutions colloïdales de platine et de rhodium fournies par G.A. Somorjai (Department of Chemistry, University of California, Berkeley (USA)) ont été utilisées ( R. M. Rioux, H. Song, J. D. Hoefelmeyer, P. Yang and G. A. Somorjai, J. Phys. Chem. B 2005, 109, 2192-2202 ; Yuan Wang, Jiawen Ren, Kai Deng, Linlin Gui, and Youqi Tang, Chem. Mater. 2000, 12, 1622-1627 .).In the following examples, colloidal platinum and rhodium solutions provided by GA Somorjai (Department of Chemistry, University of California, Berkeley, USA) were used ( RM Rioux, H. Song, JD Hoefelmeyer, Yang P., and GA Somorjai, J. Phys. Chem. B 2005, 109, 2192-2202 ; Yuan Wang, Jiawen Ren, Kai Deng, Linlin Gui, and Youqi Tang, Chem. Mater. 2000, 12, 1622-1627 .).

Exemple 9 :Example 9

Des nanoparticules de platine ont été déposées sur un support en nanotubes de carbone selon le procédé décrit à l'exemple 1. On remarque à la figure 17 la présence de nanoparticules sphériques d'environs 10nm. Cette présence de platine est confirmée par le spectre XPS à la figure 18.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 .

Exemple 10 :Example 10

Des nanoparticules de rhodium ont été déposées sur un support carbone HOPG selon le procédé décrit à l'exemple 1. On remarque à la figure 19 la présence de nanoparticules sphériques d'environs 10nm après nettoyage aux ultrasons. Cette présence de rhodium est confirmée par le spectre XPS à la figure 20.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 .

Exemple 11 :Example 11

Des nanoparticules de rhodium ont été déposées sur un support en PVC selon le procédé décrit à l'exemple 1, avec nettoyage aux ultrasons. L'image de microscopie de la figure 22 a été obtenue après avoir recouvert l'échantillon d'une couche métallique. On remarque à la figure 22 la présence de nanoparticules.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.

Exemple 12 :Example 12

Des nanoparticules d'or ont été déposées sur un support en HDPE selon le procédé décrit à l'exemple 1, avec nettoyage aux ultrasons. L'image de microscopie de la figure 23 et a été obtenue après avoir recouvert l'échantillon d'une couche métallique. On remarque à la figure 23 la présence de nanoparticules.Gold nanoparticles were deposited on an HDPE support according to the method described in Example 1, with ultrasonic cleaning. The microscopy image of the figure 23 and was obtained after covering the sample with a metal layer. We notice at the figure 23 the presence of nanoparticles.

Claims (12)

  1. A method for depositing nanoparticles on a support comprising the following steps:
    - taking a solution or a colloidal suspension of nanoparticles, and
    - nebulizing said solution or a colloidal suspension of nanoparticles on a surface of said support in atmospheric plasma,
    said atmospheric plasma being a cold atmospheric plasma comprising a plasmagenic gas, the macroscopic temperature of which in said plasma may vary between -10°C and 400°C.
  2. The method according to claim 1, further comprising a step for activating the surface of the support by subjecting said surface of said support to atmospheric plasma.
  3. The method according to claim 2, wherein the activation of the surface of the support and the nebulization of the solution or of the colloidal suspension are concomitant.
  4. The method according to any of claims 2 or 3, wherein the activation of the surface of the support is preceded with the cleaning of said surface of said support.
  5. The method according to any of the preceding claims, wherein the step for nebulization of the solution or colloidal suspension of nanoparticles is accomplished in the discharge area or in the post-discharge area of the atmospheric plasma.
  6. The method according to any of the preceding claims, wherein the plasma is generated with an atmospheric plasma torch.
  7. The method according to any of the preceding claims, wherein the nebulization of a solution or colloidal suspension of nanoparticles is accomplished in a direction substantially parallel to the surface of the support.
  8. The method according to any of the preceding claims, wherein the nanoparticles are nanoparticles of a metal, a metal oxide, a metal alloy or a mixture thereof.
  9. The method according to any of the preceding claims, wherein the nanoparticles are nanoparticles of at least one transition metal, of its corresponding oxide, of an alloy of transition metals or a mixture thereof.
  10. The method according to any of the preceding claims, wherein the support is a solid support, a gel or a nano-structured material.
  11. The method according to any of the preceding claims, wherein the support is selected from the group formed with a carbonaceous support, carbon nanotubes, a metal, a metal alloy, a metal oxide, a zeolite, a semiconductor, a polymer, glass and/or ceramic.
  12. The method according to any of the preceding claims, wherein the atmospheric plasma is generated from a plasmagenic gas selected from the group formed with argon, helium, nitrogen, hydrogen, oxygen, carbon dioxide, air or a mixture thereof.
EP08787216.4A 2007-08-14 2008-08-14 Method of depositing nanoparticles on a support Not-in-force EP2179071B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP08787216.4A EP2179071B1 (en) 2007-08-14 2008-08-14 Method of depositing nanoparticles on a support

Applications Claiming Priority (4)

Application Number Priority Date Filing Date Title
EP07114344 2007-08-14
EP08151463A EP2093305A1 (en) 2008-02-14 2008-02-14 Method of depositing nanoparticles on a support
PCT/EP2008/060676 WO2009021988A1 (en) 2007-08-14 2008-08-14 Method for depositing nanoparticles on a support
EP08787216.4A EP2179071B1 (en) 2007-08-14 2008-08-14 Method of depositing nanoparticles on a support

Publications (2)

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

Family

ID=39800555

Family Applications (1)

Application Number Title Priority Date Filing Date
EP08787216.4A Not-in-force EP2179071B1 (en) 2007-08-14 2008-08-14 Method of depositing nanoparticles on a support

Country Status (7)

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

Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100983224B1 (en) * 2008-04-10 2010-09-20 김선휘 Manufaturing process of minute-particle and graphite-colloid
KR101127121B1 (en) * 2009-06-12 2012-03-20 한국과학기술원 Method of forming metal nano-particles layer on target substrates using air-spray
DE102009037846A1 (en) * 2009-08-18 2011-02-24 Siemens Aktiengesellschaft Particle filled coatings, methods of manufacture and uses therefor
CN101840852A (en) * 2010-04-02 2010-09-22 中国科学院半导体研究所 Method for manufacturing ordered semiconductor nanostructures on graphical semiconductor substrate
WO2012028695A2 (en) * 2010-09-01 2012-03-08 Facultes Universitaires Notre-Dame De La Paix Method for depositing nanoparticles on substrates
CN102258921A (en) * 2011-05-27 2011-11-30 安徽南风环境工程技术有限公司 Oil smoke adsorption filter screen and preparation method thereof
US10243207B2 (en) * 2011-07-26 2019-03-26 Oned Material Llc Nanostructured battery active materials and methods of producing same
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
EP3028989B1 (en) * 2013-08-01 2020-09-30 LG Chem, Ltd. Method for producing a carbon carrier-metal nanoparticle composite and composite produced thereby
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 (en) * 2014-12-19 2021-05-21 (주)바이오니아 Binder Connected Carbon Nano Structure Nano-porous Mambrane and Manufacturing the Same
CN104711568B (en) * 2015-02-27 2017-11-14 南京邮电大学 A kind of preparation method and its device for wrapping up carbon nanomaterial on the metal filament
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 (en) * 2015-12-02 2016-03-02 广州有色金属研究院 Preparation method for compact oxygen ion-electron mixed conducting oxide coating
EP3484810B1 (en) 2016-07-15 2023-10-11 OneD Material, Inc. Manufacturing apparatus and method for making silicon nanowires on carbon based powders for use in batteries
KR101957234B1 (en) * 2017-03-10 2019-06-19 경북대학교 산학협력단 Apparatus For Generating Plasma
CA3117338C (en) * 2018-10-24 2023-04-04 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 (en) * 1972-12-26 1976-11-08
JPH0941251A (en) * 1995-07-28 1997-02-10 Kyodo Kumiai Zou Shudan Application of steric synthetic resin pattern on water-repelling cloth
JP3511128B2 (en) * 1998-03-02 2004-03-29 日立造船株式会社 Method for producing metal fine particles and method for supporting fine particles on porous carrier
JP3256741B2 (en) * 1998-07-24 2002-02-12 独立行政法人産業技術総合研究所 Ultra fine particle deposition method
JP2002237480A (en) * 2000-07-28 2002-08-23 Sekisui Chem Co Ltd Method of treating base material with discharge plasma
JP2002121024A (en) * 2000-10-12 2002-04-23 Seiko Epson Corp Method for manufacturing titanium oxide film, titanium oxide film and solar cell
JP2003007497A (en) * 2001-06-19 2003-01-10 Pearl Kogyo Kk Atmospheric pressure plasma processing equipment
DE10211701A1 (en) * 2002-03-16 2003-09-25 Studiengesellschaft Kohle Mbh Production of catalyst, e.g. for hydrogenation, oxidation or fuel cell electrocatalyst, involves hydrolysis and condensation of sub-group metal salt(s) in basic aqueous solution and in situ immobilization of oxide nanoparticles on support
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
EP1546056B1 (en) * 2002-07-19 2013-12-11 PPG Industries Ohio, Inc. Article having nano-scaled structures and a process for making such article
US20060196424A1 (en) * 2003-01-31 2006-09-07 Frank Swallow Plasma generating electrode assembly
JP2004356558A (en) * 2003-05-30 2004-12-16 Toshio Goto Apparatus and method for coating
CH696811A5 (en) * 2003-09-26 2007-12-14 Michael Dvorak Dr Ing Dipl Phy Process for coating a substrate surface using a plasma jet.
JP2005163117A (en) * 2003-12-03 2005-06-23 Ainobekkusu Kk Method of producing metal colloid, and metal colloid produced by the method
JP4177244B2 (en) * 2003-12-15 2008-11-05 日信工業株式会社 Method for producing porous composite metal material
JP4300105B2 (en) * 2003-12-19 2009-07-22 株式会社コーセー Antioxidant
FR2877015B1 (en) * 2004-10-21 2007-10-26 Commissariat Energie Atomique NANOSTRUCTURE COATING AND COATING PROCESS.
EP1808056B1 (en) * 2004-11-05 2015-08-26 Dow Corning Ireland Limited Plasma process
DE102006005775A1 (en) * 2006-02-07 2007-08-09 Forschungszentrum Jülich GmbH Thermal spraying with colloidal suspension

Also Published As

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

Similar Documents

Publication Publication Date Title
EP2179071B1 (en) Method of depositing nanoparticles on a support
CN107313046B (en) SERS substrate and preparation method thereof
Biggs et al. Study of anion adsorption at the gold-aqueous solution interface by atomic force microscopy
EP1802783B1 (en) Coating method
US6656339B2 (en) Method of forming a nano-supported catalyst on a substrate for nanotube growth
Luo et al. Catalytic activation of core-shell assembled gold nanoparticles as catalyst for methanol electrooxidation
US9415328B2 (en) Modified surfaces
Dudin et al. Electro-oxidation of hydrazine at gold nanoparticle functionalised single walled carbon nanotube network ultramicroelectrodes
Pron'kin et al. Nanoparticles of Pt hydrosol immobilised on Au support: an approach to the study of structural effects in electrocatalysis
WO2016009328A1 (en) Method for the synthesis of nanocomposites based on tio2 and carbonated nanostructures
Saito et al. Fabrication of silver probes for localized plasmon excitation in near-field Raman spectroscopy
EP2093305A1 (en) Method of depositing nanoparticles on a support
EP2850223B1 (en) Process for manufacturing a composite material
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
Tabet-Aoul et al. Rhodium thin film-carbon nanotube nanostructures: Synthesis, characterization and electron transfer properties
US20190217382A1 (en) Methods for synthesizing silver nanowires
FR2918214A1 (en) DISPERSION OF COMPOSITE MATERIALS, ESPECIALLY FOR FUEL CELLS
Borodinova et al. Growth of Gold Nanostructures on the MoS2 Surface Modified with Polyvinylpyrrolidone
Gatin et al. Effect of the electric potential on the interaction of gold nanoparticles deposited on a graphite substrate with molecular hydrogen
Yoshimoto et al. Spontaneous electrodeposition of gold and platinum complexes through a coronene adlayer on Au (111)
Saidani et al. Synthesis, characterization of nanostructured rhodium films and their electrochemical behavior towards carbon monoxide oxidation
EP1305610B1 (en) Method of preparing the sensing element of a reducing gas molecule sensor
Chen et al. Large-scale Uniformly Hybrid Micro-nano Structure Wetting Solid Substrate for Surface-enhanced Raman Spectroscopy
Yoshida et al. The patterned Au oxide layer formation on Au surfaces by F2 laser irradiation under the atmospheric conditions

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