Classifications

• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7701—Chalogenides
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C3/00—Glass compositions
  • C03C3/04—Glass compositions containing silica
  • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
  • C03C3/102—Glass compositions containing silica with 40% to 90% silica, by weight containing lead
• • C—CHEMISTRY; METALLURGY
  • C03—GLASS; MINERAL OR SLAG WOOL
  • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
  • C03C4/00—Compositions for glass with special properties
  • C03C4/12—Compositions for glass with special properties for luminescent glass; for fluorescent glass
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7728—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing europium
  • C09K11/7729—Chalcogenides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7743—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing terbium
  • C09K11/7744—Chalcogenides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7759—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing samarium
  • C09K11/776—Chalcogenides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7766—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals
  • C09K11/7767—Chalcogenides
  • C09K11/7769—Oxides
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
  • C09K11/00—Luminescent, e.g. electroluminescent, chemiluminescent materials
  • C09K11/08—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials
  • C09K11/77—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals
  • C09K11/7783—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing rare earth metals containing two or more rare earth metals one of which being europium
  • C09K11/7784—Chalcogenides
  • C09K11/7787—Oxides
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
  • Y10T428/00—Stock material or miscellaneous articles
  • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
  • Y10T428/131—Glass, ceramic, or sintered, fused, fired, or calcined metal oxide or metal carbide containing [e.g., porcelain, brick, cement, etc.]

Definitions

• the present invention relates to a vitreous material having visual effects, in particular fluorescence effects, when illuminated by ultraviolet radiation in the visible range. These glasses can especially find an application for the manufacture of decorative objects.
• the coloring of glasses is generally obtained by incorporating three types of elements: i) coloring ions (iron, manganese, chromium ...), ii) non-metallic centers (selenium, phosphorus ...) or some of their compounds; and iii) metal atoms (gold, silver, copper).
• the lifetime of the excited state can be influenced by the composition of the glass: in the case of uranium, it is short in an alkaline glass (the glass is therefore fluorescent) and long in a glass with a high content of silica (the glass can then be rather phosphorescent).
• the luminescence efficiency of a glass containing a luminescent center is lower than for a crystalline material containing this same active center.
• the chemical composition of the latter may also limit luminescence: iron is the main impurity that can reduce or even extinguish any luminescence; some halogens have the same effect in the glass.
• rare earth ions are a particular class.
• Fluorescent glasses can be used in various fields: - in the field of optics, these materials are used as optical components (filters, optical fibers, etc.).
• US Pat. No. 6,916,753 in particular describes a silica glass doped with thulium and whose fluorescence is around 1400 nm: such a glass finds applications in the field of optical fibers.
• US Pat. No. 6,879,609 describes, for optical fibers, a thulium-doped aluminosilicate glass whose excitation in the infrared (1060 nm) gives several fluorescence peaks in the visible according to a photon emission process. higher energy (“up-conversion" in English).
• 6,762,875 describes a method for creating optical index variations for optical components using rare earth elements, as tools for diagnosing glasses: pure glasses do not fluoresce because they do not absorb the optical elements. ultraviolet (UV) radiation.
• UV ultraviolet
• the characterization of the matrices (appearance or disappearance of vitreous zones according to the heat treatment received) and the presence of certain impurities can be demonstrated by studying the fluorescence properties of the materials, - in the field of lighting, the use remains however limited: it seems to be more efficient to excite a layer of crystalline phosphors deposited on a non-fluorescent glass rather than to excite a glass loaded with phosphors. Nevertheless, some compositions seem to give interesting results.
• patent application EP 0 338 934-A1 describes a composition based on Ce, Tb and Mn for obtaining a white fluorescence under excitation of a low pressure mercury lamp.
• the vitreous matrix used in this case is boron oxide (B 2 O 3 ) or a mixture of boron oxide and silicon dioxide (B 2 O 3 -SiO 2 ) in which the SiO 2 content is lower at 20 mol%,
• US Pat. No. 4,038,203 proposes various compositions for obtaining different colors of a alkaline phosphate glass activated with yttrium oxide.
• a pink fluorescence is obtained under excitation at a wavelength of 400, 460 or 530 nm.
• a green tint is achieved by introducing terbium oxide.
• the blue color, obtained by thallium doping has the major disadvantage of requiring an excitation of the material at a wavelength of 250 nm because no fluorescence could be obtained under excitation at 360 nm.
• Other shades, from yellow to orange, can be obtained by performing a co-doping with terbium and europium in specific proportions,
• dichroic properties color varying according to the source of white light used to illuminate the object
• UVA ultraviolet under illumination by UVA, preferably at a wavelength of between 360 and 400 nm, and whose emission intensity is sufficient to be perceived by the human eye;
• one or more luminescent active centers chosen from the following mixtures of rare earth ions: (Eu 3+ / Tb 3+ ), (Tb 3 VTm 3+ ), (Eu 3+ / Tm 3+ ) and (Eu 3 VTb 34 VTm 3+ ).
• optical transparent material is understood to mean a material which is allowed to pass through the light in such a way that it has an absorbance (ie optical density) of less than or equal to 3.5 cm -1 (in the sense of the Beer-Lambert law equation) at a wavelength between 380 and 800 nm.
• the silica is preferably from 50 to 85% by weight, a content of 53% by weight being particularly preferred.
• the lead is preferably present in an amount of between 20 and 40% by weight inclusive, and even more preferably between 25 and 35% by weight inclusive; a value of 30.5% by weight being very particularly preferred.
• lead is present in the material in the form of lead oxide (PbO).
• PbO lead oxide
• the presence of lead oxide in the vitreous matrix promotes the emission of fluorescence. Indeed, in other matrices, lead-free, the intensities of the fluorescence peaks of the rare earths are decreased: the color obtained is less pure (shift and modification of intensity ratios between fluorescence peaks) and less intense (variation of the intensity of the fluorescence peaks). Because of the "network modifier" character of lead oxide, the inventors have discovered that the silica matrix is then particularly adapted to promote the incorporation of fluorescent ions in a large quantity, which allows to obtain a very intense fluorescence of the material.
• lead oxide makes it possible to increase the amount of active center that can be incorporated into the silica matrix. In the particular case of Peuropium or terbium, this amount is at least 15%. This matrix therefore makes it possible to accept fluorescent center charge levels that are compatible with a decorative application. For comparison, the incorporation of such high levels of active centers in matrices of lead-free silica leads to the production of opaque materials indicating that the rare earth oxides are not completely solubilized.
• the materials according to the present invention are colorless transparent: the material is similar to a crystal undoped with fluorescent ions.
• UVA excitation generally at a wavelength of about 360, 380 or 390 nm
• lead-rich vitreous dies doped with rare earth ions emit intense fluorescence while maintaining the transparency of the material.
• the color of the matrix depends on the chosen rare earth ion mixture.
• the mixtures of rare earth ions present in the vitreous materials of the invention are chosen from the following mixtures: (Eu 3+ / Tb 3+ ), (Tb 3 VTm 3+ ), (Eu 3 VTm 3+ ) and (Eu 3+ / Tb 3+ / Tm 3+ )
• the mixture in controlled quantities of Eu 3+ ions and Tb 3+ ions makes it possible to obtain a hue varying from yellow to orange under UVA light, the addition to this mixture of Tm 3+ makes it possible to obtain white. Controlled mixing of Tb + ions and Tm 3+ ions results in different shades of green, whereas controlled mixing of Eu 3+ ions and Tm 3+ ions yields different shades of rosé.
• the mixture (Eu 3 VTb 3+ ) represents 10% by weight and is composed of 4 to 6 parts by weight of Eu 3+ for 6 to 4 parts by weight of Tb 3+ .
• the mixture (Tb 3 VTm 3+ ) represents 5% by weight and is composed of 2 parts by weight of Tb 3+ for 3 parts by weight of Tm 3+ .
• the mixture (Eu 3 VTm 3+ ) represents 5% by weight and is composed of 2 parts by weight of Eu 3+ for 3 parts by weight of Tm 3+ .
• the mixture (Eu 3+ / Tb 3+ / Tm 3+ ) represents 5% by weight and is composed of 0.8 parts by weight. Eu 3+ ions, 1, 2 parts of Tb 3+ ions and 3 parts of Tm 3+ ions.
• the orange and yellow colors can be obtained using a single doping. For example, it is possible to obtain orange by samarium doping or yellow by dysprosium doping. However, colors obtained with single doping have a lower intensity than the ad hoc mixture
• the rare earth ions are preferably used in the form of oxides. Indeed, when they are not in the form of oxides, the rare earth ions generally comprise negatively charged counterions (phosphate ions, fluorides for example) whose presence in the glass could lead to extinction phenomena. fluorescence.
• the active center or centers preferably represent from 0.1 to 40% by weight, and even more preferably from 1 to 18%.
• the vitreous material according to the present invention may comprise one or more additives commonly used for the manufacture of glasses among which may be mentioned in particular the modifying oxides, such as fluxes and stabilizers.
• additive or additives possibly used are compatible with the intrinsic properties attached to the vitreous material according to the present invention, in particular on its luminescence properties.
• the fluxes there may be mentioned more particularly sodium oxide, potassium oxide, magnesium oxide and mixtures thereof.
• the flux or fluxes preferably represent from 1 to 30% by weight.
• the stabilizers and in addition to lead oxide which can be classified in this category of additives, there may be mentioned more particularly the alkaline earth oxides such as calcium oxide, zinc oxide, iron and their mixtures.
• the stabilizer or stabilizers preferably represent from 1 to 30% by weight.
• vitreous materials according to the present invention can be used for the manufacture of decorative and / or utilitarian luminescent objects.
• the present invention also relates to the use of an optically transparent vitreous material as defined above for the manufacture of decorative and / or utilitarian objects in luminescent crystal, in particular in fluorescent crystal, as well as objects decorative and / or utilitarian obtained from a vitreous material according to the invention.
• the material according to the present invention can thus for example be used for the manufacture of chandeliers, lamps (feet and lampshades), jewels, vases, containers (bowls, glasses, salad bowls, carafes), Decorative glass such as stained glass, etc.
• the decorative and / or utilitarian objects according to the present invention may be prepared according to the methods conventionally used in glassware, by incorporation, during the manufacturing process of the luminescent active center (s).
• the decorative and / or utilitarian objects are manufactured using a high-temperature glassmaking process comprising at least the following steps: i) the melting of the various constituents of the vitreous material as defined according to FIG. invention, to obtain a glassy melt composition; ii) introducing, into the melt glass composition, the active center (s) in powder form, to obtain a doped vitreous composition; iii) maintaining the vitreous composition doped at high temperature, generally above 1000 ° C, for a prolonged period, generally greater than or equal to about 24 hours; iv) shaping the vitreous composition at the working temperature of the glass to obtain the expected object; this formatting step possibly comprising several operations requiring a rise in temperature; v) cooling the object obtained under ambient air; vi) a stress relieving heat treatment, at a temperature significantly lower than the softening point of the vitreous composition, in order to release the object from the thermal tensions accumulated during cooling.
• the decorative and / or utilitarian objects of the invention may also be manufactured according to the following steps: i) the preparation of a powder (more or less fine) ) glass having the vitreous composition required according to the invention (at least silica and lead); ii) mixing said glass powder, at room temperature, with the active center (s), to obtain a doped glass composition; and then iii) proceeding with steps ii) to vi) of the above process. Glass making processes using sol-gel techniques
• melt conditions can be an alternative to the high temperature melting process.
• the heat treatment can also be conducted at a higher temperature (500-1000 ° C) to densify the structure.
• the sol-gel process is more particularly adapted to the production of deposits rather than the production of bulk materials.
• this method for making deposits on a finite object can be envisaged to use this method for making deposits on a finite object:
• the invention also comprises other arrangements which will emerge from the description which follows, which refers to examples of demonstration of the effect of the presence of lead in a silica matrix doped or not by rare earth ions, to examples of preparation of vitreous materials according to the invention, and to the appended FIGS. 1 to 10 in which:
• FIG. 1 represents the absorption spectra (arbitrary units) as a function of the wavelength (nm) of a pure silica (quartz) plate (unpatented curve), of a standard composition glass (triangles). solid) and lead glass (solid circles) after excitation at a wavelength between 190 and 490 nm;
• FIG. 2 represents the excitation spectra (intensity of the emission measured at a wavelength of 610 nm) of a glass slide of standard composition doped at 13% by mass (ie 6.1% molar) by europium Eu 3+ (lowest curve) and a lead glass slide also doped at 10% by mass (ie 6.1 mol%) with europium Eu 3+ (the most high); in this figure the intensity of the emission (arbitrary units) is a function of the wavelength (nm); FIG.
• FIGS. 4 to 9 represent the fluorescence spectra of vitreous matrices containing 30% by weight of lead (ie 12.5 mol%), doped with various ions or mixtures of rare earth ions obtained according to some of the methods described in FIGS. Examples 2 to 12. These spectra were obtained under excitation by UV neon light centered at 365 nm; the intensity of the fluorescence (arbitrary units) is a function of the wavelength (in nm).
• FIG. 4 represents the fluorescence spectra of the materials obtained according to examples 2 (intermediate curve), 7 (the highest curve) and 9 (the lowest curve in dashed lines),
• FIG. 5 represents the fluorescence spectra of the materials obtained according to examples 5 (highest curve) and 6 (lowest curve, in dotted lines),
• FIG. 6 represents the fluorescence spectra of the materials obtained according to examples 3 (the lowest curve) and 4 (the highest curve),
• FIG. 7 represents the fluorescence spectrum of the material obtained according to example 8.
• FIG. 8 represents the fluorescence spectrum of the material obtained according to example 1, and
• FIG. 9 represents the fluorescence spectrum of the material obtained according to example 10.
• FIG. 10 represents the transmission spectrum under natural light and under neon white illumination of a vitreous matrix containing 30% by weight of lead, doped with holmium oxide (10% by mass).
• the transmitted intensity (expressed in arbitrary units) is a function of the wavelength (in nm).
• the highest (and least thick) curve represents the natural light transmission spectrum
• the intermediate curve represents the spectrum transmitted by the sample under natural light
• the low curve represents the spectrum of a white neon.
• the spectra thus obtained are shown in the appended FIG. 1, in which the absorption expressed in arbitrary units is a function of the wavelength in nm.
• the curve without a pattern corresponds to the spectrum of the quartz slide, the curve with the triangles solid to that of the standard glass slide and the curve with the solid circles to that of the lead glass.
• the spectra shown in FIG. 1 show that the quartz plate does not absorb any radiation of wavelength greater than 210 nm, whereas the glass of standard composition absorbs below 290 nm, and that in the case of glass with lead, the absorption front is in the UVA.
• the excitation spectra (intensity of the emission measured at a wavelength of 610 nm) of a standard molar composition glass slide (majority constituents: 6M SiO 2 , IM Na 2 O, IM CaO) doped at 13% by weight (ie 6.1 mol%) with europium Eu + and with a lead glass slide (majority constituents: 6M SiO 2 , IM K 2 O and IM PbO) doped 10% by weight (also 6.1 mol%) with europium Eu 3+ .
• the excitation spectra thus obtained are shown in FIG.
• FIG. 3 represents the excitation spectra at 395 nm of different vitreous matrices based on SiO 2 : lead glass of the following molar composition: 6 SiO 2 , 1 K 2 O, 1
• Each of these matrices contained 10% by weight of europium Eu 3+ .
• the intensity of the emission is a function of the wavelength in nm.
• the highest curve corresponds to lead glass, the intermediate curve to soda-lime glass and the low curve to glass obtained by the sol-gel process.
• Embodiments described below describe the incorporation of rare earth ions into lead-rich (crystal) silica glass matrices having the following molar composition:
• the amount of 12.5 mol% given for lead oxide corresponds to a quantity of 30% by weight of lead.
• the rare earth oxides were in the form of coarse powders.
• the powders were therefore slightly crushed with a mortar and then mixed with the crystal powder in the proportions indicated in the following Table I:
• the fluorescence spectra of the glasses obtained in Examples 2 to 11, under excitation by a UV neon light centered at 365 nm, are also represented in the appended FIGS. 4 to 8 on which the intensity of the fluorescence (expressed in arbitrary units) is a function of the wavelength (in nm).
• FIG. 4 represents the fluorescence spectra of the materials obtained according to examples 2 (intermediate curve), 7 (highest curve) and 9 (lowest curve in dotted lines).
• FIG. 5 represents the fluorescence spectra of the materials obtained according to examples 5 (highest curve) and 6 (lowest curve, in dotted lines).
• FIG. 6 represents the fluorescence spectra of the materials obtained according to examples 3 (the lowest curve) and 4 (the highest curve).
• FIG. 7 represents the fluorescence spectrum of the material obtained according to example 8.
• FIG. 8 represents the fluorescence spectrum of the material obtained according to example 11.
• FIG. 9 represents the fluorescence spectrum of the material obtained according to example 10.
• a glass having dichroic properties was prepared from the same vitreous matrix as used above for Examples 2 to 11 and using the same preparation protocol.
• Holmium oxide powder was incorporated in the proportions shown in Table III below:
• the glass thus obtained had a transparent yellow color under natural light and a transparent pink color under neon lighting.
• the transmission spectrum of the glass thus obtained, under natural light and under white neon light is represented in the appended FIG. 10, in which the transmitted intensity (expressed in arbitrary units) is a function of the wavelength (in nm).
• the highest curve (and the thinnest) represents the transmission spectrum of natural light
• the intermediate curve represents the spectrum transmitted by the sample, under natural light
• the low curve represents the transmission spectrum. white neon.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Life Sciences & Earth Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• General Chemical & Material Sciences (AREA)
• Geochemistry & Mineralogy (AREA)
• Glass Compositions (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=40328872

Family Applications (1)

Country Status (4)

Families Citing this family (5)

Family Cites Families (13)

• 2008
  • 2008-06-25 FR FR0803564A patent/FR2933089B1/fr not_active Expired - Fee Related
• 2009
  • 2009-06-24 EP EP09797559A patent/EP2303789A1/de not_active Withdrawn
  • 2009-06-24 US US13/000,541 patent/US8741793B2/en not_active Expired - Fee Related
  • 2009-06-24 WO PCT/FR2009/000764 patent/WO2010007238A1/fr active Application Filing

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events