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
  • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
  • C09K11/025—Use of particular materials as binders, particle coatings or suspension media therefor non-luminescent particle coatings or suspension media
• • 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
  • C09K11/02—Use of particular materials as binders, particle coatings or suspension media therefor
• • 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
  • C09K11/06—Luminescent, e.g. electroluminescent, chemiluminescent materials containing organic luminescent materials
• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
  • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
  • H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
  • H01L31/054—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means
  • H01L31/055—Optical elements directly associated or integrated with the PV cell, e.g. light-reflecting means or light-concentrating means where light is absorbed and re-emitted at a different wavelength by the optical element directly associated or integrated with the PV cell, e.g. by using luminescent material, fluorescent concentrators or up-conversion arrangements
• • 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
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
• • 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
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1007—Non-condensed systems
• • 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
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1003—Carbocyclic compounds
  • C09K2211/1011—Condensed systems
• • 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
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
  • C09K2211/1033—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with oxygen
• • 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
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1029—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom
  • C09K2211/1037—Heterocyclic compounds characterised by ligands containing one nitrogen atom as the heteroatom with sulfur
• • 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
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1074—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms
  • C09K2211/1077—Heterocyclic compounds characterised by ligands containing more than three nitrogen atoms as heteroatoms with oxygen
• • 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
  • C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
  • C09K2211/10—Non-macromolecular compounds
  • C09K2211/1018—Heterocyclic compounds
  • C09K2211/1025—Heterocyclic compounds characterised by ligands
  • C09K2211/1092—Heterocyclic compounds characterised by ligands containing sulfur as the only heteroatom
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
• • H—ELECTRICITY
  • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
  • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
  • H10K30/00—Organic devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation
  • H10K30/50—Photovoltaic [PV] devices
• • 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
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
  • Y02E10/00—Energy generation through renewable energy sources
  • Y02E10/50—Photovoltaic [PV] energy
  • Y02E10/52—PV systems with concentrators

Definitions

• the present invention relates to a method of manufacturing a composite material containing luminescent molecules to make the electromagnetic characteristics of this material durable and to a product obtained by this method.
• MOAs optically active molecules
• Luminescent or optically active molecules are molecules that can emit light after passing their peripheral electrons in an excited state caused by a physical factor (light absorption), mechanical (friction) or chemical.
• An excited molecule can transmit its excitation energy to another neighboring molecule in a non-radiative manner by coupling between the electronic orbitals of the two molecules. This phenomenon is called resonance energy transfer resulting from a dipole-dipole interaction between two molecules. Resonance energy transfer is possible if the emission spectrum of one molecule partially overlaps the absorption spectrum of the other molecule.
• This type of energy transfer known as the Fôster type, is commonly known as FRET, an acronym for "Fôster résonance energy transfert".
• the term "light cascade” will be understood to mean the transfer of energy occurring by the combination of a series of optically active molecules (MOAs) of two distinct groups chosen in such a way that the spectrum of emission of the first group of MOAs partially overlaps the absorption spectrum of the second group of MOAs successively, each of the two groups of MOAs being defined by a re-emission wavelength different from the absorption wavelength of the group MOAs considered.
• MOAs optically active molecules
• the "light cascade” within the meaning of this patent may further incorporate “Stokes type MOAs” whose retransmission wavelength is greater than the absorption wavelength and the "anti-type MOAs". - Stokes "whose retransmission wavelength is less than the absorption wavelength.
• the invention also relates to the manufacture of luminescent (or optically active) particles including luminescent (or optically active) molecules mixed in a protective material.
• optically active particles are dispersed in various types of polymers forming optically active composite materials, for example in film form, for different industrial uses.
• a use such as photovoltaics (PV) can be obtained by a lamination technique - under a certain pressure and heat - with an encapsulating material such as polyethylene vinyl acetate (EVA) and all other related matrices. , or by the casting technique with polymethyl methacrylate (PMMA) and all other related matrices.
• PV photovoltaics
• EVA polyethylene vinyl acetate
• PMMA polymethyl methacrylate
• photovoltaic generators are manufactured in planar modules, which are integrated in buildings and greenhouses.
• LDPE low density polyethylene
• EVA LDPE
• LLDPE low density polyethylene
• PMMA polycarbonate
• PVC polycarbonate
• French patent FR2792460 describing a photovoltaic generator comprising at least one photovoltaic cell and a transparent matrix deposited with at least one optically active material having a wavelength are known in the prior art. absorption lambda a and lambda retransmission wavelength r, the optically active material being selected such that lambda corresponds to a range of lesser sensitivity of the photovoltaic cell as lambda r, the matrix having a reflective coating.
• US Patent US4952442 describes a light cascade doped film for agricultural greenhouses so that the light is enriched in the frequency bands favorable to photosynthesis and the yield of plants is significantly improved.
• the patent application FR1000696 discloses a photovoltaic module for a greenhouse comprising a front plate intended to be in contact with sunlight, a rear substrate and a set of photovoltaic cells disposed between the front plate and the rear substrate.
• the photovoltaic module has an expansion coefficient substantially between 0.2 and 0.8 and comprises at least one layer of a light-cascade doped dopant material promoting photosynthesis capable of absorbing sunlight in at least one range of lengths. wave to re-emit in at least a second range of wavelengths favorable for photosynthesis of at least one plant species.
• FR7808150 French patent describes a polymer matrix based on a homogeneous mixture of rare earth-type optically active crystals capable of generating a light cascade, which emits photons in the infrared region. This polymeric matrix displaces incident light close to the highest sensitivity of a photocell. Disadvantages of prior art
• optically active molecules which is related to the high permeability of polymers to gases, especially oxygen or ozone. These polymers are commonly used for photovoltaics, for example, of the EVA family and for agricultural green films, for example, of the PE family.
• This aging effect is accelerated by electromagnetic radiation, such as UV rays.
• Oxygen and UV radiation - a component of solar energy - produce a conjugated effect on MOAs, which causes a rise in temperature leading to greater sensitivity to photooxidation.
• adjuvants Antioxidant, Anti-UV, HALS - heat and light stabilization - phosphite, phosphorite, antistatic type are generally added in the polymer films such as EVA, PE.
• the number of actual charges - MOAs - per unit volume is substantially limited.
• the other cause of the aging of the films is the migration of the optically active molecules in the PE / EVA type matrices, which exude with the PE / EVA plasticizers and create localized overconcentration. This aggregation leads to a phenomenon of self-extinction due to a high local concentration of optically active molecules.
• the aging effect is limited. However, the energy conversion efficiencies are too low to allow industrial and commercial use.
• Another difficulty comes from the shift in the absorption and emission spectrum of the MOAs, when they are found in the presence of a solvent. A number of environmental parameters in the solvent can modify the spectra of these molecules: the pH, the presence of organic solutes, the temperature and the polarity of the solvent. The effects of these parameters vary from one type of MOA to another type. The more the solvent is polar, the more the effect is marked. Such a type of effect also occurs on molecules with a large dipole. Solution provided by the invention
• the invention aims to solve the problems of the state of the art, in particular to ensure an interesting energy conversion efficiency, while delaying the aging of the optically active molecules. To do this, it is proposed to overcome the effects of migrations, photo-oxidation and photo-degradation of MOAs in ⁇ -polar polymers, which has a low gas permeability.
• the present invention provides an improvement of the morphology of the support matrices with respect to doping optically active molecules.
• the subject of the present invention is a method for making the electromagnetic characteristics of optically active composite materials durable, comprising: a first step of preparation of the doped organic compounds by mixing at least one type of optically active molecules with a protective material to prevent their contact with elements inducing photodegradation and migration of optically active molecules,
• said protective material consists of at least one type of polar polymer and crosslinked in three dimensions, and which has a low gas permeability.
• the invention provides optically active nanoparticles have a diameter of between 1.10 “8 meter and 2.10 " 6 meter.
• the optically active nanoparticles are inorganic.
• the optically active nanoparticles are organic, in one embodiment, the organic nanoparticles are made colloidal latex from methyl methacrylate, in another embodiment, the organic nanoparticles are produced by mechanical micronization. According to a preferred embodiment of the invention, only one type of optically active molecules is mixed with a protective material and doped in the nanoparticles to obtain the optically active nanoparticles doped unitarily.
• a set of said optically active nanoparticles doped unitarily are associated according to an optimized concentration rule to achieve the light cascade effect and integrated in the polymers to form an optically active composite material.
• a plurality of types of optically active molecules associated according to a concentration rule optimized for the light cascade effect are mixed in at least one type of protective and doped materials in the nanoparticles. to obtain optically active nanoparticles doped in light cascade.
• said optically active nanoparticles doped in light cascade are integrated in the polymers to form an optically active composite material.
• the emission spectrum of one type of MOA partially overlaps the absorption spectrum of another type of MOA successively forming a luminous cascade, and the ratio C 2 / C 1 between the concentration of the first type with respect to the concentration C 2 of the second type is between 0.13 and 0.26.
• the optically active composite materials include at least one type of optically active Stokes molecules whose retransmission wavelength is greater than the absorption wavelength and / or at least one type of the molecules optically. anti-Stokes actives whose retransmission wavelength is less than the absorption wavelength.
• optically active molecules of the organic fluorophore type having a remanence of less than 10 ns are associated with the optically active crystals of the inorganic ZnS.Ag type having a remanence greater than 10 ns, the lengths of which are emission and absorption waves respond to the light cascade effect.
• optically active composite materials having according to the invention perennial optoelectro-magnetic characteristics include optically active nanoparticles doped optically active molecules, which are mixed with the protective materials.
• the invention also relates to an application of said optically active composite material for industrial uses such as photovoltaics or agricultural greenhouses films.
• the protective material is often a polar type organic polymer and crosslinked in three dimensions, which has a low oxygen permeability. These features help to resist aging and increase the light fastness of organic matrices doped with MOAs to avoid photo-degradations and MOA migration in the PE, EVA matrix families.
• the nanoparticles have important interfacial surfaces and high cross sections. Indeed, a uniform dispersion of the active particles of submicron size leads to a consequent increase in the adsorption rate of the organic compounds doped with MOAs for a given charge mass. So a significant increase in the number of MOAs per unit volume for a given volume fraction.
• the invention thus relates to: ⁇ A method of manufacturing a luminescent composite material intended to make durable the electromagnetic characteristics of this material comprising:
• a first step of preparing an organic compound with protected light-emitting molecules by mixing at least a first group of light-emitting molecules with a protective material to avoid their contact with elements inducing the photo-degradation and the migration of the luminescent molecules,
• the protective material consists of at least one polar polymer compatible with the luminescent molecules, preferably physico-chemically stable.
• the step of manufacturing said luminescent particles consists of grinding the organic compound by grinding.
• the step of manufacturing said light-emitting particles consists, during the production of the organic compound, of initially introducing the at least first group of light-emitting molecules into a monomer to form a luminescent polymer, to integrate this polymer with an inorganic particle, then to evaporating the polymer leaving the luminescent molecules fixed on the inorganic support so as to form the luminescent particles.
• the step of manufacturing said luminescent particles consists in producing organic particles and dissolving the at least first group of light-emitting molecules in the organic particles formed so as to form the luminescent particles,
• the organic nanoparticles are made colloidally latex from methyl methacrylate.
• each luminescent particle comprises the same type of luminescent molecules, and which are capable of reacting in light cascade with a second type of luminescent molecule of a second group of luminescent particles or each luminescent particle comprises different types of luminescent molecules capable of reacting two to two in cascade light,
• the concentrations of the different types of luminescent molecules of the different groups of luminescent particles are optimized to achieve the light cascade effect.
• the polymer matrix is in the form of a film.
• the composite material comprises several films each incorporating luminescent particles, these films being stacked together to combine the effects of the luminescent particles they contain.
• the film stacking is performed at the time of a film coextrusion step.
• the luminescent molecules (MOAs) whose emission spectrum of one type of MOAs partially overlaps the absorption spectrum of another type of MOAs successively forming a luminous cascade, respect the C 2 / C 1 ratio between the concentration of a first type with respect to the C 2 concentration of a second type between 0.13 and 0.26.
• the luminescent molecules include at least one type of Stokes-type molecules whose retransmission wavelength is greater than the absorption wavelength and / or at least one type of the optically active anti-Stokes molecules whose length is greater than The retransmission wave is less than the absorption wavelength.
• the molecules the luminescent molecules include at least organic fluorophore-like molecules having a remanence of less than 10 ns are associated with optically active crystals of inorganic ZnS.Ag type having a remanence greater than 10 ns, the wavelengths of which emission and absorption respond to the light cascade effect.
• the invention relates to a material obtained according to the method above.
• FIG. 1 represents the emission spectra of the doped PMMA microsphere samples. of the formula P004NP obtained under the excitation of UV light with a wavelength of 365 nm,
• FIG. 2 shows the comparison of emission spectra of samples made in different ways, obtained under the excitation of UV light with a wavelength of 365 nm.
• the distance separating the two molecules respectively from the two groups is less than 1.8 ⁇ R 0
• R 0 is the distance between the two molecules respectively of the two groups for which the efficiency of the energy transfer is 50%
• the structure of the molecule and the number of nuclei can determine the wavelengths of absorption and emission of molecules.
• the optically active molecules of a first group are selected such that the emission ranges of these molecules correspond to the absorption ranges of the molecules of the second group, in order to fulfill the first criterion.
• the optically active molecules are of the organic phosphon scintillator type with N + 1, N + 2, N + 3, N + x nuclei phi chosen from: aromatic cyclics, Anthracene, naphthacene, penthacene, hexacene, rhodamine, oxazine, diphenyloxazol and dimethyloxazol.
• the MOAs include at least one group of MOAs stokes and at least one group of anti-Stokes MOAs. In this case, it is possible to use molecules including rare earth atoms such as anti-Stokes MOAs.
• organic polymer matrices that are luminescent because they are doped with rare earths, which give a good path for exploiting the anti-Stokes effects.
• the optically active crystals that can form organic polymer matrices doped with rare earths are generally capable of performing a reverse light cascade. For example, a two-photon absorbing molecule in the infrared region is capable of emitting a photon in the visible region.
• a first group of optically active molecules (MOAs) of organic fluorophore type having a remanence ⁇ 10 ns is associated with a second group of MOAs of inorganic photoluminescent type / optically active crystals (series ZnS doped Ag or Cu) having a remanence> 10 ns, the molecules of the two groups respectively having lengths emission and absorption waves responding to the light cascade effect.
• the remanence of the light cascade becomes longer (> 10 ns) and the effect of energy re-emission by the fluorophores then takes place over a longer time.
• a transition is often made between the excited state of the first level and the ground state.
• the table below represents two examples of formulas, composition and concentration of MOAs in gr / kg or in percentage: the first formula P004NP dosed at 21 gr / kg, the second formula 2013F dosed at 5 gr / kg.
• the doped organic compounds are obtained by a mixture of a protective polymethyl methacrylate (PMMA) material, which is physico-chemical stable, and optically active molecules.
• PMMA is polar because it effectively aligns dipole molecules and produces a CL effect statistically more prominent than isotopic materials. However, the absence of spectrum shift should be regularly monitored.
• the polymethyl methacrylate type protective material may be replaced by another type of protective material: other polar polymers (or made polar by electron bombardment or functionalization of the polymer molecules) and compatible with the molecules optically active, for example, polyesters, methylenebut-3-en-1-ol (IOH), polycarbonate (PC), silicone, and methyl methacrylate (MMA).
• other polar polymers or made polar by electron bombardment or functionalization of the polymer molecules
• other polar polymers or made polar by electron bombardment or functionalization of the polymer molecules
• compatible with the molecules optically active for example, polyesters, methylenebut-3-en-1-ol (IOH), polycarbonate (PC), silicone, and methyl methacrylate (MMA).
• a protective material suitable for the production of organic compounds with protected luminescent molecules is physico-chemically stable, polar and compatible with the luminescent molecules considered, that is to say it prevents the exudation, migration, photooxidation and photodegradation of this MOA.
• optically active nanoparticles are integrated into the polymers of industrial use, which are chosen from:
• PMMA polymethyl methacrylate
• EVA polyethylene vinyl acetate
• PC Polycarbonate
• LDPE Low density polyethylene
• PVDF Polyvinylidene fluoride
• the optically active nanoparticles are inorganic, and made for example, in alumino silicate, mesoporous silica, alumino zeolite, aluminosilicates. It is interesting in this case to be able to prepare the choice:
• a first doped solution of a first group of MOAs is produced by operating the dissolution of optically active molecules (MOAs) of a first group in an ad hoc ligand or MMAs which connect the MOA to the zeolite.
• MOAs of this first group may for example be chosen from polycyclic aromatic hydrocarbons N Phi nuclei (Anthracene or Benzenic series):
• each solution prepared with the same type of MOAs is introduced into functionalized zeolite-type inorganic nanoparticles with a magnetic stirrer at a temperature of 45 degrees Celsius in order to obtain the different groups of NOAs (optically nanoparticles).
• active) doped CL Light Cascade
• the ad hoc ligand or MMA is evaporated to obtain different groups of optically active nanoparticles each doped with the same type of MOAs attached to the inorganic nanoparticles.
• these CL doped NOAs are dried and integrated into the polymer encapsulation matrices.
• each type of doped inorganic NOAs of 3, 4, 5 or N phi respectively are associated with a polymer matrix, in concentrations optimized to produce the light cascade effect, the most adapted to the intended application:
• PV - photovoltaic - or PS - photosynthesis -
• nanoparticles each individually doped with at least two groups of MOAs capable of reacting two by two in a luminous cascade is described below.
• MOAs at concentrations and proportions optimized for the desired light cascade effect are introduced into a ligand or MMA for example, to form a solution of light cascade (CL).
• this solution is introduced into the inorganic nanoparticles of the zeolite type in a magnetic stirrer at a temperature of 45 degrees.
• the optically active nanoparticles are organic.
• the techniques for manufacturing organic nanoparticles historically fall within the context of colloidal chemistry and involve conventional sol-gel processes, or other aggregation methods.
• Macromoleccular rapid communications it is described the synthesis of poly nanometric (methyl methacrylate) initiated by 2, 2-azoisobutyronitrile by differential microemulsion polymerization; in the scientific journal “polymer” (volumn 49, issue 26, December 8, 2008, pages 5636-556), poly (methyl methacrylate) and silica nanocomposites produced by "graft through” are described using reversible by addition-fragmentation transfer of polymerization chain.
• the optically active molecules are dissolved in a colloidal solution by latex starting from the PMMA monomer.
• NOAs With a magnetic stirrer and at a temperature of 45 degrees Celsius, NOAs of a few tens to a few hundred nm are obtained.
• Each type of unitary NOA includes only one type of MOA.
• several groups of organic NOAs doped respectively with several different types of MOAs, each NOA having the same type of MOA are mixed in a twin-screw extruder with LDPE / EVA compounds, according to a rule of optimized concentration to obtain the desired cascade effect.
• a plurality of types of MOAs for example, phosphors of HAP type 2, 3, 4, N phi at concentrations and proportions optimized for the light cascade effect.
• phosphors of HAP type 2, 3, 4, N phi at concentrations and proportions optimized for the light cascade effect.
• a colloidal latex solution starting from the MMA (PMMA monomer), with a magnetic stirrer and at a temperature of 45 degrees Celsius in order to obtain the CL doped NOAs.
• These CL doped NOAs are then mixed with the PMMA polymer or the PEBD / EVA compounds in a twin-screw extruder.
• doped NOAs CL were obtained NOAs of 500 nm and 2 micrometers doped according to the formula P004NP to CL, whose analysis results are represented in FIG. 1.
• FIG. 1 contains the emission spectra of PMMA microsphere samples doped according to the formula
• the P004NP under excitation of UV light of wavelength 365 nm The PMMA microspheres doped here are performed colloidally latex from the MMA as explained in the previous paragraphs.
• the X axis represents the wavelength in nanometers, one hundred nanometers per scale, while the Y axis represents the intensity in the arbitrary unit.
• the solid line represents the lot3 sample of microspheres of size 2 micrometers, while the dotted line represents the lot5 sample of microspheres of size 500 nanometers.
• the following table shows the intensities of the peak in the light region of red and blue, respectively. This table makes it easy to classify productions in terms of energy conversion efficiency.
• Lot 3 is the most efficient for Photovoltaics.
• Lot 5 can be considered for agricultural applications, because it is very effective in the blue while being significant in the retransmission in the red.
• Optically active molecules grafted into optically active nanoparticles made of PMMA have increased light fastness and good UV and 1 ⁇ 2 resistance.
• a CL-doped PMMA matrix is micronized by grinding to form an organic pigment.
• the matrix is constituted by a rigid or flexible organic material, or is in the form of an applicable coating under the form of a resin.
• the organic material is polymethyl methacrylate (PMMA) for example.
• the PMMA matrices doped CL are micronized by grinding at 40/50 micrometers. It is a "top-down" method that reduces particle size by ball mills or planetary mills.
• the optically active dopants are organic pigments with 2, 3, 4, N + 1 phi nuclei of aromatic cyclic type, or of anthracene, naphthacene, penthacene, hexacene, rhodamine, oxazine, diphenyloxazol or dimethyloxazol type.
• the particles thus obtained are called organic pigments.
• FIG. 2 shows the comparison between the emission spectra of the samples made in different ways under the excitation of the UV light of wavelength at
• the first type is the doped PMMA compound of the 2013F formula before the micronization process; the second type is the doped PMMA compound of the 2013F formula after the cryomilling type micronization process; while the third type is the lot3 sample (the microspheres doped with the P004NP formula of size 2 micrometer).
• the X axis represents the wavelength in nanometers, one hundred nanometers per graduation, while the Y axis represents the relative intensity in arbitrary units.
• the solid line represents the doped PMMA compounds, the dashed line represents PMMA grinding-cryo compounds, while the dotted-pull line represents the sample lot 3 - the microspheres in 2 microns.
• the intensity of the emission peak microspheres 2 micrometer lot 3 is 27% lower than the cryo-crushed PMMA peak.
• the intensity of the emission peaks is of the same order for the doped PMMA compound 2013F, the cryo-milled 2013F doped PMMA compound and the micrometers 2 micrometers lot 3 (doped P004NP).
• the organic pigments thus obtained are associated with the polymer matrices of use in the industrial applications concerned: films for agricultural greenhouses or in the polyvinyl chloride (PVC) sheets, polyethylene vinyl acetate (EVA) or polycarbonate (PC).
• PVC polyvinyl chloride
• EVA polyethylene vinyl acetate
• PC polycarbonate
• nanoparticles of the above type and the polymer matrix monomers are introduced into the extruder in order to obtain an extruded film at the outlet.
• a composite material consists of a PMMA copolymer - PE / EVA, where PMMA is the polar polymer doped with MOAs, forming a light cascade.
• This type of material is the addition of two different polymers, one technical and functional and forming an agricultural film or one PE / EVA photovoltaic encapsulation, the other optically active, such as PMMA doped with MOAs. micronized.
• any other type of matrix associated with any other type of organic pigment, such as IOH or PC is compatible.

Landscapes

• Chemical & Material Sciences (AREA)
• Engineering & Computer Science (AREA)
• Materials Engineering (AREA)
• Organic Chemistry (AREA)
• Electromagnetism (AREA)
• Condensed Matter Physics & Semiconductors (AREA)
• Physics & Mathematics (AREA)
• General Physics & Mathematics (AREA)
• Computer Hardware Design (AREA)
• Microelectronics & Electronic Packaging (AREA)
• Power Engineering (AREA)
• Compositions Of Macromolecular Compounds (AREA)
• Cultivation Of Plants (AREA)

Applications Claiming Priority (2)

Publications (1)

Family

ID=51260947

Family Applications (1)

Country Status (4)

Families Citing this family (1)

Family Cites Families (9)

• 2014
  • 2014-01-13 FR FR1450244A patent/FR3016369B1/fr active Active
• 2015
  • 2015-01-13 US US15/111,131 patent/US20160333263A1/en not_active Abandoned
  • 2015-01-13 EP EP15703466.1A patent/EP3094702A1/de active Pending
  • 2015-01-13 WO PCT/EP2015/050517 patent/WO2015104432A1/fr active Application Filing

Non-Patent Citations (2)

Also Published As

Similar Documents

Legal Events