Classifications

• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/14—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing calcium sulfate cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B14/00—Use of inorganic materials as fillers, e.g. pigments, for mortars, concrete or artificial stone; Treatment of inorganic materials specially adapted to enhance their filling properties in mortars, concrete or artificial stone
  • C04B14/02—Granular materials, e.g. microballoons
  • C04B14/30—Oxides other than silica
  • C04B14/305—Titanium oxide, e.g. titanates
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B20/00—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials
  • C04B20/0076—Use of materials as fillers for mortars, concrete or artificial stone according to more than one of groups C04B14/00 - C04B18/00 and characterised by shape or grain distribution; Treatment of materials according to more than one of the groups C04B14/00 - C04B18/00 specially adapted to enhance their filling properties in mortars, concrete or artificial stone; Expanding or defibrillating materials characterised by the grain distribution
  • C04B20/008—Micro- or nanosized fillers, e.g. micronised fillers with particle size smaller than that of the hydraulic binder
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B26/00—Compositions of mortars, concrete or artificial stone, containing only organic binders, e.g. polymer or resin concrete
  • C04B26/02—Macromolecular compounds
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
  • C04B28/02—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing hydraulic cements other than calcium sulfates
  • C04B28/04—Portland cements
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/00482—Coating or impregnation materials
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/00474—Uses not provided for elsewhere in C04B2111/00
  • C04B2111/0081—Uses not provided for elsewhere in C04B2111/00 as catalysts or catalyst carriers
  • C04B2111/00827—Photocatalysts
• • C—CHEMISTRY; METALLURGY
  • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
  • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
  • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
  • C04B2111/20—Resistance against chemical, physical or biological attack
  • C04B2111/2038—Resistance against physical degradation
  • C04B2111/2061—Materials containing photocatalysts, e.g. TiO2, for avoiding staining by air pollutants or the like

Definitions

• the invention relates to a photocatalytic coating product comprising particles of titanium dioxide (TiO 2 ).
• the invention will be more particularly described with regard to use of the product as a lining of a construction, for floor, wall and / or ceiling for example, without being limited thereto.
• the coating can also be applied outdoors. Nevertheless, his field of employment is indoors.
• the product will include a coating and more particularly an interior coating. Under the term coating, it is understood that it is a mortar that is to say the mixture of at least one mineral binder, aggregates, fillers and various additives (organic additives, pigments , .).
• the mineral binder is a hydraulic binder (such as Portland cements, aluminous cements, sulphoaluminous cements, belitic cements, blast furnace slags, pozzolanic mix cements, etc.), a source of calcium sulphate (such as plaster or hemihydrate, gypsum and / or anhydrite) or lime.
• a hydraulic binder such as Portland cements, aluminous cements, sulphoaluminous cements, belitic cements, blast furnace slags, pozzolanic mix cements, etc.
• a source of calcium sulphate such as plaster or hemihydrate, gypsum and / or anhydrite
• the photocatalytic compositions are in particular known for their air pollution control properties. They comprise particles, for example of TiO 2 , which under the effect of ultraviolet (UV) radiation of wavelength lower than 380 nm, generate a photocatalytic reaction. UV causes electronic changes within TiO 2 particles leading to the adsorption of organic compounds (pollutants) in the air and on the TiO 2 surface, and by chemical reaction with oxygen in the air, pollutants turn into carbon dioxide.
• UV ultraviolet
• the photocatalytic particles consist of particles generally Ti0 2 and in the form of nanoparticles, that is to say particles whose primary crystals are a few nanometers, or a few tens of nanometers, associated with a specific surface of the order of 100 to 300 m 2 / g.
• the photocatalytic compositions based on TiO 2 nanoparticles are mainly used outdoors, since the UVs enabling the photocatalytic reaction come from solar radiation.
• compositions are not so effective, especially in rooms where the brightness from the outside is low.
• nanoparticles have a negative connotation in the eyes of the public. To date, there is no retreat on the possible risks of nanoparticles on health.
• the term “nanoparticles” is understood to mean particles whose size is between 1 and 100 nm as defined in the European Commission's recommendations of 18 October 201 1 relating to the definition of nanomaterials (text 201 1/696 / EU). Also on the basis of these recommendations, the term “composition comprising nanoparticles” means a composition comprising at least 50% (in number) of particles of dimensions between 1 and 100 nm.
• the object of the invention is to propose a coating product having pollutant degradation properties, which does not have the abovementioned disadvantages, and which can be used in particular indoors without having to be illuminated by solar radiation or lighting. exclusively UV radiation.
• the interior coating product having photocatalytic properties comprises TiO 2 titanium dioxide particles, and is characterized in that it comprises TiO 2 particles (for at least 50% in total number of particles) which are larger than nanoparticles and constitute means of reaction by photocatalysis under indoor lighting.
• the product of the invention does not constitute a product based on a nanomaterial within the meaning of the nanomaterials according to the recommendations of the European Commission (text 201 1/696 / EU).
• Interior lighting means a usual lighting for illuminating the interior of a space in a building and other than an artificial lamp with exclusively UV radiation.
• Indoor lighting is lighting whose proportion in UV is lower than that of solar radiation, and therefore also less than the proportion of a UV lamp. If until now, it was thought that it was necessary to have a consequent UV light to ensure the photocatalytic reactions, surprisingly, the inventors have demonstrated that under internal lighting, particles of TiO 2 which are not of nanometric size, but of larger size than nanoparticles, in particular of the order of a micrometer, exhibit photocatalytic properties so as to have a function of degradation of pollutants of NOx or formaldehyde type.
• the product of the invention has the advantage of not using nanoparticles, which on the one hand reduces the manufacturing costs of the product, and on the other hand does not pose environmental and health problems.
• the inventors have found, surprisingly, that the results, with regard to the degradation of pollutants, show performances comparable to those of nanoparticles under the same interior lighting.
• the TiO 2 particles are able to react by photocatalysis with an interior lighting whose ultraviolet radiation power density is that of a usual indoor lamp.
• the power density of the ultraviolet radiation to be associated with the product of the invention suffices by being between 0.1 and 0.6 W / m 2 , in particular of the order of 0.2 W / m 2 (20 ⁇ ). / cm 2 ).
• the power density of a lamp exclusively with ultraviolet radiation has its maximum precisely in the UV radiation, and that the solar light outdoors has a power density in the UV of the order of 5 to 50 W / m 2 according to the exposure. Therefore, with a radiation having a reduced power in the UV, the product of the invention makes it possible to obtain a degradation of the pollutants under optimal conditions, even greater than those of the prior art.
• the lighting source during use can be located about thirty cm. It can directly illuminate the coated surface based on the product of the invention or be from a reflective lighting to reach the surface covered.
• the product contains between 1% and 10% by weight of TiO 2 particles, distinct from TiO 2 nanoparticles, relative to the total weight of the elements contained in the product.
• a range of between 3 and 5% makes it possible to confer effective degradation properties without having to further increase the number of TiO 2 particles and thus increase the cost price of the product.
• the particles that are distinct from the TiO 2 nanoparticles are of micrometric size. They have an average diameter greater than 100 nm and in particular between 120 and 160 ⁇ . Their specific surface is between 10 and 15 m 2 / g.
• the TiO 2 particles have at least one crystallized part in anatase form.
• the coating product consists for example of a coating based on a source of calcium sulfate such as plaster, a coating based on a hydraulic binder such as cement or a coating based on polymers filled with mineral fillers.
• the coating product is used inside a construction, including ceilings, floors or walls.
• it is used to degrade NOx or formaldehyde pollutants.
• the interior coating therefore contains between 1 and 10% by weight of TiO 2 particles, distinct from TiO 2 nanoparticles, relative to the total weight of the elements of the coating.
• the invention also relates to the use of a product having photocatalytic properties comprising TiO 2 titanium dioxide particles, characterized in that the product comprises TiO 2 particles (for at least 50% of them). ) which are larger than nanoparticles and in that the product is illuminated by the light of an interior light.
• the TiO 2 particles are introduced into the mass of the product by associating them with the other constituents of the product.
• the titanium dioxide particles are dispersed in the bulk of the product. This term means that the titanium dioxide particles are found throughout the mass of the product, not just in surface or peripheral areas.
• These particles are dispersed as such in the product, either before mixing, that is to say prior to the dilution of the product in water and / or a solvent for use as a coating, or at the time mixing, or at the time of mixing which provides a homogeneous product after mixing for deposit.
• the titanium oxide particles may also be deposited on the surface of the coating, in particular in a layer, for example a paint layer.
• a layer for example a paint layer.
• the coating is coated with a layer, it is considered to be an integral part of the coating.
• the invention relates to a process for the degradation of pollutants inside constructions, such as volatile organic compounds (VOCs), for example of the formaldehyde type, and NO and NOx gases, characterized in that uses on the one hand a coating product comprising TiO 2 particles larger than 100 nm (for more than 50% of the particles contained in the product), the particles constituting means for photocatalytic reaction to UV illumination radiation. inside, and on the other hand an indoor lighting, of the usual type.
• VOCs volatile organic compounds
• NO and NOx gases characterized in that uses on the one hand a coating product comprising TiO 2 particles larger than 100 nm (for more than 50% of the particles contained in the product), the particles constituting means for photocatalytic reaction to UV illumination radiation. inside, and
• FIGS. 1a to 1c illustrate pollutant concentration curves NO and NOx, as a function of time, with regard to an exemplary embodiment of the product of the invention and two comparative examples;
• FIG. 2b is the detail of the curve of FIG. 2a for the wavelengths in the UV;
• FIG. 3 illustrates concentration versus time curves of formaldehyde pollutants with regard to three tests, respectively a second embodiment of the product of the invention, and two comparative examples.
• the product of the invention is intended to be used as a coating product, in particular for a coating deposited within a construction, as applied to a ceiling, floor or wall.
• the composition has photocatalytic properties and comprises particles of TiO 2 which, according to the invention, have a size of at least 100 nm for more than 50% of them, and are capable of reacting by photocatalysis with indoor light.
• the interior light is preferably a fluorescent source of the neon type. It has a residual power density of ultraviolet radiation of between 10 and 60 ⁇ / cm 2 .
• the product is a cementitious coating comprising 12% of white cement, and 87% of sand and fine filler, as well as microparticles of TiO 2 in a concentration by weight of 1% by weight. relative to the total weight of the mortar.
• TiO 2 microparticles correspond to the product sold under the name KRONOS 1001 from KRONOS. This product contains silica, aluminum hydroxide, aluminum oxide and more than 99% TiO 2 particles, the particles having a diameter greater than 100 nm.
• a comparative example CompB comprising the same mortar basic than Ex1 and replacing Ti0 2 of the microparticles by Ti0 2 nanoparticles with a weight concentration of 1% based on the total weight of the mortar.
• the nanoparticles of Ti0 2 correspond to the product marketed under the name "Tayca AMT 100".
• Each mortar was mixed with water in the same proportions and applied to a test surface by being hydrated, dried and cured at room temperature under the same conditions.
• pollutant injected at the entrance of the test chamber (also called “photoreactor” in English in the standard and entitled “reactor” on the - figures) comprising each sample, in a concentration of 1000 (+ or -50) ppbv;
• the interior lighting is in the example a fluorescent lighting, placed at 30 cm from each surface sample and illuminating directly the surface.
• the residual power density in UV is 20 ⁇ / cm 2 (0.2 W / m 2 ).
• the fluorescent lighting used is a lamp marketed under the name Sulvania LYNX-LE860 of 55W and 4800 Im. Its light spectrum is shown in Figure 2a, Figure 2b showing the detail of the curve for wavelengths in the ultraviolet (less than 380 nm).
• each test consists of placing the sample surface of the coating in a closed room or room, sending a pollutant from an inlet of the chamber, the continuous flow of which sweeps the surface of the sample in a laminar manner at a distance of 5 mm, then illuminate this surface with the fluorescent tube on, and measure at the outlet of the room after extracting the air from the room, the concentration of volatile inorganic products, here NO and NOx.
• the airflow and suction injection system is operated 15 minutes before the start of the illumination.
• Pollutants are sent at a time T, noted in Figures 1 by the end of the arrow on which is indicated the term "reactor”. Then we turn on, and we
• sample Ex1 of the invention it is lit 5 minutes after sending the pollutants and the lighting is left for 60 minutes.
• the CompB mortar with TiO 2 nanoparticles plays a role in the degradation of pollutants.
• the mortar of the invention comprising microparticles of TiO 2 makes it possible to degrade the pollutants.
• the two CompB and Ex1 mortars show a sharp fall in the concentration of pollutants.
• the degradation activity is surprisingly significant. As soon as the lamp is lit, the NO concentration decreases by a little more than 200 ppb and that of NOx by a little more than 100 ppb, which can be assimilated to a pollutant degrading activity, respectively close to 21% and 10.5%.
• the concentration of NO decreases by a little more than 210 ppb after illumination, and that of NOx by almost 200 ppb, respectively representing a percentage of decrease, and therefore of pollutant degradation activity. , respectively 22.5% and almost 18%.
• the degradation performance of the pollutants is relevant, and this with a reduced UV radiation (the residual radiation of a conventional indoor lighting lamp of a dwelling).
• the difference in performance between the product of the invention Ex1 and the product CompB is only 1, 7% for NO and 7.4% for NOx. Therefore, it is very advantageous to use the product of the invention which has extremely similar performance of a nanoparticle product, without presenting the disadvantages in terms of cost and health risks.
• the product is a plaster based coating comprising 23% gypsum, 72% sand and filler and 5% by weight of TiO 2 particles that are not nanometric.
• the non-nanometric TiO 2 particles correspond to the product marketed under the name Kronos 1001.
• the comparative examples are as follows: CompC: coating identical to that of Ex2 without the TiO 2 particles;
• CompD Coating identical to that of Example Ex2 with nanoparticles of TiO 2 according to 3% by weight (relative to the total weight of the plaster with the nanoparticles).
• TiO 2 nanoparticles correspond to the product marketed under the name
• pollutant injected at the entrance of the test chamber comprising each sample, in a concentration of 100 ppbv;
• the volume of the chamber is 28.1 liters
• the surface area of each sample is 0.2 m 2 (380 mm x 270 mm);
• the imposed lighting which is according to the invention an indoor lamp, here for example a lamp Osram Lumilux Warm White 830 36W.
• Each test consists of placing the sample surface of the coating in a closed room or room, illuminating this surface with the lamp, sending from a room entrance a pollutant whose continuous flow sweeps the surface of the sample in a laminar manner and measure at the outlet of the chamber the air escaping from the chamber, the concentration of volatile organic products, here formaldehyde.
• the gas is previously illuminated injected into the chamber by remaining there for 168 hours without lighting.
• Figure 3 illustrates the formaldehyde concentration curves for Example Ex2 of the invention and Comparative Examples CompC and CompD.

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• 2014
  • 2014-05-28 FR FR1454873A patent/FR3021647B1/fr active Active
• 2015
  • 2015-05-27 EP EP15729542.9A patent/EP3148952A1/fr not_active Withdrawn
  • 2015-05-27 CN CN201580027462.5A patent/CN106458758A/zh active Pending
  • 2015-05-27 WO PCT/FR2015/051393 patent/WO2015181493A1/fr active Application Filing

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