Thermal collecting film for solar thermal power generation and manufacturing method for same

专利摘要:
The present invention pertains to a thermal collecting film for solar thermal power generation that has excellent thermal oxidation resistance and a high light absorption rate and a manufacturing method for same. This thermal collecting film for solar thermal power generation has a network structure of composite particles comprising: particles of metal oxide primarily containing two or more types of metal selected from Mn, Cr, Cu, Zr, Mo, Fe, Co, and Bi; and titanium oxide that partially or wholly covers the surface of these particles. The arithmetic average roughness of the film surface is 1.0 μm or greater and the ratio of the composite particle network surface area to the film plane surface area is 7 or greater.
公开号:ES2701573A2
申请号:ES201890082
申请日:2017-09-25
公开日:2019-02-22
发明作者:Kaoru Tsuda；Murakami Yasushi
申请人:Nano Frontier Tech Co Ltd；
IPC主号:

专利说明:

[0001]
[0002] The present application claims the priority based on the Japanese patent application No.
[0003] 2017-10110 filed in Japan on January 24, 2017, and all the content described in this application is fully incorporated by reference in the present description. In addition, all the content described in all the patents, patent applications and documents cited in the present application is fully incorporated by reference in the present description.
[0004]
[0005] Technical Field
[0006] The present invention relates to a thermal collector film applicable for generating solar thermal energy and method of manufacturing thereof.
[0007]
[0008] Previous Technique
[0009] In recent years, from the point of view of environmental problems, depletion of fossil energy resources, etc., the need for alternative energy to fossil fuels is increasing. As a method to generate electricity using sunlight, which is representative resources of natural energy, the generation of photovoltaic solar energy and the generation of solar thermal energy are known. The generation of photovoltaic solar energy is a method to directly convert sunlight into electrical energy, and its practical use is now widespread throughout the world. On the other hand, the generation of solar thermal energy is a method to generate electricity by rotating turbines using the collected sunlight as a heat source. This method is attracting attention in recent years because the conversion of sunlight into heat allows a more efficient energy conversion than the conversion of sunlight into electricity (for example see Patent Document 1).
[0010] As a thermal collector film used in thermal collectors for the generation of solar thermal energy, for example, a film comprising chromium nitride is in use, but chromium nitride has a worrying problem of great environmental load. For this reason a thin film of oxynitride of titanium having properties of absorbing visible light (for example, see Patent Document 2). In addition, the improvement of the visible light absorption rate achieved through the addition of carbon in titanium oxynitride is disclosed (for example see Patent Document 3). In addition, the inventor of the present invention, prior to the present invention, invented a film comprising titanium oxide and carbon nanotubes, obtaining success in the development of a thermal collector film with a higher practicality than traditional films (see Patent Document 4).
[0011]
[0012] List of Appointments
[0013] Patent Literature
[0014] Patent Document 1: Japanese Unexamined Patent Application Publication No. 2015-148205
[0015] Patent Document 2: Japanese Unexamined Patent Application Publication No. 9-507095
[0016] Patent Document 3: Japanese Unexamined Patent Application Publication No. 2006-001820
[0017] Patent Document 4: Japanese Unexamined Patent Application Publication No. 2012-201589
[0018]
[0019] Compendium of the Invention
[0020] Problem to be solved by the Invention
[0021] In the film described in Patent Document 2, titanium oxynitride makes it possible to absorb visible light. In the film described in Patent Document 3, titanium oxynitride makes it possible to absorb visible light, and in addition, with the addition of carbon, the absorption rate of visible light and the radiation of infrared light can be improved. However, it is required to get a more efficient thermal collection through further improving the light absorption rate of the film.
[0022] The thermal collector film previously developed by the inventor of the present invention, ie the film prepared by the addition of carbon nanotubes into oxide titanium, has more excellent properties than traditional films. However, carbon presents a possibility of being consumed when oxidized at high temperatures, and therefore to promote the practical use of the generation of solar thermal energy, it is desired to achieve a film with an excellent resistance to thermal oxidation that allows its use at higher temperatures.
[0023] The present invention has been made in response to such a desire, and has the objective of providing a thermal collector film for generating solar thermal energy having an excellent resistance to thermal oxidation and a high rate of light absorption, and a method of manufacturing the same.
[0024]
[0025] Measures to Solve the Problem
[0026] As a result of the intensive studies of the inventor of the present invention and other interested parties, in order to achieve the aforementioned objective, the present invention has been realized by knowing that a suitable film can be obtained for the light collectors destined to the generation of solar thermal energy, through the formation of a film consisting of coating a titanium oxide film inside and outside a porous structural body (also called a three-dimensional film) in which the oxide particles metal with a higher thermal oxidation resistance than carbon nanotubes are partially bonded together. More specifically described, the object of the present invention has been achieved by the measures mentioned below.
[0027] [0010]
[0028] (one)
[0029] Bi; and titanium oxide that partially or entirely covers the surface of these particles; where the arithmetic mean roughness of the surface of the film is 1.0 μm or more and the ratio of the surface area of the network of composite particles to the area of the flat surface of the film is 7 or more.
[0030] (2) A further embodiment of the present invention preferably consists of a thermal collector film for generating solar thermal energy in which the metal oxide contains mainly two or more types of metals selected from Cr, Mn and Cu.
[0031] (3) A further embodiment of the present invention preferably consists of a thermal collector film for generating solar thermal energy further comprising a porous silica film on the outermost surface.
[0032] (4) A further embodiment of the present invention preferably consists of a thermal collector film for generating solar thermal energy whose light reflectance in the region of visible light with a wavelength of 400-700 nm is less than 5, 0%
[0033] (5) An embodiment of the present invention consists of a method for manufacturing any one of the preceding thermal collector films for generating solar thermal energy that includes a first stage of mixing in which titanium alkoxide (A) is mixed and at least one of acetylacetone and ethyl acetoacetate (B) so that the molar ratio between (A) :( B) is 1: 1 or more; a second mixing stage in which, in a solution obtained after the first mixing step, metal oxide particles are mixed which contain mainly two or more types of metals selected from Mn, Cr, Cu, Zr, Mo, Fe, Co, and Bi; and a film deposition stage in which a film is deposited by providing a mixture obtained after the second mixing stage in a base plate.
[0034] (6) A further embodiment of the present invention preferably consists of a method for manufacturing a thermal collector film for generating solar thermal energy in which the film deposition stage is a step for spraying the mixture onto the heated base plate at 250-400 ° C.
[0035] (7) A further embodiment of the present invention preferably consists of a method for manufacturing a thermal collector film for generating solar thermal energy in which the film deposition step includes a step to spray the mixture on the base plate with a temperature of less than 250 ° C and a stage for heating the mixture at 250 ° C-400 ° C after the spraying step.
[0036] (8) A further embodiment of the present invention preferably consists of a method for manufacturing a thermal collector film for generating solar thermal energy in which the metal oxide contains mainly two or more types of metals between Cr, Mn and Cu.
[0037] (9) A further embodiment of the present invention preferably consists of a method for manufacturing a thermal collector film for generating solar thermal energy that further includes a step of forming silica film to form a porous silica film on the surface more external
[0038] (10) A further embodiment of the present invention preferably consists of a method for manufacturing a thermal collector film for generating solar thermal energy in which the light reflectance in the region of visible light with wavelength between 400-700 nm is less than 5.0%.
[0039]
[0040] Advantageous Effects of the Invention
[0041] According to the present invention, a thermal collector film can be obtained for generating solar thermal energy having an excellent resistance to thermal oxidation and a high rate of light absorption.
[0042]
[0043] Brief Description of Drawings
[0044] Figure 1A indicates the flow of the main steps of the method of manufacturing the thermal collector film for generating solar thermal energy referred to in this embodiment.
[0045] Figure 1B indicates the flow of the main steps of the method of manufacturing the thermal collector film for generating solar thermal energy referred to by another embodiment.
[0046] Figure 1C indicates the flow of the main steps of the method of manufacturing the thermal collector film for the generation of solar thermal energy to which still another embodiment is concerned.
[0047] Figure 2 indicates the result of the respective X-ray analysis of the thermal collector film for generating solar thermal energy obtained by heating to 315 ° C and of the same film subsequently heated to 400 ° C.
[0048] Figure 3 indicates the SEM photographs to compare the forms of the films prepared with the change in the molar ratio between TTiP and AcAc (examples of experiment 1-7).
[0049] Figure 4 indicates the SEM photographs of the respective surfaces of the films prepared with the conditions of experiment examples 8-10.
[0050] Figure 5 indicates the SEM photographs of the surfaces of the films obtained with the respective conditions of the experiment example 1 and the experiment example 21 (5A is the photograph of the experiment example 1 and 5B is the photograph of the experiment example 21) . Figure 6 indicates in the diagrams the light reflectance (%) in the region of short wavelength (250-2500 nm) of the films prepared with the respective conditions of experiment example 1 and experiment example 21 (920 film three-dimensional, 920 plain film) and of the films prepared with the respective conditions of experiment example 11 and experiment example 22 (3702 three-dimensional film, 3702 plain film).
[0051] Figure 7 indicates in the diagrams the light reflectance (%) in the region of short wavelength (250-2500 nm) of the films prepared with the respective conditions of experiment example 12 and experiment example 23 (3402 film three-dimensional, 3402 smooth film) and of the films prepared with the respective conditions of experiment example 13 and of experiment example 24 (6331 three-dimensional film, 6331 smooth film).
[0052] Figure 8 indicates in the diagrams the light reflectance (%) in the region of short wavelength (250-2500 nm) of the films prepared with the respective conditions of experiment example 14 and experiment example 25 (965 film three-dimensional, 965 smooth film) and of the films prepared with the respective conditions of experiment example 15 and experiment example 26 (1G three-dimensional film, 1G smooth film).
[0053] Figure 9 indicates in the diagrams the light reflectance (%) in the short wavelength region (250-2500 nm) of the films prepared with the respective conditions of experiment example 16 and experiment example 27 (302A film three-dimensional, 302A smooth film) and of the films prepared with the respective conditions of experiment example 17 and experiment example 28 (303B three-dimensional film, 303B smooth film).
[0054] Figure 10 indicates in the diagrams the light reflectance (%) in the region of short wavelength (250-2500 nm) of the films prepared with the respective conditions of the experiment example 18 and the experiment example 29 (6301 film three-dimensional, 6301 plain film) and of the films prepared with the respective conditions of experiment example 19 and experiment example 30 (6340 three-dimensional film, 6340 plain film).
[0055] Figure 11 indicates in the diagrams the light reflectance (%) in the region of short wavelength (250-2500 nm) of the films prepared with the respective conditions of experiment example 20 and experiment example 31 (444 film three-dimensional, 444 smooth film).
[0056] Figure 12 indicates in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 1 and experiment example 21 (920 film three-dimensional, 920 smooth film).
[0057] Figure 13 indicates in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 11 and experiment example 22 (3702 film three-dimensional, 3702 smooth film).
[0058] Figure 14 indicates in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 12 and experiment example 23 (3402 film three-dimensional, 3402 smooth film).
[0059] Figure 15 indicates in the diagrams the light reflectance (%) and the rate of thermal radiation in the long wavelength region of the films prepared with the respective conditions of experiment example 13 and experiment example 24 (6331 film three-dimensional, 6331 smooth film).
[0060] Figure 16 indicates in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 14 and experiment example 25 (965 film three-dimensional, 965 smooth film).
[0061] Figure 17 indicates in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 16 and experiment example 27 (302A film three-dimensional, 302A smooth film).
[0062] Figure 18 indicates in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 17 and experiment example 28 (303B film three-dimensional, 303B smooth film).
[0063] Figure 19 indicates the SEM photographs for comparing the shape of the base film (3250 smooth film) and that of the light absorbing film (3250 three-dimensional film), prepared in experiment example 32.
[0064] Figure 20 represents a diagram indicating the light reflectance (%) in the short wavelength region (250-2500 nm) of the films prepared with the conditions of experiment example 32 (3250 smooth film, 3250 three-dimensional film) .
[0065] Figure 21 depicts diagrams indicating the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the conditions of experiment example 32 (3250 three-dimensional film, 3250 plain film).
[0066] Figure 22 indicates the measurement result of the light absorption rate before the thermal resistance test of 8 samples (three layer films) prepared in the experiment example 32.
[0067] Figure 23 indicates the measurement result of the light absorption rate before the thermal resistance test of the film (sample 8) prepared in the experiment example 32.
[0068] Figure 24 indicates the measurement result of the light absorption rate before and after the thermal resistance test at a temperature of 600 ° C of the films (samples 6 and 7) prepared in experiment example 32.
[0069] Figure 25 indicates the measurement result of the light absorption rate before and after the thermal resistance test at a temperature of 750 ° C of the films (samples 4 and 5) prepared in the experiment example 32.
[0070] Figure 26 indicates the measurement result of the light absorption rate before and after the temperature resistance test at 850 ° C of the films (samples 1, 2 and 3) prepared in experiment example 32.
[0071]
[0072] Modality for the Realization of the Invention
[0073] Next, a suitable embodiment of the present invention is described according to the Figures. Incidentally, the embodiment described below does not limit the invention to which the Claims refer, and in addition the elements described in the embodiment and their combinations are not necessarily indispensable for the resolution measures of the present invention.
[0074] one.
[0075] The thermal collector film for generating solar thermal energy referred to in the present embodiment has a network structure of composite particles comprising the particles of metal oxide and titanium oxide that partially or entirely covers the surface of these particles. The thermal collector film for generating solar thermal energy preferably comprises a porous silica film on its outermost surface. By the way, the thermal collector film for solar thermal generation can contain other materials, in addition to the particles of metallic oxide, titanium oxide that covers the surface of these particles, and porous silica that covers the outer surface of the collecting film thermal to generate solar thermal energy.
[0076] (1) Metal oxide particles
[0077] The metal oxide particles forming the thermal collector film for generating solar thermal energy preferably have an average particle size comprised between 0.5-5 μm. The particle size, including this average particle size, has been measured by the laser diffraction scattering method. The metal oxide consists of metal oxide particles containing mainly two or more types of metals selected from Mn, Cr, Cu, Zr, Mo, Fo, Co, and Bi.
[0078] As the suitable metal oxide, mention may be made of:
[0079] (a) metal oxide containing mainly each oxide of Cr, Mn, Cu, Mo, Zr;
[0080] (b) metal oxide containing mainly each oxide of Cr, Mn, Cu, Zr;
[0081] (c) metal oxide containing mainly each oxide of Mn, Fe, Co;
[0082] (d) metal oxide containing mainly each Cu, Mo, Fe oxide;
[0083] (e) metal oxide containing mainly each oxide of Cr, Cu, Zr;
[0084] (f) metal oxide containing mainly each Cr, Cu oxide;
[0085] (g) metal oxide containing mainly each oxide of Cr, Mn, Cu, Mo;
[0086] (h) metal oxide containing mainly each oxide of Cr, Mn, Cu;
[0087] (i) metal oxide containing mainly each Mn oxide, Bi;
[0088] (j) metal oxide containing mainly each Cr, Fe oxide;
[0089] (k) metal oxide containing mainly each Mn oxide, Fe; Y
[0090] (l) metal oxide containing mainly each oxide of Cr, Cu, Fe.
[0091] The metal oxide can be a mixture of several types of individual metal oxides, in addition to a compound oxide in which various types of metals make up an oxide. For example, a composite oxide having a spinel structure can be suitably indicated as an example. Among the metal oxides mentioned above as examples, the metal oxide containing mainly two or more metals between Cr, Mn and Cu is particularly preferable.
[0092] (2) Titanium oxide film
[0093] The titanium oxide has a film form that covers the surface of the metal oxide particles. Titanium oxide can cover both the entire surface and a part of the surface of these particles. The metal oxide particles form the armature of the thermal collector film for generating solar thermal energy and form a porous body of three-dimensional network shape. There are cases in which titanium oxide is interposed in the junction region between the particles, but there are also cases in which it is not interposed. The titanium oxide preferably has a crystal structure of anatase type in the stage where it is not used as part of the light collector for the generation of solar thermal energy. However, when used as part of the light collector, it is subjected to a high temperature, which can convert its crystalline structure into a rutile structure.
[0094] By the way, the titanium oxide film can have a rutile-like crystalline structure from the beginning.
[0095] (3) Porous silica film
[0096] Porous silica film is a film that covers the outermost surface of the thermal collector film for the generation of solar thermal energy. This film is required to be able to withstand thermal expansion when thermally expanding the thermal collector film for thermal solar power generation and the base plate in which this film is formed. The formation of the porous silica film is carried out so that the porous three-dimensional film is not destroyed and also resists thermal expansion.
[0097] two.
[0098] The thermal collector film for generating solar thermal energy is a film formed on a base plate and consists of a porous body film (can also be referred to as a three-dimensional film) that has a multitude of pores (can be both open pores and pores) closed). As the base plate, a plate using a metallic material with high thermal conductivity, such as steel plate, copper plate, aluminum plate, aluminum coated steel plate, steel plate coated with aluminum-based alloy is preferable , copper-plated steel plate, tin-coated steel plate, chrome-plated steel plate or stainless steel plate, nickel-based superalloy, etc. The use of a metallic material with high thermal conductivity as a plate
[0099] base facilitates that the heat transmitted to the base plate from the thermal collector film for generation of solar thermal energy is subsequently transmitted to the heating object. It is more preferable to use, among these materials, as the base plate the materials with high thermal resistance such as stainless steel plate or nickel base superalloy, etc. The porous body film preferably has a ratio of the area of the composite particle network (S2) to the projected area of the film (area of the flat surface of the film: S1) (= S2 / S1) of 7 or more , and more preferably 8 or more, The larger the S2 / S1 ratio, the larger the surface that increases due to the existence of pores in the porous body. Therefore, it is preferable that the thermal collector film for generating solar thermal energy comprises a multitude of pores having a surface area 7 times or larger, and preferably 8 times or larger than the projected area of the surface of the film . It is preferable that the roughness, defined as arithmetic mean roughness (Ra), of the surface of the thermal collector film for thermal solar energy generation is 1.0 μm or more. Furthermore, it is preferable that the maximum height (Rz) of the surface of the thermal collector film for solar thermal generation is 14 μm or more, and more preferably 16 μm or more. In case the metal oxide contains mainly two or more types of metals between Cr, Mn and Cu, it is preferable that Ra is 1.0 μm or more.
[0100] The "projected area" is an area of a measurement region (microscopic view) viewed from the vertical direction to the surface of the base plate (direction of thickness of the base plate). "Surface area 7 times or larger than the projected area" means that the actual surface area in the measurement region is 7 times or larger than the projected area of the measurement region. For the surface area with respect to the projected area, Ra and Rz, the measured values can be used by means of laser microscopy for shape measurement.
[0101] The porous body film in which the network of metal oxide particles is coated with titanium oxide film can be formed directly on the base plate, but can also be formed on a base material containing metal oxide and aluminum oxide. titanium, which is formed on the base plate.
[0102] The thermal collector film for generating solar thermal energy referred to in this embodiment is preferably a film whose light reflectance in the region of visible light with a wavelength of 400 nm-700 nm (This expression has the same meaning 400 nm or more and 700 nm or less It is understood that the sign "-" also includes the values indicated before and after it, henceforth this sign is understood in the same way.) is less than 5.0%. "The light reflectance is less than 5.0%" means that "the absorption rate of light is 95% or more". In the wavelength region of sunlight, a low light reflectance (ie, a high rate of light absorption) in the region of a certain wavelength range of 400-700 nm has an importance in the Thermal collection point of view. In case the film is used at a high temperature (800-900 ° C) as in the generation of tower-type thermal solar energy, it is considered that the thermal radiation starts at the wavelength of around 700 nm. Therefore, it is considered desirable that the light absorption rate is particularly high in the wavelength range of 400 nm-700 nm. Furthermore, not only in the region of visible light of 400 700 nm but also in the region of wavelength greater than 700 nm, it is desirable that the light reflectance of the thermal collector film is preferably less than 20%, and more preferably less than 15%, and even more preferably less than 10%.
[0103] 3.
[0104] Figure 1A indicates the flow of the main stages of a method of manufacturing a typical thermal collector film for solar thermal generation referred to in this embodiment.
[0105] The method of manufacturing the thermal collector film for generating solar thermal energy referred to in this embodiment comprises, as shown in FIG. 1A, preferably, a first mixing step (S100) for mixing titanium precursor and acetylacetone; a step of heating mixing solution (S200) to heat the mixing solution, mixed in the first mixing stage; a second mixing step (S300) for mixing, subsequently to the previous step, metal oxide particles containing mainly two or more types of metal selected from Mn, Cr, Cu, Zr, Mo, Fe, Co, and Bi; a film deposition step (S400) for depositing a film providing on the base plate a mixture obtained after the second mixing stage; and a silica film forming step (S500) to form a porous silica film on the outermost surface of the thermal collector film for thermal solar generation. Here the film deposition stage is a step to spray the mixture onto the heated base plate preferably at 250-400 ° C, and more preferably at 280-360 ° C.
[0106] In addition, a further method of manufacturing the thermal collector film for thermal solar power generation comprises, as shown in FIG. 1B, preferably, after the above-mentioned steps (S100-S300), a spraying step (S410) for spraying the mixture on the base plate with temperature below 250 ° C; and a heating step for heating, after the spraying step, the mixture at 250-400 ° C, and more preferably at 280-360 ° C (S420). In this heating step, the base plate provided with the mixture can be heated or the mixture heated by contacting or bringing the heat source closer to the mixture.
[0107] Next, the respective steps of each manufacturing method shown in Figure 1A are described in more detail.
[0108] - Respective stages of Figure 1A - (1) First stage of mixing (S100)
[0109] In the first mixing step, titanium oxide precursor and at least one of acetylacetone and ethyl acetoacetate are mixed. The titanium oxide precursor can be converted to titanium oxide by pyrolysis. As the precursor of titanium oxide, there are organic titanium compounds and inorganic titanium compounds. The mixing can be carried out using any apparatus such as stirrer, magnetic stirrer, ultrasonic generator, etc. The suitable ratio between the titanium oxide precursor (A) and at least one of acetylacetone and ethyl acetoacetate (B) is, when represented as a molar ratio, A: B = 1: 1 and more, preferably 1: 1.5 or more, and even more preferably A: B = 1: 1.5-4.
[0110] As organic titanium compounds there may be mentioned: titanium tetrametoxide, titanium tetraethoxide, titanium tetraaryloxide, titanium tetra-n-propoxide, titanium tetraisopropoxide, titanium tetra-n-butoxide, titanium tetraisobutoxide, tetra-sec-butoxide titanium, titanium tetrat-butoxide, titanium tetra-n-pentyloxide, titanium tetracyclopentyl oxide, titanium tetrahexyl oxide, titanium tetracyclohexyl oxide, titanium tetrabenzyl oxide, titanium tetraoctyloxide, titanium tetrakis (2-ethylhexyl oxide), titanium tetradecyloxide, titanium tetradecyloxide , titanium tetrastearyloxide, titanium tetrabutoxide dimer, titanium tetrakis (8-hydroxyoctyloxide), titanium diisopropoxide bis (2-ethyl-1,3-hexanediolate), bis (2-ethylhexyloxy) bis (2-ethyl-1,3- hexanodiolate) of titanium, titanium tetrakis (2-chloroethoxide), titanium tetrakis (2-bromoethoxide), titanium tetrakis (2-methoxyethoxide), titanium tetrakis (2-ethoxyethoxide), titanium trimethoxide butoxide, titanium dibuthoxide dimethoxide , titanium triethoxide butoxide, titanium dietoxide dibuthoxide, titanium triisopropoxide butoxide, titanium diisopropoxide dibuthoxide, titanium tetraphoxide, titanium tetrakis (o-chlorophenoxy) o), titanium tetrakis (mnitrophoxide), titanium tetrakis (p-methyl phenoxide), titanium tetrakis (trimethylsilyloxide), bis (acetylacetonate) diisopropoxy titanium, di-n-butoxy bis (triethanolamine) titanium, titanium stearate, isopropoxy titanium octylene glycollate, tetraisopropoxy titanium polymer, tetra-n-butoxy titanium polymer, dihydroxy bis (lactate) titanium, dioxy titanium propane bis (ethyl acetoacetate), oxotitanium bis (oxalate monoammonium oxalate), monostearate of tri-n-butoxy titanium, diisopropoxy titanium distearate, dihydroxy bis (lactate) titanium ammonium salt, etc. These organic titanium compounds are used individually or in combination of two or more types of compounds.
[0111] Of these organic titanium compounds, titanium tetraisopropoxide can be used more preferably due to the stability of preservation of materials, the selectivity of solvents, the relationship between the pyrolysis temperature and the crystallization temperature, the adhesiveness to the base plate , etc. In addition, titanium chloride (TiCl 4), etc. may be mentioned as inorganic titanium compound. By the way, organic titanium compounds and inorganic titanium compounds can be used by mixing together.
[0112] The titanium oxide precursor can be used as is, or it can also be used as a solution or dispersion liquid, such as colloidal solution, emulsion or suspension, using solvent or dispersion medium. Particularly, in case of spraying the titanium oxide precursor by means of the sprayer, it is preferable to use the titanium oxide precursor as solution or dispersion liquid to increase its fluidity.
[0113] As the solvent or dispersion medium used for the titanium oxide precursor to be used as a solution or dispersion liquid, alcohols, such as ethanol, methanol, propanol, butanol, can be suitably used; Hexane, Toluene, Chlorobenzene, Methyl Chloride, Perchlorethylene, etc. In addition, the solvent or dispersion medium may contain a small amount of water.
[0114] At least one of acetylacetone and ethyl acetoacetate contributes to raising the temperature at which the titanium oxide precursor (preferably organic titanium compound, and more preferably titanium alkoxide) is decomposed by pyrolysis, becoming titanium oxide. As a reaction result between acetylacetone or ethyl acetoacetate and the titanium oxide precursor, a titanium acetylacetone complex or the titanium-acetoacetate-ethyl complex is produced. In order for these complexes to decompose by pyrolysis and turn into titanium oxide, a relatively high temperature is needed. On the other hand, diethyl malonate has a weaker coordination bond than that of acetylacetone and ethyl acetoacetate, the decomposition temperature of the complex produced by the coordination bond being low, therefore the diethyl malonate decomposes before the oxide production. It is considered that this difference in the decomposition temperature of the titanium complex influences the formation or not of the porous film.
[0115] (2) Heating stage of mixing solution (S200)
[0116] The mixing solution heating step is a step in which the mixture solution obtained after the first mixing step is heated to react the titanium oxide precursor with at least one of acetylacetone and ethyl acetoacetate. With this reaction, the titanium-acetylacetone complex is produced if acetylacetone is used, and the titanium-acetoacetate-ethyl complex is produced if ethyl acetoacetate is used. The temperature for heating the mixing solution is 60-100 ° C, preferably 70-90 ° C, and more preferably 75-85 ° C. There is no limitation regarding the warm-up time, but suitably 2-12 hours, and more adequately 4-8 hours.
[0117] (3) Second stage of mixing (S300)
[0118] The second stage of mixing is a stage in which metal oxide particles containing mainly two or more types of metal selected from Mn, Cr, Cu, Zr, Mo, Fe, Co, and Bi are mixed in the solution obtained after of the first stage of mixing. Before mixing, it is preferable to dilute the mixture solution obtained in the first mixing stage (it can also be referred to as a reaction solution) with alcohol (suitably isopropyl alcohol), etc. The ratio between the aforementioned mixing solution (X) and the alcohol for dilution (Y) is, when represented as a mass ratio, preferably X: Y = 1: 1-6, preferably X: Y = 1: 2- Four. The metal oxide particles (A) are mixed in the diluted solution with alcohol, etc. (B) so that the mass ratio results to be A: B = 1: 10-100, and more preferably A: B = 1: 20-50. This mixture can be made, like the first stage of mixing, with any apparatus such as stirrer, magnetic stirrer, ultrasonic generator, etc.
[0119] (4) Film deposit stage (S400)
[0120] The film deposition stage is a step to deposit a film by providing on the base plate the mixture obtained after the second mixing stage. In this film deposition stage, the mixture of the previous stage is sprayed onto the base plate heated at 250-400 ° C and more preferably 280-360 ° C. The spraying step is suitably carried out using a sprayer. On the base plate whose temperature has been raised to the aforementioned temperature, the raw material prepared in the second mixing step is sprayed, by predetermined number of times, using a sprayer. The organic solvent contained in the raw material is volatilized from the pulverized raw material on the base plate, and the titanium oxide produced by pyrolysis is crystallized on the surface of metal oxide particles. In this process, components bonded to titanium are volatilized. A volatilization that is generated in a short time is more desirable than a volatilization that is generated gradually with the increase in temperature. It is because the volatilization in a short time contributes a lot to the formation of many pores in the film. In addition, by spraying the raw material on the base plate by means of the sprayer, a film is formed which presents a uniformity both in the components and in the structure.
[0121] The diameter of the nozzle of the sprayer is preferably 0.1-0.8 mm, and more preferably 0.3-0.5 mm. The air pressure for spraying is preferably 0.1-0.4 MPa, and more preferably 0.15-0.25 MPa. In addition, at this stage the next spraying can be carried out after waiting until the temperature of the base plate has risen (for example, wait 3 seconds) after the previous spraying of the raw material. In addition, it is desirable that the spraying time with the sprayer, in case of spraying on the surface of 3 cm x 3 cm, be between 50-280 seconds.
[0122] In addition, the thermal collector film for generating solar thermal energy, formed on the base plate 1 according to the aforementioned manufacturing method, has a three-dimensional grid shape with a multitude of fine pores. As a result, it increases the light-receiving area of the thermal collector film to generate solar thermal energy, and also complicates the specular reflection of the radiated light on the same film, thus allowing efficient absorption of light. Particularly, with the film deposit by means of spraying mentioned above, the light receiving area of the thermal collector film can be increased to generate solar thermal energy easily and at a reduced price without taking advantage of techniques such as sputtering, etc. In addition, a larger number of finer pores can be provided in the thermal collector film for thermal solar energy generation compared to the sputtering technique, etc.
[0123] Furthermore, as the aforementioned step allows the thermal collector film to be formed for the generation of solar thermal energy by spraying the raw material on the base plate with a sprayer, the formation of the thermal collector film for generating solar thermal energy can be perform easily and at a reduced price compared to, for example, the PVD method (Physical Vapor Deposition method) or the sputtering method. However, the method of forming the thermal collector film for thermal solar generation can employ other measures without being limited to the sprayer. In addition, the film deposition stage can also be a step in which any other film forming method such as spin coating, printing, etc., is exploited, without being limited to spraying.
[0124] (5) Silica film forming step (S500)
[0125] The silica film forming step is a step to form a porous silica film on the outermost surface of the thermal collector film for generation of solar thermal energy. This stage is optional and does not have to be done. By the way, with the formation of a porous silica film on the outermost surface, an advantage can be obtained by being able to protect the thermal collector film for generating solar thermal energy and preventing its destruction or breakage by use. To form a porous silica film, a formation consisting of spraying an organic silane solution, typically dimethyldichlorosilane, trimethoxymonoethoxysilane or tetraethoxysilane, and then heating is sprayed on the outermost surface of the thermal collector film. As an example of the method of suitable formation of the porous silica film, mention may be made of the method by which alkoxysilane, typically tetraethyl orthosilicate, and hydroxyacetone are mixed in the presence of ethanol and / or water, and the solution obtained, subsequently diluted with ethanol, is sprayed with a spray on the film obtained in step S400, then heating to an appropriate temperature between 300-500 ° C. Incidentally, in the present description there are cases in which the term "thermal collector film for generating solar thermal energy" or "thermal collector film" includes or does not include the silica film depending on the context. Next, the thermal collector film for generating solar thermal energy, formed in the film deposition stage (S400) without including the silica film, is referred to particularly as "light absorbing film".
[0126] - Respective stages of Figure 1B - Steps S100-S300 and step S500 are the same stages as the stages described above. Here only the step S400 different from the previously described flow, shown in Figure 1 (1A), is described.
[0127] (1) Spraying stage (S410)
[0128] The spraying step is a step constituting part of the film deposition step (S400) and in which the mixture obtained in the second mixing stage is sprayed onto the base plate at a temperature of less than 250 ° C.
[0129] (2) Heating stage (S420)
[0130] The heating step is a step that constitutes part of the film deposition stage (S400) and in which the mixture is heated to 250-400 ° C after the spraying step.
[0131] In this way, without spraying the mixture on the base plate heated to 250 ° C or more, a thermal collector film can also be produced for generating solar thermal energy by heating the base plate to 250 ° C or more after which The mixture has been sprayed on the same plate at a temperature below 250 ° C.
[0132] - Respective stages of Figure 1C - Steps S100-S500 are the same stages as the respective stages of Figure 1A. Here, only a new base film preparation step (S350) is described, added between the second mixing stage (S300) and the film deposition stage (S400) of Figure 1A.
[0133] (1) Base film preparation stage (S350)
[0134] The base film preparation step is a step to pre-apply a base film (lower layer film) on the base plate before depositing the film by providing the mixture obtained after the second mixing step (S300) on the base plate. This stage is optional and does not have to be done. By the way, with the formation of the base film between the three-dimensional film consisting of porous body (light absorbing film) and the base plate, an advantage of increasing the adhesiveness between the base plate and the film can be obtained of light absorption and further improve the resistance of the thermal collector film for the generation of solar thermal energy.
[0135] The material making up this base film has no particular limitation if it has an adhesiveness between the base plate and the light absorbing film and does not reduce the thermal conductivity from the light absorbing film to the base plate, but is preferable Containing metal oxide particles. This is because the contained metallic oxide increases the degree of blackness of the thermal collector film, and in addition efficiently transmits the heat to the base plate by its thermal conductivity, controlling the thermal radiation. In addition, to increase the adhesiveness to the base plate, it is preferable to form a smooth film by joining the metal oxide particles. For this, you can do the bond coating the surface of the metal oxide particles, for example with the organic titanium polymer. To form a base film there is a method by which a mixing solution containing the base film material is sprayed and heated onto the surface of the base plate under heating or non-heating conditions. As a suitable example of the method of forming the base film, mention may be made of the method according to which the organic titanium polymer, mixed with solvent, and the metal oxide particles used in the solution heating step are mixed. mixture (S200), and the solution thus obtained is sprayed onto the base plate with a spray, then heated to an appropriate temperature between 300-500 ° C. With respect to the organic titanium polymer, there is no particular limitation if it is a generally available product, and for example, this product can be manufactured by subjecting the aforementioned organic titanium compound to crosslinking and thermal polymerization.
[0136] The thickness of this base film is required to be around 2-15 pm, and preferably 5-10 pm, and more preferably 7-9 pm. After this basic film preparation step (S350), the film deposition stage (S400) and the above-mentioned silica porous film forming step (S500) are proceeded. The thermal collector film for generating solar thermal energy obtained after passing the respective stages shown in Figure 1C consists of a 3-layer structure comprising the base film, the light absorbing film, and the silica film, and its film thickness is usually 15-50 pm, and preferably 20-30 pm.
[0137] (2) Example of variant of the basic film preparation stage (S350)
[0138] Instead of the mixing solution containing the organic titanium polymer, used for the preparation of the above-mentioned base film, another metal complex can be used. For example, 4 g of the aluminum complex (ethylacetate aluminum diisopropyrate from Kawaken Fine Chemicals Co., Ltd., concentration of active components: 75% by weight, solvent: IPA) and 6 g of isopropyldiglycol (iPDG) from Nippon Nyukazai are mixed. Co., Ltd., and mixes more by exposing to ultrasonic radiation for 15 minutes in the ultrasonic washing machine. With this obtained mixture 9 g of powdered metal oxide (from Asahi Kasei Kogyo Co., Ltd., No. Black3250LM, particle size: about 700 nm) is mixed and stirred by heating 60 ° C for 24 hours. Then, it is again subjected to ultrasonic treatment for 15 minutes, and the product is sprayed by spin coating or spray to deposit the film on the base plate. After depositing the film, the base plate is placed on the heater heated to 350 ° C and left to stand for 1 hour in order to prepare a base film (smooth film).
[0139] 4. Solar thermal collector
[0140] Next, the solar thermal collector comprising the thermal collector film for generating solar thermal energy referred to in the present embodiment is described.
[0141] The solar thermal collector includes a thermal collector film for generating solar thermal energy mentioned above and a base plate that supports the thermal collector film for generating solar thermal energy. This solar thermal collector is capable of absorbing sunlight and collecting heat efficiently. This is because the thermal collector film for generating solar thermal energy has a high rate of light absorption and easily transmits the heat to the back of the film.
[0142] [0059]
[0143] The solar thermal collector has, for example, a structure in which sunlight is exposed to the tube which has a thermal collector film on its surface for generating solar thermal energy and the solvent flowing inside the tube is heated (temperature oil). low and salt melted for high temperature). The tube is directly connected to the heat exchanger, and whereby the molten salt, etc., heated can heat water, etc., in the heat exchanger part.
[0144]
[0145] Execution Example
[0146] Next, the experiment examples (including the embodiments and comparison examples) of the present invention are described. However, the present invention is not limited to the embodiments described hereinafter.
[0147] 1. Compounds used and their abbreviations
[0148] (1) Titanium oxide precursor
[0149] Titanium tetraisopropoxide: (from Kanto Chemical Co., Inc., item number indicated in the catalog: 40884-05) ... abbreviated as "TTiP".
[0150] (2) Acetylacetone: (from Kanto Chemical Co., Inc., deer first grade reagent, item number indicated in the catalog: 01040-71) ... abbreviated as "AcAc".
[0151] (3) Ethyl acetoacetate: (from Tokyo Chemical Industry Co., Ltd., item number: A0649) ... abbreviated as "EAcAc".
[0152] (4) Diethyl malonate (from Wako Pure Chemical Corporation, item number indicated in the catalog: 057-01436) ... abbreviated as "DEM".
[0153] (5) Solvent for dilution
[0154] Isopropyl alcohol: (from Wako Pure Chemical Corporation) ... abbreviated as "IPA". (6) Metal oxide
[0155] (a) Copper Chromite Black Spinel: (from Asahi Kasei Kogyo Co., Ltd., No. Black3702) ... abbreviated as "3702".
[0156] (b) Iron Cobalt Black Spinel: (from Asahi Kasei Kogyo Co., Ltd., No. Black3402) ... abbreviated as "3402".
[0157] (c) Cu (Fe, Mn) 2O4: (from Asahi Kasei Kogyo Co., Ltd., No. F-6331-2 Coal Black) ... abbreviated as "6331".
[0158] (d) (Fe, Cr) 2O3: (from Asahi Kasei Kogyo Co., Ltd., No. Black6340 Chromium Iron Oxide) ... abbreviated as "6340".
[0159] (e) (Bi, Mn) 2O3: (from Asahi Kasei Kogyo Co., Ltd., No. Black6301 Bismuth Manganate Black Rutile) ... abbreviated as "6301".
[0160] (f) CuCr2MnO5: (from Shepherd Color Japan Inc., No. BLACK 20C920 Copper Chromite Black Spinel) ... abbreviated as "920".
[0161] (g) CuCr2O4: (from Shepherd Color Japan Inc., No. BLACK 30C965 Copper Chromite Black Spinel) ... abbreviated as "965".
[0162] (h) CuCr2O4: (from Shepherd Color Japan Inc., No. BLACK 1G Copper Chromite Black Spinel) ... abbreviated as "1G".
[0163] (i) (Mn, Cu, Fe) (Mn, Fe) 2O4: (from Shepherd Color Japan Inc., No. BLACK444 Manganese Ferrite Black Spinel) ... abbreviated as "444".
[0164] (j) Cu (Cr, Mn) 2O4: (from Tokan Material Technology Co., Ltd., No. 42-302A Copper Chromite Black Spinel) ... abbreviated as "302A".
[0165] (k) Cu (Cr, Mn) 2O4: (from Tokan Material Technology Co., Ltd., No. 42-303B Copper Chromite Black Spinel) ... abbreviated as "303B".
[0166] (l) Copper Chromite Black Spinel (from Asahi Kasei Kogyo Co., Ltd., No. Black3250LM, particle size of about 700 nm) ... abbreviated as "3250".
[0167] (7) Organic silane
[0168] Tetraethyl orthosilicate: (from Tokyo Chemical Industry Co., Ltd.) ... abbreviated as "TEOS".
[0169] (8) Hydroxyacetone: (from Tokyo Chemical Industry Co., Ltd.) ... abbreviated as "HA".
[0170] The composition of each metal oxide mentioned above is shown in Table 1. The% indicated in the Table means the% by mass of each metal oxide with respect to 100% of all the metal oxide. In addition, the values indicated in Table 1 serve only as conversion values of the metal oxides indicated in the left column. The metals contained in the metal oxides can present other forms of oxide that are not those indicated in the left column.
[0171] [Table 1]
[0172]
[0173]
[0174]
[0175]
[0176] 2. Method of analysis
[0177] (1) To observe the shape of the film surface, the scanning electron microscope of Hitachi High-Technologies Corporation (SEM, model: MiniscopeTM3030Plus and S-4800) was used.
[0178] (2) To measure the surface area with respect to the projected film area, maximum height (Rz) and the arithmetic mean roughness (Ra), the laser microscope was used to measure model shapes "VK-X100" from KEYENCE CORPORATION .
[0179] (3) To identify the crystalline form of the titanium oxide in the film, the X-ray diffraction apparatus with CuKa ray source (from Rigaku Corporation, model "RINT2500HF") was used. The measurement was made adjusting the operating speed to 2 degrees / min., And the step width to 0.02 degrees.
[0180] (4) Light reflectance in the short wavelength region of 250-2500 nm was measured using the uv-visible spectrophotometer of Shimadzu Corporation (model: 3100PC).
[0181] (5) The light reflectance in the long wavelength region of 2-20 pm was measured using the Agilent Technologies spectrophotometer (model: BIO-RAD FTS 6000).
[0182] (6) The thermal radiation rate in the wavelength region of 2-25 pm was measured using the Agilent Technologies infrared spectrophotometer (model: Varian 680-IR).
[0183] (7) The light absorption rate was measured using the spectrophotometer (UV / VIS / NIRLambda1050 from PerkinElmer) and adjusting the angle of incidence to 8o and at room temperature. The spectrophotometer was provided with an integrating sphere to measure the reflection from the surface of the samples, ie "the hemispherical reflection (HDR)" and "the reflectance p". The samples were opaque, and therefore it was considered that there is no transmittance. Therefore, p (X) to (X) = 1, where a represents the absorption rate, and X represents the wavelength.
[0184] The spectrum value was obtained with interval AX = 10 nm. The spectral solar irradiance G (X) was calculated using the G173-03 standard of the American Society for Testing and Materials (ASTM). The total absorption rate with respect to the solar rays or the weighted solar absorption rate, represented with aS, was defined with the formula below.
[0185] [Formula 1]
[0186]
[0187]
[0188]
[0189]
[0190] This integral was evaluated by means of the midpoint approximation of the rectangular method. The lower limit of formula (1) was set as 280 nm so that it corresponds to the lower data limit G-173. The measurement of the absorption rate of light was carried out at room temperature of 25 ° C. According to the study carried out with another coating for high temperature (Pyromark, etc.), it is considered that the absorption rate of light does not depend on the temperature.
[0191] [0068]
[0192] 3. Preparation of the thermal collector film for solar thermal generation and film properties
[0193] (Example of experiment 1)
[0194] 61.85 g of TTiP and 43.58 g of AcAc were mixed so that it turned out to be TTiP: AcAc = 1: 2 (molar ratio), and TTiP and AcAc were reacted by heating to ca. 80 ° C. Then, 306,963 g of IPA was added to the reaction solution to dilute this solution. Then, 12.5 g of metal oxide "920" powder was mixed. Then, the mixture (also referred to as the mixing solution) obtained in the previous steps was loaded into the spray device (HARDER & STEENBECK spray gun with 0.4 mm nozzle, and with trade name: Colani). The base plate of SUS304 was heated to 315 ° C, and film deposition was performed by spraying on the base plate for 110 seconds by moving the sprayer from one end to the other end of the base plate. The pressure for the spray was adjusted to 0.2 Mpa. Then, a mixture solution of 20.83 g of TEOS and 63.36 g of ethanol and a mixture solution of 7.41 g of HA, 63.36 g of ethanol and 9.01 g of water of the same were mixed. ion exchange, this mixture was allowed to stand at 40 ° C and was then diluted with ethanol so that the solid concentration was 0.6% by mass, and this mixture was charged in the same spray device as the above mentioned. On the deposited film mentioned above, spraying was done for 2 seconds at room temperature, and immediately afterwards the base plate was kept under heating at 400 ° C for 1 hour, thus forming a porous silica film on the deposited film mentioned above.
[0195] To examine the crystalline form, when heated to 400 ° C, of the film obtained with the conditions mentioned above, the X-ray analysis of the film obtained after being subjected to heating conditions of 315 ° C and of this same film after being heated at 400 ° C for 1 hour. The X-ray diagram of each film in Figure 2 is shown. In the film obtained after being subjected to heating conditions of 315 ° C the anatase-type titanium oxide peak was not clearly observed due to the superposition of the peak of the metal oxides, but the same peak was observed (see the black arrow in the downward direction) in the film heated to 400 ° C. From this result it was found that the anatase-type titanium oxide was finally formed due to the reaction between TTiP and AcAc used for the preparation of the thermal collector film for the generation of solar thermal energy.
[0196] (Examples of experiment 2-7)
[0197] Film deposition was performed under the same conditions as experiment example 1 except that TTiP and AcAc were mixed so that the molar ratio was TTiP: AcAc = 1: 0 (experiment example 2), 1: 0.5 ( example of experiment 3), 1: 1 (example of experiment 4), 1: 1,5 (example of experiment 5), 1: 3 (example of experiment 6) and 1: 4 (example of experiment 7), and He observed the surface shape of the films using the SEM photographs. In Figure 3 these photographs are shown together with the photograph of the experiment example 1 whose molar ratio turned out to be TTiP: AcAc = 1: 2. As clearly seen in Figure 3, it was seen that a film with a greater number of fine pores can be formed when the molar ratio turns out to be TTiP: AcAc = 1: 1 or more (experiment examples 1, 4-7), and preferably 1: 1.5 or more (experiment examples 1, 5-7). The experiment examples 2 and 3 correspond to the comparison examples.
[0198] (Examples of experiment 8-10)
[0199] Film deposition was performed under the same conditions as experiment example 1 except that EAcAc was used (experiment example 8)
[0200] (Examples of experiment 11-20)
[0201] Film deposition was performed under the same conditions as experiment example 1 except that, instead of the powder metal oxide "920", the "3720" (experiment example 11), "3402" (example experiment 12), the "6331" (experiment example 13), the "965" (experiment example 14), the "1G" (experiment example 15), the "302A" (experiment example 16), the " 303B "(experiment example 17)," 6301 "(experiment example 18)," 6340 "(experiment example 19) and" 444 "(experiment example 20) respectively.
[0202] (Example of experiment 21) ... Corresponds to the comparison example.
[0203] As a comparison with experiment example 1, a smooth film was prepared with the following conditions. First, 3 g of organic titanium polymer from Nippon Soda Co., Ltd. (item number: B-10, tetra-n-butoxy-titanium polymer), 6 g of isopropyl diglycol (iPDG) from Nippon Nyukazai Co was mixed. ., Ltd., and 1.85 g of 1-butanol (first class reagent) from Wako Pure Chemical Corporation and further mixed by exposing to ultrasonic radiation for 15 minutes in the Branson Ultrasonic Washer (trade name: Bransonic). To this mixture was added 9 g of powdered metal oxide "920" and again exposed to ultrasonic radiation for 15 minutes to obtain a new mixture. TO Then, this mixture was charged to the spray device (HARDER & STEENBECK spray gun with 0.4 mm nozzle and commercial name: Colani), and with 0.2 Mpa pressure it was sprayed on non-heated SUS304 (temperature environment) for 2 seconds to deposit the film. Immediately after the film deposit, the base plate was placed over the heater heated to 400 ° C, leaving it to stand for 1 hour. A porous silica film was then formed with the same conditions as the experiment example 1.
[0204] ... They correspond to comparison examples.
[0205] (Examples of experiment 22-31)
[0206] The film deposition was performed with the same conditions as the experiment example 21 using, instead of the powder metal oxide "920", the "3720" (experiment example 22), the "3402" (experiment example 23) , "6331" (experiment example 24), "965" (experiment example 25), "1G" (experiment example 26), "302A" (experiment example 27), "303B" ( experiment example 28), "6301" (experiment example 29), "6340" (experiment example 30), and "444" (experiment example 31) respectively.
[0207] Table 2 shows various types of properties caused by the shape of the films prepared with the conditions of the experiment examples 1, 11-15. Table 3 shows various types of properties caused by the shape of the films prepared with the conditions of the experiment examples 16-20. Table 4 shows various types of properties caused by the shape of the films prepared with the conditions of the experiment examples 21-26. Table 5 shows various types of properties caused by the shape of the films prepared with the conditions of the experiment examples 27-31. In the tables the word "three-dimensional" means that a porous body film (three-dimensional film) is formed. The word "smooth" means that a porous body film (three-dimensional film) is not formed.
[0208] [Table 2]
[0209]
[0210] [Table 3]
[0211] [Table 4]
[0212]
[0213]
[0214] [Table 5]
[0215]
[0216]
[0217] As clearly seen in the comparison between Tables 2-5, the surface area / area values (ie, the ratio of the surface area of the network of composite particles "S2" to the projected surface area of the the movie "area of the flat surface of the film: S1 "= S2 / S1) of the porous body film is 8.2 or more, value greater than 8, while the S2 / S1 ratio of the smooth film is 5.6 or less, value less than 6.
[0218] Figure 5 shows the SEM photographs of the surface of the films obtained with the respective conditions of experiment example 1 and of experiment example 21 (5A corresponds to experiment example 1 and 5B corresponds to experiment example 21). The magnification for photographing is 5000 magnifications for both photographs. As clearly seen in the comparison between both SEM photographs, in the experiment example 1 subjected to the step of reacting AcAc with TTiP, a porous body film could be formed, but in experiment example 21 subjected to the single stage dispersing the tetra-n-butoxy titanium polymer with iPDG could not form a porous body film but a smooth film.
[0219] Next, it is explained, by comparison, about the reflectance of light in the short wavelength region of each type of three-dimensional film and of each type of smooth film.
[0220] Figure 6 shows in the diagrams the light reflectance (%) in the short wavelength region (250-2500 nm) of the films prepared with the respective conditions of experiment example 1 and experiment example 21 (920 film three-dimensional, 920 plain film) and of the films prepared with the respective conditions of experiment example 11 and experiment example 22 (3702 three-dimensional film, 3702 plain film). Figure 7 shows in the diagrams the light reflectance (%) in the short wavelength region (250-2500 nm) of the films prepared with the respective conditions of experiment example 12 and experiment example 23 (3402 film three-dimensional, 3402 smooth film) and of the films prepared with the respective conditions of experiment example 13 and of experiment example 24 (6331 three-dimensional film, 6331 smooth film). Figure 8 shows in the diagrams the light reflectance (%) in the short wavelength region (250-2500 nm) of the films prepared with the respective conditions of experiment example 14 and experiment example 25 (965 film three-dimensional, 965 plain film) and films prepared with the respective conditions of the example of experiment 15 and experiment example 26 (1G three-dimensional film, 1G smooth film). Figure 9 shows in the diagrams the light reflectance (%) in the short wavelength region (250-2500 nm) of the films prepared with the respective conditions of experiment example 16 and experiment example 27 (302A film three-dimensional, 302A smooth film) and of the films prepared with the respective conditions of experiment example 17 and experiment example 28 (303B three-dimensional film, 303B smooth film). Figure 10 shows in the diagrams the light reflectance (%) in the short wavelength region (250-2500 nm) of the films prepared with the respective conditions of experiment example 18 and experiment example 29 (6301 film three-dimensional, 6301 plain film) and of the films prepared with the respective conditions of experiment example 19 and experiment example 30 (6340 three-dimensional film, 6340 plain film). Figure 11 shows in the diagrams the light reflectance (%) in the short wavelength region (250-2500 nm) of the films prepared with the respective conditions of experiment example 20 and experiment example 31 (444 film three-dimensional, 444 smooth film). In each diagram of Figure 6-Figure 11 the transverse axis means the wavelength (nm) and the longitudinal axis means the light reflectance (%) respectively. In each diagram the dashed line represents the smooth film, and the solid line represents the three-dimensional film. In addition, the right side of each diagram indicates the light reflectance of each film when the wavelength is 400, 500, 600, and 700 nm.
[0221] In any three-dimensional film it was observed that the light reflectance was lower, that is, the light absorption rate was higher than that of the smooth films. In addition, the light reflectance of each three-dimensional film was less than 5% at the wavelength between 400-700 nm of the region of visible light. On the other hand, when dealing with smooth films, only the 3 films "6331", "303B" and "444" showed the light reflectance of less than 5% in the wavelength between 400-700 nm, but the rest of the smooth films had the light reflectance of 5% or more at some wavelength of the above-mentioned wavelength region.
[0222] Next, it is explained, by comparison, about the light reflectance and the rate of thermal radiation in the long wavelength region of a part of the various types of film shown in Figures 6-11.
[0223] Figure 12 shows in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 1 and experiment example 21 (920 film three-dimensional, 920 smooth film). Figure 13 shows in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 11 and experiment example 22 (3702 film three-dimensional, 3702 smooth film). Figure 14 shows in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 12 and experiment example 23 (3402 film three-dimensional, 3402 smooth film). Figure 15 shows in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 13 and experiment example 24 (6331 film three-dimensional, 6331 smooth film). Figure 16 shows in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 14 and experiment example 25 (965 film three-dimensional, 965 smooth film). Figure 17 shows in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 16 and experiment example 27 (302A film three-dimensional, 302A smooth film). Figure 18 shows in the diagrams the light reflectance (%) and the thermal radiation rate in the long wavelength region of the films prepared with the respective conditions of experiment example 17 and experiment example 28 (303B film three-dimensional, 303B smooth film). In each diagram of Figure 12-Figure 18 the transverse axis means the wavelength (pm), the longitudinal axis of the left side means the reflectance of light and the longitudinal axis of the right side means the rate of thermal radiation (the background value is 1 and the peak value is 0) respectively. The rate of thermal radiation is indicated by the ratio with respect to the thermal radiation rate of a perfect blackbody, established as 1. In each diagram the thick line represents the reflectance of light, and the thin line represents the thermal radiation rate respectively. The values of the three-dimensional film are represented in the diagram with the solid line, and the values of the smooth film are represented in the diagram with the dashed line.
[0224] Here, "thermal radiation" means emitting the absorbed solar heat as an electromagnetic wave. Therefore, it is preferable that the thermal radiation be almost zero. The perfect black body that is generally used as an object of comparison in measuring the rate of light absorption and thermal radiation has a light absorption rate of 100% and the thermal radiation for that is determined as 1. According to the Kirchhoff's law is considered that the rate of light absorption = thermal radiation, which is why it is considered that the perfect black body has a light absorption rate of 100% while thermally emitting out all the light absorbed. An ideal film has a 100% light absorption rate as a perfect black body and does not emit heat outwards (thermal radiation is zero). A film like this does not really exist, but it can be said that the bigger the difference between the light absorption rate and the thermal radiation rate, the better the film will be. On the contrary, an undesirable film is one that has a low rate of light absorption, with poor capacity to collect heat, but has a high rate of thermal radiation. This is not desirable because it has difficulty in absorbing sunlight and easily emits out the heat that is given by the absorbed light. From the relationship between the light absorption rate and the thermal radiation rate shown in Figure 12-Figure 18, we first observed a tendency for any three-dimensional film to have a lower light reflectance, ie an absorption rate of light higher than that of smooth films. In addition, it was observed that at the wavelength between 2-5 pm in which the thermal radiation energy of the solar heat at the time of high temperature turns out to be the largest, any three-dimensional film had a lower light reflectance value to the value of thermal radiation compared to smooth films. That is, three-dimensional films, despite having a low light reflectance (high light absorption rate), It had a controlled thermal radiation. As mentioned above, when taking into account that according to the Kirchhoff Law it is considered that theoretically it turns out to be the rate of absorption of light = thermal radiation, the perfect blackbody has a light absorption rate of 100% (light reflectance of 0). %) and a thermal radiation rate of 1, but it was observed that this balance can be changed by the structure of the film, etc. It is ideal that the thermal collector body for solar thermal generation has a low light reflectance (high light absorption rate) and a low rate of thermal radiation, and it is desirable that the same body has a separation as large as possible between these both values. When viewing the properties of each smooth film "920", "303B" and "302A", at the wavelength of between 2 5 qm, the light reflectance is less than or equal to or somewhat higher than the thermal radiation rate. However, at the wavelength of 5 qm or more a tendency was observed that the reflectance of light is significantly higher than the rate of thermal radiation. That is to say, it is considered that they are not suitable for the generation of solar thermal energy because even though they have a high reflectance of light (insufficient light absorption rate), the thermal radiation turns out to be high. On the contrary, in the three-dimensional films "920", "303B" and "302A", a tendency could be verified that the light absorption rate is higher than the thermal radiation rate. Also in other films (for example, "965", "6331" or "3402") the same tendency was observed when examining the three-dimensional film.
[0225] From the foregoing, it was observed that a three-dimensional film having a network structure of composite particles comprising: metal oxide particles containing mainly two or more metal types selected from Mn, Cr, Cu, Zr, Mo, Fe, Co , and Bi; and titanium oxide covering partially or entirely the surface of these particles, and in which Ra of the surface of the film is 1.0 qm or more and the ratio of the surface area of the composite particle network to the The area of the flat surface of the film is 7 or more, showed good properties with low light reflectance, and a low rate of thermal radiation with respect to the rate of light absorption.
[0226] (Example of experiment 32)
[0227] A thermal collector film with a three layer structure including a base film was prepared in accordance with the following method. First, 3 g of organic titanium polymer from Nippon Soda Co., Ltd. (item number: B-10, tetra-n-butoxy-titanium polymer), 6 g of isopropyl diglycol (iPDG) from Nippon Nyukazai Co., Ltd., and 1 , 85 g of 1-butanol (first class of reagent) from Wako Pure Chemical Corporation and further mixed by exposing to ultrasonic radiation for 15 minutes in the Branson Ultrasonic Washer (trade name: Bransonic). To this mixture was added 9 g of powdered metal oxide "3250" and again exposed to ultrasonic radiation for 15 minutes to obtain a new mixture. This mixture was then charged to the spray device (HARDER & STEENBECK spray gun with 0.4 mm nozzle and commercial name: Colani), and with the 0.2 Mpa pressure was sprayed on SUS304 at room temperature or heated for 2 seconds to deposit the film. Immediately after depositing the film, the base plate was placed on the heater heated to 400 ° C, leaving it to stand for 30 minutes. The thickness of the base film was approx. 8 pm.
[0228] Then, as a raw material of the light absorbing film, 61.85 g of TTiP and 43.58 g of AcAc were mixed so that it turned out to be TTiP: AcAc = 1: 2 (molar ratio), and were reacted TTiP and AcAc heating to approx. 80 ° C for 6 hours. Then, 306,963 g of 2-propanol was added to the reaction solution to dilute this solution. Then, 12.5 g of powdered metal oxide "3250" was mixed and subjected to ultrasonic treatment for 30 minutes. Then, the mixture (also referred to as the mixing solution) obtained from the previous steps was loaded into the spray device (HARDER & STEENBECK spray gun with 0.4 mm nozzle, and with trade name: Colani). The film deposition was performed by spraying on the base film for 110 seconds by moving the sprayer from one end to another end of the base film held at a temperature of 350 ° C. The pressure for the spray was adjusted to 0.2 Mpa. The titanium precursor which is the raw material of the light absorbing film, by thermally decomposing and crystallizing on the heater, fixes the metal oxide particles, and fine pores are created due to the evaporation of the organic solvent. This step was repeated several times maintaining the surface temperature of the base plate. Then, a mixing solution of 20.83 g of TEOS and 63.36 g of ethanol and a mixing solution of 7.41 g of HA, 63.36 g of ethanol and 9.01 g of exchange water were mixed. ionic, this mixture was allowed to stand at 40 ° C, then diluted with ethanol so that the solid concentration was 0.6% by mass, and this mixture was charged in the same spray device as above. On the aforementioned light absorption film, spraying was done for 2 seconds at room temperature, and immediately afterwards the base plate was kept under heating at 400 ° C for 1 hour, thus forming a porous silica film on the light absorbing film. above mentioned. The thickness of the light absorbing film was approx. 17 pm, the thickness of the porous silica film was approx. 5-10 nm, and the thickness of the three-layer structure consisting of base film, light absorbing film and porous silica film was approx.
[0229] 25 pm. 8 samples of four sides 3 x 3 cm (hereinafter referred to as "samples 1-8") were prepared for the thermal resistance test described below.
[0230] Table 6 shows various types of properties derived from the shape of the films prepared in experiment example 32. In addition, in Figure 19 the SEM photographs are shown to compare the respective shapes of the base film and the film of light absorption. It is seen that fine pores formed by the repeated spray coating are formed on the surface of the light absorbing film compared to the surface of the base film.
[0231] [Table 6]
[0232]
[0233]
[0234] Figure 20 shows a diagram showing light reflectance (%) in the short wavelength region (250-2500 nm) of the light absorbing film (3250 three-dimensional film) and the base film (3250 film) smooth) prepared in the experiment example 32. The three-dimensional film has a lower light reflectance than the smooth film, that is, it has a higher light absorption rate than the smooth film, which is the same result as the shown in Figure 6-Figure 11. In addition, the light reflectance of the three-dimensional film resulted in a small value of less than 4% at the wavelength of between 400-700 nm of the region of visible light, showing a significant difference compared to the smooth film.
[0235] Figure 21 depicts diagrams showing the light reflectance (%) and the thermal radiation rate in the long wavelength region (2-25 pm) of the light absorbing film (3250 three-dimensional film) and the film of base (3250 smooth film) prepared in the experiment example 32. In the 3250 smooth film a tendency was observed that the light reflectance rate was somewhat lower than the thermal radiation rate in the wavelength between 2- 5 pm, but the light reflectance rate was markedly superior to the rate of thermal radiation in a given region of the wavelength of 5 pm or more. In contrast, in the 3250 three-dimensional film there was a tendency for the value of the light reflectance rate to be small and the light absorption rate to be higher than the thermal radiation rate.
[0236] 4. Thermal resistance test and measurement of light absorption rate
[0237] (Thermal resistance test method)
[0238] The thermal resistance test and the measurement of the light absorption rate were carried out at the National University of Australia (ANU). The thermal resistance test was carried out at temperatures of 600 ° C, 750 ° C or 850 ° C and for 10 hours, 20 hours or 100 hours respectively, making comparison with a film prepared as a control with Pyromark2500, silicone coating material of high thermal resistance. The thermal resistance test was performed by placing the samples (film applied base plate) in a programmed muffle furnace. The rise and fall of temperature was adjusted to 3 ° C / min.
[0239] In this test the time it takes to reach the target temperature and lower to the initial ambient temperature is added at the time of the thermal resistance test.
[0240] (Result)
[0241] Figures 22-26 and Tables 7-9 show the result of the aforementioned test. Figure 22 indicates the measurement data of the light absorption rate before the thermal resistance test on 8 samples (films with three layer structure) prepared in the experiment example 32. In the wavelength region between 400 2500 nm, the weighted solar absorption rate of these 8 samples was 96.91% ± 0.08%, extremely uniform value. Figure 23 shows the result of the comparison between the light absorption rate before the thermal resistance test of the film with three layer structure (sample 8) (in the figure indicated as 3250) prepared in the experiment example 32 and that of the control film (in the figure it is indicated as Pyromark). The transverse axis represents the measurement wavelength and the longitudinal axis represents the absorption rate of light. Each film is applied on the same base plate of stainless steel thermal resistance (SS253MA). As indicated in Figure 23, it is noted that the film with three layer structure prepared in experiment example 32 has a much higher absorption rate than that of the control film.
[0242] Figure 24 shows the light absorption rate before and after the thermal resistance test at 600 ° C of the films with three layer structure (in the figure indicated as 3250) prepared in the experiment example 32. With the sample 7 and sample 6 were respectively tested for thermal resistance at 600 ° C for 10 hours and 100 hours. With sample 6, the thermal resistance test was carried out, first, at 600 ° C for 10 hours, with measurement of the absorption rate of light at room temperature, and then the sample was further heated to 600 ° C for 90 hours, with new measurement of the light absorption rate. The intensity of solar radiation on axis 2 is indicated as a reference. Both sample 7 and sample 6 indicated a lowering of the light absorption rate in the low wavelength region compared to the control film (Pyromark) . However, in the region of wavelength from 700 nm, despite having a higher light absorption rate than the control film, they indicated almost no decrease in the light absorption rate. Table 7 shows the absorption rate of weighted sunlight. In all cases, only a small decrease (within ± 0.1%) was observed in the range of the predicted uncertainty, compared to the light absorption rate before the thermal resistance test. As a result, it can be said that sample 7 and sample 6 have a high thermal resistance in the test at 600 ° C.
[0243] [Table 7]
[0244]
[0245]
[0246]
[0247]
[0248] Figure 25 shows the measurement result of the light absorption rate before and after the thermal resistance test at 750 ° C of the films with three layer structure (in the figure indicated as 3250) prepared in the example of Experiment 32. Using the same methodology as the thermal resistance test at 600 ° C, with the sample 5 and sample 4 the thermal resistance test was carried out at 750 ° C (for 10 hours and 100 hours (10 90 hours). With respect to sample 4, the light absorption rate was measured with the addition of 90 hours after the 10-hour thermal resistance test.The weighted light absorption rate is shown in Table 8. measurement result similar to that of the test at 600 ° C, but the light absorption rate after 100 hours showed a greater drop than the test at 600 ° C, compared to the result before the thermal resistance test. But in the test at 750 ° C , as indicated in Table 8, the decrease observed in sample 4 and sample 5 was smaller than that observed in the control film.
[0249] [Table 8]
[0250]
[0251]
[0252]
[0253]
[0254] Figure 26 shows the measurement result of the light absorption rate before and after the thermal resistance test at 850 ° C of the films with three layer structure (in the figure indicated as 3250) prepared in the example of Experiment 32. The thermal resistance test was carried out for 10 hours with sample 3, 20 hours for sample 1 and 100 hours for sample 2. With sample 1, the 10-hour thermal resistance test was performed first, and then 10 hours of the same test additionally. With sample 2, the thermal resistance test was carried out for 10 hours, followed by 90 hours for the same test. The result of the weighted solar absorption rate is shown in Table 9.
[0255] [Table 9]
[0256]
[0257]
[0258]
[0259] The result shows a decrease compared to the result of the test at 600 ° C and the test at 750 ° C. Particularly around 1500 nm a significant decrease was observed. The interesting thing is that there was almost no decrease in the solar light absorption rate weighted in the 20-hour test (-0.49%) and in the 100-hour test (-0.50%). However, it is considered that a longer thermal resistance test will be necessary to be sure of this phenomenon. The degree of lowering of the weighted sunlight absorption rate is much smaller than that of the control film (before the 96,77% thermal resistance test, after the 10 hour 94,02% test, decrease of -2.75%). In the control film, the takeoff occurred in the 100-hour test. These results show that the films prepared in experiment example 32 (3250) have not only a high light absorption rate but also a high temperature resistance compared to the control film.
[0260]
[0261] Industrial Applicability
[0262] The thermal collector film for generating solar thermal energy to which the present invention refers can be applied to the generation of solar thermal energy.

权利要求:
Claims (10)
[1]
1. - A thermal collector film for generating solar thermal energy having a network structure of composite particles comprising: metal oxide particles containing mainly two or more types of metals selected from Mn, Cr, Cu, Zr, Mo, Fe, Co, and Bi; and titanium oxide that partially or entirely covers the surface of the particles;
wherein the arithmetic mean roughness of the surface of the film is 1.0 μm or more and the ratio of the surface area of the network of the composite particles to the area of the flat surface of the film is 7 or plus.
[2]
2. - The thermal collector film for generating solar thermal energy according to claim 1 in which the metal oxide contains mainly two or more types of metals selected from Cr, Mn and Cu.
[3]
3. The thermal collector film for generating solar thermal energy according to claim 1 or 2 further comprising a porous silica film on the outermost surface.
[4]
4. The thermal collector film for generating solar thermal energy according to any one of claims 1 to 3 wherein the light reflectance in the region of visible light with a wavelength of 400-700 nm is less than 5, 0%
[5]
5. A method for manufacturing the thermal collector film for generating solar thermal energy described in any one of claims 1 to 4 that includes
a first mixing step in which titanium alkoxide (A) and at least one of acetylacetone and ethyl acetoacetate (B) are mixed so that the molar ratio between (A) :( B) is 1: 1 or more ;
a second mixing stage in which, in a solution obtained after the first mixing step, metal oxide particles are mixed which contain mainly two or more types of metals selected from Mn, Cr, Cu, Zr, Mo, Fe, Co, and Bi; Y
a film deposition step in which a film is deposited providing a mixture obtained after the second mixing step in a base plate.
[6]
6. - The method for manufacturing a thermal collector film for generating solar thermal energy according to claim 5 in which the film deposition stage is a step to spray the mixture on the base plate heated at 250-400 ° C .
[7]
7. - The method for manufacturing a thermal collector film for generating solar thermal energy according to claim 5 wherein the step of depositing film includes a step to spray the mixture on the base plate with temperature of less than 250 ° C; Y
a step to heat the mixture to 250 ° C-400 ° C after the step to spray.
[8]
8. - The method for manufacturing a thermal collector film for generating solar thermal energy according to any one of claims 5 to 7 in which the metal oxide contains mainly two or more types of metals between Cr, Mn and Cu.
[9]
9. - The method for manufacturing a thermal collector film for generating solar thermal energy according to any one of claims 5 to 8 which further includes a step of forming silica film to form a porous silica film on the outermost surface .
[10]
10. - The method for manufacturing a thermal collector film for generating solar thermal energy according to any one of claims 5 to 9 wherein the reflectance of light in the region of visible light with wavelength between 400-700 nm is lower than 5.0%.

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同族专利:

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公开号 | 公开日

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EP3575706A1|2019-12-04|

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CL2019000794A1|2019-06-28|

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AU2017395200B2|2021-10-21|

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MA45751B1|2021-02-26|

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JPWO2018138965A1|2019-01-31|

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AU2017395200A1|2019-02-21|

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US11002466B2|2021-05-11|

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US20190368781A1|2019-12-05|

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WO2018138965A1|2018-08-02|

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ES2701573R1|2019-03-13|

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ES2701573B2|2020-06-01|

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EP3575706A4|2020-07-08|

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MA45751A1|2020-03-31|

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JP6376311B1|2018-08-22|

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