KR100503929B1 - High-radiation glass base covering material, high-radiation glass film, and process for the production of high-radiation glass film - Google Patents

Abstract

The high radiation glass coating material is applied to the surface of the specific structure and calcined to provide a surface glass film having a glass structure in which pigment particles having a predetermined radiation level are dispersed, and the high radiation glass coating material includes a pigment coating film having a predetermined thickness. This film is provided to coat each pigment particle, such that the silicon dioxide content of the pigment coating film is higher than the silicon dioxide content of each part of the glass tissue adjacent to the corresponding one of the pigment particles. Silicon dioxide (SiO ₂ ).

Description

HIGH-RADIATION GLASS BASE COVERING MATERIAL, HIGH-RADIATION GLASS FILM, AND PROCESS FOR THE PRODUCTION OF HIGH-RADIATION GLASS FILM}

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a high radiation glass film adhered to the surface of various structures for the purpose of enhancing radiance, a method for producing the high radiation glass film, and an improvement of the high radiation glass coating material used to form the high radiation glass film. .

For example, insulation systems for aerospace and hypersonic aircraft require high radiation with good heat resistance. Therefore, the structure used for these uses adds the glass film which has high radiation property to the surface, as can be seen with the lightweight inorganic refractory fiber which comprises the outer wall of NASA space shuttle. For example, glass coating described in US Pat. No. 4,093,771. The glass film is, for example, a silicon boride compound such as silicon tetraboride (SiB ₄ ) or silicon hexaboride (SiB ₆ ) in a glass structure made of high silica borosilicate-based reaction cured glass (RCG). molybdenum silicide (MoSi ₂₎ consists of the high emittance pigment is dispersed, such as made of. As a result, the glass structure is composed of high-silica borosilicate-based reactive cured glass and high radiation pigments are dispersed in the glass structure, thereby obtaining high heat resistance and high radiation resistance.

The said glass film is manufactured as follows, for example. In other words, first, a predetermined amount of boron oxide is mixed with a glass powder made of high silica glass or the like, followed by calcination and pulverization to produce a reaction cured glass powder. Subsequently, a high radiation pigment is added to the reaction hardened glass powder to prepare a glass paste, and applied to the surface of a structure such as the light refractory. Then, this is dried and calcined again to form a glass structure constituting the glass film from the glass powder. In the above manufacturing process, when non-oxides, such as a silicon boride compound, are used as a high radiation pigment, it is known that oxidation suppression of a high radiation pigment is important in the baking process. This is because oxidizing the silicon boride compound decomposes into silicon oxide and boron oxide, so that desired optical characteristics such as emissivity cannot be obtained.

Therefore, the technique described in the above-mentioned U.S. Patent No. 4,093,771 suppresses decomposition of high radiation pigments by heating rapidly in the firing process. When the glass paste is rapidly heated, the glass powder melts quickly and coats the high radiation pigment, so that oxidation thereof is suppressed. However, even with such rapid heating, as shown in the reaction process schematic diagram described in the above patent, the high-radiation pigment is gradually decomposed as the firing process proceeds, so that the inhibitory effect is not sufficient.

1 is a view showing a cross section of a substrate on which a glass film of one embodiment of the present invention is formed;

FIG. 2 is a process diagram illustrating a manufacturing process of the glass film of FIG. 1; FIG.

3 is a process diagram illustrating a RCG manufacturing process in the process diagram of FIG. 2;

4 is a process chart illustrating a pigment coating process in the process of FIG. 2;

5 is a view for explaining the structure of the inorganic polymer,

6 is a diagram comparing the temperature dependence of the emissivity of the glass film of FIG. 1 with the conventional glass film,

7 is a view comparing the results of evaluating the durability of the emissivity of the glass film of FIG.

8 is an exposure test of the durability of the emissivity of the glass film of FIG. 1 at different temperatures to compare the evaluation result with a conventional glass film,

9 is a view comparing the temperature dependence of the emissivity of the glass film of the second embodiment of the present invention with the conventional glass film,

10 is a view comparing the results of evaluating the durability of the emissivity of the glass film of the embodiment of FIG.

FIG. 11 is a view comparing the results of evaluating the durability of the emissivity of the glass film of the embodiment of FIG. 9 by exposure test at different temperatures with those of the conventional glass film. FIG.

Disclosure of the Invention

Thus, as a result of further studies by the present inventors and the like for the production of a glass film having a higher radiation property, the lowering of the radiation rate of the glass film is not only caused by the oxidation of the high radiation pigment, but the glass structure constituting the glass film during the firing process. It was evident that the high radiation pigment eluted, that is, the reaction between the high radiation pigment and the glass structure, was one of the causes of the lowering of the emissivity. Such a reaction simultaneously changes the composition of the glass structure, so that the heat resistance of the glass film may be lowered. In addition, the glass film is attached to the surface of the refractory or the like as described above, and the glass film is repeatedly or normally exposed to high temperature during the use of the structure because it is intended to increase the emissivity of the structure used at high temperatures. Accordingly, the problems of lowering the emissivity and lowering of heat resistance due to the interfacial reaction between the glass structure and the high radiation pigments occur not only in the manufacturing process but also in use, and in addition to the non-oxide pigments as well as the oxide pigments.

The present invention has been made in view of the above circumstances, and a first object is to adequately suppress the interfacial reaction between a high radiation pigment and a glass structure during manufacturing and use in a glass film in which a high radiation pigment is dispersed in a glass structure. It is to provide a high radiation glass coating material, a high radiation glass film that can be. The present invention further has a second object of providing a high radiation glass film and a third object of providing a manufacturing method of the high radiation glass film.

In order to achieve the first object, the first feature of the high-radiation glass coating material of the present invention is that a pigment particle having a predetermined emissivity is attached to the surface of the structure to attach a glass film dispersed in a glass structure to the surface of a predetermined structure. A high-radiation glass coating material which is applied and fired, which is formed by (a) coating the particles and containing a pigment thickness of silicon oxide at a content rate higher than the value in the glass structure at the interface with the pigment particles. It is to include.

According to a first aspect of the present invention, a high-radiation glass coating material includes a pigment coating film having a predetermined thickness, which covers a pigment particle and contains silicon dioxide at a content higher than a value in a glass structure at an interface with the pigment particle. It is composed. Therefore, the glass film obtained by applying this high-radiation glass coating material to the surface of the structure and firing is relatively more reactive with the pigment particles because the content of silicon dioxide is higher at the interface between the pigment particles and the glass structure than the glass structure. Low pigment coating film is formed. Therefore, the interfacial reaction between the pigment particles and the glass structure during firing and use is appropriately suppressed by the pigment coating film formed at the interface. That is, since silicon dioxide is chemically stable, the interfacial reaction can be appropriately suppressed by increasing the purity of silicon dioxide at the interface with the pigment particles.

A second feature of the high-radiation glass film of the present invention for achieving the second object is a high-radiation glass film adhered to the surface of a predetermined structure, wherein pigment particles having a predetermined emissivity are dispersed in a glass structure, (a ) At the interface between the pigment particles and the glass structure, a pigment coating layer having a predetermined thickness containing silicon dioxide at a content higher than the value in the glass structure at the interface is formed by coating the pigment particles.

According to a second aspect of the present invention, there is provided a high-radiation glass film in which a pigment coating layer having a predetermined thickness containing silicon dioxide at an interface between the pigment particles and the glass structure at a content higher than the value in the glass structure at the interface. It is composed. Therefore, at the interface between the pigment particles and the glass structure, since the content of silicon dioxide is higher than that of the glass structure, a pigment coating layer having a relatively low reactivity of the pigment particles is formed, so that the interfacial reaction between the pigment particles and the glass structure during use is It is suppressed suitably by the pigment coating layer formed in the interface.

Here, in the above-mentioned first and second features of the present invention, (b) the glass structure contains silicon dioxide as a main component and also contains boric acid, and the content of silicon dioxide at the interface with the pigment particles is 80% by weight. It is preferable that it is borosilicate glass which is about%. In this way, since the borosilicate glass has high heat resistance in glass, the glass film of the structure suitable for the use which requires much higher heat resistance and high radiance is obtained. As the borosilicate glass, for example, reactive cured glass obtained by adding 5-6% of boron oxide to a high purity silica glass having a silicon dioxide content of about 96%, or a borosilicate glass having a silicon dioxide content of about 81% is preferable. Is used. The former reaction cured glass is made from high-purity silica glass particles, but since boron oxide is added to and calcined thereon, boron penetrates into the surface to form a borosilicate layer, so that the content of silicon dioxide on the surface is reduced. Therefore, even if any glass is used, the silicon dioxide content of the glass structure is low in the vicinity of the interface with the pigment particles, for example, only about 80%, so that when the pigment coating film or the pigment coating layer is not formed, the optical properties of the pigment particles It is easy to produce the interfacial reaction which lowers the characteristic. Moreover, it is preferable that the silicon dioxide purity of borosilicate glass is as high as possible from a heat resistant viewpoint, and alkali metals, such as sodium (Na) and potassium (K), magnesium (Mg), calcium (Ca) which tend to reduce heat resistance especially, are preferable. It is preferable that impurities, such as alkaline earth metal, iron (Fe), titanium (Ti), and lead (Pb), are few as possible. Preferable content of these impurities is 1 weight% or less in total amount.

(A-1) It is preferable that the said pigment coating film or the said pigment coating layer contains 85 weight% or more of silicon dioxide. In this way, since the content rate of silicon dioxide is sufficiently high, the interface reaction of a pigment particle and a glass structure is further suppressed. For example, even when a glass structure consists of the said borosilicate glass, the silicon dioxide content of a pigment coating film or a pigment coating layer becomes sufficiently higher than the value in the interface with the pigment particle in the glass structure.

(A-2) It is preferable that the said pigment coating film or the said pigment coating layer contains 99 weight% or more of silicon dioxide. In this way, since the content rate of silicon dioxide is very high, the interface reaction of a pigment particle and a glass structure is reliably suppressed.

(A-3) It is preferable that the said pigment coating film or the said pigment coating layer has thickness of about 0.5 micrometer in average value. In this way, the thickness of the pigment coating film or the pigment coating layer is thick enough to suppress the interfacial reaction between the pigment particles and the glass structure more reliably, and the thermal expansion of the pigment coating film or the pigment coating layer with the pigment particles at the time of its formation. It is damaged due to the difference in coefficient, or is thin enough so as not to significantly affect the thermal properties such as the softening point of the glass film and the thermal expansion coefficient, so that the optical properties of the pigment particles can be suppressed without particularly impairing the function of the glass film.

(A-4) It is preferable that the said pigment coating film or the pigment coating layer is formed in the thickness of about 0.1-6 micrometers. In this case, the thickness of the pigment coating film or the pigment coating layer is thick enough to further reliably suppress the interfacial reaction between the pigment particles and the glass structure, and the pigment coating film or the pigment coating layer is formed with the pigment particles at the time of its formation. It is damaged due to the difference in coefficient of thermal expansion or is thin enough so as not to significantly affect the thermal properties such as the softening point and thermal expansion coefficient of the glass film. Therefore, the degradation of the optical properties of the pigment particles can be suppressed without particularly impairing the function of the glass film. .

(C) The pigment particles are preferably composed of at least one of silicon borides such as silicon tetraboride or silicon hexaboride, molybdenum silicide, silicon carbide, iron oxide, silicon nitride and chromium oxide. In this way, since they have sufficiently high emissivity, it is possible to form a glass film having high emissivity. Moreover, it is further more preferable that the said pigment particle is a silicon boride. In this way, silicon boride is more preferably used as a pigment particle of a high radiation glass film because it has an extremely high emissivity, but on the other hand, a pigment coating film or a pigment coating layer is formed because it is non-oxide and has high reactivity with glass tissue. The effect is further remarkably obtained. More preferably, the pigment particles are silicon tetraboride. In this way, since silicon tetraboride does not fall in optical characteristics especially in silicon boride at high temperature, the glass film which has a high radiation rate at high temperature is obtained further.

(C-1) It is preferable that the said pigment particle is silicon tetraboride which has a particle diameter of about 2 micrometers on an average value. In this manner, the pigment particles can be sufficiently dispersed in the glass structure and the radiation rate of the glass film can be sufficiently increased.

(C-2) It is preferable that the said pigment particle is silicon tetraboride which has a particle diameter of about 1-10 micrometers. In this manner, the pigment particles can be sufficiently dispersed in the glass structure, and the radiation rate of the glass film can be sufficiently increased.

A third feature of providing a method for producing a high radiation glass film of the present invention for achieving the third object is a paste for preparing a paste containing (d) pigment particles having a predetermined emissivity and a predetermined glass powder. A manufacturing process, (e) a paste coating step of applying the paste to the surface of a predetermined structure, and (f) a heat treatment step of forming a glass structure from the glass powder by heat treating the coated paste, A method for producing a high-radiation glass film for attaching a high-radiation glass film in which the pigment particles are dispersed in the glass structure to the surface of the structure, wherein (g) the glass in the high-radiation glass film is carried out prior to the paste manufacturing process. A pigment coating film having a predetermined thickness containing silicon dioxide at a content higher than the value in the glass structure at the interface between the tissue and the pigment particles is used as the pigment. In that it further comprises pigment particles coated with the step of forming on the surface.

In this way, when manufacturing a high radiation glass film, the pigment coating film of the predetermined thickness which contains silicon dioxide at the content rate higher than the value in the glass structure at the interface of the glass structure in a high radiation glass film and a pigment particle is formed on the surface of the pigment particle. The pigment particle coating process to be formed on the film is performed prior to the paste manufacturing process. Therefore, in the paste manufacturing process, a paste containing a pigment particle and a glass powder containing silicon dioxide at a high content rate and having a low-reactivity pigment coating film formed on the surface thereof is produced, thereby providing an interface between the glass structure and the pigment particle. The reaction is inhibited by the pigment coating film. Also, after the high-radiation glass film is produced, the interfacial reaction is similarly suppressed by the pigment-coated film when used.

Here, in the above-mentioned third aspect of the present invention, (g) the pigment particle coating step includes: (g-1) forming an inorganic polymer film formed of an inorganic polymer containing silicon on the surface of the pigment particle (G-2) a heat generation step of producing the pigment coated film containing silicon dioxide from the inorganic polymer film at the predetermined content rate by heating the pigment particle having the inorganic polymer film formed at a predetermined temperature in an oxidation atmosphere. It is preferable to include. In this case, an inorganic polymer film containing silicon is formed on the surface of the pigment particles in the polymer film forming step, and the pigment coating film is formed from the inorganic polymer film by heat treatment with an oxidizing atmosphere in the heat generating step. Therefore, since the pigment coating film is formed on the surface of the pigment particles in the form of an inorganic polymer, a thin and uniform film can be preferably formed. However, since the inorganic polymer contains silicon, heat treatment with an oxidizing atmosphere Silicon in the polymer is oxidized to produce a pigment coating film containing silicon dioxide at a predetermined content rate. Therefore, the pigment coating film which has a predetermined thickness and contains silicon dioxide at a predetermined content rate can be formed preferably.

(G-1) The inorganic polymer film forming step includes (g-1-1) a pigment particle dispersion step of dispersing the pigment particles in a liquid containing the inorganic polymer to produce a dispersion liquid, and (g-1- 2) It is preferable to include a spray drying step of forming the inorganic polymer film on the surface of the pigment particles by spray drying the dispersion. In this way, the pigment particles are dispersed in the liquid containing the inorganic polymer in the pigment particle dispersion step to prepare a dispersion, and in the spray drying step, the dispersion liquid containing the inorganic polymer and the pigment particles is spray-dried to form inorganic on the surface of the pigment particle. A polymer film is formed. Therefore, since the inorganic polymer film is formed by rapidly drying the liquid containing the inorganic polymer covering the surface of the pigment particles by spray drying, an inorganic polymer film having a thinner and more uniform thickness can be obtained.

(G-1-3) In the inorganic polymer film forming step, it is preferable to use a compound composed substantially of hydrogen (H), nitrogen (N) and silicon (Si) as the inorganic polymer. In this way, by firing in an oxidizing atmosphere, silicon and oxygen are combined to form silicon dioxide, and an inorganic polymer film is formed on the surface of the pigment particle, while hydrogen and nitrogen are combined to form ammonia (NH ₃ ), or In addition, hydrogen gas (H ₂ ) is produced and all are quickly dissipated. Therefore, since the formed inorganic polymer film | membrane and also the pigment coating film | membrane which generate | occur | produce therein contain silicon dioxide with an extremely high content rate, the interface reaction of a pigment particle and a glass structure is further suppressed. As the compound, for example, perhydropolysilazane is preferably used, and a small amount of oxygen (O), carbon (C) or the like may be contained in addition to the above element.

In the paste manufacturing step (d-1), the pigment particles and the glass powder are preferably dispersed in an organic solvent together with an organic binder. In this case, since the paste is produced by dispersing the pigment particles and the glass powder in the organic solvent, a more uniform glass film can be formed. In addition, since the organic binder is contained in the paste, an appropriate thickness of the coating film can be obtained when applying to the surface of the structure. The addition amount of these organic binders and organic solvents is determined in consideration of the paste viscosity.

Moreover, it is preferable that (e-1) the said paste application process spray-coats the said paste. In this manner, a coating film having a substantially uniform film thickness can be easily formed on the surface of the structure.

Moreover, it is preferable to heat (f-1) the said heat processing process in non-oxidizing atmosphere. In this case, since no oxygen is present in the minor component atmosphere, oxidation of the pigment particles is further suppressed during the heat treatment. Therefore, since the need for rapid heating and rapid cooling and sintering for the purpose of preventing oxidation is further reduced, the glass film-attached structure is formed by attaching a glass film by raising and lowering the temperature at a desired temperature curve where the distortion of the structure is as small as possible. It can be manufactured with precision.

(D-2) In the paste manufacturing step, borosilicate glass containing silicon dioxide as a main component and containing boric acid is preferably used as the glass powder. In this way, since the borosilicate glass has high heat resistance in glass, the glass film of the structure suitable for the use which requires much higher heat resistance and high radiation can be produced. As the borosilicate glass, the above-mentioned cured glass, borosilicate glass, or the like is preferably used, but these are alkali earths such as alkali metals such as sodium and potassium, magnesium, calcium, etc. As few impurities as possible such as metal, iron, titanium, and lead are preferable. Preferable content of these impurities is 1 weight% or less in total amount.

Best Mode for Carrying Out the Invention

Hereinafter, one embodiment of the present invention will be described in detail with reference to the drawings. In addition, in the following description, the dimension ratio etc. of each part are not necessarily described correctly.

FIG. 1: is a figure which shows typically the cross section of the board | substrate 14 with the glass film 10 of 1st Example of this invention affixed on the surface 12. As shown in FIG. This board | substrate 14 is used, for example in heat insulation materials for baking furnaces, For example, alumina type, mullite type, or inorganic fiber type light weight refractory etc. which have a thermal expansion coefficient of about 2.0-4.0x10 <^-6> / degreeC, etc. It is a refractory consisting of. The inorganic fiber-based lightweight refractory material described in the above-mentioned US patent, for example, as a composite material mainly composed of inorganic fibers such as Sika ₂ (SiO ₂ ), borosilicate, aluminum borosilicate, aluminum silicate or the like as a binding phase For example, it has physical properties of about 90% or more of porosity, about 0.20 or less of specific gravity, about 0.06w / m * K or less of thermal conductivity, and about 7-20kgf / cm <^2> of bending strength. In addition, the surface 12 of the board | substrate 14 is hold | maintained in the state immediately after manufacture by the baking process, and processing, such as grinding processing and etching, was not performed at all. In this embodiment, the substrate 14 corresponds to the structure.

The glass film 10 has a thickness of, for example, about 0.3 to 0.5 mm, and is composed of the glass structure 16 and the pigment particles 18 uniformly dispersed in the glass structure 16. . The glass structure 16 is a reaction cured glass described in the US patent, for example, as described later in the manufacturing process, the whole is made of borosilicate glass, for example, thermal expansion of about 2 × 10 ^-6 / ℃ It is formed from a porous portion 16a of high purity silica containing borosilicate glass having a purity of about 96% by weight, which is derived from a later high purity silica glass and forms a nucleus of the glass structure 16, and is produced from the high purity silica glass and boron oxide. Thus, it is composed of the dense portion 16b having a silica content of about 82% by weight.

In addition, the said pigment particle 18 is silicon tetraboride with an average particle diameter of about 2 micrometers, for example, and is contained in the ratio of 2.5 weight% and about the glass film 10 whole. Silica glass layer 20 having a thickness of, for example, about 0.1 to 6 μm is formed around the pigment particles 18, that is, at the interface with the glass structure 16. This embodiment glass layer 20 is made of, for example, high-purity silica glass having a purity of about 99%, and this embodiment corresponds to a pigment coating layer. In other words, the silica glass layer 20, that is, the pigment coating layer has a higher silica content than the dense portion 16b located near the interface with the pigment particles 18 in the glass structure 16. As a result, the interfacial reaction between the pigment particles 18 and the glass structure 16 is suppressed, and the glass film 10 has a high emissivity of 0.8 or more even at a high temperature of, for example, about 1400 ° C as shown in FIG. In addition, since the silica dioxide purity of the silica glass layer 20 is extremely higher than the value in the glass structure 16, the silica glass layer 20 melts even at a temperature at which the glass film 10 is softened to protect the pigment particles 18. There is no loss of functionality.

By the way, the glass film 10 comprised as mentioned above is manufactured according to the process shown in FIG. 1, for example. Hereinafter, the manufacturing method will be described with reference to the drawings.

First, the reaction hardened glass raw material powder is manufactured from the glass frit in the RCG manufacturing process of Step 1A. This RCG manufacturing process is shown in detail in FIG. 3, for example. In Fig. 3, in the boron oxide dissolution step of step A1, for example, 37 g of boron oxide powder having a purity of 5 N (99.999% or more) is dissolved in 272 cc of ion-exchanged water heated to about 85 DEG C to prepare an aqueous boron oxide solution. Subsequently, in the solvent addition step of step A2, for example, 137 g of ethanol (preferably a special reagent) is added to the boron oxide aqueous solution, and in the glass frit mixing step of step A3, about 400 g of high-purity silica glass frit is added again to the aqueous solution. To prepare a slurry. Therefore, in this embodiment, the addition amount of boron oxide powder is about 8.5 weight%. In addition, as a high purity silica glass frit, for example, the composition of SiO ₂ 96%, B ₂ O ₃ 3%, Al ₂ O ₃ 0.4%, having a specific surface area of 200 m ² / g, porosity of about 28% It is preferable that porous two-component glass is used. And in the stirring process of process A4, this mixture is stirred, for example, keeping warm about 80 degreeC with a heating plate etc., and removes ethanol and water in a slurry.

In the drying step of step A5, residual ethanol and water are removed by drying the slurry whose viscosity has been increased to a degree that difficulty in stirring due to the removal of ethanol and water to some extent in step A4, for example, in an oven or the like and drying again at about 70 ° C. In this way, after drying is completed, the dried product is crushed by hand in the crushing step of step A6, and again classified using a sieve of about # 16 in the classification step of step A7, for example, to remove coarse particles of about 1 mm or more. do. In the firing step of step A8, the crushed and classified dry matter is placed in a silica container having a purity of about 63%, and fired under conditions of, for example, 1000 to 1100 ° C for 2 hours. Thereby, high purity silica glass frit and boron oxide react. And the glass frit which became agglomerated by baking at the grinding | pulverization process of process A9 was grind | pulverized using a pot type | mold ball mill etc. Finally, in the classification process of process A10, it classified into the # 330-300 sieve, and coarse particle about 45 micrometers or more By removing the reaction cured glass raw material powder is obtained.

Returning to FIG. 2, the pigment particle 18 which consists of said silicon tetraboride is coat | covered with the high purity silica glass film in the pigment coating process of process 1B. This pigment coating process is shown in detail in FIG. First, in the inorganic polymer dilution step of step B1, for example, dihydrogen perhydropolysilazane, which is a preceramic polymer (inorganic polymer that becomes ceramic by heating), is diluted to a concentration of about 10% by weight using a solvent such as xylene. do. Perhydropolysilazane is composed of silicon, nitrogen, and hydrogen. For example, it is a colorless and transparent liquid having a molecular weight of about 600 to 900 and a density of about 1.3 g / cm ³ having a structure as shown in FIG. The amount is 5-6 ppm or less and has extremely high purity.

In the pigment particle dispersing step of Step B2, silicon tetraboride particles having a purity of 98% or more as the pigment particles 18 in the diluted inorganic polymer liquid are combined so as to be about 10 to 20% by weight with respect to the inorganic polymer liquid, and a vibration mill or the like. After stirring for about 30 minutes to prepare a dispersion in which the pigment particles 18 are dispersed. In the subsequent spray drying step of step B3, the dispersion is sprayed with a spray dryer or the like to hot-air-dry. At this time, the spray drying conditions, for example, the hot air inlet temperature is about 110 ℃, the outlet temperature is about 70 ℃. As a result, the inorganic polymer liquid attached to the surface of the pigment particles 18 is dried and condensed to form an inorganic polymer film on the surface thereof. In the heat treatment step of Step B4, for example, heat treatment is performed under conditions of about 400 ° C in the air. As a result, silicon in the inorganic polymer film is combined with oxygen in the atmosphere to form silicon dioxide (silica), and nitrogen and hydrogen in the inorganic polymer film combine to form ammonia and dissipate. For this reason, the highly pure silica glass film produced | generated from the inorganic polymer film | membrane on the surface of the pigment particle 18 is formed in the film thickness of about 0.1-6 micrometers, for example. In addition, since the inorganic polymer film formed in the spraying process is not made to have a uniform thickness on the surface of each pigment particle 18, the thickness of the silica glass film formed after the heat treatment is also not uniform, but at least distributed within the above range. It is about 0.5 micrometer in average value. In this embodiment, steps B1 to B3 correspond to the inorganic polymer film forming step, and the heat treatment step of step B4 corresponds to the heat generation step, respectively, and the silica glass film corresponds to the pigment coating film.

Returning to FIG. 2, in the mixing step of Step 2, about 234 g of the cured glass raw material powder prepared as described above, about 6.0 g of the pigment particles 18 having a silica glass film, for example about 6.0 g, organic solvents such as ethanol 386g and about 39.2g of organic binders, such as 2% aqueous solution of methyl cellulose, are put together with alumina gemstones in alumina porcelain pots and sealed, and the mixture is rotated on a rotating pot, for example, by about 5 hours. As a result, a paste (slurry) in which the reaction cured glass raw material powder and the pigment particles 18 are dispersed is obtained. In addition, ethanol is a dispersing agent and methylcellulose functions as a complement agent for obtaining the appropriate thickness of a coating film in the following application | coating process, respectively, The addition amount of both is determined suitably also in consideration of the viscosity at the time of mixing. In the subsequent spray coating step of Step 3, the paste discharged from the pot is filled into the spray bottle and sprayed onto the surface 12 of the substrate 14. At this time, the discharge pressure is set to about ³ kgf / cm ² or less, for example. Then, for example, the organic solvent is removed by leaving it at room temperature for a predetermined time and further drying in an oven at a temperature of about 70 ° C., and then flowing nitrogen (N ₂ ) gas in the firing step of step 4, for example, in an atmosphere furnace. The glass film 10 is produced from the coating film by performing heat treatment on the condition of about 1250 ° C. for 1.5 hours. Moreover, the temperature increase rate in a baking process is about 200 degreeC / hour, for example. Therefore, in the glass structure 16 constituting the glass film 10, pigment particles (silicon tetraboride; 18) are contained in a state covered with a silica glass film, and the silica glass film constitutes the silica glass layer 20. have. In this embodiment, the paste corresponds to a high radiation glass coating material, the mixing step corresponds to the paste manufacturing step, and the firing step corresponds to the heat treatment step, respectively.

In this case, in the present embodiment, the pigment particles 18 are mixed with the reaction cured glass raw material powder or the like in a state where a silica glass film (i.e., silica glass layer 20) is formed on the surface and fired on the substrate 14. . Therefore, the reaction of the pigment particles 18 with the glass structure 16 produced from the reaction hardened glass raw material powder during the firing is suppressed by the silica glass film. Therefore, the change in the composition of the glass structure 16 is suppressed, and at the same time, the amount of the pigment particles 18 dissolved in the glass structure 16 to contribute to the emissivity is preferably suppressed, so that high heat resistance and high radiation resistance are suppressed. The glass film 10 which has together is obtained.

6 shows a conventional method in which the temperature dependence of the emissivity of the glass film 10 of the present embodiment manufactured as described above is mixed with the reaction cured glass raw material powder without firing the pigment particles 18 on the surface. It shows in comparison with the glass film of the comparative example. In addition, the glass film of the comparative example was manufactured on the conditions similar to this Example except not forming a silica glass film. As can be clearly seen from the figure, according to the glass film 10 of this embodiment, the radiation rate is very high at 0.95 at room temperature (about 25 ° C), and the radiation rate is maintained at about 0.85 even at a high temperature of about 1400 ° C. On the other hand, in the comparative example, the emissivity is low at 0.9 or less at room temperature and decreases to about 0.75 at 140 ° C. That is, according to the present embodiment, not only a higher emissivity is obtained immediately after firing but also a lower degree of deterioration from the value at room temperature even during use at a high temperature thereafter, and thus a high emissivity is obtained. In the range from room temperature to 800 ° C, the emissivity is determined by the well-known emission spectrum measurement by FT-IR, and at 1200 and 1400 ° C, the injection type emissivity measuring device is used to determine the ratio between the thermocouple temperature and the radiation thermometer temperature. It is the relative value of the radiation divergence with respect to the black body radiation obtained based on this. In addition, although the use temperature of the glass film 10 was also measured separately, it was confirmed that the heat resistance of the glass film 10 of the present embodiment was significantly improved to about 1350 ° C in comparison with the use temperature of the comparative example being about 1270 ° C. In addition, "using temperature" means the temperature which does not melt and there is no optical characteristic deterioration (that is, emissivity fall) after heating at constant temperature for 24 hours.

Table 1 and Table 2 show the results of evaluating the durability of the glass film 10 formed on the substrate 14 (the thermal insulator for a kiln with a thermal expansion coefficient of about 2.0 × 10 ⁻⁶ / ° C.) as shown in FIG. 1. 7 and 8 are graphs of the graphs as shown in comparison with the comparative example. Durability evaluation was performed by performing exposure test in 1200 degreeC atmosphere in Table 1, respectively in 1400 degreeC atmosphere in Table 2, and measuring the emissivity at the same temperature as the exposure test temperature with the said injection type emissivity measuring apparatus. The temperature increase rate of the exposure test is about 10 ° C / min. After reaching the set temperature, the emissivity was measured by maintaining the predetermined time and repeatedly measuring the emissivity when the cumulative exposure time reached 1, 5, 10, 24 and 72 hours. In addition, the value of Table 1 and Table 2 is the evaluation value measured with three samples, respectively for an Example and a comparative example.

Exposure time Example Comparative example One 0.88 0.80 5 0.88 0.78 10 0.88 0.77 24 0.88 0.76 72 0.88 0.75

Exposure time Example Comparative example One 0.85 0.75 5 0.85 0.74 10 0.85 0.73 24 0.85 0.71 72 0.85 0.68

As can be clearly seen from Table 1, Table 2 and Figs. 7, 8, the glass film 10 of the present embodiment shows no decrease in emissivity due to the exposure test, and even after 72 hours of exposure test, the same emissivity as before the exposure test. maintain. On the other hand, it became clear that the glass film of the comparative example in which the silica glass layer 20 is not formed on the surface of the pigment particle 18 tends to reduce emissivity with time at either 1200 degreeC or 1400 test temperature. . That is, according to the glass film 10 of the present embodiment, the surface reaction of the pigment particles 18 and the glass structure (glass matrix 16) by coating the pigment particles 18 of high radiation rate with the silica glass layer 20 of high purity is performed. Since this is suppressed and deterioration of the pigment particle 18 is suppressed, it is thought that emissivity does not fall.

In other words, in this embodiment, a silica glass film having a predetermined thickness (silica glass) formed by coating the pigment particles 18 and containing silicon dioxide at a content higher than the value in the glass structure 16 at the interface with the pigment particles 18. Glass paste, including layer 20). Therefore, in the glass film 10 obtained by apply | coating and baking this paste on the surface 12 of the board | substrate 14, at the interface of the pigment particle 18 and the glass structure 16, silicon dioxide rather than the glass structure 16 is carried out. Since the content rate is high, the silica glass film (silica glass layer 20) with which the reactivity with the pigment particle 18 was comparatively low is formed. Therefore, the interfacial reaction between the pigment particles 18 and the glass structure 16 is preferably suppressed by the silica glass film (silica glass layer 20) formed at the interface during firing and use.

In the present embodiment, the silica glass layer 20 having a predetermined thickness containing silicon dioxide at the interface between the pigment particles 18 and the glass structure 16 at a content higher than the value in the glass structure 16 is formed. The glass film 10 which coat | covers this pigment particle 18 is comprised. Therefore, at the interface between the pigment particles 18 and the glass structure 16, a silica glass layer 20 having a higher silicon dioxide content than the glass structure 16 and having a substantially lower reactivity with the pigment particles 18 is formed. Therefore, the interfacial reaction between the pigment particles 18 and the glass structure 16 during use is preferably suppressed by the pigment coating layer formed at the interface.

In the present embodiment, the silica glass layer 20 (silica glass film) contains 99% by weight or more of silicon dioxide. Therefore, since the content rate of silicon dioxide is sufficiently high, the interface reaction of the pigment particle 18 and the glass structure 16 is further suppressed.

Further, according to the present invention, silicon tetraboride used as the pigment particles 18 is preferably used to increase the emissivity of the glass film 10 because it has an extremely high emissivity. It has a high reactivity with the tissue (16). Therefore, the effect which formed the silica glass film (silica glass layer 20) is remarkably obtained. In addition, silicon tetraboride has an advantage that the reduction in emissivity is unlikely to occur at high temperatures, compared to silicon hexaboride, which is one of silicon borides. For example, the emissivity of the glass film at a temperature of 800 ° C. or higher is about 5 to 10% lower than that of the glass film 10 in which silicon tetraboride is used as the pigment particle 18 when silicon boride is used as the pigment particle. It is confirmed.

In this embodiment, the silica glass film (silica glass layer 20) is formed to a thickness of about 0.1 to 6 mu m. Therefore, since the thickness of the silica glass film (the silica glass layer 20) is sufficiently thick within a range that does not significantly affect the thermal characteristics such as the use temperature of the glass film 10 and the thermal expansion rate, the pigment particles 18 and the glass structure ( The interfacial reaction of 16) is more reliably suppressed.

In addition, in the present embodiment, in manufacturing the glass film 10, in manufacturing the glass film 10, the glass structure 16 at the interface between the glass structure 16 and the pigment particles 18 in the glass film 10. The pigment coating step of Step 1B in which a silica glass film (silica glass layer 20) having a predetermined thickness containing silicon dioxide at a content higher than the value in Fig. 1) is formed on the surface of the pigment particles 18. Is carried out earlier. Therefore, in the mixing step, a paste containing silicon particles containing silicon dioxide at a high content rate and a pigment particle 18 having a low reactivity with the glass structure 16 (silica glass layer 20) and a glass powder are produced. Therefore, the interfacial reaction between the glass structure 16 and the pigment particles 18 is suppressed by the silica glass film (silica glass layer 20) when the heat treatment is performed in the firing step of Step 4. Moreover, also when using after manufacturing the glass film 10, the interface reaction is suppressed by the silica glass film (silica glass layer 20) similarly.

In the present embodiment, the pigment coating step includes the steps of forming the inorganic polymer film of steps B1 to B3 in which the inorganic polymer film made of the inorganic polymer containing silicon is formed on the surface of the pigment particle 18, and the pigment particles having the inorganic polymer film formed thereon. Heat treating step (4) to produce the silica glass film (silica glass layer 20) containing silicon dioxide at a content of about 99% by weight from the inorganic polymer film by heat-treating (18) at a predetermined temperature in an oxidizing atmosphere. It is. In this way, an inorganic polymer film containing silicon is formed on the surface of the pigment particle 18 in the polymer film forming step, and the silica glass film (silica glass layer 20) is removed from the inorganic polymer film by heat treatment in an oxidizing atmosphere in the heat treatment step. Is generated. For this reason, the silica glass film is formed on the surface of the pigment particle 18 in the form of an inorganic polymer so that a thin and uniform film can be preferably formed. However, since the inorganic polymer contains silicon, heat treatment is performed in an oxidizing atmosphere. Silicon in the inorganic polymer is oxidized to produce a silica glass film (silica glass layer 20) containing silicon dioxide at a predetermined content rate. Therefore, the silica glass film (silica glass layer 20) which has a predetermined thickness and contains silicon dioxide at a predetermined content rate can be formed preferably.

In the present embodiment, the inorganic polymer film forming step is performed by dispersing the pigment particles 18 in a liquid containing the inorganic polymer to produce a dispersion, and by spray drying the dispersion. It includes the spray drying step of step B3 to form an inorganic polymer film. In this way, the inorganic polymer film is formed on the surface of the pigment particle 18 by spray-drying the dispersion liquid containing the inorganic polymer and the pigment particle 18. Therefore, since the inorganic polymer film is formed by rapidly drying the liquid containing the inorganic polymer covering the surface of the pigment particle 18 by spray drying, an inorganic polymer film having a thinner and uniform thickness can be obtained.

In the present embodiment, the inorganic polymer is perhydropolysilazane composed of hydrogen, nitrogen, and silicon. In this way, by firing in an oxidizing atmosphere, silicon and oxygen are combined to form silicon dioxide, and an inorganic polymer film is formed on the surface of the pigment particle 18, while hydrogen and nitrogen are combined to form ammonia and dissipate quickly. . Therefore, since the formed inorganic polymer film and further, the silica glass film (silica glass layer 20) produced therefrom contain silicon dioxide at a very high content rate, the interfacial reaction between the pigment particles 18 and the glass structure 16 is further suppressed. do.

In addition, in the present Example, the baking process of the said process 4 is heating in a non-oxidizing atmosphere. In this way, since no oxygen is present in the minor component atmosphere, the oxidation of the pigment particles 18 is further suppressed.

In this embodiment, the glass structure 16 is borosilicate glass containing silicon dioxide as a main component and containing boric acid. In this way, since the borosilicate glass has high heat resistance among glass, the glass film 10 of the board | substrate 14 suitable for the use which requires much higher heat resistance and high radiance is obtained.

Next, a second embodiment of the present invention will be described. In the second embodiment, parts common to those of the first embodiment will be omitted.

In the above embodiment, the case where the glass film 10 is attached to the substrate 14 made of the refractory material has been described. However, the same glass film may be attached to the metal body. Even in such a case, it is necessary to select the constituent material of the glass structure 16 so that the thermal expansion rate matches the thermal expansion rate of the metal. As a specific combination example, an example in which a glass film is attached to a Cr-Ni-Fe heat-resistant alloy used for engine parts and the like will be described. A Cr-Ni-Fe heat resistant alloy has a thermal expansion coefficient of about 10 × 10 ^-6 because / ℃, roneun constituent material (a glass frit) of the glass structure 16, the thermal expansion coefficient is 12 × 10 ^-6 / ℃ the MgO- B ₂ O ₃ -SiO ₂ -based glass was selected. As the high radiation pigment (pigment particles 18), silicon carbide powder having a purity of 99.9% or more and a particle size of about 0.3 to 0.5 mu m was used. Hereinafter, although the manufacturing process of the glass film using these is demonstrated, since it is substantially the same as the 1st Example shown by the said FIG. 1 thru | or FIG. 8, only a difference point is shown below.

That is, according to the second embodiment of the present invention, a MgO-B ₂ O ₃ -SiO ₂ system prepared by manufacturing a silicon carbide powder having a silica glass film formed on its surface according to the process shown in FIG. 4 and separately prepared in the mixing process of Step 2 of FIG. For example, about 234 g of glass powder, 1.2 g of coated silicon carbide powder, about 386 g of ethanol, and about 39.2 g of 2% aqueous solution of methylcellulose, for example, are placed in an alumina pot. Mix as in the Example. In the same manner as in the first embodiment, a paste film is formed on a Cr-Ni-Fe heat-resistant alloy and baked to form the same glass film as the glass film 10. The firing conditions are, for example, about 1050 占 폚 x 20 minutes in a nitrogen atmosphere.

FIG. 9 is a diagram showing the temperature dependence of the emissivity of the glass film formed as described above compared with the conventional (comparative) glass film using silicon carbide powder without silica glass film. The method of measuring the emissivity is as described above. As can be clearly seen from the drawings, according to the glass film of the present embodiment, the emissivity is high at 0.9 or more at room temperature and 0.85 or more at 1000 ° C, and the temperature dependency is low, while the glass film of the comparative example has an emissivity of about 0.85 at room temperature. , At 1000 ° C., it is greatly reduced to about 0.75. In addition, when the exposure test was conducted for 24 hours in the air, the comparative example of not coating the silicon carbide powder with the silica glass film showed no change in appearance due to the melting of the glass until about 950 ° C, but the glass was melted when the temperature was maintained at 1000 ° C. Was observed, and the emissivity after the test was lowered to 0.6 or less. On the other hand, in the glass film of this 2nd Example in which the silica glass film was formed in the silicon carbide powder, when it kept at 1000 degreeC, melting of glass and the fall of emissivity were not seen.

Therefore, also in the second embodiment, it is clear that the radiation rate and heat resistance of the glass film are improved by forming and using a silica glass film on the silicon carbide powder as the pigment particles. That is, this invention is similarly applied to the glass film formed on the surface of a metal body not only the glass film formed in a refractory body.

Here, Tables 3 and 4 show the results of evaluating the durability of the glass film when the silicon carbide powder was used as in the case of using the silicon tetraboride as the pigment particles 18, in comparison with the comparative example. 10 and 11 are graphs of each. The durability test method is the same as in Table 1 and Table 2 except that the test temperature is 800 ° C in the case of Table 3 and 1000 ° C in the case of Table 4.

Exposure time Example Comparative example One 0.89 0.75 5 0.89 0.70 10 0.89 0.67 24 0.89 0.65 72 0.89 0.64

Exposure time Example Comparative example One 0.88 0.63 5 0.88 0.60 10 0.88 0.55 24 0.88 0.51 72 0.88 0.49

As can be clearly seen from Table 3, Table 4 and Figs. 10 and 11, the glass film of the second embodiment in which the silica glass layer 20 was formed on the surface of the pigment particles made of silicon carbide was subjected to the exposure test. No decrease in emissivity is observed and remains at the same emissivity as before the exposure test, even after 72 hours of exposure. In contrast, the glass film of the comparative example in which the silica glass layer 20 was not formed on the surface of the pigment particles was compared with the emissivity of the comparative example at temperatures of 800 ° C. and 1000 ° C. when the exposure time was actually 0 as shown in FIG. 9. As is evident, at any test temperature of 800 ° C or 1000 ° C, the emissivity is remarkably lowered with a slight test time, and the emissivity tends to decrease further with time. That is, even when silicon carbide is used as the pigment particles, the surface reaction of the pigment particles and the glass structure is suppressed by coating with the silica glass layer 20 in the same manner as when silicon tetraboride is used, and the degradation of the pigment particles is suppressed. Effect is obtained.

As mentioned above, although one Embodiment of this invention was described in detail with reference to drawings, this invention can also be implemented with another aspect.

For example, in the above-described embodiment, boron oxide was added to the high silica glass frit as the glass frit constituting the glass structure 16 and a glass frit containing boron oxide was used from the beginning. Glass frit which does not contain may be used as it is. The composition of the glass used is appropriately changed depending on the use of the structure, required heat resistance, emissivity, and the like.

In the above-described embodiment, silicon tetraboride having an average particle diameter of about 2 μm and silicon carbide powder having an average particle diameter of about 0.3 μm to 0.5 μm were used as the pigment particles 18. The radiation rate, heat resistance of the pigment itself, and the like are appropriately selected. Moreover, the average particle diameter of a pigment particle is suitably set in the range from which a favorable dispersibility is obtained, For example, in the case of silicon tetraboride, about 1-10 micrometers is used, In the case of silicon carbide, about 0.1-1 micrometer is used It is preferable.

In the above-described embodiment, perhydropolysilazane was used as the inorganic polymer for forming the silica glass film (silica glass layer 20) on the surface of the pigment particles 18 (silicon tetraboride or silicon carbide powder). An inorganic polymer may be used as long as it contains silicon capable of forming a silica glass film by heating or the like indicated in the heat treatment step of B4.

In addition, in the above-described embodiment, the purity of silicon dioxide in the silica glass layer 20 covering the pigment particles 18 was about 99% by weight, but the value was in the glass structure 16 at the interface with the pigment particles 18. It is appropriately changed to a range higher than the value. However, in order to suppress the interfacial reaction of the pigment particle 18, since it is desired that the purity of silicon dioxide is as high as possible, Preferably it is 90 weight% or more, More preferably, it is 95 weight% or more.

In addition, in the first embodiment shown in FIG. 1 and the like, the amount of boron oxide added to the glass frit was about 8.5% by weight, but the addition amount was appropriately set in consideration of the heat resistance and strength of the glass structure 16, the composition of the glass frit, and the like. For example, about the glass frit containing no boron oxide, it changes suitably in the range of about 8 to 13 weight%.

Incidentally, in the above-described embodiment, the firing step is performed by heating at a slow speed under a nitrogen atmosphere, but the atmosphere is appropriately changed, and the oxidation atmosphere may be used. This is because, according to the present invention, since the pigment particles are coated with silica glass, oxidation of the pigment particles and reaction with the glass structure 16 hardly occur. As the non-oxidizing atmosphere, an inert gas atmosphere such as argon may be used instead of the nitrogen atmosphere, and firing may be performed under vacuum.

In addition, various numerical values which determine the composition of the glass film 16, such as the mixing ratio of the reaction cured glass raw material powder and the pigment particles, and further the physical properties, are appropriately set according to the purpose of use of the structure and the like.

In addition, in the above-described embodiment, the present invention has been described in the case where the present invention is applied to the substrate 14 used for the heat insulating material for the kiln, the glass film 16 attached to the heat resistant alloy used for the engine parts, and the like. It is applicable to various fields that can use high radiation such as). That is, for example, a coating material for a fire furnace, an outer wall of a gas introduction pipe of a combustion burner, a heating plate of a heat exchanger, a heat insulating material for a reactor, a turbine blade, an ultraviolet light-shielding glass, a roof tile (improving snow removal ability), a semiconductor or an electronic It is also preferably used for various applications such as substrates, packages (improved heat dissipation) of components, or grindstones (improved heat dissipation of grinding heat).

Other examples are not illustrated, but the present invention can be modified in various ways without departing from the spirit thereof.

Claims (27)

As a high-radiation glass coating material in which pigment particles having a predetermined emissivity are applied and baked on a surface of the structure to adhere a glass film dispersed in a glass structure to a surface of a predetermined structure, A high radiation glass comprising a pigment coating film formed by coating the pigment particles and containing silicon dioxide (SiO ₂ ) at a content higher than the value in the glass structure at an interface with the pigment particles. Coating materials. The high-radiation glass coating according to claim 1, wherein the glass structure is a borosilicate glass containing silicon dioxide as a main component and containing boric acid and having a silicon dioxide content of about 80% by weight at the interface with the pigment particles. material. The high radiation glass coating material according to claim 1, wherein the pigment coating film contains 85 wt% or more of silicon dioxide. The high radiation glass coating material according to claim 1, wherein the pigment coating film contains 99% by weight or more of silicon dioxide. 2. The high radiation glass coating material according to claim 1, wherein the pigment coating film has a thickness of about 0.5 mu m on average. The high radiation glass coating material according to claim 1, wherein the pigment coating film has a thickness of about 0.1 to several [mu] m. The high radiation glass coating material according to claim 1, wherein the pigment particles are silicon borides. The high radiation glass coating material according to claim 1, wherein the pigment particles are silicon tetraboride. The high radiation glass coating material according to claim 1, wherein the pigment particles are silicon tetraboride having a particle diameter of about 2 m on average. The high radiation glass coating material according to claim 1, wherein the pigment particles are silicon tetraboride having a particle diameter of about 1 to 10 µm. As a high-radiation glass film adhered to the surface of a predetermined structure, pigment particles having a predetermined emissivity is dispersed in the glass structure A high radiation glass film, characterized in that a pigment coating layer having a predetermined thickness containing silicon dioxide at an interface between the pigment particles and the glass structure at a content higher than a value in the glass structure is formed by coating the pigment particles. 12. The high radiation glass film according to claim 11, wherein the glass structure is borosilicate glass containing silicon dioxide as a main component and containing boric acid and having a silicon dioxide content of about 80% by weight at the interface with the pigment particles. The high radiation glass film according to claim 11, wherein the pigment coating layer contains 85 wt% or more of silicon dioxide. The high radiation glass film according to claim 11, wherein the pigment coating layer contains 99% by weight or more of silicon dioxide. 12. The high radiation glass film according to claim 11, wherein the pigment coating layer has a thickness of about 0.5 m on average. 12. The high radiation glass film according to claim 11, wherein the pigment particles are silicon borides. The high radiation glass film according to claim 11, wherein the pigment particles are silicon tetraboride. The high radiation glass film according to claim 11, wherein the pigment particles are silicon tetraboride having a particle diameter of about 2 µm on an average value. The high radiation glass film according to claim 11, wherein the pigment particles are silicon tetraboride having a particle diameter of about 1 to 10 µm. A paste manufacturing process for producing a paste containing a pigment particle having a predetermined emissivity and a predetermined glass powder; a paste applying step for applying the paste to a surface of a predetermined structure; and heating the coated paste In the method of manufacturing a high radiation glass film comprising a heat treatment step of forming a glass structure from the powder, wherein the pigment particle is attached to the surface of the structure, the high radiation glass film dispersed in the glass structure, A pigment particle coating step of forming a pigment coating film having a predetermined thickness on each surface of the pigment particles, wherein the pigment coating film has a value in the glass structure at an interface between the glass structure in the high radiation glass film and the pigment particle. A method for producing a high-radiation glass film containing silicon dioxide at a higher content rate, wherein the pigment particle coating step is performed before the paste manufacturing step. The method of claim 20, wherein the pigment particle coating step, An inorganic polymer film forming step of forming an inorganic polymer film made of inorganic polymer containing silicon on the surface of the pigment particle, Heat-generating step of producing the pigment coating film containing silicon dioxide at the predetermined content rate from the inorganic polymer film by heating the pigment particle having the inorganic polymer film formed at a predetermined temperature in an oxidizing atmosphere; Method for producing a high radiation glass film comprising a. The method of claim 21, wherein the inorganic polymer film forming step, A pigment particle dispersion step of dispersing the pigment particles in a liquid containing the inorganic polymer to produce a dispersion liquid; Spray drying step of forming the inorganic polymer film on the surface of the pigment particles by spray drying the dispersion liquid Method for producing a high radiation glass film comprising a. The method for producing a high radiation glass film according to claim 21, wherein the inorganic polymer film forming step uses perhydropolysilazane as the inorganic polymer. 21. The method of claim 20, wherein the paste manufacturing step comprises dispersing the pigment particles and the glass powder together with an organic binder in an organic solvent. 21. The method for producing a high radiation glass film according to claim 20, wherein the paste coating step is sprayed with the paste. The method for producing a high radiation glass film according to claim 20, wherein the heat treatment step is performed under a non-oxidizing atmosphere. 21. The method of manufacturing a high radiation glass film according to claim 20, wherein the paste manufacturing step uses borosilicate glass containing silicon dioxide as a main component and containing boric acid as the glass powder.