WO2011149127A1

WO2011149127A1 - Novel non-metallic heat emitter composition, a method for producing a non-metallic heat emitter by using the composition, and a non-metallic heat emitter produced therefrom

Info

Publication number: WO2011149127A1
Application number: PCT/KR2010/003347
Authority: WO
Inventors: 서용석
Original assignee: 주식회사 자연에너지산업
Priority date: 2010-05-27
Filing date: 2010-05-27
Publication date: 2011-12-01
Also published as: KR20130043120A; KR101419166B1

Abstract

The present invention relates to a novel non-metallic heat emitter composition, to a method for producing a non-metallic heat emitter by using the composition and to a non-metallic heat emitter produced therefrom and, more specifically, the present invention relates to a non-metallic heat emitter composition comprising, based on the weight of the composition as a whole, from 30 to 32 percent by weight of molybdenum disilicide (MoSi2), from 27 to 29 percent by weight of tungsten carbide (WC), from 20 to 22 percent by weight of stannic chloride (tin chloride, SnCl_4˙5H₂O)20, from 13 to 15 percent by weight of chromium trioxide (H₂CrO₂), and from 6 to 8 percent by weight of boric acid (H₃BO₃), and the invention relates to a method for producing the non-metallic heat emitter by using the composition and to a non-metallic heat emitter produced therefrom. The non-metallic heat emitter according to the present invention is advantageous in that the resistance value of the heat-emitting layer is uniform and the heat-emitting temperature is constant and it can be adjusted at will to low-temperature heat emission at between 10 and 100℃, mid-temperature heat emission at between 100 and 500℃ and high-temperature heat emission at between 500 and 1,000℃ while having outstanding durability and, additionally, it emits far infrared and hence is beneficial to the human body.

Description

New nonmetallic heating element composition, method for preparing nonmetallic heating element using the composition and nonmetallic heating element prepared therefrom

The present invention relates to a nonmetallic heating element composition, a method for producing a nonmetallic heating element using the composition, and a nonmetallic heating element prepared therefrom.

With the depletion of energy resources, countries around the world are investing heavily in energy conservation. In line with this trend, the planar heating element, which is recently emerging, is a product that reduces power by 20 to 40% than the electric heating element that is generally used, and is expected to have a large electric energy saving and economic ripple effect.

In general, the surface heating element is easy to control the temperature by using the radiant heat generated by the electric current, it does not pollute the air has advantages in terms of hygiene and noise is used for bedding, such as heating mats or pads. In addition, it is widely applied to heating devices in various industrial places such as floor heating in homes, industrial heating in offices and workshops, paint drying, vinyl houses, barns, agricultural equipment, automotive back mirrors, freezing prevention devices for parking lots, recreational cold protection equipment, and home appliances. It is used.

The planar heating element has recently been widely used, replacing much of the heating in Europe, and is emerging as a new material that can be applied to industrial dryers, agricultural product dryers, health care auxiliary products, and construction subsidiary materials in addition to the housing sector. The domestic heating element market is estimated to be worth about 20 billion won for home appliances and about 50 billion won for home heating elements, and the market size is over hundreds of billions due to the development of a wide range of applications using planar heating elements. In view of this, the high value-addedness of the planar heating element technology and the importance in the parts and materials industries are being highlighted.

The planar heating element uses heat generated by resistance when a voltage is applied to the conductive material, and is generally produced by forming a heat generating layer containing a conductive material on a surface of a fabric or a synthetic resin substrate.

The conductive material used to manufacture the planar heating element is classified into a metal heating element and a non-metal heating element, and in recent years, non-metal heating elements are mostly used in consideration of stability. In particular, among the non-metal heating elements, conductive carbon, carbon, graphite, and tin chloride are mainly used as conductive materials, and electrodes for applying a voltage to the flat plate to form a heating layer and applying voltage to the heating layer are applied. After the formation of the insulating layer formed on top of the planar heating element has been manufactured.

However, in the case of the planar heating element manufactured by the conventional method, the resistance value of the heating layer is not uniform, so that the heat generation temperature is very unstable, and thus the temperature deviation depending on the position of the planar heating element has a very severe disadvantage. That is, the thickness of the planar heating element is constant, but the resistance value is different, the heating state is uneven, even in the same plane has a disadvantage that the deviation of the heating temperature is severe. For this reason, there is a problem that the heating element of the portion higher than the region having a low heat generation temperature is aging first, which shortens the life of the planar heating element and makes it impossible to generate high temperature of 300 ° C. or higher.

Accordingly, the present inventors have made diligent research efforts to solve the problems of the prior art as described above, and as a result, molybdenum disulfide (MoSi ₂ ), tungsten carbide (WC), tin tin chloride (SnCl _4˙ 5H ₂ O), chromium trioxide ( When using a non-metallic heating element composition containing H ₂ CrO ₂ ) and boric acid (H ₃ BO ₃ ), the resistance value of the heating layer is uniform, so that the heating temperature is constant, and low temperature, medium temperature, and high temperature heating are possible and durable depending on the intended use. Not only is it excellent, it completed the present invention by confirming that it can achieve the heating element beneficial to a human body by radiating far infrared rays.

Accordingly, an object of the present invention is to provide a non-metallic far-infrared heating element which is excellent in durability while having low temperature, constant temperature, and high temperature heating depending on the intended use because the resistance value of the heating layer is uniform.

In order to achieve the above object, the present invention is based on the weight of the total composition molybdenum disilicide (MoSi ₂ ) 30 to 32% by weight, tungsten carbide (WC) 27 to 29% by weight, tin tin chloride (tin chloride, SnCl _4˙ 5H ₂ O) 20 to 22% by weight, chromium trioxide (H ₂ CrO ₂ ) 13 to 15% by weight and boric acid (boric acid, H ₃ BO ₃ ) 6 to 8% by weight It provides a heating element composition.

In another aspect, the present invention comprises the step of depositing the composition on the surface of the target matrix to be deposited by atmospheric pressure chemical vapor deposition (atmospheric pressure chemical vapor deposition) to form a heating layer, and then forming electrodes on both ends of the heating layer; It provides a method for producing a non-metallic heating element.

In addition, the present invention provides a non-metal heating element that emits far-infrared rays produced by the above method and is capable of low temperature, medium temperature and high temperature heating depending on the intended use.

In the nonmetal heating element according to the present invention, the initial heat is rapidly generated by the use of the nonmetal heating element composition having excellent electrical resistance to the unit area, and the resistance of the heating layer is uniform, so that the heating temperature is constant. It is possible to selectively generate low temperature, medium temperature, and high temperature of 1000 ° C. or more, but also has excellent durability. In addition, the non-metallic heating element according to the present invention is excellent in energy conversion efficiency, can significantly suppress power consumption and radiate far infrared rays, which is beneficial to the human body, and the manufacturing process is simple, economical and does not cause environmental pollution. It can be usefully applied as.

The present invention is based on the weight of the total composition molybdenum disilicide (MoSi ₂ ) 30 to 32% by weight, tungsten carbide (WC) 27 to 29% by weight, tin chloride, SnCl _4˙ 5H ₂ O) 20 to 22% by weight, chromium trioxide (H ₂ CrO ₂ ) 13 to 15% by weight and boric acid (boric acid, H ₃ BO ₃ ) It provides a non-metallic heating element composition comprising 6 to 8% by weight.

The non-metallic heating element composition according to the present invention has a molybdenum disilicide (MoSi ₂ ) 30 to 32% by weight, tungsten carbide (WC) 27 to 29% by weight, tin tin (tin) chloride, SnCl _4˙ 5H ₂ O) 20 to 22% by weight, chromium trioxide (H ₂ CrO ₂ ) 13 to 15% by weight and boric acid (H ₃ BO ₃ ) 6 to 8% by weight.

The non-metallic heating element composition according to the present invention is composed of components having excellent electrical resistance characteristics for a unit area, and the physical properties and functions of these components are as follows.

Molybdenum silicide (MoSi ₂ ) is a compound in which the molar ratio of molybdenum (Mo) and silicon (Si) is 1: 2, and has a high melting point (2030 ° C.) and a low density (6.3 g / cc). Molybdenum disulfide has been widely studied as a next-generation high temperature oxidation resistant material because silicon, which is one of the constituents, combines with oxygen in the atmosphere to form a silica (SiO ₂ ) film on the surface of a product at a high temperature in an oxidizing atmosphere.

The content of molybdenum disulphide is preferably 32 to 30% by weight based on the total weight of the composition. If the content thereof is less than 30% or more than 32% by weight, the desired level of high temperature heating may not be achieved.

Tungsten carbide (WC) is a hexagonal crystal produced by heating powder tungsten and carbon black under hydrogen gas at 1400-1600 ° C. Tungsten carbide is one of the most important components of cemented carbide, which has high temperature hardness, high density and high strength, and stable physical properties.It is used in various cutting tools, wear resistance, impact tools, and high temperature and high pressure components. It is applied to drills and precision micro molds.

The content of tungsten carbide is preferably 27 to 29% by weight based on the total weight of the composition. If the content is less than 27% or more than 29% by weight, the electric flow may become unstable at high heat.

Tin tin chloride (SnCl _4˙ 5H ₂ O) is a compound of tin and chlorine that is a colorless, _fuming liquid obtained by distillation by passing chlorine gas directly through tin. When dissolved in water, it is exothermic and slowly hydrolyzed to produce colloid of tin oxide (IV) and HSnCl of hexachlorotin (IV) acid. Soluble in organic solvents, used as a mordant, condensing agent, organotin compound. Its anhydride is one of the representative cationic polymerization catalysts.

The content of stannic chloride is preferably 20 to 22% by weight based on the total weight of the composition, but if the content is less than 20% or more than 22% by weight, it may cause instability of the exothermic layer.

Chromium trioxide (H ₂ CrO ₂ ) is a glossy green or black powdered crystalline solid with a molecular weight of 151.99 and a melting point of 1990 ° C. It is harder than quartz and hardly changes by heat, air or water. The most common pigment, also called chrome green, is used for coloring glass or pottery. Soluble in water, acidic on its own, prolong life and make electric flow strong during plating.

The content of chromium trioxide is preferably 13 to 15% by weight based on the total weight of the composition. If the content is less than 13% or more than 15% by weight, the heating element life may be shortened due to the instability of the electric flow. .

Boric acid (H ₃ BO ₃ ) is a colorless, odorless, glossy, scaly crystal, generally referred to as orthoboric acid. It is a substance obtained by treating concentrated boric acid solution with sulfuric acid. It dissolves well in hot water. The aqueous solution has a weak acidity and shows sterilization effect. It is used as a mild disinfectant to treat burns or skin wounds. Boric acid is also used as an important component in fabric fireproofing, nickel electroplating or tanning solutions and catalysts used in many organic chemical reactions.

The content of boric acid is preferably 6 to 8% by weight based on the total weight of the composition. If the content of the boric acid is less than 6% or more than 8% by weight, the bondability with other components may be reduced when the exothermic layer is formed. Can be.

The present invention provides a method for producing a non-metallic heating element by atmospheric pressure chemical vapor deposition using the non-metallic heating element composition of the above configuration.

Method for producing a non-metallic heating element according to the present invention

1) dissolving the nonmetallic heating element composition in a solvent to prepare a nonmetallic heating element stock solution;

2) evaporating the non-metallic heating element stock solution by atmospheric pressure chemical vapor deposition to deposit a heating layer on a surface of a target deposition target matrix; And

3) forming electrodes at both ends of the heating layer.

In the manufacturing method according to the present invention, when the stock solution containing the components of the non-metallic heating element composition is heated to a predetermined temperature or more and evaporated in a chemical vapor, the components of the composition are vaporized and uniformly deposited on the surface of the mother to be deposited. Atmospheric pressure chemical vapor deposition is used.

First, step 1) is a step of preparing a non-metallic heating element stock solution using the non-metallic heating element composition according to the present invention, molybdenum silicide (MoSi ₂ ), tungsten carbide (WC), tin tin chloride (SnCl _4˙ 5H ₂ O) , A suitable solvent is added to a nonmetallic heating element composition comprising chromium trioxide (H ₂ CrO ₂ ) and boric acid (H ₃ BO ₃ ), and dissolved by gradual heating.

In the present invention, since the solvent is volatilized in the subsequent atmospheric chemical vapor deposition step, the amount of the solvent need not necessarily be limited, and may be added or subtracted as necessary. In addition, the solvent in the present invention can be used without limitation as long as it can dissolve each component of the non-metallic heating element composition, for example, distilled water, butyl cellosol portion, ethyl cellosol portion, ethyl acetate, cyclohexanone, Xylene, diacetyl alcohol, toluene, ketones, mineral spirits and the like can be used. In the present invention, the solvent is added in a ratio of 1: 1 to 1: 2.2 by volume relative to the nonmetallic heating element composition. At this time, the solvent is added to the non-metallic heating element composition, and then the mixture is preferably dissolved while gradually heating to 75 to 85 ° C.

Step 2) is a step of forming an exothermic layer by evaporating the non-metal heating element stock prepared in step 1) in a chemical vapor furnace and vaporizing the components of the composition on the surface of the parent to be deposited. It is a step to perform.

First, the nonmetallic heating element stock is placed on an evaporation table in a chemical gas furnace. At this time, it is preferable that the temperature of the evaporation zone in the chemical gas furnace is maintained at 120 to 220 ° C, and the main temperature is the exothermic temperature and the non-metal to be achieved in the non-metal heating element finally obtained in the range of 300 to 1500 ° C. It may vary depending on the use of the heating element, the thickness of the matrix to be deposited. For example, at the time of production of the low-temperature heating nonmetallic heating element at 10 to 100 ° C, the main temperature is set to 400 to 450 ° C, and at the time of the production of the 100 to 500 ° C medium-temperature heating nonmetal heating element, the main temperature is 450 to 500 ° C. It is preferably set at 600 ° C, and preferably at 600 to 1100 ° C when the nonmetallic heating element for high temperature heating at 500 to 1000 ° C is manufactured.

Subsequently, the substrate to be deposited on which the heating layer is to be formed on the surface of the substrate is fixed to a fixing mechanism located at an upper portion of the substrate. The fixture may rotate the fixed deposition target matrix as necessary so that a plurality of deposition target substrates may be fixed and uniformly deposited on the surface of the substrate during the deposition process.

The substrate to be deposited suitable for the present invention may be used as all substrates to form the heating layer, as long as it does not cause physical deformation such as shrinkage or expansion by the deposition temperature of the nonmetallic heating element composition or the exothermic temperature of the finally obtained nonmetallic heating element. have. As the material of the substrate to be deposited, glass, quartz, ceramic, quartz, or the like having various shapes such as circular, elliptical, plate, tubular, etc. may be used depending on the intended use.

The substrate to be deposited is preferably preheated to 300 to 1500 ° C. for 10 to 20 minutes before being applied to atmospheric pressure chemical vapor deposition using a non-metallic heating element stock solution. This preheating process is for the safe deposition of resistance. The effect of durability and stability of resistance can be expected. The preheating temperature or time may vary depending on the shape, size, thickness and use of the matrix to be deposited, and is preferably preheated at the same temperature as the atmospheric chemical vapor deposition temperature.

After the non-metal heating element stock solution and the deposition target matrix are installed in a chemical gas furnace as described above, all of the stock solution of the evaporation table is evaporated by heating the evaporation zone and the main body at a set temperature. During evaporation, the solvent is volatilized and the non-metallic heating element components are vaporized and deposited uniformly on the surface of the mother body. In this case, in order to prevent atmospheric pressure chemical vapor deposition on a portion where the formation of a heating layer is not required on the surface of the substrate to be deposited, various processes such as masking with a coating or a tape may be performed. When all of the non-metallic heating element stock solution evaporates, the mother body on which the heating layer is deposited is taken out and cooled to room temperature.

According to the present invention, when the non-metal heating element composition is deposited on the surface of the mother body by atmospheric pressure chemical vapor deposition to form a heating layer, the electrical resistance per unit area of the heating layer may vary depending on the heating temperature required in the final non-metal heating element. . In general, the electrical resistance per unit area of the heating layer is inversely proportional to the heating temperature. The higher the electrical resistance per unit area of the heating layer, the lower the heating temperature, and the lower the electrical resistance per unit area, the higher the heating temperature. The electrical resistance per unit area of the heat generating layer can be achieved to have a desired range by adjusting the deposition thickness of the heat generating layer. Here, as the deposition thickness of the heating layer becomes thicker, the electrical resistance per unit area is lowered to increase the heating temperature, while the thinner the deposition thickness, the higher the electrical resistance per unit area is, so that the heating temperature is decreased. At this time, the deposition thickness of the heating layer may be adjusted depending on the amount of the non-metal heating element stock solution to be evaporated and the mixing method of the composition.

Step 3) is a step of forming an electrode for applying a voltage to both ends of the heating layer formed on the surface of the matrix to be deposited in step 2), the electrode is at least one pair in the longitudinal or transverse direction of the heating layer Can be formed. As an electrode material suitable for use in the present invention, it is preferable that the conductivity is higher than that of the heat generating layer, and general metals, graphite, rosin, and the like correspond to this. In a preferred embodiment of the present invention, an electrode solution made of silver powder liquid is applied to the outer circumferential surface of the heat generating layer in a band shape at a predetermined length and thickness to form an electrode.

The target non-metallic heating element is completed by putting the electrode to be deposited on the outer circumferential surface of the heating layer in a chemical gas furnace and heating it through a three-step temperature change to sinter the electrode and then take it out to room temperature and cool it. At this time, the temperature of the chemical gas furnace is initially put into the deposition target matrix and heated for 10 to 20 minutes at 150 to 400 ℃, then heated to 300 to 1500 ℃ to heat for 20 to 30 minutes, then at 150 to 400 ℃ It is set to heat for 10 to 20 minutes, wherein the temperature conditions depend on the temperature of the mains at which atmospheric pressure vapor deposition is carried out in the preceding step.

In the non-metal heating element manufactured as described above, when an electrical terminal is coupled to an electrode so that electric current is connected to the electrodes formed on the upper and lower parts, current flows from the electrode on one side to the electrode on the other side, and the heating layer acts as a resistance. This will occur.

The present invention is to selectively prepare a non-metal heating element capable of low-temperature, medium-temperature and high-temperature heating according to the intended use by controlling the temperature of the predominant temperature and the amount of the non-metal heating element stock solution deposited in the chemical gas furnace where atmospheric pressure chemical vapor deposition is performed in the above method. Can be. For example, in order to manufacture a non-metallic heating element capable of high temperature heating, the temperature of the main body in the chemical gas furnace is set to 600 to 1100 ° C according to the maximum set temperature of the heating target mother, and the heating layer is deposited on the surface of the deposition target mother. In order to decrease the electrical resistance by increasing the thickness, the amount of the non-metallic heating element stock solution may be increased. On the other hand, in order to manufacture a non-metal heating element capable of low-temperature heating, the non-metal heating element to increase the electrical resistance by setting the temperature of the main chamber in the chemical gas furnace to 400 to 450 ℃ and reducing the thickness of the heating layer deposited on the surface of the substrate to be deposited You can reduce the amount of stock solution.

The non-metallic heating element obtained according to the present invention is molybdenum disulfide (MoSi ₂ ), tungsten carbide (WC), _stannic chloride (SnCl _4˙ 5H ₂ O), chromium trioxide (H ₂ CrO ₂ ) and boric acid (H ₃ BO ₃ The non-metallic heating element composition including) is formed by evaporation of the non-metallic heating element components by atmospheric vapor chemical vapor deposition, and the heating layer is formed of molybdenum disulfide (MoSi ₂ ), tungsten carbide (WC), and tin oxide (SnO). ₂ ), chromium trioxide (H ₂ CrO ₂ ) and boron trioxide (B ₂ O ₃ ) is the main component.

The non-metal heating element according to the present invention can selectively control the exothermic temperature according to the temperature and amount of the non-metal heating element stock solution is deposited in the manufacturing process, the higher the temperature at which atmospheric pressure chemical vapor deposition is carried out, the amount of the non-metal heating element stock is deposited The more the exothermic temperature of the non-metallic heating element finally obtained increases. The amount of the non-metal heating element stock solution to be deposited may be represented by the thickness of the heating layer to be formed. If the heating layer has a thickness of 8 to 20 nm, the non-metal heating element may be heated at a low temperature of 10 to 100 ° C., and the heating layer may be 15 to 15 nm. If the non-metal heating element having a thickness of 35 nm can be a medium-temperature heating of 100 to 500 ℃, the non-metal heating element is capable of high temperature heating of 500 to 1000 ℃ if the heating layer has a thickness of 30 to 65 nm.

Molybdenum disulphide (MoSi ₂ ) in the non-metal heating element is a strong non-metal resistive heating element, a core heating material that enables high-temperature heating of 1000 ℃, tungsten carbide (WC) having a high density increases the hardness and strength when the heating element is a high temperature, Tin oxide (SnO ₂ ) plays an aggregate role in the heating layer, chromium trioxide (H ₂ CrO ₂ ) strengthens the electric flow and improves durability, and boron trioxide (B ₂ O ₃ ) fills the space between the crystals. It acts as a filler to improve transparency and brightness of the heating layer and to improve thermal stability.

In the nonmetal heating element according to the present invention, the initial heat generation is made very quickly by using a nonmetal heating element composition having excellent electrical resistance to unit area, and the resistance value of the heating layer is uniform, so that the heating temperature is constant and is used at 10 ° C. according to the intended use. It is possible to selectively generate low temperature, medium temperature, and high temperature of 1000 ° C. or more, but also has excellent durability. In addition, the non-metallic heating element according to the present invention is excellent in energy conversion efficiency, can significantly suppress power consumption and radiate far infrared rays, which is beneficial to the human body, and the manufacturing process is simple, economical and does not cause environmental pollution. It can be usefully applied as.

The non-metallic heating element according to the present invention can be applied to various heating, hot water supply, drying, food cooking, and equipment requiring high temperature or heat, for example, beddings such as heating mats or pads, apartments or general houses. Residential heating devices such as floor heating, industrial heating devices for offices or workplaces, various industrial heating devices such as printing drying and paint drying, agricultural equipment such as plastic houses and barns, agricultural product drying systems, and freezing to melt snow on roads and parking lots. It can be applied to the prevention device.

Hereinafter, the present invention will be described in more detail with reference to Examples. These examples are only for illustrating the present invention more specifically, it will be apparent to those skilled in the art that the scope of the present invention is not limited by these examples in accordance with the gist of the present invention.

실시예 1: 고온 발열용 비금속 발열체의 제조Example 1 Preparation of Nonmetallic Heating Element for High Temperature Heating

31 weight percent molybdenum disulphide (MoSi ₂ ), 28 weight percent tungsten carbide (WC), 21 weight percent tin chloride (SnCl 4 _제 5H ₂ O), 14 weight percent trioxide based on the total weight of the composition After mixing chromium (H ₂ CrO ₂ ) and 6% by weight of boric acid (H ₃ BO ₃ ), distilled water was added to the mixture in a 1: 1 volume ratio, and dissolved by heating slowly at 80 ° C. to prepare a nonmetallic heating element stock solution. . 20 g of the non-metallic heating element stock solution thus prepared was placed on an evaporation stand in a chemical gas furnace where the temperature of the evaporation stand was set to 120 ° C and the main temperature was 1100 ° C. After fixing the ceramic plate (200 mm × 250 mm × 4 mm) to the main fixture, the ceramic plate was placed in a chemical chamber and placed on the evaporation table as a substrate to be formed to form a heating layer on the surface. . At this time, the ceramic plate was preheated at 800 degreeC for 10 minutes. Subsequently, atmospheric pressure chemical vapor deposition was performed by evaporating the non-metal heating element stock solution on the evaporator while raising the temperature of the main to 1100 ° C. while rotating the holder so that the heating layer was uniformly deposited on the surface of the ceramic plate. After about 15 minutes, when all the non-metallic heating element stocks evaporated, the ceramic plate on which the heating layer was deposited was taken out and cooled to room temperature.

Subsequently, after preparing a silver powder liquid (Ag 99% purity) electrode solution, it was coated on both ends of the heating layer deposited on the surface of the ceramic plate with a constant thickness and length. The ceramic plate is placed in a chemical furnace and heated at 400 ° C. for 15 minutes, at 800 ° C. for 30 minutes, and at 300 ° C. for 15 minutes to sinter the electrode, and then take it out and cool it to room temperature to emit far-infrared rays. A ceramic plate heating element was produced as possible.

As a result of measuring the electrical resistance per unit area of the ceramic plate heating element thus manufactured, the unit resistance value was about 30 kPa.

As a result of applying a voltage of 220 V and 60 kV to the electrode of the ceramic plate heating element and measuring the surface temperature for 50 days, it was confirmed that the surface temperature was kept constant over 1000 ° C. In addition, the far-infrared emission amount of the ceramic plate heating element was measured by Fourier transform infrared spectroscopy at 100 ° C., and it was confirmed that it emits 7.63 × 10 ² W / m ² radiation energy and shows 88.6% far-infrared emissivity. It was.

실시예 2: 중온 발열용 비금속 발열체의 제조Example 2 Preparation of Nonmetallic Heating Element for Medium Temperature Heating

31 weight percent molybdenum disulphide (MoSi ₂ ), 28 weight percent tungsten carbide (WC), 21 weight percent tin chloride (SnCl 4 _제 5H ₂ O), 14 weight percent trioxide based on the total weight of the composition After mixing chromium (H ₂ CrO ₂ ) and 6% by weight of boric acid (H ₃ BO ₃ ), distilled water was added to the mixture in a 1: 1 volume ratio and dissolved by heating gradually to 80 ° C. to prepare a nonmetallic heating element stock solution. . 13 g of the non-metallic heating element stock solution thus prepared was placed on the evaporation stand in a chemical gas furnace where the temperature of the evaporation stand was set to 120 ° C and the main temperature was 700 ° C. After fixing the quartz plate (250 mm × 250 mm × 3 mm) to the main fixture, the quartz plate was placed in a chemical vapor chamber and placed on the evaporation table. . At this time, the quartz plate was preheated at 600 ° C for 10 minutes. Subsequently, atmospheric pressure chemical vapor deposition was performed by evaporating the stock solution of the non-metallic heating element on the evaporator while raising the temperature of the main to 700 ° C. while rotating the holder so that the heating layer was uniformly deposited on the quartz plate surface. After about 15 minutes, when all the non-metallic heating element stocks evaporated, the quartz plate on which the heating layer was deposited was taken out and cooled to room temperature.

Subsequently, after preparing a silver powder liquid (Ag 99% purity) electrode solution, it was coated on both ends of the heating layer deposited on the surface of the quartz plate with a constant thickness and length. The quartz plate was placed in a chemical furnace and heated at 300 ° C. for 15 minutes, at 600 ° C. for 30 minutes, and at 300 ° C. for 15 minutes to sinter the electrode, and then taken out and cooled to room temperature to emit far-infrared rays. A quartz plate heating element was produced as possible.

As a result of measuring the electrical resistance per unit area of the quartz plate heating element thus produced, the unit resistance value was about 117 kPa.

When the voltage of 220 V, 60 kV was applied to the electrode of the quartz plate heating element and the surface temperature was measured for 50 days, it was confirmed that the surface temperature was kept constant at 300 ° C. or higher. In addition, the far-infrared emission amount of the ceramic plate heating element was measured by Fourier transform infrared spectroscopy at 100 ° C., and it was confirmed that it emits 7.63 × 10 ² W / m ² radiation energy and shows 88.6% far-infrared emissivity. It was.

실시예 3: 저온 발열용 비금속 발열체의 제조Example 3 Preparation of Nonmetallic Heating Element for Low Temperature Heating

31 weight percent molybdenum disulphide (MoSi ₂ ), 28 weight percent tungsten carbide (WC), 21 weight percent tin chloride (SnCl _4˙ 5H ₂ O), 14 weight percent trioxide based on the weight of the total composition After mixing chromium (H ₂ CrO ₂ ) and 6% by weight of boric acid (H ₃ BO ₃ ), distilled water is added to the mixture in a 1: 1 volume ratio, and dissolved by gradually heating to 80 ° C. to prepare a nonmetallic heating element stock solution. It was. 5 g of the non-metallic heating element stock solution thus prepared was placed on the evaporation stand in a chemical gas furnace where the temperature of the evaporation stand was set to 120 ° C and the main temperature was 450 ° C. After fixing the heat-resistant glass plate (280 mm × 280 mm × 3 mm) to the main fixture, the heat-resistant glass plate (280 mm × 280 mm × 3 mm) was fixed to the main fixture to be placed on the evaporation table. . At this time, the heat resistant glass plate was preheated at 450 ° C for 10 minutes. Subsequently, atmospheric pressure chemical vapor deposition was performed by evaporating the non-metal heating element stock solution on the evaporator while raising the temperature of the main to 450 ° C. while rotating the holder so that the heating layer was uniformly deposited on the heat-resistant glass plate surface. After about 15 minutes, when all the nonmetallic heating element stocks evaporated, the heat-resistant glass plate on which the exothermic layer was deposited was taken out and cooled to room temperature.

Subsequently, after preparing a silver powder liquid (Ag 99% purity) electrode solution, it was coated on both ends of the heat generating layer deposited on the heat-resistant glass plate surface at a constant thickness and length. The heat-resistant glass plate is placed in a chemical gas furnace and heated at 150 ° C. for 15 minutes, at 450 ° C. for 30 minutes, and at 150 ° C. for 15 minutes to sinter the electrode, and then take it out and cool it to room temperature to emit far infrared rays. A heat resistant glass plate heating element was produced.

As a result of measuring the electrical resistance per unit area of the heat-resistant glass plate heating element thus manufactured, the unit resistance value was about 450 kPa.

When the voltage of 220 V, 60 kV was applied to the electrode of the glass plate heating element and the surface temperature was measured for 50 days, it was confirmed that the surface temperature was constantly maintained at 100 ° C. or lower. In addition, the far-infrared emission amount of the ceramic plate heating element was measured by Fourier transform infrared spectroscopy at 100 ° C., and it was confirmed that it emits 7.63 × 10 ² W / m ² radiation energy and shows 88.6% far-infrared emissivity. It was.

The specific parts of the present invention have been described in detail, and it is apparent to those skilled in the art that such specific descriptions are merely preferred embodiments, and thus the scope of the present invention is not limited thereto. something to do. Therefore, the substantial scope of the present invention will be defined by the appended claims and their equivalents.

Claims

30 to 32 wt% molybdenum disilicide (MoSi 2 ), 27 to 29 wt% tungsten carbide (WC), tin chloride, SnCl 4˙ 5H 2 O based on the weight of the total composition ) 20 to 22% by weight, chromium trioxide (H 2 CrO 2 ) 13 to 15% by weight and boric acid (boric acid, H 3 BO 3 ) 6 to 8% by weight composition.
Method for producing a non-metal heating element comprising the following steps:

1) dissolving the non-metal heating element composition according to claim 1 in a solvent to prepare a non-metal heating element stock solution;

2) depositing the exothermic layer on the surface of the matrix to be deposited by evaporating the non-metal heating element stock solution according to atmospheric pressure chemical vapor deposition; And

3) forming electrodes at both ends of the heating layer.
The method of claim 2,

A solvent is added to the nonmetallic heating element composition in step 1), and then the mixture is dissolved while slowly heating to 75 to 85 ° C to prepare a nonmetallic heating element stock solution.
The method of claim 2,

Atmospheric pressure chemical vapor deposition in step 2) is carried out by heating and evaporating the non-metal heating element stock solution to 300 to 1500 ℃.
The method of claim 4, wherein

In order to produce a low-temperature exothermic non-metallic heating element of 10 to 100 ℃, the atmospheric pressure chemical vapor deposition is carried out at 400 to 450 ℃, manufacturing method of a non-metal heating element.
The method of claim 4, wherein

Method for producing a non-metal heating element, the atmospheric pressure chemical vapor deposition is carried out at 450 to 600 ℃ for the production of a medium-temperature heating non-metal heating element of 100 to 500 ℃.
The method of claim 4, wherein

In order to produce a high temperature exothermic nonmetal heating element of 500 to 1000 ℃, the atmospheric pressure chemical vapor deposition is carried out at 600 to 1100 ℃, a method for producing a non-metal heating element.
The method of claim 2,

The method of manufacturing a non-metallic heating element further comprising the step of preheating the substrate to be deposited at a temperature at which atmospheric pressure chemical vapor deposition is performed for 10 to 20 minutes before performing atmospheric pressure chemical vapor deposition in step 2).
The method of claim 2,

The exothermic temperature of the non-metal heating element obtained in proportion to the amount of the non-metal heating element stock solution evaporated by atmospheric pressure chemical vapor deposition in step 2), the method of producing a non-metal heating element.
Exothermic layer comprising molybdenum silicide (MoSi 2 ), tungsten carbide (WC), tin oxide (SnO 2 ), chromium trioxide (H 2 CrO 2 ) and boron trioxide (B 2 O 3 ) formed on the surface of the substrate to be deposited, And electrodes for applying a voltage to both ends of the heat generating layer, and capable of selectively generating low temperature, medium temperature, and high temperature.
The method of claim 10,

Non-metal heating element capable of low-temperature heating of 10 to 100 ℃ non-metal heating element when the heating layer has a thickness of 8 to 20 nm.
The method of claim 10,

When the heat generating layer has a thickness of 15 to 35 nm, the non-metal heating element is capable of heating a medium temperature of 100 to 500 ℃.
The method of claim 10,

Non-metal heating element capable of high-temperature heating of 500 to 1000 ℃ non-metal heating element when the heating layer has a thickness of 30 to 65 nm.