KR101220726B1 - Method for manufacturing a light, flexible and thermal insulating ceramic pad by foaming process and a light, flexible and thermal insulating ceramic pad manufactured by the same method - Google Patents

Abstract

PURPOSE: A manufacturing method of light weight soft ceramics heat insulating materials using a foaming process, and the light weight soft ceramics insulating materials manufactured by the method are provided to offer non-combustible ability, high thermal resistance, lightness, and high thermal insulating properties. CONSTITUTION: A manufacturing method of light weight soft ceramics heat insulating materials comprises the following steps: adding water to inorganic fibers, and making the fibers in slurry state by pulping; mixing particulate inorganic ash with the fibers in the slurry state; mixing a foaming agent with the mixture in the previous step; and manufacturing ceramic foam by heat-treating the mixture at 25-300 deg. Celsius. The inorganic fibers are one or more kinds selected from a sepiolite fiber, an aluminum silicate fiber, rock wool, an aluminum oxide fiber, and glass wool. The mixing ratio of the inorganic fibers, the water, the particulate inorganic, the ash, and the foaming agent is 20-95 parts by weight, 100-800 parts by weight, 5-80 parts by weight and 0.1-5 parts by weight.

Description

FIELD OF MANUFACTURING A LIGHT, FLEXIBLE AND Thermal insulating ceramic pad by foaming process and a light, flexible and thermal insulating ceramic pad manufactured by the same method}

The present invention relates to a method for producing a light weight soft ceramic thermal insulation material using a foaming process and to a light weight soft ceramic thermal insulation material manufactured by the above method. To make a fibrous state of slurry, and then add and mix a particulate inorganic material on the fiber of the slurry state, mix by adding a blowing agent to the mixture, and put the mixture into a mold to heat and heat up from 25 ℃ to 300 ℃ The present invention relates to a method for producing a flexible ceramic foam, and to a lightweight soft ceramic thermal insulating material prepared by the method.

Thermal insulation materials are largely classified into organic and inorganic. Organic insulation is widely used because of its excellent thermal insulation performance and good construction properties, but it is very vulnerable in terms of fire resistance, such as the expansion of fire due to the combustion of the insulation material itself when a fire breaks out. do. On the other hand, the inorganic insulation material has better fire resistance characteristics than the organic insulation material, but the workability is relatively bad due to its relatively heavy weight and poor thermal insulation performance, which is inherent to the insulation material. Inorganic insulation materials such as fiberglass and rock wool are used as a countermeasure against actual fire hazards, but they absorb moisture and cause agglomeration, sag due to their own weight, and an upper part of the construction part creates an insulation gap so that heat flow flows. Thermal bridge phenomena easily occur, so that the thermal insulation performance is greatly degraded, and it is not free from controversy of human risk of dust and inorganic fibers. In addition, organic-based insulation can be discarded and recycled, but it is not easy to sort and separate for disposal, and inorganic fiberglass or rock wool is classified as construction waste unlike landfill's designated waste, but it is disposed of in landfill. Measures are required to prevent dust generation and inhalation into the human body.

As described above, the organic and inorganic thermal insulation materials have different advantages and disadvantages, so the situation of the thermal insulation material market varies from country to country. In foreign countries, the first reason for safety is that more than 90% of inorganic type insulation materials are used. However, in Korea, organic insulating materials emit toxic gases in case of fire due to thermal insulation properties, workability and economic feasibility. Despite severe damage, organic insulation has a 70% market share.

In order to solve this problem, inorganic type is used as the main raw material, non-flammable and high heat resistance, and no toxic gas is generated, and it is lightweight like organic thermal insulating material through special treatment process, and is easy to work with high thermal insulation and soft characteristics. There is an urgent need for the development of a new concept of thermal insulation or insulation panels that can have the characteristics of thermal insulation. Moreover, with the recent interest in maximizing energy efficiency and reducing carbon dioxide, the development of eco-friendly green materials has led to the development of a new concept of thermal insulation materials with the advantages of organic thermal insulation and inorganic thermal insulation. This is very urgent. To this end, eco-friendly flame-retardant organic binder manufacturing element technology, inorganic filler material modification and particle size distribution control technology, hybrid insulator material incombustibility technology by securing organic / inorganic hybrid dispersion technology, particulate foaming technology, molding technology, pore distribution control technology, inorganic Element technology for maximizing insulation and light weight through filler compounding technology is needed.

The present invention is a ceramic of a new concept that combines the advantages of non-combustibility, high heat resistance and toxic gas generation characteristics of inorganic thermal insulation materials and the advantages of ease of workability, such as light weight, high thermal insulation, soft properties of the advantages of organic thermal insulation materials It is to provide a thermal insulation material or a ceramic thermal insulation panel.

However, it is still difficult to find a prior art for the research or production of the manufacture of such a new concept of ceramic thermal insulation or panels thereof. In Korea, the insulation manufacturer or raw material company has almost no experience in developing organic-inorganic hybrid composite insulation material similar to the present invention. Is a necessary situation. However, there are many prior arts for simple thermal insulation. In particular, there are many patents focusing on building applications, and when looking at the composition patents of building insulation materials, many patents related to the composition and flame retardant technology of organic insulation materials and the composition and weight reduction of inorganic insulation materials have been applied. There is also a prior art for the production of thermal insulation with inorganic mineral fibers as raw materials, but hard or cement. There is also a prior art in which a panel or the like is produced by a shaping method using an inorganic adhesive such as gypsum.

As a result of domestic patent research on inorganic insulation material, the insulation material is a plate made of lightweight aggregate or light mortar (Korean Patent Registration No. 10-0481043, Korean Patent Registration No. 10-0935573 and Korean Patent Registration No. 10-0580230), Plate material using flame retardant foam glass particles (Korea Patent Registration No. 10-0799612), Lightweight porous insulating board using Korea Glass (Korea Patent Registration No. 10-0748622 and Korea Patent Registration No. 10-0857594) and calcium silicate and clay minerals Ceramic panel manufacturing (Korean Patent Registration No. 10-0803513). Other airgel related materials and vacuum insulation materials have been proposed, but they do not meet the thermal insulation performance of organic insulation materials, or in the case of aerogels, they are too expensive to limit their use for special applications and there is a problem in shaping technology. There are many patents on phenolic resin foams, and there are patents on flame retardant technology of organic insulation materials (Korean Patent Application No. 10-2006-0055832), but a small amount of organic binders and calcium carbonate It is difficult to find a domestic patent with a light and hard manufacturing method of foaming using inorganic materials. Overseas, there was a patent document about a product that obtained flame retardancy by mixing inorganic fiber and inorganic oxide (German Patent Publication No. 1975-2537345), and added inorganic filler to urethane to enhance brittleness, increase elasticity and improve bending strength. Method of making organic-inorganic composite foamed molding for insulation (US Pat. No. 6,313,186), fillers of various silicate minerals such as mica and cordierite, and magnesium oxide, manganese dioxide, aluminum hydroxide, etc. Patent (US Pat. No. 6,010,565) for a product having thermal insulation and fire resistance using a blowing agent, using inorganic phosphate containing magnesium, zinc and aluminum, the specific gravity is 0.15 or less, and the pores are 3 mm or less in size. And a patent document relating to a method of making an inorganic foamed molded article having a flame retardancy (US Pat. No. 4,207,113) has also been presented. . In particular, there is a feature of using a limited material in the domestic, but in the foreign countries to manufacture or mix a variety of insulating materials, the product of the patent application and registered. However, these are also different from the concept of the present invention. In particular, in Japan, a method of manufacturing an inorganic panel using various materials has been introduced, and an external insulation panel (Japanese Patent Laid-Open No. 11-349720) using an inorganic foam is also introduced. However, the thermal insulation performance has not yet reached the organic insulating material or did not completely solve the flame retardancy. As in the case of the present invention, there may be a case where a hard, fireproof sound insulation insulation material is prepared by incorporating granular inorganic material based on inorganic mineral fiber. Republic of Korea Patent No. 10-0665089 is a mineral fiber, such as glass fiber, rock wool, aluminum silicate fiber, aluminum oxide cotton, haemulseok fiber, silica sand, haemulseok, super gemstone, kaolin, quartz, gemstone, plagioclase, igneous, talc, basalt Using a granular inorganic material such as, as a filler and mixing them by adding water, a curing agent, etc., and then molding into a desired shape and curing curing to propose a hard fire-resistant sound insulating material. Republic of Korea Patent No. 10-0547951 is made of 30 to 70% by weight of phosphate gypsum annealed at a high temperature of 150 ~ 800 ℃ to stabilize the pollutants impregnated with moisture removal as a main material, cement loess or kaolin And a foamed concrete mortar composition having a non-combustible, heat-insulating, warming, sound-absorbing and sound-proofing function using a bubble foam in a feldspar powder and cured with concrete or the like to have a non-flammable, heat-insulating, and insulating function. Republic of Korea Patent No. 10-0764632 proposed a method of manufacturing a thermal insulation material using haemulseok. The patent document relates to a method for manufacturing a thermal insulation material which is prepared by mixing a pulverized stone, a foaming agent, water, and clay, and then performing a standing, drying, and waterproofing process, wherein the vesicular stone (50 to 70 wt%) and clay (7.5 to 12.5 wt%) ) And a blowing agent (5-12% by weight) are added to a mixture of manganese (7.5-12.5% by weight) and water (10-13% by weight) and dried at a temperature of 1270-1460 ° C. for 1-4 hours. It is disclosed that it can be obtained. Since the method needs to be carried out at a foam firing temperature of 1270 to 1460 ° C., there are many problems in practical use in terms of economic efficiency as a process requiring very high energy. There is a patent on the development of the thermal insulation insulating material by the organic-inorganic complex, but fundamentally different from the concept of the present invention. Republic of Korea Patent No. 10-0534091 relates to a urethane insulation made of a mixture of inorganic materials and urethane resin, the inorganic material is glass wool (glass wool), asbestos (mineral wool), rock wool, chemical fiber (waste fiber) or By using vegetable fiber (straw straw, straw, barley straw, sugar cane, waste cotton, etc.), by mixing inorganic materials and urethane foam resin at a certain ratio, the durability of the insulation is increased and the flame resistance is increased, as well as the tensile strength. And it is disclosed a urethane insulation material and a method of manufacturing the urethane insulation material excellent in compressive strength, light insulation material is easy to transport, excellent soundproofing and heat insulation, and does not burn well. It is difficult to expect the characteristics of the heat resistance fire resistance of the inorganic insulating material.

It is not easy to find the prior art related to thermal insulation using a new concept of organic-inorganic composite materials through various materials through non-patent literature. Although we are studying this concept, the technology itself is still in its infancy. A study on slurry foam related to the present invention has been reported. In 1998, Park Jae-gu and Lee Jung-sik (Journal of the Korean Ceramic Society 36 (12), pp 1280 ~ 1285) prepared porous bodies with porosity of 70 ~ 75% by foam molding of highly dispersed dispersion slurry of aging, silica and fly ash. The purpose of this study is not to directly manufacture thermal insulation materials, but to find a reactor for producing porous bodies by foaming three phases of slurry in solid, liquid, and gaseous phases, and maximizing the characteristics of the pores. 2004 T. Kavas, E.Sabah, M.S. Celik studied the change of structural characteristics according to the mixing ratio by mixing haemulseok into cement. In the case of adding 10% of the haemulseok, the haemulstone is reported to act as a fiber to the cement, thereby enhancing the mechanical and physical properties of the cement mortar. In 2007, Ilker Bekir Topcu and Burak Iskdag (Building & Environment 42, pp. 3450-3546), Turkey, influenced the manufacturing parameters on the process of producing lightweight thermally conductive bricks containing 30% pearlite in cement, clay and limestone. And the relationship between their effect on the mechanical properties of bricks manufactured.

An object of the present invention is to provide a new concept of thermal insulation material having a high degree of non-combustibility, high heat resistance, toxic gas generation and organic thermal insulation material, which is an advantage of the existing inorganic thermal insulation material, and has a high thermal insulation and soft properties. It is to provide a method of manufacturing using the use.

Another object of the present invention is to provide a light weight soft ceramic thermal insulation material having both the advantages of the inorganic thermal insulation material and the organic thermal insulation material produced by the above method.

In order to solve the above problems, the present invention provides a method of manufacturing a ceramic thermal insulation insulating material comprising the following steps.

1) adding water to the inorganic fibers and de-smiling to make a fibrous slurry (step 1):

2) adding and mixing a particulate inorganic material on the slurry fiber (step 2);

3) adding a blowing agent to the mixture of step 2) and mixing (step 3); And

4) preparing a ceramic foam by heat-treating the mixture of step 3) in a mold to raise the temperature from 25 ℃ to 300 ℃ (step 4).

In step 1, water is added to the inorganic fiber and processed to make a slurry fibrous shape by adding water to the inorganic fiber, and adding water to the inorganic fiber to release the entangled or agglomerated fibrous strands to form a slurry fiber phase.

The term 'inorganic fiber' used in the present invention is a general term for an inorganic fiber, and refers to glass fiber, metal fiber, rock fiber, slag fiber and the like. It is characterized by high heat resistance, and is mainly used for applications such as heat dissipation, heat resistance, and sound insulation.

In the present invention, the inorganic fiber may be one or more selected from the group consisting of haemulseok fiber, aluminum silicate fiber, rock wool, aluminum oxide fiber and glass fiber, but is not limited thereto.

The mixing ratio of the inorganic fiber and water in step 1) is preferably 20 to 95 parts by weight: 100 to 800 parts by weight.

It is preferable to further add a surfactant together with water in step 1). At this time, it is preferable that the addition amount of surfactant is 0.01-5 weight part.

The surfactant used in step 1) may be used in combination of any one or more of anionic surfactant, cationic surfactant, or nonionic surfactant, and the type of the surfactant is not limited.

Step 2 is a step of adding and mixing the particulate inorganic material on the fiber in the slurry state, the step of adding and mixing the particulate inorganic material on the fiber in the slurry state prepared in step 1).

The term 'particulate inorganic material' used in the present invention means a material of an inorganic material having a particle shape.

In the present invention, it is preferable that the particulate inorganic material has a low thermal conductivity in terms of heat insulation performance. Specifically, the particulate inorganic material is expanded pearl rock, silica sand, pearl rock, haemulseok, beginner stone, kaolin, quartz, jadeite, plagioclase, ignite, talc, basalt, geumgangsa, fluorspar, feldspar, zeolite, vermiculite, diatomaceous earth, volcanic ash, silicate clay, It may be one or more selected from the group consisting of tuff, calcined clay, shale and mica, but is not limited thereto.

In the present invention, the particulate inorganic material may be in the form of a powder or granules granulated therewith.

In the present invention, the amount of the particulate inorganic material added is preferably 5 to 80 parts by weight.

It is preferable to further add a dispersant together with the particulate inorganic material in order to uniformly mix the fibrous and particulate inorganic materials in step 2). Carboxylic acid is effective in dispersing agents. Formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, benzoic acid, heptanoic acid, propargic acid, acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, oxalic acid, malonic acid, succinic acid, glutamic acid In the group consisting of taric acid, adipic acid, pimelic acid, cork acid, azelaic acid, sebacic acid, maleic acid, phthalic acid, terephthalic acid, tartaric acid, citric acid, malic acid, ascorbic acid, cyclohexenic acid, cyclopentenoic acid and isomers thereof It is also possible to use one or two or more. At this time, it is preferable that the addition amount of a dispersing agent is 0.1-5 weight part.

In step 3, a foaming agent is added to and mixed with the mixture of step 2), and a foaming agent is added and mixed with the mixture of the fibrous and particulate inorganic materials.

As used herein, the term 'foaming agent' refers to a material that generates bubbles by generating gas when forming a foam. That is, in step 4), both organic and inorganic blowing agents capable of generating gas by being decomposed in the corresponding temperature range according to the heat treatment may be used. Specifically, the blowing agent may be at least one selected from the group consisting of ammonium persulfate, sodium bicarbonate, ammonium sulfate, sodium bisulfate, anionic surfactant, cationic surfactant and nonionic surfactant, more preferably organic blowing agent However, the present invention is not limited thereto.

In the present invention, the amount of the blowing agent added is preferably 0.1 to 5 parts by weight.

In addition to the blowing agent in step 3), it is preferable to further add a blowing aid consisting of one or more of a binder and a thickener.

In the present invention, the binder serves as an adhesive for bonding the island fiber and the fibrous bond, the island fiber and the particulate inorganic material.

Specifically, the binder may be one or a mixture of water glass or colloidal silicate, but is not limited thereto.

In the present invention, the amount of the binder added is preferably 0.1 to 5 parts by weight.

In the present invention, the thickener functions to suppress leakage of the gas phase component causing foaming rapidly between the fibrous phases.

Specifically, the thickener is carboxy methyl cellulose (CMC), methyl cellulose (methyl cellulose, MC), hydroxy ethyl cellulose (HEC) and hydroxy propyl methyl cellulose (hydroxy propyl methyl cellulose, HPMC) may be one or more selected from the group consisting of, but is not limited thereto.

In the present invention, the amount of the thickener added is preferably 0.1 to 5 parts by weight.

In the mixing of the entire raw materials of steps 1) to 3), the mixing ratio of the inorganic fiber: water: particulate inorganic material: foaming agent is 20 to 95 parts by weight: 100 to 800 parts by weight: 5 to 80 parts by weight: 0.1 to 5 It is preferable that it is a weight part.

Step 4 is a step of preparing a ceramic foam by heat-treating the mixture of step 3) in a mold to increase the temperature from 25 ℃ to 300 ℃, maintaining a high viscosity of the mixture of the fibrous and particulate inorganic material to which the blowing agent is added It is a step of preparing a ceramic foam by injecting into a mold in a slurry state to be heated to heat up to a predetermined temperature.

As used herein, the term 'temperature increase' means to gradually increase the temperature.

The heat treatment of step 4) includes a drying and preheating step (step 3-1) from 25 ° C to 100 ° C and a foaming step (step 3-2) from 100 ° C to 300 ° C. In step 3-1, about 60 to 80% by weight of water in the mixture of the fibrous and particulate inorganic materials to which the foaming agent in the slurry state is added is removed, and foaming occurs in the step 3-2.

In the present invention, it is preferable to further include a step (step 5) of stabilizing the ceramic foam by heat treatment after the step 4) from 300 ℃ to 400 ℃.

Step 5 is a step of stabilizing the ceramic foam by raising the temperature and heat treatment from 300 ℃ to 400 ℃, decomposes the organic matter remaining in the ceramic foam foamed in the previous step by stabilizing the molded body by raising the temperature from 300 ℃ to 400 ℃ This is the step. The actual temperature for forming the ceramic foam is sufficient to form a stable ceramic foam even if the temperature is raised to 300 ℃ only, but up to 400 ℃ for the complete decomposition of the remaining organic matter when excessive amounts of organic components such as blowing agent, dispersant, thickener, etc. are used. It is preferable to carry out sufficient stabilization by raising the temperature, but it is not necessary.

In the present invention, it is preferable to further include a step (step 6) of cooling the ceramic foam to 50 ° C. or lower after step 5).

Step 6 is a step of cooling the high-temperature ceramic foam to 50 ℃ or less to complete the ceramic foam.

Since the method of manufacturing the ceramic thermal insulation material according to the present invention requires heat treatment up to 400 ° C., it is preferable from an economical point of view as compared with the conventional production method requiring high heat treatment of 1000 ° C. or higher.

The foam of the present invention should be easily separated from the mold. In the step conditions of the present invention, since the raw material mixture in the slurry state is not sintered or fused in the temperature range in which the heat treatment proceeds, there is no big problem in separation, but for convenience of operation, as using a hemp cloth, nonwoven fabric, basalt fiber cloth, metal It is possible to pour various types of high heat resistant fabrics that can withstand up to 400 ° C. such as fiber cloth, metal mesh, textile mineral fiber cloth, aluminum foil, etc. on the floor to pour a slurry of raw material mixture, and to remove lightly after foaming.

The foam to be produced in the present invention is not possible to use the furnace of the type such as rotary kiln, since the raw material is contained in the molding mold in the form of slurry before foaming, it is necessary to use the furnace of the type such as tunnel kiln or to dry and preheat It is characterized in that it is used to connect a plurality of furnaces so that the preheating process and the heating for foaming can be separately and continuously.

In addition, the present invention provides a ceramic insulating insulation prepared by the above manufacturing method.

The ceramic thermal insulation insulating material of the present invention is a soft ceramic thermal insulation insulating material having characteristics such as high heat resistance, light weight, flexibility, fire resistance, and sound insulation. In particular, the ceramic thermal insulation material of the present invention is characterized by having a strong fire resistance does not catch up to 650 ℃. In addition, due to the soft properties it can be easily cut with a knife, etc. has the advantage of easy construction. Furthermore, the ceramic thermal insulation material of the present invention is an environmentally friendly and harmless ceramic thermal insulation material containing no asbestos. Therefore, the ceramic thermal insulation material of the present invention may be referred to as an environmentally friendly thermal insulation material that can replace the thermal insulation material of the urethane material of the existing soft properties.

Due to the above characteristics, the ceramic thermal insulation material of the present invention can be used as a sound insulation material for interlayer noise blocking as well as a thermal insulation material for building.

Hereinafter, the configuration of the present invention will be described in detail with reference to the accompanying drawings.

The present invention is a lightweight, high thermal insulation and soft properties of the advantages of the non-combustible, high heat resistance, toxic gas generation and the organic insulation insulation of the advantages of the existing inorganic insulation thermal insulation material eco-friendly and low energy use It is intended to provide a method of manufacture using the same.

The manufacturing method of the present invention is not easy because the process of manufacturing the thermal insulation material using the organic material or the inorganic material and the material itself is mutually opposite to each other in the present concept also contrary to each other. However, a review of the process, focusing on organic and inorganic materials, reveals the possibilities and conditions for obtaining answers. For example, in the case of manufacturing thermal insulation materials using inorganic materials as raw materials, high heat resistance, incombustibility, and no generation of toxic gases may be inherently produced, but have low heat insulation, hardness, and high weight. The foaming process can be introduced as a representative way to avoid the disadvantages of inorganic materials at the same time, but this requires a large amount of high energy because the inorganic raw materials must be introduced in a molten state, so it is a low energy efficiency and high carbon generation method. Becomes On the contrary, when organic materials are used as raw materials, they may inherently have high thermal insulation, light weight, and soft properties, but are easily destroyed or combusted at high temperatures, and have low heat resistance and decomposition. To solve this problem, various methods such as the introduction of flame retardants have been proposed, but there are no countermeasures to date. In the future, high heat-resistant polymer materials similar to inorganic ceramics may be developed to solve this problem, but economic problems will be inevitable, and heat resistance of organic materials may be increased due to the development of materials science and technology. It is predicted that high heat resistance will never be obtained.

From this point of view, for the purpose of the invention, the basic material system for manufacturing a new concept of thermal insulation material having non-combustible, high heat resistance, no toxic gas generation, high thermal insulation, and soft characteristics should be an eco-friendly inorganic ceramic material that is harmless to human body. In addition, the inorganic ceramic material should be foamed, but it should be performed at a temperature much lower than the melting point of the ceramic material or at the melting point of the organic material.

In order to be a foam, a gaseous phase must be generated in the target solid-state application, and this is called a bubble, and a bubble group in which a bubble film is formed between bubbles is generally called a foam or a cell. . In general, a method for preparing an inorganic solid foam is to completely surround the blowing agent while the inorganic particles present around the blowing agent are melted and stuck together with the blowing agent in the center at the melting point, and the foaming agent surrounded by the molten mineral is almost simultaneously. When gas is decomposed by itself or reacted with minerals, the gas expands, causing the molten minerals surrounding the blowing agent to expand, resulting in foaming. Then, the foamed state is quenched so that the expanded-melted inorganic material is stabilized, thereby producing an inorganic foam. However, the foaming process for producing a lightweight, flexible soft ceramic thermal insulation material of the present invention is not made of a conventional inorganic foam, such as a manufacturing process, such as foam glass.

Heat treatment temperature conditions in the present invention is a temperature range of 25 ~ 400 ℃ at this temperature does not melt any of the inorganic components presented in the present invention. The foam in the present invention allows the inorganic fibrous phase to maintain the skeleton of the foam and the blowing agent present in the fibrous skeleton to generate gas at low temperatures to expand and cause the fibrous minerals to expand and form cavities and to form a cavity. The foam is manufactured by filling lightweight, low thermal conductivity inorganic particles such as expanded pearlite, vermiculite, and the like. That is, the fiber-like ceramic material is processed to form a slurry in which inorganic fibers having a diameter of several microns are dispersed well, and then, the lightweight ceramic powder and foaming agent having a low thermal conductivity in the form of particles, and the foaming agent and the selective fiber are formed into the slurry. By maintaining a high viscosity slurry state by mixing a binder, a thickener and the like that can increase the foaming efficiency. In this state, the primary moisture is evaporated and removed through heat treatment, so that the mixed phase in the slurry state becomes a more viscous slurry ceramic fiber structure, and the gas escapes out of the ceramic fiber structure at a higher temperature to generate gas from the blowing agent. Becomes difficult. The bubbles thus generated are present as they are through the subsequent heat treatment process to form pores, or escape through the fibers to form waste or open pores to form a foam.

The ceramic foam formed as described above has the flexibility and ductility because the skeleton is formed in a fibrous shape, and also has the performance of thermal insulation insulation due to waste pores and sound absorption and sound insulation due to open pores. In addition, the low thermal conductivity and lightweight particulate inorganic materials present between the ceramic fibers provide mechanical stability of the obtained foam and further enhance the thermal insulation performance.

Therefore, the most important starting point for the manufacture of the lightweight, flexible, flexible ceramic thermal insulation pad of the present invention is to resolve the ceramic material to be an inorganic fiber of long fiber, and in this respect, a diameter of 20 to 200 nm Asbestos, an elongated fiber having a length of 50 μm, may be a very effective inorganic fiber, but asbestos is not preferable because its use is limited as a deadly environmental regulating material. Other inorganic fiber groups that can substitute for this may be a role such as calcite fiber, aluminum silicate fiber, aluminum oxide fiber, rock wool or glass fiber. Among them, especially Sepiolite fibers are 10 times thicker than asbestos fibers, but because the specific crystals remain connected in an irregular lattice shape, the foaming reaction mechanism of the present invention is high due to the thickening ability and high binding strength of the fibers themselves. It is the most efficient mineral fiber for.

1 is a flow chart showing step by step the manufacturing method of the ceramic thermal insulation material according to the present invention.

In step 1) of the method for preparing a ceramic thermal insulation material, the inorganic fiber serves to form a basic skeleton for manufacturing a ceramic thermal insulation material or a pad of light weight, flexibility, fire resistance, and soft state. Therefore, they consist of one or more of pulverized stone fibers, aluminum silicate fibers, rock wool, aluminum oxide fibers, and glass fibers, and if they are selected as one, they serve as the skeleton of the foam, but one is used when two are used. The other, but skeletal role is to serve as a link between the skeleton and the mutual support (see Figure 4).

The quantity of these inorganic fibers which comprise the heat insulating material aimed at by this invention is adjusted so that it may be 20-95 weight part based on 100 weight part of total amounts of an inorganic fiber and a particulate inorganic material. When the inorganic fiber is less than 20 parts by weight, the final product of the thermal insulation material or thermal insulation pad is easily broken due to the lack of fibrous shape, and when the inorganic fiber is more than 95 parts by weight, the inorganic component that can increase the thermal insulation is lowered. This may be degraded and not appropriate.

The sea fiber process of these inorganic fibers is a very important process to maintain a constant shape of the thermal insulation material that is the object of the invention. The amount of water in the sea island process is a very important factor, 100 to 800 parts by weight based on 100 parts by weight of the total amount of inorganic fibers and particulate inorganic materials required for manufacturing the ceramic thermal insulation material of the present invention. If the amount of water is less than 100 parts by weight, the fluidity of the water and the fiber mixture is insufficient, making it difficult to seam the fibers, and as the amount of water increases, the fluidity becomes better, and the islanding becomes easier. However, if it is more than 800 parts by weight, sea island efficiency is not better, but it is not appropriate because the amount of water to be evaporated during heat treatment increases.

The addition of surfactants during the decoction process is very effective and can be used alone or in combination with anionic surfactants, cationic surfactants or nonionic surfactants. That is, it is not greatly affected by the type or form. An appropriate amount of addition is suitably 0.01 to 5 parts by weight based on 100 parts by weight of the total amount of the inorganic fibers and the particulate inorganic material required for producing the ceramic thermal insulation insulating material of the present invention. That is, the necessity of the surfactant in the sea island process is not absolute, but it is preferable to use because it takes more than twice as long as compared with the case without addition. Furthermore, the surfactant used is preferably added as it functions as a blowing agent in the foaming process. If the amount of surfactant is less than 0.01 part by weight, the effect of surfactant activity does not occur. If the amount of surfactant is more than 5 parts by weight, the effect does not increase with the addition of more than one part, but is inadequate due to foaming due to excessive usage. .

In step 2), a lightweight particulate inorganic material having low thermal conductivity is added to and mixed with the slurry-form ceramic fiber prepared in step 1) in order to enhance the thermal insulation, heat insulation and heat resistance properties of the thermal insulation material. In addition, depending on the inorganic material additionally selected, the function of sound absorption or sound insulation can also be expected. For this purpose, expanded pearl rock, silica sand, pearl rock, pulverized stone, rudimentary stone, kaolin, quartz, gemstone, plagioclase, fluorite, talc, basalt, geumgangsa, fluorspar, feldspar, zeolite, vermiculite, diatomaceous earth, volcanic ash, silicate, tuff, calcined clay Various materials such as shale, mica, and the like are added in one or more trillions of powders or granulated granules and mixed with the fibrous form of the slurry prepared in step 1). The particulate inorganic material may not be added at all depending on the purpose and purpose, but in order to maximize the thermal insulation effect, the particulate inorganic material having a thermal conductivity lower than that of the fibrous material is preferably preferred. 5 to 80 parts by weight based on 100 parts by weight of the total amount of the inorganic fiber and the particulate inorganic material required for preparing the ceramic thermal insulation material of the present invention can be mixed. When more than 80 parts by weight is mixed, not only the particles cannot be bonded to each other, but also the amount of the inorganic fiber that binds them is relatively insufficient in the total solid content of the thermal insulation material or thermal insulation pad manufactured to maintain the shape It can't be broken easily. In addition, when less than 5 parts by weight is mixed, since the particles having a lower thermal conductivity than fibrous is less, it is difficult to insulate the thermal insulation, heat insulation and heat resistance properties as a thermal insulation.

The dispersant used in step 2) has a characteristic that the fibrous forms are entangled with each other when the fibrous phases are stirred, so as to facilitate mutual dispersion of the fibrous and particulate inorganic materials. It is also preferable to add a dispersant because some of the surfactants used as blowing agents and the colloidal silicates used as adhesives in step 3) exhibit anionic properties and their performance may be halved due to cations. Carboxylic acid is effective in dispersing agents. Formic acid, acetic acid, propionic acid, butyric acid, pentanoic acid, hexanoic acid, benzoic acid, heptanoic acid, propargic acid, acrylic acid, methacrylic acid, ethacrylic acid, crotonic acid, oxalic acid, malonic acid, succinic acid, glutamic acid In the group consisting of taric acid, adipic acid, pimelic acid, cork acid, azelaic acid, sebacic acid, maleic acid, phthalic acid, terephthalic acid, tartaric acid, citric acid, malic acid, ascorbic acid, cyclohexenic acid, cyclopentenoic acid and isomers thereof It is also possible to use one or two or more. At this time, it is preferable that the addition amount of a dispersing agent is 0.1-5 weight part.

Due to the addition of acid prior to addition of the blowing agent and the binder of ceramic fiber, if dispersed in water, a typical Fe ^{3 +,} or other transition metal cations been precipitated with a combination of carboxylic acid and is dropped prevent the degradation of the blowing agent and the adhesive . The amount of the dispersant should be 0.1 parts by weight or more based on 100 parts by weight of the total amount of the inorganic fibers and the particulate inorganic materials required for the manufacture of the ceramic thermal insulation material of the present invention. There is no big difference. Since a large amount of bubbles may occur when the dispersant is added, it is preferable to add small portions. In this case, dissolving the dispersant first in water and adding the solution reduces the occurrence of bubbles.

In step 3) the foaming aid consists of a binder and a thickener for viscosity control. The binder acts as an adhesive for bonding the fibrillated fibrous and fibrous bonds, and the fibrillated fibrous and particulate inorganic materials. For this purpose, various forms of colloidal silicates, including water glass, can be used. The amount of the binder is suitably 0.1 to 5.0 parts by weight based on 100 parts by weight of the total amount of the inorganic fiber and the particulate inorganic material required for the manufacture of the ceramic thermal insulation material of the present invention, and when more than 5.0 parts by weight is added, the ductility of the foam is lowered and foamed. It is not preferable because the efficiency is poor.

Thickeners play a very important role in the foaming process because they function to suppress the rapid leakage of gaseous components that cause foaming between the fibrous phases. In the present invention, the inorganic fibers or particulate inorganic materials constituting the thermal insulation material are not melted and become liquid in the temperature range of 25 to 400 ° C., which is a temperature range of the heat treatment process of the present invention. However, since it is not easy to suppress the leakage of the gaseous product that acts as a solid particle or fibrous state, it is difficult to expect foaming due to the overall expansion of the solid. Therefore, an appropriate thickener is required to maintain the viscosity required for foaming in the whole mixed mixture of the slurry-like ceramic fibers and the particulate inorganic material prepared in step 2). As the thickener suitable for the present invention, ester-based cellulose groups can be used and are widely used. Carboxymethyl cellulose (CMC), methyl cellulose (MC), hydroxyethyl cellulose , HEC) and hydroxy propyl methyl cellulose (HPMC) may be used together with one or more of them. An appropriate amount of addition is appropriately 0.1 to 5.0 parts by weight based on 100 parts by weight of the total amount of the inorganic fibers and the particulate inorganic material required for the manufacture of the ceramic thermal insulation material of the present invention. The thickener is effective in increasing the viscosity even at low temperatures, but adding more than 5.0 parts by weight does not significantly change the physical values of the foam such as density, porosity, and flexural strength. In particular, the common feature of cellulose thickeners is that the thickening effect is reduced at high temperatures, so that the effect is not greatly increased even if a large amount of thickener is added at 100 to 200 ° C., where foaming may occur, but rather carbonization of organic thickeners. This is not suitable because it may adversely affect the foam, such as gas generated.

The blowing agent can be used both organic and inorganic blowing agents capable of generating gas by decomposing at a temperature of 100 ° C. or more, which can be called a foaming step, within a range of heat treatment temperatures. Representative inorganic blowing agents can be used in the carbonate series such as ammonium persulfate, sodium bicarbonate, ammonium sulfate, sodium bisulfate, sulfate type and ammonium salt series, which have a decomposition temperature not exceeding 300 ° C. The more active the agent is and the easier it is to form bubbles, the better. They can also be used alone or in combination. Of these, anionic surfactants are effective, and sulfate, sulfonate or sulfosuccinate series are more effective. The addition amount of these is suitably 0.1 to 5.0 parts by weight based on 100 parts by weight of the total amount of the inorganic fibers and the particulate inorganic material required for producing the ceramic thermal insulation material of the present invention. If the amount of the blowing agent is less than 0.1 part by weight, the foaming effect is insignificant, which makes it difficult to form the foam, and the distribution of pores in the foam is irregular. If the amount of the blowing agent is more than 5.0 parts by weight, more droplet bubbles are formed on the slurry. It forms, over-foams, carbonizes during heat treatment, and also deforms to a degree that the mechanical strength of the foam cannot be measured.

In step 4), the mixed phase of the inorganic fibrous and particulate inorganic materials to which the blowing agent prepared in step 3) is added is transferred to a molding mold in a slurry state in which high viscosity is maintained, and then shaped and reduced by heat treatment, thereby making it lightweight, flexible, and fire resistant. A ceramic thermal insulating material having a soft state is manufactured.

The heat treatment is carried out at a temperature rising from 25 ° C to 300 ° C by introducing the raw material mixture on the slurry contained in the mold. At this time, the drying and preheating to remove 60 to 80% by weight of moisture in the slurry occurs in the temperature range of 25 ~ 100 ℃, foaming occurs while maintaining the high viscosity of the slurry in the temperature range of 100 ~ 300 ℃. In addition, it is then possible to remove the residue in the foamed ceramic and to stabilize the foam by heat treatment at elevated temperature from 300 ℃ to 400 ℃.

Finally after the heat treatment, the step of cooling the foam to below 50 ° C., preferably to room temperature, may be further carried out.

During the heat treatment process, the foam to be produced in the present invention is a raw material is contained in the formwork in a slurry form before foaming, it is impossible to use a rotary kiln and must use a furnace of the same type as the tunnel kiln. Therefore, the furnace to be subjected to the heat treatment step of step 4) has a water vaporization part whose temperature is adjusted to 25 to 100 ° C. and a foaming process part whose temperature inside the furnace is controlled to 100 to 300 ° C., and then stabilized. It is preferable that it is a turnnel kiln consisting of a stabilization process unit for which the temperature is raised up to 400 ° C. or a continuous process furnace capable of continuously heating for foaming and preheating for drying and preheating.

After the step 4), the foamed pad-shaped bulk foam may be removed from the mold to obtain a ceramic foam having a light weight and flexibility. Since the raw material mixture in the slurry state during the heat treatment process of step 4) is not sintered or fused at the heat treatment temperature range of less than 400 ° C. during the heat treatment, there is no big problem in separating the foam from the mold, When using a hemp cloth, such as basalt fibres, etc., or a variety of high-temperature fabrics, aluminum foil, etc. that can withstand the heat treatment if the temperature is less than 400 ℃ It is possible to pour a slurry of raw material mixture after application and to lightly remove it after the foaming process. In addition, preferably, the molding die itself may be made of a galvanized steel sheet, iron, aluminum, stone, or the like, and may be composite panelized or sandwich paneled by attaching or pressing internal and external materials without being removed from the foam after the foaming process.

According to the method of manufacturing a lightweight, flexible and flexible ceramic thermal insulation or insulating pad according to an embodiment of the present invention, the general inorganic ceramic thermal insulation can be produced at a high temperature of about 1000 ℃, even though it is a ceramic material Nevertheless, the foam can be manufactured under the temperature of 400 ℃ or less, so the energy efficiency can be maximized. Even if the production is made under the temperature, the fire resistance is excellent up to 600 ℃. It can be expected to produce the interior and exterior materials for construction of excellent soft ceramic material. In addition, it does not use asbestos material, which is harmful to the human body, and it is ceramic, but it has soft characteristics, so it is easy to deform and process, and additional processing is easy to have waterproof and weather resistance. It can manufacture.

1 is a flow chart showing step by step the manufacturing method of the ceramic thermal insulation material according to the present invention.
Figure 2 is a cross-sectional photo of both sides of the ceramic thermal insulation insulating material prepared according to an embodiment of the present invention.
Figure 3 is a photograph of the inner surface of the ceramic thermal insulation material prepared in accordance with an embodiment of the present invention examined through a phase analyzer.
Figure 4 is a photograph showing the appearance of the internal fibrous structure of the ceramic thermal insulation material prepared according to an embodiment of the present invention irradiated through an electron microscope. Where a is the x500 magnification and b is the x5,000 magnification.

Hereinafter, the present invention will be described in more detail with reference to Examples. These embodiments are only for describing the present invention more specifically, and the scope of the present invention is not limited by these examples.

Example  One

60 g of inorganic mineral fiber pulverized stone and 1 g of dioctyl sodium sulfosuccinate as a surfactant were added to 400 ml of water, and heated in a mechanical stirrer to maintain the temperature of the stirring tank at 80-90 ° C., at a speed of 1000 rpm. Desquamation for hours resulted in the formation of the vesicle fibers in slurry. During the island treatment, water was replenished as much as water evaporated to allow the island to proceed easily. 25 g of aluminum silicate fiber and 15 g of expanded pearlite were added to the calcified stone fibers in the slurry state, and the mixture was further stirred for 30 minutes under the same stirring conditions. Then heating was stopped and oxalic acid was added in an amount of 1.5 g as a dispersant and mixed for 10 minutes under the same stirring conditions. At this time, a large amount of foam occurs, so slowly added in small amounts. And 3g of colloidal silica (colloidal silica) as an adhesive, 2g of cellulose as a thickener, 2g of dioctyl sodium sulfosuccinate as a blowing agent was added and stirred and mixed for 10 minutes to mix well. The slurry mixture was placed in dies coated with aluminum foil (10 × 10 × 5) and loaded into a tunnel kiln controlled at a temperature ranging from 25 ° C. to 300 ° C. The mineral mixture on the slurry in the formwork was dried, preheated, foamed, cooled to leave the tunnel kernels and then the foam was separated from the formwork to obtain a ceramic foam.

Example  2

50 g of inorganic mineral fiber pulverized stone, 40 g of aluminum silicate fiber, 1 g of sodium lauryl sulfate as a surfactant was added to 400 ml of water, and heated in a mechanical stirrer to keep the temperature of the stirring tank at 80-90 ° C. to prevent foaming. The alveolar fibers were slurried by disintegrating for 24 hours at a slow stirring speed of 500 rpm. During the island treatment, water was replenished as much as water evaporated to allow the island to proceed easily. 10 g of vermiculite was added to the dissolved calcite fibers in the slurry state, followed by further mixing and stirring for 30 minutes under the same stirring conditions. Then, the heating was stopped and 2.0 g of oxalic acid was first dissolved in 100 ml of water as a dispersant, and the oxalic acid solution thus obtained was slowly added and mixed under the same stirring conditions for 10 minutes. At this time, a large amount of foam occurs, so slowly added in small amounts. And 3g of colloidal silica (colloidal silica) as an adhesive, 2g of cellulose as a thickener, 2g of dioctyl sodium sulfosuccinate as a blowing agent was added and stirred and mixed for 10 minutes to mix the components well. The slurry mixture was placed in dies coated with aluminum foil (10 × 10 × 5) and loaded into a tunnel kiln controlled at a temperature ranging from 25 ° C. to 350 ° C. The inorganic mixture on the slurry in the formwork was dried, preheated, foamed, stabilized and cooled to leave the tunnel kernels and then separated from the formwork to obtain a ceramic foam.

Example  3

45 g of inorganic mineral fiber pulverized stone, 40 g of aluminum silicate fiber, 2 g of dioctyl sodium sulfosuccinate as a surfactant was added to 500 ml of water, and heated in a mechanical stirrer to maintain the temperature of the stirring tank at 80-90 ° C., while stirring at 500 rpm. The calcined fibers were slurried by de-sintering for 24 hours. During the island treatment, water was replenished as much as water evaporated to allow the island to proceed easily. 10 g of expanded pearlite and 5 g of vermiculite were added to the pulverized calcite fiber in this slurry state, and the mixture was further stirred for 30 minutes under the same stirring conditions. Then, the heating was stopped and 2.0 g of oxalic acid was first dissolved in 100 ml of water as a dispersant, and the oxalic acid solution thus obtained was slowly added and mixed under the same stirring conditions for 10 minutes. At this time, a large amount of foam occurs, so slowly added in small amounts. And without adding a separate blowing agent 3g of colloidal silica (colloidal silica) as an adhesive, 2g of cellulose as a thickener was added and stirred and mixed for 10 minutes to mix the components well. The slurry mixture was placed in dies coated with aluminum foil (10 × 10 × 5) and loaded into a tunnel kiln controlled at a temperature ranging from 25 ° C. to 300 ° C. The mineral mixture on the slurry in the formwork was dried, preheated, foamed, cooled to leave the tunnel kernels and then the foam was separated from the formwork to obtain a ceramic foam.

Experimental Example  1: present invention ceramic Foam  Property investigation

The density, porosity, flexural strength, and thermal conductivity of the ceramic foams obtained in Examples 1 to 3 were measured, and the performance of the flexible ceramic foam having lightness, flexibility, and fire resistance was confirmed through thermal analysis and fire resistance test.

Physical properties of the foam are shown in Table 1 below.

division density
[g / cm 3] Porosity
[%] Flexural strength
[N / ㎠] Heat resistance
[° C] Thermal conductivity
[kcal / mhr ℃] Hazardous Gas Generation Example 1 0.12 84 1.9 620 0.037 Not at all Example 2 0.11 86 1.8 620 0.040 Not at all Example 3 0.11 89 1.7 620 0.039 Not at all

The density and porosity of the foam are physical properties that can be indicative of light weight and thermal insulation. Flexural strength is a value representing the bending force to bend the sample to confirm the flexibility and softness of the foam. And heat resistance shows the thermal stability and maximum safe operating temperature of the foam measured by thermal analysis and fire resistance test. The ceramic foams obtained in Examples 1 to 3 exhibited almost similar physical properties. First of all, their density is 0.11 to 0.12 g / cm 3, which is lighter than or comparable to that of foamed glass obtained by a high temperature foaming process of about 1000 ° C., and the thermal conductivity is better than that of a conventional inorganic thermal insulating material. And the texture is excellent soft softness compared to the rigidity of the inorganic thermal insulating material and workability did not lag behind the organic thermal insulating material. However, the highest safe operating temperature, which is the standard of heat resistance, is higher than 600 ℃, and shows excellent heat resistance characteristics compared to organic thermal insulation materials which are 70 ~ 110 ℃.

Although the present invention has been described with reference to certain preferred embodiments, the present invention is not limited to the above-described embodiments and is provided to those skilled in the art without departing from the concept of the present invention. Various changes and modifications are possible by this.

Claims (12)

Method of manufacturing a ceramic thermal insulation insulating material comprising the following steps:
Adding water to the inorganic fibers and processing them to form a slurry fiber phase (step 1):
Adding and mixing a particulate inorganic material on the slurry fiber (step 2);
Adding a blowing agent to the mixture of step 2) and mixing (step 3); And
Step (4) to prepare a ceramic foam by heat-treating the mixture of step 3) in a mold to increase the temperature from 25 ℃ to 300 ℃.
The method according to claim 1, wherein the inorganic fiber is at least one selected from the group consisting of haemulstone fibers, aluminum silicate fibers, rock wool, aluminum oxide fibers, and glass fibers.
The method according to claim 1, wherein the surfactant is further added together with water in the step 1).
According to claim 1, wherein the particulate inorganic material is expanded pearlstone, silica sand, pearl rock, haemulseok, rumen, kaolin, quartz, jadeite, plagioclase, igneous, talc, basalt, geumgangsa, fluorspar, feldspar, zeolite, vermiculite, diatomaceous earth, volcanic ash, A method for producing a ceramic thermal insulation material which is at least one member selected from the group consisting of silicate clay, tuff, calcined clay, shale and mica stone.
The method of claim 1, wherein the blowing agent is at least one selected from the group consisting of ammonium persulfate, sodium bicarbonate, ammonium sulfate, sodium bisulfate, and anionic surfactant.
The method according to claim 1, wherein in step 3), a foaming aid composed of one or two or more of a binder and a thickener is additionally added together with the foaming agent.
The method of claim 6, wherein the binder is a colloidal silicate.
The method of claim 6, wherein the thickener is carboxy methyl cellulose (CMC), methyl cellulose (MC), hydroxy ethyl cellulose (HEC) and hydroxy propyl methyl cellulose (hydroxy propyl). methyl cellulose, HPMC) at least one member selected from the group consisting of, a method for producing a ceramic thermal insulation.
The method according to claim 1, wherein the mixing ratio of the inorganic fiber: water: particulate inorganic material: foaming agent is 20 to 95 parts by weight: 100 to 800 parts by weight: 5 to 80 parts by weight: 0.1 to 5 parts by weight to prepare a ceramic thermal insulation. Way.
The method of claim 1, wherein the heat treatment of step 4) comprises a drying and preheating step (step 3-1) from 25 ° C to 100 ° C and a foaming step (step 3-2) from 100 ° C to 300 ° C, Manufacturing method of ceramic thermal insulation material.
The method of claim 1, further comprising the step (step 5) of stabilizing the ceramic foam by heating and heating from 300 ° C to 400 ° C after step 4).
A ceramic thermal insulation material produced by the manufacturing method of any one of claims 1 to 11.

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