KR102638819B1 - Manufacturing method for porous silica-ceramic composite molded insulation product and porous silica-ceramic composite molded insulation products therefrom - Google Patents

Abstract

The present invention is to develop a lightweight insulation material with low thermal conductivity, excellent water repellency, and a porous silica-ceramic with high viscosity and solid content by mixing a first alcohol gel slurry using alcohol and a first water-soluble slurry using distilled water with an adhesive aqueous solution. The purpose is to manufacture a composite slurry and provide a porous silica-ceramic composite insulating molded product using it.

Description

Manufacturing method for a lightweight porous silica-ceramic composite insulation molded product with excellent thermal insulation and water repellency and a porous silica-ceramic composite molded insulation product manufactured therefrom products there from }

The present invention is to develop a lightweight insulation material with low thermal conductivity, excellent water repellency, and a porous silica-ceramic with high viscosity and solid content by mixing a first alcohol gel slurry using alcohol and a first water-soluble slurry using distilled water with an adhesive aqueous solution. The purpose is to manufacture a composite slurry and provide a porous silica-ceramic composite insulating molded product using it.

In automobiles and aircraft, parts placed near heat sources such as exhaust manifolds or on engine bulkheads are exposed to harsh thermal environments, including high-temperature radiant heat transfer. In particular, various insulation materials are used in electric vehicles and energy storage systems (ESS) to prevent or delay the transmission of thermal runaway to reduce damage from fire accidents.

Insulating materials are required to protect various components from such heat sources. Insulating materials are used in various industrial fields such as construction and ships, but in particular, insulating materials used in electric vehicles and energy storage systems require unique characteristics, such as insulating properties, water repellency, and lightness.

Looking at insulation materials according to the prior art, Korean Patent Publication No. 10-2019-0035032 includes water glass, fly ash, slaked lime, iron oxide, a foaming agent, and a waterproofing agent, and the content of iron oxide is 0.5 to 2 based on the total weight of the composition. A composition for room temperature molded ceramic insulation panels and a room temperature molded ceramic insulation panel manufactured using the same are disclosed, and in Korean Patent Publication No. 10-2020-0023125, a ceramic containing ceramic wool with improved flame spread prevention function is disclosed. A method for manufacturing a wool-embedded composite insulation material and a ceramic wool-embedded composite insulation material are disclosed.

Insulating materials according to the prior art have a problem in that water or binder penetrates into the pores of the porous powder used as an insulating material during the manufacturing process, and as the water or binder vaporizes inside the pores during the drying process, the pores shrink and the insulation of the final molded product deteriorates. There is. In addition, insulation materials using ceramic materials show hydrophilicity, which has the problem of deteriorating mechanical properties due to reduced cohesion between hydrophobic powders during the drying process after molding the slurry.

Accordingly, in order to protect batteries and surrounding electronic components, which are key components in electric vehicles or energy storage devices, there is a need for the development of insulating materials that can be molded into various shapes, are lightweight, and have excellent thermal insulation and water repellency.

The present invention is intended to provide a method for manufacturing a lightweight porous silica-ceramic composite insulating molded product that is moldable and has excellent thermal insulation and water repellency, and a porous silica-ceramic composite insulating molded product manufactured therefrom. However, the technical problem to be achieved by the present invention is not limited to the problems mentioned above, and other problems not mentioned will be clearly understood by those skilled in the art from the description below.

The method for manufacturing a lightweight porous silica-ceramic composite insulation molded product with excellent thermal insulation and water repellency according to the present invention is to manufacture a porous silica-ceramic composite insulation molded product, a) adding silica hydrogel and silylating agent to alcohol and stirring. By doing so, a first step of producing a silica hydrogel whose surface is treated with a silylating agent while the silylating agent is dissolved; b) a second step of separating the silica hydrogel, the surface of which is treated with a silylating agent, prepared in the first step from the alcohol in which the silylating agent is dissolved; c) a third step of removing moisture from the alcohol in which the silylating agent separated in the second step is dissolved; d) a fourth step of preparing an oil-based adhesive by mixing amino silane with alcohol containing a silylating agent from which moisture was removed in the third step; e) a fifth step of preparing a first alcohol gel paste by mixing and pulverizing the silica hydrogel, the surface of which was separated in the second step, treated with a silylating agent, and alcohol; f) a sixth step of mixing hydrophobic fumed silica powder and short fibers with the first alcohol gel paste prepared in the fifth step; g) a seventh step of preparing a second alcohol gel paste by mixing the first alcohol gel paste containing hydrophobic fumed silica powder and short fibers prepared in the sixth step with the oil-based adhesive prepared in the fourth step; h) an eighth step of preparing a first alcohol gel slurry by mixing ceramic powder with the second alcohol gel paste prepared in the seventh step; i) a ninth step of dissolving the inorganic binder in distilled water to prepare a water-soluble inorganic binder; j) a 10th step of preparing a first water-soluble paste by mixing ceramic powder and short fibers with the water-soluble inorganic binder prepared in the 9th step; k) an 11th step of preparing a first aqueous slurry by mixing potassium carbonate with the first aqueous paste prepared in the 10th step; l) Step 12 of preparing an aqueous adhesive solution by dissolving a water-soluble adhesive in distilled water; m) Step 13 of preparing a porous silica-ceramic composite slurry by mixing the first alcohol gel slurry prepared in the 8th step, the first water-soluble slurry prepared in the 11th step, and the adhesive aqueous solution prepared in the 12th step. step; n) a 14th step of manufacturing a molded product by molding the porous silica-ceramic composite slurry prepared in the 13th step in an extruder; and o) a 15th step of drying the molded product prepared in the 14th step, wherein the silylating agent is a group consisting of tetramethoxysilane, tetraethoxysilane, trimethoxymethylsilane, and trimethoxyethylsilane. and the ceramic powder included in the 8th and 10th steps is alumina, zeolite, zirconia, silicon carbide, silica, bauxite, bentonite, and alumina toughened zirconia. It is preferable that it is at least one selected from the group consisting of Zirconia) and Zirconia Toughened Alumina.

In addition, the average particle size of the first alcohol gel paste prepared in the fifth step is 30 to 100 ㎛, the average particle size of the ceramic powder is 0.1 to 100 ㎛, and the water-soluble adhesive in the 12th step is carboxymethyl cellulose and starch. , polyacrylamide, glycerin, flurane, superabsorbent polymer, and gelatin, and in the ninth step, the inorganic binder is at least one selected from the group consisting of sodium silicate, potassium silicate, and lithium silicate. , the alcohol is at least one selected from the group consisting of butanol, pentanol, heptanol, and ethylene glycol, and the molded article dried in the 15th step contains 7 to 20% by weight of silica hydrogel and 0.5 to 1.5% by weight of silylating agent. %, 0.05 to 0.7% by weight of amino silane, 12 to 15% by weight of hydrophobic fumed silica powder, 3 to 5.5% by weight of short fibers, 45 to 55% by weight of ceramic powder, and 10 to 15% by weight of inorganic binder. It may be preferable to consist of 3 to 7% by weight of potassium carbonate and 0.017 to 0.1% by weight of water-soluble adhesive.

The porous silica-ceramic composite insulation molded product according to the present invention is made by separately performing the first to eighth steps using alcohol and the ninth to twelfth steps using distilled water, thereby producing silica hydrogel used as a porous material. It prevents moisture and inorganic binders from penetrating into the pores of the fumed silica powder, minimizes the increase in thermal conductivity, and has the effect of being manufactured with excellent insulation properties.

In addition, by performing the steps separately as described above, it is possible to prevent a gel reaction that may occur when mixing alcohol and an inorganic binder and to prevent a decrease in strength due to wetting, which is a problem with inorganic binders.

In addition, the porous silica-ceramic composite insulating molded product manufactured according to the present invention can be manufactured through a molding process such as compression molding, making it possible to manufacture molded products with various shapes of two-dimensional or three-dimensional structures, and ceramic powder and By mixing porous materials, etc., it has the effect of enabling the production of molded products that have high insulation properties and excellent mechanical properties, and are lightweight and can be applied to insulation parts.

1 is a flow chart of the manufacturing process of a porous silica-ceramic composite molded product according to the present invention;
Figure 2 is a photograph (a) of a porous silica-ceramic composite slurry and a product photograph (b) of a porous silica-ceramic composite insulating molded product according to the present invention;
Figure 3 is a photograph testing the water repellency of the porous silica-ceramic composite insulation molded product according to the present invention.

In this application, terms such as “comprise,” “have,” or “equipped with” are intended to designate the presence of features, numbers, steps, components, parts, or combinations thereof described in the specification, and are not intended to indicate the presence of one or more other features, numbers, steps, components, parts, or combinations thereof. It should be understood that this does not exclude in advance the possibility of the presence or addition of features, numbers, steps, operations, components, parts, or combinations thereof.

Additionally, unless otherwise defined, all terms used herein, including technical or scientific terms, have the same meaning as generally understood by those skilled in the art to which the present invention pertains. Terms defined in commonly used dictionaries should be interpreted as having a meaning consistent with the meaning in the context of the related technology, and unless clearly defined in the present application, should not be interpreted in an ideal or excessively formal sense. No.

Below, preferred embodiments of the present invention will be described in more detail with reference to the attached drawings. In order to facilitate overall understanding when describing the present invention, the same reference numerals are used for the same components in the drawings, and duplicate descriptions for the same components are omitted.

Hereinafter, the method for manufacturing a lightweight porous silica-ceramic composite insulating molded product 200 with excellent thermal insulation properties according to the present invention and the porous silica-ceramic composite insulating molded product 200 manufactured therefrom will be described in detail with reference to the accompanying drawings. do. Figure 1 attached to the present invention is a flow chart of the manufacturing process of the porous silica-ceramic composite insulating molded article 200 according to the present invention, and Figure 2 is a photograph (a) of the porous silica-ceramic composite slurry 100 according to the present invention. ) and a product photo (b) of the porous silica-ceramic composite insulation molded product 200, and Figure 3 is a photograph testing the water repellency of the porous silica-ceramic composite insulation molded product 200 according to the present invention.

The method of manufacturing a lightweight porous silica-ceramic composite insulating molded product 200 with excellent thermal insulation properties according to the present invention is as shown in FIG. 1, a) adding silica hydrogel and silylating agent to alcohol and stirring, A first step of producing a silica hydrogel whose surface is treated with a silylating agent while the silylating agent is dissolved; b) a second step of separating the silica hydrogel, the surface of which is treated with a silylating agent, prepared in the first step from the alcohol in which the silylating agent is dissolved; c) a third step of removing moisture from the alcohol in which the silylating agent separated in the second step is dissolved; d) a fourth step of preparing an oil-based adhesive by mixing amino silane with alcohol containing a silylating agent from which moisture was removed in the third step; e) a fifth step of preparing a first alcohol gel paste by mixing and pulverizing the silica hydrogel, the surface of which was separated in the second step, treated with a silylating agent, and alcohol; f) a sixth step of mixing hydrophobic fumed silica powder and short fibers with the first alcohol gel paste prepared in the fifth step; g) a seventh step of preparing a second alcohol gel paste by mixing the first alcohol gel paste containing hydrophobic fumed silica powder and short fibers prepared in the sixth step with the oil-based adhesive prepared in the fourth step; h) an eighth step of preparing a first alcohol gel slurry by mixing ceramic powder with the second alcohol gel paste prepared in the seventh step; i) a ninth step of preparing a water-soluble inorganic binder by dissolving the inorganic binder in distilled water; j) a 10th step of preparing a first water-soluble paste by mixing ceramic powder and short fibers with the water-soluble inorganic binder prepared in the 9th step; k) an 11th step of preparing a first aqueous slurry by mixing potassium carbonate with the first aqueous paste prepared in the 10th step; l) Step 12 of preparing an aqueous adhesive solution by dissolving a water-soluble adhesive in distilled water; m) Preparing a porous silica-ceramic composite slurry (100) by mixing the first alcohol gel slurry prepared in the 8th step, the first water-soluble slurry prepared in the 11th step, and the adhesive aqueous solution prepared in the 12th step. Step 13: n) a 14th step of manufacturing a molded product by molding the porous silica-ceramic composite slurry 100 prepared in the 13th step in an extruder; and o) a 15th step of drying the molded product manufactured in the 14th step.

Looking at this in detail, the first step in the manufacturing method of the lightweight porous silica-ceramic composite insulating molded product 200 with excellent thermal insulation properties is by adding silica hydrogel, which is a porous material, and a silylating agent together in alcohol and stirring, This refers to the step of manufacturing a silica hydrogel in which the surface of the silica hydrogel is treated with a silylating agent while the silylating agent is dissolved.

The first step can be performed using a known reactor or mixer capable of controlling temperature and stirring, and the average particle size of the silica hydrogel, which is a porous material, is 2 to 5 mm, and has multiple pores within its structure. The pores have a size of several nanometers to tens of micrometers.

In addition, the alcohol used in the first step may preferably be one or more selected from the group consisting of butanol, pentanol, heptanol, and ethylene glycol, especially It may be desirable to use butanol.

According to the present invention, silylating agents used in the first step include polydimethylsiloxane (PDMS), hexamethyldisilazane (HMDZ), and hexamethyldisiloxane (hereinafter). , HMDSO), dimethyldichlorosilane (DMDCS), and methyltrimethoxysilane (MTMS).

The first step can be performed by adding the silica hydrogel and the silylating agent prepared as above into alcohol and then stirring, and when performing the first step, the silylating agent is dissolved in alcohol and the silica hydrogel is dissolved. As the surface is treated, the moisture contained in the pores of the silica hydrogel is separated from the alcohol and is discharged as alcohol. In addition, through the first step, a silica hydrogel whose surface is treated with a silylating agent is manufactured.

After performing the first step, the second step is to separate the silica hydrogel, the surface of which is treated with a silylating agent, prepared in the first step from the alcohol in which the silylating agent is dissolved. Since the separation of particles such as silica hydrogel from alcohol as described above is a known technique in the art, further description in this regard will be omitted.

After performing the second step, the third step is to separate the silica hydrogel whose surface was treated with the silylating agent in the second step and then remove moisture from the alcohol in which the silylating agent is dissolved. The moisture released as alcohol through the first step is contained in the pores of the silica hydrogel used in the first step, and is discharged while being replaced with alcohol through the first step and exists mixed with alcohol.

The alcohol used in the first step may be selected from the group consisting of butanol, pentanol, heptanol, and ethylene glycol, butanol has a boiling point of 117°C, pentanol has a boiling point of 136°C, and heptanol has a boiling point of Since the temperature is 158°C and the boiling point of ethylene glycol is 197°C, moisture can be easily removed from the alcohol in which the silylating agent is dissolved through heating.

After performing the third step as described above, the fourth step of preparing an oil-based adhesive is performed by mixing amino silane with alcohol containing the silylating agent from which moisture was removed in the third step.

The amino silane is an adhesion promoter with excellent adhesion to inorganic and organic materials, etc. According to the present invention, the amino silane may be 3-Aminopropyltriethoxysilane or 3-Aminopropyltrimethoxysilane.

According to the present invention, the oil-based adhesive prepared in the fourth step may be composed of 0.01 to 1% by weight of a silylating agent, 1 to 3% by weight of amino silane, and the balance of alcohol.

After performing the fourth step, the fifth step is to prepare a first alcohol gel paste by mixing and pulverizing the silica hydrogel, the surface of which was separated in the second step, treated with a silylating agent, and alcohol. do. The fifth step can be performed using a ball mill, etc., and the average particle diameter of the first alcohol gel paste produced in the fifth step may preferably be 30 to 100 ㎛.

At this time, the alcohol used in the fifth step may be the same alcohol used in the first step. The viscosity of the first alcohol gel paste prepared as described above is preferably 100 to 5,000 cps.

After performing the fifth step, in the sixth step, the first alcohol gel paste prepared in the fifth step is mixed with hydrophobic fumed silica powder and short fibers.

According to the present invention, the hydrophobic fumed silica powder used in the sixth step refers to fumed silica that has undergone chemical post-treatment with a surface modifier such as a silylating agent. In other words, the hydrophobic fumed silica powder refers to a fumed silica powder whose surface has been converted to hydrophobicity by treatment with a surface modifier such as the silylating agent.

The silylating agent may be the same silylating agent used in the first step, and the silylating agent may treat the fumed silica powder to hydrophobicize the surface to produce hydrophobic fumed silica powder.

It may be particularly preferable that the hydrophobic fumed silica powder prepared by treatment with a silylating agent as described above has a BET specific surface area of 200 to 400 m ² /g and an average particle size of 0.1 to 100 ㎛.

Hydrophobic fumed silica powder, the surface of which has been treated with a silylating agent as described above, is mixed with the first alcohol gel paste, and the silylating agent is eluted by the alcohol contained in the first alcohol gel paste. As described above, the silylating agent eluted in alcohol serves as a binder to bind the first alcohol gel paste, hydrophobic fumed silica powder, and short fibers.

In addition, the single fiber mixed with the first alcohol gel paste and the hydrophobic fumed silica powder in the sixth step may be any one of glass fiber, silica fiber, carbon fiber, and ceramic fiber, and the average length of the single fiber is 1. to 10 mm, and the average diameter may be preferably 5 to 15 ㎛.

As described above, the short fibers used in the sixth step may be added to coagulate and bind the first alcohol gel paste and the hydrophobic fumed silica powder.

After mixing the first alcohol gel paste with the hydrophobic fumed silica powder and short fibers through the sixth step as described above, the first alcohol gel containing the hydrophobic fumed silica powder and short fibers prepared in the sixth step The seventh step of producing a second alcohol gel paste is performed by mixing the paste and the oil-based adhesive prepared in the fourth step.

The viscosity of the second alcohol gel paste prepared in the seventh step may preferably be 30,000 to 60,000 cps.

Afterwards, in the eighth step, ceramic powder is mixed with the second alcohol gel paste prepared in the seventh step to prepare the first alcohol gel slurry.

According to the present invention, the ceramic powder is alumina, zeolite, zirconia, silicon carbide, silica, bauxite, bentonite, and alumina reinforced zirconia. It may be preferable to use at least one selected from the group consisting of (Alumina Toughened Zirconia, Al ₂ O ₃ -Zr) and Zirconia Toughened Alumina (Al ₂ O ₃ -ZrO ₂ ).

The alumina-reinforced zirconia and zirconia-reinforced alumina are ceramic powders containing alumina and zirconia, and are ceramic composite materials with excellent wear resistance, toughness, and hardness. In particular, it is a material with very low thermal conductivity and excellent insulation properties.

In addition, it may be preferable that the average particle size of the ceramic powder is 0.1 to 100㎛ because it is easy to process.

Additionally, the viscosity of the first alcohol gel slurry prepared through the eighth step may preferably be 100,000 to 250,000 cps.

By completing the eighth step, the step of using alcohol in the method of manufacturing a porous silica-ceramic composite molded product according to the present invention is completed. After the eighth step, a step of using distilled water instead of alcohol is performed in a separate reactor or mixer.

That is, after performing the eighth step as described above, in the ninth step, the water-soluble inorganic binder is prepared by dissolving the inorganic binder in distilled water. According to the present invention, the inorganic binder may preferably be at least one selected from the group consisting of sodium silicate, potassium silicate, and lithium silicate.

The water-soluble inorganic binder prepared in the ninth step binds the ceramic powder and short fibers performed in the subsequent tenth step.

The tenth long-term step refers to the step of producing a first water-soluble paste by mixing ceramic powder and short fibers with the water-soluble inorganic binder prepared in the ninth step. The ceramic powder may be the same as the ceramic powder used in the eighth step, and the single fiber may also be the same as the single fiber used in the sixth step.

Thereafter, the first water-soluble paste prepared as above is mixed with potassium carbonate to perform the 11th step of preparing the first water-soluble slurry. The potassium carbonate is mixed with the first water-soluble paste to increase the viscosity of the first water-soluble paste and increase the solid content to prepare a first water-soluble slurry in the form of a slurry.

The viscosity of the first water-soluble slurry prepared through the 11th step may preferably be 50,000 to 150,000 cps.

After preparing the first water-soluble slurry through the 11th step, in the 12th step, an aqueous adhesive solution is prepared by dissolving the water-soluble adhesive in distilled water. According to the present invention, the water-soluble adhesive is a group consisting of carboxymethyl cellulose, starch, polyacrylamide, glycerine, pullulan, super absorbent polymer, and gelatin. It may be one or more selected from, and it may be preferable that the water-soluble adhesive is dissolved in distilled water in an amount of 1 to 5% by weight.

By completing the 9th to 12th steps, the step of using distilled water in the method of manufacturing a porous silica-ceramic composite molded product according to the present invention is completed. After the 12th step, the 13th step is to mix the first alcohol gel slurry prepared in the 8th step, the first water-soluble slurry prepared in the 11th step, and the adhesive aqueous solution prepared in the 12th step, as shown in Figure 2 A porous silica-ceramic composite slurry (100) as shown in (a) is manufactured.

The porous silica-ceramic composite slurry 100 manufactured through the 13th step has a high solid content and a high viscosity, so that molded articles can be manufactured using a molding machine, etc. As a result, it is possible to manufacture molded products with complex shapes, making it possible to manufacture insulation parts with complex shapes used in electric vehicles and energy storage systems.

The porous silica-ceramic composite slurry 100 manufactured through the 13th step is molded in the 14th step using a molding device such as a molding machine, making it possible to manufacture a molded product as shown in (b) of FIG. 2.

In addition, the porous silica-ceramic composite slurry 100 is a mixture of ceramic powder and porous materials, etc., so that it has high viscosity and solid content, so it can be molded, and has excellent mechanical properties such as high thermal insulation, water repellency, and strength, and in particular, Because it has lightweight properties, it is possible to manufacture molded products that can be applied to everything from electronic housings to insulation parts for electric vehicles.

The porous silica-ceramic composite slurry 100 can be formed through various molding methods, and according to the present invention, compression molding is particularly preferable for manufacturing molded products of complex shapes such as cylinders.

That is, the porous silica-ceramic composite slurry 100 prepared in step 13 is injected into the mold, and then compression molding is performed. The compression molding process controls the porous silica-ceramic composite insulating molded product manufactured by controlling temperature, pressure, and time, and can preferably be performed at room temperature by applying a pressure of 100 to 5,000 psi for 20 seconds to 2 minutes.

The porous silica-ceramic composite insulating molded product compression molded under the above conditions secures mechanical properties such as appropriate density, tensile strength, and elongation, and among the compression molding process parameters, the mechanical properties are most affected under pressure conditions.

That is, if the pressure applied during compression molding is outside the above pressure range, sufficient mechanical properties cannot be secured. That is, a wide range of molding pressures can be applied during the compression molding, and according to the present invention, the molding pressure may preferably be applied at a pressure of 100 to 50,000 psi for 20 seconds to 2 minutes.

The molded product manufactured as described above is then dried as the 15th step, thereby completing the production of a lightweight porous silica-ceramic composite insulating molded product 200 with excellent thermal insulation properties according to the present invention.

The drying performed in the fifteenth step preferably includes primary drying performed at 60 to 80 ° C. for 2 to 4 hours and secondary drying performed at 150 to 190 ° C. for 4 to 10 hours. By drying the molded product through primary drying and secondary drying as described above, the remaining moisture in the molded product can be completely removed, and the efficiency of the drying operation is maximized.

According to the present invention, the molded article manufactured by drying in the 15th step contains 7 to 20% by weight of silica hydrogel, 0.5 to 1.5% by weight of silylating agent, 0.05 to 0.7% by weight of amino silane, and hydrophobic fumed silica powder 12. to 15% by weight, 3 to 5.5% by weight of short fibers, 45 to 55% by weight of ceramic powder, 10 to 15% by weight of inorganic binder, 3 to 7% by weight of potassium carbonate, and 0.017 to 0.1% by weight of water-soluble adhesive. This may be desirable.

As the porous silica-ceramic composite insulating molded product prepared in the 15th step is dried and the distilled water and alcohol have been removed, and has the above composition ratio, the solid content and viscosity are suitable for compression molding, making it possible to manufacture molded products with various shapes. It has high insulation and excellent mechanical properties, and can be manufactured lightweight.

Hereinafter, the present invention will be examined in more detail through examples. However, the present invention is not limited to the following examples.

[Example 1]

In the first step, 30% by weight of silica hydrogel with an average particle size of 50 ㎛, 10% by weight of PDMS as a silylating agent, and the balance of butanol were added to a mixer and mixed by stirring. Afterwards, in the second step, the silica hydrogel whose surface was treated with the silylating agent was separated from the alcohol in which the silylating agent was dissolved using a separation net, and in the third step, it was heated to remove moisture from the alcohol in which the silylating agent was dissolved.

Afterwards, in the fourth step, moisture is removed and 250 g of butanol containing 1% by weight of PDMS, a silylating agent, and 3-Aminopropyltriethoxysilane, an amino silane, are mixed for 30 minutes to obtain 2.5% by weight of 3-Aminopropyltriethoxysilane and PDMS. An oil-based adhesive containing 4% by weight was prepared.

Afterwards, in the fifth step, 1,200 g of silica hydrogel, the surface of which was separated in the second step, treated with a silylating agent, and 981 g of butanol were mixed and stirred to produce a first alcohol gel paste with an average particle size of 50㎛ and a viscosity of 5,000 mPas. was manufactured.

In the sixth step, 600 g of the first alcohol gel paste, 152 g of hydrophobic fumed silica powder (BET specific surface area 200 m ² /g, average particle size 0.1 ㎛), and 40 g of short glass fibers (average length 2 mm, average diameter 10 ㎛) Mix, and in the seventh step, mix the first alcohol gel paste containing hydrophobic fumed silica powder and short fibers with 105 g of the oil-based adhesive prepared in the fourth step to create a second alcohol gel paste with a viscosity of 50,000 cps. Manufactured.

In the eighth step, the second alcohol gel paste prepared in the seventh step is mixed with 333 g of alumina powder (average particle size 55㎛), which is a ceramic powder, to prepare a first alcohol gel slurry with a viscosity of 150,000 cps.

Afterwards, in the ninth step, sodium silicate, an inorganic binder, was dissolved in distilled water to prepare a water-soluble inorganic binder containing 35% by weight of the sodium silicate, and in the tenth step, alumina powder (alumina powder, a ceramic powder) was added to 863 g of the water-soluble inorganic binder. A first water-soluble paste was prepared by mixing 62 g of average particle size 55 ㎛ and 8 g of short glass fibers (average length 2 mm, average diameter 10 ㎛). In the 11th step, the first water-soluble paste and 67 g of potassium carbonate were mixed to prepare a first water-soluble slurry with a viscosity of 50,000 cps, and then in the 12th step, carboxymethyl cellulose, a water-soluble adhesive, was dissolved in distilled water to prepare the carboxymethyl cellulose. An aqueous adhesive solution containing 1% by weight of was prepared.

In the 13th step, 630 g of the first alcohol gel slurry prepared as above, 210 g of the first water-soluble slurry, and 30 g of the adhesive aqueous solution were mixed and stirred to prepare a porous silica-ceramic composite slurry (100), and the porous In the 14th step, the silica-ceramic composite slurry (100) was put into a compression molding machine and molded.

In the 15th step, the porous silica-ceramic composite slurry (100) formed as described above was first dried in a hot air dryer at 80°C for 2 hours, and then secondarily dried at 190°C for 4 hours to completely remove distilled water and alcohol. removed.

As described above, distilled water and alcohol are completely removed, and 7 to 20% by weight of silica hydrogel, 0.5 to 1.5% by weight of PDMS as a silylating agent, 0.05 to 0.7% by weight of 3-Aminopropyltriethoxysilane as an amino silane, and hydrophobic fumed silica powder 12 to 15% by weight, 3 to 5.5% by weight of short glass fibers, 45 to 55% by weight of alumina powder as a ceramic powder, 10 to 15% by weight of sodium silicate as an inorganic binder, 3 to 7% by weight of potassium carbonate, and water-soluble adhesive. A porous silica-ceramic composite insulating molded product (200) containing 0.017 to 0.1% by weight of phosphorus carboxymethyl cellulose was manufactured. The porous silica-ceramic composite insulation molded product (200) prepared as described above was cut into a size of 300 x 300 x 10 mm in width x length x height to prepare a test piece.

[Example 2]

A test piece was prepared in the same manner as in [Example 1], except that HMDSO was used as a silylating agent in the first and fourth steps, and 3-Aminopropyltrimethoxysilane was used as an amino silane in the fourth step to form a porous silica-ceramic composite. An insulating molded product (200) was manufactured.

The porous silica-ceramic composite insulation molded product 200 includes 7 to 20% by weight of silica hydrogel, 0.5 to 1.5% by weight of HMDSO, a silylating agent, 0.05 to 0.7% by weight of 3-Aminopropyltrimethoxysilane, an amino silane, and hydrophobic fumed silica. 12 to 15% by weight of powder, 3 to 5.5% by weight of short glass fibers, 45 to 55% by weight of alumina powder as a ceramic powder, 10 to 15% by weight of sodium silicate as an inorganic binder, and 3 to 7% by weight of potassium carbonate and water-soluble A test piece was prepared by cutting the porous silica-ceramic composite insulation molded product (200) prepared as described above, which contains 0.017 to 0.1% by weight of carboxymethyl cellulose as an adhesive, to a size of 300 x 300 x 10 mm in width x length x height. did.

[Example 3]

A test piece was prepared in the same manner as in [Example 1], except that silica single fibers (average length 10 mm, average diameter 10 ㎛) were used as single fibers in the 6th and 10th steps, and in the 8th and 10th steps, In step 10, a porous silica-ceramic composite insulating molded product 200 was manufactured using zeolite powder (average particle size 100 ㎛) as the ceramic powder. The porous silica-ceramic composite insulation molded product 200 includes 7 to 20% by weight of silica hydrogel, 0.5 to 1.5% by weight of PDMS, a silylating agent, 0.05 to 0.7% by weight of 3-Aminopropyltriethoxysilane, an amino silane, and hydrophobic fumed silica. 12 to 15% by weight of powder, 3 to 5.5% by weight of silica short fibers, 45 to 55% by weight of zeolite powder as a ceramic powder, 10 to 15% by weight of sodium silicate as an inorganic binder, and 3 to 7% by weight of potassium carbonate and water-soluble The porous silica-ceramic composite insulation molded product (200) prepared as described above, which contains 0.017 to 0.1% by weight of carboxymethyl cellulose as an adhesive, is cut into a size of 300 x 300 x 10 mm in width x length x height. A test piece was prepared.

The thermal conductivity and density of the test pieces of Examples 1 to 3 prepared as described above were measured in the following manner, and the results are shown in [Table 1].

1) Thermal conductivity

The thermal conductivity of the test pieces of Examples 1 to 3 was measured according to KS L 9016 (Method for measuring thermal conductivity of insulation materials).

2) Density

The density of the test pieces of Examples 1 to 3 was measured according to KS M 3808 (expanded polystyrene insulation) and calculated using Equation 1 below.

Thermal conductivity (W/mK) Density (g/cm ³ ) Example 1 0.10 1.80 Example 2 0.12 1.75 Example 3 0.08 1.52

Looking at Table 1, the test specimens of Examples 1 to 3 showed a thermal conductivity of 0.08 to 0.12 W/mK and a density of 1.52 to 1.80 g/cm ³ . Typically, the thermal conductivity of alumina molded products is 20 to 30 W/mK, and the thermal conductivity of silica-alumina molded products is 0.19 W/mK, so the porous silica-ceramic composite insulating molded product 200 according to the present invention exhibits very low thermal conductivity. You can check it.

In addition, it can be confirmed that the test specimens of Examples 1 to 3 exhibit a density of 1.52 to 1.80 g/cm ³ .

The density of the commonly manufactured alumina molded body is 2.7 g/cm ³ and the density of the silica-alumina molded body is 2.19 g/cm ³ , so the porous silica-ceramic composite insulating molded article 200 according to the present invention has a very low density. You can see that it represents density.

Looking at FIG. 3, FIG. 3 is a photograph of testing water repellency using the porous silica-ceramic composite insulating molded product 200 according to the present invention. Looking at FIG. 3, it can be seen that moisture poured from the top of the porous silica-ceramic composite insulation molded product 200 according to the present invention does not penetrate into the interior, but is repelled from the surface.

The porous silica-ceramic composite insulating molded article 200 manufactured by the method for manufacturing the porous silica-ceramic composite insulating molded article 200 described above includes steps 1 to 8 using alcohol, and steps 9 using distilled water. By performing steps through steps 12 separately, the alcohol can be prevented from penetrating into the pores of the porous material and the fumed silica powder, minimizing the increase in thermal conductivity, and thus producing excellent thermal insulation properties. In addition, the porous silica-ceramic composite insulating molded product 200 manufactured according to the present invention can be manufactured through a molding process such as extrusion molding, making it possible to manufacture molded products with various shapes of two-dimensional or three-dimensional structures, and ceramic By mixing powder and porous materials together, it has the effect of manufacturing molded products that have high insulation and excellent mechanical properties, and are lightweight and can be applied even to insulation materials such as electric vehicles and energy storage systems. In addition, according to the manufacturing method of the porous silica-ceramic composite insulation molded product 200 according to the present invention, it is possible to manufacture a lightweight porous silica-ceramic composite insulation molded product 200 with water repellency and low density, thereby making it possible to manufacture electric vehicles and This has the effect of enabling the manufacture of insulation materials used in energy storage systems, etc.

In addition, the porous silica-ceramic composite insulating molded product 200 manufactured according to the present invention can be manufactured through a molding process such as compression molding, making it possible to manufacture molded products with various shapes of two-dimensional or three-dimensional structures, Ceramic powder and porous materials are mixed together, which has the effect of producing molded products that have high insulation and excellent mechanical properties, and are lightweight and can be applied to insulation parts.

The present invention has been described with reference to the experimental examples shown in the drawings, but these are merely exemplary, and those skilled in the art will understand that various modifications and other equivalent experimental examples are possible therefrom. Additionally, a person skilled in the art to which the present invention pertains will understand that the present invention can be easily modified into another specific form without changing its technical idea or essential features. Therefore, the embodiments described above should be understood in all respects as illustrative and not restrictive, and the true scope of technical protection of the present invention should be determined by the technical spirit of the appended claims.

100: Porous silica-ceramic composite insulation slurry
200: Porous silica-ceramic composite insulation molded product

Claims (9)

In the manufacturing method of a lightweight porous silica-ceramic composite insulating molded product with excellent thermal insulation and water repellency,
a) a first step of preparing a silica hydrogel whose surface is treated with a silylating agent by adding the silica hydrogel and a silylating agent to alcohol and stirring it to dissolve the silylating agent;
b) a second step of separating the silica hydrogel, the surface of which is treated with a silylating agent, prepared in the first step from the alcohol in which the silylating agent is dissolved;
c) a third step of removing moisture from the alcohol in which the silylating agent separated in the second step is dissolved;
d) a fourth step of preparing an oil-based adhesive by mixing amino silane with alcohol containing a silylating agent from which moisture was removed in the third step;
e) a fifth step of preparing a first alcohol gel paste by mixing and pulverizing the silica hydrogel, the surface of which was separated in the second step, treated with a silylating agent, and alcohol;
f) a sixth step of mixing hydrophobic fumed silica powder and short fibers with the first alcohol gel paste prepared in the fifth step;
g) a seventh step of preparing a second alcohol gel paste by mixing the first alcohol gel paste containing hydrophobic fumed silica powder and short fibers prepared in the sixth step with the oil-based adhesive prepared in the fourth step;
h) an eighth step of preparing a first alcohol gel slurry by mixing ceramic powder with the second alcohol gel paste prepared in the seventh step;
i) a ninth step of preparing a water-soluble inorganic binder by dissolving the inorganic binder in distilled water;
j) a 10th step of preparing a first water-soluble paste by mixing ceramic powder and short fibers with the water-soluble inorganic binder prepared in the 9th step;
k) an 11th step of preparing a first aqueous slurry by mixing potassium carbonate with the first aqueous paste prepared in the 10th step;
l) Step 12 of preparing an aqueous adhesive solution by dissolving a water-soluble adhesive in distilled water;
m) Step 13 of preparing a porous silica-ceramic composite slurry by mixing the first alcohol gel slurry prepared in the 8th step, the first water-soluble slurry prepared in the 11th step, and the adhesive aqueous solution prepared in the 12th step. step;
n) a 14th step of manufacturing a molded product by molding the porous silica-ceramic composite slurry prepared in the 13th step in an extruder; and
o) a 15th step of drying the molded product manufactured in the 14th step; a method of manufacturing a lightweight porous silica-ceramic composite insulating molded product with excellent thermal insulation and water repellency, comprising:
In claim 1,
Method for producing a lightweight porous silica-ceramic composite insulating molded product with excellent thermal insulation and water repellency, characterized in that the average particle diameter of the first alcohol gel paste prepared in the fifth step is 30 to 100 ㎛
In claim 1,
The silylating agent is a lightweight porous silica-ceramic with excellent heat insulation and water repellency, characterized in that it is at least one selected from the group consisting of tetramethoxysilane, tetraethoxysilane, trimethoxymethylsilane, and trimethoxyethylsilane. Manufacturing method of composite insulation molded product
In claim 1,
Ceramic powders included in the 8th and 10th steps include alumina, zeolite, zirconia, silicon carbide, silica, bauxite, bentonite, alumina toughened zirconia, and zirconia strengthened alumina. Method for manufacturing a lightweight porous silica-ceramic composite insulating molded product with excellent thermal insulation and water repellency, characterized by at least one selected from the group consisting of (Toughened Alumina)
In claim 1,
Method for manufacturing a lightweight porous silica-ceramic composite insulating molded product with excellent thermal insulation and water repellency, characterized in that the average particle size of the ceramic powder is 0.1 to 100 ㎛
In claim 1,
In the twelfth step, the water-soluble adhesive is a lightweight, porous silica with excellent thermal insulation and water repellency, characterized in that at least one selected from the group consisting of carboxymethyl cellulose, starch, polyacrylamide, glycerin, pullulan, superabsorbent polymer, and gelatin. -Manufacturing method of ceramic composite insulation molded products
In claim 1,
In the ninth step, the inorganic binder is a method of manufacturing a lightweight porous silica-ceramic composite insulating molded product with excellent thermal insulation and water repellency, characterized in that at least one selected from the group consisting of sodium silicate, potassium silicate, and lithium silicate.
In claim 1,
A method of manufacturing a lightweight porous silica-ceramic composite insulating molded product with excellent thermal insulation and water repellency, characterized in that the alcohol is at least one selected from the group consisting of butanol, pentanol, heptanol, and ethylene glycol.
A lightweight porous silica-ceramic composite insulating molded product with excellent thermal insulation and water repellency manufactured by the method for manufacturing a lightweight porous silica-ceramic composite insulated product with excellent thermal insulation and water repellency according to any one of claims 1 to 8.