阅读说明：本技术 干燥湿凝胶毡的方法和使用该方法制造气凝胶毡的方法 (Method of drying wet gel felt and method of making aerogel felt using the same ) 是由 金美利 宋珍午 金永勋 白世元 崔宰薰 于 2020-08-07 设计创作，主要内容包括：本发明提供一种干燥湿凝胶毡的方法和使用所述方法制造气凝胶毡的方法,所述干燥湿凝胶毡的方法可以通过使干燥过程中发生的凝胶网络结构的收缩最小化而具有优异的绝热性能,并且具有优异的对于时间的干燥效率。(The present invention provides a method of drying a wet gel mat which can have excellent thermal insulation properties by minimizing shrinkage of a gel network structure occurring during drying and has excellent drying efficiency with respect to time, and a method of manufacturing an aerogel mat using the same.)

1. A method of drying a wet gel mat, the method comprising:

drying a wet gel mat by irradiating the wet gel mat with Infrared (IR),

wherein, in the drying, infrared rays are irradiated so as to include a first isothermal section of 5 to 30 minutes, a temperature rise section of 5 to 30 minutes, and a second isothermal section of 20 minutes or less in a temperature profile of the wet gel mat as a function of time.

2. The method of claim 1, wherein the surface temperature of the infrared emitter is 200 ℃ to 1,100 ℃.

3. The method of claim 1, wherein the distance between the infrared emitter and the wet gel mat during drying is from 50mm to 170 mm.

4. The method of claim 1, wherein the infrared light comprises infrared light having a wavelength in a range of 2 μ ι η to 15 μ ι η.

5. The method of claim 1, wherein the drying is performed for a total of 10 to 80 minutes.

6. The method of claim 1, wherein the wet gel mat is a fiber-silica gel composite prepared by depositing a silica sol on a mat substrate and gelling.

7. A method of making an aerogel blanket, comprising:

1) mixing a precursor material, an organic solvent, water, and an acid catalyst to prepare a sol;

2) depositing the sol on a felt substrate and gelling;

3) modifying the surface of the wet gel mat formed by the gelling reaction; and

4) (ii) drying the wet gel mat,

wherein the drying is carried out by the method of any one of claims 1 to 6.

8. The method of claim 7, wherein the precursor material comprises a silicate compound and the aerogel blanket is a silica aerogel blanket.

9. The method of claim 7, further comprising aging a wet gel mat formed from a gelling reaction between said gelling and said surface modification.

10. The method of claim 7, wherein the surface modifying agent is a compound that hydrophobizes the surface of the wet gel.

Technical Field

[ Cross-reference to related applications ]

This application claims the benefit of korean patent application No.10-2019-0097517, filed by the korean intellectual property office at 09.08.2019, the disclosure of which is incorporated in its entirety by reference into the present specification.

[ technical field ]

The present invention relates to a method of drying a wet gel mat, which may have excellent thermal insulation properties by minimizing shrinkage occurring during drying and have excellent drying efficiency over time, and a method of manufacturing an aerogel mat using the same.

Background

Aerogels are highly porous materials composed of nanoparticles and have high porosity, specific surface area and low thermal conductivity, and thus, have attracted considerable attention for uses such as high-efficiency insulating materials and sound insulating materials. Since such aerogel has very low mechanical strength due to its porous structure, an aerogel composite has been developed in which aerogel is impregnated into and combined with a fiber mat having inorganic fibers, organic fibers, etc. as existing insulating fibers.

For example, silica aerogel-containing mats using silica aerogel are prepared by preparing silica sol, gelling, aging, surface modification, and drying.

In the field of aerogel blankets, generally, an atmospheric hot air drying method (hot air drying) is mainly performed. However, the hot air drying method has a limitation in that, since the dried sample is gradually heated from the outside to the inside, the solvent having higher volatility is evaporated earlier than the water having lower volatility, and thus, as the drying proceeds, the water content in the pores of the gel increases, so that a capillary phenomenon frequently occurs to destroy the pore structure due to shrinkage or the like. Aerogel blankets with disrupted pore structure have a limit to the relative deterioration of thermal insulation performance. These limitations are exacerbated in the case where drying is carried out immediately without replacement with an organic solvent having a low surface tension.

In addition, there is a limitation in that the hot air drying method takes a long time to raise the temperature of the dried sample to the optimal drying temperature, and thus, the drying is performed at a temperature lower than the optimal drying temperature, thereby reducing the drying efficiency.

A supercritical drying method is proposed as a method for compensating for low drying efficiency and deterioration of heat insulation performance of a hot air drying method. Supercritical drying is carried out by subjecting supercritical fluid, e.g. supercritical CO₂Is added into a high pressure reactor, CO₂Methods of displacing ethanol in wet gel mats and extracting the displaced ethanol, thereby drying the wet gel mats. However, there is a disadvantage in that the supercritical drying method requires a separate drying apparatus for supercritical extraction, and thus, the initial investment cost is very high. Further, since the supercritical drying method must pass through compression-extraction-decompression steps, there are limitations that a time required for drying is long, and since drying is performed in a supercritical extractor, there is a disadvantage that continuous drying treatment cannot be performed but only batch treatment can be performed.

Therefore, the following studies are required: a method of drying a wet gel mat, which can achieve economic effects due to no large consumption of initial investment costs and maintenance costs of a drying apparatus, and has excellent drying efficiency, and minimizes shrinkage during drying to ensure excellent heat insulation performance; and a method of making an aerogel blanket using the drying method.

Disclosure of Invention

Technical problem

An aspect of the present invention provides a method of drying a wet gel mat, which may have excellent thermal insulation properties by minimizing shrinkage of a gel network structure occurring during drying, and has excellent drying efficiency over time.

Another aspect of the invention also provides a method of making an aerogel blanket using the drying method.

Technical scheme

According to one aspect of the invention, there is provided a method of drying a wet gel mat, the method comprising: drying a wet gel mat by irradiating the wet gel mat with Infrared (IR), wherein in the drying, the irradiation of the infrared is such that a first isothermal interval of 5 to 30 minutes, a temperature rise interval of 5 to 30 minutes, and a second isothermal interval of 20 minutes or less are included in a temperature profile of the wet gel mat as a function of time.

According to another aspect of the invention, there is provided a method of making an aerogel blanket, the method comprising: 1) mixing a precursor material, an organic solvent, water, and an acid catalyst to prepare a sol; 2) depositing and gelling the sol on a felt substrate; 3) modifying the surface of the wet gel mat formed by the gelling reaction; and 4) drying the wet gel mat, wherein the drying is performed by the above-described drying method.

Advantageous effects

The present invention can rapidly and uniformly increase the temperature inside the gel by infrared rays, so that the solvent and moisture in the gel are simultaneously dried, thereby minimizing the shrinkage of the aerogel occurring during the drying process. Therefore, the present invention has excellent pore characteristics and physical properties such as a high specific surface area, and can secure excellent thermal insulation properties. Further, the present invention is advantageous in that drying can be performed on one side or both sides because the irradiation direction of infrared rays is free, whereby drying efficiency is not lowered even if the wet gel mat is thick, and excellent drying efficiency can be maintained, and drying can be performed in a relatively short time. In addition, the excellent drying efficiency can prevent the problem of generating a bad smell in the residual solvent.

In addition, since the present invention can control the drying time of each drying section to exhibit excellent drying efficiency and suppress the decrease in hydrophobicity, hydrophobicity can be maintained at an excellent level even after drying.

Drawings

The following drawings attached to the present specification illustrate specific embodiments of the present invention by way of example and are intended to enable the technical concept of the present invention to be further understood together with the detailed description of the invention given below, and therefore the present invention should not be construed as limited to the matters in the drawings.

Fig. 1 is a graph showing a temperature profile of a dried sample with drying time according to an embodiment of the present invention to show a temperature change during drying;

FIG. 2 is a graph showing temperature profiles over drying time for dried samples obtained from example 1, example 2 and example 4;

fig. 3 is a graph showing temperature profiles of dried samples with drying time in comparative example 4 and comparative example 5.

Detailed Description

Hereinafter, the present invention will be described in detail with reference to the accompanying drawings. The terms or words used in the present specification and claims should not be construed as limited to conventional or dictionary meanings, but should be construed as meanings and concepts consistent with technical ideas based on the principle that the inventor can appropriately define the concept of the term in order to best explain his invention.

< method for drying Wet gel felt >

The present invention provides a method of drying a wet gel mat, the method comprising: drying a wet gel mat by irradiating the wet gel mat with Infrared (IR), wherein in the drying, the irradiation of the infrared is such that a first isothermal interval of 5 to 30 minutes, a temperature rise interval of 5 to 30 minutes, and a second isothermal interval of 20 minutes or less are included in a temperature profile of the wet gel mat as a function of time.

In this case, the temperature of the sample is measured after inserting and fixing the thermocouple into the center of the sample.

In addition, the term "temperature profile over time" herein indicates a graph of temperature change over time for a wet gel mat dried sample, for example, it may refer to a graph with time on the x-axis and temperature on the y-axis as shown in fig. 1 of the present invention.

Here, the first isothermal zone refers to a drying zone from a drying start point to an isothermal drying end point which appears for the first time, and refers to a zone of a contact point (hereinafter referred to as a first contact point) of a tangent line of an isothermal line which appears for the first time after the drying start point and a tangent line of a heating line which rises at a constant inclination value in a temperature curve of a dried sample over time. The first isothermal zone may mean a zone in which the temperature of the dried sample does not increase and is dried at a constant temperature even if the ambient temperature increases due to the latent heat of vaporization of the solvent. Further, in the temperature profile of the present invention as in fig. 1, when heating is performed after isothermal drying, an equal degree of heating is exhibited after a certain time, whereby a region having an equal inclination value appears, and in this case, the heating line rising at a constant inclination value refers to the heating line in the region having an equal inclination value but the inclination value is not 0.

In addition, the temperature-increasing section means a drying section from the end point of the first isothermal drying to the end point of the heating drying, and means a section from the above-described first contact point to a contact point (hereinafter referred to as a second contact point) of a tangent line of a heating line increasing at a constant inclination value and a tangent line of an isothermal line appearing second after the start of drying in a temperature profile of the dried sample over time. The heating-drying interval may refer to an interval in which most of the solvent is dried, and thus, the temperature of the dried sample sharply rises.

In addition, the second isothermal zone refers to a drying zone from the end point of the heating drying to the end point of the final drying, and refers to a zone from the above-mentioned second contact point to a time point when the drying is completely finished in the temperature profile of the dried sample over time. The second isothermal zone may refer to a zone where additional drying is performed in order to remove catalyst residues used in the preparation of the wet gel mat, and in this case, since the sample temperature is balanced with the ambient temperature, the temperature does not rise sharply and a constant temperature can be maintained.

According to an embodiment of the present invention, the drying in the first isothermal zone may be performed for 5 to 30 minutes, specifically, 10 to 25 minutes, more specifically 10 to 20 minutes, the drying in the warming zone may be performed for 5 to 30 minutes, specifically, 5 to 25 minutes, more specifically 10 to 20 minutes, and the drying in the second isothermal zone may be performed for 20 minutes or less, specifically, 0 to 20 minutes, 0 to 15 minutes, more specifically 0 to 5 minutes.

According to an embodiment of the present invention, it is also within the scope of the present invention that drying is performed as in the above time range so that the second isothermal zone does not occur, and the desired effects of the present invention can be exhibited similarly although the second isothermal zone is not performed. That is, drying may optionally include a second isothermal zone. Thus, according to an embodiment of the invention, the drying may comprise a first isothermal zone and a temperature rise zone, or may comprise a first isothermal zone, a temperature rise zone and a second isothermal zone.

Here, the solvent dried according to the drying method may be a solvent used in the preparation of a wet gel mat, and may specifically contain water and an organic solvent. Further, the organic solvent may be specifically an alcohol, wherein the alcohol may be a monohydric alcohol such as methanol, ethanol, isopropanol, and butanol; polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and sorbitol, and one of the above or a mixture of two or more of them may be used. Among them, when taking into consideration miscibility with water and aerogel, monohydric alcohols having 1 to 6 carbon atoms, such as methanol, ethanol, isopropanol, butanol, etc., may be used, and ethanol may be particularly used.

In addition, the solvent may include 85 to 95% by weight of an organic solvent and 5 to 15% by weight of water.

When drying is performed to exceed the above-mentioned time range of the first isothermal zone or the temperature-increasing zone, since the organic solvent having higher volatility than water in the solvent is first evaporated as drying proceeds, the proportion of water in the pores of the gel is relatively increased, so that a capillary phenomenon may occur, and thus, shrinkage in which the pore structure collapses may occur. There may occur a problem in that the aerogel blanket having a pore structure collapsed by shrinkage has high thermal conductivity and has deteriorated thermal insulation performance. Further, when drying is performed to a time range lower than the above-mentioned first isothermal zone or temperature-increasing zone, the energy received by the wet gel mat during drying is too much to maintain the pore structure, and therefore, some of the pore structure may collapse, and further, there may occur a problem that a large amount of hydrophobic groups present in the wet gel mat are lost, thereby deteriorating hydrophobicity. When the first isothermal zone and the temperature-elevating zone satisfy the above time range, there are advantages in that water and an organic solvent can be simultaneously dried to stably maintain the pore structure, loss of hydrophobic groups can be minimized to maintain hydrophobicity at an excellent level, and drying of the solvent can be easily performed even in a relatively short drying time as compared to other methods, whereby drying efficiency is high.

In addition, when drying is performed to exceed the above-mentioned time range of the second isothermal zone, drying is continued even if most of the solvent is dried, and thus, there may occur a problem in that hydrophobic groups of the aerogel blanket, in particular, hydrophobic groups present on the surface thereof are lost so much that hydrophobicity is greatly deteriorated.

In addition, according to an embodiment of the present invention, the total drying time may be adjusted to have a first isothermal drying interval, a heating drying interval, and a second isothermal drying interval, and specifically, the drying may be performed such that the total drying time is 10 to 80 minutes, 15 to 70 minutes, or 15 to 50 minutes, and more specifically, the drying may be performed such that the total drying time is 20 to 45 minutes.

In addition, according to an embodiment of the present invention, the surface temperature of the infrared emitter as a heat source in the infrared drying is not limited as long as it can exhibit the drying condition as described above, and may be, for example, 200 ℃ to 1,100 ℃, specifically 250 ℃ to 900 ℃. When an emitter having a surface temperature within the above range is used, drying of the solvent is easily performed, and at the same time, loss of the hydrophobic group can be minimized to maintain excellent hydrophobicity. In order to well exhibit the drying profile (temperature profile) specified in the present invention and to ensure stability during drying, the surface temperature of the infrared emitter may be more specifically 250 ℃ to 700 ℃ or 400 ℃ to 700 ℃.

In addition, according to an embodiment of the present invention, in order to prevent the hydrophobic groups from being removed, it is preferable to use a carbon heater for Middle Infrared Rays (MIR) and a ceramic heater for Far Infrared Rays (FIR) as the type of infrared ray emitting material. Further, the wavelength of the irradiated infrared ray is not limited as long as it can exhibit the above-mentioned drying condition and can be included in the generally known mid-infrared range or far-infrared range, but, for example, an infrared ray having a wavelength range of 2 μm to 15 μm or an infrared ray having an average wavelength of a main peak of 2 μm to 15 μm when the wet gel mat is irradiated with an infrared ray can be included.

In addition, when the drying according to the present invention is performed, there is no limitation on the distance between the emitter and the wet gel mat as a dried sample as long as it can exhibit the above-described drying condition, and may be, for example, 50mm to 170 mm. When the distance is controlled to have the above range of distance, water and the organic solvent may be simultaneously dried, and thus, the drying of the solvent is easily performed, and the loss of the hydrophobic group may be minimized, thereby maintaining excellent hydrophobicity. In order to well exhibit the drying condition specified in the present invention, excellent hydrophobicity is ensured by preventing the hydrophobic group from being removed during drying, and the removal rate of the solvent is increased, and the distance may be specifically 70mm to 170mm, and more specifically, 90mm to 150 mm.

In addition, according to an embodiment of the present invention, the wet gel mat may be a fiber-silica gel composite, and specifically, may be a fiber-silica gel composite prepared by depositing a silica sol on a mat substrate as a fiber and gelling.

In the present invention, the solvent and water in the gel can be simultaneously dried by controlling the above-mentioned drying conditions, i.e., the first isothermal zone, the temperature-increasing zone, and the second isothermal zone to have the above-mentioned time, and therefore, the removal efficiency of the solvent and the residue is excellent, and the shrinkage of the network structure of the gel can be minimized, thereby ensuring excellent thermal insulation performance. Further, the above-described drying condition can prevent the hydrophobic groups from being removed due to the continuation of unnecessary drying, and the dried aerogel blanket can exhibit excellent hydrophobicity as the removal of the hydrophobic groups decreases.

< method for producing aerogel felt >

The present invention provides a method of making an aerogel blanket, the method comprising: 1) mixing a precursor material, an organic solvent, water, and an acid catalyst to prepare a sol; 2) depositing the sol on a felt substrate and gelling; 3) modifying the surface of the wet gel mat formed by the gelling reaction; and 4) drying the wet gel mat, wherein the drying is performed by the above-described drying method.

Step 1)

The sol is prepared in the above step 1), and the sol may be prepared by mixing the precursor material, the organic solvent, water, and the acid catalyst.

According to one embodiment of the present invention, the sol of the present invention may be, for example, a silica sol, and when the sol is a silica sol, the precursor material may be a silica precursor.

The silica precursor may be an alkoxide-based compound containing silicon, specifically, tetraalkyl silicate such as tetramethyl orthosilicate (TMOS), tetraethyl orthosilicate (TEOS), methyl triethyl orthosilicate, dimethyl diethyl orthosilicate, tetrapropyl orthosilicate, tetraisopropyl orthosilicate, tetrabutyl orthosilicate, tetra-sec-butyl orthosilicate, tetra-tert-butyl orthosilicate, tetrahexyl orthosilicate, tetra (dodecyl) orthosilicate, and the like. More specifically, the silica precursor may be Tetraethylorthosilicate (TEOS).

The silica precursor may be used in an amount such that the content of silica contained in the silica sol is 0.1 to 30% by weight, but is not limited thereto. When the content of silica satisfies the above range, mechanical properties, in particular, flexibility of the aerogel blanket can be secured at an excellent level, and an improved heat insulating effect can be exhibited.

The organic solvent may specifically include alcohols, more specifically, monohydric alcohols such as methanol, ethanol, isopropanol, and butanol; polyhydric alcohols such as glycerin, ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, and sorbitol, and one of the above or a mixture of two or more of them may be used. Among them, when taking into consideration miscibility with water and aerogel, monohydric alcohols having 1 to 6 carbon atoms, such as methanol, ethanol, isopropanol, butanol, etc., may be used, and for example, ethanol may be used.

Such organic solvents may be used at an appropriate level by those skilled in the art in view of promoting surface modification reactions and hydrophobicity in the finally manufactured aerogel blanket.

The acid catalyst may promote gelation of a sol, which will be described below, may include, specifically, at least one inorganic acid such as nitric acid, hydrochloric acid, acetic acid, sulfuric acid, and hydrofluoric acid, and may be used in an amount to promote gelation of the sol.

Step 2)

The above step 2) is for depositing and gelling the sol on the felt substrate to prepare a wet gel felt, and may be performed by adding an alkali catalyst to the sol and then depositing the mixture on the felt substrate.

In the present invention, the gel may form a network structure from the precursor material, and the network structure may exhibit a planar network structure in which specific polygons having one or more types of atomic arrangements are connected, or a structure in which vertices, edges, faces, and the like sharing a specific polyhedron form a three-dimensional skeleton structure.

The base catalyst, which can be used to induce the gelation reaction, increases the pH of the sol, thereby promoting gelation.

The base catalyst may include inorganic bases such as sodium hydroxide and potassium hydroxide; or an organic base such as ammonium hydroxide, but in the case of an inorganic base, there is a concern that metal ions contained in the compound may coordinate with the Si — OH compound, and therefore, an organic base may be preferable.

Specifically, the organic base may include: ammonium hydroxide (NH)₄OH), tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH),Tetrapropylammonium hydroxide (TPAH), tetrabutylammonium hydroxide (TBAH), methylamine, ethylamine, isopropylamine, monoisopropylamine, diethylamine, diisopropylamine, dibutylamine, trimethylamine, triethylamine, triisopropylamine, tributylamine, choline, monoethanolamine, diethanolamine, 2-aminoethanol, 2- (ethylamino) ethanol, 2- (methylamino) ethanol, N-methyldiethanolamine, dimethylaminoethanol, diethylaminoethanol, nitrilotriethanol, 2- (2-aminoethoxy) ethanol, 1-amino-2-propanol, triethanolamine, monopropanolamine, dibutanolamine, and the like, and a mixture of two or more of them may be used. More specifically, the base may be ammonium hydroxide (NH)₄OH)。

The content of the alkali catalyst may be such that the pH of the sol, specifically, the silica sol is 4 to 8. Gelation can be easily performed in the above pH range, thereby further improving processability. Further, since the base catalyst precipitates when added in a solid phase, it may be preferably added in a solution phase diluted with the above organic solvent of step 1), such as alcohol.

The gelation of the sol may occur in a state where the sol, in particular, the sol catalyzed by the addition of a base catalyst is deposited on the felt substrate.

The deposition may be carried out in a reaction vessel capable of holding the felt substrate, and the deposition may be carried out by pouring the silica sol into the reaction vessel or by placing the felt substrate into a reaction vessel containing the sol and wetting. In this case, in order to improve the bonding between the felt base material and the sol, the felt base material may be lightly pressed so as to be sufficiently impregnated. The mat substrate may then be pressed to a thickness at a constant pressure to remove excess sol and thereby reduce subsequent drying time.

The felt substrate may be a film, sheet, web, fiber, foam, nonwoven, or a laminate of two or more layers thereof. Further, depending on the use of the mat, surface roughness or patterning may be formed on the surface of the mat. Specifically, the base material for the felt may be a fiber that may further improve thermal insulation performance by including spaces or holes that make it easy to insert the sol into the felt base material and form the aerogel, and a base material having low thermal conductivity may be used.

Specifically, the felt substrate may be polyamide, polybenzimidazole, polyaramid, acrylic, phenolic, polyester, Polyetheretherketone (PEEK), polyolefin (e.g., polyethylene, polypropylene, or copolymers thereof), cellulose, carbon, cotton, wool, hemp, nonwoven fabric, fiberglass, ceramic cotton, or the like.

According to an embodiment of the present invention, an aging step may be further included after the above step 2).

Aging is an optional step in which the wet gel mat is left to stand at an appropriate temperature to complete the chemical change, whereby a network structure can be formed more stably and mechanical stability can also be improved.

The aging of the present invention may be performed by allowing the wet gel mat to stand in the above organic solvent at a temperature of 40 ℃ to 90 ℃ or without the organic solvent for 1 hour to 10 hours. The organic solvent may be an organic solvent as described in step 1) above. In another embodiment, the solvent in aging may be a base catalyst such as sodium hydroxide (NaOH), potassium hydroxide (KOH), ammonium hydroxide (NH)₄OH), triethylamine or pyridine in a concentration of 1% to 10% in the above organic solvent.

Step 3)

The above step 3) is a surface modification step of the wet gel formed by the gelation reaction, and may be hydrophobizing a wet gel mat, specifically, a silica wet gel mat, with a surface modifier. Specifically, this step can be performed by binding hydrophobic groups from the surface modifier on the surface of the silica wet gel.

In the silica aerogel blanket, there is a disadvantage that silanol groups (Si — OH) are present on the surface of silica, and thus, water in the air is absorbed due to its hydrophilicity, thereby gradually increasing thermal conductivity. Therefore, it is necessary to modify the surface of silica aerogel to be hydrophobic in advance in order to maintain low thermal conductivity by suppressing absorption of water in the air.

The surface modifier of the present invention is not limited as long as it is a compound hydrophobizing the surface of the wet gel, and may be, for example, a silane-based compound, a siloxane-based compound, a silanol-based compound, a silazane-based compound, or a combination thereof.

Specifically, the surface modifier may be: silane compounds including Trimethylchlorosilane (TMCS), dimethyldimethoxysilane, dimethyldiethoxysilane, methyltrimethoxysilane, trimethylethoxysilane, vinyltrimethoxysilane, ethyltriethoxysilane, phenyltriethoxysilane, phenyltrimethoxysilane, tetraethoxysilane, dimethyldichlorosilane, 3-aminopropyltriethoxysilane, etc.; siloxane compounds including polydimethylsiloxane, polydiethylsiloxane, octamethylcyclotetrasiloxane and the like; silanol compounds including trimethylsilanol, triethylsilanol, triphenylsilanol, t-butyldimethylsilanol, etc.; silazanes, 1, 2-diethyldisilazane, 1,1,2, 2-tetramethyldisilazane, 1,1,3, 3-tetramethyldisilazane, 1,1,1,2,2, 2-Hexamethyldisilazane (HMDS), 1,1,2, 2-tetraethyldisilazane, 1, 2-diisopropyldisilazane, and the like; or a combination thereof, and may specifically be hexamethyldisilazane.

The surface modifier may be used as a solution phase diluted in an organic solvent, and the organic solvent may be the organic solvent in step 1) described above, and in this case, the surface modifier may be diluted in an amount of 1 to 15 vol% with respect to the total volume of the diluted solution.

In addition, the surface modifier may be added in an amount of 0.01 to 10% by volume relative to the silica wet gel. If the amount of the surface modifier added is less than 0.01% by volume relative to the silica wet gel, there may occur a problem in that the amount of the surface modifier that can react with the silanol groups (Si — OH) in the silica wet gel is less than the amount of the silanol groups, whereby the surface modification reactivity may be reduced and the surface modification is not easily performed, and therefore, the silanol groups that are not surface-modified during the drying process undergo a condensation reaction, so that the pore diameter of the finally produced silica aerogel becomes smaller and the porosity cannot be achieved. Further, if the surface modifier is added in an amount of more than 10% by volume relative to the silica wet gel, there may occur a problem in that there are many residual surface modifiers that do not participate in the surface modification reaction, and expensive surface modifiers are wasted, thereby lowering the economy.

The above step 3) may be performed by adding the surface modifier at a temperature of 50 ℃ to 90 ℃, specifically, 50 ℃ to 70 ℃ for 1 hour to 24 hours.

Step 4)

The above step 4) is to dry the silica wet gel, and is performed by the infrared drying method of the present invention.

The description of the infrared drying method of the wet gel mat is the same as that described above.

Meanwhile, in the method of manufacturing a silica aerogel blanket according to an embodiment of the present invention, further washing may be performed before drying. Washing is used to obtain a hydrophobic aerogel blanket of high purity by removing impurities and residual ammonia generated during the reaction, and may be performed by a dilution process or a substitution process using a non-polar organic solvent.

Fig. 1 schematically shows an embodiment of the temperature variation over time during drying according to the invention. In fig. 1, a is a time point when the first isothermal section defined in the present invention ends, and B is a time point when the temperature-increasing section defined in the present invention ends. However, the following configuration described in the embodiments of the present specification and the drawings only shows the most specific example and does not show all technical ideas of the present invention, and therefore, it should be understood that there may be various equivalents and modifications capable of substituting for the configuration.

Hereinafter, the present invention will be described in detail based on examples to better understand the present invention. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these exemplary embodiments are provided so that this description will be thorough and complete, and will fully convey the scope of the invention to those skilled in the art.

Example 1

A hydrochloric acid solution (concentration ═ 0.15 wt%) diluted with water was added to a mixed solution prepared by mixing Tetraethylorthosilicate (TEOS) and ethanol in a weight ratio of 3:1 so that the pH of the mixed solution became 1, and then mixed to prepare a silica sol (silica content in the silica sol ═ 4 wt%). Then, an ammonia catalyst was added to the silica sol in an amount of 0.5 vol%, and glass fibers were deposited and then gelled to prepare a silica wet gel composite.

The prepared silica wet gel composite was placed in an ethanol solution at a temperature of 70 ℃ and aged for 5 hours.

Thereafter, a surface modifier solution prepared by mixing hexamethyldisilazane and ethanol at a volume ratio of 1:9 was added in an amount of 90 vol% with respect to the wet gel, and the wet gel was surface-modified at 70 ℃ for 24 hours to prepare a hydrophobic silica wet gel composite. Thereafter, the surface-modified wet gel mat was placed on a substrate of an infrared drying apparatus equipped with an infrared lamp, and subjected to infrared drying (double-sided drying) under the conditions listed in the following table 1 to prepare an aerogel mat.

Examples 2 to 6

Each aerogel blanket was prepared in the same manner as in example 1, except that the infrared drying conditions in example 1 above were changed to the conditions listed in table 1 below.

Comparative example 1

An aerogel blanket was prepared by the same method as in example 1, except that the wet gel blanket prepared in example 1 above was not subjected to infrared drying, but was subjected to hot air drying in an oven at a temperature of 170 c for 40 minutes.

Comparative example 2

An aerogel blanket was prepared by the same method as in example 1, except that the wet gel blanket prepared in example 1 above was not subjected to infrared drying, but to supercritical drying.

In this case, the supercritical drying is performed as follows. Placing the wet gel mat in a supercritical extractor and injecting CO therein₂. Thereafter, the temperature in the extractor was raised to 60 ℃ over 1 hour, and supercritical drying was carried out at 60 ℃ and 100 bar for 4 hours. Thereafter, the CO is introduced₂The discharge was allowed to proceed for 2 hours to prepare an aerogel blanket.

Comparative examples 3 to 7

Each aerogel blanket was prepared in the same manner as in example 1, except that the infrared drying conditions in example 1 above were changed to the conditions listed in table 1 below.

Examples of the experiments

1) Measurement of drying time

For the examples and comparative examples subjected to infrared drying, the drying time was measured for each temperature interval, and the results are shown in table 1. Specifically, a temperature profile was obtained by inserting a thermocouple into the center of a wet gel mat sample to be dried, and the drying time and the total drying time for each interval were obtained from the temperature profile.

Fig. 2 shows the temperature profile as a function of drying time for the wet gel mat samples obtained from example 1, example 2 and example 4, and fig. 3 shows the temperature profile as a function of drying time for the wet gel mat samples of comparative example 4 and comparative example 5.

In addition, for comparative example 1 in which hot air drying was performed and comparative example 2 in which supercritical drying was performed, the drying time was measured from the start point to the end point of drying, and the results are shown in table 1 below.

2) Measurement of thermal conductivity (mW/mK, 25 ℃ C.)

The thermal conductivity of the aerogel blankets prepared in the respective examples and comparative examples was measured at room temperature (25 ℃) using an HFM 436 apparatus from NETZSCH.

3) Measurement of moisture impregnation ratio (% by weight)

The moisture impregnation rate of the aerogel blankets prepared in the respective examples and comparative examples was measured according to the ASTM C1511 standard.

The lower the moisture impregnation rate, the higher the hydrophobicity of the aerogel blanket.

4) Measurement of BET specific surface area, pore volume and average pore diameter

For the aerogel blankets prepared in example 1, example 2 and comparative example 1 above, the BET specific surface area, pore volume and average pore diameter of the aerogel blanket were evaluated by measuring the adsorption/desorption amount of nitrogen gas according to partial pressure (0.11< p/po <1) using a 3FLEX apparatus from Micrometrics, and the results are shown in table 2 below.

[ Table 1]

Referring to the temperature profile of the wet gel mat samples obtained from example 1, example 2 and example 4 with respect to the drying time of example 2, in example 1 and example 2, a first isothermal zone occurred in which the temperature of the wet gel mat slowly increased at a constant ramp value for 10 minutes from the start of drying, and a temperature increase zone in which the temperature was relatively sharply increased occurred in the zone of 10 minutes to 20 minutes. In example 1, the infrared drying is completed by a first isothermal interval and a temperature rise interval, and in example 2, a second isothermal interval occurs in the interval of 20 minutes to 30 minutes, wherein the temperature is slowly raised again after the temperature rise interval. In example 4, a first isothermal zone of 20 minutes occurred from the start of drying, a temperature rise zone occurred in a zone of 20 minutes to 35 minutes, and a second isothermal zone occurred in a zone of 35 minutes to 40 minutes. As described above, the first isothermal zone, the temperature-increasing zone, and the second isothermal zone can be confirmed by the temperature change with drying time of the center of the dried sample in example 1, example 2, and example 4 shown in fig. 1.

In addition, fig. 3 shows the temperature change of the center of the dried sample according to the drying time in comparative examples 4 and 5, and referring to fig. 3, in comparative example 4, a first isothermal zone in which the temperature of the wet gel mat slowly increased at a constant inclination value for 20 minutes from the start of drying and then a temperature increase zone for 35 minutes occurred. Further, in comparative example 5, a first isothermal zone occurred in which the temperature of the wet gel mat was slowly increased at a constant inclination value for 35 minutes from the start of drying, and then a temperature increase zone occurred for 30 minutes.

Meanwhile, referring to table 1 above, it can be seen that examples 1 to 6, in which infrared drying is performed such that each time of the first isothermal zone, the temperature rise zone, and the second isothermal zone is included in the range specified in the present invention, have lower values of thermal conductivity and moisture impregnation rate, compared to comparative examples 1 to 7, in which drying is performed but infrared drying is not performed, or even infrared drying is performed but the time of each zone is out of the above time range.

Specifically, it can be seen that examples 1 to 6 exhibited significantly lower values of thermal conductivity and moisture impregnation rate than comparative example 1 in which hot air drying was performed without infrared drying, and exhibited thermal conductivity comparable to comparative example 2 in which supercritical drying was performed, but had a lower moisture impregnation rate, and in particular, the drying time was greatly shortened.

In addition, it can be confirmed that examples 1 to 6 have a shorter total drying time, a lower thermal conductivity, and particularly, a significantly lower moisture impregnation rate, compared to comparative example 3 in which the second isothermal zone is out of the range of the present invention, thereby having excellent hydrophobicity. Further, it can be seen that examples 1 to 6 have lower thermal conductivity values than comparative examples 4 and 5 in which the first equal temperature zone or the temperature-increasing zone is longer than the range of the present invention. Further, it can be seen that examples 1 to 6 have lower thermal conductivity and, in particular, significantly lower moisture impregnation rate, compared to comparative examples 6 and 7 in which the time of the first equal temperature zone or the temperature rise zone is shorter than the range of the present invention, thereby having excellent hydrophobicity.

[ Table 2]

	BET specific surface area (m)2/g)	Pore volume (cm)3/g)	Average pore diameter (nm)
				Example 1	667	2.08	9.0
Example 2	495	1.63	8.9
				Comparative example 1	413	1.14	7.4

As shown in table 2 above, it can be seen that examples 1 and 2, in which infrared drying was performed such that the respective times of the first isothermal zone, the temperature rise zone, and the second isothermal zone were included within the ranges specified in the present invention, exhibited all excellent BET specific surface area, pore volume, and average pore diameter, as compared to comparative example 1 in which hot air drying was performed.