CN112390570A - Phase-change microcapsule composite aluminum trioxide-silicon dioxide aerogel and preparation method thereof - Google Patents

Phase-change microcapsule composite aluminum trioxide-silicon dioxide aerogel and preparation method thereof Download PDF

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CN112390570A
CN112390570A CN201910740261.XA CN201910740261A CN112390570A CN 112390570 A CN112390570 A CN 112390570A CN 201910740261 A CN201910740261 A CN 201910740261A CN 112390570 A CN112390570 A CN 112390570A
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phase
sio
change microcapsule
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章伊婷
李婧
刘洪丽
李亚静
李洪彦
杨建奇
汤秋于
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Tianjin Chengjian University
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    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B28/00—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements
    • C04B28/005—Compositions of mortars, concrete or artificial stone, containing inorganic binders or the reaction product of an inorganic and an organic binder, e.g. polycarboxylate cements containing gelatineous or gel forming binders, e.g. gelatineous Al(OH)3, sol-gel binders
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2111/00—Mortars, concrete or artificial stone or mixtures to prepare them, characterised by specific function, property or use
    • C04B2111/40—Porous or lightweight materials
    • C—CHEMISTRY; METALLURGY
    • C04—CEMENTS; CONCRETE; ARTIFICIAL STONE; CERAMICS; REFRACTORIES
    • C04B—LIME, MAGNESIA; SLAG; CEMENTS; COMPOSITIONS THEREOF, e.g. MORTARS, CONCRETE OR LIKE BUILDING MATERIALS; ARTIFICIAL STONE; CERAMICS; REFRACTORIES; TREATMENT OF NATURAL STONE
    • C04B2201/00—Mortars, concrete or artificial stone characterised by specific physical values
    • C04B2201/30—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values
    • C04B2201/32—Mortars, concrete or artificial stone characterised by specific physical values for heat transfer properties such as thermal insulation values, e.g. R-values for the thermal conductivity, e.g. K-factors

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Abstract

The invention provides a phase-change microcapsule composite aluminum trioxide-silicon dioxide aerogel and a preparation method thereof, wherein the silicon dioxide aerogel and Al are mixed2O3After the sol is hydrolyzed for 1-5h, the silicon dioxide sol is added into Al drop by drop2O3Mechanically stirring in sol at room temperature for 8-26h to obtain Al2O3‑SiO2Mixing the sol with the Al2O3‑SiO2Adding fiber and phase-change microcapsule into the mixed sol, mechanically stirring at room temperature, adding sol polymerization promoter, and gelatinizing to obtain phase-change microcapsule composite Al2O3‑SiO2Gel, phase change microcapsule compounding with Al2O3‑SiO2Soaking the gel in anhydrous ethanol solution, aging for 10-40h, soaking in hydrophobic modifier, and compounding phase change microcapsule with Al2O3‑SiO2Drying the gel at normal temperature and pressure for 10-40h, and drying at 36-85 deg.C for 3-15h to obtain phase change microcapsule composite Al2O3‑SiO2An aerogel. The heat insulation performance of the aerogel is not changed, and meanwhile, the heat storage function is added, so that the heat insulation efficiency and the energy utilization rate of the silicon-based aerogel composite material are improved.

Description

Phase-change microcapsule composite aluminum trioxide-silicon dioxide aerogel and preparation method thereof
Technical Field
The invention relates to the technical field of green energy-saving building materials, in particular to phase-change microcapsule composite Al2O3-SiO2Aerogel and a preparation method thereof.
Background
At present, the application of the phase change material in the building material mainly focuses on the preparation research of porous material loading and the physical compounding of the shape-stabilized phase change material. The existence of a large number of microporous structures enables the solid material to have the advantages of light weight, low thermal conductivity, capacity of loading phase change energy storage materials and the like. The phase change material is loaded in pores of the porous material, and is mostly immersed in porous materials such as concrete blocks, gypsum boards, expanded perlite, diatomite vermiculite and the like by a vacuum injection method, and the building material with certain heat storage capacity is obtained through later-stage building material processing. Although the porosity can reach more than 40 percent, the heat storage performance of the obtained phase change energy storage building material is greatly improved compared with the materials such as common concrete blocks, the density of the material is higher, the heat storage density is lower under the condition of sucking limited phase change materials, and the leakage problem of the amorphous phase change materials in the using process directly influences the practical engineering application. Therefore, the shaped phase change material, namely the phase change microcapsule can solve the leakage problem of the non-shaped phase change material, but the low thermal energy storage density is still a restrictive factor and loses the application significance. In order to guarantee the energy storage-release efficiency of the phase-change material, the method for solving the problem is to compound the phase-change microcapsule and the ultra-low density porous material, and because the influence of the addition of the ultra-low density porous material on the heat energy storage efficiency of the phase-change microcapsule is very small, the possibility is provided for preparing the building thermal regulation material with practical value.
The nano aerogel is a super-light solid material with a nano porous structure, wherein a nano porous network structure is formed by gathering nano colloidal particles serving as a framework, and gaseous dispersion media are filled in gaps. In particular, silicon-based aerogel materials are considered by researchers to be the most potential heat insulation materials, the thermal conductivity of the materials is lower than that of 'convection-free air', and the application of the materials in the field of buildings can improve the energy-saving effect by orders of magnitude, so that the materials increasingly show great advantages and prospects. In particular Al2O3Its skeleton thermal conductivity of aerogel is higher, uses it as skeleton material load phase change microcapsule, can make the thermal current transmit phase change microcapsule inside along the aerogel skeleton under the relatively lower prerequisite of assurance body phase thermal conductivity, realizes that intelligence adjusts the temperature.
However, the inherent brittleness and poor mechanical strength of inorganic aerogels limit their practical application in the construction field, and the mechanical properties of aerogels can be effectively improved by a fiber reinforcement strategy. In addition, the traditional supercritical preparation method has higher requirements on equipment and cannot adapt to the preparation of large-batch building materials, and the research on the preparation of aerogel for buildings focuses on the normal pressure technology.
Disclosure of Invention
The invention overcomes the defects in the prior art and provides the phase change microcapsule composite Al2O3-SiO2The invention provides the aerogel and the preparation method thereof, provides a simple and easy-to-operate preparation process for preparing the heat-insulating aerogel with the special heat storage function, and has good applicability in the aspects of building material heat-insulating and heat-storing wall materials, glass interlayer materials and the like.
The purpose of the invention is realized by the following technical scheme.
Phase-change microcapsule complexAlloy of Al2O3-SiO2The aerogel and the preparation method thereof are carried out according to the following steps:
step 1, adding tetraethyl orthosilicate into an ethanol water solution, mechanically stirring uniformly at room temperature (20-25 ℃), adding an acidic catalyst into the dispersion liquid, and adjusting the pH of the dispersion liquid to 1-3 to obtain silicon dioxide sol, wherein the adding amount of the tetraethyl orthosilicate is 4-22 parts by mass;
step 2, adding aluminum chloride hexahydrate into ethanol water solution, and mechanically stirring uniformly at room temperature (20-25 ℃) to obtain Al2O3Sol, wherein the adding amount of aluminum chloride hexahydrate is 1-12 parts by mass;
step 3, the silicon dioxide sol prepared in the step 1 and the Al prepared in the step 2 are mixed2O3After the sol is hydrolyzed for 1-5h, the silicon dioxide sol is added into Al drop by drop2O3Mechanically stirring in sol at room temperature (20-25 deg.C) for 8-26 hr to obtain Al2O3-SiO2Mixing the sol with the Al2O3-SiO2Adding fiber and phase-change microcapsule into the mixed sol, mechanically stirring at room temperature (20-25 deg.C), adding sol polymerization promoter, and gelatinizing to obtain phase-change microcapsule composite Al2O3-SiO2Gel, phase change microcapsule compounding with Al2O3-SiO2Soaking the gel in anhydrous ethanol solution, aging for 10-40h, soaking in hydrophobic modifier, and compounding phase change microcapsule with Al2O3-SiO2Drying the gel at normal temperature and pressure for 10-40h, and drying at 36-85 deg.C for 3-15h to obtain phase change microcapsule composite Al2O3-SiO2Aerogels, among them, silica sol and Al2O3The mass ratio of the sol is (15-85): (5-55), the fiber adopts quartz fiber, glass fiber, bacterial nano fiber or high silica fiber, and the adding proportion of the fiber and the phase change microcapsule is (1-6): (4-32), 1,2 epoxypropane or ammonia water is adopted as the sol polymerization accelerator, the addition amount of the sol polymerization accelerator is 1-6 parts by mass, and silane coupling agent and low-molecular-weight silane coupling agent are adopted as the hydrophobic modifierThe molar ratio of the surface tension solvent to the silane coupling agent to the low surface tension solvent is 1: (1-5), and the addition amount of the hydrophobic modifier is 8-32 parts by mass.
In the step 1, the adding amount of tetraethyl orthosilicate is 5-20 parts by mass, and the mass ratio of absolute ethyl alcohol to distilled water in the ethanol water solution is (10-60): (1-10), the acid catalyst adopts hydrochloric acid, nitric acid, phosphoric acid or oxalic acid, and hydrochloric acid is preferred.
In the step 2, the adding amount of the aluminum chloride hexahydrate is 1-10 parts by mass, and the mass ratio of absolute ethyl alcohol to distilled water in the ethanol water solution is (3-30): (1-5).
In step 3, silica sol and Al2O3The mass ratio of the sol is (20-80): (10-50), the adding proportion of the fibers and the phase-change microcapsules is (1-5): (5-30), the diameter of the phase-change microcapsule is 10-25 μm, the energy storage density is 120J/g, the phase-change temperature is 25 ℃, the diameter of the fiber is 5-10 μm, and the length is 20-100 μm; the sol polymerization accelerator is added in an amount of 1-5 parts by mass, and the hydrophobic modifier is added in an amount of 10-30 parts by mass, wherein the hydrophobic modifier adopts gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, methyltrimethoxysilane or hexamethyldisilazane as a silane coupling agent, and the hydrophobic modifier adopts isopropanol, isobutanol, glycerol, n-hexane, pentane, diethyl ether, methyl ethyl ether or acetone as a low surface tension solvent.
In step 3, silica sol and Al2O3Hydrolyzing the sol for 1-4h, and mixing the silica sol and Al2O3Dripping sol, mixing and stirring for 10-24h at the dripping speed of 1-5 drops/min, and compounding phase-change microcapsule with Al2O3-SiO2Soaking the gel in anhydrous ethanol solution, aging for 12-36h, soaking in hydrophobic modifier, and compounding phase change microcapsule with Al2O3-SiO2Drying the gel at normal temperature and pressure for 12-36 hr, and drying at 40-80 deg.C for 4-12 hr.
The invention adopts tetraethoxysilane, aluminum chloride hexahydrate and hydrophobic silane coupling agent as raw materials for preparing silicon aerogel precursor, and utilizes acidHydrolyzing ethyl orthosilicate and aluminum chloride hexahydrate to obtain SiO2Sol and Al2O3Sol, preparing Al from both sols in a certain proportion2O3-SiO2Composite sol, adding nanometer modified paraffin phase change microcapsule and fiber reinforcement (micron level fiber with diameter and length up to micron level) into Al2O3-SiO2And (3) sol, namely mixing the sol with a sol polymerization promoter to generate gel, and finally performing normal-temperature aging and modification to generate the composite aerogel under the normal-pressure drying condition.
The invention has the beneficial effects that: the preparation method adopted by the invention is simple, the used raw materials are rich and easy to obtain, the reaction condition is mild, the industrial batch production is easy, the conversion into a practical technology is hopeful, the achievement is easy to convert, and the economic benefit and the environmental significance are very important; the obtained fiber-reinforced aerogel phase-change microcapsule composite material maintains the self heat insulation characteristic of aerogel, simultaneously increases the base heat storage function, removes the contradiction between heat insulation and heat storage, can directly use solar energy, electric energy or time difference heat energy and the like in a non-instant manner, namely stores energy when the supply exceeds the use amount, and automatically releases the energy for use when in need, thereby improving the heat insulation efficiency and the energy utilization rate of the silicon-based aerogel composite material; the high silica fiber added in the invention has heat-conducting property, can effectively transfer heat between the aerogel and the phase-change outer capsule, and ensures the timeliness and effectiveness of the phase-change material for absorbing and releasing heat.
Drawings
FIG. 1 shows phase change microcapsule composite Al prepared by the invention2O3-SiO2Macroscopic and microscopic topography maps of the aerogel, wherein (a) is a macroscopic topography map, and (b) is a microscopic topography map, namely a scanning electron microscope map;
FIG. 2 shows the phase change microcapsule composite Al prepared by the invention2O3-SiO2DSC curve of aerogel;
FIG. 3 shows the phase change microcapsule composite Al prepared by the present invention2O3-SiO2Thermal conductivity curve of aerogel.
Detailed Description
The technical solution of the present invention is further illustrated by the following specific examples. The phase change microcapsule is purchased from Hubei Saimer New energy science and technology Limited, the diameter is 10-25 μm, the energy storage density is 120J/g, and the phase change temperature is 25 ℃; the quartz fiber is purchased from New materials GmbH of Tian navigation in Henan province, the bacterial fiber (i.e. antibacterial fiber) is purchased from Guilin Qihong scientific and technology GmbH, the glass fiber and the high silica fiber are purchased from New materials GmbH in Shanxi Huate, and the micron-sized fiber is selected for use. In the present invention, the volume of each drop of the added amount is controlled to be 0.05ml for the use of the acidic catalyst (hydrochloric acid), the basic catalyst (aqueous sodium hydroxide solution) and the silica sol; the mass ratio of each component is 1g in parts by mass.
Example 1
(1) Tetraethyl orthosilicate, ethanol and distilled water are mixed by TEOS, EtOH and H2Mixing O8: 23:3, stirring at room temperature until the mixture is uniformly mixed, adding 5 drops of hydrochloric acid to adjust the pH of the mixed solution to 1-2, and performing catalytic hydrolysis to prepare the silica sol.
(2) Using aluminium chloride hexahydrate, ethyl alcohol, distilled water and AlCl3·6H2O:EtOH:H2Mixing the materials in a mass ratio of 3:10:1, and stirring the mixture at room temperature until the solution is uniform to obtain Al2O3And (3) sol.
(3) Hydrolyzing the sol for 2h, and then adding 30 parts of SiO 210 parts of Al are added to the sol at a rate of 1 drop/min2O3Stirring the sol for 10 hours to obtain uniform Al2O3-SiO2And mixing the sol. Adding 1 part of quartz fiber and 5 parts of phase-change microcapsule to mixed Al2O3-SiO2After the sol is uniformly stirred, 1 part of sol polymerization accelerator is added, and gelation generally occurs within 0.5 to 1 hour. Compounding phase change with Al2O3-SiO2And aging the gel by using an absolute ethyl alcohol solution for 24 hours, and then soaking the gel into n-hexane containing 30 wt% of hexamethyldisilazane for modification for 8 hours. Finally, Al is added2O3-SiO2Drying the composite gel for 24 hours at normal temperature and normal pressureDrying for 10h at 40 ℃ to obtain the phase change microcapsule composite Al2O3-SiO2An aerogel.
As shown in fig. 1, a is a macroscopic view of the aerogel prepared in example 1, which shows that the aerogel has good moldability and does not generate chalking, and b is a scanning electron microscope picture of the aerogel prepared in example 1, which shows that the aerogel maintains a good pore structure after the phase-change microcapsules are added.
As shown in FIG. 2, the phase change microcapsule is compounded with Al2O3-SiO2The crystallization enthalpy value of the aerogel is 42.24J/g, the phase change temperature of the crystallization is 15.0 ℃, and the phase change microcapsule is compounded with Al2O3-SiO2The heat of fusion of the aerogel was 30.14J/g, and the phase transition temperature of the fusion was 26.5 ℃.
As shown in FIG. 3, towards Al2O3-SiO2The addition of the phase-change microcapsules into the mixed sol can cause the heat conductivity coefficient of the aerogel to be increased, and the heat conductivity coefficient floats between 0.05 and 0.055W/(m.K), so the addition of the phase-change microcapsules has little influence on the heat insulation effect.
Example 2
(1) Tetraethyl orthosilicate, ethanol and distilled water are mixed by TEOS, EtOH and H2Mixing O-10: 20:4, stirring at room temperature until the mixture is uniformly mixed, adding 5 drops of hydrochloric acid to adjust the pH of the mixed solution to 1-3, and performing catalytic hydrolysis to prepare the silica sol.
(2) Using aluminium chloride hexahydrate, ethyl alcohol, distilled water and AlCl3·6H2O:EtOH:H2Mixing O4: 9:2 in mass ratio, and stirring at room temperature until the solution is uniform to obtain Al2O3And (3) sol.
(3) Hydrolyzing the sol for 1h, and then adding 30 parts of SiO 210 parts of Al are added into the sol at the speed of 3 drops/min2O3Stirring the sol for 8 hours to obtain uniform Al2O3-SiO2And mixing the sol. Adding 2 parts of antibacterial fiber and 5 parts of phase-change microcapsule to the mixed Al2O3-SiO2After the sol is uniformly stirred, 1 part of sol polymerization accelerator is added, and gelation generally occurs within 0.5 to 1 hour. Compounding phase change with Al2O3-SiO2The gel is aged by absolute ethyl alcohol solution for 10 hours and then is soaked in n-hexane containing 30 percent of hexamethyldisilazane for modification for 16 hours. Finally, Al is added2O3-SiO2Drying the composite gel at normal temperature and normal pressure for 10h, and drying at 36 ℃ for 12h to obtain the phase-change microcapsule composite Al2O3-SiO2An aerogel.
Example 3
(1) Tetraethyl orthosilicate, ethanol and distilled water are mixed by TEOS, EtOH and H2Mixing O8: 23:3, stirring at room temperature until the mixture is uniformly mixed, adding 5 drops of hydrochloric acid to adjust the pH of the mixed solution to 1-2, and performing catalytic hydrolysis to prepare the silica sol.
(2) Using aluminium chloride hexahydrate, ethyl alcohol, distilled water and AlCl3·6H2O:EtOH:H2Mixing the materials in a mass ratio of 3:10:1, and stirring the mixture at room temperature until the solution is uniform to obtain Al2O3And (3) sol.
(3) Hydrolyzing the sol for 3h, and then adding 40 parts of SiO 220 parts of Al are added to the sol at a rate of 4 drops/min2O3Stirring the sol for 26 hours to obtain uniform Al2O3-SiO2And mixing the sol. Adding 3 parts of glass fiber and 10 parts of phase-change microcapsule to mixed Al2O3-SiO2After the sol is uniformly stirred, 2 parts of sol polymerization accelerator is added, and gelation generally occurs within 0.5 to 1 hour. Compounding phase change with Al2O3-SiO2The gel is aged by absolute ethyl alcohol solution for 40h, and then is soaked in n-hexane containing 30% hexamethyldisilazane for modification for 24 h. Finally, Al is added2O3-SiO2Drying the composite gel at normal temperature and normal pressure for 40h, and drying at 85 ℃ for 4h to obtain the phase-change microcapsule composite Al2O3-SiO2An aerogel.
Example 4
(1) Tetraethyl orthosilicate, ethanol and distilled water are mixed by TEOS, EtOH and H2Mixing O-10: 20:4, stirring at room temperature until the mixture is uniformly mixed, adding 5 drops of hydrochloric acid to adjust the pH of the mixed solution to 1-2, and performing catalytic hydrolysis to prepare the silica sol.
(2) With aluminium chloride hexahydrateEthanol, distilled water and AlCl3·6H2O:EtOH:H2Mixing O4: 9:2 in mass ratio, and stirring at room temperature until the solution is uniform to obtain Al2O3And (3) sol.
(3) Hydrolyzing the sol for 4h, and then adding 40 parts of SiO 210 parts of Al are added to the sol at a rate of 5 drops/min2O3Stirring the sol for 10 hours to obtain uniform Al2O3-SiO2And mixing the sol. Adding 3 parts of quartz fiber and 5 parts of phase-change microcapsule to mixed Al2O3-SiO2After the sol is uniformly stirred, 3 parts of sol polymerization accelerator is added, and gelation generally occurs within 0.5-1 h. Compounding phase change with Al2O3-SiO2The gel is aged for 12h by absolute ethyl alcohol solution and then is soaked in n-hexane containing 30% hexamethyldisilazane for modification for 8 h. Finally, Al is added2O3-SiO2Drying the composite gel at normal temperature and normal pressure for 12h, and drying at 40 ℃ for 15h to obtain the phase-change microcapsule composite Al2O3-SiO2An aerogel.
Example 5
(1) Tetraethyl orthosilicate, ethanol and distilled water are mixed by TEOS, EtOH and H2Mixing O8: 23:3, stirring at room temperature until the mixture is uniformly mixed, adding 5 drops of hydrochloric acid to adjust the pH of the mixed solution to 1-2, and performing catalytic hydrolysis to prepare the silica sol.
(2) Using aluminium chloride hexahydrate, ethyl alcohol, distilled water and AlCl3·6H2O:EtOH:H2Mixing the materials in a mass ratio of 3:10:1, and stirring the mixture at room temperature until the solution is uniform to obtain Al2O3And (3) sol.
(3) Hydrolyzing the sol for 5h, and then adding 10 parts of SiO 230 parts of Al are added into the sol at a speed of 2 drops/min2O3Stirring the sol for 24 hours to obtain uniform Al2O3-SiO2And mixing the sol. Adding 1 part of high silica fiber and 10 parts of phase change microcapsule to mixed Al2O3-SiO2After the sol is uniformly stirred, 2 parts of sol polymerization accelerator is added, and gelation generally occurs within 0.5 to 1 hour. Compounding phase change with Al2O3-SiO2The gel is aged by absolute ethyl alcohol solution for 36h, and then is soaked in n-hexane containing 30% hexamethyldisilazane for modification for 24 h. Finally, Al is added2O3-SiO2Drying the composite gel at normal temperature and normal pressure for 36h, and drying at 80 ℃ for 3h to obtain the phase-change microcapsule composite Al2O3-SiO2An aerogel.
The process parameters are adjusted according to the content of the invention, so that the phase change microcapsule composite Al can be realized2O3-SiO2The preparation of aerogel, through testing, the phase change microcapsule of the invention compounds Al2O3-SiO2The crystallization enthalpy value of the aerogel is 40-45J/g, the phase-change temperature of the crystallization is 15 +/-2 ℃, the melting enthalpy value of the phase-change composite aerogel is 30-32J/g, the melting phase-change temperature is 26 +/-2 ℃, and the heat conductivity coefficient of the aerogel is increased by adding the phase-change microcapsules into the silica sol and floats between 0.04-0.06W/(m.K).
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (10)

1. The phase-change microcapsule composite aluminum trioxide-silicon dioxide aerogel is characterized in that: the method comprises the following steps:
step 1, adding tetraethyl orthosilicate into an ethanol water solution, mechanically stirring uniformly at room temperature (20-25 ℃), adding an acidic catalyst into the dispersion liquid, and adjusting the pH of the dispersion liquid to 1-3 to obtain silicon dioxide sol, wherein the adding amount of the tetraethyl orthosilicate is 4-22 parts by mass;
step 2, adding aluminum chloride hexahydrate into ethanol water solution, and mechanically stirring uniformly at room temperature (20-25 ℃) to obtain Al2O3Sol, wherein the adding amount of aluminum chloride hexahydrate is 1-12 parts by mass;
step 3, preparing the silica sol prepared in the step 1 and the silica sol prepared in the step 2To Al2O3After the sol is hydrolyzed for 1-5h, the silicon dioxide sol is added into Al drop by drop2O3Mechanically stirring in sol at room temperature (20-25 deg.C) for 8-26 hr to obtain Al2O3-SiO2Mixing the sol with the Al2O3-SiO2Adding fiber and phase-change microcapsule into the mixed sol, mechanically stirring at room temperature (20-25 deg.C), adding sol polymerization promoter, and gelatinizing to obtain phase-change microcapsule composite Al2O3-SiO2Gel, phase change microcapsule compounding with Al2O3-SiO2Soaking the gel in anhydrous ethanol solution, aging for 10-40h, soaking in hydrophobic modifier, and compounding phase change microcapsule with Al2O3-SiO2Drying the gel at normal temperature and pressure for 10-40h, and drying at 36-85 deg.C for 3-15h to obtain phase change microcapsule composite Al2O3-SiO2Aerogels, among them, silica sol and Al2O3The mass ratio of the sol is (15-85): (5-55), the fiber adopts quartz fiber, glass fiber, bacterial fiber or high silica fiber, and the adding proportion of the fiber and the phase change microcapsule is (1-6): (4-32), 1, 2-epoxypropane or ammonia water is adopted as a sol polymerization accelerator, the addition amount of the sol polymerization accelerator is 1-6 parts by mass, a silane coupling agent and a low surface tension solvent are adopted as a hydrophobic modifier, and the molar ratio of the silane coupling agent to the low surface tension solvent is 1: (1-5), and the addition amount of the hydrophobic modifier is 8-32 parts by mass.
2. The phase change microcapsule composite aluminum trioxide-silica aerogel according to claim 1, wherein: in the step 1, the adding amount of tetraethyl orthosilicate is 5-20 parts by mass, and the mass ratio of absolute ethyl alcohol to distilled water in the ethanol water solution is (10-60): (1-10), the acid catalyst is hydrochloric acid, nitric acid, phosphoric acid or oxalic acid, preferably hydrochloric acid; in the step 2, the adding amount of the aluminum chloride hexahydrate is 1-10 parts by mass, and the mass ratio of absolute ethyl alcohol to distilled water in the ethanol water solution is (3-30): (1-5).
3. The phase change microcapsule composite aluminum trioxide-silica aerogel according to claim 1, wherein: in step 3, silica sol and Al2O3The mass ratio of the sol is (20-80): (10-50), the adding proportion of the fibers and the phase-change microcapsules is (1-5): (5-30), the diameter of the phase-change microcapsule is 10-25 μm, the energy storage density is 120J/g, the phase-change temperature is 25 ℃, the diameter of the fiber is 5-10 μm, and the length is 20-100 μm; the sol polymerization accelerator is added in an amount of 1-5 parts by mass, and the hydrophobic modifier is added in an amount of 10-30 parts by mass, wherein the hydrophobic modifier adopts gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, methyltrimethoxysilane or hexamethyldisilazane as a silane coupling agent, and the hydrophobic modifier adopts isopropanol, isobutanol, glycerol, n-hexane, pentane, diethyl ether, methyl ethyl ether or acetone as a low surface tension solvent.
4. The phase change microcapsule composite aluminum trioxide-silica aerogel according to claim 1, wherein: in step 3, silica sol and Al2O3Hydrolyzing the sol for 1-4h, and mixing the silica sol and Al2O3Dripping sol, mixing and stirring for 10-24h at the dripping speed of 1-5 drops/min, and compounding phase-change microcapsule with Al2O3-SiO2Soaking the gel in anhydrous ethanol solution, aging for 12-36h, soaking in hydrophobic modifier, and compounding phase change microcapsule with Al2O3-SiO2Drying the gel at normal temperature and pressure for 12-36 hr, and drying at 40-80 deg.C for 4-12 hr.
5. A preparation method of phase-change microcapsule composite aluminum trioxide-silicon dioxide aerogel is characterized by comprising the following steps: the method comprises the following steps:
step 1, adding tetraethyl orthosilicate into an ethanol water solution, mechanically stirring uniformly at room temperature (20-25 ℃), adding an acidic catalyst into the dispersion liquid, and adjusting the pH of the dispersion liquid to 1-3 to obtain silicon dioxide sol, wherein the adding amount of the tetraethyl orthosilicate is 4-22 parts by mass;
step 2, adding aluminum chloride hexahydrate into ethanol water solution, and mechanically stirring uniformly at room temperature (20-25 ℃) to obtain Al2O3Sol, wherein the adding amount of aluminum chloride hexahydrate is 1-12 parts by mass;
step 3, the silicon dioxide sol prepared in the step 1 and the Al prepared in the step 2 are mixed2O3After the sol is hydrolyzed for 1-5h, the silicon dioxide sol is added into Al drop by drop2O3Mechanically stirring in sol at room temperature (20-25 deg.C) for 8-26 hr to obtain Al2O3-SiO2Mixing the sol with the Al2O3-SiO2Adding fiber and phase-change microcapsule into the mixed sol, mechanically stirring at room temperature (20-25 deg.C), adding sol polymerization promoter, and gelatinizing to obtain phase-change microcapsule composite Al2O3-SiO2Gel, phase change microcapsule compounding with Al2O3-SiO2Soaking the gel in anhydrous ethanol solution, aging for 10-40h, soaking in hydrophobic modifier, and compounding phase change microcapsule with Al2O3-SiO2Drying the gel at normal temperature and pressure for 10-40h, and drying at 36-85 deg.C for 3-15h to obtain phase change microcapsule composite Al2O3-SiO2Aerogels, among them, silica sol and Al2O3The mass ratio of the sol is (15-85): (5-55), the fiber adopts quartz fiber, glass fiber, bacterial nano fiber or high silica fiber, and the adding proportion of the fiber and the phase change microcapsule is (1-6): (4-32), 1, 2-epoxypropane or ammonia water is adopted as a sol polymerization accelerator, the addition amount of the sol polymerization accelerator is 1-6 parts by mass, a silane coupling agent and a low surface tension solvent are adopted as a hydrophobic modifier, and the molar ratio of the silane coupling agent to the low surface tension solvent is 1: (1-5), and the addition amount of the hydrophobic modifier is 8-32 parts by mass.
6. The preparation method of the phase-change microcapsule composite aluminum trioxide-silica aerogel according to claim 5, which is characterized in that: in the step 1, the adding amount of tetraethyl orthosilicate is 5-20 parts by mass, and the mass ratio of absolute ethyl alcohol to distilled water in the ethanol water solution is (10-60): (1-10), the acid catalyst is hydrochloric acid, nitric acid, phosphoric acid or oxalic acid, preferably hydrochloric acid; in the step 2, the adding amount of the aluminum chloride hexahydrate is 1-10 parts by mass, and the mass ratio of absolute ethyl alcohol to distilled water in the ethanol water solution is (3-30): (1-5).
7. The preparation method of the phase-change microcapsule composite aluminum trioxide-silica aerogel according to claim 5, which is characterized in that: in step 3, silica sol and Al2O3The mass ratio of the sol is (20-80): (10-50), the adding proportion of the fibers and the phase-change microcapsules is (1-5): (5-30), the diameter of the phase-change microcapsule is 10-25 μm, the energy storage density is 120J/g, the phase-change temperature is 25 ℃, the diameter of the fiber is 5-10 μm, and the length is 20-100 μm; the sol polymerization accelerator is added in an amount of 1-5 parts by mass, and the hydrophobic modifier is added in an amount of 10-30 parts by mass, wherein the hydrophobic modifier adopts gamma-aminopropyltriethoxysilane, gamma-glycidoxypropyltrimethoxysilane, gamma- (methacryloyloxy) propyltrimethoxysilane, methyltrimethoxysilane or hexamethyldisilazane as a silane coupling agent, and the hydrophobic modifier adopts isopropanol, isobutanol, glycerol, n-hexane, pentane, diethyl ether, methyl ethyl ether or acetone as a low surface tension solvent.
8. The preparation method of the phase-change microcapsule composite aluminum trioxide-silica aerogel according to claim 5, which is characterized in that: in step 3, silica sol and Al2O3Hydrolyzing the sol for 1-4h, and mixing the silica sol and Al2O3Dripping sol, mixing and stirring for 10-24h at the dripping speed of 1-5 drops/min, and compounding phase-change microcapsule with Al2O3-SiO2Soaking the gel in anhydrous ethanol solution, aging for 12-36h, soaking in hydrophobic modifier, and compounding phase change microcapsule with Al2O3-SiO2Drying the gel at normal temperature and pressure for 12-36 hr, and drying at 40-80 deg.C for 4-12 hr.
9. Use of the phase change microencapsulated composite aluminum trioxide-silica aerogel according to any one of claims 1 to 4 for the preparation of thermal insulation materials.
10. Use according to claim 9, characterized in that: phase change microcapsule composite Al2O3-SiO2The crystallization enthalpy value of the aerogel is 40-45J/g, the phase-change temperature of the crystallization is 15 +/-2 ℃, the melting enthalpy value of the phase-change composite aerogel is 30-32J/g, the melting phase-change temperature is 26 +/-2 ℃, and the heat conductivity coefficient of the aerogel is increased by adding the phase-change microcapsules into the silica sol and is between 0.04 and 0.06W/(m.K).
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CN113895101A (en) * 2021-08-25 2022-01-07 河南爱彼爱和新材料有限公司 Flexible hydrophobic aerogel heat insulation sheet with energy storage characteristic and preparation method thereof
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Publication number Priority date Publication date Assignee Title
CN113248277A (en) * 2021-07-01 2021-08-13 江苏脒诺甫纳米材料有限公司 Production process of high-temperature-resistant nano porous material
CN113895101A (en) * 2021-08-25 2022-01-07 河南爱彼爱和新材料有限公司 Flexible hydrophobic aerogel heat insulation sheet with energy storage characteristic and preparation method thereof
CN113895101B (en) * 2021-08-25 2023-09-22 河南爱彼爱和新材料有限公司 Flexible hydrophobic aerogel heat insulation sheet with energy storage characteristic and preparation method thereof
CN114181671A (en) * 2021-12-31 2022-03-15 中国科学技术大学先进技术研究院 Preparation method of silicon dioxide aerogel phase-change composite material
CN114181671B (en) * 2021-12-31 2023-09-26 中国科学技术大学先进技术研究院 Preparation method of silica aerogel phase-change composite material
CN114698903A (en) * 2022-04-26 2022-07-05 晋江市书传鞋材科技有限公司 Leather composite insole and preparation method thereof
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