CN118307834A - Basalt flake/cellulose nanofiber composite aerogel and preparation method and application thereof - Google Patents
Basalt flake/cellulose nanofiber composite aerogel and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 120
- 239000004964 aerogel Substances 0.000 title claims abstract description 102
- 239000002121 nanofiber Substances 0.000 title claims abstract description 102
- 229920002678 cellulose Polymers 0.000 title claims abstract description 100
- 239000001913 cellulose Substances 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 45
- 239000008367 deionised water Substances 0.000 claims abstract description 22
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 22
- 229910021538 borax Inorganic materials 0.000 claims abstract description 18
- UQGFMSUEHSUPRD-UHFFFAOYSA-N disodium;3,7-dioxido-2,4,6,8,9-pentaoxa-1,3,5,7-tetraborabicyclo[3.3.1]nonane Chemical compound [Na+].[Na+].O1B([O-])OB2OB([O-])OB1O2 UQGFMSUEHSUPRD-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000004108 freeze drying Methods 0.000 claims abstract description 18
- 235000010339 sodium tetraborate Nutrition 0.000 claims abstract description 18
- 239000004328 sodium tetraborate Substances 0.000 claims abstract description 18
- 238000002156 mixing Methods 0.000 claims abstract description 17
- 238000007710 freezing Methods 0.000 claims abstract description 16
- 230000008014 freezing Effects 0.000 claims abstract description 16
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 16
- 238000000967 suction filtration Methods 0.000 claims abstract description 15
- 238000010521 absorption reaction Methods 0.000 claims abstract description 13
- 238000000498 ball milling Methods 0.000 claims abstract description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 48
- 230000002209 hydrophobic effect Effects 0.000 claims description 30
- BFXIKLCIZHOAAZ-UHFFFAOYSA-N methyltrimethoxysilane Chemical compound CO[Si](C)(OC)OC BFXIKLCIZHOAAZ-UHFFFAOYSA-N 0.000 claims description 23
- 230000003213 activating effect Effects 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 19
- 239000000243 solution Substances 0.000 claims description 15
- 230000004913 activation Effects 0.000 claims description 11
- 239000012670 alkaline solution Substances 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 5
- 238000011084 recovery Methods 0.000 claims description 4
- 229920000875 Dissolving pulp Polymers 0.000 claims description 3
- 239000003344 environmental pollutant Substances 0.000 claims description 3
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- 239000003305 oil spill Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 53
- 238000009413 insulation Methods 0.000 abstract description 7
- 239000000126 substance Substances 0.000 abstract description 6
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 abstract description 4
- 230000000694 effects Effects 0.000 abstract description 4
- 239000003063 flame retardant Substances 0.000 abstract description 4
- 239000000499 gel Substances 0.000 description 44
- 238000006243 chemical reaction Methods 0.000 description 11
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- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
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- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
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- 230000005540 biological transmission Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- BRPQOXSCLDDYGP-UHFFFAOYSA-N calcium oxide Chemical compound [O-2].[Ca+2] BRPQOXSCLDDYGP-UHFFFAOYSA-N 0.000 description 1
- 239000000292 calcium oxide Substances 0.000 description 1
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- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
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- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- NDLPOXTZKUMGOV-UHFFFAOYSA-N oxo(oxoferriooxy)iron hydrate Chemical compound O.O=[Fe]O[Fe]=O NDLPOXTZKUMGOV-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses basalt flake/cellulose nanofiber composite aerogel and a preparation method and application thereof, belonging to the field of aerogel materials, and comprising the following steps: mixing the activated basalt flakes with a cellulose nanofiber solution, and performing ball milling treatment to obtain composite gel A; adding sodium tetraborate into the composite gel A, performing ultrasonic treatment, and performing ball milling treatment to obtain basalt flake/cellulose nanofiber composite gel; mixing basalt flake/cellulose nanofiber composite gel with deionized water, performing vacuum suction filtration, and finally sequentially performing pre-freezing and freeze-drying to obtain the basalt flake/cellulose nanofiber composite aerogel. According to the invention, the basalt flake/cellulose nanofiber composite aerogel achieves a flame retardant effect, and the basalt flake/cellulose nanofiber composite gives the aerogel excellent sound absorption performance and heat insulation performance, so that the problems of high chemical inertia of the basalt flake and limited application fields are solved.
Description
Technical Field
The invention belongs to the field of aerogel materials, and particularly relates to basalt flake/cellulose nanofiber composite aerogel, and a preparation method and application thereof.
Background
The product that retains the gel self-body volume and network structure after the hydrogel or organogel dries is referred to as an aerogel. Aerogel has been widely used in the fields of ocean spilled oil recovery, building energy conservation, aerospace heat insulation, etc. because of its extremely high porosity (higher than 99.0%), ultra-high specific surface area (up to 500m 2g-1), extremely low density (down to 0.12mg cm -3), and excellent adsorption performance, heat insulation performance and sound absorption performance exhibited by mesoporous (2-50 nm) and macroporous structures at mesoscale. Pure inorganic aerogel has strong chemical inertia, good weather resistance and flame combustion resistance, but the application of the pure inorganic aerogel in the field of building heat preservation is limited due to poor mechanical strength and brittleness; the organic aerogel prepared from the high-molecular polymer is strong in structure and good in mechanical strength and toughness, but poor in thermal stability, and has certain limitation in the application process. Therefore, researchers have proposed a preparation strategy of inorganic-organic composite aerogel, and have paid attention to the advantages of inorganic aerogel and organic aerogel in recent years.
Basalt flakes (Basalt scale, BS) are lamellar materials which are obtained by processing dark and black volcanic rock basalt through a specific technical means, are also inorganic nonmetallic materials, have main chemical components similar to basalt, and are metal and nonmetallic oxides such as silicon dioxide, aluminum oxide, calcium oxide, ferric oxide, magnesium oxide and the like. Basalt flakes have the advantages of low cost, wear resistance, high temperature resistance, corrosion resistance and oxidation resistance, and currently, most research is on applying basalt flakes to the field of corrosion resistance. However, the basalt flakes have smooth surface structure and higher chemical inertia, cannot be dispersed in water, and cannot be independently used as a base material to prepare aerogel materials with functional application, so that the application range of the basalt flakes is greatly limited.
Cellulose nanofibers (Cellulose nanofibrils, CNFs) derived from plant fibers have a high aspect ratio and a large specific surface area, and the surface of the cellulose nanofibers is rich in a large number of polar functional groups, so that the lightweight porous aerogel material can be prepared by a freeze drying method. The cellulose nano-fiber serving as a framework material can be compounded with basalt flakes, so that the whole has certain mechanical strength. Although the cellulose nanofiber has good biocompatibility and easy degradability, the cellulose nanofiber is easy to burn when meeting fire after being dried, swelling and decomposition can occur in water, and aerogel materials prepared from the cellulose nanofiber also have the characteristics of water instability and the like. The basalt flakes can exert the advantages of flame retardance and the like, and make up the defects of cellulose nanofibers, so that the composite aerogel has excellent comprehensive performance. At present, no report is available on the application of basalt flakes in the aerogel field.
Disclosure of Invention
The invention provides basalt flake/cellulose nanofiber composite aerogel and a preparation method and application thereof, and aims to solve the problems of high chemical inertness of basalt flakes and limited application fields.
In order to achieve the above purpose, the invention adopts the following technical scheme:
The preparation method of the basalt flake/cellulose nanofiber composite aerogel comprises the following steps:
Mixing the activated basalt flakes with a cellulose nanofiber solution, and performing ball milling treatment to obtain composite gel A;
Adding sodium tetraborate into the composite gel A, performing ultrasonic treatment, and performing ball milling treatment to obtain basalt flake/cellulose nanofiber composite gel;
Mixing basalt flake/cellulose nanofiber composite gel with deionized water, performing vacuum suction filtration, and finally sequentially performing pre-freezing and freeze-drying to obtain the basalt flake/cellulose nanofiber composite aerogel.
Further, the method also comprises the following steps:
Adding methyltrimethoxysilane and deionized water into the basalt flake/cellulose nanofiber composite aerogel to carry out hydrophobic treatment, so as to obtain the basalt flake/cellulose nanofiber composite aerogel with a hydrophobic function.
Further, the volume ratio between the methyltrimethoxysilane and the deionized water is (1-2): (1-2);
the temperature of the hydrophobic treatment is 60-100 ℃, and the time of the hydrophobic treatment is 4-6 h.
Further, the activated basalt flake is prepared by the following steps:
And (3) activating the basalt flakes by adopting an alkaline solution, and washing to neutrality to obtain activated basalt flakes.
Further, the alkaline solution adopts sodium hydroxide solution or potassium hydroxide solution, and the concentration of the alkaline solution is 2 mol/L-6 mol/L;
the time of the activation treatment is 2-6 hours, and the temperature of the activation treatment is 80-120 ℃.
Further, the cellulose nanofiber solution is prepared by dissolving cellulose nanofibers in water, and the mass ratio of the basalt flakes to the cellulose nanofibers after activation is (1-7): (9-3);
The mass concentration of the cellulose nanofiber solution is 0.75% -1.85%;
And mixing the activated basalt flakes with a cellulose nanofiber solution, and performing ball milling treatment for 5-60 min.
Further, the mass of the sodium tetraborate is 2.5-20% of the total mass of the activated basalt flakes and cellulose nanofibers after being mixed.
Further, the ultrasonic treatment time is 5-10 min;
And adding sodium tetraborate into the composite gel A, and performing ultrasonic treatment, wherein the time for performing ball milling treatment is 5-60 min.
The basalt flake/cellulose nanofiber composite aerogel is obtained by adopting the preparation method, and has the porosity of 94% -99%, the density of 0.015g/cm 3～0.030g/cm3, the heat conductivity of 0.034W m -1K-1～0.043W m-1K-1 and the average sound absorption coefficient of 0.85;
the internal water contact angle of the basalt flake/cellulose nanofiber composite aerogel with the hydrophobic function obtained by the preparation method is 138 degrees.
The application of basalt flake/cellulose nanofiber composite aerogel with a hydrophobic function in marine spilled oil recovery and pollutant treatment.
Compared with the prior art, the invention has the following beneficial effects:
The invention provides a preparation method of basalt flake/cellulose nanofiber composite aerogel, which adopts a mechanochemical method to carry out composite treatment on activated basalt flakes and Cellulose Nanofiber (CNFs), and has clear principle, simple and easy operation, so that the activated basalt flakes and CNFs have chemical bonding effect and are firmly combined, the aerogel preparation under higher inorganic content is realized, and the application value of the basalt flakes is improved. In addition, sodium tetraborate is added into the composite gel A, and the sodium tetraborate not only provides boron elements so as to be convenient for forming coordination cross-linking bonds, but also has a certain flame retardant effect, so that the flame retardant property of the aerogel material is further improved, and the basalt flake/cellulose nanofiber composite aerogel achieves the flame retardant effect. The invention also adopts a vacuum auxiliary suction filtration method to realize the directional arrangement of basalt scales, and the basalt scales are embedded in the walls of CNFs through conventional freezing and freeze drying, so that an isotropic pore structure is formed, phonon transmission is effectively prevented, and the basalt scales/cellulose nanofiber composite endows aerogel with excellent sound absorption performance and heat insulation performance.
Furthermore, the invention adopts methyltrimethoxysilane (MTMS) to further carry out hydrophobic treatment on the aerogel material, thereby realizing the characteristic of both inner and outer hydrophobic property of the aerogel, and solving the defect that cellulose nanofiber swells and decomposes when meeting water, and the prepared aerogel material is unstable in water; in addition, the basalt flake/cellulose nanofiber composite aerogel material can realize the oil absorption characteristic in water, the surface and inner self-cleaning performance and the like while the hydrophobic performance is constructed, and can be well applied to the fields of ocean spilled oil recovery, pollutant treatment and the like.
Furthermore, the method for activating the basalt flakes by adopting the alkaline reagent is simple and easy to implement, so that the basalt flakes which are smooth in original surface and chemically inert become rough in surface, polar groups are successfully exposed, and the compounding capability of the basalt flakes and other organic materials is greatly improved.
The basalt flake/cellulose nanofiber composite aerogel provided by the invention is prepared by compounding basalt flakes and CNFs which are green nontoxic raw materials, has good biocompatibility, and can be degraded and recycled.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the invention.
FIG. 1 (a) is an SEM image of basalt flake used in the present invention;
FIG. 1 (b) is an SEM image of activated basalt flakes prepared according to the present invention;
FIG. 2 is a FTIR view of basalt flakes and activated basalt flakes of the present invention;
FIG. 3 is an SEM image of the internal pore structure of basalt flake/cellulose nanofiber composite aerogel prepared by the invention;
FIG. 4 is an infrared imaging photograph of a thermal insulation performance test of basalt flake/cellulose nanofiber composite aerogel prepared by the invention;
FIG. 5 (a) is a photograph showing the surface hydrophobic contact angle of basalt flake/cellulose nanofiber composite aerogel prepared according to the present invention;
Fig. 5 (b) is a photograph of the internal hydrophobic contact angle of basalt flake/cellulose nanofiber composite aerogel prepared according to the present invention.
Detailed Description
The following describes the technical scheme provided by the invention in detail:
The preparation method of the basalt flake/cellulose nanofiber composite aerogel comprises the following steps:
1) Etching and activating basalt flakes by adopting an alkaline solvent to obtain activated basalt flakes;
specifically, the alkaline solvent is selected from one of potassium hydroxide and sodium hydroxide;
preferably, the alkaline solvent is sodium hydroxide;
specifically, the basalt flakes have an average size of 20 μm and an average thickness of 0.2 μm; in the activation treatment step, the treatment time is 2-6 h, the treatment temperature is 80-120 ℃, and the concentration of the alkaline solvent is 2-6 mol/L.
2) The cellulose nanofiber solution is prepared by dissolving Cellulose Nanofibers (CNFs) in water, mixing the activated basalt flakes with the Cellulose Nanofiber (CNFs) solution according to different proportions, and treating the mixture by adopting a high-speed shimmy ball mill to obtain composite gel A;
specifically, the mass ratio of basalt scales to CNFs after activation is controlled to be (1-7): (9-3);
preferably, the mass ratio of basalt flakes to CNFs after activation is 5:5;
specifically, the mass concentration of the CNFs solution is 0.75-1.85%;
preferably, the mass concentration of CNFs solution is 1.26%;
specifically, the time of the treatment by adopting the high-speed shimmy ball mill is 5-60 min;
preferably, the time of treatment with a high-speed shimmy ball mill is 20 minutes.
3) Adding sodium tetraborate into the composite gel A, and performing ultrasonic treatment to obtain composite gel B;
Specifically, the dosage (mass) of sodium tetraborate is 2.5% -20% of the total amount (mass) of basalt flakes and CNFs after being activated in the step 2);
Specifically, the ultrasonic treatment time is 5-10 min, and the ultrasonic power is 1000W;
4) After the composite gel B is processed by adopting a high-speed shimmy ball mill, deionized water is added and stirred uniformly, a water type circulating vacuum pump is adopted for vacuum auxiliary suction filtration, then pre-freezing is carried out at the temperature of minus 5 ℃ to minus 40 ℃, and then the basalt flake/cellulose nanofiber composite aerogel material is obtained by freeze drying in a bell jar type freeze dryer;
Specifically, the time of ball milling treatment of the composite gel B by adopting a high-speed shimmy ball mill is 5-60 min;
Preferably, the time of ball milling treatment of the composite gel B by adopting a high-speed shimmy ball mill is 20min;
Specifically, the vacuum pressure of the suction filtration is-0.1 MPa, and the concentration of the composite gel B solution at the end of the suction filtration is controlled to be 0.75-1.85% as the concentration of the CNFs solid matters in the step 2); the density of the basalt flake/cellulose nanofiber composite aerogel material is controlled to be 0.015g/cm 3～0.030g/cm3, and the porosity is controlled to be 94% -99%;
specifically, the pre-frozen loading vessel can be a glass beaker or an aluminum box;
Specifically, the pre-freezing temperature is-5 ℃ to-40 ℃, and the pre-freezing time is 6h to 12h;
preferably, the pre-freezing time is 12 hours;
specifically, the vacuum pressure of freeze drying is set to be 6Pa, and the time of freeze drying is 48-72 h;
preferably, the time of lyophilization is 48 hours.
5) And further performing hydrophobic treatment on the basalt flake/cellulose nanofiber composite aerogel material by adopting methyltrimethoxysilane (MTMS) to obtain the basalt flake/cellulose nanofiber composite aerogel material with hydrophobic performance.
Specifically, the hydrophobic treatment is performed in a high-pressure reaction kettle;
Specifically, the volume ratio of the reagent MTMS to deionized water is (1-2): (1-2), the hydrophobic treatment temperature is 60-100 ℃ and the treatment time is 4-6 h.
The invention will now be described in further detail with reference to specific examples, which are intended to illustrate, but not to limit, the invention.
It should be noted that the following detailed description is of embodiments and is intended to provide further detailed description of the application. Unless defined otherwise, all technical terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments in accordance with the application.
It should be noted that the raw materials and reagents used in the following examples are commercially available or may be prepared by known methods unless otherwise specified.
The performance test of aerogel materials in the following examples is based on:
sound absorption coefficient: the test is carried out according to the ISO 10534-2:1998 transfer function method (national standard), the diameter of a test container is 30mm, the power amplifier is 90dB, and the sound absorption frequency is 1000-6300 Hz.
Thermal conductivity coefficient: and (3) testing the heat conductivity coefficient of the aerogel material by adopting a thermal constant analyzer with the model of Hot Disk TPS2200, wherein a probe is 5465F1, the heating power is 8mW, the heating time is 10s, and the detection depth is the shortest distance from the probe to the sample.
Density and porosity: measuring the mass and the size of a sample by an electronic balance and a vernier caliper, and calculating the porosity of the material by the following formula;
P＝1-(ρ0/ρ)×100％
Wherein P is the porosity of the porous material, ρ 0 is the bulk density (g/cm 3) of the porous material, ρ is the skeleton density of the porous material, which can be calculated from the mass and the volume of the porous material, m 1 and m 2 are the mass of the activated basalt flakes and CNFs respectively, and ρ 1 and ρ 2 are the bulk densities of the activated basalt flakes and CNFs respectively.
The invention is described in further detail below with reference to examples:
example 1
A preparation method of basalt flake/cellulose nanofiber composite aerogel material comprises the following steps:
1) Etching and activating basalt scales by adopting an alkaline solvent sodium hydroxide, wherein the average size of the basalt scales is 20 mu m, the activating treatment time is 4 hours, the activating treatment temperature is 100 ℃, the concentration of sodium hydroxide is 4mol/L, deionized water is added to terminate the reaction after the treatment is finished, and the basalt scales are repeatedly washed until the pH=7 to obtain activated basalt scales as shown in figure 1;
2) Mixing the activated basalt flakes with CNFs with the concentration of 1.26% according to the proportion of 5:5, and treating the mixture for 20min by adopting a high-speed shimmy ball mill to obtain composite gel A;
3) Adding 5% sodium tetraborate into the composite gel A, and performing ultrasonic treatment for 5min to obtain composite gel B;
4) And (3) treating the composite gel B for 20min by adopting a high-speed shimmy ball mill, adding deionized water, uniformly stirring, carrying out vacuum auxiliary suction filtration by adopting a water type circulating vacuum pump, wherein the pressure of the vacuum suction filtration is-0.1 MPa, then freezing for 12h at the temperature of-5 ℃, then freeze-drying for 48h in a bell jar type freeze dryer, and obtaining the basalt flake/cellulose nanofiber composite aerogel material, wherein the freeze-drying pressure is 6Pa, and the microstructure of the obtained aerogel material structure is shown in figure 3.
The porosity of the aerogel material is higher than 98%, and the pore size is concentrated at 100-200 mu m;
the aerogel material has an average sound absorption coefficient of 0.85 in the test range of 1000-6300 Hz and excellent sound absorption performance;
The aerogel material has a thermal conductivity coefficient as low as 0.034W m -1K-1, is placed on a heating platform with a temperature set to 170 ℃ for 10min, and the temperature in the middle of the aerogel material is only 72.9 ℃ as observed by an infrared thermal imager, so that the aerogel material has excellent heat insulation performance as shown in fig. 4.
Example 2
A preparation method of basalt flake/cellulose nanofiber composite aerogel material comprises the following steps:
1) Etching and activating basalt scales by adopting an alkaline solvent sodium hydroxide, wherein the average size of the basalt scales is 20 mu m, the activating treatment time is 2 hours, the activating treatment temperature is 120 ℃, the concentration of sodium hydroxide is 6mol/L, deionized water is added to terminate the reaction after the treatment is finished, and the basalt scales are repeatedly washed until the pH=7 to obtain activated basalt scales;
2) Mixing the activated basalt flakes with CNFs with the concentration of 0.75% according to the proportion of 1:9, and treating the mixture for 5min by adopting a high-speed shimmy ball mill to obtain composite gel A;
3) Adding 2.5% sodium tetraborate into the composite gel A, and performing ultrasonic treatment for 8min to obtain composite gel B;
4) And (3) treating the composite gel B for 5min by adopting a high-speed shimmy ball mill, adding deionized water, uniformly stirring, carrying out vacuum auxiliary suction filtration by adopting a water type circulating vacuum pump, then freezing for 8h at the temperature of minus 20 ℃, and then performing freeze drying for 60h in a bell jar type freeze dryer to obtain the basalt flake/cellulose nanofiber composite aerogel material.
Example 3
A preparation method of basalt flake/cellulose nanofiber composite aerogel material comprises the following steps:
1) Etching and activating basalt scales by adopting an alkaline solvent sodium hydroxide, wherein the average size of the basalt scales is 20 mu m, the activating treatment time is 6 hours, the activating treatment temperature is 80 ℃, the concentration of sodium hydroxide is 2mol/L, deionized water is added to terminate the reaction after the treatment is finished, and the basalt scales are repeatedly washed until the pH=7 to obtain activated basalt scales;
2) Mixing the activated basalt flakes with CNFs with the concentration of 1.85% according to the proportion of 7:3, and treating the mixture for 10min by adopting a high-speed shimmy ball mill to obtain composite gel A;
3) Adding 10% sodium tetraborate into the composite gel A, and performing ultrasonic treatment for 10min to obtain composite gel B;
4) And (3) treating the composite gel B for 10min by adopting a high-speed shimmy ball mill, adding deionized water, uniformly stirring, carrying out vacuum auxiliary suction filtration by adopting a water type circulating vacuum pump, then freezing for 6h at the temperature of minus 40 ℃, and then performing freeze drying for 72h in a bell jar type freeze dryer to obtain the basalt flake/cellulose nanofiber composite aerogel material.
Example 4
A preparation method of basalt flake/cellulose nanofiber composite aerogel material comprises the following steps:
1) Etching and activating basalt scales by adopting an alkaline solvent sodium hydroxide, wherein the average size of the basalt scales is 20 mu m, the activating treatment time is 4 hours, the activating treatment temperature is 100 ℃, the concentration of sodium hydroxide is 4mol/L, deionized water is added to terminate the reaction after the treatment is finished, and the basalt scales are repeatedly washed until the pH=7 to obtain activated basalt scales;
2) Mixing the activated basalt flakes with CNFs with the concentration of 1.26% according to the proportion of 5:5, and treating the mixture for 20min by adopting a high-speed shimmy ball mill to obtain composite gel A;
3) Adding 5% sodium tetraborate into the composite gel A, and performing ultrasonic treatment for 5min to obtain composite gel B;
4) Treating the composite gel B for 20min by adopting a high-speed shimmy ball mill, adding deionized water, uniformly stirring, carrying out vacuum auxiliary suction filtration by adopting a water type circulating vacuum pump, then freezing for 12h at the temperature of minus 5 ℃, and then performing freeze drying for 48h in a bell jar type freeze dryer to obtain the basalt flake/cellulose nanofiber composite aerogel material;
5) The basalt flake/cellulose nanofiber composite aerogel material is subjected to further hydrophobic treatment by adopting methyltrimethoxysilane (MTMS), the treatment process is carried out in a high-pressure reaction kettle, the proportion of MTMS to water is controlled to be 2:1, the temperature is 100 ℃, the treatment time is 4 hours, and the basalt flake/cellulose nanofiber composite aerogel material with hydrophobic performance inside and outside is obtained, wherein the internal water contact angle reaches 138 degrees, as shown in figure 5.
Example 5
A preparation method of basalt flake/cellulose nanofiber composite aerogel material comprises the following steps:
1) Etching and activating basalt scales by adopting an alkaline solvent sodium hydroxide, wherein the average size of the basalt scales is 20 mu m, the activating treatment time is 4 hours, the activating treatment temperature is 100 ℃, the concentration of sodium hydroxide is 4mol/L, deionized water is added to terminate the reaction after the treatment is finished, and the basalt scales are repeatedly washed until the pH=7 to obtain activated basalt scales;
2) Mixing the activated basalt flakes with CNFs with the concentration of 1.5% according to the proportion of 7:3, and treating for 60min by adopting a high-speed shimmy ball mill to obtain composite gel A;
3) Adding 20% sodium tetraborate into the composite gel A, and performing ultrasonic treatment for 10min to obtain composite gel B;
4) Treating the composite gel B for 60min by adopting a high-speed shimmy ball mill, adding deionized water, uniformly stirring, carrying out vacuum auxiliary suction filtration by adopting a water type circulating vacuum pump, then freezing for 12h at the temperature of minus 5 ℃, and then performing freeze drying for 48h in a bell jar type freeze dryer to obtain the basalt flake/cellulose nanofiber composite aerogel material;
5) The basalt flake/cellulose nanofiber composite aerogel material is subjected to further hydrophobic treatment by adopting methyltrimethoxysilane (MTMS), the treatment process is carried out in a high-pressure reaction kettle, the proportion of MTMS to water is controlled to be 1:2, the temperature is 60 ℃, and the treatment time is 6 hours, so that the basalt flake/cellulose nanofiber composite aerogel material with hydrophobic properties inside and outside is obtained.
Example 6
A preparation method of basalt flake/cellulose nanofiber composite aerogel material comprises the following steps:
1) Etching and activating basalt scales by adopting an alkaline solvent sodium hydroxide, wherein the average size of the basalt scales is 20 mu m, the activating treatment time is 4 hours, the activating treatment temperature is 100 ℃, the concentration of sodium hydroxide is 4mol/L, deionized water is added to terminate the reaction after the treatment is finished, and the basalt scales are repeatedly washed until the pH=7 to obtain activated basalt scales;
2) Mixing the activated basalt flakes with CNFs with the concentration of 1.5% according to the proportion of 5:5, and treating for 60min by adopting a high-speed shimmy ball mill to obtain composite gel A;
3) Adding 20% sodium tetraborate into the composite gel A, and performing ultrasonic treatment for 10min to obtain composite gel B;
4) Treating the composite gel B for 60min by adopting a high-speed shimmy ball mill, adding deionized water, uniformly stirring, carrying out vacuum auxiliary suction filtration by adopting a water type circulating vacuum pump, then freezing for 12h at the temperature of minus 5 ℃, and then performing freeze drying for 48h in a bell jar type freeze dryer to obtain the basalt flake/cellulose nanofiber composite aerogel material;
5) The basalt flake/cellulose nanofiber composite aerogel material is subjected to further hydrophobic treatment by adopting methyltrimethoxysilane (MTMS), the treatment process is carried out in a high-pressure reaction kettle, the proportion of MTMS to water is controlled to be 1.5:1.5, the temperature is 80 ℃, and the treatment time is 5 hours, so that the basalt flake/cellulose nanofiber composite aerogel material with hydrophobic properties inside and outside is obtained.
Comparative example 1
A preparation method of basalt flake/cellulose nanofiber composite aerogel material comprises the following steps:
1) Mixing basalt flakes which are not subjected to any treatment with CNFs with the concentration of 1.26% according to the proportion of 5:5, and treating the basalt flakes with a high-speed shimmy ball mill for 20min to obtain composite gel A;
2) Adding 5% sodium tetraborate into the composite gel A, and performing ultrasonic treatment for 5min to obtain composite gel B;
3) Treating the composite gel B for 20min by adopting a high-speed shimmy ball mill, adding deionized water, uniformly stirring, carrying out vacuum auxiliary suction filtration by adopting a water type circulating vacuum pump, then freezing for 12h at the temperature of minus 5 ℃, and then performing freeze drying for 48h in a bell jar type freeze dryer to obtain the basalt flake/cellulose nanofiber composite aerogel material;
4) The basalt flake/cellulose nanofiber composite aerogel material is subjected to further hydrophobic treatment by adopting methyltrimethoxysilane (MTMS), the treatment process is carried out in a high-pressure reaction kettle, the proportion of MTMS to water is controlled to be 2:1, the temperature is 100 ℃, and the treatment time is 4 hours, so that the basalt flake/cellulose nanofiber composite aerogel material with hydrophobic properties inside and outside is obtained.
The stress of the composite aerogel material is 0.024MPa under 60% of compressive strain, and the stress of the aerogel material prepared by adding the BS with the same proportion after activation is 0.035MPa under 60% of compressive strain, so that 45.8% of the stress is improved.
Comparative example 2
Treating CNFs with concentration of 1.26% independently, and treating with a high-speed shimmy ball mill for 20min to obtain CNFs gel;
Freezing the CNFs gel for 12 hours at the temperature of minus 5 ℃, and then performing freeze drying in a bell jar type freeze dryer for 48 hours to obtain a cellulose nanofiber aerogel material;
And further carrying out hydrophobic treatment on the cellulose nanofiber aerogel material by adopting methyltrimethoxysilane (MTMS) to obtain the cellulose nanofiber aerogel material with hydrophobic performance.
Aerogel prepared by CNFs alone has a thermal conductivity of 0.043W/mK, and the activated BS (example 1) is added, so that the thermal conductivity is reduced to 0.034W/mK, and the thermal insulation performance is more excellent; in addition, the average sound absorption coefficient of the aerogel prepared by adopting CNFs alone reaches 0.65 at 1000-4000 Hz, and the average sound absorption coefficient of the activated BS (example 1) at 1000-4000 Hz reaches 0.85, so that the aerogel has more excellent sound absorption performance.
The above-described embodiments are only preferred embodiments of the present application, and should not be construed as limiting the present application, and the embodiments and features of the embodiments of the present application may be arbitrarily combined with each other without collision. The protection scope of the present application is defined by the claims, and the protection scope includes equivalent alternatives to the technical features of the claims. I.e., equivalent replacement modifications within the scope of this application are also within the scope of the application.
Claims (10)
1. The preparation method of the basalt flake/cellulose nanofiber composite aerogel is characterized by comprising the following steps of:
Mixing the activated basalt flakes with a cellulose nanofiber solution, and performing ball milling treatment to obtain composite gel A;
Adding sodium tetraborate into the composite gel A, performing ultrasonic treatment, and performing ball milling treatment to obtain basalt flake/cellulose nanofiber composite gel;
Mixing basalt flake/cellulose nanofiber composite gel with deionized water, performing vacuum suction filtration, and finally sequentially performing pre-freezing and freeze-drying to obtain the basalt flake/cellulose nanofiber composite aerogel.
2. The method for preparing basalt flake/cellulose nanofiber composite aerogel according to claim 1, further comprising the steps of:
Adding methyltrimethoxysilane and deionized water into the basalt flake/cellulose nanofiber composite aerogel to carry out hydrophobic treatment, so as to obtain the basalt flake/cellulose nanofiber composite aerogel with a hydrophobic function.
3. The method for preparing basalt flake/cellulose nanofiber composite aerogel according to claim 2, wherein the volume ratio of methyltrimethoxysilane to deionized water is (1-2): (1-2);
the temperature of the hydrophobic treatment is 60-100 ℃, and the time of the hydrophobic treatment is 4-6 h.
4. The method for preparing basalt flake/cellulose nanofiber composite aerogel according to claim 1, wherein the basalt flake after activation is prepared by the steps of:
And (3) activating the basalt flakes by adopting an alkaline solution, and washing to neutrality to obtain activated basalt flakes.
5. The method for preparing basalt flake/cellulose nanofiber composite aerogel according to claim 4, wherein the alkaline solution is sodium hydroxide solution or potassium hydroxide solution, and the concentration of the alkaline solution is 2 mol/L-6 mol/L;
the time of the activation treatment is 2-6 hours, and the temperature of the activation treatment is 80-120 ℃.
6. The method for preparing basalt flake/cellulose nanofiber composite aerogel according to claim 1, wherein the cellulose nanofiber solution is prepared by dissolving cellulose nanofibers in water, and the mass ratio of the basalt flake to the cellulose nanofibers after activation is (1-7): (9-3);
The mass concentration of the cellulose nanofiber solution is 0.75% -1.85%;
And mixing the activated basalt flakes with a cellulose nanofiber solution, and performing ball milling treatment for 5-60 min.
7. The method for preparing basalt flake/cellulose nanofiber composite aerogel according to claim 6, wherein the mass of the sodium tetraborate is 2.5% -20% of the total mass of the activated basalt flake and cellulose nanofiber after mixing.
8. The method for preparing basalt flake/cellulose nanofiber composite aerogel according to claim 1, wherein the ultrasonic treatment time is 5-10 min;
And adding sodium tetraborate into the composite gel A, and performing ultrasonic treatment, wherein the time for performing ball milling treatment is 5-60 min.
9. The basalt flake/cellulose nanofiber composite aerogel is characterized in that the basalt flake/cellulose nanofiber composite aerogel is obtained by the preparation method of any one of claims 1-8, the porosity of the basalt flake/cellulose nanofiber composite aerogel is 94% -99%, the density is 0.015g/cm 3～0.030g/cm3, the heat conductivity is 0.034W m -1K-1～0.043W m-1K-1, and the average sound absorption coefficient is 0.85.
10. The use of basalt flake/cellulose nanofiber composite aerogel with a hydrophobic function in marine oil spill recovery and pollutant treatment according to claim 9.
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN118307834A true CN118307834A (en) | 2024-07-09 |
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