CN113511656B - Silica-based aerogel, composite material thereof and preparation method and application thereof - Google Patents
Silica-based aerogel, composite material thereof and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses a silicon dioxide-based aerogel with a complex structure, a composite material thereof, a preparation method and application thereof. The skeleton of the silica-based aerogel is hybridized and crosslinked by polyacrylate polymers and polysiloxane. The hyperbranched silica chain is obtained under the acid catalysis condition by a two-step method strategy, the silane coupling agent containing the photopolymerisable group is modified, and then the photo-curing 3D printing is carried out under the alkaline condition, so that the silica-based aerogel with high complex structural integrity, high specific surface area, good mechanical property, quick normal pressure drying, fire resistance and flame retardance is prepared. Meanwhile, the obtained silica-based aerogel product with the three-dimensional complex structure is used as a reinforcing framework, and the composite material with high transparency and high mechanical property is obtained by simple illumination after the replacement of a vacuum auxiliary solvent, so that the macroscopic structure of the original aerogel is reserved, and the mechanical property of the polymer material in the field of photo-curing 3D printing is effectively improved.
Description
Technical Field
The invention belongs to the field of photo-curing 3D printing materials, and particularly relates to a silicon dioxide-based aerogel material, a composite material thereof, and a preparation method and application thereof.
Background
Silica aerogel (SiO) 2 aerogel) has been the most studied in the aerogel field since 1931 when Kistler adopted supercritical drying technology to prepare it, because it has the characteristics of low density, high specific surface area, excellent heat insulation, good electrical insulation, adjustable transparency, fire resistance and flame retardance,The most widely used class. During the decades, a large number of researchers adopt different strategies, such as polymer hybridization enhancement, coupling agent modification of a framework and the like, so as to obtain the silica aerogel which has good integrity, can be dried at normal pressure and has adjustable mechanical properties. However, the preparation process of the silicon dioxide and the hybrid aerogel thereof is harsh, so that the product of the material can only be applied to the simplest mould, and the product with a special complex structure can not be obtained, thereby limiting the further application of the silicon dioxide aerogel.
The photo-curing 3D printing is one of the most effective means for constructing a three-dimensional special structure part in the field of additive manufacturing due to high printing resolution, high printing speed, wide material coverage and strong equipment expansibility, and a large number of special custom structure glass, carbon material and other inorganic and organic polymer parts with bionic or topological super structures and the like are prepared at present. In addition, the photocuring 3D printing can also endow the complex three-dimensional structure part with special functions, such as preparing 3D porous polymer resin or hydrogel for application in the biomedical tissue engineering field. Therefore, combining photo-curing 3D printing with silica aerogel may become a new research direction.
Disclosure of Invention
The present invention provides a silica-based aerogel having a three-dimensional complex appearance free-formed using 3D printing, manufactured independent of a mold.
Preferably, the 3D printing is a photo-curing 3D printing.
According to an embodiment of the invention, the backbone of the silica-based aerogel is hybrid crosslinked by polyacrylate polymers and polysiloxanes.
According to an embodiment of the invention, the silica-based aerogel exhibits a microscopically uniform bead-like phase-separated skeletal network structure, with no apparent neck structure of the skeleton. Preferably, the silica-based aerogel has a morphology substantially as shown in b and/or c of fig. 3. Wherein the silica-based aerogel has a skeletal particle size of 1 to 50nm, for example 5 to 20nm, and exemplified by 10nm.
According to an embodiment of the invention, the average size of the pore size of the silica-based aerogel is from 1 to 50nm, for example from 5 to 20nm, exemplary 8.33nm, 10nm.
According to an embodiment of the invention, the silica-based aerogel has a pore volume of 1.4 to 1.8cm 3 /g, e.g. 1.5-1.6cm 3 Per g, exemplary 1.55cm 3 /g。
According to an embodiment of the invention, the silica-based aerogel has a skeletal intrinsic density of 1.2 to 1.8g/cm 3 For example, 1.3-1.7g/cm 3 Exemplary is 1.49g/cm 3 。
According to an embodiment of the present invention, the silica-based aerogel has a specific surface area of 500 to 1000m 2 /g, e.g. 600-900m 2 /g, exemplary 700m 2 /g、735m 2 /g、750m 2 /g、800m 2 /g。
According to an embodiment of the invention, the silica-based aerogel comprises SiO x The inorganic component is contained in an amount of 50 to 85% by mass, for example, 65 to 80% by mass, and exemplified by 68%, 70%, 73%, 75% by mass.
According to an embodiment of the present invention, the silica-based aerogel has a three-dimensional structure.
The invention also provides a preparation method of the silica-based aerogel, which comprises the following steps:
(1) Carrying out acid-catalyzed hydrolysis condensation reaction on a silane precursor in a mixed solution of ethanol and a dilute acid aqueous solution, and adding a coupling agent into a reaction solution after the reaction is completed to obtain a resin solution;
the coupling agent is selected from hyperbranched siloxanes containing substituted or unsubstituted acrylate groups;
(2) Adding an alkali catalyst and a photoinitiator into the resin solution, and performing photo-curing 3D printing to obtain wet gel;
(3) And (3) carrying out light irradiation on the wet gel, curing, aging, solvent replacement, hydrophobic modification and drying to obtain the silica-based aerogel.
According to an embodiment of the invention, in step (1), the hyperbranched of the substituted acrylate groupsThe siloxane may be selected from C 1-10 Hyperbranched siloxanes of alkyl-substituted acrylate groups, e.g. C 1-4 The alkyl-substituted hyperbranched siloxane of acrylate groups is preferably a hyperbranched siloxane of methacrylate groups. As an example, the coupling agent may be selected from at least one of methacrylate propyl trimethoxysilane, acrylate propyl trimethoxysilane, methacrylate propyl triethoxysilane, acrylate propyl triethoxysilane, etc., and is exemplified by methacrylate propyl trimethoxysilane.
According to an embodiment of the present invention, in step (1), the silane precursor may be selected from at least one of tetraethyl orthosilicate (TEOS), tetramethyl orthosilicate (TMOS), tetrabutyl orthosilicate (TBOS), tetraisopropyl orthosilicate (TPOS), etc., and is exemplified by tetraethyl orthosilicate.
According to an embodiment of the invention, in step (1), the volume ratio of the silane precursor to the coupling agent is (15-40): (0.5-15), for example (20-30): (1-10), exemplary 22:8, 23:7, 24:6, 25:5, 26:4, 27:3.
According to an embodiment of the present invention, in step (1), the silane precursor is used in an amount of 20-40% by mass of the acid-catalyzed hydrolysis condensation reaction system, for example 25-38%, illustratively 28%, 28.75%, 30%, 30.11%, 31%, 31.46%, 32%, 32.82%, 34%, 34.18%, 35%, 35.55%.
According to an embodiment of the present invention, in step (1), the coupling agent is used in an amount of 1 to 15% by mass of the reaction system, for example, 2 to 13%, and exemplified by 3%, 4%, 4.39%, 5%, 5.85%, 7%, 7.3%, 8%, 8.74%, 10%, 10.18%, 11.62%.
According to an embodiment of the present invention, in step (1), the molar ratio of ethanol to acid in the mixed solution of ethanol and dilute aqueous acid is (0.5-1.5): 1-5, for example, (0.8-1.3): 1-2, and exemplary 1:1.
According to an embodiment of the present invention, in step (1), the ethanol is absolute ethanol.
According to an embodiment of the present invention, in step (1), the molar concentration of the dilute aqueous acid solution is 0.01 to 1mol/L, and is exemplified by 0.1mol/L.
According to an embodiment of the present invention, in step (1), the acid may be selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, formic acid, citric acid, aluminum trichloride hexahydrate, etc., and is exemplified by hydrochloric acid, sulfuric acid, or nitric acid.
According to an embodiment of the present invention, in step (1), the acid-catalyzed hydrolytic condensation reaction is performed at room temperature. Wherein the room temperature is 15-40 degrees, e.g. 20-35 degrees. Further, the acid-catalyzed hydrolytic condensation reaction is carried out under stirring conditions, for example, stirring for a period of 10 to 40 hours, preferably 15 to 30 hours, and exemplified by 24 hours.
According to an embodiment of the present invention, in step (1), the reaction after the addition of the coupling agent is continued at room temperature. Further, the reaction is carried out under stirring conditions, for example, stirring for a period of 10 to 40 hours, preferably 15 to 30 hours, and exemplified by 24 hours.
According to an embodiment of the present invention, in step (2), the base catalyst is at least one selected from urotropin, urea, ammonia, sodium hydroxide, potassium hydroxide, ethylenediamine, triethylamine, tetraethylenepentamine, etc., and is exemplified by urotropin, urea, ethylenediamine, triethylamine, or tetraethylenepentamine. Further, the mass concentration of the base catalyst in the system is 0.5 to 2%, for example 1 to 1.5%, and exemplified by 1%.
According to an embodiment of the present invention, in step (2), the photoinitiator may be selected from 3D photocuring known photoinitiators, for example, at least one of (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, bis (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide, benzildimethyl ether, camphorquinone, eosin Y, etc., and exemplified by (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide. Further, the photoinitiator is present in the system at a mass concentration of 2-10%, for example 3-8%, and illustratively 4%, 5%, 6%.
According to an embodiment of the present invention, in step (2), after adding the base catalyst and the photoinitiator to the above resin solution, stirring to form a clear transparent solution.
According to an embodiment of the present invention, in step (2), the photo-cured 3D printing is a high resolution liquid crystal panel imaging (LCD) digital light processing 3D printing, preferably a pull-up high resolution liquid crystal panel imaging (LCD) digital light processing 3D printing. Wherein the printing parameters may include: the x-axis of the imaging resolution of the surface exposure is 10-100 mu m, and the y-axis is 10-100 mu m; the thickness of the exposure layer of the printing platform is 10-300 mu m (z axis), the lifting height after single exposure is 50-150mm, the single exposure time is 15-60s, and the exposure intensity is 2-30mW/cm 2 . For example, the area exposure imaging resolution has an x-axis of 30-80 μm and a y-axis of 30-80 μm; the thickness of the exposure layer of the printing platform is 30-150 mu m, the lifting height after single exposure is 80-130mm, the single exposure time is 20-50s, and the exposure intensity is 5-15mW/cm 2 . Illustratively, the area exposure imaging resolution has an x-axis of 50 μm and a y-axis of 50 μm; the thickness of the exposure layer of the printing platform is 50 mu m or 25 mu m, the lifting height is 120mm after single exposure, the single exposure time is 35s, and the exposure intensity is 10mW/cm 2 。
According to an embodiment of the present invention, in step (3), the wet gel is put in a resin solution containing a base catalyst to be photo-cured. Wherein the illumination intensity is 15-25mW/cm 2 For example 10mW/cm 2 、20mW/cm 2 . Wherein the wavelength of the illumination is 380-420nm, such as 405nm. Wherein the time of illumination is 1-5 hours, for example 2-3 hours.
According to an embodiment of the present invention, in the step (3), the aging is that the gel obtained by light curing is encapsulated in a hydrothermal kettle for aging. For example, the temperature of the aging is 80-120 ℃, such as 100-110 ℃, and is exemplified by 100 ℃. For example, the aging period may be 2-5 days, such as 3-4 days.
According to an embodiment of the invention, in step (3), the solvent replacement is performed by subjecting the aged gel to multiple (e.g., at least 3, such as 4, 5, 6) solvent replacements with anhydrous ethanol and n-hexane.
According to the embodiment of the invention, in the step (3), the hydrophobic modification is that the gel after solvent replacement is subjected to hydrophobic modification by adopting methyl silane, and the minimum content of organic matters introduced by the hydrophobic modification can be mainly ensured by utilizing the methyl silane modification. For example, the methylsilane may be at least one selected from trimethylchlorosilane, hexamethyldisilazane, hexamethyldisiloxane, etc., and trimethylchlorosilane is exemplified. For example, the modification may be selected from modification methods known in the art.
According to an embodiment of the present invention, in step (3), the drying is rapid atmospheric drying.
The invention also provides the silica-based aerogel prepared by the method.
The invention also provides the use of the silica-based aerogel as a reinforcing backbone for a polymer resin.
The invention also provides a composite material which is a hybrid material formed by photosensitive resin and the silica-based aerogel.
According to the present invention, the photosensitive resin may be selected from at least one photosensitive resin monomer prepared as follows: 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, acrylomorpholine, pentaerythritol tetraacrylate, di-pentaerythritol hexaacrylate, epoxy acrylates, polyurethane acrylates, polyester acrylates, polyether acrylates, exemplified by 1, 6-hexanediol diacrylate and/or trimethylolpropane triacrylate.
The invention also provides a preparation method of the composite material, which comprises the following steps: preparing wet gel according to the steps (1) - (2) in the preparation method of the silica-based aerogel; after the wet gel is washed by ethanol, the wet gel is semi-immersed in a photosensitive resin monomer, the ethanol volatilizes under the assistance of vacuum, and the photosensitive resin monomer is filled into the pores of the wet gel to complete the replacement of a gel solvent; and curing by photoinitiation or thermal initiation to obtain the composite material.
According to an embodiment of the present invention, the photosensitive resin monomer has the meaning as described above.
The invention also provides a composite material obtained by the preparation method.
The invention also provides application of the composite material as a 3D printing polymer material.
The invention has the beneficial effects that:
the invention adopts a photocuring 3D printing means, utilizes photosensitive resin hybrid silica aerogel to improve the mechanical property and endow a three-dimensional complex structure, and simultaneously reserves the self structural characteristic expansion of the silica aerogel to improve the performance of the photocuring 3D printing functional material. Through reasonable molecular design and acid-base strategy and based on the principle of complementary heat absorption and heat exchange by polymerization exothermic condensation, the method finds that the silicon dioxide sol-gel (sol-gel) transformation can be well induced by introducing a very small amount of (methyl) acrylate groups (about 4 wt%) into the silane precursor, so that the silicon dioxide sol-gel is matched with the photocuring 3D printing and post-treatment process. The hybrid silica-based aerogel which can be rapidly dried (APD) under normal pressure and has the structural characteristics and thermal properties equivalent to those of the traditional silica aerogel and mechanical properties far exceeding those of the traditional silica aerogel is prepared by a digital light processing 3D printing technology based on a lifting type high-resolution Liquid Crystal Display (LCD). Specifically, based on the principle that the polymerization heat release of monomers containing double bonds and the condensation heat absorption phase of silanol are complementary, a silane coupling agent with (methyl) acrylate groups is modified on hyperbranched silica chains formed by silane hydrolytic condensation under the catalysis of acid, and photoinitiation is carried out under a certain condition, so that the silica aerogel sol-gel process and the photocuring 3D printing can be well matched, and the photocuring 3D printing preparation of the silica-based wet gel process is completed. And then, the gel skeleton is further enhanced by light irradiation post-curing and aging, so that the gel can be subjected to rapid normal pressure drying after solvent replacement and hydrophobic modification, and the aerogel product with high integrity, high specific surface area, good mechanical property, fire resistance and flame retardance and complex 3D structure is obtained.
Further, the tough silica-based skeleton structure of the prepared silica-based aerogel is used as a novel continuous reinforcing phase, a strategy of filling photosensitive resin monomer or solution matched with the skeleton refractive index is adopted by replacing with a vacuum auxiliary solvent, and the transparent polymer composite material reinforced by the silica-based aerogel skeleton is obtained through illumination in one step, so that the composite material retains the macroscopic three-dimensional complex structure of the silica-based aerogel, has excellent mechanical properties, becomes a series of novel polymer composite materials with complex macroscopic structures, and effectively improves the mechanical properties of polymer materials in the field of photocuring 3D printing.
Drawings
Fig. 1 is a photo-cured 3D printing process window in example 1.
FIG. 2 is a graph showing the characterization of the sol-gel transition rheological oscillation mode of photo-cured 3D printing in example 1.
Fig. 3 is an image analysis chart (D-f) of energy dispersive X-ray spectroscopy (EDS) versus elemental plane of carbon (C), oxygen (O), silicon (Si) under the conditions of example 2 photo-cured 3D printed aerogel optical (a), scanning Electron Microscope (SEM) (b), transmission Electron Microscope (TEM) photograph (C), and High Resolution Transmission Electron Microscope (HRTEM).
Fig. 4 is a nitrogen physical adsorption and desorption characterization result of the photo-cured 3D printing aerogel of example 2.
FIG. 5 is a thermal weight loss (TGA) characterization of the photo-cured 3D printed aerogel of example 2.
FIG. 6 is a solid nuclear magnetic resonance silica spectrum [ ] of a photo-cured 3D printed aerogel of example 2 29 Si NMR)。
FIG. 7 is a photo-cured 3D printed aerogel fire resistance flame retardant test infrared imaging of example 3.
Fig. 8 is the results of the photo-cured 3D printed aerogel nanoindentation mechanical test of example 4.
Fig. 9 is a photograph of the composite of example 5.
Fig. 10 is a nanoindentation test load-displacement graph of the composite of example 5.
FIG. 11 is a nanoindentation test load-displacement curve calculation for the composite of example 5.
Detailed Description
The technical scheme of the invention will be further described in detail below with reference to specific embodiments. It is to be understood that the following examples are illustrative only and are not to be construed as limiting the scope of the invention. All techniques implemented based on the above description of the invention are intended to be included within the scope of the invention.
Unless otherwise indicated, the starting materials and reagents used in the following examples were either commercially available or may be prepared by known methods.
Instrument and reagent:
the main reagents are tetraethyl orthosilicate (TEOS, purchased from Acros), propyl trimethoxysilane methacrylate (MPTS, purchased from Sigma-Aldrich), 1, 6-hexanediol diacrylate (HDDA, purchased from Beijing Enoka), trimethylolpropane triacrylate (TMPTA, purchased from TCI), urotropin (HMTA, purchased from Aba Ding Gongsi), trimethylchlorosilane (TMCS, purchased from Acros) (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide (TPO, purchased from carboline); n-hexane and absolute ethyl alcohol are purchased from Beijing chemical plant; hydrochloric acid, 0.1mol/L, self-made; the above reagents were used without purification. The water is secondary distilled water.
The main experimental instrument is a desktop-level LCD photo-curing 3D printer (printing resolution x-axis 50 μm, y-axis 50 μm, z-axis 25 μm, printing wavelength 405nm, printing light intensity 10 mW/cm) 2 )。
The main characterization instrument: scanning electron microscope (JEOL JSM 7500F), transmission electron microscope (FEI Tecnai G20), universal stretcher (samsung longitudinal and transverse UTM 4000), nanoindenter (Agilent G200), advanced rotary rheometer (Anton Paar MCR 302), nuclear magnetic resonance spectrometer (Bruker AVANCE III 400), physical desorption analyzer (Micromeritics Instrument ASAP 2020), automated true densitometer (Mettler Toledo PEAB XS105 DU), infrared thermal imager (Fluke TiS 75) and thermogravimetric analyzer (TA instrument Pyris 1).
Example 1
A certain amount of tetraethyl orthosilicate (TEOS) is added into a mixed solution of absolute ethanol and 0.1mol/L hydrochloric acid in an equimolar ratio, and the mixture is magnetically stirred for 24 hours at room temperature to perform sufficient acid-catalyzed hydrolytic condensation. After the reaction is completed, a certain proportion of coupling agent Methacrylate Propyl Trimethoxy Silane (MPTS) is added into the solution dropwise, and magnetic stirring is continued for 24 hours at room temperature to form a resin solution. The formulation ratio of TEOS to MPTS in the solution and the mass fraction thereof are given in Table 1:
TABLE 1
1wt% urotropine and 5wt% photoinitiator (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide are added into the resin solution, and the resin solution is stirred until the resin solution is clear and transparent and then poured into a photocuring 3D printer trough. A three-dimensional structural model stl-format file containing 24 cylinders with the diameter of 7mm, the thickness of 10mm and the thickness of 8 cylinders with the diameter of 15mm is exported by using computer CAD software, the three-dimensional structural model stl-format file is sliced according to 50 mu m/layer by printer software, the lifting height of 120mm after single exposure is set, the single exposure time is 35s, and a raspberry group microcomputer (RPi) is imported to execute a printing task.
The photo-curing 3D printing processing window and the material printing state of the solutions with different proportions can be obtained by measuring the self-gelation time of the solutions with different proportions before and after printing, namely the required length of the automatic gelation process under the condition of no light after adding 1 weight percent urotropine and 5 weight percent photoinitiator and the automatic gelation process of the residual solution under the condition of no light after completing a single printing task, and measuring the single-layer exposure dynamics process of photo-curing 3D printing by combining an advanced rotary rheometer. As shown in fig. 1, as the concentration of the coupling agent in the solution gradually increases, the self-gelation time of the solution before printing increases from 3.5 hours in the 27/3 group to 41 hours in the 22/8 group, indicating that as the coupling agent content increases, the self-condensation process of the siloxane chain under alkaline conditions is hindered by its enhanced organic group steric hindrance, releasing a longer photocuring 3D processing window.
When the 3-hour one-time printing task is completed, the self-gelation time of the uncured solution in the residual trough is drastically shortened, the 24/6 group solution is shortened from 13 hours to 2 hours, the 23/7 group solution is shortened from 23 hours to 6 hours, and the 22/8 group solution is shortened from 41 hours to 13 hours. The result shows that in the 3D printing process, the photocuring reaction area is in diffusion exchange with the solute existing in the unexposed area, and scattered illumination and partial volatilization of the solvent existing in the exposure process can promote partial condensation of the silicon oxygen chain of the unexposed area and partial polymerization of the methacrylate monomer, so that the actual printing window of the solution is shortened. The shrinkage of the photo-curing printing window can cause the self viscosity of the trough solution to be obviously increased in the later stage of a printing task so as to reduce the fluidity, and the trough solution is more sensitive to the scattered light intensity caused by exposure in the printing process so as to form negative feedback to accelerate the increase of the viscosity of the solution, so that the precision and the performance of a printing workpiece are reduced.
As shown in the rheological oscillation mode characterization result of FIG. 2, as the concentration of the coupling agent in the solution gradually decreases, the gelation time after exposure of the solutions with different proportions shows a trend of increasing and decreasing, which shows that the prepared photosensitive resin is subjected to polymerization crosslinking by methacrylate groups under high coupling agent content and is subjected to dynamic transformation of polymerization exothermic induction of silicone chain condensation crosslinking curing by a small amount of polymerization exothermic induction under high inorganic content. Meanwhile, as the concentration of the coupling agent is gradually reduced, the storage modulus of the photo-curing monolayer with the thickness of 50 mu m is reduced from 12000Pa to 1800Pa at the exposure time of 30s of the monolayer after the sol-gel conversion, and is reduced from 21000Pa to 2500Pa at the exposure time of 60s of the monolayer (the platform modulus is reached), which shows that the gel produced by condensation and curing of the silicon-oxygen chain which only depends on a small amount of polymerization reaction to release heat can not obtain higher storage modulus, and the fracture, dislocation and warping of a printing layer are more easily generated due to the repeated separation of a printing platform and a bottom release film in the printing process, so that the accuracy between printing is seriously influenced. The printing defects formed by the method become internal stress concentration points in the aerogel preparation process, especially in the drying process, and macroscopic cracks can be generated to cause the loss of the integrity of the aerogel and the serious decline of the mechanical property.
Thus, in connection with the test results of fig. 1 and 2, the following can be concluded: sufficient photocuring 3D printing processing window and few-defect high-precision part printing process are ensured on a desktop-level LCD photocuring 3D printer, and meanwhile, the V prepared by printing the silica-based gel skeleton can be finished with minimum coupling agent content TEOS /V MPTS The solution ratio is preferably 23/7.
Example 2
According to V TEOS /V MPTS Resin solution was formulated in the ratio of =23/7, and the solution formulation process and the photo-curing 3D printing preparation process were the same as in example 1. After printing, the wet gel is put into the resin solution added with 1 weight percent urotropine and is placed at the light intensity of 20mW/cm 2 Is irradiated for 2-3 hours under an external light source with the wavelength of 405nm. And packaging the obtained gel in a hydrothermal kettle, and aging for 3-4 days at 100 ℃. And respectively carrying out solvent replacement on the aged gel for 6 times by using absolute ethyl alcohol and n-hexane, and then carrying out hydrophobic modification on the gel by using Trimethylchlorosilane (TMCS), and rapidly drying at normal pressure to obtain a complete aerogel product with negligible volume shrinkage.
A-f in fig. 3 are optical photographs, SEM photographs, TEM photographs, and EDS elemental analysis surface images of the photo-cured 3D printed silica-based aerogel obtained in this example. FIG. 3 shows that macroscopically photocurable 3D-printed silica-based aerogel articles are translucent, accompanied by significant Rayleigh scattering characteristics, microscopically present a uniform, beaded phase separated skeletal network, the skeleton has no significant "neck" structure, and the average size of the skeletal particles is 10nm. EDS face imaging showed uniform distribution of C, O, si elements in the framework, indicating uniform hybrid crosslinking of the organic-inorganic components in the framework.
The intrinsic density of the skeleton of the photo-cured 3D printing silica-based aerogel measured by an automatic true density meter is 1.49g/cm 3 。
As shown in fig. 4a and b, the physical adsorption and desorption experimental results show that the isothermal adsorption and desorption curve of the aerogel nitrogen is an IV-type curve and presents an obvious H1-type narrow hysteresis loop, and the photo-curing 3D printing aerogel is mainly provided with cylindrical mesopores with narrower pore size distribution and uniform skeleton particle aggregate size, which accords with the typical silica aerogel skeleton structure characteristics. Meanwhile, calculating an isothermal adsorption-desorption curve by a Brunauer-Emmett-Teller (BET) method to obtain the 3D printing silica aerogel with the specific surface area of 735m 2 /g; average pore size of 8.33nm and 1.55cm were obtained by Barrett-Joiner-Halenda (BJH) method 3 Pore volume/g, indicating that the photo-cured 3D printed silica-based aerogel has a transmissibilityThe silica aerogel has the structural characteristics of high specific surface area, large pore volume and the like.
Further by thermal weight loss (TGA) testing (test results are shown in fig. 5) and solids 29 Si NMR spectrum analysis (characterization results are shown in FIG. 6), at V TEOS /V MPTS Aerogel prepared by printing at ratio of 23/7, siO thereof x The inorganic component is present in proportions of up to 73wt% and exhibits chemical structural characteristics of the typical silica aerogel framework (T2, T3, Q4 peaks). Taken together, the results indicate that at V TEOS /V MPTS Under the condition of the ratio of 23/7, the photo-curing 3D printing requirement can be well met by only using a small amount of methacrylate ester units for polymerization; high inorganic content remains as SiO x The polymerization phase separation is a dominant skeleton growth strategy, so that the aerogel has the structural characteristics of the traditional silica aerogel; the uniformly hybridized organic polymer component can strengthen the framework of the silicon dioxide particles and enable the framework to withstand huge capillary force generated by rapid volatilization of a solvent when the framework is dried under the atmospheric pressure, and the monolithic aerogel with a reserved macroscopic three-dimensional structure is obtained in a rapid and low-cost drying mode.
Example 3
A sheet-like aerogel having a thickness of 3mm was prepared by printing as in example 2. And 3mm thick silicon dioxide aerogel is fixed by utilizing a metal bracket and is horizontally arranged above the flame, so that the outer flame of the flame is ensured to contact the central position of the bottom of the aerogel, and an ablation test is carried out on the outer flame.
In the infrared thermal imaging diagram shown in fig. 7, 3mm thick 3D printed silica aerogel exhibits good low conductance and fire-retardant properties under continuous 20s ablation with an external flame at about 500 ℃; the upper surface temperature of the aerogel is only 96 ℃ under 15s of continuous ablation; after 20s the flame was away, the aerogel did not continue to burn, the surface temperature was only 140 ℃.
Example 4
A cylindrical aerogel having a thickness of 3 to 10mm and a diameter of 10mm was prepared as in example 2, and subjected to uniaxial compression performance test. Test results As shown in FIG. 8, at a compression rate of 1mm/min, the photo-cured 3D printed silica aerogel can reach a maximum compressive strength of 7 under 33% compression strain5MPa, its compression modulus is up to 32MPa, and toughness (compression work, woC) is up to 1.33MJ/m 3 The mechanical properties of the high-strength and high-toughness hybrid silica aerogel are shown.
Example 5
Preparation of V with reference to example 2 TEOS /V MPTS The preparation method comprises the steps of (1) printing a silicon dioxide-based wet gel in a ratio of (23/7), washing the wet gel by an absolute ethyl alcohol solvent for 6-8 times, semi-immersing the wet ethyl alcohol gel in a photosensitive resin monomer, volatilizing the absolute ethyl alcohol under the assistance of a vacuum environment, and filling the photosensitive resin monomer (1, 6-hexanediol diacrylate and trimethylolpropane triacrylate mixed photosensitive resin monomer) into the pores of the wet gel to complete the replacement of the gel solvent. Because the size of the aerogel framework is far smaller than the wavelength of visible light, and the organic-inorganic composition of the framework has refractive index similar to that of most photosensitive resin monomers, the gel has higher transparency after monomer replacement, and the light intensity is 20mW/cm after passing through 405nm, illumination time for 30 minutes 2 After photoinitiation, a composite material with high transparency and high mechanical properties is obtained, as shown in fig. 9.
The nano indentation test is adopted to characterize the mechanical properties of the photosensitive resin matrix (formed by curing the photosensitive resin monomer) and the composite material. The nanoindenter was tested based on Berkovich triangular pyramid indenter and dynamic Continuous Stiffness Method (CSM). Polishing the test surfaces of the photosensitive resin matrix and the composite material sample by using an ultrathin slicer with the stepping of 200nm, and respectively carrying out 10 times of nano indentation parallel tests; the final result was taken as the average of 10 parallel test results at a depth of depression of 1200 nm.
As shown in the nanoindentation load-displacement curve of fig. 10, the composite material has improved rigidity and reduced plastic deformation under the reinforcement of the aerogel framework. Further based on the Continuous Stiffness Method (CSM) and the Oliver-Pharr quasi-static method, the elastic modulus and the hardness of the composite material are respectively improved by 360% and 725% compared with the photosensitive resin matrix as shown by a and b in FIG. 11. The micromechanics result shows that the high strength and high hardness of the inorganic component based on the silica-based skeleton and the continuous skeleton structure greatly improve the mechanical property of the composite material.
The embodiments of the present invention have been described above. However, the present invention is not limited to the above embodiment. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (29)
1. A method for preparing a silica-based aerogel, comprising the steps of:
(1) Carrying out acid-catalyzed hydrolysis condensation reaction on a silane precursor in a mixed solution of ethanol and a dilute acid aqueous solution, and adding a coupling agent into a reaction solution after the reaction is completed to obtain a resin solution;
the coupling agent is selected from hyperbranched siloxanes containing substituted or unsubstituted acrylate groups;
(2) Adding an alkali catalyst and a photoinitiator into the resin solution, and performing photo-curing 3D printing to obtain wet gel;
(3) The wet gel is cured, aged, solvent replaced, hydrophobically modified and dried after being irradiated to obtain the silica-based aerogel;
in the step (2), the photo-curing 3D printing is high-resolution liquid crystal panel imaging digital light processing 3D printing;
in the step (2), the base catalyst is at least one selected from urotropine, ammonia water, urea, sodium hydroxide, potassium hydroxide, ethylenediamine, triethylamine and tetraethylenepentamine;
the photoinitiator is at least one selected from (2, 4, 6-trimethylbenzoyl) diphenyl phosphine oxide, ethyl 2,4, 6-trimethylbenzoyl phenylphosphonate, bis (2, 4, 6-trimethylbenzoyl) phenyl phosphine oxide, benzil dimethyl ether, camphorquinone and eosin Y;
in the step (3), the illumination time is 1-5 hours;
in the step (3), the wet gel is placed in a resin solution containing a base catalyst for light curing; the illumination intensity is 15-25mW/cm 2 The method comprises the steps of carrying out a first treatment on the surface of the The wavelength of the illumination is 380-420nm;
the aging is to encapsulate gel obtained by light curing in a hydrothermal kettle for aging; the aging temperature is 80-120 ℃ and the aging time is 2-5 days;
the solvent replacement is to put the aged gel into absolute ethyl alcohol and n-hexane for multiple solvent replacement;
the hydrophobic modification is to adopt methyl silane to carry out hydrophobic modification on gel after solvent replacement;
the silica-based aerogel has a three-dimensional complex appearance free-formed using 3D printing, and is manufactured independent of a mold.
2. The method of claim 1, wherein the backbone of the silica-based aerogel is hybrid crosslinked by a polyacrylate polymer and a polysiloxane.
3. The method of claim 1, wherein the silica-based aerogel exhibits a microscopically uniform bead-like phase-separated skeletal network structure, the skeleton being free of distinct neck structures.
4. The method of claim 1, wherein the silica-based aerogel has a skeletal particle size of 1-50nm.
5. The method according to claim 1, wherein the average size of the pore size of the silica-based aerogel is 1-50nm.
6. The method of claim 1, wherein the silica-based aerogel has a pore volume of 1.4-1.8cm 3 /g。
7. The method of claim 1, wherein the silica-based aerogel has a skeletal intrinsic density of 1.2-1.8g/cm 3 。
8. The method of claim 1, wherein the silica-basedThe specific surface area of the aerogel is 500-1000m 2 /g。
9. The method of claim 1, wherein the silica-based aerogel comprises SiO x The mass content of the inorganic component is 50-85%.
10. The method of claim 1, wherein the silica-based aerogel has a three-dimensional complex structure.
11. The method of preparing silica-based aerogel according to claim 1, wherein in step (1), the hyperbranched siloxane of the substituted acrylate groups is selected from the group consisting of C 1-10 Hyperbranched siloxanes of alkyl-substituted acrylate groups.
12. The method according to claim 1, wherein the coupling agent is selected from at least one of methacrylate propyl trimethoxysilane, acrylate propyl trimethoxysilane, methacrylate propyl triethoxysilane, acrylate propyl triethoxysilane.
13. The method of claim 1, wherein the silane precursor is selected from at least one of tetraethyl orthosilicate, tetramethyl orthosilicate, tetrabutyl orthosilicate, tetraisopropyl orthosilicate.
14. The method of claim 1, wherein the volume ratio of the silane precursor to the coupling agent is (15-40): 0.5-15.
15. The method according to claim 1, wherein the silane precursor is used in an amount of 20 to 40% by mass of the acid-catalyzed hydrolysis-condensation reaction system.
16. The method according to claim 1, wherein the coupling agent is used in an amount of 1-15% by mass of the reaction system.
17. The method of claim 1, wherein the molar ratio of ethanol to acid in the mixed solution of ethanol and dilute aqueous acid is (0.5-1.5): 1-5.
18. The method of claim 17, wherein the ethanol is absolute ethanol.
19. The method of claim 1, wherein the molar concentration of the dilute aqueous acid is 0.01-1 mol/L.
20. The method according to claim 1, wherein the dilute acid is selected from at least one of hydrochloric acid, sulfuric acid, nitric acid, oxalic acid, acetic acid, formic acid, citric acid, aluminum trichloride hexahydrate; the acid catalyzed hydrolytic condensation reaction is carried out at room temperature.
21. The method according to claim 1, wherein the acid-catalyzed hydrolytic condensation reaction is carried out under stirring conditions for a period of 10 to 40 hours.
22. The method according to claim 1, wherein the reaction after the addition of the coupling agent is continued at room temperature; the reaction is carried out under stirring for 10-40 hours.
23. The method according to claim 1, wherein the mass concentration of the base catalyst in the system is 0.5-2%;
the mass concentration of the photoinitiator in the system is 2-10%.
24. The method of claim 1, wherein the resin solution is stirred to form a clear and transparent solution after adding the base catalyst and the photoinitiator to the resin solution.
25. The method of claim 1, wherein the printing parameters include: the x-axis of the imaging resolution of the surface exposure is 10-100 mu m, and the y-axis is 10-100 mu m; the thickness of the exposure layer of the printing platform is 10-300 mu m, the lifting height after single exposure is 50-150mm, the single exposure time is 15-60s, and the exposure intensity is 2-30mW/cm 2 。
26. The method of claim 1, wherein the drying is flash atmospheric drying.
27. A composite material, characterized in that the composite material is a hybrid material formed by a polymer resin and the silica-based aerogel prepared by the method of any one of claims 1 to 26, and the appearance structure of the silica-based aerogel is completely maintained;
the polymer resin is selected from photosensitive resin prepared from at least one of the following photosensitive resin monomers: 1, 6-hexanediol diacrylate, trimethylolpropane triacrylate, polyethylene glycol diacrylate, acrylomorpholine, pentaerythritol tetraacrylate, di-pentaerythritol hexaacrylate, epoxy acrylate, polyurethane acrylate, polyester acrylate, polyether acrylate.
28. A method of preparing a composite material, the method comprising the steps of:
(1) Carrying out acid-catalyzed hydrolysis condensation reaction on a silane precursor in a mixed solution of ethanol and a dilute acid aqueous solution, and adding a coupling agent into a reaction solution after the reaction is completed to obtain a resin solution;
the coupling agent is selected from hyperbranched siloxanes containing substituted or unsubstituted acrylate groups;
(2) Adding an alkali catalyst and a photoinitiator into the resin solution, and performing photo-curing 3D printing to obtain wet gel;
after the wet gel is washed by ethanol, the wet gel is semi-immersed in a photosensitive resin monomer, the ethanol volatilizes under the assistance of vacuum, and the photosensitive resin monomer is filled into the pores of the wet gel to complete the replacement of a gel solvent; and curing by photoinitiation or thermal initiation to obtain the composite material.
29. Use of the composite material of claim 27 as a 3D printed polymeric material.
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Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691227A (en) * | 2009-10-13 | 2010-04-07 | 厦门大学 | Method for preparing silica aerogel material |
| CN101973752A (en) * | 2010-10-21 | 2011-02-16 | 厦门大学 | Glass fiber reinforced silicon dioxide aerogel composite material and preparation method thereof |
| CN104556964A (en) * | 2014-12-30 | 2015-04-29 | 纳诺科技有限公司 | Hydrophobic silica aerogel heat-insulation composite material and preparation method thereof |
| CN106629750A (en) * | 2016-11-09 | 2017-05-10 | 中国科学院宁波材料技术与工程研究所 | Normal pressure preparation method for transparent silica bulk aerogel |
| US9745439B1 (en) * | 2016-05-10 | 2017-08-29 | Qatar Foundation For Education, Science And Community Development | Methods of forming aerogels |
| CN108117082A (en) * | 2017-12-27 | 2018-06-05 | 武汉理工大学 | A kind of siloxanes toughening modifying SiO2Aeroge and preparation method thereof |
| CN108423685A (en) * | 2018-04-29 | 2018-08-21 | 浙江工业大学 | The atmospheric preparation method of aerosil |
| CN110422850A (en) * | 2019-06-25 | 2019-11-08 | 华南理工大学 | High-specific surface area strong-hydrophobicity graphene oxide/silicon dioxide composite aerogel atmospheric preparation method |
-
2020
- 2020-04-09 CN CN202010275780.6A patent/CN113511656B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101691227A (en) * | 2009-10-13 | 2010-04-07 | 厦门大学 | Method for preparing silica aerogel material |
| CN101973752A (en) * | 2010-10-21 | 2011-02-16 | 厦门大学 | Glass fiber reinforced silicon dioxide aerogel composite material and preparation method thereof |
| CN104556964A (en) * | 2014-12-30 | 2015-04-29 | 纳诺科技有限公司 | Hydrophobic silica aerogel heat-insulation composite material and preparation method thereof |
| US9745439B1 (en) * | 2016-05-10 | 2017-08-29 | Qatar Foundation For Education, Science And Community Development | Methods of forming aerogels |
| CN106629750A (en) * | 2016-11-09 | 2017-05-10 | 中国科学院宁波材料技术与工程研究所 | Normal pressure preparation method for transparent silica bulk aerogel |
| CN108117082A (en) * | 2017-12-27 | 2018-06-05 | 武汉理工大学 | A kind of siloxanes toughening modifying SiO2Aeroge and preparation method thereof |
| CN108423685A (en) * | 2018-04-29 | 2018-08-21 | 浙江工业大学 | The atmospheric preparation method of aerosil |
| CN110422850A (en) * | 2019-06-25 | 2019-11-08 | 华南理工大学 | High-specific surface area strong-hydrophobicity graphene oxide/silicon dioxide composite aerogel atmospheric preparation method |
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