CN106747265B - A kind of aerogel composite and its preparation method based on self assembly opacifier fiber - Google Patents

A kind of aerogel composite and its preparation method based on self assembly opacifier fiber Download PDF

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CN106747265B
CN106747265B CN201611231458.3A CN201611231458A CN106747265B CN 106747265 B CN106747265 B CN 106747265B CN 201611231458 A CN201611231458 A CN 201611231458A CN 106747265 B CN106747265 B CN 106747265B
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fiber
opacifier
self assembly
carrying
sio
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CN106747265A (en
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吴会军
王珊
杨丽修
周孝清
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Guangzhou University
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    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
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    • C04B41/45—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements
    • C04B41/46—Coating or impregnating, e.g. injection in masonry, partial coating of green or fired ceramics, organic coating compositions for adhering together two concrete elements with organic materials
    • C04B41/49—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes
    • C04B41/4905—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon
    • C04B41/4922—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane
    • C04B41/4933—Compounds having one or more carbon-to-metal or carbon-to-silicon linkages ; Organo-clay compounds; Organo-silicates, i.e. ortho- or polysilicic acid esters ; Organo-phosphorus compounds; Organo-inorganic complexes containing silicon applied to the substrate as monomers, i.e. as organosilanes RnSiX4-n, e.g. alkyltrialkoxysilane, dialkyldialkoxysilane containing halogens, i.e. organohalogen silanes
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    • C04B41/00—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone
    • C04B41/60—After-treatment of mortars, concrete, artificial stone or ceramics; Treatment of natural stone of only artificial stone
    • C04B41/61—Coating or impregnation
    • C04B41/62—Coating or impregnation with organic materials
    • C04B41/64—Compounds having one or more carbon-to-metal of carbon-to-silicon linkages
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    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M11/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising
    • D06M11/32—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond
    • D06M11/36—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with inorganic substances or complexes thereof; Such treatment combined with mechanical treatment, e.g. mercerising with oxygen, ozone, ozonides, oxides, hydroxides or percompounds; Salts derived from anions with an amphoteric element-oxygen bond with oxides, hydroxides or mixed oxides; with salts derived from anions with an amphoteric element-oxygen bond
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    • C04B2201/50—Mortars, concrete or artificial stone characterised by specific physical values for the mechanical strength
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    • D06M2101/22—Polymers or copolymers of halogenated mono-olefins

Abstract

The invention belongs to heat-barrier material fields, disclose a kind of high-performance aerogel composite and its preparation method based on self assembly opacifier fiber.The composite material is by opacifier carrying fiber felt and SiO2Aeroge is combined, and opacifier is loaded to fiber surface using self-assembling method by the present invention, then has the fiber (opacifier carrying fiber) of opacifier for reinforcement to load, with SiO2The opacifier carrying fiber and aeroge composite heat-insulated material of stable structure are prepared in colloidal sol mixing with sol-gel processing under normal temperature and pressure conditions.The present invention enhances aeroge with opacifier carrying fiber, can make composite material that there is preferable opacifier dispersibility and heat radiation to block performance, improve the heat-insulating property of aerogel heat-proof composite material.

Description

A kind of aerogel composite and its preparation method based on self assembly opacifier fiber
Technical field
The invention belongs to heat-barrier material field, in particular to a kind of high-performance aeroge based on self assembly opacifier fiber Composite material and its preparation method.
Background technique
With the development of economy and society, the mankind are increasing to energy requirement, but as fossil energy is largely exploited, Reserves constantly decline, and go to seek new energy there is an urgent need to the mankind and improve the utilization rate of the energy.Seeking the very long road of new energy On, people put into how a large amount of energy research improves energy utilization rate simultaneously, and heat-insulating heat-preserving material becomes one of them can not The research direction of ignorance.It can effectively reduce the heat exchange between medium and its environment, be widely used in construction material, energy storage is set The fields such as standby, aerospace flight vehicle and warmth-retaining clothing.
Aeroge is the minimum solid matter of current density, is cross-linked with each other and is constituted by colloidal particle or the high-polymer molecule, tool There is nanoporous spatial mesh structure, specific surface area is up to 500~1200m2·g-1, porosity up to 99.8%, hole ruler Very little about 10nm~100nm.Due to this unique texture of aeroge, excellent heat preservation and insulation, but aeroge are made it have Stephanoporate framework intensity is low, toughness is small and heat radiation blocks that performance is poor, limit the practical application of aeroge.
Absorption and scattering process using opacifier to heat radiation weaken the radiant heat throughput by aeroge to improve The heat-insulating property of aeroge entirety is current improvement aeroge heat radiation by introducing opacifier in aeroge preparation process Block the effective ways of performance.Chinese invention patent CN 200910193479.4 is disclosed to utilize generated in-situ method in gas Metatitanic acid precipitating is introduced in gel, is avoided powder radiation resistance and is gathered every bolus, reduces the solid conductive heat of material；Chinese invention Disclosed be added in colloidal sol using Titanium alkoxides of patent CN200510031952.0 introduces infrared light screening agent titanium dioxide, can make red Outer opacifier is evenly dispersed, has effectively obstructed infrared radiation heat transfer, and used reinforcing fiber is quartz fibre, high silicon oxygen fibre Dimension, alumina silicate fibre and glass fibre, effectively improve the intensity of aerogel composite, but inorfil is relatively large in diameter, with Aeroge combination interface is also easy to produce cracking, affects the intensity, flexibility and structural stability of aeroge.
Big for aeroge brittleness caused by inorfil component brittleness, flexible poor problem, Chinese granted patent CN201310055846.0 discloses the aeroge flexibility heat-insulating material and preparation method thereof of Static Spinning micro-nano fiber enhancing, can make Composite material has preferably flexible, interfacial bonding property and structural intergrity, is improving aerogel heat-proof composite material mechanical property Its is set to keep good heat-insulating property while energy.But electrostatic spinning fiber aeroge blocks that performance is lower to ask there are heat radiation Topic, therefore the infrared of reinforced composite is needed to block performance.
Summary of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, the primary purpose of the present invention is that providing a kind of be based on from group The high-performance aerogel composite of opacifier fiber is filled, which has lower thermal coefficient and good heat radiation Block performance.
Another object of the present invention is to provide the above-mentioned high-performance aerogel composite based on self assembly opacifier fiber Preparation method.
The purpose of the present invention is realized by following proposal:
A kind of high-performance aerogel composite based on self assembly opacifier fiber, by opacifier carrying fiber felt with SiO2Aeroge is combined.
The fibre diameter of the opacifier carrying fiber felt is 50nm~1000nm.
The opacifier carrying fiber felt is that opacifier particle is loaded to reinforcing fiber using LBL self assembly technology What the fiber surface of felt obtained.Self-assembling technique is the composite fibre that preparation has both opacifier and reinforcing fiber overall characteristic Provide effective way.
Reinforcing fiber in the opacifier carrying fiber felt can be polyvinylidene fluoride, polypropylene fibre, poly- second Alkene fiber, polyethers fiber, polyester fiber, Fypro, polyimide fiber, polyacrylonitrile fibre, gathers styroflex Vinyl chloride fibers, one of polyacrylic fibre, estron, nylon cotton, silk or fiber crops polymer fiber material；Institute The opacifier stated can be TiO2, carbon black, SiC, ZrO2、Fe3O4、B4C、BN、K2Ti6O13, ATO, ilmenite, in potassium hexatitanate extremely Few one kind.
The opacifier carrying fiber felt is prepared by following methods:
(1) reinforcing fiber is subjected to hydrophilic pretreatment, obtaining has hydrophilic reinforcing fiber matrix；
(2) assembles concentration A and assembles concentration B are prepared respectively；
(3) the assembles concentration A that step (2) obtains is immersed in by pretreated reinforcing fiber matrix what step (1) obtained In 10~30min, so that the ionic group A (+/-) in assembles concentration A is adsorbed on fiber surface；Then it is dipped into again after water rinses 10~30min in the assembles concentration B that step (2) obtains makes fiber surface absorption " A (+/-)-opacifier (- /+) group ", through washing After make fiber surface assemble single layer opacifier particle；Wherein, " +/- " symbol indicates the polycation or polyanion of ionic group Property；The polyanion or polycation property of "-/+" symbol expression ionic group；
(4) step (3) n times are repeated, fiber surface is made to assemble n-layer opacifier particle, opacifier carrying fiber is made.Wherein Integer between n=1~10.
Wherein assembles concentration B is the dispersion liquid or colloidal solution of opacifier；Assembles concentration A is one kind and assembles concentration B electrical property phase Anti- polycation or polyanion solution, wherein polycation can be in POSS (+), triethylene tetramine (+), hexamethylene diamine (+) At least one, polyanion can be at least one of polyacrylic acid (-), polyacrylate (-)；
Hydrophilic preprocess method in the step (1) can in plasma treatment, chemical method hydrophilic modifying at least It is a kind of.
Preferably, the hydrophilic preprocess method operating procedure of plasma treatment in the step (1) are as follows: by reinforcing fiber Use NH3、O2、CO、Ar、N2、H2Etc. contacted with air after 1~10min of gas plasma process, can surface introducing-COOH ,- C=O ,-NH2, the groups such as-OH, increase its hydrophily to get to having hydrophilic reinforcing fiber matrix；
Preferably, the chemical method hydrophilic modifying preprocess method in the step (1) are as follows: " living to reinforcing fiber first Change " processing (such as HF is taken off in strong base solution), make to generate the substance for being easy to generate free radical or oxidation on its strand, then Selecting suitable reagent with " activation ", treated, and reinforcing fiber is reacted, to introduce the poles such as hydroxyl, carboxyl on its strand Property group or grafting hydrophilic monomer；
It is furthermore preferred that chemical method hydrophilic modifying preprocess method in the step (1) specific steps are as follows: (a) reinforcing fiber is soaked with ethyl alcohol, then impregnates 0.5h in deionized water；(b) reinforcing fiber obtained in (a) is put into Mass fraction under the conditions of 75 DEG C is (concentration of NaOH is 3mol/L) in the potassium permanganate of 3wt.% and the aqueous solution of NaOH, instead It is washed with deionized water after answering 4min；(c) reinforcing fiber in (b) is put into the NaHSO of 5wt.% again3It is reacted in aqueous solution, Until brown, which is all taken off, becomes white；(d) it is put it into after in the PVP aqueous solution of 0.5wt.% and reacts 5min, finally used Deionized water rinsing 2min completes hydrophilic preprocessing process.
The SiO2Aeroge has nanoporous spatial mesh structure, and this structure makes aeroge have excellent thermal insulation Performance.
A kind of preparation method of the above-mentioned high-performance aerogel composite based on self assembly opacifier fiber, including with Lower step:
(1)SiO2Colloidal sol preparation: by organic silicon source, dehydrated alcohol, water according to molar ratio be 1:(4~12): (0.25~6) Wiring solution-forming, and SiO is made by the two-step method of acid-base catalysis2Colloidal sol；
(2) opacifier carrying fiber felt and SiO2Gel is compound: it is placed in the vessel after opacifier carrying fiber felt is cut, Again by step (1) obtained SiO2Colloidal sol is added in opacifier carrying fiber felt, and air in fibrofelt is discharged, and is in temperature Gel is settled under conditions of 10~35 DEG C, opacifier carrying fiber felt and SiO is made2Gel complex material；
(3) ageing and aging: the opacifier carrying fiber felt and SiO that step (2) is obtained2Gel complex material is in temperature It is aged 1~2 day under conditions of being 10~35 DEG C, the mixed liquor that the volume ratio with deionized water and ethyl alcohol is 1:3~1:10 is to solidifying Glue composite material carries out primary aging, and primary ageing time is 1~72 hour, then uses the volume of ethyl orthosilicate and ethyl alcohol again Second level aging is carried out to gel complex material than the mixed liquor for 1:3~1:10, second level ageing time is 1~72 hour；
(4) solvent is replaced: carrying out solvent displacement, time swap 5 to the gel complex material that aging finishes with displacer ~48 hours；
(5) surface modification: with above-mentioned displacer being that 1:10~3:10 is mixed with hydrophobic agents by volume, and gel is compound Material impregnates wherein 1~72 hour；
(6) surface clean: carrying out surface clean to the gel complex material that surface modification finishes with above-mentioned displacer, removes Gel complex material modified outcome remained on surface, surface clean number are 2~4 times；
(7) it being dried: the gel complex material through over cleaning is placed in drying box constant pressure and dry, drying temperature is 50~ 70 DEG C, the time is 12~24 hours, obtains the high-performance aerogel composite based on self assembly opacifier fiber.
Organic silicon source described in step (1) is ethyl orthosilicate, methyl orthosilicate, methyltrimethoxysilane, methyl Triethoxysilane one of gathers more siloxanes or a variety of.
The displacer is at least one of n-hexane, normal heptane, acetone.
Hydrophobic agents described in step (5) are trim,ethylchlorosilane, dimethyldimethoxysil,ne, ethyl dibutyl silicon At least one of alkane, trimethyl diethoxy silane.
Temperature in the step (2) is preferably 18~25 DEG C.
Temperature in the step (3) is preferably 18~25 DEG C.
The present invention compared with the existing technology, have the following advantages and the utility model has the advantages that
(1) since opacifier is to be supported on fiber surface, fiber and aeroge compound tense are uniformly dispersed, can make opacifier With good dispersibility, in addition opacifier can be regulated and controled by the control self assembly number of plies and the dosage of opacifier carrying fiber Additive amount, regulation are more convenient；
(2) since opacifier carrying fiber diameter is 50nm~1000nm, when use and aeroge hole for 10nm~ When the fiber that the size of 100nm is closer to, the two can good combination, so that opacifier carrying fiber and high greatly improved The flexibility and interfacial bonding property of performance aerogel composite；
(3) according to scale effect theory, since the opacifier carrying fiber with micro-nano-scale is in conjunction with aeroge When interface residual stress it is small, reduce interface cohesion defect, and the micron order hole of opacifier carrying fiber limits fiber Between matrix ligament thickness, make matrix that can deform with fiber stress, reduce the brittle break of matrix under external force, To make the aerogel composite maintain preferable structural stability under stress；
(4) interfibrous micron order hole is filled with nanoscale aeroge, increases gas conduction thermal resistance and convection current Heat transfer resistance makes composite material have good heat-insulating property；
(5) present invention can improve the mechanical property and heat-insulating property of aerogel composite simultaneously, so that it is steady to obtain structure The high-performance aerogel composite of fixed self assembly opacifier fiber can be used for reducing thermal loss, improve heat energy utilization effect Rate has broad application prospects in fields such as aerospace, industry, buildings.
Detailed description of the invention
Fig. 1 is the process flow chart for preparing the high-performance aerogel composite of self assembly opacifier fiber of the invention.
Fig. 2 is PVDF micro nanometer fiber and the TiO after assembling before self assembly2@PVDF micro nanometer fiber spectral transmittance spectrum Figure.
Fig. 3 is the PVDF micro nanometer fiber and TiO that the spectral transmittance based on Fig. 2 is calculated2@PVDF micro nanometer fiber Spectral extinction coefficient spectrogram.
Fig. 4 is the radiant heat conductanc curve graph for two kinds of tunica fibrosas that the data based on Fig. 2 and Fig. 3 are calculated.
Specific embodiment
Below with reference to embodiment and attached drawing, the present invention is described in further detail, but embodiments of the present invention are unlimited In this.
Agents useful for same can routinely be bought unless otherwise specified from market in embodiment.
Embodiment 1
The high-performance aerogel composite of the self assembly opacifier fiber of the present embodiment, by opacifier TiO2Load PVDF (Kynoar) micro nanometer fiber felt (TiO2@PVDF composite fibrofelt) and high heat preservation and insulation SiO2Aeroge is compound It forms.
TiO2The preparation step of@PVDF composite fibrofelt is as follows:
(1) PVDF micro nanometer fiber is subjected to hydrophilic modifying pretreatment with chemical method hydrophilic modifying, makes it have hydrophily. Concrete operations are as follows: (a) soaking PVDF micro nanometer fiber with ethyl alcohol, then impregnate 0.5h in deionized water；(b) by (a) Obtained in PVDF micro nanometer fiber be put into 75 DEG C under the conditions of mass fraction be 3wt.% potassium permanganate and NaOH it is water-soluble Liquid (concentration of NaOH is 3mol/L), is washed with deionized water after reacting 4min；(c) again by the PVDF micro nanometer fiber in (b) It is put into the NaHSO of 5wt.%3It is reacted in aqueous solution, until brown, which is all taken off, becomes white；(d) it is put it into after 5min is reacted in the PVP aqueous solution of 0.5wt.%, finally completes hydrophilic preprocessing process with deionized water rinsing 2min.
(2) pH=2.5 is prepared respectively, the polyacrylic acid PAA aqueous solution and pH=2.5, quality point that concentration is 0.01mol/L Number is the TiO of 0.5wt.%2Two kinds of assembles concentrations of aqueous dispersions；
(3) step (1) obtain to be immersed in the PAA that step (2) obtains by pretreated PVDF micro nanometer fiber molten In liquid, and the ionic group PAA in PAA solution is set to be adsorbed on fiber surface after water rinses；Then step (2) are dipped into again to obtain The TiO arrived2In dispersion liquid, fiber surface is made to adsorb " PAA/TiO2Group " makes fiber surface assemble single layer opacifier after washing Particle；
(4) it repeats step (3) 3 times, fiber surface is made to assemble 3 layers of TiO2TiO is made in particle2@PVDF composite fibre.
Fig. 2 is PVDF micro nanometer fiber and the TiO after assembling before self assembly2The infrared light of@PVDF micro nanometer fiber spectrum Spectrogram, the spectrogram indicate permeable ratio when heat radiation passes through two kinds of tunica fibrosas；Fig. 3 is based on the spectral transmittance of Fig. 2 Obtained PVDF micro nanometer fiber and TiO2The spectral extinction coefficient spectrogram of@PVDF micro nanometer fiber, the spectrogram illustrate list The transmittancy of two kinds of tunica fibrosas under the thickness of position；Fig. 4 is two kinds of tunica fibrosas that the data based on Fig. 2 and Fig. 3 are calculated Radiant heat conductanc curve graph, the figure shows two kinds of tunica fibrosas to block ability to heat radiation under different temperatures environment.
It can be seen that within the scope of 2.5~25 mu m wavebands from Fig. 2~4, compared with before assembling, assembled through 4 times TiO2@PVDF composite membrane spectral transmittance significantly reduces, and spectral extinction coefficient increases, under room temperature 300K, PVDF tunica fibrosa and TiO2The Rosseland of the@PVDF composite membrane extinction coefficient that is averaged is respectively as follows: 31.9 and 325cm-1；In 230~420K temperature range It is interior, TiO2@PVDF composite membrane has radiant heat conductanc more smaller than PVDF tunica fibrosa.Such as at a temperature of 230 and 420K, group is accommodated Rice TiO2The radiant heat conductanc of fiber is reduced to 0.011 and 0.066mW/ (mK) afterwards.Show to draw using self-assembling technique Enter nano-TiO2Performance, TiO are blocked in the heat radiation that opacifier can be effectively improved porous fibre heat-barrier material2@PVDF composite fibre material Expect in terms of stopping radiant heat transmitting and heat-insulation and heat-preservation with good application prospect.
TiO2@PVDF composite fibrofelt and SiO2Gel is compound, and specific step is as follows:
(1) ethyl orthosilicate, dehydrated alcohol are mixed in beaker, are placed on magnetic stirring apparatus and stir 30min, mixing is equal A certain amount of water and hydrochloric acid are gradually instilled after even while stirring, 30min is stirred, static 24 hours, is fully hydrolyzed it, then exists Under magnetic stirrer, DMF, distilled water and ammonium hydroxide are sequentially added, and continues stirring 30min and obtains SiO2Colloidal sol；It is entire anti- Reactant molar ratio is ethyl orthosilicate: dehydrated alcohol: water: DMF: hydrochloric acid during answering: ammonium hydroxide=1:7:2:0.25:(10~ 5):3.57×10-3；
(2)TiO2@PVDF composite fibrofelt is cut into certain shapes and is placed in the vessel, by SiO obtained by step (1)2Colloidal sol TiO is added2In@PVDF composite fibrofelt, and air in fibrofelt is discharged, is coagulated after about 0.1~5 hour is stood at 18~25 DEG C TiO is made in glue2@PVDF composite fibre and SiO2Gel complex material；
(3) ageing and aging: the TiO that step (2) is obtained2@PVDF composite fibre and SiO2Gel complex material 18~ It is aged 1~2 day at 25 DEG C, gel complex material is carried out with the mixed liquor that deionized water is 1:3~1:10 with ethyl alcohol volume ratio Primary aging, primary ageing time are 1~72 hour, with the volume ratio of ethyl orthosilicate and ethyl alcohol are again then 1:3~1:10 Second level aging is carried out to gel complex material, second level ageing time is 1~72 hour；
(4) solvent is replaced: carrying out solvent displacement, time swap 5 to the gel complex material that aging finishes with displacer ~48 hours；The small solution of the surface tension is at least one of n-hexane, normal heptane, acetone；
(5) surface modification: with displacer being that 1:10~3:10 is mixed with hydrophobic agents, by gel complex material by volume It impregnates wherein 1~72 hour, the hydrophobic agents are trim,ethylchlorosilane, dimethyldimethoxysil,ne, ethyl dibutyl silicon At least one of alkane, trimethyl diethoxy silane；
(6) surface clean: surface clean is carried out to the gel complex material that surface modification finishes with displacer, removes gel The remaining modified outcome of composite material surface, surface clean number are 2~4 times；
(7) it being dried: the gel complex material through over cleaning is placed in drying box constant pressure and dry, drying temperature is 50~ 70 DEG C, the time is 12~24 hours, obtains TiO2@PVDF composite fibre enhances aerogel composite, that is, is based on self assembly TiO2The high-performance aerogel composite of@PVDF micro nanometer fiber.
Table 1 is the pure SiO tested using electronic universal tester2Aeroge and PVDF micro nanometer fiber and SiO2 The measuring mechanical property result data of the composite material of aeroge, wherein since aeroge is frangible, can not carry out its stretch-proof and Bending strength, therefore " -- " indicates that can not carry out this test (is equivalent to this index value close to 0MPa).
Table 1 is pure SiO2Aeroge and and PVDF micro nanometer fiber and SiO2The mechanical performance of the composite material of aeroge Test result
As can be seen from Table 1, aeroge by PVDF micro nanometer fiber it is compound after, tensile strength, compression strength and anti- Curved intensity is improved, crisp, the frangible pure SiO with matter2Aeroge is compared, PVDF micro nanometer fiber and SiO2Aeroge is answered Condensation material has preferable structural stability and flexibility.
It to sum up analyzes, it is known that the aerogel composite can maintain preferable structural stability under stress, obtain Flexible TiO2@PVDF micro nanometer fiber and aerogel composite stable structure and have good heat radiation block performance and Comprehensive heat-insulating property.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention, It should be equivalent substitute mode, be included within the scope of the present invention.

Claims (10)

1. a kind of high-performance aerogel composite based on self assembly opacifier fiber, it is characterised in that: loaded by opacifier Fibrofelt and SiO2Aeroge is combined；
The opacifier carrying fiber felt is that opacifier particle is loaded to reinforcing fiber surface using LBL self assembly technology It obtains.
2. the high-performance aerogel composite according to claim 1 based on self assembly opacifier fiber, feature exist In:
The fibre diameter of the opacifier carrying fiber felt is 50nm~1000nm.
3. the high-performance aerogel composite according to claim 2 based on self assembly opacifier fiber, feature exist In:
Reinforcing fiber in the opacifier carrying fiber felt be polyvinylidene fluoride, polypropylene fibre, polyethylene fibre, Styroflex, polyethers fiber, polyester fiber, Fypro, polyimide fiber, polyacrylonitrile fibre, polyvinyl chloride Fiber, one of polyacrylic fibre, estron, nylon cotton, silk or fiber crops polymer fiber material；
The opacifier is TiO2, carbon black, SiC, ZrO2、Fe3O4、B4C、BN、K2Ti6O13, ATO, ilmenite, in potassium hexatitanate At least one.
4. the high-performance aerogel composite according to claim 3 based on self assembly opacifier fiber, feature exist It is prepared in the opacifier carrying fiber felt by following methods:
(1) reinforcing fiber is subjected to hydrophilic pretreatment, obtaining has hydrophilic reinforcing fiber matrix；
(2) assembles concentration A and assembles concentration B are prepared respectively；
(3) it is immersed in the assembles concentration A that step (2) obtains, makes by pretreated fibrous material matrix what step (1) obtained Ionic group A (+/-) in assembles concentration A is adsorbed on fiber surface；Then it is dipped into the group that step (2) obtains again after water rinses It fills in liquid B, makes fiber surface absorption " A (+/-)-opacifier (- /+) group ", fiber surface is made to assemble single layer shading after washing Agent particle；
(4) step (3) n times are repeated, fiber surface is made to assemble n-layer opacifier particle, opacifier carrying fiber is made；Wherein n=1 Integer between~10；
Assembles concentration B is the dispersion liquid or colloidal solution of opacifier in (2)；Assembles concentration A is a kind of electrical with assembles concentration B Opposite polycation or polyanion solution；
" +/- " symbol indicates the polycation or polyanionic nature of ionic group in step (3)；"-/+" symbol indicates ion The polyanion or polycation property of group.
5. the high-performance aerogel composite according to claim 4 based on self assembly opacifier fiber, feature exist In:
The polycation is at least one of POSS (+), triethylene tetramine (+), hexamethylene diamine (+), and polyanion is poly- At least one of acrylic acid (-), polyacrylate (-).
6. the high-performance aerogel composite according to claim 4 or 5 based on self assembly opacifier fiber, feature Be: the hydrophilic preprocess method in the step (1) is at least one of plasma treatment, chemical method hydrophilic modifying；
The hydrophilic preprocess method operating procedure of plasma treatment in the step (1) are as follows: by reinforcing fiber gas etc. from Daughter is contacted with air in surface introducing its hydrophilic group of increase after handling 1~10min to get to hydrophilic increasing Strong fibrous matrix；
Chemical method hydrophilic modifying preprocess method in the step (1) are as follows: reinforcing fiber " activation " is handled first, makes it The substance for being easy to generate free radical or oxidation is generated on strand, then selecting suitable reagent and " activation " treated enhances Fiber-reactive, to introduce polar group or grafting hydrophilic monomer on its strand；Specific steps are as follows: (a) is used Ethyl alcohol soaks reinforcing fiber, then impregnates 0.5h in deionized water；(b) reinforcing fiber obtained in (a) is put into 75 DEG C Under the conditions of mass fraction be 3wt.% potassium permanganate and concentration be 3mol/L NaOH mixed aqueous solution, react 4min after It is washed with deionized water；(c) reinforcing fiber in (b) is put into the NaHSO of 5wt.% again3It is reacted in aqueous solution, until brown All taking off becomes white；(d) it is put it into after in the PVP aqueous solution of 0.5wt.% and reacts 5min, finally use deionized water Rinsing 2min completes hydrophilic preprocessing process.
7. a kind of high-performance aeroges based on self assembly opacifier fiber described in any item according to claim 1~6 are compound The preparation method of material, it is characterised in that the following steps are included:
(1)SiO2Colloidal sol preparation: by organic silicon source, dehydrated alcohol, water according to molar ratio be 1:(4~12): (0.25~6) is made into Solution, and SiO is made by the two-step method of acid-base catalysis2Colloidal sol；
(2) opacifier carrying fiber felt and SiO2Gel is compound: being placed in the vessel after opacifier carrying fiber felt is cut, then will Step (1) obtained SiO2Colloidal sol is added in opacifier carrying fiber felt, and air in fibrofelt is discharged, temperature be 10~ Gel is settled under conditions of 35 DEG C, opacifier carrying fiber felt and SiO is made2Gel complex material；
(3) ageing and aging: the opacifier carrying fiber felt and SiO that step (2) is obtained2Gel complex material is 10 in temperature It is aged 1~2 day under conditions of~35 DEG C, the mixed liquor that the volume ratio with deionized water and ethyl alcohol is 1:3~1:10 is multiple to gel Condensation material carries out primary aging, and primary ageing time is 1~72 hour, is then with the volume ratio of ethyl orthosilicate and ethyl alcohol again The mixed liquor of 1:3~1:10 carries out second level aging to gel complex material, and second level ageing time is 1~72 hour；
(4) solvent is replaced: carrying out solvent displacement to the gel complex material that aging finishes with displacer, time swap is 5~48 Hour；
(5) surface modification: with above-mentioned displacer being that 1:10~3:10 is mixed with hydrophobic agents, by gel complex material by volume It impregnates wherein 1~72 hour；
(6) surface clean: surface clean is carried out to the gel complex material that surface modification finishes with above-mentioned displacer, removes gel The remaining modified outcome of composite material surface, surface clean number are 2~4 times；
(7) it is dried: the gel complex material through over cleaning being placed in drying box constant pressure and dry, drying temperature is 50~70 DEG C, the time is 12~24 hours, obtains the high-performance aerogel composite based on self assembly opacifier fiber.
8. the preparation side of the high-performance aerogel composite according to claim 7 based on self assembly opacifier fiber Method, it is characterised in that:
Organic silicon source described in step (1) is ethyl orthosilicate, methyl orthosilicate, methyltrimethoxysilane, three second of methyl Oxysilane one of gathers more siloxanes or a variety of.
9. the preparation side of the high-performance aerogel composite according to claim 7 based on self assembly opacifier fiber Method, it is characterised in that:
The displacer is at least one of n-hexane, normal heptane, acetone.
10. the preparation side of the high-performance aerogel composite according to claim 7 based on self assembly opacifier fiber Method, it is characterised in that:
Hydrophobic agents described in step (5) are trim,ethylchlorosilane, dimethyldimethoxysil,ne, ethyl dibutyl silane, three At least one of methyldiethoxysilane.
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