CN106747265A - 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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CN106747265A
CN106747265A CN201611231458.3A CN201611231458A CN106747265A CN 106747265 A CN106747265 A CN 106747265A CN 201611231458 A CN201611231458 A CN 201611231458A CN 106747265 A CN106747265 A CN 106747265A
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opacifier
fiber
self assembly
sio
aerogel composite
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CN106747265B (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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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
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    • 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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    • C04B41/64—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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Abstract

The invention belongs to heat-barrier material field, a kind of high-performance aerogel composite based on self assembly opacifier fiber and its preparation method are disclosed.The composite is by opacifier carrying fiber felt and SiO2Aeroge is composited, and opacifier is loaded to fiber surface by the present invention using self-assembling method, then is reinforcement to be loaded with the fiber (opacifier carrying fiber) of opacifier, with SiO2Colloidal sol mixes, and constitutionally stable opacifier carrying fiber and aeroge composite heat-insulated material are prepared under normal temperature and pressure conditionses with sol-gel processing.The present invention strengthens aeroge with opacifier carrying fiber, can make composite that there is preferable opacifier dispersiveness and heat radiation to block performance, improves 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, more particularly to a kind of high-performance aeroge based on self assembly opacifier fiber Composite and its preparation method.
Background technology
With economic and society development, the mankind are increasing to energy requirement, but as fossil energy is largely exploited, Reserves constantly decline, in the urgent need to the mankind go to seek new energy and improve the utilization rate of the energy.Seeking the very long road of new energy On, people put into how substantial amounts of energy research improves energy utilization rate simultaneously, and heat-insulating heat-preserving material can not as one of them 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 and set The field 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 by colloidal particle or high-polymer molecular and constituted, tool There is nanoporous spatial mesh structure, specific surface area is up to 500~1200m2·g-1, porosity up to 99.8%, its hole chi 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 low intensity, toughness is small and poor performance is blocked in heat radiation, limits the practical application of aeroge.
Absorption and scattering process using opacifier to heat radiation, weaken by the radiant heat throughput of aeroge to improve The overall heat-insulating property of aeroge, opacifier is introduced by aeroge preparation process, is improvement aeroge heat radiation at present Block the effective ways of performance.Chinese invention patent CN 200910193479.4 is disclosed to utilize generated in-situ method in gas Metatitanic acid precipitation is introduced in gel, it is to avoid powder radiation resistance is poly- every bolus, reduces the solid conductive heat of material；Chinese invention Infrared light screening agent titanium dioxide is introduced in the disclosed addition colloidal sols using Titanium alkoxides of patent CN200510031952.0, can be made red Outer opacifier is dispersed, has effectively intercepted infrared radiation heat transfer, and the reinforcing fiber for being used is quartz fibre, silica high 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, have impact on the intensity of aeroge, flexible and structural stability.
For aeroge fragility caused by inorfil component fragility is big, flexible difference problem, Chinese granted patent CN201310055846.0 discloses enhanced aeroge flexibility heat-insulating material of Static Spinning micro-nano fiber and preparation method thereof, can make Composite has preferably flexible, interfacial bonding property and structural intergrity, is improving aerogel heat-proof composite material mechanical property It is set to keep good heat-insulating property while energy.But there is heat radiation and block that performance is relatively low to ask in electrostatic spinning fiber aeroge Topic, therefore need the infrared of reinforced composite to block performance.
The content of the invention
In order to overcome the shortcomings and deficiencies of the prior art described above, primary and foremost purpose of the invention is to provide a kind of being based on from group The high-performance aerogel composite of opacifier fiber is filled, the composite has relatively low thermal conductivity factor 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, its by opacifier carrying fiber felt with SiO2Aeroge is composited.
The fibre diameter of described opacifier carrying fiber felt is 50nm~1000nm.
Described opacifier carrying fiber felt is that opacifier particle is loaded into reinforcing fiber using LBL self assembly technology What the fiber surface of felt was obtained.Self-assembling technique is to prepare the composite fibre with opacifier and overall characteristic both reinforcing fiber There is provided effective way.
Reinforcing fiber in described opacifier carrying fiber felt can be polyvinylidene fluoride, polypropylene fibre, poly- second It is alkene fiber, styroflex, polyethers fiber, polyester fiber, Fypro, polyimide fiber, polyacrylonitrile fibre, poly- Vinyl chloride fibers, a kind of polymer fiber material in polyacrylic fibre, estron, nylon cotton, silk or fiber crops；Institute The opacifier stated can be TiO2, carbon black, SiC, ZrO2、Fe3O4、B4C、BN、K2Ti6O13, ATO, ilmenite, in potassium hexatitanate extremely Few one kind.
Described opacifier carrying fiber felt is prepared by following methods：
(1) reinforcing fiber is carried out into hydrophilic pretreatment, obtaining has hydrophilic reinforcing fiber matrix；
(2) assembles concentration A and assembles concentration B is prepared respectively；
(3) the reinforcing fiber matrix by pretreatment that step (1) is obtained is immersed in the assembles concentration A that step (2) is obtained In 10~30min, make the ionic group A in assembles concentration A it is (+/-) absorption in fiber surface；Then it is dipped into again after being rinsed through water 10~30min in the assembles concentration B that step (2) is obtained, makes fiber surface adsorb " A (+/-)-opacifier (- /+) group ", through washing After make fiber surface assemble individual layer opacifier particle；Wherein, " +/- " symbol represents the polycation or polyanion of ionic group Property；"-/+" symbol represents the polyanion or polycation property of ionic group；
(4) repeat step (3) n times, makes fiber surface assemble n-layer opacifier particle, and opacifier carrying fiber is obtained.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 the electrical phases of assembles concentration B Anti- polycation or polyanion solution, wherein polycation can be in POSS (+), triethylene tetramine (+), hexamethylene diamines (+) At least one, polyanion can be polyacrylic acid (-), polyacrylate (-) at least one；
Hydrophilic preprocess method in described 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 described step (1) is：By reinforcing fiber Use NH3、O2、CO、Ar、N2、H2Etc. after 1~10min of gas plasma process with air contact, can surface introduce-COOH ,- C=O ,-NH2, the group such as-OH, increase its hydrophily, that is, obtain with hydrophilic reinforcing fiber matrix；
Preferably, the chemical method hydrophilic modifying preprocess method in described step (1) is：It is " living to reinforcing fiber first Change " treatment (such as HF is taken off in strong base solution), make to produce easily generation free radical or the material of oxidation on its strand, then From the reinforcing fiber reaction after suitable reagent and " activation " treatment, so as to introduce the poles such as hydroxyl, carboxyl on its strand Property group or grafting hydrophilic monomer；
It is furthermore preferred that the concrete operation step of the chemical method hydrophilic modifying preprocess method in described step (1) is as follows： A () is soaked reinforcing fiber with ethanol, 0.5h is then soaked in deionized water；B reinforcing fiber that () will obtain 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 only after answering 4min；C () reinforcing fiber in (b) is put into the NaHSO of 5wt.% again3Reacted in the aqueous solution, Until brown is all taken off is changed into white；5min is reacted in the PVP aqueous solution that 0.5wt.% is put it into after (d), is finally used Deionized water rinsing 2min is to complete hydrophilic preprocessing process.
Described 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)SiO2It is prepared by colloidal sol：It is 1 according to mol ratio by organic silicon source, absolute ethyl alcohol, water:(4~12):(0.25~6) Wiring solution-forming, and the prepared SiO of two-step method for passing through acid-base catalysis2Colloidal sol；
(2) opacifier carrying fiber felt and SiO2Gel is combined：It is placed in the vessel after opacifier carrying fiber felt is cut, Again by the SiO obtained by step (1)2Colloidal sol is added in opacifier carrying fiber felt, and discharges air in fibrofelt, is in temperature Gel is settled under conditions of 10~35 DEG C, opacifier carrying fiber felt and SiO is obtained2Gel complex material；
(3) ageing with it is aging：The opacifier carrying fiber felt and SiO that step (2) is obtained2Gel complex material is in temperature It is 1 with the volume ratio of deionized water and ethanol to be aged 1~2 day under conditions of 10~35 DEG C:3~1:10 mixed liquor is to solidifying Glue composite carries out primary aging, and primary ageing time is 1~72 hour, then again with the volume of tetraethyl orthosilicate and ethanol Than being 1:3~1:10 mixed liquor gel complex material is carried out two grades it is aging, two grades of ageing times are 1~72 hour；
(4) solvent displacement：Solvent displacement is carried out to the aging gel complex material for finishing with displacer, time swap is 5 ~48 hours；
(5) surface modification：It is by volume 1 with hydrophobic agents and above-mentioned displacer:10~3:10 mixing, gel is combined Material soaks wherein 1~72 hour；
(6) surface clean：The gel complex material finished to surface modification with above-mentioned displacer carries out surface clean, removes The modified outcome of gel complex material remained on surface, surface clean number of times is 2~4 times；
(7) dried process：Drying box constant pressure and dry will be placed in through the gel complex material of over cleaning, 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 tetraethyl orthosilicate, methyl silicate, MTMS, methyl Triethoxysilane, one or more gathered in many siloxanes.
Described displacer is at least one in n-hexane, normal heptane, acetone.
Hydrophobic agents described in step (5) are trim,ethylchlorosilane, dimethyldimethoxysil,ne, ethyl dibutyl silicon At least one in alkane, trimethyl diethoxy silane.
Temperature in described step (2) is preferably 18~25 DEG C.
Temperature in described step (3) is preferably 18~25 DEG C.
The present invention has the following advantages and beneficial effect relative to prior art：
(1) because opacifier is to be supported on fiber surface, fiber and aeroge compound tense are uniformly dispersed, and can make opacifier With good dispersiveness, opacifier can be regulated and controled by controlling the consumption of the self assembly number of plies and opacifier carrying fiber in addition Addition, regulation and control are more convenient；
(2) due to a diameter of 50nm~1000nm of opacifier carrying fiber, when using and aeroge hole be 10nm~ During the fiber that the size of 100nm is closer to, both can good combination, so as to greatly improved opacifier carrying fiber with it is high The flexibility and interfacial bonding property of performance aerogel composite；
(3) it is theoretical according to scale effect, because the opacifier carrying fiber with micro-nano-scale is combined 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, matrix is deformed with fiber stress, reduce matrix brittle break under external force, So that the aerogel composite maintains 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 have good heat-insulating property；
(5) present invention can simultaneously improve the mechanical property and heat-insulating property of aerogel composite, so that it is steady to obtain structure The high-performance aerogel composite of fixed self assembly opacifier fiber, can be used to reduce thermal loss, improves heat energy utilization effect Rate, has broad application prospects in fields such as Aero-Space, industry, buildings.
Brief description of the drawings
Fig. 1 is the process chart of the high-performance aerogel composite for preparing self assembly opacifier fiber of the invention.
Fig. 2 is PVDF micro nanometer fibers before self assembly and the TiO after assembling2@PVDF micro nanometer fibers spectral transmittance is composed Figure.
Fig. 3 is the PVDF micro nanometer fibers and TiO that the spectral transmittance based on Fig. 2 is calculated2@PVDF micro nanometer fibers Spectral extinction coefficient spectrogram.
Fig. 4 is the radiant heat conductanc curve map of two kinds of tunica fibrosas that the data based on Fig. 2 and Fig. 3 are calculated.
Specific embodiment
With reference to embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited In this.
Agents useful for same can routinely be bought from market unless otherwise specified 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 fibrofelts) and heat preservation and insulation high SiO2Aeroge is combined Form.
TiO2The preparation process of@PVDF composite fibrofelts is as follows：
(1) PVDF micro nanometer fibers are carried out into hydrophilic modifying pretreatment with chemical method hydrophilic modifying, makes it have hydrophily. Concrete operations are as follows：A () is soaked PVDF micro nanometer fibers with ethanol, 0.5h is then soaked in deionized water；B () is by (a) In the PVDF micro nanometer fibers that obtain be put into mass fraction under the conditions of 75 DEG C for the potassium permanganate of 3wt.% is water-soluble with NaOH Liquid (concentration of NaOH is 3mol/L), is washed with deionized water net after reaction 4min；C () is again by the PVDF micro nanometer fibers in (b) It is put into the NaHSO of 5wt.%3Reacted in the aqueous solution, until brown is all taken off is changed into white；Put it into after (d) 5min is reacted in the PVP aqueous solution of 0.5wt.%, it is to complete hydrophilic preprocessing process finally to rinse 2min with deionized water.
(2) pH=2.5 is prepared respectively, and concentration is the polyacrylic acid PAA aqueous solution and pH=2.5, quality point of 0.01mol/L Number is the TiO of 0.5wt.%2Two kinds of assembles concentrations of aqueous dispersions；
(3) that the PVDF micro nanometer fibers by pretreatment that step (1) is obtained are immersed in the PAA that step (2) obtains is molten In liquid, and the ionic group PAA in PAA solution is set to adsorb in fiber surface after water flushing；Then step (2) is dipped into again to obtain The TiO for arriving2In dispersion liquid, fiber surface is set to adsorb " PAA/TiO2Group ", makes fiber surface assemble individual layer opacifier after washing Particle；
(4) repeat step (3) 3 times, make fiber surface assemble 3 layers of TiO2Particle, is obtained TiO2@PVDF composite fibres.
Fig. 2 is PVDF micro nanometer fibers before self assembly and the TiO after assembling2The infrared light of@PVDF micro nanometer fiber spectrum Spectrogram, the spectrogram represents that heat radiation passes through permeable ratio during two kinds of tunica fibrosas；Fig. 3 is the spectral transmittance meter based on Fig. 2 The PVDF micro nanometer fibers and TiO for obtaining2The spectral extinction coefficient spectrogram of@PVDF micro nanometer fibers, the spectrogram illustrates list Two kinds of transmittancies of tunica fibrosa 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 map, ability is blocked the figure shows two kinds of tunica fibrosas under different temperatures environment to heat radiation.
From Fig. 2~4 as can be seen that in the range of 2.5~25 mu m wavebands, compared with before assembling, through 4 assemblings TiO2@PVDF composite membrane spectral transmittances are significantly reduced, spectral extinction coefficient increase, under room temperature 300K, PVDF tunica fibrosas and TiO2The average extinction coefficients of Rosseland of@PVDF composite membranes are respectively：31.9 and 325cm-1；In 230~420K temperature ranges It is interior, TiO2@PVDF composite membranes have the radiant heat conductanc smaller than PVDF tunica fibrosa.Such as at a temperature of 230 and 420K, assembling is received 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 materials Material has preferable application prospect in terms of radiation heat transfer and heat-insulation and heat-preservation is stopped.
TiO2@PVDF composite fibrofelts and SiO2Gel is compound to be comprised the following steps that：
(1) tetraethyl orthosilicate, absolute ethyl alcohol are mixed in beaker, are placed in and 30min is stirred on magnetic stirring apparatus, mixing is equal A certain amount of water and hydrochloric acid are progressively instilled after even while stirring, 30min is stirred, static 24 hours, is fully hydrolyzed it, Ran Hou Under magnetic stirrer, DMF, distilled water and ammoniacal liquor are sequentially added, and continue stirring 30min obtain SiO2Colloidal sol；It is whole anti- Reactant molar ratio is tetraethyl orthosilicate during answering:Absolute ethyl alcohol:Water:DMF:Hydrochloric acid:Ammoniacal liquor=1:7:2:0.25:(10~ 5):3.57×10-3；
(2)TiO2It is placed in the vessel that@PVDF composite fibrofelts are cut into definite shape, by SiO obtained by step (1)2Colloidal sol Add TiO2In@PVDF composite fibrofelts, and air in fibrofelt is discharged, coagulated after about 0.1~5 hour is stood at 18~25 DEG C Glue, is obtained TiO2@PVDF composite fibres and SiO2Gel complex material；
(3) ageing with it is aging：The TiO that step (2) is obtained2@PVDF composite fibres and SiO2Gel complex material 18~ It is aged 1~2 day at 25 DEG C, is 1 with deionized water and ethanol volume ratio:3~1:10 mixed liquor is carried out to gel complex material Primary aging, primary ageing time is 1~72 hour, and it is 1 with the volume ratio of ethanol that tetraethyl orthosilicate is then used again:3~1:10 Gel complex material is carried out two grades it is aging, two grades of ageing times are 1~72 hour；
(4) solvent displacement：Solvent displacement is carried out to the aging gel complex material for finishing with displacer, time swap is 5 ~48 hours；The small solution of the surface tension is at least one in n-hexane, normal heptane, acetone；
(5) surface modification：It is by volume 1 with hydrophobic agents and displacer:10~3:10 mixing, by gel complex material Immersion wherein 1~72 hour, the hydrophobic agents are trim,ethylchlorosilane, dimethyldimethoxysil,ne, ethyl dibutyl silicon At least one in alkane, trimethyl diethoxy silane；
(6) surface clean：The gel complex material finished to surface modification with displacer carries out surface clean, removes gel The modified outcome of composite material surface residual, surface clean number of times is 2~4 times；
(7) dried process：Drying box constant pressure and dry will be placed in through the gel complex material of over cleaning, drying temperature is 50~ 70 DEG C, the time is 12~24 hours, obtains TiO2@PVDF composite fibres strengthen aerogel composite, i.e., based on self assembly TiO2The high-performance aerogel composite of@PVDF micro nanometer fibers.
Table 1 is the pure SiO obtained using electronic universal tester test2Aeroge and PVDF micro nanometer fibers and SiO2 The measuring mechanical property result data of the composite of aeroge, wherein because aeroge is frangible, it is impossible to carry out its stretch-proof and Bending strength, therefore " -- " represents and cannot carry out this test (equivalent to this desired value close to 0MPa).
Table 1 is pure SiO2Aeroge and and PVDF micro nanometer fibers and SiO2The mechanical performance of the composite of aeroge Test result
As can be seen from Table 1, aeroge by PVDF micro nanometer fibers it is compound after, tensile strength, compression strength and anti- Curved intensity is improved, crisp with matter, frangible pure SiO2Aeroge is compared, PVDF micro nanometer fibers and SiO2Aeroge is answered Condensation material has preferable structural stability and flexibility.
To sum up analyze, it is known that the aerogel composite can maintain preferable structural stability under stress, obtain Flexible TiO2@PVDF micro nanometer fibers and aerogel composite Stability Analysis of Structures and with good heat radiation block performance and Comprehensive heat-insulating property.
Above-described embodiment is the present invention preferably implementation method, but embodiments of the present invention are not by above-described embodiment Limitation, it is other it is any without departing from Spirit Essence of the invention and the change, modification, replacement made under principle, combine, simplification, Equivalent substitute mode is should be, is included within protection 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 composited.
2. the high-performance aerogel composite based on self assembly opacifier fiber according to claim 1, its feature exists In：
Described opacifier carrying fiber felt is that opacifier particle is loaded into reinforcing fiber surface using LBL self assembly technology Obtain；The fibre diameter of described opacifier carrying fiber felt is 50nm~1000nm.
3. the high-performance aerogel composite based on self assembly opacifier fiber according to claim 2, its feature exists In：
Reinforcing fiber in described opacifier carrying fiber felt is polyvinylidene fluoride, polypropylene fibre, polyethylene fibre, Styroflex, polyethers fiber, polyester fiber, Fypro, polyimide fiber, polyacrylonitrile fibre, polyvinyl chloride Fiber, a kind of polymer fiber material in polyacrylic fibre, estron, nylon cotton, silk or fiber crops；
Described 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 based on self assembly opacifier fiber according to claim 3, its feature exists Prepared by following methods in described opacifier carrying fiber felt：
(1) reinforcing fiber is carried out into hydrophilic pretreatment, obtaining has hydrophilic reinforcing fiber matrix；
(2) assembles concentration A and assembles concentration B is prepared respectively；
(3) the fibrous material matrix by pretreatment that step (1) is obtained is immersed in the assembles concentration A that step (2) is obtained, is made (+/-) absorption of ionic group A in assembles concentration A is in fiber surface；Then the group that step (2) is obtained is dipped into again after being rinsed through water In dress liquid B, fiber surface is adsorbed " A (+/-)-opacifier (- /+) group ", fiber surface is assembled individual layer shading after washing Agent particle；
(4) repeat step (3) n times, makes fiber surface assemble n-layer opacifier particle, and opacifier carrying fiber is obtained；Wherein n=1 Integer between~10；
Assembles concentration B is the dispersion liquid or colloidal solution of opacifier in described (2)；Assembles concentration A is a kind of electrical with assembles concentration B Opposite polycation or polyanion solution；
" +/- " symbol represents the polycation or polyanionic nature of ionic group in step (3)；"-/+" symbol represents ion The polyanion or polycation property of group.
5. the high-performance aerogel composite based on self assembly opacifier fiber according to claim 4, its feature exists In：
Described polycation is at least one in POSS (+), triethylene tetramine (+), hexamethylene diamine (+), and polyanion is poly- At least one in acrylic acid (-), polyacrylate (-).
6. the high-performance aerogel composite based on self assembly opacifier fiber according to claim 4 or 5, its feature It is：Hydrophilic preprocess method in described step (1) is at least one in plasma treatment, chemical method hydrophilic modifying；
The hydrophilic preprocess method operating procedure of plasma treatment in described step (1) is：By reinforcing fiber gas etc. from Being introduced on surface with air contact after 1~10min of daughter treatment increases its hydrophilic group, that is, obtain with hydrophilic increasing Strong fibrous matrix；
Chemical method hydrophilic modifying preprocess method in described step (1) is：First to reinforcing fiber " activation " treatment, make it Easily generation free radical or the material of oxidation are produced on strand, then from the enhancing after suitable reagent and " activation " treatment Fiber-reactive, so as to introduce polar group or grafting hydrophilic monomer on its strand；Concrete operation step is as follows：A () is used Ethanol soaks reinforcing fiber, and 0.5h is then soaked in deionized water；B reinforcing fiber that () will obtain in (a) is put into 75 DEG C Under the conditions of mass fraction for potassium permanganate and the concentration of 3wt.% be the mixed aqueous solution of the NaOH of 3mol/L, after reaction 4min It is washed with deionized water net；C () reinforcing fiber in (b) is put into the NaHSO of 5wt.% again3Reacted in the aqueous solution, until brown All take off and be changed into white；5min is reacted in the PVP aqueous solution that 0.5wt.% is put it into after (d), deionized water is finally used Rinsing 2min is to complete hydrophilic preprocessing process.
7. a kind of high-performance aeroge based on self assembly opacifier fiber according to any one of claim 1~6 is combined The preparation method of material, it is characterised in that comprise the following steps：
(1)SiO2It is prepared by colloidal sol：It is 1 according to mol ratio by organic silicon source, absolute ethyl alcohol, water:(4~12):(0.25~6) is made into Solution, and the prepared SiO of two-step method for passing through acid-base catalysis2Colloidal sol；
(2) opacifier carrying fiber felt and SiO2Gel is combined：It is placed in the vessel after opacifier carrying fiber felt is cut, then will SiO obtained by step (1)2Colloidal sol is added in opacifier carrying fiber felt, and discharges air in fibrofelt, temperature be 10~ Gel is settled under conditions of 35 DEG C, opacifier carrying fiber felt and SiO is obtained2Gel complex material；
(3) ageing with it is 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, is 1 with the volume ratio of deionized water and ethanol:3~1:10 mixed liquor 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 ethanol with tetraethyl orthosilicate again 1:3~1:10 mixed liquor gel complex material is carried out two grades it is aging, two grades of ageing times are 1~72 hour；
(4) solvent displacement：Solvent displacement is carried out to the aging gel complex material for finishing with displacer, time swap is 5~48 Hour；
(5) surface modification：It is by volume 1 with hydrophobic agents and above-mentioned displacer:10~3:10 mixing, by gel complex material Immersion wherein 1~72 hour；
(6) surface clean：The gel complex material finished to surface modification with above-mentioned displacer carries out surface clean, removes gel The modified outcome of composite material surface residual, surface clean number of times is 2~4 times；
(7) dried process：Drying box constant pressure and dry will be placed in through the gel complex material of over cleaning, 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 based on self assembly opacifier fiber according to claim 7 Method, it is characterised in that：
Organic silicon source described in step (1) is tetraethyl orthosilicate, methyl silicate, MTMS, the second of methyl three TMOS, one or more gathered in many siloxanes.
9. the preparation side of the high-performance aerogel composite based on self assembly opacifier fiber according to claim 7 Method, it is characterised in that：
Described displacer is at least one in n-hexane, normal heptane, acetone.
10. the preparation side of the high-performance aerogel composite based on self assembly opacifier fiber according to claim 7 Method, it is characterised in that：
Hydrophobic agents described in step (5) are trim,ethylchlorosilane, dimethyldimethoxysil,ne, ethyl dibutyl silane, three At least one in methyldiethoxysilane.
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CN114771077A (en) * 2022-04-29 2022-07-22 巩义市泛锐熠辉复合材料有限公司 Gel felt surface treatment equipment and modification method
CN114771077B (en) * 2022-04-29 2023-12-05 巩义市泛锐熠辉复合材料有限公司 Gel felt surface treatment equipment and modification method

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