CN103159454A - Nano-porous aerogel/fiber composite super thermal insulation material and preparation method thereof - Google Patents

Nano-porous aerogel/fiber composite super thermal insulation material and preparation method thereof Download PDF

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CN103159454A
CN103159454A CN201310056513XA CN201310056513A CN103159454A CN 103159454 A CN103159454 A CN 103159454A CN 201310056513X A CN201310056513X A CN 201310056513XA CN 201310056513 A CN201310056513 A CN 201310056513A CN 103159454 A CN103159454 A CN 103159454A
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fiber composite
insulating material
preparation
composite super
degrees centigrade
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CN103159454B (en
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徐广平
宋扬
何江荣
何洁
刘鹏程
宋一华
徐溶
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JIANGSU ZHONGLEI ENERGY SAVING TECHNOLOGY DEVELOPMENT CO., LTD.
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DONGTAI ENERGY-SAVING REFRACTORY MATERIAL FACTORY
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Abstract

The invention discloses a nano-porous aerogel/fiber composite super thermal insulation material and a preparation method thereof. The aerogel/fiber composite super thermal insulation material comprises silicon dioxide aerogel, alumina micro powder, zirconium oxide fibers and opacifying agent of titanium dioxide. The preparation method comprises that organic solvent, cross-linking agents and organic monomers make up pre-mixed solution according to a certain proportion, the silicon dioxide aerogel, the alumina micro powder, the zirconium oxide fibers, pore-forming agents, suspending agents and the titanium dioxide make up slurry through a ball milling process according to a certain proportion, then a certain amount of initiating agents and a certain amount of catalytic agents are dropwise added into the slurry through vacuum bubble removal, composite material in-situ solidification is achieved through a gel injection moulding process, and then demoulding, vacuum drying and degreasing glue discharging are conducted. The nano-porous aerogel/fiber composite super thermal insulation material has a nano-porous/ reinforced fiber composite microstructure, the heat conductivity is 0.040-0.046W*m<-1>*K<-1> (298K), and the flexure strength is as high as 12-14MPa. Preparation processes are simple, industrialized application is easily achieved on a large scale, and the nano-porous aerogel/fiber composite super thermal insulation material is suitable for thermal protection of aerospace, military affairs and severe rugged environments.

Description

A kind of nanoporous aerogel/fiber composite super insulating material and preparation method thereof
Technical field
The present invention relates to a kind of high temperature thermal insulation material, relate in particular to a kind of compound super insulating material that includes nano-hole aerogel and cellulosic lagging material.The invention still further relates to the preparation method of this composite insulation material.
Background technology
Super insulating material refers under predetermined working conditions, and its thermal conductivity is lower than the thermal insulation material of " without the convection current air " thermal conductivity (0.026W/mk, 25 ℃).Aerogel is typical nano-porous super thermal insulation material, and it includes silicon system, carbon system, sulphur system, burning system and metal system etc.; Aerogel has high hole ratio, extremely low density, high-specific surface area, superelevation pore volume rate.
SiO 2aerogel is considered to the solid-state material of current heat-insulating property the best, and it is the lightweight nano-porous materials (as shown in Figure 1) with spacial framework made by sol-gel technology and Supercritical Drying Technology, the low 3kg/m that reaches of its density 3, hole ratio is up to 99%; Nanometer porous network structure can effectively limit solid state heat conduction and gaseous state thermal conduction, makes SiO 2aerogel has excellent heat-insulating property.Therefore it is with a wide range of applications in fields such as aerospace, chemical industry, metallurgy, energy-conserving and environment-protective as a kind of efficient and light weight thermal insulation material.But SiO 2aerogel intensity is low, fragility is large, poor toughness, and nano-pore structure is the factor such as destructible under external force, becomes the Major Difficulties that limits its large-scale industrialization application.
That the cellulosic lagging material has is lightweight, fusing point and the characteristics such as softening temperature is high, heat-proof quality is good, easy machine-shaping, and has the higher mechanical properties such as tension resistance to compression, is widely used in the thermal protection structure of the heat insulation back boxing of industrial circle and spacecraft; Wherein Zirconium oxide fibre is the adiabatic strongthener (as shown in Figure 2) of the premium propertiess such as a kind of good toughness, anti-oxidant, acid-alkali-corrosive-resisting, good thermal shock and thermal insulation be good.But the cellulosic lagging material can not form nano level or micrometer grade hole gap structure, is difficult to reach super insulation effect.
Therefore, no matter be aerogel, or the cellulosic lagging material, all deposit limitation in the use, thereby limited the expansion of thermal insulation material range of application; And the simple mixing of aerogel and cellulosic lagging material can not realize all even high hole ratios, and higher bonding strength and bulk strength between the two.Industry always makes every effort to find a kind of high thermal insulation material of composite performance with excellent insulation effect and higher mechanical strength, with this, improves range of application and the use properties of thermal insulation material.
Summary of the invention
Technical problem to be solved by this invention is to provide a kind of nanoporous aerogel/fiber composite super insulating material and preparation method thereof, and it not only has high hole rate, lower thermal conductivity, and has higher intensity and fracture toughness property.Another technical problem that will solve of the present invention is that the preparation method of a kind of above-mentioned nanoporous aerogel/fiber composite super insulating material also will be provided.
In order to solve the problems of the technologies described above, nanoporous aerogel of the present invention/fiber composite super insulating material, its feed composition comprises aerosil, alumina powder, Zirconium oxide fibre and opalizer titanium dioxide, and its weight ratio is (0.6-1.3): (2.1-5.0): (1.2-3.3): (0.06-0.52).
The median size of described aerosil particle is that 23.1 μ m, thermal conductivity are 0.02 Wm when temperature is 298K -1k -1, mean pore size is that 20nm, porosity are greater than 97%, density is about 0.14 g/cm 3, specific surface area is 857 g/m 2.
The median size of described alumina powder is 0.51 μ m, the α-Al of described alumina powder 2o 3content is greater than 99.9%.
Described Zirconium oxide fibre volume density is lower than 0.15g/cm 3, the tetragonal phase zirconium oxide composition of described Zirconium oxide fibre is greater than 99.5%, described Zirconium oxide fibre thermal conductivity when temperature is 298K lower than 0.13 Wm -1k -1.
Described opalizer titanium dioxide crystal formation is rutile-type, and described opalizer titanium dioxide median size is about 0.30 μ m, Ti O in described opalizer titanium dioxide 2content higher than 98%.
More than one state the method that raw material prepares nanoporous aerogel/fiber composite super insulating material, and its preparation method comprises the following steps:
(1) the premixed liquid preparation mixes to clear liquid by organic solvent, linking agent and organic monomer, and makes premixed liquid;
(2) the suspended nitride preparation adds aerosil, alumina powder, Zirconium oxide fibre, opalizer titanium dioxide, pore-forming material and suspension agent in premixed liquid, through ball mill mixing, prepares suspended nitride;
(3) froth in vacuum is carried out froth in vacuum to above-mentioned suspended nitride, after de-bubble, successively dropwise adds initiator and catalyzer again in this suspended nitride, is stirred, to make the de-bubble slurry simultaneously;
(4) gel casting is poured into the de-bubble slurry in mould, through in-situ solidifying, obtains the gel complex body;
(5) the standing demoulding after at room temperature standing 4 ~ 8 hours, is deviate from the gel complex body and obtains shaping blank from mould;
(6) vacuum-drying is carried out vacuum-drying to shaping blank;
(7) binder removal is processed processing is heated, is incubated to the shaping blank of vacuum drying treatment, to remove organic solvent, organic monomer, linking agent, pore-forming material, suspension agent, initiator, catalyzer, and make nanoporous aerogel/fiber composite super insulating material finished product.
Described organic solvent is the trimethyl carbinol, and organic monomer is acrylamide, and linking agent is N, N '-methylene-bisacrylamide.
The described trimethyl carbinol, acrylamide and N, N'-methylene-bisacrylamide three's weight ratio is (170 ~ 200): (29 ~ 100): (1 ~ 10).
The weight ratio of described aerosil, alumina powder, Zirconium oxide fibre, opalizer titanium dioxide is (0.6-1.3): (2.1-5.0): (1.2-3.3): (0.06-0.52).
Described pore-forming material is Polyethylene glycol-2000, and the addition of this Polyethylene glycol-2000 is 1.5 ~ 7.5% of aerosil, alumina powder, Zirconium oxide fibre and opalizer titanium dioxide gross weight; Described suspension agent is tripoly phosphate sodium STPP, and the addition of this tripoly phosphate sodium STPP is 0.05 ~ 3.5% of silica aerogel, alumina powder, Zirconium oxide fibre and opalizer titanium dioxide gross weight.
The volume fraction of the solid load of described suspended nitride is 15 ~ 75%.
Described initiator is ammonium persulphate, and the addition of this ammonium persulphate is 0.5 ~ 5% of organic monomer acrylamide weight; Described catalyzer is N, N, and N', the N'-Tetramethyl Ethylene Diamine, this catalyst n, N, N', the addition of N'-Tetramethyl Ethylene Diamine is 15 ~ 45% of organic monomer acrylamide weight.
The temperature of described froth in vacuum is controlled at subzero 10 ~ 55 degrees centigrade.
When described de-bubble slurry is poured into mould, the temperature of mould is controlled at 15 ~ 85 degrees centigrade.
Described shaping blank is placed under the vacuum condition of 50 ~ 120 degrees centigrade dry 12 ~ 36 hours.
The treating processes of heating, be incubated that described binder removal is processed is followed successively by, and vacuum drying shaping blank at ambient temperature after standing 1 hour, is warming up to 105 degrees centigrade, is incubated 2 ~ 3 hours; Then with heating-up time of 1 hour, temperature is risen to 180 degrees centigrade, be incubated 1 ~ 3 hour; With heating-up time of 2 hours, temperature is risen to 300 degrees centigrade again, be incubated 1 ~ 3 hour; With heating-up time of 70 minutes, temperature is risen to 370 degrees centigrade again, be incubated 1 ~ 4 hour; With heating-up time of 30 minutes, temperature is risen to 400 degrees centigrade again, be incubated 1 hour; With heating-up time of 200 minutes, temperature is risen to 500 degrees centigrade again, be incubated 2 ~ 4 hours; With heating-up time of 200 minutes, temperature is risen to 600 degrees centigrade again, be incubated 2 ~ 4 hours; Then at room temperature cooling.
The present invention compared with prior art has following remarkable advantage:
1,, due to the raw materials that adopts component of the present invention and content, compound, guaranteed that finished product has lower thermal conductivity, high strength, high-fracture toughness, excellent thermal shock resistance and long-life advantage afterwards.From the weave construction aspect: the rich insulative properties of composing whole matrix material excellence of low density, high hole rate, microscopic appearance that aerosil is exclusive; Crack deflection, the fiber that Zirconium oxide fibre causes in matrix material extracted, fibre debonding, tiny crack are toughness reinforcing, transformation toughening and fiber bridge effect make the ultimate compression strength of whole material and fracture toughness property be significantly improved; In whole matrix material, as aggregate and mullite synthesizing, (mullite: 3Al2O32SiO2) necessary raw material adds alumina powder, it not only can improve use temperature and the work-ing life of whole matrix material, and can improve the thermal shock resistance of material; Titanium dioxide has shading stable performance, lasting as opalizer, the characteristic that chemical stability is good, with other raw materials in matrix material, do not participate in and react, the ray of titanium dioxide a large amount of infrared band in can absorptive thermal radiation, further improve the heat-proof quality of matrix material.
2, preparation method of the present invention has used gel injection molding and forming technology, form gel network under the effect of inducing at temperature or initiator by the organic monomer in suspended nitride, aerosil, alumina powder, Zirconium oxide fibre, opalizer titanium dioxide, pore-forming material are condensed together and realize the in-situ solidifying moulding.The polycondensation under the effect of catalyzer and initiator of organic monomer and pore-forming material forms intensive polymer reticulated structure, by raw materials " constraint " such as alumina powder, Zirconium oxide fibre, titanium dioxides on original position, realize that original position is solidified, moulding, thereby obtain the forming method of the blank of material of higher-strength, prevent between raw material the reunion that causes because of migration, diffusion and the appearance of impurity, and then reduce the composite inner defect, realize the near-net-shape of material.Realize the speed of in-situ solidifying and the degree of in-situ solidifying by the accurate control to temperature in preparation method's of the present invention gel injection process, and then can control polycondensation speed and the polymerization degree of macromolecule network, finally can realize the controllable property of matrix material microscopic appearance; Gel injection can realize that in-situ solidifying is not destroyed to guarantee the microscopic appearance that aerogel originally has.
3, preparation method of the present invention makes finished product have very thin nano-pore structure, realizes that thermal conductivity is extremely low, and specific surface area is very big.Nanoporous in the thermal insulation material finished product is the essential condition that finished-product material has high heat insulating ability, and there are two aspects in the source of these nano grade pores, the one, and aerogel itself has; The 2nd, in preparation process, form, it in follow-up binder removal, stays nano level pore by introduce pore-forming material in slurry on the position removed at the pore-forming material molecule.Pore-forming material Polyethylene glycol-2000 water-soluble fine, can be water-soluble and organic solvent in, in gel-casting slurry, Polyethylene glycol-2000 is dissolved in the organic solvent trimethyl carbinol, after the slurry in-situ solidifying, Polyethylene glycol-2000 exists with the structure formation of its macromolecule network, at this moment except the nanometer pore that the aerogel intrinsic possesses, other nanoporouss do not exist, after the binder removal treatment process, Polyethylene glycol-2000 is decomposed, exclude, stayed other space of polymer level on the original position of Polyethylene glycol-2000, it is nanoporous, therefore formed in the finished product is also nanoporous.
4, the present invention has adopted gel injection colloidal formation technique, other uniformity coefficient of molecular level between organic solvent, linking agent, pore-forming material, suspension agent, initiator and catalyzer, and the feed composition controllability and adjustability strong, the technique flexibility ratio is large.Because the slurry of low viscosity, high solid loading is in a liquid state, can flow and fill mould, therefore can prepare the parts of complicated shape, the complexity of parts depends on the manufacture level of mould, the green strength that this technique is prepared simultaneously is high, mechanical deep processing can be carried out, near-net-shape can be really realized.Due in premixed liquid except the solvent that can discharge, organic monomers etc. can all be used organism, and organic content very low (lower than 3wt%), are beneficial to and overcome the defect that binder removal causes.Therefore, the parts foreign matter content after sintering is very low, and purity is higher.The gel type-approval process separates fully with the injection molding operation, simultaneously the type-approval process of gel casting forming is that the gelinite that forms cross-linked structure by organic monomer in-situ polymerization in slip is realized, thus molding blank component and density all evenly, after few, the sintering of defect the base substrate contraction very little.
5, the present invention can also pass through the adjusting process parameter, and regulation and control slurry viscosity, molding time, blank strength etc. are realized serialization and the mechanization production of moulding process.Preparation method's production cost of the present invention, the production efficiency high security is good, is easy to the large-scale industrialization application.
The accompanying drawing explanation
The electron scanning micrograph that Fig. 1 is aerosil;
The electron scanning micrograph that Fig. 2 is the Zirconium oxide plasticizing continuous fibre;
The electron scanning micrograph that Fig. 3 is nanoporous aerogel of the present invention/fiber composite super insulating material.
Embodiment
The present invention will be further described by the following examples, and technical solution of the present invention is not limited to following cited embodiment, and its protection domain is not subject to the restriction of these embodiment.
Gel injection prepares the method for nanoporous aerogel/fiber composite super insulating material, carry out in the steps below: (1) is by the organic solvent trimethyl carbinol, organic monomer acrylamide, linking agent N, N '-methylene-bisacrylamide fully is uniformly mixed 24 ~ 48 hours and is configured to premixed liquid, the wherein trimethyl carbinol, acrylamide and N, the N'-methylene-bisacrylamide, three's weight ratio is work (170~200): (29~100): (1~10).(2) add aerosil in the premixed liquid in step (1), alumina powder, Zirconium oxide fibre, the opalizer titanium dioxide, pore-forming material Polyethylene glycol-2000 and suspension agent tripoly phosphate sodium STPP, planetary ball mill batch mixing 4~8 hours, prepare the suspended nitride that solid load (volume fraction) is 15~75%, silica aerogel wherein, alumina powder, Zirconium oxide fibre, the opalizer titanium dioxide, four weight ratio is (0.6~1.3): (2.1~5.0): (1.2~3.3): (0.06~0.52), the addition of pore-forming material Polyethylene glycol-2000 is silica aerogel, alumina powder, 1.5~7.5% of Zirconium oxide fibre and opalizer titanium dioxide gross weight, the addition of suspension agent tripoly phosphate sodium STPP is silica aerogel, alumina powder, 0.05~3.5% of Zirconium oxide fibre and opalizer titanium dioxide gross weight.(3) suspended nitride step (2) obtained carries out froth in vacuum 15~45 minutes, then successively dropwise add a certain amount of initiator ammonium persulfate in suspended nitride, catalyst n, N, N', the N'-Tetramethyl Ethylene Diamine, carry out magnetic agitation and temperature to control simultaneously and make the de-bubble slurry, wherein the temperature of froth in vacuum process should be controlled at subzero 10~55 degrees centigrade, the addition of initiator ammonium persulfate is 0.5~5% of organic monomer acrylamide weight, catalyst n, N, N', the addition of N'-Tetramethyl Ethylene Diamine is 15~45% of organic monomer acrylamide weight.(4) the de-bubble slurry obtained in step (3) is poured in the mould under optimal temperature, and then realizes that the in-situ solidifying of aerogel/fibre composite obtains the gel complex body, wherein the temperature of mould is controlled at 15~85 degrees centigrade during gel injection.(5) deviate from from mould after standing 4~8 hours under gel complex body room temperature step (4) obtained and obtain shaping blank.(6) shaping blank after deviating from is placed in to the vacuum drying oven 12~36 hours of 50~120 degrees centigrade.(7) under the specified temp system, the shaping blank after vacuum-drying is placed in to sintering oven and carries out the binder removal treatment process, to remove the organism such as organic solvent, monomer, linking agent, pore-forming material, suspension agent, initiator, catalyzer; The treating processes of heating, be incubated that the binder removal of this specified temp system is processed is followed successively by, and vacuum drying shaping blank at ambient temperature after standing 1 hour, is warming up to 105 degrees centigrade, is incubated 2~3 hours; Then with heating-up time of 1 hour, temperature is risen to 180 degrees centigrade, be incubated 1~3 hour; With heating-up time of 2 hours, temperature is risen to 300 degrees centigrade again, be incubated 1~3 hour; With heating-up time of 70 minutes, temperature is risen to 370 degrees centigrade again, be incubated 1~4 hour; With heating-up time of 30 minutes, temperature is risen to 400 degrees centigrade again, be incubated 1 hour; With heating-up time of 200 minutes, temperature is risen to 500 degrees centigrade again, protect 2~4h; With heating-up time of 200 minutes, temperature is risen to 600 degrees centigrade again, be incubated 2~4 hours; Then at room temperature cooling, finally obtain having the nanoporous aerogel of high mechanical strength, lower thermal conductivity/fiber composite super insulating material, its microstructure is as shown in Figure 3.
Embodiment 1
(1) by the organic solvent trimethyl carbinol, organic monomer acrylamide, linking agent N, N '-methylene-bisacrylamide fully is uniformly mixed 25 hours and is configured to premixed liquid, the wherein trimethyl carbinol, acrylamide and N, the N'-methylene-bisacrylamide, three's weight ratio is 180:37:3.5, (2) add silica aerogel in the premixed liquid in step (1), alumina powder, Zirconium oxide fibre, the opalizer titanium dioxide, pore-forming material Polyethylene glycol-2000 and suspension agent tripoly phosphate sodium STPP, planetary ball mill batch mixing 5 hours, prepare the slurry that solid load (volume fraction) is 19%, silica aerogel wherein, alumina powder, Zirconium oxide fibre, the opalizer titanium dioxide, four weight ratio is 0.7:2.3:1.4:0.08, the addition of pore-forming material Polyethylene glycol-2000 is silica aerogel, alumina powder, 2.7% of Zirconium oxide fibre and opalizer titanium dioxide gross weight, the addition of suspension agent tripoly phosphate sodium STPP is silica aerogel, alumina powder, 0.08% of Zirconium oxide fibre and opalizer titanium dioxide gross weight, (3) slurry step (2) obtained carries out froth in vacuum 18 minutes, then successively dropwise add a certain amount of initiator ammonium persulfate, catalyst n in slurry, N, N', the N'-Tetramethyl Ethylene Diamine, carry out magnetic agitation and temperature controls simultaneously, wherein the temperature of froth in vacuum process should be controlled at 18 degrees centigrade, the addition of initiator ammonium persulfate is 0.7% of organic monomer acrylamide weight, catalyst n, N, N', the addition of N'-Tetramethyl Ethylene Diamine is 21% of organic monomer acrylamide weight, (4) slurry obtained in step (3) is poured in the mould under optimal temperature, and then realizes that the in-situ solidifying of aerogel/fibre composite obtains the gel complex body, wherein the temperature of mould is controlled at 21 degrees centigrade during gel injection, (5) under gel complex body room temperature step (4) obtained, after standing 4 hours, deviate from shaping blank from mould, (6) complex material after deviating from (shaping blank) is placed in to the vacuum drying oven 14 hours of 55 degrees centigrade, (7) under the specified temp system, the complex material after vacuum-drying is placed in to electric furnace and carries out the binder removal treatment process, to remove the organism such as organic solvent, monomer, linking agent, pore-forming material, suspension agent, initiator, catalyzer, wherein the specified temp system enactment is that room temperature is warming up to 105 degrees centigrade in lower 1 hour, is incubated 2 hours, within 1 hour, rise to 180 degrees centigrade, be incubated 1 hour, within 2 hours, rise to 300 degrees centigrade, be incubated 1 hour, within 70 minutes, rise to 370 degrees centigrade, be incubated 1 hour, within 30 minutes, rise to 400 degrees centigrade, be incubated 1 hour, within 200 minutes, rise to 500 degrees centigrade, protect 2 hours, within 200 minutes, rise to 600 degrees centigrade, be incubated 2 hours, finally obtain block complete, there is high mechanical strength (ultimate compression strength reaches 12.7Mpa), lower thermal conductivity (λ=0.045Wm -1k -1, nanoporous aerogel 298K)/fiber composite super insulating material.
Embodiment 2
(1) by the organic solvent trimethyl carbinol, organic monomer acrylamide, linking agent N, N '-methylene-bisacrylamide fully is uniformly mixed 25 hours and is configured to premixed liquid, the wherein trimethyl carbinol, acrylamide and N, the N'-methylene-bisacrylamide, three's weight ratio is 175:32:2, (2) add silica aerogel in the premixed liquid in step (1), alumina powder, Zirconium oxide fibre, the opalizer titanium dioxide, pore-forming material Polyethylene glycol-2000 and suspension agent tripoly phosphate sodium STPP, planetary ball mill batch mixing 4 hours, prepare the slurry that solid load (volume fraction) is 21%, silica aerogel wherein, alumina powder, Zirconium oxide fibre, the opalizer titanium dioxide, four weight ratio is 1.1 ~ 1.3:2.8:3 ~ 3.3:0.14, the addition of pore-forming material Polyethylene glycol-2000 is silica aerogel, alumina powder, 1.5 ~ 4.5% of Zirconium oxide fibre and opalizer titanium dioxide gross weight, the addition of suspension agent tripoly phosphate sodium STPP is silica aerogel, alumina powder, 0.15 ~ 2.5% of Zirconium oxide fibre and opalizer titanium dioxide gross weight, (3) slurry step (2) obtained carries out froth in vacuum 23 minutes, then successively dropwise add a certain amount of initiator ammonium persulfate, catalyst n in slurry, N, N', the N'-Tetramethyl Ethylene Diamine, carry out magnetic agitation and temperature controls simultaneously, wherein the temperature of froth in vacuum process should be controlled at 26 degrees centigrade, the addition of initiator ammonium persulfate is 0.6 ~ 2.5% of organic monomer acrylamide weight, catalyst n, N, N', the addition of N'-Tetramethyl Ethylene Diamine is 18 ~ 25% of organic monomer acrylamide weight, (4) slurry obtained in step (3) is poured in the mould under optimal temperature, and then realizes that the in-situ solidifying of aerogel/fibre composite obtains the gel complex body, wherein the temperature of mould is controlled at 40 degrees centigrade during gel injection, (5) under gel complex body room temperature step (4) obtained, after standing 4.5 hours, deviate from shaping blank from mould, (6) complex material after deviating from is placed in to the vacuum drying oven 14 hours of 55 degrees centigrade, (7) under the specified temp system, the complex material after vacuum-drying is placed in to electric furnace and carries out the binder removal treatment process, to remove the organism such as organic solvent, monomer, linking agent, pore-forming material, suspension agent, initiator, catalyzer, wherein the specified temp system enactment is that room temperature is warming up to 105 degrees centigrade in lower 1 hour, is incubated 2.5 hours, within 1 hour, rise to 180 degrees centigrade, be incubated 1.5 hours, within 2 hours, rise to 300 degrees centigrade, be incubated 1.5 hours, within 70 minutes, rise to 370 degrees centigrade, be incubated 1 hour, within 30 minutes, rise to 400 degrees centigrade, be incubated 1 hour, within 200 minutes, rise to 500 degrees centigrade, protect 2 hours, within 200 minutes, rise to 600 degrees centigrade, be incubated 2 hours, finally obtain block complete, there is high mechanical strength (ultimate compression strength reaches 13.1Mpa), lower thermal conductivity (λ=0.044Wm -1k -1, nanoporous aerogel 298K)/fiber composite super insulating material.
Embodiment 3
(1) by the organic solvent trimethyl carbinol, organic monomer acrylamide, linking agent N, N '-methylene-bisacrylamide fully is uniformly mixed 24 ~ 48 hours and is configured to premixed liquid, the wherein trimethyl carbinol, acrylamide and N, the N'-methylene-bisacrylamide, three's weight ratio is 174:39 ~ 40:6 ~ 9, (2) add silica aerogel in the premixed liquid in step (1), alumina powder, Zirconium oxide fibre, the opalizer titanium dioxide, pore-forming material Polyethylene glycol-2000 and suspension agent tripoly phosphate sodium STPP, planetary ball mill batch mixing 4.5 hours, prepare the slurry that solid load (volume fraction) is 35%, silica aerogel wherein, alumina powder, Zirconium oxide fibre, the opalizer titanium dioxide, four weight ratio is 0.7 ~ 1.0:2.5 ~ 4.0:1.8 ~ 3.1:0.12 ~ 0.23, the addition of pore-forming material Polyethylene glycol-2000 is silica aerogel, alumina powder, 4.6% of Zirconium oxide fibre and opalizer titanium dioxide gross weight, the addition of suspension agent tripoly phosphate sodium STPP is silica aerogel, alumina powder, 0.08 ~ 1.5% of Zirconium oxide fibre and opalizer titanium dioxide gross weight, (3) slurry step (2) obtained carries out froth in vacuum 16 minutes, then successively dropwise add a certain amount of initiator ammonium persulfate, catalyst n in slurry, N, N', the N'-Tetramethyl Ethylene Diamine, carry out magnetic agitation and temperature controls simultaneously, wherein the temperature of froth in vacuum process should be controlled at subzero 33 degrees centigrade, the addition of initiator ammonium persulfate is 0.8 ~ 2.5% of organic monomer acrylamide weight, catalyst n, N, N', the addition of N'-Tetramethyl Ethylene Diamine is 22% of organic monomer acrylamide weight, (4) slurry obtained in step (3) is poured in the mould under optimal temperature, and then realizes that the in-situ solidifying of aerogel/fibre composite obtains the gel complex body, wherein the temperature of mould is controlled at 45 degrees centigrade during gel injection, (5) under gel complex body room temperature step (4) obtained, after standing 4.5 hours, from mould, deviate from, (6) complex material after deviating from is placed in to the vacuum drying oven 30 hours of 65 ~ 80 degrees centigrade, (7) under the specified temp system, the complex material after vacuum-drying is placed in to electric furnace and carries out the binder removal treatment process, to remove the organism such as organic solvent, monomer, linking agent, pore-forming material, suspension agent, initiator, catalyzer, wherein the specified temp system enactment is that room temperature is warming up to 105 degrees centigrade in lower 1 hour, is incubated 2 ~ 3 hours, within 1 hour, rise to 180 degrees centigrade, be incubated 1 ~ 2 hour, within 2 hours, rise to 300 degrees centigrade, be incubated 1 ~ 2 hour, within 70 minutes, rise to 370 degrees centigrade, be incubated 1 ~ 3 hour, within 30 minutes, rise to 400 degrees centigrade, be incubated 1 hour, within 200 minutes, rise to 500 degrees centigrade, protect 2 ~ 3h, within 200 minutes, rise to 600 degrees centigrade, be incubated 2 ~ 3 hours, finally obtain block complete, there is high mechanical strength (ultimate compression strength reaches 13.8Mpa), lower thermal conductivity (λ=0.046Wm -1k -1, nanoporous aerogel 298K)/fiber composite super insulating material.
Embodiment 4
(1) by the organic solvent trimethyl carbinol, organic monomer acrylamide, linking agent N, N '-methylene-bisacrylamide fully is uniformly mixed 36 hours and is configured to premixed liquid, the wherein trimethyl carbinol, acrylamide and N, the N'-methylene-bisacrylamide, three's weight ratio is 180 ~ 200:29 ~ 90:1 ~ 4, (2) add silica aerogel in the premixed liquid in step (1), alumina powder, Zirconium oxide fibre, the opalizer titanium dioxide, pore-forming material Polyethylene glycol-2000 and suspension agent tripoly phosphate sodium STPP, planetary ball mill batch mixing 6 hours, prepare the slurry that solid load (volume fraction) is 20%, silica aerogel wherein, alumina powder, Zirconium oxide fibre, the opalizer titanium dioxide, four weight ratio is 0.7 ~ 1.1:2.6 ~ 4.2:1.8 ~ 2.3:0.11 ~ 0.32, the addition of pore-forming material Polyethylene glycol-2000 is silica aerogel, alumina powder, 3.5% of Zirconium oxide fibre and opalizer titanium dioxide gross weight, the addition of suspension agent tripoly phosphate sodium STPP is silica aerogel, alumina powder, 0.25 ~ 1.5% of Zirconium oxide fibre and opalizer titanium dioxide gross weight, (3) slurry step (2) obtained carries out froth in vacuum 20 minutes, then successively dropwise add a certain amount of initiator ammonium persulfate, catalyst n in slurry, N, N', the N'-Tetramethyl Ethylene Diamine, carry out magnetic agitation and temperature controls simultaneously, wherein the temperature of froth in vacuum process should be controlled at 18 degrees centigrade, the addition of initiator ammonium persulfate is 0.7 ~ 3.5% of organic monomer acrylamide weight, catalyst n, N, N', the addition of N'-Tetramethyl Ethylene Diamine is 24% of organic monomer acrylamide weight, (4) slurry obtained in step (3) is poured in the mould under optimal temperature, and then realizes that the in-situ solidifying of aerogel/fibre composite obtains the gel complex body, wherein the temperature of mould is controlled at 33 degrees centigrade during gel injection, (5) under gel complex body room temperature step (4) obtained, after standing 5 hours, from mould, deviate from, (6) complex material after deviating from is placed in to the vacuum drying oven 30 hours of 80 ~ 110 degrees centigrade, (7) under the specified temp system, the complex material after vacuum-drying is placed in to electric furnace and carries out the binder removal treatment process, to remove the organism such as organic solvent, monomer, linking agent, pore-forming material, suspension agent, initiator, catalyzer, wherein the specified temp system enactment is that room temperature is warming up to 105 degrees centigrade in lower 1 hour, is incubated 2 ~ 3 hours, within 1 hour, rise to 180 degrees centigrade, be incubated 1 hour, within 2 hours, rise to 300 degrees centigrade, be incubated 2 ~ 3 hours, within 70 minutes, rise to 370 degrees centigrade, be incubated 2 ~ 4 hours, within 30 minutes, rise to 400 degrees centigrade, be incubated 1 hour, within 200 minutes, rise to 500 degrees centigrade, protect 3 ~ 4h, within 200 minutes, rise to 600 degrees centigrade, be incubated 3 ~ 4 hours, finally obtain block complete, there is high mechanical strength (ultimate compression strength reaches 12.8Mpa), lower thermal conductivity (λ=0.043Wm -1k -1, nanoporous aerogel 298K)/fiber composite super insulating material.
In the above-described embodiment, organic solvent, except adopting the trimethyl carbinol, can also adopt the long-chain alcohols such as phthalic ester, high boiling petroleum-type solvent to substitute; Initiator, except ammonium persulphate, can also be used benzoyl peroxide two acyls.

Claims (16)

1. nanoporous aerogel/fiber composite super insulating material, it is characterized in that: the feed composition of this super insulating material comprises aerosil, alumina powder, Zirconium oxide fibre and opalizer titanium dioxide, and its weight ratio is (0.6-1.3): (2.1-5.0): (1.2-3.3): (0.06-0.52).
2. nanoporous aerogel according to claim 1/fiber composite super insulating material, it is characterized in that: the median size of described aerosil particle is that 23.1 μ m, thermal conductivity are 0.02 Wm when temperature is 298K -1k -1, mean pore size is that 20nm, porosity are greater than 97%, density is about 0.14 g/cm 3, specific surface area is 857 g/m 2.
3. nanoporous aerogel according to claim 1/fiber composite super insulating material, it is characterized in that: the median size of described alumina powder is 0.51 μ m, the α-Al of described alumina powder 2o 3content is greater than 99.9%.
4. nanoporous aerogel according to claim 1/fiber composite super insulating material, it is characterized in that: described Zirconium oxide fibre volume density is lower than 0.15g/cm 3, the tetragonal phase zirconium oxide composition of described Zirconium oxide fibre is greater than 99.5%, described Zirconium oxide fibre thermal conductivity when temperature is 298K lower than 0.13 Wm -1k -1.
5. nanoporous aerogel according to claim 1/fiber composite super insulating material, it is characterized in that: described opalizer titanium dioxide crystal formation is rutile-type, described opalizer titanium dioxide median size is 0.30 μ m, Ti O in described opalizer titanium dioxide 2content higher than 98%.
6. a method for preparing nanoporous aerogel/fiber composite super insulating material with the described raw material of claim 1, it is characterized in that: this preparation method comprises the following steps:
(1) the premixed liquid preparation mixes to clear liquid by organic solvent, linking agent and organic monomer, and makes premixed liquid;
(2) the suspended nitride preparation adds aerosil, alumina powder, Zirconium oxide fibre, opalizer titanium dioxide, pore-forming material and suspension agent in premixed liquid, through ball mill mixing, prepares suspended nitride;
(3) froth in vacuum is carried out froth in vacuum to above-mentioned suspended nitride, after de-bubble, successively dropwise adds initiator and catalyzer again in this suspended nitride, is stirred, to make the de-bubble slurry simultaneously;
(4) gel casting is poured into the de-bubble slurry in mould, through in-situ solidifying, obtains the gel complex body;
(5) the standing demoulding after at room temperature standing 4 ~ 8 hours, is deviate from the gel complex body and obtains shaping blank from mould;
(6) vacuum-drying is carried out vacuum-drying to shaping blank;
(7) binder removal is processed processing is heated, is incubated to the shaping blank of vacuum drying treatment, to remove organic solvent, organic monomer, linking agent, pore-forming material, suspension agent, initiator, catalyzer, and make nanoporous aerogel/fiber composite super insulating material finished product.
7. the preparation method of nanoporous aerogel according to claim 6/fiber composite super insulating material, it is characterized in that: described organic solvent is the trimethyl carbinol, and organic monomer is acrylamide, and linking agent is N, N '-methylene-bisacrylamide.
8. the preparation method of nanoporous aerogel according to claim 7/fiber composite super insulating material, it is characterized in that: the described trimethyl carbinol, acrylamide and N, N'-methylene-bisacrylamide three's weight ratio is (170 ~ 200): (29 ~ 100): (1 ~ 10).
9. the preparation method of nanoporous aerogel according to claim 6/fiber composite super insulating material is characterized in that: the weight ratio of described aerosil, alumina powder, Zirconium oxide fibre, opalizer titanium dioxide is (0.6-1.3): (2.1-5.0): (1.2-3.3): (0.06-0.52).
10. according to the preparation method of the described nanoporous aerogel of claim 6 or 9/fiber composite super insulating material, it is characterized in that: described pore-forming material is Polyethylene glycol-2000, and the addition of this Polyethylene glycol-2000 is 1.5 ~ 7.5% of aerosil, alumina powder, Zirconium oxide fibre and opalizer titanium dioxide gross weight; Described suspension agent is tripoly phosphate sodium STPP, and the addition of this tripoly phosphate sodium STPP is 0.05 ~ 3.5% of silica aerogel, alumina powder, Zirconium oxide fibre and opalizer titanium dioxide gross weight.
11., according to the preparation method of the described nanoporous aerogel of claim 6 or 9/fiber composite super insulating material, it is characterized in that: the volume fraction of the solid load of described suspended nitride is 15 ~ 75%.
12. the preparation method of nanoporous aerogel according to claim 6/fiber composite super insulating material is characterized in that: described initiator is ammonium persulphate, the addition of this ammonium persulphate is 0.5 ~ 5% of organic monomer acrylamide weight; Described catalyzer is N, N, and N', the N'-Tetramethyl Ethylene Diamine, this catalyst n, N, N', the addition of N'-Tetramethyl Ethylene Diamine is 15 ~ 45% of organic monomer acrylamide weight.
13. the preparation method according to the described nanoporous aerogel of claim 6 or 12/fiber composite super insulating material is characterized in that: the temperature of described froth in vacuum is controlled at subzero 10 ~ 55 degrees centigrade.
14. the preparation method of nanoporous aerogel according to claim 6/fiber composite super insulating material is characterized in that: when described de-bubble slurry is poured into mould, the temperature of mould is controlled at 15 ~ 85 degrees centigrade.
15. the preparation method of nanoporous aerogel according to claim 6/fiber composite super insulating material is characterized in that: described shaping blank is placed under the vacuum condition of 50 ~ 120 degrees centigrade dry 12 ~ 36 hours.
16. the preparation method of nanoporous aerogel according to claim 6/fiber composite super insulating material, it is characterized in that: the treating processes of heating, be incubated that described binder removal is processed is followed successively by, by vacuum drying shaping blank at ambient temperature after standing 1 hour, be warming up to 105 degrees centigrade, be incubated 2 ~ 3 hours; Then with heating-up time of 1 hour, temperature is risen to 180 degrees centigrade, be incubated 1 ~ 3 hour; With heating-up time of 2 hours, temperature is risen to 300 degrees centigrade again, be incubated 1 ~ 3 hour; With heating-up time of 70 minutes, temperature is risen to 370 degrees centigrade again, be incubated 1 ~ 4 hour; With heating-up time of 30 minutes, temperature is risen to 400 degrees centigrade again, be incubated 1 hour; With heating-up time of 200 minutes, temperature is risen to 500 degrees centigrade again, protect 2 ~ 4h; With heating-up time of 200 minutes, temperature is risen to 600 degrees centigrade again, be incubated 2 ~ 4 hours; Then at room temperature cooling.
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CN103922643A (en) * 2014-03-13 2014-07-16 四川科宁泰科技有限公司 Composite SiO2 aerogel heat-insulation felt pad and preparation method
CN106298019A (en) * 2016-08-12 2017-01-04 上海新益电力线路器材有限公司 A kind of heat-insulating, fire-preventing cable and preparation method thereof
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CN109437951A (en) * 2018-11-29 2019-03-08 苏州宏久航空防热材料科技有限公司 A kind of lightweight heat-insulation integrative of resistance to ablation structure
CN111018494A (en) * 2019-12-20 2020-04-17 中国建筑材料科学研究总院有限公司 Nano-pore heat insulation material and preparation method thereof
CN114349490A (en) * 2022-01-18 2022-04-15 广州世陶新材料有限公司 Silicon dioxide aerogel thermal insulation material and preparation method thereof
CN114605107A (en) * 2022-04-06 2022-06-10 广州世陶新材料有限公司 Fiber-reinforced aerogel heat-insulating material prepared by gel injection molding method and preparation method thereof
CN114605107B (en) * 2022-04-06 2023-11-10 广州世陶新材料有限公司 Fiber reinforced aerogel heat insulation material prepared by gel casting method and preparation method thereof

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