CN203663814U - Equipment for preparing precursorsol of aerogel - Google Patents
Equipment for preparing precursorsol of aerogel Download PDFInfo
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- CN203663814U CN203663814U CN201320504946.2U CN201320504946U CN203663814U CN 203663814 U CN203663814 U CN 203663814U CN 201320504946 U CN201320504946 U CN 201320504946U CN 203663814 U CN203663814 U CN 203663814U
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Abstract
The utility model provides equipment for preparing precursorsol of aerogel. The equipment comprises a reaction part and a circulating cooling part, wherein the reaction part is formed by a reaction kettle, and the reaction kettle comprises a reaction kettle body, a reaction kettle cover as well as sol inlets and a sol outlet which are communicated with a reaction kettle fluid; thecirculating cooling part comprises a cooling liquid kettle, a cooling liquid circulating pipeline as well as a cooling liquid accommodated in the cooling liquid kettle and the cooling liquid circulating pipeline, the cooling liquid circulating pipeline is communicated with a cooling liquidkettle liquid at the near end, and the cooling liquid circulating pipeline encircles the reaction kettle at the far end. The equipment is particularly applicable to preparation of the sol with methyl silicate and water serving as raw materials and an alcohol solvent serving as a solvent, is simple and practical in structure and has the broad application prospect in preparation of high-performance aerogelcomposite materials.
Description
Technical field
The utility model relates to material preparation process technical field, and specifically, the utility model relates to controlled aerogel composite of a kind of gel and preparation method thereof and prepares the required equipment of stable sol.
Background technology
Along with developing rapidly of human economy life, the mankind are increasing to the demand of the energy, also increasing to the destruction of environment.In the face of the crisis that world energy sources shortage, environment wreck, generally pay attention to the research of energy-efficient material both at home and abroad, in the hope of reducing energy waste, improve service efficiency.The heat preservation technology level in the fields such as wherein, raising industry, building, military affairs is of great significance for energy-saving and emission-reduction tool.Aerogel material, as a kind of nano-porous materials of novel light, is the most efficient heat-barrier material of a class of finding at present.Aeroge is also referred to as " solid cigarette ", and it is lightweight, amorphous, the porous condensed state solid material being made up of nano-colloid particle or high-polymer molecular, and its particle size, between 1 to 100nm, belongs to the category of nano material.Aeroge has unique open loose structure and continuous three-dimensional network, has the excellent properties such as extremely low density, high-specific surface area and high porosity, lower thermal conductivity and low-refraction, is a kind of new and effective heat-insulating heat-preserving material.Aerogel material can effectively stop heat transmission with its unique structure, under normal temperature and pressure, thermal conductivity is less than 0.013W/mK, also lower than the thermal conductivity of still air (0.026W/mK), be the solid material that current thermal conductivity is minimum, can be described as super insulating material.Nanoporous SiO
2aeroge has certain compression strength, and at high temperature steady operation, does not decompose under high temperature, emits without pernicious gas, belongs to environmental protection shaped material.There is very wide application prospect in fields such as petrochemical industry, Aero-Space, energy saving buildings.In oil, chemical industry and metallurgy industry, pipeline, stove and other Thermal Equipment ubiquity, use SiO
2aeroge and composite thereof substitute traditional insulation material they are incubated, and can greatly reduce heat-energy losses, improve heat utilization rate.Aerogel composite can also be as the heat-barrier material of the engines such as the insulation material of liquid natural gas tank and oil storage tank etc. and automobile, aircraft and blast pipe.At building field, because aeroge had both had insulating characteristics, there are again sound absorption characteristics, and there is light transmission, therefore aeroge can be clipped in and between double glazing, make Sandwich glass, its insulation effect is than high several times of common double glazing, and has noise reduction.Window by this glass for house, can greatly reduce heat runs off, have the effect of the obvious saving energy, the heat loss rate of the glass pane take aeroge as chuck also will reduce 2/3rds than at present best window system (hydrogen filling indium oxide or silver coating with low-launch-rate).If aeroge glass is replaced to general cladding glass for skyscraper, will greatly alleviate building deadweight, and can play fireproofing function.SiO
2aerogel composite can reach better effect of heat insulation with lighter quality, less volume, and this feature has great advantage in Aeronautics and Astronautics application.Aluminosilicate refractory fiber/the SiO of U.S. NASA Ames research center research and development
2aeroge composite adiabatic is watt for space shuttle, and Muscovite Mir station has also adopted SiO
2aeroge is as heat-insulating heat-preserving material.The space suit that aeroge is just being used for wearing while logging in Mars first for the mankind is developed a kind of insulation lining.In addition, at military industry field, SiO
2aeroge can be used as the insulating layer material of aircraft cabin.Can be used as the high efficiency heat insulation material of the high-temperature steam pipeline system of nuclear reactor, evaporimeter, boiler and the complexity of nuclear submarine, steam power guided missile destroyer, can strengthen effect of heat insulation, reduce temperature in cabin, effectively reduce the consumption of heat-barrier material simultaneously, increase the usage space in cabin, effectively improve various working environments.In addition, developed soldier's protective garment with aerogel material abroad, will to protection soldier avoid ambient influnence, improve its combat capabilities very favourable.
Chinese patent CN1557778A, CN1335805A, CN1196036A, CN1592651A have all reported aerogel material; wherein; the preparation method of aeroge all adopts sol-gel process; but in sol-gel process; for promoting the generation of reaction; conventionally can in reaction system, add acid base catalysator, complex procedures.Make sol system gel within a short period of time owing to adding catalyst in reaction system, gel time cannot accurately be controlled, make fully impregnation of fibers of sol system; And the membership that adds of catalyst brings negative effect to properties of product, this brings certain restriction for preparing high-performance aerogel composite; Or can form Acidity of Aikalinity waste liquid, cause environmental issue.
Chinese patent CN101948297A adopts the silica-based hydrosol, silicon alkoxide, alcoholic solvent and water to prepare aerogel composite, preparation process is without the extra catalyst that adds, utilize the generation of the Acidity of Aikalinity catalytic reaction of the silica-based hydrosol self, and then prepared aerogel composite.Because this reaction is to utilize the Acidity of Aikalinity catalytic reaction of the silica-based hydrosol to occur, therefore, the Acidity of Aikalinity of the silica-based hydrosol is also had to requirement, can not be too high can not be too low, otherwise can affect the performance of preparing material, it is comparatively harsh to raw-material requirement.
Utility model content
In order to solve, the complicated process of preparation, the gel time that in aerogel composite technology of preparing, exist cannot accurately be controlled, catalyst type is many, be unfavorable for the shortcomings such as environmental protection, and the utility model provides the preparation method of the controlled silicon dioxide silica aerogel composite material of a kind of gel and this material.Preparation process is without the extra catalyst that adds, only need methyl silicate, alcoholic solvent and water, use reaction raw material few, preparation technology is simple, and can control sol system gel time, guarantee colloidal sol abundant impregnation of fibers before gel, solved aerogel composite preparation process complicated and cannot accurately control the problem of collosol and gel time, for preparation high-performance aerogel composite is laid a good foundation.In addition, preparation process has also been removed the pollution of catalyst for environment from without the extra catalyst that adds.
The purpose of this utility model is achieved through the following technical solutions:
1. an aerogel composite, wherein, described aerogel composite comprises aerosil and fibrous material, and described aerosil is take methyl silicate and water as raw material, prepare Ludox take alcoholic solvent as solvent, and does not add gel catalyst at described Ludox.
2. the aerogel composite as described in technical scheme 1, wherein, described Ludox is prepared at the temperature of-40 ℃ to 0 ℃.
3. the aerogel composite as described in technical scheme 1 or 2 wherein, floods described fibrous material with described Ludox at the temperature of-40 ℃ to 0 ℃.
4. the method as described in technical scheme 3, wherein, dip time is to be standing time 1 hour to 240 hours, is preferably 24 hours to 96 hours.
5. the aerogel composite as described in any one in technical scheme 1 to 4, wherein, described fibrous material is the one or more kinds of combinations of choosing in the group being made up of following fibrous material: glass fibre, quartz fibre, high silica fiber, alumina silicate fibre, carbon fiber, mullite fiber, silicon carbide fibre, silicon nitride fiber, alumina fibre, boron nitride fiber, basalt fibre, aramid fiber, polyester fiber, nylon fiber, polypropylene fiber and cellulose fibre; In addition preferably, described fibrous material is chosen one or more the combination in the group of following fibrous material composition: glass fibre, quartz fibre, high silica fiber, alumina silicate fibre, carbon fiber, mullite fiber, silicon carbide fibre, silicon nitride fiber, alumina fibre and boron nitride fiber.
6. the aerogel composite as described in any one in technical scheme 1 to 5, wherein, the bulk density of described fibrous material is 0.005g/cm
3to 1.00g/cm
3, be preferably 0.03g/cm
3to 0.50g/cm
3.
7. the aerogel composite as described in any one in technical scheme 1 to 6, wherein, described fibrous material is continuous fiber material or short fiber material.
8. the aerogel composite as described in any one in technical scheme 1 to 7, wherein, described fibrous material is the organized assembles of continuous fiber material or the organized assembles of short fiber material.
9. the aerogel composite as described in technical scheme 1 to 8 any one, wherein, described methyl silicate: alcoholic solvent: water is take molar ratio computing as 1: (1 to 60): (1 to 60).
10. the aerogel composite as described in technical scheme 1 to 9, wherein, described alcoholic solvent is one or more the combination of selecting in the group of free methyl alcohol, ethanol, normal propyl alcohol and isopropyl alcohol composition; Described water is deionized water.
11. aerogel composites as described in technical scheme 1 to 9, wherein, methyl silicate accounts for 1 quality % to 26 quality % of the quality of described aerogel composite in the quality of silica, be preferably 3% to 20%.
Prepare the equipment of aerogel composite for 12. 1 kinds, wherein, described equipment comprises:
(1) reactive moieties; With
(2) circulating cooling part;
Wherein, described reactive moieties is formed by reactor, and described reactor comprises reactor main body and reactor kettle cover and the glue-feeder and the gum outlet that are communicated with reactor fluid; And
Wherein, described circulating cooling part comprises cooling fluid still, liquid circulation pipeline and is contained in described cooling fluid still and the ducted cooling fluid of cool cycles, and described liquid circulation pipeline is communicated with and is enclosed in around described reactor at far-end with described cooling fluid still fluid at near-end.
13. equipment as described in technical scheme 12, wherein, described glue-feeder is arranged on reactor kettle cover, and described gum outlet is arranged in reactor main body.
14. as described in technical scheme 12 or 13 wherein, wherein, described glue-feeder is arranged in reactor main body, and described gum outlet is arranged on reactor kettle cover.
15. equipment as described in any one in technical scheme 12 to 14, wherein, described glue-feeder and described gum outlet are arranged in reactor main body simultaneously, or are arranged on reactor kettle cover simultaneously.
16. equipment as described in any one in technical scheme 12 to 15, wherein, described glue-feeder with enter glue pump and be connected, and/or described gum outlet is connected with plastic emitting pump.
17. equipment as described in any one in technical scheme 12 to 16, wherein, the quantity of described glue-feeder and described gum outlet is respectively done for oneself more than two.
18. equipment as described in technical scheme 17, wherein, described plural described glue-feeder is arranged on reactor main body or reactor kettle cover simultaneously; Or one or some glue-feeders are arranged on reactor kettle cover, one or some glue-feeders are arranged in reactor main body.
19. equipment as described in technical scheme 17 or 18, wherein, described in, plural described gum outlet is arranged on reactor main body or reactor kettle cover simultaneously; Or one or some gum outlets are arranged on reactor kettle cover, one or some gum outlets are arranged in reactor main body.
20. equipment as described in any one in technical scheme 12 to 19, wherein, have at least a glue-feeder to be arranged on reactor kettle cover, and/or have at least a gum outlet to be arranged in reactor main body.
21. equipment as described in any one in technical scheme 12 to 19, wherein, have at least a glue-feeder to be arranged on reactor kettle cover, and/or have at least a gum outlet to be arranged on the bottom of reactor main body.
22. equipment as described in any one in technical scheme 12 to 21, wherein, coolant duct in described cool cycles part comprises that cooling fluid goes out pipe and cooling fluid inlet pipe and is enclosed in reactor cooling fluid chuck around, make cooling fluid go out pipe by cooling fluid and leave cooling fluid still, circulation process cooling fluid chuck, then be circulated back to cooling fluid still by cooling fluid inlet pipe.
23. equipment as described in any one in technical scheme 12 to 22, wherein, go out on pipe, to be provided with low-temperature circulating coolant pump in cooling fluid.
24. equipment as described in any one in technical scheme 12 to 23 wherein, are provided with cooling fluid liquid feeding pump on cooling fluid inlet pipe, for from cooling fluid chuck by coolant pump feed liquor to cooling fluid still.
25. equipment as described in any one in technical scheme 12 to 24, wherein, described cooling fluid liquid feeding pump has pumping and refrigerating function simultaneously.
26. equipment as described in any one in technical scheme 12 to 25, wherein, described cooling fluid still comprises cooling fluid still main body and cooling fluid still kettle cover, is provided with at least one cooling fluid liquid outlet and at least one cooling fluid inlet on cooling fluid still main body or cooling fluid still kettle cover.
27. equipment as described in any one in technical scheme 12 to 26, wherein, described equipment also comprises support, for reactive moieties and/or cool cycles part are supported on to support.
28. equipment as described in any one in technical scheme 12 to 27, wherein, described support is also hung with agitator above reactor, for the content of stirred autoclave.
The preparation method of 29. 1 kinds of aerogel composites, wherein, described method comprises the steps:
(1) preparation of Ludox: using methyl silicate and water as raw material, make Ludox using alcoholic solvent as solvent;
(2) colloidal sol impregnation: use described Ludox impregnation of fibers material the temperature of-40 ℃ to 0 ℃, obtain fibrous material/sol system.
30. methods as described in technical scheme 29, wherein, described method also comprises:
(3) leave standstill: described fibrous material/sol system is left standstill to 1 to 240 hour in the temperature of-40 ℃ to 0 ℃.
31. methods as described in technical scheme 29 or 30, wherein, described method also comprises:
(4) gel: fibrous material/sol system is taken out from low temperature environment, and gelling under room temperature or heating condition, obtains silica wet gel;
(5) aging: under room temperature or heating condition, to carry out 8 hours to 168 hours aging;
(6) solvent exchange: the wet gel material after aging is put into alcoholic solvent or ketone solvent, make water content lower than 1%;
(7) supercritical drying processing: the described wet gel through hydrophobization is carried out to supercritical drying processing, make product.
32. methods as described in any one in technical scheme 29 to 31, wherein, described method also comprises after solvent exchange and before supercritical drying is processed:
(6 ') surface treatment: adopt hydrophobization reagent to soak the wet gel that completes solvent exchange.
33. methods as described in any one in technical scheme 29 to 31, wherein, described Ludox is prepared in the equipment described in any one in technical scheme 12 to 28.
34. methods as described in any one in technical scheme 29 to 33, wherein, described alcoholic solvent is one or more the combination of choosing in the group being made up of methyl alcohol, ethanol, normal propyl alcohol and isopropyl alcohol.
35. methods as described in any one in technical scheme 29 to 34, wherein, described methyl silicate: alcoholic solvent: water is take molar ratio computing as 1: (1 to 60): (1 to 60).
36. methods as described in any one in technical scheme 33 to 35, wherein, coolant temperature, between-40 ℃ to 0 ℃, is preferably-15 ℃ to-5 ℃.
37. methods as described in any one in technical scheme 29 to 36, wherein, cooling fluid is water, salt solution, ethanol, ethylene glycol, ammonia steam, more preferably salt solution.
38. methods as described in any one in technical scheme 29 to 38, wherein, chuck hollow layer thickness is 2mm to 50mm, is preferably 5mm to 20mm.
39. methods as described in any one in technical scheme 29 to 38, wherein, described fibrous material is the one or more kinds of combinations of choosing in the group being made up of following fibrous material: glass fibre, quartz fibre, high silica fiber, alumina silicate fibre, carbon fiber, mullite fiber, silicon carbide fibre, silicon nitride fiber, alumina fibre, boron nitride fiber, basalt fibre, aramid fiber, polyester fiber, nylon fiber, polypropylene fiber and cellulose fibre; In addition preferably, described fibrous material is chosen one or more the combination in the group of following fibrous material composition: glass fibre, quartz fibre, high silica fiber, alumina silicate fibre, carbon fiber, mullite fiber, silicon carbide fibre, silicon nitride fiber, alumina fibre and boron nitride fiber.
40. methods described in technical scheme 29 to 39, wherein, the bulk density of described fibrous material is 0.005g/cm
3to 1.00g/cm
3, be preferably 0.03g/cm
3to 0.50g/cm
3;
41. methods as described in any one in technical scheme 29 to 40, wherein, described fibrous material is continuous fiber material or short fiber material.
42. methods as described in any one in technical scheme 29 to 41, wherein said colloidal sol impregnation adopts following any one operation to carry out;
(1) directly described Ludox is added in the die cavity of the mould that described fibrous material is housed, then rely on gravity to carry out impregnation;
(2) first use fibrous material described in Ludox pre-preg, then by packing in the die cavity of mould through the described fibrous material of pre-preg, then add described Ludox, and rely on gravity to carry out impregnation;
(3) die cavity that directly described Ludox is injected to the mould that described fibrous material is housed by pressue device carries out impregnation;
(4) described fibrous material is packed in the die cavity of mould, then described die cavity is vacuumized, more described Ludox is injected to described die cavity and carry out impregnation.
43. methods as described in any one in technical scheme 29 to 42, wherein said leaving standstill undertaken by following operation: fibrous material/sol system is put into-40 ℃ to 0 ℃ low temperature environment, be preferably-15 ℃ to-5 ℃; Be 1 hour to 240 hours standing time, is preferably 24 hours to 96 hours;
44. methods as described in any one in technical scheme 29 to 43, wherein, described gel and aging step are undertaken by following operation: first fibrous material/sol system is taken out from low temperature environment, gel under the heating-up temperature of room temperature or 30 ℃ to 80 ℃, described heating-up temperature is preferably 30 ℃ to 50 ℃; Gel time is 10 minutes to 48 hours, for example, can be 10 minutes, 1 hour, 12 hours, 24 hours, 48 hours, is preferably: 1 to 24 hour.Then gel rubber system is carried out under room temperature or heating condition to 8 hours to 168 hours aging.
45. methods as described in any one in technical scheme 29 to 44, wherein, described surface treatment step is carried out as follows: the wet gel that completes solvent exchange is put in the ethanol solution of the hydrophobization reagent that contains 0.5 volume % to 50 volume %, room temperature leaves standstill 1 hour to 24 hours; Then wet gel is taken out, be placed on and in absolute ethyl alcohol, carry out solvent exchange; Preferably, the solvent exchange carrying out in absolute ethyl alcohol carries out at twice, each 24 hours to 120 hours.
46. methods as described in any one in technical scheme 29 to 45, wherein, described hydrophobization reagent selects the group of free HMDS, trimethoxy silane and Dimethoxyphenyl silane composition.
47. methods as described in any one in technical scheme 29 to 46, wherein, described supercritical drying is processed and is carried out in the following way: will put into supercritical fluid drying equipment through aging described wet gel, squeeze into the drying medium of 5 megapascal (MPa) to 25 megapascal (MPa)s, at 20 to 80 ℃, with the flow of 100 ls/h to 1500 ls/h, assist medium is brought to drying medium into separating still and separate; After assist medium separates completely, with 1 megapascal (MPa)/hour to 6 megapascal (MPa)s/hour speed release pressure, until the pressure in described separating still and ambient atmosphere pressure balanced.
48. methods as described in any one in technical scheme 29 to 47, wherein, described drying medium is carbon dioxide or is methyl alcohol and/or ethanol, assist medium is alcoholic solvent or ketone solvent; Preferably, described alcoholic solvent is ethanol or isopropyl alcohol, and described ketone solvent is acetone.
49. aerogel composites of being prepared by the method described in any one in technical scheme 29 to 48.
The utility model method relies on the response characteristic of methyl silicate hydrolysis gel, just can complete sol-gel technology process without the extra catalyst that adds, and technique is simple, easy to operate.But methyl silicate can be emitted a large amount of heats in hydrolytic process, can impel very supergrip of whole reaction system, be unfavorable for the control of gel time.For this reason, the utility model provides a kind of reaction-circulation cooling device, the heat discharging can be taken away in methyl silicate hydrolytic process, has avoided the generation of gel, has prepared stable sol system.Afterwards, fiber/sol system is put into low temperature environment, suppressed the generation of gel reaction, but can be the abundant impregnation of fibers of colloidal sol simultaneously.Compared with other published aerogel composite, aerogel composite tool prepared by the utility model has the following advantages: (1) the utility model in preparation process without add any catalyst, reduce the introducing of other impurity, be easy to the aerogel composite that processability is more excellent, avoided the pollution of acid base catalysator to environment simultaneously.If adopt ethyl orthosilicate as silicon source, its gel must use acid base catalysator, if catalyst-free, cannot gel; (2) the utility model can precisely be controlled reaction system gel time, can make colloidal sol fully infiltrate fiber system, is easy to the aerogel composite that processability is more excellent; (3) few, the operating process of the utility model gelation reaction operating procedure simple, be easy to expand the scale of production.Prepared aerogel composite density, structure and the performance of the utility model is controlled.Heat stability is good, heat-proof quality excellence, all has very large application potential in Industrial Boiler insulation, petrochemical industry, building, space flight and aviation and military field.
Accompanying drawing explanation
Fig. 1 is of the present utility model for reaction-circulation cooling device schematic diagram.
The specific embodiment
As mentioned before, the utility model provide a kind of aerogel composite with and preparation method thereof and equipment.
First aspect, the utility model provides a kind of aerogel composite, and wherein, described aerogel composite comprises silica aerogel material and fibrous material, described silica aerogel material is made by the rear gel of methyl silicate hydrolysis, and course of reaction is without catalyst.
Counting 1 quality % to 26 quality % as methyl silicate in the Ludox of reactant with the content of silica, for example, is 1 quality %, 5 quality %, 10 quality %, 20 quality % or 26 quality %, is preferably 3% to 20%.If too high levels, easily causes prepared material heat-proof quality to decline; If dioxide-containing silica is too low, likely cause reactant concentration low, cannot form gel.
In the utility model, type, form and composition to described fibrous material have no particular limits, as long as described fibrous material can tolerate materials'use environment temperature, plays Expected Results and totally prepared aerogel composite do not caused to negative effect In the view of improving material mechanical performance aspect, those skilled in the art can select as required suitable fibrous material in the situation that of the disclosed content of this description of reading.Described reinforcing fiber materials can be the one or more kinds of combinations of choosing in the group being made up of following fibrous material: glass fibre, quartz fibre, high silica fiber, alumina silicate fibre, carbon fiber, mullite fiber, silicon carbide fibre, silicon nitride fiber, alumina fibre, boron nitride fiber, basalt fibre, aramid fiber, polyester fiber, nylon fiber, polypropylene fiber and cellulose fibre.
In the utility model, fortifying fibre type can be selected continuous fiber or chopped strand material; Can use unordered assembly or the organized assembles of fibrous material.Can be by the goods of the forms such as the cotton of fiber, felt, blanket, plate, brick, cloth, paper and/or rope or the precast body form that fibrous material makes through machine-shaping.The bulk density of described fiber is 0.005g/cm
3to 1.00g/cm
3, for example, can be 0.005g/cm
3, 0.01g/cm
3, 0.02g/cm
3, 0.05g/cm
3, 0.10g/cm
3, 0.40g/cm
3, 0.80g/cm
3, 0.90g/cm
3, 1.00g/cm
3.Be preferably 0.03g/cm
3to 0.50g/cm
3.
Because impurity will affect heat-barrier material high-temperature stability, therefore, the utility model water used should choice for use impurity be few or ion concentration is low water, for example pure water, distilled water (comprising distilled water and tri-distilled water) or deionized water, what preferably use is deionized water.
The utility model also has no particular limits described alcoholic solvent, can use when preparing colloidal sol and especially preparing the silica-based hydrosol in order to prepare the alcoholic solvent that the silica-based hydrosol is conventional, described alcoholic solvent for example can be for choosing one or more the combination in the group being made up of methyl alcohol, ethanol, normal propyl alcohol and isopropyl alcohol; Being preferably the combination of ethanol or ethanol and ethanol described alcoholic solvent in addition, for example, is the combination of ethanol and methyl alcohol, normal propyl alcohol and/or isopropyl alcohol; The further preferably combination of ethanol or ethanol and isopropyl alcohol; Most preferably be ethanol.
Aeroge in aerogel composite of the present utility model, by using methyl silicate as above and water as reaction raw materials, is prepared as solvent using alcoholic solvent.Preferably, methyl silicate: alcoholic solvent: the mol ratio of water is 1: (1 to 60): (1 to 60), for example described ratio can be 1: (1,5,10,15,20,25,30,35,40,45,50,55 or 60): (1,5,10,15,20,25,30,35,40,45,50,55 or 60).
The mass ratio of described aeroge and fibrous material be 1: 0.2 to 20.Can be for example 1: (0.2,0.5,0.8,1,2,3,4,5,6,7,8,9,10,11,12,13,14,15,16,17,18,19 or 20).Aeroge and mass of fibre material are than more preferably 1: (0.5 to 10).If aeroge ratio is too low, the heat-proof quality of prepared aerogel composite may be not enough, if the ratio of aeroge is too high, the mechanical property of prepared aerogel composite, processing performance may be not enough.
In the utility model, described methyl silicate, water and alcoholic solvent can form gel, that is to say, utilize the characteristic of reaction system self just can form gel, and do not need additionally to add acid base catalysator.But methyl silicate hydrolysis generates silanol, its reactivity is very strong, very soon can ready-made gel in the time that temperature is higher, be unfavorable for Ludox thorough impregnation fiber, and cause finally prepd aerogel material poor-performing.Reaction-the circulation cooling device that utilizes the utility model to provide, the heat discharging in methyl silicate hydrolytic process can be taken away, avoid the generation in advance of gel, can make methyl silicate hydrolysis and next step gel reaction does not occur, formed stable sol system.
On the contrary, existing sol-gel technique generally adopts soda acid (example hydrochloric acid, ammoniacal liquor, NaOH etc.).Some catalyst example hydrochloric acids and ammoniacal liquor easily volatilize, the bad control of concentration.Difficult volatility soda acid easily residues in system, causes the aerogel material quality of preparation to decline.Meanwhile, the catalytic efficiency of catalyst is general relevant with temperature, if ambient temperature changes, will affect the catalytic efficiency of catalyst, and then affect the quality of product, and the interpolation of catalyst can bring the problem of the aspects such as operation increase and environmental protection in addition.
Second aspect, the utility model also provides a kind of method of preparing aerogel composite, and described method comprises the steps:
(1) preparation of colloidal sol: first methyl silicate and water are poured in reaction-circulation cooling device as shown in Figure 1 in proportion, fully stirred, then add alcoholic solvent in this system, continue to stir, make Ludox;
(2) colloidal sol impregnation: fibrous material is immersed in described colloidal sol;
(3) leave standstill: fibrous material/sol system is put into-40 ℃ to 0 ℃ low temperature environment;
(4) gel: fibrous material/sol system is taken out from low temperature environment, and gelling under room temperature or heating condition, obtains silica wet gel;
(5) aging: under room temperature or heating condition, to carry out 8 hours to 168 hours aging;
(6) solvent exchange: the wet gel material after aging is put into alcoholic solvent or ketone solvent, make water content lower than 1%;
(7) surface treatment: adopt hydrophobization reagent to soak the wet gel that completes solvent exchange;
(8) supercritical drying processing: the described wet gel through hydrophobization is carried out to supercritical drying processing, make exemplar.
The utility model prepare methyl silicate, alcoholic solvent, deionized water and these raw materials ratio each other that Ludox uses all as above for as described in the utility model first aspect, here just do not repeating.
Between in the utility model, coolant temperature requires to be-40 ℃ to 0 ℃, for example, can be-40 ℃ ,-30 ℃ ,-20 ℃ ,-10 ℃, 0 ℃, more preferably-15 ℃ to-5 ℃.
In the utility model, fibrous material/sol system dwell temperature is-40 ℃ to 0 ℃, for example, can be-40 ℃ ,-30 ℃ ,-20 ℃ ,-10 ℃, 0 ℃, more preferably-20 ℃ to-5 ℃.Time of repose is 1 hour to 240 hours, for example, can be 2 hours, 48 hours, 96 hours, 144 hours, 192 hours, 240 hours, is preferably 24 hours to 96 hours.
In the utility model, gelling temp is the heating-up temperature of room temperature or 30 ℃ to 80 ℃, can be for example 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃, described heating-up temperature is preferably 30 ℃ to 50 ℃, and for ease of large-scale production and the saving energy, more preferably gelling temp is room temperature; Described gel time is 1 hour to 48 hours, is preferably 1 to 24 hour.Aging temperature is preferably room temperature or 30 ℃ to 60 ℃, for example, can be room temperature, 30 ℃, 40 ℃, 50 ℃ or 60 ℃, and for ease of large-scale production and save the energy, preferably aging temperature is room temperature.Ageing time is 8 hours to 168 hours, for example, can be 8 hours, 48 hours, 96 hours, 144 hours or 168 hours, more preferably 24 hours to 96 hours.
The utility model has no particular limits described hydrophobization reagent, can use the hydrophobization reagent such as such as HMDS, trimethoxy silane and/or dimethoxy benzene base silane.
The utility model has no particular limits the method for impregnation, and for example the any-mode in a to d carries out in the following way:
A. directly described Ludox is added in the die cavity of the mould that described fibrous material is housed, then rely on gravity to carry out impregnation;
B. first use fibrous material described in described Ludox pre-preg, then by packing in the die cavity of mould through the described fibrous material of pre-preg, then add described Ludox, and rely on gravity to carry out impregnation;
C. the die cavity that directly described Ludox is injected to the mould that described fibrous material is housed by pressue device carries out impregnation;
D. described fibrous material is packed in the die cavity of mould, then described die cavity is vacuumized, more described Ludox is injected to described die cavity and carry out impregnation.
The utility model mould therefor can be metal or on-metallic article, if metal die need apply at die cavity inner surface the polytetrafluoroethylene film of anticorrosive effect.
In the utility model, the drying medium adopting in supercritical drying processing procedure is preferably carbon dioxide, and assist medium is preferably alcoholic solvent or ketone solvent.More preferably, described alcoholic solvent used herein is one or more the combination of choosing in the group being made up of methyl alcohol, ethanol, normal propyl alcohol and isopropyl alcohol, and described ketone solvent is butanone and/or acetone.
In the time carrying out supercritical drying processing, can for example carry out in the following way: will put into supercritical fluid drying still through aging described fiber composite gel, squeeze into drying medium, be warming up to 20 ℃ to 80 ℃ and (be for example warming up to 20 ℃, 30 ℃, 40 ℃, 50 ℃, 60 ℃, 70 ℃ or 80 ℃) baking temperature, again by drying medium for example, with 10 ls/h to 1500 ls/h (10 ls/h, 50 ls/h, 100 ls/h, 200 ls/h, 500 ls/h, 1000 ls/h or 1500 ls/h) flow take assist medium out of drying kettle and separate, after assist medium separates completely, drying kettle with 1 megapascal (MPa)/hour to 6 megapascal (MPa)s/hour (for example 1 megapascal (MPa)/hour, 2 megapascal (MPa)s/hour, 3 megapascal (MPa)s/hour, 4 megapascal (MPa)s/hour, 5 megapascal (MPa)s/hour or 6 megapascal (MPa)s/hour) speed release pressure, until the pressure in described separating still and ambient atmosphere pressure balanced obtain gel complex material thus.
The third aspect, the utility model also provides the aerogel composite being made by described method.The composition of this material is identical with the utility model first aspect with content.
Fourth aspect, the utility model also provides a kind of equipment of preparing aerogel composite colloidal sol.
Described equipment is reaction-circulation cooling device, in the time preparing aeroge for the preservation of colloidal sol, the dipping of colloidal sol to fibrous material or the controlled gelation of colloidal sol while preparing fiber reinforcement type aerogel composite.Described equipment comprises:
(1) reactive moieties; With
(2) circulating cooling part;
Wherein, described reactive moieties is formed by reactor, and described reactor comprises reactor main body and reactor kettle cover and the glue-feeder and the gum outlet that are communicated with reactor fluid; And
Wherein, described circulating cooling part comprises cooling fluid still, liquid circulation pipeline and is contained in described cooling fluid still and the ducted cooling fluid of cool cycles, and described liquid circulation pipeline is communicated with and is enclosed in around described reactor at far-end with described cooling fluid still fluid at near-end.
In some embodiments, described glue-feeder can be arranged on reactor kettle cover, and described gum outlet is arranged in reactor main body.Or described glue-feeder can be arranged in reactor main body, and described gum outlet is arranged on reactor kettle cover.Or described glue-feeder and described gum outlet can be arranged in reactor main body, or are arranged on reactor kettle cover simultaneously simultaneously.In some embodiments, described glue-feeder can with enter glue pump and be connected, and/or described gum outlet can be connected with plastic emitting pump.In addition, described glue-feeder and described gum outlet can arrange more than two separately.In this case, more than two glue-feeder can be arranged on reactor main body or reactor kettle cover simultaneously, or one or some glue-feeders are arranged on reactor kettle cover, and one or some glue-feeders are arranged in reactor main body.Similarly, in the situation that being provided with two gum outlets, more than two gum outlet can be arranged on reactor main body or reactor kettle cover simultaneously, or one or some gum outlets are arranged on reactor kettle cover, and one or some gum outlets are arranged in reactor main body.Preferably, have at least a glue-feeder to be arranged on reactor kettle cover, and/or have at least a gum outlet to be arranged in reactor main body, more preferably have at least a gum outlet to be arranged on the bottom of reactor main body.
In some embodiments, coolant duct in described cool cycles part comprises that cooling fluid goes out pipe and cooling fluid inlet pipe and is enclosed in reactor cooling fluid chuck around, make cooling fluid go out pipe by cooling fluid and leave cooling fluid still, circulation process cooling fluid chuck, then be circulated back to cooling fluid still by cooling fluid inlet pipe.In addition, go out on pipe to be provided with low-temperature circulating coolant pump 4 in cooling fluid, for cooling cooling fluid and cooling fluid is gone out to pipe from cooling fluid still via cooling fluid be pumped to cooling fluid chuck.In addition, on cooling fluid inlet pipe, can be provided with cooling fluid liquid feeding pump, for from cooling fluid chuck by coolant pump feed liquor to cooling fluid still.Certainly, cooling fluid liquid feeding pump also can play the effect of cooling cooling fluid simultaneously.
In addition, cooling fluid still can comprise cooling fluid still main body and cooling fluid still kettle cover, on cooling fluid still main body or cooling fluid still kettle cover, can be provided with one or more than one cooling fluid liquid outlet and cooling fluid inlet.In addition, described one or more than one cooling fluid liquid outlet and cooling fluid inlet can be arranged on cooling fluid still and cooling fluid still kettle cover with the above-mentioned gum outlet and the similar mode of glue-feeder that are arranged on reactor main body and/or reactor kettle cover.
Optionally, described equipment can also comprise support, for reactive moieties and/or cool cycles part are supported on to support.Some preferred embodiment in, described support is also hung with agitator above reactor, for the content of stirred autoclave.
Can conduct further description described equipment with reference to figure 1 below.Reaction-circulation cooling device shown in accompanying drawing 1 is made up of reactive moieties, circulating cooling part, slave part.Wherein, slave part is made up of bracing frame 1 and agitator 3.Reactive moieties by reactor main body, reactor kettle cover 10, glue-feeder 12,12 ', gum outlet 13 forms.Circulating cooling part by cooling fluid still 5, low-temperature circulating coolant pump 4, cooling fluid inlet pipe 6, chuck 2, cooling fluid go out pipe 7,7 ', cooling reactor inlet pipe 11,11 ' composition.This equipment operation principle is: at for example methyl silicate and gone ionized water to add before reactor of raw material, cooling back installation is just started working.Cooling fluid 96 is squeezed into chuck 2 from going out pipe by cooling fluid cooling fluid still 5 after low-temperature circulating coolant pump 4 is cooling, progressively fills up after chuck 2, by cooling fluid inlet pipe 7,7 ' by cooling inlet 11,11 ' get back to circulating cooling liquid still 5, complete circulation.When question response still temperature is reduced to target temperature, first for example methyl silicate, absolute ethyl alcohol and water are passed through to glue-feeder 12,12 ' inject this reactor, starting agitator 3 stirs, make methyl silicate that hydrolysis fully occur, the heat that cooling fluid in chuck discharges can take away methyl silicate hydrolysis time, has guaranteed the stable of reaction system.After methyl silicate is fully hydrolyzed, continue to be stirred to system even.Cool cycles part can be taken away the amount of heat discharging in methyl silicate hydrolytic process, avoids colloidal sol premature gelation in the time that temperature is higher, finally obtains stable colloidal sol 8.The colloidal sol making is squeezed into gel equipment by gum outlet 13.
In addition, coolant temperature is preferably between-40 ℃ to 0 ℃, and the too high meeting of liquid temperature causes collosol and gel, and the too low methyl silicate hydrolysis of liquid temperature is slower, increases mixing time, and preparation efficiency declines.Be preferably-15 ℃ to-5 ℃.
Cooling fluid is not had to special requirement, be preferably water, salt solution, ethanol, ethylene glycol, ammonia steam, more preferably salt solution; The each parts of described reaction-circulation cooling device are generally made up of metal material, surface spraying corrosion-inhibiting coating.
In addition, described chuck hollow layer thickness is generally 2mm to 50mm, is preferably 5mm to 20mm.Low-temperature circulating coolant pump for example can Nanjing Xian Ou instrument manufacturing Co., Ltd XODL-4005 type circulating pump.
Described methyl silicate, pure water, alcoholic solvent are injected by the glue-feeder shown in accompanying drawing 1, mix rear colloidal sol and are discharged by gum outlet.
In this article, except as otherwise noted, otherwise term " chooses by ... the combination of one or more in group " and refers to any one that is selected from described group, or two or more any combination arbitrarily in described group.
Except as otherwise noted, otherwise in term used herein " two or more " " more than " including given figure, for example " two or more " comprise the situation of two kinds and the situation more than two kinds.
Except as otherwise noted, otherwise described herein and number range comprise the arbitrary value between end value and endpoints thereof (being upper and lower bound).
Embodiment
Below by the form with embodiment, the utility model is described in further detail.But these embodiment are just illustrated with regard to preferred embodiment of the present utility model, protection domain of the present utility model should not be construed as and only limits to these embodiment.
The methyl silicate using in embodiment is provided by Hangzhou silicon treasured, and other reagent is from traditional Chinese medicines reagent company Beijing Company; Fibrous material is from Shandong Luyang share co.,ltd.
Embodiment 1
In reaction-circulation cooling device, add methyl silicate, deionized water and absolute ethyl alcohol and mix, making Ludox, chilling temperature is-15 ℃.The mol ratio of methyl silicate, deionized water and alcoholic solvent is 1: 8: 4.
With prepared Ludox impregnated glass fiber cotton, dipping method adopts method as herein described (a) to carry out,, directly Ludox is added and the mold cavity that bulk density is the glass fibre cotton of 0.08 gram/cc is housed (is formed by No. 45 steel, die cavity inner surface scribbles corrosion-inhibiting coating polytetrafluoroethylene (PTFE)) in, rely on gravity dipping; Then, in-15 ℃ of environment, leave standstill 48 hours, take out, within 24 hours under the gelling temp of 25 ℃, obtain fiber gel.At 25 ℃ of temperature, in the ethanol as solvent, carry out after 48 hours aging, then adopt the ethanolic solution of 10% HMDS to carry out the surface treatment of 6 hours.Fiber composite gel through aging is carried out to supercritical drying processing in the following way: will put into supercritical fluid drying still through aging described fiber composite multicomponent gel, squeeze into the carbon dioxide of 14 megapascal (MPa)s as drying medium, be warming up to the baking temperature of 50 ℃, then separate taking drying kettle out of as the ethanol of assist medium using the carbon dioxide flow of 800 ls/h; With 2 megapascal (MPa)s/hour speed release pressure, until the pressure in described separating still and ambient atmosphere pressure balanced obtain aerogel composite thus.After measured, the density of the prepared aerogel composite of the present embodiment is 0.20 gram/cc, and room temperature thermal conductivity is 0.018 watt/meter to be opened, heat-barrier material bending 90 degree flawlesses, and hydroscopicity is 2%.
Embodiment 2
First in reaction-circulation cooling device, be 1: 7: 4 in molar ratio by ethyl orthosilicate, deionized water, ethanol ammoniacal liquor, stir, add ammoniacal liquor and regulate pH to 9, prepare silicon colloidal sol, chilling temperature is-15 ℃.Then be the extra-fine glass-wool felt of 0.08 gram/cc by prepared Ludox dipping density.Dipping method adopts method as herein described (a) to carry out, and adopts direct cement-dipping method that the Ludox preparing is immersed; Then in-15 ℃ of environment, leave standstill 48 hours; Take out, under the gelation temperature of 25 ℃, carry out gelling 24 hours, obtain fiber gel.At 25 ℃ of temperature, in the ethanol as solvent, carry out after 48 hours aging, then adopt the ethanolic solution of 20% HMDS to carry out the surface treatment of 0.5 hour; Fiber composite gel through aging is carried out to supercritical drying processing in the following way: squeeze into the carbon dioxide of 16 megapascal (MPa)s as drying medium, be warming up to the baking temperature of 70 ℃, then separate taking drying kettle out of as the ethanol of assist medium using the carbon dioxide flow of 800 ls/h; With 4 megapascal (MPa)s/hour speed release pressure, until the pressure in described separating still and ambient atmosphere pressure balanced obtain aerogel composite thus.After measured, the density of the fiber-reinforcement silicon dioxide aerogel continuous felt preparing is 0.21 gram/cc, and room temperature thermal conductivity is 0.020 watt of/meter of Kelvin, and hydroscopicity is 3%, heat-barrier material bending 90 degree flawlesses.
Embodiment 3 to 15
Except content shown in table 1,2 and 3 and note content, adopt the mode identical with embodiment 1 to carry out embodiment 3 to 15.
After measured, the performance parameter of the prepared material of each embodiment is as shown in table 3.Testing standard is as follows:
Room temperature thermal conductivity is pressed GB/T13350-2000 and is measured, and density is pressed GB/T5480-2008 and measured, and quality hydroscopicity is pressed GB/T5480-2008 and measured.
Pliability method of testing is: the aerogel composite take thickness as 5mm is specimen material, and the length of this specimen material and wide size are not less than respectively 200mm, and whether by after these specimen material bending 90 degree, recording bending place has crackle and/or phenomenon of rupture.
Claims (10)
1. for the preparation of an equipment for the precursor sol of aeroge, wherein, described equipment comprises:
Reactive moieties; With
Circulating cooling part;
Wherein, described reactive moieties is formed by reactor, and described reactor comprises reactor main body and reactor kettle cover and the glue-feeder and the gum outlet that are communicated with reactor fluid; And
Wherein, described circulating cooling part comprises cooling fluid still, liquid circulation pipeline and is contained in described cooling fluid still and the ducted cooling fluid of cool cycles, and described liquid circulation pipeline is communicated with and is enclosed in around described reactor at far-end with described cooling fluid still fluid at near-end.
2. equipment as claimed in claim 1, wherein, described glue-feeder is arranged in reactor main body, and described gum outlet is arranged on reactor kettle cover.
3. equipment as claimed in claim 1 or 2, wherein, described glue-feeder with enter glue pump and be connected, and/or described gum outlet is connected with plastic emitting pump.
4. equipment as claimed in claim 1 or 2, wherein, the quantity of described glue-feeder and described gum outlet is respectively done for oneself more than two.
5. equipment as claimed in claim 1 or 2, wherein, has at least a glue-feeder to be arranged on reactor kettle cover, and/or has at least a gum outlet to be arranged on the bottom of reactor main body.
6. equipment as claimed in claim 1 or 2, wherein, coolant duct in described cool cycles part comprises that cooling fluid goes out pipe and cooling fluid inlet pipe and is enclosed in reactor cooling fluid chuck around, cooling fluid goes out pipe by cooling fluid and leaves cooling fluid still, circulation process cooling fluid chuck, then be circulated back to cooling fluid still by cooling fluid inlet pipe.
7. equipment as claimed in claim 6, wherein, goes out on pipe, to be provided with low-temperature circulating coolant pump in cooling fluid.
8. equipment as claimed in claim 1 or 2, wherein, described cooling fluid still comprises cooling fluid still main body and cooling fluid still kettle cover, is provided with at least one cooling fluid liquid outlet and at least one cooling fluid inlet on cooling fluid still main body or cooling fluid still kettle cover.
9. equipment as claimed in claim 1 or 2, wherein, described equipment also comprises support, described reactive moieties and/or cool cycles part are supported on described support.
10. equipment as claimed in claim 6, wherein, the thickness of the hollow layer of described chuck is 2mm to 50mm.
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| CN201320504946.2U CN203663814U (en) | 2013-08-19 | 2013-08-19 | Equipment for preparing precursorsol of aerogel |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105152176A (en) * | 2015-09-29 | 2015-12-16 | 泰州市鑫润天冶金保温材料有限公司 | Nano thermal insulation material production device |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105152176A (en) * | 2015-09-29 | 2015-12-16 | 泰州市鑫润天冶金保温材料有限公司 | Nano thermal insulation material production device |
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Effective date of registration: 20200428 Address after: 215000 3E Industrial Park, No.18, Chunyao Road, Caohu street, Xiangcheng economic and Technological Development Zone, Suzhou City, Jiangsu Province Patentee after: Haiying Aerospace Materials Research Institute (Suzhou) Co.,Ltd. Address before: 100074 box 19, box 7203, Beijing, Fengtai District Patentee before: AEROSPACE INSTITUTE OF ADVANCED MATERIALS & PROCESSING TECHNOLOGY |
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