CN103319141A - Aerogel composite material - Google Patents
Aerogel composite material Download PDFInfo
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- CN103319141A CN103319141A CN2012100789920A CN201210078992A CN103319141A CN 103319141 A CN103319141 A CN 103319141A CN 2012100789920 A CN2012100789920 A CN 2012100789920A CN 201210078992 A CN201210078992 A CN 201210078992A CN 103319141 A CN103319141 A CN 103319141A
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Abstract
The present invention relates to a thermal insulation material, and particularly discloses an aerogel composite material, which can be used in the thermal insulation field under low, medium and high temperature conditions, and comprises two parts such as an aerogel and three-dimensional reinforcing fibers, wherein the three-dimensional reinforcing fibers are preferably X-Y plane fiber mesh and Z-direction nonwoven or textile fibers. The novel composite material provides significantly improved mechanical properties such as flexibility, tensile strength and shrinkage resistance compared with the pure aerogel, and maintains excellent thermal insulation of the aerogel.
Description
Technical field
The invention provides be applicable to low, in and hot conditions under heat insulation/insulation purposes aerogel composite.By fiber mesh and the nonwoven of Z direction or the three-dimensional machinery performance that textile fibres improves aerogel of selecting suitable X-Y plane, kept again the heat-insulating property of aerogel excellence simultaneously.
Background technology
China is energy import big country, along with in recent years rapid development of economy, and oil, the consumption of the conventional energy resourcess such as coal has occupied first place, the world.
From the angle of economic benefit, save energy reduces consuming, and helps to reduce cost, improves the competitiveness, and can also reduce to oil the degree of dependence of coal (oil, coal reserves is limited).
From the angle of environment protection, reduce the discharging that energy consumption also can reduce greenhouse gases such as carbonic acid gas and other pollutents simultaneously.The double requirements of economic benefit and environment protection is impelled people to make a great effort and is developed power-saving technology and energy-saving material.
The invention provides a kind of silicon dioxide silica aerogel composite material; it is present best heat insulation and lagging material; can effectively reduce energy in transmission and utilize loss in the process, correspondingly improve the utilization ratio of the energy, thereby satisfy the double requirements of Economic development and environment protection.
Aerogel is to light weight, porous, and very big surface-area has the common name of nano level aperture material.Can be divided into organic and inorganic aerogels two large classes by its composition.The former comprises carbon aerogels and other Polymer Gas gel, and the latter comprises silicon-dioxide, aluminum oxide and other oxide silica aerogels.Their preparation method is familiar with by this area professional person.Low-density aerogel often is considered to good heat insulation and lagging material, and wherein aerosil is best at present, also is the heat insulation and lagging material of most study.
The very low 0.03-0.38g/cc of the density of aerogel has higher specific surface area, up to 1000m
2/ g, it also has the porosity above 95% in addition, and nano level has been full of gas in the aperture.These constructional features are specially adapted to heat insulation and insulation; Low density can reduce the power loss that conduction brings with the micropore that is full of air, and crooked nano level aperture can minimize convection current, adds suitable infrared absorbing agents such as carbon black and can effectively reduce radiation.Although aerogel has the performance of above-mentioned excellence, the low density of itself and high porosity but cause the physical strength of aerogel very low, be easy to fragmentation, thereby limited its range of application among small scale experiments and fundamental research, as think to utilize on a large scale aerogel as heat insulation and lagging material, it is easy to broken mechanical property and must be improved.
Generally accepted and fragility that very effective method is improved material can be: fiber reinforcement for one.By selecting suitable filamentary material, under the prerequisite of the excellent properties that does not affect aerogel material itself, improve its fragile mechanical property.This fibre-reinforced material is exactly new matrix material.
Summary of the invention
The object of the present invention is to provide a kind of be applicable to low, in and hot conditions under heat insulation/insulation purposes the Novel air gel complex material.
Obtain aerogel composite by fibre-reinforced method, and improve one or more in the following performance: the tensile strength of X-Y direction, Young's modulus, modulus of compression, modulus in flexure, the shrinking percentage of aerogel X-Y plane under the high temperature has kept the heat-proof quality of aerogel excellence simultaneously.Fiber among the present invention comprises two portions: the textile fibres grid of non-woven fibre and X-Y plane.This and former invention are distinguished very large.This fiber can provide three-dimensional to aerogel to be strengthened, and non-woven fibre mainly provides the machinery of Z direction to strengthen, and the fiber mesh of X-Y plane has improved the intensity of X-Y direction.
The employed material of non-woven fibre among the present invention comprises organic materials such as polyester and inorganic materials such as glass fibre and silica fiber, the employed material of textile fibres grid can be identical with non-woven fibre, also can select high temperature material such as carbon fiber, aluminum silicate fiber, basalt fibre improves the use temperature scope of matrix material, also can select natural fiber such as bamboo fibers, and cotton fibre and silky fibre are in order to environmental protection, can according to final environment for use, select different combinations.The textile fibres grid can have different geometrical shapies, can be trilateral, tetragon, rectangle, square, rhombus, pentagon, hexagon, circle and their combination.The size of fiber mesh, the length of side or diameter should be less than 3 centimetres, preferably less than 2 centimetres, particularly preferably less than 1 centimetre.
Textile fibres grid among the present invention and the relative position of non-woven fibre are very flexible, and fiber mesh can form bag-shaped, and non-woven fibre is wrapped in wherein; Fiber mesh can be embedded among the non-woven fibre, utilizes method that acupuncture or static transplants that non-woven fibre is placed among the fiber mesh, and these class methods are familiar with by this area personnel that are transferred to civilian work.The quantity of textile fibres grid also can control arbitrarily in addition, and sizing grid and quantity all are the actual parameters that changes the silicon dioxide silica aerogel composite material mechanical property.Under hot conditions, the aerogel structure has the trend of contraction, and original cavernous structure can cave in, and porosity reduces, and specific surface area reduces, thereby loses the performance of insulation.Aerogel composite among the present invention, owing to having the X-Y plane grid structure, the stress that produces during contraction can be absorbed by Gitterfasern well, effectively prevents the generation of this phenomenon.This phenomenon and enhancing concrete are closely similar, and the existence of reinforcing steel bar has improved the lower tensile strength of concrete itself greatly, thereby the performance of whole reinforced concrete soil composite material is improved.
The present invention also provides a kind of preparation method of aerogel composite, and take aerosil as example: with silicon precursor such as methyl silicate and ethanol, water, hydrolyst mix rear hydrolysis by a certain percentage, and the chemical equation of hydrolysis reaction is listed in figure below.Represent with different equations with polycondensation although be hydrolyzed, the two carries out in fact simultaneously.Then drip gel catalyst such as ammoniacal liquor, mentioned solution poured in the mould that is placed with fortifying fibre into one and flood fiber, the demoulding behind the gel was worn out 1-3 days in the ethanolic soln of hexamethyl phenodiazine silane, and gel obtains silicon dioxide silica aerogel composite material behind supercritical fluid drying.
The chemical equation of hydrolysis reaction
Fortifying fibre among the present invention is very very thin, and its diameter is less than 5 millimeters, and preferred diameter particularly preferably less than 1 millimeter, makes the aerogel composite that obtains very soft less than 3 millimeters, thereby has than pure aerogel range of application widely.
Can express more significantly in characteristics of the present invention and the advantage legend below.It relates to aerogel composite and preparation process thereof.The aerogel composite that obtains is very submissive, can be used for the insulation of different shape container and pipeline.By selecting suitable prescription and fiber, can obtain under the cold condition as refrigeration and freezer, liquified natural gas carrier (LNGC) only and the heat-preserving complex material of storage facilities, the heat-preserving complex material that also can prepare moderate temperature conditions such as steam-pipe and reactor, can also prepare kiln under the hot environment, photovoltaic stove heat-preserving complex material.Its preparation process: aerogel solution poured in the mould that contains fortifying fibre obtain gel, after the demoulding and the burin-in process, obtain submissive aerogel composite through supercritical fluid drying.
Description of drawings
Fig. 1, the outward appearance of demonstration aerogel composite, the textile fibres of 10-X direction; The textile fibres of 20-Y direction;
Fig. 2, the sectional view of demonstration aerogel composite; Grid structure is the X-Y fiber mesh, and the fiber of the 30th, Z direction is through whole silicon dioxide silica aerogel composite material.
Fig. 3, the preparation process of demonstration aerogel composite.
Embodiment
Following example further describes feature of the present invention, but not is confined to this.
Embodiment 1
Aerosil, silicon precursor are methyl silicate (TMOS), and fiber is: the polyester non-woven fibre that is embedded with one deck polyester textile fiber grid.
With 20ml methyl silicate (TMOS), 10ml water, 45ml methyl alcohol at room temperature mixes 3 hours, make the methyl silicate hydrolysis, methanol solution (5% volume) 10ml. that then drips ammoniacal liquor (the 29wt% aqueous solution) adds said mixture in the mould that is placed with fortifying fibre to form gel.In the ethanolic soln (8% volume) of hexamethyldisilazane (HMDZ), wore out 1-3 days after the demoulding, obtain silicon dioxide silica aerogel composite material through supercritical fluid drying.The aerosil density that obtains is 0.13g/cc, and thermal conductivity is 14mW/m.K.Recording coefficient of elasticity with Instron mechanical property survey meter is 4.2mPa.
Embodiment 2
Aerosil, silicon precursor are methyl silicate (TMOS), and fortifying fibre is the polyester non-woven fibre that is embedded with the silica fiber grid.All the other operations are with embodiment 1, and the silicon dioxide silica aerogel composite material density that obtains is 0.15g/cc, and thermal conductivity is 20mw/mk, and recording coefficient of elasticity with Instron mechanical property survey meter is 5.8mPa.
Embodiment 3
Aerosil, silicon precursor are tetraethoxy (TEOS), are that the glass fibre of 0.5 centimetre of square cotton fiber mesh bag strengthens aerogel with placing the length of side.
With 50g tetraethoxy (TEOS), water, ethanol, 0.1M hydrochloric acid was by weight 1: 0.35: 0.9: 8x10
3Mix and be placed on 70 ℃ of water-baths, be hydrolyzed 2 hours, then drip the ethanolic soln (5% volume) of ammoniacal liquor, (tetraethoxy and ammoniacal liquor mol ratio are 1: 0.0015). mentioned solution poured in the mould that is placed with fortifying fibre to form gel. after the demoulding in the ethanolic soln (6% volume) of hexamethyldisilazane (HMDZ) burin-in process two days, obtaining silicon dioxide silica aerogel composite material through supercritical fluid extraction. the gained sample rate is 0.18g/cc, and thermal conductivity is that to record coefficient of elasticity with Instron mechanical property survey meter be 6.4mPa to 11mw/mk..
Embodiment 4
Lanthanum trioxide aerogel, fortifying fibre are the glass fibre that is embedded with the basalt fibre grid.
Weighing is with 6 crystal water, and molecular weight is 353.5 g/mols lanthanum trichloride 13.3 grams, and it is dissolved in 100 milliliters of straight alcohol solution, then takes by weighing 32.4 gram epichlorohydrins, slowly adds in the above-mentioned mixed solution under the agitation condition not stopping.All the other operations are with embodiment 3.Gained lanthanum trioxide aerogel composite density is 0.19g/cc, and thermal conductivity is that 16mw/mk. can anti-750 ℃ of high temperature.The gained sample rate is 0.15g/cc, and thermal conductivity is that to record coefficient of elasticity with Instron mechanical property survey meter be 7.2mPa to 18mw/mk..
Embodiment 5
Alumina aerogels, fortifying fibre are the glass fibre that contains the pure aluminium silicate grid.
Weighing aluminum chloride (6 crystal water) 15 grams, molecular weight is every mole of 241.5 gram, and it is dissolved in 100 milliliters of aqueous ethanolic solutions, and (then the weight ratio of ethanol and water 50: 50 takes by weighing 45 gram propylene oxide, slowly add in the above-mentioned mixed solution under the agitation condition not stopping.All the other operations are with embodiment 3.Gained alumina aerogels composite density is 0.19g/cc, and thermal conductivity is that 16mw/mk. can anti-750 ℃ of high temperature.Recording coefficient of elasticity with Instron mechanical property survey meter is 6.0mPa.
Claims (12)
1. an aerogel composite is characterized in that: be composited by aerogel and fortifying fibre.
2. aerogel composite according to claim 1, it is characterized in that: described aerogel is selected from the one or more kinds of mixtures in carbon aerogels, aerosil, alumina aerogels, transition metal oxide silica aerogel, the lanthanide oxide aerogel.
3. aerogel composite according to claim 1, it is characterized in that: described fortifying fibre is interwoven by two portions: a part is the non-woven fibre of Z direction; Another part is the textile fibres grid on the X-Y plane; Described Z direction is the direction perpendicular to X-Y plane.
4. aerogel composite according to claim 3 is characterized in that: described non-woven fibre is selected from one or more the mixture in polyester, polypropylene, polyethylene, glass fibre, quartz, nylon or the polyacrylonitrile fibre.
5. aerogel composite according to claim 4, it is characterized in that: the density of described non-woven fibre is 0.01-0.48 g/cc.
6. aerogel composite according to claim 3 is characterized in that: the textile fibres grid on the described X-Y plane forms bag shaped structure non-woven fibre is wrapped in wherein, perhaps embeds among the non-woven fibre, perhaps their combination.
7. aerogel composite according to claim 6, it is characterized in that: the textile fibres grid of described X-Y plane is one or more.
8. aerogel composite according to claim 7 is characterized in that: the textile fibres grid material of described X-Y plane is selected one or more the mixture in polyester, polypropylene, polyethylene, nylon, polyacrylonitrile, polymethylmethacrylate, polyethyl acrylate, carbon fiber, glass fibre, silica fiber, bamboo fiber, cotton fibre, aluminum silicate fiber or the basalt fibre.
9. aerogel composite according to claim 8, it is characterized in that: the thermal conductivity coefficient of the textile fibres grid material of described X-Y plane should be less than 1w/m.k.
10. aerogel composite according to claim 8 is characterized in that: the textile fibres grid of described X-Y plane is a kind of in triangular mesh, quadrilateral mesh, rectangular node, square net, rhombic-shaped grid, pentagon grid, hexagonal mesh or the roundness mess or their combination.
11. aerogel composite according to claim 10, it is characterized in that: the length of side of described triangular mesh, quadrilateral mesh, rectangular node, square net, rhombic-shaped grid, pentagon grid, hexagonal mesh is all less than 1 centimetre, and the diameter of described roundness mess is less than 1 centimetre.
12. aerogel composite according to claim 11 is characterized in that: the Fibre diameter of the textile fibres grid of described X-Y plane is the 0.1-1000 micron.
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Cited By (21)
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| CN103526867A (en) * | 2013-10-11 | 2014-01-22 | 纳诺科技有限公司 | Silica nanometer insulation quilt flooring wood floor face insulation structure and construction technology of silica nanometer insulation quilt flooring wood floor face insulation structure |
| CN104070717A (en) * | 2014-06-24 | 2014-10-01 | 赤峰恒裕型钢有限公司 | Color-steel sandwich plate and preparation method thereof |
| CN105114761A (en) * | 2015-08-13 | 2015-12-02 | 苏州市君悦新材料科技股份有限公司 | Nanometer aerogel thermal insulation blanket |
| CN105219262A (en) * | 2015-09-16 | 2016-01-06 | 国网山东沂南县供电公司 | For the safety guard of live circuit |
| CN105415794A (en) * | 2015-12-21 | 2016-03-23 | 常熟市佳泰金属材料有限公司 | Glass fibre reinforced composition material |
| CN106450569A (en) * | 2016-10-18 | 2017-02-22 | 华霆（合肥）动力技术有限公司 | Power battery module and power battery pack safety device |
| CN106739383A (en) * | 2016-12-01 | 2017-05-31 | 湖北硅金凝节能减排科技有限公司 | A kind of preparation method of nano porous silicon dioxide aerogel cold insulation felt |
| CN107099692A (en) * | 2016-02-20 | 2017-08-29 | 金承黎 | A kind of fibre-reinforced aerogel-metallic composite and preparation method thereof |
| CN107142611A (en) * | 2017-05-24 | 2017-09-08 | 深圳市华创化工有限公司 | A kind of aeroge composite fibre Nomex and preparation method thereof |
| CN107324761A (en) * | 2017-08-15 | 2017-11-07 | 中国科学技术大学 | Three-dimensional carbon pipe fiber aeroge and preparation method thereof |
| CN107440180A (en) * | 2017-08-28 | 2017-12-08 | 尚同春 | A kind of work clothes for being used to produce protection |
| CN108602305A (en) * | 2015-11-03 | 2018-09-28 | 蓝移材料有限公司 | The aeroge and application thereof of inside enhancing |
| CN109081673A (en) * | 2018-08-14 | 2018-12-25 | 上海颐凝新材料科技有限公司 | A kind of fiber reinforcement alumina aerogels composite material and preparation method |
| CN109968685A (en) * | 2019-03-26 | 2019-07-05 | 浙江伟星新型建材股份有限公司 | A kind of composite insulating pipe preparation method |
| US11008432B2 (en) | 2015-10-30 | 2021-05-18 | Blueshift Materials, Inc. | Highly branched non-crosslinked aerogel, methods of making, and uses thereof |
| CN112919924A (en) * | 2021-04-12 | 2021-06-08 | 陈长国 | High-strength lightweight concrete and preparation method thereof |
| CN113478930A (en) * | 2021-07-22 | 2021-10-08 | 浙江圣润纳米科技有限公司 | High-pulling-resistance aerogel composite material and preparation method thereof |
| US11142622B2 (en) | 2017-12-05 | 2021-10-12 | Blueshift Materlals, Inc. | Thermally treated polyamic amide aerogel |
| US11427693B2 (en) | 2016-06-08 | 2022-08-30 | Blueshft Materials, Inc. | Polymer aerogel with improved mechanical and thermal properties |
| CN115302900A (en) * | 2022-08-09 | 2022-11-08 | 东风汽车集团股份有限公司 | Passenger compartment front wall sound insulation pad and preparation method thereof |
| CN116553908A (en) * | 2022-11-29 | 2023-08-08 | 冶赛尔 | SiO 2 Aerogel composite material, composite board containing aerogel composite material, and preparation and application of aerogel composite material |
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| CN103526867A (en) * | 2013-10-11 | 2014-01-22 | 纳诺科技有限公司 | Silica nanometer insulation quilt flooring wood floor face insulation structure and construction technology of silica nanometer insulation quilt flooring wood floor face insulation structure |
| CN103526867B (en) * | 2013-10-11 | 2016-01-20 | 纳诺科技有限公司 | Silica nanometer insulation quilt flooring Wood floor board insulation construction and construction technology |
| CN104070717A (en) * | 2014-06-24 | 2014-10-01 | 赤峰恒裕型钢有限公司 | Color-steel sandwich plate and preparation method thereof |
| CN105114761A (en) * | 2015-08-13 | 2015-12-02 | 苏州市君悦新材料科技股份有限公司 | Nanometer aerogel thermal insulation blanket |
| CN105219262A (en) * | 2015-09-16 | 2016-01-06 | 国网山东沂南县供电公司 | For the safety guard of live circuit |
| US11787916B2 (en) | 2015-10-30 | 2023-10-17 | Blueshift Materials, Inc. | Highly branched non-crosslinked aerogel, methods of making, and uses thereof |
| US11008432B2 (en) | 2015-10-30 | 2021-05-18 | Blueshift Materials, Inc. | Highly branched non-crosslinked aerogel, methods of making, and uses thereof |
| US11931999B2 (en) | 2015-11-03 | 2024-03-19 | Blueshift Materials, Inc. | Internally reinforced aerogel and uses thereof |
| CN108602305A (en) * | 2015-11-03 | 2018-09-28 | 蓝移材料有限公司 | The aeroge and application thereof of inside enhancing |
| US11192331B2 (en) | 2015-11-03 | 2021-12-07 | Blueshift Materials, Inc. | Internally reinforced aerogel and uses thereof |
| CN105415794A (en) * | 2015-12-21 | 2016-03-23 | 常熟市佳泰金属材料有限公司 | Glass fibre reinforced composition material |
| CN107099692A (en) * | 2016-02-20 | 2017-08-29 | 金承黎 | A kind of fibre-reinforced aerogel-metallic composite and preparation method thereof |
| US11427693B2 (en) | 2016-06-08 | 2022-08-30 | Blueshft Materials, Inc. | Polymer aerogel with improved mechanical and thermal properties |
| CN106450569A (en) * | 2016-10-18 | 2017-02-22 | 华霆（合肥）动力技术有限公司 | Power battery module and power battery pack safety device |
| CN106739383A (en) * | 2016-12-01 | 2017-05-31 | 湖北硅金凝节能减排科技有限公司 | A kind of preparation method of nano porous silicon dioxide aerogel cold insulation felt |
| CN107142611A (en) * | 2017-05-24 | 2017-09-08 | 深圳市华创化工有限公司 | A kind of aeroge composite fibre Nomex and preparation method thereof |
| CN107324761A (en) * | 2017-08-15 | 2017-11-07 | 中国科学技术大学 | Three-dimensional carbon pipe fiber aeroge and preparation method thereof |
| CN107324761B (en) * | 2017-08-15 | 2020-03-31 | 中国科学技术大学 | Three-dimensional carbon tube fiber aerogel and preparation method thereof |
| CN107440180A (en) * | 2017-08-28 | 2017-12-08 | 尚同春 | A kind of work clothes for being used to produce protection |
| US11142622B2 (en) | 2017-12-05 | 2021-10-12 | Blueshift Materlals, Inc. | Thermally treated polyamic amide aerogel |
| US11873379B2 (en) | 2017-12-05 | 2024-01-16 | Blueshift Materials, Inc. | Thermally treated polyamic amide aerogel |
| CN109081673B (en) * | 2018-08-14 | 2021-04-09 | 上海康达新能源材料有限公司 | Fiber-reinforced alumina aerogel composite material and preparation method thereof |
| CN109081673A (en) * | 2018-08-14 | 2018-12-25 | 上海颐凝新材料科技有限公司 | A kind of fiber reinforcement alumina aerogels composite material and preparation method |
| CN109968685A (en) * | 2019-03-26 | 2019-07-05 | 浙江伟星新型建材股份有限公司 | A kind of composite insulating pipe preparation method |
| CN112919924A (en) * | 2021-04-12 | 2021-06-08 | 陈长国 | High-strength lightweight concrete and preparation method thereof |
| CN112919924B (en) * | 2021-04-12 | 2022-12-16 | 毕节市通发电力电杆有限公司 | High-strength lightweight concrete and preparation method thereof |
| CN113478930A (en) * | 2021-07-22 | 2021-10-08 | 浙江圣润纳米科技有限公司 | High-pulling-resistance aerogel composite material and preparation method thereof |
| CN115302900A (en) * | 2022-08-09 | 2022-11-08 | 东风汽车集团股份有限公司 | Passenger compartment front wall sound insulation pad and preparation method thereof |
| CN116553908A (en) * | 2022-11-29 | 2023-08-08 | 冶赛尔 | SiO 2 Aerogel composite material, composite board containing aerogel composite material, and preparation and application of aerogel composite material |
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Addressee: Liu Fengwen Document name: Notification of Passing Examination on Formalities |
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| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| DD01 | Delivery of document by public notice |
Addressee: Liu Fengwen Document name: the First Notification of an Office Action |
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| DD01 | Delivery of document by public notice |
Addressee: Liu Fengwen Document name: Notification of Passing Examination on Formalities |
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| DD01 | Delivery of document by public notice |
Addressee: Liu Fengwen Document name: Notification of an Office Action |
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| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20130925 |