CN101440192B - Conductive / heat insulating composite material - Google Patents
Conductive / heat insulating composite material Download PDFInfo
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- CN101440192B CN101440192B CN2008101590744A CN200810159074A CN101440192B CN 101440192 B CN101440192 B CN 101440192B CN 2008101590744 A CN2008101590744 A CN 2008101590744A CN 200810159074 A CN200810159074 A CN 200810159074A CN 101440192 B CN101440192 B CN 101440192B
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Abstract
The invention belongs to the technical field of composite materials, relates to the technical field of fiber-reinforced resin based composite materials, and in particular relates to a composite material with conductive and heat-insulating functions. The conductive/heat-insulating composite material has volume resistivity which is not more than 10 ohm.cm, consists of thermosetting phenolic resin, carbon nanotubes, hollow fibers and surfactant, and is obtained after dispersion of the nanotubes, preparation of a glue solution, preimpregnation of the fibers and curing forming. The conductive/heat-insulating composite material has the advantages of low density, corrosion resistance, superior electrical conductivity, low thermal conductivity and so on, and is a functional material with superiorcomprehensive performance. The functional material not only can meet the use requirements of civilian goods but also can meet the requirements of weapon systems in the national defense fields of weapons, aviation, spaceflight, etc. on the service performance of the material in the severe work environment of high temperature, high overload and so on.
Description
One, technical field
The invention belongs to technical field of composite materials, relate to the fiber-reinforced resin matrix compound material technical field, particularly have the matrix material of conduction and heat insulating function.
Two, background technology
Matrix material is firm with height ratio, intensity is used widely, and the matrix material with conduction or electromagnet shield effect has also had certain development and the application of succeeing in recent years.Generally speaking, the conduction and heat insulation be a pair of contradiction, material also has good heat-conducting when having excellent conductive performance, the reduction of heat-proof quality is often followed in the raising of material conductivity, the conducing composite material material mainly comprises conductive fine powder filled resin base composite material and fiber reinforcement electroconductive resin based composites two classes, and the existing big quantity research report of metal or carbon dust filled resin base composite material also obtains to use.
CN200610050523 has introduced a kind of silver and has been used for nano wire filled composite materials of Electronic Packaging and preparation method thereof, with the polyacrylic ester is carrier, adopt mechanical stirring to prepare nano silver wire modified polyacrylate matrix material in conjunction with the method for ultrasonic dispersing, volume specific resistance reaches 10
-3～10
-5Ω .cm magnitude is not introduced thermal characteristics.
CN200510062318.3 has introduced a kind of preparation method of carbon nano-tube/poly vinylbenzene conductive nano composites, with polystyrene and multi-walled carbon nano-tubes is complex matrix, with the cholate is dispersion medium, with the organic solvent is dispersion agent, prepare carbon nano-tube/poly vinylbenzene conductive nano composites by solution method, volume specific resistance reaches 10
1Ω .cm, relatively poor based on the characteristic resistance toheat of polystyrene itself, do not introduce thermal characteristics.
In order to improve the heat-proof quality of material, generally be in material, to add a large amount of thermal insulating fillings, as cenosphere etc., but the too much adding of thermal insulating filling, greatly often reduce the mechanical property of material on the one hand, the conductivity to material also can produce remarkable influence simultaneously.
Three, summary of the invention
The present invention aims to provide a kind of fiber-reinforced resin matrix compound material with excellent conductive performance, has suitable heat-proof quality simultaneously.
The object of the present invention is achieved like this, employing has the resol of superior heat resistance performance as strengthening matrix, with tubular fibre as strongthener, prepare matrix material with carbon nanotube as conductive additive, when keeping suitable resistance toheat and lower density, realize the purpose of conduction, simultaneously heat-proof quality is not produced remarkably influenced.
Conduction/the heat-insulation composite material that the present invention relates to, volume specific resistance is not more than 10 Ω .cm, form and to comprise at least and obtain resol, tubular fibre, carbon nanotube and tensio-active agent that its quality group becomes by carbon nanotube dispersion, glue preparation, fiber preimpregnation, curing molding:
100 parts in resol
8～18 parts of carbon nanotubes
90～120 parts of tubular fibres
1～5 part in tensio-active agent
The preparation process of the conduction/heat-insulation composite material that the present invention relates to comprises:
(1) carbon nanotube disperses and the glue preparation: resol, carbon nanotube and tensio-active agent are mixed in proportion, mix and make mixture A;
(2) soak into evenly with mixture A in proportion, obtain prepreg B;
(3) according to the condition of cure of resol, hot-forming, the conduction/heat-insulation composite material that obtains the present invention relates to.
Conduction/the heat-insulation composite material that the present invention relates to, its quality is formed more preferably:
Resol 100 mass parts
Carbon nanotube 12～16 mass parts
Tubular fibre 90～120 mass parts
Tensio-active agent 1～5 mass parts
Conduction/the heat-insulation composite material that the present invention relates to, described resol are heat-reactive phenolic resin.
Conduction/the heat-insulation composite material that the present invention relates to, described heat-reactive phenolic resin are selected from a kind of or wherein several mixed system that can mate use in phenol-formaldehyde, cresols-formaldehyde, Resorcinol-formaldehyde, the dihydroxyphenyl propane-formaldehyde.
Conduction/the heat-insulation composite material that the present invention relates to, described tubular fibre can be a kind of in hollow glass fibre, the hollow silica fiber or their compound system.
Conduction/the heat-insulation composite material that the present invention relates to, described tubular fibre can be a kind of in fiber, cloth, the felt.
Conduction/the heat-insulation composite material that the present invention relates to, described carbon nanotube can be one or more the combinations in multi-walled carbon nano-tubes, Single Walled Carbon Nanotube, double-walled carbon nano-tube and the aligned carbon nanotube.
Conduction/the heat-insulation composite material that the present invention relates to, described tensio-active agent is general phenolic resin system tensio-active agent, includes but not limited to a kind of in Sodium dodecylbenzene sulfonate, Tweens (joining single vinegar as polyoxyethylene sorbitol), the emulsifying agent 0P class (polyoxyethylene nonylphenol ether) or the mixed surfactant system of being made up of several tensio-active agents.
The conduction that the present invention relates to/heat-insulation composite material resistivity is adjustable, has light weight, functional performance such as heat-resisting, corrosion-resistant, and preparation technology is simple.This conduction/heat-insulation composite material can satisfy the service requirements of civilian goods, also can satisfy weapons system requirement to the material use properties under harsh Working environments such as high temperature, high overload in national defence fields such as weapons, Aeronautics and Astronautics.
Four, embodiment
Below in conjunction with specific embodiment the technical scheme that invention relates to is described further, but not as the restriction to summary of the invention.
Embodiment one
With 8 parts of multi-walled carbon nano-tubes (MWNT, nanometer port, Shenzhen) the adding net content is 100 parts a S-157 heat-reactive phenolic resin (phenol-formaldehyde resin, five or three productions) and in the mixture system of 1 part of op-10, Ball milling 3 hours, soak into 90 parts of hollow glass fibres (Nanjing Glass Fibre Research and Design Institute) with the glue after disperseing, make prepreg.In 40MPa～45MPa, 10 minutes forming composite standard patterns of 160 ℃ of following curing, volume specific resistance is 9.5 Ω .cm, and thermal conductivity is 0.49W/m.K, and density is 1.53g/cm
3
Embodiment two
With 10 parts of multi-walled carbon nano-tubes (MWNT, nanometer port, Shenzhen) be that 100 parts phenol Cresol Formaldehyde Resin (Xinhua Resin Factory, Shanghai) and the mixed solution of 3 parts of DC-193 mix with net content, utilize ball mill that carbon nanotube was disperseed 3 hours, glue after disperseing is soaked into 120 parts of hollow glass fibres (Nanjing Glass Fibre Research and Design Institute), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its volume specific resistance are 5.2 Ω .cm, and thermal conductivity is 0.49W/m.K, and density is 1.59g/cm
3
Embodiment three
With 12 parts of multi-walled carbon nano-tubes (Tsing-Hua University's south wind) and net content is that the mixed solution of 100 parts of Resorcinol-formaldehyde resins and 5 parts of op-10 mixes, utilize ball mill that carbon nanotube was disperseed 3 hours, glue after disperseing is soaked into 50 parts of hollow silica fibers (Hubei FeiLiHua quartz Glass Co., Ltd) and 50 parts of hollow glass fibres (Nanjing Glass Fibre Research and Design Institute), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its volume specific resistance are 4.7 Ω .cm, and thermal conductivity is 0.49W/m.K, and density is 1.55g/cm
3
Embodiment four
With 8 parts of multi-walled carbon nano-tubes (MWNT, nanometer port, Shenzhen) and 6 parts of Single Walled Carbon Nanotube (SWNT, nanometer port, Shenzhen) be that 100 parts the S-157 heat-reactive phenolic resin and the mixed solution of 4 parts of Sodium dodecylbenzene sulfonatees mix with net content, utilize ball mill that carbon nanotube was disperseed 3 hours, glue after disperseing is soaked into 105 parts of hollow glass fibres (Nanjing Glass Fibre Research and Design Institute), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its volume specific resistance are 2.8 Ω .cm, and thermal conductivity is 0.57W/m.K, and density is 1.55g/cm
3
Embodiment five
With 8 parts of double-walled carbon nano-tube (DWNT, nanometer port, Shenzhen) be that 100 parts dihydroxyphenyl propane-formaldehyde resin and the mixed solution of 3 parts of DC-193 mix with net content, utilize ball mill that carbon nanotube was disperseed 3 hours, glue after disperseing is soaked into 115 parts of hollow silica fiber cloth (Hubei FeiLiHua quartz Glass Co., Ltd), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its volume specific resistance are 6.2 Ω .cm, and thermal conductivity is 0.52W/m.K, and density is 1.59g/cm
3
Embodiment six
With 16 parts of multi-walled carbon nano-tubes (Tsing-Hua University's south wind) and net content is that 100 parts SL-1068 resol (five or three production) and the mixed solution of 5 parts of DC-193 mixes, utilize ball mill that carbon nanotube was disperseed 3 hours, glue after disperseing is soaked into 95 parts of hollow silica fibers (Hubei FeiLiHua quartz Glass Co., Ltd), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its volume specific resistance are 2.1 Ω .cm, and thermal conductivity is 0.58W/m.K, and density is 1.54g/cm
3
Embodiment seven
With 12 parts of aligned carbon nanotube (ALIGNED-MWNT, nanometer port, Shenzhen) be 50 parts SL-1069 resol (five or three production), 50 parts S-157 heat-reactive phenolic resin (phenol-formaldehyde resin with net content, five or three productions) and the mixed solution of 4 parts of Sodium dodecylbenzene sulfonatees mix, utilize ball mill that carbon nanotube was disperseed 3 hours, glue after disperseing is soaked into 110 parts of hollow glass fibre felts (Nanjing Glass Fibre Research and Design Institute), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its volume specific resistance are 3.0 Ω .cm, and thermal conductivity is 0.57W/m.K, and density is 1.55g/cm
3
Embodiment eight
With 16 parts of multi-walled carbon nano-tubes (MWNT, nanometer port, Shenzhen) be that 100 parts SL-1068 resol (five or three production) and the mixed solution of 5 parts of DC-193 mixes with net content, utilize ball mill that carbon nanotube was disperseed 3 hours, glue after disperseing is soaked into 98 parts of hollow silica fiber felts (Hubei FeiLiHua quartz Glass Co., Ltd), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its volume specific resistance are 2.3 Ω .cm, and thermal conductivity is 0.53W/m.K, and density is 1.45g/cm
3
Embodiment nine
With 18 parts of multi-walled carbon nano-tubes (Tsing-Hua University's south wind) and net content is that 100 parts SL-1069 resol (five or three production) and the mixed solution of 5 parts of DC-193 mixes, utilize ball mill that carbon nanotube was disperseed 3 hours, glue after disperseing is soaked into 102 parts of hollow silica fiber cloth (Hubei FeiLiHua quartz Glass Co., Ltd), make prepreg.Utilize the thermocompressor curing molding, the matrix material that is prepared into, its volume specific resistance are 2.0 Ω .cm, and thermal conductivity is 0.56W/m.K, and density is 1.56g/cm
3
Claims (6)
1. conduction/heat-insulation composite material, volume specific resistance is not more than 10 Ω .cm, obtains by nanotube dispersion, glue preparation, fiber preimpregnation, curing molding, and its mass parts consists of:
Heat-reactive phenolic resin 100
Carbon nanotube 8～18
Tubular fibre 90～120
Tensio-active agent 1～5.
2. the described conduction/heat-insulation composite material of claim 1, its mass parts consists of:
Heat-reactive phenolic resin 100
Carbon nanotube 12～16
Tubular fibre 90～120
Tensio-active agent 1～5.
3. the described conduction/heat-insulation composite material of claim 1, described heat-reactive phenolic resin is selected from a kind of or wherein several mixed system that can mate use in P-F, cresols-formaldehyde, Resorcinol-formaldehyde, the dihydroxyphenyl propane-formaldehyde.
4. the described conduction/heat-insulation composite material of claim 1, described tubular fibre can be a kind of in hollow glass fibre, the hollow silica fiber or their compound system.
5. the described conduction/heat-insulation composite material of claim 1, described tubular fibre can be a kind of in fiber, cloth, the felt.
6. the described conduction/heat-insulation composite material of claim 1, described carbon nanotube can be a kind of or wherein several combination in multi-walled carbon nano-tubes, Single Walled Carbon Nanotube, double-walled carbon nano-tube and the aligned carbon nanotube.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101590744A CN101440192B (en) | 2008-11-25 | 2008-11-25 | Conductive / heat insulating composite material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008101590744A CN101440192B (en) | 2008-11-25 | 2008-11-25 | Conductive / heat insulating composite material |
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| Publication Number | Publication Date |
|---|---|
| CN101440192A CN101440192A (en) | 2009-05-27 |
| CN101440192B true CN101440192B (en) | 2010-10-13 |
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| CN2008101590744A Expired - Fee Related CN101440192B (en) | 2008-11-25 | 2008-11-25 | Conductive / heat insulating composite material |
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Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2664654A1 (en) * | 2011-01-12 | 2013-11-20 | Hodogaya Chemical Co., Ltd. | Thermosetting-resin-containing liquid having dispersed fine carbon fibers, and molded thermoset resin obtained therefrom |
| CN105061705A (en) * | 2015-08-28 | 2015-11-18 | 哈尔滨工业大学 | Simple and convenient resorcinol formaldehyde resin hollow composite material and preparing method of derivative thereof |
| CN109425812B (en) * | 2017-08-28 | 2021-03-12 | 创意电子股份有限公司 | Detection system of semiconductor packaging element and thermal barrier layer element thereof |
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