CN1309770C - High volume fraction carbon nanotube array - resin base composite materials and method for preparing same - Google Patents
High volume fraction carbon nanotube array - resin base composite materials and method for preparing same Download PDFInfo
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- CN1309770C CN1309770C CNB2004100380793A CN200410038079A CN1309770C CN 1309770 C CN1309770 C CN 1309770C CN B2004100380793 A CNB2004100380793 A CN B2004100380793A CN 200410038079 A CN200410038079 A CN 200410038079A CN 1309770 C CN1309770 C CN 1309770C
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Abstract
The present invention relates to a high volume fraction, axial orientation, penetrating continuity and high orthogonal and ordered arrangement carbon nanometer tube array-resin base composite material with a nanometer dimension and a preparation method thereof. A continuous state felt body, especially an orientation state carbon nanometer tube array felt body is used as basic material. A liquid state infiltration forming composite method of macromolecular resin is used. The resin is directly infiltrated and filled in the continuous state orientation arrangement carbon nanometer tube array felt body, and solid carbon nanometer tube-resin base composite material is obtained through solidification. The present invention has the advantages and the characteristics of a common prefabricated body, a liquid resin moulding technological technique and a composite material product. The composite method does not basically affect and change the structure, the state and the physical property of the carbon nanometer tube array felt body, but the original flexible array felt body is fixed to form solid material, even rigid material. The basic physical property is in orthogonal anisotropy. The material preparation technique has the advantages of low cost, low energy consumption, simple operation and easy control.
Description
Technical field: the present invention relates to a kind of nanoscale high volume fraction carbon nano-pipe felt body-polymer matrix composites, particularly axial orientation, connect continuously, the carbon nano pipe array-polymer matrix composites of highly orthogonal ordered arrangement and their preparation method.
Background technology: carbon nanotube has very unique mechanical, electricity and thermal property, and its axial property obviously is different from it radially.For example, prove according to Theoretical Calculation and microscope experiment, single-root carbon nano-tube axially has high strength and stiffness (Young's modulus can reach 1TPa) and thermal conductivity (the highest in the present known material), and its electroconductibility is also with the different metallicity or the semiconductives of showing as of caliber and structure.Therefore, people wish to utilize the excellent properties of carbon nanotube to prepare low density, high performance matrix material always, the matrix material of polymeric matrix particularly, and expect that this matrix material has special mechanics, electricity, calorifics and friction, polishing machine etc.
At present, the method for preparing carbon nano tube compound material with carbon nanometer tube material (it normally reunite attitude or continuous state) by conventional meanses such as mechanical stirring, mechanical vibration or shear-mixed, the macromolecule matrix that disperses feed liquor attitude or melt, allow macromolecule matrix solidify then or solidify, obtain the matrix material of filled-type.When adopting this method to prepare carbon nano tube compound material, the carbon nanotube of low-dimensional can be reunited in the high molecular polymer matrix usually once more, causes non-uniform Distribution, makes performance of composites well below its desired value.If content of carbon nanotubes is higher, also can cause the viscosity of macromolecule resin to rise, make bubble wherein be difficult to overflow, cause the porosity of matrix material higher.In addition, carbon nanotube is stochastic distribution in the high molecular polymer matrix, can not give full play to and utilize its axial performance.
Summary of the invention: the purpose of this invention is to provide a kind of high-performance, porosity low, can give full play to and utilize high volume fraction carbon nano-pipe array-polymer matrix composites of its axial property, nanoscale and preparation method thereof.
Technical solution of the present invention is,
The carbon nano pipe array felt body of carbon nanotube felt body, particularly the continuously-directional attitude of employing continuous state is as precast body.The feature of precast body felt is a continuity, comprises carbon nano pipe array orderly, that any form aligns (being the thickness direction that every carbon nanotube all runs through whole felt body in theory), and they present certain state of aggregation.In the felt body, have certain clearance between the every carbon nanotube, the surface has open-celled structure.From the viewpoint of precast body, the carbon nanotube felt body is exactly the bulk material with connected holes in fact.The present invention is not particularly limited degree of orientation, porosity (or tap density), the carbon nanotube self-characteristic (as single wall, Duo Bi) of felt body and the synthetic method for preparing this felt body etc.Generally speaking, the thickness conference of felt body is more practical, the preparation manipulation of also being more convenient for.Generally should be more than 3mm.
Flood above-mentioned carbon nanotube felt body, particularly carbon nano pipe array felt body with liquid macroimolecule, the preparation matrix material.During preparation,, the carbon nanotube felt body that aligns as precast body, is put into mould according to the macromolecule resin liquid condition shaping technology of routine; Thermosetting resin presoma or thermoplastic resin are injected mould, thermosetting resin is a small molecules, and the thermosetting resin presoma that viscosity is low, thermoplastic resin are lower molecular weight, low viscous thermoplastic resin, make it directly penetrate into the carbon nanotube felt body, and fully soak into.Then, put into the interstitial gas of vacuum chamber eliminating under field conditions (factors) or with mould; At last, again mould is put into baking oven, do not have and press or the low pressure curing type moulding.
The present invention has abandoned the technological line of traditional filled-type matrix material, do not need carbon nanotube felt body raw material is passed through mechanical stirring, conventional means such as mechanical vibration or shear-mixed disperses, be mixed into the macromolecule matrix of liquid state or melt then, but with ready-made, continuous state or directed attitude (as axial orientation, connect continuously, the carbon nano pipe array of highly orthogonal ordered arrangement) the felt body is directly as basis-in fact be exactly " precast body ", adopt the complex method of the liquid infiltration of macromolecule resin moulding, resin directly permeated to fill enter among ready-formed carbon nanotube felt body or the array, through solidifying, obtain carbon nanotube-polymer matrix composites.
The ingenious part of this inventive method is that it has avoided carbon nanotube felt body raw material with ready-made continuous state and be distributed to traditional route in the middle of the resin, thereby avoided because the problems of disperseing to be brought, can realize the uniform distribution of carbon nanotube in resin matrix easily, align, run through the connected sum high-volume fractional, this point is especially suitable to the carbon nano pipe array of continuously-directional attitude or ordered state, because it has intactly kept the textural property of carbon nano pipe array self.The essence of this inventive method is replaced as " macromolecule resin phase " with " gas phase " in the carbon nanotube felt body, and does not change the textural property of carbon nanotube felt body self especially.Obviously, traditional dispersion route has changed the textural property of this carbon nanotube felt body exactly.
The macromolecular material that the present invention need adopt must have a liquid state, low viscous moulding process window in a relatively low temperature and pressure scope, for example mold temperature is not higher than 200 ℃, and moulding viscosity is not more than 500 centipoises.Therefore, thermosetting resin is proper material, comprises Resins, epoxy, bimaleimide resin etc., especially for the resin material of liquid state molded (RTM).Meeting thermoplastic macromolecule material above-mentioned condition, can liquid condition shaping also can use as cast nylon and macromolecular material that can in-situ polymerization such as common nylon etc.Say that generally the dipping and the condition of forming and hardening all should compare gentleness, as forming pressure, mold temperature, flow etc.,, more can not cause damage carbon nanotube itself so that assurance does not influence the state of aggregation of carbon nano pipe array felt body in matrix material.
Generally speaking, the thickness of composite products equals the thickness of carbon nano pipe array felt body, its area is on deciding the requirement of matrix material volume integral number, but in principle less than the area of carbon nano pipe array felt body, its shape depends primarily on the shape of array felt body, but can suitably adjust by the shape that changes mould.
The present invention has advantage and the characteristics that general preform, liquid molding resin Technology and composite products thereof are had, and in conjunction with advantage and characteristics that oriented and ordered carbon nano pipe array preform may have, the present invention also has following characteristics:
1, the structure of carbon nano pipe array felt body, state, rerum natura etc. are exactly the basic structure and the rerum natura of matrix material in principle, because do not influence, more do not change the structure or the rerum natura of carbon nano pipe array felt body substantially by complex method of the present invention, but but original flexible array felt body is fixedly become solid material, or even rigid body material.Simultaneously, can make original array felt body densification more, its compactness extent can be regulated, and causes the volume fraction of matrix material to regulate.The ability of this matrix material withstand temp and pressure depends on macromolecule resin material, and it is usually less than the ability of withstand temp of carbon nano-tube material own and pressure.
2, because the orthogonal directed ordered state of carbon nano pipe array, make the performance of composites orthotropy, for example orthotropic specific conductivity, thermal conductivity, friction and wear behavior etc. also comprise modulus, intensity, tension set etc., and its surface hardness also presents orthotropy.
Material preparation technology low cost itself, less energy-consumption, easy and simple to handle, control are easily.
Embodiment:
Example one:
The epoxy-resin systems that this experiment is adopted is for being suitable for the resin system of resin transfer molding (RTM) moulding process, and its main component is as follows:
| Title | Consumption (part) |
| 830 Resins, epoxy | 50 |
| Resorcinol shrink acid anhydride grease Resins, epoxy | 50 |
| Methyl six hydracid anhydride curing agents | 100 |
1, adopt the felt body of the carbon nano pipe array that aligns as precast body, the felt body of the carbon nanotube that aligns is put into mould as precast body, pour mould into after the liquid resin that will go up table again mixes, make its felt body that penetrates into carbon nano pipe array, and fully soak into; Then, mould is inserted vacuum drying oven, under vacuum condition, get rid of about 1 hour of gas, realize mold filling.
2, keep vacuum, baking oven is warming up to 40～50 ℃, by adding the chemical curing reaction of resin Composition in the thermal initiation mould, specifically curing system is: 180 ℃/4h+120 ℃/12h.
3, after curing reaction finishes, the furnace cooling mould, goods are taken out in die sinking, obtain matrix material.
The carbon nanotube massfraction 18wt% of the matrix material of making, its basic friction and wear behavior obviously is better than the epoxy resin-base material, its side surface frictional coefficient approximates 1/3 of epoxy resin-base material, and wear rate approximates 1/10 of epoxy resin-base material.
Example two:
According to the prescription and the processing step 1 of example one, after the pouring liquid resin,, implement 2 and 3 of above-mentioned steps then to unreacted composite system side direction pressurization in the mould.Like this, just can be according to the relation of pressure and liquid resin extrusion capacity, the massfraction of carbon nanotube in the control solid composite material, thus regulate performance of composites.
The carbon nanotube massfraction 30wt% of the matrix material of making, its basic friction and wear behavior further improves.Correspondingly, the conduction property of matrix material (anisotropy) also is improved.
This way of regulating the matrix material massfraction is applicable to all resin systems.
Example three:
The resin system that this experiment is adopted is bismaleimides (BMI) resin that is suitable for the RTM moulding process, its main component such as following table:
| Title | Consumption (part) |
| N, N '-4,4 ' diphenyl methane dimaleimide (BMI) | 55～60 |
| The allyl group dihydroxyphenyl propane | 30～35 |
| The chavicol thinner | 5～10 |
1, with after above each component pre-mixing, according to the method for example one, implement infiltration, degasification, curing molding, obtain matrix material.Condition of cure wherein is: with the temperature rise rate of 1.5 degrees centigrade of per minutes (1.5 ℃/min), under normal pressure, be warmed up to 130 ℃ from room temperature, be incubated 1 hour, be warmed up to 190 ℃ with same speed from 130 ℃ again, be incubated 3 hours again; At last, with the cooling of the rate of temperature fall of 2 ℃ of about per minutes, but it is constant to keep in touch pressure in temperature-fall period, until cool to room temperature, thereby finishes whole solidification processs.
2,, can regulate the massfraction of carbon nanotube in the matrix material, thereby regulate performance of composites according to example two.
Because the use temperature upper limit of bismaleimides (BMI) resin is about about 200 ℃, so the matrix material that obtains can be used for the temperature higher than the carbon nano tube compound material of epoxy resin-matrix.The use temperature of this matrix material can reach about 230 ℃, this explanation, and the use temperature of carbon nano tube compound material depends on the heat resistance of resin system.
Example four:
The resin material that this experiment is adopted is a nylon.Hexanolactam is placed vessel in heating to 110 degree, after treating to fuse fully, add the NaOH of 1.4/1000ths weight ratios, give in the time of inflated with nitrogen to stir, about 30 minutes of reaction dehydration, temperature is controlled at 110～120 ℃, and its moisture content is reduced to about 0.15/1000th.
And then add 5.5/1000ths N-ethanoyl beta-lactam, after stirring, water rapidly and cast from the mould that is placed with carbon nano pipe array felt body.Die temperature is 160 ℃, keeps 20～30 minutes, can finish polymerization, obtains the carbon nano pipe array felt composite material of nylon based.
The carbon nano pipe array massfraction of this matrix material also can be regulated according to example two.
Claims (4)
1. high volume fraction carbon nano-pipe felt body-polymer matrix composites, it is characterized in that, the carbon nano pipe array felt body that adopts the continuously-directional attitude is as precast body, array felt body is successional, align in order,, have the gap between the every carbon nanotube, the surface has open-celled structure, and the thickness of felt body is 3mm.
2. the preparation method of high volume fraction carbon nano-pipe felt body-polymer matrix composites, it is characterized in that, the carbon nanotube felt body raw material that adopts continuous state is as precast body, this precast body is put into mould, thermosetting resin presoma or thermoplastic resin are injected mould, make it directly penetrate into the carbon nanotube felt body, and fully soak into; Then, put into vacuum chamber under field conditions (factors) or with mould, get rid of interstitial gas; At last, again mould is put into baking oven, curing molding.
3. the preparation method of high volume fraction carbon nano-pipe felt body-polymer matrix composites according to claim 2, it is characterized in that, but employed resin is the resin material of Resins, epoxy, bimaleimide resin or nylon resin liquid condition shaping or moulded by casting.
4. the preparation method of high volume fraction carbon nano-pipe felt body-polymer matrix composites according to claim 2, it is characterized in that the carbon nanotube felt body raw material that aligns as the continuous state of the precast body of precast body can also be the carbon nano pipe array felt body raw material that continuous state aligns.
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| CN101868059A (en) * | 2009-04-20 | 2010-10-20 | 清华大学 | Three-dimensional heat source |
| CN101868070A (en) * | 2009-04-20 | 2010-10-20 | 清华大学 | Line heat source |
| US8410676B2 (en) | 2007-09-28 | 2013-04-02 | Beijing Funate Innovation Technology Co., Ltd. | Sheet-shaped heat and light source, method for making the same and method for heating object adopting the same |
| US8450930B2 (en) | 2007-10-10 | 2013-05-28 | Tsinghua University | Sheet-shaped heat and light source |
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| CN101148245B (en) * | 2006-09-22 | 2011-08-24 | 清华大学 | Nanometer level microporous mould |
| CN101148246B (en) * | 2006-09-22 | 2011-01-26 | 鸿富锦精密工业（深圳）有限公司 | Method for manufacturing nanometer level microporous mould |
| CN101462391B (en) | 2007-12-21 | 2013-04-24 | 清华大学 | Method for preparing carbon nano-tube composite material |
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| WO2009102630A1 (en) * | 2008-02-11 | 2009-08-20 | Memc Electronic Materials, Inc. | Carbon nanotube reinforced wiresaw beam used in wiresaw slicing of ingots into wafers |
| US8129001B2 (en) * | 2008-03-17 | 2012-03-06 | The Research Foundation Of State University Of New York | Composite thermal interface material system and method using nano-scale components |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225695A (en) * | 1996-05-15 | 1999-08-11 | 海珀里昂催化国际有限公司 | High surface area nanofibers |
| CN1349478A (en) * | 1999-04-16 | 2002-05-15 | 联邦科学和工业研究组织 | Multilayer carbon nanotube films |
| US6645628B2 (en) * | 2001-11-13 | 2003-11-11 | The United States Of America As Represented By The Secretary Of The Air Force | Carbon nanotube coated anode |
-
2004
- 2004-05-19 CN CNB2004100380793A patent/CN1309770C/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1225695A (en) * | 1996-05-15 | 1999-08-11 | 海珀里昂催化国际有限公司 | High surface area nanofibers |
| CN1349478A (en) * | 1999-04-16 | 2002-05-15 | 联邦科学和工业研究组织 | Multilayer carbon nanotube films |
| US6645628B2 (en) * | 2001-11-13 | 2003-11-11 | The United States Of America As Represented By The Secretary Of The Air Force | Carbon nanotube coated anode |
Non-Patent Citations (1)
| Title |
|---|
| 碳纳米管-聚合物复合材料的研究进展 沈广霞 庄燕燕 林昌健，化学进展，第16卷第1期 2004 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US8410676B2 (en) | 2007-09-28 | 2013-04-02 | Beijing Funate Innovation Technology Co., Ltd. | Sheet-shaped heat and light source, method for making the same and method for heating object adopting the same |
| US8450930B2 (en) | 2007-10-10 | 2013-05-28 | Tsinghua University | Sheet-shaped heat and light source |
| CN101868059A (en) * | 2009-04-20 | 2010-10-20 | 清华大学 | Three-dimensional heat source |
| CN101868070A (en) * | 2009-04-20 | 2010-10-20 | 清华大学 | Line heat source |
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| CN1699452A (en) | 2005-11-23 |
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Assignee: Guodian United Power Technology Co., Ltd. Assignor: Beijing Institute of Aeronautical Materials, China Aviation Industry No.1 Group Corp. Contract fulfillment period: 2008.12.5 to 2013.12.4 contract change Contract record no.: 2008990001382 Denomination of invention: High volume fraction carbon nanotube array - resin base composite materials and method for preparing same Granted publication date: 20070411 License type: Exclusive license Record date: 2008.12.5 |
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Free format text: EXCLUSIVE LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.12.5 TO 2013.12.4; CHANGE OF CONTRACT Name of requester: STATE ELECTRIC UNITED POWER TECHNOLOGY CO., LTD. Effective date: 20081205 |