CN1328309C - Conductive composite materials with positive temperature coefficient effect and process for making same - Google Patents
Conductive composite materials with positive temperature coefficient effect and process for making same Download PDFInfo
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- CN1328309C CN1328309C CNB2004100206072A CN200410020607A CN1328309C CN 1328309 C CN1328309 C CN 1328309C CN B2004100206072 A CNB2004100206072 A CN B2004100206072A CN 200410020607 A CN200410020607 A CN 200410020607A CN 1328309 C CN1328309 C CN 1328309C
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- 239000003575 carbonaceous material Substances 0.000 claims abstract description 39
- 229910021392 nanocarbon Inorganic materials 0.000 claims abstract description 38
- 239000000463 material Substances 0.000 claims abstract description 31
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 29
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 24
- 238000003756 stirring Methods 0.000 claims abstract description 8
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 claims abstract description 7
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 27
- 229910021393 carbon nanotube Inorganic materials 0.000 claims description 24
- 239000002041 carbon nanotube Substances 0.000 claims description 24
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002109 single walled nanotube Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
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- 238000002604 ultrasonography Methods 0.000 abstract 1
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- 239000011159 matrix material Substances 0.000 description 14
- 239000006229 carbon black Substances 0.000 description 9
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- JRPBQTZRNDNNOP-UHFFFAOYSA-N barium titanate Chemical compound [Ba+2].[Ba+2].[O-][Ti]([O-])([O-])[O-] JRPBQTZRNDNNOP-UHFFFAOYSA-N 0.000 description 2
- 229910002113 barium titanate Inorganic materials 0.000 description 2
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Abstract
一种具有正温度系数效应的导电复合材料，由下述方法制备而成：取高密度聚乙烯溶于二甲苯中，一维纳米碳材料其它助剂加入乙醇中，超声分散30min，在同时进行超声和搅拌的情况下，将聚乙烯溶液加入一维纳米碳材料的乙醇分散液中，继续搅拌一昼夜，用乙醇洗涤，过滤、干燥；在平板硫化机中模压成片后，再进行吸收剂量为80KGy的γ-射线辐照。本发明复合材料在聚合物结晶熔点或玻璃化转变温度附近，具有显著的正温度系数效应。由于一维纳米碳材料具有优良的导电性能、导热性能、化学稳定性和热稳定性，改善了聚合物正温度系数材料的加工性能和使用性能，在自限温加热器、过电流保护器、传感器等方面有广泛应用前景。A conductive composite material with a positive temperature coefficient effect is prepared by the following method: take high-density polyethylene and dissolve it in xylene, add other additives of one-dimensional nano-carbon materials into ethanol, and ultrasonically disperse for 30 minutes. In the case of ultrasound and stirring, add polyethylene solution into the ethanol dispersion of one-dimensional nano-carbon materials, continue stirring for a whole day and night, wash with ethanol, filter, and dry; 80KGy of gamma-ray irradiation. The composite material of the invention has a significant positive temperature coefficient effect near the polymer crystal melting point or glass transition temperature. Due to the excellent electrical conductivity, thermal conductivity, chemical stability and thermal stability of one-dimensional nano-carbon materials, the processing performance and performance of polymer positive temperature coefficient materials are improved, and they are used in self-limiting temperature heaters, overcurrent protectors, Sensors and other aspects have broad application prospects.
Description
Technical field:
The present invention relates to a kind of composition and technology of preparing of functional 1-dimention nano carbon material conducing composite material.Particularly a kind of composition and technology of preparing with 1-dimention nano carbon material/composite conducting polymer material of significant positive temperature coefficient effect.
Background technology:
(positive temperature coefficient, PTC) effect is meant the phenomenon that the resistivity of material raises and increases with temperature to positive temperature coefficient.Material (abbreviation ptc material) with PTC effect is widely used at aspects such as self-limiting heater temperature, overcurrent protective device, transmitters.Ptc material mainly contains ceramic base ptc material and polymer matrix PTC material.Mainly by constituting through adulterated barium titanate, the PTC transformation of barium titanate ceramics occurs near the crystalline curie transition temperature pottery ptc material.Polymer matrix PTC material is normally by polymkeric substance and carbon black, the charcoal fiber, and conductive filler material blend such as metal-powder form, and when temperature raise, near polymer crystallization fusing point or second-order transition temperature, the prominent of generating material resistivity got over, and presents the PTC effect.Compare with the ceramic base ptc material, ptc polymer has advantages such as preparation technology is simple, cost is low, and geomery is unrestricted, thereby obtains application more and more widely.At present ptc polymer mainly is to be conductive filler material with the carbon black, exists the shortcoming of short, poor stability of life-span, its reason, be on the one hand because carbon black is easy to agglomeration, make that sooty distributes in the polymkeric substance, in recycling process, change, cause the PTC strength degradation; Be because carbon black is easy to oxidation on the other hand, cause that the room temperature resistance of material increases gradually in the use.
The 1-dimention nano carbon material then is one of forward position research direction in the nano material, is subjected to the extensive concern and the attention of countries in the world owing to its structure uniqueness, excellent performance.The 1-dimention nano carbon material is meant the fibrous carbon material of diameter below 500 nanometers, comprises diameter at the CNT (carbon nano-tube) of 1-50nm and the diameter carbon nano fiber at 50-500nm, and wherein CNT (carbon nano-tube) is the newcomer of the early 1990s found carbon family.Have the hollow tubular structure that curls and form by graphite flake layer, can be divided into Single Walled Carbon Nanotube and multiple-wall carbon nanotube according to the carbon-coating number that constitutes the CNT (carbon nano-tube) tube wall.The 1-dimention nano carbon material not only has excellent mechanical property, also has excellent conductive capability, heat conductivility, chemical stability and thermostability simultaneously.These characteristics of 1-dimention nano carbon material make it aspect preparation high-performance ptc material, compare with other conductive filler material, have significant advantage.
Summary of the invention:
The object of the present invention is to provide a kind of conducing composite material with positive temperature coefficient effect and preparation method thereof, the conducing composite material that this kind has positive temperature coefficient effect has good materials processing performance and use properties.
The invention provides a kind of conducing composite material with positive temperature coefficient effect, constitute by conductive filler material and high density polyethylene(HDPE), described conductive filler material is the 1-dimention nano carbon material of diameter range at 1～500nm, i.e. Single Walled Carbon Nanotube, multiple-wall carbon nanotube, carbon nano fiber or its mixture; The weight content of 1-dimention nano carbon material is 0.1～50%, it is characterized in that described conducing composite material is prepared from by following method: get high density polyethylene(HDPE) and be dissolved in the dimethylbenzene, 1-dimention nano carbon material and other auxiliary agent add in the ethanol, ultra-sonic dispersion 30min, carry out at the same time polyethylene solution being added in the alcohol dispersion liquid of 1-dimention nano carbon material under the ultrasonic and condition of stirring, continue to stir diel, use washing with alcohol, filtration, drying; After the mold pressing in flakes, carrying out absorption dose again is the gamma-radiation irradiation of 80KGy in vulcanizing press.
The present invention has in the conducing composite material of positive temperature coefficient effect, and the optimized scope of 1-dimention nano carbon material is 1～15%.
The present invention has in the conducing composite material of positive temperature coefficient effect, and described 1-dimention nano carbon material can be handled through chemical modification.
The present invention has in the conducing composite material of positive temperature coefficient effect, and described 1-dimention nano carbon material can cooperate the formation conductive filler material with carbon black, charcoal fiber etc.
The present invention has in the conducing composite material of positive temperature coefficient effect, can also contain auxiliary agents such as oxidation inhibitor, linking agent, mineral filler in addition.
The used conductive filler material of the present invention can be a Single Walled Carbon Nanotube, also can be multiple-wall carbon nanotube, or carbon nano fiber.Can be independent use, also can be wherein two or more being used, or be used with other conductive filler materials such as carbon black, charcoal fiber etc.For improve 1-dimention nano carbon material dispersed in polymkeric substance and with the interfacial interaction of polymkeric substance, can its pulverize, processing such as oxidation, coating and organic modification of surface.
The weight content of 1-dimention nano carbon material is 0.1～50% among the present invention, and optimized scope is 1～15%.When selecting different polymeric matrixs, because the 1-dimention nano carbon material is different with the interaction energy of polymkeric substance, reach the seepage flow threshold value difference that begins to form conductive network in the polymkeric substance, the one-dimensional nano carbon material usage is with different.On the other hand, also can by changing the consumption of 1-dimention nano carbon material, regulate the room temperature resistivity of mixture according to the requirement of use properties.
The preparation method of matrix material can adopt direct blend among the present invention, also can adopt original position compound.Directly blend be meant polymkeric substance with powder, solution, emulsion, melt form directly with the blend of 1-dimention nano carbon material, original position is compound to be with 1-dimention nano carbon material homodisperse in polymer monomer, re-initiation monomer in-situ polymerization generation polymer.The former technology is simply easy to implement, and the latter more helps 1-dimention nano carbon material homodisperse.The dispersion state of control 1-dimention nano carbon material in polymeric matrix is key problem in technology of the present invention.
Matrix material can adopt chemical method or high-energy ray irradiation method to make polymeric matrix crosslinked among the present invention, with the further PTC stability of improving material.
1-dimention nano carbon material of the present invention/polymer positive-temperature-coefficient material mainly has the following advantages: (1) is because the 1-dimention nano carbon material has good electroconductibility and very high length-to-diameter ratio, adopt less one-dimensional nano carbon material usage just can reach the seepage flow threshold value, less to the mechanical property and the processing characteristics influence of material.And adopt the ptc polymer of carbon black as conductive filler material, because the sooty addition is bigger, the mechanical property and the processing characteristics of material caused bigger infringement.(2) the one-dimensional nano carbon material structure is stable, is difficult for oxidation in air, so 1-dimention nano carbon material/ptc polymer room temperature resistivity is more stable.(3) the 1-dimention nano carbon material is compared with carbon black and is difficult for agglomeration, makes the ptc material cyclical stability of preparation better, and negative temperature coefficient (NTC) effect is less.
Embodiment:
Be example with the high density polyethylene(HDPE) among the embodiment, but the polymeric matrix that the present invention was suitable for is not limited to high density polyethylene(HDPE) and polypropylene, the 1-dimention nano carbon material that is adopted is a multiple-wall carbon nanotube, but the conductive filler material that the present invention was suitable for is not limited to multiple-wall carbon nanotube.The PTC intensity of matrix material is used the resistivity-resistivity at temperature relation curve upward peak place and the ratio table of room temperature resistivity not among the embodiment.
Embodiment 1
Getting high density polyethylene(HDPE) 0.95g is dissolved in the dimethylbenzene, multiple-wall carbon nanotube 0.05g and an amount of other auxiliary agent add in the ethanol, ultra-sonic dispersion 30min, carry out at the same time under the ultrasonic and condition of stirring, polyethylene solution is added in the alcohol dispersion liquid of CNT (carbon nano-tube), continue to stir diel, use washing with alcohol, filtration, drying.After the mold pressing in flakes, carrying out absorption dose again is the gamma-radiation irradiation of 80KGy in vulcanizing press.The PTC intensity of the matrix material that obtains is 2.8 * 10
4
Comparative Examples 1
Method is identical with embodiment 1, and without gamma-radiation irradiation, the PTC intensity of matrix material is 1.1 * 10
4
Embodiment 2-4
Implementation method is identical with embodiment 1, changes the consumption of high density polyethylene(HDPE) and multiple-wall carbon nanotube, and the result is as shown in table 1.
Table 1
| Embodiment | High density polyethylene(HDPE) (g) | Multiple-wall carbon nanotube (g) | PTC intensity |
| 2 3 4 | 0.97 0.92 0.90 | 0.03 0.08 0.10 | 2.6×10 3 1.6×10 4 2.0×10 3 |
Embodiment 5
Multiple-wall carbon nanotube 5g adds in the ethanol, ultra-sonic dispersion 30min, adding 45g high density polyethylene(HDPE) powder and an amount of other auxiliary agent mix, remove by filter most of ethanol, under the loose condition (of surface) that CNT (carbon nano-tube) is soaked into by ethanol, grind with the high density polyethylene(HDPE) powder and to be dispersed to the raw material substantially dry, put into vacuum drying oven thoroughly dry by the fire in.Melt blending in Banbury mixer afterwards, blend mold pressing in vulcanizing press is in blocks, and carrying out absorption dose again is the gamma-radiation irradiation of 80KGy.The PTC intensity of matrix material is 4.9 * 10
6
Comparative Examples 2
Method is identical with embodiment 5, and with the graphitized carbon black replacement multiple-wall carbon nanotube of equivalent, matrix material does not have the PTC effect substantially.
Embodiment 6
Get high density polyethylene(HDPE) 37.5g, undressed multiple-wall carbon nanotube 12.5g reaches other auxiliary agent and adds together in the Banbury mixer, and in 150 ℃ of mixing 15min, blend 150 ℃ of mold pressings in vulcanizing press are in blocks, and its PTC intensity is 1.4 * 10
6
Embodiment 7
Implementation method is same as embodiment 6, and high density polyethylene(HDPE) and multiple-wall carbon nanotube are respectively 35g and 15g, and the PTC intensity of matrix material is 6.8 * 10
5
Embodiment 8
Implementation method is same as embodiment 6, and high density polyethylene(HDPE) and multiple-wall carbon nanotube are respectively 25g and 25g, and the PTC intensity of matrix material is 41.
Claims (3)
1. conducing composite material with positive temperature coefficient effect, constitute by conductive filler material and high density polyethylene(HDPE), described conductive filler material is the 1-dimention nano carbon material of diameter range at 1～500nm, i.e. Single Walled Carbon Nanotube, multiple-wall carbon nanotube, carbon nano fiber or its mixture; The weight content of 1-dimention nano carbon material is 0.1～50%, it is characterized in that described conducing composite material is prepared from by following method: get high density polyethylene(HDPE) and be dissolved in the dimethylbenzene, 1-dimention nano carbon material and other auxiliary agent add in the ethanol, ultra-sonic dispersion 30min, carry out at the same time polyethylene solution being added in the alcohol dispersion liquid of 1-dimention nano carbon material under the ultrasonic and condition of stirring, continue to stir diel, use washing with alcohol, filtration, drying; After the mold pressing in flakes, carrying out absorption dose again is the gamma-radiation irradiation of 80KGy in vulcanizing press.
2. according to the described conducing composite material with positive temperature coefficient effect of claim 1, it is characterized in that: the weight content of described 1-dimention nano carbon material is 1～15%.
3. according to claim 1 or 2 described conducing composite materials with positive temperature coefficient effect, it is characterized in that: described 1-dimention nano carbon material is handled through chemical modification.
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| CNB2004100206072A CN1328309C (en) | 2004-05-26 | 2004-05-26 | Conductive composite materials with positive temperature coefficient effect and process for making same |
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| CNB2004100206072A CN1328309C (en) | 2004-05-26 | 2004-05-26 | Conductive composite materials with positive temperature coefficient effect and process for making same |
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Cited By (1)
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| CN101348587B (en) * | 2008-09-01 | 2011-08-03 | 武汉理工大学 | Preparation method of ultra-high molecular weight polyethylene/graphite nanoplate composite material |
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| CN101271969B (en) * | 2007-03-23 | 2010-08-25 | 清华大学 | Carbon nanotube composite electrode material, its preparation method and electrode |
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| CN101714438B (en) * | 2008-09-30 | 2011-11-09 | 清华大学 | Thermistor |
| CN101734650B (en) * | 2009-12-23 | 2012-06-20 | 沈阳建筑大学 | Method for preparing graphene-carbon nano tube hybrid composite |
| CN102200481A (en) * | 2010-03-23 | 2011-09-28 | 北京派科森科技有限公司 | Carbon Fiber Laminate Composite material used for Fiber Bragg Grating high voltage sensor |
| CN101891929B (en) * | 2010-07-13 | 2012-10-10 | 浙江华源电热有限公司 | Carbon nano-tube and polyvinylidene fluoride-based organic PTC material |
| CN102153878A (en) * | 2011-03-02 | 2011-08-17 | 青岛威东科高分子材料有限公司 | Preparation method for conductive polymer sheathing material |
| CN102757587B (en) * | 2012-06-12 | 2014-02-05 | 四川大学 | Linear high-density polyethylene composite material and preparation method thereof |
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| CN104711696A (en) * | 2015-03-04 | 2015-06-17 | 江苏神鹤科技发展有限公司 | Heat-resisting antistatic UHMWPE (ultra high molecular weight polyethylene) fiber and preparation method thereof |
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