CN102477226B - High current resistant thermistor polymer composite material and preparation method thereof - Google Patents
High current resistant thermistor polymer composite material and preparation method thereof Download PDFInfo
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- CN102477226B CN102477226B CN201010558096.5A CN201010558096A CN102477226B CN 102477226 B CN102477226 B CN 102477226B CN 201010558096 A CN201010558096 A CN 201010558096A CN 102477226 B CN102477226 B CN 102477226B
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Abstract
The invention relates to a high current resistant thermistor polymer composite material and a preparation method thereof, belongs to the fields of functional composite materials and electronic devices, and solves the problem that traditional positive temperature coefficient thermistor composite materials can not meet the requirements of high current resistance and high voltage resistance. The composite material comprises functional fillers and polymer, wherein the adding amount of the functional fillers is 4%-30% of the mass of the polymer; the functional filler is a filler with thermal conductivity and/or electrical conductivity, and the polymer is crystalline polymer. The functional fillers and the polymer are mixed by melt blending, and are hot-pressed to form a conductive polymer composite material; the conductive polymer composite material is cut; electrodes and leads are adhered to the surface; hot packaging processing is performed by using powdered epoxy resin; and the thermistor with positive temperature coefficient effect is prepared after cooling. The composite material of the invention can be used as a high performance thermistor in fields which require that the thermistor has performance of current resistance and voltage resistance, such as communication, electric power, power plant, etc.
Description
Technical field
The present invention relates to thermistor polymer composite material of a kind of resistance to large electric current and preparation method thereof, belong to functional composite material and field of electronic devices.
Background technology
Thermistor has significant positive temperature coefficient effect (Positive temperature coefficient, PTC effect), the response function characteristic that material resistance sharply increases with temperature rising.Thermistor is able to widespread use as devices such as overcurrent protection, constant temperature Automatic-heating, temperature compensation and fire alarms in industry.Ptc material is divided into pottery and the large class of polymer two conventionally, and ceramic PTC is mainly that the barium titanate by trace elements such as the lead that adulterates, strontiums forms through high temperature sintering, and it has significant PTC effect at curie transition temperature; And high molecular PTC material is mainly to take the matrix material that carbon black (CB) filling high-density polyethylene (HDPE) is representative, utilize HDPE to cause CB conductive network to disconnect in temperature-rise period Zhong crystalline region melting expansion, thereby the PTC effect that has a resistance and sharply increase with temperature rising, it has the outstanding advantages such as lightweight, preparation technology is simple, cost is low, shape is unrestricted, just progressively substitutes ceramic PTC material and is widely used in the fields such as electronics, chemical industry, machinery, automatic control.
In recent years, along with the fast development of telecommunications and large-scale integrated circuit manufacturing technology, thermistor has been proposed to an urgent demand of high voltage withstanding, resistance to large electric current, high cyclical stability.And traditional CB/HDPE matrix material is because carbon black yardstick is little, be easy to the inherent defects such as high temperature oxidation agglomeration, heat resisting temperature is low, cyclical stability is poor, be only applicable to work under the conditions such as low temperature, little electric current, low voltage; Cannot meet the industry member active demand growing to high-performance thermistor, seriously restrict the fast development of macromolecular thermosensitive resistor.
At present, the existing many reports of method of preparing high-performance thermistor by matrix material promiscuous mode, for example: Chinese patent, CN200810204387.7 Li Hua etc., " preparation method of polymeric based carbon nano tube composite ", its feature mainly comprises: carbon nanotube is directly added or be scattered in advance in liquid medium, add polymer monomer, in the solution of oligopolymer or monomer or oligopolymer, obtain mixture, with electron beam, carry out radiation treatment, make carbon nanotube realize activation modification, polymer matrix material realizes and solidifying under electron beam irradiation simultaneously, obtain carbon nano-tube/polymer composite material, Chinese patent, CN200810101472.0 Yu Jian etc., " a kind of method of utilizing conductive filler material synergy to prepare conducing composite material ", its feature mainly comprises: the feature of preparing conductive composite material method is after polymkeric substance, carbon nanotube, carbon black, graphite, carbon fiber are mixed according to a certain percentage, adopts lose money in business melting mixing, granulation of processing of high molecular material to complete.Chinese patent, the meeting of CN200410020607.2 one-tenth is bright etc., " a kind of conducing composite material with positive temperature coefficient effect and preparation method thereof ", its feature mainly comprises: its conducing composite material mainly consists of conductive filler material and polymkeric substance, conductive filler material is nano carbon material in one dimension, comprises Single Walled Carbon Nanotube, multi-walled carbon nano-tubes, nano carbon fiber or mixture.Chinese patent, the meeting of CN200510047997.7 one-tenth is bright etc., " a kind of high-temperature-resisting thermosensitive resistance composite material and preparation method ", its feature mainly comprises: high-temperature-resisting thermosensitive resistance polymer composites, and by nano-carbon material, dystectic crystalline polymer and auxiliary material entered melt blending and hot press forming technology obtains.Auxiliary material is softening agent, antioxidant and mineral filler, and wherein mineral filler is light calcium carbonate, talcum powder, silicon-dioxide and aluminum hydroxide particles.
Chinese patent, CN200910051614.1 Yuan Xiao virtue etc., " high molecular positive temperature coefficient thermal sensitive resistor and manufacture method thereof ", its feature mainly comprises: thermistor is by sheet core and the tinsel that is covered on above-mentioned sheet core two sides, the metal electrode that is welded on sheet on this tinsel outside surface or negative line shape forms, described core is by high molecular polymer, and conductive filler material mineral filler and processing aid mix.Conductive filler material is one or more in carbon black, graphite, carbon fiber, metal-powder and metal oxide, and mineral filler is one or more mixtures in magnesium oxide, aluminum oxide, silicon-dioxide, potter's clay, talcum powder, calcium carbonate, magnesium hydroxide, aluminium hydroxide.Chinese patent, CN200910100323.7 Yuan builds ripple etc., " polymer-based positive temperature coefficient thermistor material ", its feature mainly comprises: thermistor material is by conductive filler material, PTC toughener and polymkeric substance form, polymeric matrix refers to two kinds of objectionable interminglings or the mixture of the compatible polymkeric substance of part only, and conductive filler material is comprised of conducting particles and electro-conductive fiber.Conducting particles is carbon black, graphite, metallics, metal oxide particle or conductivity ceramics particle, and electro-conductive fiber is carbon fiber, steel fiber or carbon nanotube.
Above method is all to lay particular emphasis on the cost that reduces conductive filler material content, raising PTC intensity, reduction thermistor, and for the resistance to electric current and the voltage characteristic that how to improve thermistor, carries out further investigation.In the field such as communication, power transmission, communications and transportation, require thermistor to there is resistance to large electric current, high voltage withstanding characteristic, and traditional PTC matrix material cannot meet the demand of this respect.
Summary of the invention
In order to overcome prior art above shortcomings, the object of the present invention is to provide thermistor polymer composite material of a kind of resistance to large electric current and preparation method thereof, solve resistance to large electric current that conventional P TC thermistor composite material cannot meet, the problem such as high voltage withstanding.
The technical solution adopted in the present invention is:
A thermistor polymer composite material for resistance to large electric current, this matrix material comprises functional stuffing, polymkeric substance, wherein: functional stuffing addition is polymer quality 4%～30%; Functional stuffing is the filler with heat conductivility and/or conductivity, and polymkeric substance is crystalline polymer.
The thermistor polymer composite material of described resistance to large electric current, functional stuffing comprises the filler that has high thermal conductivity and conductivity concurrently, the high heat conduction of choosing and high conductive filler material are a kind of or mixture in graphitized carbon black, carbon nanotube, Graphene, and addition is polymer quality 2%～20%;
Functional stuffing also comprises the filler with high thermal conductivity, and the high heat conductive filler of choosing is one of inorganic particulates such as silica flour, silicon carbide, silicon nitride or several, and addition is polymer quality 2%～10%.
The thermistor polymer composite material of described resistance to large electric current, polymkeric substance is the polymkeric substance such as polypropylene, polyoxymethylene, fluorinated ethylene propylene, polyvinylidene dichloride or high density polyethylene(HDPE).
The preparation method of the thermistor polymer composite material of described resistance to large electric current, through melt blending, forms conducting polymer composite material by functional stuffing and polymkeric substance after hot pressing; By after conducting polymer composite material cutting, surface adhesion electrode and lead-in wire, utilize powdered epoxy resin to carry out heat-seal processing, makes the thermistor with positive temperature coefficient effect after cooling.
The preparation method of the thermistor polymer composite material of described resistance to large electric current, melt blending carries out in double roll mill, and the temperature of melt blending is that rotating speed is 50～80r/min, blend time 5～15min higher than 5～15 ℃ of the fusing points of resin; Hot-forming temperature is consistent with melt blending temperature, and pressure is 3～6MPa, and dwell time 5～15min is cooled to room temperature after moulding.
Compared with prior art, the invention has the beneficial effects as follows:
1. thermistor polymer composite material of the resistance to large electric current of the present invention and preparation method thereof, it can be under high electric current, high voltage condition, overcome traditional shortcoming that carbon black filled vinyl polymer PTC element action current is little, operation voltage is low, can under large electric current, high-tension environment, use, greatly widened the range of application of polymer temperature sensing element, as fields such as exchange board, heating zone, Communication Equipment, electromechanical components, electrochemical anti-corrosive elements.
2. the present invention adds the filler with high thermal conductivity, can significantly improve the heat conductivility of matrix material, thermistor can be spread out the heat of generation in time, thereby greatly eliminated the heat effect that electric current causes, make matrix material thermistor still can keep low resistance under higher voltage and current condition, only under high voltage and large electric current, could under the driving in heat effect, there is PTC effect, show as and there is resistance to large electric current, high voltage performance.
3. preparation technology of the present invention is simple, raw material is easy to get, condition is easily controlled, and is suitable for batch production, and the thermistor composite material making has resistance to large electric current, high voltage characteristics, is applicable in industry the field for action current and operation voltage requirement harshness.
Embodiment
Embodiment 1:
By 48.00g polyoxymethylene, 0.96g carbon nanotube and 0.96g silica flour (granularity is 325 orders) carry out in advance mechanically mixing evenly after, join in the double roll mill that is preheated to 190 ℃, mixing 10min under 64rpm rotating speed, the compound system that obtains mixing; Compound system is transferred in vulcanizing press under 190 ℃, 5MPa condition it is shaped in mould, after pressurize 10min, slowly cool to room temperature (naturally cooling in vulcanizing press), obtain the flaky composite material of pre-determined thickness; By after matrix material cutting, surface adhesion electrode and lead-in wire, utilize powdered epoxy resin to carry out heat-seal processing, make the thermistor after encapsulation after cooling.Through electrochemical workstation (LK3200A) test, room temperature resistance is 100 Ω, and action current is 35.0mA, and operation voltage is 10V, compares with the commercialization temperature-sensitive resistance with similar resistance, and action current has improved 128.6%.
Embodiment 2:
By 48.00g polypropylene, 4.80g Graphene and 2.90g silicon carbide (granularity is 325 orders) carry out in advance mechanically mixing evenly after, join in the double roll mill that is preheated to 190 ℃, mixing 10min under 64rpm rotating speed, the compound system that obtains mixing; Compound system is transferred in vulcanizing press under 190 ℃, 5MPa condition it is shaped in mould, after pressurize 10min, slowly cool to room temperature (naturally cooling in vulcanizing press), obtain pre-determined thickness flaky composite material; After matrix material is cut into, surface adhesion electrode and lead-in wire, utilize powdered epoxy resin to carry out heat-seal processing, make the thermistor after encapsulation after cooling.Through electrochemical workstation (LK3200A) test, room temperature resistance is 47.7 Ω, and action current is that 97.6mA, operation voltage are 5.0V, compares with the commercialization temperature-sensitive resistance with same resistance value, and action current has improved 145.7%.
Embodiment 3:
By 48.00g high density polyethylene(HDPE) (High Density Polyethylene, referred to as " HDPE "), 2.40g graphitized carbon black, 7.20g carbon nanotube and 4.80g silicon nitride (granularity is 325 orders) carry out in advance mechanically mixing evenly after, join in the double roll mill that is preheated to 190 ℃, mixing 10min under 64rpm rotating speed, the compound system that obtains mixing; Compound system is transferred in vulcanizing press under 190 ℃, 5MPa condition it is shaped in mould, after pressurize 10min, slowly cool to room temperature (naturally cooling in vulcanizing press), obtain pre-determined thickness flaky composite material; After matrix material is cut into, surface adhesion electrode and lead-in wire, utilize powdered epoxy resin to carry out heat-seal processing, make the thermistor after encapsulation after cooling.Through electrochemical workstation (LK3200A) test, room temperature resistance is 3.7 Ω, and action current is that 537.2mA, operation voltage are 2.0V, compares with the commercialization temperature-sensitive resistance with same resistance value, and action current has improved 168%.
Embodiment result shows, the present invention, by selecting high heat conduction and high conductivity material as filler, forms conducting polymer composite material with polymkeric substance after melt blending, hot pressing; After bonding electrode and lead-in wire, resin package, form the thermistor with positive temperature coefficient effect.Utilize the high heat conduction of functional stuffing, high conductive characteristic, in composite inner, form the electric heating transmission network of optimizing, the heat that in thermistor composite material working process, electric current produces can be discharged quickly, thereby matrix material still can keep good ohmic resistance characteristic under large electric current, high voltage condition, show as and there is resistance to large electric current, high voltage characteristics, can be used as high-performance thermistor and be applied to communication, electric power, power station etc. and require thermistor to there is the field of resistance to large electric current, the performance such as high voltage withstanding.
Claims (1)
1. a polymer composites thermistor for resistance to large electric current, is characterized in that, this matrix material comprises functional stuffing, polymkeric substance, wherein: functional stuffing addition is polymer quality 4%～30%;
Functional stuffing comprises the filler that has high thermal conductivity and conductivity concurrently, and the high heat conduction of choosing and high conductive filler material are a kind of or mixture in graphitized carbon black, carbon nanotube, Graphene, and addition is polymer quality 2%～20%;
Functional stuffing also comprises the filler with high thermal conductivity, and the high heat conductive filler of choosing is one of silica flour, silicon carbide, silicon nitride inorganic particulate or several, and addition is polymer quality 2%～10%;
Polymkeric substance is polypropylene, polyoxymethylene, fluorinated ethylene propylene, polyvinylidene dichloride or high density polyethylene polyethylene polymers;
The preparation method of the polymer composites thermistor of described resistance to large electric current, through melt blending, forms conducting polymer composite material by functional stuffing and polymkeric substance after hot pressing; By after conducting polymer composite material cutting, surface adhesion electrode and lead-in wire, utilize powdered epoxy resin to carry out heat-seal processing, makes the thermistor with positive temperature coefficient effect after cooling;
Melt blending carries out in double roll mill, and the temperature of melt blending is that rotating speed is 50～80r/min, blend time 5～15min higher than 5～15 ℃ of the fusing points of resin; Hot-forming temperature is consistent with melt blending temperature, and pressure is 3～6 MPa, and dwell time 5～15min is cooled to room temperature after moulding.
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| CN201010558096.5A CN102477226B (en) | 2010-11-24 | 2010-11-24 | High current resistant thermistor polymer composite material and preparation method thereof |
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| CN102477226B true CN102477226B (en) | 2014-01-15 |
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Families Citing this family (11)
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| CN103730219A (en) * | 2012-10-15 | 2014-04-16 | 富致科技股份有限公司 | High-molecular positive temperature coefficient overcurrent protective device |
| CN103834094A (en) * | 2012-11-21 | 2014-06-04 | 合肥杰事杰新材料股份有限公司 | Graphene-filled polypropylene composite material, and preparation method thereof |
| CN103772782A (en) * | 2013-12-03 | 2014-05-07 | 上海神沃电子有限公司 | Self-limited flexible PTC (positive temperature coefficient) exothermic material and PTC core material prepared from same and preparation method of PTC core material |
| CN105038285A (en) * | 2014-04-18 | 2015-11-11 | 台湾奈米碳管股份有限公司 | Method for producing carbon-containing polymer composite particles |
| CN104072966A (en) * | 2014-06-10 | 2014-10-01 | 东莞上海大学纳米技术研究院 | Multi-element composite heat-conducting functional master batch and preparation method thereof |
| CN104877234A (en) * | 2015-06-11 | 2015-09-02 | 贵州新碳高科有限责任公司 | Graphene fiber and polymer heat conducting composite material |
| CN105061999A (en) * | 2015-08-06 | 2015-11-18 | 殷姝媛 | High-thermal conductivity high-molecular composite material |
| CN107151416A (en) * | 2017-04-22 | 2017-09-12 | 天津大学 | A kind of epoxy resin/SiC compound inslations method for preparing slices and thin slice application |
| CN108659467B (en) * | 2018-05-07 | 2020-11-20 | 武汉理工大学 | Method for compositely modifying epoxy resin by SiC/graphene oxide |
| CN109135185A (en) * | 2018-05-23 | 2019-01-04 | 江苏时瑞电子科技有限公司 | A kind of polmer PTC elements |
| CN114736444B (en) * | 2022-03-25 | 2023-07-28 | 四川大学 | Polymer-based conductive composite material for heat tracing belt and preparation method thereof |
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