CN102675718A - Ultralow-resistance organic positive temperature coefficient (PTC) composite material and preparation method thereof - Google Patents
Ultralow-resistance organic positive temperature coefficient (PTC) composite material and preparation method thereof Download PDFInfo
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Abstract
The invention discloses an ultralow-resistance organic positive temperature coefficient (PTC) composite material and a preparation method thereof. The composite material comprises an organic macromolecular polymer matrix and a conductive filler treated by a coupling agent, wherein the organic macromolecular polymer matrix comprises 80 to 90 volume percent of high-density polyethylene, 5 to 18 volume percent of carbon black and 0 to 5 volume percent of multi-walled carbon nanotube. The method comprises the following steps of: melting and blending the high-density polyethylene and the CB-CNTs conductive filler subjected to surface treatment above a melting point of an organic polymer, and mold-pressing the uniformly-mixed composite material at constant temperature in a mold press to obtain a PTC chip; and coating conductive silver paste at the two ends of the PTC chip, and performing stabilization for 24 hours to obtain the ultralow-resistance PTC composite material. A process and required production equipment are simple, industrial production is easily realized, and the composite material and the preparation method thereof are applied to the over-current and over-voltage protection of a highly-integrated circuit and a higher-capacity battery circuit.
Description
Technical field
The present invention relates to a kind of ultralow resistance organic PTC matrix material and preparation method thereof, belong to macromolecular material and nano composite material preparing technical field.
Background technology
Polymer-based positive temperature coefficient thermistor material (PTC-Positive Temperature Coefficient) have matter soft, be prone to shape, energy-conserving and environment-protective, advantage such as cheap; The components and parts of processing are used various fields such as containing communication, computingmachine, IT, automobile, battery, medicine equipment, launch vehicle, industry class, consumer electrical equipment, are particularly suitable for overcurrent protection or overheat protector.
Polymer matrix PTC is realized applicationization technically by the auspicious Raychem company that chats about of the U.S. (existing by the safe Tyco of section purchase) invention the eighties in 20th century.Typical application comprises rechargeable battery pack, lithium cell of Battery Market etc. in recent years; The power supply of computer and peripheral produce market, charger, USB port and AC/DC power supply changeover device etc.; The programme-controlled exchange in communication equipment market, subscriber terminal equipment etc.When these electronics load instantaneous overcurrents or battery polar connect inverse time, the application of PTC element can be avoided the great number cost of the big maintenance of glitch, and these are used and bring great economic benefit for relevant manufacturer.Tyco company is capturing the technological commanding elevation in this field always, and so far, Tyco still captures 80% the market share.China still has certain gap at this technical field industrialization process and international most advanced level, and its tachnical storage lags behind the market requirement far away.Along with more and more miniaturized of electronic product, integrated, require the PTC device to smaller szie, more low-resistivity development.Like the release of communications market 3G, 4G, the capacity of battery has been proposed new requirement, will promote PTC to low room temperature resistivity development more to reduce itself energy consumption.
At present; Polymer matrix PTC material commonly used in the industrial production mainly is carbon black (CB) filled polyethylene (PE) compound system; Although there is a small amount of other matrix material to come out; Such as adopt metallic particles to fill PE, CB fills two-pack polymer blend etc., has limited its development but all higher or proof voltage is lower because of room temperature resistivity.
The CB good conductivity, particle diameter is little, and is cheap, is present more satisfactory a kind of conductive filler material, but in matrix, fills single CB particle, and its room temperature resistivity still can not reach desirable low-resistance.Carbon nanotube (CNTs) is the found a kind of novel carbon structure material of last century Mo; Generally can be divided into single wall, double-walled and multi-walled carbon nano-tubes; Theoretical prediction and experimental study find that carbon nanotube has peculiar electric property, and closely related with its rerum natura and structure.CB and CNTs all belong to carbonaceous material; Physicals and chemical property comparison match; If in carbon black and polymer composite body system, introduce carbon nanotube,, thereby can effectively reduce room temperature resistivity and seepage flow threshold value because CNTs can play the bridge joint effect between the CB particle.
More about the report of in the PTC matrix material, introducing chopped carbon fiber (SCF) or flake graphite (FG) both at home and abroad; About the research of CNTs filled composite materials mainly concentrates on the dispersion of CNT and to the influence of matrix material dielectric properties and mechanical property, and do not appear in the newspapers as yet in the research that the PTC field of compound material is used to reduce PTC device room temperature resistivity.
Summary of the invention
The invention discloses organic PTC matrix material of a kind of ultralow resistance resistivity and preparation method thereof.Method of the present invention is to add CNTs in the composite material simultaneously in common preparing with the CB filled polymer; Carbon nanotube with length-to-diameter ratio is easy between carbon black particle, form conducting bridge; Thereby effectively reduce seepage flow threshold value and room temperature resistivity, to overcome defectives such as the higher or proof voltage of polymer matrix PTC material room temperature resistivity commonly used in the existing industrial production is lower.
Technical scheme of the present invention is achieved in that
A kind of ultralow resistance organic PTC matrix material; The component that matrix material comprises is: the conductive filler material that organic high molecular polymer matrix, coupling agent treatment are crossed; Wherein said organic high molecular polymer matrix is preferably high density polyethylene(HDPE) (HDPE); The volumn concentration of high density polyethylene(HDPE) is 80～90%, and the sooty volumn concentration is 5～18%, and the volumn concentration of carbon nanotube is 0～5%; Said conductive filler material is preferably through surface-treated CB of titanate coupling agent and the mixture of CNTs.
The preparation method of ultralow resistance organic PTC matrix material, carry out according to following steps:
(1) surface treatment of CB, CNT: utilize titanate coupling agent that CB, CNT are carried out finishing, improving the dispersiveness of conductive filler material in the organism matrix, and make the bonding force of filler and matrix stronger.CB or CNTs are added respectively in the aqueous isopropanol that concentration is 0.5～3% coupling agent, and ball milling made coupling agent can cover the surface of conductive filler material uniformly in 0.5～2 hour then, and 80 ~ 100 ° of C evaporate solvent fully in baking oven.In vacuum drying oven, reacted 1～2 hour afterwards, obtain the CB or the CNTs conductive filler material of modified in 100～130 ° of C;
(2) batch mixing: with said high density polyethylene(HDPE), through the surface-treated CB of step (1) and CNTs conductive filler material more than the fusing point of organic polymer, preferred 150～170 ℃ of melt blendings 5～20 minutes, it is for use to obtain mixing uniform matrix material;
(3) compressing tablet: with the matrix material that mixes in moulding press under 150～170 ℃, pressure 5～20MPa constant temperature and pressure mold pressing in 10～20 minutes obtain the PTC chip;
(4) make electrode: the coated with conductive silver slurry at PTC chip two ends, and handle 1～2h in 80～130 ° of C promptly gets ultralow resistance organic PTC matrix material after stablizing 24h.
The torque rheometer that the present invention uses is XSS-300 type torque rheometer main frame, LH60 mixer, output torque 0～300nm, output speed 10～120r/min, mixing section capacity: 60ml, Heating temperature: room temperature～350 ° C.
The thermocompressor that the present invention uses is 769YP-24B type powder compressing machine, joins WY-99 type two channels temperature controller, pressure 0～40MPa, and ° C is controlled in temperature room temperature～300.
Advantage of the present invention and positively effect are following:
1. through carbon black and carbon nanotube are carried out coupling agent treatment, can improve its dispersiveness in matrix and with the associativity of matrix.
2. this matrix material is compared and is added single carbon black filler; Under the identical situation of filler content; Can obviously reduce the room temperature resistivity of matrix material; And the seepage flow phenomenon can appear than low sizing content the time, improves performance of composites stability, and strengthens its mechanical property through reducing filler content.
3. the total content that this PTC matrix material can be through regulating filler and the ratio of the two kinds of fillers resistivity that regulates the room temperature; And, therefore can comparatively accurately control the room temperature resistivity of matrix material because resistivity is carried out corresponding successive steady change along with filler content changes.
4. it is compound to adopt the method for melt blending to carry out, and technology is simple, and required production unit is simple, is easy to realize suitability for industrialized production.
Description of drawings
Fig. 1 matrix material room temperature resistivity is with the content of carbon nanotubes change curve;
The organic PTC matrix material that Fig. 2 carbon nanotube and carbon black are filled altogether
(a) sem photograph, (b) the bridge joint conductive chain synoptic diagram that in matrix, forms of carbon nanotube and carbon black;
Fig. 3 matrix material room temperature resistivity is with temperature variation curve, i.e. the PTC performance.
Embodiment
Below in conjunction with accompanying drawing and embodiment the present invention is elaborated.
Contained each the component volume(tric)fraction of each embodiment matrix material is listed in the table 1, claims its quality during batching, and quality is each component volume density product corresponding with it, and wherein high density polyethylene(HDPE) density is got 0.954g/cm
3, carbon black density 1.86g/cm
3, used multi-walled carbon nano-tubes density is got 1.8g/cm
3The physical properties of the PTC matrix material that makes is listed in the table 1.
Embodiment 1 (the HDPE/CB/CNTs volume ratio is 90/9/1):
(1) before batch mixing, utilize coupling agent that CB and CNTs are carried out finishing earlier.The 2.5g titanate coupling agent is dissolved in (concentration is 0.5%) in the 500ml aqueous isopropanol, adds carbon black or carbon nanotube then, insert ball milling 2h in the ball grinder, 80 ° of C dry by the fire down and desolventize in baking oven.Carbon black or carbon nanotube after the oven dry are placed vacuum drying oven, vacuumize, it is fully reacted and drying, finally obtain needed surface-functionalized carbon black or carbon nanotube at 120 ° of C constant temperature 1.5h.
(2) 45g high density polyethylene(HDPE), the surface-functionalized surface-functionalized carbon nanotube of carbon black, 0.94g of 8.77g are mixed the back and add in the torque rheometer, be warming up to 160 ° of C mixing 15 minutes, obtain polymer matrix composite.
(3) with above-mentioned matrix material on thermocompressor with the pressure of 15MPa, 160 ℃ of temperature hot pressing 10 minutes, the naturally cooling that do not reduce pressure obtains the sheet material that thickness is 1mm.
(4) with the coated on both sides conductive silver paste of above-mentioned sheet material, and handled 2 hours, promptly get the organic PTC matrix material, and then weld copper cash, obtain PTC temperature-sensitive device sample in its both sides in 100 ° of C.
Its resistivity (ρ) is as shown in Figure 1 with the change curve of content of carbon nanotubes.
Embodiment 2 (the HDPE/CB/CNTs volume ratio is 90/8/2):
(1) the 10g titanate coupling agent is dissolved in (concentration is 2%) in the 500ml aqueous isopropanol, adds carbon black or carbon nanotube then, insert ball milling 1h in the ball grinder, 100 ° of C dry by the fire down and desolventize in baking oven.Carbon black or carbon nanotube after the oven dry are placed vacuum drying oven, vacuumize, it is fully reacted and drying, finally obtain needed surface-functionalized carbon black or carbon nanotube at 100 ° of C constant temperature 2h.
(2) 45g high density polyethylene(HDPE), the surface-functionalized surface-functionalized carbon nanotube of carbon black, 1.87g of 7.80g are mixed the back and add in the torque rheometer, be warming up to 170 ° of C mixing 5 minutes, obtain polymer matrix composite.
(3) with above-mentioned matrix material on thermocompressor with the pressure of 5MPa, the hot pressing of 170 ° of C temperature 15 minutes, the naturally cooling that do not reduce pressure obtains the sheet material that thickness is 1mm.
(4) with the coated on both sides conductive silver paste of above-mentioned sheet material, and handled 1.5 hours, promptly get the organic PTC matrix material, and then weld copper cash, obtain PTC temperature-sensitive device sample in its both sides in 80 ° of C.
Its resistivity (ρ) is as shown in Figure 1 with the change curve of content of carbon nanotubes.
Embodiment 3 (the HDPE/CB/CNTs volume ratio is 90/7/3):
(1) the 15g titanate coupling agent is dissolved in (concentration is 3%) in the 500ml aqueous isopropanol, adds carbon black or carbon nanotube then, insert ball milling 0.5h in the ball grinder, 90 ° of C dry by the fire down and desolventize in baking oven.Carbon black or carbon nanotube after the oven dry are placed vacuum drying oven, vacuumize, it is fully reacted and drying, finally obtain needed surface-functionalized carbon black or carbon nanotube at 130 ° of C constant temperature 1h.
(2) 45g high density polyethylene(HDPE), the surface-functionalized surface-functionalized carbon nanotube of carbon black, 2.83g of 6.82g are mixed the back and add in the torque rheometer, be warming up to 150 ° of C mixing 20 minutes, obtain polymer matrix composite.
(3) with above-mentioned matrix material on thermocompressor with the pressure of 20MPa, the hot pressing of 150 ° of C temperature 20 minutes, the naturally cooling that do not reduce pressure obtains the sheet material that thickness is 1mm.
(4) with the coated on both sides conductive silver paste of above-mentioned sheet material, and handled 1 hour, promptly get the organic PTC matrix material, and then weld copper cash, obtain PTC temperature-sensitive device sample in its both sides in 130 ° of C.
Its resistivity (ρ) is as shown in Figure 1 with the change curve of content of carbon nanotubes.The sem photograph of corresponding matrix material is shown in Fig. 2 (a), and visible CB and CNTs are dispersed in the polymeric matrix.Shown in Fig. 2 (b), the formation of this special conductive chain possibly be the major cause that room temperature resistivity reduces at the bridge joint conductive chain synoptic diagram that forms in the matrix for carbon nanotube and carbon black.
Embodiment 4 (the HDPE/CB/CNTs volume ratio is 87/12/1):
(1) before batch mixing, utilize coupling agent that CB and CNTs are carried out finishing earlier.The 2.5g titanate coupling agent is dissolved in (concentration is 0.5%) in the 500ml aqueous isopropanol, adds carbon black or carbon nanotube then, insert ball milling 2h in the ball grinder, 80 ° of C dry by the fire down and desolventize in baking oven.Carbon black or carbon nanotube after the oven dry are placed vacuum drying oven, vacuumize, it is fully reacted and drying, finally obtain needed surface-functionalized carbon black or carbon nanotube at 120 ° of C constant temperature 1.5h.
(2) 42g high density polyethylene(HDPE), the surface-functionalized surface-functionalized carbon nanotube of carbon black, 0.91g of 11.30g are mixed the back and add in the torque rheometer, be warming up to 160 ° of C mixing 15 minutes, obtain polymer matrix composite.
(3) with above-mentioned matrix material on thermocompressor with the pressure of 15MPa, 160 ℃ of temperature hot pressing 10 minutes, the naturally cooling that do not reduce pressure obtains the sheet material that thickness is 1mm.
(4) with the coated on both sides conductive silver paste of above-mentioned sheet material, and handled 2 hours, promptly get the organic PTC matrix material, and then weld copper cash, obtain PTC temperature-sensitive device sample in its both sides in 100 ° of C.
(5) measure its resistance (R when room temperature
0) and the R-T resistance-temperature curve, calculate room temperature resistivity according to area and gauge, calculate PTC intensity simultaneously.
Its resistivity (ρ) is as shown in Figure 1 with the change curve of content of carbon nanotubes.Matrix material room temperature resistivity (ρ) is with temperature (T) change curve, and promptly the PTC performance is as shown in Figure 3.
Embodiment 5 (the HDPE/CB/CNTs volume ratio is 87/11/2):
(1) the 10g titanate coupling agent is dissolved in (concentration is 2%) in the 500ml aqueous isopropanol, adds carbon black or carbon nanotube then, insert ball milling 1h in the ball grinder, 100 ° of C dry by the fire down and desolventize in baking oven.Carbon black or carbon nanotube after the oven dry are placed vacuum drying oven, vacuumize, it is fully reacted and drying, finally obtain needed surface-functionalized carbon black or carbon nanotube at 100 ° of C constant temperature 2h.
(2) 42g high density polyethylene(HDPE), the surface-functionalized surface-functionalized carbon nanotube of carbon black, 1.82g of 10.35g are mixed the back and add in the torque rheometer, be warming up to 170 ° of C mixing 5 minutes, obtain polymer matrix composite.
(3) with above-mentioned matrix material on thermocompressor with the pressure of 5MPa, the hot pressing of 170 ° of C temperature 15 minutes, the naturally cooling that do not reduce pressure obtains the sheet material that thickness is 1mm.
(4) with the coated on both sides conductive silver paste of above-mentioned sheet material, and handled 1.5 hours, promptly get the organic PTC matrix material, and then weld copper cash, obtain PTC temperature-sensitive device sample in its both sides in 80 ° of C.
(5) measure its resistance (R when room temperature
0) and the R-T resistance-temperature curve, calculate room temperature resistivity according to area and gauge, calculate PTC intensity simultaneously.
Its resistivity (ρ) is as shown in Figure 1 with the change curve of content of carbon nanotubes.Matrix material room temperature resistivity (ρ) is with temperature (T) change curve, and promptly the PTC performance is as shown in Figure 3.
Embodiment 6 (the HDPE/CB/CNTs volume ratio is 87/10/3):
(1) the 15g titanate coupling agent is dissolved in (concentration is 3%) in the 500ml aqueous isopropanol, adds carbon black or carbon nanotube then, insert ball milling 0.5h in the ball grinder, 90 ° of C dry by the fire down and desolventize in baking oven.Carbon black or carbon nanotube after the oven dry are placed vacuum drying oven, vacuumize, it is fully reacted and drying, finally obtain needed surface-functionalized carbon black or carbon nanotube at 130 ° of C constant temperature 1h.
(2) 42g high density polyethylene(HDPE), the surface-functionalized surface-functionalized carbon nanotube of carbon black, 2.73g of 9.41g are mixed the back and add in the torque rheometer, be warming up to 150 ° of C mixing 20 minutes, obtain polymer matrix composite.
(3) with above-mentioned matrix material on thermocompressor with the pressure of 20MPa, the hot pressing of 150 ° of C temperature 20 minutes, the naturally cooling that do not reduce pressure obtains the sheet material that thickness is 1mm.
(4) with the coated on both sides conductive silver paste of above-mentioned sheet material, and handled 1 hour, promptly get the organic PTC matrix material, and then weld copper cash, obtain PTC temperature-sensitive device sample in its both sides in 130 ° of C.
(5) measure its resistance (R when room temperature
0) and the R-T resistance-temperature curve, calculate room temperature resistivity according to area and gauge, calculate PTC intensity simultaneously.
Its resistivity (ρ) is as shown in Figure 1 with the change curve of content of carbon nanotubes.Matrix material room temperature resistivity (ρ) is with temperature (T) change curve, and promptly the PTC performance is as shown in Figure 3.
Embodiment 7 (the HDPE/CB/CNTs volume ratio is 90/5/5):
(1) the 10g titanate coupling agent is dissolved in (concentration is 2%) in the 500ml aqueous isopropanol, adds carbon black or carbon nanotube then, insert ball milling 1h in the ball grinder, 95 ° of C dry by the fire down and desolventize in baking oven.Carbon black or carbon nanotube after the oven dry are placed vacuum drying oven, vacuumize, it is fully reacted and drying, finally obtain needed surface-functionalized carbon black or carbon nanotube at 110 ° of C constant temperature 1h.
(2) 45g high density polyethylene(HDPE), the surface-functionalized surface-functionalized carbon nanotube of carbon black, 4.72g of 4.87g are mixed the back and add in the torque rheometer, be warming up to 165 ° of C mixing 10 minutes, obtain polymer matrix composite.
(3) with above-mentioned matrix material on thermocompressor with the pressure of 10MPa, the hot pressing of 165 ° of C temperature 10 minutes, the naturally cooling that do not reduce pressure obtains the sheet material that thickness is 1mm.
(4) with the coated on both sides conductive silver paste of above-mentioned sheet material, and handled 1.5 hours, promptly get the organic PTC matrix material, and then weld copper cash, obtain PTC temperature-sensitive device sample in its both sides in 110 ° of C.
Embodiment 8 (the HDPE/CB/CNTs volume ratio is 80/18/2):
(1) the 5g titanate coupling agent is dissolved in (concentration is 1%) in the 500ml aqueous isopropanol, adds carbon black or carbon nanotube then, insert ball milling 1h in the ball grinder, 95 ° of C dry by the fire down and desolventize in baking oven.Carbon black or carbon nanotube after the oven dry are placed vacuum drying oven, vacuumize, it is fully reacted and drying, finally obtain needed surface-functionalized carbon black or carbon nanotube at 110 ° of C constant temperature 1h.
(2) 40g high density polyethylene(HDPE), the surface-functionalized surface-functionalized carbon nanotube of carbon black, 1.89g of 17.55g are mixed the back and add in the torque rheometer, be warming up to 165 ° of C mixing 10 minutes, obtain polymer matrix composite.
(3) with above-mentioned matrix material on thermocompressor with the pressure of 10MPa, the hot pressing of 165 ° of C temperature 10 minutes, the naturally cooling that do not reduce pressure obtains the sheet material that thickness is 1mm.
(4) with the coated on both sides conductive silver paste of above-mentioned sheet material, and handled 1.5 hours, promptly get the organic PTC matrix material, and then weld copper cash, obtain PTC temperature-sensitive device sample in its both sides in 110 ° of C.
Comparative example 1 (the HDPE/CB/CNTs volume ratio is 90/10/0):
(1) before batch mixing, utilize coupling agent that CB and CNTs are carried out finishing earlier.The 2.5g titanate coupling agent is dissolved in (concentration is 0.5%) in the 500ml aqueous isopropanol, adds carbon black or carbon nanotube then, insert ball milling 2h in the ball grinder, 80 ° of C dry by the fire down and desolventize in baking oven.Carbon black or carbon nanotube after the oven dry are placed vacuum drying oven, vacuumize, it is fully reacted and drying, finally obtain needed surface-functionalized carbon black or carbon nanotube at 120 ° of C constant temperature 1.5h.
(2) 45g high density polyethylene(HDPE), the surface-functionalized carbon black of 9.75g are mixed the back and add in the torque rheometer, be warming up to 160 ° of C mixing 15 minutes, obtain polymer matrix composite.
(3) with above-mentioned matrix material on thermocompressor with the pressure of 15MPa, 160 ℃ of temperature hot pressing 10 minutes, the naturally cooling that do not reduce pressure obtains the sheet material that thickness is 1mm.
(4) with the coated on both sides conductive silver paste of above-mentioned sheet material, and handled 2 hours, promptly get the organic PTC matrix material, and then weld copper cash, obtain PTC temperature-sensitive device sample in its both sides in 100 ° of C.
Its resistivity (ρ) is as shown in Figure 1 with the change curve of content of carbon nanotubes.
Comparative example 2 (the HDPE/CB/CNTs volume ratio is 87/13/0):
(1) before batch mixing, utilize coupling agent that CB and CNTs are carried out finishing earlier.The 2.5g titanate coupling agent is dissolved in (concentration is 0.5%) in the 500ml aqueous isopropanol, adds carbon black or carbon nanotube then, insert ball milling 2h in the ball grinder, 80 ° of C dry by the fire down and desolventize in baking oven.Carbon black or carbon nanotube after the oven dry are placed vacuum drying oven, vacuumize, it is fully reacted and drying, finally obtain needed surface-functionalized carbon black or carbon nanotube at 120 ° of C constant temperature 1.5h.
(2) 42g high density polyethylene(HDPE), the surface-functionalized carbon black of 12.24g are mixed the back and add in the torque rheometer, be warming up to 160 ° of C mixing 15 minutes, obtain polymer matrix composite.
(3) with above-mentioned matrix material on thermocompressor with the pressure of 15MPa, 160 ℃ of temperature hot pressing 10 minutes, the naturally cooling that do not reduce pressure obtains the sheet material that thickness is 1mm.
(4) with the coated on both sides conductive silver paste of above-mentioned sheet material, and handled 2 hours, promptly get the organic PTC matrix material, and then weld copper cash, obtain PTC temperature-sensitive device sample in its both sides in 100 ° of C.
(5) measure its resistance (R when room temperature
0) and the R-T resistance-temperature curve, calculate room temperature resistivity according to area and gauge, calculate PTC intensity simultaneously.
Its resistivity (ρ) is as shown in Figure 1 with the change curve of content of carbon nanotubes.Matrix material room temperature resistivity (ρ) is with temperature (T) change curve, and promptly the PTC performance is as shown in Figure 3.
Each embodiment matrix material set of dispense of table 1 is than (volume(tric)fraction) and physical properties
Annotate: wherein said high density polyethylene(HDPE) is the Kunlun 5000S; Carbon black is a Shawinigan black, particle diameter 40～50nm; Multi-walled carbon nano-tubes is produced by nanometer port, Shenzhen, diameter 20-40nm, long 1-2 μ m.
Table 1 and Fig. 1, Fig. 3 show, adopt the PTC matrix material of the present invention's preparation, and behind part carbon nanotube replacement carbon black, under identical experiment condition, the PTC device has lower room temperature resistivity when room temperature, though PTC intensity descends to some extent, amplitude is little.
Claims (2)
1. ultralow resistance organic PTC matrix material; It is characterized in that: the component that matrix material comprises is: the conductive filler material that organic high molecular polymer matrix, coupling agent treatment are crossed; Wherein said organic high molecular polymer matrix is preferably high density polyethylene(HDPE); The volumn concentration of high density polyethylene(HDPE) is 80～90%, and the sooty volumn concentration is 5～18%, and the volumn concentration of carbon nanotube is 0～5%; CB that the preferred titanate coupling agent of said conductive filler material is surface-treated and the mixture of CNTs.
2. the preparation method of a kind of ultralow resistance organic PTC matrix material according to claim 1 is characterized in that: carry out according to following steps:
(1) surface treatment of CB, CNT: utilize titanate coupling agent that CB, CNT are carried out finishing; CB or CNTs are added respectively in the aqueous isopropanol that massfraction is 0.5～3% coupling agent; Ball milling made coupling agent can cover the surface of conductive filler material uniformly in 0.5～2 hour then; And 80 ~ 100 ° of C evaporate solvent fully in baking oven, in vacuum drying oven, react 1～2 hour in 100～130 ° of C afterwards, obtain the CB or the CNTs conductive filler material of modified;
(2) batch mixing: with said high density polyethylene(HDPE), through the surface-treated CB of step (1) and CNTs conductive filler material more than the fusing point of organic polymer, preferred 150～170 ° of C melt blendings 5～20 minutes, it is for use to obtain mixing uniform matrix material;
(3) compressing tablet: with the matrix material that mixes in moulding press under 150～170 ° of C, pressure 5～20MPa constant temperature and pressure mold pressing in 10～20 minutes obtain the PTC chip;
(4) make electrode: the coated with conductive silver slurry at PTC chip two ends, and handle 1～2h in 80～130 ° of C promptly gets ultralow resistance organic PTC matrix material after stablizing 24h.
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| CN103483666A (en) * | 2013-09-29 | 2014-01-01 | 太仓金凯特种线缆有限公司 | Method for preparing PTC (positive temperature coefficient) material by compounding polyaniline/carbon black/polyolefin |
| CN106947249A (en) * | 2016-11-23 | 2017-07-14 | 德阳九鼎智远知识产权运营有限公司 | A kind of new energy car battery temperature control PTC composite material |
| CN108707265A (en) * | 2018-06-15 | 2018-10-26 | 北京科技大学 | A kind of fibre-reinforced polyolefin-carbon black composite material and preparation method thereof |
| CN109467783A (en) * | 2018-11-08 | 2019-03-15 | 上海应用技术大学 | A kind of polyethylene/carbon nanotube conducting material and preparation method thereof |
| CN115386179A (en) * | 2022-08-31 | 2022-11-25 | 洛阳理工学院 | Preparation method of polyvinyl chloride composite material with electromagnetic shielding and cold resistance |
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