CN101831090B - High-performance natural rubber vulcanized rubber of carbon-containing nano-tube, and preparation method thereof - Google Patents
High-performance natural rubber vulcanized rubber of carbon-containing nano-tube, and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a high-performance natural rubber vulcanized rubber of a carbon-containing nano-tube, which is prepared by a method comprising the steps of: plasticating the carbon-containing nano-tube with a modified surface and natural rubber together to prepare master batch; adding crude rubber, carbon black, zinc oxide, vulcanized agent and accelerating agent into the master batch, processing the obtained mixture by an open mill or an internal mixer, and obtaining natural rubber mixer modified by the carbon-containing nano-tube; and carrying out vulcanizing processing, and obtaining the modified natural rubber vulcanized rubber. By adding the modified carbon-containing nano-tube into the natural rubber material, the invention leads the comprehensive performances such as wear-resisting property, mechanism strength, anti-aging performance, heat-conducting property, anti-fatigue performance and the like of the natural rubber to be remarkably improved, thus improving the using performance of the natural rubber vulcanized rubber, reducing the using quantity of carbon black, and expanding the application scope of the natural rubber vulcanized rubber.
Description
Technical field
The invention belongs to rubber polymer Composite Preparation technical field, natural rubber vulcanized rubber of particularly a kind of carbon nanotubes modification and preparation method thereof.
Background technology
Carbon nanotube can regard that two-dimentional Graphene lamella convolution obtains as, and its ideal structure is seamless, the hollow tube that the former sub-grid of hexagonal carbon surrounds.Difference according to tube wall layer number can be divided into it multi-walled carbon nano-tubes (MWNTs) and Single Walled Carbon Nanotube (SWNTs).MWNTs is formed by some concentric graphene film convolution, and the tube wall spacing is slightly larger than the interlamellar spacing (0.335nm) of graphite greatly about 0.34nm.SWNTs is the limiting form of carbon nanotube, and diameter is many between 1nm～2nm.
When checking the grey soot that produces in the graphite arc equipment under high-resolution-ration transmission electric-lens, doctor Iijima of Japanese NEC Corporation in 1991 found since the multi-walled carbon nano-tubes (MWNTs) that carbon nanotube (CNTs) becomes a research focus in fields such as physics, chemistry, Materials science rapidly.1993, the research group of NEC and IBM successfully synthesized Single Walled Carbon Nanotube (SWNTs) simultaneously, makes the research of carbon nanotube make new breakthroughs.
Through the continuous effort of more than ten years, the throughput of multi-walled carbon nano-tubes constantly increases, and its cost reduces greatly, and its application on industrial technology more and more widely.
In recent years, the research of carbon nanotube-rubber materials also more and more widely, prepare carbon nanotube-native rubber composite material as people by modes such as mechanically milling, organic solvent dissolution and emulsions, as adopt solution blended process or emulsion hybrid system to prepare carbon nanotube-native rubber composite material (CompositeStructures, 2006,75:496-500, CN1663991A, CN1673261A CN01381483A), utilizes ultrasonic means to improve the degree of scatter of carbon nanotube in rubber.A.M.Shanmugharaj adopts the surface property of coupling agent aminopropyl triethoxysilane KH550 modification multi-walled carbon nano-tubes, improve strengthening action (the Composites Science and Technology of MWNTs to natural rubber, 2007,67 (9): 1813-1822.).Sui Gang adopts the mechanical blending legal system to be equipped with carbon nanotube to prepare matrix material with natural rubber (polymer material science and engineering, 2005,21 (3): 156-159.) carbon nanotube of comparison identical weight and carbon black are to the difference of the reinforcing property of natural rubber.In above-mentioned research, they adopt the independent Reinforced Rubber of carbon nanotube, and the matrix material that obtains often exists shortcomings such as intensity is not high, elongation is low, viscosity is low, poor processability, does not reach the use properties of rubber item.In addition because carbon nanotube does not pass through surface treatment, in rubber, disperse inhomogeneous, so that the structural uniformity of matrix material is relatively poor, and carbon nanotube can not obtain fine performance in the advantage aspect mechanical property and the heat conductivility, and the amplitude that composite property improves is little.
Summary of the invention
The structural uniformity of matrix material is relatively poor, and carbon nanotube can not obtain fine performance in the advantage aspect mechanical property and the heat conductivility, and the amplitude that composite property improves is little.
The object of the present invention is to provide a kind of carbon nanotube-native rubber composite material and preparation method thereof with high thermal conductivity and mechanical property.
The technical solution that realizes the object of the invention is: the high-performance natural rubber vulcanized rubber of carbon nanotubes of the present invention, comprise natural rubber, vulcanizing agent, promotor, carbon black,, zinc oxide, stearic acid, anti-aging agent, scorch retarder and resin, also comprise modified carbon nano-tube, the mass fraction of each component is: 100 parts of natural rubbers, vulcanizing agent 1-3 part, carbon black 30-70 part, zinc oxide 3-10 part, stearic acid 1-3 part, vulcanization accelerator 0.4-0.8 part, anti-aging agent 2-5 part, scorch retarder 0.2-2 part, resin 1-5 part, modified carbon nano-tube 1-7 part; Wherein, modified carbon nano-tube is the multi-walled carbon nano-tubes of 20-40nm, and this walled carbon nanotubes oxide treatment is passed through coupling agent coupling modification again.
The preparation method of the high-performance natural rubber vulcanized rubber of carbon nanotubes of the present invention may further comprise the steps:
Step 1: carbon nanotube is carried out surface treatment: take by weighing multi-walled carbon nano-tubes MWNTs raw material, add salpeter solution, be transferred to behind the ultra-sonic dispersion in the reaction vessel, the oil bath heating is transferred to after the back flow reaction in another container, leave standstill, remove supernatant liquid, add deionized water wash, extremely neutral until solution, use the millipore filtration suction filtration then, dry for standby in baking oven;
Step 2: surface modification of carbon nanotube: take by weighing through the MWNTs after the step 1 processing and place container, add tetra-sulfurized pair triethoxy Trisilicopropane Si69 and N, N ' dicyclohexylcarbodiimide DCC, be transferred to vessel in heating after ultra-sonic dispersion is even, reaction obtains mixing solutions and is transferred in the container, with unnecessary tetra-sulfurized pair triethoxy Trisilicopropane and the N of dehydrated alcohol cleaning reaction, N ' dicyclohexylcarbodiimide, use the micropore filtering film suction filtration then, in vacuum drying oven, dry;
Step 3: the rubber of natural rubber carries out thin-pass on two rollers, adds carbon nanotube after step 2 is handled again and carries out mixingly, and the mixture that obtains natural rubber and carbon nanotube is a master batch;
Step 4: the rubber of natural rubber is plasticated on two rollers, obtains broken-(down)rubber;
Step 5: in broken-(down)rubber, add master batch, carbon black, zinc oxide, stearic acid, promotor, anti-aging agent, scorch retarder, resin and sulphur successively, with mill or Banbury mixer said mixture is carried out mixingly, obtain carbon nanotube and carbon black enhanced natural rubber rubber unvulcanizate;
Step 6: after the rubber unvulcanizate that step 5 obtains is parked, measure its sulfurizing time with vulkameter, sulfuration makes the natural rubber vulcanized rubber of carbon nanotubes.
Description of drawings
The present invention compared with prior art, its remarkable advantage: usually improve mechanical properties of vulcanizate in the prior art, but the abrasion resistance and the tear resistance of the cross-linked rubber that obtains are not high by the heavy addition carbon black; The heat conductivility that increases cross-linked rubber by the inorganic heat conductive filler of heavy addition often makes mechanical properties of vulcanizate, abrasion resistance and tear resistance descend.Distinguishing feature of the present invention is: (1) utilizes the nano effect of carbon nanotube and carbon nanotube and sooty synergistic effect can obviously improve the abrasion resistance and the tear strength of natural rubber vulcanized rubber; (2) because the carbon nanotube good heat-conducting forms good heat transfer path with carbon black and with the back, amount of localized heat in the rubber can be derived rapidly, avoid localized hyperthermia, improve the heat conductivility of cross-linked rubber, the high temperature resistant and ageing-resistant performance of sizing material.
Embodiment
Accompanying drawing is the high-performance natural rubber vulcanized rubber preparation method's of carbon nanotubes of the present invention schematic flow sheet.
Below in conjunction with accompanying drawing the present invention is described in further detail.
The present invention utilizes coupling agent that multi-walled carbon nano-tubes is carried out modification, with improve multi-walled carbon nano-tubes in rubber dispersion and with the interface of rubber bonding, utilize carbon nanotube and sooty synergy, prepared the natural rubber vulcanized rubber of strong mechanical performance and high thermal conductivity.With independent carbon black filled comparing, the tensile strength of this matrix material, antifatigue and abrasion resistance, heatproof air aging performance and heat conductivility can effectively be improved and be improved.
The present invention can be widely used in tire, pipe racks and all kinds of specialty elastomer goods, is specially adapted to the demanding specialty elastomer goods of heat conduction and mechanical property.
The high-performance natural rubber vulcanized rubber of carbon nanotubes of the present invention, comprise natural rubber, vulcanizing agent, promotor, carbon black,, zinc oxide, stearic acid, anti-aging agent, scorch retarder and resin, also comprise modified carbon nano-tube, the mass fraction of each component is: 100 parts of natural rubbers, vulcanizing agent 1-3 part, carbon black 30-70 part, zinc oxide 3-10 part, stearic acid 1-3 part, vulcanization accelerator 0.4-0.8 part, anti-aging agent 2-5 part, scorch retarder 0.2-2 part, resin 1-5 part, modified carbon nano-tube 1-7 part.Wherein, vulcanizing agent is a sulphur, promotor is N cyclohexyl 2 benzothiazole sulfenamide CZ or N oxydiethylene 2 benzothiazole sulfenamide NOBS or is both mixture, anti-aging agent is N-sec.-propyl-N '-diphenyl-para-phenylene diamine 4010NA or 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer RD or be both mixture, scorch retarder is N-cyclohexylthiophthalimide CTP, and resin is the grand resin of solid horse.
The high-performance natural rubber vulcanized rubber of carbon nanotubes of the present invention, modified carbon nano-tube are the multi-walled carbon nano-tubes of 20-40nm, and this walled carbon nanotubes oxide treatment is passed through coupling agent coupling modification again.
The preparation method of the high-performance natural rubber vulcanized rubber of carbon nanotubes of the present invention may further comprise the steps:
Step 1: carbon nanotube is carried out surface treatment: take by weighing multi-walled carbon nano-tubes MWNTs raw material, add salpeter solution, the concentration of salpeter solution is 2-3mol/L, be transferred in the reaction vessel behind the ultra-sonic dispersion, the time of ultra-sonic dispersion is 20-60min, and the oil bath heating is transferred to after the back flow reaction in another container, return time is 10-24h, leave standstill, remove supernatant liquid, add deionized water wash, repeat above-mentioned cleaning process, to neutral, use the millipore filtration suction filtration until solution then, can select the millipore filtration suction filtration of 0.22um for use, dry for standby in baking oven, the temperature of oven dry are 80-100 ℃.
Step 2: surface modification of carbon nanotube: take by weighing through the MWNTs after the step 1 processing and place container, add tetra-sulfurized pair triethoxy Trisilicopropane Si69 and N, N ' dicyclohexylcarbodiimide DCC, the tetra-sulfurized pair triethoxy Trisilicopropane Si69 that adds is 60-150mL, the N that adds, N ' dicyclohexylcarbodiimide DCC is the 0.1-1 gram, be transferred to vessel in heating after ultra-sonic dispersion is even, reaction obtains mixing solutions and is transferred in the container, reaction times is 10-24h, with dehydrated alcohol cleaning reaction unnecessary tetra-sulfurized pair triethoxy Trisilicopropane and N, N ' dicyclohexylcarbodiimide is used the micropore filtering film suction filtration then, can select the millipore filtration suction filtration of 0.22um for use, dry in vacuum drying oven, the temperature of oven dry is 80-100 ℃.
Step 3: the rubber of natural rubber carries out thin-pass on the two rollers of XK-160 type, the carbon nanotube that adds again after step 2 is handled carries out mixing, the mixture that obtains natural rubber and carbon nanotube is a master batch, and the blending ratio of the rubber of carbon nanotube and natural rubber is 10-20 by weight: 100.
Step 4: the rubber of natural rubber is plasticated on the two rollers of XK-160 type, obtains broken-(down)rubber;
Step 5: in broken-(down)rubber, add master batch, carbon black, zinc oxide, stearic acid, promotor, anti-aging agent, scorch retarder, resin and sulphur successively, with mill or Banbury mixer said mixture is carried out mixingly, obtain carbon nanotube and carbon black enhanced natural rubber rubber unvulcanizate;
Step 6: after the rubber unvulcanizate that step 5 obtains is parked, measure its sulfurizing time with vulkameter, sulfuration makes the natural rubber vulcanized rubber of carbon nanotubes.
The invention will be further described below by embodiment and Comparative Examples.
Embodiment 1
Produce modified carbon nano-tube and strengthen the natural rubber sizing material.Selecting caliber for use is the carbon nanotube of 20-40nm, carry out acidification with rare nitric acid, filter, after 100 ℃ of dryings, adopt tetra-sulfurized pair triethoxy Trisilicopropane (Si69) to carry out making female glue of practicing after the modification, even by modification MWNTs and 1: 100 mixed of natural rubber in mill with Thailand No. 3 smoke sheet rubbers, add 4 parts of anti-aging agent RDs successively, 1 part of antioxidant 4010NA, 5 parts of ZnO, 3 parts of stearic acid, 0.3 part accelerant CZ, 0.3 part accelerant N OBS, 2 parts of coumarone indene resins, 3 parts of Sulfurs, 0.5 part anti-scorching agent CTP, 43 parts of carbon blacks, mixing even in mill.After the rubber unvulcanizate that refining is good is parked 24 hours, calculate corresponding sulfurizing time.Sulfuration makes sizing material on vulcanizing press under 143 ℃.The tensile strength 22.9MPa of this sizing material, elongation at break 508%, Akron abrasion value 0.04cm
3/ 1.61km, tear strength 67KN m
-1, thermo-oxidative ageing coefficient 90%, tensile fatigue breaks 89.3 ten thousand times, thermal conductivity 0.315w/m.k.
Embodiment 2
Repeat the method for embodiment 1 by specified each component concentration, but in prescription, adopt 40 parts of carbon blacks, 4 parts of modification MWNTs, the tensile strength 24.7MPa of the cross-linked rubber that obtains, elongation at break 545%, Akron abrasion value 0.03cm3/1.61km, tear strength 98KN.m
-1, thermo-oxidative ageing coefficient 95%, tensile fatigue breaks 97.5 ten thousand times, thermal conductivity 0.415.w/m.k
Embodiment 3
Repeat the method for embodiment 1 by specified each component concentration, but in prescription, adopt 37 parts of carbon blacks, 7 parts of modification MWNTs, the tensile strength 20MPa of the cross-linked rubber that obtains, elongation at break 470%, Akron abrasion value 0.03cm
3/ 1.61km, tear strength 87KN m
-1, thermo-oxidative ageing coefficient 89%, tensile fatigue breaks 94.5 ten thousand times, thermal conductivity 0.305w/m.k
Embodiment 4
Repeat the method for embodiment 2 by specified each component concentration, but replace No. 3 smoke sheet rubbers of Thailand, the tensile strength 26MPa of the cross-linked rubber that obtains, elongation at break 451%, Akron abrasion value 0.03cm with No. 1 smoke sheet rubber of Thailand
3/ 1.61km, tear strength 82KN m
-1, thermo-oxidative ageing coefficient 90%, tensile fatigue breaks 1,330,000 times, thermal conductivity 0.403w/m.k
Embodiment 5
Repeat the method for embodiment 2 by specified each component concentration, but replace No. 3 smoke sheet rubbers of Thailand, the tensile strength 24MPa of the cross-linked rubber that obtains, elongation at break 438%, Akron abrasion value 0.03cm with No. 1 smoke sheet rubber of Malaysia
3/ 1.61km, tear strength 89KN m
-1, thermo-oxidative ageing coefficient 91%, tensile fatigue breaks 950,000 times, thermal conductivity 0.410w/m.k
Embodiment 6
Repeat the method for embodiment 2 by specified each component concentration, but replace No. 1 smoke sheet rubber of Malaysia, the tensile strength 25MPa of the cross-linked rubber that obtains, elongation at break 470%, Akron abrasion value 0.03cm with No. 1 smoke sheet rubber of Thailand
3/ 1.61km, tear strength 81KN m
-1, thermo-oxidative ageing coefficient 89%, tensile fatigue breaks 1,570,000 times, thermal conductivity 0.414w/m.k
Comparative Examples 1
Repeat to implement 1 method by specified each component concentration, but do not use any carbon black and modified carbon nano-tube.The tensile strength 15MPa of the cross-linked rubber that obtains, elongation at break 708%, Akron abrasion value 0.72cm
3/ 1.61km, tear strength 26KN m
-1, thermo-oxidative ageing coefficient 80%, tensile fatigue breaks 900,000 times, thermal conductivity 0.181w/m.k
Comparative Examples 2
Repeat to implement 1 method by specified each component concentration, but in prescription, adopt 44 parts of carbon blacks, the tensile strength 21MPa of the cross-linked rubber that obtains, elongation at break 491%, Akron abrasion value 0.06cm
3/ 1.61km, tear strength 65KN m
-1, thermo-oxidative ageing coefficient 84%, tensile fatigue breaks 550,000 times, thermal conductivity 0.282w/m.k
Comparative Examples 3
Repeat to implement 1 method by specified each component concentration, but with 70 parts of carbon blacks, the tensile strength 18MPa of the cross-linked rubber that obtains, elongation at break 344%, Akron abrasion value 0.065cm
3/ 1.61km, tear strength 66KN m
-1, thermo-oxidative ageing coefficient 79%, tensile fatigue breaks 800,000 times, thermal conductivity 0.304w/m.k
Adopt the coupling agent treatment multi-walled carbon nano-tubes among the present invention, again with the compound use of carbon black after, can improve the mechanical property and the heat conductivility of natural rubber vulcanized rubber greatly.When using 1-7 part multi-walled carbon nano-tubes and 37-43 part carbon black in the cross-linked rubber, its tensile strength is suitable with 44 parts of carbon black filled cross-linked rubbers, but abrasion resistance and tear resistance improve, and thermal conductivity improves 1.44 times.Compare with 70 parts of carbon black filled cross-linked rubbers, tensile strength, abrasion resistance and tear resistance are improved, and thermal conductivity improves 1.37 times.The invention provides a kind of preparation method who has the cross-linked rubber of strong mechanical performance and heat conductivility concurrently.
Claims (10)
1. the high-performance natural rubber vulcanized rubber of a carbon nanotubes, comprise natural rubber, vulcanizing agent, promotor, carbon black, zinc oxide, stearic acid, anti-aging agent, scorch retarder and resin, it is characterized in that: also comprise modified carbon nano-tube, the mass fraction of each component is: 100 parts of natural rubbers, vulcanizing agent 1-3 part, carbon black 30-70 part, zinc oxide 3-10 part, stearic acid 1-3 part, vulcanization accelerator 0.4-0.8 part, anti-aging agent 2-5 part, scorch retarder 0.2-2 part, resin 1-5 part, modified carbon nano-tube 1-7 part; Wherein, modified carbon nano-tube is the multi-walled carbon nano-tubes of 20-40nm, and this walled carbon nanotubes oxide treatment is passed through coupling agent coupling modification again.
2. the high-performance natural rubber vulcanized rubber of carbon nanotubes according to claim 1, it is characterized in that: vulcanizing agent is a sulphur.
3. the high-performance natural rubber vulcanized rubber of carbon nanotubes according to claim 1 is characterized in that: promotor is N cyclohexyl 2 benzothiazole sulfenamide CZ or N oxydiethylene 2 benzothiazole sulfenamide NOBS or is both mixture.
4. the high-performance natural rubber vulcanized rubber of carbon nanotubes according to claim 1, it is characterized in that: anti-aging agent is N-sec.-propyl-N '-diphenyl-para-phenylene diamine 4010NA or 2,2,4-trimethylammonium-1,2-dihyaroquinoline polymer RD or be both mixture.
5. the high-performance natural rubber vulcanized rubber of carbon nanotubes according to claim 1, it is characterized in that: scorch retarder is N-cyclohexylthiophthalimide CTP.
6. the high-performance natural rubber vulcanized rubber of carbon nanotubes according to claim 1 is characterized in that: resin is the grand resin of solid horse.
7. the preparation method of the high-performance natural rubber vulcanized rubber of a carbon nanotubes is characterized in that may further comprise the steps:
Step 1: carbon nanotube is carried out surface treatment: take by weighing multi-walled carbon nano-tubes MWNTs raw material, add salpeter solution, be transferred to behind the ultra-sonic dispersion in the reaction vessel, the oil bath heating is transferred to after the back flow reaction in another container, leave standstill, remove supernatant liquid, add deionized water wash, extremely neutral until solution, use the millipore filtration suction filtration then, dry for standby in baking oven;
Step 2: surface modification of carbon nanotube: take by weighing through the MWNTs after the step 1 processing and place container, add tetra-sulfurized pair triethoxy Trisilicopropane Si69 and N, N ' dicyclohexylcarbodiimide DCC, be transferred to vessel in heating after ultra-sonic dispersion is even, reaction obtains mixing solutions and is transferred in the container, with unnecessary tetra-sulfurized pair triethoxy Trisilicopropane and the N of dehydrated alcohol cleaning reaction, N ' dicyclohexylcarbodiimide, use the micropore filtering film suction filtration then, in vacuum drying oven, dry;
Step 3: the rubber of natural rubber carries out thin-pass on two rollers, adds carbon nanotube after step 2 is handled again and carries out mixingly, and the mixture that obtains natural rubber and carbon nanotube is a master batch;
Step 4: the rubber of natural rubber is plasticated on two rollers, obtains broken-(down)rubber;
Step 5: in broken-(down)rubber, add master batch, carbon black, zinc oxide, stearic acid, promotor, anti-aging agent, scorch retarder, resin and vulcanizing agent successively, with mill or Banbury mixer said mixture is carried out mixingly, obtain carbon nanotube and carbon black enhanced natural rubber rubber unvulcanizate;
Step 6: after the rubber unvulcanizate that step 5 obtains is parked, measure its sulfurizing time with vulkameter, sulfuration makes the natural rubber vulcanized rubber of carbon nanotubes.
8. the preparation method of the high-performance natural rubber vulcanized rubber of carbon nanotubes according to claim 7, it is characterized in that: the concentration of the salpeter solution that adds in the step 1 is 2-3mol/L, the time of ultra-sonic dispersion is 20-60min, and return time is 10-24h, and the temperature of oven dry is 80-100 ℃.
9. the preparation method of the high-performance natural rubber vulcanized rubber of carbon nanotubes according to claim 7, it is characterized in that: the tetra-sulfurized pair triethoxy Trisilicopropane Si69 that adds in the step 2 is 60-150mL, the N that adds, N ' dicyclohexylcarbodiimide DCC is the 0.1-1 gram, reaction times is 10-24h, and the temperature of oven dry is 80-100 ℃.
10. the preparation method of the high-performance natural rubber vulcanized rubber of carbon nanotubes according to claim 7 is characterized in that: carbon nanotube is 10-20 with the blending ratio of the rubber of natural rubber by weight when making master batch in the step 3: 100.
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| CN112210130A (en) * | 2020-10-09 | 2021-01-12 | 山东玲珑轮胎股份有限公司 | Semi-steel base rubber material using carbon nanotube composite masterbatch and preparation method thereof |
| CN114716744A (en) * | 2022-04-29 | 2022-07-08 | 东南大学 | Preparation method of environment-friendly bio-based rubber for L-cysteine tire |
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| CN101418089A (en) * | 2008-12-03 | 2009-04-29 | 中国热带农业科学院农产品加工研究所 | Method for preparing natural rubber-carbon nano tube composite material by using static electricity self-assembly |
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| CN101418089A (en) * | 2008-12-03 | 2009-04-29 | 中国热带农业科学院农产品加工研究所 | Method for preparing natural rubber-carbon nano tube composite material by using static electricity self-assembly |
Non-Patent Citations (3)
| Title |
|---|
| 隋刚等.碳纳米管/ 天然橡胶复合材料的制备及性能.《复合材料学报》.2005,第22卷(第5期),72-77. * |
| 隋刚等.碳纳米管_天然橡胶复合材料的结构与性能.《合成橡胶工业》.2005,第28卷(第1期),40-43. * |
| 隋刚等.碳纳米管预处理方法对天然橡胶/ 纯化碳纳米管.《合成橡胶工业》.2004,第27卷(第6期),348-351. * |
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