聚二甲基硅氧烷/还原氧化石墨烯及酸化多壁碳纳米管织物复合材料的制备及应变传感性能（英文）

制备了聚二甲基硅氧烷(PDMS)/还原氧化石墨烯及酸化多壁碳纳米管织物(RGMWF)复合材料,研究了PDMS/RGMWF复合材料的导电性能和应变传感性能。结果表明,PDMS/RGMWF具有导电性能及可观的应变范围,可用作柔性传感材料。     

Preparation and properties of graphene/multi-walled carbon nanotube/thermoplastic vulcanizate composites

通过熔融接枝共混制备了石墨烯（Ge）/多壁碳纳米管（MWCNTs）/聚丙烯（PP）母粒,然后与丁基橡胶动态硫化制备了Ge/MWCNTs/热塑性硫化胶（TPV）复合材料,考察了Ge/MWCNTs/TPV复合材料的相态结构、热电性能和力学性能。结果表明,Ge/MWCNTs作为异相成核剂能够提高PP的结晶温度;Ge/MWCNTs/TPV复合材料呈现“海-岛”结构,Ge和MWCNTs在PP相和橡塑两相界面分散均匀、与基体结合能力强。加入质量分数均为3%的Ge和MWCNTs时,Ge/MWCNTs/TPV复合材料的直流电导率提高5个数量级,热导率提高了36.7%,拉伸强度达17.3 MPa,扯断伸长率达260%。     

碳纳米管的尺寸及用量对天然橡胶复合材料性能的影响

将碳纳米管（CNTs）添加到天然橡胶（NR）中制备了CNTs/NR复合材料,考察了CNTs的管径和用量对复合材料硫化特性、力学性能、动态力学性能和分散性的影响。结果表明,在管径相同时,随着CNTs用量的增大,复合材料的正硫化时间延长。随着CNTs用量的增大,复合材料的拉伸强度和扯断伸长率先增大后减小。相同管径件下,CNTs的用量越大,Payne效应越强,储能模量变化越大,损耗因子也越大;而在相同用量下,CNTs的管径越大,Payne效应越弱,储能模量变化越小,损耗因子也越小。当CNTs用量为15份、管径为80 nm时,其在NR基体中的分散性最好,复合材料的综合力学性能及动态力学性能最佳。     

碳纳米管/天然橡胶复合材料的结构与性能

通过机械混炼法制备了碳纳米管(CNT)／天然橡胶(NR)复合材料,研究了CNT的预处理方式对复合材料结构与性能的影响。结果表明,与NR相比,CNT／NR复合材料的硫化返原现象减轻,硫化后凝胶质量分数降低,硫化剂用量应适当增加,由混酸氧化处理的CNT填充橡胶复合材料的硫化迟滞效应明显;复合材料内部存在CNT的富集区域和CNT含量很少的橡胶区域,CNT与NR之间的界面结合作用不好;由HF处理的CNT填充橡胶复合材料的整体性能最好,但受CNT在橡胶基体中的不良分散状态及界面性质的影响,其力学性能不高。     

动态硫化法制备多壁碳纳米管/热塑性硫化胶复合材料的热电性能（英文）

采用动态硫化法制备出多壁碳纳米管(MWCNTs)/热塑性硫化胶(TPV)复合材料。结果表明,MWCNTs/TPV复合材料具有"海岛"相结构,丁基橡胶相以微米级颗粒分散于聚丙烯(PP)相中,MWCNTs则主要分散于PP相及橡塑两相界面。当MWCNTs的质量分数达到渗滤阈值(3%)时可形成MWCNTs网络,致使复合材料的体积电阻率急剧减小,即MWCNTs/TPV复合材料的热电性能均因MWCNTs的存在而得到明显改善。     

碳纳米管预处理方法对天然橡胶/纯化碳纳米管复合材料力学性能的影响

纯化后的碳纳米管(CNT)分别经过球磨、表面活性剂十二烷基苯磺酸钠或分散-黏合体系预处理,再与100份(质量)天然橡胶(NR)混炼,可制备NR/纯化CNT复合材料。结果表明,纯化CNT直接与NR混炼,前者在NR中的分散效果不好,二者的界面结合欠佳。纯化CNT经球磨后,团聚程度增加,对复合材料力学性能影响不大。经表面活性剂十二烷基苯磺酸钠处理后的纯化CNT,内聚能下降,用差示扫描量热法(DSC)测定复合材料的DSC曲线表明,复合材料的结晶熔融峰面积增大,力学性能降低。用分散-黏合体系处理纯化CNT,可同时提高纯化CNT在橡胶中的分散效果及界面黏合性,试样结晶熔融峰变得不明显,因此该复合材料的邵尔A型硬度提高,拉伸强度、300％定伸应力和撕裂强度等优于其他试样。     

Dielectric and microwave properties of carbon nanotubes/carbon black filled natural rubber composites

Abstract

Natural rubber (NR) based nanocomposites containing a constant amount (50 phr) of standard furnace carbon black and carbon nanotube (CNT) at a concentration from 1 to 5 phr have been prepared. Their dielectric (dielectric permittivity and dielectric loss) and microwave properties (coefficients of absorption and reflection of the electromagnetic waves and electromagnetic interference shielding effectiveness) have been investigated in the 1–12 GHz frequency range. The results achieved allow recommending CNTs as second filler for NR based composites to afford specific absorbing properties.     

多壁碳纳米管／环氧树脂复合材料性能研究

采用物理机械方法与化学方法相结合的手段,制备了多壁碳纳米管（MWNTS）／环氧树脂（Epoxy）复合材料。通过力学拉伸试验测试了MWNTs/Epoxy复合材料拉伸强度和拉伸模量与MWNTS添加量的关系,利用扫描电镜（SEM）分析了MWNTS／Epoxy复合材料的拉伸断面,并用表面电阻测试仪对所制备的碳纳米管复合材料进行了电学性能测试。结果表明：经过化学酸化的方法处理后的MWNTS在复合材料中的分散得到了改善,力学性能也得到了明显的提高,但酸处理后的复合材料的电学性能明显低于未处理的复合材料。     

碳纳米管/丙烯酸酯橡胶复合材料的制备及性能研究

采用自制的大分子表面改性剂对多壁碳纳米管(MWNTs)进行表面改性,制备改性MWNTs/丙烯酸酯橡胶(ACM)复合材料,研究改性MWNTs用量对复合材料性能的影响,并与炭黑补强的ACM性能进行对比.结果表明:用MWNTs填充ACM制备的材料,其性能远优于炭黑补强的ACM橡胶的性能;随着改性MWNTs用量的增大,复合材料...     

Effect of coal gangue/carbon black/multiwall carbon nanotubes hybrid fillers on the properties of natural rubber composites

The objective of this study was to investigate three kinds of filler with completely different morphology on mechanical properties of natural rubber (NR). Coal gangue (CG) are derived from natural deposits are composed principally by illite and quartz. CG, carbon black (CB), and multiwalled carbon nanotube (CNT) were used as hybrid fillers in NR. CNTs were dispersed into NR latex by ultrasonic irradiation and then the mixed latex were coagulated to obtain the CNTs/NR masterbatch, then mechanical mixing method was employed to prepare the CG/CB/CNTs/NR composites. The addition of CG, CB, and CNTs to NR was varied with the total filler loading fixed at 35 phr. The mechanical properties of NR composites were studied in terms of tensile and dynamic mechanical analysis (DMA). The results showed that the tensile strength and modulus 300% (M300) of all hybrid samples were higher than the composites only loaded CG; and the highest tensile strength of NR loaded with hybrid fillers achieved at sample of loading amount of CG 17.5, CB 15.5, and CNTs 2 phr, whose M300 and elongation at break was obviously higher than that of only CB loaded NR composites; The inclusion CG improves the tensile strength of NR without the sacrifice of its extensibility, while CB and CNTs brings together the enhancement in the ultimate strength and the reduction in the extensibility. DMA results revealed that the existence of CG can improve the dispersion of CB and CNTs in NR matrix. POLYM. COMPOS., 37:3083–3092, 2016. © 2015 Society of Plastics Engineers     

氧化石墨烯/天然橡胶复合材料的制备与性能

采用己内酰胺（CPL）改性氧化石墨烯（GO）（CPL-GO）,与天然橡胶（NR）复合后通过熔融共混法制备了CPL-GO/NR复合材料。考察了CPL-GO用量对CPL-GO/NR复合材料物理机械性能、界面相互作用和气体阻隔性能的影响。结果表明,CPL改性GO后,X射线衍射层间距增加,片层堆砌更为松散,CPL-GO与水接触角增至91.2°。当CPL-GO的质量分数为2.0%时,CPL-GO/NR复合材料的拉伸强度为26.1 MPa,较纯NR提高了50.9%。随着CPL-GO用量的增加,复合材料的储能模量增加,损耗因子的峰值减小,表明GO经CPL表面改性后与NR复合,增强了两相界面间的相互作用,从而提高了复合材料抵抗变形的能力。在40 ℃下,当CPL-GO的质量分数为3.0%时,CPL-GO/NR复合材料的气体渗透系数较纯NR下降了57.1%。     

短切碳纤维对天然橡胶/顺丁橡胶复合材料性能的影响

以天然橡胶(NR)和顺丁橡胶(BR)为基料,以短切碳纤维(SCF)为添加剂,制备了SCF/NR/BR复合材料,考察了SCF用量对NR/BR的摩擦性能及力学性能的影响。结果表明,SCF可增强NR/BR基体的强度,增大其硬度。在NR/BR混合胶中加入15份SCF可以降低混合胶的摩擦系数,减少混合胶的磨损量,提高混合胶的耐磨性能。SCF增强的NR/BR在摩擦过程中发生了磨粒磨损和黏着磨损,形成了卷曲磨屑。     

The effect of surface functionalization of carbon nanotubes on properties of natural rubber/carbon nanotube composites

The objective of this study was to prepare natural rubber composites filled with carbon nanotubes (CNTs) that show an electrical percolation threshold at very low CNT concentrations. Therefore, two methods of surface functionalization of CNTs were investigated to enable an improved dispersion of CNTs and chemical interaction between CNTs and rubber matrix. On one hand, the CNTs have been functionalized ex situ by acid treatment and silanization reaction with bis(triethoxysilylpropyl) tetrasulfide before mixing with the rubber and otherwise in situ functionalization was directly carried out during the processing of the composites in the internal mixer. The grafting of silane molecules onto CNT surface was established by Fourier transform infrared spectroscopy and scanning electron microscopy. Tensile tests revealed the outstanding properties of composites prepared by in situ silanization method. The in situ silanization led to a better dispersion of the CNTs and the formation of chemical linkages between CNT surface and rubber and this became manifest in higher reinforcement of the rubber, higher crosslink densities, and a lower electrical percolation threshold. It was also shown that the in situ silanization is retarding the vulcanization reaction. POLYM. COMPOS., 36:2113–2122, 2015. © 2014 Society of Plastics Engineer     

Carbon nanotubes/carbon black synergistic reinforced natural rubber composites

Abstract

Carbon black (CB) and carbon nanotubes (CNTs) filled natural rubber (NR) composites were prepared. In order to overcome the dispersion of CNTs in rubber matrix, the surface modification of CNTs with bis-(γ-triethoxysilylpropyl)-tetrasulphide (Si-69) was undertaken, and a two-step mixing process, i.e. the use of twin roll mill followed by mixing in a Haake Banbury mixer (TR-THM) was used. The structure and mechanical properties were investigated. The results show that the Si-69 treated CNTs (S-CNTs) were dispersed in the rubber matrix uniformly. Compared with CB/NR composites without CNTs, the S-CNTs/CB/NR composites have better mechanical properties. When the ratio of S-CNTs/CB/NR was 5 : 20 : 100, the tear strength was improved by ～60%, and the mechanical properties reached a maximum. Dynamical mechanical analysis (DMA) reveals that with increasing content of CNT, the elastic modulus of composites at room temperature increases, and the maximum loss tangent and the corresponding glass transition temperature of composites decrease.     

Self-assembled natural rubber/multi-walled carbon nanotube composites using latex compounding techniques

Functionalization of multi-walled carbon nanotubes (MWCNTs) plays an important role in eliminating nanotube aggregation for reinforcing polymeric materials. We prepared a new class of natural rubber (NR)/MWCNT composites by using latex compounding and self-assembly technique. The MWCNTs were functionalized with mixed acids (H2SO₄/HNO₃ = 3:1, volume ratio) and then assembled with poly (diallyldimethylammonium chloride) and latex particles. The Fourier transform infrared spectroscopy, transmission electron microscopy, and scanning electron microscopy were used to investigate the assembling mechanism between latex particles and MWCNTs. It is found that MWCNTs are homogenously dispersed in the natural rubber (NR) latex as individual nanotubes since strong self-aggregation of MWCNTs has been greatly depressed with their surface functionalization. The well-dispersed MWCNTs produce a remarkable increase in the tensile strength of NR even when the amount of MWCNTs is only 1 wt.%. Dynamic mechanical analysis shows that the glass transition temperature of composites is higher and the inner-thermogenesis and thermal stability of NR/MWCNT composites are better, when compared to those of the pure NR. The marked improvement in these properties is largely due to the strong interfacial adhesion between the NR phase and MWCNTs. Functionalization of MWCNTs represents a potentially powerful technology for significant reinforcement of natural rubber materials.     

硅烷改性液体聚丁二烯对天然橡胶复合材料性能的影响

研究了硅烷改性液体聚丁二烯,即三乙氧基硅烷封端聚丁二烯(TTPB)对填充炭黑和白炭黑的天然橡胶(NR)复合材料性能的影响。结果表明,TTPB通过链两端的硅氧烷接枝到白炭黑的表面,改善了白炭黑在NR中的分散性;而且TTPB主链上包含有双键,该双键参与了NR的硫黄硫化,填料-橡胶间的相互作用以及白炭黑的增强作用均得以强化,导致橡胶的交联程度提高、填料网络减少。与未添加TTPB的NR相比,随着TTPB用量的增加,NR硫化胶的拉伸强度和撕裂强度均有所提高,压缩疲劳温升下降,60℃时的损耗因子降低,耐磨性能提高。其中,TTPB用量为5.0份(质量)时NR复合材料的撕裂强度最大,60℃时的损耗因子和DIN磨耗量均为最小。     

氮掺杂石墨烯/碳纳米管/无定形炭复合材料制备及其电化学性能

碳基复合材料被认为是超级电容器广泛应用最有前景的电极材料之一。本文使用氧化石墨烯（GO）、硝酸钴［Co(NO₃)₂］、三聚氰胺为原料,利用钴对高温下热解碳源的催化作用,制备得到了氮掺杂石墨烯/碳纳米管/无定形炭（NC）复合材料,并测试了其电化学性能。探究了金属和三聚氰胺添加量对碳基复合材料结构和性能的影响,研究发现,在添加量分别为0.02mmol和0.3g时,制得的样品具有大比表面积（380.5m²/g）和高掺氮质量分数（6.29%）,并在三电极系统中体现出优异的电化学性能,电流密度为0.5A/g时样品的比电容为137.1F/g,5A/g时比电容为113.5F/g,保持率为88.5%,具有优异的倍率性能,在循环5000圈后样品的容量保持率为104%,具有良好的循环稳定性,这归因于三维结构可以加快充放电过程中的离子转移和氮掺杂可提高材料润湿性和贡献部分赝电容,为超级电容器电极材料的制备提供了理论借鉴。