碳纳米管在聚丙烯腈中的分散状态

采用原位聚合法合成了不同碳纳米管(CNT)含量的碳纳米管／聚丙烯腈(CNT／PAN)复合材料,并利用X光电子能谱(XPS)、紫外、红外、扫描电镜等对产物进行了表征。结果表明：在原位聚合反应中,碳纳米管与PAN形成化学键合,大量碳纳米管均匀地分布在基体PAN内部,与PAN形成了良好的界面。     

高聚物/碳纳米管复合材料研究进展

简要介绍了近几年高聚物／碳纳米管复合材料的研究进展，并对高聚物／碳纳米管复合材料研究中的工艺、方法、实际应用及存在问题进行了讨论。参考文献18篇。     

多壁碳纳米管对PS分子量影响的研究

由于碳纳米管（CNT）具有优异的力学、电学、光学等性能,近年来,聚合物／碳纳米管（polymer／CNT）复合材料的研究已经成为研究者关注的热点。相关的研究主要集中在：一是将CNT作为填充材料制各复合材料,使复合材料的力学、电学等性能得到提高。二是将CNT作为主体,用聚合物对CNT进行修饰,使CNT在有机溶剂中能够获得良好的溶解度。而对于在聚合反应中,CNT的加入对聚合物分子量影响的研究,相关的报道较少。本文利用悬浮聚合法制备了聚苯乙烯／多壁碳纳米管（PS／MWNT）复合材料,采用透射电镜（TEM）和凝胶渗透色谱（GPC）对其进行了分析,详细研究了MWNT对于PS分子量的影响。     

有机化学接枝-电化学沉积聚合制备CNTs/PANI纳米复合材料

通过有机化学合成法先在碳纳米管表面接枝上苯胺单体,然后在不锈钢电极表面在硫酸溶液中采用循环伏安法电化学沉积聚合制得碳纳米管/聚苯胺(CNTs/PANI)纳米复合材料.扫描电子显微镜和傅立叶变换红外光谱表征所得材料的微观结构和基团,循环伏安和恒流充放电测试用于考察所得CNTs/PANI纳米复合材料的电化学性能.所得结果与...     

非共价修饰碳纳米管/二氧化钛复合材料的合成及性能

采用溶胶-凝胶法在聚乙烯吡咯烷酮(PVP)非共价修饰的碳纳米管表面均匀沉积二氧化钛粒子制得纳米复合材料。用TEM、XRD、FTIR、N2吸脱附等对复合材料进行了表征。结果表明:纳米二氧化钛纳米粒子均匀沉积在被修饰碳纳米管表面,且二氧化钛为纯锐钛矿晶体结构,没有金红石和板钛矿相。非共价修饰碳纳米管/二氧化钛复合材料具有良好的介孔结构,其孔径分布主要集中在6～10 nm,且比表面积与纯的二氧化钛相比明显增大,在紫外光照射下降解亚甲基蓝,相比纯的二氧化钛和碳纳米管/二氧化钛,具有较高的催化活性。     

氧等离子体改性的聚苯胺/碳纳米管电化学性能

由乳液聚合法制备聚苯胺/碳纳米管复合电极材料,再利用感应耦合氧等离子体源对其进行射频放电处理,制得改性后的复合材料,进一步研究氧等离子体处理时间对材料表面性质和电化学性能的影响。通过SEM和FTIR对复合材料的表面形貌和组成进行分析和表征,结果显示复合材料在改性后的微观形貌均一,粒径变小且颗粒间团聚减轻,材料表面引入了羟基官能团。电化学测试表明,经氧等离子体改性处理10 min后,聚苯胺/碳纳米管复合材料具有突出的电化学特性,比电容为287.8 F.g-1,为改性前的1.7倍,同时等效串联电阻(ESR)降低了67.7%,是一种优良的超级电容器电极材料。由此也表明氧等离子体改性是一种高效的电极材料改性方法。     

碳纳米管负载纳米金-石墨烯量子点修饰电极电化学检测过氧化氢

采用过氧化氢刻蚀法制备石墨烯量子点(GQDs),再采用原位化学还原法制备金纳米粒子-石墨烯量子点纳米复合物(Au NPs-GQDs),最后以聚二甲基二烯丙基氯化铵(PDDA)为交联剂将上述纳米复合物组装于多壁碳纳米管表面,制得金纳米粒子-石墨烯量子点-PDDA-多壁碳纳米管复合材料(Au NPs-GQDsPDDA-MWCNTs)。通过荧光光谱法、紫外-可见吸收光谱法和透射电子显微镜对上述复合材料进行表征。采用滴涂法制得该复合材料修饰的玻碳电极,研究了过氧化氢在该电极上的电化学行为。结果表明:在石墨烯量子点、金纳米粒子和多壁碳纳米管三者的协同作用下,该电极对过氧化氢的电氧化表现出强的催化活性。在优化条件下,安培法检测H_2O_2的线性范围为2.0×10~(-8)~1.5×10~(-3)mol/L,检出限(3sb)为8.0×10~(-9)mol/L,灵敏度为61.6μA/(mmol·L~(-1))。     

SiO／CNTs：新型锂离子电池负极材料

通过化学气相沉积方法原位制备了氧化硅／碳纳米管（SiO／CNTs）极材料．扫描电镜（SEM）测试结果表明,碳纳米管沉积在氧化硅表面,形成笼状结构,将氧化硅粒子紧密包裹．SiO／CNTs负极材料的初始充放电容量分别为1171和789mAh／g,经过80次充放电循环后,可逆容量为500mAh／g．在循环过程中,碳纳米管和氧化硅之间的紧密接触使得SiO／CNTs复合材料保持了稳定的导电网络,循环性能得以提高．     

多壁碳纳米管/玻璃纤维/含邻苯二甲腈的苯并噁嗪树脂复合材料的电学与力学性质(英文)

采用溶液共混法及层压成型的方法制备了多壁碳纳米管/玻璃纤维/含双邻苯二甲腈的苯并噁嗪树脂复合材料,并考察了该纳米复合材料的力学及电学性质。材料的渗滤阀值为碳纳米管含量为0.7%,此时,材料也表现出最好的机械性能。通过扫描电镜对材料的断面进行了考察,发现在碳纳米管含量为0.7%时形成了网状结构,因此此时复合材料表现出最好的电学及力学性质。复合材料在碳纳米管含量低于7%时具有很低的吸水性。     

PS/MWNT复合材料界面上的化学反应性

利用悬浮聚合法制备了可溶于甲苯的聚苯乙烯／多壁碳纳米管（PS／MWNT）复合材料,通过透射电镜观察到MWNT完全或部分被PS包裹。拉曼光谱分析表明,复合材料中MWNT的两个特征峰D峰和G峰的位置均发生了红移,且D峰的强度及ID／IG值也较MWNT明显增大。凝胶渗透色谱测得复合材料的分子量相对于纯PS的分子量有较大幅度提高。同时比较共混法与悬浮聚合法制得的复合材料在甲苯中的溶解性。可以认为悬浮聚合法制备复合材料的过程中,MWNT参与了PS的聚合反应,与PS形成了化学键从而完全或部分地被PS包裹。     

HPAN/SPI水凝胶纤维的PH刺激响应性能

探索了聚丙烯腈(PAN)和大豆分离蛋白(SPI)在NaOH水溶液中进行PAN碱解,然后挤到凝固浴中凝固、交联,制备水解聚丙烯腈(HPAN)／SPI水凝胶纤维的方法。通过测定凝胶纤维的平衡溶胀伸长率和溶胀伸长率,观察到HPAN／SPI水凝胶纤维的滞后和可逆的伸长／收缩行为,同时在不同组成的凝胶纤维中,随着PAN含量的逐渐增大,水凝胶纤维的响应速率呈现由小到大然后减小的变化规律,当mPAN／mspt=6／4时有最好的响应性能。     

多孔碳纳米纤维负载Pd纳米颗粒用于增强电催化氧还原性能

采用溶剂热法合成了以锆为金属核心、2-氨基为配体的锆基金属有机骨架(UiO-66)纳米材料,通过静电纺丝技术制备出UiO-66自由分散的聚丙烯腈(PAN/UiO-66)纤维,可控热解得到多孔碳纳米纤维(porous carbon nanofibers,PCNFs),结合湿化学还原法在PCNFs表面沉积Pd纳米颗粒,得到PCNFs@Pd复合材料。通过扫描电子显微镜、透射电子显微镜、X射线衍射技术对其形貌、组成、结构进行表征;采用电化学工作站分别测试了PCNFs@Pd在0.1 mol·L^-1KOH和0.1 mol·L^-1HClO₄电解质中氧还原性能(oxygen reduction reaction,ORR)。结果表明,在PAN纤维中添加UiO-66显著提高了PCNFs@Pd(Pd负载量为0.34%)复合材料的ORR性能。相比40%Pt/C,在碱性电解质中,PCNFs@Pd复合材料展示出更低的Tafel斜率、更优异的循环稳定性和耐甲醇中毒性。在酸性电解质中也表现出类似20%Pt/C的催化活性和循环稳定性。     

Electrospun EGNPs reinforced precursor carbon nanofibril composites by using RSM

Response surface methodology (RSM),based on five‐level, four variable Box‐Benkhen technique was investigated for modeling the average fiber diameter of electrospun polyacrylonitrile (PAN) nanofibers. The four important electrospinning parameters were studied including applied voltage (kV), Berry's number, deposition distance from nozzle to collector (cm), and spinning angle (? in degree). The measured fiber diameters were in a good agreement with the predicted results by using RSM technique. High‐regression coefficient between the variables and the response (R² = 87.74%) indicates excellent evaluation of experimental data by second‐order polynomial regression model. The optimum PAN average fiber diameters of 208 and 37‐nm standard deviation were collected at 19 kV, Berry's number = 10, 25^° spinning angle, and 16‐cm deposition distance. The PAN/N,N‐dimethylformamide (DMF) polymer solution with the optimum weight concentration (10 wt.%) was selected to study the effect of dispersing exfoliated graphite nanoplatelets (EGNPs) in PAN/DMF solution on the electrospun EGNP/PAN fibril composite diameter. Five different EGNPs weight concentrations (2, 4, 6, 8, and 10 wt.%) were dispersed in the optimized PAN/DMF polymer solution. Morphology of EGNPs/PAN fibril composites and its distribution were investigated by scanning electron microscopy (SEM) to show the minimum fiber diameter for the above‐mentioned 5 wt. % of EGNPs. A minimum fibril composite diameter of 182 nm was obtained at 10 wt.% of EGNPs. Morphological characteristics of electrospun fibers and their distribution were tested by Raman spectroscopy, SEM, differential light scattering, and high‐resolution transmission electron microscopy.     

Effects of deformation-induced orientation on cyclization and oxidation of polyacrylonitrile fibers during stabilization process

Orientation of copolymer polyacrylonitrile(PAN) chains during their deformation prior to stabilization and the further effect on the stabilization were investigated in detail.Results reveal that the orientation of PAN chains presents a saturation point of 69.51%when the deformation ratio reaches approximately 1.07,meanwhile the cyclization rather than the oxidation has a stronger dependence on the orientation of PAN chains during stabilization.The cyclization is facilitated that the cyclization degree is increasing while the activation energy is decreasing obviously as a consequence of the developing orientation of PAN fibers before the saturation point;however,it is restrained during the further deformation of PAN fibers after the point.The resulting carbon fibers obtained from the PAN fibers prepared at the saturation point possess the highest mechanical properties of 4.07 GPa in tensile strength and 249.0 GPa in tensile modulus.     

采用静电纺丝/非溶剂致相分离制备聚丙烯腈多孔超细纤维的研究

以聚丙烯腈/二甲基亚砜/N,N'-二甲基甲酰胺三元体系为纺丝液、3℃水浴为接收介质,通过静电纺丝制备了具有纳米孔结构的静电纺聚丙烯腈多孔超细纤维.探讨了溶剂比例、接收介质、聚丙烯腈浓度、纺丝电压及接收距离等因素对纤维直径和表面孔隙率的影响.结果表明最佳制备条件为混合溶剂质量比1∶1、纺丝电压16 kV、聚丙烯腈浓度15 wt%、接收距离5 cm、纺丝速率0.7 mL/h、环境温度25℃、相对湿度40%～70%.在此条件下得到的聚丙烯腈多孔超细纤维直径在420～490 nm,平均直径468 nm,表面孔隙率3.4%,纤维内部形成大量孔径为8～30 nm的孔结构,且孔径分布均匀,孔形状相对一致.N2吸附脱附测试表明,聚丙烯腈多孔纤维的BET比表面积达43.86 m2/g,是相同直径无孔聚丙烯腈纤维比表面积理论值的6倍.通过研究聚丙烯腈/(二甲基亚砜+N,N'-二甲基甲酰胺)/水的三元相图,提出非溶剂致相分离是主要成孔机理.     

聚苯胺与聚苯甲酰胺的共混研究

在制得可溶性聚苯胺基础上，研究了聚苯胺与聚苯甲酰胺在二甲基乙酰胺（含３．５％ＬｉＣｌ）中的共混溶液行为并绘出其三元相图。研制了不同配比的聚苯胺／聚苯甲酰胺共混膜。测试结果表明，在聚苯胺中混入２０％ＰＢＡ后其拉伸强度可增加２～３倍且其导电率可达７．５Ｓ／ｃｍ。考察了混合比对共混薄膜的导电率和力学性能的影响．ＳＥＭ及Ｘ－衍射结果表明聚苯胺／聚对苯甲酰胺共混物存在着明显的微观相分离．     

同轴静电纺丝再经两步后处理制备PAN基中空碳纤维

采用聚丙烯腈(PAN)溶液作为壳层,甲基硅油作为芯层,利用同轴静电纺丝技术制备出外径为3μm的同轴PAN复合纤维,经过预氧化和炭化后可以制得直径约为1μm的中空碳纤维.采用扫描电镜(SEM)观察中空纤维形貌.傅立叶红外光谱分析仪(FTIR)表征了热处理前后纤维成分变化.分析了同轴射流结构、芯液/壳液流速比Vin/Vout对中空结构的影响.研究表明,同轴内针尖伸出外针尖的距离Zp是影响同轴射流形成的主要因素,伸出长度Zp约为外针孔半径rout的1/2时得到同轴射流,Zp>0.7rout时从冠状锥体周围产生许多射流,不能在锥顶部形成同轴射流.芯液/壳液流速比Vin/Vout对中空结构的形成有较大影响,当Vin/Vout=0.5时得到多孔纤维,增大芯液流速,当Vin/Vout=1时得到中空纤维,继续增大Vin/Vout=2时得不到同轴射流.     

The crosslinking of epoxy resins at interfaces. III. At a carbonized polyacrylonitrile surface

The crosslinking chemistry of an anhydride-cured epoxy resin, in the first 200–400 nm adjacent to a carbonized polyacrylonitrile (PAN) surface (a model for the surface of a carbon fiber), is significantly affected by the humidity history of that surface. Prior humid aging of the carbonized PAN surface increases the subsequent rate of consumption of anhydride curing agent, and decreases the yield of ester crosslinked products. The crosslinking chemistry of an amine-cured epoxy resin appears unchanged by the presence of the carbonized surface. Dynamic mechanical analysis (DMA) of unidirectional composites made from carbon fibers and the above epoxy resin matrices shows that the damping characteristics of composites made with an epoxy–anhydride matrix are sensitive to the preconditioning history of the carbon fibers, while composites made with an epoxy–amine matrix are unaffected by the preconditioning history of the fibers. Partial removal of the carbon fiber surface coating by dichloromethane extraction does not change the sensitivity of the composites to fiber preconditioning history. These results are rationalized on the basis of the effect moisture adsorbed by the carbonized PAN and by the carbon fiber has on the epoxy resin crosslinking processes.     

Samarium powder as catalyst for SET‐LRP of acrylonitrile in 1,1,1,3,3,3‐hexafluoro‐2‐propanol for control of molecular weight and tacticity

Samarium powder was applied as a catalyst for single electron transfer‐living radical polymerization (SET‐LRP) of acrylonitrile (AN) in 1,1,1,3,3,3‐hexafluoro‐2‐propanol (HFIP) with 2‐bromopropionitrile as initiator and N,N,N′,N′‐tetramethylethylenediamine as ligand. First‐order kinetics of polymerization with respect to the monomer concentration, linear increase of the molecular weight with monomer conversion, and the highly syndiotactic polyacrylonitrile (PAN) obtained indicate that the SET‐LRP of AN could simultaneously control molecular weight and tacticity of PAN. An increase in syndiotacticity of PAN obtained in HFIP was observed compared with that obtained by SET‐LRP in N,‐N‐dimethylformamide (DMF). The syndiotacticity markedly increased with the HFIP volume. The syndiotacticity of PAN prepared by SET‐LRP of AN using Sm powder as catalyst in DMF was higher than that prepared with Cu powder as catalyst. The increase in syndiotacticity of PAN with Sm content was more pronounced than the increase in its isotacticity. The block copolymer PAN‐b‐polymethyl methacrylate (52,310 molecular weight and 1.34 polydispersity) was successfully prepared. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011