Dispersion of functionalized multi-walled carbon nanotubes in multi-walled carbon nanotubes/liquid crystal nanocomposites and their thermal properties

A novel liquid crystal functionalized multi-walled carbon nanotubes (LC-MWNTs)/2-methyl-N,N′-bis(4′-methoxy benzoyloxy)-terephthalamide liquid crystal (LC) nanocomposite (LC-MWNTs/LC) was prepared via solution blend. The dispersion and thermal property of the nanocomposites with different loadings of LC-MWNTs (0.1-1 wt.%) were investigated using SEM, TGA and DSC. The results show that the dispersion of LC-MWNTs in LC matrix is more homogeneous than purified MWNTs. The decomposition temperature of nanocomposites exhibits obvious decrease at first and then increase with increasing concentration of LC-MWNTs, which is lower than that of LC for 0.1-0.4 wt.% LC-MWNT loadings and higher than that of LC for 0.5-1 wt.% LC-MWNT loadings. The addition of LC-MWNTs has little effects on the texture of smectic mesophase. These results illustrate the LC-MWNTs/LC nanocomposites, which have lower melting point and higher decomposition temperature than those of LC by adding adequate amount of LC-MWNTs, show a wide temperature range of mesophase and high thermostability. The increased mesophase temperature region of LC materials will be beneficial to their practical applications.     

碳纳米管/羟基磷灰石复合材料的制备及表征

以含钴介孔分子筛为催化剂、乙醇为碳源, 采用CVD法制备碳纳米管(CNTs)。通过原位合成法制备一系列不同碳纳米管含量的碳纳米管/羟基磷灰石(CNTs/HA)复合材料。分别采用XRD、FTIR、TEM、N₂吸附-脱附和Raman光谱等分析手段, 对所合成CNTs/HA复合材料的晶相、结构、形貌和比表面积等进行了表征。同时研究了碳纳米管的添加量对所合成CNTs/HA复合材料形貌的影响。XRD与Raman结果表明, 所得CNTs/HA复合粉体中仅有CNTs与HA两种物相, 纯度较高, 结晶度较好; TEM结果显示, CNTs/HA复合材料中CNTs表面均匀包裹着一层纳米级的针状HA晶粒, 两者形成了较强的界面结合, 且当CNTs与HA的质量比为3:17时, CNTs与HA形成最佳结合状态; N₂吸附-脱附表征结果表明, 与HA的比表面积相比, CNTs/HA复合材料具有较高比表面积。     

纳米碳管/羟基磷灰石复合材料的凝胶注模

采用凝胶浇注成型工艺制备了纳米碳管/ 羟基磷灰石复合材料坯体。研究了p H 值、分散剂、固相含量(纳米碳管和羟基磷灰石在料浆中的质量分数) 、分散工艺等因素对料浆和复合材料坯体性能的影响, 对坯体的力学性能进行了测试, 借助扫描电镜分析了坯体的微观组织。实验发现, 料浆的p H 值应控制在10～12 的范围内;聚甲基丙烯酸铵的浓度为0. 6 %时, 羟基磷灰石悬浮体流动性最好; 十二烷基磺酸钠的浓度在SDS/ CNTs = 1 %～2 %时, 纳米碳管/ 羟基磷灰石复相料浆的粘度最低; 采用球磨法制备的复相料浆固相含量达到55 % , 复合材料坯体的抗弯强度达到57. 403 MPa 。      

Studies on preparation and properties of the multi-walled carbon nanotubes (MWNTs)/epoxy nanocomposites

The MWNTs were coated with polyaniline (PANI) by in situ chemical oxidation polymerization method. FTIR spectroscopy, scanning electron microscope (SEM) and X-ray diffraction (XRD) indicated that the MWNTs were coated with PANI. The MWNTs/epoxy nanocomposites were fabricated by using the solution blending method. Differential scanning calorimetry (DSC), tensile testing, HP 4294A impedance analyzer and SEM were used to investigate the properties of the nanocomposites. The results showed that the modified carbon nanotubes were well dispersed in the polymer matrix. The nanocomposites have enhancements in mechanical, thermal and dielectric properties compare with the neat epoxy resin. The nanocomposites were proven to be a good polymer dielectric material.     

Crystallisation behaviour and morphological characteristics of poly(propylene)/multi-walled carbon nanotube nanocomposites

The objectives of this article are to study the crystallisation behaviour and morphology of melt compounded nanocomposites of poly(propylene) (PP) and multi-walled carbon nanotubes (MWNTs). A PP matrix containing different contents of 0, 1, 2, 4 and 8 wt% of the MWNTs nanofiller was prepared for this investigation. Studies using a differential scanning calorimetry and a wide angle X-ray diffraction indicated that the MWNTs promoted heterogeneous nucleation. The nucleant of the MWNTs affected the crystallisation of the PP, but was not linearly dependent on the MWNT content which meant a saturation of the nucleant effect at low carbon nanotube content. The relative amount, crystallite size and distribution of different crystallites in the PP varied because of the addition of the MWNTs, which affected the final properties of the nanocomposites. Meanwhile, the degree of crystallinity of the PP exhibited an increasing trend with the addition of MWNTs, followed by moderate decreases at higher content. Continuous scanning electron microscopy observations indicate that the nanotubes are well dispersed in the PP matrix at low content of MWNTs. Each nanotube is covered by a layer of PP molecules.     

喷涂功率对碳/碳复合材料表面羟基磷灰石涂层的影响

采用等离子喷涂技术在碳/碳复合材料表面制备了羟基磷灰石(HA)涂层,采用电子拉伸机和自制装置测定了不同喷涂功率下涂层与基体的抗剪强度,采用扫描电镜观察了涂层表面、剪切断裂表面的形貌,采用电子探针分析了试样截面的形貌和成分线分布.结果表明:随着喷涂功率的增加,涂层中HA颗粒的熔化程度和涂层与基体的抗剪强度均增加,涂层与基体的界面属于机械结合,其剪切断裂的形式主要有界面失效和涂层内部失效两种.     

多壁碳纳米管吸附异甘草苷的热力学研究

多壁碳纳米管可选择性地吸附结构相似的两种黄酮类化合物甘草苷和异甘草苷,研究了异甘草苷被多壁碳纳米管吸附的吸附热力学特征。结果表明:多壁碳纳米管吸附异甘草苷的量随着异甘草苷浓度的增加而增加,随着温度升高而降低。异甘草苷的吸附过程符合Freundlich方程。其ΔH0和ΔG0值表明该吸附反应是自发进行的放热反应。     

多壁碳纳米管/PCL-b-PNIPAM复合材料的制备

通过对多壁碳纳米管（MWCNTs）表面修饰合成羟基化的MWCNTs,利用羟基化的MWCNTs催化己内酯开环聚合,接着与溴代异丁酰溴反应,合成MWCNTs接枝聚己内酯（PCL）的大分子引发剂,利用该大分子引发剂引发N-异丙基丙烯酰胺单体进行原子转移自由基活性聚合（ATRP）,成功制备了MWCNTs/PCL-b-PNIPAM复合材料。利用FTIR、TGA、XRD、NMR及TEM对产物进行表征。考察了MWCNTs/PCL-b-PNIPAM复合材料的结晶性能及在氯仿中的溶混性。XRD结果表明:MWCNTs/PCL-b-PNIPAM复合材料的结晶峰与PCL-b-PNIPAM嵌段共聚物基本一致,并且MWCNTs/PCL-b-PNIPAM复合材料在氯仿溶液中有很好的混溶性。      

Mechanical and thermal properties of epoxy nanocomposites reinforced with amino-functionalized multi-walled carbon nanotubes

The functionalized multi-walled carbon nanotubes (MWNTs) with amino groups were prepared after such steps as oxidation, the addition of carboxyalkyl radicals, acylation and amidation. Besides oxidated-MWNTs/epoxy nanocomposites, amino-functionalized MWNTs/epoxy nanocomposites, in which MWNTs with amino groups acted as a curing agent and covalently attached into the epoxy matrix, were fabricated. Subsequently, the effects of MWNT content on the mechanical and thermal properties for the two systems were investigated. It is found that both the tensile strength and impact strength enhance with the increase of MWNT addition, and the most significant improvement of the tensile strength (+51%) and especially impact strength (+93%) is obtained with amine-treated MWNTs at an 1.5 wt.% content. Moreover, the thermal stability of the nanocomposites also distinctly improves. The improvement of the properties of the amine-treated MWNTs system is more remarkable than those of o-MWNTs system. The reasons for these changes were discussed.     

Fabrication of humidity sensors by multi-walled carbon nanotubes

Humidity sensors have multi-walled carbon nanotubes (MWNTs) as the sensing material is demonstrated. The sensor was fabricated on a silicon dioxide coated silicon wafer with metal electrodes. MWNTs were deposited and interlinked with the electrodes by means of the dielectrophoresis technique. The sensing device has the function of a hygrometer when measuring resistance variations to the local relative humidity percentage (RH%) through MWNTs. By measuring the MWNT resistances, we find that higher RH% results in a decrease of conductivity. The results indicate that electron transports in MWNTs are affected by water molecules adsorption on the outermost nanotube surface. A miniature thermocouple sensor was also fabricated and integrated with the humidity sensor. This allowed us to simultaneously sense environmental humidity and temperature. Hence, accurate humidity measurements were achieved with this prototype by calibrating the electrical resistance and temperature levels to carry out the tests with the humidity percentages.     

聚酰亚胺/多壁碳纳米管杂化薄膜力学性能研究

采用不同长径比的多壁碳纳米管通过原位聚合法制备一系列多壁碳纳米管改性的聚酰胺酸胶液,并经热亚胺化途径制备聚酰亚胺杂化薄膜。利用扫描电子显微镜(SEM)观察薄膜的断面形貌,采用红外光谱仪(FT-IR)分析酸化前后多壁碳纳米管表面官能团的变化,并采用电子万能试验机对薄膜的力学性能进行测试,分析了多壁碳纳米管的含量和长径比对杂化薄膜力学性能的影响。结果表明,小掺杂量下,长径比大的多壁碳纳米管更有利于增强PI杂化薄膜的拉伸强度;而长径比小的多壁碳纳米管使杂化薄膜拉伸强度提高的碳纳米管掺杂量范围更宽。     

TEMPO氧化纤维素纳米纤丝对多壁碳纳米管分散性的影响

以竹粉为原料,采用2,2,6,6-四甲基哌啶-1-氧自由基（TEMPO）氧化法通过改变NaClO的添加量制备出不同羧基含量及形态的纤维素纳米纤丝（CNFs）,并将制备的CNFs作为分散剂对多壁碳纳米管（MWCNTs）进行分散处理,得到不同分散浓度的CNFs/MWCNTs悬浮液,采用Beer-Lambert定律对MWCNTs的分散量进行测定,并采用原子力显微镜（AFM）、激光粒度分析仪（LPSA）等手段评价了不同羧基含量及形态的CNFs对MWCNTs的分散效果。结果表明:随着NaClO添加量的增加,CNFs的横截面直径逐渐变小,羧基含量逐渐增加,同时,CNFs对MWCNTs的分散量逐渐增大;当CNFs的羧基含量从0.635 mmol/g增加到1.646 mmol/g时,对MWCNTs的分散量从19%增加到39%;不同CNFs/MWCNTs悬浮液中的粒度分布系数（PDI）值均小于0.3,且不同悬浮液的Zeta电位绝对值均高于30 mV,表明不同羧基含量的CNFs均能对MWCNTs有较好的分散效果;同时,随着羧基含量的增加,CNFs对MWCNTs的分散效果越好,CNFs/MWCNTs复合薄膜的抗拉应力逐渐增大,而且电阻率逐渐降低,当CNFs羧基含量为1.646 mmol/L时,CNFs/MWCNTs复合薄膜抗拉应力达到了91 MPa,薄膜电阻率低至0.1460 Ωcm。      

碳纳米管增强聚合物复合材料的研究进展

论述了碳纳米管/聚合物纳米复合材料的各种制备方法和最新进展。详细讨论了碳纳米管/聚合物纳米复合材料的结构和性能,并对今后的研究方向进行了展望。     

Influence of ozone on N-doped multi-walled carbon nanotubes

Nitrogen-doped multi-walled carbon nanotubes (N-MWCNT) were selectively grown on oxidised silicon substrate by means of catalytic chemical vapour deposition with decomposition of acetonitrile in the presence of ferrocene (FeCp₂) at 900°C. The synthesised N-MWCNT film was initially treated with continuous ozone flow for various time periods and characterised by means of scanning electron microscopy and Raman spectroscopy. The electrochemical response of ozone-treated N-MWCNT film towards ferrocyanide/ferricyanide, [Fe(CN)₆]^3?/4? redox couple was investigated by means of cyclic voltammetry (CV) and electrochemical impedance spectroscopy. The results were compared with those obtained for untreated N-MWCNT film. The findings reveal the occurrence of structural defects on surface of ozone-treated N-MWCNT film due to oxidation of nanotubes. Furthermore, the handling of N-MWCNT film with ozone increases the barrier for interfacial electron transfer and slows down the kinetics of redox reaction occurring on this particular electrode.     

多壁碳纳米管的表面功能化及分散性研究

多壁碳纳米管(MWCNTs)分别经混合、强酸氧化浸泡和酰氯化处理后,再与9,10-二氢-9-氧杂-10-磷杂菲-10-氧化物(DOPO)的衍生物(DHDOPO)进行接枝反应得到表面功能化的MWCNTs。利用傅里叶变换红外光谱仪(FT-IR)、透射电子显微镜(TEM)、扫描电子显微镜(SEM)、热重分析仪(TGA)、紫外-可见分光光度仪(UV-Vis)和沉降实验等分别表征改性前后MWCNTs的结构和表面形态,估算DHDOPO在MWCNTs表面的相对接枝率,研究改性前后MWCNTs在乙醇中的分散性。结果表明,MWCNTs经混合强酸氧化后表面出现羧基;DHDOPO在MWCNTs上的相对接枝率为51%;混合强酸氧化和表面接枝DHDOPO的MWCNTs在无水乙醇中具有良好的分散性。     

聚对苯二甲酸乙二醇酯/多壁碳纳米管复合材料制备与性能研究

通过微型双螺杆挤出机熔融共混制备了聚对苯二甲酸乙二醇酯(PET)/碳纳米管(CNT)复合材料。采用表面电阻仪、场发射扫描电镜(FESEM)和差示扫描量热仪(DSC)研究了多壁碳纳米管(MWNT)和羧基化多壁碳纳米管(MWNT-COOH)对复合材料导电性能与结晶性能的影响。结果表明,当CNT含量1%(质量分数)时,CNT在PET中形成三维导电网络,复合材料具有抗静电和导电功能,MWNT-COOH分散性好,与PET有较强的界面结合和相互作用,复合材料的导电性优于PET/MWNT。复合材料的结晶放热峰温度大幅提高,比PET高40多℃,0.1%(质量分数)含量的CNT就有非常明显的异相成核与诱导结晶作用。同时,复合材料的结晶度增加,熔点略微升高。     

氟化多壁碳纳米管作正极对锂/氟电池性能的影响

通过对多壁碳纳米管(MWCNTs)进行氟化改性,获得氟碳原子比分别为0.28(CF0.28),0.56(CF0.56),0.78(CF0.78)的氟化多壁碳纳米管。将氟化多壁碳纳米管作正极活性物质涂覆于铝箔,金属锂片为对极,组装成锂/氟化多壁碳纳米管(Li/CFx)一次纽扣电池。采用热重分析(TGA)、扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射仪(XRD)、X射线光电子能谱分析(XPS)进行结构和性能表征,通过恒流放电检测电池的电化学性能。结果表明:活性物质为CF0.78的正极电极的电化学性能最佳,在电流密度为39mA/g时放电比容量达724mAh/g,同时出现了稳定的放电平台。在0.05C放电倍率时,3种电极的活性物质利用率分别达到73.4%,89.6%,92.9%。相比0.05C,2C放电倍率下的放电比容量衰减率分别为68.8%,34.1%,39.6%,表明提高氟化程度,能够降低放电比容量衰减率,虽CF0.78相对CF0.56的放电化容量衰减率有所上升,但在相同放电倍率时,其放电曲线稳定性是最好的。