多壁碳纳米管-还原氧化石墨烯杂化薄膜导电性能的调控

以氧化石墨烯(Graphene oxide,GO)水溶胶作溶剂和表面活性剂,将不同质量分数的多壁碳纳米管(Multi-walled carbon nanotubes,MWCNTs),通过超声空化作用分散于其中得到稳定均质的多壁纳米管/氧化石墨烯(MWCNT-GO)悬浮液。采用微滤自组装法制备MWCNT-GO杂化薄膜,然后将其置于真空干燥箱中进行低温(200℃)热处理1 h以脱除GO中的大部分含氧官能团,即得部分还原的多壁碳纳米管-还原石墨烯(MWCNT-RGO)杂化薄膜。结果表明:MWCNT-GO杂化薄膜呈现均质层状的"三明治"式结构,MWCNTs与GO形成3D交联导电网络,通过控制MWCNTs的添加量和低温热处理,可实现氧化石墨烯导电性的恢复和有效调控。随着MWCNTs含量的增加,所得MWCNT-GO杂化薄膜的导电率增加。掺杂质量分数50%的MWCNTs所制MWC-NT-GO-50杂化薄膜的导电率为1 120 S/m,经200℃热处理后,导电率高达5 380 S/m。     

抗静电碳系/聚酰亚胺复合薄膜的制备及表征

采用氧化石墨烯还原法制备了石墨烯(GR),同时采用混酸酸化法处理多壁碳纳米管(MWCNTs),以1%(wt,质量分数,下同)的GR和不同含量的酸化MWCNTs作为填料,通过超声搅拌分散-原位聚合法制得抗静电碳系/聚酰亚胺(GR-MWCNTs/PI)复合薄膜,并对复合薄膜的抗静电性能、热稳定性和力学性能进行表征。结果表明,2种碳系材料的添加可明显提高薄膜的导电性、机械性能和抗静电的效果,导电填料的添加对薄膜的热稳定性影响不大,在GR含量为1%,MWCNTs含量为2%时,在560℃时失重率约35%,电阻率为4.44×107Ω·cm,拉伸强度达到88.0MPa,断裂伸长率达到16.23%,拉伸强度和断裂伸长率分别比纯聚酰亚胺提高了122.4%和128.6%。     

纳米碳纤维在水性体系中的分散性能及机理讨论

以十二烷基硫酸钠（SDS）、聚丙烯酸（PAA）复合曲拉通（Tx100）、分散助剂DISPERBYK-180（D-180）和十二炕基苯磺酸钠（SDBS）等4种表面活性剂作为分散剂,采用多种表面活性剂超声分散法分散纳米碳纤维（CNFs）．结合紫外／可见分光光度计法、透射电镜（TEM）及场发射扫描电镜（FESEM）观察、Zeta电位法、表面张力测试、静置及离心分离等测试方法,全面地表征了采用不同表面活性剂的CNFs悬浮液的分散状态,探讨了表面活性剂对CNFs在水性体系中分散性的影响．实验结果表明：4种表面活性剂中,SDS对CNFs的分散效果最好,其最佳掺量为1．6g／L：SDBS的分散效果次之,D．180效果再次,而PAA复合Tx100的分散效果最差．     

多壁碳纳米管对Ti-碳纤维/反应型聚酰亚胺超混杂层板力学性能的影响

为了改善Ti/反应型聚酰亚胺（PMR）树脂界面的黏结强度,从而提高Ti-碳纤维（CF）/PMR超混杂层板的力学性能,本文探究了添加多壁碳纳米管（MWCNTs）对Ti-CF/PMR超混杂层板力学性能的影响。将不同质量分数（0wt%、2.5wt%、5.0wt%和7.5wt%）的MWCNTs利用超声分散法均匀分散于PMR树脂中,随后进行Ⅰ型断裂韧性试验,探究添加MWCNTs对Ti-CF/PMR超混杂层板界面性能的影响,最后选取最优含量的MWCNTs同时添加到PMR胶层和CF/PMR树脂中,并进行弯曲试验,探究添加MWCNTs对Ti-CF/PMR超混杂层板力学性能的影响。通过SEM观察和分析了相应的失效模式和增强机制。结果表明:当MWCNTs含量为5.0wt%时,Ⅰ型层间断裂韧性提高了74%;同时添加5.0wt% MWCNTs于PMR胶层和CF/PMR复合材料树脂中,Ti-CF/PMR超混杂层板的弯曲性能较未添加MWCNTs提高了42%。这是由于MWCNTs在PMR胶层和CF/PMR树脂中的分布均匀性较高,且能分散并承受界面层转移到纤维层的载荷,并利用自身拔出、断裂、桥接、脱黏来吸收并消耗断裂能量,进一步提升Ti-CF/PMR超混杂层板的弯曲性能。      

TEMPO氧化法制备纳米几丁质晶须粒子的优化及其产品特性表征

以虾壳几丁质为原料,利用TEMPO-NaBr-NaClO选择性氧化体系制备羧基化纳米几丁质晶须粒子。测定了反应体系中pH值与NaClO(13%有效氯)含量的变化对几丁质羧基化的影响,研究了生产高羧基含量和小颗粒粒度纳米几丁质晶须的最佳反应条件。利用傅里叶变换红外光谱、透射电子显微镜、动态光散射对制备的负电荷纳米几丁质晶须粒子进行结构表征,测定产品水悬浮液的有效粒径和有效电位;采用电导率法测定负电荷纳米几丁质的羧基含量。实验结果表明:在反应体系B1(pH=10.5,V(NaClO)=15mL)中,制备的负电荷纳米几丁质羧基含量最大,达(3.16±0.23)mmol/g,纳米晶须粒子流体动力学粒径(Z-average)为(113.97±2.29)nm,Zeta电位为(-38.73±4.49)mV;在反应体系B0(pH=10.5,V(NaClO)=18mL)中,制备的NC-晶须的羧基含量、粒子Z-average和Zeta电位分别为(3.00±0.41)mmol/g、(106.13±0.38)nm和(-41.41±6.83)mV。上述两种条件制备的纳米几丁质晶须粒子羧基含量和Zeta电位没有显著差异,但B0晶须粒子有效粒径最小。由于纳米材料的小尺寸效应是影响纳米材料生物活性的关键因素,因此制备高生物活性的纳米几丁质晶须的最佳条件是B0,即制备条件为pH=10.5,V(NaClO)=18mL(13%)。     

酸化处理多壁碳纳米管/氰酸酯树脂复合材料性能

采用酸化处理的多壁碳纳米管（MWCNTs）增强双酚A型氰酸酯-酚醛型氰酸酯（BCE-NCE）树脂。通过SEM、TEM对MWCNTs/BCE-NCE树脂复合材料微观结构进行表征,利用DSC、DMA和TG/DTA对MWCNTs/BCE-NCE树脂复合材料热性能进行研究,采用电子拉力机对MWCNTs/BCE-NCE树脂复合材料力学性能进行测试,采用谐振腔法对MWCNTs/BCE-NCE树脂复合材料介电性能进行测试。结果表明,混酸处理过的MWCNTs在BCE-NCE树脂基体中的分散效果较好。MWCNTs对BCE-NCE树脂热力学性能影响不大,当MWCNTs添加量为0.8wt%时,BCE-NCE树脂玻璃化转变温度（T_g）从298℃下降到285℃,但仍维持较高水平。当MWCNTs添加量为0.6wt%时,MWCNTs/BCE-NCE树脂复合材料冲击强度为11.40 kJ/m²,提高了40.7%。MWCNTs的加入增加了BCE-NCE树脂介电常数和介电损耗,当MWCNTs添加量为0.8wt%、频率为1 GHz时,MWCNTs/BCE-NCE树脂复合材料介电常数为5.1,介电损耗为0.032。因此,MWCNTs/BCE-NCE树脂复合材料未来可在耐高温复合材料和电子等行业应用。     

纳米碳纤维表面修饰及其在水溶液中的分散

为了研究纳米碳纤维(CNFs)在水溶液中的分散情况,对其进行高温纯化处理,以甲基纤维素(MC)为分散剂,制备分散良好的CNFs悬浮液.采用差热分析(DTA)和热重分析(TGA)研究了高温处理对CNFs的影响,通过测定悬浮液的紫外可见光吸光度、等温吸附曲线、zeta电位及表面张力等方法研究了MC对CNFs分散性能的影响,并讨论分析了MC对CNFs的分散机理.结果表明:MC的加入使CNFs悬浮液的zeta电位由-15.4 mV升至0,表面张力由38.87 mN/m降至36.54 mN/m;等温吸附曲线表明MC在CNFs的表面为"单阶段吸附",当MC的质量浓度达到0.4 g/L时,MC在CNFs表面饱和吸附;当CNFs达到最佳分散状态时,MC与CNFs的质量比为2∶1.     

纳米纤维素-碳纳米管/热塑性聚氨酯复合薄膜的制备及应变响应性能

采用2,2,6,6?四甲基哌啶?1?氧自由基(TEMPO)氧化法制备了不同羧基含量的纳米纤维素(CNF),并将其用作碳纳米管(CNTs)的分散剂,通过超声、离心处理制备出稳定均一的CNF?CNTs分散液,然后通过朗伯?比尔定律测定CNF?CNTs分散液中CNTs的浓度,研究了不同CNF羧基含量对CNTs的分散效果。此外,利用静电纺丝法制备出柔性、多孔的热塑性聚氨酯(TPU)薄膜作为基体,以CNF?CNTs分散液作为导电填料,通过真空抽滤法将CNF?CNTs负载于TPU多孔膜上,制备出CNF?CNTs/TPU复合薄膜,并探究了不同CNF羧基含量对CNF?CNTs/TPU复合薄膜应变响应性能的影响规律。结果表明,羧基含量对CNF的分散性能具有重要影响。随着CNF羧基含量的提高,CNF对CNTs分散效果越好,CNF?CNTs/TPU复合薄膜具有更大的应变响应范围。当CNF羧基含量为1.698 mmol/g时,CNF?CNTs/TPU复合薄膜的应变响应范围高达507%,灵敏度系数为335,表现出优异的应变响应性能。      

十二烷基硫酸钠对纳米碳纤维的分散作用

以十二烷基硫酸钠(SDS)为分散剂,采用超声分散法制备了分散性良好的纳米碳纤维(CNFs)悬浮液,结合紫外/可见分光光度计法、Zeta电位法、表面张力测试、透射电镜(TEM)观察、扫描电镜(FESEM)观察和静置离心法,对不同SDS浓度的CNFs悬浮液的均匀性和稳定性进行了表征,同时对SDS的分散机理进行了探讨。实验结果表明,当SDS质量浓度达到1.6g/L时,CNFs悬浮液的分散稳定性最好,Zeta电位绝对值达到最大,SDS溶液表面张力最低。TEM和FESEM观察发现,分散后的CNFs团聚现象消失,表面有吸附膜形成,证明在分散过程中,SDS会吸附于CNFs表面,使表面张力下降,并通过自身电离产生的静电斥力与疏水链段的空间排斥力共同作用来实现CNFs的分散。     

MWCNTs对环氧树脂及多尺度MWCNTs-碳纤维/环氧树脂复合材料力学性能的影响

通过对胺基化多壁碳纳米管（MWCNTs-NH₂）进行改性,得到改性MWCNTs悬浮液（MWCNTs-NH₂（M））。分别将羧基化MWCNTs （MWCNTs-COOH）和MWCNTs-NH₂（M）分散在环氧树脂（EP）中,采用热熔法制备了多尺度MWCNTs-碳纤维（CF）/EP复合材料。研究了MWCNTs对EP模量、韧性及EP与CF之间界面黏结强度的影响,并分析了MWCNTs与CF上浆剂的作用,评价了多尺度MWCNTs-CF/EP复合材料的力学性能。结果表明：官能团化的MWCNTs可对EP的模量和韧性起到更好的增强作用。MWCNTs接枝的-COOH或-NH₂可与CF上浆剂中的环氧基团发生化学反应,提高EP与CF之间的界面剪切强度。MWCNTs-NH₂（M）对多尺度MWCNTs-CF/EP复合材料力学性能的增强效果优于MWCNTs-COOH,当MWCNTs-NH₂（M）的含量为1wt%时,多尺度复合材料的0°压缩强度、90°压缩强度、弯曲强度、弯曲模量、冲击后压缩强度（CAI）分别提高了16.7%、16.3%、40.9%、30.3%、20.6%。     

TEMPO氧化体系对废纸浆纤维的氧化改性

目的利用2,2,6,6-四甲基哌啶氧化物自由基(TEMPO)/NaClO/NaBr氧化体系改善废纸浆纤维成纸的性能。方法以废纸浆为原料,在碱性条件下采用TEMPO/NaClO/NaBr氧化体系对纤维进行选择性氧化,得到不同羧基含量的氧化废纸浆,通过纤维形态分析仪及化学分析法对纤维形态和羧基含量进行分析和测定;将氧化废纸浆、氧化废纸浆与原浆进行抄片和配抄,对手抄片的强度性能进行检测和分析;从经济效益出发,研究氧化体系中TEMPO及NaBr的循环使用次数对纸张强度性能的影响。结果随着NaClO用量的增加,废纸浆纤维的羧基含量增加;纤维长度、宽度和粗度有所降低;纸张抗张强度和环压强度增长较为明显;NaClO和NaBr循环使用2次后纸张的强度性能有所降低,但降低幅度不大。结论TEMPO氧化体系可用于废纸浆的氧化,改善废纸浆的性能。NaClO和NaBr的循环使用能够降低生产成本。     

Hybrid Composite Using Natural Filler and Multi-Walled Carbon Nanotubes (MWCNTs)

This paper presents an experimental study on the development of hybrid composites comprising of multi-walled carbon nanotubes (MWCNTs) and natural filler (oil palm shell (OPS) powder) within unsaturated polyester (UP) matrix. The results revealed that the dispersion of pristine MWCNTs in the polymer matrix was strongly enhanced through use of the solvent mixing method assisted by ultrasonication. Four different solvents were investigated, namely, ethanol, methanol, styrene and acetone. The best compatibility with minimum side effects on the curing of the polyester resin was exhibited by the styrene solvent and this produced the maximum tensile and flexural properties of the resulting nanocomposites. A relatively small amount of pristine MWCNTs well dispersed within the natural filler polyester composite was found to be capable of improving mechanical properties of hybrid composite. However, increasing the MWCNT amount resulted in increased void content within the matrix due to an associated rapid increase in viscosity of the mixture during processing. Due to this phenomenon, the maximum tensile and flexural strengths of the hybrid composites were achieved at MWCNT contents of 0.2 to 0.4 phr and then declined for higher MWCNT amounts. The flexural modulus also experienced its peak at 0.4 phr MWCNT content whereas the tensile modulus exhibited a general decrease with increasing MWCNT content. Thermal stability analysis using TGA under an oxidative atmosphere showed that adding MWCNTs shifted the endset degradation temperature of the hybrid composite to a higher temperature.     

改性碳纳米管处理碳纤维的效果表征

采用浓硫酸/浓硝酸氧化处理多壁碳纳米管(MWCNTs),再将氧化后的碳纳米管与硅烷偶联剂(KH560)进行接枝,制备了硅烷偶联剂表面化学修饰的MWCNTs。在此基础上,将改性前后的碳纳米管分散在环氧树脂体系中,涂覆处理碳纤维。研究处理前后碳纤维力学性能和界面性能的变化。通过红外光谱(FTIR)和透射电镜(TEM)分析,表明KH560已成功接枝到多壁碳纳米管上;通过分散性实验证明了改性后的碳纳米管分散性提高;对处理后的碳纤维进行力学性能测试,并用扫描电镜(SEM)观察分析断面形态变化,结果表明,当碳纳米管的含量为0.5%时,改性碳纳米管处理的碳纤维拉伸强度和拉伸模量分别提高23.83%和7.11%,界面性能增强。     

Strain sensing in polymer/carbon nanotube composites by electrical resistance measurement

In this work multiwall carbon nanotubes (MWCNTs) dispersed in a polymer matrix have been used for strain sensing of the resulting nanocomposite under tensile loading. This was achieved by measuring the relative electrical resistance change (ΔR/R₀) in conductive polyvinylidenefluoride (PVDF)/MWCNTs nanocomposites prepared by melt-mixing with varying filler content from 0.5 wt.% to 8 wt.%. Two main parameters were systematically studied. The PVDF/MWCNTs mixing procedure that results in a successful MWCNTs dispersion, and the effect of MWCNTs content on material’s sensing behaviour. The samples were subjected to tensile loading and the longitudinal strain was monitored together with the longitudinal electrical resistance. The results showed that MWCNTs dispersed in insulating PVDF matrix have the potential to be used as a sensitive network to monitor the strain levels in polymer/carbon nanotube nanocomposites as the deformation level of each sample was being reflected by the resistance changes.     

MWCNTs增强聚乙二醇-聚乙烯醇复合水凝胶的制备及性能

利用冻融循环法制备了羧基化多壁碳纳米管(MWCNTs)/聚乙二醇(PEG)-聚乙烯醇(PVA)复合水凝胶。考察了不同质量配比下MWCNTs/PEG-PVA复合水凝胶的微观形貌变化,并研究了复合凝胶的溶胀性能、拉伸强度、热稳定及导电性能。结果表明,加入MWCNTs后MWCNTs/PEG-PVA复合凝胶仍具有多孔的三维网状结构但孔径尺寸变小。当MWCNTs与PVA的质量比大于1.0∶100时,MWCNTs/PEG-PVA复合凝胶的孔洞均匀性降低。随着MWCNTs量的增加,MWCNTs/PEG-PVA复合凝胶的溶胀度及拉伸强度均先升高后降低。当MWCNTs与PVA的质量比为1.0∶100时,MWCNTs/PEG-PVA复合凝胶的溶胀度达到最大(1450%),孔隙率最高(75.8%),拉伸强度及断裂伸长率达到最大值,分别为0.97 MPa和384.0%。MWCNTs的加入提高了MWCNTs/PEG-PVA复合凝胶的热稳定性,MWCNTs/PEG-PVA复合凝胶的初始热分解温度从235℃上升至260℃;随着MWCNTs量的增加,MWCNTs/PEG-PVA复合凝胶的电导率从1.10×10-6 S/cm升高至6.96×10-4 S/cm。     

Influence of ultrasonic dual mixing on thermal and tensile properties of MWCNTs-epoxy composite

Multiwalled carbon nanotubes (MWCNTs) reinforced epoxy based composites were fabricated by using an innovative ultrasonic dual mixing (UDM) process consists of ultrasonic mixing with simultaneous magnetic stirring. The effect of addition of varying amount of MWCNTs on thermal stability and tensile properties of the epoxy based composite has been investigated. It is found that the thermal stability, tensile strength and toughness of the epoxy base improves with the increase of MWCNTs addition up to 1.5 wt.% and UDM processing at certain capacity of the system. Tensile tests and thermal gravimetric analysis (TGA) were performed on each group of composites containing different amount of MWCNTs to determine their mechanical and thermal properties respectively. The dispersion of 1.5 wt.% MWCNTs fillers in epoxy nanocomposites was studied by transmission electron microscopy (TEM) as well as by field emission scanning electron microscopy (FESEM) applied on their tensile fracture surface.     

纳米纤维素/碳纳米管/纳米银线柔性电极的制备

目的以竹粉为原料制备纳米纤维素,并将其作为基底材料制备纳米纤维素/碳纳米管/纳米银线复合电极,应用于柔性超级电容器。方法采用化学机械处理法,将竹粉通过化学处理以及研磨、超声等处理,制备成纳米纤维素悬浮液;分别将多壁碳纳米管和纳米银线超声分散于溶剂中;最后,通过层层自组装制备纳米纤维素/碳纳米管/纳米银线复合电极,同时,作为对照组,制备纳米纤维素/碳纳米管复合电极。结果纳米纤维素纤丝的直径大约为30~100 nm,相互之间缠绕成网状结构,是很好的支撑材料,纳米纤维素/碳纳米管/纳米银线复合电极具有很好的成膜性和电化学性能,在扫描速率为30 m V/s时,面积比电容达到77.95 m F/cm~2。结论以纳米纤维素为基底,通过层层自组装方法制备的纳米纤维素/碳纳米管/纳米银线复合电极具有较好的电化学性能,可作为柔性超级电容器的电极。     

Fresh and mechanical properties,and strain sensing of nanomodified cement mortars: The effects of MWCNT aspect ratio,density and functionalization

A comprehensive analysis on the effect of aspect ratio, bulk density and functionalization of multi walled carbon nanotubes (MWCNTs) in the development of nanomodified mortars, reinforced with different types of MWCNTs is presented herein. A structural characterization of the pristine and functionalized carbon nanotubes was carried out with scanning electron microscopy (SEM), transmission electron microscopy (TEM), and thermogravimetric analysis (TGA). A simple one step dispersion method, involving the application of ultrasonic energy and the use of a superplasticizer (SP) was utilized for the preparation of uniformly dispersed MWCNT suspensions. The experimental determination of the fresh and 28d mechanical properties of mortars with w/c = 0.5 and s/c = 3.0, using four different types of well dispersed pristine and functionalized MWCNTs at an amount of 0.1 wt% of cement took place through: (i) flow and time of setting tests; (ii) three point bending experiments on 4 × 4 × 16 cm specimens; and (iii) uniaxial compression on the half prisms of the flexural test specimens (4 × 4 × 8 cm). The piezoresistive behavior of the mortars reinforced with the pristine MWCNTs was experimentally determined using the 4-pole method, and compared with the strain sensing ability of the mortars reinforced with the functionalized MWCNTs. All MWCNT reinforced mortars exhibit a remarkable enhancement in the mechanical properties. However, the 28d flexural strength, young's modulus and energy absorption capability of the mortars reinforced with the mechanically functionalized MWCNTs at an amount of 0.1 wt% increased by 120%, 124%, and 103% respectively. Finally, depending on the procedure of the functionalization, chemical or mechanical, a different effect on the intrinsic properties of MWCNTs was observed. The carboxylic groups attached to the surface of the chemically functionalized MWCNTs indeed provided them with the ability of a uniform and effective dispersion, without the need of a sonication procedure. On the other hand, it was found that functionalized MWCNTs do not always retain the electrical properties of pristine MWCNTs.