竹纤维和海藻酸钠提升聚乳酸的降解性能

为提高聚乳酸(PLA)的降解性，将竹纤维(BF)和海藻酸钠(SA)与PLA共混制备复合材料，并进行土壤降解试验以探究其降解性能，检测降解后复合材料的质量损失率、表面微观结构、官能团变化、热性能和结晶度等指标。结果表明：SA和BF均可提升PLA复合材料降解的质量损失率。降解21天后，BF/PLA和SA-BF/PLA复合材料的质量损失率分别为0.83%和2.54%，相较于纯PLA的0.11%分别提高了7.55和23.09倍。降解后，SA-BF/PLA复合材料的表面出现大量的裂痕与凹陷，这增大了复合材料与土壤中的接触面积，进而加速了复合材料的降解。纯PLA在降解过程中质量损失率很低，但降解后其羰基含量明显上升，表明土壤降解会导致部分PLA长链高分子断裂为小分子。相比于纯PLA,BF/PLA和SA-BF/PLA复合材料的结晶度大幅度降低，表明SA和BF可降低PLA复合材料的结晶度，提高其降解性。由此可见，SA和BF可提升PLA复合材料的降解性能。此研究结果将为高降解性PLA复合材料的制备提供理论参考。     

PLLA/CNTs复合材料的非等温冷结晶

通过溶液共混法制备了聚乳酸/碳纳米管(PLA/CNTs)复合材料,并利用差示扫描量热分析(DSC)研究了CNTs的种类、长度、直径和质量分数对不同升温速度下PLA非等温冷结晶性能的影响,结果表明,PLA/CNTs复合材料的玻璃化转变温度(Tg)和结晶峰温度(Tc)都随升温速度降低而逐渐降低,而结晶度和熔融温度(Tm)则升高。添加质量分数为0.1%的多壁碳纳米管(MWNTs)即可有效促进PLA的异相成核,提高其结晶速度和结晶度,以10℃/min升温冷结晶时,当CNTs用量达1%时会阻碍PLA的非等温结晶过程,并导致PLA复合材料的Tg、Tm和结晶度降低。MWNTs对PLA非等温结晶的促进作用比SWNTs或DWNTs明显,而较短的MWNTs比长MWNTs的作用略为明显。     

聚乳酸/碳纳米管复合材料的冷结晶及热稳定性

采用熔融共混制备了聚乳酸/碳纳米管复合材料(PLA/CNTs)。利用透射电镜(TEM)、差示扫描量热仪(DSC)和热重分析仪(TGA)对复合体系的形态、冷结晶行为以及热稳定性进行了研究。结果表明,羧基化的碳纳米管均匀分散于聚乳酸基体中形成了纳米复合材料;PLA/CNTs复合体系不从熔体冷却结晶,但可以在较慢的升温过程中固态下冷结晶,CNTs的存在一定程度上阻碍了PLA基体的冷结晶;此外,复合体系的热稳定性与纯聚乳酸相比有所提高。     

碳纤维增强聚乳酸复合材料体外降解特性

制备了碳纤维增强聚乳酸(C/ PLA) 骨折内固定复合材料, 研究了体外降解过程中其力学性能的变化。结果表明: 在体外降解过程中, C/ PLA 复合材料的各项力学性能均有不同程度的下降, 但经过硝酸处理后的C/PLA 复合材料降解速度缓慢, 表明界面结合强度的提高对降解过程起抑制作用。      

增容纳米纤维素/聚乳酸复合材料的制备与性能

采用接枝共聚法制备了马来酸酐和丙烯酸丁酯双单体接枝聚乳酸（PLA）共聚物（mPLA）,然后以mPLA为增容剂,通过溶液浇铸法制备纳米纤维素（NCC）/PLA复合材料。采用SEM、DSC、TG、广角X射线衍射（WXRD）、力学和降解性能测试研究了mPLA对NCC/PLA复合材料的结构和性能的影响。结果表明:mPLA在PLA与NCC之间起到了良好的界面增容作用,促进了NCC在PLA基体中的分散。更精细分散的NCC促进了PLA的结晶成核,复合材料的结晶温度降低,结晶度提高;NCC/mPLA/PLA复合材料的力学性能随着mPLA含量增加呈先上升后下降的趋势,当mPLA含量为8%时,复合材料的拉伸强度和弹性模量与未添加mPLA的复合材料相比,分别提高了30.2%和41.4%;亲水性的NCC加速了NCC/PLA复合材料的降解,加入mPLA后,复合材料的降解速率有所减慢,但仍然快于纯PLA的降解。      

苎麻纤维/聚乳酸复合材料在不同pH环境下的水解行为

以生物基树脂聚乳酸为基体,以植物纤维苎麻为补强剂,利用熔融共混法制备了苎麻纤维/聚乳酸(RF/PLA)复合材料,考查了RF/PLA复合材料在不同pH环境下的水解行为,并以力学性能测试、SEM、DSC和维卡软化温度检测为手段对其降解行为进行了评估。结果表明:RF/PLA复合材料在碱性(pH=12.0)环境中的降解比在酸性(pH=2.0)和中性(pH=7.0)环境中的更快,界面侵蚀空化是其性能劣化的主要原因。RF的加入提高了PLA的结晶度和维卡软化温度,同时也加快了PLA的降解速度,降解导致材料的力学强度下降。随着降解过程的加剧,RF/PLA复合材料的结晶度和维卡软化温度因材料内部产生缺陷而有所降低;而纯PLA树脂的结晶度却随碱液处理时间的延长而增加,但其维卡软化温度没有发生明显的变化。     

生物降解聚酯弹性体粒子改性聚乳酸复合材料的制备及性能

以不同粒径的羧基封端生物降解聚酯弹性体粒子(CBEP)改性聚乳酸(PLA)制备了CBEP/PLA复合材料,对复合材料的力学、结晶与降解等性能进行了测试,并研究了CBEP对PLA性能的影响及作用机理。结果表明,CBEP可显著提高PLA的韧性,复合材料样条在拉伸时出现了颈缩现象,尤其是添加了7.5% (与PLA的质量比)粒径在200 nm的CBEP-a的复合材料的断裂伸长率由纯PLA的4.6%提高至155%,而复合材料的缺口冲击强度最高达到了纯PLA的2倍。同时CBEP可提高PLA的结晶性能,其中添加7.5%粒径在200 nm的CBEP-a的复合材料的等温结晶半结晶时间较纯PLA缩短了21.4%。而降解实验结果表明,添加了10%粒径在200 nm的CBEP-a的复合材料在脂肪酶环境下与土壤掩埋环境下的降解质量损失率分别由纯PLA的0.34%与0.25%,提高至2.52%与1.20%。CBEP/PLA复合材料在生物医药与环保材料等领域具有广阔的发展与应用前景。      

不同物相电沉积CNTs对C/SiC复合材料力学性能的影响

采用电沉积法与化学气相渗透(CVI)法将碳纳米管(CNTs)分别引入到碳纤维表面和SiC基体中,制得了不同物相电沉积CNTs的C/SiC复合材料(CNTs-C)/SiC和C/(CNTs-SiC)。研究了CNTs沉积物相对C/SiC复合材料力学性能的影响,分析了不同CNTs沉积物相的C/SiC复合材料的拉伸强度及断裂机制。结果表明:相较于未加CNTs的C/SiC复合材料,CNTs沉积到碳纤维表面的(CNTs-C)/SiC复合材料的拉伸强度提高了67.3%,断裂功提高了107.2%;而将CNTs引入到SiC基体中的C/(CNTs-SiC)复合材料的断裂功有所降低,拉伸强度也仅提高了6.9%,CNTs没有表现出明显的增强增韧效果;C/(CNTs-SiC)复合材料与传统的C/SiC复合材料有相似的断裂形貌特征,断裂拔出机制类似,主要为纤维增强增韧,CNTs的作用不明显。     

竹纤维/聚乳酸可生物降解复合材料自然降解性能

通过注射成型工艺制备竹纤维/聚乳酸（BF/PLA）可生物降解复合材料。利用X射线衍射（XRD）、凝胶渗透色谱（GPC）、三维视频显微镜及扫描电镜（SEM）等分析手段研究了BF/PLA复合材料自然降解性能。研究结果表明：BF/PLA复合材料自然降解过程中BF首先降解,PLA逐步分层缓慢降解,复合材料质量逐渐减少;PLA分子链上酯基与水反应,分子链不断断裂,结晶度减小,平均分子量降低,分子量分布变窄;复合材料颜色变深,表面变得粗糙不平,部分裸露的BF清晰可见,其拉伸强度和冲击强度逐渐下降。12个月后,BF/PLA复合材料质量损失率达到8.87%,PLA重均分子量降低了25.9%,复合材料的冲击强度和拉伸强度分别降低了44.0%和43.8%。BF/PLA可生物降解复合材料在土壤中的自然降解效率较低。     

脉冲电磁场作用下碳纤维增强聚乳酸复合材料的体外降解特性

碳纤维增强聚乳酸(C/PLA)复合材料是较为理想的可降解骨折内固定材料,但由于其降解特性与人体骨骼愈合速度的不匹配,很难达到最佳治疗效果。文中将脉冲电磁场(PEF)引入C/PLA的体外降解过程,并研究了该条件下复合材料的降解特性。结果表明,PEF处理对C/PLA试样的吸水率、质量保持率、弯曲强度和剪切强度均有不同程度的影响;扫描电镜观察发现,PEF处理使界面处的PLA基体出现降解洞穴;差示扫描量热分析说明经不同降解时间的PLA基体的玻璃化转变温度没有明显变化。模型分析表明PEF处理影响降解溶液中正负离子的扩散行为,使得界面处的PLA基体出现局域降解加速区,进而影响C/PLA复合材料的体外降解行为。这一研究将为研究可降解骨折内固定装置的外部辅助治疗器械提供途径。     

Decoration of multi-walled carbon nanotubes with silver nanoparticles and investigation on its colloid stability

In this paper, multi-walled carbon nanotubes (MWCNTs) were decorated with silver nanoparticles which have been successfully synthesized by chemical reduction of Ag cations on the acid treated MWCNTs surface by sodium hydroxide. Ag/MWCNTs were characterized by TEM and XRD. The results indicated that silver nanoparticles were homogeneously dispersed on the outer surface of MWCNTs. The dispersibility of pristine, acid treated and decorated carbon nanotubes in distilled water were investigated by zeta potential and optical image. The results revealed that the dispersion of acid treated carbon nanotubes in distilled water was better than those of pristine MWCNTs and Ag/MWCNTs.     

Enhanced electron emission from titanium coated multiwalled carbon nanotubes

Enhanced field emission properties and improved crystallinity of titanium (Ti) coated multiwalled carbon nanotubes (MWCNTs), prepared by microwave plasma enhanced chemical vapour deposition have been observed. Ti films of extremely low thicknesses (0.5 nm, 1.0 nm and 1.5 nm) were coated over carbon nanotubes (CNTs) and their field emission behaviour was investigated. The turn on field of Ti coated CNTs was found to be low (~ 0.8 V/μm) as compared to pristine CNTs (~ 1.8 V/μm). The field enhancement factor for Ti coated CNTs was quite large (~ 1.14 × 10⁴) as compared to pristine CNTs (~ 6 × 10³). This enhancement in electron emission is attributed to the passivation of defects and improved crystallinity of CNTs. Surface morphological and microstructural studies were carried out to investigate the growth of pristine and Ti coated CNTs. It was observed that Ti nanoclusters adsorb on the edges of MWCNTs and increase their crystallinity. This increase is directly correlated with the thickness of Ti film deposited. Micro Raman spectroscopy confirmed the improved crystallanity of Ti coated CNTs.     

Hydroxylation of multi-walled carbon nanotubes reduces their cytotoxicity by limiting the activation of mitochondrial mediated apoptotic pathway

Hydroxylation of carbon nanotubes (CNTs) can enhance their dispersibility in water, and allows the capability to conjugate with other molecules for the expected applications. However, the cytotoxicity of hydroxylated CNTs has not been thoroughly investigated. Here, we compared the cytotoxicity of hydroxylated multi-walled carbon nanotubes (MWCNTs–OH) on a human cell line with that of pristine multi-walled carbon nanotubes (p-MWCNTs). We showed that while both MWCNTs–OH and p-MWCNTs induced apoptosis in a time- and dose-dependent manner, MWCNTs–OH triggered a significantly milder cytotoxic response than that of p-MWCNTs. We further showed that such attenuated response could be attributed to a reduced disruption of the mitochondrial membrane potential (MMP), leading to the attenuation of both cytochrome c (cyt-c) release and activation of caspases. These findings suggest that MWCNTs–OH, could be more biocompatible for in vivo applications than that of p-MWCNTs by limiting the activation of the mitochondrial mediated apoptotic pathway.     

Incorporation of liquid-like multiwalled carbon nanotubes into an epoxy matrix by solvent-free processing

Covalent attachment of 2,2'-(ethylenedioxy)-diethylamine to multiwalled carbon nanotubes (MWCNTs) produced amino-functionalized MWCNTs which behaved like liquids at ambient temperature. These liquid-like MWCNTs (l-MWCNTs) could be homogeneously dispersed and chemically embedded in an epoxy matrix by solvent-free processing. In contrast, solid MWCNTs (s-MWCNTs) functionalized by 1,8-diaminooctane were poorly dispersed in epoxy although they possess chemical structures and functionalization comparable to l-MWCNTs. An epoxy composite filled with pristine MWCNTs (p-MWCNTs) was also fabricated in the absence of a solvent at the same loading for comparison. The molecular level coupling of l-MWCNTs and epoxy provided significant improvements in overall mechanical properties relative to those composites containing p-MWCNTs and s-MWCNTs. The Young's modulus, storage modulus, tensile strength, failure strain and toughness of neat epoxy were increased by 28.4, 23.8, 22.9, 24.1 and 66.1%, respectively, by adding 0.5?wt% of l-MWCNTs. Thus, functionalized carbon nanotubes in liquid form contributed to better dispersion and superior interfacial bonding with the epoxy matrix, thereby facilitating greater mechanical reinforcement efficiency.     

Fe-Mo/Al_2O_3催化剂催化分解甲烷制备碳纳米管:温度对碳管结构的影响

利用化学气相沉积法,以Fe-Mo/Al_2O_3为催化剂,催化分解甲烷气体制备碳纳米管(CNTs).研究了温度,反应时间和气体流速对碳纳米管结构的影响.结果显示:温度是影响碳纳米管壁厚的关键参数.低温导致壁厚为2 nm～7 nm的多壁碳纳米管(MWCNTs)的生成.相对地,高温有利于双壁碳纳米管(DWCNTs)的生长,而更高的温度促使单壁碳纳米管(SWCNTs)的产生.进一步升高温度,得到了壁厚为3 nm～15 nm的MWCNTs和大的炭颗粒.     

Synthesis of individual ultra-long carbon nanotubes and transfer to other substrates

In this article, we report the synthesis of ultra-long carbon nanotubes (CNTs) by thermal chemical vapour deposition method. Ultra-long, individual and aligned CNTs were directly grown on a flat silicon substrate. The orientation of the nanotubes was found parallel to the gas flow direction. The ultra-long CNTs were grown with different transition metallic salts, such as nickel chloride, iron (III) chloride, cobalt acetate and ruthenium acetate, as the catalysts. The influence of the growth conditions, such as growth temperature, reactive gas flow on the length and alignment of the CNTs was studied in detail. By using different catalysts, ultra-long single-walled carbon nanotubes (SWCNTs) or multi-walled carbon nanotubes (MWCNTs) were successfully grown. These ultra-long CNTs were transferred to other substrates by two methods. (1) The first method is to use polydimethylsiloxane as a stamp. (2) The second method is to use KOH as an etching agent. The diameter and length of the CNTs were characterised by transmission electron microscope, scanning electron microscope, atomic force microscope and Raman spectroscopy. The results indicate that the length of the CNTs can reach up to 4?mm. The diameter of the SWCNTs is in the range of 0.7–2.1?nm and the diameter of the MWCNTs is approximately 150?nm.     

Correlation between dispersion state and electrical conductivity of MWCNTs/PP composites prepared by melt blending

Non-conductive polymers filled with conductive carbon nanotubes (CNTs) often do not show detectable conductivity due to poor dispersion of carbon nanotubes in the polymer matrix and the lack of conductive networks formed from CNTs. In this work, we attempted two ways to improve the dispersion of multi-walled carbon nanotubes (MWCNTs) in a polypropylene (PP) matrix: chemical modification of MWCNTs and addition of a master batch as a compatibilizer, followed by melt blending using a micro-compounder. The relationship between the dispersion state of MWCNTs and the electrical conductivity of the CNTs/PP composites have been investigated by controlling several factors such as CNTs modification, compatibilization by a master batch, melt mixing, and post-heat treatment. The enhanced interfacial adhesion between the CNTs and the polymer could improve the dispersion of CNTs but it could also reduce the electrical conductivity of the composites. Meanwhile, it is interestingly found that the post-heat treatment could increase the conductivity remarkably due to the connection of CNTs into networks. Thus, it is concluded that the balance between dispersion of CNTs and the formation of conductive networks plays an important role in enhancing the electrical conductivity of composites.     

Interconnected multi-walled carbon nanotubes reinforced polymer-matrix composites

A modified method for interconnecting multi-walled carbon nanotubes (MWCNTs) was put forward. And interconnected MWCNTs by reaction of acyl chloride and amino groups were obtained. Scanning electron microscopy shows that hetero-junctions of MWCNTs with different morphologies were formed. Then specimens of pristine MWCNTs, chemically functionalized MWCNTs and interconnected MWCNTs reinforced epoxy resin composites were fabricated by cast moulding. Tensile properties and fracture surfaces of the specimens were investigated. The results show that, compared with pristine MWCNTs and chemically functionalized MWCNTs, the chemically interconnected MWCNTs improved the fracture strain and therefore the toughness of the composites significantly.     

The effects of contacts and ambipolar electrical transport in nitrogen doped multiwall carbon nanotubes

The electrical transport properties of pristine single wall carbon nanotubes (SWCNTs) and lower nitrogen content doped multiwall carbon nanotubes (MWCNTs) (lower than in the experiments of Xiao et al (2005?J. Am. Chem. Soc.?127?8614)) in contact with Au and Pt were studied. Compared with pristine SWCNTs, the Fermi level of the lower nitrogen content doped MWCNTs also moved to the valence band edge with the contact metal's work function increasing. In contrast to Derycke et al' s results (2002?Appl.?Phys.?Lett.?80?2773), the lower nitrogen content doped MWCNTs exhibited ambipolar behavior, and increasing the doping level led to a reduction of the Schottky barrier height of electrons. Consistent with theoretical calculations, the results support the opinion that the degree of Fermi level pinning is minor for doped carbon nanotubes.