超临界流体中碳纳米管复合材料的制备及其性能研究

扼要介绍了近年来在利用超临界流体特性制备碳纳米管复合材料方面的研究工作，主要包括超临界水、超临界CO2混合流体和其它超临界流体中金属或金属氧化物，碳纳米管复合材料的制备及其相关性能研究。     

超临界溶液快速膨胀技术在超细粒子包覆中的应用

超临界溶液快速膨胀技术是一种新兴的超细粒子包覆技术。本文中综述了近年来利用超临界溶液快速膨胀技术进行超细粒子包覆的研究现状,介绍了超临界溶液快速膨胀技术的基本原理,总结了应用此技术制备包覆粒子的方法、特点及影响因素,并对其今后的研究方向及应用前景进行了展望。     

超临界流体制备超微粉体的研究进展

分析了国内外超微粉的研究现状及主要研究成果,着重研究了超临界流体溶液快速膨胀法制备聚合物超细粉,探索了超临界流体制备超微粉的原理及特点,论证了该技术的可行性、应用前景以及目前达到的水平与存在的问题,提出了今后发展需要解决的关键问题。     

超临界法制备超微粉体技术

超细微粒,特别是纳米级粒子的研制,在当前的高新技术中己成为一热门领域,在材料、化工、轻工、冶金、电子、生物医学等领域得到广泛应用.超临界流体技术制备超微粉体是一项新技术.本文介绍了近年来开发的一些新方法和新工艺,诸如超临界溶液快速膨胀法,超临界流体抗溶剂法,超临界流体化学反应和超临界干燥法.重点介绍了超临界溶液快速膨胀法、超临界流体抗溶剂法的研究进展及其影响因素.并指出,要将这些技术应用于工业化生产,尚需在理论上有一定的突破.     

超临界流体快速膨胀法粒子包覆中喷嘴结构对包覆效果的影响

采用超临界流体快速膨胀法,利用自制特殊喷嘴制备红磷微胶囊阻燃剂。实验研究了旋流器、前置可旋接头旋转角度对包覆效果的影响。结果表明,加旋流器时的包覆效果明显优于不加旋流器时的包覆效果。在前置可旋接头旋角为20°时,包覆效果最好,当旋角大于30°后,包覆效果随旋角的增大而逐渐变差。     

用超临界溶液快速膨胀法制备超细粉体

利用超临界溶液快速膨胀法制备超细粉体 ,是近年来提出并受到研究者重视的一种很有应用前景的新的粉体制备技术。本文介绍了该技术的基本原理、理论研究和应用研究的现状及主要成果     

碳纳米管的分散方法与分散机理

要发挥碳纳米管的优异性能,如何均匀分散碳纳米管是首先要解决的关键性问题。通过研究碳纳米管的团聚体形态,看出碳纳米管团聚体为一维纳米线团聚态,比普通颗粒粉体的零维团聚态更复杂。碳纳米管分散方法大体上分为物理法与化学法两大类,对比研究碳纳米管的各种分散方法,分析碳纳米管的分散机理,提出了均匀分散碳纳米管要满足3个必要条件:打散碳纳米管团聚体、剪断长碳纳米管、保持碳纳米管分散状态。剪切挤出分散法可以较好地满足这3个条件,制备出均匀分散的碳纳米管复合粉体。     

超临界二氧化碳介质中纳米颗粒合成研究进展

在超临界流体介质中制备纳米颗粒是一项纳米颗粒合成的新技术.介绍了超临界流体的特性,综述了超临界流体快速膨胀、超临界流体抗溶剂、超临界流体干燥、超临界流体微乳液、超临界二氧化碳制动沉降法等技术的原理、影响因素、应用研究及发展前景.利用超临界流体较好的溶解、扩散和传质能力,可制备出性能优异的纳米颗粒.     

超临界流体强制分散溶液制备天然胡萝卜素超细微粒

以二氯甲烷为溶剂,超临界CO2为抗溶剂,采用超临界流体强制分散溶液技术成功地对天然胡萝卜素进行了超细化.采用SEM照片分析微粒形貌,利用粒度分析仪测定微粒粒径.实验考察了压力、溶液浓度与流量及CO2流量对产品粒度的影响;用液体射流破碎、超临界CO2作用下的溶液体积膨胀、膨胀溶液的过饱和度及沉淀粒子团聚等解释了产品粒度随操作条件的变化规律.在实验范围内制得了平均粒径为O.6～5μm且粒度分布窄的不定形胡萝卜素微粒.微粒粒径随压力、CO2流量及溶液流量增大而减小,随溶液浓度增大而先减小后增大.     

碳纳米管溶解性及其化学修饰

详细评述了增加碳纳米管在水和有机溶剂中溶解性的途径，包括单一溶剂直接分散、电子供一受体电荷转移、可溶性聚合物或表面活性剂筒状胶束包裹等非共价键相互作用和顶端开口、化学衍生以及侧壁化学修饰等共价化学修饰。指出今后一段时期碳纳米管化学的主要任务为通过非共价的或共价的化学修饰，改善碳纳米管本身的性能和用途，并耦合其他如化学的、生物的或物理的功能扩展其应用范围。进一步深入理解碳纳米管化学(尤其是其溶液化学)反应理论。     

Hydrothermal synthesis of ceria nanoparticles supported on carbon nanotubes in supercritical water

By single-step supercritical hydrothermal synthesis method, ceria nanoparticles with diameters of 3–8 nm were successfully supported on multi-wall carbon nanotubes (MWNTs) homogeneously without additional treatment. It was found that the amount and distribution of ceria nanoparticles supported on the MWNTs depended on the pH of reaction mixture. At pH = 7, the largest amount of particles was observed on the MWNTs. At pH = 9, however, the best homogeneity was obtained for the ceria nanoparticles supported on the MWNTs. In addition, the amount of particles supported on the MWNTs treated by nitric acid was much more than that supported on the untreated MWNTs. The difference mentioned above is also discussed.     

Micronization and polymorphic conversion of tolbutamide and barbital by rapid expansion of supercritical solutions

Rapid expansion of supercritical solutions (RESS) was applied to tolbutamide and barbital. The solubility in supercritical CO₂ was determined to estimate the extraction efficiency roughly by a simple method and accurately by a direct spectrophotometric technique. The latter revealed that the solubility of tolbutamide was a function of applied pressure and temperature and was proportional to the pressure. No significant difference in solubility between polymorphic Forms I and II of tolbutamide was detected. Tolbutamide and barbital particles produced by the RESS were characterized by size distribution measurement, polymorph identification and morphological evaluation. Significant size reduction to micron or sub-micron level with narrow size distribution was achieved, while conventional mechanical grinding had only slight effect. The particle size was greatly affected by both extraction and expansion conditions. The lower the extraction temperature was, the smaller was the mean particle size. Higher extraction pressure resulted in smaller mean particle size when compared at the same extraction temperature. The mean particle size was reduced by lowering the spray nozzle temperature, by lowering the expansion chamber temperature, by increasing the CO₂ amount per spray, and by increasing the exhaust gas flow rate. The RESS processing realized the polymorphic conversion as well. As for tolbutamide, three polymorphs (Forms I, II, and IV) out of four could be produced by changing the extraction conditions, and in the case of barbital, one polymorph (Form II) out of three was produced consistently.     

Tunable amorphous carbon nanotubes prepared by a simple template

An easy versatile method is reported to synthesize tunable amorphous carbon nanotubes (a-CNTs) with different pore diameter, length and orientation of graphene layers at a low temperature of 450 °C in the absence of metal catalysts by using porous anodic aluminum oxide (AAO) as a template and citric acid as a precursor. Since citric acid was adsorbed by hydrogen bonds with the -OH groups at the walls of the AAO templates, which can be influenced by the concentration of H⁺ ions in the solution, the pH leads to the change of the orientation of graphene layers and the graphitization degree.     

Removal of gallium (III) ions from acidic aqueous solution by supercritical carbon dioxide extraction in the green separation process

Supercritical carbon dioxide extraction, which is a feasible "green" alternative, was applied in this study as a sample pretreatment step for the removal of gallium (III) ions from acidic aqueous solution. The effect of various process parameters, including various chelating agents, extraction pressure and temperature, dimensionless CO(2) volume, the concentration of the chelating agent, and the pH of the solution, governing the efficiency and throughput of the procedure were systematically investigated. The performance of the various chelating agents from different studies indicated that the extraction efficiency of supercritical CO(2) was in the order: thiopyridine (PySH)>thenoyltrifluoroacetone (TTAH)>acetylacetone (AcAcH). The optimal extraction pressure and temperature for the supercritical CO(2) extraction of gallium (III) with chelating agent PySH were found to be 70 degrees C and 3000psi, respectively. The optimum concentration of the chelating agent was found to be 50ppm. A value of 7.5 was selected as the optimum dimensionless CO(2) volume. The optimum pH of the solution for supercritical CO(2) extraction should fall in the range of 2.0-3.0.     

Thermal expansion behaviors of aluminum composite reinforced with carbon nanotubes

The coefficient of thermal expansion (CTE) of aluminum matrix composite reinforced with 1.0wt.% multi-wall carbon nanotubes (MWNTs) fabricated by cold isostatic pressing and hot squeeze technique was measured between 25 and 400 °C with a high-precision thermomechanical analyzer, and compared with those of pure aluminum and 2024Al matrix fabricated under the same processing. The results show that the CTE of the composite obviously reduces in relation to those of pure aluminum and 2024Al matrix due to the introduction of MWNTs. The addition of 1.0wt.% MWNTs to 2024Al matrix decreases the CTE by as much as 12% and 11% compared with those of pure aluminum and 2024Al matrix at 50 °C, respectively, which indicates that carbon nanotube reinforced metal matrix composite may be a promising materials with low CTE.     

Electrochemical characterization of electrodeposited carbon nanotubes

Carbon nanotubes were electrodeposited in acetonitrile solution at room temperature using Cu, and Fe-Ni nanoparticles as nucleation sites on HF-etched Si(100) wafer substrate. The electrochemical behavior of the deposition was investigated by voltammetry and chronoamperometry techniques. In order to obtain the optimum growth condition, the deposition critical parameters including current density range, potential and time were studied and calculated. Carbon nanotubes with approximate external diameter of 40-100 nm were fabricated under potentiostatic condition and diffusion control at − 20 V in 4-6 h. The film crystallinity was investigated by means of X-ray diffraction and the tubes structure was revealed using scanning electron microscope and transmission electron microscope images. Raman spectroscopy was also employed to characterize the nanostructural features and single wall carbon nanotubes were detected.     

催化剂对爆炸法合成碳纳米管的影响

通过热引发方式使炸药-催化剂前驱体-碳氢化合物体系在密闭反应管中发生爆炸合成碳纳米管。采用TEM,HRTEM,XRD和TG等方法研究了以二茂铁、甲酸镍和乙酸钴作为催化剂前驱体对所合成碳纳米管产物的形貌、微观结构和纯度的影响。以乙酸钴为前驱体可以得到纯度较高(约80%～90%)、微观结构较好的管腔中空的碳纳米管。以二茂铁为前驱体,只有约10%～20%的碳管生成且多呈竹节状形貌。以甲酸镍为前驱体,得到的碳管纯度也不高(约10%～20%),碳管管壁富含结构缺陷,相当多的碳管端口膨胀成直径约为160nm的纳米泡。XRD分析表明这些催化剂前驱体在爆炸反应后均被分解、还原为金属单质。通过对生成的碳纳米管的质量和纯度进行比较,得出本方法中催化剂的催化活性依次为:钴>铁>镍,并对本方法中高碳源浓度环境下不同催化剂的活性差异作了简要分析。     

空气氧化法提纯碳纳米管的研究

以乙炔为原料气，采用铁-镍复合催化剂，在700℃下，由化学气相沉积法(CVD)制得了直径为10nm～30nm的多壁碳纳米管(MWNT)。然后通过空气氧化法对所获碳纳米管进行提纯，去除了碳纳米管中的无定形炭、炭纳米颗粒及炭纤维等非晶碳成分，提高了碳纳米管的纯度；并研究了提纯温度和时间的关系。结果表明：碳纳米管在空气中440℃加热3h后，烧损率趋于平稳，基本上稳定在2％左右。使用透射电镜(TEM)考察提纯前后碳纳米管的形貌，发现碳纳米管在空气中440℃加热3h后，非晶碳成分基本去除，纯度得到提高。     

Synthesis of multiwalled carbon nanotubes by high-temperature vacuum annealing of amorphous carbon

Vacuum annealing of a mixture of amorphous carbon and cobalt nanoparticles supported on microporous zeolite at high-temperature results in the formation of multiwalled carbon nanotubes which are essentially filled with metal nanoparticles or nanowires as observed by transmission electron microscopy. The electronic properties of nanotubes by variable temperature ESR techniques shows that g values show little change with temperature from 77 to 327 K but the line width (ΔH_pp) of the ESR signal for nanotubes synthesized from amorphous carbon increases from 7.9 G at 77 K to 9.5 G at 327 K.