非晶空心碳球的制备及生长机制

采用射频等离子体增强化学气相沉积技术,在CH4/H2的气氛中合成了非晶空心碳球.利用SEM,TEM,拉曼光谱对样品的形貌、成分和结构进行了表征.非晶空心碳球的直径在100～800nm之间,分布在弯曲的碳纳米管丛中.非晶空心碳球的生长机制可能为膨胀生长.     

SYNTHESIS AND STRUCTURE OF CARBON NANOTUBES

The distribution, morphology and structure of carbon nanotubes and buckyonions produced from an arc discharge were investigated by means of scanning electron mi-croscopy and high-resolution transmission electron microscopy, The nanotubes and nanoonions were found to be located mainly near the porous region of the core in the deposited rods and the transition region between the growth ring-shaped graphite sheets. The tube bundles grew freely from carbon particles. Apart from the straight-line tubes, curved and bent tubes were also found. Studies on the structure of them showed that the carbon atomic sheets in the nanotubes displayed a stepped bending. Transverse sectional study predicted a helical structure of the carbon atomic sheets. In addition, the relationship between the number of pentagonal rings and cone angle at the tips of the tubes, as well as the mechanism of the formation of the steplike structure, were discussed.     

Assembly and interaction of Au/C core-shell nanoparticles

The formation of Au/C core-shell structures from C-supported Au nanoparticles, and their thermally and electron beam induced interactions are studied by real-time TEM. At temperatures below 400 °C no C-shell is assembled, and closely spaced Au nanoparticles interact by coalescence. At high temperatures (400-800 °C) the Au particles are transformed into Au/C core-shell structures via encapsulation into curved, fullerene-like C shells. The shells initially passivate the Au cores and inhibit their coalescence. But under electron irradiation, the Au cores can break free from their shells, and hence can coalesce. Surprisingly, at this stage the assembled C-sheets may actually enhance the coalescence process by driving the directed motion of Au/C particles and causing the efficient contraction of widely spaced particle ensembles.     

等离子体诱导碳纳米管到纳米金刚石的相变

采用氢等离子体，实现了碳纳米管向金刚石的结构相变，并实现了金刚石的高密度成核，有效成核密度可达10\+\{11\}／cm\+2以上，处于目前金刚石成核密度的最高行列，为制备优质的金刚石薄膜提供了保证.高分辨透射电镜、x射线衍射和拉曼光谱都证实了金刚石的形成.同时，对纳米金刚石晶粒的生成机理进行了初步探讨. 关键词： 等离子体 碳纳米管 纳米金刚石 结构相变     

Microscopic and Macroscopic Structures of Carbon Nanotubes Produced by Pyrolysis of Iron Phthalocyanine

By pyrolysis of iron phthalocyanine (FePc), either in a patterned or non-patterned fashion, under an Ar/H₂ atmosphere, we have demonstrated the large-scale production of aligned carbon nanotubes perpendicular to the substrate surface useful for building devices with three-dimensional structures. Depending on the particular pyrolytic conditions used, carbon nanotubes with a wide range of microscopic structures having curved, helical, coiled, branched, and tube-within-tube shapes have also been prepared by the pyrolysis of FePc. This, coupled with several microfabrication methods (photolithography, soft-lithography, self-assembling, micro-contact transfer, etc.), has enabled us to produce carbon nanotube arrays of various macroscopic architectures including polyhedral, flower-like, dendritic, circular, multilayered, and micropatterned geometries. In this article, we summarize our work on the preparation of FePc-generated carbon nanotubes with the large variety of microscopic and macroscopic structures and give a brief overview on the perspectives of making carbon nanotubes with tailor-made microscopic/macroscopic structures, and hence well-defined physicochemical properties, for specific applications.     

Carbon Nanotube/P(VDF-TrFE) Nano-Composite Characterization by Total Reflection X-Ray Fluorescence

In continuation of our research on carbon nanotube/P(VDF-TrFE) nano-composites [1], total x-ray fluorescence (TXRF) is engaged in a novel characterization of these materials regarding their compositions, purities, and structural analysis. Samples such as single-walled carbon nanotubes (SWCNT), multi-walled carbon nanotubes (MWCNT), P(VDF-TrFE) copolymer, SWCNT/P(VDF-TrFE), and MWCNT/P(VDF-TrFE) were analyzed by TXRF. The synthetic quartz used as a substrate was analyzed as reference material for the TXRF measurements. The ethanol and the dimethylformamide (DMF) used as solvents for carbon nanotubes and copolymers respectively were also analyzed by TXRF to determine whether they have an influence or not on the TXRF of the previous material. The preliminary results showed that single-walled and multi-walled carbon nanotubes prepared by the arc-discharge method contain catalytic particles such as Fe, Co, and Ni used to obtain SWCNT while there were no metal or impurities in MWCNT. The TXRF spectrum of CNT/P(VDFTrFE) showed the same results as we found previously with background due to the P(VDF-TrFE) copolymer scattered signal. __________ Published in Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 5, pp. 700–702, September–October, 2005.     

硅纳米颗粒在碳纳米管表面生长的分子动力学模拟

采用分子动力学模拟方法研究了硅纳米颗粒在碳纳米管上的生长，并分析了这种复合材料的基本结构.研究表明，由于硅原子和碳纳米管之间的相互作用以及碳纳米管的巨大的表面曲率，硅原子在碳纳米管表面不是形成覆盖碳纳米管的二维薄膜，而是生成具有三维结构的硅纳米颗粒.小纳米颗粒的结构和无基底条件下生成的颗粒结构基本一致.对于大纳米颗粒，不同于无基底条件下形成的球状纳米晶体硅结构，硅纳米颗粒沿管轴方向伸长，其结构为类似于硅晶体的无定形网络结构. 关键词： 纳米颗粒 碳纳米管 硅 分子动力学模拟     

Structural transformations in carbon nanoparticles induced by electron irradiation

This paper reviews the electron-irradiation effects in graphitic nanoparticles. Irradiation-induced atomic displacements cause structural defects in graphite lattice forming the basis of carbon nanoparticles such as nanotubes or carbon onions. Defects of the type of non-six-membered rings induce topological alterations of graphene layers. The generation of curvature under electron irradiation leads to the formation of new structures, such as spherical carbon onions or coalescent nanotubes. At high temperatures, the self-compression of carbon onions can promote the nucleation of diamond cores or phase transformations of foreign materials that are encapsulated by onionlike graphitic shells. Under the nonequilibrium conditions of intense irradiation, the phase equilibrium between graphite and diamond can be reversed. It is shown that graphite can be transformed into diamond even if no external pressure is applied. All electron-irradiation and electron-microscopic studies described here were carried out using in situ transmission electron microscopy.     

高压退火对碳纳米管微结构转变的影响

利用高分辨电子显微镜研究了在高压退火条件下碳纳米管的微结构变化规律，发现在5.5GPa下，770℃退火后即发生了明显的结构改变；在950℃退火25min后发现形成了类碳纳米洋葱和纳米碳条带结构.碳纳米管转变成类碳纳米洋葱可以分成几个步骤，首先碳纳米管破裂，然后形成碳纳米球，最后形成类碳纳米洋葱结构.讨论了高压和退火温度对碳纳米管结构变化的影响. 关键词：     

In situ investigation of morphological and phase changes during thermal annealing and oxidation of carbon-encapsulated copper nanoparticles

In situ electron microscope and X-ray investigations of the morphological and phase characteristics of copper nanoparticles encapsulated in a carbon shell were carried out. It was found that oxidation of the copper nanoparticles starts at a temperature of 200 °C. The formation of oxide phases occurs on the surface of the carbon shells, with the Cu₂O phase appearing first followed by the formation of the CuO phase. Upon heating to just below its melting point, the copper sublimes resulting in the formation of hollow carbon nanocapsules. Treatment of the initial or oxidized encapsulated copper nanoparticles with nitric acid and annealing can be used to obtain hollow carbon nanocapsules.     

Multi-walled carbon nanotubes formed by condensed-phase conversions of Fe-C-based nanopowder in vacuum

We describe the formation of multi-walled carbon nanotubes (MWCNTs) which have grown during annealing at 800 °C of Fe-C-based nanopowder in vacuum. The Fe-C-based nanopowder was produced by a laser pyrolysis of gas-phase reactants. The as-synthesized and annealed samples were characterised by TEM, XRD, Mössbauer spectroscopy, Raman spectroscopy, and magnetic measurements. Under the TEM, MWCNTs were observed in the annealed sample. In addition, larger particles with the graphitic shells and various graphitic structures were found. XRD and Mössbauer analysis confirmed that only two iron phases were present in the annealed sample: α-Fe and Fe₃C. Phase transformations taking place during the thermal treatment of the sample are discussed.     

Carbon nanotube synthesis from alcohols by a novel aerosol method

Single- and multiwalled carbon nanotubes (CNTs) were synthesised by a novel aerosol method using alcohols, namely ethanol and octanol, as carbon precursors. Preformed iron and nickel aerosol nanoparticles, produced by evaporation from resistively heated metal wire, were used as catalysts. Multiwalled CNTs were initiated by 10 nm sized catalyst particles and produced in the presence of ethanol vapour with the partial pressure of 7072 Pa, while combination of 2.4 nm particles and decreased alcohol vapour pressure (123 Pa) resulted in the formation of mainly single-walled and a small fraction of double-walled CNTs. The effect of a promoter (thiophene) in the system was found to be very important for the synthesis of multiwalled CNTs, while only a 30% number concentration increase was found for the single-walled CNT production.     

电子束诱导单壁碳纳米管不稳定的新观察

利用透射电镜在室温下对不同形态的单壁碳纳米管进行了原位电子束辐照研究.研究发现:在相同的辐照条件下随着辐照时间(或辐照剂量)的增加,两端固定的单壁碳纳米管径向收缩,且收缩速率越来越快;相同直径的轴向弯曲的单壁碳纳米管比平直的单壁碳纳米管更加不稳定;一端固定另端自由的单壁碳纳米管轴向收缩,但其直径基本不变.利用单壁碳纳米管纳米曲率效应和能量束诱导非热激活效应,对上述单壁碳纳米管不稳定性现象进行了新的、合理的解释.     

一种制备巴基葱的新方法纳米碳化硅高温真空热分解法

实验发现，通过真空热处理碳化硅纳米粉末可以获得巴基葱.透射电子显微镜和高分辨电子显微镜观测表明，当碳化硅完全分解时，形成空心准球状颗粒和葱状石墨颗粒；当碳化硅分解不完全时，形成碳包裹碳化硅结构，该包裹层由准同心石墨壳层构成.由实验结果知，认为平面结构是石墨的最稳定形式的传统观点是值得讨论的. 关键词：     

用微米级LaNi5为催化剂生长的碳管的ESR谱研究

用微米级LaNi₅合金粉末为催化剂, 以乙炔为原料, 采用化学气相沉积(CVD)法合成了多壁碳纳米管. 在100~290 K温度下测量了41 μm≤d≤150 μm粒径催化剂制备的不同直径分布的碳纳米管的电子自旋共振（ESR）谱,研究了测量温度、微米级催化剂粒径及制备过程的氢气氛对生成的碳纳米管的ESR谱线型、g因子、线宽的影响. 发现碳纳米管的g因子随其直径的增大而增大,分别为2.040 0（催化剂粒径41 μm≤d≤50 μm, 碳纳米管的直径分布为10 nm到20 nm）和2.089 8（催化剂粒径100 μm≤d≤150 μm,碳纳米管的直径分布为70 nm到120 nm）. 发现小管径纳米管的ESR谱图有一个峰, 而大管径纳米管的ESR谱图有两个峰A和B, 且随测量温度的升高, 峰B强度增大.     

Improving the surface properties of multi-walled carbon nanotubes after irradiation with gamma rays

The effects of gamma-irradiation on the modification of the surface and structure of multi-walled carbon nanotubes were studied. Gamma-irradiation affected the graphitization properties of functional groups, and decreased the diameter of multi-walled carbon nanotubes. The irradiated multi-walled carbon nanotubes with the absorbed dose of 100 kGy exhibited a larger specific surface area and microporous volume as compared with the other samples. The Raman spectroscopy and X-ray photoelectron spectroscopy showed that the interaction between the gamma-irradiation and the multi-walled carbon nanotubes with the absorbed dose of 150 kGy destroyed the nanostructure of carbons, leading to the formation of diamond-like structures and carbon oxides. In addition, gamma-irradiation with the absorbed dose of 100 kGy improved multi-walled carbon nanotubes graphitization and surface properties while at higher absorbed dose (150 kGy), it induced damaged structures (sp³ bonds and oxygen compositions).     

Gold nanoparticle production by laser ablation in liquid nitrogen medium followed by cryogenic medium substitution with ethanol

The use of liquid nitrogen as a medium for laser ablation made it possible to obtain Au particles shaped as cores, cores/hollow shells, and hollow shells by radiation of a picosecond Nd:YAG laser. In this case, the substitution of the cryogenic liquid medium of the colloid by evaporating on the surface of a room-temperature liquid causes the shift and broadening of the plasmon resonance peak of Au nanoparticles, which results from the formation of fractal nanoparticle aggregates.     

Spectroscopic Studies on Pure and Histidine-Functionalized Multiwalled Carbon Nanotubes

Electron paramagnetic resonance, Fourier transform infrared, and ultraviolet-visible studies were carried out for pure and histidine-functionalized multiwalled carbon nanotubes. Electron paramagnetic resonance absorption spectral data were found to be the best fit for the Gaussian lineshape. The g-values indicate the presence of magnetic impurities in the samples and the interaction between the localized electrons and delocalized electrons in the nanotubes trapped at defects or magnetic ion sites. The electron spin concentration decreases with increasing concentration of histidine, which implies that the unpaired electrons undergo a reduction process in the histidine-functionalized multiwalled carbon nanotubes. Fourier transform infrared study confirms the presence of functional groups in pure and histidine-functionalized multiwalled carbon nanotubes. Ultraviolet-visible study reveals the formation of a charge transfer complex in histidine-functionalized multiwalled carbon nanotubes.     

Morphologies and microstructures of carbon nanotubes prepared by self—sustained arc discharging

We have investigated the morphology and microstructure of carbon nanotubes and nanoparticles in cathode deposits prepared by self-sustained arc discharge. Scanning electron microscopy images indicate that there are two regions exhibiting different morphologies on the top surface of the cathode deposits. In the central region, there is a triangular pattern of spots with a diameter up to 100μm, which consists of carbon nanotubes and nanoparticles. In the fringe region, carbon nanotubes and nanoparticles are distributed randomly. In addition, carbon nanotubes in the central region have a larger inner diameter, compared with those in the fringe region. The outer diameter distribution of tubes in the central region is narrower than that of tubes in the fringe region, while the former has a smaller peak value than the latter. For the nanoparticles, they exhibit a different behaviour from the tubes existing in the same region. The difference between the microstructure of tubes or particles in the two regions is attributed to the different temperatures and temperature gradients during their formation.     

γ射线辐照下多壁碳纳米管结构转变过程研究

采用60Coγ射线辐照纯净的多壁碳纳米管,用高分辨透射电镜和拉曼光谱,研究了多壁碳纳米管由石墨结构向无定形结构转变的演化过程.发现在γ射线辐照下,碳纳米管的外部石墨层逐渐失去最初的有序结构而向无定形结构转变.而且,随着γ射线辐照剂量的增加,无定形结构不断推进,而石墨层结构则不断减小,直至使整个碳纳米管变为一个中空的无定形纳米线结构.用原子位移理论和溅射机理对这种转变过程进行了分析.γ射线轰击碳纳米管击出碳原子,碳原子停留在晶格的间隙位置上产生间隙原子,在它原来的平衡位置则留下一个空位.当轰击粒子动能足够大时导致碰撞级联效应,无序结构增加.多数空位和间隙原子可能相互复合而彼此退火,但仍有少数原子作为间隙原子而造成晶格进一步缺陷.辐射也可以引起碳原子的溅射,溅射出来的碳原子沉积在碳纳米管的外壁上形成一层无定形碳结构.