Molecular orbital study of pyrolytic carbons based on small cluster models

Molecular orbital calculations are applied to the Raman scattering and ESR of pyrolytic carbons on the basis of small cluster models. The E_2g and A_1g modes of C-C stretching vibrations of coronene, hexabenzocoronene, and circumcoronene, which belong to D_6h carbon clusters, are shown to appear around the 1550 cm⁻¹ and 1360 cm⁻¹ bands, respectively. The unpaired electrons observed in pyrolytic carbons are attributed to the bond-alternation defects on odd-numbered carbon clusters that are more easily mobile than those of trans-polyacetylene.     

Application of modified pyrolytic graphite electrode as a sensor in the simultaneous assay of adenine and adenosine monophosphate

A simple and sensitive method based on square wave voltammetry (SWV) at single-walled carbon nanotube (SWNT) modified edge plane pyrolytic graphite electrode (EPPGE) is proposed for the simultaneous determination of adenine and adenosine-5′-monophosphate (5′-AMP). The modified electrode exhibits remarkable electrocatalytic properties towards adenine and 5′-AMP oxidation with a peak potential of ∼850 and 1165 mV respectively. Linear calibration curves are obtained over the concentration range of 5-100 nM for adenine and 10-100 nM for 5′-AMP with sensitivity of 677 and 476 nA nM⁻¹ for adenine and 5′-AMP respectively. The limit of detection for adenine and 5′-AMP was found to be 37 × 10⁻¹⁰ M and 76 × 10⁻¹⁰ M, respectively. The effect of pH revealed that the oxidation of adenine and 5′-AMP at SWNT modified EPPGE involved equal number of electrons and protons. The modified electrode exhibited high stability and reproducibility.     

Chemistry and kinetics of chemical vapor deposition of pyrocarbon: VI. influence of temperature using methane as a carbon source

The chemical vapor deposition of carbon from methane was investigated at an ambient pressure of about 100 kPa, a methane partial pressure of 10 kPa and temperatures ranging from 1050–1125°C. Carbon deposition rates and compositions of the gas phase as a function of residence time have been determined using a substrate with a surface area/reactor volume ratio of 40 cm⁻¹. Increasing temperatures lead to strongly increasing deposition rates, decreasing partial pressures of ethane and increasing partial pressures of ethene, ethine and benzene. The overall activation energy of carbon deposition, determined from the initial deposition rates at a residence time versus zero amounts to 446 kJ/mol as compared to 431.5, 448 and 452.5 kJ/mol reported in earlier papers. Two possible rate-limiting steps are discussed, namely dissociation of methane, which is favored in the earlier papers, and dissociation of carbon–hydrogen surface complexes.     

A highly selective amperometric sensor for ascorbic acid based on mesopore-rich active carbon-modified pyrolytic graphite electrode

A kind of new mesopore-rich active carbon (MRAC) was firstly prepared by carbonizing bamboo micro-particles, which was utilized for constructing MRAC-modified pyrolytic graphite electrode (MRAC/PGE). The electrochemical behavior of ascorbic acid (AA) was in detail investigated at the MRAC/PGE. The proposed MRAC/PGE showed an excellent electrocatalytic response towards AA oxidation in neutral buffer solution. The oxidation potential of AA significantly decreased at MRAC/PGE. The oxidation current of AA obtained at the MRAC/PGE is 4.6-fold higher than that of the bare PGE. Using amperometric method, the anodic current is linear with AA concentration in the range of 0.5-2000 μM, with a detection limit about 0.3 μM. Furthermore, the proposed electrode can also avoid major interferences such as dopamine, uric acid, urea, and so on. This new method has been successfully applied for AA assay in urine and pharmaceutical preparations.     

Microwave absorption properties of pyrolytic carbon nanofilm

We analyzed the electromagnetic (EM) shielding effectiveness in the Ka band (26 to 37 GHz) of highly amorphous nanometrically thin pyrolytic carbon (PyC) films with lateral dimensions of 7.2 × 3.4 mm², which consists of randomly oriented and intertwined graphene flakes with a typical size of a few nanometers. We discovered that the manufactured PyC films, whose thickness is thousand times less than the skin depth of conventional metals, provide a reasonably high EM attenuation. The latter is caused by absorption losses that can be as high as 38% to 20% in the microwave frequency range. Being semi-transparent in visible and infrared spectral ranges and highly conductive at room temperature, PyC films emerge as a promising material for manufacturing ultrathin microwave (e.g., K_a band) filters and shields.     

Efficient growth of MWCNTs from decomposition of liquefied petroleum gas on a NixMg1−xO catalyst

With a solid-solution type of Ni_xMg_1−xO as catalyst, low-cost and easy-handling LPG was used as the carbon-source to efficiently synthesize CNTs of high purity. The prepared CNTs were “Herringbone-type” MWCNTs, with the outer diameters in the range of 10–40 nm and the inner diameters of 3–7 nm. The CNTs were almost the only species in the purified products. The structures of the nanocarbon were predominantly graphite-like, and the content of amorphous carbon was considerably low (6% estimated). The present study provides an alternative route to efficiently synthesize Herringbone-type CNTs of high purity without using CH₄.     

Analysis of the mechanism of the critical transition in irradiated acetylene that leads to generation of shell-shaped carbon nanoparticles

We have recently reported that onion-like shell-shaped carbon nanoparticles of high crystallinity could be generated through critical transition in the acetylene flow irradiated by a cw infrared CO₂ laser [Choi et al. Advanced Materials 2004;16:1721-25]. This transition appeared as the temperature jump above a threshold value of the laser irradiance. The present paper explains the origin of this recent discovery. The heat balance on the surface of the growing particle is shown to allow the existence of two stable particle temperatures. Then, the temperature jump observed in our recent study is a transition from the low temperature regime to the high temperature regime. Implications of the finding for the processes of the carbon nanoparticle formation from hydrocarbons are also discussed.     

化学气相沉积与渗透过程中热解炭织态结构生成机理研究

为研究热解炭织态结构的生成规律，采用不同压强的甲烷为碳源，在1100℃条件下进行了化学气相沉积和化学气相渗透实验。化学气相沉积以具有不同表面积／自由体积比（[A／V]值）的直通方形多孔陶瓷为基体；化学气相渗透实验在直径为1mm细直孔内表面沉积和对炭纤维体积分数为7％的炭毡进行致密化。借助正交偏光显微镜（消光角）和透射电子显微镜（定向角）对在不同实验条件下制备的热解炭进行分析和定量表征。研究发现：热解炭的织态结构可以在两种不同的沉积条件下形成。当甲烷压强较低时为化学生长阶段；当甲烷压强较高时为物理形核阶段。在化学生长控制阶段，热解炭的织态结构可以利用之前提出的“颗粒填充模型（P-F模型）”加以解释。该模型假设高织构热解炭的沉积一定对应于气相中存在具有合适比例的芳香化合物（例如苯）和线性小分子（主要是C2H2），当二者的浓度比偏离该最优比（或者偏大，或者偏小），均将导致中织构甚至低织构热解炭的生成。在化学生成控制阶段，化学气相沉积和化学气相渗透对热解炭织态结构影响的差别，除了[A／V]值而外，还有氢气的作用。在化学气相渗透过程中，基体内部生成的氢气快速扩散至基体表面，使内外沉积速率和织态结构均发生较大变化。     

Effect of Thermal and Material Anisotropy of Pyrolytic Carbon in Vibration-Assisted Micro-EDM Process

Pyrolytic carbon (PyC) is extremely biocompatible with high directional strength and unique directional thermal conductivity. PyC is used in biomedical devices like cardiovascular implants and finger prosthesis. Microfeatures on PyC have been proven as performance-driving agents in many cases. This work is focused on micro-electric discharge machining (micro-EDM) characterization of PyC to understand the effect of material/thermal anisotropy on the process response. An L9 Taguchi design of experiments has been performed to analyze the effect of gap voltage, capacitance, and frequency on the MRR, surface quality, and dimensional accuracy. MRR increases by 16% with vibration in AB plane machining. In C plane, the effect of vibration on MRR is not favorable. MRR reduces by 56% if the machining plane changes from AB to C due to the lower thermal conductivity along C. Surface roughness decreases by an order of magnitude if machining plane changes from AB to C; surface roughness of 65 nm has been achieved in C plane under certain conditions. The error in dimensional accuracy in C plane is 46% lower than AB plane. EDS shows noncontaminated machined surface. Finally, micro-EDM process has been used to create microfeatures in PyC, which could potentially improve/alter the desired surface quality.     

桑蚕茧丝的热裂解气相色谱研究

本文用裂解气相色谱法研究了桑蚕茧丝的热裂解行为。研究结果表明,桑蚕茧丝在管式炉中220℃左右时开始裂解,裂解的主要产物是氢、氧、氮、一氧化碳,二氧化碳和甲烷等六种气体。丝素有与此相同的裂解产物。裂解气体中各种气本的相对含量,随裂解温度和裂解时间的变化而变化。由此算出了在1000℃时的热裂解反应的动力学参数,推测了热裂解反应的历程。