自组装C60分子膜的微观摩擦行为

利用端基带－NH2的氨基酸自组装单分子膜与C60烯键反应形成共价键制成C60自组装膜，用原子力显微镜（AFM）研究了膜的微观摩擦学性能，结果表明，长链羟酸／C60分子膜的摩擦学性能优于短链羧酸分子膜；羧酸／C60分子膜的碳链中极性基团如羧基的存在，可以提高膜的平整度，改善膜的摩擦学性能。     

磁悬浮分子泵转子振动抑制研究

磁悬浮分子泵具有工作转速高、转子极转动惯量大等特点,针对磁悬浮分子泵转子在升速过程中出现的弯曲模态振动以及涡动模态振动,提出了一种基于滤波交叉反馈与陷波器的大转动惯量磁悬浮转子控制方法。建立磁悬浮轴承-大转动惯量刚性转子系统数学模型,求解得出转子涡动模态频率,根据该模型分析了滤波交叉反馈控制器对涡动模态振动的抑制效果,并且设计了陷波器用于抑制不同转速下的转子弯曲模态振动。试验结果表明,磁悬浮分子泵稳定升速至工作转速18 000 r/min,转子振动位移为35μm,弯曲模态振动以及涡动模态振动得到了有效抑制。     

碳纳米豆荚内C60分子的振荡行为

近年来C60分子与碳纳米豆荚组成的碳纳米豆荚的高频振荡行为受到了学术界的广泛关注,并有望在振荡器元器件等领域获得潜在应用。本工作基于分子动力学模拟方法,结合碳-碳多体势函数和Lennard Jones对势函数,对碳纳米豆荚中C60分子的振荡行为进行了模拟研究,并分别讨论了碳纳米管长度、直径及轴向预应力对碳纳米豆荚振荡性能的影响。研究结果表明,C60分子受到其与碳管间的长程范德华力及滑动摩擦力的作用,沿碳纳米管轴线方向做周期性往复振荡运动。碳纳米管长度和直径的增加均会导致C60分子振荡频率单调减小,且存在一个振荡发生的临界直径下限值;由于范德华力相互作用的影响,当直径较大时,C60分子将发生偏心振动,振荡轨迹偏离碳管轴线而贴近一侧管壁。轴向预应力对C60分子的振荡行为也有明显影响:随轴向拉伸预应力的增加,C60分子振荡频率单调减小;当轴向预应力为压应力时,C60分子振荡频率的衰减为分段线性模式,在越过临界压应力后急剧下降。这些研究结果将对基于碳纳米豆荚的高频振荡元器件的开发提供有益的指导与参考。     

基于振动信号时频分解-样本熵的受电弓裂纹故障诊断

构建了基于时频分解-样本熵测度的受电弓振动信号故障特征提取模型。对振动信号进行聚合经验模态分解,接着对分解得到的本征模态函数计算参数优化后的样本熵特征。将获取的故障特征输入基于粒子群参数优化的支持向量机(PSO-SVM)进行受电弓故障识别分析。结果发现,基于受电弓顶管振动信号的EEMD样本熵故障诊断效果较好,而碳滑板振动信号诊断效果较差。针对这一特点,利用二代小波样本熵进行优化,进一步提高了碳滑板振动信号故障诊断结果,验证了现代时频分析算法与信息熵联合的诊断方法在受电弓振动信号特征提取与故障诊断的可行性与有效性。     

电化学沉积DLC膜及其表征

采用电化学沉积方法，甲醇有机溶剂作碳源，在直流电源作用下在单晶硅表面沉积得到碳薄膜。薄膜不溶于苯、丙酮等有机溶剂，具有较高的硬度(16GPa左右)，用AFM、Raman和FTIR分析手段对该薄膜表面形貌和结构进行表征，Raman和FTIR结果表明电化学沉积得到的是含氢的类金刚石碳薄膜。通过研究样品薄膜的XPS和XAES谱图特征，进一步证实薄膜是DLC薄膜，并用线性插入法估算出样品薄膜中SP^3的相对含量为60％，同时推测了电化学沉积DLC薄膜的生长机理。     

抗氧化碳-碳复合材料涂层的界面研究

本文研究了碳-碳(C/C)复合材料的碳化硅抗氧化涂层系统的组成和成型工艺,给出了抗氧化性能试验和动态环境试验结果.经微观结构分析,认为在C/C基材表面反应生成的碳化硅涂层是化学转化涂层,与C/C基材是有机结合,并且具有成分连续变化的过渡界面,构成了一种功能梯度倾斜材料,使固渗碳化硅具有优异的性能.     

C60富勒烯分子的电子传输特性

采用扩展的Huckel方法与格林函数方法,分析了双Au电极作用下C60富勒烯分子的电子结构与电子输运特性。研究结果表明,C60富勒烯分子与Au电极“接触”后,其分子轨道能级发生了较大的变化,HOMO、LUMO间的能隙显著减小;C60与Au电极之间的结合既有共价键的成分,又有离子键的成分;C60富勒烯分子的电压-电导率曲线以及伏安曲线表现出了微妙的量子特性。     

微结构对碳/碳复合材料界面性能的影响

通过理论模型和界面顶出实验分析了微观结构对碳/碳复合材料界面性能的影响机制。使用高分辨Micro-CT系统获得C/C复合材料界面的微观结构特征,并对界面的微观结构特征进行统计分析,得到界面微观结构尺度分布的概率密度函数。对C/C复合材料的界面层建立力学分析模型,计算获得C/C复合材料界面力学性能,在计算过程中引入界面微观结构的随机性统计分布,获得C/C复合材料界面力学性能的分布规律。设计纤维束顶出实验,测试分析C/C复合材料的界面力学性能。将力学分析模型的计算结果与界面顶出实验获得的实验结果进行对比分析,表明通过模型计算获得的界面性能的均值和离散度与实验获得的结果具有较好的一致性。      

Au电极作用下C60、2C60与4C60富勒烯分子的电子传输特性

采用扩展的Hückel方法与格林函数方法,研究了Au电极作用下,C60富勒烯、2C60和4C60聚合体分子的电子结构与导电性,并对它们的电子结构与电子输运特性进行了对比.研究结果表明,C60、2C60或4C60富勒烯分子与Au电极 "接触"后,其HOMO、LUMO间的能隙减小;C60、2C60或4C60分子与Au电极之间的结合既有共价键的成分,又有离子键的成分,其中,C60、4C60分子与Au电极结合的离子键特征更为明显;三种富勒烯分子的电子输运性能依次具有C60>2C60>4C60分子的顺序.     

C60、Si@C60及Ge@C60富勒烯分子的电子传输特性

采用扩展的Hückel方法与格林函数方法,分析了双Au电极作用下,C60、Si@C60以及Ge@C60富勒烯分子的电子结构与导电性,并对三种富勒烯分子的电子结构与电子输运特性进行了对比.研究结果表明,C60、Si@C60或Ge@C60分子与Au电极"接触"后,其最高占据分子轨道与最低未占据分子轨道间的能隙减小,它们与Au电极之间的结合既有共价键的成分,又有离子键的成分;三种富勒烯分子的电子输运性能依次具有Ge@C60＞Si@C60＞C60的顺序.     

A combined molecular dynamics and Raman spectroscopy approach for designing ice-metal interfaces

Summary Understanding the structure and interatomic interactions of an ice-metal interface plays a fundamental role in the design of deicing coatings. This is demonstrated by a novel approach, combining vibrational results from laser Raman spectroscopy with molecular dynamics simulations to obtain insights into icing on solids which, in turn, lead to design criteria for minimizing adhesion. An atomistic model of ice-copper interaction is constructed based on electronic structure calculations and used to show that reasonable molecular geometry and binding energy at the interface can be obtained. Through molecular dynamics simulations we find that the ice layer adjacent to the copper surface is structurally more disordered than the layers further away, a result which is verified by the Raman spectra of vibrational frequencies. The primary adhesive bond is made by the adsorption of oxygen atoms at the lattice sites of the metal substrate. The information obtained by Raman spectroscopy and molecular dynamics is then exploited to arrive at specific recommendations for designing polymeric deicing coatings and materials.     

Raman spectroscopic determination of the structure and orientation of organic monolayers chemisorbed on carbon electrode surfaces

Azobenzene (AB) and 4-nitroazobenzene (NAB) were covalently bonded to carbon surfaces by electrochemical reduction of their diazonium derivatives. The N(1s) features of XPS spectra of modified surfaces had intensities expected for monolayer coverage. However, the Raman spectra were significantly more intense than expected, implying an increase in scattering cross section upon chemisorption. A likely explanation is resonance enhancement of the carbon/adsorbate chromophore analogous to that reported earlier for dinitrophenylhydrazine (DNPH) chemisorption. Vibrational assignments indicate that the C-C vibration between azobenzene and the carbon surface is in the 1240-1280 cm(-1) region, and this conclusion is supported by spectra obtained from [(13)C]graphite. Observation of depolarization ratios for 4-nitroazobenzene and DNPH on graphite edge plane indicate that NAB is able to rotate about the NAB/carbon C-C bond, while chemisorbed DNPH is not. The partial multiple bond character of the DNPH linkage to graphite is consistent with the observation that the DNPH π system remains parallel to the graphitic planes.     

Experimental measurements and finite element analysis of the coupled vibrational characteristics of piezoelectric shells

Piezoelectric plates can provide low-frequency transverse vibrational displacements and high-frequency planar vibrational displacements, which are usually uncoupled. However, piezoelectric shells can induce three-dimensional coupled vibrational displacements over a large frequency range. In this study, three-dimensional coupled vibrational characteristics of piezoelectric shells with free boundary conditions are investigated using three different experimental methods and finite element numerical modeling. For the experimental measurements, amplitude-fluctuation electronic speckle pattern interferometry (AF-ESPI) is used to obtain resonant frequencies and radial, lateral, and angular mode shapes. This optical technique utilizes a real-time, full-field, non-contact optical system that measures both the natural frequency and corresponding vibration mode shape simultaneously. The second experimental technique used, laser Doppler vibrometry (LDV), is a pointwise displacement measurement method that determines the resonant frequencies of the piezoelectric shell. An impedance analyzer is also used to determine the resonant frequencies of the piezoelectric shell. The experimental results of the resonant frequencies and mode shapes for the piezoelectric shell are verified with a numerical finite element model. Excellent agreement between the experimental and numerical results is found for the three-dimensional coupled vibrational characteristics of the piezoelectric shell. It is noted in this study that there is no coupled phenomenon at low frequencies over which radial modes dominate. However, three-dimensional coupled vibrational modes do occur at high resonant frequencies over which lateral or angular modes dominate.     

Experimental evidence of a mechanical coupling between layers in an individual double-walled carbon nanotube

We perform transmission electron microscopy, electron diffraction, and Raman scattering experiments on an individual suspended double-walled carbon nanotube (DWCNT). The first two techniques allow the unambiguous determination of the DWCNT structure: (12,8)@(16,14). However, the low-frequency features in the Raman spectra cannot be connected to the derived layer diameters d by means of the 1/d power law, widely used for the diameter dependence of the radial-breathing mode of single-walled nanotubes. We discuss this disagreement in terms of mechanical coupling between the layers of the DWCNT, which results in collective vibrational modes. Theoretical predictions for the breathing-like modes of the DWCNT, originating from the radial-breathing modes of the layers, are in a very good agreement with the observed Raman spectra. Moreover, the mechanical coupling qualitatively explains the observation of Raman lines of breathing-like modes, whenever only one of the layers is in resonance with the laser energy.     

Single-molecule reactions and spectroscopy via vibrational excitation

Inelastic tunnelling spectra of single C4 hydrocarbon molecules adsorbed on the Pd(110) surface are presented. Experimental evidence is given that the symmetry of the molecular orbital into which the tunnelling electron first enters determines which vibrational modes are excited. The action spectrum for cis-2-butene exhibits most of the vibrational modes that are expected to be excited except for nu (C[double bond]C), which may be because the molecule is pi bonded to the substrate, thus making the lifetime of the excited state short.     

Plasmon‐Driven Selective Reductions Revealed by Tip‐Enhanced Raman Spectroscopy

We successfully realized in‐situ monitoring plasmon‐driven selective reduction of 2,4‐dinitrobenzenethiol to 2,2′‐diamino‐dimercaptoazobenzene, revealed by high vacuum tip‐enhanced Raman spectroscopy (HV‐TERS). The HV‐TER spectra revealed that the 2‐nitro and the 4‐nitro of 2,4‐DNBT were selectively reduced to the 2‐amine and the –N = N– bond of 2,2′‐diamino‐dimercaptoazobenzene (2,2′DA‐DMAB). Raman‐active and IR‐active modes as well as Fermi resonance were simultaneously observed in HV‐TERS, which demonstrated the advantages of HV‐TERS over SERS, since only Raman‐active modes were observed in SERS. The intensities of molecular IR‐active modes can be manipulated by the distance between tip and substrate in the near field, due to different dependences of the plasmon gradient and plasmon intensity over the distance of nano gap. Our results in HV‐TERS are in‐situ “complete‐vibration modes” spectral analysis, which significantly extend the application of HV‐TERS in the field of ultrasensitive spectral analysis on the nano scale.     

The relation between zeolite framework structure and vibrational spectra

Using a general valence force field method, infrared and Raman spectra of pure silica zeolite crystals and molecular substructures of zeolites are calculated. Computed spectra of the substructures are directly compared with computed spectra of the crystal. Also, a comparison of the atomic displacement vectors of the vibrational modes is made. No general theoretical basis for a correlation between the presence of large structural elements and spectral features, sometimes reported, is found to exist. An extensive comparison between experimental and theoretical infrared and Raman spectra of the SiO₂ forms of sodalite and faujasite is made. Other applications of vibrational spectroscopy to zeolite structure research, such as the SiOSi angle distribution and the location of acid sites, are evaluated as well.     

Vibrational and surface-enhanced Raman spectra of 1,6-diphenyl-1,3,5-hexatriene

The vibrational spectra and surface-enhanced Raman scattering (SERS) of 1,6-diphenyl-1,3,5-hexatriene (DPH) are discussed. The fundamental vibrational frequencies, overtones, and combinations observed in the infrared and Raman spectra of DPH are reported. The interpretation of the observed vibrational spectra was supported by a complete geometry optimization, followed by vibrational frequency and intensity computations for the cis- and trans- isomers of the DPH using density functional theory at the B3LYP/6-31G(d,p) level of theory. Because the molecule is photo-chemically active on Ag metal surfaces, the best SERS results for silver islands were obtained at low temperature and low energy density of the exciting laser line. DPH SERS on Au films was obtained at room temperature.     

Analysis of the deformation of gel-spun polyethylene fibres using Raman spectroscopy

Raman spectroscopy has been used to investigate molecular deformation in a number of high-performance gel-spun polyethylene (PE) fibres. Well-defined Raman spectra can be obtained for the fibres and the study has concentrated upon the symmetric C-C stretching mode (1128 cm^–1). During mechanical deformation, the Raman spectra show the existence of a bimodal molecular stress distribution in the crystalline phase resulting in splitting of the Raman band. The changes in the Raman band peak position and area with strain for different modes of deformation, including stress relaxation and creep, have indicated the molecular response of the material to stress is highly complicated. This information, however, is particularly useful in analysing the molecular deformation both quantitatively and qualitatively and it is shown that the Young's modulus of the fibres is related to both the relative areas of the two Raman bands and their rate of shift per unit strain.