Effect of Molecular Structure on Friction and Wear of Polymer Thin Films Deposited on Si Surface

In this study, the influence of the molecular structure (linear or with bulky side groups) of polymer films covalently attached to Si surface on tribological properties is investigated. Two polymers, PE (polyethylene) and PS (polystyrene), are selected where PE has simple linear molecular structure whereas PS has linear molecular structure but contains bulky benzene groups located at the sides of the linear chain. PE and PS molecules, both with reactive maleic anhydride groups, are chemisorbed onto Si via an intermediate APTMS SAM (3-aminopropyltrimethoxysilane self-assembled monolayer). Water contact angle measurements, AFM (atomic force microscopy), ellipsometry, and XPS (X-ray photoelectron spectroscopy) are used to identify and characterize the polymer films. Tribological properties are studied using a microtribometer where a 4 mm diameter Si₃N₄ ball is used as the counterface. Among the two polymer films investigated, Si/APTMS/PE has shown very low coefficient of friction (0.08) and high wear life (∼4,400 cycles) than those of Si/APTMS/PS. Surprisingly, Si/APTMS/PS did not show any improvement in tribological properties when compared to that of bare Si. The present study proves that the polymer with linear molecular structure without the bulky side groups show good tribological properties even when it is coated as a thin film and hence such polymers can be used as thin-films for reducing friction and wear of substrates such as Si or other materials.     

A cryogenic circulating advective multi-pass absorption cell

A novel absorption cell has been developed to enable a spectroscopic survey of a broad range of polycyclic aromatic hydrocarbons (PAH) under astrophysically relevant conditions and utilizing a synchrotron radiation continuum to test the still controversial hypothesis that these molecules or their ions could be carriers of the diffuse interstellar bands. The cryogenic circulating advective multi-pass absorption cell resembles a wind tunnel; molecules evaporated from a crucible or injected using a custom gas feedthrough are entrained in a laminar flow of cryogenically cooled buffer gas and advected into the path of the synchrotron beam. This system includes a multi-pass optical White cell enabling absorption path lengths of hundreds of meters and a detection sensitivity to molecular densities on the order of 10(7) cm(-3). A capacitively coupled radio frequency dielectric barrier discharge provides ionized and metastable buffer gas atoms for ionizing the candidate molecules via charge exchange and the Penning effect. Stronger than expected clustering of PAH molecules has slowed efforts to record gas phase PAH spectra at cryogenic temperatures, though such clusters may play a role in other interstellar phenomena.     

Ions in space

We review the detection history, observation, distribution, and reactivity of molecular ions in extraterrestrial space, with particular (though not exclusive) reference to interstellar monocations. The diversity of interstellar ion chemistry is highlighted with reaction examples, drawn from the authors' own laboratories and elsewhere, and attempt to provide an overview of this broad and increasingly divergent field. Emphasis is given to the role of ions in the synthesis of molecules, including their ability to catalyze the transformation of neutral molecules.     

STM imaging of molecular collagen and phospholipid membranes

The application of STM to biological materiais has been limited by poor conductivity, sample geometry and stability of biological materials. In this paper we describe an STM study of the monomeric helical forms of collagen, a stable, conductive and widely prevalent structural protein. We have also used STM to image artificial Langmuir DPE (dipalmitoyl phosphatidyl ethanolamine) phospholipid membranes. Both molecular collagen and the phospholipid membranes were dried in air on highly oriented pyrolytic graphite (HOPG). Our STM images of collagen dried on HOPG reveal strands 15Å in diameter with a periodicity of about 30Å which correlates with that known to occur in collagen. Spikes which periodically protrude from strands in our STM images of collagen appear to represent pyrrolidine ring structures in the amino acids proline and hydroxyproline. Thus, we report the first STM imaging of native biomolecules revealing intramolecular details and what appear to be specific amino acids. STM imaging of phospholipid membranes show a lattice pattern with densities spaced ～4–5Å apart. These are thought to represent individual phospholipid molecules in an artificial membrane formed on the HOPG. We believe STM and its related technologies will have great future utility in biomolecular studies.     

Molecular dynamics study of optimal packing structure of OTS self-assembled monolayers on SiO2 surfaces

Optimal packing structure of Octadecyltrichlorosilane (OTS) self-assembled monolayer (SAM) adsorbed on a SiO₂ (1 0 0) surface with a Si substrate was studied performing molecular dynamics (MD) computational simulations. Molecular substitution, substitution pattern and molecular orientation of the OTS molecules on the SiO₂ (1 0 0) are the main factors studied in order to determine the optimal packing structure taking into account energetic balance. We have used the optimal packing structure to study other properties usually used to characterize SAMs as molecular and system tilt angles, film thickness and gauche defects. These properties and monolayer stability were studied performing MD simulations in a temperature range from 100 to 600 K and we found that results obtained agree with those from experimental measurements. We found that OTS films are stable up to 500 K. The optimal structure obtained could be used in further MD simulations studies in order to determine tribological properties of OTS–SiO₂ systems.     

Energy-loss near-edge structure (ELNES) and first-principles calculation of electronic structure of nickel silicide systems

The electronic structures of nanometre-sized nickel silicide systems, Ni(2)Si and NiSi, have been studied by energy-loss near-edge structure (ELNES) and first-principles band structure calculations. Experimental ELNES of Ni L(3)- and Si L(2,3)-edges could be explained well using theoretical spectra calculated for the ground state without the core hole, suggesting metallic properties for both silicides. It was shown that a slight difference in ELNES spectra of Ni(2)Si and NiSi comes from the coupling among the Ni d and Si p, d states in the unoccupied bands. The density of states and the contour plots of all the valence electron densities for Ni(2)Si, NiSi together with NiSi(2) show that Ni(2)Si has the bond with the strongest covalent character between Ni and Si atoms and the most transition metal-like character of the Ni 3d band among the three silicides.     

Fatty Acid Adsorption on Several DLC Coatings Studied by Neutron Reflectometry

The application of diamond-like carbon (DLC) coatings on the contacts of mechanical systems is becoming widespread thanks to their excellent tribological properties. Numerous studies of DLC coatings have been reported over the past decade and, as a result, the understanding of their lubrication has improved. The tribological properties of boundary-lubricated contacts are drastically affected by adsorbed layers; however, due to the variety of lubricant additives and coating structures, no general adsorption mechanisms for DLC coatings have been put forward until now. This has, unfortunately, hindered improvements in their lubrication performance. Many of the essential physical properties of the adsorbed layers also remain undefined. In this work, we used neutron reflectometry to determine the thickness and the density of the adsorbed layers of fatty acid molecules on coatings of a-C, a-C:H, a-C:H:F and a-C:H:Si. The results showed that a 0.9-nm-thick layer adsorbed onto the a-C and a-C:H coatings. In contrast, both doped coatings, i.e. the a-C:H:F and a-C:H:Si, showed a poorer adsorption ability towards the fatty acid molecules than the a-C and a-C:H. Continuous adsorption layers were not detected on the a-C:H:F and a-C:H:Si; however, the possibility of adsorption in lower quantities cannot be ruled out.     

Microscopy for recognition of individual biomolecules

One frontier challenge in microscopy and analytical chemistry is the analysis of soft matter at the single molecule level with biological systems as most complex examples. Towards this goal we have developed two novel microscopy methods. Both employ highly specific molecular recognition schemes used by nature-the recognition of specific protein sites by antibodies and ligands. One method uses fluorescence labeled ligands for detecting single molecules in fluid systems like membranes (Fig. 1B). Unitary signals are reliably resolved even for millisecond illumination periods. The knowledge of the unitary signal from single molecules permits the determination of stoichiometries of component association (Fig. 3). Direct imaging of the diffusional path of single molecules became possible for the first time (Fig. 4). Using linear polarized excitation, the angular orientation of single molecules can be analyzed (single molecule linear dichroism, (Fig. 5), which opens a new perspective for detecting conformational changes of single biomolecules. In the other method, an antibody is flexibly linked to the tip of an atomic-force microscope. This permits the identification of receptors in multi-component systems. Molecular mapping of biosurfaces and the study of molecular dynamics in the ms to s range become possible with atomic force microscopy.     

Scanning tunneling microscopy and spectroscopy investigations of QCA molecules

Quantum-dot cellular automata (QCA), a computation paradigm based on the Coulomb interactions between neighboring cells. The key idea is to represent binary information, not by the state of a current switch (transistor), but rather by the configuration of charge in a bistable cell. In its molecular realization, the QCA cell can be a single molecule. QCA is ideally suited for molecular implementation since it exploits the molecule's ability to contain charge, and does not rely on any current flow between the molecules. We have examined using an UHV-STM some of the QCA molecules like silicon phthalocyanines and Fe-Ru complexes on Au (111) and Si (111) surfaces, which are suitable candidates for the molecular QCA approach.     

The tribological role of surface atoms: ultra-thin carbon and silver layers on the Si(111)

A few monolayers of a carbon film on an Si(111) substrate have been studied for tribological characteristics, focusing on the tribological role of the surface atoms.A monolayer of H and Ag on Si were also tested with a macroscopic diamond slider to examine the effect of the surface atoms on the friction, and it was observed that the sliding systems show an extraordinarily low friction in ultra-high vacuum. We could draw a conclusion: the chemical characteristics of the surface layer strongly affect the friction and nano-scale structures on the surface drastically change the macroscopic slider friction in these systems.     

High-resolution scanning tunneling microscopy for molecules

Scanning tunneling microscopy (STM) can detect individual molecular configuration with its high spatial resolution ability, but some intrinsical and extrinsic factors result in the complexities of STM imaging of single molecules. By combining STM experimental work and theoretical simulation with the local density approximation based on Bardeen perturbation method, we have explored the atomic-scale configuration of the following molecular systems: C(60) molecules adsorbed on Si(111)-(7x7); alkanethiol self-assembly monolayers on Au(111); C(60) molecule imaged by STM tip adsorbed with another C(60) molecule; O(2) molecule adsorbed on Ag(110) and CO molecule adsorbed on Cu(111) imaged by CO chemically modified STM tip. Some related problems including: molecule-substrate interactions, STM imaging mechanism, chemically modified STM tip, etc., are discussed.     

大容积全多层高压储氢容器封头和筒体连接结构强度研究

以自主研制的75 MPa,2.5 m3大容积全多层高压储氢容器为对象,开展了封头和筒体连接结构强度试验研究,得到了加强箍、封头及其连接部位应力随容器内压力的变化情况。建立了精度较高的大容积全多层高压储氢容器封头和筒体连接结构弹塑性有限元分析模型。基于该模型,对封头和筒体连接结构在容器超压过程中的变形特征,及封头与加强箍配合面形成裂纹尖端在多次加载时的稳定性进行了分析,验证了加强箍结构设计方法的合理性。     

Tribological properties of self-assembled monolayers on Au,SiOx and Si surfaces

Using interfacial force microscopy (IFM), the tribological properties of self-assembled monolayers (SAM) on Si surfaces produced by a new chemical strategy are investigated and compared to those of “classical” SAM systems, which include alkanethiols on Au and alkylsilanes on SiO_x. The new SAM films are prepared by depositing n-alkyl chains with OH-terminations onto Cl-terminated Si substrates. The chemical nature of the actual lubricating molecules, n-dodecyl, is kept constant in all three thin film systems for direct comparison and similarities and differences in tribological properties are observed. The adhesion strength is virtually identical for all three systems; however, frictional properties differ due to differences in film packing. Differences in the chemical bonds that attach the lubricant molecules to the substrate are also discussed as they influence variations in film wear and durability. It is demonstrated that the new SAM films are capable of controlling the friction and adhesion of Si surfaces equally well as the classical SAMs and are potentially more reproducible and more durable.     

Reversed Micelle Structures in PFPE Lubricant Thin Films on Magnetic Disk Surface Observed by Non-Contact AFM

PFPE lubricants (Fomblin Z-dol) for hard disk surface lubrication have two hydroxyl groups, one at each end of the molecules, and form stable insoluble monolayers at the water surface. In this study, molecular weight-fractionated PFPE lubricant monolayers were transferred from the water surface to solid substrates such as a hydrophilized silicon wafer, gold-sputtered mica, and a hard disk after adjusting the two-dimensional density of the lubricant molecules. The molecular structures of the PFPE lubricant molecules at the solid surfaces were observed by the cryogenic non-contact AFM under ultra-high vacuum. At the hydrophilic silicon wafer surface we could observe a single lubricant molecule in a random coil sphere shape. However, at the non-polar gold surface we confirmed the formation of reversed micelle structures. At the hard disk surface we detected various sizes of reversed micelles of PFPE lubricant in a flat oval shape.     

TectoRNA and 'kissing-loop' RNA: atomic force microscopy of self-assembling RNA structures

RNA molecules have been much less studied by atomic force microscopy (AFM) than have DNA molecules. In this paper, AFM imaging is presented for two different RNA molecules able to self‐assemble into complex supramolecular architectures. The first one is a molecular dimer of a 230‐nt RNA fragment coming from the RNA genome of a murine leukaemia virus. The monomeric RNA fragment, which appears by AFM as an elongated structure with a mean aspect ratio of 1.4, assembles into a dimer of elongated structures through the formation of a ‘kissing‐loop’ RNA interaction. The second one is a large supramolecular fibre formed of artificial self‐assembling RNA molecular units called tectoRNA. The fibre lengths by AFM suggest that there are 50–70 tectoRNA units per fibre. Some methods and limitations are presented for measuring molecular volumes from AFM images.     

Microwave Dielectric Study on Water Structure and Physical Properties of Aqueous Systems Using Time Domain Reflectometry with Flat-End Cells

Microwave dielectric measurements were performed in the frequency range from 1 mHz up to 30 GHz using a time domain reflectometry (TDR) method for emulsions and gels. Flat-end sample cells have been used in the TDR measurement to contact a small spot of the surface of those viscoelastic and solid samples without any destruction. Relaxation processes due to various water structures were observed for these aqueous systems. Relaxation parameters thus obtained offer information about these water structures and amounts. The relaxation strength obtained from the high frequency process due to free water can be an adequate measure of water content in spite of some ambiguities for different water structures in some materials. Comparisons of actual water contents in emulsion with those estimated from the relaxation strength indicate that water structure is affected by the interaction between water and micelle. Unfreezable water observed in DNA gel under the freezing point consists of bound water and a fraction of free water. Bound water molecules are still unfreezable to keep the double helical structure of DNA, when the fraction of free water is frozen at lower temperatures. These water structures determine physical properties of moist materials. TDR measuring technique with the flat-end cell is effective to investigate water structures in viscoelastic moist materials and to evaluate physical properties and structures of complex molecular systems.     

硅基微机械表面粘附及摩擦性能的AFM试验研究

在Si（100）基片上制备了十八烷基三氯硅烷（OTS）分子润滑膜，并用原子力显微镜（AFM）对比研究了施加OTS膜前后的硅表面的粘附、摩擦磨损性能。试验考虑了相对湿度和扫描速度对粘附、摩擦性能的影响。结果表明，相对于硅构件来讲，OTS膜表面粘附力较小，具有较小的摩擦因数，呈现较好的润滑性能；硅构件受湿度变化的影响比OTS膜明显。微构件的摩擦性能由于水合化学作用生成Si（OH）。润滑膜，使得其受相互间运动速度影响很大。OTS膜不仅是一种耐磨性较好的润滑膜，而且有良好的稳定性。     

原子力显微镜在多糖分子结构研究中的应用

评述原子力显微镜在多糖分子结构和功能研究的进展,AFM不仅可以在空气和液体中对多糖分子单分子和聚集体成像,得到单分子的直径、长度等量化信息和分子聚集体形貌特征。近年来AFM还用于在液体池中操纵单个多糖分子,获取单分子力学谱研究分子的弹性与构型转变的关系,在单分子水平上对多糖进行鉴定,用于细胞表面大分子黏附作用和细胞识别的研究等。AFM新技术的不断出现,必将在高分子科学的研究中起到越来越重要的作用。     

Viscosity and Chemical Structure of Polymers

A technique is described which has been found useful for understanding the role played by molecular structure in the viscosity of liquid polyisobutylene polymers. A linear logarithmic relation, between the viscosity and the average molecular weight of low molecular weight polyisobutylenes, is demonstrated. This relationship is used to indicate an apparent difference in the molecular structures of some polyisobutylenes.

A linear relation also exists between the molar refraction and a viscosity-constitutional constant in several homologous series of polymers which is useful for classification purposes.     

Gas-phase basicities of polyfunctional molecules. Part 1: Theory and methods

The experimental and theoretical methods of determination of gas-phase basicities, proton affinities and protonation entropies are presented in a tutorial form. Particularities and limitations of these methods when applied to polyfunctional molecules are emphasized. Structural effects during the protonation process in the gas-phase and their consequences on the corresponding thermochemistry are reviewed and classified. The role of the nature of the basic site (protonation on non-bonded electron pairs or on pi-electron systems) and of substituent effects (electrostatic and resonance) are first examined. Then, linear correlations observed between gas-phase basicities and ionization energies or substituent constants are recalled. Hydrogen bonding plays a special part in proton transfer reactions and in the protonation characteristics of polyfunctional molecules. A survey of the main properties of intermolecular and intramolecular hydrogen bonding in both neutral and protonated species is proposed. Consequences on the protonation thermochemistry, particularly of polyfunctional molecules are discussed. Finally, chemical reactions which may potentially occur inside protonated clusters during the measurement of gas-phase basicities or inside a protonated polyfunctional molecule is examined. Examples of bond dissociations with hydride or alkyl migrations, proton transport catalysis, tautomerization, cyclization, ring opening and nucleophilic substitution are presented to illustrate the potentially complex chemistry that may accompany the protonation of polyfunctional molecules.