Covalently bonded networks through surface-confined polymerization

The prospect of synthesizing ordered, covalently bonded structures directly on a surface has recently attracted considerable attention due to its fundamental interest and for potential applications in electronics and photonics. This prospective article focuses on efforts to synthesize and characterize epitaxial one- and two-dimensional (1D and 2D, respectively) polymeric networks on single crystal surfaces. Recent studies, mostly performed using scanning tunneling microscopy (STM), demonstrate the ability to induce polymerization based on Ullmann coupling, thermal dehalogenation and dehydration reactions. The 2D polymer networks synthesized to date have exhibited structural limitations and have been shown to form only small domains on the surface. We discuss different approaches to control 1D and 2D polymerization, with particular emphasis on the surface phenomena that are critical to the formation of larger ordered domains.

Do bacteria differentiate between degrees of nanoscale surface roughness?

Whereas the employment of nanotechnology in electronics and optics engineering is relatively well established, the use of nanostructured materials in medicine and biology is undoubtedly novel. Certain nanoscale surface phenomena are being exploited to promote or prevent the attachment of living cells. However, as yet, it has not been possible to develop methods that completely prevent cells from attaching to solid surfaces, since the mechanisms by which living cells interact with the nanoscale surface characteristics of these substrates are still poorly understood. Recently, novel and advanced surface characterisation techniques have been developed that allow the precise molecular and atomic scale characterisation of both living cells and the solid surfaces to which they attach. Given this additional capability, it may now be possible to define boundaries, or minimum dimensions, at which a surface feature can exert influence over an attaching living organism.This review explores the current research on the interaction of living cells with both native and nanostructured surfaces, and the role that these surface properties play in the different stages of cell attachment.

The role of V2O5 on the dehydrogenation and hydrogenation in magnesium hydride : An ab initio study

Ab initio density functional theory calculations are performed to study the experimentally observed catalytic role of V2O5 in the recycling of hydrogen in magnesium hydride. We find that the Mg–H bond length becomes elongated when MgH2 clusters are positioned on single, two, and three coordinated oxygen sites (O1, O2, and O3) on the V2O5(001) surface. Molecular hydrogen is predicted to spontaneously form at the hole site on the V2O5(001) surface. Additionally, the activation barrier for the dissociation of hydrogen on V-doped Mg(0001) surface is 0.20 eV, which is only 1/5 of that on pure Mg(0001) surface. Our results indicate that oxygen sites on the V2O5(001)surface and the V dopant in Mg may be important facilitators for dehydrogenation and rehydrogenation, respectively. The understanding gained here will aid in the rational design and development of Mg-based hydrogen storage materials.

Free surface problems for static Coulomb-Mohr granular solids

This paper is concerned with some plane strain and axially symmetric free surface problems which arise in the study of static granular solids that satisfy the Coulomb-Mohr yield condition. Such problems are inherently nonlinear, and hence difficult to attack analytically. Given a Coulomb friction condition holds on a solid boundary, it is shown that the angle a free surface is allowed to attach to the boundary is dependent only on the angle of wall friction, assuming the stresses are all continuous at the attachment point, and assuming also that the coefficient of cohesion is nonzero. As a model problem, the formation of stable cohesive arches in hoppers is considered. This undesirable phenomena is an obstacle to flow, and occurs when the hopper outlet is too small. Typically, engineers are concerned with predicting the critical outlet size for a given hopper and granular solid, so that for hoppers with outlets larger than this critical value, arching cannot occur. This is a topic of considerable practical interest, with most accepted engineering methods being conservative in nature. Here, the governing equations in two limiting cases (small cohesion and high angle of internal friction) are considered directly. No information on the critical outlet size is found; however solutions for the shape of the free boundary (the arch) are presented, for both plane and axially symmetric geometries.

Effects of corrugation frequency and aspect ratio on natural convection within an enclosure having sinusoidal corrugation over a heated top surface

Natural convection of a two-dimensional laminar steady-state incompressible fluid flow in a modified rectangular enclosure with sinusoidal corrugated top surface has been investigated numerically. The present study has been carried out for different corrugation frequencies on the top surface as well as aspect ratios of the enclosure in order to observe the change in hydrodynamic and thermal behavior with constant corrugation amplitude. A constant flux heat source is flush mounted on the top sinusoidal wall, modeling a wavy sheet shaded room exposed to sunlight. The flat bottom surface is considered as adiabatic, while the both vertical side walls are maintained at the constant ambient temperature. The fluid considered inside the enclosure is air having Prandtl number of 0.71. The numerical scheme is based on the finite element method adapted to triangular non-uniform mesh element by a non-linear parametric solution algorithm. The results in terms of isotherms, streamlines and average Nusselt numbers are obtained for the Rayleigh number ranging from 10^3 to 10^6 with constant physical properties for the fluid medium considered. It is found that the convective phenomena are greatly influenced by the presence of the corrugation and variation of aspect ratios.

Mixed convection laminar flow along a horizontal plate subject to streamwise sinusoidal surface temperature

Mixed convection of a two-dimensional laminar incompressible flow along a horizontal flat plate with streamwise sinusoidal surface temperature has been numerically investigated for different values of Rayleigh number and Reynolds number for constant values of Prandtl number, amplitude and frequency of periodic temperature. The numerical scheme is based on the finite element method adapted to rectangular non-uniform mesh elements by a non-linear parametric solution algorithm. The fluid considered in this study is air. The results are obtained for the Rayleigh number and Reynolds number ranging from 102 to 104 and 1 to 100, respectively, with constant physical properties for the fluid medium considered. Velocity and temperature profiles, streamlines, isotherms, and average Nusselt numbers are presented to observe the effect of the investigating parameters on fluid flow and heat transfer characteristics. The present results show that the convective phenomena are greatly influenced by the variation of Rayleigh numbers and Reynolds number.

Beat phenomena in metal nanowires, and their implications for resonance-based elastic property measurements

The elastic properties of 1D nanostructures such as nanowires are often measured experimentally through actuation of the nanowire at its resonance frequency, and then relating the resonance frequency to the elastic stiffness using elementary beam theory. In the present work, we utilize large scale molecular dynamics simulations to report a novel beat phenomenon in [110]oriented Ag nanowires. The beat phenomenon is found to arise from the asymmetry of the lattice spacing in the orthogonal elementary directions of the [110] nanowire, i.e. the [-110] and [001] directions, which results in two different principal moments of inertia. Because of this, actuations imposed along any other direction are found to decompose into two orthogonal vibrational components based on the actuation angle relative to these two elementary directions, with this phenomenon being generalizable to <110> FCC nanowires of different materials (Cu, Au, Ni, Pd and Pt). The beat phenomenon is explained using a discrete moment of inertia model based on the hard sphere assumption, the model is utilized to show that surface effects enhance the beat phenomenon, while the effect is reduced with increasing nanowires cross-sectional size or aspect ratio. Most importantly, due to the existence of the beat phenomena, we demonstrate that in resonance experiments only a single frequency component is expected to be observed, particularly when the damping ratio is relatively large or very small. Furthermore, for a large range of actuation angles, the lower frequency is more likely to be detected than the higher one, which implies that experimental predictions of Young’s modulus obtained from resonance may in fact be under predictions. The present study therefore has significant implications for experimental interpretations of Young’s modulus as obtained via resonance testing.

Bistable regime of surface magnetoplasma waves excitation at a semiconductor-metal interface

The theoretical analysis of the bistability associated with the excitation of surface magnetoplasma waves (SWs) propagating across an external magnetic field at the semiconductor-metal interface by the attenuated total reflection (ATR) method is presented. The Kretschmann-Raether configuration of the ATR method is considered, i.e. a plane electromagnetic wave is incident onto a metal surface through a coupling prism. The third-order nonlinearity of the semiconductor medium is considered in the general form using the formalism of the third-order nonlinear susceptibilities and of the perturbation theory. The examples of the nonlinear mechanisms which influence the SW propagation are given. The analytical and numerical analyses show that the realization of bistable regimes of the SW excitation is possible. The SW amplitude values providing bistability in the structure are evaluated and are reasonably low to provide the experimental observation.

Resonant generation of the second harmonic of a surface wave on a plasma-metal boundary

The process of resonant generation of the second harmonic of the surface wave, propagating along the external magnetic field at the plasma-metal boundary is considered. The periodic process of the energy exchange between the first and the second harmonics of the wave is investigated as well. It is shown that the process under study is periodic one. The analytical expressions are obtained and numerical estimations are presented for characteristic time of nonlinear energy exchange. The self-action effect of main frequency wave is account for harmonics interaction. It is shown that the effect leads to nonlinear phenomena attenuation, which expresses in narrowing possible value interval of harmonics amplitudes during energy exchange process and in increasing the nonlinear interaction time.

Towards improved precision in the quantification of surface-enhanced Raman scattering (SERS) enhancement factors: A renewed approach

This paper demonstrates a renewed procedure for the quantification of surface-enhanced Raman scattering (SERS) enhancement factors with improved precision. The principle of this method relies on deducting the resonance Raman scattering (RRS) contribution from surface-enhanced resonance Raman scattering (SERRS) to end up with the surface enhancement (SERS) effect alone. We employed 1,8,15,22-tetraaminophthalocyanato-cobalt(II) (4α-CoIITAPc), a resonance Raman- and electrochemically redox-active chromophore, as a probe molecule for RRS and SERRS experiments. The number of 4α-CoIITAPc molecules contributing to RRS and SERRS phenomena on plasmon inactive glassy carbon (GC) and plasmon active GC/Au surfaces, respectively, has been precisely estimated by cyclic voltammetry experiments. Furthermore, the SERS substrate enhancement factor (SSEF) quantified by our approach is compared with the traditionally employed methods. We also demonstrate that the present approach of SSEF quantification can be applied for any kind of different SERS substrates by choosing an appropriate laser line and probe molecule.

Protein Molecular Surface Mapped at Different Geometrical Resolutions

Many areas of biochemistry and molecular biology, both fundamental and applications-orientated, require an accurate construction, representation and understanding of the protein molecular surface and its interaction with other, usually small, molecules. There are however many situations when the protein molecular surface gets in physical contact with larger objects, either biological, such as membranes, or artificial, such as nanoparticles. The contribution presents a methodology for describing and quantifying the molecular properties of proteins, by geometrical and physico-chemical mapping of the molecular surfaces, with several analytical relationships being proposed for molecular surface properties. The relevance of the molecular surface-derived properties has been demonstrated through the calculation of the statistical strength of the prediction of protein adsorption. It is expected that the extension of this methodology to other phenomena involving proteins near solid surfaces, in particular the protein interaction with nanoparticles, will result in important benefits in the understanding and design of protein-specific solid surfaces. © 2013 Nicolau et al.

Effect of different surface profile on wear of rail steel (AS1085.1) used in Australian heavy-haul railways

The extreme diversity of conditions acting on railways necessitates a variety of experimental approaches to study the critical wear mechanisms that present themselves at the contact interface. This work investigates the effects of contact pressure and geometry in rolling-contact wear tests by using discs with different radii of curvature to simulate the varying contact conditions that may be typically found in the field. It is commonly adapted to line contact interface as it has constant contact pressure. But practical scenario of the rail wheel interface, the contact area increase and contact pressure change as tracks worn off. The tests were conducted without any significant amount of traction, but micro slip was still observed due to contact deformation. Moreover, variation of contact pressure was observed due to contact patch elongation and diameter reduction. Rolling contact fatigue, adhesive and sliding wear were observed on the curved contact interface. The development of different wear regimes and material removal phenomena were analysed using microscopic images in order to broaden the understanding of the wear mechanisms occurring in the rail-wheel contact.