Polarized Infrared Spectra of the H(D) Bond in 2‐Thiophenic Acid Crystals: A Spectroscopic and Computational Study

Polarized IR spectra of the hydrogen bond in 2‐thiophenic acid crystals, isotopically neat and of mixed H/D isotopic content, are measured at 298 and 77 K in the “residual” νO? H and νO? D band frequency ranges. This crystalline system provides spectra in these band frequency ranges that differ considerably in intensity distribution from the spectra of other H‐bonded centrosymmetric dimeric species. This change in the spectral properties of the crystals is probably due to the influence of the sulfur atoms from the thiophene aromatic rings, which are directly linked to the (COOH)2 or (COOD)2 cycles. The magnitude of this effect correlates with the net electronic charge distribution at the 2‐ and 3‐positions of substituted thiophene rings, which in a different way influences the electron charge density in the hydrogen bonds of the two thiophenic acid isomers. The experimental results for spectral structures are compared to predictions obtained with theoretical calculations involving the combined effects of anharmonicities, Davydov coupling, Fermi resonances, and direct and indirect relaxations within the framework of the linear response theory. Numerical results show that mixing of all these effects allows satisfactory reproduction of the main features of the experimental IR line shapes of crystalline H‐ and D‐bonded 2‐thiophenic acid at room and liquid‐nitrogen temperatures.     

Note on the fall of an axisymmetric body in a perfect fluid over a horizontal ramp

In this note, we consider the fall of an axisymmetric body in a perfect fluid over a ramp. It was shown in [12] that the possibility of a collision between the body and the ramp is related to the asymptotics of the so-called added mass when the distance between the ramp and the body goes to 0. We propose here a new method to compute this added mass, which provides simultaneously an approximation of an associated fluid velocity field in the gap between the ramp and the body.     

Carbon nanohorns-coated microfibers for use as free-standing electrodes for electrochemical power sources

We report the first direct laser based synthesis of carbon nanohorns onto carbon microfibrous, for the straightforward fabrication, of free-standing (binderless) electrodes. These carbon nanohorns have diameters as small as 2–4 nm and were found to cover uniformly the microfibrous substrates. The carbon nanohorns-based electrodes developed here are shown to open new prospects for the development of advanced electrochemical power sources. In particular, their possible applications in either lithium-ion batteries or supercapacitors or fuel cell technologies are demonstrated.     

Nonparametric Estimation for Semi-Markov Processes Based on its Hazard Rate Functions

The problem of estimating the Markov renewal matrix and the semi-Markov transition matrix based on a history of a finite semi-Markov process censored at time T (fixed) is addressed for the first time. Their asymptotic properties are studied. We begin by the definition of the transition rate of this process and propose a maximum likelihood estimator for the hazard rate functions and then we show that this estimator is uniformly strongly consistent and converges weakly to a normal random variable. We construct a new estimator for an absolute continous semi-Markov kernel and give detailed derivation of uniform strong consistency and weak convergence of this estimator as the censored time tends to infinity. This revised version was published online in June 2006 with corrections to the Cover Date.     

An improved microwave Clevenger apparatus for distillation of essential oils from orange peel

Microwave Clevenger or microwave accelerated distillation (MAD) is a combination of microwave heating and distillation, performed at atmospheric pressure without added any solvent or water. Isolation and concentration of volatile compounds are performed by a single stage. MAD extraction of orange essential oil was studied using fresh orange peel from Valencia late cultivar oranges as the raw material. MAD has been compared with a conventional technique, which used a Clevenger apparatus with hydro-distillation (HD). MAD and HD were compared in term of extraction time, yields, chemical composition and quality of the essential oil, efficiency and costs of the process. Extraction of essential oils from orange peels with MAD was better in terms of energy saving, extraction time (30 min versus 3 h), oxygenated fraction (11.7% versus 7.9%), product yield (0.42% versus 0.39%) and product quality. Orange peels treated by MAD and HD were observed by scanning electronic microscopy (SEM). Micrographs provide evidence of more rapid opening of essential oil glands treated by MAD, in contrast to conventional hydro-distillation.     

Expected Distances between Two Uniformly Distributed Random Points in Rectangles and Rectangular Parallelpipeds

In this paper, the expected distance between two uniformly distributed random points in a rectangle or in a rectangular parallelepiped is computed under three different metrics: the Manhattan metric, the Euclidean metric, and the Chebychev metric.     

Numerical solution of a first-order conservation equation by a least square method

Least square methods have been frequently used to solve fluid mechanics problems. Their specific usefulness is emphasized for the solution of a first-order conservation equation. On the one hand, the least square formulation embeds the first-order problem into equivalent second-order problem, better adapted to discretization techniques due to symmetry and positive-definiteness of the associated matrix. On the other hand, the introduction of a least square functional is convenient for finite element applications. This approach is applied to the model problem of the conservation of mass (the unknown is the density ρ) in a nozzle with a specified velocity field (u, v), possibly including jumps along lines simulating shock waves. This represent a preliminary study towards the solution of the steady Euler equations. A finite difference and a finite element method are presented. The choice of the finite difference scheme and of a continuous finite element representation for the groups of variables (ρu, ρv) is discussed in terms of conservation of mass flux. Results obtained with both methods are compared in two numerical tests with the same mesh system.     

Evaluation of nanotribological behavior of amorphous polystyrene: The macromolecular weight effect

Tribological testing of polymers is of prime importance in many industrial applications. Silicon nitride AFM tips have been used to mimic the contact between amorphous polystyrene surfaces and a hard asperity, which is useful in understanding of how a multitude of asperities behave in a macroscopic contact. In this study, the adhesion force and the friction force of four PS molecular weights were measured and the average contact pressure was calculated by using the JKR contact theory. The nanotribological behavior of polystyrene showed a dependence on macromolecular weight with varying applied normal force and sliding velocity. The study indicates that the length of polymer chains noticeably influences the tribological behavior of amorphous polystyrenes. Mechanisms governing such behavior differences were ascribed to energy dissipating modes.