Mesoscopic transport equations and contemporary thermodynamics: an introduction

The local equilibrium hypothesis is a very successful basis for non-equilibrium thermodynamics over a wide range of phenomena and physical situations. However, the increasing interest in small systems in nanotechnology, in rarefied gases in high-altitude aeronautics, in high-frequency behaviour in information processing, or the search for new materials with sophisticated internal microstructures and tailored thermal properties have led one to ask about the limits of validity of this hypothesis, and to go beyond it. Here we do so in a constructive way, i.e. not only pointing out at these limits, but also embedding the local-equilibrium theory in a more general framework which explicitly exhibits these limits and suggests how to go beyond them, in search for a wider range of applications and a deeper understanding of the foundations.     

Non-equilibrium thermodynamic potential and flux fluctuation theorem

A flux fluctuation theorem proposed recently [Seitaridou, et al., J. Phys. Chem. B 111 (2007) 2288] on the relative probability of direct and reverse diffusion fluxes in a non-equilibrium steady state is related here to a non-equilibrium thermodynamic potential used in extended irreversible thermodynamics. This connection allows one to provide a new derivation of the theorem, which complements the previous one, to generalize it to other fluxes, and illustrates the thermodynamic relevance of this theorem.     

Pyrene-fluorene hybrids containing acetylene linkage as color-tunable emitting materials for organic light-emitting diodes

New blue- to yellow-emitting materials have been developed by incorporating fluorene-based chromophores on pyrene core with acetylene linkage and using multifold palladium-catalyzed cross-coupling reactions. Both mono- and tetrasubstituted derivatives have been synthesized and characterized. The tetrasubstituted derivatives displayed red-shifted emission when compared to the monosubstituted derivative indicative of an extended conjugation in the former. End-capping with a diphenylamine unit further red-shifted the absorption and emission profiles and imparted a weak dipolar character to the molecules. Amine-containing derivatives displayed positive solvatochromism in the fluorescence spectra indicating a more polar excited state due to an efficient charge migration from the diphenylamine donor to the pyrene π-acceptor. All of the derivatives were tested as emitting dopants with host material 4,4'-bis(9H-carbazol-9-yl)biphenyl (CBP) in a multilayered OLED and found to exhibit bright blue or yellow electroluminescence. The device utilizing 1,3,6,8-tetrasubstituted pyrene derivative as a dopant emitter displayed highest maximum luminescence 4630 cd/m(2) with power efficiency 3.8 lm/W and current efficiency 7.1 cd/A at 100 cd/m(2) attributable to the proper alignment of energy levels that led to the efficient harvesting of excitons. All of the devices exhibited color purity over a wide range of operating voltages.     

Robot learning schemes that trade motion accuracy for command simplification

This study was inspired by the human motor control system in its ability to accommodate a wide variety of motions. By contrast, the biologically inspired robot learning controller usually encounters huge learning space problems in many practical applications. A hypothesis for the superiority of the human motor control system is that it may have simplified the motion command at the expense of motion accuracy. This tradeoff provides an insight into how fast and simple control can be achieved when a robot task does not demand high accuracy. Two motion command simplification schemes are proposed in this paper based on the equilibrium-point hypothesis for human motion control. Investigation into the tradeoff between motion accuracy and command simplification reported in this paper was conducted using robot manipulators to generate signatures. Signature generation involves fast handwriting, and handwriting is a human skill acquired via practice. Because humans learn how to sign their names after they learn how to write, in the second learning process, they somehow learn to trade motion accuracy for motion speed and command simplicity, since signatures are simplified forms of original handwriting. Experiments are reported that demonstrate the effectiveness of the proposed schemes.     

Intramolecular C−H Amination of N-Alkylsulfamides by tert-Butyl Hypoiodite or N-Iodosuccinimide

1,3-Diamines are an important class of compounds that are broadly found in natural products and are also widely used as building blocks in organic synthesis. Although the intramolecular C−H amination of N-alkylsulfamide derivatives is a reliable method for the construction of 1,3-diamine structures, the majority of these methods involve the use of a transition-metal catalyst. We herein report on a new transition-metal-free method using tert-butyl hypoiodite (t-BuOI) or N-iodosuccinimide (NIS), enabling secondary non-benzylic and tertiary C−H amination reactions to proceed. The cyclic sulfamide products can be easily transformed into 1,3-diamines. Mechanistic investigations revealed that amination reactions using t-BuOI or NIS each proceed via different pathways.     

A Gunn-Diode Active Leaky-Wave Frequency Scanning Antenna

A frequency tunable active leaky-wave scanning antenna using Gunn-diode voltage control oscillator (VCO) as source is developed. The frequency tuning controlled by changing either the varactor diode dc bias or the Gunn diode dc bias is demonstrated. The measured scanning angle of active antenna is close to 15 degree as the Gunn VCO frequency tuned from 12.58GHz to 12.98GHz. To excite the first higher order mode of the microstrip leaky-wave antenna is fed asymmetrically. The dominant mode excitation has been successfully suppressed by adding a sequence of covered wire in the middle line of the microstrip leaky wave antenna. This is a prototype of frequency scanning antenna using two terminal device, which can be easily scaled up to millimeter wave frequency region.     

A Stable and Compact Optical Module for Fiber-Optic Gyroscope Application

Abstract

This article introduces a new design for a bi-directional optical sub-assembly for fiber-optic gyroscope applications that integrates a super-luminescent light-emitting diode, a photodiode, a beam splitter, an isolator, a fiber receptacle, and a thermal electric cooler. It is less than 1.5 cm in diameter and 2.5 cm in height. As chip temperature was kept at 30°C under environment temperature of ?35°C, 25°C, and 75°C, the bi-directional optical sub-assembly reached stability at a center wavelength of 1,539 nm and a wavelength shift of 1.5 nm. A 3D simple model with the finite-element method was used to analyze thermal performance.     

Thermal Behavior of VARIOUS sulfone-based diimid-diacids Solvated with Polar Organic Solvents

Thermal analysis techniques were performed to reveal ‘crystalline solvate’ behavior between organic compounds and polar solvents. Diimide-dicarboxylic acid (DIDA) was formed by reacting 3,3'-diaminodiphenylsulfone (3,3'-DPS) or 4,4'-diaminodiphenylsulfone (4,4'-DPS) with trimellitic anhydride (TMA) in some polar solvents (PSv). The products could crystallize upon cooling in a polar solvent media to form a solvate containing a finite quantity of solvents, leading to what can be termed as ‘crystalline solvates’ (CS). This study has demonstrated that sampling techniques in TG and DSC must be kept to be as similar as possible, which is a critical point in practices of thermal analysis techniques. DSC analysis revealed that there are two endothermic peaks in the CS, with the lower one being the de-solvate temperature of CS (T _d) at which the solvated solvent molecules were removed, and the higher peak being the melting point of the de-solvated DIDA (T _m). T _d was found to vary with the types of polar solvents and structures of DIDA. The TG result indicated that most of the sulfone-based DIDA-CS contained 2 moles of solvent per mole of solvate. X-ray analysis revealed that different crystalline structures were found for DIDA-CS solvated with different solvent molecules, but all de-solvated DIDA possessed the same crystal unit. This revised version was published online in July 2006 with corrections to the Cover Date.