Dual Stress and Thermally Driven Mechanical Properties of the Same Organic Crystal: 2,6-Dichlorobenzylidene-4-fluoro-3-nitroaniline

An elastic organic crystal, 2,6-dichlorobenzylidine-4-fluoro-3-nitroaniline (DFNA), which also shows thermosalient behavior, is studied. The presence of these two distinct properties in the same crystal is unusual and unprecedented because they follow respectively from isotropy and anisotropy in the crystal packing. Therefore, while both properties lead from the crystal structure, the mechanisms for bending and thermosalience are quite independent of one another. Crystals of the low-temperature (a) form of the title compound are bent easily without any signs of fracture with the application of deforming stress, and this bending is within the elastic limit. The crystal structure of the a-form was determined (P2(1)/c, Z = 4, a = 3.927(7) angstrom, b = 21.98(4) angstrom, c = 15.32(3) angstrom). There is an irreversible phase transition at 138 degrees C of this form to the high-temperature beta-form followed by melting at 140 degrees C. Variable-temperature X-ray powder diffraction was used to investigate the structural changes across the phase transition and, along with an FTIR study, establishes the structure of the beta-form. A possible rationale for strain build-up is given. Thermosalient behavior arises from anisotropic changes in the three unit cell parameters across the phase transition, notably an increase in the b axis parameter from 21.98 to 22.30 angstrom. A rationale is provided for the existence of both elasticity and thermosalience in the same crystal. FTIR studies across the phase transition reveal important mechanistic insights: (i) increased pi...pi repulsions along 100] lead to expansion along the a axis; (ii) change in alignment of C-Cl and NO2 groups result from density changes; and (iii) competition between short-range repulsive (pi...pi) interactions and long-range attractive dipolar interactions (C-Cl and NO2) could lie at the origin of the existence of two distinctive properties.

Effect of Chalcogens on Electronic and Photophysical Properties of Vinylene-Based Diketopyrrolopyrrole Copolymers

Three vinylene linked diketopyrrolopyrrole based donor acceptor (D-A) copolymers have been synthesized with phenyl, thienyl, and selenyl units as donors. Optical and electronic properties were investigated with UV-vis absorption spectroscopy, cyclic voltammetry, near edge X-ray absorption spectroscopy, organic field effect transistor (OFET) measurements, and density functional theory (DFT) calculations. Optical and electrochemical band gaps decrease in the order phenyl, thienyl, and selenyl. Only phenyl-based polymers are nonplanar, but the main contributor to the larger band gap is electronic, not structural effects. Thienyl and selenyl polymers exhibit ambipolar charge transport but with higher hole than electron mobility. Experimental and theoretical results predict the selenyl system to have the best transport properties, but OFET measurements prove the thienyl system to be superior with p-channel mobility as high as 0.1 cm(2) V-1 s(-1).

Organic alloys of room temperature liquids thiophenol and selenophenol

The first examples of organic alloys of two room temperature liquids, obtained and characterized via in situ cryo-crystallography, are presented. Thiophenol and selenophenol, which exhibit isostructurality and similar modes of S center dot center dot center dot S and Se center dot center dot center dot Se homo-chalcogen interactions along with weak and rare S-H center dot center dot center dot S and Se-H center dot center dot center dot Se hydrogen bonds, are shown to form solid solutions exhibiting Veggard's law-like trends.

Reactive interlayer based ultra-low moisture permeable membranes for organic photovoltaic encapsulation

Reactive interlayers consisting of zero valent iron and copper nanoparticles have been successfully incorporated into Surlyn films to fabricate moisture barrier materials with reduced water vapor permeabilities. The reactive nanoparticles dispersed in stearic acid were employed as the interlayers due to their ability to react with moisture. The water vapor transmission rates through the fabricated barrier films with reactive iron and copper interlayers decreased by over 4 orders of magnitude when compared to neat Surlyn. The flexibility and transparency of the barrier films have been evaluated by tensile and UV-visible experiments. Moreover, the accelerated aging studies conducted in accordance with the ISOS-III protocol confirmed the increased lifetimes of the organic photovoltaic (OPV) devices encapsulated with these reactive barrier films.

Joint Channel Estimation and Data Detection in MIMO-OFDM Systems: A Sparse Bayesian Learning Approach

The impulse response of wireless channels between the N-t transmit and N-r receive antennas of a MIMO-OFDM system are group approximately sparse (ga-sparse), i.e., NtNt the channels have a small number of significant paths relative to the channel delay spread and the time-lags of the significant paths between transmit and receive antenna pairs coincide. Often, wireless channels are also group approximately cluster-sparse (gac-sparse), i.e., every ga-sparse channel consists of clusters, where a few clusters have all strong components while most clusters have all weak components. In this paper, we cast the problem of estimating the ga-sparse and gac-sparse block-fading and time-varying channels in the sparse Bayesian learning (SBL) framework and propose a bouquet of novel algorithms for pilot-based channel estimation, and joint channel estimation and data detection, in MIMO-OFDM systems. The proposed algorithms are capable of estimating the sparse wireless channels even when the measurement matrix is only partially known. Further, we employ a first-order autoregressive modeling of the temporal variation of the ga-sparse and gac-sparse channels and propose a recursive Kalman filtering and smoothing (KFS) technique for joint channel estimation, tracking, and data detection. We also propose novel, parallel-implementation based, low-complexity techniques for estimating gac-sparse channels. Monte Carlo simulations illustrate the benefit of exploiting the gac-sparse structure in the wireless channel in terms of the mean square error (MSE) and coded bit error rate (BER) performance.

MOMENT ANALYSIS OF A SCROLL EXPANDER USED IN AN ORGANIC RANKINE CYCLE

Recent studies on small-scale power generation with the organic Rankine cycle suggest superior performance of positive displacement type of expanders compared to turbines. Scroll expanders in particular achieve high isentropic efficiencies due to lower leakage and frictional losses. Performance of scroll machines may be enhanced by the use of non-circular involute curves in place of the circular involutes resulting non-uniform wall thickness. In this paper, a detailed moment analysis is performed for such an expander having volumetric expansion ratio of 5 using thermodynamic models proposed earlier by one of the present authors. The working fluid considered in the power cycle is R-245fa with scroll inlet temperature of 125 degrees C for a gross power output of similar to 3.5 kW. The model developed in this paper is verified with an air scroll compressor available in the literature and then applied to an expander Prediction of small variation of moment with scroll motion recommends use of scroll expander without a flywheel over other positive displacement type of expanders, e.g. reciprocating, where a flywheel is an essential component.

Ultra-small sulphur nanoparticles configured inside a flexible organic mixed conducting network as a cathode for lithium-sulphur batteries

The major challenges in Li-S batteries are the formation of soluble polysulphides during the reversible conversion of S-8 <-> Li2S, large changes in sulphur particle volume during lithiation and extremely poor charge transport in sulphur. We demonstrate here a novel and simple strategy to overcome these challenges towards practical realization of a stable high performance Li-S battery. For the first time, a strategy is developed which does away with the necessity of pre-fabricated high surface area hollow-structured adsorbates and also multiple nontrivial synthesis steps related to sulphur loading inside such adsorbates. A lithiated polyethylene glycol (PEG) based surfactant tethered on ultra-small sulphur nanoparticles and wrapped up with polyaniline (PAni) (abbreviated as S-MIEC) is demonstrated here as an exceptional cathode for Li-S batteries. The PEG and PAni network around the sulphur nanoparticles serves as an efficient flexible trap for sulphur and polysulphides and also provides distinct pathways for electrons (through PAni) and ions (through PEG) during battery operation. Contrary to the cathodes demonstrated based on various carbon-sulphur composites, the mixed conducting S-MIEC showed an extremely high loading of 75%. The S-MIEC exhibited a stable capacity of nearly 900 mA h g(-1) at the end of 100 cycles at a 1C current rate.

Organic fluorine involved intramolecular hydrogen bonds in the derivatives of imides: NMR evidence corroborated by DFT based theoretical calculations

The rare occurrence of intramolecular hydrogen bonds (HBs) of the type N-H center dot center dot center dot F-C is detected in the derivatives of imides in a low polarity solvent by using multi-dimensional and multinuclear NMR experiments. The observation of (1h)J(FH), (2h)J(FN), and (2h)J(FF), where the spin magnetization is transmitted through space among the interacting NMR active nuclei, provided strong and unambiguous evidence for the existence of intra-molecular HBs. The variation in the chemical shifts of labile protons depending on physical conditions, such as the solvent dilution and the systematic alteration of temperature confirmed the presence of weak interactions through intramolecular HBs in all the investigated fluorine substituted molecules. The self or cross dimerization of molecules is unequivocally discarded by the analysis of the rates of diffusion obtained using pseudo-two dimensional DOSY experiments. The Density Function Theory (DFT) calculations based on the Quantum Theory of Atoms In Molecules (QTAIM) and Non Covalent Interaction (NCI), are in close agreement with the NMR experimental findings.

Tungsten-based nanomaterials (WO3 & Bi2WO6): Modifications related to charge carrier transfer mechanisms and photocatalytic applications

Heterogeneous photocatalysis is an ideal green energy technology for the purification of wastewater. Although titania dominates as the reference photocatalyst, its wide band gap is a bottleneck for extended utility. Thus, search for non-TiO2 based nanomaterials has become an active area of research in recent years. In this regard, visible light absorbing polycrystalline WO3 (2.4-2.8 eV) and Bi2WO6 (2.8 eV) with versatile structure-electronic properties has gained considerable interest to promote the photocatalytic reactions. These materials are also explored in selective functional group transformation in organic reactions, because of low reduction and oxidation potential of WO3 CB and Bi2WO6 VB, respectively. In this focused review, various strategies such as foreign ion doping, noble metal deposition and heterostructuring with other semiconductors designed for efficient photocatalysis is discussed. These modifications not only extend the optical response to longer wavelengths, but also prolong the life-time of the charge carriers and strengthen the photocatalyst stability. The changes in the surface-bulk properties and the charge carrier transfer dynamics associated with each modification correlating to the high activity are emphasized. The presence of oxidizing agents, surface modification with Cu2+ ions and synthesis of exposed facets to promote the degradation rate is highlighted. In depth study on these nanomaterials is likely to sustain interest in wastewater remediation and envisaged to signify in various green energy applications. (C) 2015 Elsevier B.V. All rights reserved.

Effect of Channel Confinement on Mixed Convective Flow Past an Equilateral Triangular Cylinder

The present work investigates the mixed convective flow and heat transfer characteristics past a triangular cylinder placed symmetrically in a vertical channel. At a representative Reynolds number, Re = 100, simulations are carried out for the blockage ratios beta = 1/3; 1/4; and 1/6. Effect of aiding and opposing buoyancy is brought about by varying the Richardson number in the range -1.0 <= Ri <= 1.0. At a blockage ratio of 1/3, suppression of vortex shedding is found at Ri = 1, whereas von Karman vortex street is seen both at beta = 1/4 and 1/6, respectively. This is the first time that such behavior of blockage ratio past a triangular cylinder in the present flow configuration is reported. Drag coefficient increases progressively with increasing Ri and a slightly higher value is noticed at beta = 1/3. For all b, heat transfer increases with increasing Ri. Flattening of Nu(avg)-Ri curve beyond Ri > 0: 75 is observed at beta = 1/3.

Thermal Modeling of Organic Light-Emitting Diode Display Panels

Power densities required to operate active-matrix organic-light-emitting diode (AMOLED) based displays for high luminance applications, lead to temperature rise due to self heating. Temperature rise leads to significant degradation and consequent reduction in life time. In this work numerical techniques based computational fluid dynamics (CFD) is used to determine the temperature rise and its distribution for an AMOLED based display for a given power density and size. Passive cooling option in form of protruded rectangular fins is implemented to reduce the display temperature.

Design for sustainability: case of designing an urban household organic waste management system

Beyond product design, if the notion of product `lifecycle design' enforces the consideration of requirements from all the lifecycle phases of products, design for sustainability enforces the consideration of lifecycle design in the context of the lifecycles of other products, processes, institutions and their design. Consequently, sustainability requirements that need to be met by design are very diverse. In this article, we portray the nature of design process to address sustainability requirements. This is done taking an example of designing a urban household organic waste management system that requires less water and reclaims the nutrients.

Power Allocation in MIMO Wiretap Channel with Statistical CSI and Finite-Alphabet Input

In this paper, we consider the problem of power allocation in MIMO wiretap channel for secrecy in the presence of multiple eavesdroppers. Perfect knowledge of the destination channel state information (CSI) and only the statistical knowledge of the eavesdroppers CSI are assumed. We first consider the MIMO wiretap channel with Gaussian input. Using Jensen's inequality, we transform the secrecy rate max-min optimization problem to a single maximization problem. We use generalized singular value decomposition and transform the problem to a concave maximization problem which maximizes the sum secrecy rate of scalar wiretap channels subject to linear constraints on the transmit covariance matrix. We then consider the MIMO wiretap channel with finite-alphabet input. We show that the transmit covariance matrix obtained for the case of Gaussian input, when used in the MIMO wiretap channel with finite-alphabet input, can lead to zero secrecy rate at high transmit powers. We then propose a power allocation scheme with an additional power constraint which alleviates this secrecy rate loss problem, and gives non-zero secrecy rates at high transmit powers.

Study of H/D exchange rates to derive the strength of intramolecular hydrogen bonds in halo substituted organic building blocks: An NMR spectroscopic investigation

Rates of hydrogen/deuterium (H/D) exchange determined by H-1 NMR spectroscopy are utilized to derive the strength of hydrogen bonds and to monitor the electronic effects in the site-specific halogen substituted benzamides and anilines. The theoretical fitting of the time dependent variation of the integral areas of H-1 NMR resonances to the first order decay function permitted the determination of HID exchange rate constants (k) and their precise half-lives (t(1/2)) with high degree of reproducibility. The comparative study also permitted the unambiguous determination of relative strength of hydrogen bonds and the contribution from electronic effects on the HID exchange rate. (C) 2015 Elsevier B.V. All rights reserved.