Crystalline ethane-1,2-diol does not have intra-molecular hydrogen bonding: Experimental and theoretical charge density studies

The X-ray structure and electron density distribution of ethane-1,2-diol (ethylene glycol), obtained at a resolution extending to 1.00 Å−1 in sin θ/λ (data completion = 100% at 100 K) by in situ cryocrystallization technique is reported. The diol is in the gauche (g′Gt) conformation with the crystal structure stabilised by a network of inter-molecular hydrogen bonds. In addition to the well-recognized O–H···O hydrogen bonds there is topological evidence for C–H···O inter-molecular interactions. There is no experimental electron density based topological evidence for the occurrence of an intra-molecular hydrogen bond. The O···H spacing is not, vert, similar0.45 Å greater than in the gas-phase with an O–H···O angle close to 90°, calling into question the general assumption that the gauche conformation of ethane-1,2-diol is stabilised by the intra-molecular oxygen–hydrogen interaction.

Effect of relative density and confining pressure on Poisson ratio from bender and extender elements tests

By using the bender and extender elements tests, together with measurements of the travel times of shear (S) and primary (P) waves, the variation of Poisson ratio (nu) was determined for dry sands with respect to changes in relative densities and effective confining pressures (sigma(3)). The tests were performed for three different ranges of particle sizes. The magnitude of the Poisson ratio decreases invariably with an increase in both the relative density and the effective confining pressure. The effect of the confining pressure on the Poisson ratio was found to become relatively more significant for fine-grained sand as compared with the coarse-grained sand. For a given material, at a particular value of sigma(3), the magnitude of the Poisson ratio decreases, almost in a linear fashion, with an increase in the value of maximum shear modulus (G(max)). The two widely used correlations in literature, providing the relationships among G(max), void ratio (e) and effective confining pressure (sigma(3)), applicable for angular granular materials, were found to compare reasonably well with the present experimental data for the fine- and medium-grained sands. However, for the coarse-grained sand, these correlations tend to overestimate the values of G(max).

High Rate Capability of Porous LiNi1/3Co1/3Mn1/3O2 Synthesized by Polymer Template Route

Layered LiNi1/3Co1/3Mn1/3O2, which is isostructural with LiCoO2, is considered as a potential cathode material for Li-ion batteries. Submicrometer sized porous particles are useful for high discharge rates. The present work involves a synthesis of submicrometer sized porous particles of LiNi1/3Co1/3Mn1/3O2 using a triblock copolymer as a soft template. The precursor obtained from the reaction is heated at different temperatures between 600 and 900 degrees C for 6 h to get the final product samples. The compound attains increased crystallinity with an increase in the temperature of preparation. However, there is a decrease in the surface area and also in the porosity of the sample. Nevertheless, the LiNi1/3Co1/3Mn1/3O2 sample prepared at 900 degrees C exhibits a high rate capability and stable capacity retention on cycling. The electrochemical performance of LiNi1/3Co1/3Mn1/3O2 prepared in the absence of the polymer template is inferior to that of the sample prepared in the presence of the polymer template. (C) 2010 The Electrochemical Society. [DOI: 10.1149/1.3364944] All rights reserved.

Influence of propellant choice on MPD arcjet cathode surface current density distribution

The radial current density on an MPD arcjet cathode surface is theoretically investigated for five propellants. It is found that excessive current concentration at the upstream end of the cathode occurs in the case of hydrogen. This undesirable effect is traced to the higher electrical conductivity of hydrogen plasma.

Studies on design, fabrication and reliability assessment of embedded passives on a high-density interconnect (HDI) organic substrate using a sequential build-up process

One of the foremost design considerations in microelectronics miniaturization is the use of embedded passives which provide practical solution. In a typical circuit, over 80 percent of the electronic components are passives such as resistors, inductors, and capacitors that could take up to almost 50 percent of the entire printed circuit board area. By integrating passive components within the substrate instead of being on the surface, embedded passives reduce the system real estate, eliminate the need for discrete and assembly, enhance electrical performance and reliability, and potentially reduce the overall cost. Moreover, it is lead free. Even with these advantages, embedded passive technology is at a relatively immature stage and more characterization and optimization are needed for practical applications leading to its commercialization.This paper presents an entire process from design and fabrication to electrical characterization and reliability test of embedded passives on multilayered microvia organic substrate. Two test vehicles focusing on resistors and capacitors have been designed and fabricated. Embedded capacitors in this study are made with polymer/ceramic nanocomposite (BaTiO3) material to take advantage of low processing temperature of polymers and relatively high dielectric constant of ceramics and the values of these capacitors range from 50 pF to 1.5 nF with capacitance per area of approximately 1.5 nF/cm(2). Limited high frequency measurement of these capacitors was performed. Furthermore, reliability assessments of thermal shock and temperature humidity tests based on JEDEC standards were carried out. Resistors used in this work have been of three types: 1) carbon ink based polymer thick film (PTF), 2) resistor foils with known sheet resistivities which are laminated to printed wiring board (PWB) during a sequential build-up (SBU) process and 3) thin-film resistor plating by electroless method. Realization of embedded resistors on conventional board-level high-loss epoxy (similar to 0.015 at 1 GHz) and proposed low-loss BCB dielectric (similar to 0.0008 at > 40 GHz) has been explored in this study. Ni-P and Ni-W-P alloys were plated using conventional electroless plating, and NiCr and NiCrAlSi foils were used for the foil transfer process. For the first time, Benzocyclobutene (BCB) has been proposed as a board level dielectric for advanced System-on-Package (SOP) module primarily due to its attractive low-loss (for RF application) and thin film (for high density wiring) properties.Although embedded passives are more reliable by eliminating solder joint interconnects, they also introduce other concerns such as cracks, delamination and component instability. More layers may be needed to accommodate the embedded passives, and various materials within the substrate may cause significant thermo -mechanical stress due to coefficient of thermal expansion (CTE) mismatch. In this work, numerical models of embedded capacitors have been developed to qualitatively examine the effects of process conditions and electrical performance due to thermo-mechanical deformations.Also, a prototype working product with the board level design including features of embedded resistors and capacitors are underway. Preliminary results of these are presented.

Synthesis based on cyclohexadienes. Part 34. A tandem cationic rearrangement-ene cyclisation route to 2-pupukeanone

A new strategy for the construction of the isotwistane skeleton is reported from easily available cyclohexadienes, which involves a one-pot cationic skeletal rearrangement and ene cyclisation of a bicyclo[2.2.2]octenone derivative and a cationic rearrangement of a tricyclo[5.3.0.0(4,8)]decane to a [4.3.1.0(3,7)]decane skeleton as the key steps in the synthesis of 2-pupukeanone.

Charge Density Analysis of Crystals of Nicotinamide with Salicylic Acid and Oxalic Acid: An Insight into the Salt to Cocrystal Continuum

Charge density analysis from both experimental and theoretical points of view on two molecular complexes: one is formed between nicotinamide and salicylic acid, and the other formed between nicotinamide and oxalic acid brings out the quantitative topological features to distinguish a cocrystal from a salt.

Topological analysis off charge density distribution in concomitant polymorphs of 3-acetylcoumarin, a case off packing polymorphism

Detailed investigation of the charge density distribution in concomitant polymorphs of 3-acetylcoumarin in terms of experimental and theoretical densities shows significant differences in the intermolecular features when analyzed based on the topological properties via the quantum theory of atoms in molecules. The two forms, triclinic and monoclinic (Form A and Form B), pack in the crystal lattice via weak C-H---O and C-H---pi interactions. Form A results in a head-to-head molecular stack, while Form B generates a head-to-tail stack. Form A crystallizes in PI (Z' = 2) and Form B crystallizes in P2(1)/n (Z = 1). The electron density maps of the polymorphs demonstrate the differences in the nature of the charge density distribution in general. The charges derived from experimental and theoretical analysis show significant differences with respect to the polymorphic forms. The molecular dipole moments differ significantly for the two forms. The lattice energies evaluated at the HF and DFT (B3LYP) methods with 6-31G** basis set for the two forms clearly suggest that Form A is the thermodynamically stable form as compared to Form B. Mapping of electrostatic potential over the molecular surface shows dominant variations in the electronegative region, which bring out the differences between the two forms.

A density matrix renormalization group study of low-lying excitations of polythiophene within a Pariser-Parr-Pople model

Symmetrized density-matrix-renormalization-group calculations have been carried out, within Pariser-Parr-Pople Hamiltonian, to explore the nature of the ground and low-lying excited states of long polythiophene oligomers. We have exploited C-2 symmetry and spin parity of the system to obtain excited states of experimental interest, and studied the lowest dipole allowed excited state and lowest dipole forbidden two photon state, for different oligomer sizes. In the long system limit, the dipole allowed excited state always lies below the lowest dipole forbidden two-photon state which implies, by Kasha rule, that polythiophene fluoresces strongly. The lowest triplet state lies below two-photon state as usual in conjugated polymers. We have doped the system with a hole and an electron and obtained the charge excitation gap and the binding energy of the 1(1)B(u)(-) exciton. We have calculated the charge density of the ground, one-photon and two-photon states for the longer system size of 10 thiophene rings to characterize these states. We have studied bond order in these states to get an idea about the equilibrium excited state geometry of the system. We have also studied the charge density distribution of the singly and doubly doped polarons for longer system size, and observe that polythiophenes do not support bipolarons.

Kinetic theory for the density plateau in the granular flow down an inclined plane

The striking lack of observable variation of the volume fraction with height in the center of a granular flow down an inclined plane is analysed using constitutive relations obtained from kinetic theory. It is shown that the rate of conduction in the granular energy balance equation is O(delta(2)) smaller than the rate of production of energy due to mean shear and the rate of dissipation due to inelastic collisions, where the small parameter delta = (d/(1 - e(n))H-1/2), d is the particle diameter, en is the normal coefficient of restitution and H is the thickness of the flowing layer. This implies that the volume fraction is a constant in the leading approximation in an asymptotic analysis in small delta. Numerical estimates of both the parameter delta and its pre-factor are obtained to show that the lack of observable variation of the volume fraction with height can be explained by constitutive relations obtained from kinetic theory.

A Novel Synthetic Route For The Preparation Of Ammonium And Alkali-Metal Tetrafluoroborates And Alkyl Substituted Ammonium Tetrafluoroborates Using Pyridinium Tetrafluoroborate As The Precursor

Ammonium and alkali metal tetrafluoroborates have been prepared by the cation exchange reaction of pyridinium tetrafluoroborate with the corresponding hydroxides/halides. The reaction of pyridinium tetrafluoroborate with primary, secondary and tertiary alkyl amines at room temperature gives rise to mono-, di- and tri-alkylammonium tetrafluoroborates, respectively. The yields are good and the samples are of high purity. The products have been characterised by elemental analysis, IR and PMR spectroscopy. The spectral data for most of the compounds are reported for the first time.

A Novel Synthetic Route for the Preparation of Silver Salts of Hexafluorophosphate, Tetrafluoroborate and Hexafluorosilicate

Silver salts of hexafluorophosphates, tetrafluoro-borates and hexafluorosilicates have been prepared by a metathetic reaction between the respective ammonium salts and silver nitrate in acetonitrile medium. This one step procedure at room temperature offers salts of high purity in good yields. The salts (AgpF6, AgBF4 and Ag2SiF6) have been characterised by IR spectral data analysis and chemical analysis.

A hybrid electrochemical-thermal method for the preparation of large ZnO nanoparticles

A simple and efficient two-step hybrid electrochemical-thermal route was developed for the synthesis of large quantity of ZnO nanoparticles using aqueous sodium bicarbonate electrolyte and sacrificial Zn anode and cathode in an undivided cell under galvanostatic mode at room temperature. The bath concentration and current density were varied from 30 to 120 mmol and 0.05 to 1.5 A/dm(2). The electrochemically generated precursor was calcined for an hour at different range of temperature from 140 to 600 A degrees C. The calcined samples were characterized by XRD, SEM/EDX, TEM, TG-DTA, FT-IR, and UV-Vis spectral methods. Rietveld refinement of X-ray data indicates that the calcined compound exhibits hexagonal (Wurtzite) structure with space group of P63mc (No. 186). The crystallite sizes were in the range of 22-75 nm based on Debye-Scherrer equation. The TEM results reveal that the particle sizes were in the order of 30-40 nm. The blue shift was noticed in UV-Vis absorption spectra, the band gaps were found to be 5.40-5.11 eV. Scanning electron micrographs suggest that all the samples were randomly oriented granular morphology.

Density-wave theory of dislocations in crystals

The density-wave theory of Ramakrishnan and Yussouff is extended to provide a scheme for describing dislocations and other topological defects in crystals. Quantitative calculations are presented for the order-parameter profiles, the atomic configuration, and the free energy of a screw dislocation with Burgers vector b=(a/2, a/2, a/2) in a bcc solid. These calculations are done using a simple parametrization of the direct correlation function and a gradient expansion. It is conventional to express the free energy of the dislocation in a crystal of size R as (λb2/4π)ln(αR/‖b‖), where λ is the shear elastic constant, and α is a measure of the core energy. Our results yield for Na the value α≃1.94a/(‖c1’’‖)1/2 (≃1.85) at the freezing temperature (371 K) and α≃2.48a/(‖c1’’‖)1/2 at 271 K, where c1’’ is the curvature of the first peak of the direct correlation function c(q). Detailed results for the density distribution in the dislocation, particularly the core region, are also presented. These show that the dislocation core has a columnar character. To our knowledge, this study represents the first calculation of dislocation structure, including the core, within the framework of an order-parameter theory and incorporating thermal effects.