Control of Molecular Weight and Polydispersity of Hyperbranched Polymers Using a Reactive B(3) Core: A Single-Step Route to Orthogonally Functionalizable Hyperbranched Polymers

Molecular weight and polydispersity are two structural features of hyperbranched polymers that are difficult to control because of the statistical nature of the step-growth polycondensation of AB(2) type monomers; the statistical growth also causes the polydispersity index to increase with percent conversion (or molecular weight). We demonstrate that using controlled amounts of a specifically designed B(3) core, containing B-type functionality that are more reactive than those present in the AB(2) monomer, both the molecular weight and the polydispersity can be readily controlled; the PDI was shown to improve with increasing mole-fraction of the B(3) core while the polymer molecular weight showed an expected decrease. Incorporation of a ``clickable'' propargyl group in the B(3) core unit permitted the generation of a core-functionalizable hyperbranched polymer. Importantly, this clickable core, in combination with a recently developed AB(2) monomer, wherein the B-type groups are allyl ethers and A is an hydroxyl group, led to the generation of a hyperbranched polymer carrying orthogonally functionalizable core and peripheral groups, via a single-step melt polycondensation. Selective functionalization of the core and periphery using two different types of chromophores was achieved, and the occurrence of fluorescence resonance energy transfer (FRET) between the donor and acceptor chromophores was demonstrated.

Control of Molecular Weight and Polydispersity of Hyperbranched Polymers Using a Reactive B(3) Core: A Single-Step Route to Orthogonally Functionalizable Hyperbranched Polymers

Molecular weight and polydispersity are two structural features of hyperbranched polymers that are difficult to control because of the statistical nature of the step-growth polycondensation of AB(2) type monomers; the statistical growth also causes the polydispersity index to increase with percent conversion (or molecular weight). We demonstrate that using controlled amounts of a specifically designed B(3) core, containing B-type functionality that are more reactive than those present in the AB(2) monomer, both the molecular weight and the polydispersity can be readily controlled; the PDI was shown to improve with increasing mole-fraction of the B(3) core while the polymer molecular weight showed an expected decrease. Incorporation of a ``clickable'' propargyl group in the B(3) core unit permitted the generation of a core-functionalizable hyperbranched polymer. Importantly, this clickable core, in combination with a recently developed AB(2) monomer, wherein the B-type groups are allyl ethers and A is an hydroxyl group, led to the generation of a hyperbranched polymer carrying orthogonally functionalizable core and peripheral groups, via a single-step melt polycondensation. Selective functionalization of the core and periphery using two different types of chromophores was achieved, and the occurrence of fluorescence resonance energy transfer (FRET) between the donor and acceptor chromophores was demonstrated.

Reactive Pulsed Laser Deposition of titanium nitride thin film: Optimization of process parameters using Secondary Ion Mass Spectrometry

Reactive Pulsed Laser Deposition is a single step process wherein the ablated elemental metal reacts with a low pressure ambient gas to form a compound. We report here a Secondary Ion Mass Spectrometry based analytical methodology to conduct minimum number of experiments to arrive at optimal process parameters to obtain high quality TiN thin film. Quality of these films was confirmed by electron microscopic analysis. This methodology can be extended for optimization of other process parameters and materials. (C) 2009 Elsevier B.V. All rights reserved.

Analytical prediction of break-out noise from a reactive rectangular plenum with four flexible walls

This paper describes an analytical calculation of break-out noise from a rectangular plenum with four flexible walls by incorporating three-dimensional effects along with the acoustical and structural wave coupling phenomena. The breakout noise from rectangular plenums is important and the coupling between acoustic waves within the plenum and structural waves in the flexible plenum walls plays a critical role in prediction of the transverse transmission loss. The first step in breakout noise prediction is to calculate the inside plenum pressure field and the normal flexible plenum wall vibration by using an impedance-mobility approach, which results in a compact matrix formulation. In the impedance-mobility compact matrix (IMCM) approach, it is presumed that the coupled response can be described in terms of finite sets of the uncoupled acoustic subsystem and the structural subsystem. The flexible walls of the plenum are modeled as an unfolded plate to calculate natural frequencies and mode shapes of the uncoupled structural subsystem. The second step is to calculate the radiated sound power from the flexible walls using Kirchhoff-Helmholtz (KH) integral formulation. Analytical results are validated with finite element and boundary element (FEM-BEM) numerical models. (C) 2010 Acoustical Society of America. DOI: 10.1121/1.3463801]

Photocatalytic activity of ZnO nanostructured film grown by activated reactive

ZnO nanostructured films were deposited at room temperature on glass substrates and cotton fabrics by activated reactive evaporation in a single step without using metal catalyst or templates. Morphological observation has shown that the nanostructured film contains seaurchin-like structures, and this seaurchin containing large number of randomly grown ZnO nanoneedles. Microstructural analysis revealed the single crystalline nature of the grown nanoneedles and their growth direction was indentified to be along [0002]. PL spectrum of nanostructured films has shown a relatively weak near-band-edge emission peak at 380 nm, and a significant broad peak at 557 nm due to the oxygen vacancy-related emission. ZnO nanostructured films grown on glass substrates and cotton fabrics have shown good photocatalytic activity against rhodamine B.

Single-step synthesis of internally functionalizable hyperbranched polyethers

Radical catalyzed thiol-ene reaction has become a useful alternative to the Huisgen-type azide-yne click reaction as it helps expand the variability in reaction conditions as well as the range of clickable entities. In this study, the direct generation of a hyperbranched polyether (HBPE) having decyl units at the periphery and a pendant allyl group on every repeat unit of the polymer backbone is described; the allyl groups serve as a reactive handle for postpolymerization modifications and permits the generation of a variety of internally functionalized HBPEs. In this design, the AB(2) monomer carries two decylbenzyl ether units (B-functionality), an aliphatic OH (A-functionality) and a pendant allyl group within the spacer segment; polymerization of the monomer readily occurs at 150 degrees C via melt transetherification process by continuous removal of 1-decanol under reduced pressure. The resulting HBPE has a hydrophobic periphery due to the presence of numerous decyl chains, while the allyl groups that remain unaffected during the melt polymerization provides an opportunity to install a variety of functional groups within the interior; thiol-ene click reaction with two different thiols, namely 3-mercaptopropionic acid and mercaptosuccinic acid, generated interesting amphiphilic structures. Preliminary field emission scanning electron microscope (FESEM) and Atomic Force Microscopy (AFM) imaging studies reveal the formation of fairly uniform spherical aggregates in water with sizes ranging from 200 to 400 nm; this suggests that these amphiphilic HBPs is able to reconfigure to generate jellyfish-like conformations that subsequently aggregate in an alkaline medium. The internal allyl functional groups were also used to generate intramolecularly core-crosslinked HBPEs, by the use of dithiol crosslinkers; gel permeation chromatography traces provided clear evidence for reduction in the size after crosslinking. In summary, we have developed a simple route to prepare core-clickable HBPEs and have demonstrated the quantitative reaction of the allyl groups present within the interior of the polymers; such HB polymeric systems that carry numerous functional groups within the core could have interesting applications in analyte sequestration and possibly sensing, especially from organic media. (c) 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013, 51, 4125-4135

Single-step synthesis of carbon nanotubes/iron/iron oxide composite films through inert-ambient CVD using ferric acetylacetonate as a precursor

We have developed a unique single-step chemical vapor deposition (CVD) route for the synthesis of composite thin films containing carbon nanotubes (CNTs). CVD was carried out in an inert ambient using only iron(III) acetylacetonate as the precursor. Depositions were conducted at 700 degrees C on stainless steel substrates in argon ambient in the absence of any reactive gases (such as oxygen, hydrogen). By changing the deposition parameters, especially the pressure in the CVD reactor, the form of carbon deposited could be changed from amorphous to carbon nanotubes, the latter resulting in Fe-Fe3O4-CNT films. X-ray diffraction, Raman spectroscopy, X-ray photoelectron spectroscopy, and electron microscopy together confirm the formation of the three-component composite and illustrate the nanoscale mixing of the components. Elemental iron formed in this process was protected from oxidation by the co-deposited carbon surrounding it. Irrespective of the substrate used, a composite coating with CNTs was formed under optimum conditions, as verified by analyses of the film formed on polycrystalline alumina and silicon substrates.

Validation of processing maps for 304L stainless steel using hot forging, rolling and extrusion

The development of a microstructure in 304L stainless steel during industrial hot-forming operations, including press forging (mean strain rate of 0.15 s(-1)), rolling/extrusion (2-5 s(-1)), and hammer forging (100 s(-1)) at different temperatures in the range 600-1200 degrees C, was studied with a view to validating the predictions of the processing map. The results have shown that excellent correlation exists between the regimes exhibited by the map and the product microstructures. 304L stainless steel exhibits instability bands when hammer forged at temperatures below 1100 degrees C, rolled/extruded below 1000 degrees C, or press forged below 800 degrees C. All of these conditions must be avoided in mechanical processing of the material. On the other hand, ideally, the material may be rolled, extruded, or press forged at 1200 degrees C to obtain a defect-free microstructure.

A Simple and Convenient One Step Method for the Reductive Deoxygenation of Aryl Ketones to Hydrocarbons

A one step, clean and efficient, conversion of arylaldehydes, ketones and ketals into the corresponding hydrocarbon using ionic hydrogenation conditions employing sodium cyanoborohydride in the presence of two to three equivalents of BF3. OEt(2) is described.

Solar powered high voltage energization for vehicular exhaust cleaning: A step towards possible retrofitting in vehicles

This paper proposes a novel way of generating high voltage for electric discharge plasma in controlling NOx emission in diesel engine exhaust. A solar powered high frequency electric discharge topology has been suggested that will improve the size and specific energy density required when compared to the traditional repetitive pulse or 50 Hz AC energization. This methodology has been designed, fabricated and experimentally verified by conducting studies on real diesel engine exhaust.

Optimum Evaluation of Reactive Power Requirements in Power Distribution-Systems

This paper presents three methodologies for determining optimum locations and magnitudes of reactive power compensation in power distribution systems. Method I and Method II are suitable for complex distribution systems with a combination of both radial and ring-main feeders and having different voltage levels. Method III is suitable for low-tension single voltage level radial feeders. Method I is based on an iterative scheme with successive powerflow analyses, with formulation and solution of the optimization problem using linear programming. Method II and Method III are essentially based on the steady state performance of distribution systems. These methods are simple to implement and yield satisfactory results comparable with the results of Method I. The proposed methods have been applied to a few distribution systems, and results obtained for two typical systems are presented for illustration purposes.

Influence of time step in the simulation modelling of evapotranspiration

Three simulations of evapotranspiration were done with two values of time step,viz 10 min and one day. Inputs to the model were weather data, including directly measured upward and downward radiation, and soil characteristics. Three soils were used for each simulation. Analysis of the results shows that the time step has a direct influence on the prediction of potential evapotranspiration, but a complex interaction of this effect with the soil moisture characteristic, rate of increase of ground cover and bare soil evaporation determines the actual transpiration predicted. The results indicate that as small a time step as possible should be used in the simulation.

Flow of metal in constrained plane-strain extrusion forging- Part II

With many innovations in process technology, forging is establishing itself as a precision manufacturing process: as forging is used to produce complex shapes in difficult materials, it requires dies of complex configuration of high strength and of wear-resistant materials. Extensive research and development work is being undertaken, internationally, to analyse the stresses in forging dies and the flow of material in forged components. Identification of the location, size and shape of dead-metal zones is required for component design. Further, knowledge of the strain distribution in the flowing metal indicates the degree to which the component is being work hardened. Such information is helpful in the selection of process parameters such as dimensional allowances and interface lubrication, as well as in the determination of post-forging operations such as heat treatment and machining. In the presently reported work the effect of aperture width and initial specimen height on the strain distribution in the plane-strain extrusion forging of machined lead billets is observed: the distortion of grids inscribed on the face of the specimen gives the strain distribution. The stress-equilibrium approach is used to optimise a model of flow in extrusion forging, which model is found to be effective in estimating the size of the dead-metal zone. The work carried out so far indicates that the methodology of using the stress-equilibrium approach to develop models of flow in closed-die forging can be a useful tool in component, process and die design.

Synthesis and Characterization of Carbon-Coated LiNi1/3Co1/3Mn1/3O2 in a Single Step by an Inverse Microemulsion Route

Layered LiNi1/3Co1/3Mn1/3O2, which is isostructural to LiCoO2, is considered as a potential cathode material. A layer of carbon coated on the particles improves the electrode performance, Which is attributed to an increase of the grain connectivity and also to protection of metal oxide from chemical reaction. The present work involves in situ synthesis of carbon-coated submicrometer-sized particles of LiNi1/3Co1/3Mn1/3O2 in an inverse microemulsion medium in the presence of glucose. The precursor obtained from the reaction is heated in air at 900 degrees C for 6 h to get crystalline LiNi1/3Co1/3Mn1/3O2. The carbon coating is found to impart porosity as well as higher surface area in relation to bare samples of the compound. The electrochemical characterization studies provide that carbon-coated LiNi1/3Co1/3Mn1/3O2 samples exhibit improved rate capability and cycling performance. The carbon coatings are shown to suppress the capacity fade, which is normally observed for the bare compound. Impedance spectroscopy data provide additional evidence for the beneficial effect of a carbon coating on LiNi1/3Co1/3Mn1/3O2 particles.

One-pot synthesis of nidorellaurenal and its one-step conversion to methyl nidorellaurinate, a constituent of Nidorella auriculata

Nidorellaurenal (4) is obtained in a one-pot reaction, involving heating of the known carbinol (8) with selenium dioxide in dimethyl sulphoxide. Conversion of 4 to methyl nidorellaurinate (6), the natural product from Nidorella auriculata, has been achieved by Corey's one-step procedure.