Efficacies of multivalent vs monovalent poly(ether imine) dendritic catalysts within a generation in multiple C-C bond forming reactions

Dendrimers are ideal platforms to study multivalent effects due to the presence of uniform end groups at their peripheries. This report concerns with a study of multivalent dendritic catalysts, both within and across dendrimer generations, and their effects to mediate C-C bond forming reactions on multivalent substrates that have two and three acrylate reactive sites. As many as fourteen multivalent dendritic catalysts were prepared using 0-3 generations of poly(propyl ether imine) dendrimers, incorporated with Pd(II) catalytic sites, both within and across the dendrimer generations. C-C Bond forming reactions of these substrates with iodobenzene, mediated by uniform concentration of the metal across all catalysts, showed formation of partially and fully functionalized cinnamates in varying ratios, depending on the extent of clustering of catalytic moieties at the peripheries of dendrimers within a dendrimer generation. In a given generation, higher clustering of catalytic moieties greatly assisted multiple C-C bond formations than presenting the same in lesser number. The studies demonstrate true benefits of clustering catalytic moieties within a dendrimer generation and the beneficial effects applicable to catalysis of substrates presenting more than one reactive center. (C) 2011 Elsevier B.V. All rights reserved.

Passive vibration isolation of reaction wheel disturbances using a low frequency flexible space platform

Reaction wheel assemblies (RWAs) are momentum exchange devices used in fine pointing control of spacecrafts. Even though the spinning rotor of the reaction wheel is precisely balanced to minimize emitted vibration due to static and dynamic imbalances, precision instrument payloads placed in the neighborhood can always be severely impacted by residual vibration forces emitted by reaction wheel assemblies. The reduction of the vibration level at sensitive payloads can be achieved by placing the RWA on appropriate mountings. A low frequency flexible space platform consisting of folded continuous beams has been designed to serve as a mount for isolating a disturbance source in precision payloads equipped spacecrafts. Analytical and experimental investigations have been carried out to test the usefulness of the low frequency flexible platform as a vibration isolator for RWAs. Measurements and tests have been conducted at varying wheel speeds, to quantify and characterize the amount of isolation obtained from the reaction wheel generated vibration. These tests are further extended to other variants of similar design in order to bring out the best isolation for given disturbance loads. Both time and frequency domain analysis of test data show that the flexible beam platform as a mount for reaction wheels is quite effective and can be used in spacecrafts for passive vibration control. (C) 2011 Elsevier Ltd. All rights reserved.

The omega phase formation during laser cladding and remelting of quasicrystal forming AlCuFe on pure aluminum

We report the formation omega phase in the remelted layers during laser cladding and remelting of quasicrystal forming Al65Cu23.3Fe11.7 alloy on pure aluminum. The omega phase is absent in the clad layers. In the remelted layer, the phase nucleates at the periphery of the primary icosahedral phase particles. A large number of omega phase particles forms enveloping the icosahedral phase growing into aluminum rich melt, which solidify as alpha-Al solid solution. On the other side it develops an interface with aluminum. A detailed transmission electron microscopic analysis shows that omega phase exhibits orientation relationship with icosahedral phase. The composition analysis performed using energy dispersive x-ray analyzer suggests that this phase has composition higher aluminum than the icosahedral phase. The analysis of the available phase diagram information indicates that the present results represent large departure from equilibrium conditions. A possible scenario of the evolution of the omega phase has been suggested.

Characterization of the dynamics of glass-forming liquids from the properties of the potential energy landscape

We develop a framework for understanding the difference between strong and fragile behavior in the dynamics of glass-forming liquids from the properties of the potential energy landscape. Our approach is based on a master equation description of the activated jump dynamics among the local minima of the potential energy (the so-called inherent structures) that characterize the potential energy landscape of the system. We study the dynamics of a small atomic cluster using this description as well as molecular dynamics simulations and demonstrate the usefulness of our approach for this system. Many of the remarkable features of the complex dynamics of glassy systems emerge from the activated dynamics in the potential energy landscape of the atomic cluster. The dynamics of the system exhibits typical characteristics of a strong supercooled liquid when the system is allowed to explore the full configuration space. This behavior arises because the dynamics is dominated by a few lowest-lying minima of the potential energy and the potential energy barriers between these minima. When the system is constrained to explore only a limited region of the potential energy landscape that excludes the basins of attraction of a few lowest-lying minima, the dynamics is found to exhibit the characteristics of a fragile liquid.

Barrier crossing by a flexible long chain molecule - The kink mechanism

The problem and related earlier work All the above problems involve the passage of a long chain molecule, through a region in space, where the free energy per segment is higher, thus effectively presenting a barrier for the motion of the molecule. This is what we refer to as the Kramers proble...

A Flexible Crypto-system Based upon the REDEFINE Polymorphic ASIC Architecture

The highest levels of security can be achieved through the use of more than one type of cryptographic algorithm for each security function. In this paper, the REDEFINE polymorphic architecture is presented as an architecture framework that can optimally support a varied set of crypto algorithms without losing high performance. The presented solution is capable of accelerating the advanced encryption standard (AES) and elliptic curve cryptography (ECC) cryptographic protocols, while still supporting different flavors of these algorithms as well as different underlying finite field sizes. The compelling feature of this cryptosystem is the ability to provide acceleration support for new field sizes as well as new (possibly proprietary) cryptographic algorithms decided upon after the cryptosystem is deployed.

Coupled Wavenumbers in an Infinite Flexible Fluid-Filled Circular Cylindrical Shell: Comparison between Different Shell Theories

Analytical expressions are found for the wavenumbers in an infinite flexible in vacuo I fluid-filled circular cylindrical shell based on different shell-theories using asymptotic methods. Donnell-Mushtari theory (the simplest shell theory) and four higher order theories, namely Love-Timoshenko, Goldenveizer-Novozhilov, Flugge and Kennard-simplified are considered. Initially, in vacuo and fluid-coupled wavenumber expressions are presented using the Donnell-Mushtari theory. Subsequently, the wavenumbers using the higher order theories are presented as perturbations on the Donnell-Mushtari wavenumbers. Similarly, expressions for the resonance frequencies in a finite shell are also presented, using each shell theory. The basic differences between the theories being what they are, the analytical expressions obtained from the five theories allow one to see how these differences propagate into the asymptotic expansions. Also, they help to quantify the difference between the theories for a wide range of parameter values such as the frequency range, circumferential order, thickness ratio of the shell, etc.

Accumulative roll bonding of aluminum alloys 2219/5086 laminates: Microstructural evolution and tensile properties

The present study describes the course of microstructure evolution during accumulative roll bonding (ARB) of dissimilar aluminum alloys AA2219 and AA5086. The two alloys were sandwiched as alternate layers and rolled at 300 degrees C up to 8 passes with 50% height reduction per pass. A strong bonding between successive layers accompanied by substantial grain refinement (similar to 200-300 nm) is achieved after 8 passes of ARB. The processing schedule has successfully maintained the iso-strain condition up to 6 cycles between the two alloys. Afterwards, the fracture and fragmentation of AA5086 layers dominate the microstructure evolution. Mechanical properties of the 8 pass ARB processed material were evaluated in comparison to the two starting alloy sheets via room temperature tensile tests along the rolling direction. The strength of the 8 pass ARB processed material lies between that of the two starting alloys while the ductility decreases after ARB than that of the two constituent starting alloys. These differences in mechanical behavior have been attributed to the microstructural aspects of the individual layer and the fragmentation process. (C) 2011 Elsevier Ltd. All rights reserved.

Microstructure and texture evolution during accumulative roll bonding of aluminium alloys AA2219/AA5086 composite laminates

Accumulative roll bonding of two aluminium alloys, AA2219 and AA5086 was carried out up to 8 passes. During the course of ARB, the deformation inhomogeneity between the two alloy layers results in interfacial instability after the 4th pass, necking of the AA5086 layers after the 6th pass and fracture along the necked regions after the 7th and 8th pass. The EBSD analysis shows deformation bands along the interfaces after 8 passes of ARB. The ARB-processed materials predominantly show characteristic deformation texture components. The weak texture after the 2nd pass results from the combination of a weakly-textured starting AA2219 layer and a strongly-textured starting AA5086 layer. A strong deformation texture forms due to the high imposed strain after a higher number of ARB passes. Subgrain formation and related shear banding induces copper/S components in the case of the small elongated grains, while planar slip leads to the formation of brass component in the large elongated grains.

Dynamics of end-to-end loop formation: A flexible chain in the presence of hydrodynamic interaction

Based on the Wilemski-Fixman approach G. Wilemski, M. Fixman, J. Chem. Phys. 60 (1974) 866], we show that, for a flexible chain in theta solvent, hydrodynamic interaction treated with a pre-averaging approximation makes ring closing faster if the chain is not very short. We also show that the ring closing time for a long chain with hydrodynamic interaction in theta solvent scales with the chain length (N) as N-1.5, in agreement with the previous renormalization group calculation based prediction by Freidman and O'Shaughnessy B. Friedman, B. O'Shaughnessy, Phys. Rev. A 40 (1989) 5950]. (C) 2012 Elsevier B.V. All rights reserved.

Tunable device properties of free-standing inorganic/organic flexible hybrid structures obtained by exfoliation

We report the fabrication of free-standing flexible inorganic/organic hybrid structures by exfoliating ZnO nanostructured films from the flat indium tin oxide (ITO)/silicon/sapphire substrates using poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate) (PEDOT:PSS). Strong interaction between ZnO and PEDOT: PSS and the thermomechanical response of PEDOT: PSS are the key issues for the exfoliation to prevail. The performance of the free-standing hybrid structures as rectifiers and photodetectors is better as compared to ITO supported hybrid structures. It is also shown that device properties of hybrid structures can be tuned by using different electrode materials. (C) 2012 American Institute of Physics. http://dx.doi.org/10.1063/1.4729550]

Development of microstructure and texture in Copper during warm accumulative roll bonding

The evolution of microstructure and texture gradient in warm Accumulative Roll Bonded Cu-Cu multilayer has been studied. Grain size distribution is multimodal and exhibits variation from middle to surface layer. Evolution of texture is largely influenced by shear, in addition to rolling deformation. This leads to the formation of a texture comprising of high fraction of Brass and rolling direction-rotated cube components. Partial recrystallization was observed. Deformed and recrystallized grains were separated using a partition scheme based on grain orientation spread and textures were analyzed for both the partition. Retention of deformation texture components in recrystallized grains suggests the mechanism of recrystallization as continuous recrystallization. Shear deformation plays an important role in grain refinement through continuous recrystallization. (C) 2012 Elsevier Inc. All rights reserved.

Adam-Gibbs Relation for Glass-Forming Liquids in Two, Three, and Four Dimensions

The Adam-Gibbs relation between relaxation times and the configurational entropy has been tested extensively for glass formers using experimental data and computer simulation results. Although the form of the relation contains no dependence on the spatial dimensionality in the original formulation, subsequent derivations of the Adam-Gibbs relation allow for such a possibility. We test the Adam-Gibbs relation in two, three, and four spatial dimensions using computer simulations of model glass formers. We find that the relation is valid in three and four dimensions. But in two dimensions, the relation does not hold, and interestingly, no single alternate relation describes the results for the different model systems we study.

Analysis of Strain Rates and Microstructural Evaluation during Metal Forming: Role of Surface Texture and Friction

The surface texture of a die plays an important role in friction during metal forming. In the present study, unidirectional and random surface finishes were produced on hardened steel plate surfaces. To understand the influence of surface texture on friction, experiments were conducted using Al-Mg alloy pins that slid against steel plates of different surface textures. In the sliding experiments, a high coefficient of friction was observed when the pins slid perpendicular to the unidirectional grinding marks and low friction occurred when the pins slid on the random surfaces. Finite element simulations were performed using the measured friction values to understand the stress and strain evolutions in the deforming material using dies with various friction. The numerical results showed that the states of stress and strain rates are strongly influenced by the friction at the interface and hence would influence the final material microstructure. To substantiate the numerical results, laboratory compression tests were conducted. Different surface textures were obtained in order to experience different friction values at different locations. A large variation in the microstructure at these locations was observed during experiments, verifying that surface texture and die friction significantly influence fundamental material formation behavior.

Asymptotic expansions for the coupled wavenumbers in an infinite orthotropic flexible fluid-filled cylindrical shell

Analytical expressions are found for the coupled wavenumbers in flexible, fluid-filled, circular cylindrical orthotropic shells using the asymptotic methods. These expressions are valid for arbitrary circumferential orders. The Donnell-Mushtari shell theory is used to model the shell and the effect of the fluid is introduced through the fluid-loading parameter mu. The orthotropic problem is posed as a perturbation on the corresponding isotropic problem by defining a suitable orthotropy parameter epsilon, which is a measure of the degree of orthotropy. For the first study, an isotropic shell is considered (by setting epsilon = 0) and expansions are found for the coupled wavenumbers using a regular perturbation approach. In the second study, asymptotic expansions are found for the coupled wavenumbers in the limit of small orthotropy (epsilon << 1). For each study, isotropy and orthotropy, expansions are found for small and large values of the fluid-loading parameter mu. All the asymptotic solutions are compared with numerical solutions to the coupled dispersion relation and the match is seen to be good. The differences between the isotropic and orthotropic solutions are discussed. The main contribution of this work lies in extending the existing literature beyond in vacuo studies to the case of fluid-filled shells (isotropic and orthotropic).