Computational tools for mechanistic discrimination in the reductive and metathesis coupling reactions mediated by titanium(IV) isopropoxide

A theoretical study has been carried out at the B3LYP/LANL2DZ level to compare the reactivity of phenyl isocyanate and phenyl isothiocyanate towards titanium(IV) alkoxides. Isocyanates are shown to favour both mono insertion and double insertion reactions. Double insertion in a head-to-tail fashion is shown to be more exothermic than double insertion in a head-to-head fashion. The head-to-head double insertion leads to the metathesis product, a carbodiimide, after the extrusion of carbon dioxide. In the case of phenyl isothiocyanate, calculations favour the formation of only mono insertion products. Formation of a double insertion product is highly unfavourable. Further, these studies indicate that the reverse reaction involving the metathesis of N,N-'-diphenyl carbodiimide with carbon dioxide is likely to proceed more efficiently than the metathesis reaction with carbon disulphide. This is in excellent agreement with experimental results as metathesis with carbon disulphide fails to occur. In a second study, multilayer MM/QM calculations are carried out on intermediates generated from reduction of titanium(IV) alkoxides to investigate the effect of alkoxy bridging on the reactivity of multinuclear Ti species. Bimolecular coupling of imines initiated by Ti(III) species leads to a mixture of diastereomers and not diastereoselective coupling of the imine. However if the reaction is carried out by a trimeric biradical species, diastereoselective coupling of the imine is predicted. The presence of alkoxy bridges greatly favours the formation of the d,l (+/-) isomer, whereas the intermediate without alkoxy bridges favours the more stable meso isomer. As a bridged trimeric species, stabilized by bridging alkoxy groups, correctly explains the diastereoselective reaction, it is the most likely intermediate in the reaction.

Simulation of length-preserving motions of flexible one dimensional oObjects using optimization

During the motion of one dimensional flexible objects such as ropes, chains, etc., the assumption of constant length is realistic. Moreover,their motion appears to be naturally minimizing some abstract distance measure, wherein the disturbance at one end gradually dies down along the curve defining the object. This paper presents purely kinematic strategies for deriving length-preserving transformations of flexible objects that minimize appropriate ‘motion’. The strategies involve sequential and overall optimization of the motion derived using variational calculus. Numerical simulations are performed for the motion of a planar curve and results show stable converging behavior for single-step infinitesimal and finite perturbations 1 as well as multi-step perturbations. Additionally, our generalized approach provides different intuitive motions for various problem-specific measures of motion, one of which is shown to converge to the conventional tractrix-based solution. Simulation results for arbitrary shapes and excitations are also included.

Microstructure and tensile properties of consolidated magnesium chips

In this study tensile properties of consolidated magnesium chips obtained from solid state re-cycling (SSR) has been examined and correlated with the microstructure. Chips machined from as-cast billet of pure magnesium were consolidated through SSR technique, comprising of compaction at ambient conditions followed by hot extrusion at four different temperatures viz., 250, 300, 350 and 400 degrees C. The extruded rods were characterized for microstructure and their room temperature tensile properties. Both ultimate tensile strength and 0.2% proof stress of these consolidated materials are higher by 15-35% compared to reference material (as cast and extruded). Further these materials obey Hall-Petch relation with respect to strength dependence of grain size. Strain hardening behavior, measured in terms of hardening exponent, hardening capacity and hardening rate was found to be distinctly different in chip consolidated material compared to reference material. Strength asymmetry, measured as a ratio of compressive proof stress to tensile proof stress was higher in chip consolidated material. (C) 2012 Elsevier B.V. All rights reserved.

Natural motion of one-dimensional flexible objects using minimization approaches

For one-dimensional flexible objects such as ropes, chains, hair, the assumption of constant length is realistic for large-scale 3D motion. Moreover, when the motion or disturbance at one end gradually dies down along the curve defining the one-dimensional flexible objects, the motion appears ``natural''. This paper presents a purely geometric and kinematic approach for deriving more natural and length-preserving transformations of planar and spatial curves. Techniques from variational calculus are used to determine analytical conditions and it is shown that the velocity at any point on the curve must be along the tangent at that point for preserving the length and to yield the feature of diminishing motion. It is shown that for the special case of a straight line, the analytical conditions lead to the classical tractrix curve solution. Since analytical solutions exist for a tractrix curve, the motion of a piecewise linear curve can be solved in closed-form and thus can be applied for the resolution of redundancy in hyper-redundant robots. Simulation results for several planar and spatial curves and various input motions of one end are used to illustrate the features of motion damping and eventual alignment with the perturbation vector.

Effect of hybridizing micron-sized Ti with nano-sized SiC on the microstructural evolution and mechanical response of Mg-5.6Ti composite

In this work, the effect of hybridizing micro-Ti with nano-SiC particulates on the microstructural and the mechanical behaviour of Mg-5.6Ti composite were investigated. Mg materials containing micron-sized Ti particulates hybridized with different amounts of nano-size SiC particulates were synthesized using the disintegrated melt deposition method followed by hot extrusion. The microstructural and mechanical behaviour of the developed Mg hybrid composites were studied in comparison with Mg-5.6Ti. Microstructural characterization revealed grain refinement attributed to the presence of uniformly distributed micro-Ti particles embedded with nano-SiC particulates. Electron back scattered diffraction (EBSD) analyses of Mg-(5.6Ti + 1.0SiC)(BM) hybrid composite showed relatively more localized recrystallized grains and lesser tensile twin fraction, when compared to Mg-5.6Ti. The evaluation of mechanical properties indicated that the best combination of strength and ductility was observed in the Mg-(5.6Ti + 1.0SiC)(BM) hybrid composites. The superior strength properties of the Mg-(5.6Ti + x-SiC)(BM) hybrid composites when compared to Mg-5.6Ti is attributed to the presence of nano-reinforcements, the uniform distribution of the hybridized particles and the better interfacial bonding between the matrix and the reinforcement particles, achieved by nano-SiC addition.

Hybrid Energy Harvesting Wireless Systems: Performance Evaluation and Benchmarking

Energy harvesting sensor (EHS) nodes provide an attractive and green solution to the problem of limited lifetime of wireless sensor networks (WSNs). Unlike a conventional node that uses a non-rechargeable battery and dies once it runs out of energy, an EHS node can harvest energy from the environment and replenish its rechargeable battery. We consider hybrid WSNs that comprise of both EHS and conventional nodes; these arise when legacy WSNs are upgraded or due to EHS deployment cost issues. We compare conventional and hybrid WSNs on the basis of a new and insightful performance metric called k-outage duration, which captures the inability of the nodes to transmit data either due to lack of sufficient battery energy or wireless fading. The metric overcomes the problem of defining lifetime in networks with EHS nodes, which never die but are occasionally unable to transmit due to lack of sufficient battery energy. It also accounts for the effect of wireless channel fading on the ability of the WSN to transmit data. We develop two novel, tight, and computationally simple bounds for evaluating the k-outage duration. Our results show that increasing the number of EHS nodes has a markedly different effect on the k-outage duration than increasing the number of conventional nodes.

Friction Stir-Welded Dissimilar Aluminum Alloys: Microstructure, Mechanical Properties, and Physical State

A356 and 6061 aluminum alloys were joined by friction stir welding at constant tool rotational rate with different tool-traversing speeds. Thermomechanical data of welding showed that increment in tool speed reduced the pseudo heat index and temperature at weld nugget (WN). On the other hand, volume of material within extrusion zone, strain rate, and Zenner Hollomon parameter were reduced with decrease in tool speed. Optical microstructure of WN exhibited nearly uniform dispersion of Si-rich particles, fine grain size of 6061 Al alloy, and disappearance of second phase within 6061 Al alloy. With enhancement in welding speed, matrix grain size became finer, yet size of Si-rich particles did not reduce incessantly. Size of Si-rich particles was governed by interaction time between tool and substrate. Mechanical property of WN was evaluated. It has been found that the maximum joint efficiency of 116% with respect to that of 6061 alloy was obtained at an intermediate tool-traversing speed, where matrix grain size was significantly fine and those of Si-rich particles were substantially small.

Prediction of the stiffness of nanoclay-polypropylene composites using a monte carlo finite element analysis approach

The present work deals with the prediction of stiffness of an Indian nanoclay-reinforced polypropylene composite (that can be termed as a nanocomposite) using a Monte Carlo finite element analysis (FEA) technique. Nanocomposite samples are at first prepared in the laboratory using a torque rheometer for achieving desirable dispersion of nanoclay during master batch preparation followed up with extrusion for the fabrication of tensile test dog-bone specimens. It has been observed through SEM (scanning electron microscopy) images of the prepared nanocomposite containing a given percentage (3–9% by weight) of the considered nanoclay that nanoclay platelets tend to remain in clusters. By ascertaining the average size of these nanoclay clusters from the images mentioned, a planar finite element model is created in which nanoclay groups and polymer matrix are modeled as separate entities assuming a given homogeneous distribution of the nanoclay clusters. Using a Monte Carlo simulation procedure, the distribution of nanoclay is varied randomly in an automated manner in a commercial FEA code, and virtual tensile tests are performed for computing the linear stiffness for each case. Values of computed stiffness modulus of highest frequency for nanocomposites with different nanoclay contents correspond well with the experimentally obtained measures of stiffness establishing the effectiveness of the present approach for further applications.

Simulations and experiments in punching spring-steel devices with sub-millimeter features

This work demonstrates the feasibility of mesoscale (100 μm to mm) punching of multiple holes of intricate shapes in metals. Analytical modeling, finite element (FE)simulation, and experimentations are used in this work. Two dimensional FE simulations in ABAQUS were done with an assumed material modeling and plane-strain condition. A known analytical model was used and compared with the ABAQUS simulation results to understand the effects of clearance between the punch and the die. FE simulation in ABAQUS was done for different clearances and corner radii at punch, die, and holder. A set of punches and dies were used to punch out a miniature spring-steel gripper. Comparison of compliant grippers manufactured by wire-cut electro discharge machining(EDM) and punching shows that realizing sharp interior and re-entrant corners by punching is not easy to achieve. Punching of circular holes with 5 mm and 2.5 mm diameter is achieved. The possibility of realizing meso-scale parts with complicated shapes through punching is demonstrated in this work; and some strategies are suggested for improvement.

Effect of nanoscale boron carbide particle addition on the microstructural evolution and mechanical response of pure magnesium

In this study, the effect of nano-B4C addition on the microstructural and the mechanical behavior of pure Mg are investigated. Pure Mg-metal reinforced with different amounts of nano-size B4C particulates were synthesized using the disintegrated melt deposition technique followed by hot extrusion. Microstructural characterization of the developed Mg/x-B4C composites revealed uniform distribution of nano-B4C particulates and significant grain refinement. Electron back scattered diffraction (EBSD) analyses showed presence of relatively more recrystallized grains and absence of fiber texture in Mg/B4C nanocomposites when compared to pure Mg. The evaluation of mechanical properties indicated a significant improvement in tensile properties of the composites. The significant improvement in tensile ductility (similar to 180% increase with respect to pure Mg) is among the highest observed when compared to the pure Mg based nanocomposites existing in the current literature. The superior mechanical properties of the Mg/B4C nanocomposites are attributed to the uniform distribution of the nanoparticles and the tendency for texture randomization (absence of fiber texture) achieved due to the nano-B4C addition. (C) 2013 Elsevier Ltd. All rights reserved.

Incipient straining in severe plastic deformation methods

Knowledge of the plasticity associated with the incipient stage of chip formation is useful toward developing an understanding of the deformation field underlying severe plastic deformation processes. The transition from a transient state of straining to a steady state was investigated in plane strain machining of a model material system-copper. Characterization of the evolution to a steady-state deformation field was made by image correlation, hardness mapping, load analysis, and microstructure characterization. Empirical relationships relating the deformation heterogeneity and the process parameters were found and explained by the corresponding effects on shear plane geometry. The results are potentially useful to facilitate a framework for process design of large strain deformation configurations, wherein transient deformation fields prevail. These implications are considered in the present study to quantify the efficiency of processing methods for bulk ultrafine-grained metals by large strain extrusion machining and equal channel angular pressing.

Effect of boron addition and processing of Ti-6Al-4V on corrosion behaviour and biocompatibility

Ti-6Al-4V is widely used to prepare biomedical implant for orthopaedic and dental applications, but it is an expensive choice relative to other implant materials such as stainless steels and Co-Cr alloys, in large part due to the high manufacturing cost. Adding boron to refine the as cast microstructure of Ti-6Al-4V can eliminate the need for extensive hot working and thereby reduce processing costs. The effect of 0.1 wt-% boron addition and the choice of processing route (forging or extrusion) was studied in the context of potential biomedical applications. Corrosion tests in simulated body fluid indicated that the presence of boron increased the corrosion rate of Ti-6Al-4V and that the increase was higher for forged alloys than for extruded alloys. Boron addition and processing route were found to have a minimal effect on the viability of osteoblasts on the alloy surfaces. It is concluded that the addition of boron could offer advantages during the processing of Ti-6Al-4V for biomedical applications.

Mg/BN nanocomposites: Nano-BN addition for enhanced room temperature tensile and compressive response

The present study elucidates the effects of nanoscale boron nitride particles addition on the microstructural and mechanical characteristics of monolithic magnesium. Novel light-weight Mg nanocomposites containing 0.3, 0.6 and 1.2vol% nano-size boron nitride particulates were synthesized using the disintegrated melt deposition method followed by hot extrusion. Microstructural characterization of developed Mg/x-boron nitride composites revealed significant grain refinement due to the uniform distribution of nano-boron nitride particulates. Texture analysis of selected Mg-1.2 boron nitride nanocomposite showed an increase in the intensity of fiber texture alongside enhanced localized recrystallization when compared to monolithic Mg. Mechanical properties evaluation under indentation, tension and compression loading indicated superior response of Mg/x-boron nitride composites in comparison to pure Mg. The uniform distribution of nanoscale boron nitride particles and the modified crystallographic texture achieved due to the nano-boron nitride addition attributes to the superior mechanical characteristics of Mg/boron nitride nanocomposites.

Tailored electrical conductivity, electromagnetic shielding and thermal transport in polymeric blends with graphene sheets decorated with nickel nanoparticles

Electromagnetic interference shielding (EMI) materials were designed using PC (polycarbonate)/SAN poly(styrene-co-acrylonitrile)] blends containing few-layered graphene nanosheets decorated with nickel nanoparticles (G-Ni). The graphene nanosheets were decorated with nickel nanoparticles via the uniform nucleation of the metal salt precursor on graphene sheets as the substrate. In order to localize the nanoparticles in the PC phase of the PC/SAN blends, a two-step mixing protocol was adopted. In the first step, graphene sheets were mixed with PC in solution and casted into a film, followed by dilution of these PC master batch films with SAN in the subsequent melt extrusion step. The dynamic mechanical properties, ac electrical conductivity, EMI shielding effectiveness and thermal conductivity of the composites were evaluated. The G-Ni nanoparticles significantly improved the electrical and thermal conductivity in the blends. In addition, a total shielding effectiveness (SET) of -29.4 dB at 18 GHz was achieved with G-Ni nanoparticles. Moreover, the blends with G-Ni exhibited an impressive 276% higher thermal conductivity and 29.2% higher elastic modulus with respect to the neat blends.

Three-dimensional plotted hydroxyapatite scaffolds with predefined architecture: comparison of stabilization by alginate cross-linking versus sintering

Scaffolds for bone tissue engineering are essentially characterized by porous three-dimensional structures with interconnected pores to facilitate the exchange of nutrients and removal of waste products from cells, thereby promoting cell proliferation in such engineered scaffolds. Although hydroxyapatite is widely being considered for bone tissue engineering applications due to its occurrence in the natural extracellular matrix of this tissue, limited reports are available on additive manufacturing of hydroxyapatite-based materials. In this perspective, hydroxyapatite-based three-dimensional porous scaffolds with two different binders (maltodextrin and sodium alginate) were fabricated using the extrusion method of three-dimensional plotting and the results were compared in reference to the structural properties of scaffolds processed via chemical stabilization and sintering routes, respectively. With the optimal processing conditions regarding to pH and viscosity of binder-loaded hydroxyapatite pastes, scaffolds with parallelepiped porous architecture having up to 74% porosity were fabricated. Interestingly, sintering of the as-plotted hydroxyapatite-sodium alginate (cross-linked with CaCl2 solution) scaffolds led to the formation of chlorapatite (Ca9.54P5.98O23.8Cl1.60(OH)(2.74)). Both the sintered scaffolds displayed progressive deformation and delayed fracture under compressive loading, with hydroxyapatite-alginate scaffolds exhibiting a higher compressive strength (9.5 +/- 0.5MPa) than hydroxyapatite-maltodextrin scaffolds (7.0 +/- 0.6MPa). The difference in properties is explained in terms of the phase assemblage and microstructure.