Development and characterization of functionalized Al2O3 and TiO2-reinforced polybenzoxazine nanocomposites

In the present work, benzoxazine was synthesized using caprolactam amine and cardanol, and its molecular structure was confirmed with FTIR and NMR spectroscopic techniques. Alumina (Al₂O₃) and titania (TiO₂) were functionalized using 3-aminopropyltrimethoxysilane (APTMS). The nanocomposites were developed by reinforcing with varying weight (1, 3, 5, and 7) percentages of functionalized Al₂O₃ (F-Al₂O₃) and functionalized TiO₂ (F-TiO₂) with benzoxazine. The developed nanocomposites (F-Al₂O₃/CPBz and F-TiO₂/CPBz) were characterized from their thermal, dielectric, and UV shielding studies. Data obtained from thermal studies show that 7 wt% of F-Al₂O₃-reinforced cardanol-based polybenzoxazine nanocomposite exhibits higher thermal stability than that of 7 wt% F-TiO₂-reinforced cardanol-based polybenzoxazine nanocomposite. Dielectric and UV shielding studies show that 7 wt% F-TiO₂ nanocomposite show higher value of dielectric constant (10.2) and UV shielding value (93%) than those of neat and other weight percentages of F-Al₂O₃ and F-TiO₂ reinforced composites.     

Stochastic optimization using a sparse grid collocation scheme

In computational sciences, optimization problems are frequently encountered in solving inverse problems for computing system parameters based on data measurements at specific sensor locations, or to perform design of system parameters. This task becomes increasingly complicated in the presence of uncertainties in boundary conditions or material properties. The task of computing the optimal probability density function (PDF) of parameters based on measurements of physical fields of interest in the form of a PDF, is posed as a stochastic optimization problem. This stochastic optimization problem is solved by dividing it into two problems—an auxiliary optimization problem to construct stochastic space representations from the PDF of measurement data, and a stochastic optimization problem to compute the PDF of problem parameters. The auxiliary optimization problem is solved using a downhill simplex method, whilst a gradient based approach is employed for solving the stochastic optimization problem. The gradients required for stochastic optimization are defined, using appropriate stochastic sensitivity problems. A computationally efficient sparse grid collocation scheme is utilized to compute the solution of these stochastic sensitivity problems. The implementation discussed, requires minimum intrusion into existing deterministic solvers, and it is thus applicable to a variety of problems. Numerical examples involving stochastic inverse heat conduction problems, contamination source identification problems and large deformation robust design problems are discussed.     

The Programmers' Playground: I/O abstraction for user-configurabledistributed applications

I/O abstraction is offered as a new high-level approach to interprocess communication. Functional components of a distributed system are written as encapsulated modules that act upon local data structures, some of which may be published for external use. Relationships among modules are specified by logical connections among their published data structures. Whenever a module updates published data, I/O takes place implicitly according to the configuration of logical connections. The Programmers' Playground, a software library and runtime system supporting I/O abstraction, is described. Design goals include the separation of communication from computation, dynamic reconfiguration of the communication structure, and the uniform treatment of discrete and continuous data types. Support for end-user configuration of distributed multimedia applications is the motivation for the work     

Increased cycling efficiency and rate capability of copper-coated silicon anodes in lithium-ion batteries

Cycling efficiency and rate capability of porous copper-coated, amorphous silicon thin-film negative electrodes are compared to equivalent silicon thin-film electrodes in lithium-ion batteries. The presence of a copper layer coated on the active material plays a beneficial role in increasing the cycling efficiency and the rate capability of silicon thin-film electrodes. Between 3C and C/8 discharge rates, the available cell energy decreased by 8% and 18% for 40 nm copper-coated silicon and equivalent silicon thin-film electrodes, respectively. Copper-coated silicon thin-film electrodes also show higher cycling efficiency, resulting in lower capacity fade, than equivalent silicon thin-film electrodes. We believe that copper appears to act as a glue that binds the electrode together and prevents the electronic isolation of silicon particles, thereby decreasing capacity loss. Rate capability decreases significantly at higher copper coating thicknesses as the silicon active material is not accessed, suggesting that the thickness and porosity of the copper coating need to be optimized for enhanced capacity retention and rate capability in this system.     

Surface structural disordering in graphite upon lithium intercalation/deintercalation

We report on the origin of the surface structural disordering in graphite anodes induced by lithium intercalation and deintercalation processes. Average Raman spectra of graphitic anodes reveal that cycling at potentials that correspond to low lithium concentrations in Li_xC (0 ≤ x < 0.16) is responsible for most of the structural damage observed at the graphite surface. The extent of surface structural disorder in graphite is significantly reduced for the anodes that were cycled at potentials where stage-1 and stage-2 compounds (x > 0.33) are present. Electrochemical impedance spectra show larger interfacial impedance for the electrodes that were fully delithiated during cycling as compared to electrodes that were cycled at lower potentials (U < 0.15 V vs. Li/Li⁺). Steep Li⁺ surface-bulk concentration gradients at the surface of graphite during early stages of intercalation processes, and the inherent increase of the Li_xC d-spacing tend to induce local stresses at the edges of graphene layers, and lead to the breakage of C-C bonds. The exposed graphite edge sites react with the electrolyte to (re)form the SEI layer, which leads to gradual degradation of the graphite anode, and causes reversible capacity loss in a lithium-ion battery.     

Detailed map of oxidative post-translational modifications of human p21ras using Fourier transform mass spectrometry

P21ras, the translation product of the most commonly mutated oncogene, is a small guanine nucleotide exchange protein. Oxidant-induced post-translational modifications of p21ras including S-nitrosation and S-glutathiolation have been demonstrated to modulate its activity. Structural characterization of this protein is critical to further understanding of the biological functions of p21ras. In this study, high-resolution and high mass accuracy Fourier transform mass spectrometry was utilized to map, in detail, the post-translational modifications of p21ras (H-ras) exposed to oxidants by combining bottom-up and top-down techniques. For peroxynitrite-treated p21ras, five oxidized methionines, five nitrated tyrosines, and at least two oxidized cysteines (including C118) were identified by "bottom-up" analysis, and the major oxidative modification of C118, Cys118-SO3H, was confirmed by several tandem mass spectrometry experiments. Additionally, "top-down" analysis was conducted on p21ras S-glutathiolated by oxidized glutathione and identified C118 as the major site of glutathiolation among the four surface cysteines. The present study provides a paradigm for an effective and efficient method not only for mapping post-translational modifications of proteins but also for predicting the relative selectivity and specificity of oxidative post-translational modifications, especially using top-down analysis.     

In situ measurements of stress evolution in silicon thin films during electrochemical lithiation and delithiation

We report in situ measurements of stress evolution in a silicon thin-film electrode during electrochemical lithiation and delithiation by using the multi-beam optical sensor (MOS) technique. Upon lithiation, due to substrate constraint, the silicon electrode initially undergoes elastic deformation, resulting in rapid rise of compressive stress. The electrode begins to deform plastically at a compressive stress of ca. −1.75 GPa; subsequent lithiation results in continued plastic strain, dissipating mechanical energy. Upon delithiation, the electrode first undergoes elastic straining in the opposite direction, leading to a tensile stress of ca. 1 GPa; subsequently, it deforms plastically during the rest of delithiation. The plastic flow stress evolves continuously with lithium concentration. Thus, mechanical energy is dissipated in plastic deformation during both lithiation and delithiation, and it can be calculated from the stress measurements; we show that it is comparable to the polarization loss. Upon current interruption, both the film stress and the electrode potential relax with similar time constants, suggesting that stress contributes significantly to the chemical potential of lithiated silicon.     

Enhancement of protection of aluminum through dopamine impregnation into hybrid sol–gel monolayers

The present work involves the incorporation of dopamine (DA) into the hybrid sol–gel monolayers (Hy) consisting of (3-glycidoxypropyl)methyldiethoxysilane and Tetraethyl orthosilicate. The resultant doped hybrid layers coated over aluminum surface was characterized by FT-IR, UV–Vis, XRD, EDX and SEM analyses. The corrosion behavior of bare and coated aluminum substrates in 3.5 % NaCl medium was examined by cyclic voltammetry, potentiodynamic polarization and electrochemical impedance spectroscopy techniques. Results from the electrochemical measurements showed that the DA impregnated Hy sol–gel monolayers offered better corrosion protection with superior coating thickness than the Hy sol–gel monolayers without DA. The enhancement of protection could be attributed to the fact that DA promote the formation of strongly bonded and densely packed monolayer films, which show better adhesion than the conventional silane systems.     

Corrosion protection behaviour of sol–gel derived N,N-dimethylthiourea doped 3-glycidoxypropyltrimethoxysilane on aluminium

The present work describes the anticorrosion features of inhibitor doped sol–gel coating on Al metal. Sol–gel coatings were prepared by using 3-glycidoxypropyltrimethoxysilane (GPTMS) as parent precursor. In order to improve the corrosion resistance property of coating, N,N-dimethylthiourea was added into the sol–gel matrix. The corrosion inhibitor doped sol–gel coating on metal was characterized by Fourier transform infrared analysis (FTIR) and scanning electron microscope (SEM). Inhibition effect of N,N-dimethylthiourea doped GPTMS coating on Al substrates in 1% NaCl solution was investigated using electrochemical impedance (EIS) and polarization studies. EIS results showed that the corrosion resistance of sol–gel coating significantly improved upon addition of N,N-dimethylthiourea. The study had outlined the nuances of doping an organic inhibitor to enhance the protection ability of sol–gel coating on Al metal.