High char‐yielding poly[acrylonitrile‐co‐(itaconic acid)‐co‐(methyl acrylate)]: synthesis and properties

Polyacrylonitrile terpolymers of various compositions consisting of acrylonitrile (AN), itaconic acid (IA) and methyl acrylate (MA) were synthesized by solution polymerization in dimethylsulfoxide. Increase in concentration of either IA or MA retarded the overall polymerization rate and the polymer molecular weight. The system consisting of AN + MA and varying IA concentration was more prone to retardation in comparison with the system composed of AN + IA with variable MA concentration. The retardation factors were quantified. Minor quantities of MA boost the reactivity of IA in the terpolymer system. The terpolymer was richer in MA vis‐à‐vis the feed. The thermal characteristics of the terpolymer were examined as a function of its composition. In contrast to the copolymer of AN and IA requiring 1–1.5 mol% IA, the terpolymer required an IA content of approximately 2.5 mol% for optimum thermal stability. The polymer with 90 mol% AN, 2.5 mol% IA and 7.5 mol% MA exhibited reasonably good char‐forming characteristics and thermal stability. The overall crystallinity and crystallite size of the polymers were found to decrease on incorporation of the comonomers. The ‘aromatization index’ of the copolymer increased with the temperature of pyrolysis through re‐organization of the tetrahydropyridine ladder structure. Copyright © 2005 Society of Chemical Industry     

Nonlinear minimum-time control with pre- and post-actuation

This article studies the time-optimal output transition problem to change the system output, from an initial value (for all time ) to a final value (for all time ), for invertible nonlinear systems. The main contribution of the article is to show that the use of pre- and post-actuation input outside the transition interval I_T=[0,T] can reduce the transition time T beyond the standard bang–bang-type inputs for optimal state transition. The advantage of using pre- and post-actuation is demonstrated with an illustrative nonlinear example.     

Iterative image-based modeling and control for higher scanning probe microscope performance

In this article, we develop an image-based approach to model and control the dynamics of scanning probe microscopes (SPMs) during high-speed operations. SPMs are key enabling tools in the experimental investigation and manipulation of nano- and subnanoscale phenomena; however, the speed at which the SPM probe can be positioned over the sample surface is limited due to adverse dynamic effects. It is noted that SPM speed can be increased using model-based control techniques. Modeling the SPM dynamics is, however, challenging because currently available sensing methods do not measure the SPM tip directly. Additionally, the resolution of currently available sensing methods is limited by noise at higher bandwidth. Our main contribution is an iterative image-based modeling method which overcomes these modeling difficulties (caused by sensing limitations). The method is applied to model an experimental scanning tunneling microscope (STM) system and to achieve high-speed imaging. Specifically, we model the STM up to a frequency of 2000 Hz (corresponds to approximately 23 of the resonance frequency of our system) and achieve approximately 1.2% error in 1 nm square images at that same frequency.     

An integral solution to a nonlinear diffusion problem

The generalized Galerkin method (or the method of integral relations) is applied to the type of problem described by quasilinear parabolic equations. As an example the problem of nonlinear transient slab diffusion with a general reservoir boundary condition is worked out. The integral relations are given for an arbitrary number of strips, and solutions using up to seven strips have been obtained in order to investigate the convergence of the method.     

Ethylene Oligomerizations by Diazene Bridged Ni(II) Catalysts Derived from Pyrazole-Scaffold-Based Binucleating Ligands with Alkyl and Aryl Pendant Arms

Abstract  

The coordination and organometallic chemistry of a series of diazene (N₂)-bridged Ni(II) catalysts derived from pyrazole-scaffold-based ligands bearing alkyl and aryl pendent arms was investigated. Binucleating ligands were obtained as products of the condensation reaction between 3,5-dichloroformyl-1H-pyrazole and aliphatic/aromatic primary/secondary amines under anhydrous conditions. The Ni(II) catalysts were activated with ethyl aluminum sesquichloride (EASC) to oligomerize the ethylene mainly into C4, C6, C8, and C10 fractions with activities up to 1.2 and 0.5 × 10⁶ g (mol-Ni)⁻¹ bar⁻¹ h⁻¹ at 30 and 50 °C, respectively. All catalysts were found to be electrochemically active in the working potential range of −2 to +2 V. A change in the potential of Ni(II) was provoked by the N₄ donor bridging ligands, increasing the ethylene oligomerization activity.     

“String and bead” model of copper modified polycarbosilane: synthesis and applications

Journal of Materials Science - The synthesis of metal modified polycarbosilanes is currently an area of significant activity. These polymers can be processed to advanced materials such as ceramic...     

Simple and low-cost synthetic route for SiBCN ceramic powder from a boron-modified cyclotrisilazane

This study reports a simple and low-cost synthetic route for preparing SiBCN ceramic powder via pyrolysis of boron-modified cyclotrisilazane (BCTS). BCTS resins were synthesized by reacting boric acid with 1, 3, 5-trimethyl-1′, 3′, 5′-trivinylcyclotrisilazane (CTS) in the molar ratio of 1:1, 1:3, and 1:5. The boron modification in CTS resin resulted in optimum properties for preceramic polymers such as solubility in common solvents, processable viscosity (<20 cps) and high ceramic yield (>80 wt. %). The polymer to ceramic conversion was carried out at 1450 and 1650°C under a nitrogen atmosphere. The study demonstrated that the changes in CTS concentration and pyrolysis temperature significantly affected the evolution of ceramic phases, morphology, and elemental composition which were thoroughly investigated through XRD, SEM, and HRTEM techniques. The results revealed the formation of β-SiC, β-Si₃N₄, and oxide ceramic phases with BCTS in the molar ratio of 1:1 and 1:3; whereas, β-SiC, β-Si₃N₄, and turbostratic BN(C) ceramic phases were obtained with BCTS in the molar ratio of 1:5.     

A comparative study on Cf/PyC/SiC minicomposites prepared via CVI process for hypersonic engine application

Carbon fiber reinforced silicon carbide (SiC) minicomposites were prepared from three variants of commercially available carbon fibers, viz., T300‐3K, T300J‐3K, and T300‐6K. The SiC matrix infiltration was done via chemical vapor infiltration process using methyltrichlorosilane as the precursor. Minicomposites were characterized for the composition and morphology of the matrix material deposited. It was found that the matrix contains 2H‐SiC along with the major phase 3C‐SiC. Cyclic tensile tests were carried out on the composites to understand the damage mechanism and load bearing characteristics under cyclic loading conditions. The dependence of peak and residual strains on the fiber volume fraction was studied. Oxidation of the CMCs in air at 1500°C was studied and the result was explained based on a five part process.     

Microfluidics assisted fabrication of microspheres by poly(2–hydroxyethyl methacrylate)-block-poly(l-histidine) hybrid materials and their utilization as potential drug encapsulants

A new series of synthetic polymer bioconjugate hybrid materials consisting of poly(2-hydroxyethyl methacrylate)[p(HEMA)]as a synthetic polymer block and poly(l-histidine) [p(His)] as a polypeptide block were synthesized by combining atom transfer radical polymerization of HEMA with ring opening polymerization of benzyl-N-carboxy-l-histidine anhydride. The resulting biocompatible p(HEMA)₂₅-b-p(His)_n (n = 15, 25, 35, and 45) hybrid polymers were investigated for their use as pH-sensitive drug delivery system. Highly uniform microspheres were fabricated by using the microfluidics assisted self-assembly of these block polymers and utilized them as carriers for a chemotherapeutic agent doxorubicin and a beta-lactam antibiotic ampicillin for the evaluation of the drug-loading and release behaviors according to pH, demonstrating the release is sensitive to pH. The capability of the new p(HEMA)-b-p(His) hybrid materials to self-assemble in microenvironments and to effectively encapsulate drug molecules serves as suitable carriers for the delivery of drug molecules with varying physiochemical properties.     

High-speed solution switching using piezo-based micropositioningstages

Motion-induced vibration is a critical limitation in high-speed micropositioning stages used to achieve solution switching. Controlled rapid solution switching is used to study the fast activation and deactivation kinetics of ligand-gated ion-channel populations isolated in excised membrane patches--such studies are needed to understand fundamental mechanisms that mediate synaptic excitation and inhibition in the central nervous system. However, as the solution-switching speed is increased, vibration induced in the piezo-based positioning stages can result in undesired, repeated, ligand application to the excised patch. The article describes a method to use knowledge of the piezo-stage's vibrational dynamics to compensate for and reduce these unwanted vibrations. The method was experimentally verified using an open-electrode technique, and fast solution switching (100 micros range) was achieved.