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     

Analysis of polar compound classes in SRC-II liquids: Comparison of non-aqueous titrametric,i.r. spectrometric and h.p.l.c. methods

Results for various types of polar compounds in SRC-11 coal-derived liquids and other fuels were obtained by one or more of the three analytical methods: non-aqueous titration, i.r. spectroscopy and h.p.l.c. Practical aspects as well as precision, accuracy and assumptions necessary for effective application of each of the methods are discussed. H.p.l.c. is applicable to the widest variety of compound types, is the most rapid, most sensitive and shows the best promise for increased development and improvement. Application and development of these techniques is a logical step toward improving process monitoring, catalyst development, toxicological screening and general fuel analysis.     

Experimental Investigation of FRP-Strengthened RC Beam-Column Joints

The results of a comprehensive experimental program, aimed at providing a fundamental understanding of the behavior of shear-critical exterior reinforced concrete (RC) joints strengthened with fiber reinforced polymers (FRP) under simulated seismic load, are presented in this study. The role of various parameters on the effectiveness of FRP is examined through 2/3-scale testing of 18 exterior RC joints. Conclusions are drawn on the basis of certain load versus imposed displacement response characteristics, comprising the strength (maximum lateral load), the stiffness, and the cumulative energy dissipation capacity. The results demonstrate the important role of mechanical anchorages in limiting premature debonding, and they provide important information on the role of various parameters, including: area fraction of FRP; distribution of FRP between the beam and the column; column axial load; internal joint (steel) reinforcement; initial damage; carbon versus glass fibers; sheets versus strips; and effect of transverse beams.     

Preparation of ultra‐low‐density microcellular materials

Microcellular polymeric materials can be obtained by the polymerization of a high‐internal‐phase emulsion. These materials are good candidates as targets toward inertial confinement fusion. This application requires severe specifications, including a very low density and a small cell size. In this study, we examined the influence of parameters such as emulsification conditions, surfactant nature, and the presence of a porogen on the obtainment of those requirements. It was possible to obtain microcellular polymeric foams with apparent densities as low as 0.0126 g/cm³. However, it was difficult to obtain very low material density and still maintain a small average pore size. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 96: 2053–2063, 2005     

Comparison between the binding of chlorpheniramine maleate to poly(sodium 4-styrenesulfonate) and the binding to other polyelectrolytes

The interactions of the antihistaminic drug chlorpheniramine maleate (CPM) with the negatively charged polyelectrolytes poly(sodium 4-styrenesulfonate) (PSS) and poly(acrylic acid) (PAA) are studied by the washing method of the diafiltration technique at conditions simulating those of the small intestine such as pH 7.5 and 0.13 M NaCl. The results are compared with those already reported involving other pharmacologically important polyelectrolytes such as alginic acid (ALG), carboxymethylcellulose (CMC), and κ- and ι-carrageenan (κ- and ι-CAR). As in the case of ALG, CMC, and CAR, interactions of CPM with PAA appear to be electrostatic and are cleaved in the presence of 0.13 M NaCl. On the contrary, apart from electrostatic interactions, additional interactions are found with PSS and residual interactions are kept in the presence of 0.13 M NaCl, a fact that may be attributed to π-π interactions and hydrophobic forces. The effect of the addition of 4 M urea, branched poly(ethyleneimine) (BPEI), and poly(vinylpyrrolidone) (PVP) is also studied. The addition of urea 4 M or 0.001 M BPEI produces a decrease on the amounts of counterions bound to PSS at infinite elution, while the addition of PVP does not produce any change on the diafiltration profiles.     

A Monte Carlo simulation study of the mechanical and conformational properties of networks of helical polymers. I. General concepts

We study the mechanical and conformational properties of networks of helical polymers with a combination of Monte Carlo simulations based on the Wang-Landau algorithm and the three-chain model. We find that the stress-strain behavior of these networks has novel features not observed in typical networks made of synthetic polymers. In particular, we find that as these networks are stretched they first strengthen, then soften and finally strengthen again. This non-monotonic behavior of the stress correlates with the one of the helical content and is rationalized by the elongation-induced formation and melting of the helical structure of the polymer. We complement these results with a study of other conformational properties of the polymer strands that clarify the molecular mechanisms behind the mechanical behavior of these networks. Finally, we present a qualitative comparison of some of our results with the theoretical ones recently reported by Kutter and Terentjev.     

Biodegradable hollow microfibres to produce bioactive scaffolds

Biodegradable hollow microfibres containing particles loaded with specific active agents can be potentially employed to produce a special kind of substrate for tissue engineering, able to function as a scaffold and at the same time to act as a drug‐releasing system. Biodegradable hollow microfibres based on poly(lactic acid) were produced by a dry–wet spinning procedure. Drug‐loaded microparticles were prepared by a simple oil‐in‐water emulsion and entrapped inside the fibres. The morphology of both fibres and particles was investigated by scanning electron microscopy. The mechanical and thermal properties of the fibres were investigated by tensile tests and differential scanning calorimetry. In vitro tests were performed to evaluate the release of the drug from the fibres loaded with the particles Copyright © 2004 Society of Chemical Industry     

Phase transition of LCP fluids confined in nanochannels through MD simulation

Manipulation of molecular orientation alignment in MCTLCPs (main-chain thermotropic liquid crystalline polymers) by pure shear at nano scale has been investigated for the first time using molecular dynamics (MD) simulation. Results indicate that high planar shear induces long-range uniform orientation ordering (liquid crystalline phase) of initially randomly orientated molecules of MCTLCP fluid confined in a nanochannel, which is confirmed by analyzing the orientation order parameter and the snapshots of MCTLCP liquid in a nanochannel under different shear rates. Insights into the origin of the phase transition phenomena are given at molecular level through investigating the thermodynamic density distribution of MCTLCP molecules in the nanochannel, suggesting that the energy shift due to a radical jump of system density affects both the magnitude and the orientation of the molecular ordering. Simulation results also show that there is a critical shear rate for transforming isotropic phase into liquid crystalline phase. The critical shear rate is dependent on the temperature of the MCTLCP system. Findings in this paper may present useful information for processing TLCP molecules at nano scale and the understanding of nanoflow.     

Nanocrystalline TiO2 photosensitized with natural polymers with enhanced efficiency from 400 to 600 nm

TiO₂ sensitization for solar applications requires not only efficient but also stable and inexpensive sensitizers. Different condensed tannins extracted from bark wastes of tropical wood trees were studied as possible sensitizers of TiO₂. These natural polymers adhere strongly to the TiO₂ even from aqueous solutions. Absorption spectra are presented for 1 mM aqueous sensitizing solutions prepared with lyophilized condensed tannins which absorb light in the visible range. Spectral photocurrent measurements and I–V characterization show that no bias is required for electron injection to the TiO₂ from all studied condensed tannins. Incident photon to current efficiency (IPCE) analysis indicates that surface complexation originates absorption bands with different electron injection efficiencies. These play a dominant role in determining IPCE spectral shape. We propose that surface modification by the sensitizer changes the surface trap density, thereby decreasing recombination losses.     

Deflection Calculation of FRP Reinforced Concrete Beams Based on Modifications to the Existing Branson Equation

Fundamental concepts of tension stiffening are used to explain why Branson’s equation for the effective moment of inertia Ie does not predict deflection well for fiber reinforced polymer (FRP) reinforced concrete beams. The tension stiffening component in Branson’s equation is shown to depend on the ratio of gross-to-cracked moment of inertia (Ig/Icr), and gives too much tension stiffening for beams with an Ig/Icr ratio greater than 3. FRP beams typically have an Ig/Icr ratio greater than 5, leading to a much stiffer response and underprediction of computed deflections as observed by others in the past. One common approach to computing deflection of FRP reinforced concrete beams has been to use a modified form of the Branson equation. This paper presents a rational development of appropriate modification factors needed to reduce the tension stiffening component in Branson’s original expression to realistic levels. Computed deflections using this approach give reasonable results with the right modification factor, and compare well with a more general unified approach that incorporates a realistic tension stiffening model. Comparison is made with the existing and past correction factors recommended by ACI 440 for predicting deflection of FRP beams. The method presently used by ACI 440 gives reasonable estimates of deflection for glass and carbon FRP reinforced beams. However, this method underestimates deflection of aramid FRP reinforced beams and is restricted to rectangular sections. A proposal is made for adoption of a simple modification factor that works well for all types of FRP bar and beam cross-sectional shape.