Polymerization of ionic monomers in polar solvents: kinetics and mechanism of the free radical copolymerization of acrylamide/acrylic acid

A precise data set describing the kinetics of the free radical copolymerization of acrylamide/acrylic acid (AM/AA) in the range of low total monomer concentration as a function of the pH, total monomer concentration, initiator concentration, and comonomer ratio is presented. Strong impact on the reactivity ratios has been identified for the pH and total monomer concentration. Specifically, at constant total monomer concentration of 0.4 mol/l and T=313 K the reactivity ratio of AM increases from 0.54 at pH 1.8 to 3.04 at pH 12. Contrarily, the reactivity ratio of AA decreases from 1.48 to 0.32. The crossover occurs at pH≈4.2. Electrostatic effects due to the variation of the degree of ionization of AA are primarily suggested to influence the kinetics. When the total monomer concentration increases from 0.2 to 0.6 mol/l at constant pH=12, the reactivity ratios of AM and AA decrease from 4.01 to 2.13 and increase from 0.25 to 0.47, respectively. Reduction of electrostatic repulsion between the ionized monomer AA and partially charged growing polymer chain ends due to higher ionic strength at higher total monomer concentration serves as explanation of the effect. The precise data set is the prerequisite for a novel approach to calculate copolymer compositions in case of variable monomer reactivity.     

A benchmark on the calculation of kinetic parameters based on reactivity effect experiments in the CROCUS reactor

Measurements in the CROCUS reactor at EPFL, Lausanne, are reported for the critical water level and the inverse reactor period for several different sets of delayed supercritical conditions. The experimental configurations were also calculated by four different calculation methods. For each of the supercritical configurations, the absolute reactivity value has been determined in two different ways, viz.: (i) through direct comparison of the multiplication factor obtained employing a given calculation method with the corresponding value for the critical case (calculated reactivity: ρ_calc); (ii) by application of the inhour equation using the kinetic parameters obtained for the critical configuration and the measured inverse reactor period (measured reactivity: ρ_meas). The calculated multiplication factors for the reference critical configuration, as well as ρ_calc for the supercritical cases, are found to be in good agreement. However, the values of ρ_meas produced by two of the applied calculation methods differ appreciably from the corresponding ρ_calc values, clearly indicating deficiencies in the kinetic parameters obtained from these methods.     

Study on the behaviour of ZnCoCu alloy electroplating

Ternary zinc–cobalt–copper alloys of wide range composition were deposited on to steel substrates from dilute metal sulphate bath. The bath consisted of 1–20 g dm⁻³ CuSO₄·5H₂O, 1–30 g dm⁻³ CoSO₄·7H₂O, 1–50 g dm⁻³ ZnSO₄·7H₂O, 20 g dm⁻³ Na₂SO₄ and 150–200 g dm⁻³ NH₂CH₂COOH. The effect of bath composition, current density and temperature on the cathodic potential, cathodic current efficiency and composition of the deposits were investigated. The codeposition of ZnCoCu alloys from these solutions can be classified as regular. Increasing current density enhances the rate of Zn deposition but suppresses that of Cu deposition. However, increasing the bath temperature favours Cu deposition. Co content in the deposits is hardly affected by changing these variables. Increasing Cu content in the bath or increasing the applied current density greatly improves the cathodic efficiency for the alloy deposition. X-ray diffraction studies showed that the deposits obtained at high current density (Zn-rich alloy) consisted of a cubic CuZn₂ phase, while that obtained at high temperature (Cu-rich alloy) consisted of a face, centred cubic CuCo phase. The structure and morphology of the deposited alloys were characterised by anodic stripping and SEM.     

A Multiagent System for the Reliable Execution of Automatically Composed Ad-hoc Processes

This article presents an architecture to automatically create ad-hoc processes for complex value-added services and to execute them in a reliable way. The uniqueness of ad-hoc processes is to support users not only in standardized situations like traditional workflows do, but also in unique non-recurring situations. Based on user requirements, a service composition engine generates such ad-hoc processes, which integrate individual services in order to provide the desired functionality. Our infrastructure executes ad-hoc processes by transactional agents in a peer-to-peer style. The process execution is thereby performed under transactional guarantees. Moreover, the service composition engine is used to re-plan in the case of execution failures. The work presented in this article was supported by the Swiss National Science Foundation as part of the project MAGIC (FNRS-68155), as well as by the Swiss National Funding Agency OFES as part of the European projects KnowledgeWeb (FP6-507482) and DIP (FP6-507483). Authors in alphabetic order     

Processing-morphology relationships of compatibilized polyolefin/polyamide blends

The emulsifying effect of a polyethylene-based ionomer on the phase size/composition relationship was studied for polypropylene/polyamide and polyethylene/polyamide blends. The particle size measured for the uncompatibilized blends increased with minor phase concentration, particularly as the region of dual phase continuity was approached. This relationship was less pronounced when ionomer was added, and the dimensions of the dispersed phase were significantly reduced. A narrowing of the region of dual phase continuity was observed due to the addition of ionomer. An increase in the torque measured during melt blending in a Brabender mixing chamber resulted when ionomer was added, due to the increase in the interactions at the interface. The particle size determined for the uncompatibilized blends increased with viscosity ratio. The effect was also less pronounced for the compatibilized blends. From these observations, it was possible to conclude that the effect of interfacial modification on morphology predominates over that of composition and viscosity ratio. The effects were interpreted in terms of the reduction of interfacial mobility due to the compatibilization.