Kinetics study of Ti[O(CH2)4OCHCH2]4 initiated ring‐opening polymerization of ε‐caprolactone by differential scanning calorimetry

Chemical shrinkage was used for the in situ measurement of the progressing chemical stabilization reactions and the influence of ozone during the stabilization of polyacrylonitrile. A method for evaluating the activation energy through the sensitivity temperature is presented. The calculated results show that the activation energies were 161.57 kJ/mol in air and 181.23 kJ/mol in ozone-enriched air. Therefore, the chemical reactions were postponed during stabilization in ozone-enriched air. Ozone seemed to act in three ways: first, ozone promoted the formation of the serious skin–core structure. Second, ozone accelerated the chemical reactions and shortened the stabilization time at lower heating rates. Third, ozone postponed the chemical reactions. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

A UML-based quantitative framework for early prediction of resource usage and load in distributed real-time systems

This paper presents a quantitative framework for early prediction of resource usage and load in distributed real-time systems (DRTS). The prediction is based on an analysis of UML 2.0 sequence diagrams, augmented with timing information, to extract timed-control flow information. It is aimed at improving the early predictability of a DRTS by offering a systematic approach to predict, at the design phase, system behavior in each time instant during its execution. Since behavioral models such as sequence diagrams are available in early design phases of the software life cycle, the framework enables resource analysis at a stage when design decisions are still easy to change. Though we provide a general framework, we use network traffic as an example resource type to illustrate how the approach is applied. We also indicate how usage and load analysis of other types of resources (e.g., CPU and memory) can be performed in a similar fashion. A case study illustrates the feasibility of the approach.

Dimensional Effects on Magnetic Properties of Fe–Si Steels Due to Laser and Mechanical Cutting

Microstructural deterioration near the cut line and presence of residual stresses both affect the magnetic properties of cut parts. In this paper, the differences between microstructural deterioration resulting from mechanical and laser cutting as well as the sample size effects observed upon hysteresis will be discussed. It will be shown that the underlying mechanism for changes in magnetic properties due to mechanical cutting is distinct from that of laser cutting.      

Methods to determine the growth domain in a multidimensional environmental space

Data from a database on microbial responses to the food environment (ComBase, see www.combase.cc) were used to study the boundary of growth several pathogens (Aeromonas hydrophila, Escherichia coli, Listeria monocytogenes, Yersinia enterocolitica). Two methods were used to evaluate the growth/no growth interface. The first one is an application of the Minimum Convex Polyhedron (MCP) introduced by Baranyi et al. [Baranyi, J., Ross, T., McMeekin, T., Roberts, T.A., 1996. The effect of parameterisation on the performance of empirical models used in Predictive Microbiology. Food Microbiol. 13, 83–91.]. The second method applies logistic regression to define the boundary of growth. The combination of these two different techniques can be a useful tool to handle the problem of extrapolation of predictive models at the growth limits.     

Kinetic and rheokinetic study of dicarboxylic fatty acid chain extension using a dioxazoline coupling agent

A kinetic and rheokinetic study of the condensation reaction of a dicarboxylic fatty acid, Pripol®1009 (C36), and a dioxazoline coupling agent (1,3‐Phenylene)‐bis(2‐Oxazoline) (OO) was made. The kinetic study showed a similar reactivity of the two acid groups of C36 and also a similar reactivity of the two oxazoline groups of OO. The reaction kinetics can be described using a second‐order kinetic model. A kinetic constant k = 16.1 × 10⁻⁴ mol⁻¹ s⁻¹ at 156°C with an activation energy E_a = 80.6 kJ mol⁻¹ was calculated. A rheological evaluation of the reactants and the obtained polymers showed that the reactive system had Newtonian behavior during all the reaction times for shear rates lower than 100 s⁻¹. Using this kinetic modeling and measured viscosity evolution of the reactive system at different temperatures, rheokinetic models were proposed for viscosity evolution with the molar mass evolution of the synthesized polymer and the reaction time and conversion. Viscosity evolution of the reactive system during the first 10 min, corresponding to a typical mean residence time in reactive extrusion, were calculated using the proposed rheokinetic model. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 74: 1017–1024, 1999     

Immiscible Blends of PC and PET,Current Knowledge and New Results: Rheological Properties

This paper deals with immiscible blends of poly(ethylene terephthalate) obtained by melt blending with polycarbonate. A large survey of the current knowledge in the field of these blends is presented. Resolved and unresolved issues concerning the effect of exchange reactions on the miscibility of the components are addressed. The experimental part of the paper focuses on the rheological behavior of PET/PC blends. Blends containing various polymer ratios were obtained by melt blending with and without transesterification catalysts. Oscillatory shear flow in the melt was used to characterize the rheology of the various samples. A plot of the oscillatory data, similar to the Van Gurp Palmen plot, is used to point out the broadening of the co‐continuity window when in situ compatibilization takes place.

     

Rheology of poly(n‐butyl methacrylate) and its composites with calcium carbonate

Poly(n‐butyl methacrylate) (PBMA) composites with calcium carbonate (CaCO₃) were prepared by in situ radical copolymerization of butyl methacrylate (BMA) and methacrylic acid (MA) with precipitated calcium carbonate. To compare the different rheological behaviors of the monomer mixtures with CaCO₃ and the composites, the steady and dynamic viscosities of BMA/MA/CaCO₃ and poly(BMA/MA/CaCO₃) were measured by means of steady and oscillatory shear flows. The viscosity of the mixture BMA/MA/CaCO₃ was found to increase evidently with the increasing of CaCO₃%. The influence of MA% on viscosity of BMA/MA/CaCO₃ was slight. During the in situ polymerization, the viscosity of the reacting system was measured to be enhanced by a factor of about 10⁴ from the monomer/CaCO₃ mixture to composites. The dependency of zero‐shear viscosity on molar mass of PBMA was also investigated. The relation between the zero‐shear viscosity and molar mass is η₀ = 10^?15 M_w^3.5. The evolution of the viscosity with the temperature for both PBMA and its composites was obtained and time–temperature superposition was used to build master curves for the dynamic moduli. The flow activation energies were found to be 115.0, 148.6, and 178.7 kJ/mol for PBMA, composite PBMA/CaCO₃ (90/10), and PBMA/MA/CaCO₃ (89/1/10), respectively. The viscosity of the composites containing less than 10% CaCO₃ was lower than that of pure PBMA with the same molar mass. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 88: 1376–1383, 2003     

Poly[ethylene‐co‐(vinyl alcohol)]‐graft‐poly(ε‐caprolactone) Synthesis by Reactive Extrusion, 1 ‐ Structural and Kinetic Study

Chemical modification of EVOH in the molten state at 185 °C by a grafting from process of poly(ε‐caprolactone) in batch was studied. ¹H NMR was used to characterize the structure evolutions of PCL grafts. In addition to grafting reactions, dynamic covalent transesterification reactions between EVOH residual alcohols and the polyester grafts led to a redistribution of the PCL grafts length. up to 27 and SR up to 80% were obtained. Experiments made in a corotating mini twin‐screw extruder also confirmed these results. The effect of the alcohol to caprolactone ratio and catalyst concentration (SnOct₂) on kinetic evolution showed that few minutes were necessary to complete the polymerization. A kinetic model was proposed and adequate conditions for the synthesis by reactive extrusion were defined.

     

Glycoalkaloids in potato tubers: the effect of variety and drought stress on the α‐solanine and α‐chaconine contents of potatoes

Six varieties of Solanum tuberosum L potato grown in the Bolivian highlands under drought stress, with and without irrigation, were analysed for their content of glycoalkaloids (GAs). The plant material consisted of three drought‐tolerant varieties from a local breeding programme (PROINPA), Potosina, Chapaquita and Pampeña, and three control cultivated varieties, Malcacho, Sani Imilla and Desiree, either susceptible or relatively tolerant to drought. α‐Solanine and α‐chaconine were quantified in both the peel and flesh of the tubers. A significant increase in GA concentration (α‐solanine + α‐chaconine) was observed under drought stress conditions in most varieties; average concentration increases of 43 and 50% were registered in the improved and control cultivars respectively. In all tested cultivars, however, the GA concentration remained lower than the recommended food safety level (200 mg kg⁻¹ fresh tubers). It ranged from 52.4 to 100 mg kg⁻¹ fresh tubers in the improved cultivars and from 55.6 to 122.3 mg kg⁻¹ fresh tubers in the controls. In the improved and control varieties the α‐solanine content averaged 42.6 and 35.4% of the total potato GAs respectively and was not significantly affected by drought stress, except in Desiree. In all conditions the peel contained the greatest proportion of total GAs. The hybrid variety Pampeña (new drought‐tolerant variety) contained the lowest amounts of GAs, which were lower than those of the control varieties, with and without irrigation. © 2000 Society of Chemical Industry     

Dispersed phase morphology and fractionated crystallization of high-density polyethylene in PET/HDPE blends

The fractionated crystallization of high density polyethylene dispersed in a poly(ethylene terephthalate) matrix at composition of 15 wt-% was studied. The effect of the molecular weight of polyethylene with and without compatibilization was particularly addressed regarding its influence on the morphology of the blends. For non-compatibilized blends, the dramatic influence of the molecular weight of the polyethylene on the viscosity ratio and therefore on the dispersion is reflected on the relative intensities of the twin crystallization peaks of polyethylene that are developed upon cooling. These peaks reflect two sets of particles that are nucleated by more or less active heterogeneities. The influence of the addition of an ethylene-glycidyl methacrylate copolymer on the morphology and on the crystallization of the blends was also investigated. For a high molecular weight polyethylene, the compatibilizer shows less efficiency as far as dispersion is concerned.