Modeling evidence in support of coagulative nucleation theory

An extensive lumped model was developed for emulsion polymerization. It incorporated all of the complex processes: aqueous‐phase radical balances for all radical species arising from initiator decomposition and from exit; determination of radical number inside the particles by balance among rates of radical entry into, exit from, and termination inside the particles; determination of the monomer concentration inside the particles and in the aqueous phase by a thermodynamic equation; and particle formation by micellar, homogeneous, and coagulative nucleation. Model validation was done for the system with styrene (monomer), potassium persulfate (initiator), and sodium dodeceyl sulfate (emulsifier) and for the variables, which included the duration of nucleation, conversion at the end of nucleation, and total number of particles formed. The validation process revealed that coagulation during nucleation needed to be included in the model, even for emulsifier concentrations above the critical micelle concentration. The model predictions were in good quantitative agreement with the experimental data. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011.     

Shelf‐life prediction of perilla oil by considering the induction period of lipid oxidation

Kinetic models for the induction period (IP) of lipid oxidation were developed to predict the shelf‐life of perilla oil during storage. The degree of lipid oxidation was measured in terms of peroxide values (PV). The perilla oil was stored in the dark at various temperatures. The IP was measured at the intersection point of two linear lines and in terms of time and PV at the IP. The IP was expressed by an Arrhenius‐like relationship. Before and after the IP, the reaction followed pseudo‐zero‐order kinetics. The oxidation degrees according to storage times were computed by considering the variables, IP and reaction rate constants. The prediction model equation that was developed to determine shelf‐life is more accurate than in previous studies. Conclusively, considering the IP of lipid oxidation is essential for predicting the shelf‐life of perilla oil and is expected to be applicable to other vegetable oils. Practical applications : In kinetic modeling for shelf‐life estimation in terms of lipid oxidation, induction period (IP) is rarely considered. Thus the estimation of peroxide values (PV) from such models might be inaccurate. The IP was observed in perilla oil oxidation and kinetic models involving the IP were developed. This work enables a better estimation of oxidation. Besides, a shelf‐life diagram of perilla oil has been constructed as a valuable tool for quality control in the food industry.     

On‐line determination of the conversion in a styrene bulk polymerization batch reactor using near‐infrared spectroscopy

A fast on‐line method for measuring the monomer conversion of a styrene batch polymerization reaction with near‐infrared spectroscopy (NIR) has been developed. Multivariate calibration was performed, using polymer samples having temperatures around the set point of the batch reactor (75–85°C) and monomer conversions up to 35%. The calibration model was built in such a way that the effect of the temperature on the predicted conversion of the sample was minimized. The method was validated in a number of batch runs. In these runs, the batch temperature and molar mass distributions of the polymer were varied. At‐line size‐exclusion chromatography was used as a reference method for measuring the monomer conversion. Results show that on‐line conversion monitoring with NIR offered overall an excellent accuracy (～ 0.32% conversion). For high and low monomer conversions a small bias in the predicted conversion is present. The method proved to be insensitive to both relative large changes (10°C) of the batch temperature and to considerable changes of the molar mass distribution of the polymer. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 84: 90–98, 2002; DOI 10.1002/app.10241     

Modelling the Effective Thermal Conductivity in Polydispersed Bed Systems: A Unified Approach using the Linear Packing Theory and Unit Cell Model

A comprehensive, unified approach, using the Linear Packing Theory and Unit Cell Model, is proposed for calculating of the effective thermal conductivity of polydispersed packed beds. In this new approach, the effect of packing density is incorporated by the use of (i) an initial porosity to take into account the packing of mono‐sized particles, and (ii) the packing size ratio as a measure of the particle‐particle interaction. The proposed approach was validated with the experimental measurements of binary and ternary beds. This new approach demonstrates that the effective thermal conductivity of beds composed of polydispersed particles can be simulated for any composition without the need to measure the in situ porosity.     

Ecological aspects of the manufacture and application of highly pure liquid substances

The action mechanism for aggressive and highly pure media on fluoropolymer constructional elements is assumed to consist of two basic microeffects: destructive changes in the fluoropolymer and contamination of the environment. Our approach to a quantitative estimation of the physicochemical stability is based on logic similar to that of a thermodynamic model of a two‐component system. A fluoropolymer and changes in its microstructure are considered the first component of the system. The second component is composed of liquid media contaminated with fluoroorganic compounds extracted from the fluoropolymer. The proposed methods for delivering aggressive and highly pure fluids to consumers allow the exclusion of pollution from working areas with gaseous products through an exception to a number of intermediate stages of product transport. The discussed principles allow the creation of a modern, highly effective, and safe (with respect to the ecology and raw materials) production of aggressive liquid chemicals for consumers. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 906–910, 2002     

Melt rheology and morphology of LLDPE/EVA blends: Effect of blend ratio,compatibilization, and dynamic crosslinking

The melt rheological properties of linear low‐density polyethylene (LLDPE)/ethylene vinyl acetate (EVA) blends were investigated with special reference to the effect of blend ratio, temperature, shear rate, compatibilization, and dynamic vulcanization. The melt viscosity of the blends determined with a capillary rheometer is found to decrease with an increase of shear rate, which is an indication of pseudoplastic behavior. The viscosity of the blend was found to be a nonadditive function of the viscosities of the component polymers. A negative deviation was observed because of the interlayer slip between the polar EVA and the nonpolar LLDPE phases. The melt viscosity of these blends decreases with the increased concentration of EVA. The morphology of the extrudate of the blends at different shear rates and blend ratios was studied and the size and distribution of the domains were examined by scanning electron microscopy. The morphology was found to depend on shear rate and blend ratio. Compatibilization of the blends with phenolic‐ and maleic‐modified LLDPE increased the melt viscosity at lower wt % of compatibilizer and then leveled off. Dynamic vulcanization is found to increase the melt viscosity at a lower concentration of DCP. The effect of temperature on melt viscosity of the blends was also studied. Finally, attempts were made to correlate the experimental data on melt viscosity and cocontinuity region with different theoretical models. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 86: 3210–3225, 2002     

The Statistical Regression Calculation in Plastics Processing – Process Analysis,Optimization and Monitoring

Plastics processing companies can only meet up to present‐day quality requirements if they adopt systematic methods. This holds particularly true for the extremely stringent demands that are now placed on injection molding technology. Working on from a sound experimental basis, it is possible to define cause/effect correlations for two sets of empirical data (the current process conditions and the molded part attributes) for each quality variable by using a statistical process model. The process model enables the processor to calculate the effect of each individual combination of parameters in the experimental area and to perform an optimization. If it proves possible to describe the cause/effect correlation between the fluctuations in the molded part attributes and those in the process parameters by means of a statistical process model, then this can be used for the continuous monitoring of production. The statistical experimentation method and continuous process monitoring are grouped together to form the so‐called CPC concept, permitting traceable, gap‐free documentation of the quality data for a production chain. Three examples are set out to illustrate the possibilities for use of the CPC concept; these are then assessed on the basis of the benefit observed.

Engine‐cooling fan.     

Valid parameter range analyses for chemical reaction kinetic models

The present work quantifies the relations between the structure of a chemical reaction kinetic model, its valid parameter range, and the truncation error tolerance of the model. General methods are presented to solve the three important problems of valid parameter range analysis: (1) identification of the valid parameter range of a kinetic model, (2) estimation of the error tolerance required when applying a kinetic model over a specified parameter range, and (3) improvement of existing model generation algorithms to construct more robust models. Finally, the relationship between a model's structure, its valid parameter range, and the truncation error tolerance are illustrated by the flexibility-tolerance-model graph. The new methods are applied to pyrolysis of methane/ethane mixtures.