Control of free-radical emulsion polymerization of methyl methacrylate by oxygen injection. II. Experimental study

Oxygen injection has been proposed and experimentally demonstrated as an effective control measure for limiting the rate of heat release and altering the rate of polymerization in emulsion processes. A detailed mathematical model has been previously developed to describe the system behavior with and without oxygen injection. A simple lab scale apparatus was constructed and run extensively. Only trace quantities of oxygen are needed to inhibit the reaction completely. The facile response makes this method attractive for fast temperature control. However, because of the rapid penetration of dissolved oxygen into the polymer particles, growing radical chains are terminated prematurely, lowering product molecular weights. To minimize this detrimental effect, pulsed oxygen control is used and extensive experimental work was performed to determine the effects of controller set points on molecular weight. Moderate oxygen flows and moderate set point temperatures are found to give the optimal response without significant lowering of the final molecular weight. Injected quantities agree well with the order-of-magnitude sparging calculations needed to completely stop initiation. However, complete agreement between model simulations and experimental results was not reached due to an unmeasured loss of monomer from the reactor. Chain transfer to monomer is found to be important in modeling the polymer molecular weight. It has, however, a negligible effect on the reaction rate.     

Modeling of polypropylene degradation during reactive extrusion with implications for process control

This paper presents the development of a model for free radical initiated polypropylene degradation during reactive extrusion that combines a kinetic model of the polypropylene degradation reaction with a simplified model of the melting mechanism in the extruder. The free radical initiated degradation of polypropylene is characterized by a narrowing of the molecular weight distribution (MWD) and a decrease in the molecular weight averages. A high temperature SEC is used to determine MWD's for three different commercially available polypropylenes degraded at various initiator concentrations in a 1.5 inch single screw extruder (L/D = 24:1). The predictions of the kinetic model alone and the combined kinetic-melting model are compared with the experimentally determined MWD's and molecular weight averages for the degraded polypropylenes. The predictions of a modified kinetic model that includes the possibility of termination by combination are also examined. The kinetic-melting model is found to provide significantly improved predictions of the experimentally determined MWD's and molecular weight averages in comparison to the original kinetic model. A viscosity-molecular weight relationship is also developed, which is then used to determine the gain of the degradation process as a function of the initiator concentration from the molecular weight averages predicted by the kinetic-melting model. Earlier work has shown such prior knowledge of the process gain can be used to significantly improve the performance of process control schemes for the degradation process.     

Polymer reactors and molecular weight distribution. VIII. A method of interpreting skewed GPC chromatograms

A new-method of interpreting GPC chromatograms which accounts for skewing and symmetrical axial dispersion has been developed. General relationships for a symmetrical axial dispersion correction and for a skewing correction are derived. The method has been verified experimentally for unimodal chromatograms and linear calibration curves over a wide range of GPC operating conditions, polymer molecular weights and polydispersities. Measurements of h and skewing factors were obtained by a once-through technique. The need for performing reverse flow experiments has been eliminated. Artificial oscillations in the corrected chromatogram due to step size (Method of Pierce-Armonas), and to number of terms in a polynomial expansion (Method of Tung and Method of Smith) are eliminated. The method has yet to be evaluated for nonlinear calibration curves and multi-modal distributions. However, suggestions for its application in these circumstances are presented.     

The compatibility of linear low density polyethylene-polypropylene blends: Viscosity ratio plots

Blends of linear low density polyethylene (LLDPE) and polypropylene (PP) show diverse mechanical property behavior in the published literature. The main objectives of this work were: to investigate the effect of viscosity of the component phases on the mechanical properties of such blends and to use the results to obtain a method for compatibilizing diaper manufacturing waste. The significant result of the study was that although LLDPE/PP blends are often termed “incompatible,” when viscosity of the components was more closely matched to each other, increases of as much as 50% in tensile strength and modulus were observed over the “rule of mixtures” line. Also, scanning electron microscopy then showed a more diffuse interface between the component phases. Three dimensional views of plots of viscosity ratio of the blend components as a function of temperature and shear rate were used to demonstrate the closer matching of viscosities for the blend components of the higher performing blends. In processing diaper manufacturing waste, addition of a high molecular weight PP in a manufacturing scale single screw extruder, to provide a closer match of viscosities of the blend components, significantly improved mechanical properties.     

Improvement of cyclodextrin glucanotransferase as an antistaling enzyme by error-prone PCR

In an effort to improve the properties of cyclodextrin glucanotransferase (CGTase) as an antistaling enzyme, error-prone PCR was used to introduce random mutations into a CGTase cloned from alkalophilic Bacillus sp. I-5 (CGTase I-5). A mutant CGTase[3-18] with the three mutations M234T, F259I and V591A was selected by agar plate assay. Sequence alignment of various CGTases indicated that M234 and F259 are located in the vicinity of the catalytic sites of the enzyme and V591 in the starch binding domain E. The cyclization activity of CGTase[3-18] was dramatically decreased by 10-fold, while the hydrolyzing activity was increased by up to 15-fold. These mutations near subsite +1 (M234T) and at subsite +2 (F259I) are likely to alter the enzyme activity in a concerted manner, promoting hydrolysis of substrate while retarding cyclization. The addition of CGTase[3-18] reduced the retrogradation rate of bread by as much as did the commercial antistaling enzyme Novamyl during 7-day storage at 4 degrees C. No cyclodextrin (CD) was detected in bread treated with CGTase[3-18], whereas 21 mg of CD per 10 g of bread was produced in bread treated with wild-type CGTase.     

Torrefied agro-industrial residue as filler in natural rubber compounds

This study explored the feasibility of using torrefied biomass as a reinforcing filler in natural rubber compounds. Carbon black was then replaced with the torrefied biomass in elastomer formulations for concentrations varying from 0% to 100% (60 parts per hundred rubber or phr total). Their influence on the curing process, dynamic properties, and mechanical properties was investigated. Results were compared with the properties of vulcanizates containing solely carbon black fillers. Time to cure (t₉₀) for compounds with torrefied biomass fillers increased, while filler-filler interactions (ΔG') decreased, compared to carbon black controls. At low strains, the tan δ values of the torrefied fillers vulcanizates were similar to the controls. Incorporation of torrefied biomass into natural rubber decreased compound tensile strength and modulus but increased elongation. Replacement with torrefied fillers resulted in a weaker filler network in the matrix. Still, results showed that moderate substitution concentrations (~20 phr) could be feasible for some natural rubber applications.     

Hypermedia Support for Software Development: A Retrospective Assessment

Hypermedia technologies have been available for about a decade. Beginning with Douglas Engelbart, researchers have become interested in applying hypermedia concepts and technologies to software development. This paper assesses this symbiosis between hypermedia and software development as described by research contributions; by our count, more than one hundred articles. To date, no collection of, or guide to, this literature has been published. A number of significant contributions are classified, described, and appraised — providing a guide into what has been a rich but perhaps under-reported research area. Hypermedia has made significant contributions to software development in three primary areas: coping with massive amounts of information associated with software development projects; establishing and maintaining linkages between various types of software engineering documents; and enabling development engineers to record, document, and preserve knowledge about development thoughts, processes and rationale. These contributions may help direct the focus of future research towards building on, combining and assessing the resulting contributions. A research agenda is proposed along these lines.     

Autobiographical Accounts of Students' Experiences Learning Mathematics: A Review

ABSTRACT

In this article, we review published literature that draws on autobiographical accounts of students' experiences learning mathematics. We summarize the main findings of the target literature and present recommendations for further research that will extend this field. Our review indicates that autobiographical and narrative methodological approaches have the potential to occasion important advances in our knowledge of students' experiences learning mathematics. However, relative to accounts of preservice teacher learning, there is a paucity of published research that documents the mathematics learning experiences of kindergarten to Grade 12 students.