Bulk free radical polymerizations of methyl methacrylateunder non-isothermal conditions and with intermediate additionof initiator: Experiments and modeling

Experimental data on the monomer conversion, x_m, and the weight average molecular weight, M_w, have been generated under several isothermal and non-isothermal conditions for the polymerization of methyl methacrylate in a rheometer-reactor assembly. The non-isothermal results, in particular, can be used to provide more stringent tests of kinetic models than isothermal data alone. A simple empirical model has been used to describe this system that accounts for the gel (Trommsdorff) and glass effects. The model involves only x_m and the temperature, and is quite general. The model parameters are tuned using only three sets of isothermal data. Good agreement is found between the experimental results and model predictions for a whole variety of experimental conditions, including non-isothermal operation and with intermediate addition of initiator. Because of its generality, this model is quite suitable for use for on-line optimizing control as well as for describing industrial reactors.     

Simulation of an industrial nylon 6 tubular reactor

A commonly used energy-efficient nylon 6 reactor is simulated under steady-state conditions. The effects of various operating conditions and parameters, e.g., feed composition, temperature and flow rate, heat transfer coefficients, and reactor dimensions, on the temperature and molecular weight profiles are studied. A temperature maximum is observed in the reactor under usual conditions of operation. The maximum value of the temperature is sensitive to the feed conditions, and one has to ensure that degradation reactions speeded up at high temperatures do not affect product characteristics. The model and the numerical technique used are fairly simple and account for most of the important features of industrial reactors. Hence, these can be used in the development of digital-control algorithms in the future.     

Polymers from renewable resources. I. Castor oil-based interpenetrating polymer networks: Thermal and mechanical properties

A number of polyurethanes (PUs) were synthesized by reacting castor oil with toluene-2,4-diisocyanate and hexamethylene diisocyanate and varying the NCO/OH ratio. All these polyurethanes were reacted with some acrylic monomers like ethyl acrylate, n-butyl acrylate, ethyl methacrylate, and butyl methacrylate using a crosslinker ethylene glycol dimethyl-acrylate and benzoyl peroxide as the initiator. The physicochemical properties of interpenetrating polymer networks (IPNs) are reported. Thermogravimetric analysis was used to study the thermal behavior of IPNs and the evaluation of kinetic parameters. Degradation mechanism has also been investigated. Some of the mechanical properties viz. tensile strength, shore-A hardness, elongation at break, etc. are also reported. © 1993 John Wiley & Sons, Inc.     

Detecting stable locality-aware predicates

In a large-scale locality-driven network such as in modular robotics and wireless sensor networks, knowing the state of a local area is sometimes necessary due to either interactions being local and driven by neighborhood proximity or the users being interested in the state of a certain region. We define locality-aware predicates (LAP) that aim at detecting a predicate within a specified area. We model the area of interest as the set of processes that are within a breadth-first search tree (BFST) of height k$k$ rooted at the initiator process. Although a locality-aware predicate specifies a predicate only within a local area, observing the area consistently requires considering the entire system in a consistent manner. This raises the challenge of making the complexities of the corresponding predicate detection algorithms scale-free, i.e., independent of the size of the system. Since all existing algorithms for getting a consistent view of the system require either a global snapshot of the entire system or vector clocks of the size of the system, a new solution is needed. We focus on stable LAP, which are those LAP that remain true once they become true. We propose a scale-free algorithm to detect stable LAP within a k$k$-height BFST. Our algorithm can detect both stable conjunctive LAP and stable relational LAP. In the process of designing our algorithm, we also propose the first distributed algorithm for building a BFST within an area of interest in a graph, and the first distributed algorithm for recording a consistent sub-cut within the area of interest. This paper demonstrates that LAPs are a natural fit for detecting distributed properties in large-scale distributed systems, and stable LAPs can be practically detected at low cost.     

Duration of slip-resistant shoe usage and the rate of slipping in limited-service restaurants: results from a prospective and crossover study

Several studies have indicated that slip-resistant shoes may have a positive effect on reducing the risk of slips and falls, a leading cause of injury at work. Few studies, however, have examined how duration of shoe usage affects their slip-resistance properties. This study examined the association between the duration of slip-resistant shoes usage and the self-reported rate of slipping in limited-service restaurant workers. A total of 475 workers from 36 limited-service restaurants in the USA were recruited to participate in a 12-week prospective study of workplace slipping. Of the 475 participants, 83 reported changing to a new pair of shoes at least once during the 12-week follow-up. The results show that slip-resistant shoes worn for less than six months were moderately more effective than those worn for more than six months. Changing to a new pair of shoes among those wearing slip-resistant shoes at baseline was associated with a 55% reduction in the rate of slipping (RR = 0.45, 95% CI = 0.23–0.89). Further research is needed to develop criteria for the replacement of slip-resistant shoes.

Practitioner Summary: The duration of usage impacts the slip-resistance properties of slip-resistant shoes. Slip-resistant shoes worn for less than six months were moderately more effective in reducing slips than slip-resistant shoes worn for more than six months. Shoe use policies should not only encourage or require their use but also include guidance on replacing slip-resistant shoes at regular intervals.     

Crystallization and phase transformation kinetics of poly(1-butene)/MWCNT nanocomposites

Poly(1-butene)/MWCNT nanocomposites were prepared by simple melt processing technique. Crystallization, crystal-to-crystal phase transformation and spherulitic morphology were studied using differential scanning calorimetry (DSC), wide angle X-ray diffraction (WAXD) and optical microscopy (OM). The non-isothermal crystallization exhibited higher values of Z_t derived from Avrami theory and lower values of F(T) obtained from Avrami-Ozawa analysis, while the isothermal crystallization revealed a significant increase in crystallization temperatures and lower crystallization half times compared to pristine PB. The observed changes in the crystallization kinetics were ascribed to the enhanced nucleation of PB in the presence of MWCNT. The nucleating activity calculated from the non-isothermal crystallization data revealed that the MWCNTs provide an active surface for the nucleation of PB. The optical micrographs exhibited significantly smaller crystallites with disordered morphology for the nanocomposites compared to the well defined spherulitic morphology for pristine PB. The rate of phase transformation from kinetically favored tetragonal to thermodynamically stable hexagonal form was noticeably enhanced as evidenced by the reduction in the half time for phase transformation from 58 h to 25 h for PB reinforced with 7% MWCNT.     

Effect of modified layered silicates and compatibilizer on properties of PMP/clay nanocomposites

The preparation and properties of poly(4‐methyl‐1‐pentene) (PMP)/clay nano‐composites are described for the first time. The effect of clay modification and compatibilizer on the formation and properties of the nanocomposites is studied. Layered silicates modified with two types of quaternary ammonium salts are used. The X‐ray diffraction results indicate intercalation of the polymer into the intergallery spacing of the clay. Thermogravimetric analysis shows a delay in the degradation process. Dynamic mechanical analysis shows an increase in the storage modulus for the nanocomposites. The use of compatibilizer containing maleic anhydride and acrylic ester groups is explored. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 3233–3238, 2003