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.     

Simultaneous sulfide and acetate oxidation under denitrifying conditions using an inverse fluidized bed reactor

BACKGROUND: Simultaneous removal of sulfur, nitrogen and carbon compounds from wastewaters is a commercially important biological process. The objective was to evaluate the influence of the CH₃COO^?/NO₃^? molar ratio on the sulfide oxidation process using an inverse fluidized bed reactor (IFBR). RESULTS: Three molar ratios of CH₃COO^?/NO₃^? (0.85, 0.72 and 0.62) with a constant S^2?/NO₃^? molar ratio of 0.13 were evaluated. At a CH₃COO^?/NO₃^? molar ratio of 0.85, the nitrate, acetate and sulfide removal efficiencies were approximately 100%. The N₂ yield (g N₂ g^?1 NO₃^?‐N consumed) was 0.81. Acetate was mineralized, resulting in a yield of 0.65 g inorganic‐C g^?1 CH₃COO^?‐C consumed. Sulfide was partially oxidized to S⁰, and 71% of the S^2? consumed was recovered as elemental sulfur by a settler installed in the IFBR. At a CH₃COO^?/NO₃^? molar ratio of 0.72, the efficiencies of nitrate, acetate and sulfide consumption were of 100%, with N₂ and inorganic‐C yields of 0.84 and 0.69, respectively. The sulfide was recovered as sulfate instead of S⁰, with a yield of 0.92 g SO₄^2?‐S g^?1 S^2? consumed. CONCLUSIONS: The CH₃COO^?/NO₃^? molar ratio was shown to be an important parameter that can be used to control the fate of sulfide oxidation to either S⁰ or sulfate. In this study, the potential of denitrification for the simultaneous removal of organic matter, sulfide and nitrate from wastewaters was demonstrated, obtaining CO₂, S⁰ and N₂ as the major end products. Copyright © 2008 Society of Chemical Industry     

A comparison of algorithms for control constrained optimal control of the Burgers equation

Abstract A comparison of three different but related numerical methods for control constrained optimal control of the Burgers equation is carried out. We develop the principal ideas of the different strategies considered and present detailed numerical examples. Lastly, conclusions about the behavior of the approaches are obtained.     

Characterisation and modelling of VBR video traffic

The impact of VBR video traffic characteristics on broadband network performance is analysed. In particular, the authors compare in a queue the behaviour of several models that adjust different statistical parameters of actual MPEG traces. It is proved that a good fit of the probability density function (PDF) is essential to approximate queuing behaviour while the effects of short range dependence (SRD) are of secondary importance and those of long range dependence (LRD) could be neglected for practical purposes if realistic scenarios, with strict QoS requirements, are considered     

Optical properties of Nd-doped Ca3(VO4)2 single crystal fiber

Optical absorption and photoluminescence of Ca₃(VO₄)₂ single crystal grown by a floating-zone technique and containing Nd³⁺ ions were investigated. High absorption coefficients and broadening of most absorption bands are present at 300 K, while substructures in some of the same bands can be evidenced at 12 K. Most features of measured spectra are characteristic of random occupation of more than a single Ca²⁺ site by the Nd³⁺ ion and of distortions provoked by different charge compensation mechanisms involving oxygen vacancies promotion in the crystal lattice. Nd³⁺ optical properties were studied by using the Judd-Ofelt theory to calculate the spectral parameters relevant for laser applications.     

Feminist identity and feminist therapy behaviors of women psychotherapists.

Investigated whether (1) feminist identity development for women therapists was related to their use of feminist therapy behaviors (FTBs) and (2) feminist identity development and use of FTBs for women therapists were related to self-identification as a feminist therapist. 153 women psychologists (aged 30–77 yrs) were administered a women's issues in therapy questionnaire, which included a short version of the Feminist Identity Scale (FIS; K. M. Rickard, 1989, 1990). Ss were categorized into stages of feminine identity development according to their scores on 4 subscales of the FIS: Passive-Acceptance (PA), Revelation (REV), Embeddedness (EMB), and Synthesis (SYN). Ss scoring high on SYN and REV, and low on PA, reported greater use of FTBs; scores on the EMB were not related to the use of FTBs. All 4 subscales were predictive of women therapists who self-identified as feminist therapists. (PsycINFO Database Record (c) 2010 APA, all rights reserved)     

Kinetic study of the decompositions involved in the thermal degradation of commercial azodicarbonamide

The transitions and reactions involved in the thermal treatment of several commercial azodicarbonamides (ADC) in an inert atmosphere have been studied by dynamic thermogravimetry analysis (TGA), mass spectrometry and Fourier transform infrared (FTIR) spectroscopy. A pseudo‐mechanistic model, involving several competitive and non‐competitive reactions, has been suggested and applied to the correlation of the weight loss data. The model applied is capable of accurately representing the different processes involved, and can be of great interest in the understanding and quantification of such phenomena, including the simulation of the instantaneous amount of gases evolved in a foaming process. In addition, a brief discussion on the methodology related to the mathematical modeling of TGA data is presented, taking into account the complex thermal behaviour of the ADC. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Biochemical changes in cerebrospinal fluid associated with the neurotoxic action of HIV-1]

Different intravascular ultrasound (IVUS) systems vary in their image presentation. The purpose of this study was to compare four IVUS systems in vitro to determine the accuracy of tissue characterization of atherosclerotic plaque compared with histology. Ninety-eight plaque segments from 23 formalin-fixed human iliac arteries were imaged in saline at room temperature with four different IVUS systems. To assess the accuracy of IVUS in describing plaque, three types of analysis were performed: (1) the ability to identify the presence and extent of lumen or plaque boundary; (2) sensitivity, specificity, and interobserver variability of IVUS in qualitatively identifying plaque components compared with histology; and (3) quantification of calcification. The synthetic aperture device had a lower sensitivity in identifying lumen and plaque boundaries (87%, 38% respectively) compared with other machines (96%-100%, 95%-100%). All three mechanically rotating systems had fair to good sensitivities for identifying calcification (57%-73%) or lipid filled areas (50%-83%). The sensitivity of discriminating fibrous tissue from fatty areas was low (39%-52%). The synthetic aperture system had a significantly lower sensitivity for identifying all three tissue types (4%-21%). There was significant interobserver variability (kappa value = 0.47-0.68) as well as machine to machine variability (kappa value = 0.52) for tissue characterization. Calcified areas were underestimated by System 1 (p < .05) and System 4 (p < .01) because of weaker echo reflections or poor image quality. There are significant differences in image representation among these four IVUS systems in the diagnosis of tissue components of complex atherosclerotic plaque. These variabilities should be considered when interpreting studies performed with different machines.