Gas phase polymerization of ethylene with a silica-supported metallocene catalyst: influence of temperature on deactivation

Ethylene was polymerized at 5 bar in a stirred powder bed reactor with silica supported rac-Me2Si[Ind]2ZrCl2/methylaluminoxane (MAO) at temperatures between 40°C and 80°C using NaCl as support bed and triethylaluminium (TEA) as a scavenger for impurities. For this fixed recipe and a given charge of catalyst. the average catalyst activity is reproducible within 10% for low temperatures. The polymerization rate and the rate of deactivation increase with increasing temperature. The deactivation could be modeled using a first order dependence with respect to the polymerization rate

An analysis of the protagonist´s face work in " As good as it gets": from an obnoxious hermit to a sociable being

Dissertação (mestrado) - Universidade Federal de Santa Catarina, Centro de Comunicação e ExpressãoO objetivo desta tese é o de oferecer um estudo interdisciplinar sob as perspectivas da análise do discurso, da semiótica e de estudos de cinema. O corpus para análise é o desempenho lingüistico do protagonista, Melvin, do filme premiado 'Melhor é Impossível'. Através da observação das escolhas lexicogramaticais reforçadas com a comunicação não-verbal examino a modificação progressiva da sua maneira rude de interagir. O foco básico é dos aspectos lingüisticos de trabalho de face em busca de qualquer alteração na natureza social de Melvin refletido por meio dessas escolhas. Trechos de diversas cenas do filme são investigados de acordo com parâmetros de análise de discurso (van Dijk, 1997). A fundamentação teórica de polidez (Goffman, 1969; Brown and Levinson, 1987; Holmes, 1995), estudos de semiótica (Kress and van Leeuwen, 1996) e de roteiro (Howard e Mabley, 1996) ponderados para realizar a investigação. Os resultados mostram que as declarações feitas por Melvin agem dialécticalmente para reforçar sua posição ideológica de preconceito. O ato de repensar seus ideais, a respeito de homosexuais e outros grupos de minoria, é demonstrado por meio das modificações progressivas de trabalho de face de Melvin. O estudo pretende promover uma conscientização do elo bidirecional entre linguagem e sociedad

Quantifying the improvement of surrogate indices of hepatic insulin resistance using complex measurement techniques

We evaluated the ability of simple and complex surrogate-indices to identify individuals from an overweight/obese cohort with hepatic insulin-resistance (HEP-IR). Five indices, one previously defined and four newly generated through step-wise linear regression, were created against a single-cohort sample of 77 extensively characterised participants with the metabolic syndrome (age 55.6±1.0 years, BMI 31.5±0.4 kg/m2; 30 males). HEP-IR was defined by measuring endogenous-glucose-production (EGP) with [6–62H2] glucose during fasting and euglycemic-hyperinsulinemic clamps and expressed as EGP*fasting plasma insulin. Complex measures were incorporated into the model, including various non-standard biomarkers and the measurement of body-fat distribution and liver-fat, to further improve the predictive capability of the index. Validation was performed against a data set of the same subjects after an isoenergetic dietary intervention (4 arms, diets varying in protein and fiber content versus control). All five indices produced comparable prediction of HEP-IR, explaining 39–56% of the variance, depending on regression variable combination. The validation of the regression equations showed little variation between the different proposed indices (r2 = 27–32%) on a matched dataset. New complex indices encompassing advanced measurement techniques offered an improved correlation (r = 0.75, P<0.001). However, when validated against the alternative dataset all indices performed comparably with the standard homeostasis model assessment for insulin resistance (HOMA-IR) (r = 0.54, P<0.001). Thus, simple estimates of HEP-IR performed comparable to more complex indices and could be an efficient and cost effective approach in large epidemiological investigations

Measurement of in situ monomer sorption in polyu(propylene)

An experimental method has been developed to compare the amount of monomer absorbed in freshly produced poly(propylene) with the amount of monomer absorbed in the same material after degassing. It has been found that propylene sorption in freshly produced poly(propylene) is significantly higher than the sorption in the same but degassed polymer. The difference depends on the degree of drying and is time-dependent. This fact can be an explanation for reduced activity often observed in the transition from liquid- to gas-phase polymerization

Modeling of free radical polymerization up to high conversion. I. A method for the selection of models by simultaneous parameter estimation

A systematic quantitative method for the selection of models for the high-conversion free radical polymerization exhibiting gel and glass effects has been developed. Four representative models were selected from the literature and were compared on the basis of the same experimental data. All models describe the isothermal time-conversion data over the entire conversion range for a single type and loading of initiator well. Models that are not considering the effect of molecular weight of the polymers on the diffusion of macro radicals fail to describe the time-conversion data if the concentration of the initiator varies at the same time. By simultaneous fitting of the conversion and polymerization degree data it was shown that the Marten-Hamielec model and its extended form (Panke-Stickler-Hamielec model) were not able to describe the number average polymerization degree Pn at the final conversion, where the glass effect occurs. This occurred because both models neglect the change of the radical efficiency f in this region, which has more effect on Pn than the change of the propagation rate coefficient (see part II of this series)

Polyphenol- and fibre-rich dried fruits with green tea attenuate starch-derived postprandial blood glucose and insulin: a randomised, controlled, single-blind, cross-over intervention

Polyphenol- and fibre-rich foods (PFRF) have the potential to affect postprandial glycaemic responses by reducing glucose absorption, and thus decreasing the glycaemic response of foods when consumed together. A randomised, single-blind, cross-over study was conducted on sixteen healthy volunteers to test whether PFRF could attenuate postprandial blood glucose in healthy volunteers when added to a source of carbohydrate (starch in bread). This is the first study to examine the effects of a meal comprised of components to inhibit each stage of the biochemical pathway, leading up to the appearance of glucose in the blood. The volunteers were fasted and attended four visits: two control visits (bread, water, balancing sugars) and two test visits (single and double dose of PFRF) where they consumed bread, water and PFRF. Blood samples were collected at 0 (fasted), 15, 30, 45, 60, 90, 120, 150 and 180 min after consumption. The PFRF components were tested for α-amylase and α-glucosidase inhibitory potential in vitro. Plasma glucose was lower after consumption of both doses compared with controls: lower dose, change in mean incremental areas under the glucose curves (IAUC)=− 27·4 (SD 7·5) %, P< 0·001; higher dose, IAUC =− 49·0 (SD 15·3) %, P<0·001; insulin IAUC was also attenuated by − 46·9 (SD 13·4) %, P<0·01. Consistent with this, the polyphenol components of the PFRF inhibited α-amylase (green tea, strawberry, blackberry and blackcurrant) and α-glucosidase (green tea) activities in vitro. The PFRF have a pronounced and significant lowering effect on postprandial blood glucose and insulin response in humans, due in part to inhibition of α-amylase and α-glucosidase, as well as glucose transport

Field-induced Bose-Einstein Condensation of triplons up to 8 K in Sr3Cr2O8

Single crystals of the spin dimer system Sr3Cr2O8 have been grown for the first time. Magnetization, heat capacity, and magnetocaloric effect data up to 65 T reveal magnetic order between applied fields of Hc1 ~ 30.4 T and Hc2 ~ 62 T. This field-induced order persists up to ~ 8 K at H ~ 44 T, the highest observed in any quantum magnet where Hc2 is experimentally-accessible. We fit the temperature-field phase diagram boundary close to Hc1 using the expression Tc = A(H-Hc1)^v. The exponent v = 0.65(2), obtained at temperatures much smaller than 8 K, is that of the 3D Bose-Einstein condensate (BEC) universality class. This finding strongly suggests that Sr3Cr2O8 is a new realization of a triplon BEC where the universal regimes corresponding to both Hc1 and Hc2 are accessible at He-4 temperatures.Comment: 4 pages, 3 figures, accepted by PR

Low temperature thermodynamic properties near the field-induced quantum critical point in DTN

We present a comprehensive experimental and theoretical investigation of the thermodynamic properties: specific heat, magnetization and thermal expansion in the vicinity of the field-induced quantum critical point (QCP) around the lower critical field $H_{c1} \approx 2$\,T in DTN . A $T^{3/2}$ behavior in the specific heat and magnetization is observed at very low temperatures at $H=H_{c1}$ that is consistent with the universality class of Bose-Einstein condensation of magnons. The temperature dependence of the thermal expansion coefficient at $H_{c1}$ shows minor deviations from the expected $T^{1/2}$ behavior. Our experimental study is complemented by analytical calculations and Quantum Monte Carlo simulations, which reproduce nicely the measured quantities. We analyze the thermal and the magnetic Gr\"{u}neisen parameters that are ideal quantities to identify QCPs. Both parameters diverge at $H_{c1}$ with the expected $T^{-1}$ power law. By using the Ehrenfest relations at the second order phase transition, we are able to estimate the pressure dependencies of the characteristic temperature and field scales.Comment: 11 paged, 10 figures, submitted to PR