Probing molecular mobility during crosslinking process of commercial resins by NMR multiexponential relaxation data analysis

In this study, we present the experimental results for the crosslinking process of a commercial polyester resin based on measurements of the spin lattice relaxation time T₁ of protons, as function of the crosslinking time evolution. Multiexponential decomposition of the evolution of magnetization measured in inversion‐recovery experiments is performed. The population of “rigid” and “mobile” nuclear spin sites was estimated as function of time evolution. In analogy to the usual monomer conversion u, site conversion from “mobile” to “rigid” sites u_M were also estimated as a function of time evolution and initial concentrations of the reagents. The multiexponential decomposition approach of T₁ relaxation data allows one to follow crosslinking processes. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

Bayesian Model Uncertainty In Smooth Transition Autoregressions

Abstract. In this paper, we propose a fully Bayesian approach to the special class of nonlinear time‐series models called the logistic smooth transition autoregressive (LSTAR) model. Initially, a Gibbs sampler is proposed for the LSTAR where the lag length, k, is kept fixed. Then, uncertainty about k is taken into account and a novel reversible jump Markov Chain Monte Carlo (RJMCMC) algorithm is proposed. We compared our RJMCMC algorithm with well‐known information criteria, such as the Akaikes? information criteria, the Bayesian information criteria (BIC) and the deviance information criteria. Our methodology is extensively studied against simulated and real‐time series.     

Microbiological status of fresh beef cuts

Fresh beef samples (n = 1,022) obtained from two processing plants in the Midwest (July to December 2003) were analyzed for levels of microbial populations (total aerobic plate count, total coliform count, and Escherichia coli count) and for the presence or absence of E. coli O157:H7 and Salmonella. A fresh beef cut sample was a 360-g composite of 6-g portions excised from the surface of 60 individual representative cuts in a production lot. Samples of fresh beef cuts yielded levels of 4.0 to 6.2, 1.1 to 1.8, and 0.8 to 1.0 log CFU/g for total aerobic plate count, total coliform count, and E. coli count, respectively. There did not appear to be substantial differences or obvious trends in bacterial populations on different cuts. These data may be useful in establishing a baseline or a benchmark of microbiological levels of contamination of beef cuts. Mean incidence rates of E. coli O157:H7 and Salmonella on raw beef cuts were 0.3 and 2.2%, respectively. Of the 1,022 samples analyzed, cuts testing positive for E. coli O157:H7 included top sirloin butt (0.9%) and butt, ball tip (2.1%) and for Salmonella included short loins (3.4%), strip loins (9.6%), rib eye roll (0.8%), shoulder clod (3.4%), and clod, top blade (1.8%). These data provide evidence of noticeable incidence of pathogens on whole muscle beef and raise the importance of such contamination on product that may be mechanically tenderized. Levels of total aerobic plate count, total coliform count, and E. coli count did not (P > or = 0.05) appear to be associated with the presence of E. coli O157:H7 and Salmonella on fresh beef cuts. E. O157:H7 was exclusively isolated from cuts derived from the sirloin area of the carcass. Salmonella was exclusively isolated from cuts derived from the chuck, rib, and loin areas of the carcass. Results of this study suggest that contamination of beef cuts may be influenced by the region of the carcass from which they are derived.     

Residential electricity consumption in Portugal: Findings from top-down and bottom-up models

An econometric study of the Portuguese residential electricity consumption is presented, with a focus on the influence of dwelling characteristics on consumption. The relationship between the dwelling and household characteristics on per capita residential electricity consumption is estimated at two different scales, involving two distinct databases: the first includes data at the municipality level for 2001, the second is the most recent Portuguese consumer expenditure survey that was collected in 2005 and 2006. The results of the analysis at both scales are consistent and indicate that household and dwelling characteristics have a significant influence on residential electricity consumption. Our results show that in Portugal the direct effect of income on electricity consumption is low and becomes smaller when more relevant control variables are included in the analysis. Future demand of electricity in Portugal will be significantly influenced by trends in socioeconomic factors as well as changes in the building stock. These trends should be taken in consideration in the formulation of policy measures to reduce electricity consumption.     

An application of chemometric techniques to analyze the effects of the wave function modifications on the intermolecular stretching frequencies of the hydrogen-bonded complexes

Factorial design and principal component models are used to determine how ab initio H-bond stretching frequencies depend on characteristics of the molecular orbital wave functions of acetylene–HX, ethylene–HX and cyclopropane–HX π-type hydrogen complexes with X=F, Cl, CN, NC and CCH. The results obtained for the three sets of complexes show that factorial design and principal component analyses complement each other. Factorial design calculations clearly show that these frequencies are affected mostly by inclusion of electron correlation on the calculation level. On average, their values are increased by about 25 cm⁻¹ due to a change from the Hartree–Fock (HF) to Möller–Plesset 2 (MP2) level. Valence, diffuse and polarization main effects as well as valence–diffuse, diffuse–correlation and polarization–correlation interaction effects are also important to better describe a factorial model to the H-bond stretching frequencies of these hydrogen complexes. This simplified model has been successful in reproducing the complete ab initio results, which correspond to two hundred and forty calculations. Principal component analyses applied only to hydrogen-bonded complexes whose experimental frequencies are known, has revealed that the six-dimensional original space can be accurately represented by a bidimensional space defined by two principal components. Its graphical representation reveals that the experimental intermolecular stretching frequencies are in closest agreement with the MP2/6–31+G and MP2/6–311+G ab initio results.     

Proposal of visual strength grading rules for Uruguayan pine timber

A previous database with bending and density data of 261 structural size specimens of currently produced Uruguayan slash pine and loblolly pine timber was adjusted to meet testing and characterization requirements of European standards. Visual parameters and mechanical properties for each specimen were evaluated and their relationship was statistically analyzed. Results suggested that all specimens can be grouped in one visual grade with engineered properties similar to those of European C14 strength class. Modulus of elasticity and characteristic bending strength were the defining properties for class assignation.     

Lumped kinetics and acute toxicity of intermediates in the ozonation of phenol in saline media

This work investigates the feasibility of ozonation for destroying phenol and removing organic matter in saline media. The reaction lumped kinetics was followed using the GLKM (General Lumped Kinetic Model). The main intermediate compounds were: catechol, hydroquinone, 4,4'-dihydroxybiphenyl, and 4-bromophenol. It could be noted no significant differences in phenol degradation, mineralization rates, and toxicity removal up to 2 g L(-1) of salt. So, ozonation appears to be a technology that can be used in low salinity media, which is characteristic of waters destined to reuse and recycling programs inside industries.