Activation energy distribution of thermal annealing of a bituminous coal

A bituminous coal was pyrolyzed in a nitrogen stream in an entrained flow reactor at various temperatures from 700 to 1475 degreesC. Char samples were collected at different positions along the reactor. Each collected sample was oxidized nonisothermally in a TGA for reactivity determination. The reactivity of the coal char was found to decrease rapidly with residence time until 0.5 s, after which it decreased only slightly. On the bases of the reactivity data at various temperatures, a new approach was utilized to obtaining the true activation energy distribution function for thermal annealing without the assumption of any distribution function form or a constant preexponential factor. It appears that the true activation energy distribution function consists of two separate parts corresponding to different temperature ranges, suggesting different mechanisms in different temperature ranges. Partially burnt coal chars were also collected along the reactor when the coal was oxidized in air at various temperatures from 700 to 1475 degreesC. The collected samples were analyzed for the residual carbon content and the specific reaction rate was estimated. The characteristic time of thermal deactivation was compared with that of oxidation under realistic conditions. The characteristic times were found to be close to each other, indicating the importance of thermal deactivation during combustion of the coal studied.

An investigation of the thermal and tensile properties of PFA following γ-radiolysis

For some applications for fluoropolymers they must be subjected to high-energy radiation, e.g., when they are grafted with styrene using an irradiation method to produce fuel cell membranes or matrix supports for combinatorial chemistry. In some of these applications they may be subjected to mechanical stress or elevated temperature, so it is important to elucidate the effects of the radiolysis on these properties. In the present work the effect of gamma-radiolysis on the glass transition, melting behavior, and thermal stability of PFA has been studied as well as the effect of the radiolysis on the tensile properties of the polymer.

Uma contribuição experimental aos fundamentos da propagação de uma frente de combustão em meio poroso

A propagação de uma frente de combustão ocorre numa variedade de situações e para diferentes propósitos industriais. O desempenho desses processos precisa melhorar e ao mesmo tempo reduzir os níveis de emissões para atender às normas de emissões internacionais. Para isso é necessário um certo grau de conhecimento tanto do processo como dos fenômenos da combustão. Em todos as situações envolvendo a combustão, a propagação é iniciada por uma fonte de calor e, após a ignição do combustível, a frente de combustão alcança o combustível adjacente. Estudos anteriores mostraram a ignição e propagação de uma frente de combustão como um fenômeno complexo que depende de processos químicos, térmicos e físicos. O presente trabalho abordou os desafios encontrados durante uma abordagem empírica para análise da propagação de uma frente de combustão em leito fixo. A partir da utilização de combustíveis simulados foram analisados: a influência da composição do combustível no comportamento da ignição do mesmo, as características da propagação da frente de combustão (regime de combustão, retração do leito e estrutura da frente) e a influência da ignição do combustível na propagação da frente de combustão. Foi possível realizar um mapeamento, para diferentes composições, do comportamento da ignição de combustíveis sólidos. A partir dos resultados de propagação da frente verificou-se que ocorrem basicamente três estágios de combustão no leito: ignição, propagação e oxidação do carbono fixo remanescente. Através das análises de gás notou-se a existência de dois regimes de combustão no leito: limitada pela reação e limitada pelo oxigênio. Foi obtido que em leitos com alta porcentagem de material inerte, onde há maior estabilidade, há uma maior influência da ignição na frente de combustão. Assim, mostrou-se como esses conhecimentos são úteis em diversas aplicações e processos industriais.

Thermal and hydrolytic degradation of electrospun fish gelatin membranes

The thermal and hydrolytic degradation of electrospun gelatin membranes cross-linked with glutaraldehyde in vapor phase has been studied. In vitro degradation of gelatin membranes was evaluated in phosphate buffer saline solution at 37 ºC. After 15 days under these conditions, a weight loss of 68 % was observed, attributed to solvation and depolymerization of the main polymeric chains. Thermal degradation kinetics of the gelatin raw material and as-spun electrospun membranes showed that the electrospinning processing conditions do not influence polymer degradation. However, for cross-linked samples a decrease in the activation energy was observed, associated with the effect of glutaraldehyde cross-linking reaction in the inter- and intra-molecular hydrogen bonds of the protein. It is also shown that the electrospinning process does not affect the formation of the helical structure of gelatin chains.

Thermal skin reference values in healthy late pregnancy

Digital thermal imaging has been employed in medicine for over 50 years. However, its use has been focused on vascular, musculoskeletal and neurological conditions, while other potential applications,such as obstetrics, have been much less explored. This paper presents a study conducted during 2011 at the Hospital of Braga on a group of healthy pregnant women in the last third of gestation. The analysis focused on characterizing typical pregnant women steady temperature profiles in specific defined regions of interest (ROI), and determining if the thermal symmetry values for late pregnant healthy women are in line with the values for non-pregnant healthy women. A temperature distribution pattern was found in the defined ROI. The obtained thermal symmetry value had a maximum of 0.370.2 1C, and there was no evidence for the influence of age (p40.05) in the observed group. The influence of the BMI requires further investigation since one ROI (P2 right) presented a p¼0.059, close to the threshold of statistical evidence in the influence of BMI. The study group presented symmetry values in line with non-pregnant reference values, but the profiles in temperature distribution are different. Assumptions can therefore now be used with higher confidence when assessing abnormalities in specific pathologic states during pregnancy using the defined ROI. This work represents a first contribution towards establishing guidelines for future research in this specific field of study.

Thermal degradation of Pb(Zr0.53Ti0.47)O3/poly(vinylidene fluoride) composites as a function of ceramic grain size and concentration

Poly(vinylidene fluoride)/Pb(Zr0.53Ti0.47)O3,([PVDF]1−x/[PZT]x) composites of volume fractions x and (0–3) type connectivity were prepared in the form of thin films. PZT powders with average grain sizes of 0.2, 0.84, and 2.35 μm in different volume fraction of PZT up to 40 % were mixed with the polymeric matrix. The influence of the inorganic particle size and its content on the thermal degradation properties of the composites was then investigated by means of thermo-gravimetric analysis. It is observed that filler size affects more than filler concentration the degradation temperature and activation energy of the polymer. In the same way and due to their larger specific area, smaller particles leave larger solid residuals after the polymer degradation. The polymer degradation mechanism is not significantly modified by the presence of the inorganic fillers. On the other hand, an inhibition effect occurs due to the presence of the fillers, affecting particularly the activation energy of the process.

Effect of neutralization and cross-linking on the thermal degradation of chitosan electrospun membranes

Thermal degradation of as electrospun chitosan membranes and samples subsequently treated with ethanol and cross-linked with glutaraldehyde (GA) have been studied by thermogravimetry (TG) coupled with an infrared spectrometer (FTIR). The influence of the electrospinning process and cross-linking in the electrospun chitosan thermal stability was evaluated. Up to three degradation steps were observed in the TG data, corresponding to water dehydration reaction at temperatures below 100 ºC, loss of side groups formed between the amine groups of chitosan and trifluoroacetic acid between 150 – 270 ºC and chitosan thermal degradation that starts around 250 ºC and goes up to 400 ºC. The Kissinger model was employed to evaluate the activation energies of the electrospun membranes during isothermal experiments and revealed that thermal degradation activation energy increases for the samples processed by electrospinning and subsequent neutralization and cross-linking treatments with respect to the neat chitosan powder.

Chemical, morphological, rheological and thermal properties of Solanum lycocarpum phosphorylated starches

The increasing need for starches with specific characteristics makes it important to study unconventional starches and their modifications in order to meet consumer demands. The aim of this work was to study physicochemical characteristics of native starch and phosphate starch of S. lycocarpum. Native starch was phosphated with sodium tripolyphosphate (5-11%) added with stirring. Chemical composition, morphology, density, binding ability to cold water, swelling power and solubility index, turbidity and syneresis, rheological and calorimetric properties were determined. Phosphorus was not detected in the native sample, but the phosphating process produced modified starches with phosphorus contents of 0.015, 0.092 and 0.397%, with the capacity of absorbing more water, either cold or hot. Rheological data showed the strong influence of phosphorus content on viscosity of phosphate starch, with lower pasting temperature and peak viscosity higher than those of native starch. Enthalpy was negatively correlated with the phosphorus content, requiring 9.7; 8.5; 8.1 and 6.4 kJ g-1 of energy for the transition from the amorphous to the crystalline state for the starch granules with phosphorus contents of 0; 0.015; 0.092 and 0.397%, respectively. Cluster analysis and principal component analysis showed that starches with 0.015 and 0.092% phosphorus have similar characteristics and are different from the others. Our results show that the characteristics of phosphate modified S. lycocarpum starch have optimal conditions to meet the demands of raw materials, which require greater consistency in stickiness, combined with low rates of retrogradation and syneresis.

The use of quantitative performance information by local elected politicians in top managers’ performance evaluation: case studies

This paper studies the use of results oriented performance information (outputs and outcomes) by local elected politicians (aldermen) in top managers’ performance evaluation. The main goal is to understand the top managers’ performance evaluation process conducted by Portuguese aldermen and to identify the dominant evaluation style. In line with Bogt (2001), an exploratory field research was developed in three large municipalities: Porto, Braga and Matosinhos. We intend to answer the following research questions: to what extent are local politicians (aldermen) 1 using results information (about outputs and outcomes) to evaluate top managers’ performance? Do aldermen give any importance to quantitative output information and report them on current planning and control documents? Will the output performance information be used on performance evaluation in a different way concerning policy field (task orientation)? Based on the Hopwood evaluation styles (adapted from the private to the public sector by Bogt, 2001), we have found that the performance evaluation process of top managers is more featured by the ‘operations-conscious styles’ (or ‘implicit style’). Portuguese aldermen recognize the importance to quantify outputs and outcomes, but these days they focus on the information about activities and the realized operations when they evaluate performance. We haven´t found significant differences between different tasks (some exceptions for culture and environment areas). However, the municipality of Matosinhos paid more attention on quantitative performance information. This finding is reinforced by the quality of quantitative data on outputs reported on its management report. Generally speaking, aldermen are aware that more attention should be paid to quantitative information about results and performance, taking into account recent reforms introduced in Portuguese municipalities (PLG) on this field, but the ‘implicit’ style is dominant.

Cristalização de Biomateriais Vitrocerâmicos e Mineralização em Meio Fisiológico Simulado

We propose new theoretical models, which generalize the classical Avrami-Nakamura models. These models are suitable to describe the kinetics of nucleation and growth in transient regime, and/or with overlapping of nucleation and growth. Simulations and predictions were performed for lithium disilicate based on data reported in the literature. One re-examined the limitations of the models currently used to interpret DTA or DSC results, and to extract the relevant kinetic parameters. Glasses and glass-ceramics with molar formulation 0.45SiO2? (0.45-x)MgO?xK2O?0.1(3CaO.P2O5) (0?x?0.090) were prepared, crystallized and studied as potential materials for biomedical applications. Substitution of K+ for Mg2+ were used to prevent devritification on cooling, to adjust the kinetics of crystallization and to modify the in vitro behaviour of resulting biomaterials. The crystallization of the glass frits was studied by DTA, XRD and SEM. Exothermic peaks were detected corresponding to bulk crystallization of whitlockite-type phosphate, Ca9MgK(PO4)7, at approximately 900ºC, and surface crystallization of a predominant forsterite phase (Mg2SiO4) at higher temperatures. XRD also revealed the presence of diopside (CaMgSi2O6 in some samples. The predominant microstructure of the phosphate phase is of the plate-type, seemingly crystallizing by a 2-dimensional growth mechanism. Impedance spectroscopy revealed significant changes in electrical behaviour, associated to crystallization of the phosphate phase. This showed that electrical measurements can be used to study the kinetics of crystallization for cases when DTA or DSC experiments reveal limitations, and to extract estimates of relevant parameters from the dependence of crystallization peak temperature, and its width at half height. In vitro studies of glasses and glass-ceramics in acelular SBF media showed bioactivity and the development of apatite layers The morphology, composition and adhesion of the apatite layer could be changed by substitution of Mg2+ by K+. Apatite layers were deposited on the surface of glass-ceramics of the nominal compositions with x=0 and 0.09, in contact with SBF at 37ºC. The adhesion of the apatite layer was quantified by the scratch test technique, having been related with SBF?s immersion time, with composition and structure of the glass phase, and with the morphology of the crystalline phase of the glass-ceramics. The structure of three glasses (x=0, 0.045 and 0.090) were investigated by MAS-NMR ( 29Si and 31P), showing that the fraction of Q3 structural units increases with the contents of Mg, and that the structure of these glasses includes orthophosphate groups (PO43-) preferentially connected to Ca2+ ions. Mg2+ ions show preference towards the silicate network. Substitution of Mg2+ by K+ allowed one to change the bioactivity. FTIR data revealed octacalcium phosphate precipitation (Ca8H2(PO4)6.5H2O) in the glass without K, while the morphology of the layer acquires the shape of partially superimposed hemispheres, spread over the surface. The glasses with K present a layer of acicular hidroxyapatite, whose crystallinity and needles thickness tend to increase along with K content.

Studies on some species of Culex (Melanoconion), with the description of a new one from Southern Brazil (Diptera: Culicidae)

Redescription of Culex (Melanoconion) oedipus Root and of Cx. (Mel.) plectoporpe Root, as well as the description of a new one, named Cx. (Mel.) rabelloi, are made. The material was collected in S.Paulo State, Southern Brazil. The descriptions include adults, pupal and larval stages, illustrating the morphological aspects and with pictures of breeding places. Some data about known distribution and bionomics are presented, remarking that all the three species seem to be closely associated with artificial manmade enviroments.

Studies in search of a suitable experimental insect model for xenodiagnosis of hosts with Chagas' disease: 3 - On the interaction of vector species and parasite strain in the reaction of bugs to infection by Trypanosoma cruzi

The reaction of nine vector species of Chagas' disease to infection by seven different Trypanosoma cruzi strains; Berenice, Y, FL, CL, S. Felipe, Colombiana and Gávea, are examined and compared. On the basis of the insects' ability to establish and maintain the infection, vector species could be divided into two distinct groups which differ in their reaction to an acute infection by T. cruzi. While the proportion of positive bugs was found to be low in Triatoma infestans and Triatoma dimidiata it was high, ranging from 96.9% to 100% in the group of wild (Rhodnius neglectus, Triatoma rubrovaria)and essentially sylvatic vectors in process of adaptation to human dwellings, maintained under control following successful insecticidal elimination of Triatoma infestans (Panstrongylus megistus, Triatoma sordida and Triatoma pseudomaculata). An intermediate position is held by Triatoma brasiliensis and Rhodnius prolixus. This latter has been found to interchange between domestic and sylvatic environments. The most important finding is the strikingly good reaction between each species of the sylvatic bugs and practically all T. cruzi strains herein studied, thus indicating that the factors responsible for the excellent reaction of P.megistus to infection by Y strain, as previously reported also come into operation in the reaction of the same vector species to acute infections by five of the remaining T.cruzi strains. Comparison or data reported by other investigators with those herein described form the basis of the discussion of Dipetalogaster maximus as regards its superiority as a xenodiagnostic agent.

Studies in search of a suitable experimental insect model for xenodiagnosis of hosts with Chagas' disease: 4 - The reflection of parasite stock in the responsiveness of different vector species to chronic infection with different Trypanosoma cruzi stocks

Previous studies (1982,1987) have emphasized the superiority of sylvatic vector species over domestic species as xenodiagnostic agents in testing hosts with acute or chronic infections by T. cruzi "Y" stock. The present study, which is unique in that it contains data on both infectivity rates produced by the same stock in 11 different vector species and also the reaction of the same vector species to seven different parasite stocks, establishes the general validity of linking efficiency of xenodiagnosis to the biotope of its agent. For example, infectivity rates produced by "São Felipe" stock varied from 82.5% to 98.3% in sylvatic vectors but decreased to 42.5% to 71.3% in domestic species. "Colombiana" stock produced in the same sylvatic vectors infectivity rates ranging from 12.5% to 45%. These shrank to 5%-22.5% in domestic bugs. The functional role of the biotope in the vector-parasite interaction has not been eluddated. But since this phenomenon has been observed to be stable and easy to reproduce, it leads us to believe that the results obtained are valid. Data presented also provide increasing evidence that the infectivity rates exhibited by bugs from xenodiagnosis in chronic hosts, are parasite stock specific. For example, infectivity rates produced by "Berenice", "Y", "FL" and "CL" varied in R. neglectus from 26.3% to 75%; in P. megistus from 56.3% to 83.8%; in T. sordida from 28.8% to 58.8% in T. pseudomaculata from 41.3% to 66.3% and in T. rubrovaria from 48.8% to 85%. Data from xenodiagnosis in the same hosts, carrying acute infections by the same parasite stocks, gave the five sylvatic vectors a positive rating of approximately 100%, thus suggesting that the heavy loads of parasites circulating in the acute hosts obscured the characteristic interspecific differences for the parasite stock. Nonetheless these latter were revealed in the same hosts with chronic infections stimulated by very low numbers of the same parasite stocks. Certain observations here described lead us to speculate as to the possibility of further results from other parasite stocks, allowing the association of the infectivity rates produced in bugs by different parasite stocks with the isoenzymic patterns revealed by these stocks.

Studies of the Antiproliferative Activity of Ruthenium (II) Cyclopentadienyl-Derived Complexes with Nitrogen Coordinated Ligands

Four cationic ruthenium(II) complexes with the formula [Ru(eta(5)-C5H5)(PPh3)(2)](+), with L = 5-phenyl-1H-tetrazole (TzH) 1, imidazole (ImH) 2, benzo[1,2-b; 4,3-b'] dithio-phen-2-carbonitrile (Bzt) 3, and [5-(2-thiophen-2-yl)-vinyl]-thiophene-2-carbonitrile] (Tvt) 4 were prepared and characterized in view to evaluate their potentialities as antitumor agents. Studies by Circular Dichroism indicated changes in the secondary structure of ct-DNA. Changes in the tertiary structure of pBR322 plasmid DNA were also observed in gel electrophoresis experiment and the images obtained by atomic force microscopy (AFM) suggest strong interaction with pBR322 plasmid DNA; the observed decreasing of the viscosity with time indicates that the complexes do not intercalate between DNA base pairs. Compounds 1, 2, and 3 showed much higher cytotoxicity than the cisplatin against human leukaemia cancer cells (HL-60 cells).