Thermal studies of solid 2-methoxybenzylidenepyruvate of lighter trivalent lanthanides

Solid-state compounds with a general formula of LnL3· nH2O, where Ln stands for lighter trivalent lanthanides (lanthanum to samarium), L is 2-methoxybenzylidenepyruvate and n=1.5, 2, 2, 1.5 and 2, respectively, have been synthesized. On heating these compounds are decompose in two or three steps. They lose their hydration water in the first step and the thermal decomposition of the anhydrous compounds occurs with the formation of the respective oxide, CeO2, Pr6O11 and Ln 2O3 (Ln=La, Nd, Sm) as final residue. The dehydration enthalpies found for these compounds (La to Sm) were: 222.7, 163.6, 497.7, 513.9 and 715.4 kJ mol-1, respectively. © 2005 Akadémiai Kiadó, Budapest.

Thermal studies on solid 2-chlorobenzylidenepyruvate of lighter trivalent lanthanides

Solid compounds of general formula LnL3 for La and Ce and LnL3·nH2O for Pr, Nd and Sm where Ln stands for trivalent lanthanides, L is 2-chlorobenzylidenepyruvate and n=2, 3 and 2 respectively, have been synthesized. On heating these compounds decompose in two or five steps. They lose the hydration water in the first step and the thermal decomposition of the anhydrous compounds occurs with the formation of the respective oxide, CeO2, Pr6O11 and Ln 2O3 (Ln=La, Nd, Sm) as final residue. The dehydration enthalpies found for these compounds (Pr, Nd and Sm) were: 140.1, 148.2 and 221.3 kJ mol-1, respectively. © 2005 Akadémiai Kiadó, Budapest.

Synthesis, characterization and thermal study of solid mandelate of some bivalent transition metal ions in CO2 and N2 atmospheres

Solid state M-L, where M stands for bivalent transition metals (Mn(II), Fe(II), Co(II), Ni(II), Cu(II) and Zn(II)) and L is mandelate, were synthesized. Simultaneous thermogravimetry and differential scanning calorimetry, elemental analysis and complexometry were used to establish the stoichiometry and to study the thermal behaviour of these compounds in CO2 and N2 atmospheres. The results show that all the compounds were obtained in the anhydrous state and in agreement with the general formula ML2. The thermal decomposition of the compounds occurs in a single (Cu(II)), two (Ni(II)) three (Fe(II), Co(II)), four (Mn(II)) and five (Zn(II)) steps. The results also provided information concerning the ligand's denticity, thermal behaviour, final residues and identification of gaseous products evolved during the thermal decomposition of these compounds. © 2012 Akadémiai Kiadó, Budapest, Hungary.

Studies on thermal-oxidative degradation behaviours of raw natural rubber: PRI and thermogravimetry analysis

Thermal-oxidative degradation behaviours of raw natural rubber (NR) have been investigated by using thermogravimetry analysis in inert and oxidative atmospheres and the plasticity retention index (PRI). The activation energy E a, was calculated using Horowitz-Metzger and Coats-Redfern methods and compared with PRI. The E a values obtained by each method were in good agreement with each other. The June samples are the least stable rubbers among the studied ones, whereas February samples exhibited the highest values of activation energy, therefore in agreement with the PRI behaviour, which indicates that the thermo-oxidative stability of the June samples are the poorest during the thermo-oxidative degradation reaction. Natural rubber is a product of biological origin, and thus these variations in the values of thermal behaviour and PRI might be related to the genetic differences and alterations of climatic conditions that act directly on the synthesis of non-rubber constituents, which are generally reflected in latex and rubber properties. © 2013 Institute of Materials, Minerals and Mining.

Thermal decomposition and stability in a series of heterobimetallic carbonyl compounds of the type [Fe(CO)4(HgX)2] (X=Cl, Br, I)

Foram preparados compostos carbonílicos heterobimetálicos do tipo [Fe(CO)₄(HgX)₂] ( X= Cl, Br, I), contendo ligação metal-metal, objetivando investigar suas estabilidades térmicas em função do halogênio coordenado aos átomos de mercúrio. A caracterização destes complexos foi feita usando-se de técnicas espectroscópicas de infravermelho e ressonância magnética nuclear, além de análise elementar. O produto final das termodecomposições foi identificado através de espectroscopia no infravermelho e difratograma de raios-X, método de pó.

Morphological, thermal and physicochemical characteristics of small granules starch from Mirabilis jalapa L

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

The role of paved surfaces in the Urban Heat Island phenomenon: Assessment of fundamental thermal parameters and finite element analysis for UHI mitigation

Nowadays the environmental issues and the climatic change play fundamental roles in the design of urban spaces. Our cities are growing in size, many times only following immediate needs without a long-term vision. Consequently, the sustainable development has become not only an ethical but also a strategic need: we can no longer afford an uncontrolled urban expansion. One serious effect of the territory industrialisation process is the increase of urban air and surfaces temperatures compared to the outlying rural surroundings. This difference in temperature is what constitutes an urban heat island (UHI). The purpose of this study is to provide a clarification on the role of urban surfacing materials in the thermal dynamics of an urban space, resulting in useful indications and advices in mitigating UHI. With this aim, 4 coloured concrete bricks were tested, measuring their emissivity and building up their heat release curves using infrared thermography. Two emissivity evaluation procedures were carried out and subsequently put in comparison. Samples performances were assessed, and the influence of the colour on the thermal behaviour was investigated. In addition, some external pavements were analysed. Albedo and emissivity parameters were evaluated in order to understand their thermal behaviour in different conditions. Surfaces temperatures were recorded in a one-day measurements campaign. ENVI-met software was used to simulate how the tested materials would behave in two typical urban scenarios: a urban canyon and a urban heat basin. Improvements they can carry to the urban microclimate were investigated. Emissivities obtained for the bricks ranged between 0.92 and 0.97, suggesting a limited influence of the colour on this parameter. Nonetheless, white concrete brick showed the best thermal performance, whilst the black one the worst; red and yellow ones performed pretty identical intermediate trends. De facto, colours affected the overall thermal behaviour. Emissivity parameter was measured in the outdoor work, getting (as expected) high values for the asphalts. Albedo measurements, conducted with a sunshine pyranometer, proved the improving effect given by the yellow paint in terms of solar reflection, and the bad influence of haze on the measurement accuracy. ENVI-met simulations gave a demonstration on the effectiveness in thermal improving of some tested materials. In particular, results showed good performances for white bricks and granite in the heat basin scenario, and painted concrete and macadam in the urban canyon scenario. These materials can be considered valuable solutions in UHI mitigation.

Transient thermal analysis during the ascent phase of a balloon-borne payload. Comparison with SUNRISE test flight measurements

The thermal design of stratospheric balloon payloads usually focuses on the cruise phase of the missions, that is, the floating altitude conditions. The ascent phase usually takes between 2 and 4 h, a very small period compared to the duration of the whole mission, which can last up to 4 weeks. However, during this phase payloads are subjected to very harsh conditions due mainly to the convective cooling that occurs as the balloon passes through the cold atmosphere, with minimum temperatures in the tropopause. The aim of this work is to study the thermal behaviour of a payload carried by a long duration balloon during the ascent phase. Its temperature has been calculated as a function of the altitude from sea level to floating conditions. To perform this analysis it has been assumed that the thermal interactions (convection and radiation) depend on the altitude, on the environmental conditions (which in turn depend also on the altitude) and on the temperature of the system itself. The results have been compared with the measurements taken during the SUNRISE test flight, launched in October 2007 by CSBF from Fort Sumner (New Mexico).

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.

Modeling and validation of the thermal behavior of buildings for the development of demand response methods

The representation of the thermal behaviour of the building is achieved through a relatively simple dynamic model that takes into account the effects due to the thermal mass of the building components. The model of a intra-floor apartment has been built in the Matlab-Simulink environment and considers the heat transmission through the external envelope, wall and windows, the internal thermal masses, (i.e. furniture, internal wall and floor slabs) and the sun gain due to opaque and see-through surfaces of the external envelope. The simulations results for the entire year have been compared and the model validated, with the one obtained with the dynamic building simulation software Energyplus.

Effect of over-doped yttrium on the microstructure, mechanical properties and thermal properties of a Zr-based metallic glass

The effects of over-doped yttrium on the microstructure, mechanical properties and thermal behaviour of an oxygen-contaminated Zr51Cu20.7Ni12Al16.3 bulk metallic glass are studied systematically. It has been found that, when yttrium doping is beyond the optimum doping, the glass-forming ability enhancement effect induced by yttrium addition decreases and the mechanical properties are adversely affected. In this study, a new phase with an orthorhombic structure (a = 0.69 nm, b = 0.75 nm and c = 0.74 nm) is identified in the yttrium over-doped alloys. (c) 2006 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.

Effect of sample preparation on the thermal degradation of metal-added biomass

The present study investigates the effect of different sample preparation methods on the pyrolysis behaviour of metal-added biomass; Willow samples were compared in the presence of two salts of zinc and lead containing sulphate and nitrate anions which were added to the wood samples with three different techniques as dry-mixing, impregnation and ion-exchange. The effect of acid and water wash as common demineralisation pre-treatments were also analysed to evaluate their roles in the thermal degradation of the biomass. Results from thermogravimetric analysis (TGA), Fourier transform infrared spectroscopy (FT-IR) and pyrolysis-mass spectrometry (Py-MS) measurements indicated that these pre-treatments change the matrix and the physical-chemical properties of wood. Results suggested that these structural changes increase the thermal stability of cellulose during pyrolysis. Sample preparation was also found to be a crucial factor during pyrolysis; different anions of metal salts changed the weight loss rate curves of wood material, which indicates changes in the primary degradation process of the biomass. Results also showed that dry-mixing, impregnation or ion-exchange influence the thermal behaviour of wood in different ways when a chosen metal salt was and added to the wood material. © 2011 Elsevier B.V. All rights reserved.

Constant wall heat flux boundary conditions in micro-channels filled with porous material with internal heat generation under local thermal non-equilibrium conditions

Forced convection heat transfer in a micro-channel filled with a porous material saturated with rarefied gas with internal heat generation is studied analytically in this work. The study is performed by analysing the boundary conditions for constant wall heat flux under local thermal non-equilibrium (LTNE) conditions. Invoking the velocity slip and temperature jump, the thermal behaviour of the porous-fluid system is studied by considering thermally and hydrodynamically fully-developed conditions. The flow inside the porous material is modelled by the Darcy–Brinkman equation. Exact solutions are obtained for both the fluid and solid temperature distributions for two primary approaches models A and B using constant wall heat flux boundary conditions. The temperature distributions and Nusselt numbers for models A and B are compared, and the limiting cases resulting in the convergence or divergence of the two models are also discussed. The effects of pertinent parameters such as fluid to solid effective thermal conductivity ratio, Biot number, Darcy number, velocity slip and temperature jump coefficients, and fluid and solid internal heat generations are also discussed. The results indicate that the Nusselt number decreases with the increase of thermal conductivity ratio for both models. This contrasts results from previous studies which for model A reported that the Nusselt number increases with the increase of thermal conductivity ratio. The Biot number and thermal conductivity ratio are found to have substantial effects on the role of temperature jump coefficient in controlling the Nusselt number for models A and B. The Nusselt numbers calculated using model A change drastically with the variation of solid internal heat generation. In contrast, the Nusselt numbers obtained for model B show a weak dependency on the variation of internal heat generation. The velocity slip coefficient has no noticeable effect on the Nusselt numbers for both models. The difference between the Nusselt numbers calculated using the two models decreases with an increase of the temperature jump coefficient.

Surface thermal analysis of North Brabant cities and neighbourhoods during heat waves

The urban heat island effect is often associated with large metropolises. However, in the Netherlands even small cities will be affected by the phenomenon in the future (Hove et al., 2011), due to the dispersed or mosaic urbanisation patterns in particularly the southern part of the country: the province of North Brabant. This study analyses the average night time land surface temperature (LST) of 21 North-Brabant urban areas through 22 satellite images retrieved by Modis 11A1 during the 2006 heat wave and uses Landsat 5 Thematic Mapper to map albedo and normalized difference temperature index (NDVI) values. Albedo, NDVI and imperviousness are found to play the most relevant role in the increase of nighttime LST. The surface cover cluster analysis of these three parameters reveals that the 12 “urban living environment” categories used in the region of North Brabant can actually be reduced to 7 categories, which simplifies the design guidelines to improve the surface thermal behaviour of the different neighbourhoods thus reducing the Urban Heat Island (UHI) effect in existing medium size cities and future developments adjacent to those cities.

Thermal Decomposition Kinetics of Humic Substances Extracted from Mid-Rio Negro (Amazon Basin) Soil Samples

In this work humic substances (HS) extracted from non-flooded (Araca) and flooded (Iara) soils were characterized through the calculation of stability and activation energies associated with the dehydration and thermal decomposition of HS using TGA and DTA, electronic paramagnetic resonance and C/H, C/N and C/O atomic ratios. For HS extracted from flooded soils, there was evidence for the influence of humidity on the organic matter humification process. Observations of thermal behaviour, with elemental analysis, indicated the presence of fossilized organic carbon within clay particles, which only decomposed above 800 C. This characteristic could explain the different thermal stability and pyrolysis activation energies for Iara HS compared to Araca HS.