Non-isothermal decomposition kinetics of the interaction of poly(ethylene terephthalate) with alkyd varnish

The recycling of soft drink bottles poly(ethylene terephthalate) (PET) has been used as an additive in varnish containing alkyd resin. The PET, called to recycled PET (PET-R), was added to the varnish in increasing amounts. Samples of varnish containing PET-R (VPET-R) were used as a film onto slides and its thermal properties were evaluated using thermogravimetry (TG). Throughout the visual analysis and thermal behavior of VPET-R it is possible to identify that the maximum amount of PET-R added to the varnish without changing in the film properties was 2%.The kinetic parameters, such as activation energy (E) and the pre-exponential factor (A) were calculated by the isoconversional Flynn-Wall-Ozawa method for the samples containing 0.5 to 2.0% PET-R. A decrease in the values of E was verified for lower amounts of PET-R for the thermal decomposition reaction. A kinetic compensation effect (KCE) represented by the lnA=-13.42+0.23E equation was observed for all samples. The most suitable kinetic model to describe this decomposition process is the autocatalytic Sestak-Berggren, being the model applied to heterogeneous systems.

Studies on the thermal decomposition behaviour, kinetics and electrical conductivity of the non-isothermal decomposition of pyridine mono carboxylic acids and some of their transition metal complexes

The thesis is divided into four chapters. They are: introduction, experimental, results and discussion about the free ligands and results and discussion about the complexes. The First Chapter, the introductory chapter, is a general introduction to the study of solid state reactions. The Second Chapter is devoted to the materials and experimental methods that have been used for carrying out tile experiments. TIle Third Chapter is concerned with the characterisations of free ligands (Picolinic acid, nicotinic acid, and isonicotinic acid) by using elemental analysis, IR spectra, X-ray diffraction, and mass spectra. Additionally, the thermal behaviour of free ligands in air has been studied by means of thermogravimetry (TG), derivative thermogravimetry (DTG), and differential scanning calorimetry (DSC) measurements. The behaviour of thermal decomposition of the three free ligands was not identical Finally, a computer program has been used for kinetic evaluation of non-isothermal differential scanning calorimetry data according to a composite and single heating rate methods in comparison with the methods due to Ozawa and Kissinger methods. The most probable reaction mechanism for the free ligands was the Avrami-Erofeev equation (A) that described the solid-state nucleation-growth mechanism. The activation parameters of the decomposition reaction for free ligands were calculated and the results of different methods of data analysis were compared and discussed. The Fourth Chapter, the final chapter, deals with the preparation of cobalt, nickel, and copper with mono-pyridine carboxylic acids in aqueous solution. The prepared complexes have been characterised by analyses, IR spectra, X-ray diffraction, magnetic moments, and electronic spectra. The stoichiometry of these compounds was ML2x(H20), (where M = metal ion, L = organic ligand and x = water molecule). The environments of cobalt, nickel, and copper nicotinates and the environments of cobalt and nickel picolinates were octahedral, whereas the environment of copper picolinate [Cu(PA)2] was tetragonal. However, the environments of cobalt, nickel, and copper isonicotinates were polymeric octahedral structures. The morphological changes that occurred throughout the decomposition were followed by SEM observation. TG, DTG, and DSC measurements have studied the thermal behaviour of the prepared complexes in air. During the degradation processes of the hydrated complexes, the crystallisation water molecules were lost in one or two steps. This was also followed by loss of organic ligands and the metal oxides remained. Comparison between the DTG temperatures of the first and second steps of the dehydration suggested that the water of crystallisation was more strongly bonded with anion in Ni(II) complexes than in the complexes of Co(II) and Cu(II). The intermediate products of decomposition were not identified. The most probable reaction mechanism for the prepared complexes was also Avrami-Erofeev equation (A) characteristic of solid-state nucleation-growth mechanism. The tempemture dependence of conductivity using direct current was determined for cobalt, nickel, Cl.nd copper isonicotinates. An activation energy (ΔΕ), the activation energy (ΔΕ ) were calculated.The ternperature and frequency dependence of conductivity, the frequency dependence of dielectric constant, and the dielectric loss for nickel isonicotinate were determined by using altemating current. The value of s paralneter and the value of'density of state [N(Ef)] were calculated. Keyword Thermal decomposition, kinetic, electrical conduclion, pyridine rnono~ carboxylic acid, cOlnplex, transition metal compJex.

Recognizing Decomposition of a Partial Boolean Function

A hard combinatorial problem is investigated which has useful application in design of discrete devices: the two-block decomposition of a partial Boolean function. The key task is regarded: finding such a weak partition on the set of arguments, at which the considered function can be decomposed. Solving that task is essentially speeded up by the way of preliminary discovering traces of the sought-for partition. Efficient combinatorial operations are used by that, based on parallel execution of operations above adjacent units in the Boolean space.

Decomposition of Boolean Functions – Recognizing a Good Solution by Traces

The problem of sequent two-block decomposition of a Boolean function is regarded in case when a good solution does exist. The problem consists mainly in finding an appropriate weak partition on the set of arguments of the considered Boolean function, which should be decomposable at that partition. A new fast heuristic combinatorial algorithm is offered for solving this task. At first the randomized search for traces of such a partition is fulfilled. The recognized traces are represented by some "triads" - the simplest weak partitions corresponding to non-trivial decompositions. After that the whole sought-for partition is restored from the discovered trace by building a track initialized by the trace and leading to the solution. The results of computer experiments testify the high practical efficiency of the algorithm.

Excited electronic state decomposition mechanisms of clusters of dimethylnitramine and aluminum

In this report, electronically non-adiabatic decomposition pathways of clusters of dimethylnitramine and aluminum (DMNA-Al and DMNA-Al-2) are discussed in comparison to isolated dimethylnitramine (DMNA). Electronically excited state processes of DMNA-Al and DMNA-Al-2 are explored using the complete active space self-consistent field (CASSCF) and the restricted active space self-consistent field (RASSCF) theories, respectively. Similar to the nitro-nitrite isomerization reaction pathway of DMNA, DMNA-Al-n clusters also exhibit isomerization pathway. However, it involves several other steps, such as, first Al-O bond dissociation, then N-N bond dissociation followed by isomerization and finally NO elimination. Furthermore, DMNA-Al-n clusters exhibit overall exothermic decomposition reaction pathway and isolated DMNA shows overall endothermic reaction channel.

Decomposition kinetics of iron (III)-diclofenac compound

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

Evaluation of Decomposition Kinetics of Poly (Ether-Ether-Ketone) by Thermogravimetric Analysis

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Country-scale carbon accounting of the vegetation and mineral soils of Finland

The increase in global temperature has been attributed to increased atmospheric concentrations of greenhouse gases (GHG), mainly that of CO2. The threat of severe and complex socio-economic and ecological implications of climate change have initiated an international process that aims to reduce emissions, to increase C sinks, and to protect existing C reservoirs. The famous Kyoto protocol is an offspring of this process. The Kyoto protocol and its accords state that signatory countries need to monitor their forest C pools, and to follow the guidelines set by the IPCC in the preparation, reporting and quality assessment of the C pool change estimates. The aims of this thesis were i) to estimate the changes in carbon stocks vegetation and soil in the forests in Finnish forests from 1922 to 2004, ii) to evaluate the applied methodology by using empirical data, iii) to assess the reliability of the estimates by means of uncertainty analysis, iv) to assess the effect of forest C sinks on the reliability of the entire national GHG inventory, and finally, v) to present an application of model-based stratification to a large-scale sampling design of soil C stock changes. The applied methodology builds on the forest inventory measured data (or modelled stand data), and uses statistical modelling to predict biomasses and litter productions, as well as a dynamic soil C model to predict the decomposition of litter. The mean vegetation C sink of Finnish forests from 1922 to 2004 was 3.3 Tg C a-1, and in soil was 0.7 Tg C a-1. Soil is slowly accumulating C as a consequence of increased growing stock and unsaturated soil C stocks in relation to current detritus input to soil that is higher than in the beginning of the period. Annual estimates of vegetation and soil C stock changes fluctuated considerably during the period, were frequently opposite (e.g. vegetation was a sink but soil was a source). The inclusion of vegetation sinks into the national GHG inventory of 2003 increased its uncertainty from between -4% and 9% to ± 19% (95% CI), and further inclusion of upland mineral soils increased it to ± 24%. The uncertainties of annual sinks can be reduced most efficiently by concentrating on the quality of the model input data. Despite the decreased precision of the national GHG inventory, the inclusion of uncertain sinks improves its accuracy due to the larger sectoral coverage of the inventory. If the national soil sink estimates were prepared by repeated soil sampling of model-stratified sample plots, the uncertainties would be accounted for in the stratum formation and sample allocation. Otherwise, the increases of sampling efficiency by stratification remain smaller. The highly variable and frequently opposite annual changes in ecosystem C pools imply the importance of full ecosystem C accounting. If forest C sink estimates will be used in practice average sink estimates seem a more reasonable basis than the annual estimates. This is due to the fact that annual forest sinks vary considerably and annual estimates are uncertain, and they have severe consequences for the reliability of the total national GHG balance. The estimation of average sinks should still be based on annual or even more frequent data due to the non-linear decomposition process that is influenced by the annual climate. The methodology used in this study to predict forest C sinks can be transferred to other countries with some modifications. The ultimate verification of sink estimates should be based on comparison to empirical data, in which case the model-based stratification presented in this study can serve to improve the efficiency of the sampling design.

空间电流体系地磁反演及理论研究

The space currents definitely take effects on electromagnetic environment and also are scientific highlight in the space research. Space currents as a momentum and energy provider to Geospace Storm, disturb the varied part of geomagnetic field, distort magnetospheric configuration and furthermore take control of the coupling between magnetosphere and ionosphere. Due to both academic and commercial objectives above, we carry on geomagnetic inverse and theoretical studies about the space currents by using geomagnetic data from INTERMAGNET. At first, we apply a method of Natural Orthogonal Components (NOC) to decomposition the solar daily variation, especially for (solar quiet variation). NOC is just one of eign mode analysis, the most advantage of this method is that the basic functions (BFs) were not previously designated, but naturally came from the original data so that there are several BFs usually corresponding to the process really happened and have more physical meaning than the traditional spectrum analysis with the fixed BFs like Fourier trigonometric functions. The first two eign modes are corresponding to the and daily variation and their amplitudes both have the seasonal and day-to-day trend, that will be useful for evaluating geomagnetic activity indices. Because of the too strict constraints of orthogonality, we try to extend orthogonal contraints to the non-orthogonal ones in order to give more suitable and appropriate decomposition of the real processes when the most components did not satisfy orthogonality. We introduce a mapping matrix which can transform the real physical space to a new mathematical space, after that process, the modified components which associated with the physical processes have satisfied the orthogonality in the new mathematical space, furthermore, we can continue to use the NOC decomposition in the new mathematical space, and then all the components inversely transform back to original physical space, so that we would have finished the non-orthogonal decomposition which more generally in the real world. Secondly, geomagnetic inverse of the ring current’s topology is conducted. Configurational changes of the ring current in the magnetosphere lead to different patterns of disturbed ground field, so that the global configuration of ring current can be inferred from its geomagnetic perturbations. We took advantages of worldwide geomagnetic observatories network to investigate the disturbed geomagnetic field which produced by ring current. It was found that the ring current was not always centered at geomagnetic equator, and significantly deviated off the equator during several intense magnetic storms. The deviation owing to the tilting and latitudinal shifting of the ring current with respect to the earth’s dipole can be estimated from global geomagnetic survey. Furthermore those two configurational factors which gave a quantitative description of the ring current configuration, will be helpful to improve the Dst calibration and understand the dependence of ring current’s configuration on the plasma sheet location relative to the equator when magnetotail field warped. Thirdly, the energization and physical acceleration process of ring current during magnetic storm has been proposed. When IMF Bz component increase, the enhanced convection electric field drive the plasma injection into the inner magnetosphere. During the transport process, a dynamic heating is happened which make the particles more ‘hot’ when the injection is more deeply inward. The energy gradient along the injection path is equivalent to a kind of force, which resist the plasma more earthward injection, as a diamagnetic effect of the magnetosphere anti and repellent action to the exotically injected plasma. The acceleration efficiency has a power law form. We use analytical way to quantitatively describe the dynamical process by introducing a physical parameter: energization index, which will be useful to understand how the particle is heated. At the end, we give a scheme of how to get the from storm time geomagnetic data. During intense magnetic storms, the lognormal trend of geomagnetic Dst decreases depend on the heating dynamic of magnetosphere controlling ring current. The descending pattern of main phase is governed by the magnetospheric configuration, which can be describled by the energization index. The amplitude of Dst correlated with convection electric field or south component of the solar wind. Finally, the Dst index is predicted by upstream solar wind parameter. As we known space weather have posed many chanllenges and impacts on techinal system, the geomagnetic index for evaluating the activity space weather. We review the most popular Dst prediction method and repeat the Dst forecasting model works. A concise and convnient Key Points model of the polar region is also introduced to space weather. In summary, this paper contains some new quantitative and physical description of the space currents with special focus on the ring current. Whatever we do is just to gain a better understanding of the natural world, particularly the space environment around Earth through analytical deduction, algorithm designing and physical analysis, to quantitative interpretation. Applications of theoretical physics in conjunction with data analysis help us to understand the basic physical process govering the universe.

In situ study of ozone and hybrid plasma Ag-Al catalysts for the oxidation of toluene: Evidence of the nature of the active sites

Silver colloids have been prepared by reducing AgNO3 in aqueous solution and embeded in alumina following a sol-gel procedure in the presence of Pluronic 84 ((EO)(19)(PO)(39)(EO)(19)), as surfactant. Plasma-catalytic experiments aimed at the mineralization of toluene showed that the selectivity to CO2 was significantly increased in the presence of Ag catalysts compared with results obtained using the plasma alone. In-situ studies of the ozone interaction with catalysts provide an insight into the nature of the active sites of supported silver colloids for mineralization reactions. It is noticeable that when ozone is chemisorbed on embedded Ag colloidal catalysts no change in the silver oxidation state or size is found. The population of the chemisorbed species is higher at lower temperatures, where the non-selective decomposition of ozone is smaller. The catalysts exhibit high stability, preserving the structural and textural properties after the catalytic tests, that is indeed very important in the presence of ozone. (C) 2011 Elsevier B.V. All rights reserved.

Decomposição de resíduos vegetais de plantas de cobertura e produtividade da cultura de milho

Pós-graduação em Agronomia (Produção Vegetal) - FCAV

Vibrational characteristics of brain magnetic resonance elastography

This thesis aims to investigate vibrational characteristics of magnetic resonance elastography (MRE) of the brain. MRE is a promising, non-invasive methodology for the mapping of shear stiffness of the brain. A mechanical actuator shakes the brain and generates shear waves, which are then imaged with a special MRI sequence sensitive to sub-millimeter displacements. This research focuses on exploring the profile of vibrations utilized in brain elastography from the standpoint of ultimately investigating nonlinear behavior of the tissue. The first objective seeks to demonstrate the effects of encoding off-frequency vibrations using standard MRE methodologies. Vibrations of this nature can arise from nonlinearities in the system and contaminate the results of the measurement. The second objective is to probe nonlinearity in the dynamic brain system using MRE. A non-parametric decomposition technique, novel to the MRE field, is introduced and investigated.

The combination of empirical mode decomposition and minimum entropy deconvolution for roller bearing diagnostics in non-stationary operation

Diagnostics is based on the characterization of mechanical system condition and allows early detection of a possible fault. Signal processing is an approach widely used in diagnostics, since it allows directly characterizing the state of the system. Several types of advanced signal processing techniques have been proposed in the last decades and added to more conventional ones. Seldom, these techniques are able to consider non-stationary operations. Diagnostics of roller bearings is not an exception of this framework. In this paper, a new vibration signal processing tool, able to perform roller bearing diagnostics in whatever working condition and noise level, is developed on the basis of two data-adaptive techniques as Empirical Mode Decomposition (EMD), Minimum Entropy Deconvolution (MED), coupled by means of the mathematics related to the Hilbert transform. The effectiveness of the new signal processing tool is proven by means of experimental data measured in a test-rig that employs high power industrial size components.

Composition dependent non-ideality in aqueous binary mixtures as a signature of avoided spinodal decomposition

We explore the potential energy landscape of structure breaking binary mixtures (SBBM) where two constituents dislike each other, yet remain macroscopically homogeneous at intermediate to high temperatures. Interestingly, we find that the origin of strong composition dependent non-ideal behaviour lies in its phase separated inherent structure. The inherent structure (IS) of SBBM exhibits bi-continuous phase as is usually formed during spinodal decomposition. We draw analogy of this correlation between non-ideality and phase separation in IS to explain observation of non-ideality in real aqueous mixtures of small amphiphilic solutes, containing both hydrophilic and hydrophobic groups. Although we have not been able to obtain IS of these liquids, we find that even at room temperature these liquids sustain formation of fluctuating, transient bi-continuous phase, with limited lifetime (tau less than or similar to 20 ps). While in the model (A, B) binary mixture, the non-ideal composition dependence can be considered as a fluctuation from a phase separated state, a similar scenario is expected to be responsible for the unusually strong non-ideality in these aqueous binary mixtures.