In recent decade growing concerns of CO2 emissions from power plants have increased, which led to development of technologies like oxy-fuel combustion process. P91 steel is profoundly used in power plants, but oxy fuel combustion exacerbates corrosion due to recycling of flue gas. This paper studied the kinetics of the corrosion rate on the boiler tubes and furnace and help achieve a corrosion resistant coating over it. Refractory metal diffusion coating is created and tested at high temperature in corrosive atmosphere. This was done by forming Ti and Zr diffusion coating on P91 steel using pack cementation. Coating thickness of 12 and 20 µm were obtained for Ti and Zr respectively. These samples were tested in thermo-gravimetric system by heating at 950˚C for 24 hours in 5% oxygen in Helium gas. Heating in an oxidizing environment lead to exfoliation corrosion on uncoated P91 steel. TGA procedure confirmed less mass change of Ti and Zr coated samples, than that of uncoated P91 steel sample. SEM and depth profiling confirms oxygen penetration is 2.7mm in uncoated P91 steel sample, whereas the Ti and Zr Coated samples oxygen penetration is just 16 and 56 µm respectively.

Coal is a chemical compound with a complex composition. Proximate and ultimate analysis as well as physical and mechanical tests which are available do not furnish all the information required by industry. Information regarding e.g. the burning properties of coal is required by furnace and boiler designers. Thermal analysis can be used for studying these properties using small masses of coal. Differential thermal analysis (DTA) where temperature variations are measured which result from reactions which occur when coal is heated and thermogravimetric analysis, (TGA) where similarly mass variations are measured, are regarded as important. Results from eg. TGA tests are usually interpreted without unified and formally accepted prescripts. It is desirable to investigate how the best use can be made of thermal analysis of coal, using DTA and TGA, and to devise a procedure for interpreting the results. The problem is approached by studying DTA and TGA results obtained from a specially selected group of coals for which other analytic data are available. The samples were prepared according to the standard procedure for the laboratory analysis of coal. At first, related information published by other researchers were integrated and parameters used by them identified and assessed in terms of fundamental scientific principles. Special experiments were conducted to probe the situation regarding orthodox kinetics of reactions and its related theory and observed discrepancies with regard to coal and its decomposition characteristics. It was found, along with other observers, that eg. activation energy values which are derived from TGA data should be used with extreme caution. In general an empirical approach for interpretation of results has much to offer. A system is developed by which various thermal techniques, executable by a single instrumental arrangement can be identified by expressing them in matrix format using as indexes, heating arrangement, reactant type and reaction environment. 5(1,1,2) e.g. designates a linearly heated mass of coal in air at atmospheric pressure. To enhance the comparison of TG characteristics of similar coals they should be classified according to a matrix arrangement C(g,t,r) which is based on three index parameters namely, grade ie. the ash content, type ie. the vitrinite content and rank. A TG test provides the basic requirements for computing the indexes using formulae provided by the originators. Information which can only be derived from a TG experiment e.g. 5(1,1,2), are referred to as specification parameters. The information consists of e.g. a series of temperatures which identify specific reaction changes in the coal. Several other parameters can be derived. Coals are assessed by comparing their specification parameters. Only two of the S(i,j,k) techniques are described in detail namely TG dispersion 5(1,1,2) and drop furnace burnout 5(3,1,2). The dispersion technique requires a linear increasing furnace temperature while the near sample temperature is also measured. This technique shows the decomposition stages of coal from dehydration to complete burnout. The drop furnace technique, involves a sudden exposure of the coal to a hot furnace environment with free air access: Actual burnout of coal is emulated. The model is not perfect for combustion but the best that can conveniently be acquired for comparing the burning responses of coals. To illustrate the type of information which can be obtained with other S(i,j,k) techniques experimental results of eg. a devolatilization test are presented. Brief reference is made to the role that particle size plays during combustion and the importance of the composition of volatiles which are released is indicated by presenting relevant information from external sources. The chemical composition and structure of the coals could not be determined but relevant information from an external source was presented which has a bearing on the practical analytic procedure which was described. After a study of the group TG characteristics of the various coals and discussion of the conclusions which are justified a practical procedure is described according to which the equipment can be used both for routine or special purpose analysis of coal. / Thesis (PhD)--University of Pretoria, 2013. / Geology / unrestricted

No description available.

M.Tech (Department of Chemistry, Faculty of Applied and Computer Sciences), Vaal University of Technology. / Dithiocarbamate ligands and their complexes has been a subject of interest in various fields but they found much interest in medical applications as potential anti-microbial agents. The dithiocarbamate ligands were used to prepare complexes of copper and zinc. All the prepared ligands and complexes were characterized using techniques such as IR and 13CNMR spectroscopy and thermogravimetric analysis (complexes). The data obtained from the spectroscopies was consistent with the coordination of the ligand to the metal ion through the sulfur atoms of the dithiocarbamate or thioureide moiety. The thermal analysis of the prepared complexes gave a final residue of metal sulfide, thus indicating the potential of the prepared complexes as single molecular precursor for the synthesis of metal sulfide nanoparticles. The prepared complexes were then used to synthesize metal sulfide nanoparticles. The nanoparticles were successfully prepared by thermal decomposition of a single-source precursor (dithiocarbamate complexes) in a solution of hexadecylamine (HDA) or tri-n-octylphosphine oxide (TOPO). The investigated parameters were the capping molecule (HDA and TOPO), and capping molecule concentration (3 g and 6 g) to see their effect on the shape and size of the synthesized nanomaterials. The synthesized metal sulfide nanoparticles were characterized using techniques such as UV-vis spectroscopy, photoluminescence spectroscopy, X-ray diffraction analysis and transmission electron microscopy. The absorption study showed some interesting features in the prepared nanomaterials. The first was the red-shifted spectra of the ZnS nanoparticles which was attributed to the impurities and that assumption was further confirmed by the XRD analysis that showed a sulfur impurity and other amorphous peaks. The second was the localized surface plasmon resonances on the copper sulfide nanoparticles that suggested the formation of electron deficient copper sulfide stoichiometry that was further confirmed by XRD analysis that gave hexagonal phase copper sulfide covellite. The TEM images of the prepared nanoparticles showed that the concentration and the capping molecule has an effect on the size and shape of the synthesized nanoparticles. The increase in capping concentration gave a decrease in particle size in most of the prepared nanoparticles, while they were few exceptions. The capping molecule effect showed that most of the nanoparticles prepared from TOPO were spherical in shape and were well dispersed compared to the mixed morphological nanoparticles prepared from HDA. There were also exceptions of the well dispersed HDA-capped nanoparticles.

Fluorinated polymers of substantial high performance such as perfluorocyclobutyl (PFCB) and fluorinated aryl vinyl ether (FAVE) polymers can readily be synthesized by thermal [2+2] cyclopolymerization as a melt or by classical polycondensation. These fluoropolymers naturally possess high thermal and chemical resistance, low conductivity properties, and other mechanical properties. In this work, a method using 0th order kinetics is proposed and thermal degradation studies were conducted on six different aromatic ether-based polymers to gauge trends in activation energy barrier and differences in thermal stability by 0th order degradation kinetics. The activation barrier (E_a) obtained can give accurate insight into the stability of the polymer based only on structure for external applications. Activation energies ranging from 17 to 41 kcal/mol were obtained for the various polymers. Overall, this study provides an established method using TGA for thermal stability studies through 0th order kinetics that can be potentially used for future lab applications.

Šioje daktaro disertacijoje pirmoje dalyje nustatyta šiuolaikinės, o antroje dalyje – archeologinės keramikos gaminių elementinė ir fazinė sudėtis, bei ištirta morfologija. Šiuolaikinės ir archeologinės keramikos pavyzdžių elementinė sudėtis nustatyta Rentgeno spindulių dispersinės analizės (EDX), liepsnos atominės absorbcinės spektrometrijos (LAAS), titrimetrinės ir spektrofotometrinės analizės metodais. Parodyta, kad visų keraminių pavyzdžių kokybinė bei kiekybinė sudėtis yra skirtinga Nustatyta, kad visuose keramikos mėginiuose pagrindiniai elementai yra silicis ir aliuminis. SiO2 sudaro 46 – 60% keramikos sudėties, Al2O3 – apie 17 – 33%. Fe, Na, Mg, K, Ca ir Ti mėginiuose rasta kelis kartus mažiau. EDX analizė gali būti sėkmingai naudojama nustatant pagrindinius elementus, kurių kiekiai viršija 0,5 % bendros elementinės sudėties. Norint nustatyti tikslią keramikos sudėtį ir pėdsakinius elementus reikia naudoti LAAS analizės metodą. Aliuminio kiekį keramikoje patikimai galima nustatyti titrimetriniu, o silicio ir titano kiekį – spektrofotometriniais metodais. Ištyrus šiuolaikę ir archeologinę keramiką Rentgeno spindulių difrakcine analize (XRD), nustatyta, kad visų keramikų pagrindinė fazė yra vienoda – silicio dioksidas SiO2, tačiau jų bendra fazinė sudėtis skiriasi. Skirtinguose kermikos pavyzdžiuose buvo aptikos šios fazės: kvarcas, dolomitas, kaolinas, albitas, mikroklinas, muskovitas, mulitas, hematitas, rutilas, diopsidas, korundas, titanitas, natrio anortitas... [toliau žr. visą tekstą] / The elemental composition of the samples of modern and archaeological ceramics was determined using the energy dispersive X-ray analysis, flame atomic absorption spectrometry, titrimetric and spectrophotometric analysis methods. It has been shown that the qualitative and quantitative composition of all the samples is different. It has been established that silicon and aluminium are the main elements in all the samples. SiO2 accounts for 46–60 % of the composition of the ceramics, Al2O3 – for some 17–33%. The amounts of Fe, Na, Mg, K, Ca and Ti discovered in the samples are several times lesser. EDX analysis can successfully be used in determining the main elements whose amounts exceed 0.5% of the overall elemental composition. In order to determine the exact composition of ceramics one has to employ the FAAS analysis method. To determine in a credible manner the amount of aluminium in ceramics, one can use the titrimetric method, and the amount of silicon and titanium – spectrophotometric methods. Upon examination of the modern and archaeological ceramics by diffraction analysis it has been established that the main phase of all the samples is the same – quartz SiO2, however their phase composition varies. In different samples the following phases have been discovered: calcite, dolomite, kaolinite, albite, microcline, muscovite, mullite, hematite, rutile, diopside, corundum, titanite, and sodium anorthite. Being aware of the phase composition, it has been established that the... [to full text]

Orientador: Massao Hionashiro / Banca: Lazaro Moscardini D'Assunção / Banca: Nedja Suely Fernandes / Banca: José Marques Luiz / Banca: Salvador Claro Neto / Resumo: Sintetizou-se o ácido 2-metoxicinamalpirúvico (2-MeO-HCP), através da reação de condensação aldólica do 2-metoxicinamaldeído (CH3O-C6H4-(CH)2-CHO), 96 % de pureza com o piruvato de sódio, (Na-2-MeO-CP), 99% puro, ambos da Aldrich. A pureza do ácido 2-metoxicinamalpirúvico sintetizado foi determinada por DSC através do pico de fusão em 125 ºC. O ácido 2-metoxicinamalpirúvico foi convertido a uma solução de aproximadamente 0,15 mol L-1 de 2-metoxicinamalpiruvato de sódio (pH~7,5). Com esse sal foram sintetizados os compostos no estado sólido (Ln-2-MeO-CP.nH2O), sendo que Ln representa os lantanídeos trivalentes e Y(III), 2-MeO-CP o ligante 2-metoxicinamalpiruvato e n o número de moléculas de água com n = 1,5 para o composto de túlio e itérbio e para os demais compostos n = 1. Os Ln-2-MeO-CP.nH2O foram obtidos no estado sólido por adição lenta do ligante aos respectivos cloretos metálicos ou nitratos sob agitação contínua até a total precipitação dos íons metálicos. Os precipitados foram filtrados em papel de filtro Whatman n 42 lavando-se os mesmos com água destilada até a obtenção de teste negativo para cloretos com AgNO3 em meio nítrico e difenilamina para nitratos. Posteriormente os precipitados foram secos em temperatura ambiente e armazenados em dessecador contendo cloreto de cálcio. Técnicas instrumentais utilizadas no estudo dos compostos: Termogravimetria e Análise Térmica Diferencial Simultânea (TG-DTA) e Calorimetria Exploratória Diferencial (DSC) e Complexometria com EDTA (padrão de 1,000 x 10-2 mol L-1 ) forneceu informações sobre grau de hidratação, comportamento térmico e estequiometria; Difratometria de Raios X pelo método do pó, informações da cristalinidade e Espectroscopia de Absorção na Região do Infravermelho sugeriu a forma de coordenação dos compostos sintetizados. Na caracterização do ácido... (resumo completo, clicar acesso eletrônico abaixo) / Abstract: The 2-methoxycinnamylidenepyruvic acid (2-MeO-HCP) was synthesized through the reaction of aldolic condensation of 2-methoxycinnamaldehyde (CH3O-C6H4-(CH) 2-CHO), 96% purity, with sodium pyruvate, (Na-2 - MeO-CP) 99% pure, both from Aldrich. The purity of 2-methoxycinnamylidenepyruvic synthesized was determined by DSC through the melting peak at 125 ºC. The 2-methoxycinnamylidenepyruvic acid was converted to a solution of about 0.15 mol L-1 of the sodium 2-methoxycinnamylidenepyruvate (pH ~ 7.5). With this salt were synthesized the solid compounds (Ln-2-MeO-CP.nH2O), where Ln represents trivalent lanthanides and Y (III), 2-MeO-CP is the methoxycinnamylidenepyruvate ligand and n the number of water molecules with n = 1.5 for the compound thulium, ytterbium and for the other compounds, n = 1. The Ln-2-MeO-CP.nH2O were obtained in the solid state by slow addition of the ligand to the respective metal chlorides or nitrates on continuous stirring until total precipitation of metal ions. The precipitates were filtered through filter paper Whatman number 42, washing them with distilled water to obtain a negative test for chloride with AgNO3 in nitric acid and diphenylamine to nitrates. Subsequently the precipitates were dried at room temperature and stored in a desiccator containing calcium chloride. Instrumental techniques used in the study of compounds: Thermogravimetry and differential thermal analysis (TG-DTA), Differential Scanning Calorimetry (DSC) and Complexometry with EDTA (standard padrão de 1,000 x 10-2 mol L-1 ) provided information on degree of hydration, thermal behavior and stoichiometry; X-ray Diffractometry by the method of powder provided information about crystallinity, and Absorption Spectroscopy in the Infrared Region suggested the form of coordination of the compounds synthesized. In the characterization of 2-methoxycinnamylidenepyruvic, apart from the DSC... (Complete abstract click electronic access below) / Doutor

Ligand-stabilized metal nanoparticles (LSNPs) have garnered significant attention for use in applications including sensing, catalysis, and thin film fabrication. Many uses rely on the size-dependent properties of the metal nanoparticle core. Therefore, preservation of nanoparticle core size is of paramount importance. In other uses, the low processing temperatures afforded by metal LSNPs make them attractive as precursors for conductive thin films. In these distinctly different applications, understanding nanoparticle thermal stability is crucial. A key finding of this research is that nanoparticle sintering is dependent upon both core size and ligand functionality. Multi-technique analysis of four types of gold nanoparticles (AuNPs) with different ligand compositions and core sizes illustrates that more volatile ligands reduce the onset temperature for sintering. Also, AuNPs of larger core size with the same ligand composition exhibit lower sintering onset temperatures. Correlation between measurements reveals that only a small amount of ligand loss is necessary to trigger rapid sintering and that ligands are excluded to the surface of the porous gold films. AuNPs with ligand shells composed of two alkanethiols of different chain length and volatility indicate that the onset temperature of sintering can be tuned further through incorporation of a small amount of more volatile alkanethiol into a ligand shell of lower volatility. Mixed LSNPs further reveal that AuNP thermal stability depends upon the ligand shell composition and its intermolecular interactions, which can result in markedly different sintering behavior for different ligand compositions. Long-chain alkanethiol AuNPs sinter after only a small amount of ligand loss, whereas short-chain alkanethiol AuNPs sinter following complete ligand loss and the formation of metastable bare AuNPs. Heated AuNP films prepared with mixed-ligand AuNPs exhibit ligand-dependent differences in film morphology. To probe AuNP thermal stability in 2D-assemblies, self-assembly using larger ‘marker’ nanoparticles enables the study of small 1.5 nm AuNP arrays with successive TEM monitoring throughout ex situ heating. Monitoring images of the same area shows short-range (1-2 nm) nanoparticle migration/coalescence. In contrast to 3D assemblies, AuNP growth occurs at temperatures as low as 60 °C. This dissertation includes previously published and unpublished co-authored material. / 10000-01-01

Made available in DSpace on 2016-12-23T14:02:51Z (GMT). No. of bitstreams: 1 Larissa Machado Alvarenga.pdf: 5166821 bytes, checksum: 9a52b626a19ffe6c666fd34df1f01780 (MD5) Previous issue date: 2013-09-06 / Coordenação de Aperfeiçoamento de Pessoal de Nível Superior / Muitos processos têm sido utilizados para a reciclagem dos resíduos de embalagens cartonadas. A pirólise se destaca como uma tecnologia promissora capaz de separar o alumínio do polietileno e gerar produtos com maior poder calorífico. Neste trabalho, realizou-se um estudo das reações de pirólise dos resíduos cartonados e de seus componentes puros, a fim de estimar os parâmetros cinéticos destas reações. Para isto, análises termogravimétricas isotérmicas e dinâmicas foram realizadas e dois diferentes tipos de modelos cinéticos foram utilizados: os isoconversionais e o das reações paralelas independentes (RPI). Os modelos isoconversionais permitiram calcular a energia de ativação global da reação de pirólise dos materiais, de acordo com as suas conversões. Os valores de energia de ativação obtidos com os modelos de Ozawa, K-A-S e Starink para a pirólise das embalagens cartonadas foram semelhantes (168,30; 166,54 e 166,78 kJ.mol-1), assim como aqueles encontrados para o polietileno (137,41; 132,49; 132,98 kJ.mol-1) e para o papel cartão (155,66; 153,46; 153,69 kJ.mol-1). Entretanto, o método de Kissinger estimou menores valores de energia de ativação para as embalagens cartonadas (121,42 kJ.mol-1) e para o papel cartão (144,89 kJ.mol-1), e um maior valor para a energia de ativação do polietileno (155,15 kJ.mol-1). O modelo RPI, por sua vez, permitiu calcular os parâmetros cinéticos de cada um dos subcomponentes da embalagem cartonada e do papel cartão. Os valores estimados para os parâmetros cinéticos dos subcomponentes dos materiais permaneceram dentro da faixa de valores encontrada na literatura. A perda de massa dos materiais simulada com o modelo RPI apresentou um bom ajuste aos dados experimentais obtidos por termogravimetria, com valores de desvios na mesma ordem de grandeza daqueles encontrados em outros trabalhos na literatura. Foi realizada ainda, uma análise de sensibilidade paramétrica do modelo RPI, através da qual se pode verificar que a energia de ativação afetou a conversão total dos materiais de forma mais acentuada do que o fator pré-exponencial. Em geral, este trabalho contribuiu na avaliação da qualidade dos ajustes dos modelos cinéticos utilizados e para o cálculo dos parâmetros cinéticos da pirólise dos materiais / Many processes have been used for recycling of carton packaging wastes. The pyrolysis highlights as a promising technology to be used for recovering the aluminum from polyethylene and generating products with high heating value. In this research, a study on pyrolysis reactions of carton packaging wastes and its pure components was performed in order to estimate the kinetic parameters of these reactions. For this, dynamic and isothermal thermogravimetric analyses were carried out and two different kinds of kinetic models were used: the isoconversional and Independent Parallel Reactions (IPR). Isoconversional models allowed to calculate the overall activation energy of the material pyrolysis reaction, in according to their conversions. The activation energy values obtained with Ozawa, KAS and Starink models for carton packaging pyrolysis were similar (168.30, 166.54 and 166.78 kJ.mol-1), as well as the results found for polyethylene (137.41, 132.49, 132.98 kJ.mol-1) and cardboard (155.66, 153.46, 153.69 kJ.mol-1). Nevertheless, the Kissinger method the method of Kissinger estimated lower values of activation energy for carton packaging (121.42 kJ.mol-1) and cardboard (144.89 kJ.mol-1), and a higher value for polyethylene activation energy (155.15 kJ.mol-1). The IPR model, in turn, allowed the calculation of kinetic parameters of each one of the carton packaging and paperboard subcomponents. The estimated values for the kinetic parameters of the material subcomponents were within the range of values found in the literature. The mass loss of materials simulated with the RPI model showed a good fit to the experimental data obtained by thermogravimetry, presenting deviation values in the same order of magnitude as those found in other literature studies. It was also performed a parametric sensitivity analysis of IPR model, that shown that the activation energy affected the total conversion of the material more strongly than the pre-exponential factor. In general, this work contributed to the quality evaluation of the kinetic models adjustment and for the calculation of the kinetic parameters of material pyrolysis

A crescente necessidade de se obter fontes de energia e materiais mais sustentáveis tem aumentado o interesse em processos baseados na conversão de biomassa. Microalgas são particularmente interessantes por não competirem com alimentos e serem facilmente adaptáveis ao meio de crescimento. Além disso, microalgas podem ser processadas termicamente para geração tanto de biocombustíveis quanto de produtos químicos úteis. Estudos de conversão térmica de microalgas tem aparecido apenas em anos recentes, endereçando principalmente temperaturas entre 350 e 500 ºC. Neste estudo, a pirólise em temperaturas entre 500 e 900 ºC foi avaliada pelo interesse em se obter biocombustíveis e produtos químicos úteis. As classes de compostos obtidos a partir da pirólise isotérmica da microalga da espécie Chlorella vulgaris foram investigadas através de um sistema composto por um pirolisador conectado a um CG/MS. Dentre as classes identificadas, houve uma predominância de compostos aromáticos e nitrogenados, principalmente derivados de proteínas. Além disso, a maioria dos compostos identificados na corrente de produtos voláteis está presente em todas as temperaturas de reação estudadas. Os parâmetros cinéticos de energia de ativação aparente, constante de reação e ordem de reação foram determinados através de três modelos cinéticos conhecidos como K-A-S, Osawa e Freeman-Carroll, a partir de dados termogravimétricos. A energia de ativação determinada para Chlorella apresentou valores entre 60 e 206 kJ/mol, enquanto a ordem de reação teve como resultado valores entre segunda e décima ordem, de acordo com o modelo cinético. / The increasing need to obtain more sustainable sources of energy and raw materials has attracted attention to processes based on biomass conversion. Microalgae are particularly interesting because they do not compete with human food and they are easily adaptable to the growth medium. Besides, microalgae can be thermally processed to produce both biofuels and useful chemicals. Studies on thermal conversion of microalgae have appeared only in recent years, addressing mainly reaction temperatures between 350 and 500 °C. In this study, pyrolysis in temperatures ranging from 500 to 900 ºC have been investigated considering the interest in producing biofuels and useful chemical compounds. The classes of products obtained by isothermal pyrolysis of the Chlorella vulgaris microalgae have been investigated using a pyrolyzer directly connected to a GC/MS system. Among the classes identified, there was a predominance of aromatic and nitrogenous compounds, mainly protein derived compounds. In addition, most products identified in the volatile products stream are present in all reaction temperatures investigated. The kinetic parameters of apparent activation energy, reaction constant and order of reaction were determined through three kinetic models known as K-A-S, Osawa and Freeman-Carroll, calculated from thermogravimetric data. The activation energy for Chlorella presented values within the range of 60 and 206 kJ/mole, while the order of reaction resulted in values between second and tenth order, from the different methods.