Made available in DSpace on 2014-10-09T12:44:55Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:01:00Z (GMT). No. of bitstreams: 1 07019.pdf: 8194512 bytes, checksum: 2e06aca4af1ce7ca845478381a7195b2 (MD5) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP

Made available in DSpace on 2014-10-09T12:47:35Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:08:49Z (GMT). No. of bitstreams: 1 08280.pdf: 6192071 bytes, checksum: 8b416b6373619895be5ca4e67e02afe0 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:96/11795-7

Made available in DSpace on 2014-10-09T12:43:48Z (GMT). No. of bitstreams: 0 / Made available in DSpace on 2014-10-09T14:09:59Z (GMT). No. of bitstreams: 1 06776.pdf: 13953559 bytes, checksum: fbb8c77f5b5bada8939f5c8e246ef8e6 (MD5) / Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP) / Tese (Doutoramento) / IPEN/T / Instituto de Pesquisas Energeticas e Nucleares - IPEN/CNEN-SP / FAPESP:95/03947-9

Submitted by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2018-06-20T14:23:09Z No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Paola- Dissertacao.pdf: 1239637 bytes, checksum: 85c1de7a05b461f7f506a5ad3652d878 (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2018-06-20T14:23:25Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Paola- Dissertacao.pdf: 1239637 bytes, checksum: 85c1de7a05b461f7f506a5ad3652d878 (MD5) / Approved for entry into archive by Divisão de Documentação/BC Biblioteca Central (ddbc@ufam.edu.br) on 2018-06-20T14:23:37Z (GMT) No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Paola- Dissertacao.pdf: 1239637 bytes, checksum: 85c1de7a05b461f7f506a5ad3652d878 (MD5) / Made available in DSpace on 2018-06-20T14:23:37Z (GMT). No. of bitstreams: 2 license_rdf: 0 bytes, checksum: d41d8cd98f00b204e9800998ecf8427e (MD5) Paola- Dissertacao.pdf: 1239637 bytes, checksum: 85c1de7a05b461f7f506a5ad3652d878 (MD5) Previous issue date: 2018-05-18 / The study of the Half-Heusler alloy has drawn a lot of attention among the researchers due to their characteristics and applications, in general, to characterize as ferromagnetic alloys, constituted by non-magnetic elements. In this research, the TiNiSn alloy was produced by the Mechanical Alloyng in two routes, the first in 3h with analysis done at each hour, and the second at 4h straight. The structure and its thermal behavior were investigated by the following techniques: X-ray diffraction (XRD), Differential Scanning Calorimetry (DSC), Thermal Treatment (TT) and Rietveld refinement. According to results obtained, respectively, it was seen that the TiNiSn alloy was produced in 4h grinding by the mechanical alloying method, its diffractograms were verified in order to discover the phases formed in the synthesized alloy in 4h, and by the analysis of differential calorimetry of scanning was seen the thermal behavior of the sample at varied temperatures in a temperature range of 30 °C and 500 °C, so it was possible to analyze the sample by the Thermal Treatment technique. / O estudo da liga Half-Heusler tem chamado muita atenção entres os pesquisadores devido as suas características e aplicações, de uma maneira geral, por caracterizarem-se como ligas ferromagnéticas, constituídas por elementos não magnéticos. Neste trabalho foi produzida e a liga TiNiSn, do tipo Half-Heusler, a fim de analisar sua estrutura. Nesta pesquisa, a liga TiNiSn foi produzida pela técnica de Moagem Mecânica de Alta Energia em dois tempos de moagem, a primeira em 3h com análise feita a cada uma hora, e a segunda em 4h sem pausas. A estrutura e seu comportamento térmico foram investigados pelas seguintes técnicas: Difração de raios X (DRX), Calorimetria Diferencial de Varredura (DSC), Tratamento Térmico (TT) e método de refinamento estrutural de Rietveld (MR). De acordo com os resultados obtidos, respectivamente, foi visto que a liga TiNiSn foi produzida em 4 h de moagem pelo método de mechanical alloying, seus difratogramas foram verificados afim de descobrir as fases formadas na liga sintetizada em 4 h, e pela análise de calorimetria diferencial de varredura (DSC) foi visto o comportamento térmico da amostra em temperaturas variadas, em uma faixa de 30 °C à 500 °C, subsequentemente, foi possível analisar a amostra pela técnica de tratamento térmico.

Master‘s thesis deals with the preparation and evaluation single-phase high-entropy alloy based on cobalt, chromium, iron, nickel and manganese and its variants strengthened by dispersion of oxidic particles. High-entropy alloy was prepared in powder form by mechanical alloying from the equiatomic proportions of atomic powders. Obtained powder was subsequently compacted by spark plasma sintering. By the method of mechanical alloying were successfully prepared single-phase high-entropy alloy and its variant strengthened by dispersion of nanometric yttria oxides. It has been found that the oxide particles present in the microstructure of high-entropy alloy significantly block mobility of grain boundary and dislocation at elevated temperatures. As a result of this behavior were observed doubling of alloy strength and decreasing of creep rate at 800 °C.

The mechanical treatment of solids is one of the most common and widely used operations. The volume of solids subjected to chemical treatment is very large too. Therefore, combining these two ways into one seems to be a logical solution. This method is called the mechanochemical processing of materials. Processing materials in this way has many advantages. On the one hand, this processing is economically as well as technologically feasible. Even the materials that not react together in conventional way can be prepare in this way. The mechanochemistry/mechanochemical synthesis utilizes the mechanical energy to activate chemical reactions and structural changes. The aluminothermic reduction reactions induced by the high – energy ball milling are gaining importance because of the potential applications like the synthesis of microcrystalline and nanocrystalline in – situ metal matrix composites. The mechanical activation of the chemical reactions by high energy ball milling often changes the reaction mechanism and produces metastable materials. Changes of reaction mechanisms during mechanical alloying on four different systems were studied. The system was based on this composition: Al - B2O3 - X (X = C, Ti, Nb, Cr). The possibility of another in – situ reactions during spark plasma sintering process (SPS) was also investigated. All systems were mechanically alloyed under the same conditions. After alloying, on each system scanning electron microscopy was performed and qualitative and quantitative analysis was performed using X-ray diffraction. The indentation hardness and the indentation modulus of elasticity were evaluated using nanoindentation. All analyzes were performed after mechanical alloying as well as SPS and the results were compared to each other. Based on the results, a change of reaction mechanisms was proposed for all systems. It has been found that metal matrix composites are formed and, when chromium is used, hybrid composite material reinforced with intermetallic phase and aluminum borate has been developed.

The subject of this thesis is preparation of CoCrFeMnNiNx high entropy mixtures via the methods of mechanical alloying and spark plasma sintering (SPS). Three series of specimens were fabricated in this thesis: samples milled in argon (benchmark materials), samples milled in nitrogen atmosphere (to observe their ability of nitrogen absorption) and samples microalloyed with CrN, FeN nitrides (to observe their dissociation into the solid solution potential). The fabricated powders and SPS compacts were subsequently observed by electron microscopy and their phase content by X-Ray diffraction (XRD) and elemental composition by EDS analysis were carried out. A method of reduction melting in inert atmosphere was used to determine the exact oxygen and nitrogen content in powders, while the respective particle size distribution measured by laser diffraction method. The influence of nitrogen content on the hardness of the samples was studied via the microhardness measured. After completing the process of mechanical alloying under the Nitrogen atmosphere was the maximal concentration of nitrogen in the structure 0,208% after 24 hours of milling (dependency on time was linear), which means, the method of milling under the Nitrogen atmosphere was successful. XRD of milled samples showed the existence of the only FCC single solid solution phase, while samples milled under the Nitrogen atmosphere showed the trend of the growth of the lattice parameter with the increasing nitrogen content. There was observed the presence of the chromium nitrides precipitates on the grain boundaries of the FCC phase in microalloyed samples. All specimen were contaminated by a mixture of metallic oxides and manganeese sulphides, which were present in the default manganeese powder. The greatest value of microhardness showed the duplex sample. The increase in values of microhardness (344 HV 0,3) in comparison with the standard sample (262,9 HV 0,3) was recorded on the samples milled under the nitrogen atmosphere, which conforms the positive influence of the nitrogen content on strength characteristics of this alloy.

No description available.

Bulk metallic glasses have interesting combination of physical, chemical, mechanical, and magnetic properties which make them attractive for a variety of applications. Consequently there has been a lot of interest in understanding the structure and properties of these materials. More varied applications can be sought if one understands the reasons for glass formation and the methods to control them. The glass-forming ability (GFA) of alloys can be substantially increased by a proper selection of alloying elements and the chemical composition of the alloy. High GFA will enable in obtaining large section thickness of amorphous alloys. Ability to produce glassy alloys in larger section thicknesses enables exploitation of these advanced materials for a variety of different applications. The technique of mechanical alloying (MA) is a powerful non-equilibrium processing technique and is known to produce glassy (or amorphous) alloys in several alloy systems. Metallic amorphous alloys have been produced by MA starting from either blended elemental metal powders or pre-alloyed powders. Subsequently, these amorphous alloy powders could be consolidated to full density in the temperature range between the glass transition and crystallization temperatures, where the amorphous phase has a very low viscosity. This Dissertation focuses on identifying the various Fe-based multicomponent alloy systems that can be amorphized using the MA technique, studying the GFA of alloys with emphasis on improving it, and also on analyzing the effect of extended milling time on the constitution of the amorphous alloy powder produced at earlier times. The Dissertation contains seven chapters, where the lead chapter deals with the background, history and introduction to bulk metallic glasses. The following four chapters are the published/to be published work, where the criterion for predicting glass formation, effect of Niobium addition on glass-forming ability (GFA), lattice contraction on amorphization, effect of Carbon addition on GFA, and observation of mechanical crystallization in Fe-based systems have been discussed. The subsequent chapter briefly mentions about the consolidation of amorphous powders and presents results of hot pressing and spark plasma sintering on one of the alloy systems. The final chapter summarizes the Dissertation and suggests some prospective research work that can be taken up in future. The Dissertation emphasizes the glass-forming ability, i.e., the ease with which amorphization can occur. In this work the milling time required for amorphization was the indicator/measure of GFA. Although the ultimate aim of this work was to consolidate the Fe-based amorphous alloy powders into bulk so as to undertake mechanical characterization, however, it was first necessary to study the glass forming aspect in the different alloy systems. By doing this a stage has been reached, where different options are available with respect to amorphous phase-forming compositions and the knowledge to improve glass-forming ability via the mechanical alloying technique. This will be ultimately useful in the powder compaction process into various shapes and sizes at optimum pressure and temperature. The study on mechanical crystallization indicates, or in a way defines, a limit to the process of amorphization, and it was also demonstrated that this phenomenon is more common in occurrence than and not as restricted as it was earlier reported to be.

Aujourd'hui, l'impact environnemental de chaque technologie fait l'objet de toutes les attentions. L'élimination des composés soufrés et surtout de H2S dans les gaz entre dans cet aspect écologique au sein de plusieurs processus industriels. L'oxyde de zinc est utilisé comme adsorbant régénérable pour la désulfuration. Le but de ce travail est la préparation de filtres monolithiques macroporeux et de nanopoudres de ZnO avec une forte capacité en soufre et facilement régénérable, ainsi que l'optimisation de leurs propriétés.Des matériaux composites ZnS/NaCl sont tout d'abord synthétisés par combustion auto-propagée à partir de mélanges de zinc, de soufre et de chlorure de sodium. NaCl est éliminé par lixiviation dans l'eau après la synthèse. Les nanopoudres de ZnS sont préparées par mécanosynthèse à partir de mélanges de zinc et de soufre. Les deux matériaux préparés ont des structures cristallines différentes, de type würtzite pour les filtres de ZnS et de type sphalerite pour les poudres. Cette différence est due aux deux voies de synthèse. Monolithes et poudres ZnS sont ensuite convertis en ZnO par traitement thermique sous air à 700 °C.Les transformations macro- et microstructurales des filtres et des poudres ont été étudiées au cours de cycles de sulfuration-oxydation par les méthodes de caractérisation telles que la diffraction des rayons X, la microscopie électronique à balayage et la porosimétrie au mercure. Les résultats montrent que les propriétés des matériaux restent très stables au cours des conversions successives. Enfin, les filtres et nanopoudres de ZnO ont été utilisés comme adsorbants au cours d'essais de désulfuration. La capacité massique en soufre des filtres est assez faible, 6,4 mg S/g ads. montrant que la porosité doit être améliorée. Quant aux nanopoudres, la capacité massique en soufre est très élevée, 272 mg S/g ads, prouvant que la surface spécifique est très importante pour ce type d'application. / Today, we have to take care of every technology's environmental effects. The removal of H2S and other sulfur compounds in hot gas enters this ecological aspect in several industrial processes. Zinc oxide is used here as a regenerable sorbent for gas desulfurization. The goal of this work is, the preparation of macroporous ZnO monolithic filters and nanopowders with high sulfur capacity and easily regenerable, and their optimization with the control of their properties. ZnS/NaCl composite materials are first obtained by Self-propagating High temperature Synthesis from mixtures of zinc, sulfur and sodium chloride powders. NaCl is then removed by lixiviation with water. ZnS nanopowders are prepared by mechanical alloying from mixtures of zinc and sulfur. The two materials have different crystalline structure, würtzite type for ZnS filters and sphalerite type for powders, because of the way of synthesis. Then, they are converted into ZnO by thermal treatment under air at 700 °C. Next, the macro- and microstructure transformations of both filter and powders during sulfidation-oxidation cycles are thus considered. Results of all characterizations like X-ray diffraction, scanning electron microscopy and Hg porosimetry show that materials properties are very stable against conversions. Afterwards, ZnO filters and nanopowders are used as adsorbent in desulfurization trials. The sulfur capacity of filters is not so high, 6,4 mg S/g ads and shows that porosity has to be improved. Regarding nanopowders, the sulfur capacity is very high, 272 mg S/g ads, proving that surface area is very important in this application.