Behaviour of Gaseous Chlorine and Alkali Metals During Biomass Thermal Utilisation

The behaviour of gaseous chlorine and alkali metals of three sorts of biomass (Danish straw, Swedish wood, and sewage sludge) in combustion or gasification is investigated by the chemical equilibrium calculating tool. The ranges of temperature, air-to-fuel ratio, and pressure are varied widely in the calculations (T=400-1800 K, gimel=0-1.8, and P=0.1-2.0 MPa). Results show that the air excess coefficient only has less significant influence on the release of gaseous chlorine and potassium or sodium during combustion. However, in biomass gasification, the influence of the air excess coefficient is very significant. Increasing air excess coefficient enhances the release of HCl(g), KOH(g), or NaOH(g) as well as it reduces the formation of KCl(g), NaCl(g), K(g), or Na(g). In biomass combustion or straw and sludge gasification, increasing pressure enhances the release of HCl(g) and reduces the amount of KCI(g), NaCl(g), KCI(g), or NaOH(g) at high temperatures. However, during wood gasification, the pressure enhances the formation of KOH(g) and KCI(g) and reduces the release of K(g) and HCl(g) at high temperatures. During wood and sewage sludge pyrolysis, nitrogen addition enhances the formation of KCN(g) and NaCN(g) and reduces the release of K(g) and Na(g). Kaolin addition in straw combustion may enhance the formation of potassium aluminosilicate in ash and significantly reduces the release of KCl(g) and KOH(g) and increases the formation of HCl(g).

Imidazolium-Based Organic Structure Directing Agents for the Synthesis of Microporous Materials

The central theme of this thesis is the use of imidazolium-based organic structure directing agents (OSDAs) in microporous materials synthesis. Imidazoliums are advantageous OSDAs as they are relatively inexpensive and simple to prepare, show robust stability under microporous material synthesis conditions, have led to a wide range of products, and have many permutations in structure that can be explored. The work I present involves the use of mono-, di-, and triquaternary imidazolium-based OSDAs in a wide variety of microporous material syntheses. Much of this work was motivated by successful computational predictions (Chapter 2) that led me to continue to explore these types of OSDAs. Some of the important discoveries with these OSDAs include the following: 1) Experimental evaluation and confirmation of a computational method that predicted a new OSDA for pure-silica STW, a desired framework containing helical pores that was previously very difficult to synthesize. 2) Discovery of a number of new imidazolium OSDAs to synthesize zeolite RTH, a zeolite desired for both the methanol-to-olefins reaction as well as NOX reduction in exhaust gases. This discovery enables the use of RTH for many additional investigations as the previous OSDA used to make this framework was difficult to synthesize, such that no large scale preparations would be practical. 3) The synthesis of pure-silica RTH by topotactic condensation from a layered precursor (denoted CIT-10), that can also be pillared to make a new framework material with an expanded pore system, denoted CIT-11, that can be calcined to form a new microporous material, denoted CIT-12. CIT-10 is also interesting since it is the first layered material to contain 8 membered rings through the layers, making it potentially useful in separations if delamination methods can be developed. 4) The synthesis of a new microporous material, denoted CIT-7 (framework code CSV) that contains a 2-dimensional system of 8 and 10 membered rings with a large cage at channel intersections. This material is especially important since it can be synthesized as a pure-silica framework under low-water, fluoride-mediated synthesis conditions, and as an aluminosilicate material under hydroxide mediated conditions. 5) The synthesis of high-silica heulandite (HEU) by topotactic condensation as well as direct synthesis, demonstrating new, more hydrothermally stable compositions of a previously known framework. 6) The synthesis of germanosilicate and aluminophosphate LTA using a triquaternary OSDA. All of these materials show the diverse range of products that can be formed from OSDAs that can be prepared by straightforward syntheses and have made many of these materials accessible for the first time under facile zeolite synthesis conditions.

掺铒钙铝硅玻璃的光学带隙

玻璃中稀土掺杂的离子的光谱性质受其周围的玻璃结构和在玻璃基质中的分布影响很大。利用熔融法制备了组分为9SiO2·26Al2O3·65CaO·1．0Er2O3·0．3Yb2O3和分别加入MgO以及La2O3的掺铒钙铝硅玻璃，并研究了其吸收边和光学带隙。计算得出离子填充比随玻璃的平均摩尔质量的增大而减小，同时利用Judd—Ofelt模型计算出该玻璃体系的Ω2，Ω4和Ω6参数，并进行了分析。随着MgO或La2O3的加入，吸收边向短波长移动，光学带隙增大，同时Ω2和Ω6值也增大。对ln（α）和hω的曲线进行线性拟

铒掺杂钠铝硅玻璃成分对其光谱性质的影响

研究了Na2O含量对Na2O-Al2O3-SiO2(NAS)玻璃的光谱性质的影响。利用Judd-Ofelt(J-O)理论和吸收光谱计算了Er^3+掺杂的铝硅酸盐玻璃的Ωt参数、自发辐射几率和自发辐射寿命，分析了Ωt参数与Na2O含量的关系以及与吸收截面，Er^3+离子^4I13 2能级的自发辐射几率和荧光半峰全宽(FWHM)等性质的关系。随Na2O含量的增加．J-O参数Ωt(t=2，4，6)减小，Er^3+离子1533nm的吸收截面和荧光半峰全宽．Er^3+离子^4I13 2能级的自发辐射几率也减小，而E

Preparation and spectroscopic properties of Er3+-doped high silica glass fabricated by sintering nanoporous glass

A compact nonporous high silica (SiO2 % > 96%) glass containing 3400 ppm Er3+ ions, which was about ten times higher than that in Er-doped silica fiber amplifier (EDSFA), was synthesized by sintering porous glass immersed into erbium nitrate solution. The 1532 nm fluorescence has a FWHM (Full Width at Half Maximum) of 45 nm wider than that of EDSFA and possesses the glass with potential application in broadband fiber amplifiers. The Judd-Ofelt theoretical analysis reflects that Er3+ ions are located in a higher covalent environment which are comparable to those of aluminosilicate glass. (c) 2005 Elsevier B.V. All rights reserved.

Preparação, caracterização e avaliação de nanocompósitos de PBAT/amido de milho e vermiculita organofilizada

Nos últimos 20-30 anos polímeros biodegradáveis vêm sendo estudados e desenvolvidos e atualmente já são comercializados. Contudo, o custo, a processabilidade e algumas propriedades ainda dificultam a penetração desses polímeros no mercado e a competição com as chamadas commodities. Não são poucos os autores que se dedicam a desenvolver aditivos e formulações para superar essas limitações. Desta forma, esta Tese se dedicou ao desenvolvimento de compósitos de Ecobras, fabricado pela Basf e comercializado pela Corn Products, utilizando como carga mineral resíduo da extração da bauxita, no município de Santa Luzia/PB, o qual consiste em sua totalidade de vermiculita. Esta vermiculita foi quimicamente modificada com sais de alquil fosfônio para melhorar a compatibilidade com a matriz polimérica e também espaçar as camadas de aluminossilicato. De fato, a modificação com o brometo de hexadecil tributil fosfônio resultou na esfoliação da vermiculita tornando-a potencialmente apropriada para a obtenção de nanocompósitos. A preparação dos compósitos foi realizada pelo método de intercalação no estado fundido e foram comparadas a utilização da câmara interna de mistura e da mini extrusora de dupla rosca, sendo esta última mais eficaz na dispersão da vermiculita, conforme revelado pela microscopia eletrônica de varredura, difração de raios-X e reometria de placas. O grau de dispersão também foi influenciado pela estrutura química do modificador da vermiculita e pelo teor dessa carga incorporada à matriz. Teores mais elevados levaram a formação de aglomerados, enquanto a modificação da carga implicou na formação de micro e nanocompósitos. Ainda houve alterações das propriedades térmicas com aumento dos valores da temperatura de transição vítrea, de cristalização e fusão, embora o grau de cristalinidade tenha sido mantido. Nitidamente, foram obtidos materiais mais rígidos, com maior módulo e menor capacidade de deformação. Cerca de 58% de perda de massa foi observada para os micro e nanocompósitos obtidos após 17 semanas de enterro em solo simulado para avaliação da biodegradabilidade, valor bem próximo ao Ecobras puro. De modo geral, a incorporação das diferentes vermiculitas retardou nas primeiras semanas a biodegradação, provavelmente em função de modificações na estrutura cristalina, conforme sugerido pelos maiores valores de temperatura de fusão observados durante o acompanhamento do processo de biodegradação. No entanto, após 7 semanas os perfis de biodegradação dos micro e nanocompósitos se aproximaram bastante do Ecobras puro. Desta forma, foi possível nesta Tese obter um nanocompósito de Ecobras com vermiculita modificada com brometo de hexadecil fosfônio utilizando ferramentas comuns de processamento no estado fundido com biodegradabilidade próxima ao polímero de partida, porém mais rígido e menos deformável

Physical properties of a hybrid and a nanohybrid dental light-cured resin composite.

This work was aimed at the study of some physical properties of two current light-cured dental resin composites, Rok (hybrid) and Ice (nanohydrid). As filler they both contain strontium aluminosilicate particles, however, with different size distribution, 40 nm-2.5 mum for Rok and 10 nm-1 mum for Ice. The resin matrix of Rok consists of UDMA, that of Ice of UDMA, Bis-EMA and TEGDMA. Degree of conversion was determined by FT-IR analysis. The flexural strength and modulus were measured using a three-point bending set-up according to the ISO-4049 specification. Sorption, solubility and volumetric change were measured after storage of composites in water or ethanol/water (75 vol%) for 1 day, 7 or 30 days. Thermogravimetric analysis was performed in air and nitrogen atmosphere from 30 to 700 degrees C. Surface roughness and morphology of the composites was studied by atomic force microscopy (AFM). The degree of conversion was found to be 56.9% for Rok and 61.0% for Ice. The flexural strength of Rok does not significantly differ from that of Ice, while the flexural modulus of Rok is higher than that of Ice. The flexural strengths of Rok and Ice did not show any significant change after immersion in water or ethanol solution for 30 days. The flexural modulus of Rok and Ice did not show any significant change either after immersion in water for 30 days, while it decreased significantly, even after 1 day immersion, in ethanol solution. Ice sorbed a higher amount of water and ethanol solution than Rok and showed a higher volume increase. Thermogravimetric analysis showed that Rok contains about 80 wt% inorganic filler and Ice about 75 wt%.

The fabrication of TiO2-supported zeolite with core/shell heterostructure for ethanol dehydration to ethylene

The TiO2-supported zeolite with core/shell heterostructure was fabricated by coating aluminosilicate zeolite (ASZ) on the TiO2 inoculating seed via in situ hydrothermal synthesis. The catalysts were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), nitrogen physisorption (BET), and Fourier transform infrared spectroscopy (FT-IR). The surface acidity of the catalysts was measured by pyridine-TPD method. The catalytic performance of the catalysts for ethanol dehydration to ethylene was also investigated. The results show that the TiO2-supported zeolite composite catalyst with core/shell heterostructure exhibits prominent conversion efficiency for ethanol dehydration to ethylene.

硅铝酸盐纳米管（imogolite）的合成与组装

纳米管是重要的一维纳米材料，在催化、分离、光电子材料、生物医药、超分子组装及复合材料等领域的应用前景广阔。探索新型的纳米管材料、研究它们的性质以及与高分子体系的杂化行为对该领域的发展具有重要意义。 Imogolite是一种纳米管状结构的硅铝酸盐，结构规整、具有独特的亲水性以及在水溶液中的分散性，是一种理想的纳米管研究对象。本论文采用正硅酸乙酯水解法合成了imogolite纳米管。使用光学显微镜，TEM，SEM，FTIR，WAXD，TGA等手段系统地研究了imogolite纳米管的生长机理、imogolite纳米管在液滴干燥过程中的自组装行为、imogolite纳米管与聚电解质的组装行为，以及imogolite纳米管/水溶性聚合物体系在液滴干燥过程中的组装行为。 Imogolite纳米管在液滴蒸发过程中可发生有序排列的自组装行为，这与液滴干燥过程中的毛细管流动、表面张力效应及润湿性质等有关。在空气中干燥imogolite液滴时，溶液浓度、pH、离子强度均会影响纳米管在液滴干燥斑中的聚集形态。低浓度液滴干燥后形成的取向纳米管束结构很好地验证了环状干燥斑的形成机理。而在乙醇气氛下干燥imogolite液滴时，毛细管流动被抑制，体系的表面能降低，因此可获得在基底上单根均匀分散的imogolite纳米管。 利用上述结果，首次实现了对合成imogolite纳米管聚合生长过程的直接观察。发现imogolite纳米管在生长过程中，直径尺寸均匀稳定；而长度的多分散性始终存在，且长度多分散性指数小于2。聚合反应初期，纳米管数量和长度均增长迅速；反应后期，纳米管长度和体系浓度的增大致使纳米管运动受限，反应为扩散控制，但体系内仍有大量imogolite短管生成并持续生长，使纳米管数量和长度在反应后期仍可继续增长。这表明合成imogolite纳米管是由扩散控制的硬棒状分子单元逐步聚合形成。 基于imogolite纳米管独特的表面性质，研究了imogolite与水溶性聚合物之间的组装行为。首次发现imogolite纳米管能够与聚电解质(PAA，PAH，PSS，PDDA)在水溶液中组装形成稳定的微米管结构。此类微米管是由椭球形的囊泡相互连接形成的超分子组装体。微米管结构稳定，骨架为无规的imogolite纳米管，聚电解质起粘结作用。微米管的形成不依赖于聚电解质的电荷性质或氢键作用，但聚电解质的浓度和分子量、聚电解质与imogolite的配比、温度、外力场以及pH均能够影响微米管的生长及最终形态。 聚阴离子聚电解质PAA和PSS与imogolite纳米管之间存在较强的相互作用，这阻碍了纳米管在液滴蒸发过程中的自组装行为，使其无法有序排列。Imogolite纳米管在PEO液滴干燥过程中的自组装行为与PEO浓度、分子量和端基性质有关。对于低浓度PEO体系，PEO能通过被氧化的端羟基与imogolite纳米管相互作用，吸附到imogolite纳米管外壁的PEO分子可以改变纳米管的排列间距。这表明在聚合物/imogolite体系中，通过改变聚合物分子的结构参数，可调控imogolite纳米管在液滴干燥过程中的排列方式。

Growth mechanism. of synthetic imogolite nanotubes

By controlling the surface effects during droplet evaporation of imogolite solutions, imogolite nanotubes were dispersed individually and directly observed by transmission electron microscopy (TEM), and the structure evolution of imogolite nanotubes in the synthetic process was investigated. It was found that the number of imogolite nanotubes continuously increased with time in the whole reaction. The average length grew slowly over time after a remarkable increase in the initial 24 h, and the length distribution experienced a similar variation with the polydispersity index always below 2. No appreciable changes in tube diameters were detected under TEM observation.

Microtubes via assembly of imogolite with polyelectrolyte

We report the self-assembly of polyelectrolyte homopolymers such as poly(acrylic acid) with imogolite to generate stable tubular structures, which were several micrometers in diameter and millimeters in length with no hierarchical ordered structure. No special polymer architecture or interaction was required for the assembly.

Individual dispersion of synthetic imogolite nanotubes via droplet evaporation

Morphology of synthetic imogolite nanotubes formed in droplet evaporation was investigated by transmission electron microscopy and electron diffraction. The nanotubes form a dense entangled network at higher concentrations, while at lower concentrations the nanotubes are liable to form oriented bundles. Under enthanol atmosphere, individual dispersion of nanotubes was observed for the first time, which reveals the length polydispersity of synthetic imogolite nanotubes.

Long lasting phosphorescence of Eu2+ in reduced SrO-B2O3 glasses

The blue long-lasting phosphorescence (LLP) phenomenon was observed for Eu2+-doped SrO-B2O3 glasses prepared in the reducing atmosphere. The phosphorescence peaks at about 450 nm due to the 4f5d -> 4f transition of Eu2+. With the doping of different amounts of Eu2+, the concentration-quenching phenomenon was observed for both the LLP and photoluminescence of the glasses, and the critical concentration for the two cases was same, i.e., 0.02 mol% Eu2+. And by the investigation of the TL curves, the content of Eu2+ had an effect on the trap depth of the samples. At last the possible mechanism of the LLP of the samples was suggested.