Precursores funcionalizantes de poros à base de alginato para obtenção de cerâmicas bioativas

A complexidade de desenvolver novas tecnologias para aplicações em reconstituição óssea se deve à necessidade de combinar várias propriedades químicas e físicas para que o material proporcione o desempenho almejado. Particularmente, em aplicações que visam osteogênese, os enxertos sintéticos devem ser bioativos, possuir porosidade com volume, geometria e interconectividade de poros controlados, além de ter boas propriedades mecânicas, dentro de limites relativamente rígidos. Por essa razão, o recobrimento de materiais bioinertes com cerâmicas bioativas se tornou o foco da presente pesquisa. O objetivo desse estudo foi desenvolver um novo método de produção de enxertos cerâmicos com macroporosidade funcionalizada, onde a formação e o revestimento dos poros são realizados em uma única etapa. Foi realizado o estudo de recobrimento com vidro bioativo e fosfato de cálcio. Para isso, agentes porogênicos na forma de grânulos (de 600 μm a 2 mm de diâmetro) foram sintetizados pelo método da gelificação de uma solução aquosa de alginato de sódio gotejada em solução de nitrato de cálcio (0,5 M), com incorporação de outros elementos para a formação de biovidro ou fosfato de cálcio. Esses grânulos foram conglomerados a um vidro ou alumina em pó, formando um compósito, que foi tratado termicamente para sinterização e formação de poros. No caso da matriz vítrea, a sinterização ocorreu com cristalização simultânea e concorrente. As cerâmicas resultantes foram caracterizadas por microscopia óptica e eletrônica de varredura, sendo possível observar a formação de macroporos aproximadamente esféricos (de 600 μm a 2 mm de diâmetro) revestidos internamente por uma camada de material com possível composição bioativa.

Estudo da substituição da fluorita por alumina ou sodalita e de cal por resíduo de mármore em escórias sintéticas dessulfurantes.

A siderurgia vem sofrendo transformações que buscam inovação e matérias-primas alternativas. Dentro deste contexto, o uso de resíduos industriais para a formação de escórias sintéticas é tido como alternativa na busca de novos materiais e rotas de reaproveitamento de resíduos. Portanto, este trabalho teve como objetivo estudar o uso de escórias sintéticas na etapa de dessulfuração do ferro-gusa, aço e ferro fundido. Assim como, propor a utilização da sodalita e da alumina em substituição à fluorita e o resíduo de mármore em substituição à cal convencional. Inicialmente, o resíduo foi caracterizado utilizando as seguintes técnicas: análise química, análise granulométrica, área de superfície específica, difração de raios-X, microscopia eletrônica de varredura (MEV) e análise de espectroscopia por energia dispersiva (EDS). Os resultados da caracterização mostraram que aproximadamente 90% das partículas do resíduo de mármore estão abaixo de 100m e sua área superficial foi de 0,24m²/g. Através da difração de raios-X foi observado que o resíduo é composto por CaCO3, MgCO3 e SiO2. Na sequência, foram feitas simulações com o software Thermo-Calc para obter dados termodinâmicos das fases presentes nas misturas e compará-los com os resultados experimentais. Além disso, também foram calculados dados de capacidade de sulfeto (Cs), partição de enxofre (Ls) e basicidade ótica () das misturas iniciais. Posteriormente, foram realizados os ensaios experimentais em escala laboratorial para ferro-gusa, ferro fundido e aço, respectivamente nas temperaturas de 1400°C, 1550°C e 1600°C. Nos ensaios de dessulfuração do aço e do ferro-gusa, utilizou-se um rotor de alumina com o objetivo de favorecer a agitação no metal e aumentar a remoção de enxofre. Na etapa de dessulfuração do ferro-gusa, constatou-se que a fase sólida de CaO é a responsável pela remoção de enxofre e que a presença das fases silicato tricálcio e aluminato tricálcio (3CaO.SiO2 e 3CaO.Al2O3) limitam a reação, sendo maiores suas concentrações nas escórias que utilizaram o resíduo de mármore e sodalita, devido a presença de SiO2 e Al2O3 nestas matérias-primas. Já para o aço e o ferro fundido, que foram estudados com escórias à base de CaO e Al2O3, observou-se que o aumento da fase líquida favoreceu a dessulfuração. Verificou-se que a dessulfuração no ferro fundido foi por escória de topo e no aço por um processo misto, onde a fase líquida e fase sólida participaram da dessulfuração.

Sinterização flash do condutor catiônico beta-alumina sintetizada pelo método dos precursores poliméricos.

A beta-alumina de sódio é uma cerâmica condutora de íons Na+ utilizada como eletrólito sólido em baterias de sódio para armazenamento de energias intermitentes como energia solar e eólica. Devido ao alto teor de sódio, esse material é instável a altas temperaturas, podendo sofrer variações de composição durante a etapa de sinterização convencional que utiliza altas temperaturas por longos períodos de tempo. A sinterização flash é uma técnica de sinterização ativada por corrente elétrica que proporciona a densificação de compactos cerâmicos em poucos segundos, a temperaturas notavelmente mais baixas que as convencionais. Uma vez obrigatória a passagem de corrente elétrica através da amostra, a sinterização flash de qualquer material condutor parece bastante razoável. Não obstante, até o presente momento a maioria dos trabalhos publicados sobre o assunto aborda apenas condutores de vacância de oxigênio ou semicondutores, materiais compatíveis com eletrodos de platina (Pt). Nesse trabalho a sinterização flash de um condutor catiônico foi estudada utilizando-se a beta-alumina como material modelo. A beta-alumina foi sintetizada pelo método dos precursores poliméricos, caracterizada e então submetida à sinterização flash. O material de eletrodo padrão (platina) provou ser um eletrodo bloqueador em contato com a beta-alumina. O sucesso da sinterização flash foi determinado pela troca do material de eletrodo por prata (Ag), o que possibilitou uma reação eletroquímica reversível nas interfaces eletrodo-cerâmica e possibilitou a obtenção de um material densificado com morfologia e composição química homogêneas. Devido à metaestabilidade da beta-alumina, a atmosfera dos experimentos precisou ser alterada para manter a integridade desse material rico em um metal alcalino (Na+). A sinterização flash de um condutor catiônico é apresentada pela primeira vez na literatura e ressalta a importância da reação de eletrodo, que é um fator limitante para o sucesso da sinterização flash e precisa ser estudada e adaptada para cada tipo de material.

Electrooxidation methods to produce pseudocapacitance-containing porous carbons

Surface oxygen groups play a key role on the performance of porous carbon electrodes for electrochemical capacitors in aqueous media. The electrooxidation method in NaCl electrolyte using a filter press cell and dimensionally stable anodes is proposed as a viable process for the generation of oxygen groups on porous carbon materials. The experimental set-up is so flexible that allows the easy modification of carbon materials with different configurations, i.e. cloths and granular, obtaining different degrees of oxidation for both conformations without the requirement of binders and conductivity promoters. After the electrooxidation method, the attained porosity is maintained between 90 and 75% of the initial values. The surface oxygen groups generated can increase the capacitance up to a 30% when compared to the pristine material. However, a severe oxidation is detrimental since it may decrease the conductivity and increase the resistance for ion mobility.

Ordered porous nanomaterials: the merit of small

This paper will introduce the reader to some of the “classical” and “new” families of ordered porous materials which have arisen throughout the past decades and/or years. From what is perhaps the best-known family of zeolites, which even now to this day is under constant research, to the exciting new family of hierarchical porous materials, the number of strategies, structures, porous textures, and potential applications grows with every passing day. We will attempt to put these new families into perspective from a synthetic and applied point of view in order to give the reader as broad a perspective as possible into these exciting materials.

Effect of the porous structure in carbon materials for CO2 capture at atmospheric and high-pressure

Activated carbons prepared from petroleum pitch and using KOH as activating agent exhibit an excellent behavior in CO2 capture both at atmospheric (∼168 mg CO2/g at 298 K) and high pressure (∼1500 mg CO2/g at 298 K and 4.5 MPa). However, an exhaustive evaluation of the adsorption process shows that the optimum carbon structure, in terms of adsorption capacity, depends on the final application. Whereas narrow micropores (pores below 0.6 nm) govern the sorption behavior at 0.1 MPa, large micropores/small mesopores (pores below 2.0–3.0 nm) govern the sorption behavior at high pressure (4.5 MPa). Consequently, an optimum sorbent exhibiting a high working capacity for high pressure applications, e.g., pressure-swing adsorption units, will require a poorly-developed narrow microporous structure together with a highly-developed wide microporous and small mesoporous network. The appropriate design of the preparation conditions gives rise to carbon materials with an extremely high delivery capacity ∼1388 mg CO2/g between 4.5 MPa and 0.1 MPa. Consequently, this study provides guidelines for the design of carbon materials with an improved ability to remove carbon dioxide from the environment at atmospheric and high pressure.

Non-porous reference carbon for N2 (77.4 K) and Ar (87.3 K) adsorption

A new non-porous carbon material from granular olive stones has been prepared to be used as a reference material for the characterization of the pore structure of activated carbons. The high precision adsorption isotherms of nitrogen at 77.4 K and argon at 87.3 K on the newly developed sample have been measured, providing the standard data for a more accurate comparative analysis to characterize disordered porous carbons using comparative methods such as t- and αS-methods.

Temperature influence on the physical and mechanical properties of a porous rock: San Julian's calcarenite

This work discusses the results from tests which were performed in order to study the effect of high temperatures in the physical and mechanical properties of a calcarenite (San Julian's stone). Samples, previously heated at different temperatures (from 105 °C to 600 °C), were tested. Non-destructive tests (porosity and ultrasonic wave propagation) and destructive tests (uniaxial compressive strength and slake durability test) were performed over available samples. Furthermore, the tests were carried out under different conditions (i.e. air-cooled and water-cooled) in order to study the effect of the fire off method. The results show that uniaxial compressive strength and elastic parameters (i.e. elastic modulus and Poisson's ratio), decrease as the temperature increases for the tested range of temperatures. A reduction of the uniaxial compressive strength up to 35% and 50% is observed in air-cooled and water-cooled samples respectively when the samples are heated to 600 °C. Regarding the Young's modulus, a fall over 75% and 78% in air-cooled and water-cooled samples respectively is observed. Poisson's ratio also declines up to 44% and 68% with the temperature in air-cooled and water-cooled samples respectively. Slake durability index also exhibits a reduction with temperature. Other physical properties, closely related with the mechanical properties of the stone, are porosity, attenuation and propagation velocity of ultrasonic waves in the material. All exhibit considerable changes with temperature.

Low metal content Co and Ni alumina supported catalysts for the CO2 reforming of methane

Low metal content Co and Ni alumina supported catalysts (4.0, 2.5 and 1.0 wt% nominal metal content) have been prepared, characterized (by ICP-OES, TEM, TPR-H2 and TPO) and tested for the CO2 reforming of methane. The objective is to optimize the metal loading in order to have a more efficient system. The selected reaction temperature is 973 K, although some tests at higher reaction temperature have been also performed. The results show that the amount of deposited carbon is noticeably lower than that obtained with the Co and Ni reference catalysts (9 wt%), but the CH4 and CO2 conversions are also lower. Among the catalysts tested, the Co(1) catalyst (the value in brackets corresponds to the nominal wt% loading) is deactivated during the first minutes of reaction because CoAl2O4 is formed, while Ni(1) and Co(2.5) catalysts show a high specific activity for methane conversion, a high stability and a very low carbon deposition.

Total oxidation of naphthalene using palladium nanoparticles supported on BETA, ZSM-5, SAPO-5 and alumina powders

A range of catalysts based on Pd nanoparticles supported on inorganic supports such as BETA and ZSM-5 zeolites, a silicoaluminophosphate molecular sieve (SAPO-5) and γ-alumina as a standard support have been tested for the total oxidation of naphthalene (100 ppm, total flow 50 ml/min) showing a conversion to carbon dioxide of 100% between 165 and 180 °C for all the analysed catalysts. From the combined use of zeolites with PVP polymer protected Pd based nanoparticles, enhanced properties have been found for the total abatement of naphthalene in contrast with other kinds of catalysts. A Pd/BETA catalyst has been demonstrated to have excellent activity, with a high degree of stability, as shown by time on line experiments maintaining 100% conversion to CO2 during the 48 h tested.

First aromatic ring acetamidation by anodic oxidation

Anodic oxidation of 1-(trifluoromethyl)benzene in dry acetonitrile/Bu4NBF4 under constant potential conditions led to 2-(trifluoromethyl) acetanilide in 86% yield. Other experimental conditions, as the use of constant current or the change in the supporting electrolyte were considered.

Structural and photoelectrochemical properties of porous TiO2 nanofibers decorated with Fe2O3 by sol-flame

The hybrid structure of Fe2O3 nanoparticles/TiO2 nanofibers (NFs), combines the merits of large surface areas of TiO2 NFs and absorption in ultraviolet light–visible light range. This structure can be used for many applications such as photoelectrochemical water splitting and photo-catalysis. Here, a sol-flame method is used for depositing Fe2O3 on TiO2 NFs that were prepared by hydrothermal on Ti sheets. The obtained materials were characterized by XRD, SEM, UV/Vis diffuse reflectance, Raman, and XPS. The results revealed the formation of rutile and anatase crystalline phases together with Fe2O3. This process moves the absorption threshold of TiO2 NFs support into visible spectrum range and enhances the photocurrent in comparison to bare TiO2 NFs, although no hole scavenger was used. The impedance measurement at low and high frequencies revealed an increase in series resistance and a decrease in resistance of charge transfer with sol-flame treatment time. A mechanism for explaining the charge transfer in these TiO2 NFs decorated with Fe2O3 nanoparticles was proposed.

Insight into the immobilization of ionic liquids on porous carbons

Very different carbon materials have been used as support in the preparation of supported ionic liquid phase samples (SILP). Some of them have been oxidized, either strongly (with ammonium persulfate solution) or weakly (with air at 300 °C, 2 h). The purpose is to establish which properties of the supports (e.g., porosity -volume and type-, surface area, oxygen surface chemistry and morphology) determine the IL adsorption capacity and the stability (immobilization) of the supported IL phase. The ionic liquid used in this work is 1-butyl-3-methyl-imidazolium hexafluorophosphate ([bmim][PF6]). For each support, samples with different amounts of ionic liquid have been prepared. The maximum IL that can be loaded depends mainly on the total pore volume of the supports. For comparable pore volumes, the porosity type and the oxygen surface content have no influence on the IL loading. The supported IL fills most of the pores, leaving some blocked porosity. The stability of the supported IL phase (especially important for its subsequent use in catalysis) has been tested in water under general hydrogenation conditions (60 °C and 10 bar H2). In general, leaching is low but it increases with the amount of IL loaded and with the oxidation treatments of the supports.

Tailoring the Surface Chemistry of Activated Carbon Cloth by Electrochemical Methods

This paper presents a systematic study of the effect of the electrochemical treatment (galvanostatic electrolysis in a filter-press electrochemical cell) on the surface chemistry and porous texture of commercial activated carbon cloth. The same treatments have been conducted over a granular activated carbon in order to clarify the effect of morphology. The influence of different electrochemical variables, such as the electrode polarity (anodic or cathodic), the applied current (between 0.2 and 1.0 A) and the type of electrolyte (HNO3 and NaCl) have also been analyzed. The anodic treatment of both activated carbons causes an increase in the amount of surface oxygen groups, whereas the cathodic treatment does not produce any relevant modification of the surface chemistry. The HNO3 electrolyte produced a lower generation of oxygen groups than the NaCl one, but differences in the achieved distribution of surface groups can be benefitial to selectively tune the surface chemistry. The porous texture seems to be unaltered after the electro-oxidation treatment. The validity of this method to introduce surface oxygen groups with a pseudocapacitive behavior has been corroborated by cyclic voltammetry. As a conclusion, the electrochemical treatment can be easily implemented to selectively and quantitatively modify the surface chemistry of activated carbons with different shapes and morphologies.

High-Pressure Methane Storage in Porous Materials: Are Carbon Materials in the Pole Position?

Natural gas storage on porous materials (ANG) is a promising alternative to conventional on-board compressed (CNG) or liquefied natural gas (LNG). To date, Metal–organic framework (MOF) materials have apparently been the only system published in the literature that is able to reach the new Department of Energy (DOE) value of 263 cm3 (STP: 273.15 K, 1 atm)/cm3; however, this value was obtained by using the ideal single-crystal density to calculate the volumetric capacity. Here, we prove experimentally, and for the first time, that properly designed activated carbon materials can really achieve the new DOE value while avoiding the additional drawback usually associated with MOF materials (i.e., the low mechanical stability under pressure (conforming), which is required for any practical application).