Towards Macroporous α-Al2O3—Routes, Possibilities and Limitations

This article combines a systematic literature review on the fabrication of macroporous α-Al2O3 with increased specific surface area with recent results from our group. Publications claiming the fabrication of α-Al2O3 with high specific surface areas (HSSA) are comprehensively assessed and critically reviewed. An account of all major routes towards HSSA α-Al2O3 is given, including hydrothermal methods, pore protection approaches, dopants, anodically oxidized alumina membranes, and sol-gel syntheses. Furthermore, limitations of these routes are disclosed, as thermodynamic calculations suggest that γ-Al2O3 may be the more stable alumina modification for ABET > 175 m2/g. In fact, the highest specific surface area unobjectionably reported to date for α-Al2O3 amounts to 16–24 m2/g and was attained via a sol-gel process. In a second part, we report on some of our own results, including a novel sol-gel synthesis, designated as mutual cross-hydrolysis. Besides, the Mn-assisted α-transition appears to be a promising approach for some alumina materials, whereas pore protection by carbon filling kinetically inhibits the formation of α-Al2O3 seeds. These experimental results are substantiated by attempts to theoretically calculate and predict the specific surface areas of both porous materials and nanopowders

On the Comparative Analysis of Different Phase Coexistences in Mesoporous Materials

Alterations of fluid phase transitions in porous materials are conventionally employed for the characterization of mesoporous solids. In the first approximation, this may be based on the application of the Kelvin equation for gas–liquid and the Gibbs–Thomson equation for solid–liquid phase equilibria for obtaining pore size distributions. Herein, we provide a comparative analysis of different phase coexistences measured in mesoporous silica solids with different pore sizes and morphology. Instead of comparing the resulting pore size distributions, we rather compare the transitions directly by using a common coordinate for varying the experiment’s thermodynamic parameters based on the two equations mentioned. Both phase transitions in these coordinates produce comparable results for mesoporous solids of relatively large pore sizes. In contrast, marked differences are found for materials with smaller pore sizes. This illuminates the fact that, with reducing confinement sizes, thermodynamic fluctuations become increasingly important and different for different equilibria considered. In addition, we show that in the coordinate used for analysis, mercury intrusion matches perfectly with desorption and freezing transitions

Determination of Rule Patterns in Complex Event Processing Using Machine Learning Techniques

AbstractComplex Event Processing (CEP) is a novel and promising methodology that enables the real-time analysis of stream event data. The main purpose of CEP is detection of the complex event patterns from the atomic and semantically low-level events such as sensor, log, or RFID data. Determination of the rule patterns for matching these simple events based on the temporal, semantic, or spatial correlations is the central task of CEP systems. In the current design of the CEP systems, experts provide event rule patterns. Having reached maturity, the Big Data Systems and Internet of Things (IoT) technology require the implementation of advanced machine learning approaches for automation in the CEP domain. The goal of this research is proposing a machine learning model to replace the manual identification of rule patterns. After a pre-processing stage (dealing with missing values, data outliers, etc.), various rule-based machine learning approaches were applied to detect complex events. Promising results with high preciseness were obtained. A comparative analysis of the performance of classifiers is discussed

Nano-casted N-Doped Carbon Created From a Task-Specific Protic Salt and Controlled Porous Glass

3-dimensionally interconnected macroporous carbons are versatile materials that can be used in catalysis, electrochemical devices, and separation technology. Herein, the synthesis of a nitrogen doped carbonaceous material with a well-defined nanoarchitecture via nano-casting is demonstrated. A novel carbon source, a task-specific protic salt, has been proposed to create nitrogen doped carbon by direct carbonization within the pores of controlled macroporous glass. After the removal of macroporous glass from the composite using an aqueous sodium hydroxide solution and upon further heat treatment, an oxidation resistant doped carbon with high nitrogen content (6 mass %) is obtained. The materials formed during the different stages of the nano-casting process exhibit interesting properties such as hierarchical porosity, very high nitrogen content (15 mass %), and increased oxidational stability. A combination of different properties to create tailor-made materials for different applications using this technique is possible

Ash transformation mechanism during combustion of rice husk and rice straw

Biomass is an alternative energy resource to fossil fuels because of its potential to reduce greenhouse gas emissions. However, ash-related problems are serious obstacles for this development, especially for the use in combustion plants. Thus, design and operation of biomass boilers require detailed understanding of ash transformation reactions during thermochemical conversion. To evaluate ash transformation in silica-rich biomass fuels, rice husk and rice straw were selected because of their abundance, limited utilization conflicts with the food sector, as well as their potential in both energy and material applications. This paper reveals ash transformation mechanisms relevant for the ash melting behaviour of silica-rich biomass fuels considering chemical and phase composition of the ashes. In this regard, several advanced spectroscopic methods and diffractometry were employed to characterize the materials. The ash transformation reactions and the viscosity were simulated using thermodynamic equilibrium calculations and a slag viscosity modeling toolbox. The results illustrate the impact of impurities on the atomic structure of the silica resulting in an altered ash melting behaviour and viscosity of the silica-rich ashes. Chemical water washing, acid leaching, and blending of rice straw with rice husk strongly influenced the chemical composition of the ashes and improved ash melting behaviour. The analysis also revealed the correlation between the crystalline fraction and the porosity in silica-rich biomass ashes, as well as a crystallinity threshold. These findings are highly relevant for future investigations in boiler designs and production of biogenic silica for material applications

Sodium Solid Electrolytes: NaxAlOy Bilayer-System Based on Macroporous Bulk Material and Dense Thin-Film

A new preparation concept of a partially porous solid-state bilayer electrolyte (BE) for high-temperature sodium-ion batteries has been developed. The porous layer provides mechanical strength and is infiltrated with liquid and highly conductive NaAlCl4 salt, while the dense layer prevents short circuits. Both layers consist, at least partially, of Na-β-alumina. The BEs are synthesized by a three-step procedure, including a sol-gel synthesis, the preparation of porous, calcined bulk material, and spin coating to deposit a dense layer. A detailed study is carried out to investigate the effect of polyethylene oxide (PEO) concentration on pore size and crystallization of the bulk material. The microstructure and crystallographic composition are verified for all steps via mercury intrusion, X-ray diffraction, and scanning electron microscopy. The porous bulk material exhibits an unprecedented open porosity for a NaxAlOy bilayer-system of ≤57% with a pore size of ≈200–300 nm and pore volume of ≤0.3 cm3∙g−1. It contains high shares of crystalline α-Al2O3 and Na-β-alumina. The BEs are characterized by impedance spectroscopy, which proved an increase of ionic conductivity with increasing porosity and increasing Na-β-alumina phase content in the bulk material. Ion conductivity of up to 0.10 S∙cm−1 at 300 °C is achieved

The Production of Biogenic Silica from Different South African Agricultural Residues through a Thermo-Chemical Treatment Method

A thermo-chemical treatment method was used to produce biogenic amorphous silica from South African sugarcane and maize residues. Different fractions of South African sugarcane (leaves, pith, and fiber) were processed for silica production. The biomass samples were leached with either 7 wt% citric acid or 7 wt% sulfuric acid at 353 K for 2 h prior to being rinsed, dried and combusted using a four-step program ranging from room temperature to 873 K in a furnace. The characterization of the pre-treated biomass samples was conducted using thermogravimetric analysis (TG/DTA), X-ray fluorescence analysis (XRF) and elemental analysis (CHN), while the final products were characterized by XRF, X-ray diffraction (XRD), elemental analysis, nitrogen physisorption and scanning electron microscopy (SEM). Citric acid pre-treatment proved to be an attractive alternative to mineral acids. Amorphous biogenic silica was produced from sugarcane leaves in good quality (0.1 wt% residual carbon and up to 99.3 wt% silica content). The produced biogenic silica also had great textural properties such as a surface area of up to 323 m2 g−1, average pore diameter of 5.0 nm, and a pore volume of 0.41 cm3 g−1