Arian Nijmeijer

Preparation of La0.3Sr0.7CoO3–δ perovskite by thermal decomposition of metal-EDTA complexes

Perovskite powders of La0.3Sr0.7CoO3–were prepared by the thermal decomposition of precursor complexes derived from nitrate solutions using ethylenediaminetetraacetic acid (EDTA) as a complexing agent. The calcination temperature is 920 °C. Powders thus obtained have a low carbon contamination. Dense ceramics with a relative density of about 96% have been prepared after sintering at 1150 °C.

Low-temperature CVI modification of γ-alumina membranes

Microporous silica membranes have been prepared by low-temperature chemical vapor infiltration (CVI) of supported mesoporous γ-alumina membranes. The best results were obtained with silicon tetra-acetate as precursor with H2:N2 membrane selectivities of >40 and a H2 permeance of 4×10−7 mol/m2 s Pa at 250°C. This permeance compares favorably with that of state-of-the-art microporous CVI silica membranes. Experiments with silane as precursor did, however, not lead to selectivity improvements of the starting membranes.

Sieving of Hot Gases by Hyper-Cross-Linked Nanoscale-Hybrid Membranes

Macromolecular networks consisting of homogeneously distributed covalently bonded inorganic and organic precursors are anticipated to show remarkable characteristics, distinct from those of the individual constituents. A novel hyper-cross-linked ultrathin membrane is presented, consisting of a giant molecular network of alternating polyhedral oligomeric silsesquioxanes and aromatic imide bridges. The hybrid characteristics of the membrane are manifested in excellent gas separation performance at elevated temperatures, providing a new and key enabling technology for many important industrial scale applications.

Experimental study of hydrogen, carbon dioxide and nitrogen permeation through a microporous silica membrane

The transport of hydrogen, carbon dioxide and nitrogen through a microporous tubular silica membrane has been investigated between 20 and 200°C and 3–9 bar upstream pressure. Pure compounds permeabilities decrease from H2 to N2 and do not show a strong dependence upon upstream pressure. Temperature variation could be described by an Arrhenius law with low apparent activation energies (3.5, 3.7 and 3.4 kJ mol−1, respectively, for hydrogen, carbon dioxide and nitrogen). The ideal separation selectivity computed from these results leads to values around 3.5 and 3 for H2/CO2 and CO2/N2 separation independent of temperature. These values are significantly smaller than those expected from a strict Knudsen mechanism (4.7 and 3.7, respectively). A viscous contribution, resulting for instance from a too large pore size distribution of the active silica layer, possibly accounts for the experimental results obtained.

Formation and prevention of fractures in sol–gel-derived thin films

Sol-gel-derived thin films play an important role as the functional coatings for various applications that require crack-free films to fully function. However, the fast drying process of a standard sol-gel coating often induces mechanical stresses, which may fracture the thin films. An experimental study on the crack formation in sol-gel-derived silica and organosilica ultrathin (submicron) films is presented. The relationships among the crack density, inter-crack spacing, and film thickness were investigated by combining direct micrograph analysis with spectroscopic ellipsometry. It is found that silica thin films are more prone to fracturing than organosilica films and have a critical film thickness of 300 nm, above which the film fractures. In contrast, the organosilica films can be formed without cracks in the experimentally explored regime of film thickness up to at least 1250 nm. These results confirm that ultrathin organosilica coatings are a robust silica substitute for a wide range of applications.

Kinetic Analysis of the Thermal Processing of Silica and Organosilica

The incorporation of an organic group into sol-gel-derived silica causes significant changes in the structure and properties of these materials. Therefore, the thermal treatment of organosilica materials may require a different approach. In the present paper, kinetic parameters (activation energy, pre-exponential constant, and reaction models) have been determined from mass loss data for the dehydration, dehydroxylation, and decomposition reactions that take place upon heating silica and organosilica. Parameters were obtained by employing model-free isoconversional methods to data obtained under multiple heating rates as well as by multivariate analysis of the kinetics using a multistep reaction model with distributed activation energy. For silica, it can be concluded that the reaction atmosphere (i.e., inert or thermo-oxidative) has no influence on the reaction rate of the dehydration and dehydroxylation reactions that are responsible for the densification of the material. Under inert atmosphere, full dehydration can be reached without affecting the organic moiety. Achieving complete dehydroxylation of the organosilica is practically impossible as decomposition does manifest itself under commonly employed calcination temperatures. This indicates that prudence is required in designing a heat treatment program for these hybrid materials. To aid in optimizing the thermal treatment, a predictive model was developed, which can be used to forecast the extent of dehydration, dehydroxylation, and decomposition reactions under a multitude of temperature programs.

Doped microporous hybrid silica membranes for gas separation

Hybrid silica (i.e., bis-triethoxysilylethane: BTESE) membranes doped with B, Ta or Nb were made through a sol–gel process. Triethyl borate, tantalum (V) ethoxide (TPE) and niobium (V) ethoxide (NPE) were selected as doping precursors. The doping concentration was optimized to produce sols, suitable for membrane fabrication. Thermal stability, structural analysis, cross-sectional micrographs and single gas permeation experiments were performed on these membranes, and results are compared with an undoped BTESE membrane. It was observed that the synthesized doped BTESE materials and membranes resulted into a more open (and, in one occurrence, SF6 permeable) pore microstructure, showing high permeances of larger gas molecules, while having a cross-sectional thickness comparable to undoped BTESE membranes.Graphical Abstract

Sorption Behavior of Compressed CO2 and CH4 on Ultrathin Hybrid Poly(POSS-imide) Layers

Sorption of compressed gases into thin polymeric films is essential for applications including gas sensors and membrane based gas separation. For glassy polymers, the sorption behavior is dependent on the nonequilibrium status of the polymer. The uptake of molecules by a polymer is generally accompanied by dilation, or swelling, of the polymer material. In turn, this dilation can result in penetrant induced plasticization and physical aging that affect the nonequilibrium status of the polymer. Here, we investigate the dilation and sorption behavior of ultrathin membrane layers of a hybrid inorganic-organic network material that consists of alternating polyhedral oligomeric silsesquioxane and imide groups, upon exposure to compressed carbon dioxide and methane. The imide precursor contains fluoroalkene groups that provide affinity toward carbon dioxide, while the octa-functionalized silsesquioxane provides a high degree of cross-linking. This combination allows for extremely high sorption capacities, while structural rearrangements of the network are hindered. We study the simultaneous uptake of gases and dilation of the thin films at high pressures using spectroscopic ellipsometry measurements. Ellipsometry provides the changes in both the refractive index and the film thickness, and allows for accurate quantification of sorption and swelling. In contrast, gravimetric and volumetric measurements only provide a single parameter; this does not allow an accurate correction for, for instance, the changes in buoyancy because of the extensive geometrical changes of highly swelling films. The sorption behavior of the ultrathin hybrid layers depends on the fluoroalkene group content. At low pressure, the apparent molar volume of the gases is low compared to the liquid molar volume of carbon dioxide and methane, respectively. At high gas concentrations in the polymer film, the apparent molar volume of carbon dioxide and methane exceeds that of the liquid molar volume, and approaches that of the gas phase. The high sorption capacity and reversible dilation characteristics of the presented materials provide new directions for applications including gas sensors and gas separation membranes.

Synthesis of Porous Inorganic Hollow Fibers without Harmful Solvents

A route for the fabrication of porous inorganic hollow fibers with high surface-area-to-volume ratio that avoids harmful solvents is presented. The approach is based on bio-ionic gelation of an aqueous mixture of inorganic particles and sodium alginate during wet spinning. In a subsequent thermal treatment, the bio-organic material is removed and the inorganic particles are sintered. The method is applicable to the fabrication of various inorganic fibers, including metals and ceramics. The route completely avoids the use of organic solvents, such as N-methyl-2-pyrrolidone, and additives associated with the currently used fiber fabrication methods. In addition, it inherently avoids the manifestation of so-called macro voids and allows the facile incorporation of additional metal oxides in the inorganic hollow fibers.

Nanofiltration of organic solvents

This article provides an insight into the mechanisms affecting solvent flux through dense membranes, and forms a basis for rejection studies of organic solute compounds from organic solvents.