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The influence of small inorganic cations (Na+ ions in this case) on the core@shell silica nanoparticles, formed by the room temperature hydrolysis of TEOS in aqueous TPAOH (subsequent addition of NaOH – SA) and NaOH/TPAOH (direct addition of NaOH – DA) solutions was investigated by DLS, AFM, pH measurements, 29Si-NMR and 23Na-NMR. The obtained results showed that the smaller Na+ ions, displace parts of the larger TPA+ ions from the shells of the core@shell primary silica nanoparticles (PNPs), by the exchange process. This causes exposition of TPA-free terminal –OH and –O- groups to the solution and thus, enables the binding of the collided nanoparticles by the Si-O-Si bonds (aggregation). The PNPs in the aggregates, formed above the critical aggregation concentration (CAC) of silicate species are separated by the “bulky” shell (TPA-polysilicate anions) that prevents the close contacts between the nanoparticles cores and thus, their coalescence. When Na+ ions are present during the formation of the nanoparticles, a part of the Na+ ions is incorporated to the nanoparticle core. Remove of the TPA+ ions from the shells of the nanoparticles, formed below the CAC, enables close contacts of the nanoparticles cores and thus, their coalescences inside the aggregates. These findings show that the selective removal of the TPA+ ions from the nanoparticle shell enables the control of the composition and size of the precursor species and thus, represent a good basis for the engineering of nanosized (alumino)silicate microporous and mesoporous materials.

Inorganic materials that enable a link between the storage and release of molecular oxygen offer a fertile ground in continuous quest for the applications that can potentially reduce energy consumption and thus minimize adverse effects on the environment. Herein, we address reversible intake/release of an oxygen within the BaAl2O4 material as evidenced by unexpected magnetic ordering. Magnetic measurements unveil that an oxygen is stored in the form of condensed matter, creating a kind of low dimensional, chain-like assembly within the tunnels of BaAl2O4 structure. We demonstrate that oxygen is adsorbed simply by staying in air, at ambient conditions, and released relatively quickly by staying in the He or other gas atmosphere of several millibars pressure even at 300 K.

Following the assumption that the crucial processes governing the formation, properties and evolution of the core(amorphous silica)@shell(organocations) nanoparticles take place during short-time, room-temperature (rt) stirring/aging of the homogeneous reaction mixtures (HmRMs) formed by hydrolysis of TEOS (tetraethyl orthosilicate) in solutions of Org(OH)n, we investigated these processes by various experimental methods (pH, ionic conductivity, 29Si-NMR, dynamic light scattering and atomic force microscopy). The analysis of the data obtained by detail and careful investigation of the "model" HmRMs having the starting chemical composition: xTEOS:0.25TPAOH:20H2O (TPAOH = tetrapropylammonium hydroxide; x = 0.05 – 1), offer some new elements for the understanding of the mechanisms of formation and rt evolution of the core@shell silica nanoparticles: (1) There is a resolute evidence of the formation of the stable, about 1.2 nm sized core(amorphous SiO2)@shell(TPA+ ions) nanoparticles below the critical aggregation concentration (CAC). (2) Due to the intensive particulate processes (growth, aggregation, disaggregation, dissolution) which take place during the rt aging of the investigated HmRMs, the equilibrated core@shell silica nanoparticles do not exist as individual primary ones, but as the aggregates (about 2 nm to about 20 nm), composed of 1 – 2 nm sized "primary" nanoparticles. (3) In spite of the most frequent meaning that the nanoparticle shell is composed of the "free" TPA+ ions adsorbed on the surface of the nanoparticle core, the results of this study show that the nanoparticle shell can be formed mainly by attachment of the polysilicate anions (silicate oligomers), associated with TPA+ ions, on the surfaces of the nanoparticles cores.

The microstructure of the starting hydrogel has extremely important role in the synthesis of the microporous materials. Due to the fact that very limited number of experimental methods (techniques) can be used for gel analysis, there are still a lot of missing information about the processes on molecular level, which occur before and during the nuclei formation. In this paper, various methods were used in characterization of pretreated (aged) hydrogel before the process of its hydrothermal transformation to zeolite A. The results obtained from different techniques (FTIR, PALS, BET, DTG) show the changes in chemical composition and in microstructure of the solid phase, indicating that the structure of the ordered phase (potential nuclei) within gel matrix (completely amorphous according to PXRD patterns) is rather of different structural units typical for FAU and SOD (or their mixture) than the final product (LTA) only!

In this work, positron annihilation lifetime spectroscopy was used for the structural characterisation of porous materials prepared from amorphous zeolite precursors acting as the starting materials and hexadecyltrimethylammonium bromide acting as a mesoporous template. The best fits of the obtained lifetime spectra provide a four-component exponential decomposition. The lifetime values of the long-lived components point to the presence of mesoporous voids. Infrared and X-ray analyses show that the obtained materials consist partly of a crystalline zeolite structure.

Positron annihilation lifetime spectroscopy has been used for observation of the free voids in low silica zeolites, of LTA and FAU structure and different crystal size, before and after their heating at different temperatures below 200 A degrees C. Sizes of crystals of the zeolite samples, as well as their structures and water contents, were characterized by X-ray diffraction, scanning electron microscopy, thermogravimetry, and particle size distribution measurements. The number of positron lifetime components as well as their values and intensities, after water removal from the zeolite structure, vary. However, changes are not uniform in all investigated zeolites. The differences are compared and discussed in the dependence of different structure types and crystal sizes of investigated zeolites.

Positron lifetime (LT) measurements have revealed that in porous media the annihilation pattern is probably dominated by a near-saturation level trapping both for the positron and the positronium as well, which masks the contribution from the ldquofree annihilationrdquo, i.e., annihilation from delocalised positrons. In this work we compare positron lifetime spectra of crystalline zeolites with bulk ceramic materials fabricated by sintering from the same constituents as the zeolites and analyse common features and differences between them. For the dense ceramic samples the contribution from long-living components to the annihilation pattern is substantially lower than that for the zeolites. The results are analysed with the aim to extract new knowledge for the zeolites and for the sensitivity limits for free volume studies in ceramics. (© 2007 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim)

Positron annihilation acquired acceptance for structural investigation of solids but results in porous media--where positron lifetime spectroscopy (LT) reveals substantial Ps formation--were ambiguous. Data on zeolites lead to the conclusion that Ps trapping in competing "extended free volume" sites, inhomogeneous regions and grain boundaries occurs. Furthermore, positron trapping must also be considered. Systematic errors due to incomplete time range selection are discussed, significance and importance of corrections for 3[gamma]/2[gamma] counting efficiency differences are shown in practice. http://www.sciencedirect.com/science/article/B6TVT-4JYTRSS-1/1/b6007344f10f5d0b3c23cc259fe1e8cb

Kinetics of the crystal growth of zeolites A and X was measured during their crystallization, at 80 °C, from an amorphous aluminosilicate precursor dispersed in a 1.4 M NaOH solution containing different amounts of dissolved NaAlO2 or Na2SiO3. The crystallization pathway and fractions of zeolites A and X in the crystalline end product strongly depend on the composition of the liquid phase of the crystallizing system. Analyses of the changes of the concentrations of aluminum, cAl, and of silicon, cSi, in the liquid phase as well as of the dimension, Lm, of the largest crystals of zeolites A and X during crystallization, have shown that the growth rate of zeolite A crystals is size-independent, and that the growth is governed by the reaction of monomeric and/or low-molecular aluminate, silicate and aluminosilicate anions from the liquid phase on the surfaces of growing zeolite crystals. Influence of the composition of the liquid phase of the crystallizing system on the course of crystallization process and on the growth rates of zeolite A and zeolite X crystals are discussed in terms of the possible distribution of aluminate, silicate and/or aluminosilicate anions in the liquid phase., Brzine rasta kristala zeolita A i X mjerene su tijekom kristalizacije pri 80 °C iz amorfnoga alumosilikatnoga prekursora dispergiranoga u 1,4 M otopini NaOH koja je sadržavala različite količine otopljenoga NaAlO2 ili Na2SiO3. Tijek kristalizacije i frakcije zeolita A i X u produktima kristalizacije značajno ovise o sastavu tekuće faze kristalizacijskoga sustava. Analizom promjena koncentracija aluminija, cAl i silicija, cSi u tekućoj fazi te veličine Lm, najvećih kristala zeolita A i X tijekom kristalizacije, utvr|eno je da je brzina rasta kristala neovisna o njihovoj veličini te da se rast kristala odvija reakcijom monomernih i/ili niskomolekularnih aluminatnih, silikatnih i alumosilikatnih aniona iz tekuće faze na površini rastućih kristala zeolita. Utjecaj sastava tekuće faze kristalizacijskih sustava na tijek procesa kristalizacije i brzinu rasta kristala zeolita A i X razmatran je u odnosu na moguće raspodjele aluminatnih, silikatnih i alumosilikatnih aniona u tekućoj fazi.

Changes of the concentrations of aluminium, C-Al, and of silicon, c(Si), in the liquid phase as well as of the dimension, L-m, of the largest crystals were measured during crystallization of zeolite A from the amorphous aluminosilicate precursor (1.03 Na2O . Al2O3 .2.38 SiO2 . 1.66 H2O) dispersed in alkaline solutions (1.2 or 1.4 M NaOH solution) containing or not containing dissolved Al2O3 and/or SiO2 Of appropriate concentrations. Analysis of the relationship between the concentration factors f(c) = f(c(Al),c(Si)) relevant to different growth models and the growth rate of zeolite A crystals have shown that the growth is governed by the reaction of monomeric and/or low-molecular aluminate, silicate and aluminosilicate anions from the liquid phase on the surfaces of growing zeolite crystals, and hence that the kinetics of the growth rate of zeolite A crystals may be expressed as: dL/dt(c) = k(g) [c(Al) - c(Al)(eq)][c(Si) - c(Si)(eq)] = k(g) f(c), where t(c) is the time of crystallization, c(Al)(eq) and c(Si)(eq) are the aluminium and silicon concentrations in the liquid phase, corresponding to the solubility of zeolite A under given crystallization conditions, and k(g) is the rate constant of the linear growth of zeolite A crystals.

KFKI Res. Inst. for Part. Nucl. Physics P.O.B. 49, H-1525 Budapest 114, Hungary Div. of Mater. Chem., Ruder Boskovic Institute Bijenicka 54, P.O.B. 180, Zagreb, Croatia Inst. of Isotopes, HAS, H-1525 Budapest, P.O.B. 77, Hungary Flerov Laboratory of Nuclear Reactions, Center of Applied Physics, JINR Ru-141980 Dubna, Russia Dept. of Mater. Physics, Eotvos Univ. Pazmany Peter setany 1A, H-1117 Budapest, Hungary f ICEMS, Dept. of Physics, University of Coimbra 3004-516 Coimbra, Portugal Dep. de Engenharia Quimica, Inst. Superior de Engenharia 3031-199 Coimbra, Portugal