Reinvestigation of the Fe-rich part of the pseudo-binary system SrO–Fe2O3

The phase relations in the Fe-rich part of the pseudo-binary system SrO–Fe₂O₃ (>33 mol% Fe₂O₃) were reinvestigated between 800 and 1500 °C in air. A combination of microscopy, electron probe micro-analysis, powder X-ray diffraction and thermal analysis was used to determine phase relations, crystal structure parameters and phase transition temperatures. M-type hexagonal ferrite SrFe₁₂O₁₉ (85.71 mol% Fe₂O₃) is stable up to 1410 °C. No indication of a significant phase width was found; Sr₄Fe₆O_13±δ appears as a second phase in compositions with <85.71±0.2 mol% Fe₂O₃. Sr₄Fe₆O_13±δ itself is stable between 800 and 1250 °C. Two other hexagonal ferrites were found to exist at high temperatures only: W-type SrFe²⁺₂Fe³⁺₁₆O₂₇ is stable between 1350 and 1440 °C and X-type ferrite Sr₂Fe²⁺₂Fe³⁺₂₈O₄₆ between 1350 and 1420 °C, respectively, which is shown here for the first time. These findings in combination with previously published data were used to derive a corrected phase diagram of the Fe-rich part of the pseudo-binary system SrO–Fe₂O₃.     

Spectroscopic characterization of porous nanohydroxyapatite synthesized by a novel amino acid soft solution freezing method

In this paper, we have reported a novel method to synthesize nanoporous hydroxyapatite (HAP) powders by freezing organic–inorganic soft solutions. The formation of porous and crystalline HAP nanopowder was achieved via calcining the samples at 600 °C followed by sintering at temperatures ranging from 900 °C to 1100 °C. The samples were analyzed by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and scanning electron microscopic (SEM) techniques. The results showed the formation of a carbon free nanoporous hydroxyapatite powders due to the decomposition of organic template enclosing the precipitated HAP. It was also observed that the rapid grain growth with retainment of pores while the crystallinity of the HAP nanopowder increased with the increase in sintering temperature which is substantiated from the XRD and SEM results. Such organized porous materials can act as a better biomaterial for bone tissue engineering.     

A pyrolysis-GC–MS investigation of poly(vinyl phenyl ketone)

The thermal decomposition process and pyrolysis products of poly(vinyl phenyl ketone) (PVPK) were investigated by thermogravimetric analysis (TGA) and on-line pyrolysis-gas chromatography–mass spectrometry (Py-GC–MS). TGA showed a largest weight loss rate around 380 °C. Py-GC–MS was used for the qualitative analysis of the pyrolysis products at 350, 500, 600, 700 and 850 °C. The major volatile thermal decomposition product was found to be 1-phenyl-2-propenone, which dominated all other volatile species especially under the least severe pyrolysis conditions (<600 °C). At higher temperatures a much wider range of pyrolysis products was obtained. The results have been interpreted assuming that primary random chain scission reactions occur followed by typical unzipping mainly producing monomer units; detachment of the side-group occurs only under more severe pyrolysis conditions. Py-GC–MS showed to be effective in PVPK detection in ink and paint formulations.     

Oxygen production at low temperature using dense perovskite hollow fiber membranes

A dense perovskite hollow fiber made of BaCo_xFe_yZr_zO_3−δ (BCFZ) was evaluated for the oxygen separation at low temperatures (400–500 °C). An oxygen permeation flux of 0.45 ml/min cm² was obtained at 500 °C, which is the first oxygen permeation data reported at such low temperature so far. A degradation of the oxygen permeation at 500 °C was observed, but the oxygen fluxes through the hollow fiber membrane can be regenerated by thermal treatment at 925 °C for 1 h in air. Energy-dispersive X-ray spectroscopy (EDXS) shows that a strong element segregation occurs in the membrane during operation at low temperature.     

Study of urea intercalation into halloysite by thermoanalytical and spectroscopic techniques

Intercalation of a kaolinite-containing halloysite from Biela Hora (Slovakia) with urea was investigated by simultaneous TG–DTA, XRD, FTIR (DRIFT), and Raman spectroscopy. The process of intercalation and thermal deintercalation was followed for the as-prepared and the washed (with isopropanol) samples. The proposed structural model was supported by molecular mechanical calculations. Incorporation of the intercalate (in 5 wt%) in molten polypropylene at 200 °C resulted in the complete delamination of the mineral. It is supposed that gas formation as a result of urea decomposition between the layers prevents reorientation and restructuring of the layers.     

X-ray diffraction and Mössbauer spectroscopy studies of LiFe0.5Ti1.5O4 – A new primitive cubic ordered spinel

LiFe_0.5Ti_1.5O₄ was synthesized by solid-state reaction carried out at 900 °C in flowing argon atmosphere, followed by rapid quenching of the reaction product to room temperature. The compound has been characterized by X-ray powder diffraction (XRD) and ⁵⁷Fe Mössbauer effect spectroscopy (MES). It crystallizes in the space group P4₃32, a = 8.4048(1) Å. Results from Rietveld structural refinement indicated 1:3 cation ordering on the octahedral sites: Li occupies the octahedral (4b) sites, Ti occupies the octahedral (12d) sites, while the tetrahedral (8c) sites have mixed (Fe/Li) occupancy. A small, about 5%, inversion of Fe on the (4b) sites has been detected. The MES data is consistent with cation distribution and oxidation state of Fe, determined from the structural data.The title compound is thermally unstable in air atmosphere. At 800 °C it transforms to a mixture of two Fe³⁺ containing phases – a face centred cubic spinel Li_(1+y)/2Fe_(5−3y)/2Ti_yO₄ and a Li_(z−1)/2Fe_(7−3z)/2Ti_zO₅ – pseudobrookite. The major product of thermal treatment at 1000 °C is a ramsdellite type lithium titanium iron(III) oxide, accompanied by traces of rutile and pseudobrookite.     

Development of polyelectrolyte complexes of chitosan and phosphotungstic acid as pervaporation membranes for dehydration of isopropanol

Using a solution technique, chitosan-based polyelectrolyte complexes (PECs) were developed as pervaporation membranes by incorporating phosphotungstic acid (PTA). The resulting membranes were characterized by Fourier transform infrared spectroscopy (FTIR), wide-angle X-ray diffraction (WAXD), scanning electron microscopy (SEM) and thermogravimetric analysis (TGA). Membranes were tested for their ability to separate water–isopropanol mixtures by pervaporation in the temperature range of 30–50 °C. The experimental results demonstrated that both flux and selectivity were increased simultaneously with increasing PTA content in the membrane. The permeation flux of pure chitosan membrane was increased dramatically from 4.13 to 11.70 × 10⁻² kg/m² h and correspondingly its separation factor was increased from 4490 to 11,241 and then decreased to 7490 at 30 °C for 10 mass% of water in the feed. The total flux and flux of water were found to be almost overlapping particularly for PECs membranes, suggesting that these could be used effectively to break the azeotropic point of water–isopropanol mixtures. From the temperature dependency of diffusion and permeation values, the Arrhenius activation parameters were estimated and discussed in the context of membranes efficiency. The pure chitosan and a small amount of PTA-incorporated PECs membranes exhibited positive heat of sorption while other PECs membranes exhibited negative heat of sorption, giving exothermic contribution.     

Novel co-extruded electrolyte–anode hollow fibres for solid oxide fuel cells

Novel CGO/NiO–CGO dual-layer hollow fibres (HFs) have been fabricated in a single-step co-extrusion and co-sintering process. LSCF–CGO cathodes layers were then deposited onto the dual-layer HFs to construct micro-tubular SOFCs. The NiO in the micro-tubular HF–SOFCs was reduced at 550 °C using hydrogen gas to form Ni anodes. Scanning electron microscope images showed that the dual-layer HFs have porous anodes and dense electrolyte layers. Preliminary measurements with a HF–SOFC fed with H₂ and atmospheric oxygen, produced maximum power densities of 420 W m⁻² and 800 W m⁻² at 450 °C and 550 °C, respectively.     

Fine tuning of gadolinium doped ceria electrolyte nanoparticles via reverse microemulsion process

Gadolinium doped ceria (Gd–CeO₂) nanoparticles have been synthesized by an reverse microemulsion system using cyclohexane as the oil phase, a non-ionic surfactant Igepal CO 520 and their mixed aqueous solutions of gadolinium III nitrate hexahydrate and cerium III nitrate hexahydrate as the water phase. The control of particle size was achieved by varying the water to surfactant molar ratio. The synthesized and calcined powders were characterized by thermogravimetry-differential thermal analysis (TGA-DTA), X-ray diffraction analysis (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS), Fourier transform infrared spectroscopy (FTIR) and Raman spectroscopy. The XRD results show that all the samples calcined at 700 °C were single phase cubic fluorite structure. The average size of the particle was found to increase with increase in water to surfactant molar ratio (R). The mean diameter of the particle for various value of R varies between 8–15 nm (SEM) and 7.5–11 nm (TEM), respectively. EDS confirm the presence of gadolinia and ceria phase in the nanopowder calcined at 700 °C. FTIR analysis was carried to monitor the elimination of residual oil and surfactant phases from the microemulsion-derived precursor and calcined powder. Raman spectroscopy and DTA evidenced the formation of a solid solution of gadolinium doped ceria at room temperature.     

Paramagnetic resonance and non-resonant microwave absorption in iron niobate

An electron paramagnetic resonance (EPR) study of FeNbO₄ powder samples in monoclinic phase (wolframite-type) at X-band (8.8–9.8 GHz), in the 90–300 K temperature range, is presented. For all the temperatures, the EPR spectrum shows a single line associated with Fe³⁺ ions. Changes in the lineshape of the EPR spectrum, which can be attributed to Fe²⁺ ions, are detected at low temperatures. This behavior can be ascribed to a strong magnetic dipolar interaction between Fe²⁺ and Fe³⁺ ions. The non-resonant microwave absorption techniques: magnetically-modulated microwave absorption spectroscopy (MAMMAS) and low-field microwave absorption spectroscopy (LFMAS), were used for a further knowledge on this material. MAMMAS response suggests also the presence of Fe²⁺ ions, that originates a change in microwave absorption regime for T < T_p (=140 K), associated with the presence of short-range magnetic correlations. LFMAS spectra showed a linear behavior with positive slope and non-hysteretic traces. The profiles obtained by plotting the slope vs. temperature of the LFMAS line are similar to those detected by the MAMMAS technique, confirming that both types of measurement show the same processes of absorption.     

Catalytic and Physicochemical Properties of Oxidative Condensation Products in the Oxidative Dehydrogenation of Propane by Sulfur Dioxide on SiO2

The effect of the deposition of oxidative condensation products in the reaction of oxidative propane dehydrogenation in the presence of SO₂ on the catalytic, acid–base, and texture characteristics of silica was studied. It was found that the oxidative condensation products exhibited high catalytic activity in this reaction. The carbonization of silica from 0 to 40 wt % was accompanied by an increase in the yield of propylene from 3.4 to 46 mol % (640°C; a C₃H₈/SO₂/He + N₂ mixture, 10 : 10 : 80 vol %). Further accumulation of condensation products resulted in a considerable decrease in the pore volume and radius; this imposed diffusion limitations on both propane conversion and selectivity to propane conversion products. The nature of active and deactivated condensation products was studied by DRIFT spectroscopy, diffuse-reflectance UV–VIS spectroscopy, EPR spectroscopy, XPS, thermal analysis, and electron microscopy.     

Synthesis and characterization of Fe2O3/SiO2 nanocomposites

Fe₂O₃/SiO₂ nanocomposites based on fumed silica A-300 (S_BET = 337 m²/g) with iron oxide deposits at different content were synthesized using Fe(III) acetylacetonate (Fe(acac)₃) dissolved in isopropyl alcohol or carbon tetrachloride for impregnation of the nanosilica powder at different amounts of Fe(acac)₃ then oxidized in air at 400–900 °C. Samples with Fe(acac)₃ adsorbed onto nanosilica and samples with Fe₂O₃/SiO₂ including 6–17 wt% of Fe₂O₃ were investigated using XRD, XPS, TG/DTA, TPD MS, FTIR, AFM, nitrogen adsorption, Mössbauer spectroscopy, and quantum chemistry methods. The structural characteristics and phase composition of Fe₂O₃ deposits depend on reaction conditions, solvent type, content of grafted iron oxide, and post-reaction treatments. The iron oxide deposits on A-300 (impregnated by the Fe(acac)₃ solution in isopropanol) treated at 500–600 °C include several phases characterized by different nanoparticle size distributions; however, in the case of impregnation of A-300 by the Fe(acac)₃ solution in carbon tetrachloride only α-Fe₂O₃ phase is formed in addition to amorphous Fe₂O₃. The Fe₂O₃/SiO₂ materials remain loose (similar to the A-300 matrix) at the bulk density of 0.12–0.15 g/cm³ and S_BET = 265–310 m²/g.     

TG-FTIR analysis of switchgrass pyrolysis

Switchgrass is a high yielding perennial grass that has been designated as a potential energy crop. One method of converting switchgrass to energy is by thermochemical conversion to syngas. This requires that the rate of thermal decomposition of switchgrass and the rate of production of components of the syngas be quantified. Ground switchgrass was pyrolyzed at heating rates of 10–40 °C/min in a thermogravimetric analyzer coupled to a Fourier Transform infrared spectrometer. The amount of gases (ppm) that were volatilized during the duration of experiment was quantified. The pyrolysis process was found to compose of four stages: moisture evaporation, hemicellulose decomposition, cellulose decomposition and lignin degradation. The peak temperature for hemicellulose (288–315 °C) and cellulose degradation (340–369 °C) increased with heating rate. FTIR analysis showed that the following gases were given off during the pyrolysis of switchgrass: carbon dioxide, carbon monoxide, acetic acid, ethanol, and methane.     

Thermal decomposition process of silver behenate

The thermal decomposition processes of silver behenate have been studied by infrared spectroscopy (IR), X-ray diffraction (XRD), combined thermogravimetry-differential thermal analysis-mass spectrometry (TG-DTA-MS), transmission electron microscopy (TEM) and UV-vis spectroscopy. The TG-DTA and the higher temperature IR and XRD measurements indicated that complicated structural changes took place while heating silver behenate, but there were two distinct thermal transitions. During the first transition at 138 °C, the alkyl chains of silver behenate were transformed from an ordered into a disordered state. During the second transition at about 231 °C, a structural change took place for silver behenate, which was the decomposition of silver behenate. The major products of the thermal decomposition of silver behenate were metallic silver and behenic acid. Upon heating up to 500 °C, the final product of the thermal decomposition was metallic silver. The combined TG-MS analysis showed that the gas products of the thermal decomposition of silver behenate were carbon dioxide, water, hydrogen, acetylene and some small molecule alkenes. TEM and UV-vis spectroscopy were used to investigate the process of the formation and growth of metallic silver nanoparticles.     

The influence of calcination on the size of nanocrystals, porous structure and acid–base properties of mesoporous anatase used as catalytic support

Mesoporous anatase was prepared following sol–gel and using urea as template. The influence of calcination temperature on the phase stability, nanocrystal/aggregate size, pore size distribution and specific surface area as well as on the acid–base behavior in aqueous solutions was studied using X-ray diffraction, laser-Raman and diffuse reflectance spectroscopies, scanning electron microscopy and laser scattering as well as N₂ adsorption–desorption isotherms and potentiometric mass titrations.The crystal structure was kept constant upon calcination over the whole temperature range, 200–500 °C. In this range anatase is constituted from primary nanocrystals. These are assembled into larger, rather spherical, clusters of about 30–40 nm and then into aggregates of various sizes (0.2–0.3 μm and 2–100 μm) with a distribution centered at about 12 μm. Increase of the calcination temperature caused an increase in the size of the primary nanocrystals from 8.1 nm at 200 °C to 17.1 nm at 500 °C, whereas calcination does not influence the morphology at micro-scale. Moreover, increase of the calcination temperature from 200 °C to 500 °C brings about a shift in the mean pore diameter from 47 nm to 91 nm accompanied by a decrease in the specific surface area and pore volume. The above effects were related with the aforementioned increase in the size of the primary nanocrystals. The value of pzc and the values of surface charge determined at various pH do not practically depend on the calcination temperature. The absence of pore space confinement effects was explained in terms of the structure and size of the interface development between the anatase surface and the electrolytic solution.     

Preparation and hydrogen permeation of BaCe0.95Nd0.05O3−δ membranes

A mixed proton–electron conducting perovskite made of BaCe_0.95Nd_0.05O_3−δ (BCN) was prepared by EDTA/citric acid complexing method. The precursor was characterized by differential scanning calorimetry (DSC), thermogravimetry (TG), and X-ray diffraction (XRD). In order to learn the perovskite formation process during the calcination, the intermediate, i.e. the sample calcined at 750 °C for 5 h, was investigated by scanning (STEM), energy-filtered (EFTEM), and high-resolution transmission electron microscopy (HRTEM) as well as electron energy-loss spectroscopy (EELS). The results revealed that the perovskite structure was formed via a solid-state reaction between barium–cerium mixed carbonate and cerium–neodymium mixed oxide particles. Dense mixed proton–electron conducting BCN membranes were made by pressing BCN powder followed by sintering. The microstructure of the sintered membranes was investigated by scanning electron microscopy (SEM). Hydrogen permeation through the BCN membrane was studied using a high-temperature permeator. The hydrogen permeation fluxes under wet conditions are higher than those under dry conditions, which is due to increased proton concentrations in the H⁺ hopping via OH groups. The hydrogen permeation increased with increasing hydrogen and steam concentrations in the feed. For a steam concentration of 15 vol.%, the hydrogen permeation flux reaches 0.026 ml/min cm².     

GaN taper rods: Solid-phase synthesis, crystal defects, and optical properties

Wurtzite GaN taper rods assembled from highly oriented nanoparticles were synthesized using NaNH₂ and the as-synthesized GaOOH prismatic rods as reactants at 600 °C for 5 h. The lengths of the GaN taper rods are in the range of 4–6 μm and the diameters are about 0.5–1.5 μm. It was found that a slow heating rate (1 °C min⁻¹) was beneficial to keeping the one-dimensional (1D) skeleton of GaN, otherwise only GaN nanoparticles were obtained with a quick heating rate (10 °C min⁻¹). Selected area electron diffraction (SAED) patterns and high-resolution transmission electron microscopy (HRTEM) observations revealed that the GaN taper rods assembled from highly oriented nanoparticles and there were crystal defects in the GaN structure. The GaN taper rods displayed luminescence emission in the blue-violet region, which may be related to crystal defects.     

Cobalt–silicon mixed oxide nanocomposites by modified sol–gel method

Cobalt–silicon mixed oxide materials (Co/Si=0.111, 0.250 and 0.428) were synthesised starting from Co(NO₃)₂·6H₂O and Si(OC₂H₅)₄ using a modified sol–gel method. Structural, textural and surface chemical properties were investigated by thermogravimetric/differential thermal analyses (TG/DTA), XRD, UV–vis, FT-IR spectroscopy and N₂ adsorption at −196 °C. The nature of cobalt species and their interactions with the siloxane matrix were strongly depending on both the cobalt loading and the heat treatment. All dried gels were amorphous and contained Co²⁺ ions forming both tetrahedral and octahedral complexes with the siloxane matrix. After treatment at 400 °C, the sample with lowest Co content appeared amorphous and contained only Co²⁺ tetrahedral complexes, while at higher cobalt loading Co₃O₄ was present as the only crystalline phase, besides Co²⁺ ions strongly interacting with siloxane matrix. At 850 °C, in all samples crystalline Co₂SiO₄ was formed and was the only crystallising phase for the nanocomposite with the lowest cobalt content. All materials retained high surface areas also after treatments at 600 °C and exhibited surface Lewis acidity, due to cationic sites. The presence of cobalt affected the textural properties of the siloxane matrix decreasing microporosity and increasing mesoporosity.     

Preparation and Characterization of Single-Phase Perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ

Single-phase perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ has been successfully prepared by using citrate-EDTA complexation method at relatively low calcination temperature. The structure and thermal decomposition process of the complex precursor have been investigated by means of differential scanning calorimetry-thermal gravimetric analysis (DSC/TGA), X-ray diffraction (XRD), and Fourier transform infrared spectroscopic (FT-IR) measurements. The precursor decomposed completely and started to form perovskite-type oxide above 420℃ according to the differential scanning calorimetry (DSC) and thermal gravimetric analysis (TGA) results. Single-phase perovskite La0.6Sr0.4Co0.8Fe0.2O3-δ obtained has been confirmed from the XRD pattern, and no peak of SrCO3 was found by XR.D of the oxides synthesized at a relatively low temperature of 800 ℃. The reducibility of La0.6Sr0.4Co0.8Fe0.2O3-δ was also characterized by the temperature programmed reduction (TPR) technique. Disk shaped dense La0.6Sr0.4Co0.8Fe0.2O3-δ membrane was prepared by the isostatical pressing method. The oxygen flux rate of dense La0.6Sr0.4Co0.8Fe0.2O3-δ membrane was (2.8-18)×10-8 mol/(cm2·s) in the temperature range of 800-1 000℃.     

Studies of the surface wettability and hydrothermal stability of methyl-modified silica films by FT-IR and Raman spectra

Fourier transform infrared (FT-IR) and Raman spectroscopy were employed to study the hydrothermal stability and the influence of surface functional groups on the surface wettability of methyl-modified silica films. The surface free energy parameters of the silica films were determined using the Lifshitz-van der Waals/acid–base approach. The thermal decomposition mechanisms of the CH₃ groups in the methyl-modified silica material are proposed. The results show that with the increase of methyltriethoxysilane (MTES)/tetraethylorthosilicate (TEOS) ratio, the surface free energy and surface wettability of the silica films decrease greatly. This is mainly because of the contribution of the acid–base term; the intensity of Si–CH₃ groups increases at the expense of the intensity of O–H groups in the samples. The surfaces of the methyl-modified silica films exhibited predominantly monopolar electron-donicity. The contact angle on the silica film surface reaches its maximum value when calcination is performed at 350 °C. Thermogravimetric analysis implies that some low molecular weight species, such as H₂, CH₄, and C, are eliminated upon thermal decomposition of the –CH₃ groups. The Si–CH₃ and –CH₃ vibrational bands diminish in intensity as the calcination temperature is increased, disappearing completely when the calcination temperature is increased to 600 °C. When the calcination temperature is increased to 750 °C, the free carbon and CSi₄ species will be formed.