Diffusion analysis of N2O cycling in a fertilized soil

The behavior of nitrous oxide (N₂O) in fertilized soil was studied in terms of soil fluxes, the production rates at various depths and the turnover in soil. The diffusive losses of N₂O to the atmosphere calculated from soil N₂O profile compared favorably with the flux directly determined with a closed chamber technique. The estimate of N₂O production rates at several depths demonstrated that the sites of N₂O production was only near the soil surface. The calculated residence time of N₂O in the entire soil column studied was only 1.4 hour during active emission period and less than 1 day even in the later period having trace N₂O emission. The prolonged N₂O emission observed after the active phase was due likely to a lasting N₂O production rather than a supply from the soil N₂O reservoir. The results suggested that most N₂O in soil was emitted quite promptly to the atmosphere after its production. A minor role of soil as an N₂O reservoir is emphasized from the viewpoint of the origin of groundwater N₂O. This revised version was published online in August 2006 with corrections to the Cover Date.     

Determination of the Diffusion Coefficient of H<Subscript>2</Subscript>O in Polyacrylonitrile Fiber Formation

An H₂O/dimethyl sulphoxide (DMSO) mixture was used as the coagulation bath of a wet-spun process. The diffusion coefficient of H₂O in the protofibers prepared by acrylonitrile homopolymers was determined. It was found that the diffusion coefficient of H₂O in the protofibers prepared by homopolymers synthesized by solution polymerization was highest compared with those of homopolymers synthesized by H₂O/DMSO mixture suspension polymerization and aqueous suspension polymerization. With an increase of polyacrylonitrile concentration in the dope, the diffusion coefficient of H₂O decreased continuously. The diffusion coefficient of H₂O increased along with the bath temperature, but the changes of diffusion coefficient values were less prominent as the temperature went beyond 60^○C. When the DMSO concentration in the coagulation bath was 55%, the value of the diffusion coefficient of H₂O was minimal. The diffusion coefficient of H₂O increased with increasing jet stretch minus ratio. When the protofiber radius was increased, there was a corresponding increase of the diffusion coefficient of H₂O.     

Textural and Thermal Properties of the Novel Fucoidan/Nano-Oxides Hybrid Materials with Cosmetic,Pharmaceutical and Environmental Potential

The main purpose of the research was to obtain and study hybrid materials based on three different nano-oxides commonly used in the cosmetic and pharmaceutical industries: Al₂O₃, TiO₂, and ZnO, with the natural bioactive polysaccharide fucoidan. Since the mentioned oxides are largely utilized by industry, there is no doubt that the presented studies are important from an environmental point of view. On the basis of the textural studies (dynamic light scattering DLS, low temperature nitrogen adsorption, X-ray diffraction analysis XRD, scanning electron microscopy SEM) it was proved that the properties of the hybrid materials differ from the pure components of the system. Moreover, the advanced thermal analysis (TG-DTG-DSC) combined with the evolved gas analysis using Fourier transformed infrared spectroscopy (FTIR) and mass spectrometry were applied to describe the thermal decomposition of fucoidan, oxides and hybrid materials. It was found that the interactions between the polymer and the oxides results in the formation of the hybrid materials due to the functionalization of the nanoparticles surface, and that their thermal stability increased when compared to the pure substrates. Such findings definitely fill the literature void regarding the fucoidan based hybrid materials and help the industrial formulators in the preparation of new products.     

Propylene-ethylene Copolymer Filled Nanocomposites: Influence of Zn-ion Coating upon Nano-SiO2 on Structural,Thermal, and Dynamic Mechanical Properties

Propylene-ethylene copolymer (EP) nanocomposites based on nano-SiO₂ with and without Zn-ion coating were developed by conventional melt blending technique in a sigma internal mixer. Two composites each with 2.5 wt% filler were developed. The first composite was made by melt blending EP with nano-SiO₂ in a co-rotating sigma internal mixer. The second one was obtained by melt blending the same EP, but with Zn-ion coated nano-SiO₂. In case of Zn-ion coated nano-SiO₂ filled EP, wide-angle X-ray diffraction study (WAXD) showed a decrease in interplanar distance and lamellar polymer crystal size when compared to nano-SiO₂ filled EP. Differential scanning calorimetric (DSC) results showed Zn-ion coated nano-SiO₂ acting more as an effective nucleating agent than that of the nano-SiO₂. Thermogravimetric analysis (TGA) results showed improved thermal stability for EP in the presence of both the nanofillers. However, the thermal stability of Zn-ion coated nano-SiO₂ filled EP is higher than that of the nano-SiO₂ filled EP. Scanning electron microscope (SEM) study reveals that the Zn-ion coated nano-SiO₂ homogeneously distributed in the matrix, whereas nano-SiO₂ forms chainlike aggregates in the matrix phase. Dynamic mechanical analysis (DMA) study indicates that both the fillers increase storage modulus, E′; this increment is more prominent in nano-SiO₂ filled EP due to the formation of chain-type aggregates of nano-SiO₂.     

Accommodation of impurities in α-Al2O3, α-Cr2O3 and α-Fe2O3

Atomic scale computer simulation was used to predict the mechanisms and energies associated with the accommodation of aliovalent and isovalent dopants in three host oxides with the corundum structure. Here we consider a much more extensive range of dopant ions than has previously been the case. This enables a rigorous comparison of calculated mechanism energetics. From this we predict that divalent ions are charge compensated by oxygen vacancies and tetravalent ions by cation vacancies over the full range of dopant radii. When defect associations are included in the model these conclusions remain valid. At equilibrium, defects resulting from extrinsic dopant solution dominate intrinsic processes, except for the largest dopant cations. Solution reaction energies increase markedly with increasing dopant radius. The behaviour of cluster binding energies is more complex.     

Thermal Decomposition of Divanadium Pentoxide V2O5: Towards a Nanocrystalline V2O3 Phase

Thermal decomposition of V₂O₅ was studied by means of transmission electron microscopy (TEM) and electron energy-loss spectroscopy (EELS). Samples were heated in a specimen chamber of an electron microscope up to 600 °C in vacuum at 10^-7 Torr. TEM and EELS reveal a sequence of transformations from V₂O₅ via VO₂ to V₂O₃, which differs from the electron-beam-induced reduction of V₂O₅. The phase transformation does not proceed topotactically. Our observation reveals that the initial thermal decomposition of V₂O₅ to V₂O₃ is followed by a combination of diffusion, coalescence, and stabilization processes. Our experiments open a new way for the preparation of single-crystalline V₂O₃ nano-particles.     

Changes in Ba Phases in BaO/Al2O3 upon Thermal Aging and H2O Treatment

The effects of thermal aging and H₂O treatment on the physicochemical properties of BaO/Al₂O₃ (the NO_x storage component in the lean NO_x trap systems) were investigated by means of X-ray diffraction (XRD), BET, TEM/EDX and NO₂ TPD. Thermal aging at 1000 °C for 10 h converted dispersed BaO/BaCO₃ on Al₂O₃ into low surface area crystalline BaAl₂O₄. TEM/EDX and XRD analysis showed that H₂O treatment at room temperature facilitated a dissolution/reprecipitation process, resulting in the formation of a highly crystalline BaCO₃ phase segregated from the Al₂O₃ support. Crystalline BaCO₃ was formed from conversion of both BaAl₂O₄ and a dispersed BaO/BaCO₃ phase, initially present on the Al₂O₃ support material after calcinations at 1000 and 500 °C, respectively. Such a phase change proceeded rapidly for dispersed BaO/BaCO₃/Al₂O₃ samples calcined at relatively low temperatures with large BaCO₃ crystallites observed in XRD within 10 min after contacting the sample with water. Significantly, we also find that the change in barium phase occurs even at room temperature in an ambient atmosphere by contact of the sample with moisture in the air, although the rate is relatively slow. These phenomena imply that special care to prevent the water contact must be taken during catalyst synthesis/storage, and during realistic operation of Pt/BaO/Al₂O₃ NO_x trap catalysts since both processes involve potential exposure of the material to CO₂ and liquid and/or vapor H₂O. Based on the results, a model that describes the behavior of Ba-containing species upon thermal aging and H₂O treatment is proposed.     

Direct synthesis of mesoporous silicalite-1 supported TiO2–ZrO2 for the dehydrogenation of EB to styrene with CO2

Direct synthesis route was developed to support TiO₂–ZrO₂ binary metal oxide onto the carbon templated mesoporous silicalite-1 (CS-1). Metal hydroxide modified carbon particles could play a role as hard template and simultaneously support metal components on the mesopores during the crystallization of zeolites. Such supported TiO₂–ZrO₂ binary metal oxides (TZ/CS-1) showed better resistance to deactivation in the oxidative dehydrogenation of ethylbenzene (ODHEB) in the presence of CO₂. These catalysts were found to be active, selective and catalytically stable (10 h of time-on-stream) at 600 °C for the dehydrogenation of ethylbenzene (EB) to styrene (Sty).     

Production of syngas plus oxygen from CO2 in a gas-diffusion electrode-based electrolytic cell

Most of the research published in electrochemical CO₂ reduction has been reported for half-cells, with little consideration of the overall system. However, it is necessary to consider the eventual involvement of full cells. We conducted CO₂ reduction and water oxidation in a CO₂-reducing full cell with larger geometric surface area (2×2 cm²) and with a relatively small inter-electrode gap (1-2 mm) in order to minimize ohmic losses. The result was an ca. 1:1 CO/H₂ (v/v) gas ratio at a current density of 10 mA cm⁻² and a cell voltage of 3.05 V, producing O₂ at the counter electrode. Based on an enthalpic voltage of 1.36 V, this constitutes an overall energy efficiency of 44.6%.     

Enhancement of oxygen storage capacity by reductive treatment of Al2O3 and CeO2–ZrO2 solid solution nanocomposite

Oxygen storage capacity (OSC) of CeO₂–ZrO₂ solid solution, Ce_xZr_(1−x)O₄, is one of the most contributing factors to control the performance of an automotive catalyst. To improve the OSC, heat treatments were employed on a nanoscaled composite of Al₂O₃ and CeZrO₄ (ACZ). Reductive treatments from 700 to 1000 °C significantly improved the complete oxygen storage capacity (OSC-c) of ACZ. In particular, the OSC-c measured at 300 °C reached the theoretical maximum with a sufficient specific surface area (SSA) (35 m²/g) after reductive treatment at 1000 °C. The introduced Al₂O₃ facilitated the regular rearrangement of Ce and Zr ions in CeZrO₄ as well as helped in maintaining the sufficient SSA. Reductive treatments also enhanced the oxygen release rate (OSC-r); however, the OSC-r variation against the evaluation temperature and the reduction temperature differed from that of OSC-c. OSC-r measured below 200 °C reached its maximum against the reduction temperature at 800 °C, while those evaluated at 300 °C increased with the reduction temperature in the same manner as OSC-c.     

Diffusion During the Supercritical Drying of Silica Gels

Drying is the most critical elaboration step of large monolithic and crack-free silica aerogel plates. In the present work, we are studying the supercritical CO₂ drying and more precisely the first step, here called the supercritical washing step. This phase consists of replacing the liquid phase contained in the nanopores with supercritical CO₂. Within this study, this step is governed by molecular diffusion through the gels. These phenomena were investigated experimentally in order to estimate the duration of the washing step. The experimental results were then fitted with an analytical mass transfer model to identify the effective diffusion coefficient.     

Influence of TiO2 and CeO2 on the hydrogenation activity of bulk Ni2P

TiO₂- and CeO₂-promoted bulk Ni₂P catalysts were prepared by impregnation and in-situ H₂ temperature-programmed reduction method. The prepared catalysts were characterized by XRD and XPS. The hydrogenation activities of the catalysts were studied using 1.5 wt.% 1-heptene in toluene and 1.0 wt.% phenylacetylene in ethanol as the model feeds. The results indicate that bulk Ni₂P possesses low hydrogenation activity but is tunable by simply controlling the content of the additives (TiO₂ or CeO₂), suggesting that TiO₂ and CeO₂ are effective promoters to enhance the hydrogenation activity of Ni₂P.     

Deuterium Recovery from H-D Gas Mixture by Thermal Diffusion in the Device of Branch Columns for Improved Performance

The strength of forced convection currents, as well as the remixing effect in a continuous-flow thermal diffusion column for recovery of deuterium from H-D gas mixture, can be reduced by employing the device of branch columns, instead of the device of single column, with the same total column length. The improvement in separation increases when the flow rate or the total column length increases. It is found that the improvement in recovery can reach about 50% for the numerical example given.     

Effect of Sizes of Nano Ca3(PO4)2 on Mechanical and Thermal Properties of Polyurethane Foam Composites

Particular sizes of nano inorganic filler, Ca₃(PO₄)₂ were prepared by following the matrix mediated growth technique. Composite foams were prepared on addition of different concentration (0.5–2.5 wt.%) of nano size filler in a single–phase polyurethane matrix. The differential Scanning Calorimetry (DSC) for composite as well as pure polyurethane was done to ascertain the degree of interaction of filler with the structure of the matrix as active sites. The degree of cell formation increases on increase in amount of reduced size nano filler in the composites where as decrease in case of larger size filler in composites. The increment in specific gravity from 0.17–0.25 for reduced nano size filler and 0.17–0.18 in case of larger size filler makes a strong support for the increment of cell numbers. The significant enhancement 250% in compressive strength, and the reduction of cell sizes shown in optical photographs satisfies the reasons of increment in heat of fusion (ΔH) in DSC. The decrement in (ΔH) cal/g in case of larger size filler for curing shows the conduction of heat is more due formation of cells less in numbers results in reduction of rate of heating more. Thermal gravimetric analysis (TGA) was done to know the degradation behavior. The TGA results, shows increment in onset temperature and mid temperature of the first step degradation in case of larger size nano filler. Decrement of flammability from 0.47–13.14 sec/mm for reduced nano size filler and 0.47–8.23 sec/mm in case of larger size filler, show that the incorporation of nano particles not only improves the mechanical properties but also retards the flammability.     

Synthesis and study on phase diagram of 1-10 mol% SnO2-doped Bi2O3

Bi₂O₃ materials doped with various SnO₂ concentrations were prepared by colloidal process and solid state reactions to achieve high density and uniform microstructure. Thermal behavior, and crystalline phases of the SnO₂-doped Bi₂O₃ (BSO) samples were investigated by differential thermal analyses, X-ray diffraction, and scanning electron microscopy. A new phase diagram of Bi₂O₃-(1-10 mol%) SnO₂ system is proposed in this study. The results show that 1 mol% SnO₂ doped concentration is totally dissolved in Bi₂O₃ without the existence of any impurity phases as compared to higher doping SnO₂ concentration.     

Effect of WSi2 addition on densification and properties of ZrB2

Abstract

Effect of WSi₂ addition on densification and properties of ZrB₂ has been investigated. Samples of the following composition with controlled addition of WSi₂ were prepared by hot pressing (1) ZrB₂, (2) ZrB₂+2·5%WSi₂, (3) ZrB₂+5%WSi₂ and (4) ZrB₂+10%WSi₂. Hot pressing of monolithic ZrB₂ at 1750°C resulted in achieving a density of only 80·1% ρ_th. Addition of WSi₂ enhanced the densification and resulted in near theoretical density. Microstructural investigations revealed the presence of reaction product containing Si and Zr. An increase in WSi₂ content led to an increase in hardness of the product. A slight increase in fracture toughness was observed with WSi₂ addition. Crack deflection was observed in the microstructure. Oxidation study of the composite samples revealed that the oxidised layer is not adherent and resulted in spallation at the end of the test.     

The catalytic performance in oxidative coupling of methane and the surface basicity of La2O3, Nd2O3, ZrO2 and Nb2O5

The catalytic performance in oxidative coupling of methane (OCM) of unmodified pure La₂O₃, Nd₂O₃, ZrO₂ and Nb₂O₅ has been investigated under various conditions. The results confirmed that the activity of La₂O₃ and Nd₂O₃ was always much higher than that of the remaining two. The surface basicity/base strength distribution of pure La₂O₃, Nd₂O₃, ZrO₂ and Nb₂O₅ was measured using a test reaction of transformation of 2-butanol and a temperature-programmed desorption of CO₂. Both methods showed that La₂O₃ and Nd₂O₃ had high basicity and contained medium and strong basic sites (lanthanum oxide more and neodymium oxide somewhat less). ZrO₂ had only negligible amount of weak basic sites and Nb₂O₅ was rather acidic. The confrontation of the basicity and catalytic performance indicated that in the case of investigated oxides, the basicity (especially strong basic sites) could be a decisive factor in determination of the catalytic activity in OCM. Only in the case of ZrO₂ it was observed a moderate catalytic performance in spite of negligible basicity. The influence of a gas atmosphere used in the calcination of oxides (flowing oxygen, helium and nitrogen) on their basicity and catalytic activity in OCM had been also investigated. Contrary to earlier observations with MgO, no effect of calcination atmosphere on the catalytic performance of investigated oxides in OCM and on their basicity was observed.     

Electrocatalytic activity of IrO2-RuO2 supported on Sb-doped SnO2 nanoparticles

Electrocatalytic IrO₂-RuO₂ supported on Sb-doped SnO₂ (ATO) nanoparticles is very active towards the oxygen evolution reaction. The IrO₂-RuO₂ material is XRD amorphous and exists as clusters on the surface of the ATO. Systematic changes to the surface chemical composition of the ATO as a function of the IrO₂:RuO₂ ratio suggests an interaction between the IrO₂-RuO₂ and ATO. Cyclic voltammetry indicates that the electrochemically active surface area of IrO₂-RuO₂ clusters is maximised when the composition is 75 mol% IrO₂-25 mol% RuO₂. Decreasing the loading of IrO₂-RuO₂ on ATO reduces the electrochemically active surface area, although there is evidence to support a decrease in the clusters size with decreased loading. Tafel slope analysis shows that if the clusters are too small, the kinetics of the oxygen evolution reaction are reduced. Overall, clusters of IrO₂-RuO₂ on ATO have similar or better performance for the oxygen evolution reaction than many previously reported materials, despite the low quantity of noble metals used in the electrocatalysts. This suggests that these oxides may be of economic advantage if used as PEM water electrolysis anodes.     

Dynamic corrosion of Al2O3-ZrO2-SiO2 and Cr2O3-containing refractories by molten frits. Part II: Microstructural study

In this work results on dynamic corrosion studies of fused cast Al₂O₃-SiO₂-ZrO₂ and isostatically pressed and sintered Cr₂O₃-based refractories by two crystalline (transparent) frits are described. Experiments have been performed using the “Merry Go Round” test at ≅1500 °C.Microstructural and mineralogical analyses of selected areas from the corroded regions of the studied refractories were performed by reflected light optical microscopy and scanning electron microscopy with analysis by X-ray dispersive energy.Significant differences between the corrosion mechanisms acting in the two types of materials were found. In the fused cast Al₂O₃-SiO₂-ZrO₂ specimens corrosion took place by the dissolution of alumina and zirconia in the frit and in the glass formed by the reaction between the frit and the refractory. In the Cr₂O₃-based materials the corrosion process was controlled by the capillar penetration of the molten frit through the open pores. The reaction between the ZnO from the frits and Cr₂O₃ led to the formation of spinel (ZnCr₂O₄), a high-melting point bonding phase that retarded the frit penetration. Results are discussed using the relevant phase equilibrium diagrams.