Surface diffusion of strong adsorbing vapours on porous carbon

Surface diffusion of strongly adsorbing hydrocarbon vapours on activated carbon was measured by using a constant molar flow method (D.D. Do, Dynamics of a semi-batch adsorber with constant molar supply rate: a method for studying adsorption rate of pure gas, Chem. Eng. Sci. 50 (1995) 549), where pure adsorbate is introduced into a semi-batch adsorber at a constant molar flow rate. The surface diffusivity was determined from the analysis of pressure response versus time, using a linear mathematical model developed earlier. To apply the linear theory over the non-linear range of the adsorption isotherm, we implement a differential increment method on the system which is initially equilibrated with some pre-determined loading. By conducting the experiments at different initial loadings, the surface diffusivity can be extracted as a function of loading. Propane, n-butane, n-hexane, benzene, and ethanol were used as diffusing adsorbate on a commercial activated carbon. It is found that the surface diffusivity of these strongly adsorbing vapours increases rapidly with loading, and the surface diffusion flux contributes significantly to the total flux and cannot be ignored. The surface diffusivity increases with temperature according to the Arrhenius law, and for the paraffins tested it decreases with the molecular weight of the adsorbate.     

The structure of model coatings: latex-bound plastic pigment coatings

The immobilization and consolidation of model coatings based on monodisperse polystyrene (plastic pigment) and S/B latexes of known particle sizes were studied in terms of their packing volumes and the extent of latex shrinkage, which was found to increase with increasing pigment volume up to the critical pigment volume concentration (CPVC). The maximum latex shrinkage was estimated from the CPVC. Then, the porosity of model coatings was calculated based on three proposed latex shrinkage models: maximum, minimum, and linearly decreasing latex shrinkage. The number of pores and the average equivalent spherical pore diameters were subsequently calculated. The opacity and gloss of model coatings on polyester films were measured and their porosity was also determined by a simple coat weight-thickness method. The CPVC values determined by the opacity, gloss, and porosity versus PVC relationships, respectively, agreed very well with each other. The CPVCs determined by the opacity and porosity versus PVC curves were identical. The comparison between the theoretically calculated and experimental porosity values showed that the linearly decreasing value between the maximum and minimum latex shrinkage would best fit the experimental porosity data. The effect of plastic pigment particle size on the optical properties and porosity of model coatings was also studied and it was observed that the coating opacity and porosity increased with increasing plastic pigment particle size, but the gloss decreased. Additionally, a minimum crack-free temperature (MCFT) of latex-bound coatings was proposed to better predict the behaviors of latexes as pigment binders. The wet state of model coating dispersions, the surfaces of consolidated model coatings, and their internal structure were examined by both electron and atomic force microscopy, and their micrographs were found to be consistent with our immobilization and consolidation models.     

Kinetics of cellobiose decomposition under subcritical and supercritical water in continuous flow system

The effects of reaction temperature, pressure and residence time were investigated with a flow apparatus. Cellobiose decomposition kinetics and products in suband supercritical water were examined at temperatures from 320 to 420 °C at pressures from 25 to 40 MPa, and at residence times within 3 sec. Cellobiose was found to decompose via hydrolysis and pyrolysis. The yield of desired hydrolysis product, glucose, was the maximum value of 36.8% at 320 °C, 35 MPa, but the amount of 5-(hydroxymethyl)furfural (HMF), fermentation inhibitor increased too because residence time increased in the subcritical region owing to decrease of reaction rate. Meanwhile, though the yield of glucose is low in the supercritical region, the yield of HMF decreased compared with the subcritical region; and at the minimum yield of HMF (380 °C, 25 MPa), the yield of glucose was 21.4%. The decomposition of cellobiose followed first-order kinetics and the activation energy for the decomposition of cellobiose was 51.05 kJ/mol at 40MPa.     

New Process for the Preparation of Monodispersed, Spherical Silica Particles

A new method is presented for preparing highly monodispersed silica particles using a two-stage semibatch/batch hydrolysis reaction of Si(OC₂H₅)₄. The slower rate of hydrolysis of the tetraethylorthosilicate (TEOS) that occurred during the semibatch process resulted in larger silica particles with a higher yield and narrower size distribution. This was in direct contrast to the batch process. In addition, the ability of four different mixed processes to produce silica particles with good packing density, narrower particle-size distribution, and higher yield were evaluated. These were batch/batch (B-B), batch/semibatch (B-S), semibatch/batch (S-B), and semibatch/semibatch (S-S) processes. The S-S system produced the largest particles with the highest yields. The size of the silica particles obtained by the S-B method decreased with increasing reaction time, while the particles obtained by the B-S process had the best particle-size distribution and packing density. In conclusion, a mixed batch/semibatch system was the best way to produce an extremely narrow particle-size distribution and a good packing density.     

Synthesis of single-crystal SnO2 nanowires for NOx gas sensors application

Single-crystal SnO₂ nanowires (NWs) were successfully synthesized and characterized as sensing materials for long-term NO_x stability detection in environmental monitoring. Reproducible and selective growths of the SnO₂ NWs on a patterned, 5 nm-thick gold catalyst coated on a SiO₂/Si wafer as substrate were conducted by evaporating SnO powder source at 960 °C in a mixture of argon/oxygen ambient gas (Ar: 50 sccm/O₂: 0.5 sccm). The as-obtained products were characterized by field-emission scanning electron microscopy (FE-SEM), high-resolution transmission electron microscopy (HRTEM), X-ray diffraction (XRD), Raman scattering, and photoluminescence (PL). The SEM and HRTEM images revealed that the products are single-crystal SnO₂ NWs with diameter and length ranges of 70 nm–150 nm and 10 μm–100 μm, respectively. The three observed Raman peaks at 476, 633, and 774 cm⁻¹ indicated the typical rutile phase, which is in agreement with the XRD results. The NWs showed stable PL with an emission peak centered at around 620 nm at room-temperature, indicating the existence of oxygen vacancies in the NW samples. The electrical properties of synthesized SnO₂ NWs sensor were also investigated and it exhibited a negative temperature coefficient of resistance in the measured range (300–525 K). The calculated activation energy E_c of SnO₂ NWs was 0.186 eV. Moreover, the SnO₂ NW sensors exhibited good response to NO_x gas. The response of the sensors to 5 ppm NO_x reached 105% at an operating temperature of 200 °C.     

Effect of Silica Surface Dopants on the Formation of Alumina/Aluminum Composites by the Directed Metal Oxidation of an Aluminum Alloy

This study focused on clarifying the effect of SiO₂ surface dopants on the formation of Al₂O₃/aluminum composites, especially on oxidation phenomena during the incubation period. The present results showed that a surface dopant decreased the incubation period of an Al-Mg-Si alloy, as well as that of an Al-Mg alloy, and that addition of an external surface dopant decreased the incubation period more effectively than did an internal alloying of silicon. A two-step oxidation process was also conducted. In the first step of the process, an aluminum alloy was oxidized without a surface dopant and cooled to room temperature during the incubation stage. In the second step, the same specimen was surface-doped with SiO₂ powder and reoxidized. The incubation time for the specimen subjected to the two-step oxidation process was the same as that for the single-step specimen oxidized with a surface dopant. The substantial decrease in the incubation period, especially for the Al-Mg alloy, is ascribed to interaction between the SiO₂ surface dopant and the MgO layer. This interaction made the MgO layer thinner and increased the number of magnesium vacancies in the MgO layer, thus providing an appropriate microstructure in the MgO layer for bulk-growth initiation.     

Flexible poly(styrene-ethylene-butadiene-styrene) hybrid nanofibers for bioengineering and water filtration applications

Among the thermoplastic elastomers that play important roles in the polymer industry due to their superior properties, styrene-based species and polyurethane block copolymers are of great interest. Poly(styrene-ethylene-butadiene-styrene) (SEBS) as a triblock copolymer seems to have the potential to meet many demands in different applications due to various industrial requirements where durability, biocompatibility, breaking elongation, and interfacial adhesion are important. In this study, the SEBS triblock copolymer was functionalized with natural (Satureja hortensis, SH) and synthetic (nanopowder, TiO₂) agents to obtain composite nanofibers by electrospinning and electrospraying methods for use in biomedical and water filtration applications. The results were compared with thermoplastic polyurethane (TPU) composite nanofibers, which are commonly used in these fields. Here, functionalized SEBS nanofibers exhibited antibacterial effect while at the same time improving cell viability. In addition, because of successful water filtration by using the SEBS composite nanofibers, the material may have a good potential to be used comparably to TPU for the application.     

Formation and Accumulation of Intragranular Pores in the Hydrothermally Synthesized Barium Titanate Nanoparticles

As highly integrated circuits are demanded for high‐performance electric devices, small sizes of barium titanate (BaTiO₃) as a dielectric material are desirable for the application of multilayer ceramic capacitors. Since the small sizes of the particles degrade the dielectric property, especially below a certain critical size, understanding the probable cause is significant for the high‐performance capacitors. Here, we have demonstrated nanosized BaTiO₃ with average size below 30 nm and a uniform size distribution. High‐resolution transmission electron microscopy (TEM) shows that the as‐synthesized BaTiO₃ contains intragranular pores. We have analyzed the correlation between the intragranular pores inside nanoparticles and their phase ratio of cubic and tetragonal. We have found that the presence of the intragranular pores affects low tetragonality of BaTiO₃ particles, and the intragranular pores are generated by the accumulation of hydroxyl groups during hydrothermal reaction. Formation and accumulation of intragranular pores have been investigated by ex‐situ synchrotron X‐ray diffraction and TEM analysis, suggesting the phase evolution model of nanosized BaTiO₃.     

Synthesis and Characterization of Segmented Block Copolymers Based on Hydroxyl‐Terminated Liquid Natural Rubber and α,ω‐Diisocyanato Telechelics

Summary: Segmented block copolymers, consisting of non‐polar soft segments from hydroxyl‐terminated liquid natural rubber (HTNR) and polar hard segments from α,ω‐diisocyanato telechelics obtained by “criss‐cross”‐cycloaddition, have been synthesized. The block copolymer formation took place under relatively mild reaction conditions at 80 °C in dichloroethane in the presence of dibutyltin dilaurate as a catalyst. The resulting block copolymers were characterized by spectroscopic techniques (¹H NMR, FTIR, UV‐vis spectroscopy) as well as GPC for molar mass determination. The block copolymers were compression molded in a hot stage press, and the resulting samples were characterized by DSC and stress‐strain measurement. The solubility and phase morphology of the materials have also been studied.

Segmented block copolymer from HTNR and α,ω‐diisocyanato telechelics     

The Synergy of the Support Acid Function and the Metal Function in the Catalytic Hydrodeoxygenation of m-Cresol

The hydrodeoxygenation (HDO) of m-cresol is investigated as a model for the HDO of phenolic compounds from lignin pyrolysis. Pt catalysts supported on ??-Al₂O₃ and SiO₂ are effective for the conversion of m-cresol to toluene and methylcyclohexane at 533?K and 0.5?atm H₂. Experiments using Pt/??-Al₂O₃ show that the reaction proceeds by a combination of Pt-catalyzed hydrogenation and acid-catalyzed dehydration reactions. Dehydration of a partially hydrogenated oxygenate intermediate is most likely the dominant reaction pathway to toluene. The acidity of the ??-Al₂O₃ support was modified by base (K₂CO₃) and acid (NH₄F) treatments, and increasing the number and strength of acid sites was found to increase the rate of HDO. Pt/SiO₂ was more active for m-cresol HDO than Pt/Al₂O₃. The reaction rate on Pt/Al₂O₃ and Pt/SiO₂ decreased after 5?h on stream, but Pt/Al₂O₃ regained initial reactivity after reductive treatment in H₂.