Influence of the pH of Water on its Electron-Accepticity and Donicity

By means of contact angle measurements on dry layers of electrostatically neutral dextran with pure water (pH 6.1), water acidified with HCl (to pH 1.94) and water made alkaline with NaOH (to pH 12.8), it could be shown that there was essentially no change as a function of pH in the ratio of γ⁺/γ^- of water as compared with the aqueous acid and alkaline solutions. (Here γ⁺ is the Lewis acid parameter of the polar surface tension component of water and γ^- is its Lewis base parameter). In contrast, with contact angles measured with the same liquids on negatively charged clean glass, a significant decrease in contact angle was observed with water at pH 12.8, which was caused by the fact that at this alkaline pH an increase in surface hydrophilicity took place. This is because surfaces that have a given surface electrical potential at neutral pH generally acquire an even higher surface potential under more alkaline conditions which, concomitantly, also gives rise to an increase in surface hydrophilicity, and thus to lower contact angles with water. Finally, contact angles with acid water, pure water, and alkaline water, deposited on hydrophobic Parafilm surfaces, were exactly the same.     

Physical characteristics of sweet potato pulp/polycaprolactone blends

Sweet potato pulp (SSP) obtained as a by‐product from starch extraction was blended with polycaprolactone (PCL) to prepare a biodegradable plastic material. In the blends, PCL was used as a reinforcing agent. The SPP/PCL blends were prepared by compression‐molding under high temperature and pressure, at different SPP/PCL ratios, and the mechanical properties of the molded specimens were tested. Matrix structure and thermal properties were measured by using a Fourier transform infrared (FTIR) spectrophotometer, scanning electron microscope (SEM), differential scanning calorimetry (DSC), and thermogravimetric analyzer (TGA). Mechanical properties (tensile and flexural properties) were also measured to find the most suitable ratio in a SSP/PCL blend. During compression molding of the SPP/PCL blends under high pressure and temperature, chemical reaction occurred between SPP and PCL, and thus, thermal stability and mechanical strength of the blends increased and water uptake decreased. Also, by increasing the PCL content in the blend, the matrix in the blend became more homogeneous, and consequently, mechanical strength of the molded specimen increased. At 7/3 or 6/4 weight ratio of SSP/PCL, water uptake of the molded specimen became substantially less than that at 8/2. © 2004 Wiley Periodicals, Inc. J Appl Polym Sci 92: 861–866, 2004     

Mechanisms of hydrocarbon conversion reactions on heterogeneous catalysts: analogies with organometallic chemistry

Catalysis is central to most industrial processes for chemical manufacturing. As catalytic processes have become more complex and more demanding, selectivity has become the central issue in their design. Selectivity is defined by the relative rates of competing reaction pathways available to crucial intermediates, and can be controlled by subtle changes in the nature of the catalyst, the reactants, and/or the reaction conditions. In order to be able to do this in a systematic manner, a good understanding of the catalytic reaction mechanisms is needed. Here a connection is drawn between the key elementary steps comprising hydrocarbon conversion reactions on surfaces and those known to occur on discrete organometallic complexes. This way, the hydrogenation, dehydrogenation, hydrogenolysis, chain growth, and isomerization reactions typical in heterogeneous catalysis are redefined in terms of hydride elimination, oxidative addition, reductive elimination, migratory insertion, and 1, 2-shift elementary steps, among others. It is suggested that the knowledge already available from organometallic chemistry can be used to further advance the understanding of the surface science involved in heterogeneous catalysis. Thanks to the commonality of the chemistry involved, a better synergy could also be established between homogeneous and heterogeneous catalytic development. These ideas are discussed in this article in a critical and personal way.*Invited contribution to the special volume entitled The Interface between Heterogeneous and Homogeneous Catalysis, stemming from contributions at the recent International Symposium on Relations between Heterogeneous and Homogeneous Catalysis, and dedicated to the memory of Robert L. Burwell.     

Influence of silicon on the growth of barrier-type anodic films on titanium

Amorphous anodic titania, stabilised by incorporation of silicon species, is shown to grow to high voltages on sputter-deposited, single-phase Ti-Si alloys during anodizing at a constant current density in ammonium pentaborate electrolyte. The films comprise two main layers, with silicon species confined to the inner layers. An amorphous-to-crystalline transition occurs at ∼60 V on the Ti-6 at.% Si alloy, while the transition is suppressed to voltages above 140 V on alloys with 12 and 26 at.% silicon. The crystalline oxide, nucleated at a depth of ∼40% of the film thickness, is associated with the presence of a precursor of crystalline oxide in the pre-existing air-formed oxide. The modified structure of the air-formed oxide due to increased incorporation of silicon species suppresses the amorphous-to-crystalline transition until the onset of dielectric breakdown. The transport numbers of cations and anions during growth of the anodic oxides are independent of the concentration of silicon species in the inner layer, despite the marked change in the field strength.     

新型碳质催化剂用于NH3选择性催化还原NOx的研究

以城市污水处理厂剩余污泥为原料制备了一种新型碳质催化剂。通过试验考察了催化剂在NH₃选择催化还原NO中的应用效果。结果表明,催化性能较好，最佳的制备和催化反应条件为：锌铁物质的量比1∶0.5，热解温度750 ℃，反应温度400 ℃，O₂浓度15%。在此条件下，NOx的最大转化率达98.3%。通过考察证明催化剂自身具有一定的还原性能。对催化剂进行了FTIR、TG、SEM和BET分析，结果表明，催化剂具有很丰富的孔结构、活性粒子和表面官能团，比表面积较大，最大可达307 m²·g^-1，分析结果显示具有良好的催化条件。     

含氟反式-1,4-二芳基环己烷类液晶化合物的合成

以4 苯基环己酮为起始原料,经Grignard反应,脱水,加氢,转型,Friedel Crafts反应,黄鸣龙还原等步骤,合成了一系列含氟反式 1,4 二芳基环己烷类液晶化合物,GC质量分数>99%,收率达16 0%～27 0%,较文献收率(<1%)有显著提高;该路线尤其适用于制备一系列不同烷基取代的衍生物;目标化合物经1HNMR、IR进行了结构鉴定,并通过差示扫描量热法(DSC)对其相变行为进行了测试。     

Curing process of powdered phenol–formaldehyde resol resins and the role of water in the curing systems

The curing behavior of two kinds of commercial powdered resol phenolic resins was studied by differential scanning calorimetry. Liquid‐state ¹³C‐NMR spectroscopy was used to aid in understanding the curing behavior by detecting the structure of powdered resins. The reaction mechanism was interpreted with the dependency of activation energy on the degree of conversion. The results indicate that there are differences in the curing mechanism between core and face phenolic resins. The curing process of core resin was faster than that of face resin at the same reaction temperature. The water added in the curing system played an important role of plasticizer or diluent according to different curing stages and water content. In the initial curing stage, water mainly diluted the system and retarded the curing reactions. However, at the higher degrees of conversion, water played the role of plasticizer to decrease the effect of diffusion on the curing reactions to make the curing reactions more complete. The excess water added in the curing system played the role of diluent at almost all stages during the curing process. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1371–1378, 2003     

Time-series primitive static states for detailing work state and flow of human-operated work machine

This paper proposes a quantification method for a comprehensive work flow in construction work for describing work states in more detail on the basis of analyzing state transitions of primitive static states (PSS), which consist of 16 symbolic work states defined by using on-off state of the lever operations and joint loads for the manipulator and end-effector. On the basis of the state transition rules derived from a transition-condition analysis, practical state transitions (PST), which are common and frequent transitions in arbitrary construction work, are defined. PST can be classified into essential state transition (EST) or nonessential state transitions (NST). EST extracts common phases of work progress and estimates positional relations between a manipulator and an object. NST reveals wasted movements that degrade the efficiency and quality of work. To evaluate comprehensive work flows modeled by combining EST and NST, work-analysis experiments using our instrumented setup were conducted. Results indicate that all the PSS definitely changes on the basis of PST under various work conditions, and work analysis using EST and NST easily reveals work characteristics and untrained tasks related to wasted movements.     

Rheological properties of bitumen in water emulsions with added solids

Experimental work was carried out to investigate the rheological properties of bitumen in water emulsions containing solids of different shape and size. The bitumen volumetric concentration was varied up to 60%, solids free basis, and the solids volume fraction (total volume basis) was varied up to 0.2. Irregular-shaped silica sand (average diameter: 9 and 33 μm) and smooth spherical glass beads (average diameter: 27 and 44 μm) were used as the added solids. In the low shear stress range, shear thinning behavior was observed for bitumen in water emulsions. At high shear stress, the viscosity of the emulsions became fairly independent of the shear stress. The addition of solids to the bitumen emulsions increased the mixture viscosity. The addition of irregular-shaped silica sand gave a higher viscosity than a similar addition of the spherical glass beads. The viscosity of the emulsion/solids mixtures was influenced by the solids size as well; the smaller size particles gave a higher viscosity. The addition of solids to the bitumen emulsions also induced shear thickening (dilatancy) behavior at high solids volume fraction. The degree of the shear thickening increased with the oil concentration.     

Characterization of poly(vinyl pyrrolidone‐co‐isobutylstyryl polyhedral oligomeric silsesquioxane) nanocomposites

Poly(vinyl pyrrolidone‐co‐isobutyl styryl polyhedral oligomeric silsesquioxane)s (PVP–POSS) were synthesized by one‐step polymerization and characterized using FTIR, high‐resolution ¹H‐NMR, solid‐state ¹³C‐NMR, ²⁹Si‐NMR, GPC, and DSC. The POSS content can be controlled by varying the POSS feed ratio. The T_g of the PVP–POSS hybrid is influenced by three main factors: (1) a diluent role of the POSS in reducing the self‐association of the PVP; (2) a strong interaction between the POSS siloxane and the PVP carbonyl, and (3) physical aggregation of nanosized POSS. At a relatively low POSS content, the role as diluent dominates, resulting in a decrease in T_g. At a relatively high POSS content, the last two factors dominate and result in T_g increase of the PVP–POSS hybrid. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 91: 2208–2215, 2004