Substrate-mediated interactions and intermolecular forces between molecules adsorbed on surfaces

Adsorbate interactions and reactions on metal surfaces have been investigated using scanning tunneling microscopy. The manners in which adsorbates perturb the surface electronic structure in their vicinity are discussed. The effects these perturbations have on other molecules are shown to be important in overlayer growth. Interactions of molecules with surface steps are addressed, and each molecule's electron affinity is shown to dictate its adsorption sites at step edges. Standing waves emanating from steps are demonstrated to effect transient molecular adsorption up to 40 A away from the step edge. Halobenzene derivatives are used to demonstrate how the surface is important in aligning reactive intermediates.     

Flow regime, hydrodynamics, floc size distribution and sludge properties in activated sludge bubble column, air-lift and aerated stirred reactors

This paper presents a comparative study how reactor configuration, sludge loading and air flowrate affect flow regimes, hydrodynamics, floc size distribution and sludge solids-liquid separation properties. Three reactor configurations were studied in bench scale activated sludge bubble column reactor (BCR), air-lift reactor (ALR) and aerated stirred reactor (ASR). The ASR demonstrated the highest capacity of gas holdup and resistance, and homogeneity in flow regimes and shearing forces, resulting in producing large numbers of small and compact flocs. The fluid dynamics in the ALR created regularly directed recirculation forces to enhance the gas holdup and sludge flocculation. The BCR distributed a high turbulent flow regime and non-homogeneity in gas holdup and mixing, and generated large numbers of larger and looser flocs. The sludge size distributions, compressibility and settleability were significantly influenced by the reactor configurations associated with the flow regimes and hydrodynamics.     

Chlorinated polyethylene modification of blends derived from waste plastics Part I: Mechanical behavior

Recycling of waste plastics as a blend of generic types is attractive since a difficult separations problem is avoided. However, blends of incompatible polymers are frequently very brittle and cannot be considered for many applications. Additives which modify the blend to give it ductility may provide a solution to this problem. Chlorinated polyethylene (CPE) made by a slurry process has been suggested for this application by Schramm and Blanchard. Further documentation of the effectiveness of this approach is given here. Addition of CPE to such a blend generally increases the elongation at break and the energy to break very dramatically with ordinarily some loss in strength and modulus. This approach works most effectively in blends of high polyethylene and poly(vinyl chloride) content. Three grades of CPE were studied here which revealed that the specific structure of the CPE molecule is a factor. The effectiveness of CPE for blend modification is believed to derive from the graded molecular structure acquired during chlorination.     

Aryl phosphate ester fire‐retardant additive for low‐smoke vinyl applications

Additives that act as flame retardants can contribute significantly to smoke generation because they decrease the efficiency of the fuel source and, as a result, create a sooty combustion. Work on a new phosphate ester material has shown interesting results and synergies that complement both flame retardancy and low smoke generation in flexible vinyl compositions. This new proprietary aryl phosphate was examined in both neat and blended systems and compared to other typical phosphate ester fire‐retardant (FR) compounds for vinyl. Additionally, the flammability and smoke effects were measured with and without other common vinyl FR additives (zinc borate and ammonium octamolybdate). J. Vinyl Addit. Technol. 10:187–192, 2004. © 2004 Society of Plastics Engineers.     

Phase behavior for blends of styrene containing triblock copolymers with poly(2,6-dimethyl-1,4-phenylene oxide)

The extent to which the styrene end-blocks of three commercially available triblock copolymers can mix with a particular poly(2,6-dimethyl-1,4-phenylene oxide) (M_n = 22,600 and M_w = 34,000) or PPO has been examined by investigation of the glass transition behavior of the PPO and polystyrene (PS) portions of the blends using differential scanning calorimetry. Each block copolymer has a butadiene-based mid-block which was hydrogenated for two of these materials, but not the third. The three copolymers differ substantially in overall molecular weight and in molecula weight of the blocks. However, in analogy with the literature on blends of homopolymer polystyrene with styrene-based block copolymers, the molecular weight of the PS block should be the principal factor affecting the phase behavior in the present blends. Mixtures of the PPO with the block copolymers having PS blocks with M = 14,500 (nonhydrogenated midblock) and with M = 29,000 (hydrogenated mid-block) exhibited single composition-dependent T_gs for the hard phase, indicating complete mixing of PS segments with the PPO, for all proportions. On the other hand, the block copolymer having a PS block with M = 7,500 and a hydrogenated mid-block exhibited two separate hard phase T_gs corresponding to an essentially pure PPO phase and a PS-rich phase. For blends of homopolymer PS with styrene-based block copolymers, the similar two-phase behavior of the glassy portion can be readily explained by entropic considerations. For the present case, the favorable enthalpic contribution for mixing PPO and PS is an additional factor which seems to influence the restrictions on molecular weight for complete mixing; however, additional work is needed to develop a more quantitative assessment of this new issue.     

Oxidation and Fracture Strength of High-Purity Reaction-Bonded Silicon Nitride

Reaction-bonded Si₃N₄ (RBSN) made from high-purity Si powder is unusually resistant to degradation caused by exposures to air for up to 50 h at temperatures up to 1400°C. The weight gain during oxidation of this SiH₄-originating RBSN is approximately 10 times less than conventional RBSN. Contrary to normally observed strength degradations, room-temperature strengths of this high-purity, oxidized RBSN (avg = 435 MPa, max. = 668 MPa) remained at their unusually high, as-processed levels after 1000° and 1400°C oxidizing exposures. Fracture toughness values were unaffected by oxidation ( K _IC= 2.3 to 2.4 MPa · m^1/2). This superior oxidation resistance results from the high purity and the small diameter pore channels (0.01 to 0.06 μm) achieved in this SiH₄-originating RBSN.     

Transient behaviour of encapsulated enzyme reactor systems

Mathematical models are developed for the transient behaviour of encapsulated enzyme reactor systems such as the continuous stirred tank reactor (CSTR) and the packed bed tubular reactor. The rate processes taking place in the encapsulated enzyme bed are approximated by using a combined rate control model of enzyme reaction and membrane diffusion. The change in transient substrate concentration is obtained by using the developed rate expression in the material balance over the substrate as a function of time for the CSTR and as a function of time and position for the packed bed tubular reactor. The effects of various parameters such as the enzymic reaction rate constant, Michaelis constant, diffusional resistance of membranes, and Peclet number on the substrate concentration distribution, which varies with respect to operating time, are investigated. This study affords insight into the transient operating characteristics of the encapsulated enzyme reactor system. The results should be useful in understanding the start-up performance of the reactor systems and to control such reactor systems at desired operating conditions.     

Investigation of Flow Patterns in Continuous‐flow Stirred Vessels by Laser Doppler Velocimetry

The flow structure of a continuous‐flow reactor stirred by a Rushton turbine was investigated by laser Doppler velocimetry for two different mean residence time‐mixing time ratios. Velocity measurements were obtained for two inlet locations, corresponding to the incoming liquid stream being fed co‐currently or counter‐currently to the flow discharged by the turbine. In all investigated configurations and for all operating conditions, it was found that the flow disruption caused by the incoming liquid stream was observable mainly in the first vessel quarter, which followed the feed‐tube plane. From comparison of the velocities encountered in the various planes in the continuous‐flow reactor to the velocities of the batch reactor, it was also concluded that it may be possible to intensify the usage of the turbine‐stirred vessel by decreasing the characteristic times ratio, without considerable flow by‐pass and/or short‐circuiting problems.     

Universal variable length coding for an integrated approach to image coding

We propose a new entropy coding scheme, denoted in this paper as the UVLC (universal variable length coding). It is universal in the sense that its efficiency is close to one for a large class of images. The UVLC, when it is applied to block orthogonal transforms, processes groups of blocks at the bit level, using universal codes designed for binary memoryless sources. It can be used for every video coding application, from high definition TV (HDTV) to high quality videotelephony (above 2 Mbit/s) for transform or subband coding. Last but not least, its implementation is very regular and can be realized in a single chip for the encoding oftv at theccir 601 format.