Formation of C4 species in the deactivation of a Pd/SiO2 catalyst during the selective hydrogenation of acetylene

The deactivation characteristics of Pd/SiO₂ in the selective hydrogenation of acetylene were correlated with changes in the amount of the C4 species produced. The amounts of butenes produced changed in parallel with the catalyst activity, indicating that the rate limiting step for butene production was the same as that for acetylene hydrogenation. On the other hand, the amount of 1,3-butadiene produced changed, showing a maximum with catalyst deactivation because 1,3-butadiene is an intermediate in the sequential reaction process which involves both the production and consumption of 1,3-butadiene. This was verified by a simultaneous TG/reaction experiment showing that 1,3-butadiene was a precursor of green oil. The catalyst showed a self-regenerative behavior in its activity and the amounts of C4 species produced during the early stage of deactivation because two opposite factors, which contributed to either the lowering or the promotion of activity, were involved in the process. A specific type of polymer species, produced during the initial period of deactivation, is proposed to be responsible for the promotion of catalyst activity.     

Monte Carlo simulation of hydrogen absorption in palladium and palladium–silver alloys

A modified Monte Carlo (MC) simulation was performed to investigate the hydrogen absorption behavior in Pd and Pd–Ag alloys of the composition Pd_xAg_1−x (x=0.7–0.8) under H₂ pressure (0.1 MPa) at different temperatures. The present method employed can consider the dissociative adsorption of hydrogen molecule and the subsequent absorption of hydrogen atom by formalizing the relationship between the pressure of hydrogen molecule and hydrogen atom. The potential parameters were determined to reproduce the solution enthalpy of hydrogen in pure metals. The results are in good agreement with experimental findings as well as previous theoretical studies. We confirmed that our method is useful to simulate the absorption of hydrogen in metals and alloys.     

Foveation-Based Error Resilience and Unequal Error Protection over Mobile Networks

By exploiting new human-machine interface techniques, such as visual eyetrackers, it should be possible to develop more efficient visual multimedia services associated with low bandwidth, dynamic channel adaptation and robust visual data transmission. In this paper, we introduce foveation-based error resilience and unequal error protection techniques over highly error-prone mobile networks. Each frame is spatially divided into foveated and background layers according to perceptual importance. Perceptual importance is determined either through an eye tracker or by manually selecting a region of interest. We attempt to improve reconstructed visual quality by maintaining the high visual source throughput of the foveated layer using foveation-based error resilience and error correction using a combination of turbo codes and ARQ (automatic reQuest). In order to alleviate the degradation of visual quality, a foveation based bitstream partitioning is developed. In an effort to increase the source throughput of the foveated layer, we develop unequal delay-constrained ARQ (automatic reQuest) and rate compatible punctured turbo codes where the punctual pattern of RCPC (rate compatible punctured convolutional) codes in H.223 Annex C is used. In the simulation, the visual quality is significantly increased in the area of interest using foveation-based error resilience and unequal error protection; (as much as 3 dB FPSNR (foveal peak signal to noise ratio) improvement) at 40% packet error rate. Over real-fading statistics measured in the downtown area of Austin, Texas, the visual quality is increased up to 1.5 dB in PSNR and 1.8 dB in FPSNR at a channel SNR of 5 dB.     

The nature and role of incoherent interphase interfaces in diffusional solid-solid phase transformations

In this article, some views on the nature of incoherent interphase interfaces, and their role in the nucleation and growth processes governing the evolution of microstructure in solid-state diffusional transformations (reconstructive transformations), are explored. It is argued that essentially incoherent interfaces can be involved in the initiation and propagation of polymorphic transformations and massive transformations as well as in various precipitation phenomena in metallic and ceramic systems. Similar views have already been advanced earlier in connection with studies of massive transformations. Faceting along the interphase interface during nucleation and growth can derive from thermodynamic, kinetic, and crystallographic factors independent of the bicrystallography of the conjugate phases. This idiomorphic behavior can be relevant to both intergranular and intragranular phase formation. The concept of one-dimensional (1-D) commensuration of phases through plane edge-to-edge/row matching is an interesting extension of the classic ideas of coherency and bicrystallography and potentially important in characterizing the behavior of certain types of boundaries. However, the general importance of these geometrical relations in real and reciprocal space will depend on the depth of the energy wells in orientation space associated with these special boundaries. This article is based on a presentation made in the “Hume-Rothery Symposium on Structure and Diffusional Growth Mechanisms of Irrational Interphase Boundaries,” which occurred during the TMS Winter meeting, March 15–17, 2004, in Charlotte, NC, under the auspices of the TMS Alloy Phases Committee and the co-sponsorship of the TMS-ASM Phase Transformations Committee.     

An efficient implementation of SELF, a dynamically-typed object-oriented language based on prototypes

We have developed and implemented techniques that double the performance of dynamically-typed object-oriented languages. Our SELF implementation runs twice as fast as the fastest Smalltalk implementation, despite SELF's lack of classes and explicit variables.To compensate for the absence of classes, our system uses implementation-levelmaps to transparently group objects cloned from the same prototype, providing data type information and eliminating the apparent space overhead for prototype-based systems. To compensate for dynamic typing, user-defined control structures, and the lack of explicit variables, our system dynamically compilesmultiple versions of a source method, eachcustomized according to its receiver's map. Within each version the type of the receiver is fixed, and thus the compiler can statically bind andinline all messages sent toself.Message splitting andtype prediction extract and preserve even more static type information, allowing the compiler to inline many other messages. Inlining dramatically improves performance and eliminates the need to hard-wire low-level methods such as+, ==, andifTrue:.Despite inlining and other optimizations, our system still supports interactive programming environments. The system traverses internal dependency lists to invalidate all compiled methods affected by a programming change. The debugger reconstructs inlined stack frames from compiler-generated debugging information, making inlining invisible to the SELF programmer.This work has been generously supported by National Science Foundation Presidential Young Investigator Grant #CCR-8657631, and by IBM, Texas Instruments, NCR, Tandem Computers, Apple Computer, and Sun Microsystems.This paper was originally published inOOPSLA '89 Conference Proceedings (SIGPLAN Notices, 25, 10 (1989) 49–70).     

Edge-to-edge matching in thin films

A peculiar type of preferential orientation was recently observed in polycrystalline films that are formed by a solid-state reaction on a single crystal substrate. This texture, for which the term axiotaxy was proposed, is characterized by the preferred alignment of a low-index plane in the film to a low-index plane with the same d-spacing in the substrate. The alignment of lattice planes with nearly identical d-spacings across the interface results in a periodic structure along one direction in the plane of the interface. As a consequence of the constraint that a set of planes in the film is preferentially parallel to a set of planes in the substrate, the texture manifests itself as an off-normal fiber texture. This article is based on a presentation made in the “Hume-Rothery Symposium on Structure and Diffusional Grwoth Mechanisms of Irrational Interphase Boundaries,” which occurred during the TMS Winter meeting, March 15–17, 2004, in Charlotte, NC, under the auspices of the TMS Alloy Phases Committee and the co-sponsorship of the TMS-ASM Phase Transformations Committee.     

New approach to environmentally benign epoxidation: the solid-phase-system using urea–H2O2 and recyclable dodecatungstate on apatite

On the basis of new concept using a solid disperse phase we have developed an efficient catalytic solid-phase-system for epoxidations of alkenes using urea–hydrogen peroxide (urea–H₂O₂) complex and cetylpyridinium dodecatungstate ((CetylPy)₁₀[H₂W₁₂O₄₂]) catalyst on fluorapatite (FAp). The recovered solid catalyst phase was reused to keep the catalytic activity after several times. In the conceptual idea it is a key point that in situ solid-phase-activation of the catalyst with urea–H₂O₂ proceeds to form microcrystals of the active species dispersed on the solid phase. The dispersion of the catalyst on FAp in the case of tungstic acid (H₂WO₄) was suggested by EPMA analysis. We proposed the peroxo type of species keeping the parent polyoxometalate framework as novel active species from FT-IR spectroscopic studies. FAp phase plays important roles of dispersing the active species on its surface to have high catalytic activity and of stabilizing the active species to lead to high reusability.     

Catalytic dehydrogenation of ethylbenzene with carbon dioxide: promotional effect of antimony in supported vanadium–antimony oxide catalyst

Alumina-supported vanadium oxide, VO_x/Al₂O₃, and binary vanadium–antimony oxides, VSbO_x/Al₂O₃, have been tested in the ethylbenzene dehydrogenation with carbon dioxide and characterized by S_BET, X-ray diffraction, X-ray photoelectron spectroscopy, hydrogen temperature-programmed reduction and CO₂ pulse methods. VSbO_x/Al₂O₃ exhibited enhanced catalytic activity and especially on-stream stability compared to VO_x/Al₂O₃ catalyst. Incorporation of antimony into VO_x/Al₂O₃ increased dispersion of active VO_x species, enhanced redox properties of the systems and formed a new mixed vanadium–antimony oxide phase in the most catalytically efficient V_0.43Sb_0.57O_x/Al₂O₃ system.