Theoretical aspects of bonding in silicon compounds

Ab initio-calculated bond dissociation energies of Si=Si and C=C are discussed by means of atomic ionization energies and p-p() AO overlap. At the same time ring strain energies of C- as well as Si-rings are estimated by homodesmic reactions where, according to Baeyer, the two-membered rings C=C and Si=Si are chosen to be the first members of the respective series. Thus, a better understanding of the double bonds can be gained. In addition, the exceptional structural and spectroscopic behavior of the five-membered Si-ring is discussed. Finally, the strikingly different results obtained in computational studies of the initial step for polymerization of the systems O=C=O and O=Si=O are discussed.     

Crystal Orientation Dependence of Macropore Formation in n-Si With Backside-Illumination in HF-Electrolyte

The formation of macropores on anodically biased n-type silicon with backside-illumination was investigated as a function of crystal orientation and bias voltage. Specimens were cut from bulk crystals with various orientations from {100} to {111}, polished and subjected to anodic etching in HF. The resulting pores were investigated on cleaved samples by SEM. All pores were found to grow in either a 100 direction or a 113 direction, depending on the misorientation angle. This finding applies also to the branching of a single pore. The results can be understood if the valence for the dissolution reaction is approximately 2.6 in 100 and approximately 4 in the 113 direction, and if all other directions are not allowed for the growth of pores in Si.     

Recovery and recrystallization of electrodeposited bright copper coatings at room temperature. II. X-ray investigation of primary recrystallization

X-ray investigations of the recrystallization processes occurring at room temperature in electrodeposited bright copper coatings were carried outin situ. As a result of the orientation transformation of the growth texture with 311, 111 and 110 components, a recrystallization texture with 100, 110 and 111 components was obtained. It was established that one of the factors which influence the microhardness of copper coatings is the orientation distribution of crystallites.     

Texture prediction of Bi2Te3 electroplated layers using Hartman's theory of crystal growth

An experimental study of electroplated thin films of bismuth telluride, R3m crystal structure, shows that fibre textures are observed during the growth of the layers. Several orientations 00.1, 10.10, 11.0, 10.4, 10.8, 01.5 and 10.0 are developed during the deposition process, then reach a final orientation. Hartman's theory of crystal growth based on the periodic bond chain (PBC) in a crystal lattice is usually applied. This explains the equilibrium shape of a crystal defined by F faces and the faces observed during the growth (S and K faces). It also successfully predicts the orientations observed in bismuth telluride from the beginning to the end of the layer deposition. The theory may also be applied to other deposition processes.     

The surface structure and composition of the low index single crystal faces of the ordered alloy Pt3Sn

The surface composition and structure of 111, 100, and 110 oriented single crystals of the ordered alloy Pt₃Sn (Ll₂ or Cu₃Au-type) were determined using the combination of low energy electron diffraction (LEED) and low energy ion scattering spectroscopy (LEISS). The clean annealed surfaces displayed LEED patterns and Sn/Pt LEISS intensity ratios consistent with the surface structures expected for bulk termination. In the case of the 100 and 110 crystals, preferential termination in the mixed (50% Sn) layer was indicated, suggesting this termination to be the consequence of a thermodynamic preference for tin to be at the surface.     

Investigation of Morphology of Porous Silicon Formed on N+ Type Silicon

The properties of porous silicon (PS) are closely connected to its morphology, much investigation has been done in order to correlate the morphological characteristics of PS with the anodisation parameters. In this paper the results of morphological analysis of PS formed on N⁺type substrates of 1 0 0 and 1 1 1 orientation are presented. The dependences of the porosity, thickness of PS, density of pores and of the effective surface on the current density are obtained. Interpretation of these results in terms of diffusion layer and energy levels is given, with special attention given to the low current density case.     

Nucleation and growth kinetics of Ag7NO11 on a platinum single crystal electrode

The process of electrochemical deposition of Ag₇NO₁₁ on a platinum single crystal anode from 5M AgNO₃ is investigated. The nucleation and growth rates are measured at different constant overpotentials. The orientation of the Ag₇NO₁₁ crystals with respect to the substrate surface is determined in the case of deposition on glassy carbon and on the 100, 111 and 110 faces of a platinum single crystal.     

Inhibition and nickel electrocrystallization

The electrocrystallization of Ni is known to be a highly inhibited process. This work gives some conclusions about the nature of the major inhibiting species. All of these species are formed in the catholyte because of the hydrogen codeposition. Depending on plating conditions, mainly pH and current density of metallic deposition, we observe a predominancy of a definite inhibitor which selectively promotes one mode of growth and leads to a deposit exhibiting definite structural properties. A careful structural investigation of Ni deposits obtained from a Watts solution, thanks to both X-ray diffractometry and electron-microscope techniques, leads us to distinguish a free mode of growth, which is characterized by [100] oriented deposits, from several inhibited modes such as 110, [210], 211 and 111. The two latter are stabilized by Ni(OH)₂ while the two former are respectively due to atomic and molecular forms of adsorbed hydrogen.     

The effects of antimony and glue on zinc electrowinning from Kidd Creek electrolyte

The individual and combined effects of antimony and glue on zinc deposition current efficiency and polarization and on the morphology and orientation of 6h zinc deposits electrowon at 500 A m^–2 and 38° C from Kidd Creek zinc electrolyte were determined. Glue increased zinc deposition polarization, reduced the deposit grain size, changed the preferred deposit orientation from basal to intermediate, but decreased the current efficiency. At concentrations above 0.02 mgl^–1, antimony had a strong depolarizing effect on zinc deposition resulting in a basal deposit orientation and very low current efficiency. Certain combinations of antimony and glue, however, optimized zinc deposition current efficiency and consistently gave an intermediate 114 112 103 102 101 preferred deposit orientation. A correlation was observed between the current efficiency (CE) and the nucleation overpotential (NOP) for zinc deposition such that the CE was a maximum when the NOP of the initial cell electrolyte was 120–130 mV and when the NOP of the final cell electrolyte was 100–110 mV.     

Structure and corrosion resistance of electrolytic nickel coatings containing codeposited nonconducting particles

The codeposition of nonconducting silicate particles with different grain size during the plating of nickel coatings with preferential orientation along with 2 1 1 axis is investigated by electron microscopy. The results confirm that small size particles, about 20 nm, are included in the twinning defects, inherent to this orientation, blocking the latter as active dissolution sites. Larger particles, approximately 1.5 m, are included in the bulk of the coating, and cause a continuous redistribution and decrease of the corrosion rate. On the other hand, when particles of 20 nm size are used, an unusual decoration of the twinning plane {111} perpendicular to the substrate, may lead to the elucidation of some theoretical problems related to the initiation of the texture 2 1 1. A dissolution mechanism is proposed, based on the mutual effect of both factors: redistribution of the corrosion current, and blocking of the twinning planes which act as active dissolution centres. This mechanism is confirmed by Corrodkote tests of codeposited nickel coatings.     

Phase composition and structure of silver-antimony alloy deposits plated from ferrocyanide-thiocyanate electrolytes

The structure and phase composition of silver-antimony alloy deposits plated from ferrocyanide-thiocyanate electrolytes is investigated. It is shown that the co-deposition of antimony leads to an abrupt decrease of twinning and the formation of perfect orientation of the crystallites in the alloy along the axis 1 1 1. The co-deposition of antimony exerts a depolarization effect upon the plating process of the alloy. At higher antimony concentrations in the electrolyte and higher deposition current both -phase and -phase of the silver-antimony alloy may be formed as well as the pure antimony phase. The concentration regions of antimony in the alloy, within which the different phases are formed and exist, are in agreement with the requirements of the phase diagram. The separate antimony phase is formed at lower antimony concentrations in the alloy than indicated by the phase diagram. The co-deposition of antimony leads to an increase of the crystal lattice parameter of silver and a substantial augmentation of the hardness of the deposited layers.     

Photopolymerization of 2-(dimethylaminoethyl)methacrylate induced by diacetoxyiodobenzene and bis(trifluoroacetoxy) iodobenzene

Summary The title hypervalent iodine compounds are efficient photoinitiators for the polymerization of 2-(dimethylaminoethyl)methacrylate. The polymer is formed in daylight but faster under UV irradiation, with high conversion; its molecular weight M_n is 9×10⁴ daltons. Copolymerization of this monomer with styrene occurs also under similar conditions at a high rate. A free radical mechanism is suggested for these polymerizations.     

Upwind searching for an odor plume is sometimes optimal

A model is presented that suggests that the optimal strategy for an animal walking or crawling on a substrate while searching for the source of a chemical carried by a shifting wind or current may be to move upwind (or against the current). The requirements are that (1) the current direction fluctuates rapidly within a range that exceeds 30 ° on both sides of the mean direction, and (2) the searching animal can move accurately up- or downwind and, once within the influence of the chemical plume, can move efficiently to the source. Under these conditions, an upwind search is shorter (on the average) by 0.9–0.3 of the range of influence of the chemical stimulus. Thus, this strategy is relatively more important when the total search path is short, i.e., when sources are typically close by. The mean length of the downwind search path is given by L _d =d +r[(1/E) + cos ]/2 and the upwind search path by L _u =d +r[(2/E) – (/sin ) – cos ]/2 whered is the starting distance up- or downwind of the source,r is the range of stimulus influence,E is the efficiency with which the searcher moves to the source within the influence of the plume,a is the angle of the maximum extent of wind direction from the mean, and the average, , is taken over all starting positions across the wind direction that lead to search paths that intercept the area swept by the plume.     

Stress Measurement Technique to Monitor Porous Silicon Processing

Macroscopic stress measurements are used to monitor Porous Silicon processing. Silicon wafer of 1 cm resistivity, n-type and 1 0 0 orientation were used as starting material. Porous Silicon layers with a porosity of 57% and a thickness of 85 m, fabricated by electrochemical anodisation, were differently dried, then the evolution of the wafer deflection has been followed with storage time in air. Thermal treatments both in inert and oxidant atmosphere have been performed up to 1000°C. The stress behaviour vs. temperature allows to estimate the hydrogen desorption activation energy.     

Electrodeposition of compositionally modulated Au/Co alloy layers

Au/Co multilayers were electrodeposited from a single bath based on acid citrate, cobalt sulphate and gold cyanide electrolyte. The Taguchi statistical method was used for experiment planning and optimisation. X-ray diffraction (XRD) investigations of the structure showed that the Au deposits exhibited a polycrystalline fcc 1 1 1 structure with an estimated grain size of 7 nm, while the Co deposits exhibited a nano-polycrystalline fcc structure with an estimated grain size ranging between 2 and 28 nm and a strong in-plane texture. The XRD investigation of the multilayer structure also indicated an interface roughness of about 1.5 nm between the Au and Co layers.     

Cooperative inclusion of sodium 1-pyrenesulfonate by γ-cyclodextrin

Summary The interaction of -cyclodextrin(-CD) with sodium 1-pyrenesulfonate(PS) was studied spectrophotometrically. -CD was found to cause much larger decrease in the absorption maxima of PS than -CD. The fluorescence spectra of PS in the presence of -CD showed excimer emission, while those of PS with -CD showed only monomer emission, indicating that -CD forms 12 (-CDPS) complexes in which two PS molecules are included in the -CD cavity in a face-to-face fashion. The binding isotherm showed a sigmoidal curve. The association constants were estimated by computer simulation of the binding curve. The 12 (CDPS) complex was found to be much more stable (K=10⁶ M^–1) than the 11 complex (K=1 M^–1). At high concentration of -CD another -CD cooperates in binding two PS molecules, resulting in the formation of a 22 complex.     

Properties ofSrMO 3-δ(M=Fe,Co) as oxygen electrodes in alkaline solution

Strontium ferrates and cobaltates with compositions SrFeO_3- (0.060.40) and SrCoO_3- (0.040.30) were synthesized. The dependence of the oxygen electrode properties on the value was examined in 1 mol dm^–3 KOH solution. In the SrFeO_3- series, the samples with 0.24<<0.29, showed the highest activity in both oxygen evolution and reduction reactions. In contrast, no strong dependence on the value was observed in SrCoO_3-, which also showed a high catalytic activity for oxygen evolution.     

Dependence of the Time‐Space Structure of the Chemical‐Reaction Zone on the Initial Density of the Explosive

The results of a study of the chemicalreaction zone structure for a number of high explosives (HEs) are discussed. It is found that an increase in the initial density of the HEs leads to a structural change in the chemicalreaction zone involving elimination of the Von Neumann spike at the critical density point. Conversely, as the initial density of the explosive decreases, the ratios of the gasdynamic parameters (in particular, mass velocities) at the Von Neumann point to the same parameters at the Jouguet point increase. It is shown that to explain the indicated regularities, one does not need to invoke the assumption of an increasing contribution of the exothermic decomposition of the HE the shock. The results can be explained within the framework of classical Zeldovich–Von Neumann–Döring theory with an ordinary shock at the detonationwave front and, hence, with a nearly zero contribution to the total energy release in the chemical reaction zone.     

Characterization of poly(diethoxyphosphazene) by size exclusion chromatography and viscometry

Two samples of poly(diethoxyphosphazene) (PDEP) having very different molecular weights have been studied by viscometry and size exclusion chromatography in THF solution. The results obtained, together with light scattering data of these samples, allow the calculation of the Mark-Houwink constants a=0.65 and K=2.5 10^-4 in THF at 25°C. The method of calculation employed takes into account the great polydispersity of the samples. The characteristic ratio of the unperturbed dimensions was also calculated giving C_n = r²_o/n² 18, a value slightly higher than those previously reported for poly(dihexoxyphosphazene), C_n13 and poly (dichlorophosphazene), C_n13.5.     

Dynamics and self-organization of catalytic systems

The kinetics of a catalytic reaction is frequently formulated in terms of simple concepts of the Langmuir type. Apart from limitations arising from the non-uniformity of the catalyst's surface and from the coverage dependence of the rate constants, several other complications may come into play. These may arise on the quantum level where energy flow between the various degrees of freedom may cause failure of simple transition state theory, as well as on the continuum level where formulation of rate equations in terms of coupled non-linear differential equations may give rise to a rich scenario of spatio-temporal self-organization, including kinetic oscillations, chaos, and formation of concentration patterns. Several of these phenomena are illustrated by selected examples.