Cation-induced collapse of low-molecular-weight polyacrylic acid in the dispersion of barium titanate

Observations on the steric layers formed by the adsorption of low-molecular-weight polyacrylic acid (PAA) were taken using the colloidal probe method in an atomic force microscope. The effects of divalent barium ions and of monovalent potassium ions at varying concentrations were observed on the repulsive interaction profiles. High ionic concentrations screened double-layer forces to small distances, whereby the acting forces were reduced to steric interactions. De Gennes scaling theory was used to model the effect of electrolyte on an aqueous barium titanate system, which was stabilized with PAA. The brush model was found to represent the force curves better than the mushroom model. The collapse of PAA layers with increasing salt approximated a grafted polymer brush in monovalent electrolyte, but the addition of barium ions caused markedly less steric collapse. It is suggested that the formation of a Ba(2+)-PAA complex in the adsorbed layer increases its compressibility parameter.     

Deposition of copper films by unbalanced d.c. magnetron sputtering

The electrical resistivity of as deposited polycrystalline copper thin films as a function of varying the process parameters has been investigated. Trying to minimize the resistivity of the copper thin films is important in the semiconductor industry, due to the fact that low resistivity copper can be employed to great advantage for new metallization schemes in advanced ultralarge scale integrated circuits. This paper presents the optimum choice of parameters that are necessary to achieve low resistivities of the thin films in reproducible experiments. All the depositions were performed using an unbalanced d.c. planar magnetron sputtering source (consisting of a circular copper target (98% purity, 0.01% Fe, 0.005% Ni, 0.005% Si) with a diameter of 100mm fitted with two electromagnets). The copper thin films were deposited onto glass substrates with argon being used as the sputtering gas. The resistivity was studied as a function of the pressure of the sputtering gas, the substrate bias, the substrate to target distance, the magnetron power, and the substrate temperature. It was found that depositions producing thin films with a resistivity of that approaching the bulk material (1.7×10^–8m) were obtained if the sputtering gas pressure was below 0.2 Pa. The effect of the substrate bias was insignificant at these pressures. The crystallographic structure of the copper thin films, determined by X-ray diffraction, is also reported.The authors would like to thank Dr. Soukup for his support during this research. We would also like to express our gratitude to Mr. A. Rajský for improving the design of the sputtering device. This work was partially financed by a grant from the Grant Agency of the Czech Republic No. 202/93/0508.     

Unique continuation theorems for the\bar \partial - Operator and applications

We formulate a unique continuation principle for the inhomogeneous Cauchy-Riemann equations near a boundary pointz ₀ of a smooth domain in complex euclidean space. The principle implies that the Bergman projection of a function supported away fromz ₀ cannot vanish to infinite order atz ₀ unless it vanishes identically. We prove that the principle holds in planar domains and in domains where the problem is known to be analytic hypoelliptic. We also demonstrate the relevance of such questions to mapping problems in several complex variables. The last section of the paper deals with unique continuation properties of the Szegő projection and kernel in planar domains. Research supported by NSF Grant DMS-8922810.     

The effects of temperature and pressure on the lifetime of benzophenone emission

The variation in the lifetime of flash-excited gaseous benzophenone with pressure and temperature indicates that (1) self-quenching is a relatively inefficient process for the long-lived emission, k_sq = 9 × 10⁵ M^?1 s^?1 (estimated from solution data) at 25°C and 1.2 × 10⁷ M^?1 s^?1 at 170°C and (2) the lifetime decreases with increasing temperature as a result of photochemical and photophysical decay pathways which have significant activation energies. The importance of diffusion to the walls on lifetime measurements is discussed.     

In situ UV-visible spectroscopic measurements of kinetic parameters and active sites for catalytic oxidation of alkanes on vanadium oxides

In situ diffuse reflectance UV-visible spectroscopy was used to measure the dynamics of catalyst reduction and oxidation during propane oxidative dehydrogenation (ODH) on VOx/gamma-Al2O3. Transients in UV-visible intensity in the near-edge region were analyzed using a mechanistic model of ODH reactions. Rate constants per site for the kinetically relevant reduction step (C-H bond activation) measured using this analysis are slightly larger than those obtained from steady-state ODH rates normalized by surface V. The ratio of these values provides a measure of the fraction of the V surface sites that are active for ODH (0.6-0.7, for V surface densities of 2.3-34 V nm(-2)). This suggests that some of the V atoms are either inaccessible or inactive. Reoxidation rate constants, which cannot be obtained from steady-state analysis, are 10(3)-10(5) times larger than those for the C-H bond activation reduction step.