Determination of Surface Functional Groups in Lignocellulosic Materials by Chemical Derivatization and ESCA Analysis

Simple and convenient methods for determining surface chemical composition of lignocellulosic materials are described. The methods are based on vapor phase fluorine surface derivatization with either trifluoro acetic anhydride (TFAA), tri-fluoro ethanol (TFE) or pentafluorophenyl hydrazine (PFPH) and subsequent Electron Spectroscopy for Chemical Analysis (ESCA). Model cellulosic surfaces with well defined functionalities were used to optimize the derivatization reaction conditions. Detection and accessibility of surface hydroxyl functional groups were investigated in cotton and regenerated cellulose as models. Carboxymethyl cellulose (CMC) was used as a model surface for detection and quantification of carboxylic acid groups. Theoretical conversion curves for derivatization reactions were calculated and used to evaluate the extent of the reactions on the model surfaces. It was found that the conversion was higher for the regenerated cellulose and CMC than for cotton. The protocols developed using the model surfaces were applied to a case study on wood fibers with different degrees of complexity, namely dissolving and chemithermomechanical (CTMP) pulp. Untreated and oxygen-plasma modified pulps were compared with respect to the surface composition of functional groups. According to the derivatization reactions, functionalities containing oxygen were significantly increased on the plasma-treated samples. The effect of the treatment was found to be dependent on the type of pulp. Fluorine derivatization is shown to be an unambiguous method for clear assessment of the chemical functionalities of cellulosic surfaces.     

Pomeron-Odderon interference effects in electroproduction of two pions

We study Pomeron-Odderon interference effects giving rise to charge and single-spin asymmetries in diffractive electroproduction of a pair. We calculate these asymmetries, originating from both longitudinal and transverse polarizations of the virtual photon, in the framework of QCD and in the Born approximation, in a kinematical domain accessible to HERA experiments. We predict a sizable charge asymmetry with a characteristic dependence on the invariant mass of the pair, which makes this observable very important for establishing the magnitude of the Odderon exchange in hard processes. The single-spin asymmetry turns out to be rather small. We briefly discuss future improvements of our calculations and their possible effects on the results. Received: 18 July 2002 / Published online: 25 October 2002     

Calculation of the Knight shift in palladium

The direct and the exchange core polarization (ECP) contributions of the conduction electrons to the Knight shift of palladium are evaluated. To obtain the wave functions for the conduction electrons and the partial densities of states at the Fermi surface a KKR energy band calculation was performed. The contributions of the core electrons to the Knight shift were determined by using the moment perturbation method (MP). Electron-electron interactions are taken into account by individual enhancement factors for thed ands electrons. The agreement between the theoretical results and the available experimental data is quite satisfactory.     

A note to the paper “An efficient algorithm for linear programming” of V Ch Venkaiah

In Venkaiah [1] an algorithm for solving linear optimization problems based on the idea of the projective algorithm of Karmarkar, is proposed. The essential simplification in the new algorithm is the use of a fixed projection operator. In this way the algorithm requires onlyO(n ² ) operations to obtain a sufficient exact solution. In this note it is shown that in some special cases the algorithm of Venkaiah yields a feasible solution that is far from the optimal one.     

Theory of Non-Equilibrium Stationary States as a Theory of Resonances

We study a small quantum system (e.g., a simplified model for an atom or molecule) interacting with two bosonic or fermionic reservoirs (say, photon or phonon fields). We show that the combined system has a family of stationary states parametrized by two numbers, T ₁ and T ₂ (‘reservoir temperatures’). If T ₁ ≠ T ₂, then these states are non-equilibrium stationary states (NESS). In the latter case we show that they have nonvanishing heat fluxes and positive entropy production and are dynamically asymptotically stable. The latter means that the evolution with an initial condition, normal with respect to any state where the reservoirs are in equilibria at temperatures T ₁ and T ₂, converges to the corresponding NESS. Our results are valid for the temperatures satisfying the bound min (T ₁,T ₂) > g ^{2 + α}, where g is the coupling constant and 0 < α < 1 is a power related to the infra-red behaviour of the coupling functions. Submitted: March 20, 2006. Revised: March 19, 2007. Accepted: May 11, 2007. Marco Merkli: Partly supported by an NSERC PDF, the Institute of Theoretical Physics of ETH Zürich, Switzerland, the Departments of Mathematics of McGill University and the University of Toronto, Canada. Matthias Mück: Supported by DAAD under grant HSP III. Israel Michael Sigal: Supported by NSERC under grant NA7901.     

Nanocrystalline ceramic films for efficient conversion of light into electricity

Transparent nanocrystalline films of oxide semiconductors such as TiO₂ and Fe₂O₃ have been prepared on a conducting glass support employing a sol-gel procedure. The films are composed of nanometer-sized particles sintered together to allow for percolative charge carrier transport. The internal surface of these films is very high, roughness factors of the order of 1000 being readily obtained. Electric polarization was applied for forward and reverse biasing of the films and the resulting optical changes have been analyzed to derive their flat band potential. Band gap excitation of such nanocrystalline semiconductors produces electron-hole pairs which migrate through the film to be collected as electric current. Steady state photolysis and time resolved laser techniques have been applied to scrutinize the mechanism of light induced charge separation within the nanostructure. When derivatized with a suitable chromophore, TiO₂ films give extraordinary efficiencies for the conversion of incident photons into electric current, exceeding 90% for certain transition metal complexes within the wavelength range of their absorption band. The underlying physical principles of these astonishing findings will be discussed. Exploiting this discovery, we have developed a new type of photovoltaic device whose overall light to electric energy conversion yield is 10% under simulated AM 1.5 solar radiation.