Differential scanning calorimetry and thermogravimetric analysis investigation of the thermal properties and degradation of some radiation‐grafted films and membranes

The influence of irradiation and grafting on the crystallinity of three base polymers has been investigated with differential scanning calorimetry. Grafting has the largest effect on the base polymer crystallinity and results in a reduction of the crystallinity. The thermal degradation of the base polymers and grafted films has been investigated with thermogravimetric analysis. The extent of the fluorination of the base polymer, the irradiation method, and the graft level all influence the thermal degradation and its activation energy. It is proposed that the variation of the chain lengths of the grafted polystyrene chains is actually a primary underlying factor responsible for the influence of these various parameters on the degradation process. The first results of a comparative thermal analysis of some fuel‐cell membranes are also presented, and the promise and shortcomings of this method are discussed. © 2004 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 42: 2612–2624, 2004     

Local Entropy Conditions in Transonic Potential Flow Problems

The transonic potential flow problem is handled as a variational problem over a closed convex set which is given by a bound for the gas velocity and by a local entropy condition. It can be shown that the minimum problem has a solution though the functional need not be convex and the given set is not compact. Furthermore, the convergence of an approximation method (KATCHANOV'S method) for the solution to the corresponding variational inequality is proved.     

Level Density of the Hénon-Heiles System Above the Critical Barrier Energy

We discuss the coarse-grained level density of the Hénon-Heiles system above the barrier energy, where the system is nearly chaotic. We use periodic orbit theory to approximate its oscillating part semiclassically via Gutzwiller’s semiclassical trace formula (extended by uniform approximations for the contributions of bifurcating orbits). Including only a few stable and unstable orbits, we reproduce the quantum-mechanical density of states very accurately. We also present a perturbative calculation of the stabilities of two infinite series of orbits (R_n and L_m), emanating from the shortest librating straight-line orbit (A) in a bifurcation cascade just below the barrier, which at the barrier have two common asymptotic Lyapunov exponents χ_R and χ_L.     

X-PEEM/NEXAFS and AFM of polypyrrole and copper micro-patterns on insulating fluoropolymer substrates

Micro-patterns (80 μm and 10 μm) of copper and semi-conducting polypyrrole on insulating fluorinated ethylene propylene substrates were characterized using synchrotron-based X-ray Photoemission Electron Microscopy (X-PEEM), Near Edge X-ray Absorption Fine Structure (NEXAFS), and Atomic Force Microscopy (AFM). Electronic states in the polypyrrole are verified using the NEXAFS data, and sample degradation upon irradiation is addressed. X-PEEM images show homogeneous distributions of the corresponding elements in the patterns. They do not exhibit dichroic effects and give information about the growth of copper and polypyrrole (i.e. nucleation of Cu, overgrowth of PPy, formation of PPy granules). AFM results are used to verify the topography of the patterns and support the findings on pattern growth.     

Preparation of micro- and nanopatterns of polymer chains grafted onto flexible polymer substrates

In this work a simple novel method for preparing micro- and nanoscale patterns of polymer chains grafted onto flexible polymer substrates is described. A combination of the two techniques of radiation grafting and "grafting-from" has been made. This combination makes it possible to prepare grafted structures having micro- or nanoscale lateral dimensions that are determined by the electron beam or X-ray irradiation patterns used. The height of the grafted features can be controlled by the irradiation dose or such grafting reaction conditions as time, temperature, or monomer concentration. Our first results for nanopatterned samples demonstrate resolution comparable to those of other polymer-based lithography processes.     

Rhodium and palladium β-diketonate determination with on-line supercritical fluid extraction-high performance liquid chromatography via solid phase extraction

 An on-line system of supercritical fluid extraction (SFE) and high performance liquid chromatography (HPLC) via solid phase extraction (SPE) is described for the determination of palladium and rhodium 2,2,6,6-tetramethyl-3,5-heptanedione-(thd) as well as rhodium-acetylacetonate-(acac) and benzylacetonate-(bzac) chelates. The chelates were extracted with supercritical CO₂ from sand and humic acid, concentrated on SPE cartridges and analysed with HPLC. Two cartridge materials were tested and compared to off-line trapping. The percentage of the breakthrough and cartridge retained material were measured in liquid dichloromethane. The SFE conditions could be optimized to separate metal chelates during the extraction. The supercritical fluid (SF) behaviour of different ligands on rhodium were investigated. Received: 19 July 1996/Revised: 11 December 1996/Accepted: 14 December 1996     

Characteristic behavior of macro-, semimicro- and microelectrodes in voltammetric and chronoamperometric measurements

The advantages of microelectrodes such as the improvement of signal-to-noise ratio, the ability to perform electrochemical measurements in high resistive solutions and small RC-time constants give the possibility of an extended use for voltammetric and chronoamperometric techniques in analytical chemistry. In this comparative study, the microelectrode properties of three selected electrodes were examined. The characterization of a RAM-microarray electrode, an epoxy-impregnated carbon electrode and a conventional glassy carbon macroelectrode was performed by cyclic voltammetry at different scan rates, by DP-voltammetric measurements using different concentrations of supporting electrolyte and by transient measurements. It could be shown, that in comparison to the microarray electrode and to the glassy carbon macroelectrode, respectively, the results obtained by using the epoxy-impregnated carbon electrode are caused by its semimicroelectrode character.     

Effect of a magnetic flux line on the quantum beats in the Henon-Heiles level density

The quantum density of states of the Henon-Heiles potential displays a pronounced beating pattern. This has been explained by the interference of three isolated classical periodic orbits with nearby actions and periods. A singular magnetic flux line, passing through the origin, drastically alters the beats even though the classical Lagrangian equations of motion remain unchanged. Some of the changes can be easily understood in terms of the Aharonov-Bohm effect. However, we find that the standard periodic orbit theory does not reproduce the diffraction-like quantum effects on those classical orbits which intersect the singular flux line, and argue that corrections of relative order variant Planck's over 2pi are necessary to describe these effects. We also discuss the changes in the distribution of nearest-neighbor spacings in the eigenvalue spectrum, brought about by the flux line. (c) 1995 American Institute of Physics.