Electrokinetic investigations of charged porous membranes

Asymmetric ultrafiltration membranes were prepared from fully aromatic polyamides differing in the diamine monomers of the polymeric backbone and from polysulfone. Nanofiltration membranes were made from polysulfone and polyethersulfone. The polysulfone as well as the polyethersulfone were chemically modified to change the surface charges of the membranes that were made from these polymers. This means neutral, positively as well as negatively charged membranes could be employed for the measurements. The surface properties of the membranes as a function of pH were determined by measuring the streaming potential in a perpendicular and horizontal mode. Applying proteins the values of the streaming potential changed depending on the original charges of the membranes as well as on the pH of the solution. The values shifted to either higher or lower absolute values. Thus, characterization of unused and used membranes can be carried out by electrokinetic measurements. This was also demonstrated using a membrane fitted out with invertase. The zeta potential of nanofiltration membranes, however, was only evaluated from the results obtained with the horizontally run cell.     

Marginal singularities,almost invariant sets,and small perturbations of chaotic dynamical systems

For a class of piecewise monotone locally noncontracting maps f:X-->X with small "traps" Y( varepsilon ) subset, dbl equals X (diam(Y( varepsilon )) infinity conditional probabilities that f(n+1)x in X\Y( varepsilon ) if x,fx,.,f(nx) in X\Y( varepsilon ) and the point x is chosen at random. Also proven is the convergence of &mgr;( varepsilon ) to smooth f-invariant measures as varepsilon -->0. By means of this construction, the numerical phenomenon of the convergence of histograms of trajectories of maps with marginal singularities to densities of nonfinite smooth invariant measures in the computer modeling was investigated.     

Brueckner calculations in harmonic oscillator basis

The binding energy (b.e.), r.m.s. radius and charge form factor of the⁴He nucleus are calculated for the Hamada-Johnston potential using the method developed in part I of this study. The single-particle spectrum is derived from that of a harmonic oscillator by means of an overall shiftC and state-dependent shifts _h of occupied levels. The's are chosen self-consistently and the dependence of results onC and oscillator frequency is examined. Third-order diagrams in the BG expansion for energy are explicitly calculated (except those belonging to the three-particle cluster) and their importance for getting a weak dependence of the b.e. onC is demonstrated. Dependence on remains rather strong; arguments are given in favour of the choice of that minimizes second-order diagrams. Effects due to the motion of the centre of mass of the nucleus are eliminated by subtracting T _CM calculated up to the second order, the usual zero-order approximation of T _CM being shown to overestimate the b.e. by 3–5 MeV. The computed b.e. and r.m.s. radius represent about 50% and 110% of experimental values respectively. The form factorF _ch(q) was computed for 0q ²20 fm^–2; the first-order approximation is a good fit to experimental data, while in the second order diagrams appear that worsen the fit forq ² > >10 fm^–2.The author thanks Professor I. Úlehla for stimulating discussions. The help of dr. J.Hoejí, who calculated a part of higher order diagrams, is gratefully acknowledged.     

Determination of oil–water partition coefficients of polar compounds: silicone membrane equilibrator vs. SPME passive sampler

Experimental determination of oil-water partition coefficients often poses difficulties associated with emulsion formation. The aim of this work was to find an appropriate technique for determination of oil–water partition coefficients of polar, nonvolatile compounds. Two different methods were tested. The first method used a “silicone membrane equilibrator.” For the second method, solid-phase microextraction (SPME) fibers with a polyacrylate (PA) coating were used as a passive sampler. With both methods, oil–water partition coefficients for 14 compounds with polar functional groups were determined at 37 °C with good repeatability (standard deviation 0.11 log units or lower). The partition coefficients determined with the silicone membrane equilibrator method ranged from 0.50 to 3.49 log units. The oil–water partition coefficients obtained with the PA-SPME passive sampling approach were significantly higher than those obtained with the silicone membrane equilibrator method for nine of 14 compounds. The differences were up to 0.39 log units (i.e., a factor of 2.5). Additional experiments suggested that this difference occurred because the sorption properties of the PA fibers used were influenced by the surrounding phase, e.g., through swelling of the polymer phase. Therefore, the SPME passive sampling method using PA fibers seems to be less reliable, whereas the silicone membrane equilibrator method was found to be a convenient technique for the determination of oil–water partitioning.     

Mechanism of current flow in alloyed ohmic In/GaAs contacts

A mechanism of current flow in an alloyed ohmic In contact to low-doped gallium arsenide (n = 4 × 10¹⁵ cm^?3) is studied. From the temperature dependence of the contact resistance per unit surface area, it is found that the basic mechanism of current flow is thermionic emission through a potential barrier 0.03 eV in height.     

Control of Intrachain Morphology in the Formation of Polyfluorene Aggregates on the Single-Molecule Level

Controlling the morphology of π-conjugated polymers for organic optoelectronic devices has long been a goal in the field of materials science. Since the morphology of a polymer chain is closely intertwined with its photophysical properties, it is desirable to be able to change the arrangement of the polymers at will. We investigate the π-conjugated polymer poly(9,9-dioctylfluorene) (PFO), which can exist in three distinctly different structural phases: the α-, β-, and γ-phase. Every phase has a different chain structure and a unique photoluminescence (PL) spectrum. Due to its unique properties and the pronounced spectral structure-property relations, PFO can be used as a model system to study the morphology of π-conjugated polymers. To avoid ensemble averaging, we examine the PL spectrum of single PFO chains embedded in a non-fluorescent matrix. With single-molecule spectroscopy the structural phase of every single chain can be determined, and changes can be monitored very easily. To manipulate the morphology, solvent vapor annealing (SVA) was applied, which leads to a diffusion of the polymer chains in the matrix. The β- and γ-phases appear during the self-assembly of single α-phase PFO chains into mesoscopic aggregates. The extent of β- and γ-phase formation is directed by the solvent-swelling protocol used for aggregation. Aggregation unequivocally promotes formation of the more planar β- and γ-phases. Once these lower-energy more ordered structural phases are formed, SVA cannot return the polymer chain to the less ordered phase by aggregate swelling.     

Hydroperoxides and aryl diazonium salts as reagents for the functionalization of non-activated olefins

Hydroperoxides, olefins, and arenediazonium salts selectively combine to give azo compounds via an iron(II)-mediated three-component reaction. Starting with a fragmentation liberating acetic acid, the hydroperoxides act as radical source and the diazonium ions as nitrogen-centered radical scavengers.     

Two-proton radioactivity of 45Fe

In an experiment at the SISSI-LISE3 facility of GANIL, the decay of the proton drip line nucleus 45Fe has been studied. Fragment-implantation events have been correlated with radioactive decay events in a 16x16 pixel silicon-strip detector. The decay-energy spectrum of 45Fe implants shows a distinct peak at (1.14+/-0.04) MeV with a half-life of T(1/2)=(4.7(+3.4)(-1.4)) ms. None of the events in this peak is in coincidence with beta particles. For a longer correlation interval, daughter decays of the two-proton daughter 43Cr can be observed after 45Fe implantation. The decay energy for 45Fe agrees nicely with several theoretical predictions for two-proton radioactivity.     

Neue Bestimmung des kritischen Punktes von leichtem und schwerem Wasser

Zusammenfassung Im Rahmen der internationalen Wasserdampfforschung [1, 2, 3] wurden in den letzten Jahren genaue Messungen verschiedener Zustandsgrößen von leichtem und teilweise auch von schwerem Wasser vorgenommen. In diesem Zusammenhang war auch die Kenntnis genauerer Werte für die kritischen Zustandsgrößen von großem Interesse.In einer zylindrischen, waagerecht liegenden Druckkammer mit durchsichtigen Beobachtungsfenstern wurden beim langsamen Durchlaufen des kritischen Punktes mit sehr geringfügigen Temperaturänderungen von 0,01 bis 0,03 °C/h fortlaufend Temperaturen und Drücke gemessen. Gleichzeitig wurde die Phasentrennfläche zwischen Flüssigkeit und Dampf beobachtet, die beim Durchlaufen des kritischen Zustandes in einem sehr kleinen Temperatur- und Druckbereich verschwindet bzw. wiedererscheint.Es ergaben sich folgende Werte für die kritischen Temperaturen und Drücke von H₂O und D₂O: H₂O t_krit=(373,91±0,03) °C P_krit=(220,45±0,03) bar D₂O t_krit=(370,66±0,03) °C P_krit=(216,59±0,03) bar.Die Temperaturangaben beziehen sich auf die Internationale Praktische Temperaturskala von 1948.

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New determination of the critical point of water and heavy water

The apparatus used for determining the critical data of water and heavy water consists in principle of a horizontal cylindrical pressure chamber of INCONEL X-750. Observation windows of synthetic saphire (Al₂O₃) are located at the ends.During the experiments the critical point was passed with very small rates of temperature change of about 0.01 to 0.03 °C/h. The disappearance and appearance of the meniscus could be observed continuously with a telescope enlarging 10 times, with simultaneous measurement of pressure and temperature.The following results were obtained for the critical temperature and critical pressure of H₂O and D₂O: H₂O t_crit=(373.91±0.03) °C P_crit=(220.45±0.03) bar D₂O t_crit=(370.66±0.03) °C P_crit=(216.59±0.03) bar.These temperatures are related to the International Practical Temperature Scale of 1948.

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Über diese Arbeit wurde auf dem VDI-Thermodynamik-Kolloquium 1967 in Bad Neuenahr berichtet.