Influence of the sulfonate countercation on the thermal stability of nafion perfluorosulfonate membranes

We report a strong dependence of the thermal stability of Nafion® perfluorosulfonate ionomer on the nature of the counterion associated with the fixed sulfonate site. These results were obtained using thermal gravimetric analysis on a series of alkali metal and alkyl ammonium cation-exchanged Nafion films. We have found that the temperature of decomposition of Nafion is inversely dependent on the size of the exchanged cation; i.e., Nafion films show improved thermal stability as the size of the counter cation decreases. We attribute this inverse relationship of thermal stability with counterion size to an initial decomposition reaction which is strongly influenced by the strength of the sulfonate-coun-terion interaction. © 1993 John Wiley & Sons, Inc.     

Randomized greedy matching

We consider a randomized version of the greedy algorithm for finding a large matching in a graph. We assume that the next edge is always randomly chosen from those remaining. We analyze the performance of this algorithm when the input graph is fixed. We show that there are graphs for which this Randomized Greedy Algorithm (RGA) usually only obtains a matching close in size to that guaranteed by worst-case analysis (i.e., half the size of the maximum). For some classes of sparse graphs (e.g., planar graphs and forests) we show that the RGA performs significantly better than the worst-case. Our main theorem concerns forests. We prove that the ratio to maximum here is at least 0.7690…, and that this bound is tight.     

Simple, expedient methods for the determination of water and electrolyte contents of cellulose solvent systems

The concentrations of water, W, and electrolytes present in solutions of LiCl in N,N-dimethylacetamide, LiCl/DMAc, and of tetrabutylammonium fluoride. x-hydrate in DMSO, TBAF.xW/DMSO can be accurately and expediently determined by three independent methods, UV–vis, FTIR and EMF measurement. The first relies on the use of solvatochromic probes whose spectra are sensitive to solution composition. It is applicable to W/LiCl/DMAc solutions but not to TBAF.xW/DMSO, because the charge-transfer complex bands of the probes are suppressed by strong interactions with the latter electrolyte. Integration of ν_OH band of water may be employed in order to determine [W], hence [electrolyte] by weight difference. EMF measurement uses ion-selective electrodes in order to determine [electrolyte], hence [W] by weight difference. Results of the latter method were in excellent agreement with those of FTIR. The reason for the failure of Karl Fischer titration is addressed, and the relevance of the results obtained to functionalization of cellulose under homogenous solution conditions is briefly commented on.     

Mathematical Modeling, Control, Computer Simulation and Laboratory Experiments of a Spatial Servopneumatic Parallel Robot

In this paper, the special construction of a parallel robot, called spatial servopneumatic multi-axis test facility, will be discussed. The investigations include the following aspects: (i) the laboratory set-up of the robot, (ii) various results obtained in laboratory experiments, taking into account quite different control algorithms and command-input signals, (iii) a comparison of the laboratory experiments with the computer simulations of Part I of this paper, and ({vi}) a quality check of the results compared with the cost of the different controller realizations. The results of both the computer simulations and the laboratory experiments show: (i) The dynamic behavior of the parallel structure can be tremendously improved by using sophisticated nonlinear control algorithms. (ii) This improvement has to be paid by a drastically increased amount of work for deriving the model equations and control algorithms, and by augmented hardware cost of the sensing elements and controller electronics. (iii) Carefully developed model equations and identified model parameters provide theoretical models of the complex parallel structure that are very close to reality. This enables the design engineer to systematically investigate constructive alternatives of the design parameters, sensor and actuator concepts, and control strategies of the MAP prior to their hardware realization.This work has been supported by the German Science Foundation (DFG) under Contract No. Ha 1666/6-3.     

A finiteness result for Heegaard splittings

In this paper we show that for a given 3-manifold and a given Heegaard splitting there are finitely many preferred decomposing systems of 3g−3 disjoint essential disks. These are characterized by a combinatorial criterion which is a slight strengthening of Casson-Gordon's rectangle condition. This is in contrast to fact that in general there can exist infinitely many such systems of disks which satisfy just the Casson-Gordon rectangle condition.     

A Triangle Inequality for Measurement

We introduce the triangle inequality for measurement. This is a property that when satisfied by a measurement enables one to construct a metric on the set of elements with measure zero that yields the relative Scott topology. The naturality of this construction permits a categorical solution to the model problem in domain theory for locally compact metric spaces. The first time such a solution has been achieved.     

Diastereoselective cycloadditions of chiral homoallylic alcohols with benzonitrile oxide

The first diastereoselective cycloaddition of a nitrile oxide with a homoallylic alcohol is discussed. The reaction of benzonitrile oxide with the magnesium alkoxides of chiral homoallylic alcohols has been shown to proceed with good diastereoselectivity, favoring the syn isomer of the resulting 2-isoxazoline.     

Volumetric and infrared measurements on amorphous ice structure

We have simultaneously used adsorption isotherm volumetry and Fourier transform infrared spectroscopy in order to take the investigations on amorphous ice structure a step further, especially concerning porosity and annealing-induced modifications. We have studied surface reorganization during annealing and found that the number of surface sites decreases before crystallization, their relative ratios being different for amorphous and crystalline ice. We also present results confirming that ice can have a large specific surface area and nevertheless be non-microporous.