Swelling equilibrium and preferential sorption of crosslinked poly(methyl methacrylate) in the mixture acetonitrile + n-butanol

Measurements of preferential sorption,( ₃), determined by refractometry, and swelling equilibrium, ₃ ^–1, of PMMA networks have been carried out in the cosolvent mixture MeCN+BuOH at 25 and 49 C. With an intermediate mixture composition, ₃ ^–1 passes through a maximum at both temperatures. At 25 C MeCN is preferentially adsorbed by the network over most of the composition range, but a small inversion is detected. At 49 C MeCN is preferentially adsorbed over all the composition range.The behavior of the system crosslinked PMMA/MeCN + BuOH is compared with the results obtained for solutions of linear PMMA in mixtures formed by the same two solvents, MeCN and BuOH.     

Sorption of binary liquid mixtures on polymer networks Part I. Determination of surface excess isotherms and free energy functions

Two groups of polymer networks (polymer resins) are investigated by selective liquid sorption fromn-propanol-water mixtures. Group 1 consists of gel polymerized polar (hydrophilic) ion exchangers which swell in the binary liquid mixture. Group 2 consists of non-polar, non-swelling, macroporous resins. The free energy isotherms accompanying the sorption processes are calculated from the excess isotherms and the bulk activities. The adsorption excess free energies reveal the differences in polarity of the polymer network.     

Sequential injection system with higher dimensional electrochemical sensor signals Part 2. Potentiometric e-tongue for the determination of alkaline ions

An intelligent, automatic system based on an array of non-specific-response chemical sensors was developed. As a great amount of information is required for its correct modelling, we propose a system generating it itself. The sequential injection analysis (SIA) technique was chosen as it enables the processes of training, calibration, validation and operation to be automated simply. Detection was carried out using an array of potentiometric sensors based on PVC membranes of different selectivity. The diluted standard solutions needed for system learning and response modelling are automatically prepared from more concentrated standards. The electrodes used were characterised with respect to one and two analytes, by means of high-dimensionality calibrations, and the response surface of each was represented; this characterisation enabled an interference study of great practical utility. The combined response was modelled by means of artificial neural networks (ANNs), and thus it was possible to obtain an automated electronic tongue based on SIA. In order to identify the ANN which provided the best model of the electrode responses, some of the network's parameters were optimised and its usefulness in determining NH₄⁺, K⁺ and Na⁺ ions in synthetic samples was then tested. Finally, it was used to determine these ions in commercial fertilisers, the obtained results being compared with reference methods.     

Swelling behavior and mechanical properties of endlinked poly (dimethylsiloxane) networks and randomly crosslinked polyisoprene networks

Measurements of the equilibrium degree of swelling and of the equilibrium modulus were performed on poly(dimethylsiloxane) networks (PDMS) and on polyisoprene vulcanizates. The results support the concept that topological interactions between network chains, e.g. entanglements or the like, have a large influence on the rubber elastic behavior, at least within a certain range of network densities.PDMS networks having network chains of different lengths and varying functionlities of the crosslinks were prepared in bulk by endlinking fractionated ,-divinyl PDMS via multifunctional hydrogen-siloxanes (f=3 to 22). Natural rubber (NR) and synthetic liquid polyisoprene (IR) were cured in bulk with various amounts of dicumyl peroxide to give randomly crosslinked samples.The experimentally determined moduli and degrees of swelling were compared with theoretical predictions based on the phantom network theory and affine network theory, taking into account only chemical crosslinks. The observed discrepancies can be traced back to a contribution of topological interactions (trapped entanglements) to the total effective network density. The modulus and swelling data are consistent, thus ruling out non-equilibrium effects.     

Light traffic for workload in queues

General exact light traffic limit theorems are given for the distribution of steadystate workloadV, in open queueing networks having as input a general stationary ergodic marked point process {(t _n ,K _n )n0 (where t_n denotes the arrival time and K_n the routing and service times of the nth customer). No independence assumptions of any kind are required of the input. As the light traffic regime, it is only required that the Palm distribution for the exogenous interarrival time converges weakly to infinity (while the service mechanism is not allowed to change much). As is already known in the context of a single-server queue, work is much easier to deal with mathematically in light traffic than is customer delayD, and consequently, our results are far more general than existing results forD. We obtain analogous results for multi-channel and infinite-channel queues. In the context of open queueing networks, we handle both the total workload in the network as well as the workload at isolated nodes.Research supported in part by the Japan Society for the Promotion of Science during the author's fellowship in Tokyo, and by NSF Grant DDM 895 7825.     

A multineuron interaction model for neural networks

A multineuron interaction model (RS model) with an energy function given by the product of the squared distances in phase space between the state of the net and the stored patterns is studied in detail within a mean-field approach. Two limits are considered: when the patterns and antipatterns are stored (as in the Hopfield model), PAS case, and when only the patterns are taken into account, OPS case. TheT=0 solutions for the proper memories are exactly obtained for all finite values of, as a consequence of the energy function: whenever one of the overlaps is exactly one the corresponding equations decouple and no configuration average is required. Special interest is focused on the OPS situation, which presents a peculiar phase space topology. On the other hand, the PAS configuration recovers the Hopfield model in the appropriate limit, while keeping associative memory abilities far beyond the critical values of other models when the full Hamiltonian is considered.     

Phenomenology of nonlocal cellular automata

Dynamical systems with nonlocal connections have potential applications to economic and biological systems. This paper studies the dynamics of nonlocal cellular automata. In particular, all two-state, three-input nonlocal cellular automata are classified according to the dynamical behavior starting from random initial configurations and random wirings, although it is observed that sometimes a rule can have different dynamical behaviors with different wirings. The nonlocal cellular automata rule space is studied using a mean-field parametrization which is ideal for the situation of random wiring. Nonlocal cellular automata can be considered as computers carrying out computation at the level of each component. Their computational abilities are studied from the point of view of whether they contain many basic logical gates. In particular, I ask the question of whether a three-input cellular automaton rule contains the three fundamental logical gates: two-input rules AND and OR, and one-input rule NOT. A particularly interesting edge-of-chaos nonlocal cellular automaton, the rule 184, is studied in detail. It is a system of coupled selectors or multiplexers. It is also part of the Fredkin's gate—a proposed fundamental gate for conservative computations. This rule exhibits irregular fluctuations of density, large coherent structures, and long transient times.     

Solid-State NMR Study of Phase Separation and Order of Water Molecules and Silanol Groups in Polysiloxane Networks

Homogeneity and structure of organically modified polysiloxane networks prepared by sol-gel co-condensation, as well as location and nature of water molecules and silanol groups were studied by 1D and 2D solid-state NMR. ¹H–²⁹Si and ¹H–¹H interatomic distances were estimated from variable contact-time CP/MAS experiments, ¹H NMR chemical shifts and off-resonance WISE NMR. A structure model of these networks is proposed and discussed. The fraction of proton-inaccessible units Q⁴ in the networks decreases with increasing amounts of dimethylsiloxane (D) and methylsiloxane (T) units. In contrast to systems prepared by co-condensation of tetraethoxysilane (TEOS) with dimethyl(diethoxy)silane (DMDEOS), proton-inaccessible units form essential fraction in networks prepared by co-condensation of TEOS with methyl(triethoxy)silane (MTEOS). The proton-accessible part of the networks with high O/Si ratios is nano-heterogeneous phase, which is composed of water containing Q ⁱ particles separated by copolymer domains. The overall homogeneity and uniformity of binding sites around silanol groups increases by co-condensation TEOS with DMDEOS or MTEOS, while the amount of physisorbed water as well as the hydrogen bond strength decreases, as compared with neat silica gel prepared by polycondensation of TEOS.