Syntactic characterization of closure under connected limits

Summary We give a syntactic characterization of (finitary) theories whose categories of models are closed under the formation of connected limits (respectively the formation of pullbacks and substructures) in the category of all structures. They are also those theories whose consistent extensions by new atomic facts admit in each component an initial structure (respectively an initial term structure), and also thoseT for whichM(T) is locally finitely multi-presentable in a canonical way. We also show that these two properties of theories are nonuniform.     

Constraint Programming and Operations Research: Comments from an Operations Researcher

This paper relates the author's personal experience with constraint programming and gives a personal assessment of the relationships between constraint programming and operations research.     

Dependence of the kinetics of the anionic polymerization of methyl methacrylate on the concentration in active centers

Studies on the anionic polymerization of methyl methacrylate in tetrahydrofuran and in the presence of sparteine have revealed a beneficial effect due to this additive, resulting in a decrease in the extent of termination. Better control of the definition of the polymers formed can thus be achieved in the presence of this additive. On the other hand, macromolecular engineering requires a range of active species concentrations lower than 10^?3 mol L^?1 and particularly the synthesis of polymers of high molar masses. For a better understanding of the mechanism of chain growth under such concentration conditions, the kinetics of polymerization have been investigated with a technique based on adiabatic calorimetry. Sparteine has been found to lack sufficient cation‐binding power to prevent the propagating enolate ion pairs from aggregating. The rate constant of propagation of nonaggregated species has been estimated, as well as the aggregation constant of equilibrium. For very low initiator concentrations, termination reactions have been shown to profoundly alter the control of the polymerization and to prevent a quantitative monomer conversion. Theoretical maximal conversions have been calculated from kinetic data and compare well with the experimental values. © 2004 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 42: 4964–4975, 2004     

Elliott-Morse measures and Kakutani's dichotomy theorem

Dedicated to the memory of John Oxtoby     

Bayesian Object Identification: Variants

We present a Bayesian theory of object identification. Here, identifying an object means selecting a particular observation from a group of observations (variants), this observation (the regular variant) being characterized by a distributional model. In this sense, object identification means assigning a given model to one of several observations. Often, it is the statistical model of the regular variant, only, that is known. We study an estimator which relies essentially on this model and not on the characteristics of the “irregular” variants. In particular, we investigate under what conditions this variant selector is optimal. It turns out that there is a close relationship with exchangeability and Markovian reversibility. We finally apply our theory to the case of irregular variants generated from the regular variant by a Gaussian linear model.     

Diffusion-limited annihilation in inhomogeneous environments

We study diffusion-limited (on-site) pair annihilation A + A → 0 and (on-site) fusion A + A → A which we show to be equivalent for arbitrary space-dependent diffusion and reaction rates. For one-dimensional lattices with nearest neighbour hopping we find that in the limit of infinite reaction rate the time-dependent n-point density correlations for many-particle initial states are determined by the correlation functions of a dual diffusion-limited annihilation process with at most 2n particles initially. Furthermore, by reformulating general properties of annihilating random walks in one dimension in terms of fermionic anticommutation relations we derive an exact representation for these correlation functions in terms of conditional probabilities for a single particle performing a random walk with dual hopping rates. This allows for the exact and explicit calculation of a wide range of universal and non-universal types of behaviour for the decay of the density and density correlations.     

ARXPS-analysis and morphology of sputtered nanocrystalline TiC/SiC coatings

ARXPS (angle resolved X-ray photoelectron spectroscopy) measurements are used to obtain informations about surfaces and grain boundaries. Data acquired from nanocrystalline carbidic hard coatings have been employed to establish structural models. Magnetron-sputtered coatings of TiC, SiC and TiC/SiC were examined. In such coatings, partly defective TiC nanocrystallites are surrounded by interfacial carbide. This excess carbon shows a binding state similar to that of doped graphite or fullerenes. X-ray amorphous SiC is found in the residue. On top of sputtered SiC coatings, less oxide and graphite is found as compared to TiC/SiC or TiC coatings.     

Kinetics and mechanisms of chlorine transfer from chloramine to amines in aqueous medium

The kinetics and the equilibrium constant of the chlorine transfer reaction between monochloramine NH₂Cl and the amines: C₂H₅NH₂, (CH₃)₂CHNH₂, (CH₃)₂NH, and (C₂H₅)₂NH are investigated by spectrophotometry in aqueous medium at 25°C, in the pH range from 8 to 13 and for an ionic strength equal to 1.03 ± 0.05M. For a concentration of total ammonia equal to 1M, the observed rate constant is pH independent below 8 and above 12.8 and reaches a maximum located between the pK_as of NH₄⁺ and RR'NH₂⁺. From these results and those obtained earlier for NH₂Cl and CH₃NH₂, the reaction is shown to involve an interaction between neutral molecules NH₂Cl and RR'NH, subject to general acid catalysis. The ability of an interaction corresponding to a specific catalysis and involving NH₃Cl⁺ and RR'NH rather than NH₂Cl and RR'NH₂⁺ is also discussed. The activation parameters are given for each reaction.