Ageing of wet-synthesized oxide powders

Wet chemical synthesis of precursor oxide ceramics is a method to obtain small particulate powders. Such powders are far more prone to ageing in air than more traditional precursors. Thermogravimetric analysis is used to highlight the species responsible for the ageing of ceramic precursors. Indeed water and carbon dioxide are observed to evolve from aged powders. Ceramics obtained from aged precursors can reach a very low final density with respect to the theoretical value. A large degree of the original sintering properties can be recovered after washing the aged powders with ethanol in a basic medium.     

Dynamic Nonlinear Modelization of Operational Supply Chain Systems

Supply Chain Management (SCM) is an important activity in all producing facilities and in many organizations to enable vendors, manufacturers and suppliers to interact gainfully and plan optimally their flow of goods and services. To realize this, a dynamic modelling approach for characterizing supply chain activities is opportune, so as to plan efficiently the set of activities over a distributed network in a formal and scientific way. The dynamical system will result so complex that it is not generally possible to specify the functional forms and the parameters of interest, relating outputs to inputs, states and stochastic terms by experiential specification methods. Thus the algorithm that will presented is Data Driven, determining simultaneously the functional forms, the parameters and the optimal control policy from the data available for the supply chain. The aim of this paper is to present this methodology, by considering dynamical aspects of the system, the presence of nonlinear relationships and unbiased estimation procedures to quantify these relations, leading to a nonlinear and stochastic dynamical system representation of the SCM problem. Moreover, the convergence of the algorithm will be proved and the satisfaction of the required statistical conditions demonstrated. Thus SCM problems may be formulated as formal scientific procedures, with well defined algorithms and a precise calculation sequence to determine the best alternative to enact. A “Certainty equivalent principle” will be indicated to ensure that the effects of the inevitable uncertainties will not lead to indeterminate results, allowing the formulation of demonstrably asymptotically optimal management plans.     

Chemometric approaches in environmental problems concerning PCDD and PCDF. Data interpretation and source correlation. Mechanisms of formation and destruction in MSW combustion process

Summary The role of multivariate analysis methods in evaluating, rationalizing, and working out complex environmental problems is discussed. The discussion is organized in two sections; a literature analysis of the application of chemometric methods to PCDD/PCDF data interpretation and source correlation and a review of the role of chemometric methods in analysing the results obtained by the Authors studying PCDD/PCDF formation and destruction mechanisms in MSW combustion processes.     

Learning Markov chains in fractal compression of image data

In a recent paper [17] we proposed a stochastic algorithm which generates optimal probabilities for the decompression of an image represented by the fixed point of an IFS system (SAOP). We show here that such an algorithm is in fact a non trivial example of Generalized Random System with Complete Connections. We also exhibit a generalization which could represent the solution to the inverse problem for an image with grey levels, if a fixed set of contraction maps is available. Received: 1 July 2002     

Time-Resolved Photoacoustic Calorimetry: From Carbenes to Proteins

Why have molecules only been seen but not heard? For over a century chemists have probed reactions with various spectroscopic methods to learn about structures, dynamics, and reactivities of their molecules. What they have not done is to listen to their molecules react. Although the photoacoustic phenomenon has been known since 1880, it is only in the last twenty years that technology has developed to the point where sound waves produced by reacting molecules can be time resolved and the information contained within the waves deciphered. The information content within the photoacoustic wave is indeed rich, for one can learn about the dynamics and the magnitude of enthalpy changes associated with the reaction as well as the changes in molecular volume. This review article chronicles the development of time-resolved photoacoustic calorimetry and its application to a variety of reactions encountered in organic and organometallic chemistry and biochemistry.     

Chain “stationary” insertion mechanism and production of isotactic polypropylene with C 1 symmetric catalyst systems

In this contribution, the stereochemistry of propylene insertion/propagation reactions with a variety of C ₁ symmetric metallocene catalysts, containing bridged cyclopentadienyl-fluorenyl ligand for the preparation of highly stereoregular polypropylene is presented. The impact of the distal substitutent’s size and composition and changes that the catalytic sites undergo upon such substitution is elaborated. A comprehensive mechanism is proposed to explain the resulting catalytic changes that bring about the irreversible C _s/C ₁ site transformation and tactic behavior inversion. Furthermore the cyclopentadienyl’s combined distal/proximal and fluorenyl’s frontal substituent effects on molecular weight, regio-, and stereoregularity of the final polymers are discussed. Finally, stereoselectivities of C ₂ and C ₁ symmetric catalyst systems are compared. It is shown that current high performance C ₁ symmetric catalyst systems with central site chirality can be isotactic selective as well or even better in certain aspects than the C ₂ symmetric bridged bisindenyl-based metallocene catalysts. The text was submitted by the authors in English.