Parameter estimation in simultaneous phase and reaction equilibria

The estimation of parameters of models describing simultaneous phase and reaction equilibria is generally difficult to accomplish, due to strong correlation between the parameters. We show in this paper that these models possess intermediate properties between reduced and implicit models. This makes it convenient to develop ad-hoc algorithms for this class of problems which are of considerable importance in process design. We present a method for parameter estimation based on implicit differentiation, which makes it possible to use a gradient algorithm with respect to a reduced number of parameters, which greatly enhances global convergence.     

Comparison of photo-oxidative degradation of polyamide 6,6 films stabilized with HALS and CuCl2+KI mixtures

The photo-oxidative stability of polyamide 6,6 (PA 6,6) doped with a hindered amine light stabilizer (HALS) and a mixture of cupric chloride and potassium iodide was examined.Several analytical techniques were employed, in order to evaluate the correlation between chemical modifications, morphology and mechanical properties of PA 6,6 films irradiated at λ>300 nm, 90 °C, and 50% relative humidity.Infrared spectroscopy showed a build-up of carbonyl absorption in the range 1700-1780 cm⁻¹ due to primary and secondary photo-oxidation products. The increase in content of carbonyl groups was greatest in the case of the pure polymer, and it was also appreciable in the case of PA 6,6 stabilized with copper/KI system. On the other hand, the use of the HALS additive brought about a substantial increase in the amount of carboxylic acids formed.The morphology of the samples was found to have an effect on the kinetics of the accumulation of carbonyls, and it was observed that at a later stage of exposure the crystalline phase was also involved in the oxidation process.Tensile tests on films revealed a large reduction in ductility as a result of ageing for both neat polymer and HALS-doped polymer. Only a slight reduction in ductility was found for the polymer stabilized with the inorganic mixture.This study evidenced that the mixture of CuCl₂ and KI has a far better long-term stabilizing efficiency in comparison with the HALS stabilizer.     

Systematical analysis of chemical methods in metal nanoparticles synthesis

We propose a short review paper on the mainly adopted techniques for the production of metal nanoparticles in industrial and laboratory scale. The methods are grouped according to the wellknown classification in bottom-up and top-down schemes, with a particular emphasis on the operating conditions specifically adopted. Namely, some aspects concerning the experimental setup, the choice of precursors and reactants and the relevant technical advantages/limitations of the methods are discussed and compared in light of the most recent issues in matter of metal nanoparticles synthesis.     

Process data reconciliation in the presence of non-uniform measurement errors

The goal of flow rates reconciliation was to adjust measured values and estimate unmeasured streams so as to balance both measured and unmeasured values, identify gross errors and detect leaks and losses. Thus, data reconciliation plays a key role in the monitoring of industrial plants for the early detection of critical events which might cause environmental and economic damages, and it is,therefore, an essential component of any clean technology process. Consequently, any method that improves the accuracy of the reconstructed data by considering more realistic assumptions on the statistical nature of the data can add considerably to the overall reliability of the process. The reconciliation procedure is statistical in nature and requires adequate information on the structure of the random errors of the flow rates measured. A frequent assumption is the homoscedasticity and the independence of the errors affecting different streams. This assumption leads to efficient algorithms based on advanced linear algebra decompositions, such as QR or Singular Value Decomposition, but it frequently leads to biased estimates, especially when the values of flow rates vary over two or more orders of magnitude. The goal of this article was to show the importance of considering general heteroscedasticity when reconciling flow rates. Errors are supposed to be normally distributed according to \(\varepsilon_{\text{i}} \cong N(0,\,\sigma_{0} L_{\text{i}}^{ 2\eta } )\) , where \(L_{\text{i}}\) is the measurement of the ith flow rate and \(\theta\)  =  \(\left\{ {\theta |\sigma_{0} ,\eta } \right\}\) is a set of two parameters to be estimated along with the adjustments to the measured flow rates. Therefore, the overall variance–covariance is characterised by 3 parameters \(\sigma_{0} ,\eta\) and the correlation factor among measurement errors ρ. The algorithm here proposed is based on conditional optimality, and it carries out the whole optimisation in terms of the parameters \(\theta\) only, the unknown adjustments being expressed at each iteration as functions of \(\theta\) .     

Grape variety related trans-resveratrol induction affects Aspergillus carbonarius growth and ochratoxin A biosynthesis

The paper reports the results of a study performed to investigate the influence of the grape variety on the growth of Aspergillus carbonarius on grape berries and the correlation between the amount of ochratoxin A (OTA) and the content of trans-resveratrol produced after fungal contamination. Variations in the amount of OTA produced by the fungus are observed depending on both grape variety and on the induction of trans-resveratrol determined during the infection. The obtained data suggest that if an increase in trans-resveratrol production in grape berries occurs early after the fungal infection, the berry exploits this compound to control OTA synthesis. If the increase in trans-resveratrol concentration is delayed after fungal infection (40 h), a control of OTA accumulation can not be achieved. The possibility of exerting significant control of OTA biosynthesis by this phytoalexin seems to rely in the promptness of its production, as occurs also in other fungus plant interactions and, in turn, seems to be dependent also on grape cultivar. In this fungus-plant system, trans-resveratrol appears to represent a defence-related compound toward A. carbonarius and OTA contamination.     

Influence of electrode thickness on the performance of composite electrodes for SOFC

Measurements on half-cells consisting of yttria-stabilized zirconia (YSZ) electrolyte pellets and slurry-coated cathodes of different thickness were performed in order to determine the active area for oxygen reduction in composite cathodes of lanthanum strontium manganite (LSM) and YSZ. Electrochemical impedance spectroscopy was used to evaluate the main electrochemical parameters of the cathodic process. The temperature range was between 500 and 900 °C. The experimental results show a remarkable effect of the electrode thickness on the overall reaction rate in all the temperature range. At 750 °C a change in the controlling regime of the oxygen reduction is detectable and has been ascribed to the transition of the rate-determining step from a charge transfer to a mass transfer of the ionic species. A simplified theoretical model of the cathode that accounts for charge transfer and ionic conduction was developed to give insight into the experimental results. The model simulations compared satisfactorily with the experimental data confirming that the behaviour experimentally observed could be approached with the proposed model.     

A Replicated Experiment to Assess Requirements Inspection Techniques

This paper presents the independent replication of a controlled experiment which compared three defect detection techniques (Ad Hoc, Checklist, and Defect-based Scenario) for software requirements inspections, and evaluated the benefits of collection meetings after individual reviews. The results of our replication were partially different from those of the original experiment. Unlike the original experiment, we did not find any empirical evidence of better performance when using scenarios. To explain these negative findings we provide a list of hypotheses. On the other hand, the replication confirmed one result of the original experiment: the defect detection rate is not improved by collection meetings.The independent replication was made possible by the existence of an experimental kit provided by the original investigators. We discuss what difficulties we encountered in applying the package to our environment, as a result of different cultures and skills. Using our results, experience and suggestions, other researchers will be able to improve the original experimental design before attempting further replications.