Study of the hydrolysis and condensation of γ-Aminopropyltriethoxysilane by FT-IR spectroscopy

The hydrolysis and condensation reactions of γ-APS have been studied in different acid content aqueous solution by using Fourier Transform infrared (FT-IR) spectroscopy. The hydrolysis of γ-APS under the studied conditions can be followed by the increase of the ethanol band located at 882 cm⁻¹ and the decrease of the band due to the ρ(CH₃) of γ-APS molecules located at 959 cm⁻¹. Hydrolysis reaction is faster by increasing both H₂O and acid concentrations, and it is completed when 3 moles of H₂O per mole of γ-APS are used. The increase of the vibrational band located at 1146 cm⁻¹ shows that condensation of the hydrolysed γ-APS molecules take place forming linear chains in poorly cross-linked structures. Besides, both 8-membered cyclic siloxane formations and poorly cross-linked structures are formed and increase as the water and acid content are increased. On the other hand, highly connected cross-linked structures do not appear due to the steric hindrance of the non-hydrolysable aminopropyl group. The silanol band shows that hydrolysis is faster than condensation except for samples with the lowest H₂O content.     

Co- and Ni-exchanged ferrierite: The contribution of synchrotron X-ray diffraction data to siting of TMIs

High-silica zeolites exchanged with transition metal ions (TMIs) are the subject of great interest for their unusual catalytic activity and selectivity. Structural information like coordination and accessibility of TMIs in zeolites are important factors for understanding their catalytic activity. Siting of TMIs in zeolites is typically obtained by spectroscopic (EXAFS, EPR, UV–vis and IR) and computational methods, as in the case of Co-ferrierite. However, some controversy exists in the literature concerning the model for incorporation of bare Co ions in ferrierite. We show here that the results of our synchrotron X-ray powder diffraction studies on Co- and Ni-exchanged ferrierite (Si/Al = 8.5) are in a good agreement with the model of Co siting based on an indirect spectroscopic approach and help to validate this model. By direct structural evidences, a possible explanation for the larger catalytic activity of Co sites in the main channels of ferrierite can be inferred. A combination of data from in situ XRD continuous monitoring of the Co ion migration during calcination and crystal-chemical considerations allows to device a strategy for the design of optimised co-cations containing Co-ferrierite catalysts.     

Playing with Maude

This paper is an introduction to rule-based programming in Maude. We illustrate in particular the use of operator attributes to structure the state of a system, and the difference between equations and rules. We use well-known mathematical games and puzzles for our examples illustrating the expressive power of Maude.     

Determination of peroxide value by conventional difference and difference-derivative spectrophotometry

The spectrophotometric behavior of the system iodide-iodine-iodate-oxygen was studied, and a simple iodometric method to determine peroxide value by conventional, difference or difference-derivative spectrophotometry was developed. The procedures are carried out inside standard photometric cells containing iodide solution to which the sample is added. Absorbance or its first derivative with respect to wavelength is measured to determine iodine concentration by means of calibration curves. No special care to avoid iodide oxidation by atmospheric oxygen is necessary. The method is applicable even to lipids that give emulsions with water, such as phosphatides, and precise results are obtained even at low peroxide values. The use of a digital spectrophotometer with data processing and programming facilities allowed development of an interactive program for automatic operation, which is outlined.     

Hydrocarbon exploration risk evaluation through uncertainty and sensitivity analyses techniques

The evaluation of the exploration risk in the oil industry is a fundamental component of the decision process related to the exploratory phase. In this paper the two basic components of the exploratory risk: trap geometry and trapped hydrocarbon quantities (fluid), are compounded in a single coherent uncertainty and sensitivity approach. The results clarify that the model geometry influences each Petroleum System Modeling step and that the geometric uncertainty is correlated with the fluid uncertainty. The geometric uncertainty evaluation makes use of geostatistical techniques that produce a number of possible realizations of the trap geometry, all compatible with available data. The evaluation of the fluid uncertainty, through a Monte Carlo methodology, allows us to compute the possible quantities of oil and gas, generated in a basin and migrated from the hydrocarbon source location to each single trap. The final result is the probability distribution of oil and gas for each trap in the basin, together with other useful indicators like: the hydrocarbon filling probability map, the closure probability map, the drainage area probability map, the spilling paths probabilities, the trap-filling scenarios.     

Hydrodechlorination of 3-chloropyridine and chlorobenzene in methanol solution over alkali-modified zirconia-supported palladium catalysts

The liquid-phase hydrodechlorination of 3-chloropyridine and chlorobenzene has been studied over alkali-modified zirconia-supported palladium catalysts. The modification of the ZrO₂ with alkali metal carbonates improves the catalytic activity of the final palladium catalyst. Therefore, the larger the ionic radii (Li⁺ < Na⁺ < K⁺), the greater the catalytic activity (TOF) of the palladium catalyst. For 3-chloropyridine, hydrodechlorination proceeds without catalyst deactivation. This is explained as the result of the interaction of reaction products (pyridine and HCl) forming pyridinium chloride, thus avoiding the detrimental effect of HCl on the palladium particles. Catalytic hydrodechlorination of chlorobenzene over Pd catalysts exhibits an initial catalytic activity (TOF) much lower than that of 3-chloropyridine and the Pd catalysts deactivate as the reaction proceeds. Finally, chlorobenzene hydrodehalogenation has also been carried out in the presence of an equimolecular amount of pyridine resulting in a decrease in the initial reaction rate on the one hand, but also in an increase in final conversion on the other.     

Comments on “Is the cause of size effect on structural strength fractal or energetic-statistical?” by Ba?ant & Yavari [Engng Fract Mech 2005;72:1-31]

Aim of this letter to the Editor is at replying to the criticisms raised by Ba?ant and Yavari [Ba?ant ZP, Yavari A. Is the cause of size effect on structural strength fractal or energetic - statistical? Engng Fract Mech 2005;72:1-31] against the fractal approach to the size-scale effects on the mechanical properties of materials and the concept of the Multi-Fractal Scaling Law presented by Carpinteri [Carpinteri A. Scaling laws and renormalization groups for strength and toughness of disordered materials. Int J Solids Struct 1994;31:291-302]. These criticisms will be analysed thoroughly, showing how they also contain some mistakes and misunderstandings. The presented elucidations should redirect the discussion to a more correct scientific debate.     

Learning Recursive Bayesian Multinets for Data Clustering by Means of Constructive Induction

This paper introduces and evaluates a new class of knowledge model, the recursive Bayesian multinet (RBMN), which encodes the joint probability distribution of a given database. RBMNs extend Bayesian networks (BNs) as well as partitional clustering systems. Briefly, a RBMN is a decision tree with component BNs at the leaves. A RBMN is learnt using a greedy, heuristic approach akin to that used by many supervised decision tree learners, but where BNs are learnt at leaves using constructive induction. A key idea is to treat expected data as real data. This allows us to complete the database and to take advantage of a closed form for the marginal likelihood of the expected complete data that factorizes into separate marginal likelihoods for each family (a node and its parents). Our approach is evaluated on synthetic and real-world databases.     

Analysis of run-in process for PC manufacturing

This paper gives a review of the methodology used to tune the run-in process of a PC manufacturing line. It shows in some detail the analysis carried-out on the test data gathered on the manufacturing line and presents a clear picture of the run-in process in order to choose the best compromise between process efficiency and costs.