Temperature‐induced phase transformations in Na2WO4 and Na2MoO4 crystals

Temperature‐dependent Raman studies on Na₂WO₄and Na₂MoO₄ crystals were performed in order to obtain information on structural changes induced by temperature evolution. The stability of the cubic phase of Na₂WO₄and Na₂MoO₄crystals was assessed and our results indicate that this phase is stable in the 8–823 K and 15–773 K ranges for Na₂WO₄ and Na₂MoO₄, respectively. The crystal of Na₂WO₄ shows a phase transition occurring at 833 K. Na₂MoO₄undergoes a sequence of three phase transitions, which were observed at 783–803, 823–913 and 943–950 K. In both crystals, a strong first‐order phase transition occurs as indicated by the behavior of the Raman modes: the Raman bands split and new bands appear below 100 cm⁻¹. These transitions are connected with tilting and/or rotations of the WO₄and MoO₄ tetrahedra, which leads to a disorder at the WO₄and MoO₄ sites. Copyright © 2010 John Wiley & Sons, Ltd.     

Polylactide compositions. The influence of ageing on the structure, thermal and viscoelastic properties of PLA/calcium sulfate composites

High-performance composites prepared by melt-blending polylactide (PLA, l/d isomer ratio of 96/4) with various amounts of β-anhydrite II (AII), the dehydrated form of calcium sulfate hemihydrate obtained by a specific thermal treatment at 500 °C, have been aged to study the evolution of their physical and mechanical properties with time. The effect of 1-year ageing under ambient conditions (below T_g of PLA) for selected composites, i.e., filled with 20 and 40 wt% AII, was determined and compared to unfilled PLA with the same processing and ageing history. Samples with an initial amorphous PLA matrix, obtained by fast quenching from the melt, were characterized before and during ageing. The changes in physical parameters have been studied using dynamic mechanical thermal analysis (DMTA), differential scanning calorimetry (DSC), X-ray diffraction (XRD) and density measurements. Surprisingly, for all the samples, an increase of the storage modulus (E′) was recorded, as a result of ageing. This improvement was ascribed to the reorganization of the PLA structure induced by ageing. The structural reorganization was also reflected by a slight increase of PLA density and changes in thermal behaviour. The X-ray investigations showed unchanged crystallographic structure of AII both during blending with molten PLA and in the composite systems after ageing. The surprising stability of the thermo-mechanical properties of PLA and PLA/AII composites is in agreement with the results of size exclusion chromatography analysis (SEC) which did not show significant changes of PLA molecular weights brought out by ageing.     

Spectroscopic studies of dynamically compacted monoclinic ZrO2

The properties of dynamically compacted monoclinic zirconia have been studied by X-ray powder diffraction, IR, Raman, EPR and luminescence spectroscopy. Compaction introduces a large number of defects into the sample, which leads to a broadening of the X-ray lines, and IR and Raman bands. Besides, Raman spectra of compacted samples recorded with both 1064 and 488 nm excitation show additional bands in comparison with original monoclinic zirconia. The bands in the region 540–730 nm with 488 nm excitation are ascribed to electronic transitions of Sm³⁺ ions. The nature of the extra bands in the 3000–1830 cm⁻¹ region observed with 1064 nm excitation is unknown. Their intensity depends on the concentration of defects, but these bands are still observed for a sample containing no paramagnetic defects. In contrast to uncompacted zirconia, the EPR spectrum of the dynamically compacted material shows defects, most likely related to V′_O (oxygen vacancies), which might be an indication for ionic conduction. As monoclinic zirconia is not an ionic conductor, it could be that shock-compaction introduces sample conductivity, e.g. ionic conduction, which can be important for the development of new applications such as batteries.     

Compressor Blade Health Monitoring with Use of Tip Timing and Modal Analysis Method

The intended aim of this report is to deliver a short review of AFIT experience in the field of the blade health monitoring. A special attention has been put down for diagnostic methods (tip timing, modal analysis, metal magnetic memory) and symptom verification. Knowledge, which is necessary for reliable diagnosis and prognosis, during engine operation, as well as during overhaul and numerical simulation. It has been proven that the resonance characteristic shape analysis gives an ability to determinate if we deal with fatigue or with a blade crack. Early fatigue symptoms, i.e. modal properties of material strengthening and weakening phases have been shown. A new source of diagnostic information to ‘actively’ control blade fatigue (VHCF, HCF & LCF) has been described. The discussed problems have been illustrated with some examples. (© 2009 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim)     

The solution existence and convergence analysis for linear and nonlinear differential-operator equations in Banach spaces within the Calogero type projection-algebraic scheme of discrete approximations

The projection-algebraic approach of the Calogero type for discrete approximations of linear and nonlinear differential operator equations in Banach spaces is studied. The solution convergence and realizability properties of the related approximating schemes are analyzed. For the limiting-dense approximating scheme of linear differential operator equations a new convergence theorem is stated. In the case of nonlinear differential operator equations the effective convergence conditions for the approximated solution sets, based on a Leray-Schauder type fixed point theorem, are obtained.     

Detection of drug active ingredients by chemometric processing of solid-state NMR spectrometry data -- the case of acetaminophen

This paper presents a preliminary study in building discriminant models from solid-state NMR spectrometry data to detect the presence of acetaminophen in over-the-counter pharmaceutical formulations. The dataset, containing 11 spectra of pure substances and 21 spectra of various formulations, was processed by partial least squares discriminant analysis (PLS-DA). The model found coped with the discrimination, and its quality parameters were acceptable. It was found that standard normal variate preprocessing had almost no influence on unsupervised investigation of the dataset. The influence of variable selection with the uninformative variable elimination by PLS method was studied, reducing the dataset from 7601 variables to around 300 informative variables, but not improving the model performance. The results showed the possibility to construct well-working PLS-DA models from such small datasets without a full experimental design.     

Copper(II) and oxovanadium(IV) complexes of α-hydroxymethylserine

Summary Potentiometric and spectroscopic measurements were used to characterize the binding ability of -hydroxy-methylserine (Hms) with copper(II) and oxovanadium(IV) ions. The ligand was found to be generally a more efficient chelating agent than serine. Both of the deprotonated hydroxyl groups of Hms can be involved in coordination to vanadyl ions, whereas copper(II) binds in the same way as with serine.     

PM3 study of the proton affinities of 2-, 3-, and 4-monosubstituted pyridines in the gas phase

Heats of formation (ΔH_f) and proton affinities (PA) of 2-, 3-, and 4-monosubstituted pyridines in the gas phase are calculated using the AM1 and PM3 semiempirical methods. The following substitutents are considered: NO₂, CN, CF₃, CHO, F, Cl, COCH₃, H, CH₃, OCH₃, SCH₃, NH₂, and N(CH₃)₂. The results are compared with the experimental data. Both methods reproduce the ΔH_f with comparble accuracy; the rms deviations are 4.1 (AM1) and 4.5 kcal/mol (PM3) for the free bases and 9.5 (AM1) and 9.7 kcal/mol (PM3) for their conjugated acids. The PA are systematically underestimated by both methods, but AM1 appears to be clearly better than PM3 for reproducing the experimental values. The rms deviations for AM1 and PM3 are 5.1 and 9.6 kcal/mol, respectively. This is due to a cancellation of systematic errors in the calculated ΔH_f in the AM1 case and to a summation of the errors in the PM3 case. Both methods correctly reproduce conformations of the molecules under consideration.     

Anion radical formation in the reaction of chloranilic acid with n-methylpiperidine in acetonitrile

Reaction of chloranilic acid with N-methylpiperidine in acetonitrile has been studied. The product of the reaction is an unusually stable anion radical of quinone. The presence of radicals has been confirmed by EPR measurements. Stability constant, extinction coefficients and thermodynamic reaction parameters are reported. Mechanism of the reaction is proposed. This revised version was published online in June 2006 with corrections to the Cover Date.