Ultrasound‐activated Knoevenagel condensation of malononitrile with carbonylic compounds catalysed by alkaline‐doped saponites

α,β‐Unsaturated nitriles have been synthesized by Knoevenagel condensation of a carbonylic compound with malononitrile, assisted by sonochemical irradiation. Two alkaline‐promoted clays (Li⁺‐ and Cs⁺‐exchanged saponites) have been employed as catalysts. The influence of the carbonylic compound (benzaldehyde or cyclohexanone) and the use of a solvent on the catalytic activity have been studied. Remarkable increase in the conversion values has been found when the reaction is activated by ultrasound, as compared with the thermal activation. In this green, solvent‐free procedure, α,β‐unsaturated nitriles have been produced in very high yields (97%) when the Cs⁺‐saponite is used as catalyst. Copyright © 2004 Society of Chemical Industry     

Quantitative determination of non-defect unstable structures in PVC through selective nucleophilic substitution with C6H5SNa

Summary The nucleophilic substitution with C₆H₅SNa, at -30°C, is compared for five PVC samples with various contents of isotactic triads. The conversion curves consist of a very fast stage followed by a steady one. All the samples are found to behave in the same way except for the content of the structures involved in the fast period. This content is estimated by extrapolating the straight lines of the steady stages to zero time. The obtained values are found to be a linear function of the content of isotactic triads. The results, together with some earlier ones, allow for the content of the labile non-defect structures in PVC to be determined.     

Modified determination of 2-thiobarbituric acid value in fats and oils

Several methods for the determination of TBA-value were compared with a new direct modification (omitting the previous distillation), using 1-butanol as the sole solvent. The absorbance is measured at 530 nm after heating to 95 degrees C for 120 min, and cooling. The effect of variables was tested by the Youdens ruggedness test (reaction time, temperature, cooling, concentration of sample, thiobarbituric acid, water, heavy metals, antioxidants, chelating agents, bubbling with oxygen or nitrogen). The Lambert-Beers law is valid in the absorbance range between 0.05 and 0.8. The repeatability is better than that of the Dzikowskis procedure and comparable with those of more complicated distillation methods. The standard deviation is in a linear relation with the absorbance (range 0.1-1.0). The method was found satisfactory for evaluating lard, cooking fat, soybean, sunflower, and rapeseed oils in the stage of beginning rancidity.     

Mechanical improvement of hydroxyapatite by TiO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> nanoparticles deposition

Deposition of Ti was carried out by laser ablation onto hydroxyapatite porous discs in an Ar atmosphere. Ti nanoparticles were deposited onto HAp surface in order to modify its roughness and morphology as it is observed by scanning electron microscopy (SEM) and scanning probe microscopy (SPM). A homogeneous distribution of Ti over the disc surface was corroborated by elemental mapping. A comparison of the hydroxyapatite hardness before and after deposition was performed using SPM nanoindentation. Transmission Electron Microscopy (TEM) showed that the Ti nanoparticles obtained were covered by an oxygen shell. It is shown that surface modifications of the covered HAp by Ti result in better mechanical properties, reducing the possible damage to the HAp ceramic by friction or impacts as it often happens in meniscus, bone junctions and the inclusion of prosthesis for human treatments.     

Low temperature and strain rate dependence of fracture stress and fracture toughness on thin Fe40Ni40B20 amorphous ribbon

The fracture stress and the critical stress intensity factor of the Fe₄₀Ni₄₀B₂₀ amorphous metallic ribbons 20 μm thick were measured in the temperature range 4.2–300 K and at deformation rates from 3.3×10⁻⁶ to 1.25×10⁻³ m⁻¹ with the aim to obtain more information on the condition for the onset and development of the inhomogeneous plastic deformation and fracture.     

Efficient and accurate approach for powder compaction problems

 In this paper, a new approach for powder cold compaction simulations is presented. A density-dependent plastic model within the framework of finite strain multiplicative hyperelastoplasticity is used to describe the highly nonlinear material behaviour; the Coulomb dry friction model is used to capture friction effects at die-powder contact; and an Arbitrary Lagrangian–Eulerian (ALE) formulation is used to avoid the (usual) excessive distortion of Lagrangian meshes caused by large mass fluxes. Several representative examples, involving structured and unstructured meshes are simulated. The results obtained agree with the experimental data and other numerical results reported in the literature. It is shown that, contrary to other Lagrangian and adaptive h-remeshing approaches recently reported for this type of problems, the present approach verifies the mass conservation principle with very low relative errors (less than 1% in all ALE examples and exactly in the pure Lagrangian examples). Moreover, thanks to the use of an ALE formulation and in contrast with other simulations, the presented density distributions do not present spurious oscillations. Received: 20 March 2002 / Accepted: 15 October 2002 The partial financial support of the Ministerio de Ciencia y Tecnología (grant number DPI 2001-2204) is gratefully acknowledged.