Microwave‐improved polymerization of ϵ‐caprolactone initiated by carboxylic acids

The ring‐opening polymerization of ε‐caprolactone (ε‐CL), initiated by carboxylic acids such as benzoic acid and chlorinated acetic acids under microwave irradiation, was investigated; with this method, no metal catalyst was necessary. The product was characterized as poly(ε‐caprolactone) (PCL) by ¹H NMR spectroscopy, Fourier transform infrared spectroscopy, ultraviolet spectroscopy, and gel permeation chromatography. The polymerization was significantly improved under microwave irradiation. The weight‐average molecular weight (M_w) of PCL reached 44,800 g/mol, with a polydispersity index [weight‐average molecular weight/number‐average molecular weight (M_w/M_n)] of 1.6, when a mixture of ε‐CL and benzoic acid (25/1 molar ratio) was irradiated at 680 W for 240 min, whereas PCL with M_w = 12,100 and M_w/M_n = 4.2 was obtained from the same mixture by a conventional heating method at 210 °C for 240 min. A degradation of the resultant PCL was observed during microwave polymerization with chlorinated acetic acids as initiators, and this induced a decrease in M_w of PCL. However, the degradation was hindered by benzoic acid at low concentrations. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 13–21, 2003     

Crack path instabilities in DCDC experiments in the low speed regime

We studied the low speed fracture regime (10⁻⁴-10⁻⁹ m s⁻¹) in different glassy materials (soda-lime glass, glass ceramics) with variable but controlled length scale of heterogeneity. The chosen mechanical system enabled us to work in pure mode I (tensile) and at a fixed load on double cleavage drilled compression specimen. The internal residual stresses of studied samples were carefully relaxed by appropriate thermal treatment. By means of optical and atomic force microscopy techniques fracture surfaces have been examined. We have shown for the first time that the crack front line underwent an out-of-plane oscillating behavior as a result of a reproducible sequence of instabilities. The wavelength of such a phenomenon is in the micrometer range and its amplitude in the nanometer range. These features were observed for different glassy materials providing that a typical length scale characterizing internal heterogeneities was lower than a threshold limit estimated to few nanometers. This effect is the first clear experimental evidence of crack path instabilities in the low speed regime in a uniaxial loading experiment. This phenomenon has been interpreted by referring to the stability criterion for a straight crack propagation as presented by Adda-Bedia et al. [Phys. Rev. Lett. 76 (1996) 1497].     

A study of the atmospheric lead pollution in Seville, Spain. Influence of meteorology and traffic, and relationship with other traffic-generated pollutants

A study of the atmospheric pollution by suspended particulate lead in the city of Seville, Spain, was carried out during the period between March 1983 and February 1984. The results obtained from seven sampling stations allowed us to study the site to site variations; there are two locations with average annual concentrations higher than 2 micrograms X m-3. In one station, the meteorological and traffic effects and relationship with other traffic-related pollutants, were investigated. The regression analyses performed on the average monthly data have shown an inverse correlation with wind speed and temperature and a direct correlation with carbon monoxide and smoke concentrations, but no significant correlation was found with the lead deposition levels.     

Elastoplastic torsion theory for whisker crystals

Translated from Zhurnal Prikladnoi Mekhaniki i Tekhnicheskoi Fiziki, No. 2, pp. 127–134, March–April, 1991.     

A generalization of the H-theorem to steady non-equilibrium states. Part 1: A basic decomposition and the linear case

A generalized relative entropy functional is associated to the evolution of gas in a container with (generally) non-uniform boundary data. A decomposition for its rate in ‘bulk’ and in ‘boundary’ terms is given; for the linear case both have a definite sign. The relation with the strong L₁ stability is pointed out.     

Asymptotics of Dirichlet Spectrum on Some Class of Noncompact Domains

We investigate the asymptotic behaviour of the counting function of Dirichlet eigenvalues on some class of noncompact manifolds. We prove that in cases when the volume or the perimeter (the volume of the boundary) of the manifold is infinite, some additional (nonclassical) terms appear in the precise asymptotics. The coefficients at the classical terms in those are regularized in some special way volume (resp. perimeter) of the manifold.     

Kinetics of Hydrogen Peroxide Decomposition in Guaiacol Solution, Catalyzed by Hexacyanoferrate(II)

The kinetics of hydrogen peroxide decomposition in a guaiacol solution, catalyzed by potassium hexacyanoferrate(II), were studied. The reaction mainly follows the pathway of guaiacol hydroxylation. The reaction order is 1 with respect to H₂O₂, 0.5 with respect to hexacyanoferrate, and from 0.4 to 0 with respect to guaiacol (the latter parameter decreases with increasing guaiacol concentration). The apparent activation energy is 105 kJ mol^{- 1}. A kinetic scheme of the process was proposed. An expression consistent with the experiment was obtained for the rate of hydrogen peroxide decomposition in the presence of guaiacol, catalyzed by hexacyanoferrate(II).