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     

Diffusion of 99Tc in granite under aerobic and anoxic conditions

Summary  Vezetéknév     

Ionic conductivity of epitactic MBE-grown BaF2 films

We studied parallel conductivities of pure BaF₂ films with thicknesses ranging from 35 to 300 nm, epitaxially grown on Al₂O₃(0 1 2) substrates by molecular beam epitaxy technique. The overall conductivities of the films are found to increase with decreasing thickness. The detailed investigation of the overall conductance as a function of the thickness permits the deconvolution of bulk and boundary effects, the latter being attributed to distinct space charge effects in the interface between BaF₂ film and Al₂O₃ substrate. The (extrinsic) Debye length (λ) is estimated to be about 8 nm at T=593 K, which corresponds to an impurity content of 10¹⁸/cm³ (singly ionized dopant assumed). This is consistent with the fact that we observed a constant boundary contribution for all investigated films (film thickness >4λ). It is also consistent with the Debye length observed in a previous report on CaF₂/BaF₂ heterolayers fabricated by the same technique, in which the low temperature enhancement was also attributed to space charges in BaF₂ [Nature 408 (2000) 946]. Only at low temperatures (below 370 °C), the conductance seems to be influenced by strain effect.     

Thermal degradation of two liquid fuels and detonation tests for pulse detonation engine studies

The use of liquid fuels such as kerosene is of interest for the pulse detonation engine (PDE). Within this context, the aim of this work, which is a preliminary study, was to show the feasibility to initiate a detonation in air with liquid-fuel pyrolysis products, using energies and dimensions of test facility similars to those of PDEs. Therefore, two liquids fuels have been compared, JP10, which is a synthesis fuel generally used in the field of missile applications, and decane, which is one of the major components of standard kerosenes (F-34, Jet A1, ...). The thermal degradation of these fuels was studied with two pyrolysis processes, a batch reactor and a flow reactor. The temperatures varied from 600°C to 1,000°C and residence times for the batch reactor and the flow reactor were, respectively, between 10–30 s and 0.1–2 s. Subsequently, the detonability of synthetic gaseous mixtures, which was a schematisation of the decomposition state after the pyrolysis process, has been studied. The detonability study, regarding nitrogen dilution and equivalence ratio, was investigated in a 50 mm-diameter, 2.5 m-long detonation tube. These dimensions are compatible with applications in the aircraft industry and, more particularly, in PDEs. Therefore, JP10 and decane were compared to choose the best candidate for liquid-fuel PDE studies. This paper was based on work that was presented at the 20th International Colloquium on the Dynamics of Explosions and Reactive Systems, Montreal, Canada, July 31 – August 5, 2005.     

Nanostructures in calcia stabilized hafnia thin films observed by PAC as a function of temperature

The hyperfine quadrupole interaction at Hf sites in films and powders of 14 mol% CaO–HfO₂ and 20 mol% CaO–HfO₂ has been determined as a function of temperature. Results indicate the formation of a cubic solid solution and other microstructures assigned to the ?₁ (CaHf₄O₉) and ?₂ (Ca₆Hf₁₉O₄₄) phases. Dynamical effects on the electric field gradient reveal the existence of oxygen vacancies movements in the solid solution. The thermal behavior of the relaxation constant observed in films allowed the determination of activation energies of 0.54 eV and 0.70 eV for the 14 mol% and 20 mol% CaO doped hafnias, respectively. The influence of the microdomains and the stability of the cubic solid solution are discussed.     

Spin dynamics investigated by EPR in the paramagnetic regime of La2/3Ca1/3Mn1−x Me x O3 (Me = Al, In) manganites

We report an electron paramagnetic resonance (EPR) investigation of the spin dynamics in the paramagnetic regime of the colossal magnetoresistive manganites La_2/3Ca_1/3Mn_1?x Me _x O₃ (Me=Al, In;x≤0.05). The temperature dependences of the EPR linewidth and integral intensity have been analyzed in terms of the bottleneck spin relaxation and small-polaron hopping models. The exchange coupling integral between Mn³⁺ and Mn⁴⁺ ions and the polaron activation energy decrease with increasing doping level. A discussion is given concerning the factors which could explain the observed changes.     

Integrable semiclassical deformations of general algebraic curves and associated conservation laws

Based on the Lenard relations, we completely classify integrable deformations of general algebraic curves. We construct the general solution of the Lenard relation from the invariance condition with respect to an element of the Galois group of the curve. We give some examples and also some associated conservation laws. __________ Translated from Teoreticheskaya i Matematicheskaya Fizika, Vol. 151, No. 3, pp. 458–469, June, 2007.     

Fabrication of bamboo-shaped GaN nanorods

Bamboo-shaped GaN nanorods were formed through a simple sublimation method. They were characterized by means of X-ray powder diffraction (XRD), transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HRTEM) and selected-area electron diffraction (SAED). The TEM image showed that the nanorods were bamboo-like. XRD, HRTEM and SAED patterns indicated that the nanorods were single-crystal wurtzite GaN. Received: 8 January 2001 / Accepted: 28 April 2001 / Published online: 20 December 2001