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].     

20-relative neighborhood graphs are hamiltonian

For any two points p and q in the Euclidean plane, define LUN_pq = { v | v ∈ R², d_pv < d_pq and d_qv < d_pq}, where d_uv is the Euclidean distance between two points u and v . Given a set of points V in the plane, let LUN_pq(V) = V ∩ LUN_pq. Toussaint defined the relative neighborhood graph of V, denoted by RNG(V) or simply RNG, to be the undirected graph with vertices V such that for each pair p,q ∈ V, (p,q) is an edge of RNG(V) if and only if LUN_pq (V) = ?. The relative neighborhood graph has several applications in pattern recognition that have been studied by Toussaint. We shall generalize the idea of RNG to define the k-relative neighborhood graph of V, denoted by kRNG(V) or simply kRNG, to be the undirected graph with vertices V such that for each pair p,q ∈ V, (p,q) is an edge of kRNG(V) if and only if | LUN_pq(V) | < k, for some fixed positive number k. It can be shown that the number of edges of a kRNG is less than O(kn). Also, a kRNG can be constructed in O(kn₂) time. Let E_c = {e_pq| p ∈ V and q ∈ V}. Then G_c = (V,E_c) is a complete graph. For any subset F of E_c, define the maximum distance of F as max_epq∈Fd_pq. A Euclidean bottleneck Hamiltonian cycle is a Hamiltonian cycle in graph G_c whose maximum distance is the minimum among all Hamiltonian cycles in graph G_c. We shall prove that there exists a Euclidean bottleneck Hamiltonian cycle which is a subgraph of 20RNG(V). Hence, 20RNGs are Hamiltonian.     

Finite element computations of two-dimensional arterial flow in the presence of a transverse magnetic field

A finite element solution of the Navier-Stokes equations for steady flow under the magnetic effect through a double-branched two-dimensional section of a three-dimensional model of the canine aorta is discussed. The numerical scheme involves transforming the physical co-ordinates to a curvilinear boundary-fitted co-ordinate system. The shear stress at the wall is calculated for a Reynolds number of 1000 with the branch-to-main aortic flow rate ratio as a parameter. The results are compared with earlier works involving experimental data and found to be in reasonable qualitative agreement. The steady flow, shear stress and branch flow under the effect of a magnetic field have been discussed in detail.     

Microstructural assessment of InN-on-GaN films grown by plasma-assisted MBE

The structural properties of InN thin films, grown by rf plasma-assisted molecular beam epitaxy on Ga-face GaN/Al₂O₃(0001) substrates, were investigated by means of conventional and high resolution electron microscopy. Our observations showed that a uniform InN film of total thickness up to 1 μm could be readily grown on GaN without any indication of columnar growth. A clear epitaxial orientation relationship of , was determined. The quality of the InN film was rather good, having threading dislocations as the dominant structural defect with a density in the range of 10⁹–10¹⁰ cm⁻². The crystal lattice parameters of wurtzite InN were estimated by electron diffraction analysis to be a=0.354 nm and c=0.569 nm, using Al₂O₃ as the reference crystal. Heteroepitaxial growth of InN on GaN was accomplished by the introduction of a network of three regularly spaced misfit dislocation arrays at the atomically flat interface plane. The experimentally measured distance of misfit dislocations was 2.72 nm. This is in good agreement with the theoretical value derived from the in-plane lattice mismatch of InN and GaN, which indicated that nearly full relaxation of the interfacial strain between the two crystal lattices was achieved.     

Numerical study of simultaneous natural convection heat transfer from both surfaces of a uniformly heated thin plate with arbitrary inclination

 Numerical studies were conducted to investigate the natural convection heat transfer around a uniformly heated thin plate with arbitrary inclination in an infinite space. The numerical approach was based on the finite volume technique with a nonstaggered grid arrangement. For handling the pressure–velocity coupling the SIMPLE-algorithm was used. QUICK scheme and first order upwind scheme were employed for discretization of the momentum and energy convective terms respectively. Plate width and heating rate were used to vary the modified Rayleigh number over the range of 4.8×10⁶ to 1.87×10⁸. Local and average heat transfer characteristics were compared with regarding to the inclination angle. The empirical expressions for local and average Nusselt number were correlated. It has been found that for inclination angle less than 10^∘, the flow and heat transfer characteristics are complicated and the average Nusselt number can not be correlated by one equation while for inclination angle larger than 10^∘, the average Nusselt number can be correlated into an elegant correlation. Received on 18 April 2001 / Published online: 29 November 2001     

A rapid and sensitive extractive spectrophotometric determination of copper(II) in pharmaceutical and environmental samples using benzildithiosemicarbazone.

Benzildithiosemicarbazone (BDTSC) is proposed as a sensitive and selective analytical reagent for the extractive spectrophotometric determination of copper(II). BDTSC reacts with copper(II) in the pH range 1.0-7.0 to form a yellowish complex. Beer's law is obeyed in the concentration range 0.5-0.4 microg cm(-3). The yellowish Cu(II)-BDTSC complex in chloroform shows a maximum absorbance at 380 nm, with molar absorptivity and Sandell's sensitivity values of 1.63 x 10(4) dm3 mol(-1) cm(-1) and 0.00389 microg cm(-2), respectively. A repetition of the method is checked by finding the relative standard deviation (RSD) (n = 10), which is 0.6%. The composition of the Cu(II)-BDTSC complex is established as 1:1 by slope analysis, molar ratio and Asmus' methods. An excellent linearity with a correlation coefficient value of 0.98 is obtained for the Cu(II)-BDTSC complex. The instability constant of the complex calculated from Edmond and Birnbaum's method is 7.70 x 10(-4) and that of Asmus' method is 7.66 x 10(-4), at room temperature. The method is successfully employed for the determination copper(II) in pharmaceutical and environmental samples. The reliability of the method is assured by analyzing the standard alloys (BCS 5g, 10g, 19e, 78, 32a, 207 and 179) and by inter-comparison of experimental values, using an atomic absorption spectrometer.