Morphology of homogeneous copolymers of ethylene and 1‐octene. III. Structural changes during heating as revealed by time‐resolved SAXS and WAXD

The structural changes of two linear polyethylenes, LPEs, with different molar mass and of two homogeneous copolymers of ethylene and 1‐octene with comparable comonomer content but different molar mass were monitored during heating at 10 °C per minute using synchrotron radiation SAXS. Two sets of samples, cooled at 0.1 °C per minute and quenched in liquid nitrogen, respectively, were studied. All LPEs display surface melting between room temperature and the end melting temperature, whereas complete melting, according to lamellar thickness, only occurs at the highest temperatures where DSC displays a pronounced melting peak. There is recrystallization followed by isothermal lamellar thickening if annealing steps are inserted. The lamellar crystals of slowly cooled homogeneous copolymers melt in the reverse order of their formation, that is, crystals melt according to their thickness. Quenching creates unstable crystals through the cocrystallization of ethylene sequences with different length. These crystals repeatedly melt and co‐recrystallize during heating. The exothermic heat due to recrystallization partially compensates the endothermic heat due to melting resulting in a narrow overall DSC melting peak with its maximum at a higher temperature than the melting peak of slowly cooled copolymers. With increasing temperature, the crystallinity of quenched copolymers overtakes the one of slowly cooled samples due to co‐recrystallization by which an overcrowding of leaving chains at the crystal surfaces is avoided. © 2000 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 38: 1975–1991, 2000     

Andreev-type states induced by quantum confinement

The properties of a clean superconductor with nanoscale dimensions are governed by quantum confinement of the electrons. This results in a spatially inhomogeneous superconducting condensate and in the formation of new Andreev-type quasiparticle states. These states are mainly located beyond regions where the superconducting condensate is enhanced. A numerical self-consistent solution of the Bogoliubov-de Gennes equations for a cylindrical metallic nanowire shows that these new Andreev-type states decrease the ratio of the energy gap to the critical temperature. The text was submitted by the authors in English.     

DFB lasers with integrated electroabsorption modulator

We present high-performance 1550 nm DFB lasers with butt-coupled, bulk type integrated electroabsorption modulators of good manufacturability and reliability. Key issues in device design are reviewed and the strong influence of the exact detuning between lasing wavelength and modulator bandgap is demonstrated. Fibre-coupled output powers as large as 6 dBm and attenuation efficiencies as high as 12 dB V^–1 are obtained. Butterfly-packaged devices show only 1 dB penalty for 10 Gbit s^–1 NRZ transmission over 50-km standard single-mode fibre (SMF) without the use of an optical amplifier. With an optical booster amplifier, self-phase-modulation in the fibre is exploited and repeaterless 10 Gbit s^–1 transmission is possible over 150-km standard SMF.     

Kinetics of alpha-hydroxy-alkylperoxyl radicals in oxidation processes. HO2*-initiated oxidation of ketones/aldehydes near the tropopause

A comparative theoretical study is presented on the formation and decomposition of alpha-hydroxy-alkylperoxyl radicals, Q(OH)OO* (Q = RR'C:), important intermediates in the oxidation of several classes of oxygenated organic compounds in atmospheric chemistry, combustion, and liquid-phase autoxidation of hydrocarbons. Detailed potential energy surfaces (PESs) were computed for the HOCH2O2* <==>HO2* + CH2O reaction and its analogues for the alkyl-substituted RCH(OH)OO* and R2C(OH)OO* and the cyclic cyclo-C6H10(OH)OO*. The state-of-the-art ab initio methods G3 and CBS-QB3 and a nearly converged G2M//B3LYP-DFT variant were found to give quasi-identical results. On the basis of the G2M//B3LYP-DFT PES, the kinetics of the approximately equal to 15 kcal/mol endothermal alpha-hydroxy-alkylperoxyl decompositions and of the reverse HO2*+ ketone/aldehyde reactions were evaluated using multiconformer transition state theory. The excellent agreement with the available experimental (kinetic) data validates our methodologies. Contrary to current views, HO2* is found to react as fast with ketones as with aldehydes. The high forward and reverse rates are shown to lead to a fast Q(OH)OO* <==>HO2* + carbonyl quasi-equilibrium. The sizable [Q(OH)OO*]/[carbonyl] ratios predicted for formaldehyde, acetone, and cyclo-hexanone at the low temperatures (below 220 K) of the earth's tropopause are shown to result in efficient removal of these carbonyls through fast subsequent Q(OH)OO* reactions with NO and HO2*. IMAGES model calculations indicate that at the tropical tropopause the HO2*-initiated oxidation of formaldehyde and acetone may account for 30% of the total removal of these major atmospheric carbonyls, thereby also substantially affecting the hydroxyl and hydroperoxyl radical budgets and contributing to the production of formic and acetic acids in the upper troposphere and lower stratosphere. On the other hand, an RRKM-master equation analysis shows that hot alpha-hydroxy-alkylperoxyls formed by the addition of O(2) to C(1)-, C(2)-, and C(3)-alpha-hydroxy-alkyl radicals will quasi-uniquely fragment to HO2* plus the carbonyl under all atmospheric conditions.     

Role of kinetic effects on the polarization current around a magnetic island

The polarization current due to a magnetic island rotating in a tokamak plasma is believed to play a central role in the initial evolution of the neoclassical tearing mode. Monte Carlo delta f simulations are performed which also cover a parameter range that is not amenable to analytic treatment but is relevant to experiments. It is shown that the polarization current can change sign when the island rotation frequency is of the order of the ion parallel streaming around the island. Moreover, the current is reduced when the island width is of the order of the ion banana width. Finally, the transition to the enhanced high-collisionality regime is shown to occur for collision frequencies higher than those typical of today's experiments.     

Slow proton andΔ ++ production inK + p interactions at 70 GeV/c

The inclusive inelastic processesK ⁺ p→pX ⁺ andK ⁺ p→Δ ⁺⁺ X ⁰ are studied at an incident momentum of 70 GeV/c. The data comes from the Big European Bubble Chamber BEBC filled with hydrogen, exposed to an rf reparatedK ⁺ beam at the CERN SPS accelerator. The inclusive cross section for protons with laboratory momentump _LAB≦1.2 GeV/c is equal to (6.1±0.1) mb. InclusiveΔ ⁺⁺-production is studied for |t _{p, Δ}|<1.0(GeV/c)². Comparisons are made with otherK ⁺ p data and withpp data at 69 GeV/c. Evidence is found for Pomeron exchange at the beam vertex both for slow proton andΔ ⁺⁺-production as well as for absorptive pion exchange at the (p,Δ ⁺⁺) vertex.     

Influence of strain on the Stark effect in InP/GaInP quantum discs

In InP/GaInP quantum discs it is shown that strain induces a type I to type II transition with increasing thickness of the disc. When an external electric field is applied along the cylindrical axis of the disc, the exciton energy exhibits a Stark effect, which for the light hole exciton becomes linear even for a small field value, while for the heavy hole it is more quadratic.     

L'utilisation d'orbitales localisées dans l'étude théorique des molécules

The five simplest alkanes have been studied in terms of localized orbitals. The transferability of the Fock matrix elements in this basis allows us to elaborate a simple parametric procedure adapted for saturated hydrocarbons. Some original applications of this procedure are performed.