Chemically controlled pattern formation in phase-separating materials

Summary The role of chemical reactions in the selection of patterns in phase-separating mixtures is presented. Linearized theory and computer simulation show that the initial long-wavelength instability characteristic of spinodal decomposition is suppressed by chemical reactions, which restrict domain growth to intermediate length scales even in the late stages of phase separation. Our findings suggest that chemical reactions may provide a novel way to stabilize and tune the steady-state morphology of phase-separating materials. Paper presented at the I International Conference on Scaling Concepts and Complex Fluids, Copanello, Italy, July 4–8, 1994.     

Deactivation reactions in the modeled 2,2,6,6‐tetramethyl‐1‐piperidinyloxy‐mediated free‐radical polymerization of styrene: A comparative study with the 2,2,6,6‐tetramethyl‐1‐piperidinyloxy/acrylonitrile system

The competitiveness of the combination and disproportionation reactions between a 1‐phenylpropyl radical, standing for a growing polystyryl macroradical, and a 2,2,6,6‐tetramethyl‐1‐piperidinyloxy (TEMPO) radical in the nitroxide‐mediated free‐radical polymerization of styrene was quantitatively evaluated by the study of the transition geometry and the potential energy profiles for the competing reactions with the use of quantum‐mechanical calculations at the density functional theory (DFT) UB3‐LYP/6‐311+G(3df, 2p)//(unrestricted) Austin Model 1 level of theory. The search for transition geometries resulted in six and two transition structures for the radical combination and disproportionation reactions, respectively. The former transition structures, mainly differing in the out‐of‐plane angle of the N? O bond in the transition structure TEMPO molecule, were correlated with the activation energy, which was determined to be in the range of 8.4–19.4 kcal mol^?1 from a single‐point calculation at the DFT UB3‐LYP/6‐311+G(3df, 2p)//unrestricted Austin Model 1 level. The calculated activation energy for the disproportionation reaction was less favorable by a value of more than 30 kcal mol^?1 in comparison with that for the combination reaction. The approximate barrier difference for the TEMPO addition and disproportionation reaction was slightly smaller for the styrene polymerization system than for the acrylonitrile polymerization system, thus indicating that a β‐proton abstraction through a TEMPO radical from the polymer backbone could diminish control over the radical polymerization of styrene with the nitroxide even more than in the latter system. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 232–241, 2007     

Melt rheology of polylactide/montmorillonite nanocomposites

In this article, the linear and nonlinear shear rheological behaviors of polylactide (PLA)/clay (organophilic‐montmorillonite) nanocomposites (PLACNs) were investigated by an Advanced Rheology Expanded System rheometer. The nanocomposites were prepared by master batch method using a twin‐screw extruder with poly(ε‐caprolactone) (PCL) as a compatibilizer. The presence of org‐MMT leads to obvious pseudo‐solid‐like behaviors of nanocomposite melts. The behaviors caused by the formation of a “percolating network” derived from the reciprocity among the strong related sheet particles. Therefore, the storage moduli, loss moduli, and dynamic viscosities of PLACNs show a monotonic increase with MMT content. Nonterminal behaviors exists in PLACNs nanocomposites. Besides the PLACNs melts show a greater shear thinning tendency than pure PLA melt because of the preferential orientation of the MMT layers. Therefore, PLACNs have higher moduli but better processibility compared with pure PLA. © 2007 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 3189–3196, 2007     

Radiation heat transfer in axisymmetric quartz glass tubes

A mathematical model is proposed to describe the heat transfer in quartz glass axisymmetric tubes. Heat is transferred inside the glass by radiation and conduction. Scattering of thermal radiation inside the glass is ignored. At the boundaries of the tube the radiative intensity is specularly reflected. The spectral dependent radiative intensity and the temperature distribution inside the tube are determined. The model is applied to simulate the cooling process of a quartz glass tube. The calculated temperature is in agreement with that obtained from an experiment. Furthermore, steady-state temperature distributions in quartz glass tubes of different lengths have been determined.     

Zur Synthese und Struktur von K3N

Synthesis and Structure of K₃N Two phases in the binary system K/N have been obtained via co‐deposition of potassium and nitrogen onto polished sapphire at 77 K and subsequent heating to room temperature. The powder diffraction pattern of one of these phases can be satisfactorily interpreted by assuming the composition K₃N, and the anti‐TiI₃ structure‐type, which is also adopted by Cs₃O. The resulting hexagonal lattice constants are: a = 779.8(2), c = 759.2(9) pm, Z = 2, P6₃/mcm. Comparison with possible structures of K₃N generated by computational methods and refined at Hartree‐Fock‐ and DFT level, reveals that the energetically most favoured structure has not formed (presumable Li₃P‐type), but instead one of those with very low density. In this respect, the findings for K₃N are analogous to the results on Na₃N. The thermal evolution of the deposited starting mixture has been investigated. Hexagonal K₃N transforms to another K/N phase at 233 K. Its XRD can be fully indexed resulting in an orthorhombic cell a = 1163, b = 596, c = 718 pm. Decomposition leaving elemental potassium as the only residue occurs at 263 K.     

Solid-phase oxidative halodecarboxylation of β-arylacrylic acids with the ceric ammonium nitrate—alkali halide system

The solid-phase oxidation of cinnamic, 4-methoxy- and 3,4-dimethoxycinnamic acids with Ce(NH₄)₂(NO₃)₆—MHal system leads to β-halostyrenes. Similar procedure in the absence of a metal halide results in a cleavage of the C=C bond giving the corresponding benzaldehydes. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 114–118, January, 2008.     

Effect of Ga doping on magneto-transport properties in colossal magnetoresistive La0.7Ca0.3Mn1−xGaxO3 (0<x<0.1)

Samples of La_0.7Ca_0.3Mn_1−xGa_xO₃ with x=0, 0.025, 0.05 and 0.10 were prepared by standard solid-state reaction. They were first characterized chemically, including the microstructure. The magnetic properties and various transport properties, i.e. the electrical resistivity, magnetoresistivity (for a field below 8 T), thermoelectric power and thermal conductivity measured each time on the same sample, are reported. The markedly different behaviour of the x=0.1 sample from those with a smaller Ga content, is discussed. The dilution of the Mn³⁺/Mn⁴⁺ interactions with Ga doping considerably reduces the ferromagnetic double exchange interaction within the manganese lattice leading to a decrease of the Curie temperature. The polaron binding energy varies from 224 to 243 meV with increased Ga doping.     

Study of thermal aging effect on space charge in poly(methyl methacrylate)

Charges evolution in poly(methyl methacrylate) (PMMA) samples under thermal aging effect has been studied by means of two complementary techniques, thermal step method (TSM) and thermally stimulated depolarization current (TSDC). For the first method, measurements reveal that injected charges, whose quantity is found depending on the number of applied temperature cycles, remain close to the surface sample. TSDC measurements have been carried out for different temperatures ranging from 25 °C to 140 °C. Three distinguishable dipolar relaxations (β₁, β₂ and α) have been highlighted. In the same way, the presence of polarization and injected charges has been confirmed. In support of electric characterization, X-ray reflectometry has been used. The obtained results equally emphasized the thermal aging effect on the material.     

Two types of the effective mass divergence and the Grüneisen ratio in heavy-fermion metals

The behavior of the specific heat c_p, effective mass M^*, and the thermal expansion coefficient of a Fermi system located near the fermion condensation quantum phase transition (FCQPT) is considered. We observe the first type behavior if the system is close to FCQPT: the specific heat , , while the thermal expansion coefficient . Thus, the Grüneisen ratio Γ(T)=/c_p does not diverges. At the transition region, where the system passes over from the non-Fermi liquid to the Landau Fermi liquid, the ratio diverges as . When the system becomes the Landau Fermi liquid, Γ(T,r)∝1/r, with r being a distance from the quantum critical point. Provided the system has undergone FCQPT, the second type takes place: the specific heat behaves as , M^*∝1/T, and =a+bT with a,b being constants. Again, the Grüneisen ratio diverges as .