Degradative chain transfer in vinyl acetate polymerizations using toluene as solvent

In this work, we propose that retardation in vinyl acetate polymerization rate in the presence of toluene is due to degradative chain transfer. The transfer constant to toluene (C_trs) determined using the Mayo method is equal to 3.8 × 10^?3, which is remarkably similar to the value calculated from the rate data, assuming degradative chain transfer (2.7 × 10^?3). Simulations, including chain‐length‐dependent termination, were carried out to compare our degradative chain transfer model with experimental results. The conversion–time profiles showed excellent agreement between experiment and simulation. Good agreement was found for the M_n data as a function of conversion. The experimental and simulation data strongly support the postulate that degradative chain transfer is the dominant kinetic mechanism. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3620–3625, 2007     

Poly(L‐lysine) and clay nanocomposite with desired matrix secondary structure: Effects of polypeptide molecular weight

Nanocomposites (NC) were formed using cationic poly(L ‐lysine) (PLL), a semicrystalline polypeptide, that was reinforced by sodium montmorillonite (MMT) clay via solution intercalation technique. By varying solution conditions such as pH, temperature, and polypeptide concentration in the presence of clay platelets, the secondary structure of PLL was controllably altered into α‐helical, β‐sheet, and random coil. The high molecular weight polypeptide shows a strong propensity to fold into the β‐sheet structure when cast as films, irrespective of the initial secondary structure in solution. Nanocomposite local morphology confirms intercalated MMT platelets with PLL over a wide range of compositions. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 45: 239–252, 2007.     

Diblock copolymers based on allyl methacrylate: Synthesis,characterization, and chemical modification

Different diblock copolymers constituted by one segment of a monomer supporting a reactive functional group, like allyl methacrylate (AMA), were synthesized by atom transfer radical polymerization (ATRP). Bromo‐terminated polymers, like polystyrene (PS), poly(methyl methacrylate) (PMMA), and poly(butyl acrylate) (PBA) were employed as macroinitiators to form the other blocks. Copolymerizations were carried out using copper chloride with N,N,N′,N″,N″‐pentamethyldiethylenetriamine (PMDETA) as the catalyst system in benzonitrile solution at 70 °C. At the early stage, the ATRP copolymerizations yielded well‐defined linear block copolymers. However, with the polymerization progress a change in the macromolecular architecture takes place due to the secondary reactions caused by the allylic groups, passing to a branched and/or star‐shaped structure until finally yielding gel at monomer conversion around 40% or higher. The block copolymers were characterized by means of size exclusion chromatography (SEC), ¹H NMR spectroscopy, and differential scanning calorimetry (DSC). In addition, one of these copolymers, specifically P(BA‐b‐AMA), was satisfactorily modified through osmylation reaction to obtain the subsequent amphiphilic diblock copolymer of P(BA‐b‐DHPMA), where DHPMA is 2,3‐dihydroxypropyl methacrylate; demonstrating the feasibility of side‐chain modification of the functional obtained copolymers. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 3538–3549, 2007     

Aeolian Tones of a Honeycomb Lattice Cell

Aeroacoustic resonant oscillations (aeolian tones) are studied for flow past two plates forming a cross in a square cross section channel. Possible oscillation modes are classified on the basis of admissible symmetry groups and the existence of the modes is proved. The infinite linear system of equations for these modes obtained by the sewing method was simplified and studied numerically. Curves of eigenfrequency versus plate length are constructed. The form of the eigenfunctions is studied.     

Scientific heritage of Boris Lukich Laptev (4/23/05–1/15/89)

Biographical information on the eminent Soviet geometer Boris Lukich Laptev (4/23/05–1/15-89) is given as well as a survey of his research in the areas of differential geometry and history of mathematics.Translated from Itogi Nauki i Tekhniki, Seriya Problemy Geometrii, Vol. 21, pp.27–42, 1989.     

Lieb-thirring integral inequalities and sharp bounds for the dimension of the attractor of the Navier-Stokes equations with friction

A two-dimensional Navier-Stokes system with friction is considered in a large rect-angular periodic domain with area on the order of α^?1, α → 0. Bounds for the dimension of the attractor are obtained, which are sharp both as α → 0 and v → 0, where v is the viscosity coefficient.     

Influence of barrier parameters on tunneling in ferromagnet-insulator-ferromagnet contacts

The contribution of electrons moving at large angles to the barrier junction plane to the tunnel current is calculated. This contribution turns out to be small only if the Fermi energy of the electrons equals several electron volts. Otherwise, specifically, when the Fermi energy is no higher than 1–2 eV, this contribution dominates in high and thin potential barriers. It is found that the tunnel magnetic resistance in ferromagnet-insulator-ferromagnet contacts correlates with this contribution. It is this correlation that is responsible for a decrease in this contribution as the potential barriers get lower and thicker.     

Method of linear prediction in the ultrasonic spectroscopy of rock

The possibility of using the resonant acoustic spectroscopy method for testing the internal state of rock is considered. This method can be used for the determination of the concentration of defects and their spatial distribution. A rock specimen with defects is characterized by a high loss of vibrational energy, which leads to the overlapping of the resonant responses. In this case, the complex resonant frequencies are determined as the parameters of a model that describes the measured transfer function of the response of the mechanical system. The linearity of the vibratory system is used as the a priori information for presetting the functional dependences of the model. An algorithm is developed for the determination of the parameters of the resonances in conditions of their partial overlapping. Examples are presented to demonstrate the possibility of analyzing the complex elastic constant tensor of rock by the acoustic spectroscopy method. The proposed method of experimental data processing provides the possibility for the determination of the weak anisotropy that occurs in the velocity of sound because of a partial fracture of rock.