Nuclear forward scattering vs. conventional Mössbauer studies of atomically tailored Eu-based materials

With the decrease in size of devices, rapid characterization of nano-devices is an inevitable necessity. It is shown that Mössbauer spectroscopy using synchrotron radiation from the advanced photon source provides such a tool of investigation. Results are presented and compared for conventional Mössbauer and Nuclear Forward Scattering for ¹⁵¹Eu-doped magnesium sulfide as an example, especially at low concentrations.     

Odd triplet superconductivity in superconductor ferromagnet structures: a survey

We review the main features of odd triplet superconductivity in superconductor-ferromagnet (S/F) structures. We discuss the different types of superconducting condensate that can be experimentally observed and pay special attention to the triplet component induced in a ferromagnet which is in contact with a superconductor. The triplet component is an even function of the momentum and an odd function of the frequency and leads to novel phenomena. PACS 74.78.Fk; 73.23.-b; 74.50.+r; 75.70.-i     

The simulation of molecular and organic devices: a critical review and look at future developments

Molecular devices have lately attracted increased attention due to some appealing features such as their low production cost, flexibility in the substrate choice, possibility of large area deployment, and possibly higher integration capabilities. Starting from a series of results obtained from our groups, we critically review the state-of-the-art in the field of simulation of organic and molecular systems, by analyzing and comparing existing approaches, and looking at the open problems and possible solutions and future developments. PACS 72.80.Le     

On the growth strain origin and stress evolution prediction during oxidation of metals

High temperature oxidation of metals leads to residual stresses in the metal and in the oxide. In this work, we try to predict the evolution of the residual stresses in the growing oxides layers, during isothermal oxidation. The origin of these stresses is based on the microstructural model of Clarke, however, another justification is proposed, assuming a proportional dependence of the growth strain with the oxide layer thickness. Using the mechanics of thin layers, as well as the analysis proposed to describe the growth strain, a system of equations are deduced that predict the stresses evolution with oxidation time. Numerical analysis is performed, leading to a set of theoretical curves.     

ZnS and ZnSe Nanoparticles via Solid-State and Solution Thermolysis of Zinc Silylchalcogenolate Complexes

The thermolysis of the zinc trimethylsilylchalcogenolate complexes (N,N′-tmeda)Zn(ESiMe₃)₂ (E = S, 1; E = Se, 2) and (3,5-Me₂-C₅H₃N)₂Zn(ESiMe₃)₂ (E = S, 3; E = Se, 4) has been investigated. Solid-state thermal decomposition of complexes 1–4 above 250°C results in the formation of hexagonal ZnS and cubic ZnSe, respectively, via the liberation of TMEDA (1–2) or 3,5-lutidine (3–4) and E(SiMe₃)₂. Solid-state or solution thermolysis of these complexes up to 200°C produces nanocrystalline ZnS and ZnSe materials whose surface is protected by either coordinated TMEDA or 3,5-lutidine ligands. The progress of the step-wise solid-state decomposition of these complexes was monitored by thermogravimetric and single differential thermal analysis and volatile decomposition products in both solution and solid-state experiments were identified by GC/MS.Dedicated to Professor Brian F. G. Johnson on the occasion of his retirement.     

Synthesis and comparative solution properties of single‐, twin‐, and triple‐tailed associating ionic polymers based on diallylammonium salts

The cycloterpolymerizations of single‐, twin‐, and triple‐tailed hydrophobes with hydrophilic monomer N,N‐diallyl‐N‐carboethoxymethylammonium chloride and sulfur dioxide afforded a series of cationic polyelectrolytes (CPEs) in excellent yields. These CPEs, upon the acidic hydrolysis of the pendent ester groups, gave the corresponding pH‐responsive cationic acid salts, which, upon a treatment with sodium hydroxide, were converted to polybetaines (PBs), anionic polyelectrolytes (APEs), and PB/APE polymers containing various proportions of zwitterionic (PB) and anionic fractions (APE) in the polymer chain. At a shear rate of 0.36 s⁻¹ at 30 °C, salt‐free water solutions of the CPEs (2 g/dL) containing 8, 4, and 2.67 mol % of the single‐, twin‐, and triple‐tailed hydrophobes (all having 8 mol % octyloxy tails) had apparent viscosity values of 70, 2800, and 396,000 cps, respectively. The PB/APE polymer with a ratio of 33:67 for the zwitterionic and anionic fractions in the polymer chain gave the highest viscosity value. The superior viscosity behavior of the polymers containing the triple‐tailed hydrophobe was attributed to the blocky nature of the comonomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 5480–5494, 2006     

The phase diagram of a single polymer chain: New insights from a new simulation method

We present simulation results for the phase behavior of a single chain for a flexible lattice polymer model using the Wang-Landau sampling idea. Applying this new algorithm to the problem of the homopolymer collapse allows us to investigate not only the high temperature coil–globule transition but also an ensuing crystallization at lower temperature. Performing a finite size scaling analysis on the two transitions, we show that they coincide for our model in the thermodynamic limit corresponding to a direct collapse of the random coil into the crystal without intermediate coil–globule transition. As a consequence, also the many chain phase diagram of this model can be predicted to consist only of gas and crystal phase in the limit of infinite chain length. This behavior is in agreement with findings on the phase behavior of hard-sphere systems with a relatively short-ranged attractive square well. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 2542–2555, 2006     

Nitroxide‐mediated radical polymerization of 2‐(dimethylamino)ethyl acrylate and its sequential block copolymerization with styrene and N‐butyl acrylate

Nitroxide‐mediated radical polymerization (NMRP) of 2‐(dimethylamino)ethyl acrylate (DMAEA) was carried out at 100–120 °C, initiated by MONAMS, an alkoxyamine based on N‐tert‐butyl‐N‐(1‐diethyl phosphono‐2,2‐dimethylpropyl)nitroxide, SG1. Controlled polymerization can be achieved by the addition of free SG1 (the initial molar ratio of SG1 to MONAMS ranged from 0.06 to 0.12), giving a linear first‐order kinetic plot up to 55–70% conversion depending on the reaction conditions. The molecular weights show a near linear increase with conversion; however, they deviate to some extent with theoretical values. SG1‐mediated polymerization of DMAEA at 112 °C is also controlled in organic solvents (N,N‐dimethylformide, anisole, xylene). Polymerization rate increases with increasing solvent polarity. Chain transfer to polymer produces ～1 mol % branches in bulk and 1.2–1.9 mol % in organic solvents, typical of those for acrylates. From poly(styrene) (pS) and poly(n‐butyl acrylate) (pBA) macroinitiators, amphiphilic di‐ and triblock copolymers p(S‐b‐DMAEA), p(DMAEA‐b‐S‐b‐DMAEA), p(BA‐b‐DMAEA), and p(DMAEA‐b‐BA‐b‐DMAEA) were synthesized via NMRP at 110 °C. Polymers were characterized by GPC, NMR, surface tension measurements, and DSC. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 414–426, 2006     

Synthesis and characterization of multiblock copolymers composed of poly(5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one) outer blocks and poly(L‐lactide) inner blocks

Ethylene glycol (EG) initiated, hydroxyl‐telechelic poly(L ‐lactide) (PLLA) was employed as a macroinitiator in the presence of a stannous octoate catalyst in the ring‐opening polymerization of 5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one (MBC) with the goal of creating A–B–A‐type block copolymers having polycarbonate outer blocks and a polyester center block. Because of transesterification reactions involving the PLLA block, multiblock copolymers of the A–(B–A)_n–B–A type were actually obtained, where A is poly(5‐methyl‐5‐benzyloxycarbonyl‐1,3‐dioxan‐2‐one), B is PLLA, and n is greater than 0. ¹H and ¹³C NMR spectroscopy of the product copolymers yielded evidence of the multiblock structure and provided the lactide sequence length. For a PLLA macroinitiator with a number‐average molecular weight of 2500 g/mol, the product block copolymer had an n value of 0.8 and an average lactide sequence length (consecutive C₆H₈O₄ units uninterrupted by either an EG or MBC unit) of 6.1. For a PLLA macroinitiator with a number‐average molecular weight of 14,400 g/mol, n was 18, and the average lactide sequence length was 5.0. Additional evidence of the block copolymer architecture was revealed through the retention of PLLA crystallinity as measured by differential scanning calorimetry and wide‐angle X‐ray diffraction. Multiblock copolymers with PLLA crystallinity could be achieved only with isolated PLLA macroinitiators; sequential addition of MBC to high‐conversion L ‐lactide polymerizations resulted in excessive randomization, presumably because of residual L ‐lactide monomer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6817–6835, 2006