Synthesis of microspheres with microphase‐separated shells

Novel structural microspheres of the Janus type, with microphase‐separated polystyrene (PS) and poly(tert‐butyl methacrylate) (PBMA) shells and crosslinked poly(2‐vinyl pyridine) (PVP) cores, were synthesized with the crosslinking of PVP spherical domains in poly(styrene‐block‐2‐vinyl pyridine‐block‐tert‐butyl methacrylate) ABC triblock terpolymer film with PS/PBMA lamellae–PVP spherical structures. For the formation of lamellae‐sphere structures, toluene, which was a selective solvent for the ABC triblock terpolymer, was used. With the crosslinking of PVP spheres in the microphase‐separated film with 1,4‐diiodobutane gas, the microphase structure of the terpolymer was fixed, and microspheres composed of microphase‐separated PS and PBMA shells and P2VP cores were obtained. The size distribution of the purified microspheres was narrow. The characteristics of the microspheres and their aggregation behaviors in selective solvents were investigated by transmission electron microscopy and light scattering methods. © 2000 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 38: 2091–2097, 2000     

Rupture and regeneration of colloidal crystals as studied by two-dimensional ultra-small-angle X-ray scattering

The structure of colloidal crystals of silica particles in water was studied by using the two-dimensional (2D) ultra-small-angle X-ray scattering (USAXS) technique. By violent shaking of the dispersion, large (body-centered cubic, bcc) crystals were broken into microcrystals while the lattice structure and lattice constant were preserved. The 2D-USAXS profiles revealed that the [111] direction of bcc microcrystals was parallel to the capillary axis and their orientational distribution with respect to the capillary axis was random. While a prepeak was observed in the one-dimensional USAXS measurements, no such peak was detected by the 2D-USAXS technique. The prepeak was concluded to be due to {110} being rotated by 54.7 degrees (the angle between [001] and [111]) from the capillary axis. The diffraction from the plane was out of the horizontal plane and was observed at a lower angle as a prepeak by detector scanning in the horizontal direction.     

Modeling of incorporation of oxygen and carbon impurities into multicrystalline silicon ingot during one-directional growth

We propose a simple numerical model for incorporation of oxygen and carbon impurities into multicrystalline Si during one-directional crystal growth in comparison with experimental results. The model includes parameters that are oxygen and carbon concentrations in the melt in the beginning of the growth, carbon flux form the atmosphere, oxygen fluxes from the crucible and to the atmosphere. Variation of oxygen and carbon concentrations in multicrystalline Si ingots with a diameter of 30 cm and a height of 7.5 cm solidified one-directionally was measured by infra red absorption spectroscopy at room temperature. By fitting the numerical results on the experimental results, the parameters were evaluated. In the modeling we found fruitful suggestions for suppressing and controlling the oxygen and carbon concentrations in multicrystalline Si for solar cells.     

"Click"-modification of a functionalized poly(3,4-ethylenedioxythiophene) (PEDOT) soluble in organic solvents

A PEDOT-based conductive copolymer soluble in organic solvents was synthesized electrochemically using dihexyl-EDOT and azidomethyl-EDOT as monomers and was successfully post-functionalized by "click"-cycloaddition reaction with a functionalized terminal alkyne under mild heterogeneous conditions.     

Double-Pullback Transitions and Coalgebraic Loose Semantics for Graph Transformation Systems

The classical algebraic approach to graph transformation is a mathematical theory based on categorical techniques with several interesting applications in computer science. In this paper, a new semantics of graph transformation systems (in the algebraic, double-pushout (DPO) approach) is proposed in order to make them suitable for the specification of concurrent and reactive systems. Classically, a graph transformation system comes with a fixed behavioral interpretation. Firstly, all transformation steps are intended to be completely specified by the rules of the system, that is, there is an implicit frame condition: it is assumed that there is a complete control about the evolution of the system. Hence, the interaction between the system and its (possibly unknown) environment, which is essential in a reactive system, cannot be modeled explicitly. Secondly, each sequence of transformation steps represents a legal computation of the system, and this makes it difficult to model systems with control. The first issue is addressed by providing graph transformation rules with a loose semantics, allowing for unspecified effects which are interpreted as activities of the environment. This is formalized by the notion of double-pullback transitions, which replace (and generalize) the well-known double-pushout diagrams by allowing for spontaneous changes in the context of a rule application. Two characterizations of double-pullback transitions are provided: the first one describes them in terms of extended direct DPO derivations, and the second one as incomplete views of parallel or amalgamated derivations. The issue of constraining the behavior of a system to transformation sequences satisfying certain properties is addressed instead by introducing a general notion of logic of behavioral constraints, which includes instances like start graphs, application and consistency conditions, and temporal logic constraints. The loose semantics of a system with restricted behavior is defined as a category of coalgebras over a suitable functor. Such category has a final object which includes all finite and infinite transition sequences satisfying the constraints.     

Synthesis of polymers by template polymerization. I. Template polymerization of poly(methacrylic acid) with β‐cyclodextrin

A novel template monomer with multiple methacryloyl groups was synthesized with β‐cyclodextrin by the acetylation of primary hydroxyl groups and the esterification of secondary hydroxyl groups with methacrylic acid anhydride. The average number of methacryloyl groups in the monomer was 11. The radical polymerization of the monomer was carried out with the following initiators: α,α′‐azobisisobutylonitrile, H₂O₂? Fe²⁺ redox initiator, p‐xylyl‐N,N‐dimethyldithiocarbamate (XDC), and α‐bromo‐p‐xylyl‐N,N‐dimethyldithiocarbamate (BXDC). When the concentration of the monomer was less than 4.12 × 10^?3 M, polymerization was limited inside the molecule, and gelation of the system was hindered. For controlled radical photopolymerization with XDC and BXDC, the methacryloyl groups of the monomer were homogeneously polymerized, and poly(methacrylic acid) with a narrow molecular weight distribution was obtained by the hydrolysis of the polymerized products. © 2001 John Wiley & Sons, Inc. J Polym Sci Part A: Polym Chem 39: 3539–3546, 2001     

A synchrotron X‐ray study of triclinic LiCa2Nb3O10 with perovskite‐type slabs

The triclinic superstructure of a small crystal of LiCa₂Nb₃O₁₀, lithium dicalcium triniobium decaoxide, has been investigated by synchrotron X‐ray diffraction. The unit cell is an almost rectangular parallelepiped, although there is a 0.245° offset from orthogonality for β. The structure essentially belongs to a homologous series of Li[Na_n?3Ca₂Nb_nO_3n+1] with n = 3, where the moiety in square brackets has a perovskite‐type slab structure. The superstructure has a doubled unit‐cell volume with respect to the tetragonal aristotype. The NbO₆ octahedra are rotated about axes parallel to [110] by approximately 10°. Adjacent slabs are connected by Li atoms and are geo­metrically related by 4₂ pseudosymmetry lying parallel to c . There are twice as many sites as Li atoms, providing a variation of population at these Li sites.