Preparation of flexible polyhedral particles via concentrated emulsion templating polymerization

This paper presents recent efforts on the preparation of flexible polyhedral particles via concentrated emulsion templating polymerization in which the hydrophilic monomer (acrylamide) and hydrophobic monomer (butyl acrylate) are polymerized simultaneously in the continuous and dispersed phase, respectively. Such templating polymerization has been enhanced in our systems owing to the introduction of acrylamide monomer and their higher polymerization rate in continuous phase as compared with butyl acrylate in dispersed phase. Diffusion between the different phases was also inhibited. Furthermore, the stability of the concentrated emulsion and the molecular weight of the produced poly(butyl acrylate) were found to be significantly affected by the amount of redox initiator. The morphology of the particles could be controlled by varying the volume fraction of the dispersed phase and the polyhedral particles were achieved at higher volume fraction. Copyright © 2005 Society of Chemical Industry     

Crystallization behavior of star-shaped poly(ethylene oxide) with cubic silsesquioxane (CSSQ) core

The crystallization behavior of well-defined star-shaped cubic silsesquioxane-poly(ethylene oxide) (CSSQ-PEO) and linear PEO were studied in terms of differential scanning calorimetry (DSC) and wide-angle X-ray scattering (WAXS). It was found in DSC analysis that the glass transition temperature (T_g) and the crystallization temperature (T_c) of CSSQ-PEO are different from those of linear PEO. The presence of CSSQ in PEO reduced the overall crystallization growth rate. This effect can be ascribed to the reduction of the mobility of the PEO crystallites in the presence of CSSQ and the star structure of the polymer. The Ozawa method is qualitatively satisfactory for describing the nonisothermal crystallizations of linear PEO and CSSQ-PEO. The presence of CSSQ leads to the diffusion- and nucleation-controlled mechanisms in the crystallization process of CSSQ-PEO whilst only the nucleation-controlled mechanism was observed in the case of linear PEO. The apparent activation energy required for crystallization was calculated using the Kissinger method. The isothermal crystallization morphology of PEO and CSSQ-PEO were also examined by cross-polarizing optical microscopy (CPOM). The CPOM images indicated the spherulite growth is slower in CSSQ-PEO as compared to linear PEO. It was also investigated that more number of PEO spherulites in CSSQ-PEO were observed, which sizes are markedly smaller than the spherulites developed in linear PEO. Wide-angle X-ray scattering (WAXS) studies showed that the crystallization peaks for linear PEO and CSSQ-PEO appeared at different temperature revealing the crystallization process and crystal growth rate are different from each other. However, no significant distortion of the crystal structure of PEO was evaluated in the presence of CSSQ.     

Zirconium-Embedded Polyhedral Oligomeric Silsesquioxane Containing Phosphaphenanthrene-Substituent Group Used as Flame Retardants for Epoxy Resin Composites

A zirconium hybrid polyhedral oligomeric silsesquioxane derivative (Zr–POSS–bisDOPO) is synthesized by the corner-capping and Kabachnik–Fields reactions. It is characterized by Fourier transform infrared spectroscopy (FTIR) and nuclear magnetic resonance spectroscopy (NMR), and then used as a flame retardant in diglycidyl ether of bisphenol A (DGEBA) to endow epoxy resin (EP) with flame retardancy. The flame retardancy, thermal stability, and mechanical properties of the cured EP/Zr–POSS–bisDOPO composites are investigated. The results show that when Zr–POSS–bisDOPO is added by 5–7 wt%, the EP/Zr–POSS–bisDOPO composites pass the UL-94 V-0 rating test. In addition, they have a better flame-retardant effect than pure EP. The combination of Zr atom embedded in the Si O cubic cage and the two phosphaphenanthrene substituent groups in one corner of cubic cage is expected to realize the Zr/Si/P ternary intramolecular hybrid synergistic effect and achieve the possibility of dispersing metal–POSS cages at a sub-micrometer-scale level into polymer matrix. It also proves that Zr–POSS–bisDOPO produces phosphorus-containing free radicals and terminates the chain reactions in gas phase. Meanwhile the Si O Si and Zr O units are retained in the solid phase, which promote the char formation and enhance the flame retardancy. This kind of Zr-doped POSS will be helpful for developing the new metal–POSS hybrid flame-retardant and polymer composites.     

Preparation and thermal property of hybrid nanocomposites by free radical copolymerization of styrene with octavinyl polyhedral oligomeric silsesquioxane

The poly(styrene‐co‐octavinyl‐polyhedral oligomeric silsesquioxane) (PS–POSS) organic–inorganic hybrid nanocomposites containing various percent of POSS were prepared via one‐step free radical polymerization and characterized by FTIR, high‐resolution ¹H NMR, ²⁹Si NMR, GPC, DSC, and TGA technologies. The POSS contents in these nanocomposites were determined using FTIR calibration curve. The result shows that the POSS contents in nanocomposites can be tailored by varying the POSS feed ratios. On the basis of the POSS contents in the nanocomposites and the ¹H NMR spectra, the number of reacted vinyl groups of each octavinyl‐POSS macromonomer were calculated to be 6–8. DSC and TGA measurements indicate that the incorporation of POSS into PS homopolymer can apparently improve the thermal properties of the polymeric materials. The dramatic T_g and T_dec increases are mainly due to the formation of star and low cross‐linking structure of the nanocomposites, where POSS cores behave as the joint points and hinder the motion and degradation of the polymeric chains. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci 2007     

Effect of catalyst on regioselectivity and vinyl/H exchange on silicon in the hydrosilylation of vinyl-siloxanes by T8 hydrogen silsesquioxane

We have recently reported the synthesis of octopus molecules of defined shape and size with molecular weights well into the thousands. These octopus molecules were made by placing eight pendant groups symmetrically about a central silsesquioxane core via the H₂PtCl₆ catalyzed hydrosilylation of 1-alkenes as well as vinyl- and allyl-siloxanes by T₈ hydrogen silsesquioxane, (HSiO₃₂)₈. The chemistry of addition was studied and it was found that while the addition of the 1-alkenes to T₈ was regioprecise with only -addition being observed, both - and -addition occurred with vinyl-siloxane. In addition, H-vinyl exchange on silicon was observed to occur with addition of vinyl-siloxane to T₈. In the current studies, the effect of the hydrosilylation catalyst. homogeneous and heterogeneous, on the regioselectivity of addition and on the extent of exchange on silicon was evaluated. It was found that the heterogeneous catalysts Pt–C, sulfided Pt–C, and Rh–C required higher temperature and longer times to get complete reaction than the homogeneous catalysts. H₂PtCl₆ and the tetramethyldivinyldisiloxane complex of Pt. Pd supported catalysts were not effective catalysts for this hydrosilylation. The extent of exchange on silicon and the degree of the second mode of addition occurring were higher with the heterogenous catalysts and may be a result of the higher reaction temperatures.     

以氨基笼型倍半硅氧烷为固化剂的环氧树脂灌封胶

用笼型β-氨乙基-γ-氨丙基倍半硅氧烷(CAAPOSS)和4,4-二氨基二苯醚(DDO)为固化剂,间苯二酚双缩水甘油醚为活性稀释剂,制备了双酚-A型环氧树脂灌封胶,并研究了胶粘剂各组分从而获得了较高的物理机械性能。测定了与碳钢的粘接强度,热性能和耐老化性能。结果表明,该胶粘剂是一种热稳定性好、耐高温、粘度低的优良结构胶粘剂。     

面向多面体模型的非规则程序SIMD投机优化技术

多面体模型具有规范化、健壮性、灵活性等特点,被认为是最有前途的编译优化技术之一,SIMD优化是重要应用领域之一。由于静态编译技术的限制,大量非规则循环无法建立多面体模型,例如复杂依赖关系,导致无法利用该模型实现SIMD循环优化与代码生成。文章通过分析、利用SIMD优化所需的程序运行剖面信息,将静态编译未知情况转化为已知情况,为多面体模型建立创造条件。SPEC2000和PolyBench的测试结果显示,通过本文提出的方法,可将适用多面体模型的非规则循环个数提高2．3倍,经过SIMD优化后,平均加速比提高了1．53倍。     

Inner approximations of completely positive reformulations of mixed binary quadratic programs: a unified analysis

Every quadratic programming problem with a mix of continuous and binary variables can be equivalently reformulated as a completely positive optimization problem, that is, a linear optimization problem over the convex but computationally intractable cone of completely positive matrices. In this paper, we focus on general inner approximations of the cone of completely positive matrices on instances of completely positive optimization problems that arise from the reformulation of mixed binary quadratic programming problems. We provide a characterization of the feasibility of such an inner approximation as well as the optimal value of a feasible inner approximation. In particular, our results imply that polyhedral inner approximations are equivalent to a finite discretization of the feasible region of the original completely positive optimization problem. Our characterization yields, as a byproduct, an upper bound on the gap between the optimal value of an inner approximation and that of the original instance. We discuss the implications of this error bound for standard and box-constrained quadratic programs as well as general mixed binary quadratic programs with a bounded feasible region.     

Generation of Efficient Nested Loops from Polyhedra

Automatic parallelization in the polyhedral model is based on affine transformations from an original computation domain (iteration space) to a target space-time domain, often with a different transformation for each variable. Code generation is an often ignored step in this process that has a significant impact on the quality of the final code. It involves making a trade-off between code size and control code simplification/optimization. Previous methods of doing code generation are based on loop splitting, however they have nonoptimal behavior when working on parameterized programs. We present a general parameterized method for code generation based on dual representation of polyhedra. Our algorithm uses a simple recursion on the dimensions of the domains, and enables fine control over the tradeoff between code size and control overhead.     

Representing Animations by Principal Components

In this paper, we present a representation for three-dimensional geometric animation sequences. Different from standard key-frame techniques, this approach is based on the determination of principal animation components and decouples the animation from the underlying geometry. The new representation supports progressive animation compression with spatial, as well as temporal, level-of-detail and high compression ratios. The distinction of animation and geometry allows for mapping animations onto other objects.