Highly Efficient and Thermally Stable Second-Order Nonlinear Optical Chromophores and Electrooptic Polymers

Organic polymeric electro-optic (E-O) materials have attracted significant attention because of their potential use as fast and efficient components of integrated photonic devices (1,2). However, the practical application of these materials in optical devices is somewhat limited by the stringent material requirements imposed by the device design, fabrication processes and operating environments. Among the various material requirements, the most notable ones are large electro-optic coefficients (r(33)) and high thermal stability (3). The design of poled polymeric materials with high electro-optic activity (r(33)) involves the optimization of the percent incorporation of efficient (large beta mu) second order nonlinear optical (NLO) chromophores into the polymer matrices and the effective creation of poling-induced non-centrosymmetric structures. The factors that affect the material stability are a) the inherent thermal stability of the NLO chromophores, b) the chemical stability of the NLO chromophores during the polymer processing conditions, and c) the long-term dipolar alignment stability at high temperatures. Although considerable progress has been made in achieving these properties (4), organic polymeric materials suitable for practical E-O device applications are yet to be developed. This chapter highlights some of our approaches in the optimization of molecular and material nonlinear optical and thermal properties.

Combinatorial effect of rolling and carbonaceous nanoparticles on the evolution of crystallographic texture and structural properties of ultra high molecular weight polyethylene

Ultra high molecular weight polyethylene (PE) is a structural polymer widely used in biomedical implants. The mechanical properties of PE can be improved either by controlled crystalline orientation (texture) or by the addition of reinforcing agents. However, the combinatorial effect has not received much attention. The objective of this study was to characterize the structure and mechanical properties of PE composites incorporating multiwall carbon nanotubes (MWCNT) and reduced graphene oxide (RGO) subjected to hot rolling. The wide angle X-ray diffraction studies revealed that mechanical deformation resulted in a mixture of orthorhombic and monoclinic crystals. Furthermore, the presence of nanoparticles resulted in lower crystallinity in PE with smaller crystallite size, more so in RGO than in MWCNT composites. Rolling strengthened the texture of both orthorhombic and the monoclinic phases in PE. Presence of RGO weakened the texture of both phases of PE after rolling whereas MWCNT only mildly weakened the texture. This resulted in a reduction in the elastic modulus of RGO composites whereas moduli of neat polymer and the MWCNT composite increased after rolling. This study provides new insight into the role of nanoparticles in texture evolution during polymer processing with implications for processing of structural polymer composites.

Thermocapillary Effect in a Thermal Rheological Jet

The process of die swell in polymer jets is an important feature within polymer processing and can be explained through a study of its rheological effects. The existence of a thermocapillary effect, driven by the gradient of its surface tension, should be considered when examining a thermal jet that has a non-uniform temperature distribution on its free surface, as in various polymer processings. Both the rheological effect and thermocapillary effect on die swell can be studied numerically through a finite element method as used on a two-dimensional and unsteady model, in which a Coleman-Noll second-order fluid model is employed. The results show that the expanding angle depends on both the rheological property of the fluid and the pressure at the vessel exit. Although both the thermocapillary and the rheological effects contribute to the cross-section expansion of the fluid jet, the latter is more important in determining the expansion.

Rheological flow from a die and painting on a moving solid wall

Die swell is an important, phenomenon. in polymer processing, and is explained usually by rheological properties of the fluid. Because of the nonuniform of temperature distribution on the free surface of the liquid jet, the thermo capillary convection driven by surface tension gradient exists. The rheological fluid flowing out of a die and painting on a moving solid wall is studied by the numerical finite element method of a two-dimensional and unsteady model in the present paper, and both the rheological effect of a non-Newtonian fluid and the thermocapillary effect are considered. The results show that both,effects; will enlarge the cross-section of the fluid jet, and the rheological effect of non-Newtonian fluid dominates the process in general.

国内非牛顿流体力学进展

非牛顿流体;;本构方程;;流变测量;;流动稳定性;;收缩流动;;聚合物加工;;石油工业;;生物流体力学

Preparação de nanopartículas funcionalizadas do tipo casca-núcleo à base de poliestireno e poli(acrilato de butila) para processamento baroplástico

Copolímeros casca-núcleo de poli(acrilato de butila) (núcleo) e poliestireno (casca) foram sintetizados por meio de polimerização em emulsão, conduzida em duas etapas. A adição de ácido itacônico como monômero funcional na polimerização do núcleo foi realizada para verificar seu efeito sobre suas propriedades mecânicas e de processamento. Os copolímeros foram caracterizados por espalhamento dinâmico de luz (DLS), microscopia eletrônica de transmissão (MET), cromatografia de exclusão por tamanho (SEC), espectrometria na região do infravermelho (FTIR) e calorimetria diferencial por varredura (DSC). A incorporação do monômero funcional foi confirmada por DSC e quantificada por titulação. A proporção de poli(acrilato de butila) e poliestireno influenciou diretamente o processamento e as propriedades mecânicas do polímero. Os copolímeros com teores de poliestireno acima de 50% foram processados por compressão e extrusão a temperatura ambiente, apresentando comportamento baroplástico. A presença do monômero funcional não alterou o processamento do polímero e melhorou significativamente sua resistência à tração, aumentando sua tenacidade

Computer simulation of reactive extrusion processes for free radical polymerization

The reactive extrusion for polymerization is an integrated polymer processing technology. A new semi-implicit iterative algorithm was proposed to deal with the complicated relationships among the chemical reaction, the macromolecular structure and the chemorheological property. Then the numerical computation expressions of the average molecular weight, the monomer conversion, and the initiator concentration were deduced, and the computer simulation of the reactive extrusion process for free radical polymerization was carried out, on basis of which reactive processing conditions can be optimized.

The Role of Tool/Sheet Contact in Plug-Assisted Thermoforming.

Plug-assisted thermoforming produces a wide range of polymer products through a combination of deformation by air pressure and contact with tool surfaces. In this paper the role of tool/sheet contact in determining the process output is investigated. A combination of thermoforming, friction and heat transfer tests were carried out on common tool and sheet materials. The results show that the typical friction coefficients for the material combinations are within the range 0.1 to 0.3, but the values rise sharply on approaching thermoforming temperatures. Thermal imaging tests demonstrate that all of the plug materials significantly cool the heated sheet on contact, even over very short periods of time. The temperature of the plug is very important. At low plug temperatures heat transfer effects predominate, whereas at high plug temperatures friction effects predominate. A plug temperature of approximately 100oC balances these effects and creates the most effective material distribution.