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

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.

Liquid crystalline polymer as a processing agent in blends of poly(ether-ketone)/LCP70

Blends of a liquid crystalline thermotropic copolyester (LCP70) and an amorphous phenolphthalein based poly(ether-ketone)(PEK-C) with two viscosities were prepared by melt blending. The blends' morphology, rheological and mechanical properties were investigated by DSC, SEM, mechanical and rheological tests. It was observed that the optimum composition of the PEK-C/LCP70 blend was 10 wt% LCP for both mechanical and rheological properties. When the LCP content was less than 10%, the LCP phase existed as finely dispersed fibrous domains with a diameter of about 1 mu m in the matrix, and both tensile and flexural properties were improved. In contrast, when the LCP content reached 20% or more, the LCP domains coalesced to ellipsoidal particles with a diameter of about 5 mu m, and the mechanical properties decreased as a result. It is demonstrated that pure PEK-C with a high viscosity which was difficult to process by melt extrusion, could be extruded conveniently when 10% LCP70 was incorporated. It is emphasized that LCP not only can be used as a reinforcing phase but also an effective processing agent for engineering thermoplastics, especially for those with high viscosity and narrow processing window. (C) 1997 Elsevier Science Ltd.

Investigation on the nonlinear optical properties of the DCNP/PEK-c guest-host polymer films

The polyetherketone (PEK-c) guest-host polymer thin films doped with 3-(1,1-dicyanothenyl)-1-phenyl-4,5-dihydro-1H-pryazole (DCNP) were prepared. The polymer films were investigated with in situ second-harmonic generation (SHG) measurement. The corona poling temperature was optimized by the temperature dependence of the in situ SHG signal intensity under the poling electric field applying. The temporal and temperature stability of the second-order properties of the poled polymer film were measured by the in situ SHG signal intensity probing. The second-order NLO coefficient chi ((2))(33) = 32.65 pm/V at lambda = 1064 nm was determined by using the Makel fringe method after poling under the optimal poling condition. The dispersion of the NLO coefficient of the guest-host polymer system was determined by the measured value of chi ((2))(33) at 1064 nm and the two-level model.

Integrated processing-structure-property analysis on rubber in-mold vulcanization

On the basis of the quantitative relationship among rubber processing, structure and property, the methodology of the integrated processing-structure-property analysis on rubber in-mold vulcanization is presented, and then the temporal evolution and spatial distribution characteristics of silicone rubber hot processing parameters, crosslinking structure parameters and mechanical property parameters are obtained by means of the finite element method. The present work is helpful for optimizing curing conditions, and then the design of rubber vulcanization processes according to certain requirements can be done.

Controlled phase separation for efficient energy conversion in dye/polymer blend bulk heterojunction photovoltaic cells

Low-cost photovoltaic energy conversion using conjugated polymers has achieved great improvement due to the invention of organic bulk heterojunction. in which the nanoscale phase separation of electron donor and acceptor favors realizing efficient charge separation and collection. We investigated the polymer photovoltaic cells using N, N'-bis(1-ethylpropyl)-3,4,9,10-perylene bis(tetracarboxyl diimide)/poly(3-hexyl thiophene) blend as an active layer. It is found that processing conditions for the blend films have major effects on its morphology and hence the energy conversion efficiency of the resulting devices. By optimizing the processing conditions, the sizes of donor/acceptor phase separation can be adjusted for realizing efficient charge separation and collection. The overall energy conversion efficiency of the photovoltaic cell processed with optimized conditions increases by nearly 40% compared to the normally spin-coated and annealed cell.

Toward high-performance polymer solar cells: The importance of morphology control

Polymer solar cells have the potential to become a major electrical power generating tool in the 21st century. R&D endeavors are focusing on continuous roll-to-roll printing of polymeric or organic compounds from solution-like newspapers-to produce flexible and lightweight devices at low cost. It is recognized, though, that besides the functional properties of the compounds the organization of structures on the nanometer level-forced and controlled mainly by the processing conditions applied-determines the performance of state-of-the-art polymer solar cells. In such devices the photoactive layer is composed of at least two functional materials that form nanoscale interpenetrating phases with specific functionalities, a so-called bulk heterojunction. In this perspective article, our current knowledge on the main factors determining the morphology formation and evolution is introduced, and gaps of our understanding on nanoscale structure-property relations in the field of high-performance polymer solar cells are addressed. Finally, promising routes toward formation of tailored morphologies are presented.

Stress transfer and damage evolution simulations of fiber-reinforced polymer-matrix composites

The stress transfer from broken fibers to unbroken fibers in fiber-reinforced thermosetting polymer-matrix composites and thermoplastic polymer-matrix composites was studied using a detailed finite element model. In order to check the validity of this approach, an epoxy-matrix monolayer composite was used as thermosetting polymer-matrix composite and a polypropylene (PP)-matrix monolayer composite was used as thermoplastic polymer-matrix composite, respectively. It is found that the stress concentrations near the broken fiber element cause damage to the neighboring epoxy matrix prior to the breakage of other fibers, whereas in the case of PP-matrix composites the fibers nearest to the broken fiber break prior to the PP matrix damage, because the PP matrix around the broken fiber element yields. In order to simulate composite damage evolution, a Monte Carlo technique based on a finite element method has been developed in the paper. The finite element code coupled with statistical model of fiber strength specifically written for this problem was used to determine the stress redistribution. Five hundred samples of numerical simulation were carried out to obtain statistical deformation and failure process of composites with fixed fiber volume fraction.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone). V: Estimation of temperature distribution during cure process

A numerical method to estimate temperature distribution during the cure of epoxy-terminated poly(phenylene ether ketone) (E-PEK)-based composite is suggested. The effect of the temperature distribution on the selection of cure cycle is evaluated using a suggested alternation criterion. The effect of varying heating rate and thickness on the temperature distribution, viscosity distribution and distribution of the extent of cure reaction are discussed based on the combination of the here-established temperature distribution model and the previously established curing kinetics model and chemorheological model. It is found that, for a thin composite (<=10mm) and low heating rate (<=2.5K/min), the effect of temperature distribution on cure cycle and on the processing window for pressure application can be neglected. Low heating rate is of benefit to reduce the temperature gradient. The processing window for pressure application becomes narrower with increasing thicknesses of composite sheets. The validity of the temperature distribution model and the modified processing window is evaluated through the characterization of mechanical and physical properties of E-PEK-based composite fabricated according to different temperature distribution conditions.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .3. Determination of the time of pressure application

The curing temperature, pressure, and curing time have significant influence on finished thermosetting composite products. The time of pressure application is one of the most important processing parameters in the manufacture of a thermosetting composite. The determination of the time of pressure application relies on analysis of the viscosity variation of the polymer, associated with curing temperature and curing time. To determine it, the influence of the time of pressure application on the physical properties of epoxy-terminated poly(phenylene ether ketone) (E-PEK)-based continuous carbon fiber composite was studied. It was found that a stepwise temperature cure cycle is more suitable for manufacture of this composite. There are two viscosity valleys, in the case of the E-PEK system, associated with temperature during a stepwise cure cycle. The analysis on the effects of reinforcement fraction and defect content on the composite sheet quality indicates that the width-adjustable second viscosity valley provides a suitable pressing window. The viscosity, ranging from 400 to 1200 Pa . s at the second viscosity valley, is the optimal viscosity range for applying pressure to ensure appropriate resin flow during curing process, which enables one to get a finished composite with optimal fiber volume fraction and low void content. (C) 1997 John Wiley & Sons, Inc.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .4. Cure cycle simulation

Epoxy-terminated poly(phenylene ether ketone) (E-PEK) developed in this Institute is a candidate matrix resin for polymer composites as structural materials. Cure cycles for this reaction system were simulated according to the previously established processing model. It is found that for the E-PEK system, the curing process is best completed by a stepwise cure cycle comprising two isothermal processes at different temperatures, T-1 and T-2. The cure cycles over a wide range of processing parameters simulated, based on the established processing model, indicate that the processing window is width-adjustable. Analysis of the mechanical properties of the composite sheets showed that the simulated cure cycles are acceptable and reliable. (C) 1997 John Wiley & Sons, Inc.

Cure processing modeling and cure cycle simulation of epoxy-terminated poly(phenylene ether ketone) .1. DSC characterization of curing reaction

The curing reaction process of epoxy-terminated poly(phenylene ether ketone) (E-PEK) with 4,4'-diaminodiphenyl sulfone (DDS) and hexahydrophthalic acid anhydride (Nadic) as curing agents was investigated using isothermal differential scanning calorimetry (IDSC) and nonisothermal differential scanning calorimetry (DDSC) techniques. It was found that the curing reactions of E-PEK/DDS and E-PEK/Nadic are nth-order reactions but not autoaccelerating. The experimental results revealed that the curing reaction kinetics parameters measured from IDSC and DDSC are not equivalent. This means that, in the curing reaction kinetics model for our E-PEK system, both isothermal and nonisothermal reaction kinetics parameters are needed to describe isothermal and nonisothermal curing processes, The isothermal and nonisothermal curing processes were successfully simulated using this model. A new extrapolation method was suggested. On the basis of this method the maximum extent of the curing reaction (A(ult)) that is able to reach a certain temperature can be predicted. The A(ult) for the E-PEK system estimated by the new method agrees well with the results obtained from another procedure reported in the literature. (C) 1997 John Wiley & Sons, Inc.