几种不同PE和PP树脂的粘流活化能研究

测试了几种常用PE和PP树脂在一系列温度下的流变曲线,研究剪切速率对粘流活化能的影响。结果发现,相同剪切速率下,PP、LDPE、LLDPE的粘流活化能相对较高,HDPE树脂的粘流活化能相对较低,说明PP、LDPE和LLDPE对温度的敏感性较高,即升温有利于LDPE和LLDPE的加工;PP树脂的粘流活化能随剪切速率的增加而减小的幅度较大,表现出切力敏感性;剪切速率对PE树脂的粘流活化能的影响较小,在较宽的剪切速率范围内,温度对其流变性能的影响更明显。     

PVC melt rheology III: The effect of order and molecular weight on the shear rate dependence

The effect of polymerization temperature on the melt flow behavior of PVC of varying molecular weights has been studied over a wide shear rate range. For the same molecular weight, higher melt viscosities are observed for polymers prepared at lower temperatures. The shear rate dependence of the viscosity vs molecular weight plot is shown to be nonlinear over the shear rates examined. The inability to achieve a limiting zero-shear viscosity is discussed.     

聚烯烃弹性体的结构与熔体黏度关系的研究

采用凝胶渗透色谱仪和核磁共振仪表征了一系列聚烯烃弹性体（POE）样品的结构,并用毛细管流变仪考察了其挤出稳定性、剪切依赖性和黏温依赖性,分析了熔体黏度与聚合物结构的关系。结果表明,随着剪切速率的提高,高相对分子质量的POE熔体易出现不稳定流动,挤出物表面发生畸变;相对分子质量越大、温度越低、共聚单体含越高,发生不稳定流动的临界剪切速率c越低;POE的剪切黏度很大程度上受相对分子质量的影响,与共聚单体的含量关系不大;不同相对分子质量及组成的POE熔体的黏流活化能相近,约为2.8×10^4 J/mol。基于Carreau、Cross和Arrhenius等方程,分别建立了关联熔体零切黏度与聚合物重均相对分子质量和温度关系的半经验式、关联熔体表观黏度与零切黏度和剪切速率关系的半经验式;两式可用于预测POE熔体的黏度,其适用范围为温度为130~190 ℃,剪切速率为10~2 000 s-1,重均相对分子质量（Mw）为4.2×10^4~1.24×10^5 g/mol。     

Rheological properties of partially hydrolyzed ethylene–vinyl acetate copolymers

Studies have been made of steady-shear and dynamic viscosities for melts of two ethylene–vinyl acetate copolymers and their partially hydrolyzed derivatives using a Weissenberg rheogoniometer over the temperature range of 123–150°C with some tests at 160°C. The flow activation energy of all samples studied was essentially independent of shear stress. The introduction of hydroxyl groups in controlled concentrations, however, produced a complicated flow behavior. At low concentrations, there is a marked increase in Newtonian viscosity, flow activation energy, and shear dependence of viscosity. In contrast to previous reports, a further increase in all three functions was not observed with increasing vinyl alcohol concentration. Dynamic viscosities, in contrast, show monotonic increases with increasing hydroxyl group content, as do activation energies derived from the temperature dependence of the dynamic viscosity. These data may result from an increased chain cohesion due to hydrogen bonding of hydroxyl groups.     

The particle flow of polystyrene during capillary extrusion

The melt flow of emulsion polymerized polystyrene has been investigated in accordance with the particle flow concepts developed by Berens and Folt. Particles were found to be present in the extrudate up to 210°C and resins with larger particles were found to have lower viscosities. The molecular weight appears to have no significant effect on the melt viscosity above a certain molecular weight. The energy of activation for viscous flow at 190°C and at shear stress of 5 × 10⁵ dynes/cm² was found to be 29–33 kcal/mol depending on type of resin.     

Viscosities of moderately concentrated solutions of polyethylene in ethane,propane, and ethylene

The viscosities of moderately concentrated solutions of low-density polyethylenes in ethane, propane, and ethylene have been measured at low shear rate in the temperature range of 150–250°C and in the pressure range of about 15000–30000 psi. Within the precision of the measurements, the relative viscosity is independent of pressure over the range investigated but increases as the solvent is changed from propane through ethane to ethylene. The activation energy for the relative viscosity in ethane varies from about 0.5 to 2.5 kcal/mole as the concentration changes from 5 to 15 g/dl. Effects of polymer concentration and molecular weight on solution viscosity in ethane at 150°C have been determined, and all of the data can be represented by a single straight-line plot of the logarithm of relative viscosity versus the intrinsic viscosity (in p-xylene at 105°C) times concentration. This simple relation is valid over wide ranges of polymer concentration and molecular weight and over more than two orders of magnitude of relative viscosity. The solution viscosities of the polyethylenes in the three supercritical fluid solvents used appear surprisingly low at first sight. This behavior is partly a result of the low solvent viscosities but also might mean that the polymer has an abnormally low segmental friction factor compared to that in solutions under more familiar conditions.     

The effect of molecular weight blending on PVC melt rheology

The effect of molecular weight blending on melt flow characteristics has been studied with a 50/50 mixture of suspension PVC resins with the respective M _w of 56,300 and 123,000. The dynamic shear measurements were made with the Rheometrics Visco-Elastic Tester at angular frequencies of 0.1 to 40 radians/s. In the temperature range of 160 to 215° C, all samples showed three distinct flow regions marked by three different values of the activation energy. The high molecular weight fraction introduced a relatively strong influence on the melt flow characteristics of the blend due to the effect of its relatively high crystalline content. These samples also failed to show a Newtonian flow behavior at 190°C at an extremely low shear rate corresponding to 10^?4 radians/s., possibly reflecting the effect of the remnant crystallinity of the material.     

Flow properties of thermally depolymerized liquid natural rubber

The flow behavior of liquid natural rubber (LNR) with reference to the effect of molecular weight, shear rate, and temperature has been studied. LNR samples were prepared by thermal depolymerization of rubber (NR) through the combined effect of mechanical, chemical, and thermal energies. High molecular weight samples, especially at lower temperatures, showed pseudoplastic behavior, whereas the low molecular weight samples were Newtonian at all temperatures. The viscosity of LNR considerably decreases with increase in temperature. The activation energy of flow was also calculated. © 1995 John Wiley & Sons, Inc.     

Rheological Behaviors of Polyacrylonitrile/1-Butyl-3-Methylimidazolium Chloride Concentrated Solutions

One of the room temperature ionic liquids (RTILs), 1-butyl-3-methylimidazolium chloride ([BMIM]Cl) was chosen to prepare the concentrated solutions of Polyacrylonitrile (PAN). The rheological behaviors of the solutions were measured with rotational rheometry under different conditions, including temperatures, concentration, and molecular weight of PAN. The solutions exhibited shear-thinning behaviors, similar to that of PAN/DMF solutions. The viscosities decreased with the increasing of shear rates. However, the viscosity decreased sharply at high shear rates when the concentration was up to 16wt%. The dependence of the viscosity on temperature was analyzed through the determination of the apparent activation energy. Unusually, the viscosity of solutions of higher concentration is lower than that of lower concentration. Similarly, the viscosity of low molecular weight PAN was higher than high molecular weight PAN at high shear rates. The dynamic rheological measurement indicates the loss modulus is much higher than storage modulus. The trend of complex viscosity is similar with the result of static rheological measurement. The interaction between PAN and ionic liquid [BMIM]Cl was discussed.     

Rheological properties of branched low-density polyethylene

The shear flow properties of six commercially available long-chain branching low-density polyethylene resins were determined, using a cone-and-plate rheometer at low shear rates and a capillary rheometer at high shear rates. Also determined were the elongational viscosities of the resins, using an apparatus developed by Ide and White. Interpretation of the rheological measurements is given with the aid of the molecular parameters, namely, molecular weight and molecular weight distribution.     

Influence of molecular weight on some rheological properties of acrylic solutions during newtonian flow

The effect of molecular weight in a narrow range on some rheological properties of acrylic solutions during Newtonian flow at different temperatures and concentrations was investigated. The results showed that the change in viscosity with temperature and concentration was dependent on the molecular weight. It was found that the molecular weight in a closer range influenced the activation entropy and the free energy of activation during Newtonian flow.     

Melt rheology of segmented polyamides: Effect of block molecular weight

Segmented polyamides, also known as polyether‐ester‐amides, are composed of polyether and polyamide structural units. The rheological behavior of segmented polyamides with respect to the variations in the molecular weight of hard and soft blocks has been studied using a Monsanto Processability Tester. These systems exhibit pseudoplastic flow behavior. The shear viscosity of the segmented polyamides decreases with a decrease in hard block molecular weight up to 1500. However, at low shear rates, the shear viscosity shows marginal change with an increase in soft segment molecular weight. The equilibrium die swell increases with an increase in shear rate, but decreases with increasing temperature. The stress relaxation study of the segmented polyamides reveals that the stress developed during extrusion relaxes exponentially for all the systems. The equilibrium die swell at a fixed temperature and shear rate, the time required to relax a fixed amount of stress and the stress developed after a certain time interval decrease with a decrease in hard block molecular weight up to 1500, but increase with an increase in soft segment molecular weight. The activation energy of the melt flow process increases with the rate of shear in most of the cases. © 1999 John Wiley & Sons, Inc. J Appl Polym Sci 71: 1739–1747, 1999     

Rheological behavior of low molecular weight polystyrene composites containing monodisperse crosslinked polystyrene beads

Steady shear viscosities and dynamic moduli of polymer composites, consisting of crosslinked polystyrene beads and low molecular weight polystyrene matrix, were measured in a cone-and-plate rheometer at different temperatures. Viscosities and dynamic moduli were found to be very sensitive to filler loading and measurement temperature. Steady shear viscosities of 30% and 40% loaded low molecular polystyrene composites showed a power-law behavior over the entire range of shear rates. Storage and loss moduli were initially linear with frequency on double logarithmic plots, with limiting slopes of 0.3 and 0.1. At high concentration of filler particles, they showed a flat plateau at low frequencies, indicating that these systems exhibit a yield behavior. A 20% PS composite loaded with beads of high crosslink densities resulted in poor dispersion of beads as a result of poor dispersion of particles. PS beads 1.16 μm in diameter showed a higher viscosity. It is due to the apparent increase in loading resulting from broken particles. At low measurement temperature, filler effects were suppressed by high viscosity matrix and showed a similar rheological behavior to high molecular weight by PS matrix. We suggest that rheological behavior reflects the state of dispersion of beads in the matrix.     

The influence of molecular weight on the melt rheology of polypropylene

Melt viscosity and melt elasticity data were obtained over a broad range of temperatures and shear rates on a series of four polypropylenes of different molecular weight but approximately the same molecular weight distribution. The superposition technique was used with both temperature and molecular weight to shift flow curves for all four materials at three temperatures each along the shear rate axis to generate a master flow curve at a given temperature and molecular weight. For polypropylenes of this type, and molecular weight distribution shift, factors which can be used to extend the useful range of experimentally obtained flow data were determined. The dependency of apparent viscosity on weight average molecular weight at shear stresses as high as 10⁶ dynes/cm² is shown. The dependency of melt elasticity on molecular weight and temperature is discussed.     

Blends of poly[ethylene(vinyl acetate)] and polychloroprene: Studies on capillary and dynamic flows

Rheological properties of the blends of poly[ethylene(vinylacetate)] (EVAc; vinylacetate content 28%) and polychloroprene (CR) have been measured through capillary and dynamic uniaxial elongational flows. Capillary flow indicates their shear thinning behavior. The decrease in the out of phase viscosities with increasing frequency is in accordance with the power law equation, whereas dynamic elongational viscosities follow nonlinear relationship in log-log plot with an initial increase at 11 Hz, followed by a very sharp drop. With an increase in temperature, the viscosity for capillary flow of all blends goes down due to their positive activation energy of flow but for dynamic elongational flow of EVAc blended with CR, viscosity increases, except for 30/70 blend and pure CR, in which case the dynamic elongational viscosity decreases with an increase in temperature. This abnormal behavior in dynamic elongational viscosity is due to the process of melting and recrystallization of EVAc at low heating rate (1°C/min) beyond the melting temperature. Capillary viscosities of all blends show positive deviation from the log additive values of pure polymers. But in the case of dynamic elongational flow, all blends show positive deviation at frequencies of 3.5 and 35 Hz and at higher temperatures (80–120°C). © 1997 John Wiley & Sons, Inc.     

Investigation of the Moisture-Desorption Characteristics of Epoxy Resin

Moisture-diffusion characteristics, which include weight changes, hygrothermally induced expansion, diffusion coefficients, and activation energy, have been investigated for epoxy resins. The experimental results show that hygroscopic swelling behavior of the epoxy system is consistent; it increases with temperature and decreases sharply at approximately 135°C. Desorption from high moisture saturation tended to leave a small residual moisture content which could be removed only by heating at relatively high desorption temperatures. Further interpretation of this phenomenon are discussed on the basis of experimental results and molecular dynamics (MD) simulations.     

A rheological study of long branching in polyethylene by blending

Steady shear viscosities, dynamic viscosities and moduli, and the corresponding activation energies for flow were examined for a branched polyethylene, a linear polyethylene, and three of their blends at 150° and 190°C. The polyethylenes were chosen to have closely matched molecular weights and distributions. An R-17 Weissenberg rheogoniometer and an Instron capillary rheometer were used. At lower stress, the branched polymer had a higher viscosity than the linear one, possibly because of the contribution of long branches to entanglements. At high stress, this contribution is reduced and the inherently smaller coil dimensions likely become responsible for the lower viscosity of the branched polymer. The activation energy for the branched polymer is high and decreases with stress, in contrast to the low and almost-constant value for the linear polymer. The effects here of pressure on compression are considered. The entanglements of long branches may also decrease with increasing temperature. With decreasing stress, the activation energy for branched polymer tends to become constant, corresponding to an absence of pressure effects and an equilibrium entanglement of long branches for a given temperature range. The linear relationship between activation energy and blend composition problably means that any compressional effects, like free volume, are additive and that long-branch entanglements rearrange with added linear molecules. The linearity may be the result, in part, of a broad distribution for the lengths of long branches.     

Rheological behavior of molten epoxide prepolymers

Flow properties of four molten epoxide prepolymers of number average molecular weight 900(I), 1,500(II), 2,100(III) and 4,000(IV), were measured at temperatures ranging from 361 to 463K, and shear rates from 500 to 10,000 s^?1. Apparent shear viscosities showed that all prepolymers used have Newtonian behavior up to shear rates of 2,000 s^?1. Shear thinning occurs at higher shear rates. Flow activation energies at constant shear rates in the range of 500 to 7,000 s^?1 vary for prepolymer III from 5 to 24 kcal/mol, and for prepolymer IV from 9 to 25 kcal/mol. Flow indices in the same shear rate range vary for prepolymer III from 1.0 to 0.7 and for prepolymer IV from 1.0 to 0.3.     

A generalized melt viscosity-temperature dependence for styrene and styrene-acrylonitrile based polymers

The dependence of the melt flow of polymers on temperature is of both theoretical and commercial importance. A useful representation of the temperature dependence of the shear-dependent viscosity, based on superposition of flow curves at various temperatures, has previously been presented by the author for several olefin polymers. This method is extended in the current work to styrene and styrene-acrylonitrile based polymers. The melt viscosity-temperature dependence of a broad range of styrenic polymers and copolymers, ranging from polystyrene to 82 percent AN styrene-acrylonitrile copolymer, with and without rubber inclusions, was investigated. Flow curves at the various temperatures were found to be superimposable, as had earlier been found to be the case for olefin polymers, and a unique quantitative relationship between the superposition shift factors and temperature was found applicable to the entire family of polymers. The resultant energy of activation for viscous flow is in excellent agreement with previously published results for polystyrene Newtonian viscosities, and the magnitude of the shift factors is consistent with a limited set reported for ABS polymers. Independent tests of the derived relationships provided excellent prediction of measured viscosities. Thus, it is considered that a general viscosity-temperature relationship has been defined for this family of polymers, independent of molecular structural detail.     

添加高相对分子质量聚丙烯腈对纺丝溶液的流变性能与可纺性的影响

在聚丙烯腈/二甲基亚砜(PAN/DMSO)纺丝溶液体系中添加高相对分子质量PAN,通过锥板流变仪对该体系的稳态和动态流变行为进行了研究.结果表明:纺丝溶液为切力变稀流体,在较高剪切速率下,溶液出现明显的剪切变稀现象;在较低的剪切速率下,随温度的升高,溶液粘度逐渐变低.通过添加高相对分子质量PAN,溶液粘度增大,有利于表...