Heterogeneous polymeric reaction under shear flow

The effects of different shear flows on polymeric reaction between poly(styrene/maleic anhydride) (SMA) and polyamide 6 (PA6) in heterogeneous blending system were investigated. FTIR, SEM, rheometry, and GPC were used to qualitatively analyze the reaction, and the reaction apparent activation energy was determined as 75.7 kJ/mol by a rheological method. To study the effects of different shear flows on heterogeneous polymeric reaction, a more practical technique was developed to select the data that only responds to the reaction without the effect of different shear flows. Avrami's equation was employed to analyze the reaction process under shear flow and the results showed that the half period (t_1/2) of reaction process decreased with the increase of the shear rate in this study. Moreover, the decease rates were different in the different shear modes as follows: the half period decreased slightly under the oscillatory shear, whereas it decreased strongly under the steady shear. The possible reasons for these phenomena were discussed. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Conversion measurement in polyethylene/peroxide coupling system under steady shear flow

The coupling reaction of melt linear low density polyethylene (LLDPE) initiated by dicumyl peroxide (DCP) in steady shear flow field was investigated. The conversion of DCP was measured by electron spin resonance (ESR) and chemical titration. An absolute method was proposed to calculate the actual conversion of DCP from rheological data. The coupling efficiency of DCP was obtained from those analyses, which was shown to increase at first, reach a maximum and then decrease in the end stage. A linear relationship between the coupling efficiency of DCP and the concentration of macroradicals was also found in the experiments.     

The steady flow shear modulus of polymer melts

Relaxation times of polyethylene melts have been measured by Aloisio, Matsuoka, and Maxwell. One implication regarding their observations is that the elastic properties of polymer melts must be time-dependent. In particular, the steady-flow shear modulus depends on the strain rate. Some interpretations of data in the literature have been based on concepts in rubber elasticity where the steady-flow modulus is an equilibrium value, independent of strain rate. We have used Pao's theory for viscoelastic flow together with measurements of relaxation times to discuss the strain rate dependence of the steady-flow shear modulus of melts. The existence of a strain rate-dependent shear modulus leads naturally to a nonlinear relation between shear stress and recoverable shear strain. The conclusions regarding the molecular weight dependence of the modulus also differ from interpretations based on rubber elasticity.     

Shear-induced pre-crystallization structures of long chain branched polypropylene under steady shear flow near the melting temperature

Shear-induced crystallization of a long chain hyper-branched polypropylene (LCB-PP, denoted PP-3) was carried out at a relatively high temperature of 170 °C, close to its melting temperature of 158 °C. Small-angle X-ray scattering (SAXS) showed that the intensity ratio of the normal to the perpendicular to the shear (V/H) was always larger than 1 for PP-3, indicating that shish-like structures were predominately formed and further growth to kebab was suppressed in PP-3. The crystallization behavior of PP-3 can be explained by the nature of PP-3 that there were a large amount of crystallization nuclei due to their branching points, and the point-like precursors formed from these nuclei were arrayed linearly along the shear direction and transformed into thread-like precursors or premature shishs; however, owing to the large amount of branching, further progress in crystallization was suppressed.     

纤维增强聚合物熔体的非等温流动数值模拟

建立了基于聚合物Carreau 4参数模型和纤维取向模型相耦合的数学模型,采用有限体积法和有限差分法相结合的方法对模型控制方程组进行了数值离散。通过对4∶1平板收缩腔内的纤维悬浮非等温聚合物流动的数值模拟,得到了流场的温度和黏度分布规律,并分析了不同温度对纤维取向和流场应力的影响。结果表明:较低的温度不仅有助于纤维的旋转取向,还有助于熔体黏弹性能的提高。该数学模型能够用于纤维增强聚合物复合材料加工过程的性能分析。     

Effects of the shear flow on a homogeneous polymeric reaction

The reaction kinetics of the postamidation of polyamide 6 in the melt was studied by a new rheological method, and the reaction rate constant was calculated to be about 0.087 kg/mol min at 250°C. To study the effects of the shear flow on a homogeneous polymeric reaction, a more practical technique was used to select the data that responded only to the reaction without the effect of different shear flows. The experimental results showed that the reaction rate constant decreased with an increase in the shear rate. Moreover, the decreases in the rates were different under different shear modes: the reaction rate constant decreased slightly under oscillatory shear but strongly under steady shear. Possible reasons for these phenomena were examined. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3056–3061, 2006     

Effects of high molecular weight component on crystallization of polyethylene under shear flow

Crystallization of polyethylene (PE) blends of low and high molecular weight components under shear flow was studied using time-resolved depolarized light scattering (DPLS), focusing on effects of the high molecular weight component on the shish-kebab structure formation. Anisotropic two-dimensional scattering pattern due to shish-like structure formation was observed above a certain concentration of the high molecular weight PE. The threshold was about 2.5-3 times larger than the chain overlap concentration, suggesting an important role of entanglements of the high molecular weight component. On the basis of these results a gel-spinning-like mechanism for the shish-like structure formation has been proposed. The DPLS results also implied that the shish-like structure was mainly formed from the high molecular weight PE. This was confirmed by small-angle neutron scattering (SANS) and small-angle X-ray scattering (SAXS) measurements on an elongated PE blend of low molecular weight deuterated PE and high molecular weight hydrogenated PE (3 wt%).     

用旋转剪切法测量聚合物熔体零切粘度时应注意的几个问题

本文研究了不同测试条件下用旋转剪切法测量聚合物熔体零切粘度值的变化规律,并通过比较旋转剪切法所得数据与蠕变法及动态法数据,得出对于均聚物或均相共混体系零切粘度的测量,旋转剪切法与蠕变法及动态法同样适用。     

An empirical model relating the molecular weight distribution of high-density polyethylene to the shear dependence of the steady shear melt viscosity

An empirical model has been developed to relate molecular weight distribution to the shear dependence of the steady shear viscosity in high-density polyethylene melts. It uses a molecular weight, M_c, which partitions molecular weights into two classes; those below M_c contribute to the viscosity as they do at zero shear, and those above M_c contribute to the viscosity as though they were of molecular weight M_c at zero shear. Each individual molecular weight species contributes on the basis of its weight fraction. M_c is proposed to be a unique function of the shear rate. Using this method of treating the molecular weight distribution, and the zero shear relation for relating η0 to molecular weight, the calculated steady shear viscosities at various shear rates for polyethylene samples of widely varying polydispersities agree well with experimental results. The model makes no judgment on the existence or importance of entanglements in non-Newtonian behavior since it has no specific parameters involving an entanglement concept. Use of the model suggests that for the samples studied, only the upper portion of the molecular weight distribution contributes toward the experimentally observed decrease of steady shear viscosity with shear rate for shear rates of up to 10,000 sec^?1. The lower molecular weight species are assumed to behave in a Newtonian manner.     

Simulation of the polymeric fluid flow in the feed distributor of melt blowing process

The polymeric fluid flow in the feed distributor of melt blowing process is simulated using three‐dimensional finite element method. The numerical results are experimentally verified quantitatively and qualitatively using laser Doppler velocimetry and particle image velocimetry respectively. The effects of the distributor's geometric parameters on the uniformity of the transverse flow distribution are investigated. As the manifold angle increases, the flow distribution curve appears to transform gradually from a “hill” shape to a “bone” shape. The uniformity of flow distribution at distributor outlet, especially the fluctuation at the central part, will be improved by increasing the land height. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 1570–1574, 2006     

Energy model of the interfacial slip of polymer blends under steady shear

Interfacial slip at high‐density polyethylene (HDPE)/polystyrene (PS) and high‐impact polystyrene (HIPS)/PS interfaces under steady shear was studied. The multilayer structure and energy model for steady shear proposed by Lam and colleagues was employed. Results indicated that there was no interfacial slip at the HIPS/PS interface. However, interfacial slip was detected for HDPE/PS under steady shear. Small interfacial thickness and weak interactions between HDPE and PS was proposed as the reason for interfacial slip at the HDPE/PS interface. Chain orientation under shear was believed to promote chain disentanglement in the interfacial layer and therefore increase interfacial slip. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1164–1470, 2003     

Relationship between shear stress and shear strain of polymer melt under vibrating force field

Abstract

When a sinusoidal vibration was superimposed in parallel on the flow direction of a polymer melt being extruded through a capillary, the shear stress and shear rate of the polymer melt were analysed with a constant velocity type dynamic rheometer of capillary (CVDRC) devised by the authors. By measuring the instantaneous data of capillary entry pressure, capillary volume flux (or absolute velocity of piston rod) and their phase difference in a vibrating force field, it was found that the relationship between the pulsating amplitude value coefficient of entry pressure and that of volumetric flowrate was an approximate power series; the wall shear stress and wall shear rate of low density polyethylene (LDPE) melt extruded dynamically under various amplitudes and frequencies also exhibited a non-linear proportional relationship.     

Rheological characteristics of wheat starch pastes measured under steady shear conditions

Wheat starch pastes consist basically of swollen gel particles of various sizes which are dispersed in a continuous phase containing dissolved polysaccharides. The rheological properties of such pastes have been measured in the steady shear mode. At high shear rates the pastes behave as shear thinning liquids, while at low shear rates they exhibit a yield stress. The rheological properties vary with wheat starch variety and paste preparation conditions; this variation is of considerable economic importance to the starch industry. The present investigation shows that the flow behavior of pastes depends largely on two factors, namely, the volume which the starch gel particles would occupy when close packed if excess solvent were present, and the size distribution of the particles. Starch variety and paste preparation conditions influence these two factors and hence steady shear properties.     

Upgrading the melt flow index to rheogram approach in the low shear rate region

The unified viscosity function curves proposed earlier by the authors have an inherent limitation in the low shear rate region. This limitation is the effect of using the melt flow index as a normalizing factor to obtain the coalesced curves, which itself is insensitive to molecular parameters such as molecular weight distribution. A single integral constitutive equation of the BKZ type is used to derive the viscosity function which would be useful in generating unified curves based on the melt flow index but devoid of the limitation of molecular weight distribution effects in the low shear rate region.     

聚酯熔体在喷丝孔中剪切流动对纺丝动力学的影响

通过建立动力学模型,采用有限元的方法研究了喷丝孔结构对涤纶熔纺动力学的影响;通过改变喷丝孔微孔直径、增加微孔出口倒角,计算得到了喷丝孔内熔体的挤出速度和压力分布,以及纺程段丝条的速度、速度梯度、直径、温度、拉伸应力、取向和结晶分布;进一步讨论了微孔直径和微孔出口倒角对于喷丝孔内熔体的流动行为、压力降、挤出胀大以及纺程段丝条的结构性能的影响。结果表明:改变喷丝孔微孔直径能够有效地调控喷丝孔内熔体的挤出速度和压力降,从而改变挤出胀大比和拉伸应力;微孔出口倒角对喷丝孔内熔体流动影响不大,主要影响纺程段丝条的结构与性能;喷丝孔微孔带有出口倒角时,可以削弱纺丝过程的挤出胀大现象,纺程段丝条的拉伸应力、取向度和结晶度都有不同程度的提高,并且会使发生取向和结晶的位置更加靠近喷丝板。     

Relationship in polypropylene melt between its linear viscoelasticity and its steady capillary flow properties

It is the object of the present study to obtain clear knowledge of the relations in the polypropylene melt between its linear viscoelasticity and its nonlinear steady capillary flow, paying particular attention to the elastic properties in its capillary flow. By representing the linear viscoelasticity numerically with zero-shear viscosity, η₀, and steady-state compliance, J, evaluation has been made of the properties concerning the elasticity of polymer melt in the capillary flow, such as non-Newtonianity, the entrance pressure loss, the end correction, the Barus effect, and the melt fracture. The steady flow viscosity η, the entrance pressure loss P₀, the critical shear stress, τ_c, and the critical shear rate $\dot \gamma _c$ at which melt fracture begins to occur are subject to η₀ as follows: From the well-known relationship between η and the weight-average molecular weight M?_w, these quantities are governed by M?_w. Meanwhile, for such quantities as structural viscosity index N, end correction coefficient ν, and elastic pressure loss ratio P₀/P, following correlations hold: As η₀ and J are respectively determined mainly by M?_w and the molecular weight distribution MWD, these quantities are governed by both M?_w and MWD. Physical meanings of η₀·J and η₀² · J are, respectively, mean relaxation time and a measure of stored energy in steady flow. The Barus effect has a positive correlation to J, ν, and P₀/P. (The symbol ∝ employed here means positive correlation.)