Mechanical degradation of semi-dilute polymer solutions in laminar flows

Mechanical degradation of a semi-dilute solution of non-hydrolyzed polyacrylamide was studied under laminar flow conditions through fine capillary systems. Using a multi-pass device and capillary tubes of the same diameter and of various lengths we have shown that mechanical degradation (i) occurs at a critical value of the wall shear rate, chosen as a reference deformation rate, which is slightly higher than that of the appearance of high pressure losses in the entrance region of the capillary tube; (ii) is independent of the capillary tube length; (iii) increases with the number of passes N up to a maximum value for a limiting number of passes N_lim which is a decreasing function of deformation rates but does not depend on capillary length. The amount of degradation is expressed in terms of loss of viscous dissipation in shear and transient elongational flow. This last point is determined by studying the total end pressure loss through the capillary tube as a function of the pass number. The high pressure loss is related to viscous dissipation on macromolecules stretched by rapid converging flow. A comparison between a fresh and a fully degraded solution indicates that the degradation affects shear viscosity much less than viscous dissipation in rapid converging flow which is related to the properties of extended macromolecules. Both experimental results and theoretical interpretation suggest that, in our capillary system, the mechanical degradation occurs in the entrance region of the capillary where macromolecules are stretched and consequently submitted to extensional forces which can overcome the C–C bonds strength.     

The effect of viscous heating on the observed temperature dependence of mechanochemical reactions

The temperature dependence of mechanochemical reactions of high polymers is investigated in light of viscous dissipation in the flow field. The viscosity of the polymer melt is assumed to depend exponentially upon temperature, and the power-law model is used to describe the shear stress–shear rate relationship. Using equations previously reported in in the literature for the temperature profile generated in capillary flow, evidence that such an experimental system operates under decidedly nonisothermal conditions is presented. These equations, together with the classical Arrhenius equation for the temperature dependence of chemical reactions, predict that the average reaction rate in a capillary decreases, passes through a minimum, and increases as the capillary wall temperature is increased. Good agreement exists between the temperature at the minimum rate found in this work and that found experimentally for polystyrene, natural rubber, and polyisobutylene.     

Rheological behavior of semi‐aromatic transparent polyamide

The rheological behaviors of semi‐aromatic transparent polyamide (SATPA) melt are investigated using a capillary rheometer. The effects of shear rate, shear stress, and temperature on the apparent viscosity η_a of SATPA are discussed. A correlation of non‐Newtonian index with temperature is obtained. The results show the shear thinning of SATPA; meanwhile η_a decreases with increasing temperature and shear rate, and the viscous flow activation energy is further obtained from temperature dependence of the samples. It was concluded that the apparent viscosity η_a is sensitive to temperature at lower shear rate owing to the higher viscous flow activation energy; on the contrary, the influence of temperature effect on the apparent viscosity becomes minor at higher shear rate due to the lower viscous flow activation energy. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 1586–1589, 2005     

微尺度通道中聚合物熔体的黏性耗散效应

以双料筒毛细管流变仪和自行研制的黏性耗散测量装置为实验平台,通过对聚甲醛(POM)和聚苯乙烯(PS)两种聚合物熔体在不同剪切速率下,流经长径比相同的直径/当量直径分别为350 μm和500 μm的圆形及矩形截面微通道出口熔体温升的测量,研究了微尺度通道中聚合物熔体流动时的黏性耗散效应及其对熔体流变行为的影响。结果表明,两种截面微通道中的熔体黏性耗散效应均随剪切速率和微道直径/当量直径的增大而明显增强,其中矩形截面微通道中熔体的黏性耗散作用尤为强烈;且在相同实验条件下,结晶性的POM熔体因黏性耗散效应引起的微通道出口熔体温升值,高于非晶性的PS熔体。     

Viscous dissipation in capillary flow of rigid PVC and PVC degradation

The steady state, non-isothermal behavior of rigid polyvinyl chloride melt, flowing in capillaries of circular cross-section, was investigated by solving, with the aid of a digital computer, the momentum and energy balance equations. It was assumed that the polymer melt can be described by the “Power Law” constitutive equation. The shear rate, temperature and pressure dependent properties of the fluid were obtained experimentally. The effects of the thermal degradation of PVC on its viscosity, were also introduced in the equations of momentum and energy. The velocity, temperature and pressure profiles, obtained for both adiabatic flow and flow through a tube of constant wall temperature, indicate that considerable heating of the melt, due to viscous dissipation, can be achieved at moderate flow rates. Thermal degradation occurs in the capillary under certain conditions of temperature history and residence time of the fluid. The results of this work are in fair agreement with experimental results in this area.     

高黏度聚酯流变行为的研究

采用毛细管流变仪研究了高黏度聚酯(PET)的表观黏度及黏流活化能随温度(280～300℃)及剪切速率(20～104s-1)的变化。结果表明:高黏度PET熔体随着剪切速率的增加出现切力变稀现象,随着熔体温度升高,剪切速率对熔体的表观黏度的影响降低;高黏度PET的黏流活化能随着剪切速率的提高而降低;在温度为300℃,剪切速率为3 000 s-1时,高黏度PET熔体具有较好的流动性。     

纺丝用可熔性聚四氟乙烯的流变性能研究

采用毛细管流变仪,对PFA熔体的流变性能进行研究。讨论了温度、剪切速率对纺丝用PFA熔体的非牛顿指数、表观粘度、结构粘度指数等方面的影响。结果表明,PFA熔体非牛顿指数随温度上升而升高。在不同温度下,PFA熔体的粘度均随着剪切速率的增大而减小,表观粘流活化能随剪切速率增加而减小。PFA熔体的结构粘度指数Δη随熔体温度的增高而逐渐减小。     

固相缩聚半芳香透明聚酰胺的流变性能

采用毛细管流变仪对固相缩聚半芳香透明聚酰胺(Semi-AromaticTransparent Polyamide,简称SATPA)的流变性能进行了研究。研究结果表明:固相缩聚SATPA熔体属假塑性流体,非牛顿指数随剪切速率的增大而减小;表观黏度随温度、剪切速率和剪切应力的升高而降低。随着剪切速率的增大,黏流活化能减小,表观黏度对于温度的敏感性减弱。     

Superimposed effects in high‐shear‐rate capillary rheology of polystyrene melt

During micro‐injection molding, the polymer melt may undergo a shear rate up to 10⁶ s^?1, at which the rheological behaviors are obviously different from those in conventional molding process. Using both online and commercial rheometers, high‐shear‐rate capillary rheology of polystyrene (PS) melt is analyzed systematically in this work. The accurate end pressure drop and pressure coefficient of viscosity are determined via the enhanced exit pressure technique. Experimental and theoretical investigations are conducted on four significant effects, that is, the dissipative heating, end pressure loss, pressure dependence, and melt compressibility in capillary flow. For the PS melt, which exhibits distinct temperature and pressure dependence of viscosity, both dissipation and end effects become pronounced as the shear rate exceeds 2 × 10⁵ s^?1. From lower to higher shear rates (10³–10⁶ s^?1), the competition between dissipation and pressure effects results in the overestimation to underestimation of Bagley‐corrected pressure drop, and finally the comprehensively corrected viscosity becomes about half of the uncorrected one owing to the enhanced superimposed effects. Moreover, the compressibility shows a minor influence on the shear viscosity. Under the shear rate range investigated, the power‐law relationship is sufficient for describing the corrected viscosity curve of PS melt used. POLYM. ENG. SCI., 2013. © 2012 Society of Plastics Engineers     

聚碳硅烷流变性能的研究

采用 Instron毛细管流变仪 ,研究了不同温度下聚碳硅烷的流变性。结果表明 ,聚碳硅烷为典型的切力变稀流体 ,而且由牛顿流动向“切力变稀”流动的临界切变速率随温度升高而增大。其粘度温度关系基本满足 Arrhenius方程 ,粘流活化能很高 ,表观粘度随温度升高下降显著 ,为了提高纺丝的稳定性 ,必须严格控制纺丝温度     

同向旋转双螺杆挤出机计量段中聚合物挤出的模拟

建立了非牛顿粘性聚合物熔体在同向旋转双螺杆挤出机计量段中的三维 非等温流动模型,利用网络叠合技术分析挤出机计量段内速度、温度、压力、粘度、粘性耗散热的分布以及螺杆转速、轴向压差对挤出量的影响。     

进口聚苯硫醚树脂流变性能的研究

采用毛细管流变仪研究了日本聚苯硫醚(PPS)树脂的流变性能。结果表明:随着剪切速率的增加,PPS的表观粘度降低;当温度升高时,PPS的表观粘度也降低;剪切速率越高,温度对剪切速率的影响越小;随着温度的增加,非牛顿指数增加且趋近于1,PPS熔体为假塑性流体;PPS的粘流活化能随着温度的增加而减小;此外,随着温度的增加,结构粘度指数减小。     

聚丙烯/丙烯-乙烯共聚物共混体系的流变行为研究

采用毛细管流变仪和旋转流变仪研究了聚丙烯(PP)纤维专用料/丙烯-乙烯共聚物(PEC)共混体系的流变行为,探究了剪切速率、温度、共混物组成对熔体流变行为的影响。结果表明,随着剪切速率的增加,PP、PP/PEC和PEC均表现出"剪切变稀"行为;随着温度的升高,聚合物的表观黏度逐渐降低,特别是在低剪切速率下的这种现象更明显;随着PEC含量的增加,体系的非牛顿指数增加,黏流活化能降低,黏度对温度的敏感性降低,熔体剪切模量增加,熔体弹性增加。     

Stratified two-phase flog of molten polymers in circular dies

A theoretical study has been carried out on the steady, axisymmetric two-phase flow of molten polymers in circular dies. For both fluids, the shear rate dependence of the viscosity is described by a power law and the temperature dependence by an exponential function. Taking into account viscous dissipation, a numerical program has been developed to predict the radial position of the interface between the two fluids, the developing temperature and velocity fields, the shear rates, the shear stresses, the pressure drop as well as the field of shear deformation and the residence time distribution for different thermal boundary conditions. The numerical program is applied to the flow of a high-viscous polymer melt, (high density polyethylene), surrounded by a small annulus of less viscous polymer ni lt, (low density polyethylene). Computed results are shown graphically.     

A comparison of the flow behavior of linear polyethylene,poly(butylene terephthalate), and poly(ethylene terephthalate)

The viscous and elastic properties of linear high density polyethylene (HDPE), poly(butylene terephthalate) (PBT), and poly(ethylene terephthalate) (PET) are investigated using an Instron capillary rheometer and the Philippoff–Gaskins–Bagley analysis. The viscous properties studied are the shear viscosity and the constant shear rate activation energy and the elastic properties studied are the entrance pressure drop and the end correction. The variables are shear rate and temperature. The order of decreasing viscosity is HDPE>PET>PBT; the order of decreasing activation energy is PB>PET>HDPE; the order of decreasing entrance pressure drop is HDPE>PET>PBT; and the order of decreasing end correction is PBT>PET>HDPE. As temperature increases, both viscosity and entrance pressure drop decrease. The observed behavior is discussed in terms of the difference in number of terephthalic acid moities in the polymer chains and in terms of oligomer plasticization.     

Capillary flow of low‐density polyethylene

The capillary flow of a commercial low‐density polyethylene (LDPE) melt was studied both experimentally and numerically. The excess pressure drop due to entry (Bagley correction), the compressibility, the effect of pressure on viscosity, and the possible slip effects on the capillary data analysis have been examined. Using a series of capillary dies having different diameters, D, and length‐to‐diameter L/D ratios, a full rheological characterization has been carried out, and the experimental data have been fitted both with a viscous model (Carreau‐Yasuda) and a viscoelastic one (the Kaye—Bernstein, Kearsley, Zapas/Papanastasiou, Scriven, Macosko, or K‐BKZ/PSM model). Particular emphasis has been given on the pressure‐dependence of viscosity, with a pressure‐dependent coefficient β_p. For the viscous model, the viscosity is a function of both temperature and pressure. For the viscoelastic K‐BKZ model, the time‐temperature shifting concept has been used for the non‐isothermal calculations, while the time–pressure shifting concept has been used to shift the relaxation moduli for the pressure‐dependence effect. It was found that only the viscoelastic simulations were capable of reproducing the experimental data well, while any viscous modeling always underestimates the pressures, especially at the higher apparent shear rates and L/D ratios. POLYM. ENG. SCI., 2012. © 2012 Society of Plastics Engineers     

Anomalous behavior of unplasticized PVC compounds in capillary flow

Capillary rheometry was performed over a temperature range of 170°–200°C and a shear-rate range of 3–3000 sec^?1 on an unplasticized poly(vinyl chloride) compound. The data were corrected for the effect of pressure on viscosity, for pressure loss in the barrel and at the capillary entrance, and for the non-Newtonian velocity profile. The pressure coefficient of viscosity was found to be in the same order of magnitude as those previously found with linear polyethylene and butadieneacrylonitrile copolymers. The pressure–shear-rate superposition of the flow curves is valid at least approximately, although the temperature–shear-rate superposition is inapplicable. The shape of flow curves at 180°, 190°, and 200°C are concave downward when they are expressed as log-shear-stress-log-shear-rate. Similar plots at 170° and 175°C, however, are very different; shear stress is independent of shear rate at low shear rates, increases somewhat and becomes independent of shear rate again at high shear rates. There is no detectable temperature dependence of flow behavior at 170° and 175°C. Irregularly shaped extrudates were obtained at higher shear rates. At constant shear rate the irregularity increased with the length of the capillary. The effect of thermal-mechanical history on the particulate and crystalline structure is discussed with possible influence on the reproducibility of the rheological data.     

Viscosity measurement in a pipe flow using a numeric recursion approach for in-line quality control

The use of a pipe as a sensor for measuring viscosity and shear rate would require a separated flow rate instrument and would result in a more complicated mechanism for in-line quality control. In this study, a method of applying numeric recursion to the pipe pressure drop to directly calculate the viscosity and the shear rate is proposed. This viscosity sensor was verified by using it to measure the viscosity and shear rate for low-density polyethylene. The viscosity and shear rate obtained by this approach differ little from those obtained by using a standard off-line capillary rheometer. Therefore, this viscosity measurement method is applicable for in-line quality control.     

Viscous and elastic behaviour of SEBS triblock copolymer

The viscous and elastic behaviour of the saturated triblock copolymer polystyrene-block-poly(ethylene-co-butylene)-polystyrene (SEBS) was investigated using a capillary viscometer. The viscous behaviour was evaluated from the variation of viscosity with shear and temperature, and the elastic behaviour from the capillary entrance pressure loss, die swell ratio and surface roughness. The melt behaviour was found to result from the two-phase structure which existed up to a particular shear and/or temperature and thereafter from the single-phase structure.     

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。