Effect of oxalic acid on the rheological properties of dope solution of poly[acrylonitrile‐co‐(methyl acrylate)‐co‐(itaconic acid)]

The very high dope viscosity of concentrated dope of poly[acrylonitrile‐co‐(methyl acrylate)‐co‐(itaconic acid)] (with M?_v = 10.67 × 10⁵g mol^?1) in DMF could be diminished significantly by the addition of oxalic acid (OXA). The change in steady shear rheological behaviour caused by OXA has been analysed for the dope using a rheometer working in the viscosity mode. The temperature dependence of η₀ conformed to the Arrhenius‐Frenkel‐Eyring equation. ΔG_v decreased marginally with OXA concentration, and the least value was observed at an OXA concentration of 0.63 % by weight. Shear thinning behaviour was observed under higher shear rates for the terpolymer solutions in the presence and absence of OXA. The pseudoplasticity index (n) showed an abrupt initial increase on addition of OXA. The OXA concentration of 0.63 % by weight was advantageous for decreasing the viscosity of the polymer dope. The reduction in viscosity is attributed to the disturbed polymer‐polymer interactions by way of H‐bonding of OXA with the polymer. OXA‐containing dope at higher shear rate could achieve very low viscosities. Copyright © 2004 Society of Chemical Industry     

Poly(p‐phenylene benzoxazole) fiber chemically modified by the incorporation of sulfonate groups

Two kinds of modified poly(p‐phenylene benzoxazole) (PBO), the copolymer of TPA (SPBO) and p‐SPBO, containing ionic groups in the macromolecular chains were obtained by copolymerization from 1,3‐diamino‐4,6‐dihydroxybenzene dihydrochloride (DAR) and terephthalic acid (TPA), with the addition of selected amounts (1.5–5.0% molar ratio over DAR) of 5‐sulfoisophthalic acid monosodium salt or sulfoterephthalic acid monopotassium salt in place of the TPA, respectively, in poly(phosphoric acid) (PPA). The resultant PBO/PPA, SPBO/PPA, and p‐SPBO/PPA lyotropic liquid‐crystalline solutions were spun into fibers by a dry‐jet wet‐spinning technique. Chemically modified PBO fibers with sulfonate salt pendants in the polymer chains were obtained for the first time. The surface wetting behavior and interfacial shear strength between the fiber and epoxy resin were investigated. The interference of sulfonate salt pendants on the crystalline morphology was measured. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci 2008     

Viscosity behavior of microwave‐heated and conventionally heated poly(ether sulfone)/dimethylformamide/lithium bromide polymer solutions

This article investigates the viscosity behavior of new membrane dope solutions of poly(ether sulfone) (PES) and dimethylformamide with low‐molecular‐weight halogenated lithium bromide (LiBr) additives prepared with two different techniques: (1) a microwave (MW) technique and (2) a conventional heating (CH) technique. In addition, the influence of different concentrations of anhydrous halogenated LiBr additives (0–5 wt %) on the viscosity behavior is analyzed. The viscosity of the dope solutions was assessed with a conical rheometer equipped with a high‐viscosity adapter. The results revealed that the pure PES solutions prepared by the MW and CH techniques exhibited pseudoplastic and Newtonian behavior, respectively. Both the MW and CH PES solutions containing the LiBr additives exhibited dilatant behavior, which obeyed the power law. The apparent viscosity of all the dope solutions prepared with the MW technique was lower than that of those prepared with the CH technique. © 2007 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Rheological properties of poly(trimethylene terephthalate) in capillary flow

The shear viscosity, extensional viscosity, and die swell of the PTT melt were investigated using a capillary rheometer. The results showed that the PTT melt was a typical pseudoplastic fluid exhibiting shear thinning and extensional thinning phenomena in capillary flow. There existed no melt fracture phenomenon in the PTT melt through a capillary die even though the shear rate was 20,000 s^?1. Increasing the shear rate would decrease the flow activation energy and decline the sensitivity of the shear viscosity to the melt temperature. The molecular weight had a significant influence on the flow curve. The flow behavior of the PTT melt approached that of Newtonian fluid even though the weight‐molecular weight was below 43,000 s^?1 at 260°C. The extensional viscosity decreased with the increase of the extensional stress, which became more obvious with increasing the molecular weight. The sensitiveness of the extensional viscosity to the melt temperature decreased promptly along with increasing the extensional strain rate. The die swell ratio and end effect would increase along with increasing the shear rate and with decreasing the temperature, which represented that the increase of the shear rate and the decrease of temperature would increase the extruding elasticity of the PTT melt in the capillary die. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 97: 705–709, 2005     

聚丙烯熔体拉伸流变行为的研究

采用双料筒毛细管流变仪,对两种不同摩尔质量的等规聚丙烯的剪切及拉伸流变行为进行了研究,并采用Cogswell方法计算了熔体的拉伸强度。结果表明：聚丙烯为假塑性流体,随着剪切速率的增加,熔体的表观剪切黏度下降,呈现出假塑性流体典型的“剪切变稀”行为。在相同的温度和剪切速率下,平均摩尔质量较小、分布较宽的聚丙烯的表观剪切黏度及拉伸黏度均较小,但熔体的拉伸强度较大,意味着其具有较好的流动性能,并具有较高的可拉伸性,可以达到较大的拉伸比。     

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     

Rheology of polymers containing carbon black

In order to elucidate the flow behavior of electrophotographic toner systems, shear stress was measured as a function of shear rate in a cone and plate rheometer for polymer melts containing carbon blacks of surface area 24 and 625 m²/g at several concentrations and temperatures. Polymers included high and low molecular weight polystyrene and poly(butyl methacrylate). The addition of carbon black to the polymers caused a large increase in viscosity, especially at low shear rates and shear stresses. As the concentration of carbon black was increased, the viscosity at low shear rates became unbounded below a value of the shear stress designated the yield stress. The absolute magnitude of the yield stress depended primarily on the concentration and surface area of the carbon black and was independent of the polymer and temperature. Apparently, carbon black forms an independent network within the polymer at low shear rates which precludes flow. In some cases, the viscosity of polymers filled with carbon black was lower than that of the pure polymer. This effect was favored for polystyrene compared to poly(butyl methacrylate) and was facilitated by increasing the molecular weight of polystyrene, reducing the surface area and concentration of carbon black, and by increasing the temperature and shear rate.     

Rheological behavior of ethylene–octene copolymer vulcanizates: Effect of blowing agent and precipitated silica filler

An experimental study of the rheological behavior of ethylene–octene copolymer vulcanizates in extrusion containing blowing agent has been carried out. The cell morphology development has been studied through a scanning electron microscope. Rheological properties of unfilled and precipitated silica‐filled systems with variations of blowing agent, extrusion temperature, and shear rate have been studied by using a Monsanto processibility tester (MPT). The total extrusion pressure (P_T), apparent shear stress (τ_wa), apparent viscosity (η_a), and die swell (%) of the unfilled and silica‐filled compounds have been determined by using MPT. The effect of blowing agent (ADC) on the rheological properties of the vulcanizates has also been investigated. There is a reduction of stress and viscosity with blowing agent loading. It was observed that the incorporation of a blowing agent led to decreased shear thinning behavior resulting in an increase in power law index. The viscosity reduction factor (VRF) of unfilled vulcanizates is found to be dependent on the concentration of the blowing agent, shear rate, and temperature, whereas VRF of silica‐filled vulcanizates is found to be dependent on shear rate, temperature, and blowing agent concentration. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 1132–1138, 2003     

Linear and nonlinear melt‐state viscoelastic properties of polypropylene/organoclay nanocomposites

Rheological behavior of polypropylene (PP)/organoclay nanocomposites varying in compatibilizer (PP‐g‐MA) and organoclay concentration was investigated. The samples were prepared by melt intercalation method in an internal mixer. The wide angle X‐ray diffraction patterns and results of rheological measurements showed that the compatibilizer had strong influence in increasing the interlayer spacing. The observed low frequency liquid‐like to solid‐like transition and apparent yield stress in simple shear flows, along with convergence of transient shear stress to nonzero values in stress relaxation after the cessation of flow experiments, were found to be consistent with formation of a physical network in quiescent conditions which could be easily ruptured with applying low shear rates. The values of stress overshoot strain in flow reversal experiments were independent of shear rate, organoclay, and compatibilizer content. From the results of frequency sweep experiments in different nonlinear strain amplitudes it was shown that extended Cox‐Merz analogy was valid in nonlinear dynamic deformations while the shear viscosity showed positive deviation from this analogy with higher deviations at lower shear rates. Results of storage modulus recovery and flow reversal experiments at different shear rates suggested that network structure is reformed with a much slower rate compared to the rotational relaxation of organoclay platelets. POLYM. ENG. SCI., 2008. © 2008 Society of Plastics Engineers     

Melt rheology of polypropylene reinforced with polyaniline‐coated short glass fibers

This research deals with the melt rheology of isotactic polypropylene (iPP) reinforced with short glass fibers (SGF) coated with electrically conductive polyaniline (PAn). Composites containing 10, 20, and 30 wt % PAn‐SGF were studied. Moreover, a composite of 30 wt % PAn‐SGF was also prepared with a blend of iPP and PP‐grafted‐maleic anhydride (iPP/PP‐gMA). The composites showed linear viscoelastic regime at small strain amplitudes. The onset of nonlinearity decreased as the concentration of filler increased. The time‐temperature superposition principle applied to all composites. The filler increased the shear moduli (G′, G″) and the complex viscosity η*. Steady‐state shear experiments showed yield stress for the composites with 20 and 30 wt % PAn‐SGF. Strikingly, the 10 wt % composite showed higher steady state viscosity than the 20 wt %. Rheo‐optics showed that shear induced disorder of microfibers at a concentration of 10 wt %. However, at 20 wt % concentration shear aligned the microfibers along the flow axis, this would explain the anomalous steady state viscosity values. The viscosity exhibited a shear thinning behavior at high shear rates for all composites. Creep experiments showed that the filler induced greater strain recovery in the composites and that the amount of strain recovery increased as the PAn‐SGF concentration increased. However, the enhancement of strain recovery (as well as shear viscosity) was more significant when using the iPP/PP‐gMA blend, suggesting greater adhesion between this matrix and the filler PAn‐SGF. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008     

Study of rheological property of nylon‐1212 with Haake Rheometer

Rheological properties of nylon‐1212 have been studied by means of Haake Rheometer. The effect of shear rate and temperature on the apparent vicosity of nylon‐1212 was discussed. A correlation of non‐Newtonian index with the temperature was obtained. The results showed that the apparent viscosity decreases with the increase of the temperature. With increasing shear rate, shear thinning of nylon‐1212 was observed clearly. From the relation of the temperature dependence of the polymer, we obtained the viscous flow activation energy. We conclude that the apparent viscosity is sensitive to temperature at lower shear stress because of higher viscous flow activation energy, and the temperature affect on the apparent viscosity becomes weaker at higher shear stress because of lower viscous flow activation energy. We have investigated the creep and elastic recovery of nylon‐1212. A creep test was carried out to define the linear viscoelastic range as 1.0 and 5.0 Pa for 195 and 190°C nylon‐1212 melts, respectively. A time‐dependent response was found for the creep and recovery phases at a lower applied shear stress. However, at higher shear stress, the creep and recovery phases were time‐independent. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 89: 379–385, 2003     

Thermal degradation kinetics of poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate)

The degradation kinetics of poly(3‐hydroxybutyrate‐co‐3‐hydroxyhexanoate), a member of the Nodax family of polymers, were investigated using transient constant shear rate and dynamic time sweep rheological tests. The rate of chain scission at several times and temperatures was correlated with viscosity data and verified using molecular weight determination of the degraded samples. The experimental results show that the molecular weight and the viscosity of Nodax decrease with time over the range of temperatures that were studied (155–175°C). The degradation kinetics, which exhibited first‐order behavior, were determined as a function of the flow history and thermal history. An apparent activation energy of 189 ± 5 kJ/mol for thermal degradation was found by modeling variations in the rate with temperature using an Arrhenius law model. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 98: 66–74, 2005     

A Survey of Rheological Properties of One-Component Epoxy Adhesives

Flow characteristics of seven commercially available one-component epoxy adhesive pastes were measured using a controlled shear stress rheometer and a controlled shear rate rheometer over a temperature range from 5°C to 60°C. Combining data obtained from both controlled rate and controlled stress experiments over a wide range of shear rates, we observed Newtonian flow (shear stress proportional to shear rate) at very low shear rates, a plateau “shear thinning” region at intermediate shear rates, and a second region of linear dependence of shear stress on shear rate at high shear rates. The adhesive pastes exhibited a very broad range of rheological behavior. Two flow parameters important to adhesive application technology, the plastic viscosity and the apparent yield stress, were measured for each adhesive. The plastic viscosity ranged from 11.6 to 329.5 Pa. s; the apparent yield stress ranged from 56.2 to 413 Pa. The temperature dependence of the rheological parameters of the epoxy adhesive pastes was also determined. The results are reported as the activation energies, E_η and E_σ , of plastic viscosity and apparent yield stress, respectively. The apparent yield stress of each adhesive paste was much less sensitive to changes in temperature than was the plastic viscosity. This suggests that the processing characteristics are likely to show qualitative as well as quantitative changes with temperature.     

Molecular characterization and rheological properties of modified poly(ethylene terephthalate) obtained by reactive extrusion

The use of a tetrafunctional epoxy‐based additive to modify the molecular structure of poly(ethylene terephthalate) (PET) was investigated with the aim of producing PET foams by an extrusion process. The molecular structure analysis and shear and elongation rheological characterization showed that branched PET is obtained for 0.2, 0.3 and 0.4 wt% of a tetrafunctional epoxy additive. Gel permeation chromatography (GPC) analysis led to the conclusion that a randomly branched structure is obtained, the structure being independent of the modifier concentration. The evolution of shear and extensional behavior as a function of molecular weight (M_w), degree of branching, and molecular weight distribution (MWD) were studied, and it is shown that an increase in the degree of branching and M_w and the broadening of the MWD induce an increase in Newtonian viscosity, relaxation time, flow activation energy and transient extensional viscosity, while the shear thinning onset and the Hencky strain at the fiber break decrease markedly.     

Non‐newtonian rheological behavior of semi‐dilute ultra‐high molecular weight polyethylene solution in gel‐spinning process. 1: Concentration effect on the fundamental rheological properties

The rheological properties of a semi‐dilute ultra‐high molecular weight polyethylene (UHMw‐PE)/paraffin wax solution were investigated by mainly focusing on the influence of its concentration on the shear flow viscosity. It was found that the UHMw‐PE solution exhibits a shear‐thinning behavior at a very wide shear rate range from 10^?4 to higher than 10³ sec^?1. Furthermore, this typical non‐Newtonian behavior was more obvious with a concentration increase. From the concentration dependence of the zero‐shear creep compliance or other rheological factor, it was found that the extremely large M_e value of the system gives rise to various kinds of non‐Newtonian behaviors, especially those highly elastic in nature. Finally, the origin of the abnormal stress fluctuation during the steady shear measurement was found to be related to the shear‐induced structural development of the solution.     

醋酸纤维素/壳聚糖纺丝原液的流变性能研究

采用锥板式旋转粘度计法对醋酸纤维素/壳聚糖共混原液的流变性能进行测定。结果表明,醋酸纤维素/壳聚糖共混原液无第一牛顿区,为非牛顿流体。随着剪切速率的加大,原液呈现切力变稀现象。温度在较大剪切速率范围内影响着原液的粘度,粘度随温度的上升而下降,但在高剪切速率区间,温度的影响很小。总体来说,粘流活化能?Eη随原液总固浓度的提高而降低,但在总固浓度为8%左右时出现了一个极大值。原液的结构化程度随体系温度上升、总固浓度下降而减小。     

BOPP专用树脂的流变行为研究

利用高压毛细管流变仪,对三种不同BOPP专用树脂的流变性能进行测定,BOPP专用料均表现为剪切应力随剪切速率增加而增加,但增加速率明显减弱,表观粘度随剪切速率增加而减小的特点,具有明显的假塑性的流动行为。通过分析温度、剪切速度和分子量及其分布对树脂的表观粘度的影响,确定不同树脂改善熔体粘度最有效的方法。     

Rheological and mechanical properties of thermoplastic polyurethane elastomer derived from CO2 copolymer diol

CO₂ copolymer diol‐based thermal polyurethane elastomers (PPC‐TPU) were prepared by the reaction of CO₂ copolymer diol and methylene diphenyl diisocyanate and chain extender (ethylene glycol/1,4‐butanediol/1,6‐hexanediol) (EG/BDO/HG). The rheological and mechanical properties of PPC‐TPU were analyzed. The effects of shear rate, shear temperature, hard segment content, and variety of chain extender on the properties of PPC‐TPU were studied. The results showed that the apparent viscosity (η) of PPC‐TPU decreased with the increasing shear rate (τ), and the non‐Newtonian index (n) was less than 1. PPC‐TPU exhibited a typical character of pseudoplastic non‐Newtonian rheological behavior. The degradation during the processing was obviously inhibited by adding plasticizer and antioxidant. It was also discovered that the apparent viscosity varied with the content of hard segment and chain extender. Under the same temperature (185 °C) and shear rate (50 s^?1), the apparent viscosity increased considerably with the raise of hard segment content, and the apparent viscosity and tensile strength of PPC‐TPU with EG as chain extender was the maximum. It can be seen that with the apparent shear rate increasing, the variation tendency of apparent shear stress levels off, and the nonlinear relationship of τ–γ curve tended to be obvious. PPC‐TPU exhibited a typical character of pseudoplastic non‐Newtonian rheological behavior. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45974.     

Comparative studies of rheological properties of polyacrylamide and partially hydrolyzed polyacrylamide solutions

The present work is concerned with experimental results of rheological characteristics of polyacrylamide (PAM) and of partially hydrolyzed polyacrylamide (HPAM) (degree of hydrolysis up to 80%) in aqueous and aqueous/sodium chloride solutions with changing experimental conditions such as polymer concentration, temperature, solvent quality, and shear rate applied. It has been observed that the all‐aqueous and aqueous/NaCl solution of PAM and of HPAM exhibited the non‐Newtonian behavior with shear‐thinning and shear‐thickening areas. The onset of shear‐thickening at depends mainly on the degree of HPAM hydrolysis, as well as on solution concentration, temperature, solvent quality, and polymer molecular weight. Rheological parameters from power law (Ostwald de Waele model) and activation energy of viscous flow (E_a) are determined and discussed. The changes in apparent shear viscosity during aging of solutions of PAM and HPAM are also described. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2235–2241, 2007     

Effects of extrusion conditions on rheological behavior of acrylonitrile–butadiene–styrene terpolymer melt

The influence of temperatures and flow rates on the rheological behavior during extrusion of acrylonitrile–butadiene–styrene (ABS) terpolymer melt was investigated by using a Rosand capillary rheometer. It was found that the wall shear stress (τ_w) increased nonlinearly with increasing apparent shear rates and the slope of the curves changed suddenly at a shear rate of about 10³ s^?1, whereas the melt‐shear viscosity decreased quickly at a τ_w of about 200 kPa. When the temperature was fixed, the entry‐pressure drop and extensional stress increased nonlinearly with increasing τ_w, whereas it decreased with a rise of temperature at a constant level of τ_w. The relationship between the melt‐shear viscosity and temperature was consistent with an Arrhenius expression. The results showed that the effects of extrusion operation conditions on the rheological behavior of the ABS resin melt were significant and were attributable to the change of morphology of the rubber phase over a wide range of shear rates. © 2002 Wiley Periodicals, Inc. J Appl Polym Sci 85: 606–611, 2002