Rheological properties of molten polymers. II. Two-phase systems

A study is carried out for characterizing two-phase systems of molten polymers by their viscous and elastic properties. The two-phase systems chosen for study are blends of polystyrene and polypropylene, and blends of polystyrene and high-density polyethylene. For the study, measurements of wall normal stresses are made by use of a capillary melt rheometer described in part I of this series. The concept of the “exit pressure” is used to determine the elastic properties of the two-phase polymer systems. The present study shows anomalous viscous and elastic properties of two-phase systems, which are difficult to predict from knowing the viscous and elastic properties of their individual components. A detailed discussion is given on the state of dispersion of two incompatible polymer systems in the molten state, by presenting pictures of the microstructure of the extrudate samples. The state of dispersion appears to vary depending on the blending ratio, extrusion temperature, melt viscosities of individual components, and blending method.     

Rheological study of mixing in molten polymers: 2-mixing of reactive systems

Three reactive polymer systems have been examined with a new mixing device adapted on a classical rheometer in order to investigate reactive mixing situations encountered in polymer blends. After having characterized the bulk polymerization of ε-caprolactone (ε-CL), the polymerization of 40 wt% of ε-caprolactone into a copolymer of ethylene and vinyl acetate (EVA) was run into the rheo-mixer. The kinetics of the reaction in dispersed media was observed slightly different from that in bulk since the characteristic time of ε-caprolactone diffusion into EVA is much lower than its time of mixing. On the other hand, it was observed that the molecular weight distribution of the poly(ε-caprolactone) is broader in dispersed media (I_p=2.6) than in bulk (I_p=1.6). A broadening of the molecular weight distribution in dispersed media was pointed out due to the fact that ε-CL monomer is partitioned between the EVA and PCL phases leading to a non-homogeneous concentration of monomer in the reactive phase.The polycondensation of 40 wt% of a epoxy-amine system into a polystyrene matrix was also investigated and the morphology of the resulting material examined. A gradient of structure and conversion was detected in a blend obtained from the assembly of two initially non-reactive layers. The gradient reveals that the amine diffuses faster than the epoxy leading to non-stoichiometry of the reactive functions across the sample. When the blend was polymerized under shear, the kinetic of the reaction remained unchanged regardless the level of shear. However, the morphologies were significantly different, pointing out the importance of the coalescence and droplet deformation phenomena. Spherical droplets were observed at 0.15 s⁻¹, elongated droplets and fibers at 1.5 and 15 s⁻¹.     

Measurement of the rheological properties of polymer melts with slit rheometer. I. Homopolymer systems

Two slit dies have been designed, having aspect ratios of 10 and 20. Three melt pressure transducers were flush-mounted on the long side of the rectangular slot, along the longitudinal centerline of each die. The dies were then used to measure wall normal stresses along the longitudinal direction of polymer melts flowing through the thin slit. The polymeric materials investigated were high-density polyethylene, low-density polyethylene, polypropylene, and polystyrene. The measurement of wall normal stresses were used to determine the rheological properties of melts, namely, the melt viscosity from the slope of axial pressure profiles and the melt elasticity from exit pressures. The present study shows that the rheological properties determined from the slit rheometer are in good agreement with those from the capillary rheometer reported in the author's earlier papers. Therefore it may be concluded that a slit die also may be used as a means of characterizing polymeric materials by their viscous and elastic properties in the molten state.     

Rheological properties of molten poly(ethylene terephthalate)

The complete steady-state flow properties of molten poly(ethylene terephthalate) for shear stresses ≦4.14 × 10⁶ dynes/cm² were determined. A single, complete master curve had been constructed in earlier work by Gregory and Watson; the curve interrelates the shear stress, shear rate, temperature, and molecular weight (inherent viscosity) by using a temperature superposition scheme from the literature and a similar molecular weight superposition scheme. Equations in agreement with theory and with other published experimental data were derived from the master curve. Results presented here make possible the direct calculation of the melt viscosity of poly(ethylene terephthalate) at shear stresses ≦4.14 × 10⁶ dynes/cm². The effects of a unit temperature change and/or a unit change in inherent viscosity (I. V.) on the melt viscosity were determined. For poly(ethylene terephthalate) with a 0.6 I. V., a 0.0025 change in I. V. accounts for about the same change in melt viscosity as a 1°C change in temperature.     

Rheological control in foaming polymeric materials: I. Amorphous polymers

The influence of rheological properties, especially melt strength, on foam structures, such as cell size, cell density and cell size distribution, of amorphous polymer was investigated. The rheology of polystyrene (PS) was controlled by molecular modification with free radical reaction, and PS with long chain branching (LCB) level ranging from 0.15 to 1.6 branching point per 10⁴ carbon atom was gotten. The shear and elongational rheology were found to be dependent on the LCB structure, and the strain hardening behavior of modified samples in transient elongational viscosity confirmed the existence of long branched chain. The effects of chain structure and foaming conditions such as temperature and pressure were studied by the analysis on the foam structures obtained by supercritical CO₂. The experimental results revealed that increasing LCB level would decrease cell size, make cell size distribution narrower and slightly increase cell density. The effects of chain topology on the foam structures were also investigated by numerical simulation, where Pom-Pom model was used to describe the effect of backbone length and arm length. The dependence of cell size on the arm length was consistently observed in experiments and simulation. It suggested that the arm length had greater influence on the cell radius than the backbone length. Therefore, the relationship among foam structures, rheological properties and molecular structures can be established from both experiments and simulation, which can be used as a guidance to control the foam structure by designing and controlling the molecular structures and the corresponding rheological properties.     

Rheological properties of mixtures of molten polymer and fluorocarbon blowing agent. I. Mixtures of low-density polyethylene and fluorocarbon blowing agent

The viscosities of mixtures of low-density polyethylene and fluorocarbon blowing agent were determined from the measurement of wall normal stress along the longitudinal axis of a capillary die. For the study, three different grades of commercial high-pressure low-density polyethylene were used, together with the following fluorocarbon blowing agents, dichlorodifluoromethane (FC-12), dichlorotetrafluoroethane (FC-114), and blends of FC-12 and FC-114. In the experiment, blowing agent concentration and melt temperature were varied for each combination of polymer and blowing agent employed. Analysis of the experimental data has led to a correlation between the viscosity reduction factor (VRF) and the blowing agent concentration, in which VRF is defined as the ratio of the viscosity of polymer-blowing agent mixture to that of the polymer alone. It was found that the correlation obtained is independent of shear rate and temperature and dependent upon only the type of fluorocarbon blowing agent. The practical significance of the correlation is discussed. We have shown that the entrance pressure drop obtained in the absence of phase separation in the entrance region may be used as a measure of the elastic properties of mixtures of fluorocarbon blowing agent and low-density polyethylene resin.     

Rheological characteristics of proanthocyanidin polymers from Pinus radiata. I. Rheological behavior of water-soluble extract fractions and phlobaphenes

The rheological characteristics of the solutions of the whole extracts and their fractions from the Pinus radiata bark were investigated. The viscosity changes upon addition of aqueous NaOH solution into the solutions of the hot water extracts are due mainly to the dissolution of the phlobaphene fraction. The polyelectrolyte character was established from the solutions of the hot-water extracts. The kinetics of the size growth of naturally forming phlobaphenes could be observed by photon correlation spectroscopy (PCS) from the solutions of hot-water extracts. Mild sonication could degrade phlobaphenes partly and this indicates that the formation of phlobaphenes is partly associated with colloidal interaction. © 1995 John Wiley & Sons, Inc.     

Rheological study of mixing in molten polymers: 1-mixing of low viscous additives

A new mixing device has been designed and developed in order to investigate complex mixing situations encountered in polymer blends and formulations. This mixing device called here rheo-mixer has been adapted on a classical rheometer and calibrated in terms of shear/stress that both permanent and dynamic regimes may be quantitatively run. The ability of the mixer to bring interesting information about complex polymeric systems was demonstrated by following the process of incorporation of a miscible liquid or partially miscible into a high viscosity polymer. As examples, EVA/diethyl 2-hexyl phtalate, poly(ε-caprolactone)/ε-caprolactone, and EVA/ε-caprolactone systems were tested.It was demonstrated that the viscosity ratio is not the predominant parameter for mixing process control because the mixing is mainly controlled by the diffusion for these low viscosity ratio systems (λ<10⁻⁵) as miscible systems (EVA/DOP and PCL/ε-CL) and partially miscible systems (EVA/ε-CL) are concerned. Actually, the mixing efficiency of these fluids is poor because the shear migration diminishes the rate of mixing due to a decrease of the deformation in the high viscous media. The mixing by thick striation is only effective when the viscosity ratio becomes, by the diffusion process, typically higher than 10⁻³. Furthermore, the discussion based on the mutual diffusion coefficient agrees well with the experimental finding, at least qualitatively.     

Transport properties of molten tetra-alkylammonium picrates—I. Viscosity

Viscosities and densities of some molten tetra-alkylammonium picrates have been measured near the glass temperature. The temperature dependence of viscosity shows systematic departures from Arrhenius behaviour and is better expressed by the free volume theory. The calculated T_O values allow the assumption that the existence of short range forces due to polarization of the CC bonds, originating on the far CH₃ groups by the inductive effect, have an important effect on transport phenomena in these melts.Comparison of our results with those of the Adam-Gibbs theory suggests that a corresponding temperature scale based on isoentropic states is probably the most useful basis for correlating liquid structural properties.     

疏水缔合聚合物交联弱凝胶流变性能研究

疏水缔合聚合物交联弱凝胶体系含有化学交联和物理缔合双重性能,采用Bohlin CVO流变仪测试了该体系的流变性,并采用Carreau模型和幂律模型对测试数据进行拟合。结果表明,疏水缔合聚合物交联弱凝胶体系完全满足这些模型,其零剪切粘度和稠度系数均随着交联剂和聚合物浓度的增加而增加。     

The non-linear viscoelastic properties of molten polymers and concentrated solutions

For polymer melts and concentrated solutions highly nonlinear effects dominate all aspects of both the transient and steady state mechanical behavior. The first part of this paper will review the salient features of the experimental results and focus attention on those common features which should be understood in a coherent manner. The various constitutive equations, especially the integral representations that have been proposed to describe polymer melts will also be discussed. They fall roughly into three classes: those where the relaxation function depends on the deformation rate, deformation, or stress history. Evidence will be presented which indicates that the stress history rather than the deformation history may be the more relevant variable to account for the non-linearities. The last part of the paper will briefly review the theories that have been proposed to understand the mechanism for non-linear behavior at the microscopic level and the influence of molecular weight and concentration.     

Degassing of molten polymers

Degassing is a key-step in polymer processing. Low-molecular-weight components are removed from a polymeric system. The transport of these components takes place by diffusion to the polymer-vapour interface. This interface can be formed by free surfaces of single-phase polymer melts or by bubbles. In this study, the transport with and without bubble nucleation is investigated independently from each other in a special designed apparatus similar to a degassing extruder.The mass transport in thin films and in rotating pools with surface renewal is measured. High surface renewal rates and thick films enhance the mass transfer for single phase flow and bubbly flow. Dimensionless mass transfer coefficients are given as a function of the surface renewal rate, the area of the free surface and the total mass of the polymer. The conditions for bubble nucleation and foam formation are investigated. The bubble nucleation is observed in the rotating pool in the area of high shear velocity.     

Rheological properties of polypropylene/high-density polyethylene blend melts. I. Capillary flow properties

Three kinds of isotactic polypropylenes (PP) with different melt flow indexes (MFIs) were melt-blended with three kinds of high-density polyethylenes (HDPE) with different MFI using a screw extruder, and the morphologies and capillary flow properties such as flow curve, entrance effect, Barus effect, and melt fracture were studied. When HDPE contents were 70 wt % or above and PP particles formed the disperse phase, the size of the particles decreased with decreasing viscosity of PP. When HDPE contents were 30 wt % or below and HDPE particles formed the disperse phase, the size of the particles was minimum when the viscosities of PP and HDPE were similar. The die swell ratios of the blends were higher than those of the components. On the other hand, the entrance correction coefficients of the blends were intermediate between those of the components. There was no correlation between the die swell ratio and the entrance corretion coefficient. Therefore, it is not always appropriate to regard the entrance correction coefficient as a measure of melt elasticity in the case of inhomogeneous polymer systems such as PP/HDPE blend.     

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.     

Mechanical and optical properties of block polymers I. Polyester-urethanes

The extraordinary physical properties exhibited by block polymers have been ascribed to the presence of a multiphase microstructure in which the higher modulus phase acts as a quasi-crosslink or filler particle. Recently, the optical examination of these materials combined with mechanical testing has given investigatiors new insight into this complex morphology. In this investigation, simultaneous stress, strain, and birefringence data have been collected on a block polyester urethane elastomer. Stress-softening is observed in cyclic stress-strain experiments, giving rise to significant hysteresis in the stressstrain and birefringence-stress curves. In these tests, prestrain causes a large increase in the stress-optical coefficient, but has little effect on the strain-optical coeffcient. As the temperature is increased, the strain-optical coefficent decreases while the stress-optical coefficient increases with the latter exhibiting a larger temperature dependence than predicted by the kinetic theory of rubber elasticity. The good agreement between the mechanical-optical response of polyester urethanes and that of other block polymer systems provides further evidence of their morphological similarity.     

Pressure-volume-temperature behaviour of molten polymers

Summary The solubility parameter theory of Hildebrand and Scott extended for polymer blends originally has accounted for dissimilarities only between contact energies of the blend components, neglecting free volume effects which are predicted by the corresponding states theories. Biro et al., however, have shown that using expressions of the Prigogine-Flory corresponding state theories for energy and volume, effects of free volume will be implicity included in the solubility parameter approach too. The results are similar then to those derived by the corresponding state theories. In addition, it is shown that in this case the temperature and pressure dependencies of the solubility parameters are predicted qualitatively correct.We performed this procedure with the Sanchez- Lacombe EOS theory instead of the Prigogine-Flory approach, Formally, identical expressions result, and the calculated solubility parameters evaluated according to the two EOS theories are in good agreement. However, because Sanchez-Lacombe's approach is not a corresponding state theory, it is able to predict additionally qualitatively correct the dependence of the solubility parameters on chain length.     

Wall slip of molten polymers

There is considerable experimental evidence that the classical no-slip boundary condition of fluid mechanics is not always a valid assumption for the flow of high molecular weight molten polymers. In fact, molten polymers slip macroscopically at solid surfaces when the wall shear stress exceeds a critical value. Moreover, for linear polymers there exists a second critical wall shear stress value at which a transition from a weak to a strong slip occurs. These two modes of slip (weak and strong) are due to flow-induced chain detachment/desorption at the polymer/wall interface and to chain disentanglement of the polymer chains in the bulk from a monolayer of polymer chains adsorbed at the interface. In this review, the two physical mechanisms of slip are discussed and validated on the basis of published experimental data. The slip velocity of molten polymers is a complex function and has been reported to depend on wall shear and normal stresses, temperature, and molecular characteristics of polymers (molecular weight and its distribution). Proposed slip models, static and dynamic, are also reviewed and their significance on the rheology and flow simulations of molten polymers is discussed.     

Reversible mechanochemical systems based on stimuli-responsive polymers. I. Fundamental aspects

Polymer gels can be used to prepare mechanical systems that convert chemical free energy into mechanical work. These gels have characteristics that cause shape changes or generate tensile stress that can lead to mobility.

The polymer gel network can be produced by several physical and chemical methods. The principle of reversible contraction and dilatation is based on different mechanisms that depend on the type of stimuli applied.

The kinetics of gel swelling has been studied and understood as a combination of two consecutive processes: the collective diffusion and the relaxation process. The response time of gel depends on the thermodynamic quality of the solvent. Gels based on “intelligent” polymers have many interesting applications. Hence, these gels can form the basis of future “soft, wet” technology.     

Morphological and mechanical properties of polypropylene [PP]/poly(ethylene vinyl acetate) [EVA] blends. I. Homopolymer PP/EVA systems

Morphological and mechanical properties of polypropylene [PP]/poly(ethylene vinyl acetate) [EVA] blends have been studied. Infrared results using thin films first indicated a transition toward compatibility between both components at concentrations above 40% EVA. The transition was verified with different experimental techniques and it was associated to morphological changes and mechanical properties. The PP/EVA blends were mechanically evaluated in terms of impact and tensile strength to determine the influence of blending on the performance properties of these materials. Agreement was found between the transition and the enhancement of both elongation at break and impact strength.