Improving Melt Flow Behavior via Melt Vibration

A self‐made melt vibration extrusion device was used to study the melt flow behavior in a vibration field. A pulse pressure was superimposed on the flowing melt during extrusion, called vibration assisted extrusion (VAE); conventional extrusion (CE) was studied for comparison. A die (L/D=17.5) was attached to the device to study melt flow behavior of an amorphous polymer (polystyrene) and semi‐crystalline polymers (high density and linear low polyethylene). Results show that the melt vibration technique is an effective processing tool to improve polymer melt flow behavior for both crystalline and amorphous polymers. Increasing with vibration frequency for extrusion at constant vibration pressure amplitude, the viscosity decreases sharply, and also with increasing vibration pressure amplitude at a constant vibration frequency. The effect of vibration field on melt flow behavior depends greatly on the melt temperature, with the largest change in viscosity obtained at low temperature. Increasing with vibration frequency at constant pressure vibration amplitude, the maximum decrease percentages of viscosities are 82.9, 66.7, and 48.9%, for HDPE, LLDPE, and PS, respectively; increasing with pressure vibration amplitude at a constant vibration frequency, the maximum decrease percentage of viscosities are 99.0, 94.3, and 99.0%, for HDPE, LLDPE, and PS, respectively.     

The Effect of Melt Vibration on Polystyrene Melt Flowing Behavior During Extrusion

Vibration extrusion (VE) is achieved by superimposing a mechanical vibration on the flowing melt during extrusion. The effect of melt vibration on the melt flow behavior of polystyrene (PS) was studied. The melt flow behavior during conventional extrusion (CE) was studied for comparison. With the application of the melt vibration technology, the melt flow behavior of PS was greatly improved. The melt viscosity during the VE strongly depends on the vibration frequency and vibration amplitude. Extruded at constant vibration amplitude, the melt viscosity decreases sharply with increasing vibration frequency and also does so for increasing vibration amplitude when extruded at a constant vibration frequency. The improved melt flow property is explained in terms of shear-thinning criteria. The effect of melt vibration on the melt flow behavior is also related to the melt temperature and extrusion pressure; the greatest decease in viscosity is obtained at low temperature and low extrusion pressure.     

Effects of Viscosity Ratio on Morphological,Rheological and Mechanical Properties of PP/PBT Melt Spun Alloy Fibers

Phase morphology formation plays an important role in the mechanical properties of polymer alloy fibers. The development of the blend morphology depends not only on the intrinsic properties of the component polymers but also on extrinsic factors such as viscosity ratio, λ, in the melt spinning process. The effects of blend component viscosity ratio on the morphological, rheological, and mechanical properties of polypropylene/poly(butylene terephthalate) (PP/PBT) melt spun alloy fibers were investigated. Accordingly, two kinds of PP as matrix phase and two kinds of PBT as dispersed phase, with various melt viscosity, were physically mixed and then blended during the extrusion step of melt spinning. SEM micrographs and rheological and mechanical properties evaluations showed that the morphology of PP/PBT alloy fibers strongly depend on the viscosity ratio, λ. Finer diameter PBT fibrils were observed for Viscosity ratios less than 1 (λ < 1) compared to samples with λ > 1. The best mechanical properties in alloy fiber samples were obtained for the viscosity ratio closest to unity (sample with λ = 0.9). The lowest differences among measured complex viscosities at various shear rates (0.1, 10, and 100 s^?1) were also observed in samples with λ = 0.9. The results showed that the mechanical properties of alloy fiber samples are affected not only by morphological properties observed at different viscosity ratios but also by the properties of the individual polymer components.     

Micro-Structure and Fracture Behavior of High-Melt-Strength PPs Prepared by Reactive Extrusion

In this study, high-melt-strength polypropylenes (PPs) were prepared by reactive extrusion of PP and varied amount of divinylbenzene in the presence of dicumyl peroxide and an antioxidant, and the dynamic rheological behavior, crystalline morphology, and fracture behavior of the resultant materials were investigated. It was found that at relatively low frequency, with the cross-linking and branching structures increasing, the complex viscosity of the melt of the modified PP increased significantly and then leveled off. The modulus of the melt, particularly the storage modulus, increased. The storage moduli of the melts with higher content of cross-linking and branching structures were higher than the loss modulus in the whole range of testing frequency, indicative of a completely elastic behavior. The crystallinity and the size of spherulites of the modified PP decreased, while the number of spherulites increased. The specific essential work of fracture and the specific non-essential work of fracture of the modified PP were found to be reduced compared with pure PP, but the specific essential work of fracture showed an increasing trend with the cross-linking and branching structures increasing.     

Determination of the Pressure Dependence of the Shear Viscosity of Polymer Melts Using a Capillary Rheometer with an Attached Counter Pressure Chamber

A capillary rheometer with an attached counter pressure chamber was used to determine the effect of pressure on the shear viscosity of several polymer melts, i.e., poly(?-caprolactam) (PA6), poly(ethylene terephthalate) (PET), low-density polyethylene (LDPE), and polypropylene (PP). In order to study the rheological properties of the polymer melts at a constant pressure, the measured values of shear viscosity were recalculated with respect to a series of pressures by the least square fitting based on the Barus equation. Different calculation methods were used to calculate the pressure coefficients from the recalculated viscosity values. The resulting pressure coefficients of the shear viscosity demonstrated that the degree of the pressure dependence was highest for PP, followed by PET and then LDPE. PA6 exhibited the lowest pressure coefficient.     

Melt Vibration Improved Melt Flow Behavior and Mechanical Properties of High Density Polyethylene

A pulse pressure was superimposed on the melt flow resulting in melt vibration. With application of the melt vibration technology, the melt flow behavior and mechanical properties of high‐density polyethylene were studied. For vibration‐assisted extrusion (VAE) at constant vibration pressure amplitude, the viscosity decreases sharply with increasing vibration frequency, and also does so when increasing vibration pressure amplitude for VAE at constant vibration frequency. The effect of vibration field on melt rheological behavior is also related to the melt temperature; a large decease in viscosity is obtained at low melt temperature. Compared with the mechanical properties obtained by conventional injection molding (CIM), the mechanical properties for vibration‐assisted injection molding (VAIM) samples were improved by changing the vibration frequency and vibration pressure amplitude. Injected at constant low vibration pressure amplitude, the VAIM sample prepared at high vibration frequency shows large elongation at break; injected at constant low vibration frequency, the VAIM sample prepared at high vibration pressure amplitude shows greatly improved yield strength. The above two VAIM processing routes produce different VAIM samples with different fracture behaviors; a distinct layered structure for VAIM samples was observed by SEM.     

Processing Polymer Melts under Rheo-Fluidification Flow Conditions,Part 2: Simple Flow Simulations

The flow equations for melts submitted to conditions of Rheo-Fluidification processing described in Part 1 are determined and solved numerically. The pressure flow from an extruder feed end and drag flow from the modulated rotation of the rotor, i.e., under extrusion conditions with both cross-rotational and oscillatory flow, are combined. The value of pressure, shear stress, and viscosity along the flow path of the melt (a helicoidal motion around a divergent conic surface), for a given throughput and temperature, as the melt is moved through an annular gap of constant thickness are calculated. The simulation is restricted to the simpler case of low throughput where elongational flow can be assumed to be negligible and shear dominates the viscosity expression. The classic lubrication approximation hypothesis applied to a power law fluid is used. This assumption appears justified because of the geometry of the die, which consists of a thin annulus of 2 mm extended over a die length of 570 mm (see Part 1). The viscosity is expressed as a function of strain rate, which is calculated from the contribution of pressure flow, rotational flow, and superposed oscillation. The combined shear rate is calculated assuming a vectorial combination of the individual shear rates, following Cogswell who verified this hypothesis, and according to our own validation of this assumption on the same polymer, using a Couette without vibration.     

Online Research on Plasticizing Process of Starch Under Superimposed Vibration Field

A novel testing machine, integrating plastic vibration processing with molding, based on a multipass rheometer, was used to investigate the effect of the complex force field on plasticization of taro and wheat thermoplastic starch (TPS) melts. Various kinds of continuous vibration fields could be tested by controlling the movement of pistons. A superimposed vibration field, combining the effects of vibration and shear, was obtained by adding a high-frequency low-amplitude oscillation on a low-frequency high-amplitude oscillation. The rheological properties of starch were directly monitored during and after the plasticization process without removing the starch melts out of the testing machine. The apparent viscosity of the TPS melts were obtained for different high-frequency oscillation conditions by monitoring the pressure difference in the cavity. The plasticization preparation time was used to characterize the benefit provided by the superimposed vibration field. The results showed the decrease of the percentage of the average plasticizing preparation time for taro starch was 3.4%, while that for wheat starch was 1.6% compared to single, low-frequency, high-amplitude oscillation. Comparison of the plasticizing preparation time under different vibration frequencies showed that the plasticization was promoted by applying the superposed vibration field, and the effective degree was related to the vibration frequency and starch type. Both TPS exhibited shear-thinning behavior after the plasticization, and samples of both types of starch which were plasticized under higher vibration frequency presented lower apparent viscosities at certain shear rates.     

Modified Single-Mode Leonov Rheological Equations for Polymer Melts and Solutions

The shear viscosity and the normal stress coefficients are important parameters in the flow of polymer melts and polymer solutions. Based on the Leonov model, modified single-mode rheological equations are presented by introducing relaxation time and temperature functions, and the shear viscosity and the normal stress coefficients are predicted. Without a complex statistical simulation, the experimental data of a low-density polyethylene melt, a poly(ethylene oxide) solution and a mixed decalin/polybutene oil solution were compared to verify the modified equations in very wide range of deformation rates. Furthermore, based on the equations, the relationship between the stress overshoot and the temperature is discussed. In addition, the predicted shear thinning behavior for the modified equations is also compared with other single-mode models.     

Mode-coupling theory for structural and conformational dynamics of polymer melts

A mode-coupling theory for dense polymeric systems is developed which unifyingly incorporates the segmental cage effect relevant for structural slowing down and polymer chain conformational degrees of freedom. An ideal glass transition of polymer melts is predicted which becomes molecular-weight independent for large molecules. The theory provides a microscopic justification for the use of the Rouse theory in polymer melts, and the results for Rouse-mode correlators and mean-squared displacements are in good agreement with computer simulation results.     

Structural relaxation and dynamic heterogeneity in a polymer melt at attractive surfaces

Molecular dynamics simulations of polymer melts at flat and structured surfaces reveal that, for the former, slow dynamics and increased dynamic heterogeneity for an adsorbed polymer is due to densification of the polymer in a surface layer, while, for the latter, the energy topography of the surface plays the dominant role in determining dynamics of interfacial polymer. The dramatic increase in structural relaxation time for polymer melts at the attractive structured surface is largely the result of dynamic heterogeneity induced by the surface and does not resemble dynamics of a bulk melt approaching T(g).     

Investigation on Properties of Polypropylene/Multi-walled Carbon Nanotubes Nanocomposites Prepared by a Novel Eccentric Rotor Extruder Based on Elongational Rheology

The properties of polymer matrix composites are related not only to the chemical composition of the materials but also to the processing equipment used for their preparation which has a direct influence on the microstructure of the composites. In this paper polypropylene (PP)/multi-walled carbon nanotubes (MWCNTs) nanocomposites were prepared by melt blending through a self-developed, eccentric rotor extruder (ERE). The structure and elongational deformation mechanism of an ERE were described in detail. The morphological, rheological, thermal and mechanical properties of the resulting PP/MWCNTs nanocomposites were investigated. Scanning electron microscopy (SEM) and rheological analysis showed that the MWCNTs were well dispersed in the PP matrix. The thermal stability was investigated by thermogravimetric analysis (TGA) and indicated that the addition of MWCNTs could effectively improve the thermal stability of pure PP. The percentage of crystallinity and tensile strength of the composites were improved as a result of the heterogeneous nucleation effect of the MWCNTs in the PP matrix. The research results revealed that the enhancement of the properties of PP/MWCNTs composites could be attributed to a better dispersion of the MWCNTs in the matrix as compared to samples prepared by conventional extrusion.     

Nonviscous metallic liquid Se

Viscosity is one of the fundamental physical properties of liquids; for different melts it varies in an extremely wide range. Selenium is among the first elementary substances to have manifested, at compression, a phase transformation in the liquid state accompanied by melt metallization. Direct measurements by means of a real-time radiography show that the viscosity of liquid Se under pressure drops by 500 times to a very low level of 8 mPa s. This is the first case of viscosity measurements being performed both for a relatively viscous semiconducting state and a low-viscous metallic state of the same liquid substance. The viscosity of the Se melt strongly decreases with pressure along the melting curve in a semiconducting state and experiences a further significant drop at melt metallization. A similar phenomenon is expected to be observed in many chalcohenide, halogenide, and oxide melts.     

Sonoluminescence of elementary sulfur melt

The sonoluminescence of liquid sulfur has been observed for temperatures of 120–180°C. The sonoluminescence intensity of the sulfur melt is 10⁹ photons/s at 120°C. As the temperature increases, the luminescence intensity decreases nonmonotonically, a maximum is observed at 160–175°C, and cavitation and luminescence cease at 180°C. The dependence obtained correlates with the temperature dependence of the viscosity of the sulfur melt. The sonoluminescence spectrum obtained with a resolution of 10 nm for 130–150°C contains one band with λ_max = 560 nm, the emitter of which is likely an (S⁺)* ion. When the melt is saturated with argon, the sonoluminescence intensity increases by an order of magnitude; in this case, the spectral band shape changes only slightly. The results confirm the “electric” theory of multibubble sonoluminescence. In the process of the sonolysis of the sulfur melt, biradical fragments are formed in cavitation bubbles consisting of sulfur molecules, which initially have the form of cyclooctasulfur S₈. These fragments can enter into the melts and can be involved in various chemical reactions. This circumstance makes it possible to recommend ultrasonic activation for reactions of sulfurization of hydrocarbons.     

The Effect of Orientation Relaxation on Polymer Melt Crystallization Studied by Monte Carlo Simulations

We use dynamic Monte Carlo simulations to study the athermal relaxation of bulk extended chains and the isothermal crystallization in intermediately relaxed melts. It is found that the memory of chain orientations in the melt can significantly enhance the crystallization rates. The crystal orientation and lamellar thickness essentially depend on the orientational relaxation. Moreover, there is a transition of the nucleation mechanism during the isothermal crystallization from the intermediately relaxed melts. These results explain the mechanism of the self-nucleation by orientation and suggest that in flow-induced polymer crystallization, the orientational relaxation of chains decides the crystal orientation.     

Structure and Properties of In-Situ Reactive Compatibilized Polypropylene/Poly (Butyl Methacrylate-Co-Hydroxyethyl Methacrylate) Blend Fibers

In this study, in-situ compatibilized polymer blends of polypropylene (PP) and poly (butyl methacrylate-co-hydroxyethyl methacrylate) P(BMA-co-HEMA) were prepared in a corotating twin screw extruder through the reactive extrusion of mixtures of PP, P(BMA-co-HEMA), butyl methacrylate, and benzoyl peroxide. In the process of reactive extrusion, butyl methacrylate and benzoyl peroxide were used as the monomer and the initiator, respectively. Thereafter the polymer blend was made into fibers via melt spinning. The miscibility of PP and P(BMA-co-HEMA) in the blend fibers was investigated using field emission scanning electron microscopy. The absorption percentage of the blend fibers for organic liquids and their remaining ratios after the absorption tests were also determined and used to prove the generation of the third phase. The changes in the fiber morphology during organic liquid absorption were observed using polarized light microscopy. In addition, the effect of the miscibility on the crystal structure and melting characteristic of the blend fibers were analyzed using wide-angle X-ray diffractometry and differential scanning calorimetry. Finally, the thermal stability of the blend fibers that was associated with the miscibility of PP and P(BMA-co-HEMA) in the blend fibers were characterized by using thermogravimetry and dynamic thermomechanical analysis.     

Rheological Behavior of Blends of Poly(Phenylene Sulfide) with a Thermotropic Liquid Crystalline Aromatic Poly(Ether Ester)

A new type of thermotropic liquid crystalline aromatic poly(ether ester) (PEE) was prepared from 1,3-bis(4′-carboxyphenoxy)benzene, 1,4-diacetoxybenzene, and p-acetoxybenzoic acid through a melt transesterification process. The rheological behavior of blends of poly(phenylene sulfide) (PPS) with PEE was studied using a high-pressure capillary rheometer with the shear rate range of 50 s^?1 to 3000 s^?1. The results show that according to the range of shear rate, the flow curves of PEE/PPS blends can be divided into three zones: a first shear-thinning zone (n < 1, “n” represents non-Newtonian indexes), a shear-thickening zone (n > 1), and a second shear-thinning zone (n < 1), and the former two zones are more obvious with the increase of PEE content or elevated temperature. In the second shear-thinning zone, the PPS melt is close to a Newtonian fluid at high temperature and high shear rate; meanwhile the non-Newtonian behavior of the PPS melt at high temperature is enhanced with the addition of PEE. The apparent viscosity of PPS melts sharply dropped after adding PEE, especially at relatively low temperature and low shear rate. The curve of apparent viscosity vs. shear rate starts to flatten out after adding PEE, suggesting that the addition of PEE lowers the sensitivity of PPS to shear rate. As the content of PEE increases, the activation energy of the viscous flow, ΔE_η, of PPS decreases, which means that adding PEE weakens the temperature sensitivity of the apparent viscosity of the PPS melt. It can clearly be seen that the addition of PEE is beneficial to the processing of PPS.     

Melt Elongation Properties of Linear Low-Density Polyethylene

The melt extensional properties of a linear low-density polyethylene (LLDPE) were measured using melt spinning techniques in a range of temperature varying from 150 to 200°C, and the entry flow method in the capillary extrusion at 170°C was used to investigate the effects of elongation strain rate, temperature, and extrusion velocity in the capillary on the melt elongation stress and viscosity. The melt stretching force at break decreased nonlinearly with a rise of temperature. A low melt elongation viscosity might be beneficial to improve the melt drawability. With the increase of elongation strain rate, the melt elongation stress increased while the melt elongation viscosity decreased nonlinearly. Both melt elongation stress and viscosity decreased with a rise of temperature. Under the experimental conditions, the melt elongation stress and viscosity decreased with an increase of extrusion velocity in the capillary. Moreover, the relationship between the elongation viscosity determined from the entry flow and strain rate was similar to that from the melt spinning flow.     

Studies on Rheological Behavior and Structure Development of High‐Density Polyethylene in the Presence of Ultrasonic Oscillations During Extrusion

The effects of ultrasonic oscillations on properties and structure of extruded high‐density polyethylene (HDPE) were studied. The experimental results show that ultrasonic oscillations can improve the surface appearance of the HDPE extrudates; increase the productivity of the HDPE extrudates; and decrease the die pressure, melt viscosity, and flow activation energy of the HDPE. The processing properties of the HDPE improve greatly in the presence of ultrasonic oscillations. Linear viscoelastic properties tests show that dynamic shear viscosity and zero shear viscosity decrease in the presence of ultrasonic oscillations. Ultrasonic oscillations can improve crystal perfection and thermal stability of HDPE. At appropriate ultrasound intensity, ultrasonic oscillations could also increase the mechanical strength of extruded HDPE. The gel permeation chromatography (GPC) results show that at high ultrasound intensity and low rotation speed of extrusion, ultrasonic oscillations causes chain scission of HDPE, which result in a decrease of molecular weight and an increase of melt flow index.