Rheological and foaming behavior of linear and branched polylactides

In this work, a chain extender (CE) was added to polylactide (PLA) to improve its foamability. The steady and transient rheological properties of neat PLA and CE-treated PLA revealed that the introduction of the CE profoundly affected the melt viscosity and elasticity. The linear viscoelastic properties of CE-enriched PLA suggested that a long-chain branching (LCB) structure was formed from the reaction with the CE. LCB-PLA exhibited an increased viscosity, more shear sensitivity, and longer relaxation time in comparison with the linear PLA. The LCB structure was also found to affect the transient shear stress growth and elongational flow behavior. LCB-PLA exhibited a pronounced strain hardening, whereas no strain hardening was observed for the linear PLA. Batch foaming of the linear and LCB-PLAs was also examined at foaming temperatures of 130, 140, and 155 °C. The LCB structure significantly increased the integrity of the cells, cell density, and void fraction.     

Viscoelastic melt rheology and time–temperature superposition of polycarbonate–multi-walled carbon nanotube nanocomposites

This work investigates the linear and non-linear viscoelastic melt rheology of four grades of polycarbonate melt compounded with 3 wt% Nanocyl NC7000 multi-walled carbon nanotubes and of the matching matrix polymers. Amplitude sweeps reveal an earlier onset of non-linearity and a strain overshoot in the nanocomposites. Mastercurves are constructed from isothermal frequency sweeps using vertical and horizontal shifting. Although all nanocomposites exhibit a second plateau at ～10⁵ Pa, the relaxation times estimated from the peak in loss tangent are not statistically different from those of pure melts estimated from cross-over frequencies: all relaxation timescales scale with molar mass in the same way, evidence that the relaxation of the polymer network is the dominant mechanism in both filled and unfilled materials. Non-linear rheology is also measured in large amplitude oscillatory shear. A comparison of the responses from frequency and amplitude sweep experiments reveals the importance of strain and temperature history on the response of such nanocomposites.     

Design of new HDPE/silica nanocomposite and its enhanced melt strength

Linear polymers are restricted to use in processes that involve severe extensional deformation, such as fiber spinning, film blowing, and thermoforming. To extend their applicability, the extensional properties of polymer melts should be enhanced such that strain hardening, which is defined as an increase in extensional viscosity under a large strain that deviates from the linear viscoelastic curve, is pronounced. In this study, a novel preparation method of linear polymer/inorganic nanocomposites was proposed with a main focus on enhanced melt strength. The design of molecular structure consists of three components—linear polymer, compatibilizer, and surface-modified particles. High-density polyethylene was used as a linear polymer while polyethylene grafted with maleic anhydride was used as a compatibilizer. Silica particles were synthesized and modified on their surfaces by 3-aminopropyltriethoxysilane. The strain hardening behavior of the surface-modified silica composites was pronounced. However, such a result was not observed for the composites of the same composition with pure-silica. In addition, the dispersion of the modified silica was much better than that of pure-silica.     

Brownian dynamics simulation of multiphase suspension of disc-like particles and polymers

A computational model is proposed for simulating the flow of polymer nanocomposites. This model is based on a multiphase suspension of disc-like particles and polymers. The particles are represented by oblate spheroid particles that interact with each other via the Gay-Berne (GB) potential, and the polymers are modeled by finitely extensible nonlinear elastic (FENE) chains that interact with each other via the repulsive Lennard-Jones potential. The interaction between an oblate spheroid particle and a FENE chain is also considered using a modified GB potential. A Brownian dynamics simulation of the shear flows of this system was conducted to investigate the orientation behavior of disc-like particles and the rheological properties of this system. The orientation of disc-like particles was affected by polymers, and the particles in a suspension were well aligned in flows because of the flow orientation property of polymers. The predicted shear viscosity exhibited shear thinning, and the normal stress differences agree qualitatively with experimental measurements of polymer/clay nanocomposites. The simulation results suggest that the present model has the potential to be used as a computational model for polymer nanocomposites.     

Elongational and shear flow in polymer-clay nanocomposites measured by on-line extensional and off-line shear rheometry

Rheological behaviour of polymer nanocomposites has been usually characterized by rotational as well as capillary rheometry, which are both time and cost consuming. We have already published that reinforcement in polymer-clay nanocomposites can be estimated very fast using extensional rheometer in combination with a capillary rheometer. It has been proven that the magnitude of melt strength can be correlated with that of tensile strength, i.e. 3D physical network made of layered silicate and polymer matrix, which is responsible for material reinforcement, can be monitored directly using extensional rheometry. Therefore, additional time for samples preparation by press or injection moulding as well for long measurements by tensile testing is not required any more. In this contribution, results of extensional rheometry measured directly during compounding process are presented. In this manner, further reduction in time required for material characterization has been achieved. The samples have been prepared by advanced compounding using a melt pump and special screw geometries. With the use of on-line extensional rheometry and off-line rotational rheometry, different nanocomposites have been tested and the effect of processing conditions (screw speed and geometry in the twin-screw extruder) on elongational and viscoelastic properties has been investigated. It has been found that the level of melt strength measured by extensional rheometry correlates with a high accuracy with dynamic rheological data measured by rotational rheometry. It was hereby confirmed that the network structure made of silicate platelets in polymer melt is reflected in both elongational and shear flow in the same way.     

Shearing and mixing effects on synthesis and properties of organoclay/polyester nanocomposites

Mixing of solid nanoparticles in viscous fluids is a key stage in synthesis of nanocomposites and can affect their final properties. A multi-step preparatory mixing is developed to synthesize the nanocomposites of layered silicate in thermosetting polymers. This study aims to investigate the influences of mixing conditions and steps taken to process the thermosetting nanocomposites on the viscoelastic properties of suspensions. We also examine subsequent influences of mixing on the microstructure and dispersion state of cured hybrids of organically modified clays in a polyester resin. The nanocomposites were prepared in a sequential mixing process developed for the model nanocomposites of organoclays and thermoset resin. Depending on the mixing conditions, the final nanocomposites showed mixed intercalated and moderately to highly delaminated structure. TEM images show that the nanoclay galleries are dispersed in the polymer phase after curing reactions. The startup viscosities and linear viscoelastic properties of the nanocomposites are significantly influenced by the extent and the time duration of mixing. These observations indicate that extensive mechanical mixing combined with a stationary step followed by moderate shear mixing can improve the polymer and nanoparticle interactions at the interface. In the last part of this work, we develop a simple but efficient mathematical formulation on the flow of oblate spheroids in viscous media and compare selected model predictions with the measured startup shear viscosities of suspensions.     

Strain hardening of fibrin gels and plasma clots

Biological macromolecules have unique rheological properties that distinguish them from common synthetic polymers. Among these, fibrin has been studied extensively to understand the basic mechanisms of viscoelasticity as well as molecular mechanisms of coagulation disorders. One aspect of fibrin gel rheology that is not observed in most polymeric systems is strain hardening: an increase in shear modulus at strain amplitudes above 10%. Fibrin clots and plasma clots devoid of platelets exhibit shear moduli at strains of approximately 50% that are as much as 20 times the moduli at small strains. The strain hardening of fibrin gels was eliminated by the addition of platelets, which caused a large increase in shear storage modulus in the low strain linear viscoelastic limit. The reduction in strain hardening may result from fibrin strand retraction which occurs when platelets become activated. This interpretation is in agreement with recent theoretical treatments of semi-flexible polymer network viscoelasticity.Dedicated to Prof. John D. Ferry on the occasion of his 85th birthday.     

Melt strengthening of poly (lactic acid) through reactive extrusion with epoxy-functionalized chains

Poly (lactic acid) is an industrially mature, bio-sourced and biodegradable polymer. However, current applications of this eco-friendly material are limited as a result of its brittleness and its poorly melt properties. One of the keys to extend its processing window is to melt strengthen the native material. This paper considers the chain extension as a valuable solution for reaching such an objective. An additive based on epoxy-functionalized PLA was employed during reactive extrusion. The reaction times as a function of chain extender ratios were determined by monitoring the melt pressure during recirculating micro-extrusions. Once residence times were optimized, reactive extrusion experiments were performed on a twin screw extruder. Size exclusion chromatography provided information about the molecular weight distributions (MWD) of the modified PLAs and revealed the creation of a high molecular weight shoulder. The rheological experiments highlighted the enhancement of the melt properties brought about by the chain extension. Shear rheology revealed some enlarged and bimodal relaxation time spectra for the extended materials which are in accordance with the MWD analysis. Such a modification directly amplified the shear sensitivity of modified PLAs. Regarding the rheological temperature sensitivity, it was found to be decreased when the chain extender content is raised as shown from the Arrhenius viscosity fit. The reduction of the polar interactions from neat to highly chain-extended PLAs is here proposed to explain this surprising result. Chain extension was also found to impact on the elongational melt properties where strain hardening occurred for modified PLAs. Investigation of the chain extension architecture was made from the rheological data and revealed a long-chain branched topology for the modified PLAs.     

The rheology of recycled EVA/LDPE modified bitumen

This paper describes linear viscoelasticity, at low and intermediate temperatures, and the flow behaviour, at high temperatures, of polymer modified bitumen (PMB) containing 5 and 9 wt% recycled EVA/LDPE. The relationship between flow behaviour and microstructure of the modified bitumen was also considered, by comparison of experiments carried out in capillary and rotational rheometers and photomicrographs taken using a microscopy system whilst the sample was being sheared. Blends of 60/70 penetration grade bitumen and waste plastic (EVA/LDPE) were processed in an open mixer using a four blade propeller. Rheological tests, differential scanning calorimetry (DSC) and microscopy showed that the bitumen performance was improved by adding the recycled polymer. As a consequence, the use of recycled EVA/LDPE in PMBs can be considered a suitable and interesting alternative from both an environmental and economical point of view. The experimental results also show that pure bitumen has shear-thinning characteristics. The blending of polymer into the bitumen modifies the melt processing characteristics of the blend, whilst the viscoelastic properties of the semi-solid composite are enhanced.This paper was presented at the first Annual European Rheology Conference (AERC) held in Guimarães, Portugal, September 11-13, 2003.     

Comparative rheological studies of polyamide-6 and its low loaded nanocomposite based on layered silicates

We study some rheological properties for polyamide-6 (PA-6) and a low concentrated clay nanocomposite melt based on polyamide-6 and montmorillonite. Simple shear experiments, carried out for both the neat system and nanocomposite at two different temperatures, include start up shear flows, stress relaxation after cessation of steady flow and oscillatory shear. The dynamic data for the neat PA-6 matrix differ markedly from that of the nanocomposite system, even if it has very low nanofiller concentration. Thermal stability of the PA-6 matrix imposed many restrictions on rheological studies of our systems. Therefore an experimental window was established via rheological and thermal characterization of the materials, wherein the polymer matrix was confirmed to be thermally stable. The relaxation spectra for both polymer systems were determined from linear dynamic experiments using the Pade-Laplace procedure. A rough estimation of nanocomposite volume fraction at percolation allowed us to attribute the occurrence of extra (relative to the neat polymer) Maxwell modes observed for the nanocomposite to the formation of a particulate network above the percolation threshold.     

Prediction of steady-state viscous and elastic properties of polyolefin melts in shear and elongation

The linear and nonlinear steady-state viscosities and elastic compliances were measured in shear and elongational flows for two low-density polyethylenes, a linear polypropylene, and two metallocene catalyzed polyethylenes (one linear and one long-chain branched) by Wolff et al. (Rheol Acta 49:95?C103, 2010) and Resch (dissertation, 2010). Comprehensive data of this type are rarely found in the literature, and comprehensive modeling of both viscous and elastic effects is even rarer. In this contribution, the reliability of a modeling approach proposed by Laun (J Rheol 30(3):459?C501, 1986) and based on the damping function concept is tested. The strain hardening seen for the long-chain branched polymers and its absence in the case of the linear polymer, the stronger decrease of the tensile compliance in comparison to the shear compliance with increasing stress, as well as the extended linear-viscoelastic regime of the shear viscosity in contrast to the shear compliance are correctly modeled. While the modeling of the nonlinear response in shear can be achieved with only one material parameter for most of the polymers considered here, the nonlinear modeling in elongation is achieved with two parameters. The same parameter values are shown to describe viscous as well as elastic properties of the melts, and thus the relations of Laun can be used to test the consistency of viscosity and compliance measurements.     

Selection of ethylene-vinyl-acetate properties for modified bitumen with enhanced end-performance

Bitumen modification with ethylene-vinyl acetate (EVA), in a wide range temperatures (between ??30 and 100 °C), has been studied as a function of polymer concentration and EVA characteristics (vinyl acetate (VA) content and melt flow index (MFI)). Viscous flow, dynamic shear (DSR) temperature sweep, and technological tests were conducted to assess binder performance at medium-to-high in-service temperatures. Evaluation of binder low-temperature viscoelastic behavior has been performed using a solid rectangular fixture (SRF) in torsional mode, either in the linear viscoelastic region or under non-linear conditions (by strain breakage tests between ??30 and 0 °C). Further microstructural analysis based on modulated differential scanning calorimetry (MDSC) and optical microscopy was conducted to support rheological and technological results. Hence, total crystalline fraction (related to the VA content and polymer concentration) turned out to be a key parameter to achieve a suitable binder modification at medium-high temperatures. In addition, MFI appears to be an important EVA parameter at low temperatures, as it was found that lower MFI values enhanced resistance to low-temperature cracking.     

Melt shear rheology of carbon nanofiber/polystyrene composites

The rheological behavior and morphology of carbon nanofiber/polystyrene (CNF/PS) composites in their melt phase have been characterized both through experimental measurements and modeling. Composites prepared in the two different processes of solvent casting and melt blending are contrasted; melt-blended and solvent-cast composites were each prepared with CNF loadings of 2, 5, and 10 wt%. A morphological study revealed that the melt blending process results in composites with shorter CNFs than in the solvent-cast composites, due to damage caused by the higher stresses the CNFs encounter in melt blending, and that both processes retain the diameter of the as-received CNFs. The addition of carbon nanofiber to the polystyrene through either melt blending or solvent casting increases the linear viscoelastic moduli, G′ and G″, and steady-state viscosity, η, in the melt phase monotonically with CNF concentration, more so in solvent cast composites with their longer CNFs. The melt phase of solvent-cast composites with higher CNF concentrations exhibit a plateau of the elastic modulus, G′, at low frequencies, an apparent yield stress, and large first normal stress difference, N ₁, at low strain rates, which can be attributed to contact-based network nanostructure formed by the long CNFs. A nanostructurally-based model for CNF/PS composites in their melt phase is presented which considers the composite system as rigid rods in a viscoelastic fluid matrix. Except for two coupling parameters, all material constants in the model for the composite systems are deduced from morphological and shear flow measurements of its separate nanofiber and polymer melt constituents of the composite. These two coupling parameters are polymer–fiber interaction parameter, σ, and interfiber interaction parameter, C _I. Through comparison with our experimental measurements of the composite systems, we deduce that σ is effectively 1 (corresponding to no polymer–fiber interaction) for all CNF/PS nanocomposites studied. The dependence of CNF orientation on strain rate which we observe in our experiments is captured in the model by considering the interfiber interaction parameter, C _I, as a function of strain rate. Applied to shear flows, the model predicts the melt-phase, steady-state viscosities, and normal stress differences of the CNF/PS composites as functions of shear rate, polymer matrix properties, fiber length, and mass concentration consistent with our experimental measurements.     

Anisotropic Elastic-Viscoplastic Properties at Finite Strains of Injection-Moulded Low-Density Polyethylene

Injection-moulding is one of the most common manufacturing processes used for polymers. In many applications, the mechanical properties of the product is of great importance. Injection-moulding of thin-walled polymer products tends to leave the polymer structure in a state where the mechanical properties are anisotropic, due to alignment of polymer chains along the melt flow direction. The anisotropic elastic-viscoplastic properties of low-density polyethylene, that has undergone an injection-moulding process, are therefore examined in the present work. Test specimens were punched out from injection-moulded plates and tested in uniaxial tension. Three in-plane material directions were investigated. Because of the small thickness of the plates, only the in-plane properties could be determined. Tensile tests with both monotonic and cyclic loading were performed, and the local strains on the surface of the test specimens were measured using image analysis. True stress vs. true strain diagrams were constructed, and the material response was evaluated using an elastic-viscoplasticity law. The components of the anisotropic compliance matrix were determined together with the direction-specific plastic hardening parameters.     

Uniaxial extensional flow behavior of immiscible and compatibilized polypropylene/liquid crystalline polymer blends

In this work liquid crystalline polymer (LCP) and thermoplastic (TP) blends with and without compatibilizer were studied with respect to their elongational flow behavior, under uniaxial extensional flow. This knowledge is important because in processes involving dominantly extensional deformations, like the case of the formation of the LCP fibrillation, transient extensional flow properties become more important than transient or steady-shear properties. In systems characterized by disperse phase morphologies (10 and 20 wt%) the LCP acts as a plasticizer, decreasing the viscosity of the system and increasing its durability with respect to that of the matrix. On the other hand, for a system in which a co-continuous morphology is present (40 wt% LCP) fibrils and droplets deformation occurs simultaneously, leading to a much higher strain hardening and durability. Moreover, the addition of compatibilizers to the blends gives rise to an increase of the strain hardening and to a decrease of the durability, which is in accordance with the mechanical properties, namely a higher Young’s modulus and lower elongation at break, in comparison with noncompatibilized systems.     

Fingerprinting the processing behavior of polyethylenes from transient extensional flow and peel experiments in the melt state

The flow curves of linear (linear-low and high density) and branched polyethylenes are known to differ significantly. At increasing shear rates, the linear polymers exhibit a surface melt fracture or sharkskin region that is followed by an unstable oscillating or stick-slip flow regime when a constant piston speed capillary rheometer is used. At even higher shear rates, gross melt fracture appears. Unlike their linear counterparts, branched polyethylenes rarely exhibit sharkskin melt fracture and although gross melt fracture appears at high shear rates there is no discontinuity in their flow curve. The various flow regimes of these two types of polyethylenes are examined by performing experiments in the melt state using a unique extensional rheometer (the SER by Xpansion Instruments) that is capable of performing accurate extensional flow and peel experiments at very high rates not previously realized. The peel strength curves of these linear and branched polyethylenes exhibit all of the distinct flow regimes exhibited in their respective flow curves, thereby providing a fingerprint of their melt flow behavior. Moreover, these extensional flow and peel results in the melt state provide insight into the origins and mechanisms by which these melt flow phenomena may occur with regard to rapid tensile stress growth, melt rupture, and adhesive failure at the polymer wall interface.     

Morphological and rheological properties of PET/clay nanocomposites

This work investigates the effects of clay chemistry and concentration on the morphology and rheology of polyethylene terephthalate (PET)/clay nanocomposites. The complex viscosity of the PET nanocomposites exhibited a more solid-like behavior, in contrast to the matrix that had a frequency-independent viscosity. In addition, at high frequencies where the behavior of the matrix should be dominant, a lower complex viscosity of the nanocomposites was observed due to PET degradation in the presence of the organoclays. The high-frequency data were used to estimate the matrix degradation using the Maron–Pierce equation. The apparent molecular weight of the PET matrix was found to decrease from 65 kg/mol for the neat PET to 30 kg/mol for a PET nanocomposite containing 8 wt% Cloisite®; 30B. The apparent yield stress in the nanocomposites was determined using the Herschel–Bulkley model. Yield stress increased with the level of exfoliation and clay concentration, from ～0 to 166 Pa when the clay concentration increased from 2 to 8 wt%.     

Processing and characterization of epoxy/clay nanocomposites

Nanocomposite materials consisting of an epoxy matrix and silicate clay particles have been processed and characterized mechanically. The clay material used was a modified natural montmorillonite. The clay particles consisted of 1 nm thick layers with aspect ratios in the range of 100–1000. The clay particles were mixed with acetone and sonicated, then mixed with the polymer, deaerated and cured. The ultimate objective of processing was to produce a polymer/clay nanocomposite with separated (exfoliated) platelets, dispersed as uniformly as possible. Samples were prepared with clay concentrations of up to 10 wt%. The process used resulted in limited exfoliation but mostly intercalation, i.e., infusion of polymer between the silicate layers and increase of interlayer spacing. The characteristics of the nanocomposite were assessed by transmission electron microscopy and x-ray diffraction. Results from these observations show that the basal spacing of clay platelets increased from an initial pre-processing value of 1.85 nm to 4.5 nm. Enhancement of mechanical properties was measured by tensile testing of coupons. Stiffness increases of up to 50% over that of the unfilled epoxy were measured for clay concentrations of 5 wt%. Strength increases were also measured for low clay concentrations and low strain rate loading. Micromechanics modeling of mechanical behavior is discussed as a function of clay platelet dispersion.     

Rheological and electrical properties of EVA copolymer filled with bamboo charcoal

The electrical and rheological properties of an ethylene vinyl acetate (EVA) copolymer filled with bamboo charcoal were investigated. The composites were prepared by melt process in an internal batch mixer. Size distribution analysis showed that d₍₅₀₎ and d₍₉₀₎ values of the bamboo charcoal particles are 12.7 and 40 μm, respectively, with a mean diameter of 22 μm. Scanning electron microscopy proved that the particles of bamboo charcoal present a rectangular shape. The electrical percolation threshold was observed at 0.18 volume fraction (35 wt%) of bamboo. Beyond the percolation threshold, a considerable increase in electrical properties was observed up to a limit value of 10^-2 S/m. The rheological percolation was studied from different rheological models. As a result, the rheological percolation threshold was observed at 0.3 volume fraction (50 wt%) of bamboo charcoal contents. So, the electrical percolation occurs before the rheological percolation. This is principally due to the filler’s characteristics such as the specific surface area, the aspect ratio, and the surface properties. Finally, the bamboo charcoal confers high electrical properties to the EVA composite without inducing strong changes in its viscoelastic properties.