Process rheokinetics and microstructure of recycled EVA/LDPE-modified bitumen

Knowledge of the kinetics of the manufacturing process of polymer–bitumen blends is of great interest because it provides information on the behaviour of the binder at different stages of the mixing operation, which is useful for the establishment of the optimum processing conditions, involving temperature and operation time. The purpose of this research was to study the evolution of the rheological properties and microstructure of a polymer-modified bitumen during its processing. A 60/70-penetration grade bitumen and recycled EVA/LDPE were mixed under different processing conditions. Measurements of the evolution of viscosity with time, at different temperatures and agitation speeds, were carried out with an experimental device known as ‘rheomixer’, that is, a helical ribbon impeller inside a mixing vessel coupled with the transducer and motor of a conventional rheometer. Under the experimental conditions selected (within the laminar region, Re<10), temperature is the most important processing variable. Hence, low agitation speeds and a processing temperature of around 180°C should be chosen for bitumen modification with the polymer used.     

In situ monitoring the sol–gel transition for polyacrylamide gel

The effects of heating rate and shear stress on the sol–gel transition for a polyacrylamide gel during in situ preparation were investigated by dynamic rheology. The gelation evolution was also studied through monitoring of the static gelation process by means of temperature, pH, and conductivity variation. The gels were prepared by polymerization of acrylamide crosslinked with N,N′-methylenebisacrylamide using a redox initiation based on potassium persulfate/ascorbic acid. In situ gelation process was studied using oscillatory deformation tests at constant frequency of 0.1 Hz for different heating rate (from 0.5 to 5 °C/min) and shear stress (in the range of 0.1 to 10 Pa). The paper was presented at the third annual rheology conference, AERC 2006, Crete, Greece, 27–29 April 2006.     

Novel bitumen/isocyanate-based reactive polymer formulations for the paving industry

Reactive modification is lately gaining acceptance as a successful way to give added value to bitumen, a crude oil refining by-product. In order to study the effect of both bitumen type and processing method, isocyanate-based reactive modification was carried out with four types of bitumen from different sources, by following two different procedures (“water-free” and “water-involved” processing). The polymer used (MDI–PPG) was synthesized from the reaction of 4,4^′-diphenylmethane diisocyanate with a low molecular weight polypropylene glycol. The results obtained demonstrate that the addition of small quantities of this reactive polymer to bitumen endows the resulting modified binder with an improved performance at high in-service temperatures. Interestingly, two different modification pathways have been identified: the first one, which occurs during mixing, is the result of chemical reactions between -NCO groups of the reactive polymer with functional groups containing active hydrogen atoms (mainly, –OH), such as those typically present in the most polar bitumen fractions; the second one has been proved to be a consequence of series reactions involving water. Both pathways, but mainly the latter, lead to bituminous paving materials showing a more complex microstructure, with the consequent change in their rheological response. Finally, very different degrees of modification, depending on the colloidal features of the as-received bitumen, were observed.     

Shear-induced crystallization of PB-1 up to processing-relevant shear rates

Two experimental methods to study shear-induced crystallization of poly(butene-1) (PB-1) in the high shear rate region are presented: one using a concentric cylinder rheometer and the other a capillary rheometer equipped with a cylindrical die. The crystallization onset time (t _on) is used as the parameter to monitor crystallization progress through the output signal from each device. By combining the new data with the results from a previous paper (2005) in which a plate–plate rheometer was used, onset time data covering a shear rate range from 10^-4 to 500 s^-1 at temperatures 99–107°C are obtained. In this range, a decrease in onset time spanning five decades is observed. The onset times obtained from the capillary rheometer are larger compared to those from the other two methods, which can be explained from the different type of flow. The data also confirm the procedure to construct a temperature-invariant curve, which can be extended to high shear rates for three PB-1 samples having different molecular weight distributions. The slope of the fitted curve for all three cases is −1, which suggests that a critical value is required for shear-induced crystallization. The morphology of the formed crystals (spherulitic or rod-like) depends on the molecular weight, but this does not affect the validity of the T-invariant curve. Above the melting point, it is shown that the amount of long chains influences the temperature limit where shear-induced crystallization can still take place.The paper was presented at AERC 2005, Grenoble, with the title “Shear-Induced Crystallization of Polybutene-1 Covering a Wide Shear Rate Range.”An erratum to this article can be found at     

Structure development during crystallization of polycaprolactone

In this paper, the quiescent crystallization of polycaprolactone (PCL) melts is studied by rheological measurements coupled to calorimetry and optical microscopy. Based on a comparison between the different techniques, we find that the increase in viscoelastic properties during crystallization starts only when a relatively high degree of crystallinity is reached, which corresponds to a much developed crystalline microstructure. Like other semicrystalline thermoplastic polymers, the crystallization of PCL can be seen as a gelation process. In this case, however, we find a peculiar critical gel behavior, as the liquid-to-solid transition takes place at a very high (~20%) relative crystallinity, and this value is independent of temperature. These facts, and the comparison with optical microscopy observations, suggest that the microstructure at the gel point is controlled by the interactions between the growing crystallites. The gel time (from rheometry) and the half-crystallization time [from differential scanning calorimetry (DSC)] both show an Arrhenius-like behavior and have the same pseudoactivation energy. A practical implication of this parallel behavior of t _gel and t _0.5 is that the rheological measurements can be used to extend to higher temperatures the study of crystallization kinetics where DSC is not sufficiently sensitive.This paper was presented at the second Annual European Rheology Conference (AERC) held in Grenoble, France, 21–23 April 2005.     

Viscoelastic properties of phosphoric and oxalic acid-based chitosan hydrogels

In a previous work, we have shown that chitosan true physical gelation occurs in some organic and inorganic acids (Hamdine et al. 2004). Two systems presenting similar gelation mechanisms were characterized furthermore in order to investigate the sol–gel transition: the chitosan–phosphoric acid and the chitosan–oxalic acid systems. By performing rheological measurements in the framework of linear viscoelasticity, we have investigated the effect of time, temperature, and polymer concentration on the gelation evolution. For both acid-based systems, gelation occurred above a critical polymer concentration around 5% w/v (g/100 ml) of chitosan. Isothermal time sweep experiments showed that the gelation occurs in three stages: (i) incubation; (ii) rapid increase of G′; and (iii) a last stage where G′ slowly reached its equilibrium value due to slow molecular diffusion. At the gel point, G′ and G′′ scaled with ω ⁿ , with n=0.55 for both acid-based systems and a fractal dimension d _f of 1.9. Cooling–heating cycles revealed that the gels showed thermoreversibility after one sequence, but became permanent during subsequent cycles.This revised version was published online in October 2005 with corrections to the author's name.     

High-speed fiber spinning process with spinline flow-induced crystallization and neck-like deformation

The dynamics and stability of the high-speed fiber spinning process with spinline flow-induced crystallization and neck-like deformation have been studied using a simulation model equipped with governing equations of continuity, motion, energy, and crystallinity, along with the Phan-Thien–Tanner constitutive equation. Despite the fact that a simple one-phase model was incorporated into the governing equations to describe the spinline crystallinity, as opposed to the best-known two-phase model [Doufas et al. J Non-Newton Fluid Mech, 92:27–66, 2000a]; [Kohler et al. J Macromol Sci Phys, 44:185–202, 2005] that treats amorphous and crystalline phases separately in computing the spinline stress, the simulation has successfully portrayed the typical nonlinear characteristic of the high-speed spinning process called neck-like spinline deformation. It has been found that the criterion for the neck-like deformation to occur on the spinline is for the extensional viscosity to decrease on the spinline, so that the spinning is stabilized by the formation of the spinline neck-like deformation. The accompanying linear stability analysis explains this stabilizing effect of the spinline neck-like deformation, corroborating a recent experimental finding [Takarada et al. Int Polym Process, 19:380–387, 2004].This paper was presented at the 2nd Annual European Rheology Conference 2005 on April 21–23, 2005, in Grenoble, France.     

Shear banding during nonlinear creep with a solution of monodisperse polystyrene

Creep experiments with a solution of polystyrene (M _w = 2.6 MDa, 16 vol.%, 25 °C) in diethyl phthalate are reported for stresses between 100 and 2,500 Pa (≈ 3G _N ⁰/4). The aim was to look for a flow transition as reported for strongly entangled poly(isobutylene) solutions. The experiments with the polystyrene solution were repeated for cone angles of 2, 4, and 6° (radius 15 mm) and showed no dependence on cone angle. The Cox–Merz rule was not fulfilled for stresses beyond about 800 Pa. The tangential observation with a CCD camera showed that the edge took a concave shape because of the second normal stress difference. Beyond 1,000 Pa, the concave edge develops into a crevice, thus substantially reducing the effective cross-section. This leads to runaway in a constant torque experiment. At p ₂₁ = 800 Pa, head-on particle tracking confirms that the originally linear velocity profile takes a gooseneck shape, thus revealing shear banding. When the creep stress is stepped down to 100 Pa, this velocity profile evolves back to a linear one. The conclusion from this work is that even if nonlinear creep experiments are reproducible and a steady state is reached, this does not mean that the flow field is homogeneous. This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006.     

Rheological properties of binary associating polymers

Dynamics of associating polymer solutions above the reversible gelation point are studied. Each macromolecule consists of a soluble backbone (B) and a small fraction of specific strongly interacting groups (A or C stickers) attached to B. A mixture of B–A and B–C associating polymers with 1:1 stoichiometric ratio is considered. As a result of AC association, the polymers reversibly gelate above the overlap concentration. It is shown that (1) the network strands are linear complexes (double chains) of B–A and B–C; (2) “diffusion” of the network junction points is characterized by an apparent activation energy, which can be significantly higher than the energy of one AC bond; (3) most importantly, the randomness of sticker distribution along the chain can significantly slow down the network relaxation leading to a markedly non-Maxwellian viscoelastic behavior. The theory elucidates the most essential features of rheological behavior of polysaccharide associating systems (with A = adamantyl moiety, C = β-cyclodextrin, B = either chitosan or hyaluronan) including similar behavior of G ^′ and G ^″ in a wide frequency range, strong temperature dependence of the characteristic frequency ω _x , and an extremely strong effect of added free stickers (fC) on the dynamics. This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006.     

The MSF model: relation of nonlinear parameters to molecular structure of long-chain branched polymer melts

The elongational viscosity data of model PS combs (Hepperle J, Einfluss der Molekularen Struktur auf Rheologische Eigenschaften von Polystyrol- und Polycarbonatschmelzen. Doctoral Thesis, University Erlangen-Nürnberg, 2003) are reconsidered by including the interchain pressure term of Marrucci and Ianniruberto [Macromolecules 37:3934–3942, 2004] in the Molecular Stress Function model [Wagner et al., J Rheol 47(3):779–793, 2003, Wagner et al., J Rheol 49:1317–1327, 2005d]. Two nonlinear model parameters are needed to describe elongational flow, β and . The parameterβ determines the slope of the elongational viscosity after the inception of strain hardening. It is directly related to the molecular structure of the polymer and represents the ratio of the molar mass of the (branched) polymer to the molar mass of the backbone alone. β follows from the hypothesis of Wagner et al. [J Rheol 47(3):779–793, 2003] that side chains are compressed onto the backbone. We consider also the case that side chains are oriented by deformation, but not stretched, and found little difference in the model predictions. The parameter represents the maximum strain energy stored in the polymeric system and determines the steady-state value of the viscosity in extensional flows. The relation of this energy parameter to the molecular structure is discussed. Good correlations between the energy parameter and different coil contraction ratios, as determined either experimentally or calculated theoretically by considering the topology of the macromolecule, are found. The smaller the relative size of the polymer coil, the larger is the energy parameter and the more strain energy can be stored in the polymeric system. Presented at the 3rd Annual European Rheology Conference, AERC2006, Crete, Greece.     

Rheological properties of polyacrylates used as synthetic road binders

Most adhesives and binders, including bitumen for asphalt mixture production, are presently produced from petrochemicals after the refining of crude oil. The fact that crude oil reserves are a finite resource means that in the future, it may become necessary to produce these materials from alternative and probably renewable sources. Suitable resources of this kind may include polysaccharides, plant oils and proteins. This paper deals with the synthesis of polymer binders from monomers that could, in future, be derived from renewable resources. These binders consist of polyethyl acrylate (PEA) of different molecular weight, polymethyl acrylate (PMA) and polybutyl acrylate (PBA), which were synthesised from ethyl acrylate, methyl acrylate and butyl acrylate, respectively, by atom transfer radical polymerisation. The rheological properties of these binders were determined by means of oscillatory testing using a dynamic shear rheometer and combinations of stress/strain, temperature and frequency sweeps. The results indicate that PEA can be produced to have rheological properties similar to that of ‘soft’ 100/150 penetration grade bitumen, PMA with similar rheological properties to that of ‘hard’ 10/20 penetration grade bitumen, while PBA, due to its highly viscous nature and low dynamic moduli, cannot be used on its own as a binder. The synthetic polymers were found to be thermo-rheologically simple, and the shift factors, used to produce the dynamic moduli master curves, were found to fit an Arrhenius function.     

Passive scalar measurements in a planar mixing layer by PLIF of acetone

 Quantitative passive scalar measurements were performed in an incompressible planar mixing layer at Re _δ up to 10⁴ using planar laser-induced fluorescence of acetone seeded into one side of the layer. Probability density functions compiled from sets of images showed a preferred mixture composition, favoring the high-speed fluid, which extended across the layer. This preferred composition produced non-marching PDFs and an inflection in the average mixture fraction profile. The spatial resolution of the experiment was found to be sufficient to accurately measure the fraction of mixed fluid within the layer. The mixed fluid fraction was found to increase to an asymptotic value of 0.5 by Re _δ  ≈ 5,000, the approximate location of turbulent transition, in contrast to high Schmidt number experiments which show minimal mixing before the transition point. Received: 5 October 1999 / Accepted: 9 February 2001     

Processing,characterisation and rheology of transparent concentrated fibre-bundle suspensions

Highly concentrated planar fibre-bundle suspensions with a transparent PMMA matrix were processed with various initial bundle contents and orientations. They were submitted to simple compression and plane strain compression deformation modes. First rheological measurements are presented. They highlight the role of the bundle content and orientation on recorded stress levels. The transparent matrix allows the observation of fibrous microstructures before and after compressions: The in-plane deformation of bundles (flattening and bending) as well as the evolution of their orientation are analysed and discussed. This paper was presented at the 3rd Annual European Rheology Conference (AERC) 2006, held in Hersonisos, Crete, Greece, April 27–29, 2006.     

The computer simulations of polymer dynamics in porous media

We designed and developed a simple model of polymer chains. Three types of model chains with different internal macromolecular architecture were studied: linear, star-branched with f=3 arms of equal length and rings. The chains consisted of identical united atoms (segments) and were restricted to a simple cubic lattice with the excluded volume interactions only (the athermal system). The macromolecules were confined between two parallel impenetrable walls with a set of irregular obstacles that can be treated as a crude model of porous media. The properties of the model studied were determined by the Monte Carlo simulations. A Metropolis-like sampling algorithm with local changes of chains’ conformation was used. The short- and long-time dynamic properties of the model system were studied. The differences in the mobility of chains and their fragments for different internal polymer architectures were shown and discussed. The possible mechanisms of chain’s motion were discussed.This paper was presented at the 2nd Annual European Rheology Conference (AERC) held on April 21–23, 2005 in Grenoble, France.     

On the dynamics of grafted branched polymers—a Monte Carlo simulation study

A simplified model of grafted branched polymers was designed and investigated. The model consisted of star-branched chains constructed on a simple cubic lattice. The star polymers were built of three arms of equal lengths. The chains were attached to an impenetrable flat surface with one arm’s end. The arm attached to the surface (a stem) was built of segments different from those in two remaining arms (branches). During the Monte Carlo simulation of the system, the conformation of each chain was modified according to the metropolis sampling algorithm with local changes of chain conformations. The simulations were performed for different chain lengths and the temperature of the system (solvent conditions). The structure of a polymer film formed on the grafting surfaces depended strongly on the temperature and the low temperature films consisted of two separate layers with the insoluble layer located near the grafting surface. The short-time relaxation of the branches and stems of chains was also investigated. The analysis of the dynamics of the model system shows the influence of the structure of the system on relaxation times of various parameters. Paper presented at the AERC 2005 held on April 21–23, 2005 in Grenoble, France.     

Rheology and microstructure of asphalt binders

The viscous and linear viscoelastic properties of different asphalt binders have been analyzed in this paper. Thus, an unmodified bitumen, a polymer-modified (SBS) bitumen, a commercial synthetic binder, and two model synthetic binders with different polymer (SBS) concentrations have been studied. The mechanical spectra of these binders are quite different, mainly influenced by SBS concentration. Thus, up to three regions may be observed for a synthetic binder with high polymer concentration. The temperature dependence of the zero-shear-rate-limiting viscosity is described by an Arrhenius-like equation, in a temperature range that depends on binder composition. These results have been discussed taking into account the development of a polymer-rich phase in SBS-modified bitumen and model synthetic binders. Received: 6 February 2000 Accepted: 8 August 2000     

Effect of a hydrotrope on the viscoelastic properties of polymer-like micellar solutions

Low-viscosity micellar aqueous solutions of cetyltrimethylammonium bromide (CTAB) undergo a major change in the presence of the hydrotrope, potassium 1-phenylmethylsulfate (KPhMS), producing a highly viscoelastic entanglement network of polymer-like micelles. The system studied here shows typical shear banding flow behavior, which tends to disappear with increasing the hydrotrope-to-surfactant concentration ratio (C _H / C _S). The linear rheological response was analyzed with the model of Granek–Cates, whereas the nonlinear behavior was reproduced with the Bautista–Manero–Puig (BMP) model. Both models introduce a kinetic equation to account for the breaking and reformation of the micelles, and they predict the linear and nonlinear rheological data very well. This paper was presented at Annual European Rheology Conference (AERC) held in Hersonisos, Crete, Greece, April 27–29, 2006.     

Shear and elongational flow behavior of acrylic thickener solutions. Part II: effect of gel content

We have investigated the effect of crosslink density on shear and elongational flow properties of alkali-swellable acrylic thickener solutions using a mixing series of the two commercial thickeners Sterocoll FD and Sterocoll D as model system. Linear viscoelastic moduli show a smooth transition from weakly elastic to gel-like behavior. Steady shear data are very well described by a single mode Giesekus model at all mixing ratios. Extensional flow behavior has been characterized using the CaBER technique. Corresponding decay of filament diameter is also well fitted by the Giesekus model, except for the highest crosslink densities, when filament deformation is highly non-uniform, but the non-linearity parameter α, which is independent of the mixing ratio, is two orders of magnitude higher in shear compared to elongational flow. Shear relaxation times increase by orders of magnitude, but the characteristic elongational relaxation time decreases weakly, as gel content increases. Accordingly, variation of gel content is a valuable tool to adjust the low shear viscosity in a wide range while keeping extensional flow resistance essentially constant.     

Large amplitude oscillatory shear behavior of PEO-PPO-PEO triblock copolymer solutions

Rheological properties of poly(ethylene oxide)-poly(propylene oxide)-poly(ethylene oxide) (PEO-PPO-PEO) triblock copolymer solution in both linear and nonlinear regions have been investigated. PEO-PPO-PEO triblock copolymer solution shows a dramatic change in mechanical properties as temperature changes. PEO-PPO-PEO triblock copolymer undergoes a transition from sol to gel with increase of temperature. During this transition the copolymer solution passes through three different stages, namely sol, soft gel, and hard gel. In our previous research (Hyun et al. in J Non-Newtonian Fluid Mech 55:51–65, 2002), large amplitude oscillatory shear (LAOS) behavior was found to be very sensitive to the generated microstructures. In this study, we investigated the relationship between the LAOS type and the microdomain structure. Newtonian behavior is observed in sol region, while there appear two kinds of LAOS types in the soft gel region. One is type I (G′, G′′ decreasing) and the other is a combination of type I and type IV (G′, G′′ increasing followed by decreasing). Type III (G′ decreasing, G′′ increasing followed by decreasing) is observed in the hard gel region. We compared the shape of stress curves, Lissajous pattern, and Fourier transform (FT) rheology of hard gel and soft gel under LAOS, and tried to relate the complex LAOS behavior with the microstructural change. From these investigations, it was found that the LAOS behavior and the stress pattern at large strain are closely related to the microdomain structure of PEO-PPO-PEO triblock copolymer, and provide a lot of useful information on the microstructures induced by large deformation.