Rheological properties of styrene butadiene styrene polymer modified road bitumens

The use of polymers for the modification of bitumen in road paving applications has been growing rapidly over the last decade as government authorities and paving contractors seek to improve road life in the face of increased traffic. Currently, the most commonly used polymer for bitumen modification is the elastomer styrene butadiene styrene (SBS) followed by other polymers such as styrene butadiene rubber, ethylene vinyl acetate and polyethylene. This paper describes the polymer modification of two penetration grade bitumens with SBS. Six polymer modified bitumens (PMBs) were produced by mixing the bitumens from two crude oil sources with a linear SBS copolymer at three polymer contents. The rheological characteristics of the SBS PMBs were analysed by means of conventional as well as dynamic mechanical analysis using a dynamic shear rheometer (DSR). The results of the investigation indicate that the degree of SBS modification is a function of bitumen source, bitumen-polymer compatibility and polymer concentration, with the higher polymer concentrations in a high aromatic content bitumen producing a highly elastic network which increases the viscosity, complex modulus and elastic response of the PMB, particularly at high service temperatures. However, ageing of the SBS PMBs tends to result in a reduction of the molecular size of the SBS copolymer with a decrease in the elastic response of the modified road bitumen.     

Effect of polymer additives and process temperature on the physical properties of bitumen‐based composites

Polymer modified bitumen (PMB) is a binder obtained by the incorporation of polymer into the bitumen by mechanical mixing or chemical reaction. This study deals with the modification of bitumen with three types of polymers (LDPE, EVA, and SBS) in the presence of filler (CaCO₃). The morphological, mechanical, rheological properties, and thermal conductivity of the PMBs have been analyzed by scanning electron microscopy, tensile testing, melt flow index (MFI) measurements and hot wire method, respectively. The results indicate that the above‐mentioned properties of PMBs are influenced by polymer and bitumen nature and its composition. The mechanical properties of composites prepared at different temperatures exhibit small differences. In general, the inclusion of polymer increases tensile strength and Young's modulus and reduces percentage strain and MFI values, also, polymer inclusion reduces the thermal conductivity values of the composites. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Preparation and properties of bitumen modified with the maleic anhydride grafted styrene‐butadiene‐styrene triblock copolymer

A procedure to improve the properties of styrene‐butadiene‐styrene (SBS) copolymer modified bitumen by grafting of maleic anhydride (MAH) onto SBS in the presence of benzoyl peroxide (BPO) as initiator was proposed. The effects of the grafting degree (GD) on the properties of modified bitumen were investigated. FTIR spectroscopy was employed to verify the grafting of MAH onto SBS. The GD of MAH onto SBS was determined by a back titration procedure. To assess the effects of the GD of grafted SBS on properties of modified bitumen, the softening point, penetration, ductility, elastic recovery, penetration index, viscosity, storage stability, and dynamic shear properties were tested. Experimental results indicated that the SBS grafted with maleic anhydride (SBS‐g‐MAH) copolymer was successfully synthesized by solvothermal method, and different GD of the SBS‐g‐MAH was obtained by control the MAH concentration. The GD of the MAH onto SBS has great effect on the rheological properties of the modified bitumen, and the high temperature performance and storage stability of modified bitumen were improved with the GD of the MAH onto SBS increasing. POLYM. ENG. SCI., 2011. © 2011 Society of Plastics Engineers     

Evaluation of the properties of bitumen modified by SBS copolymers with different styrene–butadiene structure

Four styrene–butadiene–styrene(SBS) modified bitumens had been prepared by a base bitumen, a crosslinking agent and four SBS copolymers which differ in styrene blocks content and molecular configuration (radial or linear) under the same experimental conditions. Conventional properties, morphology, thermal behavior and microstructure were investigated by means of conventional tests, fluorescence microscopy, differential scanning calorimetry (DSC), and Fourier transform infrared (FT‐IR) spectroscopy. In terms of linear SBS polymers, the SBS molecule with the styrene content of 30% has a perfect dispersion and complete stretching in bitumen matrix, and in this case, the conventional properties and thermal stability of bitumen are enhanced substantially. However, the star SBS polymer due to long branched chains forming the preferable steric hindrance to enhance the intensity of base bitumen, plays a more important role in improving the conventional properties of base bitumen than linear SBS polymers. Furthermore, the FT‐IR spectra indicate that, the main bands assignations of four modified bitumens are identical and the significant variation is the peak intensity. And a noncomplete crosslinking reaction happens between the bitumen and each SBS polymer, which can efficiently prevent excessive cross‐linking from affecting the intrinsic bitumen characteristics. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2014 , 131, 40398.     

Evaluation of physical,rheological, and structural properties of vulcanized EVA/SBS modified bitumen

In this study, the performance and modification mechanism of EVA (ethylene‐vinyl‐acetate) modified (EM), EVA/SBS (Styrene‐Butadiene‐Styrene) modified (ESM), and EVA/SBS/sulfur modified (ESSM) bitumens were evaluated. The physical, rheological, morphological, and structural properties were determined before and after aging, and compared with those of base bitumen. These properties were evaluation using conventional physical methods, Fourier transform infrared spectrometer, optical microscopy, dynamic shear rheometer, and bending beam rheometer, respectively. The results showed that sulfur was useful in bitumen, EVA, and SBS modification by forming a vulcanized crosslinking polymer network. The vulcanization improved most of the physical properties of ESM bitumen, especially high‐ and low‐temperature performance, and toughness and tenacity (previously not evaluated in the literature). Meanwhile, vulcanization improved the compatibility between polymers and bitumen and increased the aging resistance of ESM bitumen. Vulcanization reactions took place without new functional groups being presented in the infrared spectrum. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 44850.     

Processing,rheology, and storage stability of recycled EVA/LDPE modified bitumen

The optimum processing conditions for the manufacture of polymer‐modified bitumens (PMBs), as well as the rheological properties of the final polymer‐bitumen blends, strongly depend on the characteristics of the mixing device used. The present work is focused on the comparison among the kinetics of the mixing process and the rheological properties and microstructural characteristics of PMBs manufactured in two different mixers. Thus, blends of 60/70 penetration grade bitumen and recycled EVA/LDPE were processed in both high and low‐shear devices. Knowledge on the evolution of shear viscosity and microstructure with time, as well as on the mechanical properties of the final polymer‐bitumen blends, was gained from rheological and modulated DSC tests, and optical microscopy. The results obtained demonstrate that processing in the high‐shear device yields a significant decrease in the time needed for the polymer‐bitumen blend to reach the final stage of the manufacturing process, as well as an important reduction in bitumen oxidation and enhanced properties in a wide range of in‐service temperatures. However, polymer‐bitumen blends manufactured in the high‐shear device are not stable during its storage at high temperature. POLYM. ENG. SCI., 47:181–191, 2007. © 2007 Society of Plastics Engineers     

Temporary networks in polymer‐modified asphalts

The viscosity functions of several polymer‐modified asphalts (PMAs) were studied at different temperatures in steady‐state rate sweep tests. The materials were obtained by mixing different base asphalts with either styrene‐butadiene‐styrene (SBS), ethylene‐vinylacetate (EVA) or reactive ethylene terpolymers (RET). The first two polymers form a physical network that is swollen by the asphalt, while the latter is functionalized with glycidylmethacrylate (GMA) and can crosslink and/or chemically bond with the molecules of asphaltenes. In the presence of SBS or EVA, at certain temperatures, the viscosity curves exhibit a Newtonian behavior at low shear rates, followed by two distinct shear‐thinning phenomena. In some cases, the first shear‐thinning is preceded by a small shear‐thickening region. Similar phenomena are not present in the viscosity curves of the RET‐modified asphalts and can be related to a temporary nature of the physical polymer network. Polym. Eng. Sci. 44:2185–2193, 2004. © 2004 Society of Plastics Engineers.     

Effect of montmorillonite on properties of styrene–butadiene–styrene copolymer modified bitumen

Clay/styrene–butadiene–styrene (SBS) modified bitumen composites were prepared by melt blending with different contents of sodium montmorillonite (Na‐MMT) and organophilic montmorillonite (OMMT). The structures of clay/SBS modified bitumen composites were characterized by XRD. The XRD results showed that Na‐MMT/SBS modified bitumen composites may form an intercalated structure, whereas the OMMT/SBS modified bitumen composites may form an exfoliated structure. Effects of MMT on physical properties, dynamic rheological behaviors, and aging properties of SBS modified bitumen were investigated. The addition of Na‐MMT and OMMT increases both the softening point and viscosity of SBS modified bitumens and the clay/SBS modified bitumens exhibited higher complex modulus, lower phase angle. The high‐temperature storage stability can also be improved by clay with a proper amount added. Furthermore, clay/SBS modified bitumen composites showed better resistance to aging than SBS modified bitumen, which was ascribed to barrier of the intercalated or exfoliated structure to oxygen, reducing efficiently the oxidation of bitumen, and the degradation of SBS. POLYM. ENG. SCI., 47:1289–1295, 2007. © 2007 Society of Plastics Engineers     

Fundamental characterization of SBS‐modified asphalt mixed with sulfur

The purpose of this study was to characterize the mechanical behavior of asphalt modified by styrene–butadiene–styrene (SBS) and sulfur. Viscosity, microscopy, and rheological tests were conducted to understand the engineering properties of the polymer‐modified asphalt (PMA). Without the addition of sulfur, the polymer‐modified asphalt was microheterogeneous and was made up of two distinct finely interlocked phases, especially at high SBS concentrations. After the addition of sulfur, the PMA was observed to have smaller asphalt domains and a fairly homogeneous dispersion of the asphalt in the SBS matrix. The compatibility between polymer and asphalt produced an elastic network into the asphalt. The addition of sulfur resulted in an excellent elastic system and substantially increased the rheological properties of the PMA. Because of the colloidal nature of asphalt cements, their engineering properties were greatly improved because of the reinforcement of the SBS polymer and the physical‐chemical interaction between SBS and asphalt. The difference in the softening point between the top and bottom layers decreased significantly, and elastic recovery increased when was sulfur was present. A viscoelastic model was examined and shown to be appropriate for predicting the rheological properties ofthe asphalt–SBS blend mixed with sulfur. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 103: 2817–2825, 2007     

Artificial aging of polymer modified bitumens

This paper presents an investigation of artificial aging of polymer modified binders, prepared from three base bitumens and six polymers. Aging of the binders was performed using the Thin Film Oven Test (TFOT), the Rolling Thin Film Oven Test (RTFOT), and modified RTFOT (MRTFOT). The binders were characterized by means of infrared spectroscopy, different types of chromatography, and dynamic mechanical analysis. It was found that the effect of aging on the chemistry and rheology of the modified binders was influenced by the nature of the base bitumens and was strongly dependent on the characteristics of the polymers. For styrene–butadiene–styrene (SBS) and styrene–ethylene–butylene–styrene (SEBS) modified binders, aging decreased the complex modulus and increased the phase angle. Aging also increased the temperature susceptibility of these modified binders. The rheological changes of SBS modified bitumens were attributed to polymer degradation and bitumen oxidation. However, for SEBS modified bitumens, the mechanisms of aging are unclear. In the case of ethylene vinyl acetate (EVA) and ethylene butyl acrylate (EBA) modified binders, the process of aging increased the complex modulus and elastic response (decreased phase angle), and reduced temperature susceptibility. These changes were mainly due to the oxidative hardening of the base bitumens. The study also showed statistically significant correlation between TFOT, RTFOT, and MRTFOT. However, no definite conclusions could be drawn regarding the difference in severity of aging between these methods. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 76: 1811–1824, 2000     

Comparative study of the effect of sulfur on the morphology and rheological properties of SB‐ and SBS‐modified asphalt

The modification of asphalt with styrene‐ butadiene block copolymers and sulfur was studied to elucidate the effect of the molecular characteristics of the polymer, polymer content, and sulfur/polymer ratio on the physical properties of modified asphalts. Two types of styrene‐butadiene copolymers were used (SB and SBS), which differed considerably in terms of their chain architecture, average molecular weights, and size and distribution of their polybutadiene and polystyrene blocks, as shown by gel permeation chromatography, infrared spectroscopy, nuclear magnetic resonance, and differential scanning calorimetry. Sulfur/polymer/asphalt blends were prepared by a hot mixing process and characterized by conventional tests, fluorescence microscopy, and rheology. The results revealed that the morphology of the blends is strongly dependent on polymer concentration and sulfur/polymer ratio. In‐depth rheological characterization showed that the thermomechanical properties changed considerably upon addition of small amounts of sulfur. Collectively, these results suggest that sulfur increases the compatibility between polymer and asphalt by crosslinking polymer chains. Interestingly, the rheological behavior of blends prepared with a combination of SB and sulfur was similar to that exhibited by blends prepared with SBS either in the presence or absence of sulfur. This is explained by assuming that the addition of small amounts of sulfur to SB‐modified asphalt facilitates the formation of an elastomeric network that resembles the one found in SBS‐modified asphalt, effectively contributing to asphalt reinforcement. Nonetheless, the exact dosage of sulfur must be carefully controlled to prevent gel formation. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

Viscous properties and microstructure of recycled eva modified bitumen

This paper deals with the viscous properties of recycled-polymer modified bitumens (PMBs) in a wide range of temperatures. With this aim, two different penetration grade bitumens (60/70 and 150/200) and recycled EVA copolymer (EVA_R) from agriculture films were processed in an open reactor using a four blade propeller. Polymer concentration ranged from 0 to 9 wt%. Viscous flow and DSC measurements, from 5 to 165 °C, and optical microscopy, at room temperature, were performed on the samples. From the experimental results obtained, we may conclude that the viscous properties of bitumen, at high temperature, are improved by adding recycled EVA copolymer in amounts that depend on bitumen penetration grade. Moreover, significant microstructural changes, related to the development of a polymer-rich phase, tend to occur in the bitumen as polymer concentration increased. These changes in microstructure have a significant influence on the flow behaviour of the binder and on its in-service performance. As a consequence, the use of recycled EVA in PMBs can be considered a suitable alternative from both environmental and economical points of view.     

The impact of chaotic advection on the microstructure of polymer‐modified bitumen

Owing to the high viscosity of the materials involved, mixing is often a critical step when processing polymer‐modified bitumen (PMB), directly influencing the microstructure and the stability of final products. We provide experimental evidence suggesting that laminar chaotic advection may prove a valuable strategy for obtaining a homogeneous and finely interdispersed polymer‐bitumen mixture in affordable time. As a case study, we investigate the mixing performance of a lab‐scale flat‐bottomed cylindrical vessel stirred by a radial impeller, either located symmetrically or eccentrically with respect to the vessel axis. The same geometries with a flat‐disk impeller are also considered for comparison. The Mix‐Norm is used in combination with image analysis as an objective measure of mixing performance. Results of mixing performance are independently validated by rheological tests. The experiments pinpoint kinematic chaos as the fundamental transport mechanism enhancing both the dispersion process and the microstructural quality of the resulting PMBs mixture. © 2014 American Institute of Chemical Engineers AIChE J, 60: 1870–1879, 2014     

Morphology and rheological behavior of maltene–polymer blends. I. Effect of partial hydrogenation of poly(styrene‐block‐butadiene‐block‐styrene‐block)‐type copolymers

Because of the importance of the maltene–polymer interaction for the better performance of polymer‐modified asphalts, this article reports the effects of the molecular characteristics of two commercial poly(styrene‐block‐butadiene‐block‐styrene‐block) (SBS) polymers and their partially hydrogenated derivatives [poly{styrene‐block[(butadiene)_1?x–(ethylene‐co‐butylene)_x]‐block‐styrene‐block} (SBEBS)] on the morphology and rheological behavior of maltene–polymer blends (MPBs) with polymer concentrations of 3 and 10% (w/w). Each SBEBS and its parent SBS had the same molecular weight and polystyrene block size, but they differed from each other in the composition of the elastomeric block, which exhibited the semicrystalline characteristics of SBEBS. Maltenes were obtained from Ac‐20 asphalt (Pemex, Salamanca, Mexico), and the blends were prepared by a hot‐mixing procedure. Fluorescence microscopy images indicated that all the blends were heterogeneous, with polymer‐rich and maltene‐rich phases. The rheological behavior of the blends was determined from oscillatory shear flow data. An analysis of the storage modulus, loss modulus, complex modulus, and phase angle as a function of the oscillatory frequency at various temperatures allowed us to conclude that the maltenes behaved as pseudohomogeneous viscoelastic materials that could dissipate stress without presenting structural changes; moreover, all the MPBs were more viscoelastic than the neat maltenes, and this depended on both the characteristics and amount of the polymer. The MPBs prepared with SBEBS were more viscoelastic and possessed higher elasticity than those prepared with SBS. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Rheological characteristics of synthetic road binders

Most adhesives and binders, including binders for asphalt mixture production, are presently produced from petrochemicals through 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 polymerization (ATRP). The fundamental rheological properties of these binders were determined by means of a dynamic shear rheometer (DSR) using a combination of temperature and frequency sweeps. The results indicate that PEA has rheological properties similar to that of 100/150 penetration grade bitumen, PMA similar rheological properties to that of 10/20 penetration grade bitumen, while PBA, due to its highly viscous nature and low complex modulus, cannot be used on its own as an asphalt binder. The synthetic binders were also combined with conventional penetration grade bitumen to produce a range of bitumen–synthetic polymer binder blends. These blends were batched by mass in the ratio of 1:1 or 3:1 and subjected to the same DSR rheological testing as the synthetic binders. The blends consisting of a softer bitumen (70/100 pen or 100/150 pen) with a hard synthetic binder (PMA) tended to be more compatible and therefore stable and produced rheological properties that combined the properties of the two components. The synthetic binders and particularly the extended bitumen samples (blends) produced rheological properties that showed similar characteristics to elastomeric SBS PMBs, although their precise viscoelastic properties were not identical.     

Evaluation of the properties and microstructure of plastomeric polymer modified bitumens

This paper presents a laboratory study of modified bitumen containing plastomeric polymers; Evatane® 2805, Elvaloy® 3427, and Elvaloy® 4170. A 50/70 penetration grade base bitumen has been mixed with plastomeric polymers at different proportions by means of a high shear laboratory type mixer. The properties and microstructure of the samples have been determined and characterized using conventional and empirical test methods and fluorescence microscopy respectively. Qwin Plus image analysis has also been investigated in order to determine the % area distribution of plastomeric polymers throughout the base bitumen. The results indicated that polymer modification improved the conventional properties of the base bitumen such as; penetration, softening point, temperature susceptibility, etc. The microstructure and properties of the polymer modified bitumens are dependent on the type of polymer, the solubility of polymer in bitumens and polymer content. At low polymer contents, the samples revealed the existence of dispersed polymer particles in a continuous bitumen phase, whereas at high polymer contents a continuous polymer phase has been observed for the Evatane® 2805 and Elvaloy® 3427 polymers. Among the plastomeric polymers no significant polymer phase has been observed for the reactive terpolymer Elvaloy® 4170 although its conventional properties have been improved. It is also found out that a relationship exists between the polymer content and percent area distribution of polymers except for reactive terpolymer.     

Influence of poly(phosphoric acid) on the properties and structure of ethylene–vinyl acetate‐modified bitumen

Ethylene–vinyl acetate (EVA) modified (EM) bitumen was modified further by the addition of poly(phosphoric acid) (PPA). Owing to the gelation and acidification effect of PPA, the high‐temperature properties and compatibility of EM bitumen were improved greatly. Part dissolution of EVA after acidification was confirmed by the viscous behavior of EVA/PPA‐modified (EPM) bitumen in rheological tests to some extent. Morphology observation illustrated the decomposition of EVA in bitumen after PPA modification and ageing. Fourier transform infrared analysis proved that the hydrolysis reaction took place between the vinyl acetate segment of EVA molecule and the extra hydrogen protons of PPA. Thermal analysis displayed the thermodynamic behaviors of EM and EPM bitumens before and after ageing and confirmed the part dissolution of EVA further after PPA acidification. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 46553.     

Polymer‐modified bitumen of recycled LDPE and maleated bitumen

Maleated bitumen was prepared by the reaction of penetration grade bitumen (80/100) with maleic anhydride at 150°C for 2 h under nitrogen atmosphere. The effectiveness of maleation was assessed in bitumen–recycled low‐density polyethylene (LDPE) blends in terms of their softening point and elastic recovery. It was observed that the softening point and elastic recovery of the blends increased after maleation of the base bitumen owing to the formation of an asphaltene‐linked‐LDPE system. To obtain the desired elasticity, a recoverable composition was worked out with the help of maleated bitumen, recycled LDPE and styrene–butadiene–styrene. The storage stability of the blends was assessed in terms of their difference in softening points, rheological parameters, and microstructure of the top and bottom portions of test tube samples. The difference in softening point of the recoverable maleated bitumen blend was 5°C as compared to 60°C for the base bitumen blend. The phase angle was also reduced to 7.4° at 70°C compared with the 44.30° for the base bitumen blend. Scanning electron micrographs indicate that polymers existed in both the top and the bottom portions of the aged test tube maleated blend samples. The stability of the blend was further improved when LDPE is colloidal milled with maleic anhydride in the blend preparation. Roofing bitumen was also made with maleated bitumen containing 9 wt % recycled LDPE content. Based on the rheological data, it was found that the maleated bitumen–LDPE blend exhibited superior time‐/temperature‐dependent response and higher creep recovery compared with the base bitumen blend. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2013     

Physical and rheological properties of crumb rubber/styrene–butadiene–styrene compound modified asphalts

In order to improve the storage stability and tenacity of crumb rubber modified (CRM) asphalt, CRM compound modified asphalt was prepared by the addition of styrene–butadiene–styrene (SBS) and sulfur. The addition of SBS improved the tenacity of CRM asphalt, due to the formation of a dense polymer network. The storage stability of crumb rubber (CR)/SBS‐modified (CRSM) asphalt was improved by the addition of sulfur. The rheological tests confirmed the effect of SBS and sulfur on the physical properties of CRM asphalt to some extent and showed the susceptibility of CR/SBS/sulfur‐modified (CRSSM) asphalt to dynamic shearing. The morphology observation showed the compatibility of CRSM asphalt was improved greatly by vulcanization. POLYM. COMPOS., 38:1918–1927, 2017. © 2015 Society of Plastics Engineers     

Toughening study of fire‐retardant high‐impact polystyrene

Fire‐retardant high‐impact polystyrene (HIPS) was modified by melt blending with varying amounts of three types of tougheners. The effects of the tougheners on the properties of the fire‐retardant HIPS were studied by mechanical, combustion tests, and thermogravimetric analysis. The morphologies of fracture surfaces and char layers were characterized through scanning electron microscopy. The results show that the impact properties of styrene–butadiene–styrene (SBS)‐containing composites were better than those of ethylene–propylene–diene monomer (EPDM)‐containing or ethylene–vinyl acetate copolymer (EVA)‐containing composites. The tensile strength and flexural modulus of the fire‐retardant HIPS decreased evidently with the addition of tougheners. It is found that the compatibility between SBS copolymer and HIPS matrix was best among the three types of tougheners. The addition of SBS had little influence on the thermal property, residue, flammability, and morphology of char layer of the fire‐retardant HIPS, but the addition of EPDM rubber or EVA brought adverse influence on the residue, flammability, and morphology of char layer of the fire‐retardant HIPS, especially for EPDM. Copyright © 2009 John Wiley & Sons, Ltd.