Evaluation of rheological and image properties of styrene‐butadiene‐styrene and ethylene‐vinyl acetate polymer modified bitumens

This article presents a laboratory evaluation of conventional, fundamental, rheological, and morphological characteristics of styrene‐butadiene‐styrene (SBS) and ethylene vinyl acetate (EVA) polymer modified bitumens. Polymer modified bitumen (PMB) samples have been produced by mixing a 50/70 penetration grade unmodified (base) bitumen with SBS and EVA copolymer at different polymer contents. The fundamental viscoelastic properties of the PMBs were determined using dynamic (oscillatory) mechanical analysis and presented in the form of temperature and frequency‐dependent rheological parameters. The morphology of the samples as well as the percent area distribution of polymers throughout the base bitumen have been characterized and determined by means of fluorescent light optic microscopy and Qwin Plus image analysis software, respectively. The results indicated that polymer modification improved the conventional and rheological properties of the base bitumen. It was also concluded that the temperature and frequency had a significant effect on complex modulus of PMBs. The behavior of EVA and SBS PMBs had exhibited quite difference at 50°C. Moreover, it was found out that 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. © 2011 Wiley Periodicals, Inc. J Appl Polym Sci, 2011     

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     

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     

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.     

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     

Blends of bitumen with polymers having a styrene component

The properties of a 100 penetration grade bitumen are modified considerably, and in a number of ways by the addition of 10 to 40 parts per hundred (pph) of a homopolystyrene and graft, block and random copolymers of styrene with butadiene and acrylonitrile. At low temperatures some blends have a similar stiffness to or even lower stiffness than the bitumen, but generally the blends are more than one order of magnitude stiffer, even when a rubber is added. The contrasting behavior is displayed by a polystyrene and a high impact polystyrene, ～3% to 4% of grafted rubber on the latter being sufficient to cause the enhancement, even at the 10 pph level, by two different random styrene‐butadiene copolymers, and also by blends consisting of different amounts of SBS block copolymer. Some polymers apparently trigger a Hartley inversion of the micellar structure of the asphaltene micelles. High low temperature stiffness correlates roughly with a lower Tg' as measured by the peak maximum in the E″ plots of the dynamic mechanical thermal analysis (DMTA) and by the steps in the differential scanning calorimetry (DSC) curves at temperatures below O°C. Tan δ maxima and DSC traces detected the glass transition in the continuous phase and in the dispersed phases, but none of these amorphous polymers formed a crystalline phase, though the DSC traces of the polystyrene and the SBS blends suggested that the polymer‐rich phases underwent an aging/ordering process on cooling. Our SBS blends differ in phase inversion behavior and the pattern of loss processes from others that had a smaller asphaltene component.     

Influence of styrene-butadiene-styrene polymer modification on bitumen viscosity

Effects of polymer content/structure and bitumen type on viscosity characteristics of styrene-butadiene-styrene (SBS) polymer modified bitumens were investigated. The study indicated that SBS polymers were not inert additives and increases in kinematic and dynamic viscosities of the modified bitumens were not directly proportional to polymer content; a marked viscosity increase was observed when the polymer content increased from 3 to 6% by weight of the blend. Modification with a sufficiently high polymer content also increased the degree of non-Newtonian behaviour of the bitumens. The base bitumens and modified bitumens containing 3% SBS were observed to be essentially shear rate independent, while those containing 6 or 9% SBS displayed shear-thinning behaviour. Compared to the modified bitumens with linear SBS, the modified bitumens with branched SBS demonstrated a higher degree of shear-thinning behaviour. These effects were dependent on ranges of shear rate and temperature. The increased degree of non-Newtonian behaviour was observed to influence the correlations between kinematic and dynamic viscosities.     

丁二烯-苯乙烯共聚物改性沥青的研究进展

介绍了丁二烯-苯乙烯共聚物改性沥青的发展状况,分析了聚合物改性剂苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)、丁苯橡胶(SBR)与基质沥青的分散性、溶胀性和相容性问题,着重论述了丁二烯-苯乙烯共聚物化学改性沥青的可能性。指出SBS、SBR与沥青适当相容并达到均匀分散,是充分发挥改性效果的前提;化学改性以及复合改性技术是提高沥青性能的重要手段。     

Effect of processing variables on the linear viscoelastic properties of SBS‐oil blends

Block copolymers, especially styrene‐butadiene‐styrene three‐block copolymers (SBS), are recognized as especially effective asphalt modifiers because of their thermoplastic elastomeric properties. The concentration of copolymer, its ability to swell by the maltenic oils, and the processing variables are essential in the development of a three‐dimensional network in the polymer‐rich phase that enhances the vis‐coelastic properties of these modified binders. This swollen polymer phase may influence the mechanical properties of the modified bitumens and synthetic binders. This paper deals with the influences that processing variables exert on the linear viscoelastic properties of oil/SBS mixtures in a wide range of temperatures. From the experimental results obtained we may conclude that most of the oil/SBS blends studied are highly structured thermoplastic gels above a critical SBS concentration that depends upon temperature, time of processing and surrounding atmosphere.     

Rheological examination of temperature dependence of conventional and polymer‐modified road bitumens

Rheological characterization of two types of road bitumens, conventional and polymer‐modified, has been examined in the temperature range between 20°C and 140°C. Tests were carried out before and after ageing following a thin‐film oven test. Polymer‐modified bitumens exhibit non‐Newtonian behaviour up to the 120°C due to a complex secondary structure formed by added polymers. For conventional bitumens, Newtonian behaviour was observed above 60°C. Special attention was paid to measurements and to analysis of the dynamic data of oscillatory shear. The mechanical spectra in a wide frequency range have been obtained using the WLF time‐temperature superposition principle. The analysis of viscoelastic data clearly showed the differences between the two types of bitumen. Conventional bitumens were more sensitive to temperature and to the ageing effects. For polymer modified bitumens, the elastic contribution to viscoelastic response was more pronounced, and independent of temperature and ageing.     

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.     

沥青改性用SBS市场分析及生产开发建议

通过对国内外苯乙烯类热塑性弹性体SBS产品在制鞋、沥青改性、聚合物改性和粘合剂等方面的市场及消费需求分析,预测了SBS产品在改性沥青行业的需求情况和发展趋势。随着国内高等级高速公路的快速发展,我国对改性沥青用SBS的需求量将会有较大的增长。针对我国目前的生产实际情况,提出了下一步改性沥青用SBS的生产开发建议。     

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     

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.     

Grafting of N‐carbamyl maleamic acid onto a styrene–butadiene–styrene copolymer

A styrene–butadiene–styrene block copolymer (SBS) was functionalized with N‐carbamyl maleamic acid (NCMA) using two peroxide initiators with the aim of grafting polar groups onto the molecular chains of the polymer. The influence of the concentration of benzoyl peroxide (BPO) and 2,5‐dimethyl, 2,5‐diterbuthylperoxihexane (DBPH) was studied. The concentration of peroxy groups ranged between 0.75 and 6 × 10^?4 mol % while the concentration of NCMA was constant at 1 wt %. The reaction temperature was chosen according to the type of peroxide employed, being 140°C for BPO and 190°C for DBPH. FTIR spectra confirmed that NCMA was grafted onto the SBS macromolecules. It was found that the highest grafting level was achieved at a concentration of peroxy groups of about 3 × 10^?4 mol %. Contact angle measurements were used to characterize the surface of the SBS and modified polymers. The contact angle of water drops decreased with the amount of NCMA grafted from 95°, the one corresponding to the SBS, to about 73°. T‐peel strength of polymer/polyurethane adhesive/polymer joints made with the modified polymers was larger than those prepared with the original SBS. The peel strength of SBS modified with 1.5 and 3 × 10^?4 mol % of peroxy groups from BPO were five times larger than that of the original SBS. The materials modified using BPO showed peel strengths higher than the ones obtained with DBPH. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 4468–4477, 2006     

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     

Rheological properties of bitumen modified with ethylene butylacrylate glycidylmethacrylate

This article presents experimental results related to rheological viscoelastic properties of polymer modified bitumens, PmBs. Experiments were performed by a dynamical shear rheometer before and after thermo‐oxidative aging. Two types of bitumens with different asphaltene contents were modified by the addition of two types of reactive ethylene terpolymers, Elvaloy AM, and Elvaloy 4170, with a different percentage of reactive functional group, glycidylmethacrylate, GMA. Results of the investigation indicate that the degree of reactive polymer modification is a function of bitumen type, bitumen‐polymer compatibility, and polymer concentration. Polymer modification improves the following physical properties of the base bitumen: penetration, softening point, temperature susceptibility, and elastic recovery. Reactive polymers are effective binder modifiers that improve the susceptibility to high temperature of asphalt mixes, and also their rutting resistance, contribute to their good storage stability and make them less sensitive to aging. This is a result of the formation of a chemical bond between the polymer and molecules of asphaltenes. POLYM. ENG. SCI., 54:1056–1065, 2014. © 2013 Society of Plastics Engineers     

Optical transparency,thermal resistance,intermolecular interaction,and mechanical properties of poly(styrene‐butadiene‐styrene) copolymer‐based thermoplastic elastomers

The optical transparency, thermal resistance, intermolecular interaction, and mechanical properties of poly(styrene‐block‐butadiene‐block‐styrene) (SBS), which were modified by blending with crystalline polypropylene (PP) or amorphous polystyrene (PS), were analyzed. The dynamic mechanical test indicated that the PP exhibited an intermolecular interaction with SBS and PS was compatible with SBS. The optical properties indicated that the direction of the light was changed due to the difference between the refractive indices of SBS and the added modifiers. Additionally, refraction and reflection occurred at the interface, reducing the transparency of SBS. The thermal resistance of SBS clearly improved upon modification by the addition of crystalline PP polymer. The thermal treatment increased the tensile strength and the elongation at breakage of modified SBS by reducing the internal stress, which was generated during the blending process. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

High vinyl high styrene solution SBR

Objective: the objective of this study is to prepare high vinyl copolymers containing various levels of styrene and butadiene, and also to prepare random butadiene in high styrene content styrene-butadiene copolymers (SBR) while controlling the styrene block length. These materials could be used in race tread applications. Summary: This reports presents the synthesis and characterization of random, high vinyl copolymers containing styrene and butadiene (SBR's). The styrene content of these SBR's ranged from 10 to 80%. These SBR's were synthesized via anionic polymerization initiated by a catalyst system with a ratio of 1/0.4/5 of n-butyllithium (n-BuLi) to sodium dodecylbenzene sulfonate (SDBS) to N,N,N′,N′-tetramethylethylenediamine (TMEDA). Kinetic data as well as NMR and ozonolysis techniques confirm that random SBR copolymers are being produced for low styrene content polymers. The glass transition temperature (T_g), increased dramatically as the styrene content was increased. The amount of vinyl based upon the polymer's total composition within the copolymer was found to decrease linearly as you increase the amount of styrene in the polymer. TGA results show that high styrene content polymers degrade at lower temperatures. The RPA confirms that as the styrene content increases, the elastic modulus decreases. As the frequency increased, the tan delta decreased for each polymer. Tan delta does not appear to be a function of styrene content. TEM results helped to describe polymer microstructure.     

Rapid FTIR method for quantification of styrene‐butadiene type copolymers in bitumen

The mid‐IR molar absorptivity for polystyrene (PS) and polybutadiene (PB) blocks were obtained for five styrene‐butadiene‐styrene (SBS) and SB copolymers, including linear, branched, and star copolymers, and their blends with bitumen. The average absorptivity for PS and PB blocks was 277 and 69 L mol⁻¹ cm⁻¹ and it was little affected by the S/B ratio or the copolymer architecture. In the presence of bitumen, Beer's law was obeyed but the respective PS and PB absorptivity was 242 and 68 L mol⁻¹ cm⁻¹, possibly because of weak interactions between the copolymer and bitumen. The absorptivity values were used to calculate the concentration of SB‐type copolymers in blends with bitumen with an accuracy of 10% or better. The method can be used to probe the stability of bitumen–copolymer blends in storage at 165°C, to determine the copolymer concentration in commercial polymer modified bitumen (PMB), and to assess the resistance of PMB to weathering. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 79: 1034–1041, 2001