Improved properties of SBS‐modified asphalt with dynamic vulcanization

Storage‐stable styrene‐butadiene‐styrene triblock copolymer (SBS)‐modified asphalt was prepared by dynamic vulcanization. The vulcanization characteristics of the asphalt/SBS/sulfur blend were studied using a strain‐controlled rheometer. The vulcanization of SBS in the asphalt resulted in a marked increase in the torque of the blend. In addition, the vulcanization of a butadiene rubber (BR)/sulfur blend was significantly influenced by the addition of asphalt through a curemeter. The existence of asphalt can accelerate the vulcanization of BR/sulfur blend and reduce its reversion. The preparation process of storage‐stable SBS‐modified asphalt by dynamic vulcanization was identified by a plot of the electric current versus time. The addition of sulfur to the SBS‐modified asphalts resulted in the formation of chemically vulcanized network structures in the modified binders. The physical properties of the SBS‐modified asphalt containing sulfur were compared to those of the modified binders without sulfur. The storage stability of the SBS‐modified asphalt was effectively improved by the addition of sulfur. The rheological properties of the SBS‐modified asphalts before and after adding sulfur were characterized by using dynamic shear rheometry and a rotational viscometer. As indicated by the monitored morphology, the compatibility and high‐temperature storage stability of SBS‐modified asphalts were improved by the addition of sulfur.     

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     

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     

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     

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.     

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     

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     

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.     

Investigation of physiochemical and rheological properties of waste cooking oil/SBS/EVA composite modified petroleum asphalt

The objective of this research is to investigate the physiochemical and rheological properties of waste cooking oil (WCO)/styrene-b-butadiene-b-styrene/ethylene vinyl acetate (SBS/EVA) composite modified asphalt. A petroleum asphalt composite modified with SBS/EVA and oil/SBS/EVA were prepared to undergo the physical, rheological, and microscopic experiments. Comparing these tests results with the properties of unmodified petroleum asphalt, SBS and EVA cause an improvement in pavement performance, but weaken the storage stability. Although the high-temperature performance undermined by the addition of WCO, the thermal stability, fatigue property, and low temperature crack resistance improved obviously. In addition, WCO mainly composed by low-weight components, and these can supplement the light components in the polymer-modified asphalt. EVA could increase the percentage of large molecular size of asphalt, while WCO relieves this trend. The reactions between WCO and these polymers (SBS and EVA) are physical reactions. Atomic force microscopy morphology results reflect that SBS and EVA increase the surface complexity and roughness, and WCO makes the asphalt surface smooth. This indicates WCO increases the dispersion of polymers in asphalt. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48828.     

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     

Ethylene vinyl acetate copolymer nanocomposites based on (un)modified sepiolite: Flame retardancy,thermal, and mechanical properties

Flame retardant ethylene‐vinyl acetate (EVA) nanocomposites were prepared by melt blending using unmodified and modified sepiolite. Modification process of sepiolite was carried out by using 3‐aminopropyltrimethoxysilane in water/ethanol medium. Thermal, mechanical, and flame retardancy properties of the prepared nanocomposites were evaluated and compared with each other. X‐ray diffraction and scanning electron microscopy indicated that sepiolite fibers are well‐dispersed in EVA matrix. By the addition of (un)modified sepiolite, both flame retardancy and thermal stability characteristics first improved, and then deteriorated, indicating a direct relationship between these properties. It was also found that sepiolite protects carbonyl groups of EVA from further degradation. Most interestingly, a simultaneous increase in both ductility and toughness was observed in the prepared composites. Whatever the evaluated properties were, whether the mechanical, thermal, or flame retardancy, the improved properties were more remarkable when modified sepiolite was utilized. POLYM. COMPOS., 38:1302–1310, 2017. © 2015 Society of Plastics Engineers     

Bitumen modification with reactive and non-reactive (virgin and recycled) polymers: A comparative analysis

The main goal of this research was to compare the modification capability of two different types of bitumen modifiers: non-reactive plastomers and elastomers, and reactive polymers. The group of non-reactive polymers included a block copolymer (SBS), recycled thermoplastic polymers (EVA/LDPE blends), and crumb tire rubber, which were mixed at a processing temperature of 180 °C. In the second group, a reactive MDI–PEG prepolymer, a low processing temperature modifier (90 °C), was considered. The study was mainly focused on the characterization of the thermorheological behaviour of selected modified bitumen samples. In addition, the thermal behaviour (by modulated DSC), and morphology (by optical microscopy) of these modified bitumen samples were also evaluated. All of these bitumen modifiers significantly improve the thermomechanical properties of the resulting binder, especially at high in-service temperatures. However, whereas bitumen modified by non-reactive polymers undergo marked oxidation events due to the high processing temperature used (180 °C), MDI–PEG modified bitumen does not experience this phenomenon because of the lower processing temperature involved (90 °C). In general, non-reactive polymers should be added in much larger concentrations than the reactive polymer to obtain similar results, although the latter requires a further period of curing, at room temperature, to induce suitable modification. Finally, only MDI–PEG modified bitumen is stable when stored at high temperature (163 °C), whereas all the non-reactive polymer-modified bitumen studied undergo either phase separation or particle precipitation.     

SBS／EVA改制PP力学性能的研究

研究了PP／EVA、PP／SBS和PP／EVA／SBS共混体系,对其不同配比的共混体系进行了物理机械性能测试与讨论。结果表明,SBS和EVA并用增韧PP时,当质量份大于17份时有着显著的协同效应,PP／EVA／SBS三元共混物具有优良的抗冲击性能。     

Preparation and properties of high viscosity modified asphalt

High viscosity modified (HVM) asphalt was prepared by the addition of styrene–butadiene–styrene (SBS), plasticizer, crosslinker. The effect and proportion of each modifier in the preparation of HVM asphalt were studied. SBS was the major modifier and determined the basic properties of HVM asphalt. Plasticizer (furfural exact oil) and crosslinker (sulfur) as additional modifiers were necessary in improving the workability, stability, and aging resistance of modifier. The effect of aging and additional modifiers on the structure and rheological behavior of SBS modified (SM) asphalt was displayed by adopting various rheological tests. Plasticizer declined the rutting resistance of SM asphalt and increased the viscous behavior of SM asphalt after aging. The use of crosslinker led to the formation of polymer network and improved the aging resistance of SM asphalt. The morphology observation shows crosslinker led to the formation of polymer network and improved the compatibility between SBS and asphalt. Plasticizer prompted the swelling and dispersion of SBS in asphalt and improved the effect of crosslinker further. Aging destroyed the polymer phase seriously and there was still residual polymer phase in asphalt. POLYM. COMPOS., 38:936–946, 2017. © 2015 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     

相容剂及硫化体系对EPDM/LDPE热塑性弹性体性能的影响

采用两种不同硫化体系通过动态硫化工艺制备EPDM/LDPE热塑性弹性体(TPE),并采用EVA对体系进行相容.结果表明:随着EVA用量的增大,EPDM/LDPE共混物的剪切粘度逐渐减小,加工流动性提高;与硫黄硫化EPDM/LDPE TPE相比,过氧化物硫化EPDM/LDPE TPE的物理性能较差,耐热性能较好;当EVA用量为18份时,EPDM/LDPE TPE的综合性能较好.     

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     

BR/EVA/HIPS TPV的制备和性能研究

采用苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)改善BR/乙烯-乙酸乙烯酯共聚物(EVA)/高抗冲聚苯乙烯(HIPS)共混物的界面相容性,通过动态硫化法制备BR/EVA/HIPS TPV,并对其性能进行研究.结果表明:未加入SBS的BR/EVA/HIPS共混物未表现出橡胶类弹性体特征,而加入适量SBS的共混物表现出典型橡胶类弹性体特征;当SBS用量为8～12份时,BR/EVA/HIPS TPV的综合物理性能较好,拉伸断面平滑,界面相容性良好.     

Flame retardancy and toughening of high impact polystyrene

Flame retardant high impact polystyrene (HIPS) was prepared by melt blending HIPS, nano‐modified aluminum trihydrate (nano‐CG‐ATH), red phosphorus masterbatch (RPM), and modified polyphenylene oxide (MPPO). Styrene‐butadiene‐styrene (SBS) was used as a toughener in this research. The effects of nano‐CG‐ATH, RPM, MPPO, and SBS on properties of HIPS composites were studied by combustion test, mechanical tests, and thermogravimetric analysis. The morphologies of fracture surfaces and char layers were characterized through scanning electron microscopy (SEM). The HIPS/nano‐CG‐ATH/RPM/MPPO (60/6/9/25) composite and its combustion residues at various temperatures were characterized by Fourier transform infrared (FTIR) spectra analysis. The results showed that the UL‐94 rating of the HIPS/nano‐CG‐ATH/RPM/MPPO (60/6/9/25) composite reached V‐0 and its char layer after flame test was integrated, but its impact strength was low. Addition of SBS improved its impact property and did not influence its thermal and flame retardant properties but lowered its tensile strength and flexural modulus to some extent. The FTIR spectra confirmed that the P O C group was present in the charred substance. POLYM. COMPOS., 28:551–559, 2007. © 2007 Society of Plastics Engineers     

动态硫化BR/EVA/SBS/HIPS热塑性弹性体的增强研究

采用动态硫化法制备了顺丁橡胶(BR)/乙烯-醋酸乙烯共聚物(EVA)/苯乙烯-丁二烯-苯乙烯共聚物(SBS)/高抗冲聚苯乙烯(HIPS)热塑性弹性体(TPE),通过在BR中充填炭黑的方式对复合体系进行增强,对其力学性能及断面微观结构进行了研究。结果表明,对于动态硫化BR/EVA/SBS/HIPS共混型TPE,当BR相中炭黑填充量在0~80phr的范围内,其动态硫化产物均表现出TPE的特征;随着炭黑用量的提高,复合体系的拉伸强度、撕裂强度、邵氏硬度趋于显著提高,断裂伸长率趋于下降,而扯断永久形变则趋于不变;未填充炭黑TPE的拉伸断面上两相界面结合良好;炭黑填充后的TPE的断面起伏较大但平滑,表明弹性较强。