Styrene butadiene styrene polymer modification of road bitumens

This paper describes the polymer modification of road bitumens with SBS. Six polymer modified bitumens (PMBs) were produced by mixing bitumen from two crude oil sources with an SBS copolymer at three polymer contents. The rheological characteristics of the SBS PMBs were analysed by means of 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. When the polymer concentration and bitumen-polymer compatibility allow a continuous polymer network to be established, modification is provided by a highly elastic network which increases the viscosity, stiffness 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.     

Characterization of bitumens modified with SEBS, EVA and EBA polymers

A laboratory evaluation of the modified bitumens containing styrene-ethylene-butylene-styrene (SEBS), ethylene vinyl acetate (EVA) and ethylene butyl acrylate (EBA) copolymers is presented. The morphology, storage stability and rheological and ageing properties of the modified binders were studied using fluorescence microscopy, dynamic mechanical analysis, creep test (bending beam rheometer) and conventional methods. The results indicated that the morphology and storage stability of the modified binders were largely dependent on the polymer content and were influenced by the characteristics of the base bitumens and the polymers. At a low polymer content (3% by weight), the modified binders showed dispersed polymer particles in a continuous bitumen matrix. At a sufficiently high polymer content (6% by weight), a continuous polymer phase was observed. Regardless of the nature of the two phases, the storage stability of the modified binders decreased as polymer content increased. Polymer modification improved bitumen rheological properties such as increased elastic responses at high temperatures and reduced creep stiffness at low temperatures. The degree of improvement generally increased with polymer content, but varied with bitumen source/grade and polymer type. Polymer modification also influenced bitumen ageing properties. Evaluation of ageing effect was dependent on testing conditions (e.g. temperature and frequency).     

Influence of polymer modification on low temperature behaviour of bituminous binders and mixtures

Effects of polymer modification on low-temperature properties of bituminous binders and mixtures were studied. Three bitumens were blended with 6% SBS, SEBS, EVA or EBA. Dense graded asphalt mixtures were prepared using a gyratory compactor. The low-temperature properties of the binders were characterised using dynamic shear rheometer and bending beam rheometer, and the low-temperature cracking of the mixtures evaluated by tensile stress restrained specimen test. The results indicated that low-temperature parameters were greatly dependent on the base bitumen, and in most cases, polymer modification did not show significant benefits as compared to the corresponding base bitumen. The mixture cracking temperature was found to correlate with the limiting temperatures (in bending beam rheometer) of the binders, weakly with Fraass breaking point, but not with parameters obtained using dynamic shear rheometer. Upon isothermal storage at low temperatures, the bitumens displayed physical hardening, and effect of polymer modification was small. However, physical hardening as measured by TSRST (tensile stress restrained specimen test) was not observed for the mixtures studied.     

Rheological properties of SEBS, EVA and EBA polymer modified bitumens

The rheological properties of various polymer modified bitumens were studied. Three bitumens from two different sources were mixed with styrene-ethylenbutylene-styrene (SEBS), ethylene vinyl acetate (EVA) and ethylene butyl acrylate (EBA) copolymers at different polymer contents. The rheological properties of the modified binders were investigated by means of dynamic mechanical analysis and creep test (bending beam rheometer). The results indicated that polymer modification increased binder elastic responses and dynamic moduli at intermediate and high temperatures, and reduced binder complex and stiffness moduli at low temperatures. Polymer modification also reduced temperature susceptibility, glass transition temperature as well as limiting stiffness temperature. The degree of the improvement generally increased with polymer content, but varied with bitumen source/grade and polymer type.     

Effect of ageing on different modified bituminous binders: comparison between RTFOT and radiation ageing

Standard laboratory ageing methods of bitumen only take into account the effect of thermo-oxidation during the service life of a pavement but the effect of high energy cosmic radiation on site is not simulated in these procedures. The aim of the present work is to compare the laboratory simulated short term bitumen ageing (rolling thin film oven test) with ageing produced by short exposures of bitumen samples to Ultra Violet and gamma radiation. The influence of ageing agents on the thermal properties and rheological performance of the pristine and modified bitumen binders has been evaluated in this study. The thermal behavior of various aged bitumens is characterized by both isothermal as well as non-isothermal thermogravimetric analysis. The thermoanalytic investigations on bituminous samples are carried out to evaluate the thermal stabilities and activation energies of the binders and the life time prediction of the materials is made with the help of the kinetic information. It is found that modified bituminous binders are more resistant to heat and radiation. Different rheological tests are conducted by dynamic shear rheometer to examine the effect of ageing in terms of bitumen oxidation and polymer phase degradation which has a major consequence on high temperature rutting or low temperature cracking. Type of modifier is found to be of decisive importance. Creep and recovery tests show that the structure-time dependency of pristine aged bitumen is influenced much by stress and temperature than in the case of modified aged bitumens. The study has revealed that the elastomeric modifier protects the bituminous binder more than plastic modifier or nano filler. Finally, a fair correlation has been made between standard RTFO ageing and radiation aging.     

Evolution of bituminous mix behaviour submitted to UV rays in laboratory compared to field exposure

Laboratory methods to simulate the short and long term ageing occurring during the service life of pure and polymer modified bitumens in a pavement are standardized but none of them takes into account the influence of ultraviolet (UV) radiations. Recently, attentions have been paid to the laboratory ageing tests with UV radiation applied to the bituminous binders. Even if this effect of UV radiation on binder’s films have been largely demonstrated and studied, however there are few studies dealing with the photo-oxidation of binders in a bituminous mix in relation with voids, film thickness and permeability. So, the aim of our study was to investigate whether the influence of UV light on bitumen ageing might be assessed in the bituminous mixes using an experimental apparatus dedicated to the ageing of paint. The results show that the influence of UV radiation on the ageing of bituminous mixes containing an elastomer modified bitumen can not be totally ignored: compared with thermal aging, the UV impact can be distinguished and found to be dominant for the production of carbonyl functions, the disappearance of C=C double bond of SBS and the increase of binder’s hardening. So, this study has highlighted, on the one hand, that inside the bituminous mix, the UV radiations do increase the rate of oxidation and, on the other hand, that the evolution’s kinetics due to a pure thermal oxidation or a photo-oxidation processes are different: the evolution due to 44 months of on site ageing is better assessed by photo-oxidation process than by pure thermal oxidation. Consequently, the UV exposure may affect the bitumen’s properties of pavement upper layers more strongly than the PAV simulation in laboratory (without UV action) does.     

Compatibility and storage stability of styrene-butadiene-styrene copolymer modified bitumens

The compatibility and storage stability of styrene-butadiene-styrene copolymer (SBS) modified bitumens were studied using fluorescence microscopy and dynamic mechanical analysis. Chemical characteristics of base bitumens and SBS polymers were determined by means of thin layer and gel permeation chromatography, respectively. The results showed that the morphology and phase separation of the modified binders varied with the characteristics of bitumens and polymers and were influenced by polymer content. At a given polymer content, the modified binders produced from bitumens with a higher content of aromatics exhibited better compatibility and higher storage stability. An increase in asphaltenes was observed to adversely affect storage stability. When mixing a small amount of polymer with bitumen, the modified binder showed dispersed polymer particles. At relatively high polymer content, depending on the base bitumens used, a continuous SBS phase was observed. On the other hand, the storage stability of modified binders decreased with increasing SBS content. Compared with branched SBS polymer, linear SBS displayed a finer dispersion in modified binder, and consequently, a lower phase separation was observed during hot storage. The degree of SBS dispersion in bitumen influenced storage stability and the rheological properties of modified binders; however, no definite relationships among them could be established.

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Résumé La compatibilité et la stabilité au stockage des bitumes modifiés par des copolymères styrène-butadiène-styrène (SBS) ont été étudiées au moyen de la microscopie à fluorescence et de l'analyse rhéologique dynamique. Les caractéristiques chimiques des bitumes de base ont été déterminées par chromatographie en couche mince alors que celles des polymères SBS l'ont été par chromatographie à pennéation de gel. Les résultats ont montré que la morphologie et la séparation de phases des liants modifiés variaient sclon les caractéristiques des bitumes et des polymères et qu'elles étaient influencées par le contenu en polymères. Pour une teneur en polymères donnée, les liants modifiés à base de bitumes ayant un fort taux d'aromatiques ont montré une meilleure compatibilité et une plus grande stabilité au stockage. Il a été observé qu'une augmentation de la teneur en asphaltènes dégradait la stabilité au stockage. Pour des teneurs en polymère faibles, l'observation des liants modifiés montre des particules de polym``ere dispersées dans la phase bitume. à des teneurs relativement importantes en polymère, mais variables selon le bitume de base utilisé, on observe une phase polymère continue. Par contre, la stabilité au stockage des liants modifiés diminue lorsque la teneur en SBS augmente. En comparaison avec un polymère SBS de type radial (ramifié), le polymère SBS de type linéaire donne des dispersions plus fines qui se traduisent par une moindre tendance à la séparation de phases lors du stockage à chaud. Le degré de dispersion du polymère SBS dans le bitume influence à la fois la stabilité au stockage et les propriétés rhéologiques des liants modifiés. On n'a cependant pas pu établir de relations précises entre ces propriétés.

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Editorial note Mr. Ulf Isacsson is a RILEM Senior Member. He is a member of TC 152-PBM on Performance of Bituminous Materials.     

Determination of polymer content in modified bitumen

Polymer-modified bitumen (PMB) has been increasingly used to enhance pavement performance. Two styrenebutadiene-styrene (SBS) copolymers were mixed with two bitumens by weight of the blend. This paper aims at developing the procedure to determine the proper polymer content to be mixed with bitumen. Tests including storage stability test, dynamic shear rheometer and scanning electron microscopy (SEM) were conducted to investigate the viscoelastic properties and microstructures of PMB. The addition of polymers increased the viscosity, softening point, toughness and complex modulus of bitumens. SEM results indicated that, as the polymer content increased, SBS gradually became the dominant phase that resulted in an increase in PMB's mechanic properties. Good compatibility produced an elastic network into the PMB up to 6% polymer concentration. The optimum polymer content was determined based on the rheological properties and the formation of the critical network. Adding higher polymer contents could lead to the separation of polymer and bitumen. The softening point temperature difference between top and bottom samples should be controlled within 2°C to monitor PMB's stability.     

Analysis of styrene-butadiene-styrene polymer modified bitumen using fluorescent microscopy and conventional test methods

This paper presents a laboratory study of modified bitumen containing styrene-butadiene-styrene (SBS) copolymer. Polymer modified bitumen (PMB) samples have been produced by mixing a 50/70 penetration grade unmodified (base) bitumen with SBS Kraton D1101 copolymer at five different polymer contents. The fundamental characteristics of the SBS PMB samples have been determined using conventional methods. The morphology of the samples as well as the percent area (%) distribution of SBS polymers throughout the base bitumen have been characterized and determined by means of fluorescence microscopy and Qwin Plus image analysis program, respectively. The mechanical properties of the hot-mix asphalt (HMA) containing SBS PMBs have also been analyzed and compared with HMA incorporating base bitumen. The effect of polymer addition on the short and long term aging characteristics of HMA have been evaluated by indirect tensile strength (ITS) test. The results indicated that polymer modification improved the conventional properties (penetration, softening point, etc.) and the mechanical properties (Marshall, ITS, etc.) of the base bitumen. It was also concluded 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. Moreover, it was found out that the polymer addition minimizes the short and long term aging of HMA.     

Dynamic mechanical behavior of polymer modified bitumen

The dynamic mechanical behaviour of bitumen (BIT) modified with styrene/butadiene/styrene block copolymer (SBS) were investigated. Dynamic mechanical analysis (DMA) were performed in the temperature range –80 to 60 °C. The primary viscoelastic functions were determined at the traffic frequency, 5 Hz. The BIT+SBS blends were investigated in creep fatigue regime at temperature 10, 20, 30, 40 and 50 °C. Dynamic mechanical behaviour of BIT+SBS blends depends on their morphological characteristics, number of phases, phase compositions and phase content in blend, as well as time and temperature. The curves of primary viscoelastic functions, storage modulus (E′), loss modulus (E′′) and loss tangent (tg δ) vs. temperature of polymer modified bitumen differ from unmodified bitumen and indicate the presence of the swollen polybutadiene and polystyrene phases in bitumen phase. The curve E′ vs. temperature of polymer modified bitumen show the rubbery plateau. With the increment of SBS content the rubbery plateau is shifted to high temperatures. At the constant load the creep values of BIT-SBS blends increase and those of creep modulus decrease over a period of time. These effect are more pronounced in samples with higer content of SBS. The time-temperature correspondence principle was applied to create master curves for the reference temperature 10 °C for the creep modulus of BIT + SBS blends. The data were analysed using WLF and Arrhenius equations. Electronic Publication     

SBS改性沥青高温流变性能与相态结构的关系

为量化表征SBS改性沥青网络化程度,确定控制其高温性能的形态学参数,采用荧光形态学方法、多重应力蠕变回复试验、频率扫描试验分别对5种掺量、6个剪切时间的线型SBS改性沥青在64℃下的荧光数字图像、不可恢复蠕变柔量、频率敏感性进行了定量分析。结果表明:通过增大改性剂掺量、延长剪切时间,SBS改性沥青高温流变性能得到改善。SBS掺量低于5%时,仅靠延长剪切时间无法形成网络结构;相同剪切时间下,增大SBS掺量即可形成网络结构。本文选取图像连通域和面积比率共同描述SBS改性沥青的相态变化特征,并建立了流变指标与形态学参数间的关系模型,为直接利用形态学方法预估、评价改性沥青高温性能提供理论依据。     

From virgin to recycled bitumen: A microstructural view

In the present work, soft and hard bitumens recovered from unaged, aged and recycled asphalt concrete (AC) mixtures, which in laboratory tests performed mechanically as well as an AC mixture produced with virgin materials, were investigated regarding rheological, thermal and surface microstructural aspects. For comparison purposes, bitumen containing 50 wt% of virgin bitumen and 50 wt% of bitumen recovered from reclaimed asphalt pavement (RAP) was studied. Some properties of the bitumens remained unchanged throughout the preparation of the AC mixture, aging and recycling: Soft and hard bitumens retained their general rheological properties significantly, and their thermal and surface microstructural properties partially. Soft bitumens presented larger “bee” structures and, therefore, higher surface roughness, while hard bitumens presented smaller “bee” structures and, thus, lower surface roughness. Furthermore, soft bitumens seemed to contain higher crystalline-like content than hard bitumens. For the soft cases, the unaged recovered bitumen did not show the same characteristics (rheological and surface microstructure) as the virgin bitumen. Similarly the recovered recycled bitumen did not show the same characteristics (surface microstructure) as the bitumen prepared from the mixture of virgin bitumen and RAP bitumen. Aging of the AC mixture changed the rheological properties of the soft bitumen by increasing the complex modulus and decreasing the phase angle. Similarly, recycling changed the rheological properties by increasing the complex modulus and decreasing the phase angle. Compositional changes occurred during AC mixture preparation (possibly also aging and recycling) for both soft and hard bitumens. Consequently, more “phases” were observed on the surface microstructure for the recovered bitumens as compared with the virgin bitumens. However, no significant trend was found for the surface microstructure characteristics between the unaged, aged and recycled recovered bitumens. Moreover, the nature of the virgin bitumen influenced the properties of the recycled recovered bitumen, e.g. the glass transition temperature.     

纳米粘土/聚苯乙烯-丁二烯-苯乙烯嵌段共聚物复合改性沥青短期老化前后性能研究

为探究纳米粘土与聚苯乙烯-丁二烯-苯乙烯嵌段共聚物(SBS)复合改性沥青的流变特性和抗老化性能,采用物理试验、动态剪切流变(DSR)、多应力蠕变回复试验(MSCR)和弯曲梁流变试验(BBR),对旋转薄膜烘箱加热老化试验(RTFOT)前后的不同纳米粘土掺量的纳米粘土/SBS复合改性沥青进行对比,探讨短期老化前后不同纳米粘土掺量下纳米粘土/SBS复合改性沥青的抗老化性能。结果表明:添加纳米粘土能明显地提高SBS改性沥青的高温、低温性能和抗老化性能;随着纳米粘土掺量的增加,纳米粘土/SBS复合改性沥青短期老化后的抗车辙因子、不可恢复蠕变柔量等性能指标不同程度改善;十六烷基三甲基溴化铵活化的纳米粘土表现出较好的化学活化效果和抗老化性能。     

Ageing in modified bitumen using FTIR spectroscopy

Modified binders exhibit complex rheological behaviour due to the interaction of the modifiers with the base binder and the manner in which they age during field applications. Quantification of the interaction and the ageing of such modified binders is currently a necessity. In this investigation, three modified binders (elastomer, plastomer, and crumb rubber) and the base bitumen were subjected to different ageing conditions and the evolution of the chemical functionalities during ageing were tracked using FTIR spectroscopy. Analysis of the spectra of modified binders immediately after the production process showed that while the elastomer modified binders exhibited physical interaction, the plastomer and crumb rubber modified binders exhibited physical and chemical interactions. During ageing, there was no subsequent evolution of the interactions and one could only see chemical functionalities related to oxidation. Analysis of the spectra showed that the carbonyl and sulphoxide exhibit identical trends whereas aliphaticity and aromaticity deviate drastically.     

Polymer modified bitumen: Optimization and selection

Polymer modification of bitumen has been commonly performed since the 1980s in order to decrease bitumen (and pavement) susceptibility to high and low temperatures, allowing reduction in common failure mechanisms as rutting and cracking. Bitumen modification has been commonly performed by addition of thermoplastic or elastomeric polymers. However, there are just a few studies on bitumen blends using multiple materials, seeking for specific advantages provided by addition of these modifiers. This work describes the results obtained after the preparation of multicomponent polymer-bitumen blends (MC) based on an 80/100 penetration grade bitumen with varying amounts of (i) Polyethylene wax (PW); (ii) Styrene–Butadiene–Styrene copolymer (SBS); and (iii) crumb rubber (CR). Ideal blends depending on the amount of polymer modifiers added were found by using an experimental design procedure. It was possible to propose charts allowing optimizing and selecting appropriate polymer modified bitumens (PMB) depending on target properties for a given application by following Ashby’s materials selection methodology.     

Structural characteristics of peat bitumen and peat/petroleum bitumen blends,and consideration of their potential use as road binder materials

Bitumen derived from peat was blended with petroleum bitumen and subjected to laboratory evaluation for use as road binder material. Standard empirical procedures used included penetration, softening point and Fraass brittle point determinations. Rheological behaviour has been assessed at low shear rate using a sliding plate microviscometer and at high shear rate using a cone and plate instrument. Thermal analysis techniques including calorimetry and dielectric thermal analysis have been used to obtain fundamental structural information. Properties have also been measured after accelerated ageing. Peat bitumen is shown to differ significantly from petroleum bitumen in having a relatively high (30%) crystal content; however, as crystal melting commences below 20 ° C, the initial effect obtained in blending with petroleum bitumen is that of a plasticizer, reducing blend viscosity and increasing penetration. Crystallinity in the blends is lower than expected and this is ascribed to diffusional control of the crystallization process. Peat bitumens show a marked propensity to harden on heating, presumably due to condensation reactions increasing molecular weight, and this more than compensates for the plasticizing effect. The results suggest that age hardening will limit technically useful blends to a maximum of 17% wt/wt peat bitumen.     

Investigation of microstructures and ultraviolet aging properties of organo-montmorillonite/SBS modified bitumen

Organo-montmorillonite(OMMT)/Styrene-butadiene-styrene(SBS) modified bitumen nanocomposites were prepared by melt blending. The microstructures of OMMT/SBS modified bitumen were characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR) and atomic force microscopy (AFM), respectively. The effect of OMMT on ultraviolet (UV) aging properties of SBS modified bitumen was investigated. FTIR and XRD analyses indicate that the OMMT/SBS modified bitumen forms an intercalated structure. It is observed that the phase contrast between the dispersed domains and the matrix is inverted in SBS modified bitumen, which is decreased with the introduction of OMMT according to AFM analysis. As a result of UV aging, both viscosity aging index and softening point increment of OMMT/SBS modified bitumen decrease significantly. There is a single phase trend in the morphology of the bitumen after aging, which is accelerated by the existence of SBS. However, these changes can be effectively prevented under the influence of OMMT, indicating the good UV aging resistance of OMMT/SBS modified bitumen.     

Attenuated total reflection (ATR) Fourier transform infrared (FT-IR) spectroscopy of oxidized polymer-modified bitumens

Oxidative age hardening of bitumen results in increasing fatigue susceptibility of bituminous mixtures, thus reducing the service life of asphalt pavements. Polymer additives to bitumen have been shown to improve its viscoelastic properties and, in some cases, reduce the level of bitumen hardening. Fourier transform infrared (FT-IR) spectroscopy enables evaluation of oxidation levels in bitumen by measuring the concentration of oxygen-containing chemical functionalities. This paper summarizes the results of the investigation of oxidative age hardening of polymer-modified bitumens (PMB) caused by accelerated aging in laboratory conditions. The PMB samples are prepared with different concentrations of styrene-butadiene-based co-polymers. Next, the PMB samples are aged using standard procedures that employ air blowing at 163 °C for 85 min followed by conditioning the samples at 100 °C and 2.1 MPa pressure for 20 to 48 hours. The resultant changes in their chemical composition are evaluated by portable attenuated total reflection (ATR) spectrometer. Measurements of ketone, sulfoxide, and hydroxyl content in PMB samples indicated similar oxidation pathways to those of non-modified bitumens. In addition, no evidence of polymer degradation due to accelerated aging of PMB was found in this study.     

Effect of ultraviolet aging on rheology, chemistry and morphology of ultraviolet absorber modified bitumen

Seeking a new method to solve the ultraviolet (UV) aging of bitumen is of great importance for road applications since the UV aging is considered to be one of the main causes leading to the performance deterioration of bitumen. In this paper, two UV absorbers (octabenzone and bumetrizole) were applied to modify the bitumen by melt blending. Effect of UV aging on rheology, chemistry and morphology of the UV absorber modified bitumens was investigated, by means of dynamic shear rheometer, thin-layer chromatography with flame ionization detection, Fourier transform infrared spectroscopy and atomic force microscopy, to reveal the mechanisms of action for bitumen and UV absorbers. Results show that the two UV absorbers show opposite influences on the UV aging performance of bitumen depending on the type of UV absorbers. The bumetrizole improves the UV aging resistance of bitumen remarkably since the bumetrizole can inhibit reactions of aromatization and oxidation of bitumen molecules to a certain extent during the UV aging, and thus slows down the rate at which the bitumen transforms from sol to gel. The bumetrizole modified bitumen has the potential to be used in pavement for improvement of the UV aging resistance during service life.