Influence of ageing on rheology of SBR/sulfur‐modified asphalts

The effect of short‐term and long‐term oxidative ageing on the rheological, physical properties, the morphology, and thermodynamic behavior of the styrene‐butadiene rubber (SBR)‐ and SBR/sulfur‐modified asphalts is studied respectively. The dynamic rheological tests show the two major effects of ageing on the rheological behavior of the asphalt binders. Ageing prompts the degradation of polymer and increases the viscous behavior of the binders, on the other, ageing improves the elastic behavior of the binders due to the changed asphalt components, the final rheological behavior of the aged binders depends on the combined effect. The SBR/sulfur‐modified asphalt is more susceptible to ageing and dynamic shear due to the structural instability and show a viscous behavior with increasing the sulfur level after ageing. Under the influence of repeated shear force, the high‐temperature property of the SBR/sulfur‐modified asphalts declines. The morphology observation shows the compatibility between polymer and asphalt is improved with further ageing especially for the SBR/sulfur‐modified asphalt. POLYM. ENG. SCI., 2012. © 2011 Society of Plastics Engineers     

The composition and ageing of high‐viscosity and elasticity asphalts

Different kinds of plasticizers and crosslinkers were used to prepare high‐viscosity modified (HVM) asphalt and high‐elastic modified (HEM) asphalt and the major physical properties were studied and compared. The kinds of plasticizers were optimized and the difference in composition between HVM and HEM asphalts was clarified. The plasticizers with different thickness and flexibility were available for HVM or HEM asphalts respectively. The kinds of crosslinkers were also compared and optimized and it was found that the most effective crosslinker was sulfur. The effect of anti‐ageing reagent on HEM asphalt was confirmed and it was found that one of the most effective way to retain the properties of HVM and HEM asphalt before ageing was to increase the SBS content further. POLYM. COMPOS., 38:2509–2517, 2017. © 2015 Society of Plastics Engineers     

非晶态α-烯烃共聚物/丁苯橡胶复合改性沥青的流变性能及微观分布状态

为改善丁苯橡胶（SBR）改性沥青的高温性能,选取非晶态α-烯烃共聚物（APAO）作为改性剂,制备了高低温性能良好兼顾流变性能的APAO/SBR复合改性沥青。研究了不同掺量APAO/SBR复合改性沥青的高中低温流变性能;利用荧光电子显微镜观察了沥青中聚合物的分布状态,以从微观上反应流变性能。结果表明,APAO的加入降低了沥青的不可恢复蠕变柔量和高温区温度敏感性,提高了沥青的软化点、抗车辙因子、弹性恢复率及疲劳破坏加载次数,说明APAO提高了沥青的高温性能和耐疲劳性能。尽管APAO对沥青的低温蠕变劲度模量（S）和蠕变速率（m）都有负面影响,但APAO掺量不大于5％（质量分数,下同）时基于K（S/m）指标的低温性能仍好于苯乙烯-丁二烯-苯乙烯嵌段共聚物改性沥青。综合考虑各项性能,建议选用APAO掺量为5％,在此掺量下APAO与SBR的相容性较好。     

The research for high‐elastic modified asphalt

High‐elastic modified (HEM) asphalt was prepared by the addition of styrene‐butadiene‐styrene (SBS), plasticizer, and crosslinker to base asphalt. The effect and proportion of each modifier in asphalt were studied using physical and rheological tests. It was found that SBS determined the high‐temperature performance of HEM asphalt mainly. Plasticizer (dioctyl phthalate) is very helpful in improving the low‐temperature flexibility and elastic recovery. Crosslinker (sulfur) is necessary in maintaining high‐temperature stability. In this study, Fourier transform infrared, hydrogen nuclear magnetic resonance analysis, and microscopy observation were used to investigate the structural characteristics of modified asphalts further before and after ageing. The research showed the structural characteristics of modified asphalt were influenced evidently by ageing. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42132.     

The viscoelastic properties of polymer‐modified asphalts

The linear viscoelastic properties of one family of base asphalts, unmodified or modified by the simple addition of an elastomer or by further in‐situ crosslinking, have been investigated. The time‐temperature superposition principle was shown to be valid for the base as well as for the modified asphalts. The addition of the elastomer styrene‐butadiene (SB) copolymer increased drastically the storage modulus and the elastic character of the asphalts. The thermal susceptibility of the polymer modified asphalts was considerably reduced and this combined with an increased resistance to deformation (larger complex modulus) suggests much better performances for road applications. The chemically modified asphalt containing 3% SB showed similar viscoelastic properties as the physical blend containing 6% SB.     

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.     

丁苯橡胶改性沥青的高性能化和稳定化

在丁苯橡胶(SBR)改性沥青时加入稳定剂，运用反应共混方法研制出了高性能、高温贮存稳定的SBR改性沥青。利用动态力学性能分析和相形态观察分别比较了加入稳定剂对SBR改性沥青的动态力学性能和体系相形态在高温下的影响。结果表明，与未加稳定剂时相比，加入稳定剂的SBR改性沥青除能保持良好的低温性能之外，其高温物理机械性能有了明显的改善，且在高温下贮存数天后仍稳定。稳定剂的加入使得改性沥青体系内形成了弹性交联网络结构，显著改善了SBR改性沥青的高温贮存稳定性能和高温物理机械性能。     

Internal structure of bitumen/polymer/wax ternary mixtures for warm mix asphalts

Polymer modified asphalts (PMA) and warm mix asphalts (WMA) are technologies widely adopted in the paving industry. The first one is well established, while the second one is relatively new, but rapidly growing since it guarantees economic and environmental advantages. Until now PMA and WMA have been used disjointedly, but it would be useful to combine them to keep the advantages of both. One of the adopted solutions to obtain a warm effect is the addition of waxes to the asphaltic binder. Therefore, a “warm mix polymer modified asphalt” may be potentially obtained with a ternary asphalt/polymer/wax system. However, the final warm effect and performances of the binder will depend on the interactions between the three components. A preliminary investigation was done by mixing asphalt, styrene‐butadiene‐styrene block copolymer and a wax chosen among the following three categories: paraffinic, partially oxidized and maleic anhydride functionalized. The morphological and calorimetric analyses and solubility tests allowed identifying different behaviors depending on the wax type, which may preferentially interact either with the asphalt or with the polymer, thus influencing the whole binder structure. With regard to the ternary mixes, it was found that: (i) the paraffinic wax preferentially resides in the polymer‐rich phase, and slightly enhances the asphalt‐polymer compatibility; (ii) the partially oxidized wax prefers the asphaltene‐rich phase and reduces the compatibility; (iii) it is not clear where the functionalized wax is located, but it has a considerable compatibilizing effect and strongly alters the colloidal equilibrium of the asphalt‐polymer blend. © 2013 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

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     

Low‐density polyethylene/silica compound modified asphalts with high‐temperature storage stability

Low‐density polyethylene (LDPE) modified asphalts with improved high‐temperature storage stability are prepared by incorporating silica into the LDPE compounds. The effect of silica on the high‐temperature storage stabilities, dynamic rheological and mechanical properties, and morphologies of the modified asphalts are studied. It is found that the LDPE/silica ratio in the compound has a great effect on the high‐temperature storage stability. The modified asphalts are stable when the ratio of LDPE/silica is around 100/60 (w/w). The silica content in the modified asphalts is less than 3.2%, and it has a slight influence on the mechanical properties of the modified asphalts. Silica can improve the rheological properties of the modified asphalt to some extent. The high‐temperature storage stability can be increased by a decreasing density difference between the LDPE/silica compound and the asphalt or in terms of equalizing the polarity differences between asphalt and LDPE by silica. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 101: 472–479, 2006     

Rheological investigation of the influence of acrylate polymers on the modification of asphalt

The effect of ethylene, ethylene acrylate and glycidyl methacrylate (EA) terpolymer, and ethylene butyl acrylate (EBA) copolymer on asphalt modification was investigated at 4, 6 and 8% polymer concentrations. Both melt state rheology and asphalt concrete mix (ACM) were investigated. In the melt state analysis, dynamic shear rheology, storage stability, artificial ageing, and performance grading (PG) were studied. The PG grading of polymer modified asphalt (PMA) is correlated to the elastic properties of the polymers. Both resins improved the rheological properties, reduced the temperature susceptibility, showed better storage stability, and increase the upper grading (performance) temperature of the base asphalt. The two polymers showed similar ageing characteristics with little influence on flow activation energy. In asphalt concrete mix analysis, Marshall stability, stripping (durability), resilient modulus, and permanent deformation tests were performed. Polymer‐modified asphalt concrete mix (PMACM) has increased percent retained stability and the resilient modulus when compared with ACM. The elastic modulus of PMA and the resilient modulus of their ACM followed the same trend. Weak influence on water sensitivity was observed, but excellent rutting resistance was obtained for PMACM over ACM. EA (much cheaper than EBA) produced satisfactory properties of PMA and superior ACM properties when blended with the high asphaltenes Arabian asphalt. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 3446–3456, 2006     

Use of rheological compatibility criteria to study SBS modified asphalts

Polymer‐modified asphalts (PMAs) were prepared using Bachaquero asphalt and styrene–butadiene–styrene (SBS) type copolymers. Their rheological behavior was compared to that of unmodified asphalt and of a compatible commercial PMA. Materials were submitted to frequency sweeps between 10^?1 and 10² rad/s from 0 to 50°C. Storage stability tests were performed for 72 h at 160°C. Ring and ball softening points from the top and the bottom of the blends were compared and were used along with fluorescence microscopy to evaluate stability. Samples prepared with styrene–ethylene–butylene–styrene (SEBS) showed improved compatibility and stability as compared with SBS‐modified asphalts, probably because of a higher stability to thermal degradation from the absence of double bonds. An additional improvement in stability and compatibility was observed for SEBS functionalized with maleic anhydride (SEBS‐g‐MAH)–modified blends. Better compatibility, however, did not improve rheological behavior at low temperatures. The systems studied are so complex from a chemical point of view that the rheological criteria normally used to predict compatibility of polyblends did not give enough information regarding the compatibility of the modified asphalts. © 2003 Wiley Periodicals, Inc. J Appl Polym Sci 90: 1772–1782, 2003     

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     

Synthesis and characterization of styrene butadiene rubber—Bentonite clay nanocomposites

In the present study, naturally occurring unfractionated bentonite clay was used to prepare styrene butadiene rubber/bentonite clay nanocomposite by latex stage blending. The bentonite clay was organo‐modified by in situ resol formation by the reaction of resorcinol and formaldehyde. The latex clay mixture was co‐coagulated with acid. The resulting clay masterbatch was compounded and evaluated by Fourier Transform Infrared spectroscopy, X‐ray diffraction (XRD), Transmission Electron Microscopy (TEM), Energy Dispersive X‐ray spectroscopy (EDS), Scanning Electron Microscopy, Thermogravimetric analysis, and Differential Scanning Calorimetry. XRD showed that the interplanar distance of the in situ resol‐modified bentonite clay increased from 1.23 to 1.41 nm for the unmodified bentonite. TEM analysis indicated partial exfoliation and/or intercalation. EDS (Si and Al mapping) of the clay revealed the nature of the dispersion in the nanocomposites vis‐à‐vis the conventional styrene‐butadiene rubber (SBR)/bentonite clay composite. Thermogravimetric analysis was used to compare the decomposition trends of the SBR/clay nanocomposites with the SBR/clay composite. The glass transition temperature of SBR/clay nanocomposites increased as compared with that of neat SBR. Substantial improvement in most of the other mechanical properties was also observed in case of the nanocomposites. POLYM. ENG. SCI., 2009. © 2009 Society of Plastics Engineers     

Dynamically vulcanized thermoplastic elastomer nanocomposites based on linear low-density polyethylene/styrene-butadiene rubber/nanoclay/bitumen: morphology and rheological behavior

Dynamically crosslinked thermoplastic elastomer nanocomposites were synthesized as modifier for the bitumen binder-based asphalts. Linear low-density polyethylene (LLDPE) and styrene-butadiene rubber (SBR), with the ratio of 80/20, bitumen, and organically modified clay (OC) were all melt mixed in the presence of the sulfur curing system. The proposed mixing was carried out in an internal mixer at 160 °C with a rotor speed of 120 rpm. To enhance the molecular interactions between the polymer phases and the clay silicate layers, maleic anhydride-grafted LLDPE (PE-g-MA) with the maleiation degree of 50% was also incorporated into the mixture. Observation of the composite samples, using the scanning electron microscopy (SEM), revealed the matrix dispersed type of morphology for all dynamically vulcanized samples. X-ray diffraction (XRD) and transmission electron microscopy (TEM) examinations evidenced the exfoliation of the clay silicate layers with good dispersion. Rheomechanical spectrometry (RMS) was performed on the prepared nanocomposites. All dynamically vulcanized nanocomposites comprising 2.5% of OC exhibited shear-thinning behavior and non-terminal characteristics with a low frequency range. These indicate the formation of three-dimensional physical networks by the clay nanolayers throughout the LLDPE matrix. The presence of the bitumen in the composition of the prepared nanocomposites improved the flowability of the samples. This is a promising feature of the prepared nanocomposites to be used as an elastic and resistant modifier in the composition of the bitumen-based asphalts.

     

LDPE/SBR复合改性沥青的贮存稳定性

比较了直接添加LDPE、SBR改性沥青与LDPE／SBR熔融共混物改性沥青的高温贮存稳定性，并利用光学显微镜观察了各种改性沥青在高温下随时间的变化。结果表明：直接添加LDPE、SBR所得到的改性沥青，其高温贮存稳定性很差。而采用预先制备含有部分共聚物的LDPE／SBR共混物所得到的改性沥青能够在高温下稳定贮存。同时，相形态观察也表明，这种共混物改性沥青的高温相形态也不随时间变化，这一点与稳定性测试结果想吻合。     

硫化胶粉与脱硫胶粉改性沥青性能研究

对比分析了硫化胶粉和脱硫胶粉微观结构及其改性沥青基本路用性能,研究了硫化胶粉和脱硫胶粉在改性沥青过程中表现出的共性与差异及其原因。结果表明,加入硫化胶粉与脱硫胶粉,均能提高沥青基本路用性能,相同目数下,脱硫胶粉较硫化胶粉交联密度低,表面粗糙,表面极性增加,脱硫胶粉与沥青具有更好的相容性和稳定性,一定掺量下,硫化胶粉能赋予沥青更好的高温稳定性,脱硫胶粉能显著提高沥青低温延度,界面作用及胶粉网络结构的形成对改性沥青路用性能有重大影响。     

Reinforcement of polyurethane/epoxy interpenetrating network nanocomposites with an organically modified palygorskite

An organophilic palygorskite (o‐PGS) prepared by the treatment of natural palygorskite with hexadecyl trimethyl ammonium bromide was incorporated into interpenetrating polymer networks (IPNs) of polyurethane (PU) and epoxy resin (EP), and a series of PU/EP/clay nanocomposites were obtained by a sequential polymeric technique and compression‐molding method. X‐ray diffraction and scanning electron microscopy analysis showed that adding nanosize o‐PGS could promote the compatibility and phase structure of PU/EP IPN matrices. Tensile testing and thermal analysis proved that the mechanical and thermal properties of the PU/EP IPN nanocomposites were superior to those of the pure PU/EP IPN. This was attributed to the special fibrillar structure of palygorskite and the synergistic effect between o‐PGS and the IPN matrices. In addition, the swelling behavior studies indicated that the crosslink density of PU/EP IPN gradually increased with increasing o‐PGS content. The reason may be that o‐PGS made the chains more rigid and dense. As for the flame retardancy, the PU/EP nanocomposites had a higher limiting oxygen index than the pure PU. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

POE弹性体改性沥青的结构与性能

研究了聚烯烃弹性体（POE）改性沥青的结构和性能,考察了POE用量对两种基质沥青常规性能的影响,并用光学显微镜观察了POE在沥青中的分布状态。结果表明,随着POE用量增加,沥青的软化点增加,25℃针入度减小,高温性能变好。通过储存稳定性实验发现,POE改性沥青后稳定性较差。POE改性沥青相结构研究发现,随着POE用量的增加,POE由分散相变为连续相,POE质量分数为6%时,基质沥青发生相转变。     

纳米有机膨润土/丁苯橡胶复合改性沥青的制备及性能

以纳米有机膨润土和丁苯橡胶(SBR)制备复合改性沥青,并考察了复合改性沥青的针入度、软化点、延度、储存稳定性及流变性能,同时对比了液体SBR和粉末SBR对复合改性沥青性能的影响.结果表明,复合改性沥青中,纳米有机膨润土的最佳质量分数为4％.随着SBR用量的增加,沥青的针入度降低,软化点升高,延度先增大后减小.粉末SBR...