Effect of composition on the properties of SEBS modified asphalts

We characterised, from both a morphological and a rheological point of view, polymer modified asphalts prepared by the addition of styrene-(ethylene-co-butylene)-styrene block copolymer to a soft base asphalt. It was found that, even if the two components showed poor compatibility and interfacial adhesion, storage-stable mixtures could be obtained if the polymer content was maintained below about 4 wt%, with respect to the total mass. In this case, the more polar part of asphalt stabilises the dispersed polymer-rich domains, which act similarly to a filler and do not change significantly the viscoelastic behaviour of the base asphalt. On the contrary, at higher polymer concentrations, a swelled polymer-rich phase creates a network that strongly influences the viscoelastic properties. In this case the material becomes unstable and tends to give macroscopic phase separation if stored at high temperature without stirring.     

煤直接液化残渣对道路沥青改性作用的初步评价

现代交通具有轴载重、通量大和轮胎内压高的特点,因此,对公路路面提出了更高的要求。沥青是路面材料的重要组分之一,起黏结剂的作用,但由于沥青自身的温度敏感性,直接来自原油的道路沥青或重交通道路沥青自身不能满足要求。随着四季自然条件的变化,沥青变软或变硬,以致老化变脆,使路面发生损坏如车辙、开裂、剥离等。为了改善道路沥青路面的使用性能,使用改性沥青是解决这一问题的重要方法。改性沥青是在常规道路沥青中添加改性剂后的均匀沥青混合物。目前,大部分的高速公路的铺设均使用改性沥青。     

Improvements of properties of asphalt by poly(methyl methacrylate) additives

This article presents the effect of adding poly(methyl methacrylate) (PMMA) with different molecular weights on the mechanical properties of asphalt in terms of durability, strength, and resistance to rutting. By controlling the time of reaction we obtained PMMA of two different molecular weights: PMMA1 and PMMA2. The ageing properties of polymer modified asphalts were studied using the thin film over (oven) a test. A hot storage stability test was carried out for polymer modified binder. The physical properties of asphalt modified with PMMA including penetration value and softening point were examined at two different temperatures. Resilient modulus test was evaluated by a Universal Testing Machine. Results showed that an incorporation of PMMA into asphalt binder has significantly improved its properties under studies. Indirect tensile strength test and durability performance of the modified asphalts was evaluated as well. The resulted modification was found to be dependent on the polymer molecular weight. The PMMA1 exhibited effective and cheerful results.     

Rheology of asphalts modified with glycidylmethacrylate functionalized polymers

Asphalt is known to be a colloidal suspension in which asphaltenes are covered by a stabilizing phase of polar resins and form complex micelles that are dispersed in the oily maltenic phase. In order to enhance its mechanical properties (e.g., in road paving), asphalts are often loaded with polymeric materials, thereby obtaining blends that can have different physical or chemical structures, depending on the composition of the added polymer. Asphalts modified by the addition of reactive ethylene terpolymers were prepared and their dielectric and rheological properties were measured both before and after a cure at high temperature. Even if it is not possible to determine the exact nature of the chemical interactions between asphalt and polymer, master curves obtained from dynamic data clearly show that during the cure the material tends to the behavior of a cross-linked network.     

Improving the aging resistance of styrene-butadiene-styrene tri-block copolymer modified asphalt by addition of antioxidants

The aging properties of base asphalt and styrene-butadiene-styrene tri-block copolymer (SBS) modified asphalts (PMA) are evaluated using Fourier Transform Infrared (FTIR) spectroscopy. An aging cell fitted to the FTIR microscope was used to continually and directly study the oxidation of the PMA. In particular, Attenuated Total Reflectance, ATR, with a zinc selenide prism was used to quantify the changes in the spectra of the PMA before and after thin film oven test (TFOT). The effect of a small amount (1 wt%) of some modifiers, zinc dialkyldithiophosphate (ZDDP), zinc dibutyl dithiocarbamate (ZDBC) or naphthenoid oil, on the chemical and physical properties of the PMA was studied. The modification extent of the modifiers increases in the order: oil, ZDBC, ZDDP. With the aging of the PMA, carbonyl groups formed and the intensity of the absorption peak at 965 cm⁻¹ (the characteristic peak of SBS) decreased. Antioxidants, ZDDP or ZDBC modified PMA are resistant to the formation of carbonyl to some extent, indicating the improvement of aging resistance of the PMA by the addition of the antioxidants. ZDDP and ZDBC as antioxidants can retard the oxidation of the PMA through the inhibition of peroxides and radical scavenging. Furthermore, ZDDP in a liquid state at room temperature acts as plasticiser, giving rise to a good aging resistance of PMA.     

The research for low-temperature rheological properties and structural characteristics of high-viscosity modified asphalt

High-viscosity modified (HVM) asphalt was prepared by the addition of styrene–butadiene–styrene, furfural exact oil (FEO, plasticizer), sulphur (crosslinker). The low-temperature rheological properties of HVM asphalt were investigated by using bending beam rheometer, and different analysis ways including Fourier transform infrared (FTIR) analysis, thermal analysis, ¹hydrogen nuclear magnetic resonance (¹NMR) analysis, elemental analysis, optical microscopy were used to investigate the structural characteristics of modified asphalts and FEO. Rheological tests demonstrated the effect of each modifier on low-temperature rheological performances of asphalt and displayed the structural characteristics of each binder to some extent. FTIR analysis indicated the effect of ageing and modifier on the distribution of functional groups of modified asphalt before and after ageing. Morphology observation showed the distribution of polymer in asphalt with different modifications or ageing. The thermal analysis showed the effect of each modifier on thermal behaviour of asphalt before and after ageing and confirmed the result of FTIR analysis and morphology observation further. Besides, the constituents of base asphalt and plasticizer were also investigated and compared further by adopting elemental analysis, and ¹HNMR and FTIR tests.     

Viscosity function in polymer-modified asphalts

Asphalt is a multidisperse micellar system with rheological behavior resembling that of a low-molecular-weight polymer. Nowadays, asphalt is frequently modified by blending it with various polymers. Such modified asphalt has rheological properties that differ from the properties of the base asphalt. It is quite common to study asphalt in dynamic experiments. Such studies, however useful, cannot reveal all characteristic features of polymer-modified asphalts. Asphalt modification by polymers is strongly manifested in the region of transitions from a viscoelastic fluid to the Newtonian fluid. The viscosity study in this region can reveal behavior characteristic of the used polymer modifier, thus complementing the dynamic studies of these materials. The viscosity of base asphalt modified by styrene-butadiene-styrene and by ethylene-vinyl acetate polymers (in several concentrations) is studied and discussed in this note.     

Internal structure and linear viscoelastic properties of EVA/asphalt nanocomposites

The effect of the addition of two different organoclays as a third component in polymer-modified asphalts has been investigated. Ternary mixtures were prepared by adding clay and poly(ethylene-co-vinyl acetate) to the asphalt, either separately, or in the form of a premixed master batch. The performed characterizations allowed the determination of how the two methods of mixing influence the interactions between asphalt and polymer and therefore the final rheological properties. In particular, it was shown that the clay had a compatibilizing effect on asphalt and polymer and that a high compatibility between clay and polymer led to a better dispersion of the polymer in the asphalt, thus influencing the final rheological properties of the studied systems.     

Influence of aging on thermal behavior and characterization of SBR compound-modified asphalt

Sulfur and polyphosphoric acid (PPA) were used to improve the thermal stability and high-temperature property of styrene–butadiene rubber (SBR)-modified asphalt before and after short-term and long-term aging. The physical, rheological properties, and thermal behavior of asphalt binders were studied. The study showed that the addition of PPA improved the thermal stability and high-temperature property of SBR-modified asphalt evidently, and the improved property caused by the gelation effect of PPA was not influenced by aging further. Though sulfur also improved thermal stability and high-temperature property of SBR-modified asphalt before aging, the improved properties declined evidently with further aging, due to the susceptibility of SBR/sulfur-modified asphalt to aging. It is reasonable to assume that the SBR-modified asphalt could be improved further only by the addition of PPA. In the study of polymer-modified asphalts, thermodynamic analysis can reflect the structural characteristics of asphalt binders before and after aging efficiently and confirms the conclusions of physical and rheological testings to some extent.     

Thermo-rheological properties and storage stability of SEBS/kaolinite clay compound modified asphalts

Styrene-ethylene-butadiene-styrene block copolymer (SEBS) modified asphalts with improved high-temperature storage stability are prepared by incorporating kaolinite clay (KC) into the SEBS compounds. The effect of KC on the high-temperature storage properties, dynamic rheological and mechanical properties and morphologies of the modified asphalts are studied. It is found that the SEBS/KC ratio in the compound has a great effect on the high-temperature storage behavior. The modified asphalts are stable when the ratio of SEBS/KC is around 2. However, KC decreases the dynamic rheological and mechanical properties of the modified asphalts to some extent. The high-temperature storage property can be increased by improving the compatibility and decreasing the density difference between SEBS and asphalt.     

Rheological properties of asphalt/SBS/clay blends

The effect of the addition of clay as a third component in polymer modified asphalts has been investigated. After a preliminary investigation on the binary asphalt/clay and polymer/clay blends, the tertiary blends were prepared by adding the clay and polymer to the asphalt, either separately or in the form of a premixed master batch. Intercalated nanocomposites with comparable interlayer distances and glass transition temperatures were obtained in both cases. However, the results show that the mixing procedure significantly affected the final rheological properties. The master curves built in the linear viscoelastic range and represented in both the frequency and the temperature domains help to visualize and evaluate such differences.     

煤基重质产物对滨州90#沥青的改性作用

对照优质道路沥青改性剂TLA,考察了六种煤基重质产物对滨州90#沥青的改性作用及作用原理。实验结果表明,六种改性剂对滨州90#沥青均表现出一定的改性作用。依据美国ASTM D5710-95以及英国BSI BS3690对TLA改性沥青的标准,六种改性沥青中,四种符合标准要求,其余两种不符合延度指标要求。FT-IR谱图分析表明,煤液化或煤油共处理重质产物的添加,没有生成新官能团,但使官能团的分布发生了变化,从而改善了基质沥青的路用性能,添加TLA,可增加C=O和S=O极性官能团,可增加沥青与石料的作用;煤焦油沥青过高的芳香结构,妨碍了其与基质沥青的混合作用。结合四组分分析结果,基于沥青胶体化学理论分析,发现不符合要求的改性沥青具有较高的饱和分含量,导致了较小的CI值(胶体指数),不利于沥青胶体结构的稳定。按线性加和法计算得到的改性沥青CI值与实测值的差距表明,改性过程包含有一定程度的化学反应。     

DCLR与TLA共混改性沥青的性能对比

以SK-90沥青为基质沥青,分别加入相同掺量(与沥青质量比为5%、10%、15%和20%)的DCLR和TLA,利用SHRP PG、针入度分级体系、红外光谱仪和凝胶色谱仪对比分析DCLR和TLA共混改性沥青的宏观性能和微观结构的变化。结果表明,DCLR和TLA的加入均可以改善沥青的高温性能,但对沥青的低温性能和疲劳性能产生一定的不利影响。同时,根据DCLR和TLA共混改性沥青的官能团和分子量分布的变化可以判断DCLR和TLA对沥青的改性作用主要为物理改性,在某种程度上,DCLR不能完全替代TLA。     

增容剂对煤直接液化残渣改性沥青低温性能的影响

为了评价不同增容剂对煤直接液化残渣改性沥青低温性能的影响,首先,通过正交实验确定出三种增容剂（硅烷偶联剂、苯甲醛、二甲苯）各自的最佳掺量及掺入方式;其次,采用双边缺口拉伸（DENT）试验评价加入三种增容剂后沥青的低温抗延性断裂性能;最后,结合SEM照片并利用Image Pro plus图像处理软件计算加入三种增容剂后沥青中煤直接液化残渣的分散面积比,以定量地表征三种增容剂对煤直接液化残渣改性沥青低温性能的改善效果。结果表明,加入适量增容剂在一定程度上有助于煤直接液化残渣在沥青中的分散,提高两者之间的相容性,保持煤直接液化残渣改性沥青体系的长期稳定状态,避免因煤直接液化残渣的沉淀聚集而在相界面产生应力集中,增强煤直接液化残渣改性沥青的低温抗延性断裂性能。三种增容剂对煤直接液化残渣改性沥青低温性能改善效果不同,硅烷偶联剂最优,次之为苯甲醛,最差为二甲苯。     

3-氨丙基三乙氧基硅烷对聚氨酯/Al-Sm_2O_3复合涂层自然老化性能的影响

通过硅烷偶联剂3-氨丙基三乙氧基硅烷(KH550)改性聚氨酯(PU)/Al-Sm_2O_3复合涂层,从功能特性和力学性能角度系统研究了改性前后涂层自然老化性能的变化规律。结果表明,改性后PU/Al-Sm_2O_3复合涂层的红外发射率对自然老化的稳定性得到明显增强,在同等条件下改性后的涂层发射率要明显低于未改性的涂层发射率。改性后涂层表面的Sm_2O_3颗粒分散更加均匀,对近红外光的吸收强度有所增强,从而使改性后涂层对1.06μm近红外光的反射率要明显低于未改性涂层。改性前后涂层的硬度对自然老化具有良好的稳定性,其硬度可保持在3 H;未改性涂层的附着力和耐冲击强度受自然老化影响明显,但改性后涂层的附着力和耐冲击强度得到明显加强,经自然老化4个月后仍然可保持在1级和50 kg·cm。     

Modification of Paving Asphalts with an Elastoplastic

BND 60/90 and BND 89/130 paving asphalts were modified by addition of DST-30 elastoplastic and petroleum plasticizers. Their performance at temperatures from -(32-35) to +(90-95)°C was examined in comparison with that of commercial unmodified asphalts, which are efficient at temperatures from -(23-27) to +(44-50)°C.     

Aging properties and mechanism of the modified asphalt by packaging waste polyethylene and waste rubber powder

For the consideration of the environmental and economic issues, retrieved packaging waste polyethylene and waste rubber powder were selected as modifiers to modify the ordinary oil asphalt, and the rotating film oven test was adopted to study the aging process of the modified asphalt. The results showed that the performance of the modified asphalt deteriorated, as indicated by the increase in the softening point and the reduced ductility and penetration. However, compared with nonmodified asphalt, the rangeability of the performance indicators of the modified asphalt before and after aging became narrow, indicating that the aging properties of the modified asphalt were improved. In the modified asphalt system, the swelling of the polymer modifiers was caused by the absorption of the light components of the asphalt, thereby reducing the formation of asphaltenes in the aging process. The polymer modifiers absorb the light oil of the asphalt, which can reduce the content of free radicals and improve the aging properties of the asphalt. In addition, the waste rubber power containing antioxidants and anti‐ozone agents effectively improves the antiaging properties of the asphalt. Copyright © 2012 John Wiley & Sons, Ltd.     

Time Scales in Polymer Modified Asphalts

Historically, Maxwell was probably the first one who recognized the importance of time scales for understanding the mechanical response of asphalt. In instantaneous response asphalt behaves as an elastic, solid-like material, on the other hand its long time response is that of a viscous, fluid-like material. In the linear viscoelastic region asphalt behaves as a low molecular weight polymer. However, in the nonlinear region of high strains or rates of strain the behavior of some asphaltic systems can be rather complicated. In asphalts, asphaltenes, resins and alkanes compose a complex colloidal system, in which alkanes act as a solvent, asphaltenes as micelles and the polar resins as stabilizers. In order to enhance the mechanical properties of asphalts they are frequently modified by blending them with appropriate polymers. Changes in the impermanent network that can be formed in some of these blends can lead to an unexpected behavior of the steady shear viscosity function. Several different time scales emerge from this behavior. A possible relation of these “nonlinear” time scales to the linear viscoelastic time scales is discussed and examples of anomalous behavior of polymer-modified asphalts are given.     

A comparison of plasma and electron beam-sterilization of PU catheters

Polyurethane (PU) catheters made of Pellethane 2363-80AE^® were treated in two different ways: a new treatment with low temperature plasma that could be used to decontaminate reusable polymer devices in hospitals, and an e-beam (EB) irradiation. Polymer structure and bulk properties were studied by differential scanning calorimetry (DSC), thermogravimetric analysis (TGA), infrared spectroscopy (FTIR) and size exclusion chromatography (SEC). Although PU was strongly modified by the e-beam irradiation leading to branching of polymer chains, it had no or little impact on the thermo-mechanical properties of the catheters and on the hard/soft segment organization of PU. For plasma-treated samples, no modification in the polymer bulk was observed, confirming that plasma treatment might be considered as an alternative to e-beam irradiation. The analysis of surface modifications showed an evolution of superficial topology and chemical composition (grafting of oxygen and nitrogen species) of the catheters after treatment, with a more polar and hydrophilic surface.     

Glass transition measurements of asphalts by DSC

The glass transition temperature (T_g), measured by Modulated Differential Scanning Calorimetry (MDSC), is related to the flow characteristics of asphalt at low temperatures as is the rate of change of the creep stiffnessm. This study compared the glass transition temperature of different asphalts (neat, chemically modified, and crumb rubber modified asphalts) with the creep stiffness, the rate of change of creep stiffness, and the low specification temperature of the continuous PG grading of those asphalts.From the rheological data (BBR) and the thermal data (MDSC) for the virgin and the modified asphalts, the modified products had the same variations of values ofm, S, and T_g at lower temperatures as those of their corresponding virgin asphalts. A correlation between the T_g andm value was observed for both the modified and unmodified asphalts. Since DSC measurements for asphalt low temperature properties use less operator time, less sample, and have less measurement and operator error than rheological methods, T_g has promise to be considered as a fast and easy laboratory method to obtain the low temperature useful range of asphalts in pavements.The authors would like to acknowledge Susan P. Needham for her work in conducting rheological testing for the modified and unmodified asphalts.