Effect of Chemical Nature on the Susceptibility of Asphalt to Aging

Abstract

The knowledge of the factors affecting the susceptibility of asphalt to aging can be of help when selecting the asphalt binders for the construction of durable pavements. Investigated were the aging-induced changes in the chemical composition and colloidal nature of asphalts differing in origin and technology. It was shown that the course of the changes in the generic composition of asphalt upon aging under laboratory conditions depends on the chemical type of the feedstock from which the asphalt has been derived. During aging of the asphalts from the paraffin–naphthenic crudes, the resins undergo partial decomposition, which results in the increase of the cyclic fraction content. Although the increase of the asphaltene content in air-blown asphalts after the Thin Film Oven Test was found to be lower than that in the corresponding straight-run asphalts, the much higher value of the instability index and smaller size distribution of asphaltenes in the air-blown asphalts permit us to expect that their utilization as binders in pavement construction will lead to the reduction of pavement durability. It follows from the results of this study that not only the generic composition but also the structure of the fractions affect the resistance of asphalt to aging.     

CHANGES IN ASPHALT CHEMISTRY AND DURABILITY DURING OXIDATION AND POLYMER MODIFICATION

The Gulf Countries' environmental conditions are very severe. The temperature zoning study indicate that more than half of Gulf areas experience a maximum seven consecutive days pavement temperature of 76°C (Al-Abdul Wahhab et al., 1997). This has resulted in damage to the road networks in the form of cracking, rutting and deformation. Polymer modification of asphalt is required to increase the resistance to permanent deformation at relatively high temperatures without adversely affecting the properties of the asphalts at low temperature. In this work chemical and performance-related properties of fresh, oxidized, and polymer modified asphalts were evaluated. The physical properties and performance characteristics of asphalts were found to depend on the chemical composition of asphalt. The interactions of polar functionalities actually present or formed during oxidative aging or due to polymer modification, influence the viscosity and related flow properties. The changes in composition of fresh, oxidized and polymer-modified asphalts can be clearly identified from Infrared spectroscopy. NMR spectroscopy enables detailed information about the Carbon-and-hydrogen-types and average molecular/structural parameters of asphalt without separating it into different components.     

CHANGES IN ASPHALT CHEMISTRY AND DURABILITY DURING OXIDATION AND POLYMER MODIFICATION

The Gulf Countries' environmental conditions are very severe. The temperature zoning study indicate that more than half of Gulf areas experience a maximum seven consecutive days pavement temperature of 76°C (Al-Abdul Wahhab et al., 1997). This has resulted in damage to the road networks in the form of cracking, rutting and deformation. Polymer modification of asphalt is required to increase the resistance to permanent deformation at relatively high temperatures without adversely affecting the properties of the asphalts at low temperature. In this work chemical and performance-related properties of fresh, oxidized, and polymer modified asphalts were evaluated. The physical properties and performance characteristics of asphalts were found to depend on the chemical composition of asphalt. The interactions of polar functionalities actually present or formed during oxidative aging or due to polymer modification, influence the viscosity and related flow properties. The changes in composition of fresh, oxidized and polymer-modified asphalts can be clearly identified from Infrared spectroscopy. NMR spectroscopy enables detailed information about the Carbon-and-hydrogen-types and average molecular/structural parameters of asphalt without separating it into different components.     

COMPARISON OF OXIDATION OF SHRP ASPHALTS BY TWO DIFFERENT METHODS

An objective of the Strategic Highway Research Program is the development of a test procedure that accurately predicts changes in asphalt pavement properties with aging. Many of the methods now in use do not give reliable results. It is desirable to develop a method that takes into account maximum temperatures to which asphalts are subjected in mix plants (about l60°C or 320°F) and during service (60° C or 140°F), but is not impractically long. Therefore, test conditions must involve increased temperature, pressure, or the addition of a chemical accelerant but yield artificially aged materials that have certain properties similar to those of aged pavement binders.|In this study, rheological and chemical properties of asphalts subjected to thin-film oven followed by pressure vessel oxidation under two sets of conditions were compared with properties of asphalts aged in the thin-film accelerated-aging test at two temperatures. Oxidations of asphalts for 144 hours (6 days) at 60°C (I40°F) and 2.07 × 10⁶ Pa pressure following a standard thin-film oven treatment yielded products having characteristic aging indices and enhanced sulfoxide and carbonyl absorbances in their infrared spectra. Oxidation of asphalts under thin-film accelerated-aging lest conditions at 85°C (185°F) for 144 hours provides aged asphalts with rheological properties similar to those obtained from the 60°C (140°F) pressure oxidations. When the pressure oxidation was run at 80°C (176°F) for 144 hours. materials were obtained that were more extensively aged. The aging indices of these materials were somewhat similar to asphalts oxidized for 72 hours at 113°C (235.4°F) under thin-film accelerated-aging test conditions. The aging lendencies of the eight asphalts tested were ranked by the two latter methods in approxmiately the same order.|The thin-film accelerated-aging test procedures are readily performed in a standard oven. but utilize smaller samples (resulting in less material for subsequent analysis) than the pressure oxidations. It is not certain that the mechanism or kinetics of the asphalt oxidations in the higher temperature oven procedures are identical to the mechanisms of oxidation of asphalts in pressure aging. The procedures used in this study, although not themselves definitive test conditions for asphalt-binder aging. should aid in the selection of conditions for an improved aging lest.     

Short- and long-term rheological and chemical characteristics of nanomodified asphalt binder

Due to the special characteristics of nanoparticles, pavement engineers have used nanoparticles as an additive in asphalt pavement to improve pavement performance. This study focuses on characterizing modified asphalt performance using nanoclay particles compared to the unmodified asphalt binder. For this evaluation, 3% of nanoclay particles were added to a neat binder to prepare the nanomodified binder. Then, the modified and unmodified binders underwent a short- and long-term aging process using the Rolling Thin Film Oven (RTFO) and two cycles of Pressure Aging Vessel (PAV). Finally, the Dynamic Shear Rheometer (DSR), Bending Beam Rheometer (BBR), and Fourier-Transform Infrared Spectroscopy - Attenuated Total Reflection (FTIR-ATR) tests were carried out in each aging step to assess and monitor the rutting, fatigue, low-temperature performance, durability, and chemical changes of binders during the aging process. The results of this study proved the enhanced properties and performances of the nanomodified binder compared to the unmodified binder. These results can pave the path with the use of nanomodified binders in the recycling of aged pavement and construction of roads that experience poor weather conditions and high traffic loads.     

沥青老化机理分析

利用红外光谱测试手段,探讨了韩国SK AH-70沥青和SBS沥青在热老化作用下发生的化学组成变化情况;碳氧双键、硫氧双键、氮氧双键含量的增加是沥青老化的重要标志,如果能够通过某种物理或化学手段来减小他们的含量,尤其是能够找到一种廉价易得的试剂来打破这些双键,可能是一种比较有效的沥青再生的方法。     

碱性物质对沥青热老化的影响

对两种沥青进行薄膜烘箱试验（ＴＦＯＴ）和掺加碱性物质的ＴＦＯＴ试验，用沥青蒸发损失率随ＴＦＯＴ时间的变化、沥青化学组成的变化和沥青红外光谱的变化阐述沥青热老化的原因，时比沥青抗老化性能的优劣，考察线性物质对沥青热老化的影响．结果发现：碱性物质使沥青蒸发损失率降低，可能是碱性物质促进沥青吸氧所致；碱性物质促进沥青中重胶质和沥青质的生成，使沥青在１７Ｏｃｍ－１附近的红外吸收强度明显增强，进一步说明碱性物质促进沥青吸氧．沥青ＴＦＯＴ后其重胶质和沥青质增加程度及其在１７０ｃｍ－１处的红外吸收强度变化程度能够表征其抗吸氧老化性能优劣，反映沥青胶体体系变化程度．     

A STUDY OF LOW TEMPERATURE HARDENING ON THIN FILM ASPHALT BINDER IN CONTACT WITH AGGREGATE SURFACE

The interaction between asphalt and aggregate surfaces before and after low temperature storage (reversible and/or irreversible) at various film thickness was investigated by means of the sliding plate geometry with standard Pyrex glass plates and machined aggregate plates. Significant differences in behavior of asphalts in contact with aggregate plates have been observed, especially at low shear rates. One asphalt shows substantial aggregate surface-induced structuring while another shows essentially none. Moreover, the study of the film thickness effect on the rheological properties of asphalt binders and asphalt aggregate mixtures show that thin films of asphalts on an aggregate surfaces have substantially changed rheological properties from bulk asphalt properties and further, physical properties in thin films are not easily predicted from bulk properties. In addition, the study of storage and setting in thin films of asphalts on aggregate surfaces indicates that oxidative aging occurred after long-term storage (5 months) at room temperature of 25°C. Infrared spectroscopic analytical results on asphalt binders show that sulfoxide and ketone form during storage. It is interesting to note that the molecular structuring effect in asphalt-aggregate mixtures could be partially eliminated by heating to a temperature above 100°C for a short period of time (20 seconds). The results also show that the aggregate surface-induced structuring as well as the asphalt composition contribute to the long-term storage hardening of asphalt-aggregate mixtures at low temperature.     

Study on Aging Capability of Paving Asphalt

The changes of softening point, penetration, and ductility of two asphalts after aging were studied. Two methods are simultaneously used to study the aging kinetics of two asphalts and some kinetic parameters are given in this paper. The results show that the softening points increase while penetration and ductility values decrease after aging. It was concluded that the aging capability of AH-70 asphalt is better than AH-90 asphalt. The aging kinetic models of two asphalts based on softening points are compared with a pentane asphaltene aging kinetic model and the results are consistent. A new and easy method for studying the aging of asphalt was developed.     

A STUDY OF LOW TEMPERATURE HARDENING ON THIN FILM ASPHALT BINDER IN CONTACT WITH AGGREGATE SURFACE

ABSTRACT

The interaction between asphalt and aggregate surfaces before and after low temperature storage (reversible and/or irreversible) at various film thickness was investigated by means of the sliding plate geometry with standard Pyrex glass plates and machined aggregate plates. Significant differences in behavior of asphalts in contact with aggregate plates have been observed, especially at low shear rates. One asphalt shows substantial aggregate surface-induced structuring while another shows essentially none. Moreover, the study of the film thickness effect on the rheological properties of asphalt binders and asphalt aggregate mixtures show that thin films of asphalts on an aggregate surfaces have substantially changed rheological properties from bulk asphalt properties and further, physical properties in thin films are not easily predicted from bulk properties. In addition, the study of storage and setting in thin films of asphalts on aggregate surfaces indicates that oxidative aging occurred after long-term storage (5 months) at room temperature of 25°C. Infrared spectroscopic analytical results on asphalt binders show that sulfoxide and ketone form during storage. It is interesting to note that the molecular structuring effect in asphalt-aggregate mixtures could be partially eliminated by heating to a temperature above 100°C for a short period of time (20 seconds). The results also show that the aggregate surface-induced structuring as well as the asphalt composition contribute to the long-term storage hardening of asphalt-aggregate mixtures at low temperature.     

Study on Aging Capability of Paving Asphalt

Abstract:

The changes of softening point, penetration, and ductility of two asphalts after aging were studied. Two methods are simultaneously used to study the aging kinetics of two asphalts and some kinetic parameters are given in this paper. The results show that the softening points increase while penetration and ductility values decrease after aging. It was concluded that the aging capability of AH-70 asphalt is better than AH-90 asphalt. The aging kinetic models of two asphalts based on softening points are compared with a pentane asphaltene aging kinetic model and the results are consistent. A new and easy method for studying the aging of asphalt was developed.     

Study on Aging Kinetics of Panjin Paving Asphalt

In this paper, the changes of n-pentane asphaltene content, penetration, softening point, and ductility of two Panjin paving asphalts have been studied during aging. Further, based on the change of n-pentane asphaltene content, a study on aging kinetics of asphalt has been conducted. Some correlative kinetic parameters were calculated, and the aging kinetic equation of asphalt was gained. The value calculated, depending on the equation, was in accordance with the experimental data. In addition, the relationship between the composition of the high grade paving asphalt and its aging resistant performances was revealed. It showed that the aging of high grade paving asphalt was a first order reaction. Moreover, the kinetic model was proved to be reliable by investigating the changes of penetration, softening point, and ductility of asphalt during aging.     

THE EFFECT OF ASPHALT COMPOSITION ON THE FORMATION OF ASPHALTENES AND THEIR CONTRIBUTION TO ASPHALT VISCOSITY

Interactions among asphalt components have significant effects on the performance of asphalt binder. To understand those interactions, four asphalts, SHRP AAA-I, AAD-I, AAF-I, and AAG-I, were fractionated into three generic fractions according to Corbett's procedure and reblended into asphaltenes/aromatics/saturates ternary mixtures in various ratios. Mixtures were oxidatively aged with atmospheric air at temperatures of 87.7, 93.3, and 98.8°C for 5 to 33 days. The changes in chemical composition and physical properties were monitored using fourier transform infrared spectroscopy (FT-IR) and dynamic mechanical rheometry

The formation of asphaltenes is a major factor in the hardening of asphalt with aging. The data collected in this study indicate that the saturate content in the maltene phase has a profound impact on the contribution that asphaltenes have on the viscosity of aged asphalt. The data also suggest that the aromatics fraction is solely responsible for the formation of asphaltenes as an asphalt oxidizes.     

Study on Aging Kinetics of Saudi Arabian Paving Asphalt

The changes of n-pentane asphaltene content, penetration, softening point, and ductility of two Saudi Arabian paving asphalts have been studied during aging. Further, aging kinetics of asphalt, based on the change of n-pentane asphaltene content, has been studied. Some correlative kinetic parameters were calculated and the aging kinetics equation of asphalt was gained. The value calculated depending on the equation was in accordance with the experimental data. And the relationship between the composition of the high grade paving asphalt and its aging resistant performances was revealed. It showed that the aging of high grade paving asphalt was a first-order reaction. AH-70 paving asphalt has the following characteristics: higher reaction active energy, less reaction velocity constant, lower aging velocity, and better aging resistance performance compared with AH-90 paving asphalt. The changes of penetration, softening point, and ductility of asphalt during aging further proved that the kinetic model is reliable.     

南阳渣油溶剂脱沥青生产道路沥青的研究

南阳减压油属典型的高含蜡渣油,南阳减压渣油溶剂脱沥青可以获得较高收率的优质脱肝油作为催化裂化原料,但脱油沥青只能掺竞为燃料油,不能生产合格道路沥青高在一定程度上制约了溶剂脱沥青工艺的应用,脱油沥青生产合格道路沥青是提高脱油沥青价值的有效方案,本研究对南阳渣油溶剂脱沥青生产道路沥青的技术方案进行了研究,究结果表明,通过采用本研究的技术方案,南阳渣油溶剂脱沥青的脱油沥青可以生产出满足要求的合格道路沥青     

THE EFFECT OF ASPHALT COMPOSITION ON THE FORMATION OF ASPHALTENES AND THEIR CONTRIBUTION TO ASPHALT VISCOSITY

ABSTRACT

Interactions among asphalt components have significant effects on the performance of asphalt binder. To understand those interactions, four asphalts, SHRP AAA-I, AAD-I, AAF-I, and AAG-I, were fractionated into three generic fractions according to Corbett's procedure and reblended into asphaltenes/aromatics/saturates ternary mixtures in various ratios. Mixtures were oxidatively aged with atmospheric air at temperatures of 87.7, 93.3, and 98.8°C for 5 to 33 days. The changes in chemical composition and physical properties were monitored using fourier transform infrared spectroscopy (FT-IR) and dynamic mechanical rheometry

The formation of asphaltenes is a major factor in the hardening of asphalt with aging. The data collected in this study indicate that the saturate content in the maltene phase has a profound impact on the contribution that asphaltenes have on the viscosity of aged asphalt. The data also suggest that the aromatics fraction is solely responsible for the formation of asphaltenes as an asphalt oxidizes.     

NMR Fingerprinting of Chemical Changes in Asphalt Fractions on Oxidation

Abstract

The composition of asphalt has been the subject of much study because such data are required in determining its performance-related properties. A problem inherent in studying asphalt composition is its chemical complexity; however, the characterization of asphalt can be better achieved by separating into fractions. In this work, the chemical property of commercial-grade asphalt obtained from BAPCO refinery, Bahrain (BH), was carried out. The rolling thin-film oven (RTFO), used for short-term aging, and pressurized aging vessel (PAV), used for long-term aging, ASTM D4124 (1991) method was used to separate fresh and aged asphalt into four generic fractions such as asphaltenes, polar aromatics, naphthene aromatics, and saturates. The Corbett fractionation procedure was used to separate fresh and aged asphalt into four generic fractions such as asphaltenes, polar aromatics, naphthene aromatics, and saturates. Nuclear magnetic resonance (NMR) was employed to fingerprint the chemical changes that occurred in asphalt during the aging processes. NMR measurements of asphalt fractions showed that during aging, isomerization and dehydrogenation types of reactions took place. Significant differences were observed between the structure and composition of fresh and aged fractions of asphalt. Results from NMR spectrometry provided significant information concerning the chemical transformations that occurred during the aging processes.     

Influence of Chemical Composition on the Physical Characteristics of Paving Asphalts

The simplest general compositional model considers asphalt to be made up of asphaltenes, heavy oils, and resins. In the present study the extent of similarity between the properties and composition of various types of asphalt obtained from different sources has been carefully explored. It shows how ductility, penetration, and softening point are related to the chemical nature of paving asphalts in the range 41-58 softening points. Asphalt properties are found to be a direct function of its chemical constituents. The relationship between softening point and asphaltene content was found to be linear while asphalts of the same softening point are easily distinguished by the content of the resins. Evaluation of the two asphalt indices—the asphaltene index (I_A) and the Gaestel index (I_C), reveals that they both vary linearly with the composition of asphaltenes and resins thus confirming their suitability in the characterization of asphalts. Comparison of the two indices shows that IC is more suitable in estimating the colloidal stability of different groups of asphalts. The observed correlations can be found useful in the areas of asphalt blending and rejuvenating through the appropriate selection of asphalt components.     

Studies on Nigerian Crudes IV. Improvement of Asphaltic Properties of Residual Asphalts

Residual asphalts obtained from 25 samples of Nigerian light, medium, and heavy crude oils were chemically treated by air-oxidation and sulfurization to improve their characteristic properties. The asphalt yield for light crudes varied from 27.7-33.7 wt% and 33.4-67.5 wt% for medium crudes. The chemical treatment brought about changes in chemical composition, increase in molecular mass and modification of consistency resulting in highly improved asphaltic properties. There were manifold increases in viscosity and softening points, which came as a result of the higher asphaltene content of the treated materials. The asphalts obtained meet quality specifications for typical commercial grade products thus confirming the suitability of Nigerian crude oils for the production of residual asphalts.     

Study on Aging Kinetics of Saudi Arabian Paving Asphalt

Abstract

The changes of n-pentane asphaltene content, penetration, softening point, and ductility of two Saudi Arabian paving asphalts have been studied during aging. Further, aging kinetics of asphalt, based on the change of n-pentane asphaltene content, has been studied. Some correlative kinetic parameters were calculated and the aging kinetics equation of asphalt was gained. The value calculated depending on the equation was in accordance with the experimental data. And the relationship between the composition of the high grade paving asphalt and its aging resistant performances was revealed. It showed that the aging of high grade paving asphalt was a first-order reaction. AH-70 paving asphalt has the following characteristics: higher reaction active energy, less reaction velocity constant, lower aging velocity, and better aging resistance performance compared with AH-90 paving asphalt. The changes of penetration, softening point, and ductility of asphalt during aging further proved that the kinetic model is reliable.