Asphalt Aging: Dual Oxidation Mechanism and Its Interrelationships with Asphalt Composition and Oxidative Age Hardening

The kinetic data and chemistry of asphalt oxidative age hardening suggested a sequential, dual mechanism for asphalt oxidation. The dual mechanism rationalizes conflicts between earlier mechanistic investigations and explains the hyperbolic-like, time-versus-property plots characteristic of asphalt oxidative aging. The oxidation kinetics provide further confirmation of the asphalt microstructural model. It is proposed that the rapid initial oxidation rate of asphalt results from reaction of oxygen with limited amounts of highly reactive hydrocarbons. Final oxidation products of this initial reaction are sulfoxides and, most likely, ring aromatization. During this initial reaction, a slower oxidation reaction of asphalt benzylic carbons is initiated; final products are ketones and sulfoxides. The ratio of ketones to sulfoxides formed and the rate of age hardening were found to be dependent on temperature and oxygen pressure. Low-temperature oxidative aging, as occurs in pavements, was found significantly more sensitive to variations in temperature and asphalt composition than 100°C pressure vessel aging.

[1]  Jung-Do Huh,et al.  Modeling of Oxidative Aging Behavior of Asphalts from Short-Term, High-Temperature Data as a Step toward Prediction of Pavement Aging: , 1996 .

[2]  J Claine Petersen,et al.  Chemical composition of asphalt as related to asphalt durability , 1984 .

[3]  J. C. Petersen,et al.  A DUAL, SEQUENTIAL MECHANISM FOR THE OXIDATION OF PETROLEUM ASPHALTS , 1998 .

[4]  J. C. Petersen,et al.  Identification of dicarboxylic anhydrides in oxidized asphalts , 1975 .

[5]  George W. Mushrush,et al.  FUEL INSTABILITY 1: ORGANO-SULFUR HYDROPEROXIDE REACTIONS , 1992 .

[6]  J F Branthaver,et al.  COMPATIBILITIES OF STRATEGIC HIGHWAY RESEARCH PROGRAM ASPHALTS , 1991 .

[7]  Meng Liu,et al.  The kinetics of carbonyl formation in asphalt , 1996 .

[8]  G. King,et al.  OXYCYCLICS: UNDERSTANDING CATALYZED OXIDATION MECHANISMS IN BITUMEN AND OTHER PETROLEUM PRODUCTS , 1993 .

[9]  J. C. Petersen,et al.  Quantitative determination of carboxylic acids and their salts and anhydrides in asphalts by selective chemical reactions and differential infrared spectrometry , 1981 .

[10]  J Claine Petersen,et al.  EFFECTS OF PHYSICOCHEMICAL FACTORS ON ASPHALT OXIDATION KINETICS , 1993 .

[11]  E. Sheu,et al.  Development of Solid Properties and Thermochemistry of Asphalt Binders in the 25−65 °C Temperature Range , 1996 .

[12]  J. C. Petersen,et al.  Factors affecting the kinetics and mechanisms of asphalt oxidation and the relative effects of oxidation products on age hardening , 1996 .

[13]  T. Mill,et al.  The role of hydroaromatics in oxidative aging in asphalt , 1996 .

[14]  J. C. Petersen,et al.  Direct evidence of ketones in oxidized asphalts , 1974 .

[15]  J Claine Petersen,et al.  QUANTITATIVE FUNCTIONAL GROUP ANALYSIS OF ASPHALTS USING DIFFERENTIAL INFRARED SPECTROMETRY AND SELECTIVE CHEMICAL REACTIONS--THEORY AND APPLICATION , 1986 .

[16]  K. G. Martin Influence of stabilisers on bitumen durability , 1966 .

[17]  J. C. Petersen,et al.  THE EFFECT OF MATTALOPORHYRINS ON ASPHALT OXIDATION. II. THE EFFECT OF VANADYL CHELATES FOUND IN PETROLEUM , 1984 .

[18]  J. C. Petersen,et al.  Oxidation of sulfur compounds in petroleum residues: reactivity-structural relationships , 1981 .

[19]  Theodore Mill,et al.  Homolytic decompositions of hydroperoxides. III. Radical-induced decompositions of primary and secondary hydroperoxides , 1968 .

[20]  George W. Mushrush,et al.  Reaction of Organosulfur Compounds with Naturally Occurring Peroxides in Jet Fuel , 1996 .