ASPHALT CHEMISTRY

MOLECULAR STRUCTURE - Diverse molecular structures - Predominantly composed of carbon and hydrogen. - Most molecules contain one or more heteroatoms, such as sulfur, nitrogen and oxygen. - The type of molecular structure is more important than the total amount of each element present.

TYPICAL ELEMENTAL ANALYSIS (Petroleum Asphalts)

ELEMENT
Carbon Hydrogen Sulfur Nitrogen Oxygen

PERCENT
83 - 87 10 -11 1-5 0.3 - 1,1 0.2 - 0.8

Vanadium, ppm 4 - 1400 Nickel, ppm 0.4 - 110 ______________________________________

FUNCTIONAL OR POLAR GROUPS

- Heteroatoms (e.g. sulfur, nitrogen, oxygen) are attached to carbon atoms in asphalt molecules in different configurations and form different polar molecules or functional groups. - These molecules are polar because of imbalance of electrochemical forces which produces a dipole. - Molecular interactions among these polar molecules and other asphalt molecules strongly influence the physical properties and performance of the asphalt. - A small amount of polar molecules can have a great effect. - Resistance to stripping is thought to be affected by the adsorption of polar molecules by aggregate surface.

CONCEPTUAL COMPOSITION OF ASPHALT

ASPHALT
N-Heptane Soluble Precipitate

MALTENES
Liquid Propane Soluble Precipitate

ASPHALTENE

OIL

RESIN

ASPHALTENES
- Dark brown, friable solids - Highest polarity - Insoluble in nonpolar solvents (e.g. heptane, pentane) - Strong tendency to associate in conglomerates - Highest molecular weights - Carbon to hydrogen ratio greater than 0.8 - Higher asphaltene content is related to higher viscosity of asphalt. - Low asphaltene content has been linked to the problem of tender asphalt mixtures.

RESINS
- Dark semi-solid - Fluid when heated & brittle when cold - Soluble in n-heptane or n-pentane - Have a lower molecular weight than that of asphaltene. - Carbon to hydrogen ratio of greater than 0.6 - Act as dispersing agents to the asphaltenes (disperse the asphaltenes throughout the oils to provide a homogeneous liquid).

OILS
- Colorless or white liquid - Soluble in most solvents - Lowest molecular weight among the three components - Carbon to hydrogen ratio of less than 0.6 - Oxygen and nitrogen usually not present - Can change into resins or asphaltenes upon oxidation.

Resins

Oils

Asphaltenes

ASPHALT AS A COLLOIDAL SYSTEM

(1) Asphaltenes are peptized (dispersed) by the resins throughout the oils. (2) Relative amounts and characteristics of asphaltenes, resins and oils influence the physical properties and performance of an asphalt. (3) When the asphaltenes are highly peptized, the asphalt acts as a SOL, which has a highly Newtonian behavior. (4) When the resins are not effective in peptizing the asphaltenes, the asphalt acts as a GEL, which has a nonNewtonian behavior. (5) SOL-GEL is intermediate between a SOL and a GEL.

CHEMICAL PRECIPITATION METHOD (developed by Rostler and Sternberg) Bitumen

Soluble in n-pentane Insoluble in n-pentane

Maltenes

Asphaltenes (A)

Nitrogen Bases (N)

Precipitates with 85% sulfuric acid

First Acidaffins (A1)

Precipitates with 98% sulfuric acid

Second Acidaffins (A2)

Precipitates with fuming sulfuric acid (with 30% SO3)

Paraffins (P)

USES OF THE RESULTS OF CHEMICAL PRECIPITATION METHOD

Compatibility Ratio = N / P
( >0.5 considered to be good)

Durability Parameter = (N+A1) / (P+A2) = (most reactive) / (least reactive)

Durability rating of asphalt binders from 60 to 100 penetration grade

Group 03 I II III IV V N + A11 Average Abrasion Loss2 P + A2 Percent milligram/rev Durability <0.4 0.4 1.0 1.0 1.2 -0 10 5 15 -0.00 0.40 0.20 0.60 0.40 1.60 1.20 2.40 >2.00 Decreasing durability with decreasing parameter value Superior Good Satisfactory Fair Inferior

1.2 1.5 10 40 1.5 1.7 30 60 >1.7 >50

1Based

on original composition. of abrasion at 25C (pellet method) before and after aging. and putty-like products of consistency not associated with highway asphalt

2Average 3Cheesy

binders. (After Rostler)

SELECTIVE ADSORPTION-DESORPTION METHOD (Corbett Method)

CORBETT METHOD
DISSOLVING ASPHALT IN N-HEPTANE

CORBETT METHOD FILTERING OUT ASPHALTENE

CORBETT METHOD Chromatographic Column

SATURATES (from Corbett Method)

- The first fraction to emerge from the chromatographic column when eluted with nheptane . - Non polar - Liquid at ambient temperatures - Hardly change with time - Increase temperature susceptibility of asphalt

NAPHTHENE AROMATICS (from Corbett Method)

- Emerge as the second fraction when eluted with a more polar aromatic solvent (benzene or toluene). - Molecules may contain the heteroatoms oxygen, nitrogen and sulfur. - Liquid at ambient temperatures. - Softening component in asphalt. - Aging fraction in asphalt.

POLAR AROMATICS (from Corbett Method) - The final fraction to emerge when eluted with a mixture of methanol and benzene. - Molecules contain more functional groups. - Solid or semi-solid at ambient temperatures. - Aging fraction in asphalt.

CHARACTERIZATION BY MOLECULAR SIZE DISTRIBUTION

- HP-GPC (High Pressure Gel Permeation Chromatography) - Analogous to sieving of aggregate. - Asphalt is dissolved in THF (tetrahydrofuran) and the solution is passed through gel permeation columns. - Large molecules are eluted first and smallest molecules are eluted last. - Plots of relative molecular size distributions are obtained as a result of GPC tests.

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RESULTS OF GPC TEST ON AN ASPHALT

CHARACTERIZATION BY INFRARED ABSORPTION SPECTRUM

- FTIR (Fourier Transform Infrared) Spectroscopy. - The infrared absorption spectrum (absorption intensity versus wavelength plot) is related to the type and amount of functional groups present.. - Can be used to measure changes in functional groups due to oxidation of asphalt. - The functional groups, Sulfoxide, Anhydride, Carboxylic Acid and Ketone, are formed on oxidative aging and can be characterized by FTIR spectroscopy.

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INFRARED ABSORPTION SPECTRUM of an asphalt

Ketones & Anhydrides
Carbon-Carbon Double bonds

Peterson identified Polar functional groups

Natural

By Aging

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