NanotechnologyPresented by Troy Pauli

Prepared for Federal Highway Administration Project ReviewContract No. DTFH61-07-D-00005Fundamental Properties of Asphalts and Modified Asphalts, IIIWashington, DC

January 18, 2008

Principal Researchers:Troy Pauli, William Grimes,Julie Miller, James Beiswenger

www.westernresearch.org

2008 Federal Highway Administration Project Review

Nanotechnology

Hypothesis:

Mechanisms of phase separation of asphalt components contribute to fatigue cracking and healing

2008 Federal Highway Administration Project Review

Atomic Force Microscopy, AFM

AFM with heating-coolingsolidification sample stage

2008 Federal Highway Administration Project Review

Nano Thin-film Chromatography

2008 Federal Highway Administration Project Review

AAD-1 Spinodal-Blend Thin-Film Optical Microscope Image

Crazing patterns

2008 Federal Highway Administration Project Review

AFM Phase and Topography ImagesAAD-1 Spinodal-Blend Thin-Film

2008 Federal Highway Administration Project Review

AFM Phase and Topography ImagesAAD-1 Spinodal-Blend Thin-Film

2008 Federal Highway Administration Project Review

AFM Phase Image, AAF-1 IEC Neutral Fraction

Crazing patterns?

2008 Federal Highway Administration Project Review

Visual Example of Self-healing in a Model Asphalt-Polymer “Mastic” System?

2008 Federal Highway Administration Project Review

Reaction Coordinate

Ene

rgy

COHO +

COH + 2

COHOCOH k +⎯→←+ 2

2008 Federal Highway Administration Project Review

Reaction Coordinate

Ene

rgy

Gibbs Free Energy for Reaction to Occur, ΔG

STHG Δ−Δ=Δ

2008 Federal Highway Administration Project Review

Reaction Coordinate

Ene

rgy

∗∗∗ Δ−Δ=Δ STHG

RTEH a −=Δ ∗

Activation Energy

STHG Δ−Δ=Δ

2008 Federal Highway Administration Project Review

Aging Index Plots

2008 Federal Highway Administration Project Review

Aging Index vs. Reversible State of Peptization

[ ] 0ln( *) Prev

Absorbance

G dy yCO dx

Δ ⎛ ⎞= +⎜ ⎟⎝ ⎠

2008 Federal Highway Administration Project Review

Activation Energies vs. Change in Healing Index

0

( ) ( ) ( ) ( )( ) ( )

a b a b

a a

E rest E rest E rest E restdHE rest E rest

∞

⎛ ⎞ ⎛ ⎞− −= −⎜ ⎟ ⎜ ⎟⎝ ⎠ ⎝ ⎠

2008 Federal Highway Administration Project Review

Reversible State of Peptization vs. Change in Healing Index

0P re v d y d H yd x

⎛ ⎞= +⎜ ⎟⎝ ⎠

2008 Federal Highway Administration Project Review

y = 0.5712x + 50.491R2 = 0.7551

30.00

32.00

34.00

36.00

38.00

40.00

42.00

44.00

-35.00 -30.00 -25.00 -20.00 -15.00 -10.00

Fractor Temperature, Tfracture °C

Act

ivat

ion

Ener

gy o

f Vis

cous

Flo

w, E

a, kc

al/m

ol

0*lna fracture

dyE RT T yA dxη⎛ ⎞ ⎛ ⎞≡ ≈ +⎜ ⎟ ⎜ ⎟⎝ ⎠ ⎝ ⎠

Activation Energy vs. Fracture Temperature

2008 Federal Highway Administration Project Review

Moisture Resistance Experiment

Beaker of water

Sample cast on glass slide

2008 Federal Highway Administration Project Review

Five-Week Water-Soaked Films

2008 Federal Highway Administration Project Review

AAB-1AAK-1

Five-Week Water-Soaked Films

2008 Federal Highway Administration Project Review

SHRP Asphalt AAK-1 After H2O Soak

2008 Federal Highway Administration Project Review

SHRP Asphalt AAK-1 After H2O Soak

2008 Federal Highway Administration Project Review

SHRP Asphalt AAF-1 After H2O Soak

2008 Federal Highway Administration Project Review

SHRP Asphalt AAG-1 After H2O Soak

2008 Federal Highway Administration Project Review

Blister?

SHRP Asphalt AAA-1 After H2O Soak

2008 Federal Highway Administration Project Review

Number of Carbon Atoms in Molecule

0 20 40 60 80 100

Surfa

ce T

ensi

on, γ

dyn

es/c

m

0

20

40

60

80

100

120

140 # of C vs alkanes # of C vs alicyclic chains# of C vs aromatic chains # of C vs ketones # of C vs aromatic sheets # of C vs asphalt AMS predicted-alkanes predicted-aromatics predicted-cyclics # of C vs alicyclic sheets# of C vs asphalt NMR # of C vs asphalt AFM

H

H

H

H

H

H

H

HH

H

H

H

Organic Compound Type as Function of Surface Free Energy

γH2O

2008 Federal Highway Administration Project Review

0 200 400 600 800 1000 1200 1400 1600

Effe

ctiv

e M

olar

Con

cent

ratio

n, [c

eff,

mol

/L]

0.05

0.10

0.15

0.20

0.25

0.30

0.35

Reaction Time, t (seconds)

"Floc Formation"ti < trxn <

ti t∞

t∞

Deposition-AFT (Automated Flocculation Titrimetry)

2008 Federal Highway Administration Project Review

Deposition-AFT (Automated Flocculation Titrimetry)

2008 Federal Highway Administration Project Review

Titrant Delivery Time, t (sec) @ constant titrant flow rate addition

0 500 1000 1500 2000 2500 3000 3500

Effe

ctiv

e M

olar

Con

cent

ratio

n,[c

, (m

ol/L

)](Is

o-O

ctan

e A

spha

ltene

s)

0.000

0.005

0.010

0.015

0.020

0.025

0.030

0.035

AAA-1 AAB-1AAC-1AAD-1AAF-1AAG-1AAK-1AAM-1

[c]initial

[c]dep

Δ[c]

Deposition-AFT Data

2008 Federal Highway Administration Project Review

Conclusions

• Cracking and healing processes have been modeled based on transition state theory.

• Aging index correlates with reversible state of peptization (i.e., colloidal-like structure of asphalt model).

• Activation energies, (i.e., flow (stiffness)/temp slope) of SHRP asphalts correlate with fracture temperature and change in healing index.

• Moisture damage (i.e., thin-film water soak) in model asphalt-mastic systems correlate with polyaromatichydrocarbon concentration.

• Deposition-AFT data predict moisture damage in model systems.