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Evaluation of Thermal Oxidative Aging Effect on the
Rheological Performance of Modified Asphalt Binders
Thesis Defense
Cheng Zhu
Advisor: Prof. Peter E. Sebaaly, Ph.D. , P.E.
Nov. 17th 2015
www.wrsc.unr.edu 11/17/2015
1
Outline
o Background of Asphalt Binder Aging
o Objective of Study
o Experimental Plan
 Aging Materials
 Aging Conditions
 Binder Test Methods
o Analysis Methodologies
oTest Results
o Field Asphalt Aging Prediction
o Conclusion and Future Consideration
2
www.wrsc.unr.edu 7/17/2017
Background of Asphalt Binder Aging
• Generally, asphalt binder becomes more brittle and stiffer
under the effect of the oxidative aging condition.
• Therefore, the tensile stress relaxation capability
dramatically dropped that the aging induced cracking
occurred.
• The asphalt binder aging mechanism has been studied
for more than one century ( Hubbard, et al. 1913).
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Background of Asphalt Binder Aging
• Binder Aging Researches conducted mainly focus on:
 Chemistry issues- material reaction with the ubiquitous oxygen.
 Physical properties- rheological performance field pavement
performance.
• Asphalt binder has very complex compositions which
makes a challenge to characterize the oxidative aging
mechanism at a molecular level.
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Background of Asphalt Binder Aging
• Some finding
- Generally, dividing the asphalt binder to several fractions by the
similar molecular weight or properties, i.e. SARA. (Robert, 1969)
- With the asphalt binder aging, the nonpolar fractions, such as
aromatics and saturates, reacted with the ubiquitous oxygen, then
produced higher molecular and polar fractions- asphaltenes. This
process has several different steps.
- Usually, the final products-carbonyl and sulfoxide were used to
identify the asphalt binder aging reaction (Arrhenius kinetic).
- The advanced microscopic methodologies are implemented to
characterize the chemical component change during the aging.
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Background of Asphalt Binder Aging
• Some finding
- Master curve is a good tool to characterize the asphalt binder mechanical
properties, shear modulus-G*, viscosity-η, phase angle.
- SHRP project report A-368: Binder Characterization and Evaluation, volume 2:
Chemistry. (1993)
- NCHRP project 9-10: Superpave Protocols for Modified Asphalt Binders.
- NCHRP project 9-52: Short-Term Laboratory Conditioning of Asphalt Mixtures.
- NCHRP project 9-54: Long-term Aging of Asphalt Mixtures.
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Background of Asphalt Binder Aging
• Some References
- Petersen, J.C., 2009. A Review of the Fundamentals of Asphalt Oxidation:
Chemical, Physicochemical, Physical Property, and Durability Relationships, Trans
Res Circular, E-C140, Transportation Research Board, Washington, DC.
- McNally, Tony, ed. Polymer Modified Bitumen: Properties and Characterization.
Elsevier, 2011.-Chapter 9
- Huang, Shin-Che, and Hervé Di Benedetto, eds. Advances in Asphalt Materials:
Road and Pavement Construction. Woodhead Publishing, 2015.- Chapter 9
- Several Texas DOT Projects reports- Dr. Glover’s group conducted, such as:
FHWA/TX-05/1872; FHWA/TX-05/0-4468; FHWA/TX-08/0-6009 etc.
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Background of Asphalt Binder Aging
However, most of the researches finished were based on
the neat asphalt binder, and the study of modified asphalt
binder aging mechanism was limited.
www.wrsc.unr.edu 11/17/2015 8
Example of the benefit of SBS, TR-modified asphalt binder (Courtesy of Dr. Glover)
Objective of Study
• Base on the previous asphalt binder aging research
finished at UNR under ARC contracts, this study was
extended to evaluate:
- The kinetic reaction of different modified asphalt binders
under the oxidative aging conditions.
- The rheological performance change caused by the
thermal oxidative aging effect.
- The hardening susceptibility of the objective asphalt
binders.
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Experimental Plan
• Materials (14 different asphalt binders)
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Binder ID Base A Base B - - Base C Base D
Tire-rubber - B_TR - - - -
Additional
component
(X, Y, Z)
- B_TR_X B_TR_Y B_TR_Z - -
SBS A_PM B_TR_X_PM B_TR_Y_PM B_TR_Z_HPM C_PM D_HPM
Experimental Plan
• Aging Conditions (air forced draft ovens)
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Aging
Temperature
50℃ 60℃ 85℃
Aging Duration
4, 8, 15, 30, 60,
120, 180, 240 days
2, 4, 8, 15, 30, 60,
100, 160 days
0.5, 1, 2, 4, 8, 15,
25, 40 days
Experimental Plan
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Clean Aging
FTIR-ATR Test
DSR Test
Experimental Plan
• Test Condition-FTIR-ATR
• Fourier Transform Infrared Spectroscopy (FTIR)-Attenuated Total
Reflectance (ATR) :
Each asphalt sample test 2 replicates and each for 3 measurements.
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Nicolet 6700
Experimental Plan
• Test Condition-FTIR-ATR
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AASHTO T302-15 Standard Method of Test for Polymer Content of
polymer-modified Emulsified Asphalt Residue and Asphalt Binders.
Experimental Plan
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Oxidative Aging
Oxidative Aging
Carbonyl
Sulfoxide
Experimental Plan
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Oxidative Aging
Due to the tire rubber (black), the absorption ratio
is so high that the right part jumps up, use the base
line correction function to make it flat.
Experimental Plan
• Test Condition-DSR
• Frequency Sweep Mode-
-8 mm dia. Spindle, 2 mm gap, 1% shear strain, 0.1
rad/s to 100 rad/s with 6 points/decades (19 data
points per isotherm).
-25 mm dia. Spindle, 1 mm gap for 52-80 ℃ test,
0.5 mm gap for above 85 ℃ test, both run 1%
shear strain, 0.01 to 100 rad/s, 2.25
points/decades (10 data points per isotherm).
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Experimental Plan
• Test Condition-DSR
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DSR Geometry
8mm dia. 25mm dia.
2mm gap 1mm gap 0.5mm gap
Binder type 15--2 46-22 52-60-64 60-70-80 85-95-100 100 100-110
Base A √ √ √ - - - -
A_PM √ √ - √ √ √ -
Base B √ √ √ - - - -
B_TR √ √ - √ - - -
B_TR_X √ √ √ - - - -
B_TR_Y √ √ - √ - - -
B_TR_Z √ √ - √ - - -
B_TR_X_PM √ √ - √ √ √ -
B_TR_Y_PM √ √ - √ √ - √
B_TR_Z_HPM √ √ - √ √ - √
Base C √ √ - √ √ √ -
C_PM √ √ - √ √ √ -
Analysis Methodologies
• Analysis Method-Rheology-Master Curve Development
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10
1
10
2
10
3
10
4
| *|
10
-1
10
0
10
1
10
2
10
3
10
4
10
5
Pa
G'
G''
0.001 0.01 0.1 1 10 100Hz
Frequency f
Text
FS
Anton Paar GmbH
PG64-28_NV_85C_40d_85-95-100_A 1
PP25/PE-SN26830; [d=0.5 mm]
| *| Complex Viscosity
G' Storage Modulus
G'' Loss Modulus
PG64-28_NV_85C_40d_85-95-100_A 2
PP25/PE-SN26830; [d=0.5 mm]
| *| Complex Viscosity
G' Storage Modulus
G'' Loss Modulus
PG64-28_NV_85C_40d_85-95-100_A 3
PP25/PE-SN26830; [d=0.5 mm]
| *| Complex Viscosity
G' Storage Modulus
G'' Loss Modulus
DSR Measures – Example PG64-28 (SBS)
Test Results Analysis
• Master Curve Shifting Functions (more than 20)
Follow Time Temperature Superposition Principle
- The frequency sweep test LVE region.
- TTSP-exact isothermal curve, same shift factor, aT
has a reasonable form, i.e. Arrhenius, WLF, Kaelble.
- Thermorheologically Simple same temperature
dependence. (a very complex topic-not simple)
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Outline
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Master curve
was shifted by
RHEA 1.29
software
RHEA Software Shifting Process-1
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RHEA Software Shifting Process-2
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RHEA Software Shifting Process-3
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Cautious of extrapolation
Arms of Prony Series
Master Curve for the Modified asphalt binders
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Binder slippage
Master Curve for the Modified asphalt binders
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Phase angle
rotation
Phase angle
rotation
Master Curve for the Modified asphalt binders
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Platform-phase
transition
Platform-phase
transition
Master Curve for the Modified asphalt binders
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Modified asphalt binder
has more complicate
amorphous phase than
neat binder
Rheological Indices
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Low-Shear Viscosity (LSV) |𝜼∗
| = 𝜼′ 𝟐 + 𝜼" 𝟐
1.00E+01
1.00E+02
1.00E+03
1.00E+04
1.00E-03 1.00E-01 1.00E+01 1.00E+03 1.00E+05 1.00E+07 1.00E+09
η*,(Poise)
Frequency (rad/s)
Base A-ORIG LSV
Base A-ORIG η* Poise
LSV Reference Temperature-60℃
Rheological Indices
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Crossover Modulus G*c -Analogous to rheological index, R
1.00E-02
1.00E-01
1.00E+00
1.00E+01
1.00E+02
1.00E+03
1.00E+04
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E-03 1.00E-01 1.00E+01 1.00E+03 1.00E+05 1.00E+07 1.00E+09
G',G''(Pa)
Frequency (rad/s)
Base A-orig-Loss Modulus
Base A-orig-Storage Modulus
fc
G*c, fc when the
phase angle
at 45º
R=G*g-G*c
Rheological Indices
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DSR Function 𝐃𝐒𝐑𝐅𝐧 =
𝐆′
𝛈′
𝐆′
(Dr. Glover)
y = 9E+13x-3.567
R² = 0.9945
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
100 300 500 700 900 1100 1300 1500
G'(15°C,0.005rad/s)
η'/G' (s) (15°C, 0.005 rad/s)
Base A DSR function
Rheological Indices
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Glover-Rowe Parameter G-R =
𝑮∗ 𝝎 𝒄𝒐𝒔 𝟐 𝜹
𝒔𝒊𝒏 𝜹
1.00E+02
1.00E+03
1.00E+04
1.00E+05
1.00E+06
1.00E+07
1.00E+08
1.00E+09
0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00
|G*|(Pa)(15°C0.005rad/s)
Phase Angle (°)
Base A Black Space Diagram
Base A G-R
G-R at 180 kPa
G-R at 450 kPa
G*/sin(phase angle)≥2.2kpa
G*sin(phase angle)≤5000kpa
85°C, 40d
85°C, 25d
Rheological Indices-Conditions
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Rheological Indices Applicable Conditions
Name Symbol
Temperature
(°C)
Frequency
(rad/s)
Notes
Low Shear
Viscosity
LSV 60 0.001 Has also been measured at 0.1 rad/s
DSR Function DSRFun 15 0.005 Can be shifted from 10 rad/s at 44.7°C
Glover-Rowe
Parameter
G-R 15 0.005 or Var.
Also evaluated at 20°C, potential for
representative Int. temps.
Crossover
Modulus
G*c 25 fc
Corresponds to a phase angle of 45°
Crossover
Frequency
fc 25
Kinetic Aging Parameters
• Arrhenius Equation-
-Where, A = the frequency factor,
P = the oxygen pressure,
α= the reaction order,
E =the activation energy (kJ/mol),
R=the gas constant (8.314 J.mol/°K),
T= the absolute temperature.
It is a formula for the temperature dependence of
reaction rates.
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RTE
CA eAP
t
CA
r /



 
Kinetic Aging Parameters
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y = 0.0008x + 1.0211
R² = 0.9612
y = 0.0019x + 1.0725
R² = 0.9805
y = 0.0213x + 0.8413
R² = 0.9964
0.5
0.7
0.9
1.1
1.3
1.5
1.7
1.9
0 50 100 150 200 250 300 350
AverageCarbonylArea
Time (Days)
PG 64-28
50°C 60°C 85°C
Example-Kc
Kinetic Aging Parameters
Example of Arrhenius Parameters
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y = 2.50E+12e-9.79E+01x
y = 1.08E+08e-6.11E+01x
0.0001
0.001
0.01
0.1
1
10
0.33 0.335 0.34 0.345 0.35 0.355 0.36 0.365 0.37 0.375
Kc,Kf(CA/day)
1/RT
B_TR_X-Kc, Kf
Kc
Kf
Expon. (Kc)
Expon. (Kf)
Kinetic Aging Parameters-CA fitting Model
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0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
0 50 100 150 200 250
CA
Time (day)
B_TR_X
Reg fitting-85℃ Reg fitting-60℃ Reg fitting-50℃
85°C 60°C 50°C
Fast Rate Reaction
Constant Rate Reaction
kc
tk
CAtkeMCA f
tan
*
*)1( 

Hardening Susceptibility
• Generally, there is a good correlation between the
rheological indexes and the carbonyl area
parameter-exponential function.
or
ln(𝑅𝐼) = 𝐻𝑆 ∗ 𝐶𝐴 + 𝑚
RI-Rheological Indexes.
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𝑅𝐼 = 𝑒 𝐻𝑆∗𝐶𝐴
𝑒 𝑚
Hardening Susceptibility-Examples
www.wrsc.unr.edu 11/17/2015 39
y = 7.5245e11.109x
R² = 0.9513
y = 327.4e7.9403x
R² = 0.9247
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
0.000 0.200 0.400 0.600 0.800 1.000
LSV(Pa.s,60°C,0.001rad/s)
Carbonyl Area (arb. unit)
Base A
A_PM
Expon. (Base
A)
Expon. (A_PM)
y = 54503e-5.603x
R² = 0.9701
y = 27635e-4.653x
R² = 0.9126
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
0.000 0.200 0.400 0.600 0.800 1.000
G*c(kPa,25°C)
Carbonyl Area (arb. unit)
Base A
A_PM
Expon. (Base
A)
Expon. (A_PM)
y = 0.0037e17.172x
R² = 0.9746
y = 0.4427e10.155x
R² = 0.9652
1.E-02
1.E-01
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
0.000 0.200 0.400 0.600 0.800 1.000
G-R(kPa,15°C,0.005rad/s)
Carbonyl Area (arb. unit)
Base A
A_PM
Expon. (Base
A)
Expon. (A_PM) y = 0.0163e17.418x
R² = 0.9781
y = 2.2151e10.154x
R² = 0.9653
1.E-02
1.E-01
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
0.000 0.200 0.400 0.600 0.800 1.000
DSRfunc.(pa/s,15°C,0.005rad/s)
Carbonyl Area (arb. unit)
Base A
A_PM
Expon. (Base
A)
Expon. (A_PM)
Test Results Analysis-Kinetic Parameters
Asphalt
Binder
Modifier
Influence of Modification on
kf Eaf kc Eac
A SBS ↓ ↓ ↓ ↓
C SBS ↓ ↓ ↓ ↑
D SBS ↓ ↑ ↓ ↑
B TR ↓ ↓ ↓ ↑
B_TR_X SBS ↑ ↑ ↑ ↓
B_TR_Y SBS ↑ ↑ ↓ ↓
B_TR_Z SBS ↑ ↓ ↑ ↓
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Test Results Analysis-LSV vs CA
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1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
0.000 0.200 0.400 0.600 0.800 1.000
LSV(Pa.s,60°C,0.001rad/s)
Carbonyl Area (arb. unit)
Base A
A_PM
Base C
C_PM
Base D
D_HMP
Expon. (Base A)
Expon. (A_PM)
Expon. (Base C)
Expon. (C_PM)
Expon. (Base D)
Expon. (D_HMP)
Test Results Analysis-LSV vs CA
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1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
0.000 0.200 0.400 0.600 0.800 1.000
LSV(Pa.s,60°C,0.001rad/s)
Carbonyl Area (arb. unit)
Base B
B_TR
B_TR_X
B_TR_X_PM
B_TR_Y
B_TR_Y_PM
B_TR_Z
B_TR_Z_HPM
Expon. (Base B)
Expon. (B_TR)
Expon. (B_TR_X)
Expon. (B_TR_X_PM)
Expon. (B_TR_Y)
Expon. (B_TR_Y_PM)
Expon. (B_TR_Z)
Expon. (B_TR_Z_HPM)
Test Results Analysis-G*c vs CA
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1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
0.000 0.200 0.400 0.600 0.800 1.000
G*c(kPa,25°C)
Carbonyl Area (arb. unit)
Base A
A_PM
Base C
C_PM
Base D
D_HMP
Expon. (Base A)
Expon. (A_PM)
Expon. (Base C)
Expon. (C_PM)
Expon. (Base D)
Expon. (D_HMP)
Test Results Analysis-G*c vs CA
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1.E+02
1.E+03
1.E+04
1.E+05
0.000 0.200 0.400 0.600 0.800 1.000
G*c(kPa,25°C)
Carbonyl Area (arb.unit)
Base B
B_TR
B_TR_X
B_TR_X_PM
B_TR_Y
B_TR_Y_PM
B_TR_Z
B_TR_Z_HPM
Expon. (Base B)
Expon. (B_TR)
Expon. (B_TR_X)
Expon. (B_TR_X_PM)
Expon. (B_TR_Y)
Expon. (B_TR_Y_PM)
Expon. (B_TR_Z)
Expon. (B_TR_Z_HPM)
Test Results Analysis-G-R vs CA
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1.E-02
1.E-01
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
0.000 0.200 0.400 0.600 0.800 1.000
G-R(kPa,15°C,0.005rad/s)
Carbonyl Area (arb. unit)
Base A
A_PM
Base C
C_PM
Base D
D_HMP
Expon. (Base A)
Expon. (A_PM)
Expon. (Base C)
Expon. (C_PM)
Expon. (Base D)
Expon. (D_HMP)
Test Results Analysis-G-R vs CA
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1.E-02
1.E-01
1.E+00
1.E+01
1.E+02
1.E+03
1.E+04
0.000 0.200 0.400 0.600 0.800 1.000
G-R(kPa,15°C,0.005rad/s)
Carbonyl Area (arb. unit)
Base B
B_TR
B_TR_X
B_TR_X_PM
B_TR_Y
B_TR_Y_PM
B_TR_Z
B_TR_Z_HPM
Expon. (Base B)
Expon. (B_TR)
Expon. (B_TR_X)
Expon. (B_TR_X_PM)
Expon. (B_TR_Y)
Expon. (B_TR_Y_PM)
Expon. (B_TR_Z)
Expon. (B_TR_Z_HPM)
Test Results Analysis-HS results table
Binder ID
LSV (Pa.s, 60°C, 0.001 rad/s)
Gc*
(kPa, 25°C)
G-R Parameter (kPa,
15°C, 0.005rad/s)
em HS em HS em HS
Base A 8 11.1 54,503 5.6 0.004 17.2
A_PM 327 7.9 27,635 4.7 0.44 10.2
Base B 47 7.4 24,703 3.0 0.06 13.8
B_TR 243 10.0 13,479 3.6 0.83 14.7
B_TR_X 55 9.1 23,558 4.1 0.04 14.8
B_TR_X_PM 1,190 6.6 15,982 3.8 1.53 8.9
B_TR_Y 104 8.0 28,945 3.4 0.07 13.9
B_TR_Y_PM 16,536 5.1 21,971 5.4 2.64 9.8
B_TR_Z 218 7.4 23,562 2.7 0.36 11.6
B_TR_Z_HPM 17,940 4.8 15,176 5.5 4.13 6.4
Base C 11 9.6 54,166 5.0 0.003 16.7
C_PM 11,481 8.0 59,321 11.8 2.52 9.9
Base D 33 9.8 33,750 4.5 0.04 15.1
D_HPM 92,337 5.2 26,352 5.2 7.50 7.5
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Test Results Analysis-HS Summary
Binder Modifier
LSV (Pa.s, 60°C,
0.001 rad/s)
Gc*
(kPa, 25°C)
G-R Parameter (kPa,
15°C, 0.005rad/s)
A SBS ↓ ↓ ↓
C SBS ↓ ↑ ↓
D SBS ↓ ↑ ↓
B TR ↑ ↑ ↑
B_TR_X SBS ↓ ↓ ↓
B_TR_Y SBS ↓ ↑ ↓
B_TR_Z SBS ↓ ↑ ↓
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Test Results Analysis-RI Correlation
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1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
1.E+08
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
0.10 1.00 10.00 100.00 1000.00 10000.00
CrossoverModulus,G*c(pa,25°C)
LSV(Pa.s,60°C,0.001rad/s)
DSR Fn (15°C 0.005rad/s))
Base A, LSV
A_PM, LSV
Base C, LSV
C_PM, LSV
Base D, LSV
D_HPM, LSV
Base A_G*c
A_PM_G*c
Base C_G*c
C_PM_G*c
Base D_G*c
D_HPM_G*c
Aging
Aging
Test Results Analysis-RI Correlation
www.wrsc.unr.edu 11/17/2015 50
Aging
y = 119.63x0.601
R² = 0.9225
y = 2E+07x-0.288
R² = 0.9027
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
1.E+08
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
0.10 1.00 10.00 100.00 1000.00 10000.00
CrossoverModulus,G*c(pa,25°C)
LSV(Pa.s,60°C,0.001rad/s)
DSR Fn (15°C 0.005rad/s))
Base A, LSV
Base C, LSV
Base D, LSV
Base A_G*c
Base C_G*c
Base D_G*c
Aging
Test Results Analysis-RI Correlation
www.wrsc.unr.edu 11/17/2015 51
Aging
1.E+01
1.E+02
1.E+03
1.E+04
1.E+05
1.E+06
1.E+07
0.10 10.00 1000.00 100000.00
LSV(Pa.s,60°C,0.001rad/s)
DSR Fn (15°C 0.005rad/s)
Base B, LSV
B_TR, LSV
B_TR_X, LSV
B_TR_X_PM, LSV
B_TR_Y, LSV
B_TR_Y_PM, LSV
B_TR_Z, LSV
B_TR_Z_HPM, LSV
Aging
Test Results Analysis-RI Correlation
www.wrsc.unr.edu 11/17/2015 52
1.E+04
1.E+05
1.E+06
1.E+07
1.E+08
0.10 1.00 10.00 100.00 1000.00 10000.00 100000.001000000.00
CrossoverModulus,G*c(Pa,25°C)
DSR Fn (15°C 0.005rad/s)
Base B, G*c
B_TR, G*c
B_TR_X, G*c
B_TR_X_PM, G*c
B_TR_Y, G*c
B_TR_Y_PM, G*c
B_TR_Z, G*c
B_TR_Z_HPM, G*c
Aging
Aging
Field Asphalt CA Prediction
• Reno Int. Airport-Freeze thaw
• Phoenix Sky Harbor Int. Airport- Warm Climate
• Glasgow Int. Airport-Cold Climate
www.wrsc.unr.edu 11/17/2015 53
Reno Int. Airport
Phoenix SH Int. Airport
Glasgow Int. Airport
Field Asphalt CA Prediction
• CA Prediction Procedure
 Preparing Climate Data-TEMPS input file
 Run TEMPS Output file-Pavement Temperature
 Using Dr. Alavi’s pavementaging.m Matlab code to
calculate the CA at different location, different time and
different asphalt binder film thickness.
www.wrsc.unr.edu 11/17/2015 54
Field Asphalt CA Prediction
• Pavement Structure
(Thickness: 0.15 m HMA+0.35 m Gravel Base)
www.wrsc.unr.edu 11/17/2015 55
Material Parameters HMA Gavel Stone Soil
Specific Heat Capacity (J/kg°K) 920 850 800
Conductivity (W/m°K) 1 0.75 1
Density (Kg/m^3) 2250 2100 2000
Field Asphalt CA Prediction
• Climate Data
http://gis.ncdc.noaa.gov/map/
http://rredc.nrel.gov/solar/old_data/nsrdb/
www.wrsc.unr.edu 11/17/2015 56
Air Temperature, Wind speed-2010
Solar Radiation
Field Asphalt CA Prediction
• TEMPS
www.wrsc.unr.edu 11/17/2015 57
User friendly software
Field Asphalt CA Prediction
• Input data of TEMPS
www.wrsc.unr.edu 11/17/2015 58
-20
-10
0
10
20
30
40
50
0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000
AirTemperature(℃)
Time (hour)
Air Temperature
Reno Air Temperature
Phoenix Air Temperature
Glasgow Air Temperature
Field Asphalt CA Prediction
• Input data of TEMPS
www.wrsc.unr.edu 11/17/2015 59
-15
-10
-5
0
5
10
15
20
25
0 200 400 600 800
AirTemperature(℃)
Time (hour)
Air Temperature-January
Reno Air
Temperature
Phoenix Air
Temperature
Glasgow Air
Temperature
Field Asphalt CA Prediction
• Output files of TEMPS-Examples
www.wrsc.unr.edu 11/17/2015 60
-6
-4
-2
0
2
4
6
8
10
0 120 240 360 480 600 720 840
Temperature(℃)
Time (hour)
Pav. Temperature-January
Reno Air Temperature
Reno Pav. 0.01m depth
Temperature
Reno Pav. 0.07m depth
Temperature
Reno Pav. 0.15m Depth
Temperature
Field Asphalt CA Prediction
• Pavementaging.m Matlab Calculation
www.wrsc.unr.edu 11/17/2015 61
Field Asphalt CA Prediction-Results
• Reno-0.01m
www.wrsc.unr.edu 11/17/2015 62
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0 50000 100000 150000 200000
CarbonylArea(Arb.unit)
Time (hour)
Reno-0.01 m depth film surface
A_PM
B_TR_X_PM
B_TR_X
B_TR_Y_PM
B_TR_Y
B_TR_Z_HPM
B_TR_Z
B_TR
Base A
Base B
Base C
Base D
C_PM
D_HPM
o.58
Field Asphalt CA Prediction-Results
• Reno-0.07m
www.wrsc.unr.edu 11/17/2015 63
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0 50000 100000 150000 200000
CarbonylArea(Arb.unit)
Time (hour)
Reno-0.07 m depth film surface
A_PM
B_TR_X_PM
B_TR_X
B_TR_Y_PM
B_TR_Y
B_TR_Z_HPM
B_TR_Z
B_TR
Base A
Base B
Base C
Base D
C_PM
D_HPM
o.53
Field Asphalt CA Prediction-Results
• Reno-0.15m
www.wrsc.unr.edu 11/17/2015 64
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0 50000 100000 150000 200000
CarbonylArea(Arb.unit)
Time (hour)
Reno-0.15 m depth film surface
A_PM
B_TR_X_PM
B_TR_X
B_TR_Y_PM
B_TR_Y
B_TR_Z_HPM
B_TR_Z
B_TR
Base A
Base B
Base C
Base D
C_PM
D_HPM
o.49
Field Asphalt CA Prediction-Results
www.wrsc.unr.edu 11/17/2015 65
0.34115
0.3412
0.34125
0.3413
0.34135
0.3414
0.34145
0 24000 48000 72000 96000 120000 144000 168000 192000
CarbonylArea(abs.unit)
Time(hour)
Reno Base B CA Field Prediction
0.01m depth film surface
0.07m depth film surface
0.15m depth film surface
0
0.02
0.04
0.06
0.08
0.1
0.12
0.14
0.16
0.18
0 24000 48000 72000 96000 120000 144000 168000 192000
CarbonylArea(abs.unit)
Time(hour)
Reno B_TR CA Field Prediction
0.01m depth film surface
0.07m depth film surface
0.15m depth film surface
0.1
0.12
0.14
0.16
0.18
0.2
0.22
0.24
0.26
0.28
0 24000 48000 72000 96000 120000 144000 168000 192000
CarbonylArea(abs.unit)
Time(hour)
Reno B_TR_Z CA Field Prediction
0.01m depth film surface
0.07m depth film surface
0.15m depth film surface
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0 24000 48000 72000 96000 120000 144000 168000 192000
CarbonylArea(abs.unit)
Time(hour)
Reno B_TR_Z_HPM CA Field Prediction
0.01m depth film surface
0.07m depth film surface
0.15m depth film surface
Field Asphalt CA Prediction-Results
www.wrsc.unr.edu 11/17/2015 66
0.3411
0.3412
0.3413
0.3414
0.3415
0.3416
0.3417
0.3418
0.3419
0.342
0 24000 48000 72000 96000 120000 144000 168000 192000
CarbonylArea(abs.unit)
Time(hour)
Base B CA Field Prediction
Reno-0.01m depth film surface
Phoenix-0.01m depth film surface
Glasgow 0.01m depth film surface
0
0.1
0.2
0.3
0.4
0.5
0.6
0 24000 48000 72000 96000 120000 144000 168000 192000
CarbonylArea(abs.unit)
Time(hour)
B_TR_Z CA Field Prediction
Reno-0.01m depth film surface
Phoenix-0.01m depth film surface
Glasgow 0.01m depth film surface
0
0.05
0.1
0.15
0.2
0.25
0.3
0.35
0.4
0.45
0.5
0 24000 48000 72000 96000 120000 144000 168000 192000
CarbonylArea(abs.unit)
Time(hour)
B_TR CA Field Prediction
Reno-0.01m depth film surface
Phoenix-0.01m depth film surface
Glasgow 0.01m depth film surface
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
0 24000 48000 72000 96000 120000 144000 168000 192000
CarbonylArea(abs.unit)
Time(hour)
B_TR_Z_HPM CA Field Prediction
Reno-0.01m depth film surface
Phoenix-0.01m depth film surface
Glasgow 0.01m depth film surface
Conclusion and Further Consideration
• Conclusion
 Temperature and aging duration played an important role on the asphalt
binder aging hardening, this conclusion was justified by the multi linear
regression analysis.
The asphalt binder aging rate increased with increasing temperature,
carbonyl area is a good parameter to evaluate the oxidative aging extent.
TR reduced the asphalt binders’ fast rate and constant rate reaction, X, Y, Z
asphalt components had modest variation for the fast rate and increased
the constant rate; the SBS modifiers had different direction effect on these
two parameters.
www.wrsc.unr.edu 11/17/2015 67
Conclusion and Further Consideration
• Conclusion
 With the SBS modification, both of the hardening susceptibility of the
rheological indexes-LSV and G-R decreased compared with the
corresponding base binder. The TR increased the hardening susceptibility
of all the rheological indexes. While for the G*c, SBS increases the slope of
the most modified asphalt binders except A and B_TR_X series binders.
 The temperature variation of the pavement structure decreased with the
increasing pavement depth, the predicted CA value range for all the asphalt
binders decreased when the evaluated pavement depth was increasing.
The oxygen diffusion effect on the asphalt binder film aging was highly
binder resource dependent.
www.wrsc.unr.edu 11/17/2015 68
Conclusion and Further Consideration
• Further Consideration
 Other microscopic analysis tools, such as NMR, AFM, can be used to
compensate the FTIR to get more chemical information for the binder
aging.
The related asphalt mixture aging and real field pavement aging are needed
to investigate the correlation between the laboratory binder aging and field
asphalt binder aging.
How to minimize the field asphalt pavement aging rate is a good extension
for the future study.
 More related asphalt binder aging researches or projects are needed to
study the asphalt binder aging oxidative aging mechanism.
www.wrsc.unr.edu 11/17/2015 69
Acknowledgement
• Thank you to Dr. Sebaaly, Dr. Hajj, Dr. Morian, and Dr. Lin for their
consistent supporting, teaching, and advising.
• Thanks to Dr. John Hellgeth of Applied Materials Solutions, LLC for
his assistance on the FTIR measurements.
• Thanks to all of my colleagues at UNR pavement program- Dario,
Farzan, Hadi, Jay, Jhony, Luis, Mohamed, Nick, Piratheepan, Sara,
Sendeep, and Victor for their help and friendship.
• I Love Asphalt
www.wrsc.unr.edu 11/17/2015 70
Question?
Thank you
www.wrsc.unr.edu 11/17/2015 71

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Oxidative aging and rheological performance of modified asphalt binder

  • 1. Evaluation of Thermal Oxidative Aging Effect on the Rheological Performance of Modified Asphalt Binders Thesis Defense Cheng Zhu Advisor: Prof. Peter E. Sebaaly, Ph.D. , P.E. Nov. 17th 2015 www.wrsc.unr.edu 11/17/2015 1
  • 2. Outline o Background of Asphalt Binder Aging o Objective of Study o Experimental Plan  Aging Materials  Aging Conditions  Binder Test Methods o Analysis Methodologies oTest Results o Field Asphalt Aging Prediction o Conclusion and Future Consideration 2 www.wrsc.unr.edu 7/17/2017
  • 3. Background of Asphalt Binder Aging • Generally, asphalt binder becomes more brittle and stiffer under the effect of the oxidative aging condition. • Therefore, the tensile stress relaxation capability dramatically dropped that the aging induced cracking occurred. • The asphalt binder aging mechanism has been studied for more than one century ( Hubbard, et al. 1913). www.wrsc.unr.edu 11/17/2015 3
  • 4. Background of Asphalt Binder Aging • Binder Aging Researches conducted mainly focus on:  Chemistry issues- material reaction with the ubiquitous oxygen.  Physical properties- rheological performance field pavement performance. • Asphalt binder has very complex compositions which makes a challenge to characterize the oxidative aging mechanism at a molecular level. www.wrsc.unr.edu 11/17/2015 4
  • 5. Background of Asphalt Binder Aging • Some finding - Generally, dividing the asphalt binder to several fractions by the similar molecular weight or properties, i.e. SARA. (Robert, 1969) - With the asphalt binder aging, the nonpolar fractions, such as aromatics and saturates, reacted with the ubiquitous oxygen, then produced higher molecular and polar fractions- asphaltenes. This process has several different steps. - Usually, the final products-carbonyl and sulfoxide were used to identify the asphalt binder aging reaction (Arrhenius kinetic). - The advanced microscopic methodologies are implemented to characterize the chemical component change during the aging. www.wrsc.unr.edu 11/17/2015 5
  • 6. Background of Asphalt Binder Aging • Some finding - Master curve is a good tool to characterize the asphalt binder mechanical properties, shear modulus-G*, viscosity-η, phase angle. - SHRP project report A-368: Binder Characterization and Evaluation, volume 2: Chemistry. (1993) - NCHRP project 9-10: Superpave Protocols for Modified Asphalt Binders. - NCHRP project 9-52: Short-Term Laboratory Conditioning of Asphalt Mixtures. - NCHRP project 9-54: Long-term Aging of Asphalt Mixtures. www.wrsc.unr.edu 11/17/2015 6
  • 7. Background of Asphalt Binder Aging • Some References - Petersen, J.C., 2009. A Review of the Fundamentals of Asphalt Oxidation: Chemical, Physicochemical, Physical Property, and Durability Relationships, Trans Res Circular, E-C140, Transportation Research Board, Washington, DC. - McNally, Tony, ed. Polymer Modified Bitumen: Properties and Characterization. Elsevier, 2011.-Chapter 9 - Huang, Shin-Che, and Hervé Di Benedetto, eds. Advances in Asphalt Materials: Road and Pavement Construction. Woodhead Publishing, 2015.- Chapter 9 - Several Texas DOT Projects reports- Dr. Glover’s group conducted, such as: FHWA/TX-05/1872; FHWA/TX-05/0-4468; FHWA/TX-08/0-6009 etc. www.wrsc.unr.edu 11/17/2015 7
  • 8. Background of Asphalt Binder Aging However, most of the researches finished were based on the neat asphalt binder, and the study of modified asphalt binder aging mechanism was limited. www.wrsc.unr.edu 11/17/2015 8 Example of the benefit of SBS, TR-modified asphalt binder (Courtesy of Dr. Glover)
  • 9. Objective of Study • Base on the previous asphalt binder aging research finished at UNR under ARC contracts, this study was extended to evaluate: - The kinetic reaction of different modified asphalt binders under the oxidative aging conditions. - The rheological performance change caused by the thermal oxidative aging effect. - The hardening susceptibility of the objective asphalt binders. www.wrsc.unr.edu 11/17/2015 9
  • 10. Experimental Plan • Materials (14 different asphalt binders) www.wrsc.unr.edu 11/17/2015 10 Binder ID Base A Base B - - Base C Base D Tire-rubber - B_TR - - - - Additional component (X, Y, Z) - B_TR_X B_TR_Y B_TR_Z - - SBS A_PM B_TR_X_PM B_TR_Y_PM B_TR_Z_HPM C_PM D_HPM
  • 11. Experimental Plan • Aging Conditions (air forced draft ovens) www.wrsc.unr.edu 11/17/2015 11 Aging Temperature 50℃ 60℃ 85℃ Aging Duration 4, 8, 15, 30, 60, 120, 180, 240 days 2, 4, 8, 15, 30, 60, 100, 160 days 0.5, 1, 2, 4, 8, 15, 25, 40 days
  • 12. Experimental Plan www.wrsc.unr.edu 11/17/2015 12 Clean Aging FTIR-ATR Test DSR Test
  • 13. Experimental Plan • Test Condition-FTIR-ATR • Fourier Transform Infrared Spectroscopy (FTIR)-Attenuated Total Reflectance (ATR) : Each asphalt sample test 2 replicates and each for 3 measurements. www.wrsc.unr.edu 11/17/2015 13 Nicolet 6700
  • 14. Experimental Plan • Test Condition-FTIR-ATR www.wrsc.unr.edu 11/17/2015 14 AASHTO T302-15 Standard Method of Test for Polymer Content of polymer-modified Emulsified Asphalt Residue and Asphalt Binders.
  • 15. Experimental Plan www.wrsc.unr.edu 11/17/2015 15 Oxidative Aging Oxidative Aging Carbonyl Sulfoxide
  • 16. Experimental Plan www.wrsc.unr.edu 11/17/2015 16 Oxidative Aging Due to the tire rubber (black), the absorption ratio is so high that the right part jumps up, use the base line correction function to make it flat.
  • 17. Experimental Plan • Test Condition-DSR • Frequency Sweep Mode- -8 mm dia. Spindle, 2 mm gap, 1% shear strain, 0.1 rad/s to 100 rad/s with 6 points/decades (19 data points per isotherm). -25 mm dia. Spindle, 1 mm gap for 52-80 ℃ test, 0.5 mm gap for above 85 ℃ test, both run 1% shear strain, 0.01 to 100 rad/s, 2.25 points/decades (10 data points per isotherm). www.wrsc.unr.edu 11/17/2015 17
  • 18. Experimental Plan • Test Condition-DSR www.wrsc.unr.edu 11/17/2015 18 DSR Geometry 8mm dia. 25mm dia. 2mm gap 1mm gap 0.5mm gap Binder type 15--2 46-22 52-60-64 60-70-80 85-95-100 100 100-110 Base A √ √ √ - - - - A_PM √ √ - √ √ √ - Base B √ √ √ - - - - B_TR √ √ - √ - - - B_TR_X √ √ √ - - - - B_TR_Y √ √ - √ - - - B_TR_Z √ √ - √ - - - B_TR_X_PM √ √ - √ √ √ - B_TR_Y_PM √ √ - √ √ - √ B_TR_Z_HPM √ √ - √ √ - √ Base C √ √ - √ √ √ - C_PM √ √ - √ √ √ -
  • 19. Analysis Methodologies • Analysis Method-Rheology-Master Curve Development www.wrsc.unr.edu 11/17/2015 19 10 1 10 2 10 3 10 4 | *| 10 -1 10 0 10 1 10 2 10 3 10 4 10 5 Pa G' G'' 0.001 0.01 0.1 1 10 100Hz Frequency f Text FS Anton Paar GmbH PG64-28_NV_85C_40d_85-95-100_A 1 PP25/PE-SN26830; [d=0.5 mm] | *| Complex Viscosity G' Storage Modulus G'' Loss Modulus PG64-28_NV_85C_40d_85-95-100_A 2 PP25/PE-SN26830; [d=0.5 mm] | *| Complex Viscosity G' Storage Modulus G'' Loss Modulus PG64-28_NV_85C_40d_85-95-100_A 3 PP25/PE-SN26830; [d=0.5 mm] | *| Complex Viscosity G' Storage Modulus G'' Loss Modulus DSR Measures – Example PG64-28 (SBS)
  • 20. Test Results Analysis • Master Curve Shifting Functions (more than 20) Follow Time Temperature Superposition Principle - The frequency sweep test LVE region. - TTSP-exact isothermal curve, same shift factor, aT has a reasonable form, i.e. Arrhenius, WLF, Kaelble. - Thermorheologically Simple same temperature dependence. (a very complex topic-not simple) www.wrsc.unr.edu 11/17/2015 20
  • 21. Outline www.wrsc.unr.edu 11/17/2015 21 Master curve was shifted by RHEA 1.29 software
  • 22. RHEA Software Shifting Process-1 www.wrsc.unr.edu 11/17/2015 22
  • 23. RHEA Software Shifting Process-2 www.wrsc.unr.edu 11/17/2015 23
  • 24. RHEA Software Shifting Process-3 www.wrsc.unr.edu 11/17/2015 24 Cautious of extrapolation Arms of Prony Series
  • 25. Master Curve for the Modified asphalt binders www.wrsc.unr.edu 11/17/2015 25 Binder slippage
  • 26. Master Curve for the Modified asphalt binders www.wrsc.unr.edu 11/17/2015 26 Phase angle rotation Phase angle rotation
  • 27. Master Curve for the Modified asphalt binders www.wrsc.unr.edu 11/17/2015 27 Platform-phase transition Platform-phase transition
  • 28. Master Curve for the Modified asphalt binders www.wrsc.unr.edu 11/17/2015 28 Modified asphalt binder has more complicate amorphous phase than neat binder
  • 29. Rheological Indices www.wrsc.unr.edu 11/17/2015 29 Low-Shear Viscosity (LSV) |𝜼∗ | = 𝜼′ 𝟐 + 𝜼" 𝟐 1.00E+01 1.00E+02 1.00E+03 1.00E+04 1.00E-03 1.00E-01 1.00E+01 1.00E+03 1.00E+05 1.00E+07 1.00E+09 η*,(Poise) Frequency (rad/s) Base A-ORIG LSV Base A-ORIG η* Poise LSV Reference Temperature-60℃
  • 30. Rheological Indices www.wrsc.unr.edu 11/17/2015 30 Crossover Modulus G*c -Analogous to rheological index, R 1.00E-02 1.00E-01 1.00E+00 1.00E+01 1.00E+02 1.00E+03 1.00E+04 1.00E+05 1.00E+06 1.00E+07 1.00E+08 1.00E-03 1.00E-01 1.00E+01 1.00E+03 1.00E+05 1.00E+07 1.00E+09 G',G''(Pa) Frequency (rad/s) Base A-orig-Loss Modulus Base A-orig-Storage Modulus fc G*c, fc when the phase angle at 45º R=G*g-G*c
  • 31. Rheological Indices www.wrsc.unr.edu 11/17/2015 31 DSR Function 𝐃𝐒𝐑𝐅𝐧 = 𝐆′ 𝛈′ 𝐆′ (Dr. Glover) y = 9E+13x-3.567 R² = 0.9945 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 100 300 500 700 900 1100 1300 1500 G'(15°C,0.005rad/s) η'/G' (s) (15°C, 0.005 rad/s) Base A DSR function
  • 32. Rheological Indices www.wrsc.unr.edu 11/17/2015 32 Glover-Rowe Parameter G-R = 𝑮∗ 𝝎 𝒄𝒐𝒔 𝟐 𝜹 𝒔𝒊𝒏 𝜹 1.00E+02 1.00E+03 1.00E+04 1.00E+05 1.00E+06 1.00E+07 1.00E+08 1.00E+09 0.00 10.00 20.00 30.00 40.00 50.00 60.00 70.00 80.00 90.00 |G*|(Pa)(15°C0.005rad/s) Phase Angle (°) Base A Black Space Diagram Base A G-R G-R at 180 kPa G-R at 450 kPa G*/sin(phase angle)≥2.2kpa G*sin(phase angle)≤5000kpa 85°C, 40d 85°C, 25d
  • 33. Rheological Indices-Conditions www.wrsc.unr.edu 11/17/2015 33 Rheological Indices Applicable Conditions Name Symbol Temperature (°C) Frequency (rad/s) Notes Low Shear Viscosity LSV 60 0.001 Has also been measured at 0.1 rad/s DSR Function DSRFun 15 0.005 Can be shifted from 10 rad/s at 44.7°C Glover-Rowe Parameter G-R 15 0.005 or Var. Also evaluated at 20°C, potential for representative Int. temps. Crossover Modulus G*c 25 fc Corresponds to a phase angle of 45° Crossover Frequency fc 25
  • 34. Kinetic Aging Parameters • Arrhenius Equation- -Where, A = the frequency factor, P = the oxygen pressure, α= the reaction order, E =the activation energy (kJ/mol), R=the gas constant (8.314 J.mol/°K), T= the absolute temperature. It is a formula for the temperature dependence of reaction rates. www.wrsc.unr.edu 11/17/2015 34 RTE CA eAP t CA r /     
  • 35. Kinetic Aging Parameters www.wrsc.unr.edu 11/17/2015 35 y = 0.0008x + 1.0211 R² = 0.9612 y = 0.0019x + 1.0725 R² = 0.9805 y = 0.0213x + 0.8413 R² = 0.9964 0.5 0.7 0.9 1.1 1.3 1.5 1.7 1.9 0 50 100 150 200 250 300 350 AverageCarbonylArea Time (Days) PG 64-28 50°C 60°C 85°C Example-Kc
  • 36. Kinetic Aging Parameters Example of Arrhenius Parameters www.wrsc.unr.edu 11/17/2015 36 y = 2.50E+12e-9.79E+01x y = 1.08E+08e-6.11E+01x 0.0001 0.001 0.01 0.1 1 10 0.33 0.335 0.34 0.345 0.35 0.355 0.36 0.365 0.37 0.375 Kc,Kf(CA/day) 1/RT B_TR_X-Kc, Kf Kc Kf Expon. (Kc) Expon. (Kf)
  • 37. Kinetic Aging Parameters-CA fitting Model www.wrsc.unr.edu 11/17/2015 37 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 0 50 100 150 200 250 CA Time (day) B_TR_X Reg fitting-85℃ Reg fitting-60℃ Reg fitting-50℃ 85°C 60°C 50°C Fast Rate Reaction Constant Rate Reaction kc tk CAtkeMCA f tan * *)1(  
  • 38. Hardening Susceptibility • Generally, there is a good correlation between the rheological indexes and the carbonyl area parameter-exponential function. or ln(𝑅𝐼) = 𝐻𝑆 ∗ 𝐶𝐴 + 𝑚 RI-Rheological Indexes. www.wrsc.unr.edu 11/17/2015 38 𝑅𝐼 = 𝑒 𝐻𝑆∗𝐶𝐴 𝑒 𝑚
  • 39. Hardening Susceptibility-Examples www.wrsc.unr.edu 11/17/2015 39 y = 7.5245e11.109x R² = 0.9513 y = 327.4e7.9403x R² = 0.9247 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 0.000 0.200 0.400 0.600 0.800 1.000 LSV(Pa.s,60°C,0.001rad/s) Carbonyl Area (arb. unit) Base A A_PM Expon. (Base A) Expon. (A_PM) y = 54503e-5.603x R² = 0.9701 y = 27635e-4.653x R² = 0.9126 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 0.000 0.200 0.400 0.600 0.800 1.000 G*c(kPa,25°C) Carbonyl Area (arb. unit) Base A A_PM Expon. (Base A) Expon. (A_PM) y = 0.0037e17.172x R² = 0.9746 y = 0.4427e10.155x R² = 0.9652 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 0.000 0.200 0.400 0.600 0.800 1.000 G-R(kPa,15°C,0.005rad/s) Carbonyl Area (arb. unit) Base A A_PM Expon. (Base A) Expon. (A_PM) y = 0.0163e17.418x R² = 0.9781 y = 2.2151e10.154x R² = 0.9653 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 0.000 0.200 0.400 0.600 0.800 1.000 DSRfunc.(pa/s,15°C,0.005rad/s) Carbonyl Area (arb. unit) Base A A_PM Expon. (Base A) Expon. (A_PM)
  • 40. Test Results Analysis-Kinetic Parameters Asphalt Binder Modifier Influence of Modification on kf Eaf kc Eac A SBS ↓ ↓ ↓ ↓ C SBS ↓ ↓ ↓ ↑ D SBS ↓ ↑ ↓ ↑ B TR ↓ ↓ ↓ ↑ B_TR_X SBS ↑ ↑ ↑ ↓ B_TR_Y SBS ↑ ↑ ↓ ↓ B_TR_Z SBS ↑ ↓ ↑ ↓ www.wrsc.unr.edu 11/17/2015 40
  • 41. Test Results Analysis-LSV vs CA www.wrsc.unr.edu 11/17/2015 41 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 0.000 0.200 0.400 0.600 0.800 1.000 LSV(Pa.s,60°C,0.001rad/s) Carbonyl Area (arb. unit) Base A A_PM Base C C_PM Base D D_HMP Expon. (Base A) Expon. (A_PM) Expon. (Base C) Expon. (C_PM) Expon. (Base D) Expon. (D_HMP)
  • 42. Test Results Analysis-LSV vs CA www.wrsc.unr.edu 11/17/2015 42 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 0.000 0.200 0.400 0.600 0.800 1.000 LSV(Pa.s,60°C,0.001rad/s) Carbonyl Area (arb. unit) Base B B_TR B_TR_X B_TR_X_PM B_TR_Y B_TR_Y_PM B_TR_Z B_TR_Z_HPM Expon. (Base B) Expon. (B_TR) Expon. (B_TR_X) Expon. (B_TR_X_PM) Expon. (B_TR_Y) Expon. (B_TR_Y_PM) Expon. (B_TR_Z) Expon. (B_TR_Z_HPM)
  • 43. Test Results Analysis-G*c vs CA www.wrsc.unr.edu 11/17/2015 43 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 0.000 0.200 0.400 0.600 0.800 1.000 G*c(kPa,25°C) Carbonyl Area (arb. unit) Base A A_PM Base C C_PM Base D D_HMP Expon. (Base A) Expon. (A_PM) Expon. (Base C) Expon. (C_PM) Expon. (Base D) Expon. (D_HMP)
  • 44. Test Results Analysis-G*c vs CA www.wrsc.unr.edu 11/17/2015 44 1.E+02 1.E+03 1.E+04 1.E+05 0.000 0.200 0.400 0.600 0.800 1.000 G*c(kPa,25°C) Carbonyl Area (arb.unit) Base B B_TR B_TR_X B_TR_X_PM B_TR_Y B_TR_Y_PM B_TR_Z B_TR_Z_HPM Expon. (Base B) Expon. (B_TR) Expon. (B_TR_X) Expon. (B_TR_X_PM) Expon. (B_TR_Y) Expon. (B_TR_Y_PM) Expon. (B_TR_Z) Expon. (B_TR_Z_HPM)
  • 45. Test Results Analysis-G-R vs CA www.wrsc.unr.edu 11/17/2015 45 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 0.000 0.200 0.400 0.600 0.800 1.000 G-R(kPa,15°C,0.005rad/s) Carbonyl Area (arb. unit) Base A A_PM Base C C_PM Base D D_HMP Expon. (Base A) Expon. (A_PM) Expon. (Base C) Expon. (C_PM) Expon. (Base D) Expon. (D_HMP)
  • 46. Test Results Analysis-G-R vs CA www.wrsc.unr.edu 11/17/2015 46 1.E-02 1.E-01 1.E+00 1.E+01 1.E+02 1.E+03 1.E+04 0.000 0.200 0.400 0.600 0.800 1.000 G-R(kPa,15°C,0.005rad/s) Carbonyl Area (arb. unit) Base B B_TR B_TR_X B_TR_X_PM B_TR_Y B_TR_Y_PM B_TR_Z B_TR_Z_HPM Expon. (Base B) Expon. (B_TR) Expon. (B_TR_X) Expon. (B_TR_X_PM) Expon. (B_TR_Y) Expon. (B_TR_Y_PM) Expon. (B_TR_Z) Expon. (B_TR_Z_HPM)
  • 47. Test Results Analysis-HS results table Binder ID LSV (Pa.s, 60°C, 0.001 rad/s) Gc* (kPa, 25°C) G-R Parameter (kPa, 15°C, 0.005rad/s) em HS em HS em HS Base A 8 11.1 54,503 5.6 0.004 17.2 A_PM 327 7.9 27,635 4.7 0.44 10.2 Base B 47 7.4 24,703 3.0 0.06 13.8 B_TR 243 10.0 13,479 3.6 0.83 14.7 B_TR_X 55 9.1 23,558 4.1 0.04 14.8 B_TR_X_PM 1,190 6.6 15,982 3.8 1.53 8.9 B_TR_Y 104 8.0 28,945 3.4 0.07 13.9 B_TR_Y_PM 16,536 5.1 21,971 5.4 2.64 9.8 B_TR_Z 218 7.4 23,562 2.7 0.36 11.6 B_TR_Z_HPM 17,940 4.8 15,176 5.5 4.13 6.4 Base C 11 9.6 54,166 5.0 0.003 16.7 C_PM 11,481 8.0 59,321 11.8 2.52 9.9 Base D 33 9.8 33,750 4.5 0.04 15.1 D_HPM 92,337 5.2 26,352 5.2 7.50 7.5 www.wrsc.unr.edu 11/17/2015 47
  • 48. Test Results Analysis-HS Summary Binder Modifier LSV (Pa.s, 60°C, 0.001 rad/s) Gc* (kPa, 25°C) G-R Parameter (kPa, 15°C, 0.005rad/s) A SBS ↓ ↓ ↓ C SBS ↓ ↑ ↓ D SBS ↓ ↑ ↓ B TR ↑ ↑ ↑ B_TR_X SBS ↓ ↓ ↓ B_TR_Y SBS ↓ ↑ ↓ B_TR_Z SBS ↓ ↑ ↓ www.wrsc.unr.edu 11/17/2015 48
  • 49. Test Results Analysis-RI Correlation www.wrsc.unr.edu 11/17/2015 49 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 1.E+08 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 0.10 1.00 10.00 100.00 1000.00 10000.00 CrossoverModulus,G*c(pa,25°C) LSV(Pa.s,60°C,0.001rad/s) DSR Fn (15°C 0.005rad/s)) Base A, LSV A_PM, LSV Base C, LSV C_PM, LSV Base D, LSV D_HPM, LSV Base A_G*c A_PM_G*c Base C_G*c C_PM_G*c Base D_G*c D_HPM_G*c Aging Aging
  • 50. Test Results Analysis-RI Correlation www.wrsc.unr.edu 11/17/2015 50 Aging y = 119.63x0.601 R² = 0.9225 y = 2E+07x-0.288 R² = 0.9027 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 1.E+08 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 0.10 1.00 10.00 100.00 1000.00 10000.00 CrossoverModulus,G*c(pa,25°C) LSV(Pa.s,60°C,0.001rad/s) DSR Fn (15°C 0.005rad/s)) Base A, LSV Base C, LSV Base D, LSV Base A_G*c Base C_G*c Base D_G*c Aging
  • 51. Test Results Analysis-RI Correlation www.wrsc.unr.edu 11/17/2015 51 Aging 1.E+01 1.E+02 1.E+03 1.E+04 1.E+05 1.E+06 1.E+07 0.10 10.00 1000.00 100000.00 LSV(Pa.s,60°C,0.001rad/s) DSR Fn (15°C 0.005rad/s) Base B, LSV B_TR, LSV B_TR_X, LSV B_TR_X_PM, LSV B_TR_Y, LSV B_TR_Y_PM, LSV B_TR_Z, LSV B_TR_Z_HPM, LSV Aging
  • 52. Test Results Analysis-RI Correlation www.wrsc.unr.edu 11/17/2015 52 1.E+04 1.E+05 1.E+06 1.E+07 1.E+08 0.10 1.00 10.00 100.00 1000.00 10000.00 100000.001000000.00 CrossoverModulus,G*c(Pa,25°C) DSR Fn (15°C 0.005rad/s) Base B, G*c B_TR, G*c B_TR_X, G*c B_TR_X_PM, G*c B_TR_Y, G*c B_TR_Y_PM, G*c B_TR_Z, G*c B_TR_Z_HPM, G*c Aging Aging
  • 53. Field Asphalt CA Prediction • Reno Int. Airport-Freeze thaw • Phoenix Sky Harbor Int. Airport- Warm Climate • Glasgow Int. Airport-Cold Climate www.wrsc.unr.edu 11/17/2015 53 Reno Int. Airport Phoenix SH Int. Airport Glasgow Int. Airport
  • 54. Field Asphalt CA Prediction • CA Prediction Procedure  Preparing Climate Data-TEMPS input file  Run TEMPS Output file-Pavement Temperature  Using Dr. Alavi’s pavementaging.m Matlab code to calculate the CA at different location, different time and different asphalt binder film thickness. www.wrsc.unr.edu 11/17/2015 54
  • 55. Field Asphalt CA Prediction • Pavement Structure (Thickness: 0.15 m HMA+0.35 m Gravel Base) www.wrsc.unr.edu 11/17/2015 55 Material Parameters HMA Gavel Stone Soil Specific Heat Capacity (J/kg°K) 920 850 800 Conductivity (W/m°K) 1 0.75 1 Density (Kg/m^3) 2250 2100 2000
  • 56. Field Asphalt CA Prediction • Climate Data http://gis.ncdc.noaa.gov/map/ http://rredc.nrel.gov/solar/old_data/nsrdb/ www.wrsc.unr.edu 11/17/2015 56 Air Temperature, Wind speed-2010 Solar Radiation
  • 57. Field Asphalt CA Prediction • TEMPS www.wrsc.unr.edu 11/17/2015 57 User friendly software
  • 58. Field Asphalt CA Prediction • Input data of TEMPS www.wrsc.unr.edu 11/17/2015 58 -20 -10 0 10 20 30 40 50 0 1000 2000 3000 4000 5000 6000 7000 8000 9000 10000 AirTemperature(℃) Time (hour) Air Temperature Reno Air Temperature Phoenix Air Temperature Glasgow Air Temperature
  • 59. Field Asphalt CA Prediction • Input data of TEMPS www.wrsc.unr.edu 11/17/2015 59 -15 -10 -5 0 5 10 15 20 25 0 200 400 600 800 AirTemperature(℃) Time (hour) Air Temperature-January Reno Air Temperature Phoenix Air Temperature Glasgow Air Temperature
  • 60. Field Asphalt CA Prediction • Output files of TEMPS-Examples www.wrsc.unr.edu 11/17/2015 60 -6 -4 -2 0 2 4 6 8 10 0 120 240 360 480 600 720 840 Temperature(℃) Time (hour) Pav. Temperature-January Reno Air Temperature Reno Pav. 0.01m depth Temperature Reno Pav. 0.07m depth Temperature Reno Pav. 0.15m Depth Temperature
  • 61. Field Asphalt CA Prediction • Pavementaging.m Matlab Calculation www.wrsc.unr.edu 11/17/2015 61
  • 62. Field Asphalt CA Prediction-Results • Reno-0.01m www.wrsc.unr.edu 11/17/2015 62 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0 50000 100000 150000 200000 CarbonylArea(Arb.unit) Time (hour) Reno-0.01 m depth film surface A_PM B_TR_X_PM B_TR_X B_TR_Y_PM B_TR_Y B_TR_Z_HPM B_TR_Z B_TR Base A Base B Base C Base D C_PM D_HPM o.58
  • 63. Field Asphalt CA Prediction-Results • Reno-0.07m www.wrsc.unr.edu 11/17/2015 63 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0 50000 100000 150000 200000 CarbonylArea(Arb.unit) Time (hour) Reno-0.07 m depth film surface A_PM B_TR_X_PM B_TR_X B_TR_Y_PM B_TR_Y B_TR_Z_HPM B_TR_Z B_TR Base A Base B Base C Base D C_PM D_HPM o.53
  • 64. Field Asphalt CA Prediction-Results • Reno-0.15m www.wrsc.unr.edu 11/17/2015 64 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0 50000 100000 150000 200000 CarbonylArea(Arb.unit) Time (hour) Reno-0.15 m depth film surface A_PM B_TR_X_PM B_TR_X B_TR_Y_PM B_TR_Y B_TR_Z_HPM B_TR_Z B_TR Base A Base B Base C Base D C_PM D_HPM o.49
  • 65. Field Asphalt CA Prediction-Results www.wrsc.unr.edu 11/17/2015 65 0.34115 0.3412 0.34125 0.3413 0.34135 0.3414 0.34145 0 24000 48000 72000 96000 120000 144000 168000 192000 CarbonylArea(abs.unit) Time(hour) Reno Base B CA Field Prediction 0.01m depth film surface 0.07m depth film surface 0.15m depth film surface 0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0 24000 48000 72000 96000 120000 144000 168000 192000 CarbonylArea(abs.unit) Time(hour) Reno B_TR CA Field Prediction 0.01m depth film surface 0.07m depth film surface 0.15m depth film surface 0.1 0.12 0.14 0.16 0.18 0.2 0.22 0.24 0.26 0.28 0 24000 48000 72000 96000 120000 144000 168000 192000 CarbonylArea(abs.unit) Time(hour) Reno B_TR_Z CA Field Prediction 0.01m depth film surface 0.07m depth film surface 0.15m depth film surface 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0 24000 48000 72000 96000 120000 144000 168000 192000 CarbonylArea(abs.unit) Time(hour) Reno B_TR_Z_HPM CA Field Prediction 0.01m depth film surface 0.07m depth film surface 0.15m depth film surface
  • 66. Field Asphalt CA Prediction-Results www.wrsc.unr.edu 11/17/2015 66 0.3411 0.3412 0.3413 0.3414 0.3415 0.3416 0.3417 0.3418 0.3419 0.342 0 24000 48000 72000 96000 120000 144000 168000 192000 CarbonylArea(abs.unit) Time(hour) Base B CA Field Prediction Reno-0.01m depth film surface Phoenix-0.01m depth film surface Glasgow 0.01m depth film surface 0 0.1 0.2 0.3 0.4 0.5 0.6 0 24000 48000 72000 96000 120000 144000 168000 192000 CarbonylArea(abs.unit) Time(hour) B_TR_Z CA Field Prediction Reno-0.01m depth film surface Phoenix-0.01m depth film surface Glasgow 0.01m depth film surface 0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4 0.45 0.5 0 24000 48000 72000 96000 120000 144000 168000 192000 CarbonylArea(abs.unit) Time(hour) B_TR CA Field Prediction Reno-0.01m depth film surface Phoenix-0.01m depth film surface Glasgow 0.01m depth film surface 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 24000 48000 72000 96000 120000 144000 168000 192000 CarbonylArea(abs.unit) Time(hour) B_TR_Z_HPM CA Field Prediction Reno-0.01m depth film surface Phoenix-0.01m depth film surface Glasgow 0.01m depth film surface
  • 67. Conclusion and Further Consideration • Conclusion  Temperature and aging duration played an important role on the asphalt binder aging hardening, this conclusion was justified by the multi linear regression analysis. The asphalt binder aging rate increased with increasing temperature, carbonyl area is a good parameter to evaluate the oxidative aging extent. TR reduced the asphalt binders’ fast rate and constant rate reaction, X, Y, Z asphalt components had modest variation for the fast rate and increased the constant rate; the SBS modifiers had different direction effect on these two parameters. www.wrsc.unr.edu 11/17/2015 67
  • 68. Conclusion and Further Consideration • Conclusion  With the SBS modification, both of the hardening susceptibility of the rheological indexes-LSV and G-R decreased compared with the corresponding base binder. The TR increased the hardening susceptibility of all the rheological indexes. While for the G*c, SBS increases the slope of the most modified asphalt binders except A and B_TR_X series binders.  The temperature variation of the pavement structure decreased with the increasing pavement depth, the predicted CA value range for all the asphalt binders decreased when the evaluated pavement depth was increasing. The oxygen diffusion effect on the asphalt binder film aging was highly binder resource dependent. www.wrsc.unr.edu 11/17/2015 68
  • 69. Conclusion and Further Consideration • Further Consideration  Other microscopic analysis tools, such as NMR, AFM, can be used to compensate the FTIR to get more chemical information for the binder aging. The related asphalt mixture aging and real field pavement aging are needed to investigate the correlation between the laboratory binder aging and field asphalt binder aging. How to minimize the field asphalt pavement aging rate is a good extension for the future study.  More related asphalt binder aging researches or projects are needed to study the asphalt binder aging oxidative aging mechanism. www.wrsc.unr.edu 11/17/2015 69
  • 70. Acknowledgement • Thank you to Dr. Sebaaly, Dr. Hajj, Dr. Morian, and Dr. Lin for their consistent supporting, teaching, and advising. • Thanks to Dr. John Hellgeth of Applied Materials Solutions, LLC for his assistance on the FTIR measurements. • Thanks to all of my colleagues at UNR pavement program- Dario, Farzan, Hadi, Jay, Jhony, Luis, Mohamed, Nick, Piratheepan, Sara, Sendeep, and Victor for their help and friendship. • I Love Asphalt www.wrsc.unr.edu 11/17/2015 70