oxidation and kinetics of aging in asphalt binders · oxidation and kinetics of aging in asphalt...
TRANSCRIPT
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Oxidation and Kinetics of Aging in Asphalt Binders (and so what?)
Charles J. Glover Artie McFerrin Department of Chemical
Engineering, Texas A&M University/
Texas Transportation Institute
International Workshop on Binders and Mastics Madison, Wisconsin
September 16, 2010
CJG, IWABM 9-16-10
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Presentation Overview
• Oxidation kinetics – fast-rate and constant-rate • Oxygen diffusivity in binders and mastics • Binder rheology: hardening due to oxidation • Mixture hardening and changes to fatigue
resistance due to oxidation • Modeling oxidation and hardening in pavements • References
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Oxidation Kinetics
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Asphalt Oxidation Kinetics - Our Laboratory -
Previous work: Constant-rate oxidation kinetics Lau, C. K., K. M. Lunsford, C. J. Glover, R. R. Davison, and J. A.
Bullin, “Reaction Rates and Hardening Susceptibilities as Determined from POV Aging of Asphalts,” Transp. Res. Rec., 1342, 50-57 (1992).
Liu, M., K.M. Lunsford, R.R. Davison, C.J. Glover and J.A. Bullin, “The Kinetics of Carbonyl Formation in Asphalt,” AIChE J., 42(4), 1069-1076 (1996). (Includes pressure effects)
Domke, C.H., Davison, R.R. and Glover, C.J., “Effect of Oxygen Pressure on Asphalt Oxidation Kinetics,” Ind. Eng. Chem. Res., 39(3), 592-598 (2000).
Recent work: Fast-rate; constant-rate oxidation kinetics Xin Jin, et al., Petersen Asphalt Research Conference
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Alon PG64-22 Aged in Air Pressure
0 20 40 60 80Time (Days)
0.6
0.8
1
1.2
1.4
1.6
1.8
2
CA
62.1 C69.5 C78.7 C86.8 C97.2 C
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Hypothetical parallel-reaction model in terms of CA:
Fast-rate – Constant-rate Kinetics Model
CA = M[1 – exp(-kft)] + CAtank + kct
Aging Time
Carb
on
yl A
rea
Constant-rate ReactionFast-rate Reaction
CA0
CAtank
M = CA0 – CAtank
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Constant-rate Reaction Kinetics
0.32 0.33 0.34 0.35 0.361/RT (mol/KJ)
0.01
0.1 y = 3.68e+10*e^(-83.24x), r=-0.997
k c (CA
/day
)
kc = A’c exp(-Eac/RT)
CA = M[1 – exp(-kft)] + CAtank + kct CJG, IWABM 9-16-10
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Fast-rate Reaction Kinetics
0.325 0.33 0.335 0.34 0.345 0.35 0.3551/RT (mol/KJ)
0.1
y = 8.37e+07*e^(-58.87x), r=-0.966
k f (per
day
)
kf = A’f exp(-Eaf/RT)
CA = M[1 – exp(-kft)] + CAtank + kct CJG, IWABM 9-16-10
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Fast-rate Reaction Kinetics
335 340 345 350 355 360 365 370Temperature (K)
0.1
M (C
A)
y = 2.438e-3*e^(0.0127x), r=0.800
CA = M[1 – exp(-kft)] + CAtank + kct CJG, IWABM 9-16-10
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How well does the model work?
0 20 40 60 80Time (Days)
0.6
0.8
1
1.2
1.4
1.6
1.8
2
CA
62.1 C69.5 C78.7 C86.8 C97.2 C
CA = M•[1 – exp(-kf •t)] + CAtank + kc •t
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Table of Kinetics Parameters Constant Rate Kinetics Fast Rate Kinetics
Binders A’c (CA/day) Eac (KJ/mol) A’f (1/day) Eaf (KJ/mol)
SEM PG64-22 2.15E+08 68.4 7.97E+05 43.5 SEM PG70-22 9.51E+09 79.4 3.61E+06 48.1 MARTIN PG64-22 9.30E+08 72.2 2.07E+07 52.7 MARTIN PG70-22 2.05E+11 87.7 1.21E+07 58.7 ALON PG64-22 3.68E+10 83.2 8.37E+07 58.9 ALON PG76-22 4.02E+09 77.0 3.07E+05 41.4 Valero-H PG64-22 7.91E+07 65.5 Valero-H PG70-22 3.38E+07 62.7 Lion PG70-22 4.77E+08 70.1
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What’s The Point?
• With oxidation kinetics parameters known, together with T(t) and P(t), one can calculate binder oxidation as a function of time.
CA = M•[1 – exp(-kf •t)] + CAtank + kc •t
kf = A’f exp(-Eaf/RT)
kc = A’c exp(-Eac/RT)
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Oxygen Diffusivity in Asphalt
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Thin Film Model
Impermeable Boundary
Exposed Surface (ES)
Substrate Interface (SI)
0
L x
y z
Oxygen Profile f(x, t)
GASEOUS OXYGEN
Schematic of asphalt thin film model
h=h0(1+0.00215(T-Tr))
Governing Equation
BCs & IC
P = Pgas at x=L Exposed Surface
at x=0 Substrate Interface
at t=0 Initial Condition P = 0
Model Concept and Mathematical Expression
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Thin Film Model Calculation of a Value and Time for PSI
PSI Value
PSI Time
Close to medium point of testing time
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DO2/T and (ηo*): Empirical Correlation
Values of DO2
DO2/T =3.01 x 10-11 (η0*)-0.54
R2=0.9437
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DO2 in Mastics
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Effect of Φ of Aggregate Fines on DO2 Maxwell Model
Rayleigh Model
Non-spherical Model
DO2 in Mastics
€
keffk0
=1+3φ
k1 + 2k0k1 − k0
−φ +1.569 k1 − k0
3k1 − 4k0
φ
10 / 3 + •••
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Diffusivity Conclusions Oxygen diffusivity in asphalt materials is highly dependent on temperature and viscosity of asphalt; A correlation was established between log Do2/T and log (η0*).
Oxygen diffusivity in mastics decreases with an increase of volume fraction of aggregate fines; this effect of fines on oxygen diffusivity can be estimated using conventional prediction models
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Effects of Oxidation on Asphalt Rheology
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Asphalt Master Curves
Ruan, PhD Dissertation, data from Figs V-1, V-5 (2002) €
η*(ω) ≡G*(ω)ω
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Hardening Susceptibility
Lau et al., TRR 1342, 50-57 (1992) CJG, IWABM 9-16-10
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Field Binder Aging
Woo et al., FHWA/TX-07/0-4688-1, 5-38 (2007) CJG, IWABM 9-16-10
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So what? Pavement Performance Depends upon:
• Pavement Structure • Mixture Parameters:
– Aggregate type/gradation – Binder Content – Compaction
• Traffic Loading • Thermal Loading
Cont’d…
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Pavement Performance Depends upon:
• Binder Properties – Rheology
• Temperature – TTS shift factor • Oxidation
– Hardening Susceptibility – Temperature – Diffusivity
– Water Susceptibility – Healing
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Pavement Performance Depends upon:
Pavement Performance
Mixture Parameters
Binder Rheology (z,t)
Pavement T(z,t)
Meteorology
Traffic and Thermal Loading
Pavement Structure
Mixture Fatigue Resistance
Hardening Susceptibility (HS)
Oxidation kinetics; Diffusivity
DSR Function
Mixture Performance Characteristics
Master Curves
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Mixture BB Fatigue Cycles-to-Failure vs Strain
Walubita et al., FHWA/TX-05/0-4468-2, 169 (2005)
!
! "#$
!"#$%#&
!"#$%#'
!"#$%#(
!"#$%#)
!## !###
*+,-./0-1+2
3.14567,89/5:;<
=-712>5#5*.20?/
=-712>5@5*.20?/
=-712>5(5*.20?/
Figure 10-1(a). N vs. !t at 20 "C (68 "F) (Bryan Mixture).
!
!"#$%#&
!"#$%#'
!"#$%#(
!"#$%#)
!## !###
*+,-./0-1+2
3.14567,89/5:;<
A.1BCD>55#5*.20?/
A.1BCD>5@5*.20?/
A.1BCD>5(5*.20?/
Figure 10-1(b). N vs. !t at 20 "C (68 "F) (Yoakum Mixture).
%&'(!')*'!')(!+*',-.(!/(0.1'0!,2!3,-./(!"45"!6(/(!7*0(8!&2!'6&!'(0'!0'/*,2!1(9(10!+&/!(*:)!
;,<'./(!=(/!*-,2-!:&28,',&2>!3&/!7(''(/!!"#=/(8,:',&20!*28!0'*',0',:*1!*2*1?0,0@!;&/(!8*'*!=&,2'0!
A:&11(:'(8!*'!;&/(!')*2!'6&!'(0'!0'/*,2!1(9(10B!*/(!/(:&;;(28(8>!C(2(/*11?@!;&/(!'(0',2-!*'!
8,++(/(2'!0'/*,2!1(9(10!6&.18!1(*8!'&!*!7(''(/!+*',-.(!/(1*',&20),=@!7.'!7(*/,2-!,2!;,28!')*'!DD!
'(0',2-!,0!E.,'(!*!1(2-')?!'(0'>!F&6(9(/@!(*:)!8*'*!=&,2'!,2!3,-./(!"45"!,0!*!;(*2!9*1.(!&+!')/((!
/(=1,:*'(!;(*0./(;(2'0!&+!8,++(/(2'!FGHI!7(*;!0=(:,;(20>!
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Mixture Fatigue MIXTURE FATIGUE
|SLOPE| = K1
Mix
ture
Fie
ld N
f
Binder (G'/(!'/G')) MPa/s 15 oC, 0.005 rad/s
10-4
10-3
10-210
6
107
108
109
For Bryan Field Nf: y = a*x^b R^2 = 0.994a 664b -1.37
For Yoakum Field Nf: y = a*x^b R^2 = 0.998a 71100b -0.908
YKM-Nf(CMSE) (Field) BRY-Nf(CMSE) (Field)
Increasing
Aging
Field Nf vs Binder DSR Function
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Mixture Fatigue MIXTURE FATIGUE
Bin
de
r (G
'/(!
'/G
'))
MP
a/s
15
oC
, 0
.00
5 r
ad
/s
Aging Time (months at 60 oC, 1 atm)
10-4
10-3
10-2
0 1 2 3 4 5 6 7
BRY-SAFT+ 3, 6M
YKM-SAFT+ 3, 6M
y = 0.000117 * e^(0.327x)
y = 0.000484 * e^(0.2x)
Original
SLOPE = K2
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Fatigue Life Decline With Aging
Nf (t) =Nf0e-K1K2t
Bin
de
r (G
'/( !
'/G
'))
MP
a/s
15
oC
, 0
.00
5 r
ad
/s
Aging Time (months at 60 oC, 1 atm)
10-4
10-3
10-2
0 1 2 3 4 5 6 7
BRY-SAFT+ 3, 6M
YKM-SAFT+ 3, 6M
y = 0.000117 * e^(0.327x)
y = 0.000484 * e^(0.2x)
Original
SLOPE = K2|SLOPE| = K
1
Mix
ture
Fie
ld N
f
Binder (G'/(!'/G')) MPa/s 15 oC, 0.005 rad/s
10-4
10-3
10-210
6
107
108
109
For Bryan Field Nf: y = a*x^b R^2 = 0.994a 664b -1.37
For Yoakum Field Nf: y = a*x^b R^2 = 0.998a 71100b -0.908
YKM-Nf(CMSE) (Field) BRY-Nf(CMSE) (Field)
Increasing
Aging
Field Nf vs Binder DSR Function
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FATIGUE LIFE
RL = Pavement Loading Rate, ESALs/yr
Nf = Field Fatigue Life - Cycles, ESALs
DEFINITIONS
FOR CONSTANT Nf
Nf / RL = Field Fatigue Life - Time, years
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Fatigue Life FOR Nf (t) A FUNCTION OF TIME:
CUMMULATIVE DAMAGE:
Nf (t) = Nfoe-K1K2t
tend =ln(K1K2Nfo / RL + 1)
K1K2= Service Life
At life’s end, fractions sum to 1:! tend
0
dtNf (t) / RL
= 1
Fraction of Life Expended During Time dt =dt
Nf (t) / RL
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Pavement Fatigue: Remaining Service Life
Woo et al., FHWA/TX-07/0-4688-1, 7-20 (2007) CJG, IWABM 9-16-10
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Pavement Performance Depends upon:
Pavement Performance
Mixture Parameters
Binder Rheology (z,t)
Pavement T(z,t)
Meteorology
Traffic and Thermal Loading
Pavement Structure
Mixture Fatigue Resistance
Hardening Susceptibility (HS)
Oxidation kinetics; Diffusivity
DSR Function
Mixture Performance Characteristics
Master Curves
Model
CA(z,t)
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TRANSPORT MODEL CALCULATIONS OF BINDER HARDENING IN PAVEMENTS
• Calculation of hardening is based on fundamentals: oxidation kinetics, diffusivity, HS, DSRFn, master curves
• Oxygen in pavements appears to be ubiquitous – little evidence that oxygen supply to pavements is very restricted (tentative hypothesis); pores allow air permeation
• Includes effect of binder oxidative hardening on mixture properties, fatigue resistance decline, e.g.
CJG, IWABM 9-16-10
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Thermal Transport
Solar radiation
Atmospheric downwelling
longwave radiation
Outgoing longwave radiation
Heat convection by wind
pavement Heat conduction
εa ε hc (Ts,Ta,U)
к
Modeling Concept
Mathematical Modeling
Surface Boundary Condition: Hourly Heat Flux Balance
Heat Conduction inside Pavement
Bottom Boundary Condition:
k: Thermal conductivity ρ: Density C: Heat capacity К : Thermal diffusivity
α: Stefan-Boltzmannn constant; Ts: Surface temperature ε: emissivity coefficient; Ta: Air temperature εa: absorption coefficient; qs: Solar radiation hc: heat convection coefficient; :Albedo
Depth Independent heat flux based on field measurement
Temperature Modeling concept and mathematical expression
MODEL DEVELOPEMENT
Solar radiation
Atmospheric downwelling
longwaveradiation
Outgoing longwave radiation
Heat convection
by wind
pavement Heat conduction
!a!
hc (Ts,Ta,U)
"
Modeling Concept
x
TkTThTTq
t
TxC s
ascsaass
!
!+"""+"=
!
!#)()1(
2
44 $%%$&'
Mathematical Modeling
Surface Boundary Condition: Hourly Heat Flux Balance
Heat Conduction inside Pavement
Bottom Boundary Condition
K: Thermal conductivity!!!!: DensityC: Heat capacity"""" : Thermal diffusivity
!!!!: Stefan-Boltzmannn constant; Ts: Surface temperature
"""": emissivity coefficient; Ta: Air temperature
""""a: absorption coefficient; qs: Solar radiationhc: heat convection coefficient; :Albedo
Depth Independent heat flux based on
field measurement
2
2
x
T
C
k
t
T
!
!=
!
!
'
Modeling concept and mathematical expression
MODEL DEVELOPEMENT
Solar radiation
Atmospheric downwelling
longwaveradiation
Outgoing longwave radiation
Heat convection
by wind
pavement Heat conduction
!a!
hc (Ts,Ta,U)
"
Modeling Concept
x
TkTThTTq
t
TxC s
ascsaass
!
!+"""+"=
!
!#)()1(
2
44 $%%$&'
Mathematical Modeling
Surface Boundary Condition: Hourly Heat Flux Balance
Heat Conduction inside Pavement
Bottom Boundary Condition
K: Thermal conductivity!!!!: DensityC: Heat capacity"""" : Thermal diffusivity
!!!!: Stefan-Boltzmannn constant; Ts: Surface temperature
"""": emissivity coefficient; Ta: Air temperature
""""a: absorption coefficient; qs: Solar radiationhc: heat convection coefficient; :Albedo
Depth Independent heat flux based on
field measurement
2
2
x
T
C
k
t
T
!
!=
!
!
'
Modeling concept and mathematical expressionMODEL DEVELOPEMENT
Solar radiation
Atmospheric downwelling
longwaveradiation
Outgoing longwave radiation
Heat convection
by wind
pavement Heat conduction
!a!
hc (Ts,Ta,U)
"
Modeling Concept
x
TkTThTTq
t
TxC s
ascsaass
!
!+"""+"=
!
!#)()1(
2
44 $%%$&'
Mathematical Modeling
Surface Boundary Condition: Hourly Heat Flux Balance
Heat Conduction inside Pavement
Bottom Boundary Condition
K: Thermal conductivity!!!!: DensityC: Heat capacity"""" : Thermal diffusivity
!!!!: Stefan-Boltzmannn constant; Ts: Surface temperature
"""": emissivity coefficient; Ta: Air temperature
""""a: absorption coefficient; qs: Solar radiationhc: heat convection coefficient; :Albedo
Depth Independent heat flux based on
field measurement
2
2
x
T
C
k
t
T
!
!=
!
!
'
Modeling concept and mathematical expression
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THERMAL TRANSPORT Sample calculation results Comparison of sample calculations with field measurements, pavement
48-1068, Mar-1994.
Tem
pera
ture
(OC
) Te
mpe
ratu
re (O
C)
Tem
pera
ture
(OC
)
Han, Rongbin, Xin Jin, Charles J. Glover, Modeling Pavement Temperature for Use in Binder Oxidation Models and Pavement Performance Prediction, JMCE, in press.
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Transport Model Calculations of Binder Oxidation in Pavements (Texas)
Model from: Prapaitrakul et al., Rd Mtls and Pvmt Des, 10, 95-113 (2009) CJG, IWABM 9-16-10
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Transport Model Calculations of Binder Hardening in Pavements (Minnesota)
Model from: Prapaitrakul et al., Rd Mtls and Pvmt Des, 10, 95-113 (2009) CJG, IWABM 9-16-10
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Pavement Performance Depends upon:
Pavement Performance
Mixture Parameters
Binder Rheology (z,t)
Pavement T(z,t)
Meteorology
Traffic and Thermal Loading
Pavement Structure
Mixture Fatigue Resistance
Hardening Susceptibility (HS)
Oxidation kinetics; Diffusivity
DSR Function
Mixture Performance Characteristics
Master Curves
Model
CA(z,t)
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Summary • Binder oxidation occurs in pavements • Oxidation kinetics can be described by parallel
fast-rate and constant-rate reactions • The fast-rate reaction is product limited; the
constant-rate reaction proceeds indefinitely • Oxygen diffusivity correlates well to T and binder
viscosity (base binder for PMA). Fines affect diffusivity in accordance with common models
• Oxidative hardening adversely affects mixture fatigue life and thus pavement durability
• A transport model serves as a foundation for pavement performance predictions
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Acknowledgments
• Texas Department of Transportation • Federal Highway Administration, ARC • Texas Transportation Institute • Artie McFerrin Department of Chemical
Engineering
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References
Martin, K. L., R. R. Davison, C. J. Glover, and J. A. Bullin, “Asphalt Aging in Texas Roads and Test Sections,” Transp. Res. Rec., 1269, 9-19 (1990).
Burr, B. L., R. R. Davison, C. J. Glover, and J. A. Bullin, “Solvent Removal from Asphalt,” Transp. Res. Rec., 1269, 1-8 (1990).
Burr, B. L., R. R. Davison, H. B. Jemison, C. J. Glover, and J. A. Bullin, “Asphalt Hardening in Extraction Solvents,” Transp. Res. Rec., 1323, 70-76 (1991).
Cipione, C. A., R. R. Davison, B. L. Burr, C. J. Glover, and J. A. Bullin, “Evaluation of Solvents for the Extraction of Residual Asphalt from Aggregates,” Transp. Res. Rec., 1323, 47-52 (1991).
Lau, C. K., K. M. Lunsford, C. J. Glover, R. R. Davison, and J. A. Bullin, “Reaction Rates and Hardening Susceptibilities as Determined from POV Aging of Asphalts,” Transp. Res. Rec., 1342, 50-57 (1992).
Burr, B. L., Davison, R. R., Glover, C. J., and J. A. Bullin, “Softening of Asphalts in Dilute Solutions at Primary Distillation Conditions”, Transp. Res. Rec., 1436, 47-53 (1994).
Liu, M., K.M. Lunsford, R.R. Davison, C.J. Glover and J.A. Bullin, “The Kinetics of Carbonyl Formation in Asphalt,” AIChE J., 42(4), 1069-1076 (1996). (Includes pressure effects).
Liu, M., Lin, M.S., Chaffin, J.M., Davison, R.R., Glover, C.J. and Bullin, J.A., “Oxidation Kinetics of Asphalt Corbett Fractions and Compositional Dependence of Asphalt Oxidation,” Petroleum Sci. and Technol., 16(7&8), 827-850 (1998).
Liu, M., Ferry, M.A., Davison, R.R., Glover, C.J. and Bullin, J.A., “Oxygen Uptake as Correlated to Carbonyl Growth in Aged Asphalts and Asphalt Corbett Fractions,” Ind. Eng. Chem. Res., 37, 4669-4674 (1998).
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References (Cont’d)
Liu, M., Chaffin, J.M., Davison, R.R., Glover, C.J. and Bullin, J.A., “Changes in Corbett Fraction Composition during Oxidation of Asphalt Fractions,” Transp. Res. Rec., 1638, 40-46 (1998).
Domke, C.H., Davison, R.R., and Glover, C.J., “Effect of Oxidation Pressure on Asphalt Hardening Susceptibility,” Transp. Res. Rec., 1661, 114-121 (1999).
Domke, C.H., Davison, R.R. and Glover, C.J., “Effect of Oxygen Pressure on Asphalt Oxidation Kinetics,” Ind. Eng. Chem. Res., 39(3), 592-598 (2000).
Chipps, J.F., Davison, R.R. and Glover, C.J., “A Model for Oxidative Aging of Rubber- Modified Asphalts and Implications to Performance Analysis,” Energy and Fuels, 15, 637-647 (2001).
Ruan, Y., Davison, R.R., and Glover, C.J., “An Investigation of Asphalt Durability: Relationships between Ductility and Rheological Properties for Unmodified Asphalts,” Petroleum Science and Technology, 21(1&2), 231-254 (2003).
Ruan, Y., Davison, R.R. and Glover, C.J., “The Effect of Long-Term Oxidation on the Rheological Properties of Polymer Modified Asphalts,” Fuel, 82(14), 1763-1773 (2003).
Ruan, Y., Davison, R.R. and Glover, C.J., “Oxidation and Viscosity Hardening of Polymer Modified Asphalts,” Energy and Fuels, 17(4), 991-998 (2003).
Al-Azri, N.A.., Jung, S.H., Lunsford, K.M., Ferry, A., Bullin, J.A., Davison, R.R., and Glover, C.J., “Binder Oxidative Aging in Texas Pavements: Hardening Rates, Hardening Susceptibilities, and the Impact of Pavement Depth,” Transp. Res. Rec., 1962, 12-20 (2006).
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References (Cont’d)
Walubita, L.F., Epps Martin, A., Glover, C.J., Jung, S.H., Cleveland, G.C., Lytton, R.L, and Park, E.S., “Application of the Calibrated Mechanistic Approach with Surface Energy (CMSE) Measurements for Fatigue Characterization of Asphalt Mixtures,” J. Assoc. of Asphalt Paving Technol., 75, 457-490 (2006).
Woo, W. J., Hilbrich, J. H., and Glover, C. J. “Loss of Polymer Modified Binder Durability with Oxidative Aging: Base Binder Stiffening vs. Polymer Degradation,” Transp. Res. Rec., 1998, 38-46 (2007).
Woo, W. J., Chowdhury, A., and Glover, C. J. “Field Aging of Unmodified Asphalt Binder in Three Texas Long-Term Performance Pavements,” Transp. Res. Rec., 2051, 15-22 (2008).
Prapaitrakul N., Jin X., Han R., and Glover, C. J. “A Transport Model of Asphalt Binder Oxidation in Pavements,” Road Materials and Pavement Design, 10 (Special Issue), 95-113 (2009).
Juristyarini, P., Davison, R.R. and Glover, C.J., “Development of an Asphalt Aging Procedure to Assess Long-Term Binder Performance,” Petroleum Science and Technology, in press.
Juristyarini, P., Davison, R.R. and Glover, C.J., “Oxidation and Hardening Kinetics of rheological Function G’/(h’/G’),” Petroleum Science and Technology, in press.
Han, Rongbin, Jin, Xin., and Glover, C. J., “Modeling Pavement Temperature for Use in Binder Oxidation Models and Pavement Performance Prediction,” Journal of Materials in Civil Engineering, in press.
Jin, Xin and Glover, C.J., Fast-rate; constant-rate oxidation kinetics, presented at the 47th Petersen Asphalt Research Conference, July 2010, and paper in preparation.
Han, Rongbin and Glover, C.J., Oxygen Diffusivity in Asphalt, presented at the 47th Petersen Asphalt Research Conference, July 2010, and paper in preparation.
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