ASPHALT SOLIDIFICATION no 2 Asphalt Solidification Asphalt Solidification Model Equilibrium

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Transcript of ASPHALT SOLIDIFICATION no 2 Asphalt Solidification Asphalt Solidification Model Equilibrium

  • ASPHALT SOLIDIFICATION THEORY Troy Pauli, Appy Beemer, and Julie Miller

    43rd Petersen Asphalt Research Conference Pavement Performance Prediction Symposium June 21-23, 2005 Laramie, Wyoming Models Used to Predict Pavement Performance Compositional Models Session

  • ACKNOWLEDGEMENTS

    FHWA for their Financial Support under Contract No. DTFH61-98-R-00093

    NCHRP 9-37: Using Surface Energy Measurements to Select Materials for Asphalt Performance

    ICAR-505: Surface Energy Measurements as Performance Indicators of Hot-Mix Asphalts (HMA) and Portland Cement Concrete (PCC) Performance

  • Towards a Unified Physico-Chemical Model of Asphalt Binder

    Asphalt Microstructure Model Introduction to micro-Emulsion Colloid Mechanics The Onion Model and Colligative Properties Equilibrium Thermodynamics in micro-Emulsion Colloid Mechanics Kinetics in micro-Emulsion Colloid Mechanics

    Asphalt Solidification Model Equilibrium Thermodynamics of Surfaces and Interfaces Phase Transformations and Colligative Properties non-Equilibrium Thermodynamics of Surface micro-Structuring Dissipative Structure Theory Application to Fracture Mechanics

    Further Thoughts on Fatigue and Moisture Damage, Rutting, and Thermal Cracking

  • Asphalt Surface Energy And Molecular Structure

    Dependence of Surface Energy On Molecular Weight

    And Molecular Structure

  • Some onions may have thick layers

    While other onions will have thin layers

  • Number of Carbon Atoms in Molecule

    0 20 40 60 80 100

    S ur

    fa ce

    E ne

    rg y,

    γ , e

    rg s/

    cm 2

    0

    20

    40

    60

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    100

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    140 # of C vs alkanes predicted-alkanes

    Surface Energy vs. #C-atoms (Homologous Series)

    R CH3

    n-Alkanes

  • Number of Carbon Atoms in Molecule

    0 20 40 60 80 100

    S ur

    fa ce

    E ne

    rg y,

    γ , e

    rg s/

    cm 2

    0

    20

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    140 # of C vs alkanes # of C vs aromatic chains predicted-alkanes predicted-aromatics

    Aromatic Chains

  • Number of Carbon Atoms in Molecule

    0 20 40 60 80 100

    S ur

    fa ce

    E ne

    rg y,

    γ , e

    rg s/

    cm 2

    0

    20

    40

    60

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    140 # of C vs alkanes # of C vs aromatic chains # of C vs aromatic sheets predicted-alkanes predicted-aromatics

    Aromatic Chains

    Aromatic Sheets

  • Number of Carbon Atoms in Molecule

    0 20 40 60 80 100

    S ur

    fa ce

    E ne

    rg y,

    γ , e

    rg s/

    cm 2

    0

    20

    40

    60

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    140 # of C vs alkanes # of C vs alicyclic chains # of C vs aromatic chains # of C vs aromatic sheets predicted-alkanes predicted-aromatics predicted-cyclics

    Aromatic Chains

    Aromatic Sheets

    Alicyclic Chains

  • Number of Carbon Atoms in Molecule

    0 20 40 60 80 100

    S ur

    fa ce

    E ne

    rg y,

    γ , e

    rg s/

    cm 2

    0

    20

    40

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    140 # of C vs alkanes # of C vs alicyclic chains # of C vs aromatic chains # of C vs ketones # of C vs aromatic sheets predicted-alkanes predicted-aromatics predicted-cyclics # of C vs alicyclic sheets

    Aromatic Chains

    Aromatic Sheets

    Alicyclic Chains

    Alicyclic Sheets

  • Molecular Formula = C42 H65 N S2 Formula Weight = 648.104 Composition = C(77.83%) H(10.11%) N(2.16%) S(9.90%) Index of Refraction = 1.556 ± 0.02 Surface Tension = 39.8 ± 3.0 dyne/cm Density = 1.006 ± 0.06 g/cm3

    AAD-1

    Jennings, P.W. et al., SHRP-A-335, Strategic Highway Research Program, National Research Council, Washington, DC, 1993.

    CH3

    CH3

    NH CH3

    CH3

    CH3

    Molecular Formula = C85 H135 N Formula Weight = 1170.988 Composition = C(87.18%) H(11.62%) N(1.20%) Index of Refraction = 1.561 ± 0.03 Surface Tension = 44.3 ± 5.0 dyne/cm Density = 0.98 ± 0.1 g/cm3 AAM-1

  • Number of Carbon Atoms in Molecule

    0 20 40 60 80 100

    S ur

    fa ce

    E ne

    rg y,

    γ , e

    rg s/

    cm 2

    0

    20

    40

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    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

    SHRP Asphalts

  • Number of Carbon Atoms in Molecule

    0 20 40 60 80 100

    S ur

    fa ce

    E ne

    rg y,

    γ , e

    rg s/

    cm 2

    0

    20

    40

    60

    80

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    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 AFM

    SHRP Asphalts

  • Number of Carbon Atoms in Molecule

    0 20 40 60 80 100

    S ur

    fa ce

    E ne

    rg y,

    γ , e

    rg s/

    cm 2

    0

    20

    40

    60

    80

    100

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    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

    SHRP Asphalts

  • Number of Carbon Atoms in Molecule

    0 20 40 60 80 100 120

    S ur

    fa ce

    E ne

    rg y,

    γ , e

    rg s/

    cm 2

    0

    20

    40

    60

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    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 # of C vs Col 20

    Alicyclic Sheets

  • Number of Carbon Atoms in Molecule

    0 20 40 60 80 100 120

    S ur

    fa ce

    E ne

    rg y,

    γ , e

    rg s/

    cm 2

    0

    20

    40

    60

    80

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    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 # of C vs Col 20

    Alicyclic Sheets

  • Number of Carbon Atoms in Molecule

    0 20 40 60 80 100 120

    S ur

    fa ce

    E ne

    rg y,

    γ , e

    rg s/

    cm 2

    0

    20

    40

    60

    80

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    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 # of C vs Col 20

    Alicyclic Sheets

  • Physical Properties, Number Average Molecular Weight, Density, Refractive Index and Surface Tensions (AFM Measurement) Measured and Reported for Eight SHRP Asphalts

    83.9, 59 82.3, 60 86.5, 70 81.6, 52 84.5, 61 85.6, 50 83.7, 61 86.8, 87

    46.3± 4.7 47.3± 0.7 44.0± 6.4 40.1± 4.3 48.3± 5.4

    38.1 45.6 49.0

    1.565 1.560 1.535 1.555 1.560 1.540 1.530 1.530

    1.016 1.024 1.009 1.023 1.024 1.018 1.024 0.989

    850 870 970 770 870 700 870 1200

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

    %C a, # of

    Carbons

    Surface Tension γ, ergs/cm2

    AFM

    Index of Refraction

    n(RI)

    Density b ρ, g/mL

    Number Average Molecular Weight

    a Mn , Da Sample

  • Solubility Parameters Calculated, Based on AFM, NMR and Asphalt Average Molecular Structure Surface Tension, Density and Molecular Weight

    8.20 8.27 7.94 7.60 8.20 8.39 7.86 7.99

    8.06 ± 0.26

    8.13 8.19 7.80 7.76 8.26 7.69 8.06 7.90

    7.97 ± 0.21

    8.00 7.91 7.81 7.91 7.68 7.68 7.69 7.58

    7.78 ± 0.15 8.23

    8.18 b 8.02

    AAA-1 AAB-1 AAC-1 AAD-1 AAF-1 AAG-1 AAK-1 AAM-1 AVERAGE Alicyclic sheet (C42 H60) Cyclohexane Methylcyclohexane

    δ, cal1/2/mL3/2 by γ(NMR) d

    δ, cal1/2/mL3/2 by γ(AFM) c

    δ, cal1/2/mL3/2 by γ(AMS) a

    Solubility Parameter Sample

    ( )

    43.0

    3/1/M 1.4 ⎟⎟

    ⎞ ⎜⎜ ⎝

    ρ γ

    ≈δ

  • Solubility Parameters Calculated, Based on AFM, NMR and Asphalt Average Molecular Structure Surface Tension, Density and Molecular Weight

    8.20 8.27 7.94 7.60 8.20 8.39 7.86 7.99

    8.06 ± 0.26

    8.13 8.19 7.80 7.76 8.26 7.69 8.06 7.90

    7.97 ± 0.21

    8.00 7.91 7.81 7.91 7.68 7.68 7.69 7.58

    7.78 ± 0.15 8.23

    8.18 b 8.02

    AAA-1 A