Petersen Conference 2004/JPP/07-04 1 Jean Jean-Pascal Planche Pascal Planche – Total France Total France Petersen Asphalt Research Conference 2004 Petersen Asphalt Research Conference 2004 Symposium on Additives Symposium on Additives After PIARC C8 Rome 1998, Total published results, and After PIARC C8 Rome 1998, Total published results, and others… others… Special Features Special Features of Polymer Modified Binders of Polymer Modified Binders
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Petersen Conference 2004/JPP/07-04 1
JeanJean--Pascal Planche Pascal Planche –– Total FranceTotal FrancePetersen Asphalt Research Conference 2004Petersen Asphalt Research Conference 2004
Symposium on AdditivesSymposium on Additives
After PIARC C8 Rome 1998, Total published results, and After PIARC C8 Rome 1998, Total published results, and others…others…
Special Features Special Features of Polymer Modified Bindersof Polymer Modified Binders
2Petersen Conference 2004/JPP/07-04
Contents
•• Main polymer used in Bitumen modificationMain polymer used in Bitumen modification•• General mechanism of bitumen modificationGeneral mechanism of bitumen modification•• Special features of PmB’sSpecial features of PmB’s
-- Polymer nature and structure influencePolymer nature and structure influence•• Plastomer modified bindersPlastomer modified binders•• Elastomer modified bindersElastomer modified binders
-- Relationships microstructure Relationships microstructure –– propertiesproperties•• Base asphalt influenceBase asphalt influence•• Effect on ageing stabilityEffect on ageing stability•• Effect on storage stabilityEffect on storage stability
ELASTOMERS FOR BITUMEN MODIFICATIONSTRUCTURE of THERMOPLASTIC ELASTOMERSSTRUCTURE of THERMOPLASTIC ELASTOMERS
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Various styrene Various styrene contentscontentsMw = 180000Mw = 180000
00 200200 400400 600600 80080000
1010
2020
3030
Elongation (%)Elongation (%)
Str
ess
(S
tres
s ( M
Pa
MP
a ))
7575
1515
303039395555
6363
ELASTOMERS FOR BITUMEN MODIFICATIONINFLUENCE of the STYRENE CONTENT on SBS INFLUENCE of the STYRENE CONTENT on SBS ELASTOMER PROPERTIESELASTOMER PROPERTIES
Diani Diani et al Eurobitume 1989et al Eurobitume 1989
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ELASTOMERS FOR BITUMEN MODIFICATION
INFLUENCE of MACROSTRUCTURE on SBS VISCOUS INFLUENCE of MACROSTRUCTURE on SBS VISCOUS BEHAVIOURBEHAVIOUR T = 140 °CT = 140 °C
•• Thermoplastic elastomer featuresThermoplastic elastomer features-- Soft (PB) and hard blocks (PS), incompatibleSoft (PB) and hard blocks (PS), incompatible
•• Elastomers for bitumen modification: mainly SB(S)Elastomers for bitumen modification: mainly SB(S)-- Block copolymers with radial or linear structuresBlock copolymers with radial or linear structures
-- Styrene content between 15 and 30% Styrene content between 15 and 30%
-- Mw between 80000 and 300000 DaltonsMw between 80000 and 300000 Daltons
•• Plastomer featuresPlastomer features-- Soft (coSoft (co--monomer effect) and hard crystalline segments (PE)monomer effect) and hard crystalline segments (PE)
-- Physical properties, Cristallinity and Mw (MI) dependentPhysical properties, Cristallinity and Mw (MI) dependent
•• Plastomers for bitumen modification: mainly EVAPlastomers for bitumen modification: mainly EVA-- Melt flow index 5 to 150Melt flow index 5 to 150
-- VA content between 15 and 35% (by weight)VA content between 15 and 35% (by weight)
-- Functional ethylene copolymers coming into playFunctional ethylene copolymers coming into play
PLASTOMER MODIFIED BINDERSEMA modified BITUMENSEMA modified BITUMENSInfluence of Melt Index (Mw) on R&B softening pointInfluence of Melt Index (Mw) on R&B softening point
•• TheThe relaxation relaxation is shifted towards higher temperatureis shifted towards higher temperatureas as polymerpolymer content content increasesincreases
Environmental chamber at Environmental chamber at --20°C20°CCutting of the rupture faces for Cutting of the rupture faces for CSEMCSEM or or ESEMESEM observationsobservations
PParticle pullarticle pull--out (crack deflection) without (crack deflection) with
Plastic Deformation of SBS NodulesPlastic Deformation of SBS Nodules
SBS in rubbery state SBS in rubbery state ðð High KHigh KICIC
AfterAfter Lapalu et al, Eurobitume 2000Lapalu et al, Eurobitume 2000
Petersen Conference 2004/JPP/07-04 44
PolymerPolymer--modified Bitumens modified Bitumens agingagingAfter L. Lapalu, JAfter L. Lapalu, J--P. Planche, V. Mouillet, P. Dumas, F. P. Planche, V. Mouillet, P. Dumas, F. Durrieu Durrieu –– Eurobitume Eurobitume Eurasphalt Eurasphalt Congress May 2004Congress May 2004
Collaboration between TOTAL and the LCPCCollaboration between TOTAL and the LCPC
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Formation and association of polar molecules during ageing
Aged bitumens
0
30
60
90
1E+01 1E+03 1E+05 1E+07
BcBc after RTFOT + PAV Bo after RTFOT+PAV
G* (Pa)
1E+09
Plain bitumensPlain bitumens
ð More « elastic » behavior of the bitumenð Oxidation effect more pronounced for Bo
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after ageing
0
30
60
90
1E+01 1E+03 1E+05 1E+07 1E+09G* (Pa)
Del
ta (
°)
Bc after RTFOT+PAVBc-EVA (6%) after RTFOT+PAVBc-SBS* (6%) after RTFOT+PAV
• After ageing, EVA is not oxidized but its compatibility with the oxidised bitumen matrix decreases, compared to SBS which keeps its reinforcement properties
Effect of polymer nature : EVA vs. SBSEffect of polymer nature : EVA vs. SBS
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EVA EVA mBmB microstructure evolutionmicrostructure evolutionafter after DurrieuDurrieu et alet al
Before ageingBefore ageing
ÆÆ Phase inversion @ 6% EVAPhase inversion @ 6% EVA
ÆÆ EVAEVA swollen by slightly swollen by slightly condensed aromatics condensed aromatics substituted by aliphaticssubstituted by aliphatics7.6%
0.8%+ 6% EVA
7.6%7.6%7.6%
0.8%+ 6% EVA
7.6%
0.8%+ 6% EVA
7.6%7.6%
After RTFOT+PAV ageingAfter RTFOT+PAV ageing
ÆÆ Increase in EVA content in Increase in EVA content in the nodulesthe nodules
ÆÆ Stability of aromatics, but Stability of aromatics, but decrease in aliphatics and decrease in aliphatics and condensedcondensed
àà migration of the fraction migration of the fraction involved in EVA swelling to involved in EVA swelling to the surrounding matrixthe surrounding matrix
9.2%
0.4%+ 6% EVA
9.2%
0.4%+ 6% EVA
9.2%
0.4%+ 6% EVA
9.2%
0.4%+ 6% EVA
9.2%
0.4%+ 6% EVA
9.2%
0.4%+ 6% EVA
9.2%
0.4%+ 6% EVA
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0
30
60
90
1E+01 1E+03 1E+05 1E+07 1E+09G* (Pa)
Bc-SBSlin (3%)Bc-Styr1 (3%)Bc-SBSlin (3%) after RTFOT+PAVBc-Styr1 (3%) after RTFOT+PAVBc-Styr1 (6%) after RTFOT+PAV
Effect of a crosslinking reactionEffect of a crosslinking reaction
• In case of crosslinked PmB's, the polymer and the matrix remain compatible after ageing •è elasticity on a large domain of temperature
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Effect of the bitumen base: physical blendsEffect of the bitumen base: physical blends
In case of physical blends prepared out of oxidablebitumen (Bo), the compatibility between the polymer and the matrix is bad before and after ageingð Poor rheological properties
0
30
60
90
1E+01 1E+03 1E+05 1E+07 1E+09
G* (Pa)
Bo-SBSlin (6%)
Bo-SBSlin (6%) after RTFOT+PAV
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PmB Aging: Impact on low temperature PmB Aging: Impact on low temperature propertiesproperties
Bc + XL SBSEVA/BA
Bo + XLSBS
EVA/BA
•• AC evolution is a function of its AC evolution is a function of its oxidabilityoxidability•• Influence of AC Influence of AC oxidabilityoxidability on the PmBon the PmB•• Positive effect of the X linked PmBPositive effect of the X linked PmB•• Negative impact of the EVA type polymersNegative impact of the EVA type polymers
0
5
10
15
20
D T
iso
(°C
)
Bc 3 XLl3 XLr
6 XLl6 XLr
3 SBSl
3 SBSr
6 SBSl
6 SBSr
3 EVA6 EVA
3 EBA
6 EBABo 3 XLl
3 XLr6 XLl
6 XLr3 SBS l
3 SBSr
6 SBS l
6 SBSr
3 EVA6 EVA
3 EBA6 EBA
D Tiso 300
D Tiso 300
BBR parameters evolution vs. RTFOT+PAV aging
D T iso 0.3
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Conclusions : what to keep in mind ?Conclusions : what to keep in mind ?
•• Modified binders are complex organized molecular Modified binders are complex organized molecular systemssystems
•• They are highly dependent of polymerThey are highly dependent of polymer-- NatureNature
-- StructureStructure
-- Concentration … but …Concentration … but …
•• not only ! They also depend :not only ! They also depend :-- on bitumen nature and gradeon bitumen nature and grade
-- Mixing processMixing process
-- Addition of oils or crosslinking reagentsAddition of oils or crosslinking reagents
•• Finally, care should be given to characterization toolsFinally, care should be given to characterization tools-- relevance, artifacts, accuracy…relevance, artifacts, accuracy…
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Thank you for your attentionThank you for your attention
•• Have a nice ride on a road paved with Polymer Have a nice ride on a road paved with Polymer Modified AsphaltModified Asphalt