recycled plastics for performance ... - dow chemical company
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RECYCLED PLASTICS FOR PERFORMANCE GRADED ASPHALTS
C.J. DUBOIS*, HAYLEY BROWN, RISHI MUNJ, CRISTINA SERRAT
DOW INC.
PACKAGING & SPECIALTY PLASTICS
DOW TEXAS INNOVATION CENTER, LAKE JACKSON, TX
July 15th, 2019
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
Dow
Gerardo Cespedes
Sean Doughty
Ann Johnson
Preston McDaniel
Leslie O’Leary
Cyndi Rickey
Testing Support - Andrew Hanz, MTE
Commercial Partners
Martin Asphalt
American Materials
Vernor Material & Equipment
Bit-Mat Products/K-Tech Specialty Coatings
Central Asphalt - Fisher Companies
Midland County Road Commission
ACKNOWLEDGEMENTS
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
What applications are PLASTICS used?
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
Recycled plastic use in pavement has bipartisan support in US House and Senate
US Senate Environmental and Public Works Committee is considering funding research to study recycled plastics as part of the 2019 Highway Bill
Save Our Seas 2.0 also has research monies allocated in the latest draft
Key stakeholder groups such as AI, NAPA, and NCAT have kicked-off work groups
INTEREST IN RECYCLED PLASTICS IS GROWING
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WHAT COMPONENTS ARE WE TALKING ABOUT?
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
Pure saturated hydrocarbon in most cases, but insoluble in asphalt
Semi-crystalline: Poorer intermediate and low temperature performance
Elastic properties of a PE-modified binder are inferior
Commercial attempts have been unsuccessful
Can a compatibilizer solve separation and improve low/intermediate temperature performance while enabling the blend to meet all other performance properties?
POLYETHYLENE (PE) IN ASPHALT BINDERS
EVA, EBA
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
SUMMARY
• RET enables the use of polyethylene-rich recycled plastics (RPE) in Performance Graded Asphalts– Exceed TX DOT PG 70-22 and MDOT PG64-28P performance specifications
• Alone RPE does not pass– ASTM D5976 – 48 hour separation test
– AASHTO M320 or M332 – Performance Grading
• Binders containing RPE with RET meet above– Including intermediate and low temperature performance criteria
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
Reactive terminal functionality of bitumen
S
S
O
NHNH2NNH
O
NHO
OHO
OH
HOO
OOHOO
O
OO O
HO
O
OO
HOO
asphalteneor resin
O
RET Modified Asphalt
RET reactive group
thermal via SN1
OO
HO
O
O
RET Modified Asphalt
OP
O
OH
accelerated via co-reactant
OO
O
O
OP
O
O
rapid cyclization
RET REACTS CHEMICALLY WITH ASPHALT FUNCTIONAL GROUPS
0 1 2 3 4 574
76
78
80
82
Time Post-PPA addition / minutes
Per
form
ance
Gra
de
62
64
66
68
70
72
74
Ph
ase An
gle
Non-Polar/Polar sections soluble in asphaltReactive elastic propertiesControlled crystallinity tunable temperature performance
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
EXPERIMENTAL SUMMARY
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
• Two asphalt binders – PADD 2 (Marathon Detroit) and PADD 3 (Valero)
• One RPE for each
• Valero – linear low density PE-rich system (LLDPE)
• Marathon – low density PE-rich system (LDPE)
• Partial factorial DOE chosen to balance exploration of RPE/RET dosage interaction and minimize experiments
• PPA fixed at 20 wt % of RET
10
DESIGN OF EXPERIMENT
2.001.751.501.251.000.750.50
1.3
1.2
1.1
1.0
0.9
0.8
0.7
0.6
0.5
PCR
EP
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Scatterplot of EP1177 vs PCR
RET
%
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2.0
1.5
1.0
0.5
0.0
PCR
EP
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Scatterplot of EP1177 vs PCR
RET
%
RPE % RPE %
Valero binder – PADD 3PE-rich Post-Consumer
Marathon binder – PADD 2PE-rich Post-Industrial
Plus 3% RPE + 1.8% SBS + 0.2% BGA control
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
ASTM D5976 (48 HOUR SEPARATION TEST) – RET IMPROVES SEPARATION VALUES
RPE RET
RPE RET
PADD 3 binder exhibits a large response vs RET and RPE dosage
PADD 2 binder exhibits minimal response vs dosage
PADD 3
PADD 2
Separation - PADD 2 and 3 binders display increased with RPE and decreased with RET
PCR
EP
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1.8
1.6
1.4
1.2
1.0
0.8
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0.0
>
–
–
–
–
–
–
< 0
0 2
2 4
4 10
10 20
20 30
30 40
40
°C
Separation
Contour Plot of Separation °C vs EP1177, PCR
RET
%
RPE %
PADD 3
PCR
EP
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1.2
0.8
>
–
–
–
–
–
–
< 0
0 2
2 4
4 10
10 20
20 30
30 40
40
separation
48 hr
Contour Plot of 48 hr separation vs EP1177, PCR
RET
%
RPE %
PADD 2
• = SBS control
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
OPTICAL MICROSCOPY COMPARISON OF MODIFIED ASPHALT – PADD 3 BINDER
• No distinguishable differences between base binder and RET-only sample• RPE-only sample displayed distinguishable domains• Combination of RPE and RET demonstrated differences vs RPE-control
Acknowledgement – Ann Johnson and Preston McDaniel
3% RPE + 0.2% PPABinder + 0.2% PPA 3% RPE + 1.8% RET + 0.2% PPA0% RPE + 1.8% RET + 0.2% PPA
No specific domains visible No specific domains visible
Low Magnification epi-Fluorescence Optical Images
Large domains visible Domains smaller than RPE control
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
LOW/INTERMEDIATE TEMPERATURE TESTING
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
PCR
EP
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1.2
0.8
>
–
–
–
< 2000
2000 3000
3000 4000
4000 5000
5000
G* x sin d 22C
Contour Plot of G* x sin d 22C vs EP1177, PCR
INTERMEDIATE TEMPERATURE TESTS – ALL DOSAGES MET SPECIFICATION
PCR
EP
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1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
>
–
–
–
< 2000.00
2000.00 3000.00
3000.00 4000.00
4000.00 5000.00
5000.00
G* x sin δ
Contour Plot of G* x sin δ vs EP1177, PCR
RPE RET
RPE RET
PADD 3
PADD 2
PADD 3 binder similar response vs dosage
PADD 2 binder similar response vs dosage
PADD 2 and 3 binders display increasing values with RPE and
decreasing with RET
RET
%
RPE %
RET
%
RPE %
PADD 3
PADD 2
• = SBS control
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
LOW TEMPERATURE TESTS – HIGHER RET % ENABLES RPE TO MEET SPECIFICATION
PCR
EP
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1.0
0.8
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0.2
0.0
>
–
–
–
< 150
150 200
200 250
250 300
300
S -12°C
Contour Plot of S -12°C vs EP1177, PCR
PCR
EP
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1.2
0.8
>
–
–
–
< 150.0
150.0 200.0
200.0 250.0
250.0 300.0
300.0
-18C S-value
Contour Plot of -18C S-value vs EP1177, PCR
maximum
PADD 3
PADD 2
PADD 3 binder slight RPE dosage effect
PADD 2 binder significant dosage effect with RET
PADD 2 and 3 binders display different dosage responses
RET
%
RPE %
RET
%
RPE %
RPE RET
RPE RET
PADD 3
PADD 2
• = SBS control (off-scale) 149 MPa
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
LOW TEMPERATURE TESTS – HIGHER RET % ENABLES RPE TO MEET SPECIFICATION
PCR
EP
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1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
>
–
–
–
< 0.30
0.30 0.31
0.31 0.32
0.32 0.33
0.33
m -12°C
Contour Plot of m -12°C vs EP1177, PCR
PCR
EP
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1.2
0.8
>
–
–
–
< 0.30
0.30 0.31
0.31 0.32
0.32 0.33
0.33
-18C m-value
Contour Plot of -18C m-value vs EP1177, PCR
RPE RET
maximum
maximum
RET
%
RPE %
RET
%
RPE %
RPE RET
PADD 3 binder significant RPE dosage effect
PADD 2 binder small RPE dosage effect
PADD 2 and 3 binders display similar dosage responses
PADD 3
PADD 2
• = SBS control
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
STIFFNESS-BASED TESTING
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PCR
EP
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1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
>
–
–
–
–
< 70
70 76
76 82
82 88
88 94
94
Cont
Upper
Contour Plot of Upper Cont vs EP1177, PCR
PADD 3RET
%
RPE %
UPPER CONTINUOUS GRADING – BOTH RPE AND RET IMPROVE PERFORANCE
RPE RET
PCR
EP
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1.2
0.8
>
–
–
< 64
64 67
67 70
70
PG
Upper
Contour Plot of Upper PG vs EP1177, PCR
minimum
preferred
RET
%
RPE %
PADD 2
PADD 3 binder significantly more responsive vs dosage
PADD 2 binder significantly less responsive vs dosage
PADD 2 and 3 binders display increased upper PG with both
RPE and RETRPE RET
PADD 3
PADD 2
• = SBS control
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
NON-RECOVERABLE CREEP – BOTH MATERIALS IMPROVE PERFORMANCE
PCR
EP
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1.2
0.8
>
–
–
–
< 0.5
0.5 1.0
1.0 2.0
2.0 4.0
4.0
Jnr3.2
58C
Contour Plot of 58C Jnr3.2 vs EP1177, PCR
PCR
EP
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1.6
1.4
1.2
1.0
0.8
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0.4
0.2
0.0
>
–
–
–
< 0.5
0.5 1.0
1.0 2.0
2.0 4.0
4.0
67°C Jnr3.2
Contour Plot of 67°C Jnr3.2 vs EP1177, PCR
RET
%
RPE %
RET
%
RPE %
PADD 3 binder significantly more responsive vs dosage
PADD 2 binder more response to RET vs dosage
PADD 2 and 3 binders display improved Jnr,3.2 with both RPE and RET
RPE RET
RPE RET
• = SBS control
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
ELASTIC PROPERTY TESTING
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PCR
EP
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0.8
>
–
–
–
–
–
< 20.0
20.0 30.0
30.0 40.0
40.0 50.0
50.0 60.0
60.0 70.0
70.0
25C ER
Contour Plot of 25C ER vs EP1177, PCR
ELASTIC RECOVERY – COMBINATION OF RET AND RPE MEET PERFORMANCE
minimum
PCR
EP
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1.0
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0.0
>
–
–
–
–
–
< 0.2
0.2 0.3
0.3 0.4
0.4 0.5
0.5 0.6
0.6 0.7
0.7
10°C ER
Contour Plot of 10°C ER vs EP1177, PCR
PADD 3
PADD 2
PADD 3 binder most responsive to RET vs dosage
PADD 2 binder most responsive to RET vs dosage
PADD 2 and 3 binders display similar dosage responses
RET
%
RPE %
RET
%
RPE %
RPE RET
RPE RET
PADD 3
PADD 2
SBS control with RPE = 52%
• = SBS control
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
PCR
EP
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1.2
0.8
>
–
–
–
–
–
–
< 20
20 30
30 40
40 50
50 60
60 70
70 80
80
58C %R3.2
Contour Plot of 58C %R3.2 vs EP1177, PCR
MSCR %R – COMBINATION OF RET AND RPE MEET PERFORMANCE
PCR
EP
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0.0
>
–
–
–
–
–
–
< 20
20 30
30 40
40 50
50 60
60 70
70 80
80
%R3.2
67°C
Contour Plot of 67°C %R3.2 vs EP1177, PCR
PADD 3
PADD 2
PADD 3
PADD 2
PADD 3 binder is highly reactive to RET
PADD 2 binder has high reactivity to RET
PADD 2 and 3 binders most responsive to RET dosage
RPE RET
RPE RET
RET
%
RPE %
RET
%
RPE %
SBS control with RPE = 52%
• = SBS control
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
PCR
EP
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1.8
1.6
1.4
1.2
1.0
0.8
0.6
0.4
0.2
0.0
>
–
–
–
< 65
65 70
70 75
75 80
80
δ
Contour Plot of δ vs EP1177, PCR
PHASE ANGLE – COMBINATION OF RET AND RPE MEET PERFORMANCE
PCR
EP
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1.2
0.8
>
–
–
–
< 65
65 70
70 75
75 80
80
d @ 64C
Contour Plot of d @ 64C vs EP1177, PCR
PADD 3
PADD 2
PADD 3
PADD 2
PADD 3 binder is highly reactive to RET
PADD 2 binder has high reactivity to RET
PADD 2 and 3 binders most responsive to RET dosage
RET
%
RPE %
RET
%
RPE %
RPE RET
RPE RET
• = SBS control
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
135°C VISCOSITY – RET HAS THE LARGEST DOSAGE RESPONSE
PCR
EP
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1.2
0.8
>
–
–
< 500.00
500.00 700.00
700.00 900.00
900.00
135C Vis
Contour Plot of 135C Vis vs EP1177, PCR
PCR
EP
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1.4
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1.0
0.8
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0.0
>
–
–
–
–
–
–
< 1000
1000 2000
2000 3000
3000 4000
4000 5000
5000 6000
6000 7000
7000
135°C Viscosity
Contour Plot of 135°C Viscosity vs EP1177, PCR
PADD 3
PADD 2
preferred
PADD 3 binder significantly more responsive vs dosage
PADD 2 binder significantly less responsive vs dosage
PADD 2 and 3 binders display increased viscosity with both
RPE and RET
RPE RET
RPE RET
maximum
RET
%
RPE %
RET
%
RPE %
PCR
EP
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1.6
1.2
0.8
>
–
–
< 500.00
500.00 700.00
700.00 900.00
900.00
135C Vis
Contour Plot of 135C Vis vs EP1177, PCR
• = SBS control
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FIELD PROJECTS
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
MET TX DOT PG70-22 BINDER SPECIFICATION
• Utilized 750 kg of LLDPE-rich recycled plastic in total 1 kT hot mix
• Blend of LLDPE-rich 1.5% Post-Consumer Recycle + 0.6% RET + 0.2% PPA• PCR supplier: Avangard Recycling (Houston TX)
• Texas DOT type D (340-DG-D) mix design - 1.50” lift thickness
• 5.2% asphalt binder with 19.1% RAP
• Limestone/dolomite aggregate
• Passed – AASHTO T322 Indirect Tensile (IDT) Strength Test
*Mix also contained 19% recycled asphalt pavement® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
FIELD PLACEMENT AT JOB SITE – NO DIFFERENCES THAN NORMAL PROJECT
® ™Trademark of The Dow Chemical Company ("Dow") or an affiliated company of Dow
THIS IS ONLY A STARTING POINT …
Planned Future Work
• Mix testing to validate performance - in progress– Hamburg
– IL-SCB
– IDEAL-CT
– DCT
• Glover-Rowe/Blackspace study of modified binders
• Optimize formulations to determine maximum recycled plastics loadings in asphalt binders with RET while meeting performance specifications
• More controlled demonstration projects to generate field data!
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Any physical properties described in this presentation are typical values and should not to be construed as specifications. Users should confirm results by their own tests.
Any photographs of end-use applications in this document represent potential end-use applications but do not necessarily represent current commercial applications, nor do they represent an endorsement by Dow of the actual products. Further, these photographs are for illustration purposes only and do not reflect either an endorsement or sponsorship of any other manufacturer for a specific potential end-use product or application, or for Dow, or specific products manufactured by Dow.
The data provided in this slide presentation was collected during 2019, and is included to illustrate approximate trends in the industry. The data provided in this slide presentation is given in good faith for informational purposes only. Dow assumes no obligation or liability for the industry data presented herein. NO WARRANTIES ARE GIVEN; ALL IMPLIED WARRANTIES OF MERCHANTABILITY OR FITNESS FOR A PARTICULAR PURPOSE ARE EXPRESSLY EXCLUDED.
No freedom from infringement of any patent owned by Dow or others is to be inferred. Because use conditions and applicable laws may differ from one location to another and may change with time, the user is responsible for determining whether products and the information in this document are appropriate for the user’s use and for ensuring that the user’s workplace and disposal practices are in compliance with applicable laws and other government enactments. The product(s) shown in this literature may not be available for sale and/or available in all geographies where Dow is represented. The claims made may not have been approved for use in all countries. References to "Dow" or the "Company" mean the Dow legal entity selling the products to the customer unless otherwise expressly noted.
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