recycled plastics for performance ... - dow chemical company

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


What applications are PLASTICS used?


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


WHAT COMPONENTS ARE WE TALKING ABOUT?


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


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


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


EXPERIMENTAL SUMMARY


• 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

11

77

Scatterplot of EP1177 vs PCR

RET

%

3.02.52.01.51.00.50.0

2.0

1.5

1.0

0.5

0.0

PCR

EP

11

77

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


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

11

77

3.02.52.01.51.00.50.0

1.8

1.6

1.4

1.2

1.0

0.8

0.6

0.4

0.2

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

11

77

2.001.751.501.251.000.750.50

1.6

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


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


LOW/INTERMEDIATE TEMPERATURE TESTING


PCR

EP

11

77

2.001.751.501.251.000.750.50

1.6

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

11

77

3.02.52.01.51.00.50.0

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


LOW TEMPERATURE TESTS – HIGHER RET % ENABLES RPE TO MEET SPECIFICATION

PCR

EP

11

77

3.02.52.01.51.00.50.0

1.8

1.6

1.4

1.2

1.0

0.8

0.6

0.4

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

11

77

2.001.751.501.251.000.750.50

1.6

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


LOW TEMPERATURE TESTS – HIGHER RET % ENABLES RPE TO MEET SPECIFICATION

PCR

EP

11

77

3.02.52.01.51.00.50.0

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

11

77

2.001.751.501.251.000.750.50

1.6

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


STIFFNESS-BASED TESTING


PCR

EP

11

77

3.02.52.01.51.00.50.0

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

11

77

2.001.751.501.251.000.750.50

1.6

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


NON-RECOVERABLE CREEP – BOTH MATERIALS IMPROVE PERFORMANCE

PCR

EP

11

77

2.001.751.501.251.000.750.50

1.6

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

11

77

3.02.52.01.51.00.50.0

1.8

1.6

1.4

1.2

1.0

0.8

0.6

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 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


ELASTIC PROPERTY TESTING


PCR

EP

11

77

2.001.751.501.251.000.750.50

1.6

1.2

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

11

77

3.02.52.01.51.00.50.0

1.8

1.6

1.4

1.2

1.0

0.8

0.6

0.4

0.2

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


PCR

EP

11

77

2.001.751.501.251.000.750.50

1.6

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

11

77

3.02.52.01.51.00.50.0

1.8

1.6

1.4

1.2

1.0

0.8

0.6

0.4

0.2

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


PCR

EP

11

77

3.02.52.01.51.00.50.0

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

11

77

2.001.751.501.251.000.750.50

1.6

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


135°C VISCOSITY – RET HAS THE LARGEST DOSAGE RESPONSE

PCR

EP

11

77

2.001.751.501.251.000.750.50

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

PCR

EP

11

77

3.02.52.01.51.00.50.0

1.8

1.6

1.4

1.2

1.0

0.8

0.6

0.4

0.2

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 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

11

77

2.001.751.501.251.000.750.50

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


FIELD PROJECTS


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


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!


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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recycled plastics for performance ... - dow chemical company

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