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Isocyanate-based Asphalt Additive Brian Orr Senior Asphalt Technologist
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Page 1: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Isocyanate-based Asphalt Additive

Brian Orr

Senior Asphalt Technologist

Page 2: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Agenda

2

Study Background

Research Project 1 Binder Study and Assessment

• PG Grading and UTI

Research Project 2 Paving Trials

• Rutting & Cracking

Research Project 3 Formulation Study and Assessment

• SBS + Isocyanate-based Modification

Conclusion

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 3: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

BASF Study Sponsor Located In Wyandotte, MI

San Diego, CA◼ Enzymes

Advanced Materials & System Research (GM)

Bioscience Research (GB)

Process Research & Chemical Engineering (GC)

Multiple Research units at one site

RTP, NC◼ Crop Protection

◼ Plant Technologies

Wyandotte, MI◼ Functional solutions◼ Polyurethanes and

specialty plastics

Charlotte, NC◼ Dispersions

and pigments◼ Care chemicals

Tarrytown, NY◼ Polymers ◼ Industrial Biotechnology◼ Functional fluids and

inorganic pigments

Iselin, NJ◼ Chemical & refining

catalysis◼ Environmental

catalysis

Houston, TX◼ Chemical

engineering

Beachwood, OH◼ Catalyst scale-up◼ Battery materials

3 © Copyright 2020 BASF Corporation; All Rights Reserved

Page 4: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Study Background

4

1. Asphalt has been modified since the

1960s to improve performance.

2. However, only a limited number of

modifiers are approved in asphalt.

3. Use of alternative modifiers might

yield several benefits.

• Less disruption in construction

due to shortage of modifiers

• Improved performance

• Reduced maintenance costs

▪ Source: AMAP Modifier Brochure© Copyright 2020 BASF Corporation; All Rights Reserved

Page 5: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Reactive Modifiers Show Great Promise in Asphalt

Current Reactive Polymers used as alternative modifiers in asphalt

▪ Reactive Terpolymers

▪ Reactive Copolymers

▪ Selected Epoxies

Isocyanate-based reactive modifiers

▪ Can these modifiers improve binder properties?

▪ Can these modifiers make binders equivalent to or better than conventionally modified binders?

5

© Copyright 2020 BASF Corporation; All Rights Reserved5

Page 6: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Construction

Appliance

Footwear

Synthetic leather

Spandex (textile)

Fertilizer

Automotive

Roofing

Tire Fill

Pipe Liners

Cast Elastomers

Packaging

Isocyanate-based Chemistry is Very Flexible

Common Industries & Applications

© Copyright 2020 BASF Corporation; All Rights Reserved6

Page 7: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Advantages - Replace rubber and plastics

Polyurethanes – Excellent Functional Properties

Polyurethanes Plastics Rubber Metal

Impact Resistance + -

Elastic Properties (shape

retention)+ -

Resilience (Rebound) + -

Low Temperature Resistance + -

Abrasion Resistance + - -

Load Bearing Capacity + -

Chemical/Corrosion Resistance + - -

Weight + -

Noise + -

Wear + -

© Copyright 2020 BASF Corporation; All Rights Reserved7

Page 8: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Isocyanate-based Asphalt Modification– A New Paradigm

8

Isocyanate-based modification paradigmCurrent modification paradigm

ELASTOMER & PLASTOMER

DRY SOLID

INCREASES VISCOSITY

BLENDED & CAN SEPARATE

THERMOPLASTIC

Isocyanate-based chemistries demonstrate utility in asphalt applications

ADHESIVE

LIQUID

LOW VISCOSITY

REACTIVE & DOES NOT SEPARATE

THERMOSET

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 9: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Isocyanate-based Modification Improves Functional Properties

▪ Isocyanate-based modification uses crosslinking instead of

physical mixing – increased binder performance and durability

▪ Isocyanate-based modification improves binder performance –

lower deformation of asphalt at high temperatures and same

properties at low temperatures

Paving grade binder

Standard asphalt modifiers Isocyanate-

based Modifier

9

CrosslinkingPhysical mixing

unmodified Isocyanate-based modification

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 10: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

3% SBS or 3% Isocyanate-based Modification

10

Isocyanate-based

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 11: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

2019 Petersen Asphalt

Research Conference Summary

11

TTI RESEARCH TEAM:

Pravat Karki, PI

Edith Arámbula Mercado, PI

David E. Newcomb, Sr. PI

Binder Study and Assessment

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 12: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

TTI Research Objectives

12

Evaluate the performance of binders modified with SBS and binders

modified with isocyanate-based modifier.

▪ Performance Grade

▪ UTI Expansion

Determine optimum dosage of isocyanate-based modifier that would

yield similar binder properties as SBS.

© Copyright 2020 BASF Corporation; All Rights Reserved

Solid Asphalt Modifier

Liquid Asphalt Modifier

Page 13: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

TTI Experimental Materials

13

Binders

PG 64-22: S1

PG 64-22: S2

PG 64-22: S3

PG 70-22: S4

PG 64-16: S5

Aging

Unaged

RTFO + PAV0

RTFO + PAV20

Tests

PG-High

PG-Low

Modification

0% (Control)

3% SBS: 𝑠

3% Isocyanate: 𝑖

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 14: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

PG Testing: High Temperature

14

High temperature continuous grade

▪ Increased with SBS

▪ Increased more with isocyanate-based

Lower % isocyanate-based modification could yield

equivalent high temperature PG. 77

73 74

93

77

64

70

76

82

88

94

100

S1 S2 S3

64-22 70-22 64-16

Neat 3s 3i

30

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 15: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

PG Testing: Low Temperature

15

Low temperature continuous grade

▪ Similar effects from SBS and isocyanate-based

modifier

Lower % of isocyanate-based modifier could

yield equivalent low temperature PG.

-24

-20-19

-21

-19

-34

-28

-22

-16

-10

S1 S2 S3

64-22 70-22 64-16

Neat 3s 3i

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 16: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

PG Testing: Useful Temperature Range

16

Useful Temperature Interval (UTI)

▪ Greater increase with Isocyanate-based modifier than

with SBS at equivalent loading

Lower % isocyanate-based modifier could yield

equivalent UTI.

102

94 93

114

96

80

92

104

116

128

S1 S2 S3

64-22 70-22 64-16

Neat 3s 3i

30

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 17: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

TTI Conclusions

© Copyright 2020 BASF Corporation; All Rights Reserved17

3% Isocyanate-based modifier compared to 3% SBS:

• Increased PG equivalent to same or more than SBS

• Increased UTI to equivalent to same or more than SBS

It may be possible to use less % of isocyanate-based modifier to achieve results equivalent to

3% of standard modification.

Page 18: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Establishing Operational Feasibility

Summer & Fall 2019

© Copyright 2020 BASF Corporation; All Rights Reserved

Paving Trials

18

Page 19: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Evaluating Operational Feasibility of Isocyanate-based Modification

Asphalt Terminal Mix Plant Construction

Stability

Mixing time

Reheat/recycle

Pumpability

Aggregate interaction

Stiffness

Performance

Compaction

Sticking/rolling

© Copyright 2020 BASF Corporation; All Rights Reserved19

Page 20: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

2019 Isocyanate-based Paving Trials in Europe and North America

20

Successful paving trials are crucial to assess environmental and paving conditions

Jun 2019 – Bavaria

◼ PWC site at A96

◼ 230 m, one layer

◼ First public paving

Sep 2019 – Westphalia

◼ Regional road

◼ 100 m, two layers

◼ 2nd layer paved in Nov

Sep 2019 – Midwest 1

◼ Four rural roads

◼ 7 miles, one layer

Oct 2019 – Midwest 2

◼ Neighborhood road

◼ ½ mile one layer

Oct 2019 – Munich

◼ City Autobahn 96, 0.5 km

◼ Asphalt laydown at

140 °C instead of 170°C

◼ Paving emissions

reduced by 35-65%Anecdotal Feedback “Excellent workability of mix while…,

containing 50% reclaimed asphalt”“Less asphalt smell and odor”

“Released well from off-loader”

“Great workability of mix at only 140 °C”

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 21: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Rutting Assessment: Midwest 1 Paving Trial

Hamburg Wheel Tracker (HWT) @50°C with reheated field sample

© Copyright 2020 BASF Corporation; All Rights Reserved21

Mixture Air Voids (%) Passes Rut Depth, mm Average

Control7 20,000

3.323.4

12% RAP / 4% RAS 3.41

Isocyanate-based

modifier7 20,000

4.043.9

12% RAP / 4% RAS 3.83

Page 22: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Cracking Assessment: Midwest 1 Paving Trial

IDEAL-CT at 25°C with reheated field sample

© Copyright 2020 BASF Corporation; All Rights Reserved22

MixtureAir Voids

(%)

Disp.

(mm)

Post-

Peak

Slope

(kN)

IDT

Strength

(kPa)

Fracture

Energy,

J/m2

CT IndexAvg. CT

IndexCOV, %

Control7.2 4.2 -4.1 867.6 6,658 45.7

41.6 6.66.9 3.9 -4.2 901.6 6,696 41.8

12% RAP / 4% RAS7 3.9 -4.2 911.4 6,529 40.6

6.8 3.6 -4.5 984.7 7,109 38.1

Isocyanate-based

Modifier

6.8 4.5 -2.9 825.8 7,186 75.7

73.8 6.76.5 4.9 -3.1 829.7 7,775 80.9

12% RAP / 4% RAS6.7 4.8 -3.2 845 7,031 69.6

6.9 4.6 -3.2 858.4 7,168 68.8

Page 23: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Summary: Midwest 1 Paving Trial

County paving trial

• Compared PG 58-28 to same binder modified to PG 64-28

• Mix design: DOT design, all crushed aggregate

• 12% RAP / 4 % RAS

• Same mix, only variable was adding isocyanate-based modifier

What was proven

• Normal paving, no surprises

• Little viscosity change when binder was modified

• No sticking, but very adhesive when cooled (tacky on shoes) →

happy contractor

• Improvement in IDEAL-CT (cracking resistance)

• Similar HWT results (rutting/stripping)

© Copyright 2020 BASF Corporation; All Rights Reserved23

Page 24: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

BASF Corporation Internal Study

© Copyright 2020 BASF Corporation; All Rights Reserved

Formulation Study and Assessment

24

Page 25: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

25

Formulation Study: Isocyanate-based, SBS, and Combined (PG 64-22)

Viscosity mPa.S (cP) SHRP Grading Temperature Range (°C)

Unmodified 404 64-22 91

1% Isocyanate-based Modifier 550 70-22 94

2% Isocyanate-based Modifier 675 70-22 97

3% Isocyanate-based Modifier 688 76-16 98

1% SBS 583 64-22 94

2% SBS 817 70-22 98

3% SBS 1138 76-22 101

1% SBS 1% Isocyanate-based Modifier 813 70-22 98

1% SBS 2% Isocyanate-based Modifier 938 76-22 105

1% SBS 3% Isocyanate-based Modifier 950 82-22 108

2% SBS 1% Isocyanate-based Modifier 1209 76-22 104

2% SBS 2% Isocyanate-based Modifier 1446 82-22 111

2% SBS 3% Isocyanate-based Modifier 1338 88-22 114

3% SBS 1% Isocyanate-based Modifier 1917 82-22 109

3% SBS 2% Isocyanate-based Modifier 2221 88-22 116

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 26: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

MSCR Results for SBS, Isocyanate-based, and Combined (PG64-22)

26

Key discovery: SBS + Isocyanate-based modification are highly complementary

ISO 1ISO 2

ISO 3

SBS 1

SBS 2

SBS 3

1S 1I1S 2I

1S 3I

2S 1I

2S 2I

2S 3I

3S 1I

3S 2I

0

20

40

60

80

100

120

0 0.5 1 1.5 2 2.5

% R

eco

very

Jnr, kPa-1

Indication of Elastic Response

y=29.371x^-0.2633

ISO 1

ISO 2

ISO 3

SBS 1

SBS 2

SBS 3

1S 1I

1S 2I

1S 3I

2S 1I

2S 2I

2S 3I

3S 1I

3S 2I

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 27: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Isocyanate-based Modification Research Conclusions

Binder Improvements

1. SBS compatibility and enhancement.

2. Significantly increased UTl.

3. Does not separate when stored after modification.

4. Limited increase in viscosity after modification.

5. No change to Superpave testing and PG Grading.

Mix Improvements

1. Superior binder and aggregate adhesion.

2. IDEAL-CT cracking resistance improved.

3. Better HWT rutting and no stripping.

4. Improved compaction with less roller passes.

5. Less asphalt build-up on truck beds and/or hand tools.

27

Isocyanate-based modification is an extremely promising innovation for asphalt applications

27 © Copyright 2020 BASF Corporation; All Rights Reserved

Page 28: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

Acknowledgements

28

Texas A & M Transportation Institute (TTI)

• Dr. Pravat Karki

• Dr. Edith Arambula

• Dr. Jon Epps

• Dr. David Newcomb

Western Research Institute

• Dr. Jean-Pascal Planche

• Dr. Michael Elwardany

Blankenship Asphalt Tech & Training

• Mr. Phillip Blankenship, P. E.

• Mr. Zachary McKay

© Copyright 2020 BASF Corporation; All Rights Reserved

Page 29: Senior Asphalt Technologist Isocyanate-based Asphalt Additive · Senior Asphalt Technologist. Agenda 2 Study Background Research Project 1 Binder Study and Assessment • PG Grading

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