High Vinyl SB/S Copolymers for Modified Asphalt Emulsion Applications

Chris Lubbers

Tech. Sales and Market Development Manager – Emulsions Kraton Performance Polymers, Inc.

15710 John F. Kennedy Blvd. Suite 300

Houston, TX 77032 chris.lubbers@kraton.com

936-524-9262

AEMA Annual Meeting February 19-22, 2013

Indian Wells, CA

Outline Asphalt emulsion polymer modification primer

High vinyl butadiene (Bd) SB/S technology overview

Pre-modified chip seal base asphalt properties

Chip seal emulsion and residue properties

Job story – CRS-2P in Madison County, NE

HiMA micro surfacing program 6 wt% Kraton D0243 in softer base AC Job Stories – MN, MO, and TX 2

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What are Polymers?

Comprised of many small molecules Poly = many

Monomers = small molecules or repeat units

Monomers chemically react larger molecules Water-based polymers – latex form (SBR, NR latex)

Solvent-based polymers – pellets, bale (SB-,SBS)

Properties are determined by: Types and sequence of monomers

Molecular weight

Polymer Modification of Asphalt Emulsions – SBR

Add latex external to asphalt

Methods soap batching co-milling – soap line co-milling – asphalt line

Polymers – SBR, NR latex Lower asphalt process T No special mill, handling

Polymer in water phase Continuous polymer film formation on curing

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Polymer Modification of Asphalt Emulsions – SB/S

Emulsify polymer modified asphalt

“Pre-modified” emulsion Polymers – SBS, SB- Higher mod. asphalt viscosity Higher asphalt + mill temp. Exit temp. > 100oC Heat exchanger, back pressure

Polymer inside asphalt droplet

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High Vinyl Butadiene SB/S Technology Butadiene monomer addition via 1,2 vs 1,4 polymerization

Results in smaller effective molecular volume for same MW

Thermal reactivity of 1,2 vinyl Bd pendant groups

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High Vinyl Butadiene SB/S for Emulsions

High vinyl Bd microstructure leads to: Improved compatibility in pre-modified base asphalt Substantially reduced viscosity at a given loading level Eliminates emulsification issues associated with SB/S

No need for specialized equipment, storage, or handling

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Pre-Modified Asphalt Props. – Chip Seal Base asphalt – PG 52-34/200 dmm PEN

Calumet Specialty Refining, LLC – Superior, WI 3 wt% dry polymer loading on asphalt Vs conventional linear SBS

Improved compatibility – D0243 vs Linear SBS

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D0243 Dispersion Linear SBS Dispersion

Pre-Modified Asphalt Props. – Chip Seal Substantially reduced asphalt viscosity

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Test Method Spec58-28Latex D0243 Lin SBS

280°F Report 365 592300°F Report 232 367

Softening Point °F AASHTO T53 Report 125 114Elastic Recovery, % 25°C AASHTO T301 Report 66 68

58°C - 1.7964°C 1.49 0.8970°C 0.79 -----

Limiting Stiffness Temp °C AASHTO T315 Report 67.8 63.0

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G*/sinδ, 10 rad/sec, kPa AASHTO T315 1.0 min

Property Sample ID

D0243 + Linear SBS Pre-Mod Emulsion Base Asphalt 52-34

Brookfield Viscosity, cps AASHTO T316

CRS-2P Emulsion – Form. + Liquid Props. Base asphalt – PG 52-28 for Latex + PG 52-34 for SB/S

Calumet Specialty Refining, LLC – Superior, WI 3 wt% dry polymer loading on asphalt Charlotte G5 continuous pilot mill

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Latex D0243 Lin SBS3.0 3.0 3.0

0.30 0.30 0.372.0 2.0 2.0285 280 330

Test Method Spec Latex D0243 Lin SBSMedian, µm 8.1 2.3 5.7

d90, µm 13.7 4.0 12.0ASTM D244 100-400 116 126 118

24 hrs 0.3 0.1 05 days 0.6 0 N/A

ASTM D6936 Report 63.6 82.2 96.4ASTM D6933 <0.10 0.01 0.02 0.02ASTM D6997 >65.0 70.1 71.4 78.8ASTM D6934 >65.0 69.9 70.4 77.1

Demulsibility, %Sieve, %

Residue by Distillation, 350°F/400°F, %Residue by Evaporation, 325°F, %

Emulsified Asphalt - AASHTO T59

Particle Size Distribution ----- Report

Saybolt Furol Viscosity, 50oC, sec

Storage Stability, % Diff ASTM D6930 <1.0

Emulsion Preparation ParametersPolymer Loading Level, wt % on asphalt

Surfactant Loading Level, wt % on emulsionSoap Solution pH

Asphalt Temperature,°F

CRS-2P Emulsion – Part. Size/Distribution D0243 req’d lowest feed T + gen’d lowest/narrowest

PS/PSD

Needed back-pressure and heat exchange for linear SBS Generated poor quality emulsion at high residue content

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CRS-2P Emulsion Residue Testing D6934 oven-evaporated and D7497 low T recovery

methods

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Test Method Spec Latex D0243ASTM D6934 >65 69.9 70.4AASHTO T49 100-250 103 96AASHTO T53 Report 121 130AASHTO T51 >30 94 23

Break, cm Report 100+ 57Force Ratio >0.30 0.11 0.49

AASHTO T301 >50 68 73Test Method Spec Latex D0243

Residue Content % ASTM D7497 Report 71.5 71.2Elastic Recovery, % 25°C AASHTO T301 Report 65 69

64°C 2.45 --70°C 1.30 1.3176°C 0.73 0.69

Limiting Stiffness Temp °C AASHTO T315 Report 72.7 72.5

% Recovery, 0.1 kPa 31.8 54.2Jnr, 0.1 kPa 0.47 0.28

% Recovery, 3.2 kPa 20.0 45.8Jnr, 3.2 kPa 0.58 0.35

% Recovery, 0.1 kPa 65.5 76.2Jnr, 0.1 kPa 0.0038 0.0031

% Recovery, 3.2 kPa 62.3 75.9Jnr, 3.2 kPa 0.0041 0.0033

MSCR Testing - AASHTO TP 70

52°C AASHTO TP 70 Report

25°C AASHTO TP 70 Report

AASHTO T300

Elastic Recovery, 10oC, %Low Temp Residue - ASTM D7497

G*/sinδ, 10 rad/sec, kPa AASHTO T315 1.0 min

Evaporation Residue - ASTM D6934Residue Content, %

PEN, 25oC, 100 g, 5 sec, dmmSoftening Point, oF

Ductility, 4oC, 5 cm/min, cm

Force Ductility Ratio, 4oC

CRS-2P w/Hi Vinyl SBS – Madison Cty, NE

Chip seals key PP treatment in NE – state and local agencies Emulsion producer – Jebro, Inc. – Sioux City, IA

Difficulty in past using conventional SBS Required back pressure and/or heat exchange Poor storage, viscosity, and shear stability

150,000 gallons of CRS-2P used on job Stored at 180oF without continuous agitation

Contractor – Sta-bilt Construction Co. – Harlan, IA Emulsion applied at 175oF at 0.25 gallons/yd2

Crushed gravel – 100% passing 3/8”, 3% passing #200 Application rate – 22 to 25 lbs/yd2

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CRS-2P w/Hi Vinyl SBS – Producer Obs. “We [can now] store SBS polymer-modified emulsion for up to two weeks without any loss of stability…Even with good storage stability, the emulsion bonds with the cover stone very quickly after application. This helps the chip seal develop strength shortly after application and minimizes the chance of aggregate loss”

Kevin Carlson – Technical Director, Jebro

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CRS-2P w/Hi Vinyl SBS - Contractor Obs. “Now we’re working with this new type of SBS polymer-modified emulsion from Jebro. It isn’t gummy, it’s less viscous, and it doesn’t come off the distributor nozzle in strings on a windy day like some emulsions do”

Keith Burchett – VP, Sta-bilt Construction Co.

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HiMA Micro Surfacing Emulsion Program 6 wt% D0243 in PG 58-28 base AC Standard AC for conventional micro emulsion – PG 64-22 Softer base for colder climates – i.e. PG xx-34 in Minnesota

More durable, fatigue resistance mat Improved resistance to reflective and thermal cracking?

Participating contractors

ASTECH – St. Joseph, MN Vance Brothers, Inc. – Kansas City, MO Viking Construction – Georgetown, TX

NCAT – Auburn University Pavement preservation research program w/State

DOT’s/FP2

Feeder road/track sections – when distresses develop Lee Road – distressed sections – lower PCI

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MN HiMA Micro Surfacing Job Story

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MN HiMA Micro Surfacing Project – 6/2013

Emulsion producer – Flint Hills Resources – Wichita, KS

6 wt% D0243 in PG xx-34 base AC – >200 dmm PEN SP – 156oF PEN – 122 dmm at 25C

Control – 3.5 dry wt% cationic SBR latex in PG 64-22 base AC

Two trial sections

MN Road Cell #1 – Interstate 94 – 16 wt% emulsion with no control ADT – 28,000 vehicles/day including heavy truck traffic

TH 23 – 13 wt% emulsion with control ADT – >5000 vehicles/day PCC slab (original) + 6 in. of bituminous concrete (‘98) + chip seal

(‘04)

Contractor – ASTECH Corporation – St. Joseph, MN Leveling course and surface course applied to both trial sections

Type II gradation Application rate – net 30 lbs/yd2

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HiMA Micro Emulsion Application Mn Road Cell #1 – Before/After – 6/2013

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Before Passing Lane – PG 58-28 Asphalt Concrete – 12 yrs old over PCC slab

Slow Lane – PG xx-34 Asphalt Concrete – 6 yrs old over PCC slab

MO HiMA Micro Surfacing Job Story

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MO HiMA Micro Surfacing Project – 7/2013 Emulsion producer – Vance Brothers – Kansas City, MO

6 wt% D0243 in PG 58-28 base AC SP – 180+oF, PEN – 65-70 dmm at 25C

Control – 3.0-3.5 dry wt% cationic SBR latex in PG 64-22 base AC SP – 140+oF, PEN – 40-90 dmm at 25C

Trial sections – 13 wt% emulsion

20 cul-de-sacs in Lee’s Summit, MO – suburb of Kansas City, MO Residential neighborhood, BUT Two to five, 40,000 lb front-axle trash trucks per day Control micro surfacing mat failed

Contractor – Vance Brothers – Kansas City, MO Single course applied Type II gradation HiMA – Limestone aggregate Control – Granite aggregate Aliti t 24 25 lb / d2

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HiMA Micro Emulsion Application Cul-de-Sac – Lee’s Summit, MO – 7/2013

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TX HiMA Micro Surfacing Job Story

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TX HiMA Micro Surfacing Project – 7/2013

Emulsion producer – Ergon, Inc. – Jackson, MS

6 wt% D0243 in PG 58-28 base AC

Control – 3.0 dry wt% cationic SBR latex in PG 64-22 base AC

Trial sections – 12 to13 wt% emulsion City of Dallas, TX Collector road as well as residential street

Contractor – Viking Construction – Georgetown, TX Single course applied Type II gradation Application rate – 26 lbs/yd2

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HiMA Micro Emulsion Application City Street – Dallas, TX – 9/2013

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HiMA Micro Surfacing Projects Field Observations

HiMA emulsion handled/applied/cured ~ control systems No special requirements for storage/handling/application

Initial durability/toughness of HiMA mat >> control systems Resistance to reflective cracking ~ control systems

4th HiMA Trial w/Ergon/Sealcoating, Inc. – Hingham, MA Applied at end of season in much cooler, wet conditions in the NE HiMA micro emulsion more “forgiving” under adverse conditions?

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Publication Disclaimer We believe the information set forth above to be true and accurate,

but any findings, recommendations or suggestions that may be made in the foregoing text are without any warranty or guarantee whatsoever, and shall establish no legal duty or responsibility on the part of the authors or any Kraton Polymers entity. Furthermore, nothing set forth above shall be construed as a recommendation to use any product in conflict with any existing patent rights. All Kraton Polymers entities expressly disclaim any and all liability for any damages or injuries arising out of any activities relating in any way to this publication or the information set forth herein.

©2013 Kraton Performance Polymers, Inc. All rights reserved.

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