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 [email protected]
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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Kraton, the Kraton logo and design, the Cariflex logo, Cariflex, Nexar and the Giving Innovators Their Edge tagline and, in some cases, their expression in other languages are trademarks of Kraton Performance Polymers, Inc. and are registered in many countries throughout the world
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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