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

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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

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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 4
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

D0243 Dispersion Linear SBS Dispersion

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

Property Test Method Spec Sample ID

58-28 52-34
D0243 + Linear SBS Pre-Mod Emulsion Base Asphalt
Latex D0243 Lin SBS
280°F Report 365 592
Brookfield Viscosity, cps AASHTO T316
300°F Report 232 367
Softening Point °F AASHTO T53 Report 125 114
Elastic Recovery, % 25°C AASHTO T301 Report 66 68
-----
58°C - 1.79
G*/sinδ, 10 rad/sec, kPa 64°C AASHTO T315 1.0 min 1.49 0.89
70°C 0.79 -----
Limiting Stiffness Temp °C AASHTO T315 Report 67.8 63.0

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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
Emulsion Preparation Parameters Latex D0243 Lin SBS
Polymer Loading Level, wt % on asphalt 3.0 3.0 3.0
Surfactant Loading Level, wt % on emulsion 0.30 0.30 0.37
Soap Solution pH 2.0 2.0 2.0
Asphalt Temperature,°F 285 280 330
Emulsified Asphalt - AASHTO T59 Test Method Spec Latex D0243 Lin SBS
Median, µm 8.1 2.3 5.7
Particle Size Distribution ----- Report
d90, µm 13.7 4.0 12.0
Saybolt Furol Viscosity, 50oC, sec ASTM D244 100-400 116 126 118
24 hrs 0.3 0.1 0
Storage Stability, % Diff ASTM D6930 <1.0
5 days 0.6 0 N/A
Demulsibility, % ASTM D6936 Report 63.6 82.2 96.4
Sieve, % ASTM D6933 <0.10 0.01 0.02 0.02
Residue by Distillation, 350°F/400°F, % ASTM D6997 >65.0 70.1 71.4 78.8
Residue by Evaporation, 325°F, % ASTM D6934 >65.0 69.9 70.4 77.1 10
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
methodsEvaporation Residue - ASTM D6934 Test Method Spec Latex D0243
Residue Content, % ASTM D6934 >65 69.9 70.4
o
PEN, 25 C, 100 g, 5 sec, dmm AASHTO T49 100-250 103 96
o
Softening Point, F AASHTO T53 Report 121 130
Ductility, 4oC, 5 cm/min, cm AASHTO T51 >30 94 23
Break, cm Report 100+ 57
Force Ductility Ratio, 4oC AASHTO T300
Force Ratio >0.30 0.11 0.49
o
Elastic Recovery, 10 C, % AASHTO T301 >50 68 73
Low Temp Residue - ASTM D7497 Test Method Spec Latex D0243
Residue Content % ASTM D7497 Report 71.5 71.2
Elastic Recovery, % 25°C AASHTO T301 Report 65 69
64°C 2.45 --
G*/sinδ, 10 rad/sec, kPa 70°C AASHTO T315 1.0 min 1.30 1.31
76°C 0.73 0.69
Limiting Stiffness Temp °C AASHTO T315 Report 72.7 72.5
MSCR Testing - AASHTO TP 70
% Recovery, 0.1 kPa 31.8 54.2
Jnr, 0.1 kPa 0.47 0.28
52°C AASHTO TP 70 Report
% Recovery, 3.2 kPa 20.0 45.8
Jnr, 3.2 kPa 0.58 0.35
% Recovery, 0.1 kPa 65.5 76.2
Jnr, 0.1 kPa 0.0038 0.0031
25°C AASHTO TP 70 Report
% Recovery, 3.2 kPa 62.3 75.9
Jnr, 3.2 kPa 0.0041 0.0033 12
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 16
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 18

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

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
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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 21
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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 ©2013 Kraton Performance Polymers, Inc. All rights reserved.

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