Update on Research into the Phosphoric Acid Modification of Asphalt John D Angelo Office of Pavement Technology 1
Effect of Acid Grade and Asphalt Source All acid grades give similar stiffness increase Grades containing water may give foaming problems Stiffness change is asphalt dependent
Degrres Centigrade Acid has varied effect on different asphalts Effect of 115% PPA Acid Modification on Original PG Grade 160 150 140 130 120 110 100 90 80 AAD-1 AAK-1 AAM-1 ABM-1 60% Bach 94% Bach Whiting Holly 70 60 0 1 2 3 4 % Acid
Moisture Sensitivity Does adding a hydrophilic material like phosphoric acid impart moisture sensitivity to the binder?
Moisture Sensitivity BBR Beams and DT samples of neat binder and 50% mastics were soaked in a 45 o F water bath Beams were dried with a paper towel and weighed For this Asphalt (Citgo) water absorption increases with increasing PPA particularly at levels greater than 1-1.5%
Hamburg Testing Rationale There is no perfect test to measure stripping We chose Hamburg at 50 o C The tests are not meant to be exhaustive Criterion is Does PPA make it better or worse Tests are done in duplicate Both results are shown on the charts
Materials Used Asphalt from Citgo Stripping Sandstone Aggregate from MD (Banned by MDDOT) Limestone Aggregate from MD Granite from GA Amine Antistrip from Arr-Mazz- LA-2, LOF65-00 Non Amine from Innophos Innovalt-W (a phosphate ester) Lime from Chemical Lime Company
Rut Depth mm Hamburg 50degC Citgo Asphalt Lime Treated Sandstone Aggreagte 35 30 25 20 15 10 5 0 Control 1% Lime 1% Lime 0.5% PPA 1% Lime 3% PPA 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 Passes
Rut Depth mm Hamburg 50degC Citgo Asphalt Lime Treated Limestone Aggregate 35 30 25 20 15 10 Control Control 1% Lime 1% Lime 1% Lime 1% PPA 1% Lime 1% PPA 5 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 Passes
Rut Depth mm Hamburg 50degC Citgo Asphalt GA Granite Aggregate 35 30 25 Control Control 1% Lime 1% Lime 1% Lime 1% PPA 1% Lime 1% PPA 20 15 10 5 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 Passes
Lime Treated Aggregate Lime showed up very well in the tests Stripping was unaffected by PPA modification
Rut Depth mm Hamburg 50degC Citgo Asphalt Sandstone Aggregate 35 30 25 20 15 Control Control 0.5% LA-2 0.5% LA-2 0.5% LA-2 1% PPA 0.5% LA-2 1% PPA 10 5 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 Passes
Rut Depth mm 35 30 25 20 15 0.5% LA-2 0.5% LA-2 0.5% LA-2 1% PPA 0.5% LA-2 1% PPA Control Control Hamburg 50degC Citgo Asphalt Limestone Aggregate 10 5 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 Passes
Rut Depth mm Hamburg 50degC Citgo Asphalt GA Granite Aggregate 35 30 25 Control Control 0.5% LA-2 0.5% LA-2 0.5% LA-2 1% PPA 0.5% LA-2 1% PPA 20 15 10 5 0 0 2000 4000 6000 8000 10000 12000 14000 16000 18000 20000 Passes
Conclusions Hamburg Testing Test is only an indication and was with a single asphalt PPA increased moisture sensitivity of the neat binders Action of amine and phosphate ester antistrips is aggregate specific- PPA generally increases moisture sensitivity With lime treated aggregates the moisture sensitivity is unaffected by PPA modification Users need to test each asphalt/aggregate/antistrip combination.
Degree C Binders mixed with limestone agg. and extracted 76 70 64 Asphalt 1 Asphalt 1 & PPA 58 Control Limestone 1 Limestone 2 Limestone 3
Effect of Limestone Aggregate on PPA modified binder Multiple Limestone aggregates, Dolomitic, Calcium Carbonate, did not neutralize the PPA modified binders. There was no loss of PG grade. 20
degree C Binders mixed with hydrated lime and then extracted. Original Binder Lime Treated Binder-Recovered PPA + Lime Treated Binder-Recovered Original Binder-Recovered Original Binder + PPA 82 76 70 64 58 52 Holly Oil #1 Holly Oil #2 CITGO Lion Oil Asphalt ID
Results of Lime Extraction Study The extraction of the lime from the original binder reduced the grade. This amount varied from binder to binder. In most cases the reduction in grade of PPA modified binder was similar to the reduction of grade of the base asphalt by the lime. 22
MSCR testing of binder with hydrated lime still in binder One binder source Lion Asphalt, 58-28 & 64-22. 1.2% PPA 20% lime by wt 9% by volume. Mix binders with Lime, Lime and PPA Evaluate binder properties with Lime still in the binder 23
continuous temp MSCR test of Lion binder & PPA mixed with hydrated lime as mastic. 80.0 60.0 56.8 59.9 MSCR PG S continuous temp 63.3 62.0 67.0 69.2 40.0 20.0 0.0-20.0-40.0-28.8-26.1-29.3-24.9-24.9-21.7 MSCR 3.2 1/kPa PAV DSR BBR S BBR m 24
MSCR testing of binder with hydrated lime still in binder Lime increased the stiffness of the binder 2 to 3 degrees. PPA increased the stiffness of the binder 6 degrees of one full grade. The combined lime and PPA only increased the grade 5 degrees. This is less than what would be expected from the combined, but only a 1/3 loss. 25
Processing and additive study One Binder NuStar 58-28 3% SBS linear polymer 0.5% PPA 0.02 % sulfur / % SBS Evaluate MSCR properties of blends of SBS and PPA with different processing procedures, using different mixing temperatures and times. 26
% Recovery at 3.2kPa and 64C, % Relationship of MSCR Jnr and % Recovery to processing and additives MSCR - Relationship of % Recovery vs J nr 100 80 60 Cross Linked + PPA PPA No PPA 188C - No PPA 200C - No PPA 188C - 0.5% PPA 200C - 0.5% PPA New Jnr Spec 40 Cross Linked 20 PG 64S-XX J nr <= 4.0 PG 64H-XX J nr <= 2.0 PG 64V-XX J nr <= 1.0 0 0.0 0.5 1.0 1.5 J nr at 3.2kPa and 64C, 1/kPa 27
Processing and additive study The combined PPA, SBS has a greater effect on the increase in stiffness and elastic response of the binder then either one by its self. PPA seems to act as a cross linker as well as a stiffener. 28
Fatigue Testing Binder Lab Ref Modification PG Grade Citgo B-6362 Control 64 Citgo B6362 1.1% PPA 76.2 Citgo B6362 3% Kraton 1101 74.3 Citgo B6362 1.5% Kraton 1101 + 0.5%PPA 74.6
Air Voids (%) Air Voids 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0 Control PPA ( 1.1% PPA) SBS (3.0% Kraton 1101) SBS+PPA (1.5% SBS and 0.5% PPA)
Number of cycles to failure Cycles to Failure 25000.0 20000.0 15000.0 10000.0 5000.0 0.0 Control PPA ( 1.1% PPA) SBS (3.0% Kraton 1101) SBS+PPA (1.5% SBS and 0.5% PPA)
PPA Workshop Fact and Fiction April 7 th and 8 th Minneapolis, MN 32
Thank You Questions 33