Asphalt Emulsion VOC Testing Presentation To PPRA Meeting Florida - 2016 Arlis Kadrmas
Presentation Outline Background Why VOC testing of emulsified asphalt? Recovery Procedures used for residue VOC testing Distillation Low Temperature Evaporation VOC Procedures ASTM D6886 EPA 25 BASF TVOC Procedure Test Results Conclusions
Background Why VOC testing? Request to ASTM for VOC Method ASTM subcommittee on Emulsion Testing was asked for methods of measuring VOC on emulsions (as is, and applied) They were currently using the %oil distillate from D6997 as the VOC s of emulsions Subcommittee decided that the %oil distillate did not give an accurate reading, as most felt it gives too high of a measurement for VOC s Subcommittee decided since no Standard existed, to gather data to check validity before making any decisions
Background testing plan Emulsion Type and Formulation Round 1 - Standard Micro-surfacing Emulsion 1.4% imidazoline and 3.75% cationic SBR 64% Residue 2 nd set post-added cutters and added a cutback Round 2 - Customer Emulsions (anionic and inverted) Test Emulsions and Residues for VOC content Modified ASTM D6997 Distillation Procedure Low Temperature Evaporation Procedure
Distillation Apparatus ASTM D6997
Modifications to D6997 Distillation Residue Recovery Technique ASTM D6997 - Distillation High Temperature 500ºF (260ºC), but reduced to 350ºF for polymer/latex modified emulsions, but Still much higher than pavement surface temperatures that these materials are applied, and expected to perform under.
Evaporation Procedure ASTM D7497 ASTM D7497 Procedure Procedure similar to EN13074 60 grams in silicone mold 24 hours in 25ºC forced air oven 24 hours in 60ºC forced air oven Issues 48 hours to get sample for testing Oven racks checked for level
Evaporation Setup ASTM D7497
TVOC Method Background Uses dry headspace-capillary gas chromatographic analysis BASF Method chosen, modification of ASTM procedure. Based on VOC definition given in decision 1099/10/EG (Dec.18, 2008) of the European Commission EPA procedure uses solvent that will not work with asphalt residues TVOC Procedure Highlights Calibration curves developed with known solvents Calculates VOC of materials with boiling points < 250 o C
Math Test for ppm to %oil distillate 1,000 ppm is 0.1% 5,000 ppm is 0.5% 10,000 ppm is 1% 50,000 ppm is 5% 100,000 ppm is 10% < 5,000 ppm is the limit on calling a paint product VOC-free
Initial VOC Data on Micro-surfacing Asphalt Emulsions Data on base micro-surfacing emulsions and residues Sample I.D. TVOC/ppm NS 58-28 257 Emulsion (NS58-28 base) 448 350 o F DistRes (NS58-28 Emul.) 80 LTR-A (NS58-28 Emulsion) 326 NS 64-22 218 350 o F DistRes (NS64-22 Emul.) 152 Emulsion (NS64-22 base) 492 LTR-A (NS64-22 Emulsion) 85 350 o F distillations only had a trace of oil distillate
Initial VOC Data Analysis Procedure can work well with emulsions and the residues from the emulsions Good data on asphalt bases Emulsion values are also acceptable, and can be tested satisfactorily Recovered residue can be tested and the values are in line with what is expected Secondary Testing PG58-28 based emulsion had distillates post-added for analysis Cutback was produced for evaluation
Second Set - VOC Data on Micro-surfacing Asphalt Emulsions Sample I.D. TVOC/ppm NS 58-28 + 20% #2 fuel oil cutback* 44207 Emulsion (NS58-28 base) + 5% naphtha 21745 350 o F DistRes (NS58-28 Emul. + naphtha) 1054 LTR-A (NS58-28 Emulsion + naphtha) 2564 Emulsion (NS58-28 base) + 5% diesel* 6135 350 o F DistRes (NS58-28 Emul. + diesel)* 3318 LTR-A (NS58-28 Emulsion + diesel)* 2244
Oil Distillate from Modified ASTM D6997 of Emulsions with added cutters ASTM D6997 Emulsion + 5% Naphtha 7.5 mm of oil distillate ASTM D6997 Emulsion + 5% Diesel 2.5 mm of oil distillate Penetration 5% Naphtha 5% Diesel Pen 25 C 106 D5 81 141 Pen 25 C 106 D5 79 135 Pen 25 C 106 D5 80 138 AVG 80.0 138.0
Second Set - VOC Data Analysis Procedure showed good evaluation of the emulsions with 5% post-added naphtha and diesel fuel Emulsions had much higher VOC than the residues Residue evaluation makes sense based on temperatures used to recover that residue The emulsions with diesel fuel had the VOC testing that went beyond the 250 o C temperature, which is the reason for the (*) Cutback Testing Values are in line with what is expected for the product
Round Two - VOC Data on Customer emulsions from cold climate area Sample I.D. TVOC/ppm HFE-150SP Emulsion 21212 350 o F DistRes (HFE-150SP Emulsion) 11672 LTR-A (HFE150SP Emulsion) 11105 HF-150S Emulsion 13984 350 o F DistRes (HFE-150S Emulsion) 10303 LTR-A (HFE-150S Emulsion) 6162 SS-1 Emulsion 5310 350 o F DistRes (SS-1 Emulsion) 3642 LTR-A (SS-1 Emulsion) 3682 VIE Emulsion 129436 LTR-A (VIE Inverted Emulsion) 13610 The data is an average of two tests on each material
Oil Distillate from Modified ASTM D6997 of Round Two Customer Emulsions ASTM D6997 HFE-150SP Emulsion 5.5 mm of oil distillate ASTM D6997 SS-1 Emulsion 2.0 mm of oil distillate ASTM D6997 HF-150S Emulsion 4.5 mm of oil distillate Penetration HFE-150SP SS-1 HF-150S Pen 25 C ASTM D5 175 191 Hit Pen 25 C ASTM D5 177 190 Bottom Pen 25 C ASTM D5 173 189 of cup AVG 175.0 190.0 0.0
Round Two Customer VOC Data Analysis Emulsions from customer showed variation in VOC levels with the cool weather emulsions There is a variation in VOC due to possible cutter differences The inverted emulsion had a very high VOC level and may need to have further evaluation The VOC numbers from the %oil distillate were still well above the VOC level from the test procedure One emulsion had close values
VOC Comparison Emulsified Asphalts Oil Distillate vs. Measured Emulsion Type % Oil Dist. VOC OD VOC Measured Micro (PG58-28) trace 0 448 +5% naphtha 7.5ml = 3.75% 37500 21745 +5% diesel 2.5ml = 1.25% 12500 6135 HFE-150SP 5.5ml = 2.75% 27500 21212 HF-150S 4.5ml = 2.25% 22500 13984 SS-1 2.0ml = 1.0% 10000 5310
Comments and Conclusions TVOC procedures can be run on emulsions and their residues successfully Asphalt emulsions without petroleum distillate addition are well below the 5000 ppm that is the baseline for VOC-free product designations Using 2% (bwe) or less of any petroleum distillate will usually fall below 5000ppm measured VOC The VOC measurements based on test measurements are lower than those based on VOC calculated on %oil distillate
Questions? Arlis Kadrmas BASF Corporation 1547 Woodridge Drive Wichita, KS 67206 E-mail: arlis.kadrmas@basf.com Phone: (316) 200-7326