Evaluating Applications of Field Spectroscopy Devices to Fingerprint Commonly Used Construction Materials (2013)

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179 Nuclear magnetic resonance (NMR) spectroscopy was applied to all materials included in Phase 2 experiments to verify the feasibility of identifying these materials and their compo- nents under laboratory conditions. NMR is known for its high effectiveness in identifying organic compounds, includ- ing hydrocarbons and compounds with heteroatoms, such as oxygen, nitrogen, sulfur, silicon, halogens, and others. For that reason, all materials that were soluble with no phase separation in D-chloroform (the solvent used for sample preparation) yielded meaningful NMR spectra. In most cases, the exact chemical formula of the matter was revealed (see Appendix H). Table M.1 summarizes the applicability of the NMR method to all materials included in the labora- tory phase of experiments. Once the feasibility of NMR spectroscopy was confirmed, especially for researching petroleum products, the team eval- uated the applicability of NMR to identifying the presence of modifiers, contaminants, and recycled asphalt pavement (RAP) in asphalt binders and hot-mix asphalt (HMA) mixes. In addition, an attempt was made to quantify the amount of modifiers and RAP based on NMR data. The results of these experiments are presented in Appendix O. A p p e n d i x M NMR Spectra

180 Table M.1. Summary of NMR Applicability Material Category Brand Name Applicability (Yes/No) Reason not Applicable Structural coatings Carbozinc 859 Part A Yes Carbozinc 859 Part B Yes Scotchkote 413 Part A Yes Scotchkote 413 Part B Yes Pavement markings All Weather paint white Yes LS 50 White Yes LS 50 Yellow Yes LS 50 Hardener Yes Epoxy adhesives for concrete repair Ultrabond 1100 Part A Yes Ultrabond 1100 Part B Yes Sikadur 31 Part A Yes Sikadur 31 Part B Yes Chemical admixtures for portland cement concrete (PCC) Air Mix 200 No Phase separation Retarder 75 Yes Accelguard 80 No Phase separation ADVA 190 Yes Curing compounds for PCC Sealtight 1100 Yes Safe-Cure 1200 Yes Safe-Cure Clear Yes Neat asphalt binders PG 58-28 Yes PG 64-22 Yes Polymer modifiers for asphalt binders Elvaloy 4170 Yes Kraton Yes Butonal Yes Asphalt emulsions CRS-1 Yes CRS-1P Yes Antistripping agents Kling Beta 2912 Yes Kling Beta 2700 Yes AD-here 65 Yes Polymer-modified asphalt binders PG 52-34 1.5% SBR Latex Yes PG 64-28 3.3% SBR Latex Yes PG 64-22E + 1%–6% SBS Yes RAP-modified asphalt binders PG 64-22W + RAP Yes Oxidation in RAP RAP mixes extracted from aggregate Yes RAP-modified HMA HMA + RAP + 1%–6% SBS Yes Antistripping-modified asphalt binders PG 64-22W + AD-here 65, Kling Beta 2912 Yes Cured epoxy adhesives for concrete repair Cured Ultrabond 1100 No Unable to dissolve Cured Sikadur 31 No Unable to dissolve

1.01.52.02.53.03.54.04.55.05.56.06.57.07.5 f1 (ppm) 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 In te ns ity Carbozinc 859 Part A 9. 18 5. 72 24 .7 8 6. 88 0. 93 0. 90 1. 00 25 .0 5 4. 71 0. 95 3. 51 3. 25 13 .9 6 1 2 3 4 5 6 7 1 2 3 4 5 6 7 CH38 CH3 9 10 11 12 13 14 15 O 16 O 17 18 1920 O 21 22 23 OH 24 12 O 3 4 Cl5 1 2 3 4 5 6 7 CH38 CH39 10 11 12 13 14 15 OH 16 OH 17 A B C D B1, 5 C1, 5 B2, 4 C2, 4 A7 A2-4 B19B20B24 C16 B18 B8 C8 Figure M.1. NMR spectrum for Carbozinc 859 Part A. 1.01.52.02.53.03.54.04.55.05.56.06.57.07.5 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 In te ns ity Carbozinc 859 Part B 5. 97 0. 39 3. 96 1. 00 3. 78 1 2 3 4 5 6 CH3 7 CH31 2 CH33 OH 4 A2-4 A7 A B B1 B2 B4 Figure M.2. NMR spectrum for Carbozinc 859 Part B. 181

1.01.52.02.53.03.54.04.55.05.56.06.57.0 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 In te ns ity Scotchkote 413 Part A 1. 73 0. 40 1. 59 1. 43 0. 98 1. 00 12 3 4 5 6 CH3123 O 4 12 O 3 12 O 3 CH31 CH32 Figure M.3. NMR spectrum for Scotchkote 413 Part A. 0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.8 f1 (ppm) -50 0 50 100 150 200 250 300 350 400 450 500 In te ns ity Scotchkote 413 Part B Figure M.4. NMR spectrum for Scotchkote 413 Part B. 182

183 0.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.8 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 In te ns ity All Weather Paint White Figure M.5. NMR spectrum for 3M All Weather white paint.

184 0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5 f1 (ppm) -200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 In te ns ity LS 50 Yellow 1. 07 1. 00 1. 06 5. 13 5. 22 1 2 3 4 5 6 7 CH38 CH3 9 10 11 12 13 14 15 O 16 O 17 18 1920 O 21 22 2324 O 25 1O 2 3 O 4 O 5 6 7 O 8 9 CH2 10 CH3 11 12 O 13 14CH2 15 O 16 17 CH2 18 A B A2, 4 A1, 5 B18 B18B17 A18 A8 A20 A19 B11 Figure M.6. NMR spectrum for Epoplex LS50 yellow paint.

185 0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5 f1 (ppm) -50 0 50 100 150 200 250 300 350 400 450 500 550 600 650 700 In te ns ity LS 50 Hardener 1. 11 0. 71 0. 47 0. 99 1. 00 0. 45 0. 53 0. 52 0. 11 NH21 2 3 NH 4 5 6 NH27 A1, 4, 7 A3, 5 A2, 6 1 2 3 4 5 6 7 CH38 CH39 10 11 12 13 14 15 OH 16 OH 17 B B2, 4, 12, 14 B1, 5, 11, 15 B8, 9 1 2 3 4 5 6 7 8 9 1011 12 1314 OH 15 CH316C C10, 11, 13, 14 C4-9 A Figure M.7. NMR spectrum for Epoplex LS50 hardener.

186 1.01.52.02.53.03.54.04.55.05.56.06.57.0 f1 (ppm) -200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 In te ns ity Ultrabond 1100 Part A 0. 71 1. 54 1. 04 0. 60 0. 52 0. 55 1. 01 1. 00 1 2 3 4 5 6 7 CH38 CH39 10 11 12 13 14 15 O 16 O 17 18 1920 O 21 22 2324 O 25 A A2, 4 A1, 5 A18 A8 A20 A19 Figure M.8. NMR spectrum for Ultrabond 1100 Part A.

187 0.51.01.52.02.53.03.54.04.55.05.56.06.57.07.5 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 In te ns ity Ultrabond 1100 Part B 0. 59 1. 54 2. 72 2. 07 0. 92 1. 25 1. 00 1 2 3 4 5 6 7 8 9 1011 12 13 14 OH 15 CH3 16 A10, 11, 13, 14 A4-9 A A16 1 NH 2 3 4 N 5 6 7 8 NH29 B1, 3 B7 B4, 6, 8 B9 B Figure M.9. NMR spectrum for Ultrabond 1100 Part B.

188 1.01.52.02.53.03.54.04.55.05.56.06.57.0 f1 (ppm) -200 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 In te ns ity Sikadur 31 Part A 0. 94 3. 09 0. 91 0. 87 0. 88 0. 93 1. 00 1. 95 1. 99 1 2 3 4 5 6 7 CH38 CH39 10 11 12 13 14 15 O 16 O 17 18 1920 O 21 22 23 24 O 25 A A2, 4 A1, 5 A18 A8 A20 A19 Figure M.10. NMR spectrum for Sikadur 31 Part A.

189 1.01.52.02.53.03.54.04.55.05.56.06.57.07.5 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 In te ns ity Sikadur 31 Part B 0. 87 1. 97 1. 71 2. 49 0. 31 0. 70 0. 52 1. 00 0. 30 3. 81 Figure M.11. NMR spectrum for Sikadur 31 Part B.

190 0.70.91.11.31.51.71.92.12.32.52.72.93.13.33.53.73.9 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 In te ns ity Air Mix 200 0. 68 1. 00 0. 88 water Figure M.12. NMR spectrum for Air Mix 200.

191 1.11.31.51.71.92.12.32.52.72.93.13.33.53.73.94.1 f1 (ppm) -200 -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000 2100 In te ns ity Retarder 75 1. 03 2. 06 1. 00 1. 00 OH 1 2 3 4 5 6 7 O- 8 OH 9 OH 10 OH 11 OH 12 O 13 Figure M.13. NMR spectrum for Eucon Retarder 75.

192 0.00.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.65.86.0 f1 (ppm) -50 0 50 100 150 200 250 300 350 400 450 500 550 In te ns ity Accelguard 80 Figure M.14. NMR spectrum for Accelguard 80.

193 0.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.4 f1 (ppm) -50 0 50 100 150 200 250 300 350 400 450 500 550 600 In te ns ity Adva 190 0. 08 1. 00 0. 11 * 1 2 3 * 4 5 O 6 CH3 7 O 8 2, 3 7 Figure M.15. NMR spectrum for ADVA 190.

194 1.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.6 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 In te ns ity Sealtight 1100 Figure M.16. NMR spectrum for Sealtight 1100.

195 0.70.91.11.31.51.71.92.12.32.52.72.93.13.33.53.7 f1 (ppm) -500 0 500 1000 1500 2000 2500 3000 3500 4000 4500 5000 5500 6000 In te ns ity Safe-Cure 1200 CH3CH2CH3 water Figure M.17. NMR spectrum for Safe-Cure 1200.

196 0.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.45.6 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 In te ns ity Safe-Cure Clear Figure M.18. NMR spectrum for Safe-Cure Clear.

197 0.30.50.70.91.11.31.51.71.92.12.32.52.72.93.13.33.53.7 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 In te ns ity PG 64-28 CH3CH2CH3 CH(CH3)3 CH2CH3 Figure M.19. NMR spectrum for PG 64-28 asphalt binder.

198 0.20.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.4 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 In te ns ity PG 52-34 CH3CH2CH3 CH2CH3 CH(CH3)3 Figure M.20. NMR spectrum for PG 52-34 asphalt binder.

199 0.51.01.52.02.53.03.54.04.5 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 In te ns ity Elvaloy 4170 2. 81 7. 168.2 7 11 3.0 7 11 .4 7 5. 79 10 .33 2. 16 1. 020.9 4 1. 01 1. 00 4. 95 1. 00 CH3CH2CH3 O 1 2 O 3 4 5 6 CH3 7 8CH2 9 O 1 2 O 3 45 6 O 7 8CH2 9 A B A7 A5 A4A6 B4B5B6 A8, 9 B8, 9 Figure M.21. NMR spectrum for Elvaloy 4170.

200 0.51.01.52.02.53.03.54.04.55.05.56.06.57.0 f1 (ppm) 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 In te ns ity Kraton D1101 3. 14 14 .5 4 7. 09 2. 00 3. 00 0. 86 1 2 3 4 5 6 78* 9 CH310 1 2 *3* 4 B2, 4, 6 B A A1 B3, 5 A3 B7, 8 Figure M.22. NMR spectrum for Kraton D1101.

201 0.70.91.11.31.51.71.92.12.32.52.72.93.13.33.53.73.9 f1 (ppm) -50 0 50 100 150 200 250 300 350 400 450 500 550 600 In te ns ity CRS-1 CH3CH2CH3 CH2CH3 CH(CH3)3 Figure M.23. NMR spectrum for CRS-1 asphalt emulsion.

202 -0.20.20.61.01.41.82.22.63.03.43.84.24.65.05.45.8 f1 (ppm) 0 20 40 60 80 100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 In te ns ity CRS-1P CH3CH2CH3 CH2CH3 CH(CH )3 3 Figure M.24. NMR spectrum for CRS-1P asphalt emulsion.

203 0.70.91.11.31.51.71.92.12.32.52.72.93.13.33.53.73.9 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 In te ns ity Klingbeta 2912 Figure M.25. NMR spectrum for Kling Beta 2912 antistripping agent.

204 0.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.8 f1 (ppm) -50 0 50 100 150 200 250 300 350 400 450 500 550 600 650 In te ns ity Klingbeta 2700 Figure M.26. NMR spectrum for Kling Beta 2700 antistripping agent.

205 0.40.60.81.01.21.41.61.82.02.22.42.62.83.03.23.43.63.84.04.24.44.64.85.05.25.4 f1 (ppm) -100 0 100 200 300 400 500 600 700 800 900 1000 1100 In te ns ity AD-here 65 Figure M.27. NMR spectrum for AD-here 65 antistripping agent.