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

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127 Laboratory Results For Raman spectroscopy using 1,064 excitation, a National Institute of Standards and Technology (NIST) standard refer- ence material (SRM) 2244 has become available to remove instrument effects as well as obtain a spectrum that does not include the variability associated with the use of alternative laser sources (and thus detectors with varying response functions, see Figure J.1). The 3M MBR9 yellow sample spectra are displayed as an example of the processing that can be done to enhance Raman spectra (compare Figures J.2 and J.3). Figure J.2 depicts the raw spectrum for the 3M MBR9; notice the waviness from 1,800 to 2,800 cm-1. In Figure J.3 the spectrum is corrected for variability in the instrument response, and the underlying fluo- rescence background is better represented. Subsequently, a bet- ter pure Raman spectrum can be produced by fluorescence removal with inclusion of the proper number of factors and fit to the appropriate polynomial (Figure J.4). However, band shape variability artifacts do persist as a result of this processing. Ideally, sampling conditions would be optimized to reduce the necessity of significant postprocessing of data. Additional corrected spectra are attached as well for AD-here, ADVA 190, Air 200, Aquaspar, Epoplex LS50 pB, Epoplex LS50 White, Epoplex LSS Yellow, Kling Beta 2700, Kling Beta 2912, Eucon Retarder 75 IL, Sealtight 1100, Sikadur Part A, Sikadur Part B, Ultrabond 1100 Part A, Safe-Cure 1000, and Safe-Cure Clear. A p p e n d i x J Raman Spectra 1. 00 0. 00 0. 10 0. 20 0. 30 0. 40 0. 50 0. 60 0. 70 0. 80 0. 90 Raman Shift, cm−1 Re la tiv e In te ns ity 320299 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Figure J.1. NIST SRM raw (black trace) and corrected (green trace).

128 16. 39 0. 66 2. 00 3. 00 4. 00 5. 00 6. 00 7. 00 8. 00 9. 00 10. 00 11. 00 12. 00 13. 00 14. 00 15. 00 320099 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.2. Raw spectra for 3M MBR9 yellow. 2. 00 0. 08 0. 20 0. 40 0. 60 0. 80 1. 00 1. 20 1. 40 1. 60 1. 80 320099 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.3. SRM 2244 corrected spectrum of 3M MBR9 yellow. Note the removal of wavy baseline present in Figure J.2.

129 1. 20 -0.0 1 0. 10 0. 20 0. 30 0. 40 0. 50 0. 60 0. 70 0. 80 0. 90 1. 00 1. 10 319999 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.4. Fluorescence background removed based on a seven-group LU decomposition for 3M MBR9 yellow. The prominent sharp band at 1,085 cm1 is typical of the carbonate anion CO3. 0. 20 -0.0 2 0. 00 0. 02 0. 04 0. 06 0. 08 0. 10 0. 12 0. 14 0. 16 0. 18 3202102 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.5. AD-here SRM 2244 fluorescence corrected. Peaks at 1,450 and 2,800 to 2,970 cm1 are representative of C–H modes.

130 0. 51 -0.0 2 0. 00 0. 05 0. 10 0. 15 0. 20 0. 25 0. 30 0. 35 0. 40 0. 45 350199 250 500 750 1000 1250 1500 1750 2000 2250 2500 2750 3000 3250 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.6. ADVA 190 SRM 2244 fluorescence corrected. Note similarity to AD-here, with water peak at 3,250 cm1. 2. 00 0. 00 0. 20 0. 40 0. 60 0. 80 1. 00 1. 20 1. 40 1. 60 1. 80 3201297 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.7. Air 200 SRM 2244 fluorescence corrected. The 1,680 cm1 peak is typical of alkenes. Note similarities to ADVA 190.

131 40. 00 0. 00 2. 50 5. 00 7. 50 10. 00 12. 50 15. 00 17. 50 20. 00 22. 50 25. 00 27. 50 30. 00 32. 50 35. 00 37. 50 320299 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.8. Aquaspar SRM 2244 baseline corrected. Note similarities to 3M MBR9 yellow. The prominent sharp band at 1,085 cm1 is typical of the carbonate anion CO3 , with additional peaks at lower wave numbers typical of salts. 0. 46 0. 11 0. 15 0. 20 0. 25 0. 30 0. 35 0. 40 3336265 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 3200 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.9. Epoplex LS50 pB SRM 2244 corrected. This overall spectrum is typical for epoxy. Note aromatic C–H stretch at 3,100 cm1.

132 0.50 -0.02 0.00 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 0.45 32683200139 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.10. Epoplex LS50 White SRM 2244 corrected. Note similarity to Aquaspar, although the epoxy may be interfering with the carbonate band. 2.50 -0.06 0.20 0.40 0.60 0.80 1.00 1.20 1.40 1.60 1.80 2.00 2.20 2.40 33003200100 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.11. Epoplex LSS Yellow SRM 2244 corrected. Note additional fine structure from the presence of the organic yellow dye.

133 0. 19 -0.0 1 0. 00 0. 02 0. 04 0. 06 0. 08 0. 10 0. 12 0. 14 0. 16 0. 18 3200179 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.12. Kling Beta 2700 SRM 2244 baseline corrected. Note amine C–H band at 1,300 cm1. 0. 19 -0.0 1 0. 00 0. 02 0. 04 0. 06 0. 08 0. 10 0. 12 0. 14 0. 16 0. 18 3200179 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.13. Kling Beta 2912 SRM 2244 baseline corrected, similar to 2,700 cm1 with pronounced alkane stretch at 2,850 cm1.

134 0. 06 -0.0 1 0. 00 0. 01 0. 02 0. 03 0. 04 0. 05 3200200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.14. Eucon Retarder 75 IL SRM 224 baseline corrected, with possible nitrile peak at 2,150 cm1. 0. 50 0. 00 0. 05 0. 10 0. 15 0. 20 0. 25 0. 30 0. 35 0. 40 0. 45 3200200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.15. Sealtight 1100 SRM 2244 corrected, a typical hydrocarbon spectrum.

135 0. 15 0. 00 0. 01 0. 02 0. 03 0. 04 0. 05 0. 06 0. 07 0. 08 0. 09 0. 10 0. 11 0. 12 0. 13 0. 14 3200200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.16. Sikadur pA SRM 2244 corrected. Although a weak spectrum overall, numerous unique peaks are present, consistent with ceramics. 0. 03 -0.0 0 0. 01 0. 02 3200201 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.17. Sikadur pB SRM 2244 corrected. Although weak, the peak at 450 cm1 (potential oxide) is quite sharp.

136 0. 50 0. 01 0. 05 0. 10 0. 15 0. 20 0. 25 0. 30 0. 35 0. 40 0. 45 32503200200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.18. Ultrabond 1100 pA SRM 2244 corrected, another typical epoxide spectrum. 0. 65 -0. 00 0. 05 0. 10 0. 15 0. 20 0. 25 0. 30 0. 35 0. 40 0. 45 0. 50 0. 55 0. 60 320050 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.19. Safe-Cure 1000 SRM fluorescence corrected. Note that the single low-frequency mode is typical for heavier elements.

137 0. 25 0. 24 -0.0 2 0. 00 0. 02 0. 04 0. 06 0. 08 0. 10 0. 12 0. 14 0. 16 0. 18 0. 20 0. 22 3200300 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600 2800 3000 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.20. Safe-Cure Clear SRM 2244 corrected, typical hydrocarbon with unique C–H stretch features (2,800 to 3,000 cm1). Figure J.21. Butonal NX1138 corrected Raman spectrum.

138 Figure J.22. Elvaloy 4170 corrected Raman spectrum. Kraton D1101 SBS Figure J.23. Kraton D1101 SBS corrected Raman spectrum.

139 Table J.1. Summary of Laboratory Raman Testing Results Material Category Sample ID Success (Yes/No) Relative Signal Intensity Wave Number Peakb (cm1) Noise (SD) Signal-to- Noise Ratio Structural coatings Carbozinc 859 Part A Yes 16.42 1,086.5 0.001 1,500 Carbozinc 859 Part B Yes 2.305 1,000 0.0125 209 Carbozinc 859 Zinc Filler Yes 1.195 1,110a 0.0116 8 3M Scotchkote Part A Yes 3.824 2,930 0.01160 351 3M Scotchkote Part B No NA NA NA NA Pavement markings 3M All Weather HB-R1 White Yes 25.33 1,090 0.00895 2,820 Epoplex LS50 Part B Yes 0.6963 824 0.00895 79.4 Epoplex LS50 White Yes 3.641 448 0.00717 508 Epoplex LS50 Yellow Yes 16.66 1,330 0.0216 989 Epoxy adhesives for concrete repair Sikadur Part A Yes 0.8661 465 0.00708 129 Sikadur Part B Yes 0.4408 465 0.00718 75.8 Ultrabond 1100 Part A Yes 1.864 640 0.101 75.9 Ultrabond 1100 Part B No NA NA NA NA Portland cement Lehigh cement No NA NA NA NA Lafarge cement No NA NA NA NA Chemical admixtures for PCC Accelguard 80 Yes 1.776 1,050 0.00945 188 ADVA 190 Yes 0.2468 1,470 0.00749 33 Air Mix 200 Yes 0.4061 1,650 0.00762 56 Retarder 75 Yes 0.1408 3,230 0.00509 27.6 Curing compounds for PCC Safe-Cure 1000 Yes 4.437 143 0.00792 561 Safe-Cure clear Yes 1.472 2,930 0.00751 196 Sealtight 1100 Yes 1.518 1,440 0.00814 186 Polymer additives to asphalt binder Elvaloy 4170 Yes 6.919 2,880 0.00899 782 Kraton SBS Yes 1.82 1,000 0.00758 240 BASF Butonal Il Yes 2.126 1,670 0.00844 257 Neat asphalt binders PG 58-28 No NA NA NA NA PG 64-22 No NA NA NA NA Polymer-modified asphalt binders PG 52-34 1.5% SBR Latex No NA NA NA NA PG 64-28 3.3% SBR Latex No NA NA NA NA Asphalt emulsions CRS-IP No NA NA NA NA CRS-1 No NA NA NA NA Antistripping agents for asphalt AD-here LOF 65 Yes 2.421 1,470 0.00749 33 Kling Beta 2700 Yes 0.9226 1,450 0.00673 147 Kling Beta 2912 Yes 1.01 1,450 0.00787 133 Mineral aggregates Stone aggregate No NA NA NA NA Note: NA = not available; PCC = portland cement concrete. a Thermal emission. b Not baseline adjusted.

140 Field Results Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.24. (Top) Real-Time Analyzers’ (RTA’s) portable Raman analyzer. (Bottom) TAMMSCURE Raman spectrum recorded in the field (top green trace) showing contributions from ambient light (broad band from 1,400 to 2,000 cm1). The bottom trace shows the corrected spectrum calculated using RTA’s Raman Vista advanced calculator and subtraction of background. Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.25. White paint measured on glass corrected to remove fluorescence and ambient light contributions.

141 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.26. Yellow paint measured on glass corrected to remove fluorescence and ambient light contributions. Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.27. White paint (old) corrected to remove fluorescence and ambient light contributions.

142 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.28. A-80 spectrum averaged for three collections (12 equivalent scans, no background subtraction necessary). Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.29. Air 200 spectrum averaged for 20 scans (five spectra measured at four scans, no background subtraction necessary).

143 Raman Shift, cm−1 Re la tiv e In te ns ity Figure J.30. R-75 spectrum averaged for 40 scans (10 spectra measured at four scans, no background subtraction necessary). Table J.2. Field Raman Spectral Results and Signal-to-Noise Ratio Calculations Material Category Sample ID Success (Yes/No) Relative Signal Intensity Wave Number Peak (cm1) Noise (SD) Signal-to- Noise Ratio Field-tested materials White paint Yes 4.00 1,086 0.0435 85 Yellow paint Yes 1.00 1,295 0.036 27 TAMMSCURE Yes 1.19 1,110 0.0116 8 A-80 Yes 1.29 2,843 0.040 0.71 Air 200 No NA NA NA NA R-75 No NA NA NA NA White paint strip (old) Yes 2.43 443.4 0.058 46 Note: NA = not available.