Photobleaching in Cotton Fibers Dyed Using Red, Yellow, and Blue Direct Dyes During Examination with Microspectrophotometry (MSP) Amanda L

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Photobleaching in cotton fibers dyed using red, yellow, and blue direct dyes during examination with microspectrophotometry (MSP) Amanda L. Forster, Julie L. Bitter, Sydney Brooks, Samuel Rosenthal, and Stephanie S. Watson National Institute of Standards and Technology, 100 Bureau Dr. M/S 8102 Gaithersburg, MD 20899-8102, USA

Introduction Observation of Photobleaching- Red Dye • Microspectrophotometry (MSP) is a rapid, nondestructive technique for analysis of color in textile fibers. Introduction • MSPThe combines ballistic microscopy performance and ultraviolet/visible of ultra-high molar (UV-Vis) mass spectroscopy polyethylene and eliminates(UHMMPE) the need fibres for time for consuming ballistic protection and destructive is predicated extraction on of dyes the fromdevelopment textile fibers of when a highly examining aligned colored molecular fibers with structure traditional that allows techniques the suchpolymer as thin to layer exhibit chromatography a superior strength (TLC) in the or axial high direction performance of the liquidfibre. 0 minutes: red chromatographyHowever, even (HPLC). an ideal molecular structure will be subjected to 10 minutes: pink/white 30 minutes: almost completely white degradation during use, which can reduce the high strength of these 2nd Red 1 2nd Red 1 Change in Absorbance • 0.5 1.02 Whilefibres, MSP and is generally impact their expected ability to to be protect a nondestructive the wearer. evaluation method, a Time = 0 min Time = 1 min Time = 2 min loss of color during analysis, or photobleaching can occur. Time = 3 min Time = 4 min 1.00 0.4 Time = 5 min Time = 6 min Time = 7 min Time = 8 min Time = 9 min 0.98 Time = 10 min 0.3 Time = 11 min Time = 12 min Materials and Methods Time = 13 min Time = 14 min 0.96 Absorbance Time = 15 min Loss Percent Time = 16 min 0.2 Time = 17 min Dyeing Experiments: Direct Blue 71 Time = 18 min 0.94 Time = 19 min 518nm Time = 20 min • Direct dye was applied to cotton fibers in the 405nm 293nm laboratory. 0.1 0.92 • Direct Blue 71, 200 400 600 800 0 5 10 15 20 Wavelength (nm) Exposure Time (min) • Direct Red 81 3rd Red 1 3rd Red 1 Change in Absorbance 0.5 Time = 0 min 1.00 Time = 1 min • Direct Yellow 27 Time = 2 min Time = 3 min 0.98 Time = 4 min Time = 5 min • Various dyebath concentrations were used. Time = 6 min Time = 7 min 0.96 0.4 Time = 8 min Time = 9 min • 0.05 % m/v, 0.033 % m/v, 0.025 % m/v, Time = 10 min Time = 11 min 0.94 Time = 12 min Time = 13 min and 0.005 % m/v Time = 14 min 0.92 Time = 15 min 0.3 Time = 16 min Time = 17 min Time = 18 min 0.90 Direct Red 81 Time = 19 min Percent Loss Percent

Absorbance Time = 20 min Microspectrophotometery Measurements: 0.88 • 0.2 0.86 Absorbance spectra of single fibers mounted in 518nm 0.84 405nm glycerol on quartz were obtained using a MSP 121 293nm 0.82 0.1 microspectrophotometer from CRAIC 0 5 10 15 20 200 400 600 800 Exposure Time (min) Technologies. Wavelength (nm)

• Analysis was repeated at specified intervals. Direct Yellow 27 • Poor repeatability between changes in absorbance in dyed fibers. • Due to nonuniform dye uptake- common in natural fibers. Comparison of Dyes and Dyed Fibers

Dyes Observation of Photobleaching- Blue and Yellow Dyes • A portion of each dyebath solution was 3rd Blue 1 3rd Blue 1 Change in Absorbance 1.00 0.30 Time = 0 min Time = 1 min Time = 2 min analyzed using UV/Vis spectroscopy. Time = 3 min 0.98 Time = 4 min Time = 5 min 0.25 Time = 6 min Time = 7 min 0.96 Time = 8 min Time = 9 min Time = 10 min 0.94 0.20 Time = 11 min • Allows for comparison of spectra between Time = 12 min Time = 13 min Time = 14 min 0.92 Time = 15 min Time = 16 min the dye solution and the dyed fiber. 0.15 Time = 17 min Time = 18 min 0.90 Time = 19 min Percent Loss Percent

Absorbance Time = 20 min 0.10 0.88

0.86 0.05 MSP of Dyed Fibers 0.84 587 nm 0.05 % 293 nm 0.00 0.82 200 400 600 800 02468101214 Wavelength (nm) Exposure Time (min) • The overall shape and position of

absorbance peaks was found to be 2nd Yellow 1 Change in Absorbance 2nd Yellow 1 0.20 1.00 T = 0 min similar for each dye. T = 1 min T = 2 min 0.98 T = 3 min T = 4 min 0.15 T = 5 min T = 6 min 0.96 • Some slight differences, especially T = 7 min T = 8 min T = 9 min 0.94 between the yellow and red dye T = 10 min 0.10 T = 11 min T = 12 min 0.92 T = 13 min around 400 nm. T = 14 min Percent Loss Absorbance T = 15 min 0.90 0.05

0.88 • Overall, absorbance was lower, as 409 nm

0.00 0.86 expected since MSP is a microanalysis 02468101214 200 400 600 800 Exposure Time (min) technique. Wavelength (nm)

• Similar trends were observed for the fibers dyed with blue and yellow dyes in the highest concentration. Photobleaching • Repeatability still an issue due to nonuniform dye uptake. • Lower concentrations of yellow (not shown) did not demonstrate much of an • MSP generally expected to be a nondestructive effect, possibly since there was so little dye on the fiber at time zero. evaluation method. • Photobleaching[1] Boller, A., and B. Wunderlich " Journal can of thermalbe analysisminimized 49.1 (1997): 343-349. [4] Kwon,by Y.using K., et al. Polymer a 41.16 glass (2000): 6237-6249. slide or UV filter (results Dyed fabric showing poor [2] Rotter, G., and H. Ishida. Macromolecules 25.8 (1992): 2170-2176. [5] Sultanov, V. I., et al. JETP letters 98.5 (2013): 294-297. • High intensity UV light sources can cause a reduction in not[3] Karacan, shown !.Fibres and Textiles here) in Eastern to Europe protect 13.4 (2005): 15. the fiber[6] Fu, while Yigang, et al.setting Journal of Macromolecular upa Science, measurement. Part B: Physics 35.1 (1996): 37-87. the intensity of absorption during analysis, a lightfastness. phenomenon typically referred to as photobleaching. • Historically, dye chemists have been concerned with Conclusions and Future Work lightfastness of dyed fabrics. • • Fading of dyed fabrics after exposure to sunlight is well- Photobleaching is readily observed on cotton fibers dyed with red, yellow, and blue direct known and related, but the lamps used in the MSP dyes, and forensic scientists should be aware of this phenomenon. • cause fading to occur rapidly. Photobleaching can be minimized by careful control of measurements on susceptible fibers • A recent review article found that approximately half (reduction in time of exposure, careful use of shutters, etc.) • of the scientific papers on spectroscopic analysis of Additional measurements will be made to better quantify repeatability. • Recommendations for exposure time and filtering procedures will be developed. textile fibers focused on UV-Vis MSP, but http://craftyc0rn3r.blogspot.com/2010/05/patio‐ furniture‐reupholstering.html [1] R. Palmer, W. Hutchinson, and V. Fryer, “The discrimination of (non‐denim) blue cotton,” Sci. Justice, vol. 49, no. 1, pp. 12–18, 2009. [9] K. Lunstroot, D. Ziernicki, and T. Vanden Driessche, “A study of black fleece garments: Can fleece fibres be recognized and how variable are they?,” Sci. Justice, vol. 56, no. 3, photobleaching was only mentioned in a few papers [2] S. Suzuki, Y. Suzuki, H. Ohta, R. Sugita, and Y. Marumo, “Microspectrophotometric discrimination of single fibres dyed by indigo and its derivatives using ultraviolet‐visible pp. 157–164, 2015. transmittance spectra,” vol. 41, no. 2, pp. 107–111, 2001. [10] K. de Wael, K. van Dijck, and F. Gason, “Discrimination of reactively‐dyed cotton fibres with thin layer chromatography and UV microspectrophotometry,” Sci. Justice, vol. 55, [3] J. Zięba‐Palus and B. M. Trzcińska, “Comparing the Color of Forensic Traces,” Anal. Lett., vol. 45, no. 11, pp. 1333–1346, 2012. no. 6, pp. 422–430, 2015. [4] P. Buzzini and G. Massonnet, “The Analysis of Colored Acrylic, Cotton, and Wool Textile Fibers Using Micro‐Raman Spectroscopy. Part 2: Comparison with the Traditional [11] J. Was‐Gubala and R. Starczak, “UV–Vis microspectrophotometry as a method of differentiation between cotton fibre evidence coloured with reactive dyes,” Spectrochim. from Was-Gubala and Starczak. Methods of Fiber Examination,” J. Forensic Sci., vol. 60, no. 3, pp. 712–720, 2015. Acta Part A Mol. Biomol. Spectrosc., vol. 142, pp. 118–125, 2015. [5] K. Wiggins and J. a Holness, “A further study of dye batch variation in textile and carpet fibres.,” Sci. Justice, vol. 45, no. 2, pp. 93–6, 2005. [12] J. Was‐Gubala and R. Starczak, “Nondestructive identification of dye mixtures in polyester and cotton fibers using Raman spectroscopy and ultraviolet‐visible (UV‐Vis) [6] P. P. Meleiro, “Spectroscopic techniques for the forensic analysis of textile fibers,” vol. 51, no. 4, pp. 258 – 281, 2016. microspectrophotometry,” Appl. Spectrosc., vol. 69, no. 2, pp. 296–303, 2015. [7] K. Wiggins, R. Palmer, W. Hutchinson, and P. Drummond, “An investigation into the use of calculating the first derivative of absorbance spectra as a tool for forensic fibre [13] R. Starczak and J. Wąs‐Gubała, “UV–Vis microspectrophotometric study of wool and polyamide fibres dyed with analogous gryfalan dyes,” Dye. Pigment., vol. 132, pp. 58–63, analysis,” Sci. Justice, vol. 47, no. 1, pp. 9–18, 2007. 2016. [8] T. W. Biermann, “Blocks of colour IV: The evidential value of blue and red cotton fibres,” Sci. Justice, vol. 47, no. 2, pp. 68–87, 2007. [14] D. McCreight, R. Feil, J. Booterbaugh, and E. Backe, Short Staple Yarn Manufacturing. Durham, NC: Carolina Academic Press, 1997.