- Open Access
Thermo-oxidative and weathering degradation affecting coloration performance of lac dye
© The Author(s) 2016
- Received: 25 March 2016
- Accepted: 2 August 2016
- Published: 28 September 2016
Thermo-oxidative stability of lac dye was studied by simultaneous thermogravimetry (TG) and differential scanning calorimetry under nonisothermal and isothermal modes in air. The thermal stability change of lac dye was characterized by FTIR and UV–Vis spectroscopy. The TG profiles of lac dye showed at least three steps of mass loss. The first mass loss (about 8 %) found in the range of 40–150 °C mainly corresponded to the evaporation of moisture whereas the next two major steps were found with mass losses of 50 (150–440 °C) and 25 % (440–550 °C). The FTIR results indicate that the degradation of the major mass loss step (150–440 °C) mainly involved the thermo-oxidative reaction at carboxylic groups in conjugation with the C=C bonds of the anthraquinone ring. The absorbance profiles of lac dye solutions showed that the remarkable drop of absorbability was observed when the dye was heated to elevated temperatures (>150 °C). The results obtained from isothermal investigation also indicated the thermo-oxidative stability dependence of heating temperature. The apparent activation energy of lac dye calculated using isoconversional methods was higher under dynamic than under isothermal heating. Long period of weathering exposure mainly affected the O–H bonds of hydroxyl and carboxylic groups, and hence lowering the absorbability of lac dye. These results provided helpful information that can give support in the maintenance, preparation, dyeing and application stages of lac dye.
The natural dyes have been widely used, especially for textile dyeing, coloring food, painting and in printing. However, with the rapid incursion of synthetic dyes, natural dyes undergo a setback. During the past few decades, the problems concerning the environmentally harmful effects and serious health hazards have been raised regarding the use of synthetic dyes. Therefore, the use of natural dyes is considerable current interest as these dyes are eco-friendly, safe for body contact, unsophisticated, harmonized and renewable (Nayar et al. 1994; Downham and Collins 2000).
For the dye molecules, the chemical structure is normally divided as the chromophore (main skeleton) and auxochrome (substituent groups) parts. The chromophore part generally determines the light fastness properties. Oppositely, the change in fastness properties is dominated by the auxochromes (Cristea and Vilarem 2006). Flavonoid compounds are mostly found as the main components in natural dyes and the remaining components anthraquinones, naphtoquinones and indigoids. Anthraquinones and indigoids typically exhibit superior light fastness. Although the numerous advantages have been gained from the natural dyes, the color fading due to the degradation of dye is still be one of the major problems in textile color. Normally, the color fading directly affects in the loss of intact dye molecule resulting in the change of original dye color (Ahn et al. 2014). In general, the stability of natural dye is mostly influenced by the chemical and physical states of the dye. Moreover, the source and the intensity of illumination, humidity, temperature (heat), and the atmospheric pollution as the external factors can affect the stability of natural dyes as well. The light source containing UV radiation is one of the important factors that affect the stability of the dyes by photofading process (McLaren 1956; Padfield and Landi 1996; Gantz and Sumner 1957). Under exposing to light, both temperature and humidity can influence the fading rate of dyed textiles (Egerton and Morgan 1970). In addition, the natural dyes can react with gas contaminants in the atmosphere, e.g., sulfur dioxide and oxides of nitrogen and ozone even in the absence of light. In terms of thermal affecting stability, it is known that higher temperature accelerates the oxidation of the natural dyes. It has been reported that the oxidation reaction of amor cork tree dye is accelerated two times by every 2 °C increase in temperature under heating in 100 °C oven (Ramos et al. 1995; Ahn 2011). Thermal degradation behavior of the alizarin and Phellodendron bark, alizarin and indirubin has also been studied by GC–MS and HPLC–DAD-MS (Ahn 2011; Ahn and Obendorf 2004). In addition, Ahn et al. (2014) investigated the thermal resistance of the natural dyes. The thermal stabilizing performance of alizarin and purpurin was attributed to the formation of fiber-metal-dye chelated complex by aluminum or iron ions mordanting prior to dyeing.
Crude stick lac was provided by the local villagers living in the Khon Kean province, Thailand. The lac dye was prepared in the form fine powder. The preparation procedure was described in our previous article (Sribenja and Saikrasun 2015).
Nonisothermal and isothermal gravimetric analysis
TA instruments, SDT Q600 (Luken’s drive, New Castle, DE) was employed for thermal degradation investigation. The lac dye sample of about 10 mg was loaded in alumina crucible and then dynamically heated from ambient temperature to the selected temperatures as 60, 70, 80, 90, 110, 130, 150, 250, 350 and 600 °C using a heating rate of 10 °C/min. The total times used for dynamic heating to the selected temperatures were 3, 4, 5, 6, 8, 10, 12, 22, 32 and 57 min., respectively. The experiment was carried out in air atmosphere with the gas flow rate of 100 mL/min. The analysis of TG and DSC data was similarly done as described in our previous communication (Saengsuwan and Saikrasun 2012). In case of isothermal test, the isothermal degradation was investigated at 90, 110, 130, and 150 °C for 100 min. The procedure of isothermal heating analysis was also described in our previous article (Saengsuwan and Saikrasun 2012). In this work, the TG analysis data were gained from three measurements. The activation energy of thermo-oxidative decomposition for the lac dye was examined using isoconversional kinetic analysis.
The structural change of lac dye was characterized by FT-IR spectroscopy (Spectrum GX-1, Perkin Elmer Co., Ltd., UK). A resolution of 4 cm−1 and 32 scans from 4000 to 400 cm−1 were used for each sample.
Weathering procedure and instruments
The powder dye sample of 0.250 g was loaded in a ceramic container. Each sample was kept out-door under the realistic atmosphere for 5, 10, 15 and 50 days. UV–Vis spectrophotometry (Thermo Scientific 4001/4, Thermo Electron Co., Ltd., MA, USA) was used to measure the absorbance of aqueous lac dye solution. The absorbance of aqueous dye solution with a fixed concentration of 0.15 g/L (150 ppm) was scanned from 100–900 nm. The optical images of the lac dye solutions were examined using digital camera (Canon, EOS-500D, Tokyo, Japan). The data of weathering investigation were gained from three measurements.
FTIR characterization of lac dye
Thermo-oxidative stability of lac dye under dynamic heating
Thermo-oxidative activation energies (E a) at various mass losses of lac dye
% Mass loss
E a (kJ/mol)
Thermo-oxidative stability of lac dye under isothermal heating
Effect of dynamic heating on absorbability of lac dye solution
Effect of atmospheric weathering on absorbability of lac dye solutions
In this work, effects of thermo-oxidative heating and atmospheric weathering on stability of lac dye were investigated. Under dynamic heating, the lac dye started to degrade at temperatures higher than 150 °C which mainly involved the thermo-oxidative reaction at carboxylic groups in conjugation with the C=C bonds of the anthraquinone ring. Before and after dynamic heating to 60–150 °C, the absorbance profiles of each lac dye solution were not significantly different. Under heating the lac dye to higher temperatures, the absorbance significantly dropped resulting from the degradation of the chromophores. Under long weathering period, the chemical change mainly involved O–H bonds of hydroxyl and carboxylic groups. This change also strongly lowered the absorbability of lac dye solution. The obtained results provided helpful information about thermo-oxidative and weathering stability of lac dye which is useful for maintenance, preparation, dyeing process and realistic applications.
Both authors read and approved the final manuscript.
The authors would like to acknowledge Center of Excellence for Innovation in Chemistry (PERCH-CIC) and Mahasarakham University (Fast-track Grant 2015) for their partial financial supports.
The authors declare that they have no competing interests.
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- Ahn, C. (2011). Analysis of amur cork tree extract and dyed silk upon thermal degradation treatment. Journal of the Korean Society of Clothing and Textiles, 35(10), 1228–1241.View ArticleGoogle Scholar
- Ahn, C., & Obendorf, S. K. (2004). Dyes on archaeological textiles: Analyzing alizarin and its degradation products. Textile Research Journal, 74(11), 949–954.View ArticleGoogle Scholar
- Ahn, C., Zeng, X., Li, L., & Obendorf, S. K. (2014). Thermal degradation of natural dyes and their analysis using HPLC-DAD-MS. Fashion and Textiles, 1, 22.View ArticleGoogle Scholar
- Boonla, K., & Saikrasun, S. (2013). Influence of silk surface modification via plasma treatments on adsorption kinetics of lac dyeing on silk. Textile Research Journal, 83, 288–297.View ArticleGoogle Scholar
- Chairat, M., Rattanaphani, S., Bremner, J. B., & Rattanaphani, V. (2005). An adsorption and kinetic study of lac dyeing on silk. Dyes and Pigments, 64, 231–241.View ArticleGoogle Scholar
- Cristea, D., & Vilarem, G. (2006). Improving light fastness of natural dyes on cotton yarn. Dyes and Pigments, 70, 238–245.View ArticleGoogle Scholar
- Dokmaisrijan, S., Payaka, A., Tantishaiyakul, V., Chairat, M., Nimmanpipug, P., & Lee, V. S. (2013). Conformations and spectroscopic properties of laccaic acid A in the gas phase and in implicit water. Spectrochimica Acta Part A: Molecular and Biomolecular Spectroscopy, 105, 125–134.View ArticleGoogle Scholar
- Downham, A., & Collins, P. (2000). Colouring our foods in the last and next millennium. International Journal of Food Science & Technology, 35, 5–22.View ArticleGoogle Scholar
- Egerton, G. S., & Morgan, A. G. (1970). The photochemistry of dyes. II. Some aspects of the fading Process. Journal of the Society of Dyers and Colourists, 86, 242–249.View ArticleGoogle Scholar
- Flynn, J. H., & Wall, L. A. (1966). General treatment of the thermogravimetry of polymers. Journal of research of the National Bureau of Standards, 70A, 487–523.View ArticleGoogle Scholar
- Gantz, G. M., & Sumner, W. G. (1957). Stable ultraviolet light absorbers. Textile Research Journal, 27, 244–251.View ArticleGoogle Scholar
- Janhom, S., Griffiths, P., Watanesk, R., & Watanesk, S. (2004). Enhancement of lac dye adsorption on cotton fibres by poly(ethyleneimine). Dyes and Pigments, 2004(63), 231–237.View ArticleGoogle Scholar
- Kamel, M. M., El-Shishtawy, R. M., Youssel, B. M., & Mashaly, H. (2007). Ultrasonic assisted dyeing. IV. Dyeing of cationised cotton with lac natural dye. Dyes and Pigments, 73, 279–284.View ArticleGoogle Scholar
- Kongkachuichay, P., Shitangkoon, A., & Chinwongamorn, N. (2002). Thermodynamics of adsorption of laccaic acid on silk. Dyes and Pigments, 53, 179–185.View ArticleGoogle Scholar
- McLaren, K. (1956). The spectral regions of daylight which cause fading. Journal of the Society of Dyers and Colourists, 72, 86–99.View ArticleGoogle Scholar
- Moeyes, M. (1993). Natural dyeing in Thailand. Bangkok: White Lotus.Google Scholar
- Nam, J. D., & Seferis, J. C. (1991). A composite methodology for multistage degradation of polymers. Journal of Polymer Science Part B: Polymer Physics, 29, 601–608.View ArticleGoogle Scholar
- Nayar, T. S., Binu, S., & Pushpagandhan, P. (1994). Uses of plants and products in traditional Indian mural paintings. Economic Botany, 53, 41–50.View ArticleGoogle Scholar
- Oka, H., Ito, Y., Yamada, S., Kagami, T., Hayakawa, J., Harada, K. I., et al. (1998). Separation of lac dye components by high-speed counter-current chromatography. Journal of Chromatography A, 813, 71–77.View ArticleGoogle Scholar
- Ozawa, T. (1965). A new method of analyzing thermogravimetric data. Bulletin of the Chemical Society of Japan, 38, 1881.View ArticleGoogle Scholar
- Padfield, P., & Landi, S. (1996). The light-fastness of the natural dyes. Studies in Conservation, II(4), 181–196.Google Scholar
- Ramos, P., Gieseg, S. P., Schuster, B., & Esterbauer, H. (1995). Effect of temperature and phase transition on oxidation resistance of low density lipoprotein. Journal of Lipid Research, 36(10), 2113–2128.Google Scholar
- Saengsuwan, S., & Saikrasun, S. (2012). Thermal stability of styrene–(ethylene butylene)–styrene-based elastomer composites modified by liquid crystalline polymer, clay, and carbon nanotube. Journal of Thermal Analysis and Calorimetry, 110, 1395–1406.View ArticleGoogle Scholar
- Sribenja, S., & Saikrasun, S. (2015). Adsorption behavior and kinetics of lac dyeing on poly(ethyleneimine)-treated bamboo fibers. Fibers and Polymers, 16(11), 2391–2400.View ArticleGoogle Scholar
- Svobodová, E., Bosáková, Z., Ohlídalová, M., Novotná, M., & Němec, I. (2012). The use of infrared and Raman microspectroscopy for identification of selected red organic dyes in model colour layers of works of art. Vibrational Spectroscopy, 63, 380–389.View ArticleGoogle Scholar
- Tanaka, H. (1995). Thermal analysis and kinetics of solid state reactions. Thermochimica Acta, 267, 29–44.View ArticleGoogle Scholar
- Vyazovkin, S. (2000). Computational aspects of kinetic analysis: Part C. The ICTAC Kinetics Project—the light at the end of the tunnel? Thermochimica Acta, 355, 155–163.View ArticleGoogle Scholar
- Vyazovkin, S., & Wight, C. A. (1997). Isothermal and nonisothermal reaction kinetics in solids: In search of ways toward consensus. The Journal of Physical Chemistry A, 101(44), 8279–8284.View ArticleGoogle Scholar