Available online at http://www.urpjournals.com International Journal of Natural Products Research Universal Research Publications. All rights reserved ISSN: 2249-0353 Original Article Comparative study of the natural dyes derived from two indigenous plants of north-eastern India on silk and cotton fabrics Warjeet S. Laitonjam,1* Lunalisa Potsangbam,2 Sujata D. Wangkheirakpam1 1 2 Department of Chemistry, Manipur University, Imphal – 795003, Manipur, India Laksmikumaran and Sridharan, Attorneys B6/10 Safdarjung Enclave, New Delhi-110029, India. [email protected],[email protected] Received 01 March 2014; Accepted 20 March 2014 Abstract Eco-friendly natural dyes derived from the three plants – Bridelia retusa (bark) and Parkia javanica (skin of fruit-pods). The dyeing property of these plants was found to be from the content of anthraquinones, tannins and flavonoid moieties. This investigation was done by extraction of the parts of the three plants with different solvents, the skin of fruit-pods of Parkia javanica and Bridelis retusa were extracted in methanol.The extracts were concentrated and loaded on glass column for the separation of colorants.The separated compounds were identified from their UV, IR, MASS and NMR spectra. The dyeing capacity was investigated by using the dye on silk and cotton fabrics.The color strength in terms of K/S values measurements were done by recording the reflectance of the extracted dyes. The fastness of the dyes were improved by adding mordants such as CuSO4, K2Cr2O7, SnCl2 and Al(NH4)(SO4)2. Colorfastness tests to light, washing and crocking or rubbing was carried out in a Fade-o-meter, Launder-O-meter and Crock-O-meter respectively and the degree of degree of fastness was given in grey scales.The pre-mordanted dyed samples for silk and cotton showed good fastness properties. © 2014 Universal Research Publications. All rights reserved Key words- natural dyes, textiles, anthraquinones, tannins, mordants and absorbance. 1. Introduction The Indian flora offers a vast source of natural colorants which can be obtained from many plant parts, e.g., leaves, fruits, seeds, flowers, barks and roots. The northeastern region of India has an abundance of plant species with dye yielding properties. The villagers of this region are extracting dyes from leaves, roots, flowers or barks of some plant species mostly by fermenting, boiling, scrapping, powdering and mixing with other materials to get the desired color1.There are many drawbacks of synthetic dyes for example its carcinogenic property pollution and waste water and many vegetable dyes are developed to combat the problem2-3. The fastness of the dyes is enhanced by adding metallic mordants4. But there is no complete documentation available of this for scientific literature. Though various workers have reported results on the extraction of color components from different dyebearing plant species, many species remain unexplored. It is, therefore, not only imperative but also necessary to explore the extraction of natural colorants from abundantly occurring plant sources. Herein we report the extraction of the principal colorants from two plant species – Bridelia retusa called sahi 15 locally from its stem barks and from Parkia javanica locally called yongchak from the fruit pods and evaluation of the dyeing and fastness properties on silk and cotton fabrics. The dyeing property of these plants were found to be from the content of anthraquinones, tannins and flavonoid moieties5,6. Epilgallactocatechin was also obtained from Bridelia. Materials and Methods 2.1. Different parts of three plant species which were selected for the present work are: (1) Parkia javanica, it belongs to family leguminaceae, is a tropical leguminous medium sized tree which reaches a height of about 40 meters and bears flat fruits which are 20-50 cm. long, blackish in coloration on maturity. Each pod has about 15 black seeds. The pods have very nutritional seeds. The skin of the fruit was used for dye extraction. (2) Bridelia retusa belongs to Euphorbiaceae, it is a tree which has color yielding stem bark. Plant parts 3-4 kgs were collected from Manipur. The collected plant parts were put into plastic containers and transported to the laboratory. The samples were washed under free flowing water to remove dust and other particles and air-dried. Dried plant parts were International Journal of Natural Products Research 2014; 4(1): 15-18 pulverized and used for further use. The cotton fabric was scoured in a non-ionic detergent solution. The material to liquor (M:L) ratio was maintained at 1:30, after which the fabrics were washed with distilled water, dried and ironed. Prior to dying or mordanting, the fabric samples were soaked in de-ionized water for half an hour for better absorbency. Pure Jaypee wool and pure silk were soured by standard methods by mild non-ionic surfactants (Mukherjee et al 1999, Nishida et al 1992). Mordants such as copper sulphate (CuSO4-5H2O)(LR,SD Fine ), Potassium dichromate(K 2 Cr2O7) (LR,SD Fine ), Stannous chloride (Sncl2-2H2O)(LR,SD Fine), Stannic chloride (Sncl2-2H2O) (LR,Spectrochem), Ferrous sulphate (FeSO4) (Loba Chemie) and alum (Al(NH4) (SO4)2-12H2O) (LR,SD Fine ) were used. Distilled water was used in extraction and for preparation of all chemical solutions and for dyeing processes (Saligram et al 1993). 2.2. Preparation of samples for extraction of color components: The air-dried samples of each plant part containing about 12-15% moisture were ground in a domestic mixie and sieved with a 2 mm BIS sieve and stored at room temperature (25-300 C). The extract was prepared from the ground powder using mostly hot water and rarely in cold water. 2.3 Determination of absorbance and color strength measurements: Dye solutions of 4% for all the extracted dyes were prepared and definite amounts were taken in the dyebath by maintaining M:L ratio at 1:10. The absorbance of the dye solutions was recorded (Mathur et al 2001),before and after dyeing on a Lamda 40 PE UV/Vis spectrophotometer. An average of 3 measurements at each concentration was recorded. The amount of dye absorbed was calculated11-12 12 (Mathur J. P. and Bhandari C. S., 2001b by using the relation. % Dye Absorbance = 100 x Absorb. before dyeing –Absorb. after dyeing/absorb. before dyeing. The color strength (K/S) values of the dyed samples were evaluated by light reflectance technique and the values were assessed using the Kubelka-Munk equation. K/S=(1 – R)2/2R where R is the observed reflectance; K, the absorption coefficient and S, the light scattering coefficient (AATCC, Technical Manual, 1968). 2.4 Dyeing of silk and cotton fabrics: The cotton fabrics were pre-treated with 2% tannic acid keeping the M:L ratio at1:10 at 80° C for 30 min.The fabrics were dyed7.It was dyed in a dye bath containing 4% of Parkia, Bridelia dye keeping the M:L ratio at 1:10. The dyeing was carried out at 700C for 45 min, after which 2% sodium chloride solution was added to the dye bath and the system was further kept at that temperature for 15minThe fabrics were then washed thoroughly with de-ionized water and dried at room temperature 8. 2.5 Method of mordanting: The pre-mordanting method involved using 2% solutions each of CuSO4, K2Cr2O7, SnCl2, SnCl4 and Al(NH4)(SO4)2 which were employed at M:L ratio 1:10. Mordanting was carried out for 30min at 60 0C. The fabrics 16 were then washed and dried (Nishida, et al 1992),. 2.6 Measurement of fastness properties: Colorfastness tests to light, washing and crocking or rubbing was carried out in a Fad-O-meter, Launder-Ometer and Crock-O-meter respectively and the fastness ratings were given in Grey-scales (AATCC, Technical Manual,1968). 2.7 CIElab coordinates: The CIE coordinates L, a and b of the samples dyed and mordanted with 2% solution of each mordants were evaluated. The higher values of a and b indicte brightness, which is more due to redness and yellowness, respectively, and the negative values indicate greenness and blueness, which are more towards the dull side. The lower the value of L, the greater is the depth. Table-6 shows L*, a*, b* values for cotton fabric while table-7 shows L*, a*, b* values for silk fabrics (Colorimetry, CIE No.15.2,1986). 3 Results and Discussion: 3.1 Effect of concentration of dye on absorption and color strength. The absorption of dye (%) increased with increasing in concentration and reached a maximum at 56% concentration for Bridelia and 4% concentration for Parkia similarly, K/S values also increased with an increase in the dye concentration. Though the K/S values continued to increase, maximum absorption .The variation of the K/S values are seen from the graph plotted with different mordants in figure 1 and 2. Therefore, these concentrations of the dyes in the dye bath might be taken as optimal. Figure 1. Change in K/S values with different mordants for Bridelia Figure 2. Change in K/S value with different mordants for Parkia 3.2 Effect of mordanting conditions: It was observed that pre mordanting technique imparted better fastness properties to the cotton and silk fabric and wool yarn, the fabrics were mordanted with International Journal of Natural Products Research 2014; 4(1): 15-18 Table 1. Bridelia retusa for Cotton Fabric Dye Bridelia retusa Stannic Chloride Pot dichromate Copper Sulphate Stannous Chloride Ferrous Sulphate Bridelia (Aq) Mordant Alum SnCl4 K2Cr2O7 CuSO4 SnCl2 FeSO4 Alum SnCl4 K2Cr2O7 CuSO4 SnCl2 FeSO4 Fabric Cotton Cotton L* 55.510 62.907 52.959 52.123 56.241 38.455 55.163 60.809 53.065 60.965 66.576 44.811 a* 14.149 8.566 3.493 9.737 15.033 3.404 11.452 8.582 2.266 4.730 8.975 4.409 b* 25.959 25.336 23.983 28.804 25.450 11.205 25.599 23.707 22.884 11.901 23.059 12.115 46.965 28.475 40.706 42.486 52.276 33.753 8.820 1.544 6.873 7.526 8.603 4.463 19.100 3.695 18.421 18.338 15.545 10.302 Table 2. Parkia javanica for Cotton Fabric Parkia Parkia javanica Alum Cotton Tannic Acid K2Cr2O7 CuSO4 SnCl2 FeSO4 CuSO4- 5H2O, (K 2 Cr2O7, nCl2-2H2O and Al(NH4)(SO4)212H2O. The mordant activity of metal ions followed the sequences: Fe(II)→Cu(II) → Cr(VI) →Al(III) →Sn(II) →TA and → Cr(VI) → Cu(II) → Sn(II) → Al(III)→TA in samples dyed with Parkia javanica. Fe(II)→ Cr(IV) →Cu(II) →Al(III) →Sn(II) →TA and respectively in silk and cotton dyed with Bridelia retusa The color intensity was found to be maximum when mordanted with Cu(II) and Cr(VI) as compared to Al(III) and Sn(II) for both the fibres. Further, bright shades were obtained by using 2% of Cu, Fe and Cr, which implied that the absorption of color by fabric was better when using Cu(II), Fe(II) and Cr(VI) as mordants. Experimentation with PEG, amylase and TA was done to evaluate if these showed any improvement in dye uptake. However metal mordanting was better in all the cases. This might be due to the maximum absorption and easy formation of metal-complexes with the fabrics. The fastness tests were applied to mordanted-dyed fabrics and yarn. Fair to good washing and crocking fastness properties (Table 1 and Table 2) were obtained with Cu and Cr mordants, while light shades were obtained with SnCl22H2O and alum. 3.3 Evaluation of color co-ordinates of dyed fibres: The color coordinates were positive with respects to brightness L, red-green a, yellow-value b and was in the yellow-red quadrant of the color space diagram (Table 2 and Table 5). Further, the L values decreased corresponding to deeper shades on mordanting. The fibres dyed and postmordanted with CuSO4-5H2O and K2Cr2O7 showed the low L values indicating deeper shades obtained on mordanting 17 with these metal salts compared to that obtained with SnCl2-2H2O and alum with high L values. Thus, for all the dyes, Cu(II) and Cr (VI) may effectively be used as mordant salts. Such type of research has been carried out for manufacturing natural dyes15. 4.Conclusions The investigation for colorant compounds was done by extraction of the parts of the three plants with different solvents from the skin of fruit-pods of Parkia javanica, the young leaves of tectona and bark of Bridelia. The natural color isolated from the skin of fruit-pods of Parkia javanica and those isolated from the stem barks of Bridelia contained mainly anthraquinone, tannins and flavonoid moieties. Epilgallactocatechin was also reported from Bridelia. The extracted dyes were tried on silk and cotton fabrics, the color strength in terms of K/S values measurements were done by recording their absorbance. The absorption of dye (%) increased with increasing in concentration and reached a maximum at 5-6% concentration for Bridelia and 4% concentration for Parkia similarly, K/S values also increased with an increase in the dye concentration. Though the K/S values continued to increase, maximum absorption .The pre-mordanted dyed and samples for cotton and silk showed good fastness properties. The fastness of the dyes were increased by adding mordants such as CuSO4, K2Cr2O7, SnCl2 and Al(NH4)(SO4)2. Colorfastness tests to light, washing and crocking or rubbing was carried out in a Fad-O-meter, Launder-O-meter and Crock-O-meter respectively and the fastness ratings were given in Grey-scales. The fibres dyed and post-mordanted with CuSO4-5H2O and K2Cr2O7 showed the low L values indicating deeper shades obtained on mordanting with these metal salts compared to that International Journal of Natural Products Research 2014; 4(1): 15-18 obtained with SnCl2-2H2O and alum with high L values. Thus, for all the dyes, Cu(II) and Cr (VI) may effectively be used as mordant salts. Therefore, the dyes obtained from native plants might be alternative sources to synthetic dyes for dyeing of cotton, silk and wool. 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