Newer Natural Dyes for Various Textiles

Chapter 1

Newer Natural Dyes for Various Textiles Natural dyes and their use in dyeing is probably the most ancient art of all times. People started using natural dyes as their first intellectual tool to portray their surroundings and themselves by this art. No important or specified information was with them to use the natural colors available near to them. From that period on, this art and its important component, that is, natural dye, has improved itself in terms of stability, shades, and its working archetype until the invention of natural dye's strongest rival “synthetic dye.” Since then, natural dyes haven't seen any silver lining until again slowly but steadily the new age customers started to realize the importance of natural dye as “revival of new optimism” in terms of acknowledgment of new and earthy shades provided by colors of nature. One of the most amazing things about natural dye is its source from various plant parts. It can come from wood, fruit, roots, flowers, and even insects. Nature is unique. Such variety of color can be seen is flowers and fruits. Every color of the rainbow can be produced. One of the favorite hot pink dye comes from the wood lumen of sappanwood (Caesalpinia sappan); other source is the exoskeleton of a little bug living exclusively and thriving on the beaver tail cactus in Oaxaca, Mexico. The shells are harvested and traditionally mixed with lime juice to create a vibrant hot pink or red dye. Dyeing with plants and animals is a craft with its roots in early times. Although it is time-consuming, labor-intensive, and challenging to do on a large scale, as a result, the art of natural dyeing is slowly becoming obsolete in the industrialized world; however, its smooth color can give tranquilizing effect. The choice to use all natural dyes sources for many reasons. The most obvious reason is the low impact that they have on people and the environment. In using dye materials that come only from nature, our environment and us can be protected by reducing exposure to toxic chemicals. The revival of natural dyes has kept the ancient knowledge alive. By using natural dyes, a demand for these products can be created, providing income and incentive for people to maintain practices of local sustainability, remaining close to family and tradition. It is rewarding to know that by using natural dyes, the indigenous communities are gaining support in doing what they and their families have done for thousands of years. However, commercial utility of natural dyes on a large scale for export and domestic market has not been explored New Trends in Natural Dyes for Textiles. https://doi.org/10.1016/B978-0-08-102686-1.00001-9 © 2019 Elsevier Ltd. All rights reserved.

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2  New Trends in Natural Dyes for Textiles

much with newer sources. The term natural dye covers all the dyes derived from natural resources such as plants, insects, and animals. Natural dye applications to industrial products release their medicinal properties of the goods and improve the esthetic value of the product. Natural dyes are unique in that they are eco-friendly and noncarcinogenic. There is a growing demand for eco-friendly/nontoxic colorants, specifically for health-sensitive applications such as coloration of food and dyeing of child textile/leather garments. Recently, dyes derived from natural sources for these applications have emerged as an important alternative to potentially harmful synthetic dyes and pose need for suitable effective extraction methodologies. Dyeing is the most important part in the production of fabric. The dye is generally applied in an aqueous solution and may require a mordant to improve the fastness of the dye on the fiber. Since the process of adding dyes takes place in the last stage of the process, even the smallest error in the dye application can render the entire batch useless. So, it is vital that the fabric dyeing process is controlled in a cost-efficient manner. Handling of natural dye and its dyeing process needs scientific interventions at four main steps: (1) Extraction (2) Isolation of dye molecule (3) Dyeing (4) Dye fixing

1.1  Innovation in Extraction Process Dye extraction is required as dyes are made in aqueous solution and then to be dyed on cloth/fabric. Efficient extraction of the dyes from plant material is very important for standardization and optimization of vegetable/natural dyes. Proper extraction and concentration of dye can give very good/lasting washfastness for any material. Natural dyes from plants may also have many compounds, and their proportions vary with climate and terrain. As mostly all the sources of natural dyes have to be extracted efficiently to get its genuine color in extract, extraction sometimes can be very costly and time-consuming that's why innovation for this process can help in reducing time and cost and increasing “application worth” of dye in question. Extraction of dyes from weld using Soxhlet apparatus was studied. The natural dye extract obtained from the weld was used for the dyeing of wool fiber. The results indicated that the exhaustion rate for the extracted dye increases by 49% compared with the raw dye. Furthermore, for comparative studies between synthetic and this natural dye, all dyed specimens were tested for wash- and lightfastness properties, making weld a viable alternative to synthetic acid dyes [1]. Supercritical fluid extraction of natural dye from Eucalyptus bark for cotton dyeing in microwave and sonicator was carried out. SCFE is a superior technique over traditional solvent extraction for natural dyes. In the Eucalyptus bark that is shredded off, a plant waste has been exploited for natural dyeing

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of cotton. Bright yellow color was obtained with stannic chloride mordant that showed very good fastness both in the case of microwave and sonicator dyeing, though the latter was superior [2]. Alkanna tinctoria (alkanet) belongs to family Boraginaceae. The root, which is often very large in proportion to the size of the plant, yields in many of the species a red dye. Alkanet root is a good source of natural color from the roots. The plant is also called Anchusa tinctoria. It was earlier used for soap; traditionally, the color was extracted from the root by infusing in oil and then using the oil in soap manufacture. It gave burgundy and purples in alkaline medium. Only nylon and polyester fibers have been dyed by alkanet. This dye has been conventionally used as a food dye [3]. The coloring matter in alkanet root is anchusin, a naphthoquinone derivative containing three hydroxyl groups, two of which are phenolic. The main pigment is alkannin that was earlier called anchusin. As alkanet is a naphthoquinone-based dye, theoretically, it is expected to behave as a disperse dye. The dye pigment is insoluble in water but has been used to dye wool, silk, and cotton at 40°C for 1 h with the addition of alcohol. Fruits of Cayratia plant source were crushed, and color was extracted from fruits by the end of 3 h. The extraction of anthocyanins from fruit skins is comparatively simple. The dark bluish purple skins of the berries are separated from the rest of the fruit, freed completely from pulp by hydraulic pressure, and are extracted with water without delay and used for dyeing. This dye is inexpensive and abundantly available, and the method of application is very simple, producing no pollutants. The results are very encouraging; it is for the first time that Cayratia fruits have been used as a dye source for textile dyeing. The shades obtained were bright and have very good fastness properties. This dye can be used for dyeing in various shades of blue-dark blue and purple shades for cotton, silk, and wool. The findings of colorfastness tests of all the samples to rubbing under dry conditions showed that the samples had fair-to-excellent fastness as compared with dry rubbing. Cayratia shows good prospects for textile dyeing [4]. Pigment from Canna indica flower in different media was used; aqueous, ethanolic, and oil/water microemulsions were prepared and used for dyeing cotton. The highest dye uptake was observed for ethanolic extract of Canna flower [5]. A new approach for natural dyeing with anthocyanin has been discussed along with a convenient method of extraction. Anthocyanin from Hibiscus flowers has been extracted by developing a method using methanolic solution of 4% citric acid. The new method gave better yield of anthocyanin as compared with methanolic solution of 0.1% hydrochloric acid. The pH of the extract plays an important role on the dye; thus by adjusting the pH of the extract at 4, dyeing of cotton and silk together with metal mordanting gave different colors. The best dyeing results were obtained for stannous mordanted fabrics in terms of fastness properties. The role of metal ion is to make complexation of stannous salt with the dye extract. Antioxidant activity of the anthocyanin extract seemed to have contributed to enhance the fastness properties of the dyed fabrics [6].

4  New Trends in Natural Dyes for Textiles

Dyes derived from natural sources have emerged as an important alternative to synthetic dyes. Therefore, there is a need for developing better solid-liquid extraction techniques for leaching natural colorants from plant materials for applications in plant research, food, and dyeing industries. The influence of ultrasound on natural colorant extraction from different potential dye-yielding plant materials has been studied in comparison with magnetic stirring process as control. The color yielding plant includes green wattle bark, marigold flowers, pomegranate rinds, 4 o’clock plant flowers, and cockscomb flowers. The results indicate that there is a significant 13%–100% improvement in the extraction efficiency of the colorant obtained from different plant materials due to the use of ultrasound. Therefore, this methodology could be employed for extracting coloring materials from plant materials in a faster and effective manner [7]. Optimization of dyeing conditions of unripe Citrus unshiu extract on silk fabric and antimicrobial activity of the dyed fabric for its potential use as a functional natural dye was carried out. Unripe fruits of C. unshiu in Jeju Island, Korea, extracted in 80% ethanol solution to final solid dye powder were dyed on silk fabric under a variety of conditions such as dye bath concentrations, temperature, and dyeing duration together with mordanting. Dyeing fastness properties to washing, rubbing, perspiration, and light were tested, and the antimicrobial activities of the dyed fabric against Staphylococcus aureus and Klebsiella pneumoniae were investigated quantitatively. The fabric showed the maximum dye uptake (K/S) under the conditions of 80°C for temperature, 30 min for duration, and 600% (owf) for dye concentration. Both pre- and postmordanting seemed not to be effective on increasing K/S values of the dyed silk fabrics under the optimum dyeing conditions. Fastness ratings to washing, rubbing, and perspiration were all very good (4–5 grades) for both 300% and 600% dyed silk fabrics. Excellent antimicrobial activities over 99% reduction rate against two both bacteria were exhibited for all of dyed fabrics that undergone more than 300% of dye concentration. From these results, it was concluded that the dye concentration of 300% of unripe C. unshiu could be employed to produce antimicrobial silk fabric. Furthermore, to get more saturated shades on the fabric by the citrus, higher dye concentration such as 600% was available as well [8]. The alkaline conditions for the extraction of natural dye from Lawsonia (henna) leaves were optimized, and the resulting extract was used to further optimize its dyeing conditions on cotton by exhaust method. Dyeing without any mordant was compared with those obtained with premordanting and postmordanting with alum and iron. It was found that dyeing produced with alkaline extracts of Henna leaves have better color strength than the dye extracts obtained in distilled water. Furthermore, dyeing with alkaline extracts has moderate to good fastness properties and that mordanting did not result in any significant improvement in fastness properties. Finally, in comparative studies between synthetic and this natural dye, it was inferred that natural dye has good potential to act as copartner with synthetic dye [9].

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Illicium griffithii (local name—lissi) produces yellow-colored natural dye from its stem and leaves, which has been used to dye textiles. Innovative dyeing with I. griffithii has been done where premordanting with 1%–2% metal mordants, namely, alum, copper sulfate, ferrous sulfate, potassium dichromate, stannous chloride, and stannic chloride, and using 5% (owf) of plant aqueous solution of the extract are found to be satisfactory and gave very good fastness properties for cotton, wool, and silk fabrics. The innovative solvent extraction of the dry stem-leaves of I. griffithii is an easy process; the solvent is removed, and the aqueous extract was used for dyeing. The CIELAB and color strength (K/S) of the dyed fabrics are also evaluated. The superiority of solvent extraction over conventional extraction has been established through this study [10]. Microwave-assisted extraction of yellow-red natural dye from seeds of Bixa orellana (annatto) was studied. Response surface methodology (RSM) and artificial neural network (ANN) were used to develop predictive models for simulation and optimization of the dye extraction process [11].

1.2  Innovation in Dyeing Novelty in the use of natural colorant is important for expansion of not only new dyes sources but also application of these on different fabrics to get new shades and better dye qualities as wash- and lightfastness. Research for newer dye sources and their effluent treatment as well is the need of the hour. That's how the whole dyeing process can be made a green process. Study is also required to ensure the high quality of the products and to build up sustainable and environmental friendly processes for natural colors and cloth material. With increasing awareness for eco-friendly materials from sustainable resources, natural dyes attracted researchers in traditional and diversified applications to develop effective eco-friendly and cleaner process technologies [12]. The possibility of using bentonite-type clay as a promising substitute for mordants in the natural dyeing of wool with madder was accessed. The results of color measurements showed that the color strength of the dyed samples improved with an increasing amount of clay in the pretreatment baths. Wool yarn was treated with nanoclay by using three conventional methods of pretreatment (before dyeing), simultaneous dyeing with madder in the presence of clay, and after treatment (after dyeing). Madder was used as a natural source of colorant. The results of color measurements showed that the color strength of the dyed samples improved with an increasing amount of clay in the pretreatment baths [13]. In another study, indigo carmine has been used as a source of blue dye for wool and hair dyeing. The option to use indigo carmine in combination with other natural dyes in a one-bath procedure as a hybrid dyeing concept is of interest both for natural dyeing and for coloration of hair. Indigo carmine dyeing on wool exhibited substantial sorption in the range of pH 4–5 and temperature between 40°C and 60°C. Experiments with human hair samples indicated that the experiments on wool could serve as a model that can be applied for hair ­dyeing.

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Comparisons of the energy, water, and chemical consumption between two-bath dyeing with indigo and natural dyes separately and a one-bath dyeing using indigo carmine together with other natural dyes demonstrated the advantages of the one-bath hybrid dyeing concept [14]. The sorption and dyeing properties of indigo carmine on wool were studied as a prerequisite for the successful application in combination with natural dye. The dyeing and sorption characteristics on wool were detected on the basis of spectrophotometry and color measurement. Both high dye sorption and color strength were obtained when dyeing at elevated temperature, for example, 80°C, and lower pH, for example, pH 3. However, there is significant potential to apply the dyestuff also at temperature in the range of 40–60°C and pH values of 4–5. A fast dyeing method of indigo was developed having four steps as (1) feeding indigo plant (indigo plant leaves) and water of 15–30 L in a container and soaking to separate water-soluble indigo plant pigment; (2) adding lime powder and air, agglutinating and settling insoluble indigo plant pigment (formed through the combination of the water-soluble indigo plant pigment with oxygen) via the agglutination force through a chemical reaction of the lime powder, and removing water from the insoluble indigo plant pigment together with the lime powder to obtain indigo plant dye; (3) aging dyeing solution containing the indigo plant dye and lye for a given time, adding sugar, fermenting with microorganism for a given time, and reducing into water-soluble indigo plant pigment; and (4) impregnating fibers in the indigo plant dye and dyeing. The dyeing speed is high, and dyeing fastness is good [15]. Standardization and optimization of dye extraction was carried out for Terminalia arjuna bark. The dyeability of the aqueous extract was evaluated for dyeing cotton fabric. Dyed cotton fabric shows good fastness properties. It is a commercially viable natural dye source [16]. In two-step ultrasonic dyeing of cotton and silk fabrics with natural dyes, T. arjuna, Punica granatum, and Rheum emodi have been developed in which an enzyme is complexed with tannic acid first as a pretreatment. This was found to be comparable with one-step simultaneous dyeing. The effectiveness of three enzymes—protease-amylase, diastase, and lipase— was determined. The enzymatic treatment gave cotton and silk fabrics rapid dye adsorption kinetics and total higher adsorption than untreated samples for all the three dyes. The CIELAB values also showed improvement by enzymatic treatment. The tannic acid-enzyme-dye combination method offers an environmentally benign alternative, “soft chemistry” to the metal mordanted natural dyeing [17]. The forest waste Eucalyptus bark showed good dyeing properties. Mordanting with eco-friendly mordants enhanced the properties. The color of the cotton fabric has been evaluated in terms of L* a* b* values [18]. The extract of the Berberis vulgaris can be considered as a natural dye of acceptable fastness properties together with excellent antibacterial activity for woolen textiles [19].

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Cassia fistula bark that is scraped off is a plant waste that can be exploited as a good source of natural dyeing ranging from light peach, to brown and light green, to dark brown depending on the choice of mordants [20]. Artocarpus heterophyllus (jackfruit) belongs to the family Moraceae. It produces natural dye from bark, which shows as a prospective natural dye source for textile [21]. Dyeing properties of cotton and hosiery material with alroot by using sonicator dyeing have been reported. Aqueous extract of alroot gave very deep ­reddish-brown color with tin mordant [22]. Babul (Acacia arabica) belongs to the class Dicotyledonous of family Fabaceae, subfamily Mimosoideae, and genus Acacia. It is primarily used for fuel wood, timber, agroforestry, and vegetable tanning. Bark is gray to brownish black, rough, and longitudinally fissured. The bark powder is astringent in nature, and there is only one report where Acacia has been used as dye in Nigeria. It was observed that dyeing with babul bark (A. catechu) powder gave fairto-good fastness properties in sonicator dyeing. The color range with babul varies from skin color in the case of stannous chloride to dark brown in the case of ferrous sulfate. A marked improvement in these properties is observed in sonicator dyeing of cotton fabric. Overall, it could be said that babul bark dye can be considered for commercial purpose and the dyed fabric attains acceptable range [23]. Coscinium fenestratum (venivel) belongs to family Menispermaceae. It produces natural dye from its stem, which has been used for dyeing textiles. Innovative dyeing with venivel has been shown to give good dyeing results. Pretreatment with 1%–2% metal mordant and by using 5% of plant extract (owf) was found to be optimum and gave very good fastness properties for cotton, wool, and silk-dyed fabrics [24]. Natural dyes are eco-friendly, harmless, and nontoxic in nature. Some natural dyes provide ultraviolet protection to the wearer. Garcinia indica is called an “Indian spice and kokum” plant. From G. indica, waste bark dye components were extracted in neutral media. Optimization of conditions for the extraction of dye and its effect on various parameters like extraction time, dye material concentration, pH, temperature, dyeing time, and dye concentration had been thoroughly investigated. Extraction and dyeing of organic cotton fabric had been carried out by using G. indica bark extract by simultaneous mordanting techniques using alum, pomegranate rind, myrobalan fruit rind, and used tea leaves powder as a mordant. Ultraviolet protection factor testing shows that G. indica extract dye has got excellent ultraviolet protection [25]. The dyeing of cationized cotton fabric with 3-chloro-2-­hydroxypropyltrimethyl ammonium chloride 69% (Quat 188) using cochineal dye was studied using both conventional and ultrasonic techniques. Factors affecting dye extraction and dye bath exhaustion were investigated. The results indicated that the dye extraction by ultrasound at 300 W was more effective at lower temperatures and times than conventional extraction. Also, the color strength values obtained

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were found to be higher with ultrasound than with conventional techniques. However, the results showed that the fastness properties of the dyed fabrics with ultrasound are similar to those of the conventional dyed fabrics. The scanning electron microscope (SEM) and X-ray diffraction (XRD) were measured for cationized cotton fabrics dyed with both conventional and ultrasound techniques, thus showing the sonicator efficiency [26]. A study was carried out to optimize the dyeing conditions for silk fabrics using a new natural dye, Vervain barks at different pH values in the absence of mordants. Also, expects are implemented to investigate the effects of processing conditions on color difference, color scale, color strength, and lightfastness characteristics. The pH in the acidic range 1–5 is optimum for dyeing, showing very good fastness properties for silk-dyed fabrics [27]. The dyeing of wool fabrics using lac as a natural dye has been studied in both conventional and ultrasonic techniques. The extractability of lac dye from natural origin using power ultrasonic was also evaluated in comparison with conventional heating. The results of dye extraction indicates that power ultrasonic is rather effective than conventional heating at low temperature and short time. The effects of dye bath pH, salt concentration, ultrasonic power, dyeing time, and temperature were studied, and the resulting shades obtained by dyeing with ultrasonic and conventional techniques were compared. Color strength values obtained were found to be higher with ultrasonic than with conventional heating. The results of fastness properties of the dyed fabrics were fair to good. Dyeing kinetics of wool fiber with lac dye using conventional and ultrasonic conditions was compared. The time/dye uptake isotherms are revealing the enhanced dye uptake in the second phase of dyeing (diffusion phase). The values of dyeing rate constant, half-time of dyeing, and standard affinity and ultrasonic efficiency have been calculated and discussed [28]. The dyeing of cationized cotton fabrics with lac natural dye has been studied using both conventional and ultrasonic techniques. The effects of dye bath pH, salt concentration, ultrasonic power, dyeing time, and temperature were studied, and the resulting shades obtained by dyeing with ultrasonic and conventional techniques were compared. Color strength values obtained were found to be higher with ultrasonic than with conventional heating. The results of fastness properties of the dyed fabrics were fair to good. Dyeing kinetics of cationized cotton fiber with lac dye using conventional and ultrasonic conditions were compared. The values of dyeing rate constant, half-time of dyeing, and standard affinity and ultrasonic efficiency have been calculated and discussed [29]. An ultrasound energized dyeing technique of Terycot and cotton fabric with lac dye has been developed. Pretreatment of the fabrics with mild acids followed by dyeing and mordanting gave very good fastness properties to the fabric. Complete dye exhaustion was facilitated for Terycot fabric dyeing for maximum dye uptake [30]. Aqueous extract of Salvia flowers yield brown to green shades on cotton and silk fabric with good fastness properties. The color strength (K/S values)

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is good particularly for cotton mordanted by ferrous sulfate and silk mordanted by copper sulfate [31]. Natural dyes can be used on most types of material or fiber, but the level of success in terms of fastness and clarity of color varies considerably. Dyeing of wool with Portulaca flower extracts using metal mordants shows different shades of red/orange with good quality of wash- and lightfastness [32]. Few natural dyes are colorfast with fibers; mordants are substances that are used to fix a dye to the fibers. They also improve the dye uptake of the fabric and help improve color- and lightfastness. Similarly, Mirabilis jalapa (gulabas, Nyctaginaceae) was used for the dyeing of fabric. And it was observed that the use of mordants enhances the dye uptake ability and gave different shades of brick red to black [33]. Carthamus tinctorius yields yellow-red dye. The pigment carthamin present is a mixture of quinchalcone and precarthamin. Dyeing of cotton, silk, and wool showed excellent fastness properties. Bright shades were produced differed by changing the mordanting agent. Dye was extracted from the petals of the flower by alkaline solution maintaining the pH between 8 and 9. Thus, safflower dye has potential for commercial natural dyeing and can be considered as safe alternative for azoic dye-Direct Yellow 1 [34]. Deep-red Celosia cristata was used for the dyeing of diamine pretreated wool that showed darker shade as compared with morpholine and sodium hydroxide yellow to green [35]. There are several plants or plant parts that provide natural dyes that are used in the textile industry. When Gomphrena globosa flower was used for dyeing wool, beautiful shades of mustered yellow and deep brown to green colors were obtained with high dye uptake values [36]. The standardized dyeing processes proposed are simple, reproducible, and perfectly reliable for the use of textile dyeing. Natural dye is environmentfriendly that is usually extracted from vegetative material. Bright red flower of Rhododendron was used for silk and cotton dyeing and showed green shades with high dye uptake values [37]. The dyeing of fabric with a natural dye extracted from parijat (Nyctanthes arbor-tristis L.) flower stem. Yellow to green colors were obtained on fabric and provide effective utilization of natural resources as eco-friendly method in current situation of global environmental concern. The color yields of the dye on the fabric were found to be good [38]. It is clear that samples dyed with Canna have good fastness properties. The color range obtained with Canna is from pinkish purple to dark purple by premordanting in stannic chloride, green with alum, dark green by premordanting with ferrous sulfate, and mustard yellow by postmordanting with ferrous sulfate. More concentrated dye extract if used can give better results. Preparation of the dye extract by sonicator for better, faster, and efficient extraction of the natural colorant from Canna flowers and to preserve it by adsorbing on solid support was also carried out [39].

10  New Trends in Natural Dyes for Textiles

The flowers of Nerium were found to give out color in hot water very easily. The flowers were frozen after collection and then dipped in hot boiling water to get the maximum color in 30 min that shows deepening of hue color. Flower dye yielded cream, green to purple shades on wool with good fastness properties [40]. It was observed that dyeing with Nerium gave fair-to-good fastness properties in sonicator dyeing. Dyeing in sonicator for 1 h showed good dye uptake. The L*, a*, and b* values with different mordants show higher value of L* and lighter shades, while lower L* values signify deeper shades. Similarly, negative a* and negative b* represents green and blue, respectively, for cotton and silk fabrics. The results clearly show that dyeing in sonicator is better in terms of better dye uptake, reduced dyeing time, and cost-effectiveness. Overall, it could be used for commercial purpose; the dyed fabrics attain acceptable range in terms of fastness properties [41]. Balsam flowers (Impatiens balsamina) were extracted in both methanol and water. The dye uptake was better in methanolic extract of flowers, while aqueous extract showed better fastness properties although the shades were lighter in this case [42]. Lawsonia inermis leaves have been used for dyeing textiles since ancient times. This powder shows color range from orangish brown to dark brown in different medium; it can be a potentially good source of natural colorant for fabric [43]. Evaluation of the efficiency of ultrasonication on new natural dye obtained from leaves and stem extracts of Daphne papyracea using metal mordant for good cotton, silk, and wool dyeing was carried out. It also proposes to effect the characterization of the colorant. For effective natural dyeing with leaves and stem extracts of D. papyracea, both conventional and sonication methods for cotton, silk, and wool dyeing were carried out [44]. Bougainvillea shows a full gamut of colors from dark magenta in acidic medium to yellow basic medium. Basic extract gives mehendi green color with alum; the washing fastness is fairly good [45]. Cotton fabric was dyed with deep purple flowers of Cineraria. Results were excellent with stannic chloride mordants; however, alum ferrous sulfate and stannous chloride also give fairly good fastness properties [46]. Hibiscus mutabilis (Gulzuba)/cotton rose produces natural dye that has been used for dyeing textiles. Aqueous extract of Gulzuba flowers yield shades with good fastness properties. The dye has good scope in the commercial dyeing of cotton, silk for garment industry, and wool yarn for carpet industry. Pretreatment with 2%–4% metal mordants and keeping M-L ratio as 1:40 for the weight of the fabric to plant extract is optimum showing very good colors and fastness properties for cotton, silk, and wool-dyed fabrics [47]. Nephelium lappaceum (rambutan) pericarp grows in Sri Lanka, which is a waste material and has been shown to have good dyeing prospects. This fruit was used for dyeing fabric with different types of mordants. The effect of mordant concentration on the color strength was apparent [48].

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Symplocos spicata (Dom sheng) belonging to family Symplocaceae produces yellowish-brown natural dye that has been used for dyeing textiles since ancient times by the Monpas tribe of Arunachal Pradesh. Leaves of the plant are used by the Monpas and Tibetans for the extraction of dye. Innovative sonicator dyeing with S. spicata showed that pretreatment with 2%–4% metal mordant of the weight of the fabric is optimum showing very good fastness properties for dyed natural polymers such as cotton, wool, and silk. CIELAB and K/S of the dyed fabrics were also evaluated. The superiority of sonicator dyeing over conventional dyeing has been established through this study [49]. Walnut (Juglans regia Linn) is a large deciduous, monoecious tree, mostly grown in unreclaimed and poor soil. An attempt has been made to dye cotton yarns with walnut bark dye and to test the colorfastness of dyed material against light, crocking, perspiration, and washing. It has been found that walnut dye can be successfully used for dyeing of cotton. This dye may be useful in imparting number of fast shades on cotton using common mordants like alum, FeSO4, CuSO4, and chrome with good fastness properties. Thus, this dye may find its use in dyeing of cotton fabrics [50].

1.3  Isolation of Dye Molecule Extensive investigation is now being done by researchers worldwide for the extraction of colorants from different plant parts. Most commonly available raw materials for natural dyes are the different parts of the plants that are indispensable for the survival of plants. In India, huge amount of herbal materials are unutilized and dispose of daily that can be used for the extraction of natural dyes for application in textile industry as a substitute of synthetic dyes. Besides application in textile industry, these dyes can also be used for coloration purpose in food industry, preparation of herbal gulal, and manufacture of colorful candles [51]. A chalcone compound isosalipurposide was qualitatively isolated from A. cyanophylla yellow flowers. The dyeing of wool fabrics with this chalcone compound as a natural dye has been studied. The effect of dye bath pH and dyeing temperature was investigated. The obtained shades were bright with generally good fastness. A postmordanting method was used in the dyeing of wool with this chalcone dye. It was found that, generally, mordanting improved lightfastness especially in the case of zinc sulfate. Chalcone dyes are very old natural colorants, but they are not mainly investigated on textile dyeing. A chalcone compound isosalipurposide was qualitatively isolated from the flowers of A. cyanophylla, a cheap and abundantly available plant in Tunisia, and used to dye woolen fibers at different dyeing conditions. The results indicate that isosalipurposide must be used at low dyeing temperatures in order to avoid its degradation and consequently a fall of the color yield. The obtained shades were bright yellow with good colorfastness properties. Postmordanting improved generally lightfastness especially in the case of zinc sulfate as mordant [52].

12  New Trends in Natural Dyes for Textiles

Berberine, a natural cationic colorant, is the major component of Amur cork tree extract. Due to ionic interactions, while it shows high exhaustion toward protein fibers such as wool and silk, it exhibits little substantivity onto cellulosic fibers. In order to apply the colorant to cellulosic fibers, the new approach of employing the anionic agent containing a dichloro-s-triazinyl reactive group was conducted. A functional colorant, berberine, extracted from B. vulgaris wood was applied onto wool fiber using the extract of roots of Rumex hymenosepalus as biomordant. The effect of treatment variables on the color strength of dyed fibers was examined. The fastness properties of dyed wool against washing, light, dry, and wet rubbing were evaluated. Tannin present in the roots of R. hymenosepalus when used as a biomordant on wool increased the color strength of the dyed goods. Increase in dyeing time, temperature, and pH caused deeper shades. Biomordanting increased lightfastness, rub fastness, and washfastness of dyed samples. The dyed wool represented a high level of antibacterial activity. Berberine could display considerable substantivity toward anionic agent finished fibers. It was found that the anionic agent was covalently bonded to the cellulosic substrates by the virtue of the covalent nature of its attachment to the fibers and also gave anionic sites to the substrate for electrostatic interaction with cationic berberine. The effectiveness of the anionic agent in improving the exhaustion of berberine on the cellulosic fibers was achieved [53]. A reactive anionic agent containing dichloro-s-triazinyl reactive group was synthesized and applied to the cotton fabric. Berberine as a natural cationic colorant showed considerable substantivity toward anionic agent modified fabric. This berberine can be also employed in antimicrobial finishes as a natural agent due to its characteristic of cationic quaternary ammonium salt. It was found that the adsorption of berberine onto cotton fabric pretreated with the anionic agent was greatly increased when compared with that of untreated counterpart. The addition of neutral salts was greatly effective to increase the exhaustion-fixation efficiencies (%EF) of the anionic agent onto the cotton fabric. In terms of antimicrobial activity of berberine dyeing, the dyed sample with berberine showed very effective antimicrobial functions showing about 99.5% of bacterial reduction against S. aureus [54]. Serratula tinctoria L. is a perennial Asteraceae that was used as a yellow dye until the 19th century. The phytochemical study shows that leaves rather than stems should be used and harvested at the end of the plant growing cycle, when flavonoids are particularly concentrated. Microspectrofluorometry showed a specific distribution of the flavonoid aglycone and luteolin in stomatal cells, whereas the corresponding glycoside (luteolin-7-O-glucoside) was observed in palisade parenchyma cells. The flavonoids luteolin-4′-O-glucoside and 3-­methylquercetin were isolated for the first time in S. tinctoria leaves and identified by NMR spectroscopy. Using a rapid and simple method, it was demonstrated that sawwort contained high concentrations of luteolin derivatives and could be considered for use again as a natural dye [55].

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Two anthraquinone compounds are described that were produced by liquid cultures of Fusarium oxysporum, isolated from the roots of citrus trees affected with root rot disease. These anthraquinone compounds are 2-acetyl-3,8-­ dihydroxy-6-methoxy anthraquinone or 3-acetyl-2,8-dihydroxy-6-methoxy anthraquinone. Dyeing of wool fabrics with these new anthraquinone compounds as natural dyes has been studied. The values of dyeing rate constant, half-time of dyeing, and standard affinity were determined. The effect of various dyeing variables such as dye bath pH, salt concentration, dyeing time, and temperature was carried out. Color strength values and the dye uptake were high. The results of fastness properties of the dyed fabric were good [56]. Coloring pigment from Ixora flower has been extracted and used for dyeing cotton and silk fabrics. It is observed that dyeing with Ixora gives fair-to-good fastness properties in sonicator in 1 h and shows good dye uptake as compared with conventional dyeing. The pigment is found to contain chrysin 5-O-β-dxylopyranoside, 4′,5,7-trihydroxyflavone, and 4′-β-d-glucopyranoside. The shade ranges from green to purple in the presence of 2%–4% of mordants. Aqueous extract of red Ixora flowers give dark green to purple shades on cotton and silk with good fastness properties both by conventional and by sonicator dyeing. The mordants used are in 2%–4% only. Although the dye extract is red in color and varies slightly with change in pH, the dye gives shades of green and purple mainly; however, in the case of silk dyeing on Fe mordanted fabric, it gives black shade. The dye has good scope in the commercial dyeing of cotton and silk for garment dyeing for both domestic and international market [57]. Coloring pigment from Plumeria (pink champa) flower has been extracted and used for dyeing wool yarn and silk fabric. It is observed that the dyeing with dark pink flowers gives fair-to-good fastness properties in sonicator in 1 h and shows good dye uptake as compared with conventional dyeing. The pigments found in Plumeria are rutin and quercitrin. The shade ranges from green to purplish gray in the presence of 2%–4% of mordants. It was observed that dyeing with Plumeria gave fair-to-good fastness properties in conventional dyeing for 1 h that showed good dye uptake. The structure of both the colorant, rutin and quercitrin molecules, shows the presence of 3,5-hydroxyl groups that are rightly suited for metal chelation. L*, a*, and b* values and fastness properties for different mordants for silk and cotton, respectively, value of L* showing lighter shades while lower L* values signifies deeper shades. The colorfastness to washing was between 5 and 4–5, for wool and silk, respectively. The sonicator dyeing with conventional method. Sonicator dyeing was found to be better in terms of better dye uptake, reduced dyeing time, and cost-effectiveness. Overall, it could be used for commercial purpose; the dyed wool yarn and silk fabrics attain acceptable range [58]. Coloring pigment from hollyhock (Alcea rosea) flower has been extracted and used for dyeing wool yarn, silk, and cotton fabrics. It is observed that the dyeing with hollyhock gives fair-to-good fastness properties in sonicator in 1 h and shows good dye uptake as compared with conventional dyeing. The

14  New Trends in Natural Dyes for Textiles

p­ igment is found to contain cyanidin-3-glucoside, delphinidin-3-glucoside, and ­malvidin-3,5-diglucoside. The shade ranges from green to brown in the presence of 2%–4% of mordants [59]. A natural dye (anthocyanin) was extracted from red onion (Allium cepa L.) using different buffers as extractant at 25°C for 20 min. The dyeing behavior of these color components on wool has also been evaluated. Dyeing processes were carried out using the mordant mixtures (tannic acid + metal salts) according to pre- and postmordanting methods by using buffer solutions at pH 2–8 for 1 h at 98–100°C with open-bath dyeing technique. Color differences in CIE L*a*b* unit and grayscale classifications are reported. Dyeing conditions and other characteristics show that the mordant mixture is more beneficial than dye as it shows good lightfastness and antibacterial property. The dye obtained from the red onion may be an alternative source to synthetic dyes for the dyeing of wool [60]. The waste parts of the walnut could be used as a natural dye for dyeing textile fibers. The dyeing properties of leaves, husk, and shell of the walnut were examined on various textile fibers (wool, cotton, and viscose) by using different metal salts. Mordants used in dyeing process were chosen as potassium dichromate, copper sulfate, iron sulfate, and aluminum sulfate. Color performance and fastness properties were investigated after dyeing process. The experimental results indicate that walnut-based products can be used in textile dyeing as natural dyes [61]. Antimicrobial activity of wool fabric dyed with the dye was obtained from the fruits of red prickly pear plants that were tested according to diffusion agent. Test organisms as Escherichia coli, Bacillus subtilis, Pseudomonas aeruginosa, and S. aureus were used, and the results indicated that the samples exhibited a high inhibition zone [62]. The dyeing characteristics of lawsone (active ingredient in henna)-indigo mixtures on wool yarn and their electrochemical properties were studied as a model for natural dyeing. To determine the optimum conditions for dyeing, experiments with different levels of pH in the oxidizing and reducing states were considered. The color depth of the dyeing was strongly dependent on the pH of the solution. Dyeing of lawsone in oxidizing and reducing states at pH 4–6 showed the highest color depth. For lawsone-indigo mixtures, the pH of the maximum color strength shifted to pH 6–7. The dyeing properties of henna showed similar behavior to the lawsone dyeing. The electrochemical properties of the lawsone-indigo mixtures were studied using cyclic voltammetry. The cathodic peak current increased with the increasing lawsone concentration. Furthermore, the cathodic peak current of the lawsone-indigo mixtures, which was less than the cathodic peak current of pure lawsone, indicates the sorption of lawsone molecules on the surface of dispersed indigo [63]. In two-step ultrasonic dyeing of cotton and silk fabrics with natural dyes, T. arjuna, P. granatum, and R. emodi have been developed in which an enzyme is complexed with tannic acid first as a pretreatment. The effectiveness of three

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enzymes—protease-amylase, diasterase, and lipase—was determined. The enzymatic treatment gave cotton and silk fabrics rapid dye adsorption kinetics and total higher adsorption than untreated samples for all the three dyes. The CIELAB values also showed improvement by enzymatic treatment. The tannic acid-enzyme-dye combination method offers an environmentally benign alternative, “soft chemistry,” to the metal mordanted natural dyeing [64]. Mimosa tenuiflora extract has been used in food industry as an additive and in textile and leather industry as a colorant. Two types of fabrics, ready to be dyed white and indigo-dyed fabrics, were dyed with M. tenuiflora extract. The fabrics were mordanted after dyeing with six different metal salts. Colorfastness to washing, rubbing, and lighting were performed. Color strength of fabrics was calculated from Kubelka-Munk formula. Highest vividness (C*) values were obtained by Ni mordant. Moderate fastness values were observed. However, poor wet rubbing fastness values were observed in the case of indigo-dyed fabrics due to the lack of good wet rubbing fastness of indigo itself [65]. Melastoma malabathricum is an abundantly available shrub in the northeastern forests of India. Dye extraction was carried out by conventional heating and sonicator. The dyeability of the aqueous extract of Melastoma was evaluated for dyeing cotton fabric by two methods—sonication and conventional heating. It can be industrially very economical and useful dye for handloom and garment sectors [66]. The dyeing of cotton fabric using Eclipta as natural dye has been studied in both conventional and sonicator method. The effects of dyeing show higher color strength values obtained by the latter. The time/dye uptake reveals the enhanced dye uptake showing sonicator efficiency. The results of fastness properties of the dyed fabrics were fair to good. CIELAB values have also been evaluated [67]. Mahonia napaulensis DC. (local name—Taming) family Berberidaceae produces natural dye from its stem that has been used for dyeing textiles by the Apatanis (a tribe of Arunachal Pradesh) since ancient times. Sonicator dyeing with M. napaulensis showed marked improvement in dye uptake. It showed that pretreatment with metal mordant (2%, w/w with respect to the fabric) improved substantially the fastness properties for dyed cotton, silk fabrics, and wool yarn. Five fractions were isolated from column chromatography of the stem extract of Mahonia. These fractions were identified by matching the spectral data that indicated that they were from a well-known isoquinoline alkaloid family [68]. A natural dye extracted from Eucalyptus leaves was applied to a silk and wool fabric by the use of two padding techniques, namely, the pad-batch and pad-dry techniques, under different conditions. Silk and wool fabrics dyed in a solution composed of Eucalyptus extract from leaves showed a shade of pale yellow to brown. The exception was when the fabric was dyed with ferrous mordant, resulting in a shade of dark grayish brown. The fastness properties ranged from good to excellent, while lightfastness was fair to good [69].

16  New Trends in Natural Dyes for Textiles

The genus Colquhounia contains six species of evergreen or semidecidious shrubs that are native to the Himalayas and in Arunachal Pradesh, commonly found in northeast India. The conventional dyeing properties of cotton fabric and wool yarn with the aqueous extract of Colquhounia whole plant (red variety) by using metal mordants was carried out. CIELAB values, K/S values, and fastness properties were ascertained. The aqueous extract of Colquhounia whole plant yields brown to green shades on cotton and wool fabrics with good fastness properties. The color strength is good, particularly for cotton mordanted by ferrous sulfate and wool mordanted by copper sulfate. The dye has good scope in the commercial dyeing of cotton and wool fabric for the garment industry. This dye can be popularized as a cheap source of natural dye [70]. Rubia cordifolia (Tamin, local name) produces anthraquinone reddish-­ orange dyes in roots, stem, and leaves, which has been used for dyeing textiles since ancient times. Commercial sonicator dyeing with Rubia showed that pretreatment with biomordant Eurya acuminata DC var euprista Karth. (Theaceae family) (local names Nausankhee (Apatani tribe) and Turku (Nyishi tribe) in 2%) shows very good fastness properties for dyed cotton using dry powder as 10% of the weight of the fabric is optimum. Use of biomordant replaces metal mordants making natural dyeing eco-friendly [71]. In recent years, the use of low-environmental impact biotechnology giving rises to new types of treatment in the textile industry. The use of protease enzymes to improve some physical and mechanical properties such as smoothness, drape ability, dyeing affinity, and water absorbency is particularly interesting. Wool yarns were first treated with different concentrations of protease enzymes in water solution including 1%, 2%, 4%, and 6% owf for 60 min. The dyeing process was then carried out on the treated yarns with madder (50% owf). Tensile strength of treated yarns was decreased due to enzyme treatment, and it continued to decrease with an increase in enzyme concentration in solution. The L* values decreased for the samples treated with enzyme. The wash- and lightfastness properties of samples were measured according to ISO 105-CO5 and Daylight ISO 105-BO1. The washing fastness properties of treated samples were not changed. In the case of lightfastness properties, it was increased a little for 4% and 6% enzyme-treated samples [72].

1.4  Innovation in Dye fixing Selective premordanting (single and double) and natural dyeing of 6% H2O2 (50%) bleached jute fabric have been carried out using myrobolan (harda) and metallic salts (potash alum and aluminum sulfate) as mordants and aqueous extract of tesu (palash flower petals) as dyeing agent under varying dyeing condition to optimize the dyeing process variables. It is found that the 20% myrobolan followed by 20% aluminum sulfate in sequence is a most potential double premordanting system rather than using them as single mordant separately, considering the results of important textile-related properties and color

Newer Natural Dyes for Various Textiles  Chapter | 1  17

yield. Effects of dyeing process variables (time, temperature, pH, MLR, mordant concentration, dye concentration, and salt concentration) on surface color strength have been evaluated to optimize dyeing conditions. Colorfastness to washing, rubbing, and light, in general, and dyeing pH sensitivity, in particular, for selective fiber-mordant-dye systems have also been assessed, and it is found that dyeing at pH 11 for the system offers overall good color yield and colorfastness properties. Improvement in wash- and lightfastness is also achieved with suitable chemical posttreatment [73]. The combination of dyeing using gallnut-Al, Cu, and Fe-sappanwood and gallnut-Al, Cu, and Fe-gardenia was performed on bast fiber of mulberry, cotton, and silk, and their K/S values, colors, and sunlight fastness were measured. The gallnut-Al, Cu, and Fe-gardenia dyeing showed the highest K/S values when the dyeing concentration of gallnut is 3%. It tended to show the higher K/S values than gallnut-Al, Cu, and Fe-sappanwood. The silk showed the highest values of in K/S and then followed by cotton and bast fiber of mulberry. The mordants developed different colors on the bast fiber and the cotton treated with gallnut-Al, Cu, and Fe-sappanwood [74]. Natural pigments from Crocus sativus stigmas were used for the dyeing of cotton and wool fibers after treatment with the enzymes α-amylase and trypsin, respectively. The separation of various compounds and pigment constituents of the stigmas was effected by the fractionation of the methanolic extract on a silica gel column, and the use of these fractions for dyeing is described. The dyeing properties of the fractions were compared with those of commercial trans-β-carotene [79]. Cotton and wool fabrics were dyed with the natural dyes chlorophyll and carmine after treatment with the enzymes cellulase, α-amylase, and trypsin. Enzymatic pretreatment resulted in an increase in pigment uptake in all cases compared with the corresponding untreated samples and did not affect fastness properties. Pretreatment with metallic salts and dyeing of pretreated samples were also carried out, and the fastness properties of the dyed materials were studied. The effect of conventional mordanting with metallic salts was compared with that of enzymatic treatment on the dyeing properties of the dyes used [75]. The effect of pH value on color of purple sweet potato solution was studied. The dyeing behavior of natural dyestuff, extracted from purple sweet potato, on wool fabric was carried out. The effects of mordants and dyeing methods were investigated, and the air permeability, breaking strength, and anti-UV properties of the dyed fabric were tested. Results showed that at pH ≤3, the color of purple sweet potato natural dye solutions was red; with the increase of pH value, the color of natural dyestuff solution changed from red to blue. The good effect was achieved after pad dyeing using rare earth as the mordant; the air permeability and breaking strength of the dyed fabric dropped in a certain degree, but the anti-UV property improved markedly [76]. The influence of process parameters for ultrasound-assisted leaching of coloring matter from plant materials was checked. In the present work, extraction

18  New Trends in Natural Dyes for Textiles

of natural dye from beetroot using ultrasound has been studied and compared with static/magnetic stirring as a control process at 45°C. The influence of process parameters on the extraction efficiency such as ultrasonic output power, time, pulse mode, effect of solvent system, and amount of beetroot has been studied. The use of ultrasound is found to have significant improvement in the extraction efficiency of colorant obtained from beetroot. Based on the experiments, it has been found that a mixture of 1:1 ethanol-water with 80 W ultrasonic power for 3 h contact time provided better yield and extraction efficiency. Pulse mode operation may be useful in reducing electric energy consumption in the extraction process. The effect of the amount of beetroot used in relation to extraction efficiency has also been studied. Two-stage extraction has been studied and found to be beneficial for improving the yield for higher amounts of beetroot. Significant 8% enhancement in percent yield of colorant has been achieved with ultrasound, 80 W as compared with MS process both using 1:1 ethanol-water. The coloring ability of extracted beet dye has been tested on substrates such as leather and paper and found to be suitable for dyeing. Ultrasound is also found to be beneficial in natural dyeing of leather with improved rate of exhaustion. Both the dyed substrates have better color values for ultrasonic beet extract as inferred from reflectance measurement. Therefore, the present study clearly offers efficient extraction methodology from natural dye resources such as beetroot with ultrasound even dispensing with external heating, thereby also making ecofriendly nontoxic dyeing of fibrous substances a potential viable option [77]. A single-bath dyeing of linen fabric with natural dyes, Curcuma longa, logwood, and pomegranate has been developed. In this process, one or more enzymes are complexed with tannic acid and a natural dye. On the basis of the developed enzyme complexes of the natural dyes, a comparison was made between the three dyeing methods, exhaustion, pad dry, and pad-dry-cure methods. The effectiveness of the four enzymes, neutral cellulase, protease, α-amylase, and lipase, and three mixtures of these enzymes, α-amylase + lipase, neutral cellulase + lipase, and neutral cellulose + α-amylase, was determined. A broad variation in shade, hue, and color depth can be achieved by applying enzymes and mixtures of enzymes complexes in the three dyeing methods. Colorimetric data show dyeing improvement using these enzymic complexes. It was found that each of the four enzymes and their mixtures were very effective, when used in conjunction with tannic acid in improving the washing fastness of the three natural dyes. The use of enzyme/tannic acid/natural dye complexes replaces metal mordants making natural dyeing process more eco-friendly [78]. Aqueous extract of natural dye tea was dyed on the wool fabric with dark brown for 2% and 5% shade. The tea contains tannins as the main colorant species to produce different shades with different mordant salts. The mordant salts alum, CuSO4, FeSO4, ZnSO4, Na2SO4, and MgSO4 were used to dye fabric using three different dyeing methods: premordanting, metamordanting, and postmordanting. The color of the fabric was investigated in terms of K/S and CIELAB-color difference values. The postmordanting method gave the great

Newer Natural Dyes for Various Textiles  Chapter | 1  19

depth of shade of natural dye tea with 2% and 5% shade; it also gives good lightfastness and washfastness properties. Copper was found as a good mordant to achieve the best results with transition metal ion effect. Deep shades (K/S = 17.50) were obtained for original sample of 5% with color difference ΔE value of 0.17, as compare with 2% original sample of tea of light brown shades (K/S = 10.50) with color difference ΔE value of 0.50 under maintained temperature at 85°C for 35 min of dyeing [79]. Polyacrylonitrile fiber cured by enzyme was dyed by natural dye cochineal. The effect of pretreating agent and enzyme concentration, temperature, time and pH value was discussed. The conclusion was that the dye uptake of polyacrylonitrile fiber pretreated by benzyl alcohol was higher than that of pretreated by ethylene glycol methyl ether; the dye uptake of polyacrylonitrile fiber cured by enzyme was highest when enzyme concentration was 5% and enzyme cure time was 50 h, as well as enzyme cure temperature was 40°C and pH value was 7. The water return rate of polyacrylonitrile fiber cured by enzyme was increased noteworthily [80]. The roots of R. tinctorum L. have a long tradition of being used in dyeing processes of textiles from centuries ago until the present time. The coloring principles belong to the class of hydroxyl anthraquinones. Concern arose because several of these compounds were recognized as mutagenic in vitro and even carcinogenic in rodents. To assess the possible risk to humans caused by colored textiles, mutagenicity was investigated with two madder root samples of different origin (Iran and Bhutan) along the entire dyeing process from root extracts to the dyed wool. The salmonella/microsome test (Ames assay) with the different strains was used. Significant mutagenic effects could be detected in madder root extracts and also in the final product, the dyed wool. Madder root from Iran showed considerably higher mutagenic responses than samples from Bhutan. Analytic investigations of the extracts by high-pressure liquid chromatography (HPLC) showed the presence of a spectrum of anthraquinones typical for madder root. Three mutagenic compounds, lucidine, rubiadine, and purpuroxanthine, together with the nonmutagenic alizarin could be detected. The mutagenic response of the different samples was positively correlated with the concentration of the mutagenic anthraquinones and with lucidine in particular. Based on these investigations, a risk to dye-house workers and users of textiles dyed with R. tinctorum must be anticipated [81]. Aqueous extract of Garcinia was prepared by sonicator for quick extraction of colorant and has been used for dyeing of cotton, wool, and silk yarn. One to two percent premordanting with metal salts of Al, Sn, Fe, Cr, and Cu was done. Fe, Cu, and Cr are best suited mordant for Garcinia. The color ranged from camel brown to dark chocolate brown. The color strength K/S has been found to be very good in dyed samples. The fastness properties have also been evaluated and were found to be well above the acceptable limits [82]. The art of making vegetable dyes is one of the oldest known to man and dates back to the dawn of civilization. In India, it was widely used for coloring

20  New Trends in Natural Dyes for Textiles

of fabrics and other materials. Henna plant leaves (L. inermis) contain dye along with other ingredients. Myrabolan is a fruit of tree T. chebula (Harda). This is used as greenish-yellow dyestuff for textile. This is also used as natural mordant in many cases. This is also used as a substitute of tannic acid. Catechu is purified extract of wood A. catechu. This is mainly composed of catechutannic acid with catechin, catechu red, and quercetin. The colorfastness of dyed silk fiber of water and soap solution at different treatment temperature was satisfactory. Considering dye ability and colorfastness, dye from henna matured leaves was highly applicable on dyeing of silk fiber and other protein fibers [83]. For a trial to improve, the natural dyeing cultural heritage to meet the environmental future demands technology to reach high-quality dyed patterns. The work deals with extraction, dyeing of woolen fabric with “Sticta coronata” under ultrasonic energy, and glucose/hydrogen peroxide-based redox system. The efficiency of ultrasonic-assisted extraction in the presence of 9:1 wateracetone solvent and dyeing in the presence of redox system, followed by alum mordanting, has been studied in comparison with the system that was absent and the traditional thermal technique. The influence of redox system, ultrasonic energy, and alum mordanting on the rate of dyeing and dye fixation has been demonstrated, and the mechanism of glucose/hydrogen peroxide redox system has been tentatively suggested. The extraction with 9:1 water-acetone solvent possesses higher absorbency in shorter extraction time compared with the aqueous one. Redox system reduced the rate of dyeing at lower temperature with significant enhancement on the dye exhaustion and fixation, involving covalent bonding in addition to the usual coulombic bond. Mordanting process exhibited negligible effect and might decline the percentages of dye exhaustion and fixation in the presence of redox system. Ultrasonic energy provided easy efficient route for dye extraction, dyeing, and mordanting processes in comparison with the traditional thermal technique [84]. The environmental safe treatment methods were used to improve the penetrability of wool fibers with natural dye (madder) in the presence of chemically and physically modified natural soybean lecithin. The dyeing conditions of wool fiber with madder were optimized by response surface methodol (RSM). The five independent variables were selected at low and high level values. The ANOVA results of the quadratic model show that the model terms such as dyeing temperature, dyeing time, lecithin concentration, plasma treatment duration, dyeing method, and their interactions are significant. Moreover, the optimum conditions that were proposed for the natural dyeing of LTP-treated wool fibers cause dyeing temperature to reach 76°C in the presence of acetylated lecithin [85]. Natural dyeing properties of best fiber were investigated; properties of premordanting dyeing of sappanwood, gardenia, and gallnut such as K/S values, developed color, and fastness were evaluated. Silk showed the most increased K/S values by premordanting treatment when Fe was used as a mordant. The optimized amount of Fe was 3%. The colors of sappanwood were a series of

Newer Natural Dyes for Various Textiles  Chapter | 1  21

YR. After premordanting treatment with Fe, the colors of bast fiber of mulberry and silk showed a series of RP, and the color of cotton showed a series of Y. The color of gallnut was a series of Y regardless of premordant treatment. Sappanwood (YR), gardenia (Y), and gallnut (Y) showed various colors such as YR, R, and RP, respectively. Sunlight fastness was not improved by premordanting treatment. The effect of premordanting treatment was not good. Especially, the treatment with Al showed poor sunlight fastness [86]. The study of the natural pigment from sappanwood was used for the dyeing of wool fabrics after treatment with the protease and transglutaminase. The influences of protease and transglutaminase on the UV/visible absorption spectrum of aqueous extract of sappan were studied. The enzymatic-modified wool was compared with nonmodified wool in K/S value and fastness after direct dyeing and mordant dyeing. It was shown that protease and transglutaminase made the absorbance at the λmax 540 nm in visible region increase. It suggested that there might be some interaction between the enzymes and sappan dye, and the residual enzyme on wool fabric might affect the color of the following dyeing. Compared with untreated wool, treatments with protease and transglutaminase enhance K/S value of wool dyed subsequently with sappan. Modification of protease led to some decrease in wet rubbing fastness, whereas transglutaminase had almost no influence on rubbing fastness. Enzymatic treatments have no influence on the washing fastness for samples dyed with sappan [87]. The introduction of natural dyes into modern textile dye houses requires the classification of products of standardized quality with regard to color depth and shade of the dyeing. Canadian golden rod was chosen as a representative example to test the methods that are available to assess the quality of different crops of plant material that had been collected over a period of 5  years. Aqueous solutions containing the extracted flavonoid dyes were characterized by means of direct photometry, measurement of absorbance after the addition of FeCl2, analysis of total phenolics (TPH) in the extract, and dyeing on wool yarn. TPH calculated as gallic acid varied from 62 to 97 g/kg of plant material; only one sample exceeded this range with a value for TPH of 142 g/kg. Correlation among TPH, photometry in the presence of FeCl2, and lightness of the dyeing can be used to characterize samples. However, correlation between the photometric results and color depth of dyeing is not sufficient to permit the characterization of the plant material with regard to the final dyeing [88]. Research work involving dyeing of wool with indicaxanthin, a natural dye extracted from fruits of Opuntia ficus-indica was carried out. The optimal conditions for dye extraction were to mix 50 g of juice from cactus pears with 100 mL of 80% aqueous ethanol as solvent for dye extraction. Liquid chromatography was applied for the separation. Two main dyes were obtained, which were identified as indicaxanthin (75 mg/50 g) and betanin (5 mg/50 g). The effect of dye bath pH, salt concentration, dyeing time, and temperature was studied. The optimal conditions for wool dyeing with indicaxanthin dye were carried out at 70°C for 90 min with the pretreatment of various metal salts as mordant. The color

22  New Trends in Natural Dyes for Textiles

yields of the dye on the wool were found to be highly dependent of the pH, optimum results being obtained at pH 4. The K/S of wool increased in the order of the dyeing using KAl (SO4)2 > MnSO4 > CoSO4 > FeSO4 > none > ZnSO4 > CuS O4. Unmordanted samples have good properties of water and washing fastness. Mordants KAl (SO4)2 and CoSO4 were found to give good lightfastness [89]. Six weld genotypes (Reseda luteola L.) were evaluated for their agronomic characteristics in a 4-year field study carried out under rain-fed condition in central Italy in order to point out productive potential and the best harvest time to maximize yield of dye. Good agronomic performances were observed with an overall dry yield of about 40 g per plant and an estimated dry yield per hectare of 2.8 tons. Differences were found among the six accessions and some of them with stand well to drought conditions experienced in drier growing seasons. The dry powder from leaves and reproductive structures was used in the dyeing of cotton, wool, and silk yarns. Good and bright yellow colors were observed using a ratio 30:100 (weight/weight) of weld on the textile materials. Separated weld organs showed different dyeing capacities being the leaves, inflorescences, and fruits the most effective ones. Weld showed a progressive decrease in resistance to fading going from cotton to the other kinds of yarns. Finally, all dyed specimens exhibited good resistance to light- and washfastness making the use of weld a viable alternative to synthetic yellow dyes [90]. Wool fabric was dyed by shikonin. The optimum conditions of dyeing wool fabric with shikonin were obtained by the orthogonal and single-factor analysis experiments. The specific process conditions are as follows: liquor ratio 1:40, dye concentration 80 mL/L, pH 4, temperature 80°C, and time 60 min. The results indicated that fastness to washing and to rubbing of wool fabrics dyed with shikonin was good and has reached more than three level [91]. Brassica oleracea var. capitata f. rubra is the purple cabbage that belongs to family Brassicaceae. It is a sort of cabbage, also known as red cabbage. Its leaves are colored dark mauve. However, the plant changes its color according to the pH value of the soil. The aqueous extract of purple cabbage has been used for dyeing cotton, silk, and wool. Optimization of dye extraction has been carried out. Different mordants with premordanting techniques were adopted to get different shades; their fastness properties were assessed, and the CIELAB values were determined by cotton dyeing that shows that potassium dichromate mordanted fabric showed poor color strength and stannic chloride mordanted fabric showed good color strength. Similarly, the case of silk fabrics showed good color strength for stannic and average color strength in the case of alum and copper. In the case of wool yarn, stannous chloride shows best results followed by stannic and potassium dichromate that showed least color strength. The results are very encouraging; it is for the first time that purple cabbage has been used as a dye source for silk and wool dyeing. Dried bark of Salacia prinoides (Kothala) was analyzed for natural dyes with three different kinds of fibers, namely, cotton, silk, and wool, using different mordants, namely, chrome, copper sulfate and ferrous sulfate, alum, and stannous chloride. The aqueous extract of the bark exhibits good range of colors [92].

Newer Natural Dyes for Various Textiles  Chapter | 1  23

The efficiency of dyeing on cotton wool and silk fabrics with natural dye obtained from kitchen waste of dry skin extract of A. cepa was evaluated. The dry skin of onion produces natural dye that has been used for dyeing textiles. In this study, innovative dyeing with onion has been shown to give good dyeing results. Pretreatment with 2% metal mordant and using 5% of plant extract was found to be optimum and showed very good fastness properties for cotton, wool, and silk-dyed fabrics. For effective natural dyeing with dry skin extract of A. cepa, conventional method of dyeing was carried out using metal mordants. The purpose of using this source was with an idea to produce value addition dyed product from kitchen waste as the dye has very good potential of uptake, adherence to the fabric, and good wash- and lightfastnesses. Results show very attractive hue colors. The preference of using easily and cheaply available material for dyeing by conventional dyeing lowers the cost of natural dyeing and enhances resource productivity and as a result reduces waste. This makes onion scale one of the easily available materials for natural dyeing industry. Although metal mordanting with copper sulfate and potassium dichromate is not ecofriendly, we have used only 2% of these metal salts to prepare different shades with dry scales of A. cepa extract [93]. Bischofia javanica Bl. (local name—Maub) was used for dyeing, which belongs to family Euphorbiaceae for natural dye production for textile dyeing. Innovative sonicator dyeing with Bischofia has been shown to give good dyeing results. Pretreatment with 1%–2% metal mordant and using 5% of plant extract (owf) is found to be optimum and shows very good fastness properties for cotton, wool, and silk-dyed fabrics. The net enhancement of dye uptake due to metal mordanting and sonication was found to range from 30% to 50% (cotton), 37% to 52% (silk), and in wool, it was 38% to 50% [94]. The efficiency of ultrasonication on new natural dye obtained from leaves extract of Acer pectinatum Wallich using metal mordant for good cotton dyeing prospects was evaluated. For effective natural dyeing with leaves extract of A. pectinatum Wallich, both conventional and sonication methods of dyeing were carried out using metal mordants. The purpose of using sonication was for the improvement of dye uptake, improved dye adherence, and good wash- and lightfastnesses. Results show marked improvement for this dyeing method [95]. The method developed for natural dyeing of cotton, silk, and wool fabrics using ultrasound energy to dye with sappanwood in conjunction with metal mordanting has shown very deep coloration. The stepwise dyeing of cotton fabric with metal mordant by this natural dye, showed very good result. The dye uptake in case of stepwise dyeing was from 65% to 68% in the case of cotton, 70% to 74% in silk, and 78% to 82% in wool with different mordants [96]. The method developed for natural dyeing of cotton, silk, and wool fabrics using Parkia javanica in conjunction with metal mordanting has shown marked improvement in terms of dye adherence and fastness properties and can thus be recommended for industrial application. The technique is adopted to get different shades in aqueous medium and shows good prospects for textile dyeing [97].

24  New Trends in Natural Dyes for Textiles

Malus sikkimensis (local name—Chap shaw sheng) belongs to family Rosaceae and is being primarily used for preparing tea by Monpas tribes of Arunachal Pradesh. In the present study, sonicator dyeing with Malus extract has been demonstrated. Pretreatment with 1%–2% metal mordant and using 5% of plant extract (owf) was found to be optimum and showed very good hue colors for cotton, wool, and silk-dyed fabrics. The use of sonication in conjunction with metal mordanting has a synergistic effect on better dye uptake, dye adherence, and eventually on good fastness properties of the dyed swatches of cotton, silk, and wool [98].

1.5 Conclusion Naturally derived pigments are available in nature with various hues and tones. New sources of biomass-based pigments need to be available in sufficient quantities for stability during processing and storing for large-scale cultivation, industrial extraction, formulations, harvesting and storage, and application of biotechnological tools including cell and tissue cultures and genetic engineering, promoted by experts as a replacement for conventional growing techniques. Extensive investigation is now being done by researchers worldwide for extraction of colorants from different plant parts. Most commonly available raw materials for natural dyes are different parts of the plants that are indispensable for the survival of plants. In India, huge amount of herbal materials is unutilized and disposed of daily that can be used for the extraction of natural dyes for application in textile industry as a substitute of synthetic dyes. Besides application in textile industry, these dyes can also be used for coloration purpose in food industry, preparation of herbal gulal, and manufacture of colorful candles [99]. Natural dyes produce an extraordinary diversity of rich and complex colors that complement each other. Dye extracts may look a little expensive at first, but they are very economical when their concentration has been taken to account. So much of work has already been done on most of the old dyes that the need of newer dye sources has emerged to keep alive the use of these dyes. Many scientists/researchers are doing a great deal of work in the area of amelioration of natural dyes, and this period can be considered as the renaissance of natural dyes. The increasing knowledge of different natural sources providing beautiful colors is expanding the shade cards of different fabrics. Revamping of this ancient art has another distinctive attribute, that is, the empowerment of such tribes that used to thrive on this form of art.

References [1] Mirjalili M, Nazarpoor K, Karimi L. Eco-friendly dyeing of wool using natural dye from weld as co-partner with synthetic dye. J Clean Prod 2011;19(9–10):1045–51. [2] Vankar PS, Tiwari V, Ghorpade B. Supercritical fluid extraction of natural dye from eucalyptus bark for cotton dyeing in microwave and sonicator. Asian Text J 2001;10(2):68–70.

Newer Natural Dyes for Various Textiles  Chapter | 1  25 [3] Tiwari V, Vankar P. Unconventional natural dyeing using microwave and sonicator with alkanet root bark. Colourage 2001;48(5):25–8. [4] Vankar PS, Shanker R. Dyeing cotton, silk and wool with Cayratia carnosa Gagn. or Vitis trifolia. Asian Text J 2006;38:38–45. [5] Srivastava J, Seth R, Shanker R, Vankar P. Solubilisation of red pigments from Canna indica flower in different media and cotton fabric dyeing. Int Dyer 2008;1:31–6. [6] Vankar PS, Shukla D. Natural dyeing with anthocyanins from Hibiscus rosa sinensis flowers. J Appl Polym Sci 2011;122(5):3361–8. [7] Sivakumar V, Vijaeeswarri J, Anna JL. Effective natural dye extraction from different plant materials using ultrasound. Ind Crop Prod 2011;33(1):116–22. [8] Lee AR, Hong J-U, Yang YA, Yi E. Dyeing properties and antimicrobial activity of silk fabric with extract of unripe Citrus unshiu fruits. Fibers Polym 2010;11(7):982–8. [9] Ali S, Hussain T, Nawaz R. Optimization of alkaline extraction of natural dye from Henna leaves and its dyeing on cotton by exhaust method. J Clean Prod 2009;17(1):61–6. [10] Vankar PS, Dixit S. Natural dyeing of cotton, wool and silk with the stem and leaves extract of Illicium griffithii. Res J Text Apparel 2011;15(2):77–83. [11] Sinha  K, Chowdhury  S, Saha  PD, Datta  S. Modeling of microwave-assisted extraction of natural dye from seeds of Bixa orellana (Annatto) using response surface methodology (RSM) and artificial neural network (ANN). Ind Crop Prod 2013;41:165–71. [12] Shahid M, Ahmad A, Yusuf M, Khan MI, Khan SA, Manzoor N, et al. Dyeing, fastness and antimicrobial properties of woolen yarns dyed with gallnut (Quercus infectoria Oliv.) extract. Dyes Pigments 2012;95(1):53–61. [13] Parvinzadeh Gashti M, Katozian B, Shaver M, Kiumarsi A. Clay nanoadsorbent as an environmentally friendly substitute for mordants in the natural dyeing of carpet piles. Color Technol 2014;130(1):54–61. [14] Komboonchoo S, Bechtold T. Natural dyeing of wool and hair with indigo carmine (CI Natural Blue 2), a renewable resource based blue dye. J Clean Prod 2009;17(16):1487–93. [15] Hwang SH. Natural dyeing method of fiber using an indigo plant. Google Patents; 2013. [16] Tiwari V, Vankar PS. Standardization, optimization and dyeing cotton with Terminalia arjuna. Int Dyer 2007;6:31–3. [17] Vankar PS, Shanker R, Verma A. Enzymatic natural dyeing of cotton and silk fabrics without metal mordants. J Clean Prod 2007;15(15):1441–50. [18] Vankar P, Mishra A, Ghorpade B, Tiwari V. Sonicator dyeing of cotton with eucalyptus bark using copper and chromium mordants, yet ecofriendly. Colourage 2000;47(9):25–8. [19] Haji A. Functional dyeing of wool with natural dye extracted from Berberis vulgaris wood and Rumex hymenosepolus root as biomordant. Iran J Chem Chem Eng 2010;29(3):55–60. [20] Vankar PS, Mishra A, Tiwari V, Ghorpade B. Ultrasonic energised dyeing of cotton fabric with Cassia fistula bark (Amaltas). Asian Text J 2001;10(11):56–8. [21] Vankar PS, Shanker R, Wijayapala S. Dyeing of cotton, silk and wool with bark extract of Artocarpus heterophyllus Lam. Res J Text Apparel 2011;15(2):52–60. [22] Tiwari  V, Ghaisas  A, Vankar  P. Improved dyeing of hosiery material and cotton fabric by sonicator with Al root bark. Asian Text 2001;111–4. [23] Tiwari V, Shanka R, Vankar PS. Ultrasonic dyeing cotton fabric with Babool bark (Acacia arabica) for preparation of eco-friendly textile. Chemical World; 2001. [24] Vankar PS, Shanker R, Wijayapala S, Silva NGHD, Alwis AD. Dyeing of cotton, wool and silk with the stem extracts of Coscinium fenestratum (Venivel). Asian Text J 2007;16(10):59–64. [25] Kauvery Bai S, Hegde MG. Eco friendly dyeing of organic cotton fabrics with Garcinia indica bark extract. Text Trends 2011;54(1):37–41.

26  New Trends in Natural Dyes for Textiles [26] Kamel  M, El Zawahry  M, Ahmed  N, Abdelghaffar  F. Ultrasonic dyeing of cationized cotton fabric with natural dye. Part  2: cationization of cotton using Quat 188. Ind Crop Prod 2011;34(3):1410–7. [27] Al-Amoudi  E, Osman  E. Optimization of dyeing performance of an eco friendly natural dye “Vervain Barks” applied to silk fabrics at different pH values. Res J Text Apparel 2009;13(1):34–45. [28] Kamel M, El-Shishtawy RM, Yussef B, Mashaly H. Ultrasonic assisted dyeing: III. Dyeing of wool with lac as a natural dye. Dyes Pigments 2005;65(2):103–10. [29] Kamel MM, El-Shishtawy RM, Youssef B, Mashaly H. Ultrasonic assisted dyeing. IV. Dyeing of cationised cotton with lac natural dye. Dyes Pigments 2007;73(3):279–84. [30] Tiwari V, Ghorpade B, Vankar PS. Dyeing Terycot and cotton fabric with lac dye in sonicator. Asian Text J 2000;9(6):68–70. [31] Vankar PS, Kushwaha A. Salvia splendens, a source of natural dye for cotton and silk fabric dyeing. Asian Dyers 2011;6:29–32. [32] Shanker R, Verma S, Vankar PS. Ultrasound energised dyeing of wool with Portulaca flower extracts using metal mordants. Colourage 2004;51(10):41–6. [33] Shanker  R, Vankar  PS. Ultrasonic energised dyeing of wool with Mirabilis jalpa flowers. Colourage 2005;52(2):57–61. [34] Vankar P, Tiwari V, Shanker R, Singh S. Carthamus tinctorius (safflower), a commercially viable dye for textiles. Asian Dyers 2004;1:25–9. [35] Shanker  R, Vankar  PS. Dyeing with Celosia cristata flower on modified pretreated wool. Colourage 2005;52(7):53. [36] Shanker  R, Vankar  PS. Dyeing wool with Gomphrena globosa flower. Colourage 2005;52(4):35–8. [37] Vankar P, Shanker R. Natural dyeing of silk and cotton by Rhododendron flower extract. Int Dyers 2010;7:37–40. [38] Vankar  PS, Shanker  R. Dyeing cotton, wool and silk with parijat with aqueous extract of flower stem. Asian Dyers 2005;2(4):59. [39] Ghorpade  B, Tiwari  V, Vankar  P. Ultrasound energised dyeing of cotton fabric with canna flower extracts using eco friendly mordants. Asian Text J 2000;3:68–9. [40] Shanker R, Vankar DPS. Dyeing with Nerium oleander flower on pretreated wool. Asian Text J 2005;14(11):75–7. [41] Vankar  PS, Shanker  R. Ultrasonic dyeing of cotton and silk with Nerium oleander flower. Colourage 2008;55(4):90–4. [42] Tiwari V, Ghorpade B, Vankar P. Ultrasonic dyeing with impatiens balsamina (balsam) using ecofriendly mordants on cotton. Colourage 2000;47(3):21–2. [43] Vankar PS, Tiwari V, Shankar R. Commercial viability of dyeing cotton with aqueous extract of Lawsonia (henna) using eco-friendly mordant. Asian Text J 2008;76(1):207. [44] Vankar PS, Shanker R, Dixit S, Mahanta D, Tiwari SC. Chemical characterization of the colorants from leaves and stem of Daphne papyraceae wall and sonicator dyeing of cotton, silk and wool with the plant extract. Pigm Resin Technol 2009;38(3):181–7. [45] Tiwari V, Ghorpade B, Vankar PS. Ultrasound energised dyeing with aqueous extract of Bougainvillea using eco friendly mordants. Asian Text J 2000;9(2):28–30. [46] Vankar PS, Mishra A, Ghorpade B, Tiwari V. Ultrasound energized dyeing of cot- ton fabric with Cineraria flowers using ecofriendly mordants. Asian Text J 2000;9(7):58–9. [47] Shanker R, Vankar PS. Dyeing cotton, wool and silk with Hibiscus mutabilis (Gulzuba). Dyes Pigments 2007;74(2):464–9. [48] Vankar P, De Alwisb A, De Silvab N. Dyeing of dyeing cotton, wool and silk with extract of Nephelium lappaceum (Rambutan) pericarp. Asian Text J 2007;66–70.

Newer Natural Dyes for Various Textiles  Chapter | 1  27 [49] Vankar PS, Shanker R, Dixit S, Mahanta D, Tiwari S. Sonicator dyeing of natural polymers with Symplocos spicata by metal chelation. Fibers Polym 2008;9(2):121. [50] Sharma  A, Grover  E. Colour fastness of walnut dye on cotton. Indian J Nat Prod Resour 2011;2(2):164–9. [51] Sinha K, Saha PD, Datta S. Extraction of natural dye from petals of flame of forest (Butea monosperma) flower: process optimization using response surface methodology (RSM). Dyes Pigments 2012;94(2):212–6. [52] Ghouila H, Meksi N, Haddar W, Mhenni M, Jannet H. Extraction, identification and dyeing studies of Isosalipurposide, a natural chalcone dye from Acacia cyanophylla flowers on wool. Ind Crop Prod 2012;35(1):31–6. [53] Kim T-K, Yoon S-H, Son Y-A. Effect of reactive anionic agent on dyeing of cellulosic fibers with a berberine colorant. Dyes Pigments 2004;60(2):121–7. [54] Kim  T-K, Son  Y-A. Effect of reactive anionic agent on dyeing of cellulosic fibers with a berberine colorant—part 2: anionic agent treatment and antimicrobial activity of a berberine dyeing. Dyes Pigments 2005;64(1):85–9. [55] Guinot P, Gargadennec A, La Fisca P, Fruchier A, Andary C, Mondolot L. Serratula tinctoria, a source of natural dye: flavonoid pattern and histolocalization. Ind Crops Prod 2009;29(2–3):320–5. [56] Nagia F, El-Mohamedy R. Dyeing of wool with natural anthraquinone dyes from Fusarium oxysporum. Dyes Pigments 2007;75(3):550–5. [57] Vankar P, Shanker R. Sonicator dyeing of cotton and silk fabric by Ixora coccinea. Asian Text J 2006;77–80. [58] Vankar  P, Shankar  R. Dyeing silk and wool with Plumeria (pink) flower. Asian Text J 2007;104–7. [59] Vankar PS, Shanker R. Dyeing silk, wool and cotton with Alcea rosea flower. Fibre 2 Fashion; 2006. [60] Gümrükçü G. Effect of tannic acid and metal salts on dyeing of woolen fabrics with red onion (Allium cepa L.). Asian J Chem 2011;23(4):1459. [61] Tutak M, Benli H. Colour and fastness of fabrics dyed with walnut (Juglans regia L.) base natural dyes. Asian J Chem 2011;23(2):566. [62] Ali N, El-Mohamedy R. Eco-friendly and protective natural dye from red prickly pear (Opuntia Lasiacantha Pfeiffer) plant. J Saudi Chem Soc 2011;15(3):257–61. [63] Komboonchoo S, Bechtold T. A study on the dyeing characteristics and electrochemical behaviour of lawsone–indigo mixtures. Color Technol 2011;127(3):153–8. [64] Vankar PS, Shanker R. Ecofriendly ultrasonic natural dyeing of cotton fabric with enzyme pretreatments. Desalination 2008;230(1–3):62–9. [65] Erkan G, Şengül K, Kaya S. Dyeing of white and indigo dyed cotton fabrics with Mimosa tenuiflora extract. J Saudi Chem Soc 2014;18(2):139–48. [66] Vankar PS, Tiwari V, Singh LW, Potsangbam L. Sonicator dyeing of cotton fabric and chemical characterization of the colorant from Melastoma malabathricum. Pigm Resin Technol 2009;38(1):38–42. [67] Vankar PS, Shanker R, Srivastava J. Ultrasonic dyeing of cotton fabric with aqueous extract of Eclipta alba. Dyes Pigments 2007;72(1):33–7. [68] Vankar PS, Shanker R, Dixit S, Mahanta D, Tiwari S. Sonicator dyeing of modified cotton, wool and silk with Mahonia napaulensis DC. and identification of the colorant in Mahonia. Ind Crop Prod 2008;27(3):371–9. [69] Mongkholrattanasit  R, Kryštůfek  J, Wiener  J. Dyeing and fastness properties of natural dyes extracted from eucalyptus leaves using padding techniques. Fibers Polym 2010;11(3):346–50.

28  New Trends in Natural Dyes for Textiles [70] Vankar P, Shankar R, Mahanta D. Natural dyeing of wool and cotton with extract of Colquhounia coccinea. Asian Dyers 2010;51–4. [71] Vankar  PS, Shanker  R, Mahanta  D, Tiwari  S. Ecofriendly sonicator dyeing of cotton with Rubia cordifolia Linn. using biomordant. Dyes Pigments 2008;76(1):207–12. [72] Parvinzadeh M. Effect of proteolytic enzyme on dyeing of wool with madder. Enzyme Microb Technol 2007;40(7):1719–22. [73] Samanta  AK, Konar  A, Chakraborti  S, Datta  S. Dyeing of jute fabric with tesu extract: part 1—effects of different mordants and dyeing process variables. Indian J Fibre Text Res 2011;36:63–73. [74] Park M-O, Yoon S-L. Properties of natural dyeing of bast fiber (part 3) combination dyeing of gallnut-sappan wood and gardenia. J Korea Techn Assoc Pulp Paper Ind 2011;43(1):1–10. [75] Liakopoulou-Kyriakides  M, Tsatsaroni  E, Laderos  P, Georgiadou  K. Dyeing of cotton and wool fibres with pigments from Crocus sativus—effect of enzymatic treatment. Dyes Pigments 1998;36(3):215–21. [76] Tsatsaroni E, Liakopoulou-Kyriakides M. Effect of enzymatic treatment on the dyeing of cotton and wool fibres with natural dyes. Dyes Pigments 1995;29(3):203–9. [77] LI H, Zhao X. Dyeing performance of natural dyestuff from purple sweet potato to wool fabric. Wool Text J 2010;10:003. [78] Sivakumar V, Anna JL, Vijayeeswarri J, Swaminathan G. Ultrasound assisted enhancement in natural dye extraction from beetroot for industrial applications and natural dyeing of leather. Ultrason Sonochem 2009;16(6):782–9. [79] El-Zawahry M. Ecofriendly dyeing of linen fabric with natural dyes using different enzymes complexes. Man-Made Text India 2009;52:10. [80] Moiz A, Ahmed MA, Kausar N, Ahmed K, Sohail M. Study the effect of metal ion on wool fabric dyeing with tea as natural dye. J Saudi Chem Soc 2010;14(1):69–76. [81] Z-p G, Ma D-g. Dyeing behaviour of polyacrylonitrile fiber cured by enzyme for natural dye cochineal. Wool Text J 2011;7:009. [82] Jäger I, Hafner C, Welsch C, Schneider K, Iznaguen H, Westendorf J. The mutagenic potential of madder root in dyeing processes in the textile industry. Mutat Res Genet Toxicol Environ Mutagen 2006;605(1):22–9. [83] Vankar PS. Dyeing cotton, silk and wool yarn with extract of Garcinia mangostana pericarp. J Text Apparel Technol Manage 2009;6(1). [84] Vankar  DPS, Heena  H. Catechu and babool for textile dyeing. Nat Prod Radiance 2002;1(4):15–17. [85] Mansour HF. Environment and energy efficient dyeing of woollen fabric with sticta coronata. Clean Technol Environ Policy 2010;12(5):571–8. [86] Barani H, Maleki H. Plasma and ultrasonic process in dyeing of wool fibers with madder in presence of lecithin. J Dispers Sci Technol 2011;32(8):1191–9. [87] Park M-O, Yoon S-L. Properties of natural dyeing of bast fiber (Part 2) pre mordanting dyeing of sappan wood, gardenia and gallnut. J Korea Techn Assoc Pulp Paper Ind 2010;42(4):1–14. [88] Bechtold  T, Mahmud-Ali  A, Mussak  R. Natural dyes for textile dyeing: a comparison of methods to assess the quality of Canadian golden rod plant material. Dyes Pigments 2007;75(2):287–93. [89] Guesmi A, Hamadi NB, Ladhari N, Sakli F. Dyeing properties and colour fastness of wool dyed with indicaxanthin natural dye. Ind Crop Prod 2012;37(1):493–9. [90] Angelini LG, Bertoli A, Rolandelli S, Pistelli L. Agronomic potential of Reseda luteola L. as new crop for natural dyes in textiles production. Ind Crop Prod 2003;17(3):199–207.

Newer Natural Dyes for Various Textiles  Chapter | 1  29 [91] Lv LH, Wei CY, Ye F, Zhang H, editors. Dyeing property of shikonin on wool fabric. In: Advanced materials research. Trans Tech Publ; 2011. [92] Alwis A, Shankar R, Wijayapala S, Vankar P. Dyeing of cotton. wool and silk with the leaves extract of Salacia prinoides (Kothala). Asian Text J 2007;16(6):69–74. [93] Vankar PS, Shanker R, Wijayapala S. Dyeing of cotton, wool and silk with extract of Allium cepa. Pigm Resin Technol 2009;38(4):242–7. [94] Vankar P, Shanker R, Mahanta D, Tiwari S. Characterisation of the colorants from leaves of Bischofia javanica. Int Dyer 2007;192:31–3. [95] Vankar P, Shanker R, Dixit S, Mahanta D, Tiwari S. Sonicator dyeing of cotton with the leaves extract Acer pectinatum Wallich. Pigm Resin Technol 2008;37(5):308–13. [96] Ghorpade B, Darvekar M, Vankar PS. Ecofriendly cotton dyeing with Sappan wood dye using ultrasound energy. Colourage 2000;47(1):27–30. [97] Vankar  PS, Singh  LW, Tiwari  V, Potsangbam  L. Chemical characterization of the colorant from Parkia javanica and dyeing cotton fabric. Int Dyer 2007;192(1):11–4. [98] Vankar PS. Sonicator dyeing of cotton, wool and silk with the leaves extract. J Text Apparel Technol Manage 2009;6(1). [99] Yusuf M, Shabbir M, Mohammad F. Natural colorants: historical, processing and sustainable prospects. Nat Prod Bioprospect 2017;7(1):123–45 [PubMed PMID: PMC5315675].

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Chapter 1.1

Newer Natural Dyes for Cotton 1.1.1 Introduction Newer natural dyes have to be identified from the flora of various places. Due to diversity of climatic zones and altitudes and geographic variety, colossal substrates providing different colors are present in our biosphere. It has also resulted in a rich biodiversity that has gifted flora and fauna that yields an array of dye-producing shrubs and perennials not only in India but also globally. Natural dyeing has been an ancient art, and the people used natural dyestuffs obtained from vegetables, minerals, and animals, all easily obtained in their own vicinity. In India, it was widely used for coloring of fabrics and making paintings on the walls. In order to meet the growing demand for natural colorants, new pigment crops are being sought. The newer sources need to be tapped. However, for some sources such as lac dye (bye product of lac industry), catechu, P. granatum, alroot (Morinda tinctoria), manjistha, safflower, and indigo, there has been an organized cultivation because of their exceptional color content and dye ability. Increased acreage is devoted to their cultivation purely because of their dye qualities. More plants need to be considered as agronomically viable plantations. Natural dyes are basically elements of natural resources, and these dyes are generally classified as plant, animal, mineral, and microbial dyes based on their source of origin, although plants are the major sources of natural dyes in substantial quantities. Natural dyes per se are sustainable as they are renewable and biodegradable. The vibrant colors of tropical plants have given the experience with natural dyeing the insight to explore plants in the neighborhood for their dye content. Finding fiber colors in plants that grow easily and fast has lead into a new world of fiber colors that give a gamut of shades. The main challenge is to preserve the natural colors as they appear in natural form. If that can be done by technological intervention, then the richness and luster of these natural colors can be attained on fabric as well. It has become a common misconception that natural dyes only produce beiges and browns and other washed out shades. In reality, vibrant, fast natural colors can be produced that are comparable with and often surpass the colors of synthetics. Apart from the sources of these dyes, it is perhaps the commitment of those propagating them and the near clinical efficiency with which dye is extracted, produced, and used that is responsible for the unique nature of natural dyeing and producing stable coloration. Dye-yielding plants have now been cultivated very systematically, and organized farming has led to substantial yield. Proper plantation, modern farming style, and enough manure for best propagation of dye-yielding plants are being practiced.

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The utilizable plant parts were subjected to specific dehydration processes to retain the color content, or the dyestuff was extracted as per the given strategy. Several newer sources of natural dyes particularly for dyeing cotton are being discussed in this chapter. This would show the gamut of colors that have been explored. This will increase the availability of newer shades and new choices of fabric dyed with natural dyes. The possibility of their feasibility of providing high-quality natural dyes from new plant sources, leading to creating new opportunities for both farmers, is envisaged. This would lead the fabric industry to be in line with the current consumer trends in order to be in style with ethnic fabric and natural products. In the present section, the aim is to show feasibility of providing high-­quality natural dyes from plants, creating new opportunities for both farmers and the fabric industry—in line with the current consumer trends toward ethnic fabric and natural eco-friendly products. A large number of new plant sources have been explored for natural dyeing, and the following section is a brief introduction of the plants used from screening experience. Many of them have potentially rich natural colorant content. It is imperative to make a documentation of these plants for the future use as sources of natural dyes.

1.1.1.1  Acacia catechu Plant: Acacia catechu Family: Fabaceae or Leguminosae Genus: Acacia Part: Inner wood lumen Catechu is also known as cutch or katha and is obtained from A. catechu Willed. The plant is used for fodder, fuel, and katha powder/paste [1]. The term cutch refers to several kinds of raw materials that are useful in making dyes and in tanning. Black cutch or catechu is the source of an important brown dye. It is from the heartwood of A. catechu, a tree native to Burma and India (Fig. 1.1). Catechu is an important brown natural dye that derives from the heartwood of the cutch tree (A. catechu). It belongs to Leguminosae family. It is easily available and handled and can be used for natural dyeing. With the help of mordants, the dye uptake by the fabric can be improved along with good wash- and lightfastness. Catechu is an excellent dye for cottons as it has inherent high tannin contents. Catechu contains catechuic acid, catechutannic acid (25%–33%), acacatechin (10%–12%), catechu red, quercetin, catechin (2%–12%), epicatechin, phlebotanin (25%–33%), gummy matter, quercitrin, and quercetin. Catechu gives dark brown, golden brown, and fawn, and it is a very good dye having compatibility with other dyes. Catechu is a difficult dye to exhaust and will continue to produce beige colors for several subsequent dyeing. It is recommended to expose the catechu dyed fibers to the air to oxidize before rinsing the dyed fibers for better color buildup.

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FIG. 1.1  Acacia catechu.

It is describe that though natural coloration is known from ancient times as artisanal practice for handicrafts, paintings, and handloom textiles, the chemistry of interaction of such colorant with textile material is of relatively recent interest for producing eco-friendly textile [2]. It has been stated that by proper selection of natural mordants and extraction along with best application of technology and ecological process, it is possible to commercialize some plant dyes for coloration of textile material that is needed for the local rural dyers and plant cultivators [3]. The textile printing possibility of A. catechu in the fine powder form in printing cotton fabric using reactive printing technique has been studied [4]. Cotton fabric samples were printed with A. catechu wild that shows that the specified printing paste gave the highest K/S value. The fastness properties were fair to good. Catechu-related dyeing procedure was elaborately described by Ref. [5]; predried powder of catechu was initially crushed to powder form and then extracted in aqueous medium using an optimized condition of extractions by heating in water bath at 90°C having MLR 1:20, and then, it was filtered to obtain 40% (w/w) extract of colored aqueous solution of catechu having pH 12. Eco-friendly ultrasonic textile dyeing with natural dyes such as A. catechu and Tectona grandis shows better and faster dye uptake after enzyme pretreatment on cotton fabric, and results of dyeing are better than metal mordanted fabric [6].

1.1.1.2  Allium cepa Plant: Allium cepa Family: Amaryllidaceae Genus: Allium Part: Outer skin

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Allium cepa, onion (also called bulb onion), is a monocot bulbous perennial (often biannual). It is the most widely cultivated species of the genus Allium; onions are widely used on cooking in nearly all regions of the world and have been used in diverse cultures and rituals throughout history. Onions produce various sulfur-containing compounds (such as cysteine sulfoxide) and produce their distinctive odor, flavor, and lachrymatory (tear-stimulating) properties (Fig. 1.2).

FIG. 1.2  Allium cepa.

The use of red onion peel (A. cepa) pigment as a natural source for dyeing of cotton and silk fabric was carried out [7]. Determination of time for extraction of pigment, time for dyeing, concentration of dye source and mordants, and time for dye fixation was carried out without any damage to fabric, and testing of colorfastness properties of dyed fabric was analyzed. The comparative results of the dyeing efficiency of grafted flax fabrics, using both ultrasound and conventional dyeing methods, were compared. The dyeing process involved the use of a natural red dye extracted from red onion (A. cepa). The obtained results showed the superiority of sonication dyeing over the conventional dyeing procedure. Moreover, the research emphasizes the idea of the mesoporosity of the inclusion complex formed by encapsulating dye molecules inside the cavity of monochloro triazinyl-β-cyclodextrin (MCT-β-CD) [8]. Powder of onion shells as a source of natural flavonoid dye (quercetin) and cotton fabrics was exposed to absorbed doses of 2, 4, 6, 8, and 10 kGy using ­Cs-137 gamma irradiator [9]. Irradiated and unirradiated dye powder was used

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for extraction of quercetin. Furthermore, color strength and colorfastness of irradiated fabrics were improved by using pre- and postmordants such as alum and iron. Dyeing of irradiated fabric at 60°C keeping MLR of 1:30 using 10% alum as premordant and 6% alum as postmordant was carried out. Authors claim that γ-irradiation not only has improved the color strength of the dye using irradiated cotton but also has made significant contribution toward the improvement of colorfastness properties. The efficiency of dyeing on cotton wool and silk fabrics with natural dye obtained from kitchen waste of dry skin extract of A. cepa was done [10]. The dry skin of onion produces natural dye that has been used for dyeing textiles. Innovative dyeing with onion has been shown to give good dyeing results. Pretreatment with 2% metal mordant and using 5% of plant extract (owf) was found to be optimum and showed very good fastness properties for cotton. For effective natural dyeing with dry skin extract of A. cepa, conventional method of dyeing was carried out using metal mordants. The dye has very good potential of uptake, adherence to the fabric, and good wash- and lightfastness. The method developed for natural dyeing of cotton fabrics using skin extract of allium in conjunction with metal mordanting has shown very deep coloration. The stepwise dyeing of cotton fabric with metal mordant by the natural dye A. cepa gave very good result. The dye uptake in case of stepwise dyeing was from 65% to 68% in the case of cotton, with different mordants. The experiments were carried out on scoured and bleached cotton fabric using a natural dye extracted from onion skins with cationic agents—bireactive (bichlorotriazine) and monoreactive (monochlorotriazine). It was found that pretreatment with reactive cationic agents produced a significant increase in the adsorption and fixing of the dye relative to nontreated fabrics. Pretreatment with the bireactive agent produced greater adsorption than the monoreactive agent [11]. The total amount of dyeing substances present in onion (A. cepa L.) was determined by using the extraction method. The extracted substance was used in the dyeing of woolen strips, feathered leather, and cotton. Dyeing conditions and other characteristics were determined, and the repeatable specifics were evaluated for these processes so that lightfast colors could be obtained [12].

1.1.1.3  Artocarpus heterophyllus Plant: Artocarpus heterophyllus Family: Moraceae Genus: Artocarpus Part: Bark The bark of jackfruit tree (A. heterophyllus), from which a yellow dye is obtained, is among the minor dye-yielding plants used in India [13]. From the sawdust of jack wood or chips of the heartwood, boiled with alum, a yellow dye is commonly used for dyeing silk and the cotton robes of Buddhist priests.

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A 5% solution of a yellow dye obtained from jackfruit bark was used to color wool various shades of brown using five different mordants [14]. Grated jackfruit wood produces yellow dye, although the tree is more popular for its edible fruit. It is being used as dye for yellow clothes of priests and for silk in India and Java. The dye is known to give olive yellow with chromium, light yellow with aluminum, and dark yellow with tin mordants (Fig. 1.3).

FIG. 1.3  Artocarpus (jackfruit) bark.

In the book on Textile Chemicals [15], it has been mentioned that yellow dye (C.I. Natural Yellow 11) from jackfruit wood has been used for wool and silk dyeing using alum as mordant to obtain golden-yellow color. Yellow dye from debarked jackfruit wood was isolated by solvent extraction method using sawdust of the wood and was used for dyeing after removal of the solvent [16]. Dyeing of jute with vegetable dyes particularly with Artocarpus leaves had been attempted [17].

1.1.1.4  Bixa orellana Plant: Bixa orellana Family: Bixaceae Genus: Bixa Part used: Seeds The colored constituents of B. orellana, commonly known as annatto, possess properties that find good application in textile industry. The colorant is obtained from the outer layer of seeds of this tropical tree. The chemical constituents of the colorants in annatto are a mixture of bixin, which is a monomethyl

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ester of a dicarboxylic carotenoid compound, and norbixin, which is a dicarboxylic derivative of same carotenoid as in bixin [18]. Both these constituents occur in cis form, and a small percentage of both is likely changed into the more stable trans form upon heating. Bixin is a half-ester, and this property gives it some solubility in lipids (Fig. 1.4).

FIG. 1.4  Bixa orellana seeds.

Recently, some researchers [19] reported about the optimization of dyeing conditions and fastness properties of the cotton fabric dyed with annatto imparting beautiful shades to cotton fabric, when used with mordants and with some inorganic salts at alkaline pH. Though fastness of the dyed fabric to light was found to be moderate in general, fastness to perspiration, washing, and crocking was found to be moderate to excellent. Thus, they reported that there is a scope to improve the fastness properties by finding the means to make the dye more stable and thus resistant to fading. Annatto seeds were used for dyeing of nylon and polyester fibers [20]. They observed that though both the fibers have good affinity for this dye, the mechanism of dye adsorption, as indicated by the isotherms, is different in each case. They observed that the dye has moderate fastness to washing but poor to light. Other properties of annatto colorants include their unstability to oxidation, nontoxicity, and flexibility. Traditionally, annatto seeds have been used in medicines to cure wounds, skin eruptions, and burns. Annatto colorants are also used for the coloration of wool and silk. The less toxic properties of annatto colorants make it a widely used colorant in the textile industry. Colorants derived from the seeds of Bixa are extensively used in the food industry [21]. Their peculiar characteristic, as that which permits obtaining water-soluble and lipid-soluble colorants through small alterations of the production process, was one of the factors responsible for the success of this pigment. Similarly improved procedures leading to better dye fixation on textiles

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for annato dye have been shown [22]. The optimum proportions for dyeing with annato on cotton have been discussed using myrobalan as mordant.

1.1.1.5  Bougainvillea spectabilis Plant: Bougainvillea spectabilis Family: Nyctaginaceae Genus: Bougainvillea Part used: Flower bract Bougainvillea glabra (Bougainvillea) is an evergreen vine that is just as happy spreading horizontally or hanging downward as it is climbing upward; it makes itself at home in almost any situation. It can be grown as a hedge, groomed as a ground cover, pruned as an espalier, trained as a tree, or contained in a variety of shapes. Red, violet, orange, yellow, or white bracts appear on the ends of new growth stem. These flowers bloom most heavily in winter and early spring, but some plants put forth scattered clusters all year (Fig. 1.5).

FIG. 1.5  Bougainvillea glabra.

Single- and double-flower forms are available. Double forms tend to carry their blooms near the end of the stems rather than distributing them evenly over the plant. The colorful, papery “blooms” are not flowers; they are bracts. The true flowers are white, trumpet-shaped, and almost unnoticeable within

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the bracts. Bougainvilleas are available in a variety of species, each having its unique characteristics flower. Dyeing with Bougainvillea bract extract was carried out. The study was conducted with magenta (purple) variety, as these flowers are rich in color [23]. Betacyanins from the bracts of B. glabra were isolated and characterized by a combination of spectroscopic techniques as gomphrenin-I (betanidin 6-Obeta-glucoside) and various derivatives of bougainvillein-v (betanidin 6-O-betasophoroside), that is, mono- and diglucosylsophorosides that are acylated with 4-coumaric and caffeic acid (mono- and diesters). Large amounts of flavonols (kaempferol and quercetin conjugates) reaching ratios of flavonol to betacyanin of 1:1 were also isolated. Bougainvillea flower flavonoid glycoside; quercetin glycoside isorhamnetin glycoside [24]. The colorant of Bougainvillea flower was extracted by solid-liquid ratio method to get very good yield of the colorant. The process was better in acidic condition than in alkaline, with a solid-liquid ratio of 0.1. The equilibrium time was reached after 60 min of the extraction process [25]. Taguchi technique was used for the optimization process. The results showed that 150 μm particle size, 1:20 solid-solvent ratio, 1 h extraction, and enzyme addition as assistance were the optimum conditions for extraction. The optimum and control extraction results were compared. The respective absorbance values were 0.255 and 0.280. It was encouraging to observe 9.88% of increase in the dye yield. Yield improvement in the optimized extraction indicated enhancement in the extraction efficiency [26]. Another method of extraction of colorant from bracts of Bougainvillea was shown by using sonicator [27]. One hundred to one hundred fifty grams of bracts were immersed in 1000 mL water and were left for 1 h in sonicator. These bracts gave bright magenta color. The solid was squeezed out, and the solution was filtered. By varying the pH of the Bougainvillea bract's extract with the mild acid and sodium hydroxide solution (app. 0.1 N), color change was observed. In acidic medium and basic medium, it gave dark magenta and bright yellow, respectively. The extract of Bougainvillea flowers was used for wool dyeing using two mordants—lanthanum and chromium [28]. Optimum conditions for dyeing have been at pH 4.5; extract-wool ratio was 0.06:1 g of wool at 97.5°C for 45 min. It was observed that the use of lanthanum along with chromium reduces the quantity of chromium in the effluent, and it was also observed that less damage to the wool fiber was an added advantage.

1.1.1.6  Brassica oleracea Plant: Brassica oleracea Family: Brassicaceae Genus: Brassica Part used: Outer leaves

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Brassica oleracea var. capitata F. rubra is the purple cabbage that belongs to family Brassicaceae. It is a sort of cabbage, also known as red cabbage. Its leaves are colored dark mauve. However, the plant changes its color according to the pH value of the soil. On acidic soils, the leaves grow more reddish while an alkaline soil will produce rather blue colored cabbages. This explains the fact that the very same plant is known by different colors in various regions. Furthermore, the preparation of the vegetable as a dish, especially during the addition of acid (vinegar) or alkaline additive has influence on its color. Brassica needs well fertilized soil and sufficient humidity to grow. It is a seasonal plant that is seeded in spring and harvested in late fall. It has been used for this rich natural colorant for dyeing study, and some cotton dyeing work has been attempted that showed promising results [29]. Purple cabbage dye is a natural pigment used mainly as a food color or in pharmaceutical industry [30]. It belongs to a class of compounds called anthocyanins. Colorants rich in acylated anthocyanins as purple cabbage display great stability due to intramolecular copigmentation (Fig. 1.6).

FIG. 1.6  Purple cabbage/Brassica oleracea.

Brassica oleracea L. var. capitata F. rubra (Red Cabbage) dye is composed mainly of natural pigment called anthocyanins used as a natural colorant. Wool and silk fibers were dyed with the aqueous extract obtained from red cabbage. The dyeing process was investigated, and the combined effects of dyeing conditions on the color yield parameter (K/S) were studied. Resulted fastness to wash, rubbing, and light of the dyed fabrics was evaluated [31]. The aqueous extract of purple cabbage has been used for dyeing cotton, silk, and wool. Different mordants with premordanting techniques were adopted to get different shades, their fastness properties were assessed, and the CIELAB values were determined. Cotton dyeing shows that potassium dichromate mordanted fabric showed poor color strength and stannic chloride mordanted fabric showed good color strength. Similarly, the case of silk fabrics showed good color strength

40  New Trends in Natural Dyes for Textiles

for stannic and average color strength in the case of alum and copper. The case of wool yarn stannous chloride shows best results followed by stannic and potassium dichromate that showed least color strength. The results are very encouraging; it is for the first time that purple cabbage has been used as a dye source [32].

1.1.1.7  Cassia fistula Plant: Cassia fistula Family: Fabaceae Genus: Cassia Part used: Bark Cassia fistula, known as the golden rain tree, is a flowering plant in the family Fabaceae. The species is native to the Indian subcontinent. It is a popular ornamental plant and is also used in herbal medicine. Cassia fistula (amaltas) grows in tropical to subtropical to deciduous forests, ascending to 1200 m in the sub-Himalayan tract, common in Uttar Pradesh, Madhya Pradesh, and South India. This genus, which includes 450 species, forms the preponderant vegetation and most valuable timber producing trees. The reddish wood, hard and heavy, strong and durable bark has been employed in tanning, as well (Fig. 1.7).

FIG. 1.7  Cassia fistula bark.

Cassia fistula bark, as natural dye, is the coloring matter of which has ample natural tannins and oxy anthraquinone substances, which probably consist of emodin and chrysophanic acid. Stem bark contains cassiamin A, cassiamin B, lupeol, beta-sitosterol, and hexacosanol [33].

Newer Natural Dyes for Various Textiles  Chapter | 1  41

Antiinflammatory and antioxidant activities of the aqueous and methanolic extracts of the C. fistula Linn. bark were found to possess significant antiinflammatory effect. Cassia fistula bark extracts showed significant radical scavenging by inhibiting lipid peroxidation as well. Both extracts exhibited significant antioxidant activity in DPPH, nitric oxide, and hydroxyl radical-induced in vitro assay methods [34]. Cassia fistula barks are known to be a source of flavonoids, phenolic acids, and xanthine glycosides [35]. Cassia fistula bark has been used as natural colorant for dyeing of unirradiated and irradiated cotton fabric. Dyeing parameters such as temperature and time were optimized using pre- and postmordanting using copper and iron as mordants. Using copper as premordant (4%) has given not only good color strength with darker shades but also acceptable fastness properties that were obtained. It is concluded that γ-irradiation has a promising effect in the improvement of color strength and colorfastness properties [36]. Wool fabric has been dyed with aqueous extracts of powder bark of C. fistula. The dyeing characteristics of the coloring matter on wool have also been studied with or without mordants. Three anthraquinones have been isolated, one of them being, 1,8-dihydroxy-6-­methoxy-3-methyl anthraquinone from the bark of C. fistula has been isolated and characterized with the help of chromatographic and spectroscopic techniques. These anthraquinones are responsible for dyeing properties in both plants [37]. Cassia fistula bark [38], which can be scraped off, is a plant waste that can be exploited as a good source of natural dye for cotton dyeing ranging from light peach to brown, to light green, to dark brown, to black depending on the choice of the mordants and different concentration of mordants. Best results were obtained with stannic chloride as mordant. Use of copper and chromium mordants is not considered to be eco-friendly, only to examine how much of the mordant is still adhering to the fabric after dyeing. It was found that premordanting the fabric with these noneco-friendly mordants is quite safe as the metal content in the fabric is less than 0.02 ppm; at the same time, their fastness properties are fairly good. Maturing the fabric for 1 week after quenching with these mordants and then dyeing still renders the fabric safe. Natural dyes are again getting importance due to harmful effects caused by synthetic dyes during their production and use. Cassia fistula bark can be used as a source of natural dye, which imparts fast color on cotton fabric. Thus, C. fistula bark can be exploited as a good source of natural dye for dyeing cotton fabric by ultrasonic energy in a very efficient manner. Interestingly, the bark after extraction of dye can be successfully used for the removal of heavy metal from textile and other industrial effluent [39].

1.1.1.8  Camellia sinensis Leaves Plant: Camellia sinensis Family: Theaceae Genus: Camellia Part used: Dried leaves

42  New Trends in Natural Dyes for Textiles

Camellia sinensis or tea is an evergreen plant. Tea leaves contain many compounds, such as polyphenols (catechins and flavonoids). Tea tannins called catechins include gallocatechin, epicatechin (EC), epigallocatechin (EGC), epicatechin gallate (EGC), and epigallocatechin gallate (EGCG) and have been considered as potential natural dye source. Cotton and jute fabrics were dyed with an aqueous extract of tea, containing tannins as the main colorant species [40]. Earlier attempts of using tea extract for wool dyeing was carried out with and without metal salts as mordants, using three different dyeing methods: premordanting, metamordanting, and postmordanting. They utilized four different kinds of tea leaves. About one third of the catechin was shown to be absorbed by wool fabric during dyeing [41]. A study was conducted with green tea and black tea with the purpose of assessing the dyeing properties. The extracted dyes were applied with and without mordants on silk fabric [42] (Fig. 1.8).

FIG. 1.8  Camellia sinensis.

In another study of tea extract dyeing, elaborate extraction conditions, including solid-liquid ratio, extraction temperature, acidity of extractant, and reaction time, were shown to have immense effect on the stability of dyes. The dye was significantly affected by pH value, oxidant, and reductant, but its thermal stability was good. Metal irons such as Ca2+, Cu2+, Zn2+, Mg2+, Na+, K+, Pb2+, Sn2+, and Ni2+ had no effect on the color, but Al3+, Fe2+, and Fe3+ had harmful effect [43]. Green tea has been used for dyeing cotton, the dyeing was carried out by using with and without metal mordants, and the light- and washfastnesses were found to be moderate to good [44]. It has been found that leaching tea pigments for dyeing cotton fabrics gave fairly good results and they discussed the influence of the factors of dyeing [45].

Newer Natural Dyes for Various Textiles  Chapter | 1  43

Black tea leave powder from Sri Lankan origin has been used as natural dyestuff used as indigenous source that has been developed scientifically for shades of light brown to dark brown as shown in cotton, silk, and wool-dyed samples [46].

1.1.1.9  Coscinium fenetratum Plant: Coscinium fenestratum Family: Menispermaceae Genus: Coscinium Part used: Stem Coscinium fenestratum (venivel) belongs to family Menispermaceae. It is a climbing smooth shrub, reaching a height of 4 m or more. Coscinium fenestratum (venivel) is economically important, naturally growing species in the disturbed habitats of lowland rain forests in Sri Lanka. It occurs in humid valley forest of Sri Lanka for local handloom sector for shades of light yellowish green (Fig. 1.9).

FIG. 1.9  Coscinium fenestratum (venivel).

Alcoholic extract of the stems of C. fenestratum, a medicinal plant indigenous to India and Sri Lanka used in Ayurveda and Siddha medicine for treating diabetes [47], was studied for its carbohydrate metabolism effect and ­antioxidant

44  New Trends in Natural Dyes for Textiles

status in streptozotocin-nicotinamide-induced type 2 diabetes cases. This investigation demonstrates significant antidiabetic activity of C. fenestratum [48]. Antioxidant effect of methanol extract of C. fenestratum stem powder was also measured [49].

1.1.1.10  Butea monosperma Plant: Butea monosperma Family: Fabaceae Genus: Butea Part used: Flower Extraction and dyeing conditions of natural dyes from flowers of B. monosperma had been optimized in neutral medium, that is, water and various beautiful shades developed on cotton fabrics using different chemical mordants are being described. Also, the phytochemical screening of extracted dyes is described [50] (Fig. 1.10).

FIG. 1.10  Butea monosperma.

Sunlight-dried flower petals of B. monosperma (Lam) Kuntze (palash) have good quantity of crude dye that was extracted from dried flower petals of palash. The flower compounds were analyzed and identified as chalcone, butein, orange yellow needles and flavanone, butein, and its glycoside butrin. The crude flower petal dye after further purification and refining has tremendous scope as a medicine and can also serve as coloring material in soft drinks and other food products like jam, chow mein, noodles, and sausage. Natural dye from the flower petals of palash and its probable application in the field of textile, food items, and pharmaceutical industry has been investigated [51]. Natural colorant from the petals of the flame of forest (B. monosperma) flower was extracted under different operating conditions such as extraction

Newer Natural Dyes for Various Textiles  Chapter | 1  45

time (45–120 min), temperature (60–90°C) and mass of the petals (0.5–2 g) by conventional extraction technique. Response surface methodology (RSM) with the help of Design Expert version 7.1.6 was used for the optimization of the extraction process and evaluation of interaction effects of different operating parameters [52].

References [1] Vankar PS, Tiwari V, Shankar R. Commercial dyeing with aqueous extract of Acacia catechu (Katha) using ecofriendly mordants. Asian Text J 2002;9:60–4. [2] Samanta AK, Agarwal P. Application of natural dyes on textiles. 2009. [3] Prabhu K, Bhute AS. Plant based natural dyes and mordants: a review. Indian J Fibre Text Res 2009;34:384–99. [4] Klaichoi C, Mongkholrattanasit R, Sarikanon C, Intajak P, Saleeyongpuay W, editors. Ecofriendly printing of cotton fabric using natural dye from acacia catechu weld. RMUTP international conference; Textiles & Fashion; 2012. [5] Samanta AK, Konar A. Dyeing of textiles with natural dyes. In: Natural dyes. InTech; 2011. [6] Vankar PS, Shanker R. Ecofriendly ultrasonic natural dyeing of cotton fabric with enzyme pretreatments. Desalination 2008;230(1–3):62–9. [7] Siddiqui I, Siddiqui K, Khan N. Red onion peel (Allium cepa) pigment—a good dye source for dyeing of cotton and silk. Man-Made Text India 2017;45(4):130–2. [8] Coman D, Oancea S, Vrinceanu N, Stoia M. Sonication and conventional dyeing procedures of flax fibres with Allium cepa anthocyanin extract. Cellul Chem Technol 2014;48(1–2):145–57. [9] Rehman F-u, Adeel S, Shahid M, Bhatti IA, Nasir F, Akhtar N, et al. Dyeing of γ-irradiated cotton with natural flavonoid dye extracted from irradiated onion shells (Allium cepa) powder. Radiat Phys Chem 2013;92:71–5. [10] Vankar PS, Shanker R, Wijayapala S. Dyeing of cotton, wool and silk with extract of Allium cepa. Pigm Resin Technol 2009;38(4):242–7. [11] Mousa AA, Youssef YA. The use of reactive cationic agents in cotton fabrics to improve the adsorption of natural dye from Allium cepa. Tinctoria 2003;100(2):41–5. [12] Adem Ö. Extraction of dyestuff from onion (Allium cepa L.) and its application in the dyeing of wool, feathered-leather and cotton. Turk J Chem 1996;20(3):194–203. [13] Mell C. Interesting sources of natural dyestuffs. Text Colorist 1936;58. 128-130343-344484-487. [14] Jahan S, Singhal P. Wool dyeing with jackfruit bark. Colourage 2002;49(9):25–9. [15] Lacasse K, Baumann W. Textile chemicals: environmental data and facts. Springer Science & Business Media; 2004. [16] Patra  S, Nanda  B, Nayak  A, Das  N. Yellow dye from debarked jackfruit wood. Colourage 2000;47(8):17–8. [17] Pan N, Chattopadhyay S, Day A. Dyeing of jute with natural dyes. Indian J Fibre Text Res (IJFTR) IJFTR 2003;28:339–42. [18] Sekar N. Annatto colorants. Colourage 2004;51(7):66–70. [19] Kawlekar S, Mukundan U. Dyeing of cotton fabric with annatto (Bixa orellana). International Dyer; 2011. [20] Gulrajani M, Gupta D, Maulik S. Studies on dyeing with natural dyes: part I—dyeing of annato on nylon and polyester. Indian J Fibre Text Res (IJFTR) IJFTR 1999;24(2):131–5. [21] Carvalho P. Annatto: technological advances and perspectives. Arch Latinoam Nutr 1999;49(3 Suppl. 1):71S–3S.

46  New Trends in Natural Dyes for Textiles [22] Devi AS, Katyayini VKLT, Sumanthy BS. Annato—a bright natural colourant for cotton. Text Trends 2002;45(1):29. [23] Tiwari V, Ghorpade B, Vankar PS. Ultrasound energised dyeing with aqueous extract of Bougainvillea using ecofriendly mordants. Asian Text J 2000;(2):28–32. [24] Heuer S, Richter S, Metzger JW, Wray V, Nimtzt M, Strack D. Betacyanins from bracts of Bougainvillea glabra. Phytochemistry 1994;37(3):761–7. [25] Sabarudin NA, Munaim MSA, Wahid ZA, Gambang K. Effect of extraction condition of natural dye pigment from Bougainvillea flowers’ bract. Aust. J. Basic Appl. Sci. 2016;10(17):172–5. [26] Patil PD, Rao C, Wasif A, Nagla J. Taguchi optimization for efficient extraction of a natural dye from Bougainvillea glabra bracts. Int J Res Eng Technol 2014;3(04):23–30. [27] Vankar PS. Handbook on Natural Dyes for Industrial Applications. National Institute of Industrial; 2007. [28] Mathur J, Bhandari C. Physico-chemical study of dyed wool: part I—Bougainvillaea as wool colourant with mixed mordant. Indian J. Fibre Text. Res. (IJFTR) IJFTR 2001;26:432–7. [29] Senthilkumar  P, Umasankar  P, Sujatha  B. Ultrasonic dyeing of cotton fabric with cabbage leaves. Man-Made Text India 2002;45(2):71–4. [30] Chigurupati N, Saiki L, Gayser Jr C, Dash AK. Evaluation of red cabbage dye as a potential natural color for pharmaceutical use. Int J Pharm 2002;241(2):293–9. [31] Haddar W, Ben Ticha M, Meksi N, Guesmi A. Application of anthocyanins as natural dye extracted from Brassica oleracea L. var. capitata f. rubra: dyeing studies of wool and silk fibres. Nat Prod Res 2018;32(2):141–8. [32] Vankar PS, Shanker R. Dyeing cotton, silk and wool with Brassica oleracea or purple cabbage. Asian Dyers; 2006, p. 75–80. [33] Lee CK, Lee PH, Kuo YH. The chemical constituents from the aril of Cassia fistula L. J Chin Chem Soc 2001;48(6A):1053–8. [34] Ilavarasan  R, Malika  M, Venkataraman  S. Anti-inflammatory and antioxidant activities of Cassia fistula Linn bark extracts. Afr J Tradit Complement Altern Med 2006;2(1):70–85. [35] Gupta V, Agrawal A, Singh J, Tiwari H. Isolation and characterization of 2 flavonol and a xanthone glycosides from the stem bark of Cassia-Fistula Linn. New Delhi, India: Council Scientific Industrial Research Publ & Info Directorate; 1989, p. 282–4. [36] Adeel S, Gulzar T, Bhatti IA, Qaiser S, Abid A. Dyeing behaviour of g-irradiated cotton using Amaltas (Cassia fistula) bark extracts. Asian J Chem 2013;25(5):2739. [37] Ledwani L, Gupta K. Isolation and characterization of anthraquinones from the bark of two Cassia species and optimization of dyeing process on wool by their bark extracts. Asian J Chem 2009;21(9):7131. [38] Vankar PS. Dyeing of cotton with Amaltas. Asian Text J 2001;10(11):56–8. [39] Tiwari V, Ghorpade B, Vankar P. Removal of chromium and copper by barks of eucalyptus and Cassia fistula. Colourage 2000;47(11):18–20. [40] Deo H, Desai B. Dyeing of cotton and jute with tea as a natural dye. Color Technol 1999;115(7– 8):224–7. [41] Chan  PM, Yuen  CWM, Yeung  KW. Dyeing- natural-dye wool-fiber. Text Asia 2000;31(2):28–30. [42] Kim S. The application of tea dyeing to silk. J Dong Hua Univ (Engl Ed) 2001;18(3):58–61. [43] Wu R, Lai Y, Ou S, Hu X. Extraction of natural tea dyes and its application on silk fabrics. J Adv Text Technol 2011;5(19):1–4. [44] Kaur V. Dyeing of cotton with tea as natural dye. Int J Eng Innov Res 2015;4(1):184–7. [45] He Z-p, Z-m W. The application research on cotton fabric of natural tea pigments. In: Soft computing in information communication technology. Springer; 2012. p. 365–72.

Newer Natural Dyes for Various Textiles  Chapter | 1  47 [46] Vankar PS, Shukla D, Wijayapala S. Low temperature optimized dyeing of cotton, wool and silk with extract of Camellia Sinensis (tea leaves). J Text Eng Fash Technol 2017;2(1):00045. [47] Punitha  ISR, Rajendran  K, Shirwaikar  A, Shirwaikar  A. Alcoholic stem extract of Coscinium fenestratum regulates carbohydrate metabolism and improves antioxidant status in streptozotocin–nicotinamide induced diabetic rats. Evid-Based Complement Alternat Med 2005;2(3):375–81 [PubMed PMID: PMC1193540]. [48] Vankar PS, Shanker R, Wijayapala S, de Silva NGH, de Alwis A. Dyeing of cotton,wool and silk with the stem extracts of Coscinium fenestratum (venivel). Asian Text J 2007;16(10):59–64. [49] Venukumar M, Latha M. Antioxidant effect of Coscinium fenestratum in carbon tetrachloride treated rats. Indian J Physiol Pharmacol 2002;46(2):223–8. [50] Saxena H, Tiwari R, Pandey A. Optimization of extraction and dyeing conditions of natural dye from Butea monosperma (Lam.) Kuntze flowers and development of various shades. Int J Sci Technol 2012;7:29–35. [51] Singh RP, Agarwal K, Singh R. Extraction and characterization of Butea monosperma (Lam.) Kuntze flower petals dye for its uses in the colouration of food, pharmaceutical and textile industries. Extraction 2017;2(5). [52] Sinha K, Saha PD, Datta S. Extraction of natural dye from petals of Flame of forest (Butea monosperma) flower: process optimization using response surface methodology (RSM). Dyes Pigments 2012;94(2):212–6.

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Chapter 1.2

Newer Natural Dyes for Silk Studies on silk: Pure munga khadi silk and plain and white pure silk, which is generally used for dyeing, were selected. Standard brand of pure silk was procured from market. Various natural dyes were used to dye pure silk to get many bright colors.

1.2.1  Eclipta alba Plant: Eclipta alba Family: Asteraceae Genus: Eclipta Part used: Leaves The dyeing of cotton fabric using Eclipta as natural dye has been studied by both conventional and sonicator method. The effects of dyeing show higher color strength values obtained by the latter. Dyeing kinetics of cotton fabrics were compared for both the methods. The time/dye uptake reveals the enhanced dye uptake showing sonicator efficiency. The results of fastness properties of the dyed fabrics were fair to good. CIELAB values have also been evaluated [1] (Fig. 1.11).

FIG. 1.11  Eclipta alba.

Eclipta species commonly known as “Bhringraj” have been known to restore the color of hair and impart softness and sheen. The alkaloids were isolated and characterized from Eclipta. The dyeing properties of different extracts

Newer Natural Dyes for Various Textiles  Chapter | 1  49

at different pH were evaluated qualitatively. It was found to provide permanent golden-yellow tint to hair, and a permanent color could be produced in combination with other fixatives like triphala in the presence of iron [2]. The methanolic extract of Eclipta is a dark green solution with characteristic odor. Its principal constituent contains wedelolactone and demethyl wedelolactone that were isolated by column chromatography. The presence of flavones apigenin and luteolin, as the flavone-7-O-glycoside and the flavone-C-­ glucosides are the main colorant have been reported. The chemical compounds that give Eclipta its medicinal value are wedelolactone and demethyl wedlolactone. Wedelolactone is a furanocoumarin with the chemical formula C16H10O7. It is a yellow-green solid with a molecular weight of 314.3 [3]. The bamboo fabrics were dyed with two natural colorants, namely annatto gold and eclipta green. The dyeing parameters were optimized. The ultraviolet protection factor of the fabric with respect to fabric construction, weight, thickness, and dyeing was also measured in vitro. The results indicate that there is positive correlation between the weight of the fabric and ultraviolet protection factor. Similarly, the thicker the fabric, the more is the protection. Dyeing with natural colorants dramatically increased the UV protection of all three fabric constructions. Thus, dyeing bamboo fabrics with natural colorants increases the ultraviolet protection of the fabrics and can be considered as an effective protection against ultraviolet rays [4]. Natural dyeing of biotreated silk with E. prostrata extract was carried out. Biomordant Pyrus pashia and enzymes were used in place of metal mordants as pretreatment. The dyeing results were very good and comparable with metal mordanted swatches. Fastness properties of dyed silk swatches were very good. These results make such textile dyeing an eco-friendly process by the use of biomordant or enzyme offering a benign and safe textile processing. The results of the one-step process are satisfactory fairly good results; it is industrially viable.

1.2.2  Eucalyptus globules Plant: Eucalyptus globulus Family: Myrtaceae Genus: Eucalyptus Part used: Bark Eucalyptus globulus (eucalyptus) grows in desert, swamp land, valleys, and mountains. This genus, which includes 450 species, forms the preponderant vegetation and most valuable timber producing trees. Eucalyptus trees are characterized by their leathery, whitish leaves and their ragged bark shredded periodically and have peculiar aroma. Many species are known as gum trees for their resinous exudation. The iron barks such as E. sideroxylon are not grown in India. Eucalyptus resinifera has hard gray bark. Botany Bay kino is a dark red-brown bark; E. corymbosa yields odorless gum that is used for tannin and

50  New Trends in Natural Dyes for Textiles

dyeing, but it is not grown in India. In the past, only leaves of Eucalyptus were used for obtaining yellow dye. Eucalyptus finds nourishment in a complexity of soils and can survive in different types of climate [5] (Fig. 1.12).

FIG. 1.12  Eucalyptus globulus.

Eucalyptus is known for its shredding bark and its smooth white almost porcelain appealing surface underneath. Eucalyptus bark, which is shredded off and is a plant waste, can be exploited as a good source of natural dye for cotton dyeing ranging from light peach to brown, to light green, to dark olive green depending on the choice of the mordants and different concentration of mordants. Use of both eco-friendly and noneco-friendly mordants, for dyeing study, showed a full gamut of colors and shades. Interestingly, the bark after extraction of dye could be successfully used for removal of heavy metal from textile effluents [6]. Eucalyptus bark has been used for the first time as natural dye; the coloring matter in the aqueous extract has ample of natural ellagitannins and polyphenols varying from 10% to 12%. Ellagitannins are esters of hexa hydroxyl diphenyl (HHDP) with a sugar core having galloyl group. Bark extracted by supercritical fluid extraction (SCFE) gave a bright yellow dye. The important compounds found in the SCF extract of Eucalyptus bark are eriodictyol, naringenin, quercetin, rhamnazin, rhamnetin, and taxifolin of which some are colorants [7] and used for silk dyeing.

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1.2.3  Eupatorium adenophorum Plant: Eupatorium adenophorum Family: Asteraceae Genus: Eupatorium Part used: Leaves and stem The herbaceous plant E. adenophorum can be explored as a very good green color source for dyeing of silk yarn with excellent fastness properties. Leaves of the Eupatorium plants were collected and shade dried, crushed, and packed. Sericin was removed so as not to interfere with luster and dye absorption. The dye material was entered into the dye liquor and boiled. Four mordants were used with three methods of mordanting. A mordant ranged from 1% to 5% was selected for the study. The concentration of dye material was optimized by taking seven concentration prepared by boiling. Yarn was dyed in the dye bath for varying time. The time at which the absorption was high was selected as optimum dyeing time and then evaluated for colorfastness. Results show that 10% alum with postmordanting method has yielded yellowish-green shade, while with 4% chrome in premordanting sap, green color has been obtained. Light army green and dark army green shades on silk were obtained with 4% CuSO4 and 4% FeSO4 using postmordanting method. Excellent fastness to light and outstanding fastness to washing were shown by dyed silk yarn using 4% mordant. Little noticeable staining and color change was found for dry and wet crocking samples [8] (Fig. 1.13).

FIG. 1.13  Eupatorium adenophorum.

Flavonoid constituents from the aqueous extract of the leaves of E. odoratum, an invasive weed in Thailand, have potential use as dyestuffs for cotton dyeing. It was found that cotton yarn, which was pretreated with a chitosan solution

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(with and without a cross-linking glyoxal solution), followed by dyeing with E. odoratum extract in the presence of the inorganic mordant, alum, provided better depth of shade (K/S) and also gave better fastness to light and washing than the untreated cotton yarn. Pretreated cotton yarn with the biomordant solution from Memecylon scutellatum leaves gave relatively poor light- and washfastness of the resultant dyed cotton in the presence of alum. Therefore, there are good numbers of dye-yielding plants from the newer sources very apt for silk dyeing.

1.2.4  Caesalpinia sappan Plant: Caesalpinia sappan Family: Fabaceae Genus: Caesalpinia Part used: Wood lumen Sappanwood belongs to Caesalpinia family commonly called as Patang wood. The sappanwood is historically one of the most important natural dyes for dark shades on silk and wool. However, dyeing cotton fabric with this natural dye has led to dyed fabric having poor fastness properties. An effort has been made to rejuvenate this dye by using environmentally safe mordants especially for cotton dyeing. This potentially rich dye can be used to develop various shades from pink to dark maroon by proper manipulation of the mordant. Sappanwood is a mordant dye, and the fiber gets dyed through the medium of a metallic mordant, the coloring matter being alkaline in nature [9] (Fig. 1.14).

FIG. 1.14  Sappanwood tree and sappanwood lumen.

A nontoxic natural dye was fabricated from an extract from C. sappan (sappanwood). Oily natural dye for industrial application was made from extracted sappanwood by using a microemulsion method. The absorbance of the dye extracted from sappanwood by distillation was measured with an ultraviolet/ visible spectrometer. The highest absorbance was obtained from the mordant containing 2 wt% aluminum [10].

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The sappanwood has the inner part, the lumen filled with dye substance along with tannin, tannic acid, gallic acid, and a special flavonoid called brazilin. The coloring matter brazilin (C16H14O5) is nearly colorless and freely soluble in water, alcohol, and ether and gets oxidized to brazilein (C16H12O5), which gives red rose color with orange fluorescence in water. On exposure to air, brazilin quickly absorbs oxygen and gets converted to brazilein and is obtained as minute dark crystals, which have a metallic gray luster. When crushed, they become brown-red powder. This powder is freely soluble in hot water. The solution has a pale orange yellowish-pink color. Further oxidation breaks the brazilin into inactive β-resorcylic acid (2,4-dihydroxy benzene-1-carboxylic acid) and 3,7-dihydroxy-chromone. The chemical structure closely resembles to the flavones but are actually substituted dihydropyrans [11]. The effect of a low-temperature plasma and/or chitosan pretreatment as a mordant on the dyeing of poly(ethylene terephthalate) fabrics with an aqueous extract of C. sappan L. wood, which showed a remarkably high coloring property in a natural dyeing, is investigated. Dyeing with the C. sappan L. extract led to fair-to-good fastness properties in conventional natural dyeing. The results clearly show that the pretreatment with chitosan and/or plasma is better than a metal mordant in terms of the dye uptake and reduction in the dyeing time without the need for redyeing [12]. Tedious extraction of coloring component from the raw material, low color value, and long dyeing time pushes the cost of dyeing with natural dyes considerably higher than with synthetic dyes. In the case of sappanwood, prolonged exposure to air converts the colorant brazilin to brazilein, causing a color change from red to brown. To overcome this drawback, a sonicator was used and found that the dye extraction was much faster [13].

1.2.5  Carthamus tinctorius Plant: Carthamus tinctorius Family: Asteraceae Genus: Carthamus Part used: Flower Carthamus tinctorius (safflower) is a seasonal plant of the family Asteraceae; its flower forms the basis of the safflower dye, which was used extensively in the past for dyeing wool for carpet industry in European countries. At the same time, safflower floret pigments are also found to be good replacements for synthetic food colors. Studies have been carried out for the standardization of extraction conditions for water-soluble safflower yellow B and water insoluble carthamin red dyes. There are other minor components of yellow dyes apart from these two major fractions [14] (Fig. 1.15). Petals of safflower that were obtained were exposed to dyeing without using mordant and by using copper sulfate, iron sulfate, potassium bichromate, sodium chloride, and sodium sulfate mordants. Colors obtained as a result of the

54  New Trends in Natural Dyes for Textiles

FIG. 1.15  Carthamus tinctorius.

dyeing were evaluated subjectively, and colorful wools were assessed in terms of light, rubbing, and waterdrop fastness values [15]. Investigation of the adsorption of safflower yellow dye on wool protein fiber and the optimum dyeing conditions to test color reproducibility was checked. In addition, the effects of mordants on dye adsorption, color, fastness, and photofading rate were also studied. The prepared dye in powder form was characterized with ­UV-vis spectroscopy and FT-IR spectrometric analysis. The color of dyed fabrics was characterized by CIE coordinates, H V/C, and K/S values. The color reproducibility of the dyed wool fabrics was examined. The amount of dye adsorption increased, and also, the shade of the dyed wool fabrics became deeper and more saturated with increasing temperature, time, and dye concentration. The maximum color strength was obtained at pH 3.0. The shade of dyed wool fabrics ranged from light yellow to dark mustard yellow as the pH of the dye bath shifted from alkaline to acidic. Color reproducibility was reliable with color differences in the range of 0.53–1.75. Fastness to dry cleaning was relatively good at 4/5 rating irrespective of mordanting. Fe and Cu mordants showed the least color change of the dyed wool fabrics after exposure to light. Mordants did not contribute to improve dye uptake and colorfastness, although they made variations in color tone. Safflower yellow dye can be used satisfactorily [16]. Natural dyes have better biodegradability and generally have higher compatibility with the environment. They are nontoxic, nonallergic to skin, noncarcinogenic, easily available, and renewable [17]. Silk has been known as the “queen of fibers” since its discovery. Clothes made from silk are luxurious and have many excellent qualities including the material's luster, light weight, superior mechanical performance, fine and smooth texture, excellent moisture

Newer Natural Dyes for Various Textiles  Chapter | 1  55

t­ransportation, and excellent draping quality [18]. Thus, natural dyeing of silk can give many beautiful and amazing shades of colors. There is prospect to extract color from different natural dyes for the use in dyeing of silk fabric in order to get different color tones.

References [1] Vankar PS, Shanker R, Srivastava J. Ultrasonic dyeing of cotton fabric with aqueous extract of Eclipta alba. Dyes Pigments 2007;72(1):33–7. [2] Wasule D. Hair dyeing activity of Eclipta species. J Pharm Res Opin 2014;1(5). [3] Mithun N, Shashidhara S, Vivek KR. Eclipta alba (L.): a review on its phytochemical and pharmacological profile. Pharmacologyonline 2011;1:345–57. [4] Sri Vidhya M, Bhanu Rekha V. Effect of knitted bamboo structures dyed with natural colorants on ultraviolet radiation protection. J Text Sci Eng 2012;2(115):2–4. [5] Ghorpade B, Tiwari V, Mishra A, Vankar PS. Ultrasound energised dyeing of cotton fabric with Eucalyptus bark. Asian Text J 2000;(8):30–6. [6] Vankar P, Mishra A, Ghorpade B, Tiwari V. Sonicator dyeing of cotton with eucalyptus bark using copper and chromium mordants, yet ecofriendly. Colourage 2000;47(9):25–8. [7] Vankar PS, Tiwari V, Ghorpade B. Supercritical fluid extraction of natural dye from Eucalyptus bark for cotton dyeing in microwave and sonicator. Can Text J 2002;32–7. [8] Sharma A, Bansal A, Rani S, Sood A. Eupatorium: an excellent natural dye source for Mulberry silk. Colourage 2007;54(1):45–8. [9] Ghorpade B, Darvekar M, Vankar PS. Ecofriendly cotton dyeing with Sappan wood dye using ultrasound energy. Colourage 2000;47(1):27–30. [10] Lee D-K, Cho D-H, Lee J-H, Shin HY. Fabrication of nontoxic natural dye from sappan wood. Korean J Chem Eng 2008;25(2):354–8. [11] Vankar PS. Handbook on natural dyes for industrial applications (extraction of dyestuff from flowers, leaves, vegetables). NIIR Project Consultancy Services; 2016. [12] Park Y, Koo K, Kim S, Choe J. Improving the colorfastness of poly (ethylene terephthalate) fabrics with the natural dye of Caesalpinia sappan L. Wood extract and the effect of chitosan and low-temperature plasma. J Appl Polym Sci 2008;109(1):160–6. [13] Vankar PS. Chemistry of natural dyes. Resonance 2000;5(10):73–80. [14] Vankar P, Tiwari V, Shanker R, Singh S. Carthamus tinctorius (safflower), a commercially viable dye for textiles. Asian Dyers 2004;1:25–9. [15] Basalma D, Kayabasi N, Gurbuz B. Determination of dyeing properties in petals of different safflower (Carthamus tinctorius L.) varieties. Asian J Chem 2008;20(8):6358. [16] Shin Y-S, Son K-H, Yoo D-I. Optimization of wool dyeing with yellow dye from Carthamus Tinctorius L. J Korean Soc Cloth Text 2009;33(12):1971–8. [17] Kulkarni S, Gokhale A, Bodake U, Pathade G. Cotton dyeing with natural dye extracted from pomegranate (Punica granatum) peel. Univ J Environ Res Technol 2011;1(2). [18] Cai Z, Jiang G, Yang S. Chemical finishing of silk fabric. Color Technol 2001;117(3):161–5.

56  New Trends in Natural Dyes for Textiles

Chapter 1.3

Newer Natural Dyes for Wool 1.3.1  Gomphrena globosa Plant: Gomphrena globosa Family: Amarantheceae Genus: Gomphrena Part used: Flower Gomphrena globosa, commonly known as globe amaranth, is an edible plant from the family Amaranthaceae. Flowers are globular in shape but actually consist of numerous individual flowers. The most common color is magenta, but there are also white and pale mauve varieties. The round-shaped flower inflorescences are a visually dominant feature, and cultivars have been propagated to exhibit shades of magenta, purple, red, orange, white, pink, and lilac. Within the flower heads, the true flowers are small and inconspicuous (Fig. 1.16).

FIG. 1.16  Gomphrena globosa.

At least 27 phytochemicals have been detected in G. globosa including 6 phenolic acid derivatives and 15 specific flavonoids. The most abundant phenolic compounds present are flavonoids. A major phenol was found to be kaempferol 3-O-rutinoside based on chromatographic and mass spectrometry techniques. Gomphrenol derivatives also contribute to phenolic content. Other flavonols include quercetin, kaempferol, and isorhamnetin derivatives.

Newer Natural Dyes for Various Textiles  Chapter | 1  57

The flowers of G. globosa are rich in betacyanins that have a wide range of applications as additives and supplements in the food industry, cosmetics, and livestock feed. Stable between pH 3 and 7, the betacyanins in globe amaranth are well suited to be used as natural food dye and have a red-violet color [1]. Gomphrena globosa L. is a source of betacyanins, molecules with high colorant power. In order to replace conventional extraction techniques, microwave (MAE) and ultrasound-assisted extraction (UAE) processes were optimized by the response surface methodology (RSM) to maximize the recovery of betacyanins from G. globosa [2]. Gomphrena globosa L. flowers, as an alternative plant source to obtain these pigments and to evaluate the best acid to be used within the extraction procedure has been investigated. For that purpose, three different acids (acetic, hydrochloric, and phosphoric acids, all of them allowed by the food industry) were adjusted at the same pH and were tested during a maceration extraction procedure. After the extraction, a purification through C18 column was performed in order to obtain a more concentrated extract in betacyanins [3]. The dye was found to be very good for dyeing woolen yarn.

1.3.2  Impatiens balsamina Plant: Impatiens balsamina Family: Balsaminaceae Genus: Impatiens Part used: Flower Impatiens balsamina (garden balsam) is a species of Impatiens native to Southern Asia in India, Bangladesh, and Burma. It is an annual plant growing to 20–75 cm tall, with a thick but soft stem. The flowers are pink, red, mauve, lilac, or white and 2.5–5 cm in diameter; they are pollinated by bees and other insects and also by nectar-feeding birds. The ripe seed capsules undergo explosive dehiscence (Fig. 1.17). The flowers of balsam contain some flavonoids pigments, flavonols, kaempferol 3-O-glucoside, lawsone, and several varieties of hosenkoside [3]. The optimum dye concentration for balsam flower dyes on woolen fabrics. Optimum dye extraction times and mordant concentrations were determined, as well as the best method for mordanting. Colorfastness of balsam-dyed fabrics to washing and light was also evaluated. A concentration of 5 g of flowers in 100 mL of water, a dye extraction time of 60 min, and a dyeing time of 120 min were the optimum dyeing parameters for red balsam flower dye on Australian Merino wool. Simultaneous mordanting and dyeing gave the best result with all mordant tested, except chlorine. Colorfastness to light and washing was acceptable [4]. The search for production of floral dye from different flowers is available in West Bengal for textile and dye industry. Balsam flower was used as one

58  New Trends in Natural Dyes for Textiles

FIG. 1.17  Impatiens balsamina.

of the floral dyes [5]. Different extraction methods were used for extracting maximum dye content.

1.3.3  Lawsonia inermis Plant: Lawsonia inermis Family: Lythraceae Genus: Lawsonia Part used: Leaves Lawsonia inermisis, commonly called as hina, belongs to the family Lythraceae. It is a shrub 8–15 ft bearing small white sweet-smelling flowers. It thrives in hot dry climates. Powdered (young) leaves of the plant have been used from ancient times in Middle East and Southern Asian countries for dyeing hair and nails. The dyeing process is due to the brown resinoid substance called henno-tannic acid. The main colorant in Lawsonia is lawsone, an alpha naphthoquinone-hydroxy derivative. Although there are reports on dyeing cotton, silk and viscose with Lawsonia are using only alum [6] and silk with caustic soda/salt [7]. There are other papers [8] on Lawsonia describing different aspects of cotton, viscose, wool, and silk dyeing. The commercial aspect of coloring capacity of brightly colored plant product for value addition products was also tried [9,10] (Fig. 1.18).

Newer Natural Dyes for Various Textiles  Chapter | 1  59

FIG. 1.18  Lawsonia (hina).

1.3.4  Mirabilis jalpa Plant: Mirabilis jalapa Family: Nyctaginaceae Genus: Mirabilis Part used: Flowers Mirabilis jalapa flowers offer huge potential as natural colorants for the dyeing of wool. A research was conducted to dye wool using the aqueous extracts of the pink variety of Mirabilis flowers. The flower contains a pigment called betacyanins, which are hydroxyl-cinnamoyl derivative of betaine and isobetaine. The dye was extracted by warming the flowers with distilled water for an hour, crushed by glass rod, and then filtered (Fig. 1.19). The colorfastness tests were carried out for the dyed wool yarn according to the specified standards. Sonicator dyeing efficiency with M. jalpa flowers can be industrially very economical and useful as the sonicator machine can be used for the extraction of the dye and dyeing. Mordanting was carried out using 2%–4% concentration of mordants, including SnCl4, SnCl2, CuSO4, K2Cr2O7, alum, and FeSO4. The results showed that stannic chloride mordanting gave good shade of color with optimum concentration of SnCl4. The findings of colorfastness tests of wool samples to rubbing under dry conditions showed that the samples had fair-to-excellent fastness as compared with dry rubbing. The colors obtained ranged from bright red, to brown, to black depending on the choice of mordant [11]. A study was undertaken to find out the effect of selected M. jalapa lower on cotton and wool fabric with different mordants [12]. Depth of

60  New Trends in Natural Dyes for Textiles

FIG. 1.19  Mirabilis jalapa flower.

shade and e­ venness of dye was also evaluated. Mirabilis jalapa flower, which is abundantly available in the season, can be exploited as a good source of natural dye for the wool and cotton dyeing range from olive green to brown depending upon the choice of mordant. The efficiency of various mordant is correlated with possible chemical interactions on the dyeing of wool and cotton.

1.3.5  Nyctanthes arbor tristis Plant: Nyctanthes arbor-tristis Family: Oleaceae Genus: Nyctanthus Part used: Flower stem Aqueous extract of the flower stem of Nyctanthes was used [13] for dyeing of cotton, silk, and wool. Good color depths were obtained for all the three natural fabrics (Fig. 1.20). The corolla of N. arbor-tristis L. was used as a natural color for dyeing and painting of cotton and silk with kalamkari technique using bamboo stick. From the present work, it can be concluded that cotton and silk painted and dyed with corolla of N. arbor-tristis Linn exhibited fair-to-excellent wash and sunlight fastness. The use of N. arbor-tristis Linn corolla extract was a very good option

Newer Natural Dyes for Various Textiles  Chapter | 1  61

FIG. 1.20  Nyctantes arbor-tristis.

for yellow and yellow orange color as a value addition to fashion fabric and ultimately in eco-friendly clothing [14]. Bleaching of organic cotton fabric can be done with hydrogen peroxide in which catalase, a nontoxic, environmentally friendly biocatalyst, is used to remove the residual H2O2 in a cost-effective way for the better improvement of the cellulosic fabric properties. Enzyme-treated organic cotton fabric was dyed with a natural dye obtained from orange corolla tube of N. arbor-tristis flower with the use of ultrasonic power (38.5 kHz and 500 W) and conventional heating conditions. Ultrasonic power dyed fabric was compared with conventional dyeing by studying their dyeability. Optical density measurements were done for both dyed organic cotton samples. The ultrasoundassisted dyeing process gave better dye absorption and fastness properties than that of conventional method using mordants [15].

1.3.6  Punica granatum Plant: Punica granatum Family: Lythraceae Genus: Punica Part used: Epicarp of the fruit Punica granatum is a small tree, not more than 15 ft high, with pale, brownish bark. The buds and young shoots are red; the leaves are opposite, lanceolate, and almost evergreen. The flowers are large and solitary; the crimson petals are alternating with the lobes of the calyx. The fruit is the size of an orange, having a thick, reddish-yellow rind, an acid pulp, and large quantities of seeds. The rind of the fruit is in curved, brittle fragments, rough, and yellowish brown outside that has good amount of natural colorant (Fig. 1.21).

62  New Trends in Natural Dyes for Textiles

FIG. 1.21  Punica granatum.

The coloring pigment in pomegranate is lysine-derived alkaloids called pelletierine and methyl- and pseudopelletierine along with about 19% tannin. It is known that tannate of pelletierine is the main constituent in the rind. This amorphous yellow powder is very soluble in water, about 250 parts. The actual composition of the rind of the fruit when dry is brown externally and yellow from within containing about 18.8% tannin [16]. Enzymatic natural dyeing was attempted with Punica dye extract [17]. In the two-step ultrasonic dyeing of cotton and silk fabrics with natural dyes, P. granatum has been developed in which an enzyme is complexed with tannic acid first as a pretreatment. This was found to be comparable with one-step simultaneous dyeing. The effectiveness of three enzymes, namely, protease-amylase, diasterase, and lipase, was determined. The enzymatic treatment gave cotton and silk fabrics rapid dye adsorption kinetics and total higher adsorption than untreated samples for all the three dyes. The CIELAB values also showed improvement by enzymatic treatment. The tannic acid-enzyme-dye combination method offers an environmentally benign alternative, “soft chemistry,” to the metal mordanted natural dyeing. The fruit is typically in season in the Northern Hemisphere from September to February and in the Southern Hemisphere from March to May. Pomegranate peel (P. granatum) with solid applications is one of the most important sources of natural dyes. The major coloring component in

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­ omegranate is tannins, extracted from the fresh and dried peels. Dyeing of difp ferent textiles and synthetic and natural fabrics with the extract of pomegranate powder has been carried out, and dyeing has been optimized after extraction by conventional and traditional method. Finally, dyed fabric has been subjected to different textile laboratory tests, for example, colorfastness, lightfastness, washing fastness, and rubbing fastness (dry and wet) [18].

1.3.7  Reseda luteola Plant: Reseda luteola Family: Resedaceae Genus: Reseda Part used: Flower Reseda luteola is a plant species in the genus Reseda. Common names include dyer's rocket, dyer's weed, weld, and yellow weed. The plant is rich in luteolin, a flavonoid that produces a bright yellow dye (Fig. 1.22).

FIG. 1.22  Reseda luteola.

Reseda luteola L. fresh extract of the flower, stem, and leaves was found to have good colorant quality. As the dyed cotton, silk, and wool fabrics as well as yarn showed very good wash- and lightfastness properties; exploration of dyeing potential of this wonderful dye extract under different pretreatment conditions, pre- and postmordanting with metal mordants, biomordant, enzymes, and surfactants was carried out. Reseda extract showed bright yellow color with alum, olive green with copper sulfate, and dark brown with ferrous sulfate. Sodium salt of dodecylbenzene-sulfonic acid (SDBS) and cetyl trimethyl ­ammonium

64  New Trends in Natural Dyes for Textiles

bromide (CTAB) as pretreatment have also been used. Combination of other natural dye extracts with Reseda extract has been attempted. A wide spectrum of colors has been obtained ranging from canary yellow, to olive green, to orange [19]. The most appropriate leaching solvent for luteolin from leaves, stems, and flowers of R. luteola was found to be methanol. Optimal luteolin extraction was 8.6 g/kg of plant material. Preliminary dyeing tests on premordanted raw cotton and wool standard specimens gave greenish-yellow hue; acid perspiration fastness was found to be resistant to fading of dyed wool specimens that was generally greater than that of cotton dyed samples [20]. The luteolin amount in agronomic performance of Reseda variety was affected by climatic conditions and by the plant phenological stages at harvest. Luteolin was found most abundant in the driest year and in plants harvested during flowering. The dry powder from leaves and flowers was used in the dyeing of cotton, wool, and silk yarns. Good and bright yellow colors were observed using a ratio 30:100 (weight/weight) of weld on the textile materials [21].

1.3.8  Rosa rosa Plant: Rosa rosa Family: Rosaceae Genus: Rosa Part used: Flower Rose is a woody perennial flowering plant of the genus Rosa, in the family Rosaceae, or the flower it bears. There are over a hundred species and thousands of cultivars. They form a group of plants that can erect shrubs, climbing or trailing with stems that are often armed with sharp prickles. Flowers vary in size and shape and are usually large and showy, with colors ranging from white to yellows and reds (Fig. 1.23). Red rose is a one of the most important ornamental plant mainly growing in garden and rich in red and pink pigments. The dyeing pigments present in flowers of red rose were extracted by using four different solvent extraction methods. The three different mordents were used to set isolate dye on cotton fabric by forming a coordination complex. The result revealed that different shades of pink and yellow color were obtained from the dye when subjected to mordent. Thus, the color dye extracted from red rose flower can be used for coloration of cotton, silk, and wool fabrics [22]. Rosa centifolia is one flower offered to the deity; the valuable flower was being immersed in the river or dumped at the available place that creates an ecological imbalance and other health hazards. The work was undertaken to extract natural color from the floral waste (R. centifolia) [23]. The dyeing was carried out on premordant mulberry silk fabric. Further optimum conditions for dyeing were evaluated. On the basis of result, it was found that temperature also significantly influence the dyeing process.

Newer Natural Dyes for Various Textiles  Chapter | 1  65

FIG. 1.23  Rosa rosa.

1.3.9  Salacia prinoides Plant: Salacia prinoides Family: Celastraceae Genus: Salacia Part used: Root and Bark Salacia prinoides (Kothala) that belongs to family Celastraceae is a climbing smooth shrub, reaching a height of 4 m or more. It occurs in tropical, humid valley forest of Sri Lanka. The leaves are oblong with petiole 8–16 cm in length. The different tribes of Sri Lanka have been engaged in extraction, processing, and preparation of dyes using barks and roots of this plant. Among the other significant uses of Kothala is it is used to reduce the diabetic effect in blood glucose. Hence, it has medicinal properties as well [24] (Fig. 1.24). The roots of Salacia are with golden-yellow cork layer (phelloderm). Inner root is reddish brown with several circles of bark and wood. The stem cross section also shows several rings due to the development of several layers of bark tissue alternating with wood tissue. The root and stem wood are well known for its antidiabetic activity. Now, it is taken up for cultivation in southern states of India. Kothala leaves have been used as natural dyestuff used as indigenous systems that has been developed scientifically and can be substituted for the chemical dyes for local handloom sector for shades of light brown-dark brown as shown in cotton, silk, and wool-dyed samples [25].

66  New Trends in Natural Dyes for Textiles

FIG. 1.24  Salacia tree and bark.

1.3.10  Tectona grandis Plant: Tectona grandis Family: Verbenaceae Genus: Tectona Part used: Leaves Tectona grandis (teak) that belongs to Verbenaceae family is well known for containing an orange-red dye that is used by the Manipur women for dyeing silk, although the tree is used as source of timber. However, the bark of the roots and the young leaves produce a yellowish-brown-reddish dye that is used for paper, edibles, clothes, and matting by the rural people of Manipur. The young leaves are reported to contain a yellow or red dye that is used for dyeing silk, in yellow, olive, or related shades; however, the chemical composition of the dye is not well documented in the literature [26] (Fig. 1.25). Process development for the extraction of natural dye from the waste leaves of teak plant (T. grandis) and their application on different yarns has been carried out successfully. Light salmon and maroon color shade for silk yarn has been achieved using the isolated coloring materials [27]. The leaves of T. grandis Linn are used for dye production. Dye was extracted from the T. grandis Linn that was used for assessing the dyeing behavior of the color components on cotton. The dyeing was carried out with and without the use of mordants, and the colorfastness properties of the fabrics were determined. The absorbance (%) and color strengths (K/S) of the dyes were evaluated, and the color changes were recorded in Hunter coordinates and converted to CIELAB coordinates. It is seen that the fastness of all dyed samples to wet rubbing was very good, but unmordanted dyed samples had very poor fastness to light and washing, though staining on adjacent fabric is not observed. Mordanting with alum improved the washing fastness to moderate levels, and adding iron salt to alum further improved it to good and very good category [28].

Newer Natural Dyes for Various Textiles  Chapter | 1  67

FIG. 1.25  Tectona grandis.

The development of an alternative natural dye from the Philippine teak leaves (T. philippinensis). The leaves were boiled for 1 h using tap water as the solvent for extraction of natural dye. The extracted dye was reddish in color. Quantitative determination revealed that 10.95 g (1.095%) of powder dye was produced for every 1 kg of dye sample with 30 L of water. Different shades of colors appeared when the dye was applied to cotton, linen, jusi, piña-seda, and silk cocoon using different mordants. The dyed fabrics were subjected to colorfastness to washing, perspiration, and sunlight using Launder-O-Meter, incubator, and Atlas Ci+3000 Xenon Weather-Ometer. Results showed that it is acceptable to technical evaluators [29]. As this dye has given good shades with silk, this can be potentially very good for wool as well. Natural dyes are believed to be harmless because of their nontoxic and biodegradable nature. The rapid changes in trends and fashion and the demand for good fastness properties on different substrates require many new sources of newer natural dyes. Thus these newer dye sources must be compatible for almost all the substrates including wool. Natural wool or pure wool doesn't hinder in accepting most of the natural dye colors thus a potential substrate for these new entrants.

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References [1] Shanker  R, Vankar  PS. Dyeing wool with Gomphrena globosa flower. Colourage 2005;52(4):35–8. [2] Roriz  CL, Barros  L, Prieto  M, Barreiro  MF, Morales  P, Ferreira  IC. Modern extraction techniques optimized to extract betacyanins from Gomphrena globosa L. Ind Crop Prod 2017;105:29–40. [3] Roriz CL, Carvalho AM, Morales P, Barros L, Ferreira IC. Extraction of betacyanins from Gomphrena globosa L. flowers: choosing na acid as adjuvant. In: 5° Encontro Português de Jovens Químicos (PYCheM) e o 1° Encontro Europeu de Jovens Químicos (EYCHeM); 2016. [4] Jahan R, Gupta K. Balsam flowers useful in wool dyeing. Colourage 1991;38(1):48–9. [5] Saha P, Dutta S. Production of floral dyes from different flowers available in west bengal for textile and dye industry; 2007, folk.ntnu.no/skoge/prost/proceedings/ecce6_sep07/upload/386.pdf [6] Gogoi A, Ahmed SS, Barua N. Natural dyes & silk. Indian Text J 1997;8:64–8. [7] Gupta VK, Sachan RA, Singh VP, Sharma S. Natural dyes. Indian Text J 1998;108(4):78–80. [8] Paliwal  J. Effect of mordents on henna, dyed cotton and silk fabrics. Text Mag Madras 2001;42:79–81. [9] Vankar PS, Tiwari V, Shanker R. Commercial dyeing with aqueous extract of Lawsonia using ecofriendly mordants. Asian Text J 2002;58–60. [10] Vankar PS, Tiwari V, Shankar R. Commercial viability of dyeing cotton with aqueous extract of Lawsonia (Henna) using eco-friendly mordant. Asian Text J 2008;76(1):207. [11] Shanker  R, Vankar  PS. Ultrasonic energised dyeing of wool with Mirabilis jalpa flowers. Colourage 2005;52(2):57–61. [12] Annapoorani G, Sundarraj D. Dyeing of cotton and wool fabric using Mirabilis Jalapa flower. Int J Sci Res 2014;3(7):2012–5. [13] Vankar PS, Shanker R. Dyeing cotton, wool and silk with Nyctanthes arbor tristis L. with aqueous extract of flower stem. Asian Dyers 2005;8:59–63. [14] Deshmukh A, Dongre S. Natural yellow colour from corolla of Nyctanthes arbortristis Linn. for dyeing and painting on cotton and silk for value addition. Biolife 2015;3(2):353–7. [15] Gandhi RR, Suresh J, Gowri S, Selvam S, Sundrarajan M. Ultrasonic dyeing of enzyme treated organic cotton using nyctanthes arbor-tristis. Chem Sci Trans 2013;2:642–8. [16] Vankar PS. Handbook on natural dyes for industrial applications. National Institute of Industrial RE; 2007. [17] Vankar PS, Shanker R, Verma A. Enzymatic natural dyeing of cotton and silk fabrics without metal mordants. J Clean Prod 2007;15(15):1441–50. [18] Adeel S, Ali S, Bhatti IA, Zsila F. Dyeing of cotton fabric using pomegranate (Punica granatum) aqueous extract. Asian J Chem 2009;21(5):3493. [19] Shukla  D, Vankar  PS. Spectrum of colors from Reseda luteola. J Text Eng Fash Technol 2018;4(2):106–19. [20] Cerrato A, De Santis D, Moresi M. Production of luteolin extracts from Reseda luteola and assessment of their dyeing properties. J Sci Food Agric 2002;82(10):1189–99. [21] Angelini LG, Bertoli A, Rolandelli S, Pistelli L. Agronomic potential of Reseda luteola L. as new crop for natural dyes in textiles production. Ind Crop Prod 2003;17(3):199–207. [22] Patil D, Patil K, Gaikwad P, Patil P, Shewale U, Bhamburdekar S. Extraction of natural dye from rose flower for dyeing cotton fabrics. Int J Innov Res Multidiscip Field 2016;2(8):135–7. [23] Kalsy M, Srivastava S. Dyeing of silk with Rosa centifolia: an eco-friendly approach. Technology 2016;43:46.

Newer Natural Dyes for Various Textiles  Chapter | 1  69 [24] Deokate U, Khadabadi S. Phytopharmacological aspects of Salacia chinensis. J Pharm Phytother 2012;4(1):1–5. [25] Vankar PS, Shanker R, Wijayapala S, Alwis A. Dyeing of cotton,wool and silk with the leaves extract of Salacia prinoides (Kothala). Asian Text J 2007;16(6):69–74. [26] Vankar  PS, Tiwari  V, Cotton  SRD. Wool and silk with tectona leaves dye. Asian Text J 2003;(3)86–90. [27] Prusti A, Purohit A, Nayak A, Das N. Waste leaves of Tectona grandis as a suitable natural dye for textile. Colourage 2010;57(1):55–6. [28] Rane  S, Hate  M, Hande  P, Ajitkumar  B, Datar  A. Dyeing of cotton with Tectona grandis leaves and Terminalia arjuna bark extracts. Int J Text Sci 2017;6(2):72–7. [29] Asiong JB, Facto SA, Nidua JO, Gebe AN. Development of an alternative natural dye from Philippine teak leaves (Tectona philippinensis). J BIMP-EAGA Reg Dev 2017;3(2):30–9.