**1. Introduction**

Dyeing was known as early as in the Indus Valley period (2600-1900 BC); this knowledge has been substantiated by findings of colored garments of cloth and traces of madder dye in the ruins of the Indus Valley Civilization at Mohenjodaro and Harappa. Natural dyes, dye‐ stuff and dyeing are as old as textiles themselves. Man has always been interested in colors; the art of dyeing has a long past and many of the dyes go back into prehistory. It was prac‐ ticed during the Bronze Age in Europe. The earliest written record of the use of natural dyes was found in China dated 2600 BC. [1-4] Primitive dyeing techniques included sticking plants to fabric or rubbing crushed pigments into cloth. The methods became more sophisti‐ cated with time and techniques using natural dyes from crushed fruits, berries and other plants, which were boiled into the fabric and which gave light and water fastness (resist‐ ance), were developed. After the accidental synthesis of mauveine by Perkin in Germany in 1856 and its subsequent commercialization, coal-tar dyes began to compete with natural dyes. With advances in chemical techniques, the manufacture of synthetic dyes became pos‐ sible, leading to greater production efficiency in terms of quality, quantity and the potential to produce low-cost raw materials. As a result, natural dyes were progressively replaced by synthetic dyes, whereas over 80% of which is constituted of the aromatic azo type [5]. How‐ ever, researches have shown that synthetic dyes are suspected to release harmful chemicals that are allergic, carcinogenic and detrimental to human health. In addition, textile indus‐ tries produce huge amounts of polluted effluents that are normally discharged to surface water bodies and ground water aquifers. These wastes cause many damages to the ecologi‐ cal system of the receiving surface water, creating a lot of disturbance to the ground water resources [6-9]. Therefore, in 1996, ironically Germany became the first country to ban cer‐ tain azo dyes [10].

© 2013 Mansour; licensee InTech. This is an open access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited. © 2013 Mansour; licensee InTech. This is a paper distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/3.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

The world-wide demand for fibers and safety dyes is increasing probably according to the greater awareness of the general consumers in the USA, Europe and Japan towards the highly pollutant procedures affecting fiber and textile coloration when using synthetic dyes which act as a sources of skin cancer, disorders and allergic contact dermatitis [11]. There‐ fore, interest in returning back to natural dyes as synthetic dyes substitute has increased considerably on account of their high compatibility with environment, relatively low toxici‐ ty and allergic effects, as well as availability of various natural coloring sources such as from plants, insects, minerals and fungi [12]

out by three methods; i- Pre-mordanting; dipping the fabric in the mordant solution before dye‐ ing, ii- Simultaneous mordanting; addition of mordant in the dye bath during the dyeing, and

Textile Dyeing: Environmental Friendly Osage Orange Extract on Protein Fabrics

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209

Osage orange (Maclura pomifera) is a tree in the Moraceae family [18]. The common name is derived from its fruit, which resembles the shape of an orange, and from the fact that its hardwood was used by the Osage Indian tribe to make bows. It is native to Southern Okla‐ homa and Northern Texas, and is planted throughout the United States. Several compounds have been isolated and identified in various parts of this tree namely, isoflavonoids from the fruit, flavonols and xanthones from the heartwood and stem bark, and flavanones and xan‐ thones from the root bark [19] It contains lectins, triterpenes, xanthones and flavone-type compounds such as Scandenone and auriculasin as shown in Figure 1 [20] Two predomi‐ nant isoflavones, pomiferin and osajin, are derived from the simple isoflavone genistein by

iii- post mordanting; dipping the fabric in the mordant solution after dyeing [17].

prenyl substitutions [21] as shown in Figure 2.

**Figure 1.** Chemical structures of scandenone (I) and auriculasin (II)

**Figure 2.** Chemical structures of Osajin (i) and pomiferin (ii)

Natural dyes can be obtained from plants, animals and minerals, producing different colors like red, yellow, blue, black, brown and a combination of these. For technical application of natural dyes, a number of requirements have to be fulfilled;

Most problems are derived from technical demands, for example:


From an industrial point of view it would be easier to resort to extracts despite there is at present no definite answer to this prospective solution. The simplest extract would be a wa‐ tery one although not all the dye pigments are water-soluble. Use of organic solvents might give rise to extracts which are not completely water-soluble [15], provided that the solvent chosen guarantees a series of properties as follows:


Natural dyes are substantive and require a mordant to fix to the fabric, and prevent the col‐ or from either fading with exposure to light or washing out. These compounds aid a chemi‐ cal reaction between the dye and the fiber, so that the dye is absorbed. Traditionally, mordants were found in nature. Wood ash or stale urine may have been used as an alkali mordant, and acids could be found in acidic fruits or rhubarb leaves.

There are three types of mordant: i) Metallic mordants; Metal salts of aluminium, chromium, iron, copper and tin, ii) Tannins; Myrobalan and sumach, iii) Oil mordants; mainly used in dyeing Turkey red color from madder by forming a complex with alum.

In order to obtain high color yield, different shades and good fastness properties, metallic salt mordants are normally employed [16]. The application of mordants for dye fixation was carried out by three methods; i- Pre-mordanting; dipping the fabric in the mordant solution before dye‐ ing, ii- Simultaneous mordanting; addition of mordant in the dye bath during the dyeing, and iii- post mordanting; dipping the fabric in the mordant solution after dyeing [17].

Osage orange (Maclura pomifera) is a tree in the Moraceae family [18]. The common name is derived from its fruit, which resembles the shape of an orange, and from the fact that its hardwood was used by the Osage Indian tribe to make bows. It is native to Southern Okla‐ homa and Northern Texas, and is planted throughout the United States. Several compounds have been isolated and identified in various parts of this tree namely, isoflavonoids from the fruit, flavonols and xanthones from the heartwood and stem bark, and flavanones and xan‐ thones from the root bark [19] It contains lectins, triterpenes, xanthones and flavone-type compounds such as Scandenone and auriculasin as shown in Figure 1 [20] Two predomi‐ nant isoflavones, pomiferin and osajin, are derived from the simple isoflavone genistein by prenyl substitutions [21] as shown in Figure 2.

**Figure 1.** Chemical structures of scandenone (I) and auriculasin (II)

The world-wide demand for fibers and safety dyes is increasing probably according to the greater awareness of the general consumers in the USA, Europe and Japan towards the highly pollutant procedures affecting fiber and textile coloration when using synthetic dyes which act as a sources of skin cancer, disorders and allergic contact dermatitis [11]. There‐ fore, interest in returning back to natural dyes as synthetic dyes substitute has increased considerably on account of their high compatibility with environment, relatively low toxici‐ ty and allergic effects, as well as availability of various natural coloring sources such as from

Natural dyes can be obtained from plants, animals and minerals, producing different colors like red, yellow, blue, black, brown and a combination of these. For technical application of

**•** selection of plant material and processes that yield products with acceptable fastness

From an industrial point of view it would be easier to resort to extracts despite there is at present no definite answer to this prospective solution. The simplest extract would be a wa‐ tery one although not all the dye pigments are water-soluble. Use of organic solvents might give rise to extracts which are not completely water-soluble [15], provided that the solvent

**•** Its extraction capacity is extremely high for practically all the natural pigments present in

**•** Its boiling temperature and latent heat of vaporization is quite low to allow its separation

**•** Its reactivity with colors and pigments is insignificant to avoid any loss in the color quali‐

Natural dyes are substantive and require a mordant to fix to the fabric, and prevent the col‐ or from either fading with exposure to light or washing out. These compounds aid a chemi‐ cal reaction between the dye and the fiber, so that the dye is absorbed. Traditionally, mordants were found in nature. Wood ash or stale urine may have been used as an alkali

There are three types of mordant: i) Metallic mordants; Metal salts of aluminium, chromium, iron, copper and tin, ii) Tannins; Myrobalan and sumach, iii) Oil mordants; mainly used in

In order to obtain high color yield, different shades and good fastness properties, metallic salt mordants are normally employed [16]. The application of mordants for dye fixation was carried

plants, insects, minerals and fungi [12]

208 Eco-Friendly Textile Dyeing and Finishing

properties [14]

ty [15].

natural dyes, a number of requirements have to be fulfilled;

chosen guarantees a series of properties as follows:

at low temperatures with minimum energy consumption;

mordant, and acids could be found in acidic fruits or rhubarb leaves.

dyeing Turkey red color from madder by forming a complex with alum.

the raw materials of interest.

Most problems are derived from technical demands, for example:

**•** adaptation of traditional dyeing processes on modern equipment [13] **•** supply of dye-houses with the required amount of plant material [13] **•** standardization of extraction and dyeing of the plant material [14]

The compounds, osajin, iso-osajin, pomiferin, and iso-pomifcrin have been characterized and their chemical structures determined. They are isoflavones with the following structures as shown in Figure 3. [19, 21].

An analytical grade alum and the commercially cream of tartar were used as mordantas.

To select the best solvent for Osage orange, distilled water and other co-solvents, such as water-acetone, and water- ethanol mixtures all of analytical grade, were tested at concentra‐ tions of 10% v/v. 2 g of Osage orange powder (Hands Ashford NZ, LTD, ChristChurch, NZ) was suspended in 20 cm3 of solvent, and in thermostatic as well ultrasonic baths at 60 ◦C, for 120 min. Once water-acetone co-solvent, and ultrasonic assisted extraction were chosen as the preferable technique of extraction, 10 % w/v Osage orange powder, dissolved in (2.5- 25)

1 % Osage orange extract was filtered and used as a dyeing bath. Silk and wool samples were added to the extract, and the dyeing parameters were studied ultrasonically keeping the material to liquor ratio at L: R of 1:30, for time intervals varied between 30- 120 min, at

On studying the mordanting methods, the optimum concentration of 8% w/v Osage orange extract was carried out. Stock solutions of 50 gm/ l alum and 25 g/l mixture of each of alum and cream of tartar were prepared. Two different methods of mordanting were used: (1) pre-mordanting method: the samples were first mordanted and then dyed without inter‐ mediate washing; and (2) post-mordanting method: the samples were first dyed and then mordanted. Ultrasonic assisted mordanting was carried out in comparison with the conven‐

material to liquor ratio at 1:50. Finally washed with water, and dried at ambient tempera‐

Dyestuff content of the dyed fabrics was determined according Kubelka–Munk equation

R is the absolute reflectance of the sampled layer, K is the molar absorption coefficient and s

After which the samples were tested for color fastness to light and washing according to AATCC107-1997 [29] The CIE-Lab values of the dyeings were measured and the cylindrical co-ordinates of color were determined after exposure to arc lamp irradiation for 1, 2, 4, 6, 24, 48, and 72 hrs. The colors are given in an internationally commission (CIE L\*a\*b\*) coordi‐

C, for 30- 120 min, were carried out to determine the standardiza‐

Textile Dyeing: Environmental Friendly Osage Orange Extract on Protein Fabrics

C. In terms of the pH used for dyeing; the pH values ranging from

C, for 90 min, at pH 5. samples were rinsed, washed with 0.5

C for 30 min, keeping the

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211

**2.2. Pigment leaching and estimation of extraction yields**

% v/v acetone, at (25- 60) o

tion method of extraction. [24]

**2.3. Dyeing and mordanting**

temperatures from 30-60o

tional heating method at 50-60o

[28] using *Cary 100 UV-Vis Spectrophotomete*r

ture. [23, 26, 27]

*<sup>f</sup>* (*R*)= (1 <sup>−</sup> *<sup>R</sup>*)

**2.4. Measurements**

2 <sup>2</sup>*<sup>R</sup>* <sup>=</sup> *<sup>k</sup> s*

is the scattering coefficient.

(3-11) were carried out to control the dye uptake.

g/L sodium carbonate and 2 g/L of non-ionic detergent at 40-45o

**Figure 3.** Chemical Structure of iso-pomifcrin

As well as Osage orange was applied as an eco-friendly dye acting as one of the environ‐ mental problems solutions. New concepts in the cleaner production are being evaluated to solve the high water and energy consumption in textile industries.

The use of ultrasonic as a renewable source of energy in textile dyeing has been increased due to many advantages associated with it [22-25]. Ultrasonic energy represents a promising technique for assisting silk treatment, dyeing, and mordanting processes in comparison with the conventional heating technique. Sonic energy succeeded in accelerating the rate of, dye‐ ing, and mordanting at lower temperatures rather than the conventional heating technique

Therefore, the present investigation was aimed at identifying the most appropriate leaching solvent for Osage orange pigments to produce an optimum concentrated extract used for dyeing protein fibers; silk and wool fabrics. This has been carried out ultrasonically in com‐ parison with the classical thermal method, using water, in addition to the co-solvents of wa‐ ter-acetone, and water-ethanol mixtures at different concentrations, temperature and time intervals. The optimum condition of the efficiency of ultrasonic assisted dyeing and mor‐ danting methods of Osage orange extraction on the quality of the dyed protein based mate‐ rials were determined
