Development of Natural Additives in Dyeing of Cotton Fabric Using Reactive Dyes

Development of Natural Additives in Dyeing of Cotton Fabric Using Reactive Dyes
Mr.V.Arunprakash
1 & Mrs.C.Premalatha2
 M.Tech in Textile Chemistry1
Professor and Head2 
Dept of Textile Chemistry
SSM College of Engineering, Komarapalayam – 638 183
Emai: cpl.aap104@gmail.com
1


ABSTRACT

The major environmental issue in textile industry is caused by the textile wet processing unit. Effluent treatment has become tedious and ineffective because of the various toxic chemicals used in the wet processing and it thus affects the eco-friendly impact of the process. Their impact on the environment can be minimized by bringing some changes in the processing technique adopted and by replacing the chemicals used with biodegradable alternatives. In this work, the existing reactive dyes are dyed with Natural materials as additives to see the colour yield evaluation and Environmental effects on the same.

Introduction:

REACTIVE DYEING
Reactive dyes are typically azo-based chromophores combined with different types of reactive groups. The relative large chromophores place reactive dyes in the molar weight area of 700-1000 g/mol. The reactive groups can be based on dichlortriazin or vinyl sulphonic acid and will be negatively charged. Beside the reactive groups, other negatively charged groups are found, too typically sulfonic acid groups. The reactive groups react with hydroxyl groups in the cellulose fibre during the dyeing reaction as shown in Figure 2.1.
Reactive dyeing mechanism
Figure.2.1 Reactive dyeing mechanism
Reactive dyes are water soluble in nature. Dyeing is commenced in neutral solution, often in the presence of salt to promote exhaustion of the dye onto the cotton. During this period, the dye does not react with the fibre and migration from fibre to fibre is possible. Then, an appropriate alkali is added to the dye bath to increase its pH. This initiates the desired dye–fibre reaction. The hydroxyl groups in cellulose are weakly acidic and absorption of hydroxide ions causes some dissociation, forming electron deficient group. It is these that react

REACTIVE DYEING METHOD
In the conventional reactive dyeing method, the addition of salt is carried out in three stages for the uniform dye uptake. The alkali is added at the final stage and its treated for an hour for complete fixation of the dye molecule.

NEW METHOD OF REACTIVE DYEING
In the new reactive dyeing method, instead of the addition of salt in three stages for the uniform dye uptake, a natural extract is added a single time initially. Then again a natural extract is added after working for some time for fixation.

NATURAL DYEING
The use of non allergic, non toxic and eco friendly natural dyes on textile has become a matter of significant importance due to increased environmental awareness in order to avoid some hazardous synthetic dyes. In addition, when properly applied, natural dyes are fast, resisting fading due to exposure to sunlight. Natural dyes produce very uncommon, soothing and soft shades as compared to synthetic dyes .

MORDANTS
Mordants are substances which are used to fix a dye to the fibres. They also improve the take-up quality of the fabric and help improve colour and light-fastness. The term is derived from the Latin mordere, to bite. Mordant will generally give much better, brighter and more permanent colours. The most commonly used mordant is alum, which is usually used with cream of tartar as an additive or assistant. Other mordants are iron (ferrous sulphate),tin (stannous chloride), chrome (bichromate of potash), copper sulphate,tannic acid, and oxalic acid.

TYPES OF MORDANT
Mordants can be classified by the following ways:
  • Metallic mordants,
  • Tannin and tannic acid, and
  • Oils mordant
TANNIN
They are a number of plants and minerals which will yield a suitable mordant for application. Tannin found in many plants and also functions as a mordant. Tannin acid is the most common mordant for cellulose fibres such as cotton. Tannin is often combined with alum and iron.The tannins are somewhat heterogeneous group of astringent vegetable principles which have in common the properties of precipitating collagen, of yielding blue or green colourations with ferric salts, of precipitating chromium, copper and lead salts under certain condition of acidity, and of precipitating many organic bases, including a number of alkaloids compounds. Some tannin appears to be glycosidal in character.

SOURCES OF TANNIN
Tannin includes in many plant sources. Plant sources mean root, bark, wood, twig, leaf, fruit, flower, and seed. The vegetable tannins are produced during the metabolism of plants and trees. The parts of the plant in which the tannin occurred vary with the species. They have been found in the bark and trunks, in leaves, roots, and rhizome fruits. Typical materials used for bark tanning include any of the oaks, fir, certain willows, chestnut, sumac leaves, oak galls, canaigre root, birch, alder, hemlock. Bearberry (leaves), heather, bloodroot, alfalfa, tea, sweet gale, pomegranate rinds, certain fern's rhizomes and wood-hops have also been used

MYRICA NAGI (KAYPHAL)
MyricaNagi trees are found in North Punjab, Garhwal, Kumau hills, Khasiya mountain and Silhat in India up to 2100 metres and also in Nepal, China etc. It is an evergreen, medium sized tree, with a big crown, giving shade. The bark is reddish, very fragrant, with bark skin nearly 10 cm in thickness, with oval dots on its inner surface. The trunk core is grey and hard. The leaves are simple, 10-12 cm long, 3-5 cm broad and fragrant. The fruits, berries, 1.5cm, become red when ripe and are sweet – sour in taste. The flowers are red in color, with small stalk and covered with tiny hairs. MyricaNagi blooms in winter and bears fruits later on.
Myrica Nagi
Figure 2.2. Myrica Nagi
The botanical name of kayphal is Myricanagi (Synonym – M. esculenta) and it belongs to family Myricaceae. Other names include kainaryamy (Andhra Pradesh); nagatenga (Assam); kaiphal, satsarila (Bengal); kariphal (Gujrat); kaphal, kaiphal (Himachal Pradesh); kaiphal (Hindi); kaphal (Jaunsar); kirishivani (Karnataka); maruta (Kerala); soh-phi (Khasi); kaphal (Kumaon); keiphang (Lushai); kayaphala (Maharashtra); kobuli, katphala (Nepal); kaiphal, kahela, kahi (Punjab) kathphala, aranya, krishnagarbha (Sanskrit); masudam (Tamilnadu).

The bark reveals the presence of steroids, tannins, glycosides, saponins and volatile oils. The hexane extract of the plant roots shows presence of sitosterol and friedelin. New metabridged biphenyls – myricanol and myricanone – isolated from stem and bark and their structure elucidated. Myricanol glucoside, isolated from stem bark together with myricanol and myricanone. Kayphal contains 14% tannin.

LOTUS
Nelumbo nucifera, known by a number of names including Indian Lotus, Sacred Lotus, Bean of India, or simply Lotus, is a plant in the monogeneric family Nelumbonaceae. The Linnaean binomial Nelumbo nucifera is the currently recognized name for this species, which has been classified under the former names, Nelumbiumspeciosum and Nymphaea nelumbo, among others. Names other than Nelumbo nucifera are obsolete synonyms and should not be used in current works. This plant is an aquatic perennial. Under favorable circumstances its seeds may remain viable for many years, with the oldest recorded lotus germination being from that of seeds 1,300 years old recovered from a dry lakebed in northeastern China. Native to Tropical Asia and Queensland, Australia, it is commonly cultivated in water gardens. The white and pink lotuses are national flowers of India and Vietnam, respectively.
Nelumbo nucifera
Figure 2.3. Nelumbo nucifera
The roots of Nelumbo nucifera are planted in the soil of the pond or river bottom, while the leaves float on top of the water surface. The flowers are usually found on thick stems rising several centimeters above the water. The plant normally grows up to a height of about 150 cm and a horizontal spread of up to 3 meters, but some unverified reports place the height as high as over 5 meters. The leaves may be as large as 60 cm in diameter, while the showy flowers can be up to 20 cm in diameter.

Researchers report that the lotus has the remarkable ability to regulate the temperature of its flowers to within a narrow range just as humans and other warmblooded animals do. Dr. Roger S. Seymour and Dr. Paul Schultze-Motel, physiologists at the University of Adelaide in Australia, found that lotus flowers blooming in the Adelaide Botanic Gardens maintained a temperature of 30–35 °C (86–95 °F), even when the air temperature dropped to 10 °C (50 °F). They suspect the flowers may be doing this to attract coldblooded insect pollinators. The study, published in the journal Nature, is the latest discovery in the esoteric field of heat-producing plants. Two other species known to be able to regulate their temperature include Symplocarpusfoetidus and Philodendron selloum.

The traditional Sacred Lotus is distantly related to Nymphaea caerulea and possesses similar chemistry. Both Nymphaea caerulea and Nelumbo nucifera contain the alkaloids nuciferine and aporphine.

APORPHINE
Aporphine is one of a class of quinoline alkaloids. Many different analogues of this compound have been purified from plants. The chemical formula of aporphine is C17H17N.
Chemical structure of Aporphine
Figure 2.4. Chemical structure of Aporphine
NUCIFERINE
Nuciferine is an alkaloid found within the plants Nymphaea caerulea and Nelumbo nucifera. It has a profile of action associated with dopamine receptor blockade. It induces catalepsy, it inhibits spontaneous motor activity, conditioned avoidance response, amphetamine toxicity and stereotypy. It is structurally related to apomorphine. The chemical formula of nuciferine is C19H21NO2.
Chemical structure of Nuciferine
Figure 2.5. Chemical structure of Nuciferine
HOLARRHENA ANTIDYSENTRICA (KUTAJA)
The plant is indigenous to India and found all over the country in deciduous forests up to 900 meters. The small tree, 9-12 meters in height and the bark pale, grayish in color. The leaves, 9-18 cm long and 4-8 cm broad, broadly ovate to elliptic. Flowers in terminal corymbs cymes, white, slightly fragrant. The fruit pod, 20 to 40 cm long, in pairs, cylindrical and narrow. The seeds are linear-oblong, 1 cm long. 25-30 seeds per pod, smoky in color. Parts used are Bark, seeds and leaves.Bark and seeds contain an non-oxygenated alkaloid wrightine or conessine or kurchisine and holarrhenine. Wrightine or conessine is an amorphous powder soluble in water, alcohol and dilute acids. Holarrhenine crystallizes from ethyl acetate in silky needles is insoluble in alcohol or chloroform. Kurchisine is a white crystalline substance; it is bitter to taste. conessine is an alkaloid from the seeds at melting point of 125˚c (empirical formula C24H40N2). Some derivatives of conessine are Apoconessine(empirical formula C22H33N) at melting point 68.5˚c and Picrate at melting point 100-111˚c. the contents of alkaloids in the bark is found to be about 1.25% , .025% in the seeds and. 22% in the leaves. It is found that there are 2 other alkaloids present, namely, kurchicine and kurchine. The alkaloid, kurchine is characterized by a low melting point of 75˚c and it is the most abundant alkaloid present in the bark. Both kurchine and kurchicine have the molecular formulas of C23H38Nand C20H36ON2 respectively.

The seeds and the skin of the bark is used for medicinal purpose. Kutaja plant is used both internally as well as externally. Externally, to promote healing, the wounds are cleansed with the decoction of its skin. The paste of the skin is also applied on the boils. The oozing wounds are dressed with its seed powder. It works well in the treatment of diarrhea and dysentery, associated with bleeding as well. Since centuries, it has been used as a household remedy for the same.
HOLARRHENA ANTIDYSENTRICA
Figure 2.6. HOLARRHENA ANTIDYSENTRICA
CONESSINE
Conessine is a steroidalkaloid found in a number of plant species from the Apocynaceae family, including Holarrhena floribunda, Holarrhenaantidysenterica and Funtumiaelastica, several of which are used in traditional herbal medicine as a treatment for amoebic dysentery. It acts as a histamine antagonist, selective for the H3 subtype. The chemical structure of conessine is C24H40N2.
Chemical structure of Conessine
Figure 2.7. Chemical structure of Conessine
COCOS NUCIFERA
The coconut palm is grown throughout the tropics for decoration, as well as for its many culinary and non-culinary uses; virtually every part of the coconut palm can be utilized by humans in some manner. However, the extent of cultivation in the tropics is threatening a number of habitats such as mangroves; an example of such damage to an ecoregion is in the Petenes mangroves of the Yucatan.

The coconut has spread across much of the tropics, probably aided in many cases by seafaring people. Coconut fruit in the wild is light, buoyant and highly water resistant, and evolved to disperse significant distances via marine currents. Fruit collected from the sea as far north as Norway are viable. In the Hawaiian Islands, the coconut is regarded as a Polynesian introduction, first brought to the islands by early Polynesian voyagers from their homelands in Oceania. They are now almost ubiquitous between 26°N and 26°S except for the interiors of Africa and South America.

Coconut water contains a variety of inorganic ions and these ions contribute to the therapeutic value inherent in coconut water. As the basic ion composition of coconut water can replenish the electrolytes of the human body excreted through sweat, such as sodium, potassium, magnesium and calcium, it can serve as an effective rehydration drink . The concentration of these electrolytes in coconut water generates an osmotic pressure similar to that observed in blood , and it also does not affect hemostasis (plasma coagulation) . As a result, coconut water can be used as a short term intravenous hydration fluid under certain emergency situations. Interestingly coconut water has cardioprotective effects in experimental myocardial infarction induced in rats and this was probably attributed to the rich content of mineral ions in coconut water, especially potassium
Tender coconut
Figure 2.8. Tender coconut
Materials & Methodology

Specifications of fabrics
  • Type: Plain
  • Count: 30s X 30s
  • EPI-88
  • PPI-76
  • GSM-117
Fabric was purchased from Super Spinning Mills, Coimbatore.

Dyes used
Three Reactive dyes namely
  • C. I. Reactive Red 120A
  • C. I. Reactive Yellow 81 and
  • C. I. Reactive Blue 198
Supplied by Jaysynt Chemicals, Mumbai were used.

Chemicals used
Laboratory grade sodium chloride (NaCl) and sodium carbonate (Na2CO3) were used in dyeing of the fabrics.

Natural Materials used
Natural materials namely
  • Kayphal
  • Kutaja
  • Lotus and
  • Tender Coconut were used.
The dry extracts namely Kayphal, Kutaja and Lotus were supplied by Konark Herbal & Health Care, India and Tender Coconut was made avail from the local market.

Methods

Preparation of dyed samples
Each dye was used individually at different proportions for dyeing of the fabric samples for different set of combinations. Dyed samples were produced with 0.5%, 2.0%, 3.5% shades. Liquor to material ratio of 1:50 was used. The fabric was introduced in a bath containing the required quantity of dye and the extracts required for that particular combination and shade was added as shown in the Tables 4.1 to Table 4.3 . Temperature of the bath was gradually raised to 95ºC and the dyeing was continued for 60 min. During this duration, calculated quantity of exhausting agents were added initially and after an interval of 30 min fixing agents were added. Washing of dyed samples were carried out by using alternate cold wash with running tap water for 5 min and soaping for 5 min. Finally, the samples were thoroughly washed with running tap water.

Table 4.1

Recipe for 0.5% shade
S.NO
EXHAUSTING AGENT(EA)
FIXING AGENT (FA)
EA QUANTITY
(gpl)
FA QUANTITY
(gpl)
1
NaCl
Na2CO3
15
15
2
NaCl
Lotus
15
20
3
NaCl
Kutaja
15
20
4
Tender coconut*
Na2CO3
100
15
5
Kayphal
Na2CO3
30
15
6
Tender coconut*
Lotus
100
20
7
Tender coconut*
Kutaja
100
20
8
Kayphal
Lotus
30
20
9
Kayphal
Kutaja
30
20
*- quantity in cc/l

Table 4.2

Recipe for 2% shade

S.NO
EXHAUSTING AGENT(EA)
FIXING AGENT (FA)
EA QUANTITY
(gpl)
FA QUANTITY
(gpl)
1
NaCl
Na2CO3
25
20
2
NaCl
Lotus
25
40
3
NaCl
Kutaja
25
40
4
Tender coconut*
Na2CO3
200
20
5
Kayphal
Na2CO3
60
20
6
Tender coconut*
Lotus
200
40
7
Tender coconut*
Kutaja
200
40
8
Kayphal
Lotus
60
40
9
Kayphal
Kutaja
60
40
*- quantity in cc/l

Table 4.3

Recipe for 3.5% shade

S.NO
EXHAUSTING AGENT(EA)
FIXING AGENT (FA)
EA QUANTITY
(gpl)
FA QUANTITY
(gpl)
1
NaCl
Na2CO3
35
25
2
NaCl
Lotus
35
60
3
NaCl
Kutaja
35
60
4
Tender coconut*
Na2CO3
300
25
5
Kayphal
Na2CO3
90
25
6
Tender coconut*
Lotus
300
60
7
Tender coconut*
Kutaja
300
60
8
Kayphal
Lotus
90
60
9
Kayphal
Kutaja
90
60
*- quantity in cc/l

Determination of colour difference (ΔE*ab) value

The colour difference (ΔE*ab) value of the fabric was calculated using the formula given below .

ΔE*ab  = [(ΔL*)2 + (Δa*)2 + (Δb*)2]1/2

Where,

ΔL* = L*sample – L*standard
Δa* = a*sample – a*standard
Δb* = b*sample – b*standard
L* = 116(Y/Yn)1/3 - 16
a* = 500[(X/Xn)1/3 – (Y/Yn)1/3]
b* = 200[(Y/Yn)1/3 – (Z/Zn)1/3]

Where

Xn, Yn, Zn - tristimulus values of reference white
X, Y, Z - tristimulus values of dyed sample
The X, Y and Z values of the fabric were calculated from the reflectance value at an interval of 400-20-700 nm.

Determination of ΣK/S value

700

ΣK/S =     Σ [(1-R)2/(2R)]

λ=400

The values of summative KubelkaMunk function (ΣK/S) of fabric was calculated using the formula given below from reflectance value (R) at wavelength from 400 to 700 nm at an interval of 10 nm measured using Datacolour 600, spectrophotometer, USA.

Results and Discussions
The below table shows the color difference values of the dyed samples as analyzed in the spectrophotometer.

Table 5.1. COLOR DIFFERENCE (∆E) VALUES


This research work was focused on the development of eco-friendly dyeing of cotton fabric. To prepare dyed samples, a plain woven cotton fabric, three reactive dyes namely C.I.Reactive Red 120A, C.I.Reactive Yellow 81 and C.I.Reactive Blue 198 were selected. Initially the fabric was dyed at three different percentage shades such as 0.5%, 2% and 3.5%, using sodium chloride and sodium carbonate as exhausting and fixing agents respectively. Then the fabric was dyed at the same percentage shades by using the natural materials such as tender coconut and kayphal for exhaustion and lotus and kutaja for fixation.

The dyed samples were taken for colour analysis by determining K/S value of the samples. The colour difference (∆E*ab) value was also calculated between the samples produced with synthetic and natural additives.

From the K/S values determined, the fabric dyed using natural additives have low value than the fabric dyed with synthetic additives. The fabric dyed with natural fixing agents have better value when compared to the fabrics dyed with natural exhausting agents as well as natural exhausting and fixing agents. The usage of natural materials for both exhaustion and fixation has lowest value than the other two.

Though the fabric dye uptake is lower with natural additives, it is almost nearer to the conventional dyeing. This can be improved by modifying the dyeing procedure or by changing the dyeing conditions and by means of adding extra dye so that the expected depth of colour can be achieved.

SCOPE FOR THE FUTURE WORK
This research work has the following scope for the future work.
  • The same type of work can be carried out with other cellulosic dyes on cotton fabric
  • Other type of natural materials can be identified and utilized for this purpose
  • The mechanism of natural materials as dyeing additives may be taken for future study
  • Natural additives may be identified for other dyes and fibres
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