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As an ongoing study of cotton goods dyeing using natural color, in this paper, the methods employed for the extraction of natural dyes, effects of mordants and the fastness properties of natural dyed fabrics were signified separately. Tagetes erecta L., Lawsonia inermis, Rosa L., Allium cepa and Camellia sinensis were used as natural sources for the extraction of natural colorants and their availability in Bangladesh was the prime selection criteria. For the extraction of liquid dyes, solvent extraction method using acetone and ethanol and boiling extraction method using water were adopted for better comparison in which solvent extraction method had dominating results over the later one. This paper highlights the use of ferrous sulphate, copper sulphate, alum and tannic acid as mordants in the pre-mordanting bath with cotton fabrics. After dyeing ferrous sulphate imparted darker impact whereas copper sulphate showed saddening effect on dyed fabrics, alum was responsible for increasing lightness but tannic acid made the dyed samples brilliant. Ferrous sulphate and copper sulphate mordanted samples showed good washing and light fastness but alum and then tannic acid helped the dyed fabrics to be poor to fair color fast to washing and light but fair to good to rubbing. Almost all the mordants had less impact on perspiration fastness and shown appreciable loss of color.
Key words: Natural dyes, Tagetes erecta L., Lawsonia inermis, Rosa L., Allium cepa, Camellia sinensis, Solvent and boiling extraction methods, mordants, color fastness.
The concept of value addition of costumes, lathers, papers with colors is older than the history of synthetic dyes. Dyeing and drawing on the walls into caves with colorants taken from the nature had been practiced since the Bronze Age by the cave dwellers. Evidence of dyeing relics had been found by Archaeologists dating back Neolithic period. Dyeing with plants, barks, and insects had been traced back in china more than 5,000 years ago [Good win, 1982]. In Egypt dyeing craft could be dated 3200 B.C. In fact just before 1850s and some later of that anything must had been dyed with natural plants. In 1850s the ones of the first synthetic dyes were introduced and they are not for the general use in deed although they dominated the market by 1900s. Since then health conscious issues and safety modes of ecology have been reversely going on with the acceleration of the development of synthetic dyes. The commercially used synthetic dyes cause carcinogenesis and inhibition of benthic photosynthesis [Adeel et al., 2009] although they impart strong color. Germany later Netherlands, India and some other countries have banned some azoic containing dyes because of their harmful effect on application [pattel, 2011]. Now the consumers are foreshadowing to replace synthetic dyes with natural ones in order to pay for a sound ecology for coming future.
Nature has gifted us more than 500 dye yielding plants [mahanta et al., 2005]. Dyes can be extracted from leaves and stems, flower heads, barks, roots, outer skins, hulls, husks, seed coats etc. of these plants [Kartz, 2004]. Dyes obtained from natural origins can be categorized as substantive dyes and adjective dyes [P.S Vankar]. Substantive dyes that can be extracted from Indigo, walnut, lichens etc need no mordant while applying on textile goods. On the contrary most of the natural dyes fall into the category of adjective dyes. The plants that were selected for this research also fall into this category that requires using mordants for color fixation. Five plants that are available in Bangladeshi climate named marigold, henna, rose, onion, and tea were collected for this work and different parts of these plants were used for color extraction. Mordant is an anchoring agent that anchor dye components with fibers. Mordants may be the salts of transitional metals (Fe, Cu) alum, chrome etc. [Siva, 2007, Samanta et al., 2009] or organic acids (oxalic acid, tannic acid etc.) or even natural origins (tamarind seed coat, date palm etc.). The present work was conducted using alum, tannic acid, ferrous sulphate and copper sulphate as mordants.
2. Experimental- Materials:
2.1. Selection of plant sources
For the present study, such plants a plentiful quantity of that grows in Bangladeshi climate in a commercial scale and a noticeable quantity of which is found as wastage after meeting the internal demands, are selected. About 0.15 million people of Bangladesh are directly or indirectly involved in floriculture business [Chowdhury, 2010]. But total of the unsold quantity is, however, left as wastage due to lacking of modern storage facilities. [Sultana,1995]. Marigold and rose flowers that suffer this a lot are selected in this consideration. This two with 3 other selected plants with their binomial name and collecting fields have been listed in table-01.
Table-1: Sources of raw materials
Marigold in its petal contains Xanthophylls, oxygen containing carotenoid, for the expression of its beautiful color that to be extracted. The flower heads exhibit a high yield of Xanthophylls content [Pratheesh, et al., 2009].
The central chain of Xanthophylls consists of 18 carbon atoms bonded alternatively with single and double covalent bonds with four methyl groups attached always in the same position. This single and double bonds act as conjugated system for color construction.
2.1.2 Henna (Lawsonia inermis)
In most of the lawsones 2- hydroxy-1-4-naphthoquinone is the prominent colorant which contains a –OH group in the position 2 of ringed structure of naphthoquinone replacing a –H atom with it.
2.1.3 Rose (Rosa L.)
Rose flowers exhibit colors due to the presence of anthocyanins, the highly colored flavonoids. In fact anthocyanins are the glucosides of anthocyanidins and they may have different sugars bonded to their ringed structure. It has been found pH dependent [V.B Gerritsen et al., 2005]
2.1.4. Onion (Allium cepa)
Flavones and flavonols that are the derivatives of flavonoids, water soluble color component, are found in the family of onion a nd tea.
A plain single jersey knitted fabric that was scoured and bleached and bio-polished, was taken as substrate for dyeing.
Yarn type: 100% cotton , Yarn count: 32s, GSM: 160, Sample weight = 5 gm
Ethanol (C2H5OH b.p-78.3oC) and acetone (CH3COCH3 b.p-56oC) were used as extracting solvents and Ferrous sulphate (FeSO4), copper sulphate (CuSO4), Alum and tannic acid (C76H52O46) were employed as mordants.
3. Experimental- Methods:
Extraction of colorants, separation of color components, making substrate suitable for dyeing, treatment involved anchoring of dye-fiber, application of dye extracts on substrates and testing of color retention capability of dyed fabrics were carried in following methods.
3.1: Extraction of colorants
The flower heads of marigold and rose, outer skins of onion and leaves of henna were cut as precise as possible keeping an average size of 1 cm.
200 gm of each of these four plants were weighed and blended by a blending machine separately. Then the blended quantity of each plant was divided into three equal parts which were allowed to dissolve in water, acetone and ethanol (amount must cover the entire sample). On the other hand, 100 gm grains of tea leaves was divided into three equal parts which also were allowed to dissolve in water, acetone and ethanol respectively.
All the extraction samples were, however, then heated in water bath for 1 hour at the temperature depending on the boiling point of solvents used.
Solvents used b.p Extraction Temperature
Water 100oC 80oC
Ethanol 78.3oC 60oC
Acetone 56oC 45oC
At the end of 1 hour all the extraction samples were kept for 24 hours for further extraction of colorants at room temperature. After 24 hours all were strained when almost all the color components had been extracted .Then the strained solutions were double filtered to obtain dye extracts. The solvents (ethanol and acetone) were removed by heating at their boiling point (ethanol b.p-78.3oC, acetone b.p -56oC). Amount of ethanol and acetone could be recovered by soxhlet apparatus [Kulkarni et al.,2011, Chowdhari et al., 2004].
Mordant that is in fact a chemical link, fixes the dye to a substrate [Eartheus]. Natural dyes are not so much color fast with fabrics. This is why all of the twenty samples were treated with 5% (owf) CuSO4, FeSO4, alum and tannic acid before dyeing. Treatment of mordanting was carried out for 60 minutes at 100 oC temperature with M: L ratio 1: 20.
3.3 Application of dye extracts
Four mordanted samples (mordanted with alum, CuSO4, FeSO4, and tannic acid) were dyed with every of 5 natural dye solutions (Extracted from Marigold, Henna, Rose, Onion skin, Tea). In the recipe formulation the ratio of material to liquor was kept 1:20, dyeing running time was 60 minutes at 100 oC temperature (1.5 oC /min). It is needed to be mentioned that no salt or soda was used. Rinsing sequence was cold wash- cold wash-hot wash –cold wash after dyeing. At last 20 dyed samples were collected.
3.4: Assessing color fastness
The resistance of color to fading when dyed fabric was exposed to washing,light, perspiration and rubbing , was assessed according to ISO-Standards: ISO 105 C03, ISO 105 B02, ISO 105 E04 and ISO 105 X12 respectively.
4. Results and discussions
Natural dyes extracted form the selected plants using ethanol and acetone had a well depth of color. The prominence of ethanol and acetone extracted dye solutions over water extracted dyes solutions was observed. It was reported that solvent extraction of natural dyes can lower cost of dyeing while improving their color strength [J.S.K Ngo et al., 2013].
Extracted dyes behaved differently when in contact with different agents, for instance, the dyes which were fast to washing in water might not be fast to light. More over the use of mordants influenced color fastness properties in a wide range. The total test results according to ISO standard has been displayed with mordants used in the figures below.
The resistance of a dye or pigment to a chemical or photochemical attack is an inherent property of dye chromophores [Padma. 2000]. Using mordants in the present work ,this property was intensified .From the testing reports the present study proves that dyed fabrics had exhibited slight loss in depth while using FeSO4 and CuSO4 as mordants for all the plant extracts resulting in fair to good color fastness to washing whereas alum and then tannic acid mordanted dyed fabrics had contributed to poor to fair washing fastness in grey scale rating for changing .Good washing fastness in case of FeSO4 and CuSO4 was due to making dye- fibre complex by Cu2+ and Fe2+ ions and this complex compound had the effect of insolubilizing the dye molecules in the faber making it color fast. On the contrary poor washing fastness for alum and tannic acid might be assessed due to more than one factors such as detaching the dye molecules from fiber components due to the wear of week dye-fiber bonds, ionization of color components as they contain –0H groups etc.
The performance of CuSO4, FeSO4, alum and tannic acid as mordants to make the fabrics color fast to washing has been represented by the following diagrammatic evaluation.
But the effect of mordants was quiet different in case of rubbing fastness where alum and tannic acid imparted fair to good grey scale rating for staining but CuSO4 and FeSO4 did significant to appreciable loss of depth of color that have been expressed in fig 6.
Most of the natural dyes behave like weak acids. Flavonoids color components from onion skins, tea leaves, Xanthophylls from marigolds, Anthocyanins from roses all are PH dependent and are sensitive to alkaline and then acidic solutions. The dyes having –OH groups ionize in alkaline solution[D. Jothi 2008]. Hence color fastness to perspiration was not so pleasant i,e; there was significant loss in depth of color in alkaline solution whereas in acidic solution the loss was appreciable.The figure 7 exhibits the effects of CuSO4, FeSO4 , alum and tannic acid in both of acidic and alkaline perspiration tests.
ISO 105 B02 test method for light fastness provided very pleasant results that FeSO4 and CuSO4 mordanted colored samples had shown good to very good light fastness in which degree of fading was moderate to slight respectively in Blue Wool rating.Tannic acid and alum also resulted moderate to good fastness to light. Diagram -04 represents the performance of CuSO4, FeSO4, alum and tannic acid in Blue wool rating.
Good light fastness was due to the formation of co-ordination complex between colorants and fibers with Fe2+,Cu2+ or Al3+ ions which protect the chromophore from photolytic degradation and the photons sorbed by chromophoric groups dissipate their energy by resonanting within six members ring thus formed and hence protecting the dye . Thus Fe2+ and then Cu2+ form stronger co-ordination comlpex than that of Al3+ with dye molecules to anchor them with fiber components (co-ordination numbers of Fe2+, Cu2+ are 6, 4 respectively).
The function that in fact, a transitional metal performs as mordant to increase light fastness has been represented by the following figure:
Fig-9: Function of a mordant
It has been shown from the obtained result that there is a potentiality of the utmost utilization of unsold quantity of marigolds and roses and unused quantity of onion skins, henna and tea in Bangladesh for yielding natural color which will serve environment and earth protecting from pollution and ecological imbalances in other way. It is reported that precise knowledge, compatible documentations and suitable assessment of dye-yielding plants are well-below the necessity. Good washing and light fastness using CuSO4 and FeSO4 mordants may be a pleasant source of thinking about the commercialization of natural dyes for such textile goods which is in its end uses needed to be colour fast while washing and exposing to light specially. To cope with the existing traditional practices and so called disadvantages of natural dyeing, a much more reseaches and scientific practices are required to go in this area.
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