Beruflich Dokumente
Kultur Dokumente
Dyeing of Silk Fabric Using Vegetable Dyes and Study on the Effects of Mordants on the Observed Dyeing Properties
By
Shariful Islam
B. Sc. Tex. Tech.
!
Acknowledgement
First of all, we would like to thank Almighty Allah for enabling us to finish the project work successfully. We would like to express our heartiest thanks to our project supervisor Mr. Mohammad Gias Uddin, Assistant Professor, Department of Textile Engineering, Ahsanullah University of Science & Technology (AUST) for his guidelines, valuable suggestions, constructive criticism and for providing all necessary supports. We are also grateful to our project co-supervisor Ms. Nahida Akter, Lecturer of the same department for her necessary advice and cordial supervision. Special thanks to Professor Dr. Mustafizur Rahman, Head of Department of Textile Engineering, AUST for his continuous encouragement and co-operation in managing certain requisites of the project. Finally, we like to thank the respected teachers of our Department for their insights and suggestions.
Table of Contents
Chapter Abstract 1
1.1
Title
Page
Introduction
Objectives
2
2.1 2.2 2.3 2.4 2.5 2.5.1 2.5.2 2.6 2.6.1 2.6.2 2.7 2.7.1 2.7.2 2.7.3 2.7.4 2.7.5 2.8 2.8.1 2.8.2 2.8.3 2.9 2.10
Literature Review
History of Silk Production of Silk Chemical Composition of Silk Types of Silk Properties of Silk Physical Properties Chemical Properties Pretreatment of Silk Degumming of Silk Bleaching of Silk Vegetable Dyes Henna (Lawsoniainermis) Guava (Psidiumguajava) Mango (Mangiferaindica) Onion (Allium cepa) Standardization of Dyestuff Mordants Alum Iron (ferrous sulphate) Tin (Stannous Chloride) Chemistry of Natural Dyes Colour Fastness
3
3.1 3.2 3.3 3.4 3.4.1 3.4.2 3.5 3.5.1
3.5.2 3.6 3.6.1 3.6.2 3.6.3 3.7 3.7.1 3.7.2 3.7.2 3.8 3.8.1 3.8.2 3.8.3 3.8.3 3.9 3.9.1 3.9.2 3.9.3 3.9.4 3.9.5 3.9.6 3.9.7 3.9.8
Selection of Dye Extraction Media Mordanting Pre-Mordanting Post-Mordanting Selection of Mordanting Method Dyeing Dyeing in Acidic Condition Dyeing in Alkaline Condition Selection of Dyeing Media Colour Measurement Transmittance % and Colour Strength Reflectance and K/S values Colour Co-ordinates Colour difference, !cmc Colour Fastness Methods Dry Cleaning Fastness Perspiration Fastness Light Fastness Wash Fastness Rubbing Fastness Evaluation of Change in Colour Evaluation for Staining Evaluation for Light Fastness
28 28 28 28 29 29 29 29 29 29 29-30 31 31 32 33 33 33 34 34 34 34 35 35 36 37 38 39 39 39-43 44-45 46 46-49 50-57 58-60 61-63 64-66 67-70 71-72 73-74 75-76 77-78
4
4.1 4.2 4.3 4.4 4.4.1 4.4.2 4.5 4.5.1 4.5.2 4.5.3 4.5.4 4.5.5 4.6
5 6
List of Tables
Table
2.1 2.2 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10 4.11 4.12 4.13 4.14 4.15 4.16 4.17
Name
World silk production in comparison with other textile fibres (Thousand tons) Side groups in silk fibres % Transmittance and colour strength% of different dye extraction condition ! cmc values of silk fabric using pre-mordanting and post-mordanting technique K/S value and wash fastness of silk fabric dyed under alkaline and acidic condition Reflectance and K/S values of natural dyed silk fabric using various mordants K/S values at various wavelength of the natural dyed silk fabric The colour co-ordinates of silk fabric dyed with natural dyes using various mordants Dyed silk fabric samples Dry cleaning fastness ratings of mordanted silk fabrics dyed with natural dyes Perspiration (alkaline) fastness ratings of mordanted silk fabric dyed with natural dyes Perspiration (acidic) fastness ratings of mordanted silk fabric dyed with natural dyes Light fastness ratings of mordanted silk fabrics dyed with natural dyes Wash fastness ratings of mordanted silk fabrics dyed with natural dyes Rubbing fastness ratings of mordanted silk fabrics dyed with natural dyes Levelness data of silk fabric dyed with guava extract using various mordants Levelness data of silk fabric dyed with mango extract using various mordants Levelness data of silk fabric dyed with onion extract using various mordants Levelness data of silk fabric dyed with henna using various mordants
Page
7 9 37 38 39 40 41 44 46 47 50 51 58 61 64 67 68 69 70
List of Figures
Figure
2.1 2.2 2.3 2.4 2.5 2.6 2.7 2.8 2.9 2.10 2.11 2.12 2.13 2.14 2.15 3.1 3.2 4.1 4.2 4.3 4.4 4.5 4.6 4.7 4.8 4.9 4.10
Name
Increment of silk production from year 1975 to 2010 Henna leaves Lawsone [2-Hydroxy-1,4-naphthaquinone] Guava Quercetin [2-(3,4-dihydroxyphenyl)-3,5,7-trihydroxy-4Hchromen-4-one] Mango Mangiferin [2-beta-d-glucopyranosyl-1,3,6,7-tetrahydroxy-9hxanthen-9-on] Onion Pelargonidin [2-(4-Hydroxyphenyl)chromenylium-3,5,7-triol] Schematically presentation of three different mordanting strategies Alum Ferrous sulphate Tin (Stannous Chloride) Mechanism of pre-mordantation Mechanism of post-mordantation The L, a, b colour scale Parameters of CMC colour discrimination ellipsoid Formation of naphthaquinone salt in alkali solution Aqueous extracts of henna, guava and mango leaves and onion skin extracted in alkaline condition K/S values of the silk fabrics dyed with natural dyes using various mordants K/S against Wavelength curve of silk fabric dyed with henna extract K/S against Wavelength curve of silk fabric dyed with guava extract K/S against Wavelength curve of silk fabric dyed with mango extract K/S against Wavelength curve of silk fabric dyed with onion extract Changes in L* of silk fabric dyed with natural dyes using various mordants Dry cleaning fastness rating of silk fabric dyed with henna extract (Colour Change) Dry cleaning fastness rating of silk fabric dyed with guava extract (Colour Change) !
Page
8 15 15 16 16 17 17 17 18 19 20 20 21 21 22 31 32 37 38 40 42 42 43 43 45 48 48
4.11 4.12 4.13 4.14 4.15 4.16 4.17 4.18 4.19 4.20 4.21 4.22 4.23 4.24 4.25 4.26 4.27 4.28 4.29 4.30 4.31
Dry cleaning fastness rating of silk fabric dyed with mango extract (Colour Change) Dry cleaning fastness rating of silk fabric dyed with onion extract (Colour Change) Perspiration fastness rating of mordanted silk fabric dyed with henna extract (Colour Change) Perspiration fastness rating of mordanted silk fabric dyed with guava extract (Colour Change) Perspiration fastness rating of mordanted silk fabric dyed with mango extract (Colour Change) Perspiration fastness rating of mordanted silk fabric dyed with onion extract (Colour Change) Perspiration fastness rating of mordanted silk fabric dyed with henna extract (Staining of Wool) Perspiration fastness rating of mordanted silk fabric dyed with guava extract (Staining of Wool) Perspiration fastness rating of mordanted silk fabric dyed with mango extract (Staining of Wool) Perspiration fastness rating of mordanted silk fabric dyed with onion extract (Staining of Wool) Perspiration fastness rating of mordanted silk fabric dyed with henna extract (Staining of Cotton) Perspiration fastness rating of mordanted silk fabric dyed with guava extract (Staining of Cotton) Perspiration fastness rating of mordanted silk fabric dyed with mango extract (Staining of Cotton) Perspiration fastness rating of mordanted silk fabric dyed with onion extract (Staining of Cotton) Light fastness rating of mordanted silk fabric dyed with henna extract Light fastness rating of mordanted silk fabric dyed with guava extract Light fastness rating of mordanted silk fabric dyed with mango extract Light fastness rating of mordanted silk fabric dyed with onion extract Wash fastness rating of mordanted silk fabric dyed with henna extract (Colour Change) Wash fastness rating of mordanted silk fabric dyed with guava extract (Colour Change) Wash fastness rating of mordanted silk fabric dyed with mango extract (Colour Change)
49 49 52 52 53 53 54 54 55 55 56 56 57 57 59 59 60 60 62 62 63
Wash fastness rating of mordanted silk fabric dyed with onion extract (Colour Change) Rubbing fastness rating of mordanted silk fabric dyed with henna extract Rubbing fastness rating of mordanted silk fabric dyed with guava extract Rubbing fastness rating of mordanted silk fabric dyed with mango extract Rubbing fastness rating of mordanted silk fabric dyed with onion extract
63 65 65 66 66
Abstract
The main focus of the study was to analyze the dyeing properties of the mordanted silk fabrics dyed with vegetable dyes. Degummed, bleached silk fabrics were mordanted with chemical mordants and then dyed with the dyes extracted from mango, guava, henna leaves and onion skins. The better results were obtained when dye extraction was carried out in alkaline condition (pH 9) and dyeing in acidic medium (pH 5). The dyeing results had been analytically assessed by measuring the K/S values of dyed samples using reflectance spectrophotometer and by different fastness properties. CIE Lab co-ordinates of the dyed silk had also been presented of the controlled and mordanted samples. Different hues were obtained on silk fabric from the same dye extract by using different mordants and their combinations. Better build up was obtained by using mordants compared to dyeing without mordants. Deeper shades were obtained with ferrous sulphate mordants whereas tin mordants produced lighter shades. The results of dry cleaning, perspiration, light, wash and rubbing fastness tests were analytically assessed for the dyed samples and comparative analysis was also done between dyeings with and without mordants. Furthermore, fabrics that were dyed without using mordant were found most evenly dyed. Use of ferrous sulphate mordant produced somewhat lesser even dyeing.
Chapter 1 Introduction
1!
The use of natural dyes for textile dyeing purposes, decreased to a large extent after the discovery of synthetic dyes in 1856. As a result, with a distinct lowering in synthetic dyestuff costs, the natural dyes were virtually unused at the beginning of twenties century [1]. Presently there is an excessive use of synthetic dyes, estimated at around 10,000,000 tons per annum, the production and application of which release huge amount of waste and unfixed colourants causing serious health hazards and disturbing the eco-balance of nature [2]. Today all over the world environmental regulations against control of effluents or hazards of synthetic dyes, are becoming more strict and are forcing the shift of technology towards less or non-polluting areas of technological development. The need to realize the importance and explore the technology of natural dyes is arguably more urgent. Moreover, natural dyes produce very uncommon, specialty, soothing, and soft shades as compared to synthetic dyes [3]. Worldwide the use of natural dyes for the colouration of textiles mainly has been confined to artisan/craftsman, small scale/cottage level dyers and printers as well as small-scale exporters and producers dealing with highvalued eco-friendly textile production and sales. These dyes exhibit better biodegradability and generally have higher compatibility with the environment. They are non-toxic, non-allergic to skin, non-carcinogenic, easily available and renewable [4]. In this sense natural dyes are more acceptable to the environmentally conscious people. Hence recently there has been revival of the growing interest on the application of natural dyes on natural fibres. In many of the worlds developing countries, natural dyes can offer not only rich and varied source of dyestuff, but also the possibility of an income through sustainable harvest and sale of these plants [4]. However, all natural colourants are not eco-friendly. There may be presence of heavy metals or some other form of toxicity in natural dye. So, these colourants also need to be tested for toxicity before their use. But plant based vegetable dyes are eco-friendly in nature. Nowadays, primarily natural colourants isolated from vegetable materials are used as the potential dyestuff source. For this purpose, traditional dye plants have also been cultivated in many countries. As an estimate 1 kg of plant material will be required to dye 1 kg of textile goods [5], this indicates that the use of plant dyes available from different sources including secondary products will be competitive in cost to that of synthetic dyes. Mango, henna and guava leaves as well as onion skins are good sources of natural dyes. Mango trees are easily available in Rajshahi, Chapainawabganj, Nawabganj, and Dinajpur while in Barisal, Pirojpur, Jhalokathi and Chittagong guava trees are grown abundantly. Henna is also cultivated in Bangladesh and onions are widely used in Bangladesh cuisine, so onion skins can be easily found in abundance. As these are so readily available in Bangladesh, these can be used commercially for dyeing. In this study colour extracted from leaves of mango, henna and guava and onion skin were carried out to dye silk fabric using alum, tin, iron and their combinations as mordants to focus the dyeing properties like colour co-ordinates, colour build up, fastness properties, levelness etc. In addition, silk fibre has good affinity towards natural dyes [6]. Therefore, silk fibre was chosen for this study.
2!
1.1 Objectives
The main objectives of this study are: 1. To study the colour yield, colour co-ordinates and levelness of silk fabric dyed with natural colour extracted from henna, mango, guava leaves and onion skins. 2. To investigate the effects of various mordants such as alum, tin, iron and their combinations on the different dyeing properties of the natural dyed silk fabric. 3. Also to carry out the comparison of the silk fabrics between dyeings with and without mordants. 4. To determine %transmittance and colour strength of the natural dye extracted solution. 5. To analyze the colour fastness to dry cleaning, perspiration, light, wash and rubbing of natural dyed silk fabric. 6. To develop the suitable extraction method as well as extraction medium of natural dyes. 7. To develop natural dyeing technology that can be applied in industrial and domestic levels.
3!
4!
! The environment friendly dyes are enjoying resurgence in popularity as a result of concern with the carcinogenic, toxic and sensitizing characteristics of synthetic dyes. The ban on certain synthetic dyes has stimulated the entry of the golden era of natural dyes. Different literatures were studied regarding application of natural dyes on silk fabrics: Paul et al. (1996) in the article Natural dyes classification, extraction and fastness properties defined natural dyes as Dyes derived from natural resources. Natural dyes were classified based on chemical classes as, indigoid, anthraquinone, alphanaphthoquinones, flavones, dihydropyrans, anthocyanidions and carotinoids. On the basis of color natural dyes were classified into red dyes, yellow dyes, blue dyes, black dyes, brown dyes, green dyes and orange dyes [7]. Singh (2000) studied on Natural dyes: The pros and cons, and defined natural dyes as a Colourant (dye or pigment) obtained from vegetable or animal matter without any chemical processing [8]. Almost any organic material will produce a colour when boiled in a dye-bath but only certain plants will yield a colour that will act as a dye. Natural dyes fall into following categories: Leaves and stems, barks, roots, outer skins, berries and seeds, insect dyes etc. (Padma S. Vankar, 2000) [6]. Frigerio (1992) compared characteristics of natural dyes with synthetic dyes to minimize environment pollution. Logwood, tropical legume dyes, yellow woad of Cuba, dyes extracted from insect, indigo, mollusks extraction and extraction from Sandalwood, saffron, henna and lichens are described [9].
Shaukat Ali (2007) in the article Evaluation of cotton dyeing with aqueous extracts of natural dyes from indigenous plants represented cotton fabric dyeing by using henna leaves, eucalyptus bark, and acacia bark, turmeric rhizomes where different extraction and dyeing procedures were maintained along with different mordant compositions. In the article it was shown that the alkaline conditions for extraction of dye from henna leaves were optimized and resulting extract was used to further optimize its dyeing conditions on cotton by exhaust method [10]. M. M Alam et al (2007) carried out Extraction of Henna Leaf Dye and its Dyeing Effects on Textile Fibre and found that the dye uptake by silk fibre was decreased with increase of dye concentration. Similarly the absorption of dye was increased with the decrease of dye concentration. The maximum dye absorption had been observed at 0.9% dye with 10% alum [11]. Guinot, et al (2007) investigated aqueous extracts of plant by-products (Onion, carrot, sage, spinach and thyme) for dyeing capacity on fibres. Light fastness of onion, thyme and sage samples, evaluated following a normalized test, was very promising considering industrial restrictions [12].
5!
! Zin Mar Win & Moe Moe Swe (2008) carried out Purification of the Natural Dyestuff extracted from Mango Bark for the application on Protein fibres and found purified natural dyestuff extracted from mango bark gives subtle and soft colour to yarn [13].
Padma S Vankar et al (2009) in the article Dyeing of cotton, wool and silk with extract of allium cepa showed that pretreatment with 2% metal mordant and usage of 5% onion skin extract on silk had satisfactory fastness properties [14].
6!
! were looked after by organizations like Directorate of Industries and BSCIC. With a view to expand sericulture throughout the country a separate organization "Bangladesh Sericulture Board (BSB)" started functioning from February, 1978 with its Headquarters at Rajshahi - the Silk City [15].
Silk%Production%%%(Thousands%tons)%
250! 200! 150! 100! 50! 0! 1975! 1985! 1995! Year% 2005! 2010!
Figure 2.1: Increment of silk production from year 1975 to 2010. Bangladesh has no position in the world silk market as it produces only 40 MT of raw silk per year. Interestingly the production of raw silk remains more or less same over the years. The low amount of raw silk production may be attributed to scattered small scale farming of mulberry plantation and silkworm rearing. Due to small amount of cocoon production in different places no reeling industry has yet been established in the country. Only a few reeling units have so far been in operation in some places most of which are not fit for good quality raw silk production. As such the silk industries, mostly located in Rajshahi, have to depend on imported raw silk for fabric production. The extension activities of sericulture in Bangladesh are conducted at small-scale level, which is limited only with the landless and marginal farmers. It is mainly based on tree mulberry leaves except for Bholahat area under Chapai-nawabganj district where bush mulberry is cultivated for silkworm rearing. Most of the reapers of Bangladesh are landless poor and have no separate silkworm rearing houses of their own and as such they have to rear the silkworms in their dwelling houses where hygienic environment cannot be maintained for successful cocoon crop production. As a result sometimes silkworm diseases occur and cocoon production is greatly hampered. Whenever Bangladesh Sericulture Board (BSB) gets fund through development projects they provide mulberry saplings to the farmers for plantation in the road and embankment sides. They also provide silkworm eggs to those farmers when planted mulberry trees become productive. But when the project period is over the extension activities are greatly hampered due to fund constrained as the next project sometimes gets approval after 2 -3 years. Again they have to start with new plantation of mulberry. BSB has so far implemented 16 development projects during the period of 33 years since its inception in 1978. But it could not able to increase a tangible amount of 8!
! raw silk production in the country. This is mainly due to lack of proper extension policy and cocoon production planning. The sericulture projects implemented by BSB were more or less similar and routine in nature, which did not help develop sericulture in the country. To meet the local demand we have to produce about 300 MT of raw silk per year. BSB should continue the program without any interval to meet the remaining demand of raw silk. BSB need to develop Package of sericulture practices for small, medium and large scale farming with the technical assistance of Bangladesh Sericulture Research and Training Institute (BSRTI). Then draw attention to the interested farmers and enterprises for implementation of the programs [15].
R1, R2 represents the side groups present in the silk structure. Table 2.2 below shows the side groups present in silk fibres [17]. Table 2.2: Side groups in silk fibres
Type Neutral Neutral Acidic Acidic Basic Basic Side group -H -CH3 -CH2COOH -CH2CH2COOH -CH2. CH2.CH2. CH2.NH2 -CH2CN.CH.CH.NH2 Amino Acid Glycine Alanine Aspartic acid Glutamic acid Lysine Histidine g amino acid per 100g of protein in silk 43.80 26.4 3.00 2.03 0.88 0.47
9!
! [18]
Silk fibre as it comes from the cocoon is coated with a protective layer called silk gum, or sericin. The silk gum is dull and stiff. Silk with all of its gum is termed raw silk.
10!
11!
! garments, then the fabric drapes well and this is why it can be tailored well too. 2.5.1.10 Abrasion resistance - Silk fabric possess good abrasion resistance as well as resistance to pilling. 2.5.1.11 Effect of sunlight - Silk is more sensitive light than any other natural fibre. Prolonged exposure to sunlight can cause partially spotted color change. Yellowing of silk fibre is generally occurred due to photo degradation by the action of UV radiation of sunlight. The mechanism of degradation is due to the breaking of hydrogen bonds followed by the oxidation and the eventual hydrolytic fission of the polypeptide chains.
12!
! 1. At the peptide bonds of adjacent amino groups, 2. At the N-terminal residues and 3. At the side chains Though fibroin is not severely affected by hydrogen peroxide solution, nevertheless may suffer from the reduction of nitrogen and tyrosine content of silk indicate that hydrogen peroxide may cause breakage of peptide bonds at the tyrosine residues resulting in the weight loss of the fibre. The action of chlorine solution on the silk fibroin is more harmful than does the solution of hypochlorite. These solutions, even at their lower concentration, cause damage to fibroin.
2.5.2.5 Action of reducing agents - The action of reducing agents on silk fibre is still a little bit obscure. It is, however, reported that the reducing agents that are commonly found in use in textile processing such as hydrosulfite, sulfurous acids and their salts do not exercise any destructive action on the silk fibre.
13!
! sometimes given a very mild scouring for the purpose of softening the fibre. This is called as "Ecru silk in which only 2 to 5% in weight of silk gum is removed. Ecru silk can be prepared by simply washing the raw silk in hot water without the use of soap. This is used mainly for warp; hence the gum is left purposely.
! branched shrub or, small tree frequently cultivated in many tropical and warm temperature regions of Bangladesh, Pakistan, India, Egypt, Sudan, Iran, Yemen and Kenya. Large-scale cultivation for the sake of leaves that yield dye confined to India, Egypt, Pakistan, Bangladesh and Sudan. Powdered leaves of this plant (aqueous paste) are used as a cosmetic for staining hands and hairs. The picture of plant is given in Figure 2.2 [10].
Figure 2.2: Henna Leaves Unbroken henna leaves will not stain hand, hair or textile materials. Henna's colouring properties are due to lawsone, a burgundy organic compound that has an affinity for bonding with protein. Lawsone is primarily concentrated in the leaves, especially in the petioles of the leaf [10]. The structure of the coloring component, Lawsone, is given in Figure 2.3.
15!
Figure 2.4: Guava The leaves of guava contain many essential oils and so it is used for many purposes like producing anti-microbial finishes, providing anti-diarrheal action, having anti-inflammatory effect, etc. The leaves can also be used for dyeing textiles. Quercetin present in the guava leaves is the chemical that is responsible for having the coloring effect on textile material [20]. The chemical structure of Quercetin is given in Figure 2.5.
16!
Figure 2.6: Mango The chemical that is responsible for colour in the mango leaf is mangiferin. Figure 2.7 is the chemical structure of Mangoferin.
Figure 2.8: Onions The dyestuff present in onion skin is called Pelargonidin (3,5,7,4 tetrahydroxyantocyanidol) [21]. The structure of Pelargonidin is given in Figure 2.9.
17!
2.8 Mordants
Mordants are metal salts that can form metal complex with the natural colourants, which exhibit increased affinity to the substrate. Depending on the metal character the complex formation does not only strengthen dyestuff fixation on the substrate but also changes the colour of the dyeing. In some cases the resulting change in shade can be seen as an opportunity to steer colour in a wider range [5]. Some mordants will also change the hue of certain dyes (different mordants on the same dye may darken, brighten or drastically alter the colour-may be a desired effect as well as an unwanted phenomenon). Basically, three different types of mordanting strategies can be distinguished: pre, after and meta-mordanting. The processes mainly vary in the time of mordant addition. While pre- and after-mordanting require an additional treatment step in a separate bath (a
18!
mordant solution with defined concentration of the metal salt), the simple addition of a concentrated salt solution directly to the dye bath is used in the so-called metamordanting process. Generally small variations in the colour depth are found if the three mordanting types are compared. In most cases pre-mordanting leads to darker shades compared to meta-mordanting, as shown in the literature [5]. Figure 2.10 represents the three mordanting strategies schematically.
! !
Raw! Substrate!
!
Type Pre mordanting After mordanting Meta mordanting Step 1 Mordanting Dyeing Step 2 Dyeing Mordanting Number of Baths 2 2 1
! ! ! Coloured Substrate
! Figure 2.10: Schematically presentation of three different mordanting strategies Generally mordants that were used over time were divided into two types; acid and basic, where acid mordants are used to bond acid dyes and basic mordants to bond basic dyes. Acid mordants have generally been derived from tannin, readily available from oak balls or bark; occasionally they are vegetable oils. Basic mordants, however, come from the salts of various metals, particularly aluminium, chromium, iron, copper, zinc or tin [5]. Most of the vegetable dyes, however, require some sort of mordant to set permanently in any fibre.
2.8.1 Alum
The mordants used in Egypt in early Christian times included alum, but also salts of iron, such as the acetate, specially prepared from iron and vinegar, and the sulfate, which occurs frequently as an impurity in alum [5]. Alum is translucent crystalline watersoluble element, which has a pH of 3.2. It is also known as potassium aluminum sulphate. Alum attracts moisture and is used in textile processing as a dye fixative. A pinch of alum
19!
! makes colour flow but if too much is used it will make the fibre harsh and sticky. Alum is best suited to be used on wool and silk fibre. It is considered non-toxic and is for water treatment. Alum is also used for pickling fruits and vegetables and in baking process [22]. Alum salts as mordants intensify the obtained colour brilliance but do not influence the colour shade to the same extent as iron do [5].
20!
Silk ------------------ Mordent (Men+) ------- Dyestuff Figure 2.14: Mechanism of pre-mordantation
21!
! During pre-mordantation the mordant first bonds with amino and carboxyl groups in silk by covalent bonds and co-ordinate bonds and then the mordants bonds with the dyestuff by covalent bonds and co-ordinate bonds. This way the mordant creates a bridge between silk and dyestuff and thus causes fixation of the dyestuff to the silk fibre.
Silk ---------------------- Dyestuff--------------- Mordent (Men+) Figure 2.15: Mechanism of post-mordantation During post-mordantation the dyestuff first bonds with amino and carboxyl groups in silk by covalent bonds and co-ordinate bonds and then the dyestuff bonds with the mordant by covalent bonds and co-ordinate bonds. Here the mordants do not act as a bridge; instead the mordants block the active sites of the dye molecule so that it cannot react with other chemicals and become detached from the dye. During meta-mordanting the dyestuff and mordants are added simultaneously during dyeing. Both types of reactions as shown in Figure 2.13 and Figure 2.14 take place during meta-mordanting.
22!
23!
3.1 Materials
3.1.1 Fabric
Greige 100% silk fabric of plain construction EPI 132, PPI 132, warp count 22 denier and weft count 22 denier, was collected from Sopura Silk Mills Ltd. Dhanmondi, Dhaka, Bangladesh.
3.1.2 Leaves
Henna, guava and mango leaves were collected from Botanical Garden, Mirpur, Dhaka.
24!
3.2 Chemicals
3.2.1 Mordants
Alum (potassium aluminium sulphate), iron (ferrous sulphate) and tin (stannous chloride) were used as mordants. The chemicals were collected from M/S. R. Traders, Armanian Street, Bongshal, Dhaka, Bangladesh.
25!
3.2.11 Perchloroethylene
Perchloroethylene of Russian commercial grade was collected from M/S. R. Traders, Armanian Street, Dhaka, Bangladesh. It was use during dry cleaning fastness.
3.3.3 Gyrowash
Gyrowash of James H. Heal Co. Ltd., Halifax, England was used for wash fastness testing and dry cleaning fastness testing.
3.3.4 Crockmeter
Crockmeter of James H. Heal, Halifax, England was used for rubbing fastness testing.
26!
3.3.9 Miscellaneous
Electronic Balance Electric Heater Thermometer Dryer Pipette pH strip Beaker Measuring Cylinder Stirrer Steel Container (dye bath) Mortar
3.4 Pretreatment
3.4.1 Degumming
The raw silk fabric was degummed by treating with soap (15 g/l), sequestering agent (1 g/l) and wetting agent (1 g/l), maintaining a material and liquor ratio of 1:50 at pH 9 and temperature 80C for 60 minutes in the IR sample dyeing machine [23].
3.4.2 Bleaching
The degummed silk fabric was bleached by treating with hydrogen peroxide (3 g/l), sequestering agent (1 g/l) and wetting agent (1 g/l), maintaining a material and liquor ratio of 1:50 at pH 10 and temperature 85C for 60 minutes. Tri-sodium phosphate was used as a stabilizer and the bleaching was carried out in IR sample dyeing machine [23].
27!
3.6 Mordanting
Mordanting was done in two different ways.
3.6.1 Pre-Mordanting
The silk fabrics were pretreated with the solution of different mordants (25% of the weight of fabric) maintaining material to liquor ratio 1:10 at 70C for 60 minutes in the dyeing machine. Then the pretreated silk fabric was introduced into the dye bath containing required amount of dye extract and water [24].
3.6.2 Post-Mordanting
In this method, samples were first dyed using the dye extract. Then the dye fabric was introduced in the bath containing the mordant. Material to liquor ratio of 1:10 was maintained. Mordanting was done at 70C for 60 minutes in the IR sample dyeing machine [24].
28!
3.7 Dyeing
3.7.1 Dyeing in Acidic Condition
Pre-mordanted silk fabric was dyed with the extracted dye solution, maintaining material and dye solution ratio of 1:30 at pH 5 and temperature 80C for 60 minutes in the dyeing machine. The dyed samples were taken out, squeezed, washed with water and dried at room temperature. Acetic acid was used to decrease pH [10].
29!
! The two laws may be combined and stated as follows. I = I!!! !!"# Or, log
!! !
(eq. 1) (eq. 2)
= !!"#
Here, I = intensity of transmitted light Io = intensity of incident light ! = molar extinction coefficient (litre/mole/cm) c = concentration of the absorbing solute (mole/litre) L = path length or thickness of the absorbing layer, cm Transmittance (T),
!
T = !! = ! !!"# log! =
!! !
(eq. 3) (eq. 4)
= !"# = !
The optical density or absorbance, D has a linear relation with concentration up to a certain limit. The laws are valid only for monochromatic radiation and for nonscattering solution of very low concentration. Colour strength value is a numerical value related to the amount of colourant in a solution. It is often used to calculate the difference in strength % between two coloured solutions. The relative colour strength, S of two solutions may be given by ! = 100! !! !!
! !
! !
(eq. 5)
Where, C is the dye concentration. Assuming equal concentration of the dyes (C1= C2), the equation can be simplified as equation 6. ! ! = 100! !! (eq. 6) Where the subscript 1 and 2 refer to the reference dye and dye under test respectively [25]. For selection of dye extraction media, transmittance % of the dye extracted in different condition was found using spectrophotometer. In addition, the colour strength of dye extracted in alkaline condition and dye extracted in acidic condition were found by comparing the two with dye extracted in neutral condition.
!
30!
=!
(! ! ! )! !!
(eq. 7)
R= reflectance of the coloured fabric K= absorption co-efficient S= scattering co-efficient The reflectance and K/S values were found using the spectrophotometer.
+ ! !"
+ !"
(eq. 8)
31!
! cmc= SL = SC =
! 2! ! 1 ! !"!
+!
! 2! ! 1 ! !"!
!!ab ! !!
(eq. 9)
!.!"!#$%!!1
(eq. 10)
SH = Sc(Tf+1-f) f= T=
! 1! !1! !!"##
0.56 + ! 0.2!cos!(1 + 168) 164 !1! 345! 0.36 + ! 0.4!cos!(1 + 35) otherwise!!!!!!!!!!!!!!!!!!
(eq. 14)
Here l and c are the relative lightness and chroma tolerances required for a particular application. For perceptibility data l:c should be 1:1. For acceptability l:c should be 2:1, lightness difference is less significant. SL, SC and SH indicates the length of half-axes of the ellipsoid defining unit !around the standard (Std) as shown in figure 3.2.
32!
! For gradual transition from neutral to saturated colours in treatment of half-axis SH, an addition function f is considered. f increases gradually as chroma increases. When f = 0, SH and SC are equal and difference in hue and chroma are considered to be equivalent. This corresponds to a uniform Cartesian coordinates. When f = 1, SH and SC are unequal and the equation corresponds to polar coordinate system with unequal radial and tangential discrimination [27]. For evaluating levelness, !cmc values were measured on four different places of the dyed fabric. One value was taken as standard and other values were considered as batch and mean values were calculated.
33!
34!
35!
36!
The reason can be attributed to acidic hydroxyl group in naphthaquinone, which reacts with alkali and form naphthaquinone salt (Figure 4.1), which is more soluble in water. Thus the extraction of colouring component becomes more in alkaline medium. Furthermore, as cell wall of leaves is made up of cellulose material, this gains anionic charge in alkaline medium. Due to these anionic repulsive forces around cell walls, it loses its strength and ruptures easily in alkaline medium. This gives more colouring component in alkaline medium [10].
37!
! It was observed that the colour of the dye extracted from henna leaves, guava leaves and onion skins were dark brown while the dye extracted from mango leaves was of orange. The colour of the extract baths has been shown in Figure 4.2.
Figure 4.2: Aqueous extracts of henna, guava and mango leaves and onion skin extracted in alkaline condition
As the results of pre-mordanting were better than post-mordanting technique, dyeings were done using pre-mordanting method. Again, the affinity between dyes and mordant were more compared to that of dyes and fibre. Therefore during postmordanting, the mordant pulled out the dyes from the fibre, which resulted in uneven dyeing [10].
38!
Mango Leaves
12.91 16.58
Alum
It was observed that the wash fastness of silk fabric dyed in alkaline condition was not satisfactory. Grey scale ratings for colour change were found good to excellent when dyed in acidic condition. The silk fibre dyed in alkaline condition became damaged and could not form bonds with the natural dyes and mordants adequately [18]. So the wash fastness was not found satisfactory in this condition. Therefore, natural dyeings were carried out on silk fabric using acidic condition.
39!
! Table 4.4: Reflectance and K/S values of natural dyed silk fabric using various mordants
Veg. Dye Mordant No mordant Ferrous Sulphate Ferrous Sulphate and Alum Ferrous Sulphate, Alum and Tin Alum Alum and Tin Tin No mordant Ferrous Sulphate Ferrous Sulphate and Alum Ferrous Sulphate, Alum and Tin Alum Alum and Tin Tin No mordant Ferrous Sulphate Ferrous Sulphate and Alum Ferrous Sulphate, Alum and Tin Alum Alum and Tin Tin No mordant Ferrous Sulphate Ferrous Sulphate and Alum Ferrous Sulphate, Alum and Tin Alum Alum and Tin Tin Reflectance % (= 360 nm) 4.00 3.00 3.00 3.50 3.00 3.50 3.50 4.00 2.00 2.90 3.50 3.00 3.90 3.90 4.50 2.50 2.50 3.00 3.00 3.50 4.00 6.00 3.00 3.50 3.00 3.50 4.50 4.00 K/S (= 360 nm) 12.94 15.87 17.11 17.12 16.01 17.78 16.03 12.45 15.74 14.23 12.96 14.32 13.00 12.49 11.48 18.03 17.13 15.20 14.86 13.77 14.37 7.09 15.36 16.48 15.24 16.36 12.74 14.08
Henna Leaves
Guava Leaves
Mango Leaves
Onion Skins
Figure 4.3 showed the bar diagrams of K/S values of the vegetable dyes obtained from Table 4.4.
20! 15! K/S% 10! 5! 0! No!mordant! Ferrous!Sulphate! Ferrous!Sulphate! and!Alum! Ferrous!Sulphate,! Alum!and!Tin! Alum! Alum!and!Tin!
Henna%Leaves%%%%%%%Guava%Leaves%%%%%%%%%Mango%Leaves%%%%%%%%Onion%Skin% % Vegetable%Dye%
Tin!
Figure 4.3: K/S values of the mordanted silk fabrics dyed with natural dyes 40!
! Table 4.5: K/S values at various wavelengths of the natural dyed silk fabric
Veg. Dyes K/S = 360nm 12.94 15.87 17.11 17.12 16.01 17.78 16.03 12.45 15.74 14.23 12.96 14.32 13.00 12.49 11.48 18.03 17.13 15.20 14.86 13.77 14.37 7.09 15.36 16.48 15.24 16.36 12.74 14.08 = 380nm 9.87 15.25 15.97 15.54 15.42 16.06 14.40 11.68 14.99 13.70 11.70 13.57 12.27 11.45 10.91 18.19 18.48 15.47 16.58 14.17 15.21 7.73 16.78 18.26 16.87 18.14 14.58 16.18 = 420nm 4.06 11.60 10.96 9.27 10.58 9.28 7.94 3.64 9.91 6.53 2.60 4.91 2.81 2.28 1.67 13.39 15.15 4.81 14.28 3.06 2.63 1.46 14.60 15.10 9.09 12.00 5.88 5.31 = 460nm 3.08 8.91 7.56 7.82 6.72 6.35 5.42 2.25 7.91 3.31 2.29 1.95 1.39 1.19 0.81 9.31 6.69 1.95 2.19 0.95 0.89 0.79 9.85 8.94 4.45 5.00 2.86 2.62 = 500nm 2.49 7.31 5.89 4.91 4.65 4.25 3.81 1.79 7.88 2.75 1.71 1.38 0.91 0.79 0.69 7.81 4.91 1.51 1.11 0.59 0.55 0.71 6.61 5.71 2.98 2.69 1.92 2.15 = 540nm 1.71 7.15 4.31 3.52 3.23 2.88 2.55 1.21 7.85 2.58 1.29 0.96 0.71 0.59 0.54 7.21 4.29 1.15 0.91 0.49 0.51 0.65 5.29 4.51 2.21 1.71 1.19 1.30 = 580nm 1.11 6.05 4.28 2.51 2.16 1.86 1.58 0.89 7.56 2.19 0.89 0.75 0.59 0.51 0.35 6.62 3.75 0.91 0.79 0.34 0.45 0.51 4.45 3.77 1.55 1.19 0.55 0.69 = 620nm 0.86 4.45 3.69 1.91 1.51 1.29 0.95 0.71 6.59 1.83 0.59 0.62 0.31 0.38 0.31 6.29 2.81 0.71 0.59 0.29 0.31 0.32 3.55 2.89 1.19 0.89 0.31 0.41 = 660nm 0.71 3.75 1.94 1.34 1.19 0.88 0.85 0.39 5.21 1.39 0.55 0.51 0.38 0.31 0.21 3.91 2.15 0.59 0.31 0.31 0.29 0.15 2.75 2.19 0.89 0.61 0.25 0.21 = 700nm 0.55 2.91 1.59 0.95 0.82 0.59 0.61 0.29 4.79 0.94 0.49 0.45 0.21 0.29 0.19 2.81 1.58 0.48 0.29 0.12 0.19 0.09 2.15 1.78 0.62 0.45 0.15 0.11
Mordants
No mordant Ferrous Sulphate Ferrous Sulphate and Alum Ferrous Sulphate, Alum and Tin Alum Alum and Tin Tin No mordant Ferrous Sulphate Ferrous Sulphate and Alum Ferrous Sulphate, Alum and Tin Alum Alum and Tin Tin No mordant Ferrous Sulphate Ferrous Sulphate and Alum Ferrous Sulphate, Alum and Tin Alum Alum and Tin Tin No mordant Ferrous Sulphate Ferrous Sulphate and Alum Ferrous Sulphate, Alum and Tin Alum Alum and Tin Tin
Henna Leaves
Guava Leaves
Mango Leaves
Onion Skin
41!
! Figure 4.4 to Figure 4.7 are drawn using the data of Table 4.5, plotting K/S values against wavelengths, which showed the similar trends in case of all the dyed fabrics.
20.00! 18.00! 16.00! 14.00! 12.00! 10.00! 8.00! 6.00! 4.00! 2.00! 0.00! No!mordant! Ferrous!Sulfate! Ferrous!Sulfate!and! Alum! Ferrous!Sulfate,Alum! and!Tin! Alum! Alum!and!Tin! Tin!
K/S%
wavelength!
Figure 4.4: K/S against wavelength curve of silk fabric dyed with henna extract
18.00! 16.00! 14.00! 12.00! K/S% 10.00! 8.00! 6.00! 4.00! 2.00! 0.00!
wavelength!
Tin!
Figure 4.5: K/S against wavelength curve of silk fabric dyed with guava extract
42!
20.00! 18.00! 16.00! 14.00! K/S% 12.00! 10.00! 8.00! 6.00! 4.00! 2.00! 0.00!
wavelength!
Figure 4.6: K/S against wavelength curve of silk fabric dyed with mango extract
20.00! 18.00! 16.00! 14.00! 12.00! 10.00! 8.00! 6.00! 4.00! 2.00! 0.00!
K/S%
wavelength!
Tin!
Figure 4.7: K/S against wavelength curve of silk fabric dyed with onion extract It was obvious that K/S values were increased by using mordants. Therefore it can be said that mordants increased the amount of dye absorbed by the fabric. Ferrous sulphate has affinity for both the colourant and the fibre. This forms an insoluble complex with dye on substrate. When it was applied before dyeing, it enhanced the uptake of colourant. Tin and alum has more affinity towards dye compared to silk fibre. So tin and alum has a tendency to move out of the fabric into the dye bath during dyeing. Therefore the uptake was less when tin and alum was used as mordants. [10]
43!
Henna Leaves
Guava Leaves
Mango Leaves
Onion Skin
44!
! The DL* values displayed in Table 4.6 were shown through the following bar diagram in Figure 4.8.
Ferrous!Sulfate! Ferrous!Sulfate! and!Alum! Ferrous!Sulfate,! Alum!and!Tin! Alum! Alum!and!Tin! Tin!
Henna%Leaves%% %Guava%Leaves%%%%%%%%%%%%%%Mango%Leaves%%%%%%%%%%%%%Onion%Skin%
%
Figure 4.8: Changes in L*(DL*) of mordanted silk fabric dyed with natural dyes This higher DL* values and hence lighter shades of the fabric can be attributed to the fact that alum and tin forms quite strong bonds with dye but not with the fabric [10]. Thus it bleeds during dyeing from treated silk fabric and formed insoluble coloured complexes into dye bath. Ferrous sulphate has substantively for both the colourant and the fibre, this forms an insoluble complex with dye on substrate. When it was applied before dyeing, it enhanced the uptake of colourant and also formed complex which changed shade as well. Thus high concentration of ferrous sulphate gives deeper shades [10]. From the Table 4.6 it was found in case of all the dyes, tin and alum increased Db* value while ferrous sulphate decreased Db* value. So it can be said that tin and alum mordants made the colour yellower and ferrous sulphate mordant made the colour bluer. Again, in case of mango and guava dyes, Da* values were less for tin and alum mordants while the Da* values were comparatively more for ferrous sulphate mordants. So it can be concluded that tin and alum mordants produced greener shades and ferrous sulphate produced redder shades. The phenomenon was opposite in case of henna and onion dyes. Furthermore, the DC* values, in Table 4.6, were positive when tin and alum mordants were used while these values were negative when ferrous sulphate mordants were used. Therefore it is evident that brighter shades were obtained using alum and tin mordants whereas ferrous sulphate produced duller shades. Various hues that were obtained from pre-mordanted silk fabric with ferrous sulphate, alum, tin and their combinations were shown in Table 4.7.
45!
! Table 4.7: Dyed silk fabric samples Mordant Henna Leaves Guava Leaves Mango Leaves Onion Skin
No mordant
Ferrous Sulphate
Alum
Tin
46!
47!
! The results of Table 4.8 have been expressed in Figure 4.9 to Figure 4.12.
4/5!
4/5!
4/5!
%Rating%
Ferrous! Sulfate!
Alum!
Alum!and! Tin!
Tin!
Figure 4.9: Dry cleaning fastness rating of silk fabric dyed with henna extract (Colour Change)
5!!!!! 4!!!!!
Alum!
Alum!and! Tin!
Tin!
Figure 4.10: Dry cleaning fastness rating of silk fabric dyed with guava extract (Colour Change)
48!
!
5!!!!! 5! 4!!!!! 4! %Rating% 3! 2! 1! 0! No! Ferrous! mordant! Sulfate! Ferrous! Ferrous! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant% Alum! Alum!and! Tin! Tin! 4/5! 4!!!!! 4!!!!! 5!!!!! 4/5!
Figure 4.11: Dry cleaning fastness rating of silk fabric dyed with mango extract (Colour Change)
5!!!!! 5! 4! Rating% 3! 2! 1! 0! No! Ferrous! mordant! Sulfate! Ferrous! Ferrous! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant% Alum! Alum!and! Tin! Tin! 4/5! 4!!!!! 4/5! 4!!!!! 4/5! 5!!!!!
Figure 4.12: Dry cleaning fastness rating of silk fabric dyed with onion extract (Colour Change) It was observed that all the dyed samples showed satisfactory fastness ratings in case of colour change scales. There were very slight to almost no staining of the perchloroethylene solution. It can be said that the selected natural dyes were resistant to perchloroethylene solution.
49!
Henna Leaves
Guava Leaves
Mango Leaves
Onion Skin
50!
! Table 4.10: Perspiration (acidic) fastness ratings of mordanted silk fabric dyed with natural dyes
Veg. Dyes Mordant 25% No mordant Ferrous sulphate Ferrous sulphate and alum Ferrous sulphate, alum and tin Alum Alum and tin Tin No mordant Ferrous sulphate Ferrous sulphate and alum Ferrous sulphate, alum and tin Alum Alum and tin Tin No mordant Ferrous sulphate Ferrous sulphate and alum Ferrous sulphate, alum and tin Alum Alum and tin Tin No mordant Ferrous sulphate Ferrous sulphate and alum Ferrous sulphate, alum and tin Alum Alum and tin Tin Colour Change 4 4 4 3/4 4/5 4 4 4/5 4 3/4 4/5 3 4/5 4/5 4/5 4 4 4/5 4/5 4/5 4/5 4 3 3/4 3/4 3/4 3/4 3/4 Diacetate 4 3 3/4 3 3/4 4 4 5 5 4/5 4/5 4/5 5 4/5 4/5 4 4/5 4/5 4/5 4 4 5 4/5 4/5 4/5 4/5 4/5 4/5 Bleached cotton 3 4 3 4/5 4 4 4/5 4 4 4 3/4 4 3/4 4 4 3 3 4/5 4 4 3/4 3 3/4 3/4 Staining PolyAcrylic amide 4 4 3 4 3 3 3 3 4/5 4/5 4/5 4/5 4 4/5 4 4 4/5 4 4 4 3/4 3/4 4/5 4/5 3/4 4 3/4 3/4 4/5 4 4 4 4/5 4/5 4 4/5 4 4 4 4 4 4 3 4/5 4 4 4/5 Polyester 4 3/4 3/4 3/4 4 3/4 4 4/5 4/5 4 4/5 4 4 4 4 4 3/4 4 3/4 3 3 4/5 4 3/4 4 3/4 3/4 4/5 Wool 3/4 3 3/4 3 3 3 3 3/4 3/4 3/4 4 3/4 3/4 3/4 4 3/4 3/4 3/4 3/4 3/4 3 4 4 3 3/4 3 3
Henna Leaves
Guava Leaves
Mango Leaves
Onion Skin
51!
! The results of colour change ratings displayed in Table 4.9 and Table 4.10 were expressed through Figure 4.13 to Figure 4.16.
5! 4! Rating% 3! 2! 1! 0!
4/5! 4!!!!!
4!/5! 4!!!!!
Alum!
Alum!and! Tin!
Figure 4.13: Perspiration fastness ratings of mordanted silk fabric dyed with henna extract (Colour Change)
5! 4! %Rating% 3! 2! 1! 0!
4/5! 4!!!!!
4/5!
4/5! 4!!!!!
Alum!
Alum!and! Tin!
Tin!
Alkaline!Perspiration! Acidic!Perspiration!
Figure 4.14: Perspiration fastness ratings of mordanted silk fabric dyed with guava extract (Colour Change)
52!
5! 4! Rating% 3! 2! 1! 0!
4/5! 4!!!!!
4/5! 4/5!
4/5! 4/5!
4/5! 4/5!
Alum!
Alum!and! Tin!
Tin!
Alkaline!Perspiration! Acidic!Perspiration!
Figure 4.15: Perspiration fastness ratings of mordanted silk fabric dyed with mango extract (Colour Change)
5! 4! Rating% 3! 2! 1! 0!
4/5! 4!!!!! 3/4! 3!!!!! 4!!!!! 3/4! 3/4! 3/4! 4!!!!! 3/4! 4!!!!! 3/4! 3/4! 3/4!
No! Ferrous! Ferrous! Ferrous! mordant! Sulfate! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant%
Alum!
Alum!and! Tin!
Tin!
Alkaline!Perspiration! Acidic!Perspiration!
Figure 4.16: Perspiration fastness ratings of mordanted silk fabric dyed with onion extract (Colour Change)
53!
! From the data in Table 4.9 and Table 4.10 as well as from Figure 4.13 to Figure 4.16, it was obvious that fastness to perspiration (both alkaline and acidic) was between good and excellent in case of silk fabrics dyed with guava, mango and henna extract. But for silk fabrics dyed with onion extract, fastness to perspiration (both alkaline and acidic) was between fair and good. The results of staining of wool fibre and cotton fibre of multi-fibre fabric displayed in Table 4.9 and Table 4.10 have been expressed through Figure 4.17 to Figure 4.24.
5!!!!! 4!!!!! 3!!!!! Rating% 2!!!!! 2!!!!! 1!!!!! 0!!!!! No! mordant! Ferrous! Sulfate! Ferrous! Ferrous! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant% Alum! Alum!and! Tin! Tin! 2!!!!! 2!!!!! 1/2! 1/2! 3!/4! 3!!!!! 2/3! 2!!!!! 3/4! 3!!!!! 3!!!!! 3!!!!! 3!!!!!
Alkaline!Perspiration! Acidic!Perspiration!
Figure 4.17: Perspiration fastness ratings of mordanted silk fabric dyed with henna extract (Staining of wool)
5!!!!! 4!!!!! 4!!!!! 3!!!!! Rating% 2!!!!! 1!!!!! 0!!!!! No! mordant! Ferrous! Sulfate! Ferrous! Ferrous! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant% Alum! Alum!and! Tin! Tin! 1/2! 3/4! 3/4! 3!!!!! 3/4! 3!!!!! 3!!!!! 3/4! 3!!!!! 3/4! 3!!!!! 3/4! 3!!!!!
Alkaline!Perspiration! Acidic!Perspiration!
Figure 4.18: Perspiration fastness ratings of mordanted silk fabric dyed with guava extract (Staining of wool) 54!
5!!!!! 4!!!!! 4!!!!! 3!!!!! Rating% 2!!!!! 2!!!!! 1!!!!! 0!!!!! No! mordant! Ferrous! Sulfate! Ferrous! Ferrous! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant% Alum! Alum!and! Tin! Tin! 3/4! 3!!!!! 3/4! 3!!!!! 2/3! 3/4! 3/4! 3!!!!! 2/3! 2/3! 3/4! 3!!!!!
Alkaline!Perspiration! Acidic!Perspiration!
Figure 4.19: Perspiration fastness ratings of mordanted silk fabric dyed with mango extract (Staining of wool)
5!!!!! 4!!!!! 4!!!!! 3!!!!! Rating% 2!!!!! 1!!!!! 0!!!!! No! mordant! Ferrous! Sulfate! Ferrous! Ferrous! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant% Alum! Alum!and! Tin! Tin! 3/4! 3!!!!! 3!!!!! 2/3! 2/3! 2/3! 4!!!!! 3/4! 3!!!!! 2/3! 3!!!!! 3/4! 3!!!!!
Alkaline!Perspiration! Acidic!Perspiration!
Figure 4.20: Perspiration fastness ratings of mordanted silk fabric dyed with onion extract (Staining of wool)
55!
5!!!!! 4!!!!!
4/5! 4!!!!! 3/4! 3!!!!! 3!!!!! 3!!!!! 2/3! 2/3! 2/3! 2/3! 2/3! 2/3! 3/4! 3/4!
No! mordant!
Ferrous! Sulfate!
Alum!
Alum!and! Tin!
Tin!
Alkaline!Perspiration! Acidic!Perspiration!
Figure 4.21: Perspiration fastness ratings of mordanted silk fabric dyed with henna extract (Staining of cotton)
No! mordant!
Ferrous! Sulfate!
Alum!
Alum!and! Tin!
Tin!
Alkaline!Perspiration! Acidic!Perspiration!
Figure 4.22: Perspiration fastness ratings of mordanted silk fabric dyed with guava extract (Staining of cotton)
56!
5!!!!! 4! 4!!!!! 3!!!!! 2!!!!! 1!!!!! 0!!!!! No! mordant! Ferrous! Sulfate! Ferrous! Ferrous! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant% Alum! Alum!and! Tin! Tin! 3/4! 3/4! 3/4! 3/4! 3!!!!! 4!!!!! 3/4! 3!!!!! 3!!!!! 3!!!!! 3!!!!! 3!!!!! 4!
Rating%
Alkaline!Perspiration! Acidic!Perspiration!
Figure 4.23: Perspiration fastness ratings of mordanted silk fabric dyed with mango extract (Staining of cotton)
5!!!!! 4!!!!! 4!!!!! 3!!!!! Rating% 2!!!!! 1!!!!! 0!!!!! No! mordant! Ferrous! Sulfate! Ferrous! Ferrous! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant% Alum! Alum!and! Tin! Tin! 3/4! 3/4! 3!!!!! 3/4! 4!!!!! 3/4! 3!!!!! 3!!!!! 3!!!!! 3/4!!!!! 3!!!!! 3/4! 3!!!!!
Alkaline!Perspiration! Acidic!Perspiration!
Figure 4.24: Perspiration fastness ratings of mordanted silk fabric dyed with onion extract (Staining of cotton) It was observed that staining of both wool and cotton fibres were more in alkaline perspiration compared to acidic perspiration. This can be attributed to the fact that the natural dyes are converted to their salt forms in alkaline condition. The dye salts are soluble in water and so comes out of the fibre more easily. Therefore staining was found more in alkaline perspiration [10].
57!
! Staining of wool fibre was more compared to staining of cotton fibre in both alkaline and acidic perspiration. The ratings of staining were between poor and fair in alkaline perspiration and it was between fair and good in acidic perspiration. It was also found that staining was most in case of the silk fabrics dyed with henna extract.
Henna Leaves
Guava Leaves
Mango Leaves
Onion Skin
! The results shown in Table 4.11 have been expressed as bar diagram through Figure 4.25 to Figure 4.28.
8!!!!! 7!!!!! 6!!!!! 5!!!!! Rating% 4!!!!! 3!!!!! 2!!!!! 1!!!!! 0!!!!! 3!!!!!
7!!!!! 6!!!!!
Alum!
Alum!and! Tin!
Tin!
Figure 4.25: Light fastness rating of mordanted silk fabric dyed with henna extract
8!!!!! 7!!!!! 6!!!!! Rating% 5!!!!! 4!!!!! 3!!!!! 2!!!!! 1!!!!! 0!!!!! 3!!!!!
7!!!!!
5!!!!!
3!!!!!
Alum!
Alum!and! Tin!
Tin!
Figure 4.26: Light fastness rating of mordanted silk fabric dyed with guava extract
59!
8!!!!! 7!!!!! 6!!!!! Rating% 5!!!!! 4!!!!! 3!!!!! 2!!!!! 1!!!!! 0!!!!!
7!!!!!
7!!!!!
7!!!!!
Alum!
Alum!and! Tin!
Tin!
Figure 4.27: Light fastness rating of mordanted silk fabric dyed with mango extract
8!!!!! 7!!!!! 6!!!!! Rating% 5!!!!! 4!!!!! 3!!!!! 2!!!!! 1!!!!! 0!!!!! No! Ferrous! mordant! Sulfate! 6!!!!! 6!!!!! 6!!!!!
7!!!!!
7!!!!!
3!!!!!
3!!!!!
Alum!
Alum!and! Tin!
Tin!
Figure 4.28: Light fastness rating of mordanted silk fabric dyed with onion extract It was observed from Table 4.11 that when ferrous sulphate was used light fastness was found better but when tin was used as mordant it was found lesser. Again, better light fastness was achieved in case of silk fabrics dyed with mango extract. As it has been discussed earlier, ferrous sulphate has more affinity towards dye and fibre compared to tin [10]. Therefore ferrous sulphate can bind with more dye molecules than tin. During exposure to light, the fabrics mordanted with ferrous sulphate and the fabrics mordanted with tin may have the same number of dye molecules destroyed. But as the fabrics mordanted with ferrous sulphate had deeper shades, it seemed to fade less compared to the fabric mordanted with tin [33]. 60!
Henna Leaves
Guava Leaves
Mango Leaves
Onion Skin
61!
! The results shown in Table 4.12 were expressed through Figure 4.29 to Figure 4.32.
5! 4! 4! 3!!!!! 3! Rating% 2! 1! 0! No! Ferrous! mordant! Sulfate! Ferrous! Ferrous! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant% Alum! Alum!and! Tin! Tin! 2!/3! 3!!!!! 3!!!!! 3!!!!! 4!!!!!
Figure 4.29: Wash fastness rating of mordanted silk fabric dyed with henna extract (Colour Change)
5! 4!!!!! 4! 3! 2! 1! 0! No! Ferrous! mordant! Sulfate! Ferrous! Ferrous! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant% Alum! Alum!and! Tin! Tin! 3/4! 3!!!!! Rating% 3!/4! 4!!!!! 3!/4! 3!/4!
Figure 4.30: Wash fastness rating of mordanted silk fabric dyed with guava extract (Colour Change)
62!
5! 4! 3! 2! 1! 0!
4!/5!
4/5!
4!/5!
Rating%
No! mordant!
Ferrous! Sulfate!
Alum!
Alum!and! Tin!
Tin!
Figure 4.31: Wash fastness rating of mordanted silk fabric dyed with mango extract (Colour Change)
5! 4! 3! 2! 1! 0!
%Rating%
No! mordant!
Ferrous! Sulfate!
Alum!
Alum!and! Tin!
Tin!
Figure 4.32: Wash fastness rating of mordanted silk fabric dyed with onion extract (Colour Change)
63!
! The wash fastness was found better for the samples dyed without mordant compared to the samples dyed while using mordanted fabric. This is because the affinity of the colourant components towards the fibre by H-bonds and van der Waals force is better compared to affinity of the colourant components towards mordants [10]. Wash fastness was found fair when ferrous sulphate and alum mordants combination was used. Comparatively wash fastness was found better in case of fabric samples dyed with mango extract. There was slight staining in case of wool fibre of the multi-fibre fabric while there was almost no staining on the other fibres of the multi-fibre fabric. It was observed that there was moderate staining on the fibres of the multi-fibre fabric in case of the samples that were pre-mordanted with ferrous sulphate, alum and tin combination and dyed using onion extract.
Henna Leaves
Guava Leaves
Mango Leaves
Onion Skin
64!
! The results of staining shown in Table 4.13 were expressed through Figure 4.33 to Figure 4.36.
5!!!!! 5!!!!! 4/5! 4/5! 4!!!!! 4/5! 4!!!!! 4!!!!! 4!!!!! 5!!!!! 5!!!!! 4/5! 4/5! 4!!!!!
5! 4! Rating% 3! 2! 1! 0!
No! mordant!
Ferrous! Sulfate!
Alum!
Alum!and! Tin!
Figure 4.33: Rubbing fastness ratings (staining) of mordanted silk fabric dyed with henna extract
5! 4!
Rating%
3! 2! 1! 0! No! mordant! Ferrous! Sulfate! Ferrous! Ferrous! Sulfate! Sulfate,! and!Alum! Alum!and! Tin! Mordant% Alum! Alum!and! Tin! Tin! Dry!Rubbing! Wet!Rubbing!
Figure 4.34: Rubbing fastness ratings (staining) of mordanted silk fabric dyed with guava extract
65!
!
5!!!!! 5!!!!! 4/5! 4!!!!! 4!!!!! 4/5! 4!!!!!
5! 4! 3! Rating% 2! 1! 0!
4/5! 4!!!!!
4/5!
4/5!
Alum!
Alum!and! Tin!
Figure 4.35: Rubbing fastness ratings (staining) of mordanted silk fabric dyed with mango extract
5!!!!!
5!
4/5! /4!
4!
%Rating%
3!
2!
1!
0!
Alum!
Alum!and! Tin!
Figure 4.36: Rubbing fastness ratings (staining) of mordanted silk fabric dyed with onion extract In all the cases, dry rubbing fastness was found to be better than wet rubbing fastness. Fastness rating was between good and excellent for staining of the crocking cloth used during dry rubbing while it was within fair and good during wet rubbing.
66!
!cmc ! cmc
0.07 0.17 0.22 0.10 0.45 0.47 0.43 0.45 0.32 0.35 0.29 0.31 0.27 0.25 0.31 0.33 0.08 0.27 0.27 0.30 0.18 0.18 0.23 0.28 0.28 0.07 0.23 0.29 0.14
Average
Ferrous Sulphate
0.45
0.32
Guava Leaves
0.29
Alum
0.23
0.22
Tin
0.22
67!
Table 4.15: Levelness data of mordanted silk fabric dyed with mango extract
Veg. Dye Mordant No mordant DL*/lSL 0.07 -0.14 -0.13 -0.12 0.00 0.03 0.47 0.11 0.38 0.39 0.32 0.32 0.15 0.22 0.25 0.15 -0.24 -0.05 -0.05 -0.23 0.09 0.07 0.23 0.20 0.03 0.03 -0.05 -0.05 DC*/cSC -0.09 0.21 0.20 -0.05 0.42 0.43 0.16 -0.06 0.20 0.25 0.29 0.36 0.03 -0.19 0.16 0.01 -0.06 0.13 0.07 -0.06 -0.20. -0.21 -0.21 -0.22 0.03 -0.02 0.09 0.05 DH*/SH 0.11 0.08 0.07 -0.03 0.03 0.23 0.05 0.04 -0.16 -0.13 -0.07 -0.08 0.11 0.05 0.16 0.09 -0.01 -0.15 -0.16 -0.08 0.16 0.11 0.11 0.18 0.20 0.21 0.13 0.18
!cmc ! cmc
0.12 0.27 0.25 0.13 0.42 0.48 0.49 0.13 0.35 0.37 0.26 0.28 0.19 0.25 0.29 0.17 0.25 0.20 0.19 0.23 0.25 0.22 0.20 0.21 0.21 0.21 0.18 0.19 0.19
Average
Ferrous Sulphate
0.38
0.31
Mango Leaves
0.23
Alum
0.22
0.23
Tin
0.20
68!
! Table 4.16: Levelness data of mordanted silk fabric dyed with onion extract
Veg. Dye Mordant No mordant DL*/lSL -0.02 -0.14 -0.12 0.01 0.40 0.26 0.15 0.15 -0.20 -0.18 0.19 0.20 -0.02 0.00 0.22 0.21 -0.16 -0.15 0.22 0.21 0.03 -0.12 0.04 -0.10 -0.01 -0.09 -0.08 -0.01 DC*/cSC -0.09 0.09 -0.15 0.10 -0.06 -0.15 0.16 0.12 0.05 0.10 0.06 0.07 -0.22 -0.22 0.00 -0.02 0.07 0.05 0.01 0.00 0.03 0.20 0.05 0.16 -0.02 -0.01 0.07 0.10 DH*/SH 0.19 0.14 0.18 0.09 0.32 0.25 0.28 0.22 0.28 0.21 0.17 0.17 0.17 0.18 0.23 0.21 0.16 0.15 0.19 0.19 0.16 0.18 0.12 0.15 0.23 0.20 0.19 0.16 !cmc 0.20 0.17 0.22 0.10 0.48 0.34 0.33 0.26 0.32 0.25 0.21 0.21 0.22 0.23 0.28 0.25 0.19 0.17 0.24 0.23 0.16 0.23 0.12 0.19 0.23 0.21 0.20 0.17 Average !cmc 0.17
Ferrous Sulphate
0.35
0.25
Onion Skin
0.24
Alum
0.21
0.18
Tin
0.20
69!
Table 4.17: Levelness data of mordanted silk fabric dyed with henna extract
Veg. Dye Mordant No mordant DL*/lSL -0.06 -0.04 -0.08 -0.01 -0.13 0.11 0.10 -0.14 -0.03 -0.01 -0.03 -0.05 0.02 0.12 0.03 0.10 0.17 0.18 -0.01 0.14 -0.11 0.02 0.04 -0.10 -0.13 -0.01 -0.23 -0.12 DC*/cSC 0.17 0.19 0.13 0.23 -0.41 -0.27 -0.27 -0.40 -0.22 -0.12 -0.18 -0.20 0.24 -0.33 0.24 -0.33 0.08 0.08 0.14 -0.16 0.02 0.22 0.22 0.03 0.03 0.24 0.24 0.06 DH*/SH 0.11 0.12 0.11 0.17 0.18 0.35 0.34 0.13 0.28 0.28 0.29 0.27 0.22 0.35 0.23 0.34 0.35 0.38 0.18 0.33 0.00 0.19 0.22 0.00 -0.01 0.18 -0.11 0.02
!cmc
0.17 0.18 0.12 0.18 0.49 0.32 0.32 0.45 0.36 0.30 0.35 0.36 0.26 0.35 0.26 0.36 0.22 0.24 0.21 0.24 0.12 0.22 0.23 0.11 0.14 0.25 0.23 0.16
Average
!cmc
0.16
Ferrous Sulphate
0.40
0.34
Henna Leaves
0.31
Alum
0.23
0.20
Tin
0.19
70!
! The extraction of dyes from henna, guava and mango leaves and onion skin was tedious and the colouring component extracted was very little. In order to obtain 350 g to 450 g of the dye powder about 1 kg leaves were required. As the mango, guava and henna trees are scarce in Dhaka city, it was difficult to obtain large amount of leaves in Dhaka. The perchloroethylene for dry cleaning fastness test of dyed silk fabric was very difficult to acquire. Laboratory grade perchloroethylene was expensive and unavailable in the market. Therefore the cheaper, commercial grade perchloroethylene was used for dry cleaning fastness test. Also perchloroethylene was very toxic and difficult to handle. It was so toxic that it dissolved some parts of the rubber gloves that were worn during testing. WPT lab of AUST needs to have the proper safety gears to handle toxic chemicals. The pH of the dye bath could not be measured directly because of unavailability of electronic pH meters. During light fastness test, the samples were exposed under mercury lamp instead of ISO 105 BO2 recommended Xenon Arc Lamp. The light fastness tester in TTQC II Lab of AUST did not have the Xenon Arc Lamp. Also due to limitations of the machine, the method stated in ISO 105 B02 could not be followed exactly. Last but not the least limitation is in the type of colour components of the vegetable dyes. The chemical structure those are found in the selective leaves or skins are the most common colouring components. But in addition there are lots of undefined colouring components exist in the natural colourants according to various literatures the properties of those were undefined. During last decade, several studies on dyeing with natural colourants have been carried out but most of them have been empirical in nature, systematic investigations into the theoretical basis of dyeing with these dyes are rather limited. It is well-known that natural colouration is known from ancient time as artisanal practice for handicrafts, paintings or handloom textiles; the chemistry of interaction of such colourants with textile materials is of relatively recent interest for producing ecofriendly textiles. Thus there are needs of many more knowledge based database with production of appropriate shade cards for different textiles. It will help to popularize the use of natural dyes by solving the associated problems of natural dyeing. In addition, it must be remembered that the colour fastness of natural dyes not only depends on the chemical nature and type of natural colourants, but also on chemical nature and type of mordants being used. So, a dyer must know the use of proper combinations of fibre mordant to achieve the best colour fastness. For successful commercial use of vegetable dyes, the appropriate and standardized dyeing techniques need to be adopted. Therefore, to obtain newer shades with acceptable dyeing behaviour and reproducible colour yield, appropriate scientific procedures need to be derived from scientific studied on dyeing methods, dyeing kinetics, dyeing process variables and compatibility of selective vegetable dyes.
72!
Chapter 6 Conclusion
73!
! Different hues were obtained on silk fabric from the same dye extract by using different mordants and their combinations in pre-mordanting method. The best results were obtained when extraction from vegetable dyes was done in alkaline condition (pH 9) and silk fabric dyeing was carried out in acidic medium (pH 5). Ferrous sulphate mordants produced deeper shades while tin mordants produced lighter shades. The use of mordants not only produced shade variation but also improved the amount of dye uptake of the pre-mordanted dyed fabric compared to the fabric dyed without using mordant. Fastness to dry cleaning of all the vegetable dyed silk fabrics was between good and excellent with very slight to almost no staining of the perchloroethylene solution. Better ratings of colour change were found for dyed silk in case of mongo, guava and henna leaves in comparison to onion skin under both perspiration tests. Staining of the multifibre fabric, mainly wool and cotton, was major in alkaline perspiration compared to that in acidic perspiration. In case of all dyes, light fastness ratings were found better for the ferrous sulphate mordanted fabrics and found lesser when tin was used as mordant. The silk fabrics dyed with mango extract showed better light fastness compared to the silk fabric dyed with the others. For all the dyed samples, wash fastness was better when fabric was dyed without using mordant. Comparatively mango extracted dyed silk fabrics exhibited better wash fastness for colour change. There was moderate staining during wash fastness test in case of onion extracted dyed fabrics which was pre-mordanted with ferrous sulphate, alum and tin combinations. In all the cases, dry rubbing fastness was better than wet rubbing fastness. Fastness rating was between good and excellent for dry rubbing while it was between fair and good in case of wet rubbing. Furthermore, fabrics that were dyed without using mordant were most evenly dyed. The dyeing was more even when alum or tin or their combinations were used as compared to the use of ferrous sulphate. Here from the study it can be concluded that when considerations regarding changes of hues, dye uptake or light fastness are not important, in these cases, dyeing of silk fabric using vegetable dyes can be carried out without using mordants.
74!
Glossary
Absorbance - It is also called optical density. Absorbance of a material is a
logarithmic ratio of the radiation falling upon a material, to the radiation transmitted through a material.
BSB - Bangladesh Sericulture Board. BSCIC - Bangladesh Small and Cottage Industries Corporation. BSRTI - Bangladesh Sericulture Research and Training Institute. CIE - Commission internationale de l'clairage (English- International Commission on
Illumination)
CMC Colour Measurement Committee Color Fastness to Dry Cleaning- The resistance of the transference of color by dry
cleaning solvent (perchloroethylene) from one colored textile material to another.
Color Fastness to Light- The resistance of the transference of color when exposed
to light from one colored textile material to another.
Color Fastness to Wash- The resistance of the color to fade or bleed by washing. Coordinate Bond- a covalent bond in which both electrons are provided by one of the
atoms
Covalent Bond- a chemical bond that involves sharing a pair of electrons between
atoms in a molecule
75!
EPI-Ends (No. of warp) per Inch. Fibroin- Fibroin is an insoluble white protein that is the essential component of raw
silk filaments. It is the part of silk thread that remains after the gum has been removed.
K/S K (absorption) S(Scattering) the ratio of total light absorbed and scattered by a
mixture of dyes is equal to the sum of the ratio of light absorbed and scattered by dyes measured separately is called Kubelka-Munk equation.
PPI-Picks (No. of weft) per Inch. Sequestering Agent (Dekol SN) - It deactivates metallic ions. Sericin-Sericin is a gelatinous protein, comprising 20% to 30% by mass of raw silk,
cementing the two fibroin filaments in a silk bave.
Sericulture - silk farming. It is the rearing of silkworms for the production of raw silk.
Sericulture was started in 2700 BC.
Van Der Waals' forces- The magnetic attraction between different molecules or the
adjacent parts of one molecule arising from permanent or transient polarities within the molecules.
Wetting Agent (Kiralon)-It reduces surface tension between liquid and fabric.
76!
Reference
[1]. A Purohit, S. Mallick, A Nayak, N. B. Das, B. Nanda, S. Sahoo, Developing multiple natural dyes from parts of Gulmohur, 2007, Current Science, Vol. 92, No. 12, p 1681 [2]. H. Goodarzian and E. Ekrami, 2010, World Applied Sciences Journal, Vol. 9, No 4, p 434-436 [3]. A. Kumar, Samanta, P. Agarwal, Application of natural dyes on textile, Indian Journal of Fibres and Textile, Vol. 34, p 384 [4]. D. Jothi, 2008, Extraction of natural dyes from African marigold flowers (Tagetes Ereectal) for textile coloration, AUTEX Research Journal, Vol. 8, No. 2, p. 49. [5]. Handbook of natural colorants edited by Thomas Bechtold, Rita Mussak, 2009, John Wiley and Sons Ltd, p 35, 169, 320, 330, 331 [6]. Padma S Vankar, 2000, Chemistry of Natural dyes, Resonance, Vol. 5, No. 10), 79 [7]. Paul. 1996, Fastness properties of cotton dyed with ecofriendly kilmora roots. Colourage, 53(9): 49-52. [8]. R. Singh, A Jain, S. Panwar, D. Gupta, S. K. Khare, 2005, Antimicrobial activity of some natural dyes, Dyes and Pigment, p 1-4 [9]. Frigerio, M. 1992. Natural dyes. Tinctoria, 89(12): 46-54 [10]. Shaukat Ali, 2007, Evaluation Of Cotton Dyeing With Aqueous Extracts Of Natural Dyes From Indigenous Plants, p 3, 50, 63, 76, 78, 89. [11]. M. M. Alam, M. L. Rahman and M. Z. Haque, 2007 Extraction of Henna leaf dye and its Dyeing Effects on Textile fibre Bangladesh J. Sci. Ind. Res. Vol. 42, No. 2, p 217-222 [12]. P. Guinot, I. Benonge, G. Nicolet, A Gargadence, C. Andary, S. Rapior, 2007, Combined dyeing and antioxidation properties of some plant by-products, Acta Bot Gallica, Vol. 154, No.1 p 43-52 [13]. http://www.ncbi.nlm.nih.gov/pmc/articles/PMC3249901 [14]. Padma S Vankar et al, 2009, Dyeing of cotton, wool and silk with extract of allium cepa. Pigment and Resin Technology, Vol. 38, p 242-247 [15]. http://www.bsb.gov.bd/history.asp [16]. http://cmerti.res.in/sericulture&silk.html, http://www.theindependentbd.com/index.php?option=com_content&view=article&i d=71735:boosting-of-silk-production-needed [17]. Muhammad Ahsen Khan (2011), Dyeing of Wool and Silk with a Conductive Polyelectrolyte and Comparing their Conductance, University of Boras. p 5 [18]. Apparel Fibres, by Dr. Md. Nazirul Islam p 191, 201-206 and Handbook of Textile Fibres, Gordon Cook, p 159 (reference file introduction to silk)
77!
! [19]. A.K. Annepu, Preparatory Process, p 18-25 [20]. Anthony C. Dweck, Review of Guava (Psidium guajava) p 1-3 [21]. Aden Onal, 1996, Extraction of dyestuff from onion (Allium cepa L) and its application in the dyeing of wool feathered leather and cotton. Tr. J. of Chemistry, Vol. 20, p 200-201 [22]. http://griffindyeworks.com/understanding-mordants/ [23]. Textile Preparation and Dyeing by Asim Kumar Roy Choudhury, p 233, 309 [24]. Kumaresan, P. N. Palnisamy and P. E. Kumar, 2011, Application of Ecofriendly Natural Dye Obtained from flower of Spathodea Campanulata on Silk, European Journal of Scientific Research,Vol.52, No.3, 306-312 [25]. Textile Preparation and Dyeing by Asim Kumar Roy Choudhury, p 337-339 [26]. Basic Principles of Textile Coloration, Arthur D Broadbent, 2001 Society of Dyers and Colourists. P 534-536 [27]. Modern Concepts of Color and Appearance by Asim Kumar Roy Choudhury p [28]. ISO 105-D01, 1993. Textiles: Test for colour fastness, Part D01, Colour fastness to dry cleaning. [29]. ISO 105-E04:1994 Textiles Test for colour fastness. Part E04: Colour fastness to perspiration [30]. ISO 105B02:1994, Tests for colour fastness to artificial light: Xenon arc fading lamp test. [31]. ISO 105-C02, 1994. Textiles: Test for colour fastness, Part C02, Colour fastness to washing. [32]. ISO 105-X12: 1993 Textiles Tests for colour fastness, Part X12: Colour fastness to rubbing. [33]. P. Cox-Crews, The influence of mordant on the light fastness of yellow natural dyes, Journal of American Institute for Conservation, 21(1982), 43-58
78!