Textile Dyeing - Theory of Dyeing & Classification of Dyes

 Dyeing & Printing  Classification of Dyes, Application of Dyes on Textile Materials, Introduction to Different types of Dyeing Machineries

Dyeing & Printing

Title of Contents

1.0.

Introduction to Textile Dyeing

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2.0.

Classification of Dyes

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3.0.

Dyeing Process

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3.1.

Dyeing Methods

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3.2.

Comparison of Dyeing in Various Stages

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3.3.

Special Dyeing Effects

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3.4.

Application of Dyes on Textile Materials

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3.5.

Direct Dyes

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3.6.

Azoic Colors

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3.7.

Reactive Dyes

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3.8.

Vat Dyes

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20

3.9.

Acid Dyes

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25

3.10.

Basic Dyes

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28

3.11.

Sulphur Dyes

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29

3.12.

Disperse Dyes

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30

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31

4.0.

Introduction to Different Dyeing Machineries

Dyes, Theory of Dyeing, Classification of Dyes and its application

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Dyeing & Printing

Title of Contents

1.0.

Introduction to Textile Dyeing

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03

2.0.

Classification of Dyes

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05

3.0.

Dyeing Process

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07

3.1.

Dyeing Methods

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07

3.2.

Comparison of Dyeing in Various Stages

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09

3.3.

Special Dyeing Effects

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10

3.4.

Application of Dyes on Textile Materials

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11

3.5.

Direct Dyes

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11

3.6.

Azoic Colors

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12

3.7.

Reactive Dyes

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15

3.8.

Vat Dyes

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20

3.9.

Acid Dyes

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25

3.10.

Basic Dyes

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28

3.11.

Sulphur Dyes

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29

3.12.

Disperse Dyes

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30

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31

4.0.

Introduction to Different Dyeing Machineries

Dyes, Theory of Dyeing, Classification of Dyes and its application

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1.0. Introduction to Textile Dyeing

Dyeing is the process of imparting colours to a textile material in loose fibre, yarn, cloth or garment form by treatment with a dye. Dyeing is also the process of coloring textile materials by immersing them in an aqueous solution of dye, called dye liquor. Normally the dye liquor consists of dye, water and an auxiliary. To improve the effectiveness of dyeing, heat is usually applied to the dye liquor. 1.1. Color –  Definition

Color or colour is the visual perceptual property corresponding in humans to the categories called red, green, blue and others. Color derives from the spectrum of light (distribution of light energy versus wavelength) interacting in the eye with the spectral sensitivities of the light receptors. Color categories and physical specifications of color are also associated with objects, materials, light sources, etc., based on their physical properties such as light absorption, reflection, or emission spectra. By defining a color space, colors can be identified numerically by their coordinates. Because perception of color stems from the varying sensitivity of different types of cone cells in the retina to different parts of the spectrum, colors may be defined and quantified by the degree to which they stimulate these cells. These physical or physiological quantifications of color, however, do not fully explain the psychophysical perception of color appearance. The science of color is sometimes called chromatics. It includes the perception of  color by the human eye and brain, the origin of color in materials, color theory in art, and the physics of electromagnetic radiation in the visible range (that is, what we commonly refer to simply as light). 1.2. Definition  –  Dye

By definition Dyes can be said to be coloured, ionizing and aromatic organic compounds which shows an affinity towards the substrate to which it is being applied. It is generally applied in a solution that is aqueous. Dyes may also require a mordant to better the fastness of the dye on the material on which it is applied. The dyes were obtained from animal, vegetable or mineral origin with no or very little processing. By far the greatest source of dyes has been from the plant kingdom, notably roots, berries, bark, leaves and wood, but only a few have ever been used on a commercial scale. 1.3. Definition  –  Pigment Pigment is the substance or powder that makes up the color of paint. Pigments are either organic (derived from plant or animal sources, e.g. ivory black, indigo) or inorganic (derived from salts or metallic oxides e.g. ocher, cobalt blue). Dyes, Theory of Dyeing, Classification of Dyes and its application

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Pigment is a substance that can absorb light and reflect some lights to show color but it is water insoluble substances. Normally it is used for printing (with the presence of  binder) or mass-coloration of the synthetic fibers. 1.4. Theory of Dyeing

The general theory of dyeing explains the interaction between dye, fiber, water and dye auxiliary. More specifically, it explains: i. Force of repulsion which are developed between the dye molecules and water and ii. Force of attraction which are developed between the dye molecules and fibres. These forces are responsible for the dye molecules leaving the aqueous dye liquor entering and attaching themselves to the polymers of the fibres 1.4.1. Dye Molecule

Dye molecules are organic molecules, which can be classified as: 1. Anionic – in which the color is caused by the anionic part of the dye molecule; 2. Cationic – in which the color is caused by the cationic part of the dye molecule; 3. Disperse – in which the color is caused by the whole molecule. The first two dye molecule types are applied from an aqueous solution. The third is applied from an aqueous dispersion. A dye stuff is a substance which is capable of coloring a textile material in such a manner that it associate closely with the fiber, that it is not removable by simple physical means (e.g.: rubbing or mild deterging). It must be soluble in water, are capable of going into solution by chemical means, whereby a highly dispersed condition may be regarded as a form of solution An essential feature of the dyeing process is that the dye molecule must be capable of entering the fiber structure, the path for the dye molecules is provided by the intermolecular spaces in the fiber and once the dye has entered the fiber structure it becomes firmly attached to the surface of the molecules either by purely physical forces (Secondary Valences) or by chemical combination. The former mode of attachment is believed to be prevalent in the dyeing of cellulosic fibres, the latter mode in the dyeing of  protein fibres. Acetate rayon and synthetic fibres resist penetration by the dye molecules, but certain dyes are capable of forming a solid solution with the fibrous molecule; for dyeing with other dyes, the synthetic fibres may be swollen with suitable agents. Swelling of the fibers appears to play a large part in dyeing of all fibres, and is principally affected by water (or solvents in the case of synthetics) and by raising the temperature of the dye bath. Dyes, Theory of Dyeing, Classification of Dyes and its application

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1.4.2. The Dyeing Process

The dyeing process can thus be considered as taking place in three phases (i) Attachment of the dye molecule to the surface of the fiber (ii) Penetration into the intermolecular spaces as well as diffusion through the fiber & (iii) Orientation (and fixation) along the long chain molecules. Dyeing is governed by three factors, the dye, the fiber and the dye liquor. All the three lead an independent assistance which influences the technique of dyeing. A dye must be water soluble in order to dye textile materials. It may be soluble by nature of its chemical interference. The solution of the dye from which it is applied is called the „dye bath‟. A dye may have direct „affinity‟ for a fiber (or vice versa) i.e., it is held by the fibre either  physically (absorption) or chemically (combination) as soon as the fiber is immersed in the dye bath. Accumulation of the dye in the fiber is a gradual process, the rate of such building up being referred to as the „rate of dyeing‟. 1. This rate of dyeing is governed by the condition of the dye bath, namely concentration of dye, temperature, and presence of electrolytes; it is proportional to all three factors. 2. The rate of dyeing is also influenced by the „Material to liquor‟ which is expressed by a fraction, e.g. 1:20, which means one part (by weight) of the textile material dyed in twenty times its weight of dye bath. 3. The rate of dyeing decreases with increasing ratio of goods to liquor. Dyeing is carried out to produce a certain „Shade‟ by which is meant a certain color, difference in shade being due to different ‟Hue‟. A blue shade may, for instance, have a greenish or a reddish hue. The amount of dye needed for the production of a certain depth of shade is expressed as a percentage of the weight of the material. A 1% dyeing represents a shade produced by the coloring of 100 lbs. of material with one lb. of (commercial) dye under well defined dyeing conditions. It is necessary to define these conditions because of their influence on the „exhaustion‟ of the dye bath. Exhaustion determines that amount of dye which is taken up the fiber or in directly, that amount which remains in the dye bath after „equilibrium‟ between dye and fiber is reached, i.e., at that point wher e no further dyeing takes place. 2.0. Classification of Dyes

Dyestuffs can be classified by many methods as follows: y their ionic e.g. Cationic, anionic and non-ionic) y their fiber dye abilities e.g. On cellulosic, protein, polyester, polyamide etc.) y their names e.g. Acid, direct, disperse, reactive, basic etc.) Dyes, Theory of Dyeing, Classification of Dyes and its application

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y their chemical structures e.g. azo, anthraquinone, stilbene etc.) y their origins e.g. Natural, synthetic) y their colors e.g. Red, green, black etc.) 2.1. Classification of Dyes by their Names

Though several classifications were available classification of dyes by their names is the widely used one. COLOURING MATTER

DYES

PIGMENTS

Ready made dyes

Ingrain dyes

Azoic

Oxidation

Water-soluble

Water insoluble

Vat

Direct

Acid

Mineral

Basic

Sulphur

Disperse

Reactive

So the Colouring matters can be classified as pigments and dyes. Dyes may be of  readymade dyes and ingrain dyes. Ready made dyes are dyes which are readily available in powder form, liquid form. These ready made are available in both water soluble and water in soluble form. Ingrain dyes are those which will not be available in ready made form, two or more compounds are combined together in the dyeing process to obtain the color in the final finished product.

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3.0. Dyeing Process

Dyeing is the process of imparting colors to a textile material through a dye (colour). Dyes are obtained from flowers, nuts, berries and other forms of  vegetables and plants as well as from animal and mineral sources. These are known as natural dyes. The other classes of dyes are known as synthetic dyes. These are based on a particular type of  chemical composition. Some of these dyes are- Acid (Anionic) dyes, Basic (Cationic) dyes, Neutral- Premetalized dyes, sulfur dyes, vat dyes, reactive dyes, pigment dyes etc. 3.1. Dyeing Methods

Colour is applied to fabric by different methods of dyeing for different types of  fiber and at different stages of the textile production process. Dyeing can be done during any stage in the textile manufacturing process. Textiles may be dyed as fibre, as yarn, as fabric, as garments, depending upon the type of the fabric or garment being produced. These methods include direct dyeing; Stock dyeing; top dyeing; Yarn dyeing; Piece dyeing; Solution pigmenting or dope dyeing; Garment dyeing etc. Of these Direct dyeing and Yarn Dyeing methods are the most popular ones. 3.1.1. Direct Dyeing

When a dye is applied directly to the fabric without the aid of an affixing agent, it is called direct dyeing. In this method the dyestuff is either fermented (for natural dye) or chemically reduced (for synthetic vat and sulfur dyes) before being applied. The direct dyes, which are largely used for dyeing cotton, are water soluble and can be applied directly to the fiber from an aqueous solution. Most other classes of synthetic dye, other than vat and sulfur dyes, are also applied in this way . 3.1.2. Stock Dyeing

Stock dyeing refers to the dyeing of the fibers, or stock, before it is spun in to yarn. It is done by putting loose, unspun fibres in to large vats containing the dye bath, which is then heated to the appropriate temperature required for the dye application and dyeing process. Stock dyeing is usually suitable for woolen materials when heather like color effects are desired. Wool fibre dyed black, for example, might be blended and spun with un-dyed (white) wool fibre to produce soft heather like shade of grey yarn. Tweed fabrics with heather like color effects such as Harris Tweed are examples of stock dyed material. Other examples include heather like colours in covert and woolen cheviot.

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3.1.3. Top Dyeing

Top dyeing is also the dyeing of the fibre before it is spun in to yarn and serves the same purpose as stock dyeing  – that is, to produce soft, heather like color effects. The term top refers to the fibres of wool from which the short fibres have been removed. Top is thus selecting long fibres that are used to spin worsted yarn. The top in the form of  sliver is dyed and then blended with other colors of dyed top to produce desired heather shades. 3.1.4. Yarn Dyeing

Yarn dyeing is the dyeing of the yarns before they have been woven or knitted into fabrics. Yarn dyeing is used to create interesting checks, stripes and plaids with different-colored yarns in the weaving process. In yarn dyeing, dyestuff penetrates the fibers in the core of the yarn. There are many forms of  yarn dyeing- Skein (Hank) Dyeing, Package Dyeing, Warp-beam Dyeing, and Space Dyeing . 3.1.4.1. Skein (Hank) Dyeing

Skein dyeing consists of immersing large, loosely wound hanks (skeins) of yarn into dye vats that are especially designed for this purpose. Soft, lofty yarns, such as hand knitted yarns are usually skein dyed. Skein dyeing is the most costly yarn-dye method. 3.1.4.2. Package Dyeing

In package dyeing the yarn is wound on a small perforated spool or tube called a package. Many spools fit into the dyeing machine in which the flow of the dye bath alternates from the center to the outside, and then from the outside to the center of the package. Package dyed yarns do not retain the softness and loftiness that skein-dyed yarns do. They are however satisfactory and very widely used for most types of yarns that are found in knitted and woven fabrics. 3.1.4.3. Warp Beam Dyeing

Beam dyeing is the much larger version of package dyeing. An entire warp beam is wound on to a perforated cylinder, which is then placed in the beam dyeing machine, where the flow of the dye bath alternate as in the package dyeing. Beam dyeing is more economical than skein or package dyeing, but it is only used in the manufacture of woven fabrics where an entire warp beam is dyed. Knitted fabrics, which are mostly produced from the cones of the yarn, are not adaptable to beam dyeing. 3.1.5. Piece Dyeing

The dyeing of cloth after it is being woven or knitted is known as piece dyeing. It is the most common method of dyeing used. The various methods used for this type of  dyeing include jet dyeing. Jig dyeing, pad dyeing and beam dyeing. Dyes, Theory of Dyeing, Classification of Dyes and its application

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3.1.6. Garment Dyeing

Garment dyeing is the dyeing of the completed garments. The types of apparel that can be dyed are mostly non-tailored and simpler forms, such as sweaters, sweatshirts, T-shirts, hosiery, and pantyhose. The effect on sizing, thread, zippers, trims and snaps must be considered. Tailored items, such as suits or dresses, cannot be dyed as garments because the difference in shrinkage of the various components and linings disort and misshape the article. Garment dyeing is done by placing a suitable number of garments (usually about 24 sweaters or the equivalent, depending on the weight) into large nylon net bag. The garments are loosely packed. From 10 to 50 of the bags are placed in large tubs containing the dye bath and kept agitated by a motor  – driven paddle in the dye tub. The machine is appropriately called a paddle dryer. 3.2. Comparison of Dyeing in various stages.

Stage of  Dyeing

Features and Advantages

Limitations and Disadvantages

Stock Top

Fabrics have soft, heather like coloration. Easiest dye penetration.

Most costly dyeing method. Dyeing long before season begins carries the risk of fashion changing. High percentage of  fibre loss from dyeing and later in yarn spinning Second most costly method. Dyeing before season begins carries the risk of fashion changing, but less than for stock  dyeing Limited to solid colors

and

Yarn

Used for fabrics with stripes, checks, plaids, and other multi colored patterns.

Piece

Least costly stage for dyeing of fabrics. Adaptable to all fabricswoven and knitted. Dyeing is close to fashion seasons; minimal color risk  Choice of colors closest to fashion season. Elimination of material (yarn and fabric) waste from prior processing.

Garment

Limited to garments of simple construction

Dyes, Theory of Dyeing, Classification of Dyes and its application

Typical Dyed Fabrics Chevoit covert molten tweed.

Chambray gingham brocade  jacquard knits Batiste broadcloth challis corduroy satin.

Hosiery panty hose sweaters tshirts.

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3.3. Special Dyeing Effects

Piece dyeing, as described previously, primarily produces a solid color throughout the goods being dyed. It is possible, however, to create effects such as multi-colours or multishades by any yarn-dye or piece-dye method. 3.3.1. Cross Dyeing

Cross dyeing is a type of dyeing in which a yarn, a fabric, or even a garment made with two or more genetic fibres types having different dye affinities is dyed in a single bath containing two different class of dyes. Each class of dye colors only one type of the fibre. Two different colors can be dyed in one bath or either type of fibre may be dyed, leaving the other one white. If different fibres are blended in the same yarn, a stock-dyed effect can be obtained. If yarns of one kind of fibre and yarns of another kind of fibres are used in the warp direction, vertical stripes can be produced after dyeing. A plaid effect can be produced by weaving yarns of different kinds of fibre both in warp and filling directions and then dyeing the fabric in single bath with a mixture of two kinds of dyes. Whereas certain fibre combination allow for one bath process, other fibre combinations may require a two – step dyeing process to produce two colours. Cross dyeing is the more economical and quicker way to produce the same effects obtained by other methods. The effects achieved by expensive stock dyeing method can be replicated easily by this cross dyeing method. 3.3.2. Union Dyeing

Union dyeing is same as like cross dyeing, except that instead of multi color effects, one solid color is produced. The dyer accomplishes this by using two or more classes of dye, each of the same color. For example, a fabric composed of rayon and acetate can be dyed by a solid green color by using a direct dye for rayon and disperse dye for acetate. 3.3.3. Tone – on Tone Effects

Tone on tone effect is also possible by using one dye bath. They are light and dark  shades of the same color in a fabric containing only one generic fibre  – for example, deep red and light red colors on the same piece dyed polyester fabric. The effect can be produced by combining two different types of polyester in the same fabric. Both types are capable of combining with the same dye class, but one fibre has strong affinity for dye than the other. The fibre with the stronger affinity combines with greater quantity of dye, becoming deeper in shade, and second fibre remains a lighter shade of the same color. Tone on tone effects can only be achieved with the specific varieties of nylon, polyester and acrylic fibres. These special properties are imparted during the manufacture Dyes, Theory of Dyeing, Classification of Dyes and its application

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of the fibre, and the fibres are marketed to textile producers as deep  – dye types. In addition nylon is produced in both deep-dye and ultra-deep-dye varieties, thus providing the possibility for three-tone effects of the same color. The tone on tone effects is widely used in the carpet industry for producing tweed-effect designs on piece dyed carpeting. 3.4. Applications of Dyes on the textile materials

Let us discuss the application of following dyes in the textile materials Direct Dyes Azoic Dyes Reactive Dyes Vat Dye Acid Dyes Basic Dyes Sulphur Dyes Disperse Dyes 3.5. Direct Dyes

These colors are known as substantive dyes or Salt dyestuffs or even simply cotton colors. The colors are well known for its use in dyeing cellulose fibres like cotton, viscose rayon, animal fibres such as wool and silk. Selected substantive dyes can be used to give solid shades on wool and cotton mixtures. Direct dyes are also called Substantive dyes because of their excellent substantively for cellulose textile materials like cotton and viscose rayon. This class of dyes derives its name from its property of having direct affinity for cellulosic fibres when applied from an aqueous solution. 3.5.1. Properties of Direct Dyes

1. Direct dyes are readily soluble in water. 2. Some of the dyes need a little amount of soda ash (Sodium Carbonate) for complete dissolve them in water. 3. Direct dyes are used for dyeing cotton, viscose rayon, wool and silk fibres. 4. If common salt or Glauber‟s salt (Sodium sulphate) is added to the dye during dyeing, more dye is taken up by the fiber i.e. the dye bath gets exhausted to a greater extent. Hence these salts are exhausting agents for direct while dyeing or cotton. 5. Direct dyes have poor washing fastness and poor light fastness. These fastness properties can be improved by certain after-treatments. If a piece of cotton dyed with a direct dye is boiled with soap and water which contains also a small piece of un-dyed cotton, the latter generally becomes stained with the dye from former. This is known as bleeding.

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6. All direct dyestuffs combine with basic dyes to give compounds which are less soluble that the original direct dyes. The process of dyeing the direct dye on cotton with basic color is known as topping. 3.5.2. Application of Direct Dyes to Cotton/Viscose

The dye bath is usually made up with twenty items as much water as the material. Take for example, for 100 kilograms of cotton fabric 2,000 liters of water can be taken. For dyeing only soft water should be used. From 0.5 to 5% of the dyestuff according to the shade required to be taken. The dyestuff is pasted with cold water and sufficient boiling water is then added, with constant stirring to bring it into solution. It is then added to the dye liquor through a strainer. Some direct dyestuffs give better results in a slightly alkaline bath. In fact it is advantageous in most cases, since it renders the dyestuff more completely soluble in the dye bath. From 0.5 to 2% of Sodium carbonate may be used. The cotton material is wetted out in water and entered into the dye bath at 41ºC to 50 ºC and the liquid is raised to the boil over a period of 30 to 40 minutes and then common salt or Glauber‟s salt is added to the dye bath for the complete exhaustion of the dye bath. These salts are exhausting agents for direct dyes while dyeing on cotton. The dyeing is continued at the boil for ¾ to 1 hour. At the end of the dyeing the material is rinsed in cold water and dried without soaping. Direct dyes have poor washing fastness and poor light fastness. However, these fastness properties can be improved by certain after treatments. 3.5.3. After Treatments

A dye fixing treatment may give in a fresh bath containing a cationic dye-fixing agent before drying; this process improves the wet fastness of the dyed goods. Fastness properties of Direct dyed goods - Both washing and light fastness of  most of the direct dyed goods are generally poor; to improve the fastness properties after  – treatments may be given improve the fastness 3.6. Azoic Dyes

Azoic dyes are so called because their molecules contain azo group. (N=N) Azoic dyes are also called naphtha dyes or developed colors. The fibres most readily colored with azoic dyes are the man-made and natural cellulose fibres, e.g. Viscose, Cotton etc.

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3.6.1. Dyeing Cotton with Azoic Dyes

Coloring of textile materials with azoic dyes involved the reaction within the fibre polymer system of the two components, which constitute the azoic dye. These two components are the naphtha or coupling component, and the base or di-azo components. The application of azoic colors involved two steps  –  naptholation (dyeing with naphtha) and development (coupling of diazotized base with naphtha). The Application of Azoic colors involves the following steps. Preparation of Naphtha solution. Dyeing of cotton yarn with Naphtha solution. Preparation of Diazotized base solution. After treatment of the dyed cotton material. 3.6.1.1. Preparation of Naphthol Solution

  Naphtha‟s are insoluble in water. They can be dissolved in water by coveting them into sodium compounds which are soluble in water. For this caustic soda i.e. sodium hydroxide (NaoH) is used. The Naphtha is pasted with its own weight of turkey  – red oil and little hot water avoiding any lump formation. The required amount of boiling water is then added to the paste, followed by the required amount sodium hydroxide (NaoH) solution is added. The mixture is boiled till a clear solution is obtained. Cool the solution to 50ºC by adding about some quantity of cold water. 3.6.1.2. Dyeing of Cotton with Naphthol Solution

The well scoured wet yarn is entered in the cold Naphtha bath are kept turned for several times. In some cases the addition of common salt or Glauber‟s salt increases the absorption of the naphtha solution. The impregnated material must not be touched with wet hand or exposed to direct sunlight or brought into contact with metals. In most cases the amount of Naphtha which is absorbed decreases as temperature raises and the operation is therefore carried out at 25º - 30ºC for 20  – 30 minutes. After impregnation the goods should be hydro extracted or squeezed thoroughly, to avoid carrying over retained liquor into the coupling bath where it would cause surface deposition of the pigment cause the poor rubbing fastness. The sodium salts of the coupling components are usually somewhat unstable towards exposure to air, especially when in a wet state. If the impregnated goods lie about for any period the decomposition will not occur uniformly and the final result will be patchy. Therefore the naphthalene material should be developed without any delay.

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3.6.1.3. Preparation of Diazotized Base Solution

1) The base is insoluble in water. It should be converted into water soluble salt (hydro chloride of the base) using concentrated hydrochloric acid. 2) The reaction of hydro chloride of the base with Nitrous acid usually at low temperatures (Oº - 5ºc) for 20 – 30 minutes is called the Diazotization of the Base. This is carried out by adding Sodium Nitrite to a solution of hydro chloride of the base in the presence of excess of HCL.acid. Now the base is converted into diazonium chloride (diazotized Base). The base is pasted with a little amount of con. Hcl. Acid and a few drops of cold water the mixture is then added cold water to dissolve the paste. The mixture is stirred till a clear solution obtained. In some cases the mixture is to be heated or even boiled complete conversion of Base into salt. The solution is cooled to 18º - 20 ºC by adding Crushed ice directly into the solution when the required temperature is obtained the predissolved sodium Nitrite is added with constant stirring. Allow the solution for 20  – 30 minutes for the reaction to go to completion. Now the diazonium chloride which is generally highly soluble in water is formed and a very clear solution is obtained. Now the pH of the solution is too low. The reaction between diazonium chloride and Naphtha (Coupling or developing) takes place quickly over the pH range of 5 to 6. The pH of the solution is therefore raised by adding Sodium acetate. Sodium acetate converts the free Hcl. Acid into acetic acid, after which the pH of the solution become in the range of 5  –  6. Coupling will also be retarded if the liquor becomes alkaline, too high a pH and this can occur easily on account of sodium hydroxide (NaoH) which may be left in the cotton after it has been impregnated with Naphtha solution. Excess of alkali can be neutralized by adding acetic acid or sodium bicarbonate or Aluminum Sulphate. The developing both should be maintained the pH of 5  – 6 and temperature should be kept below 20ºC in the above manner. Now the base solution is ready for dyeing. 3.6.1.4. Dyeing of Naphthalene material with the Base Solution

The naphthalene material is entered the diazotized Base solution. It is turned several times and kept for 20  –  30 minutes. This is called coupling (Or) developing process. During coupling the Azoic color is formed on the cotton material. Through the coupling process the pH should maintain 5-6 and temperature should below 20 ºC. 3.6.1.5. After treatment

After the dyeing the dyed material are rinsed in the cold water bath to which a little Hcl acid is preferably added and are then treated in a soaping bath at boil for 30 minutes to remove the loosely combined dye stuffs.

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3.6.2. Dyeing of Viscose Rayon with Azoic Dyes

Azoic colors have a much greater affinity for Viscose rayon than for cotton. The method of application is as follow, Preparation of Naphtha solution Dyeing of Viscose rayon with Naphtha solution. Preparation of diazotized Base solution Dyeing of Naphthalene mat. In the Base solution. After treatment of Azoic Dyed Viscose Rayon mat. Note: The procedure for dyeing viscose rayon with azoic dyes is the same as that of  cotton. 3.6.3. Properties of Azoic Dyes

1. It is insoluble in water. 2. It is not a readymade dye but is formed in the fibre substance by the dyer from Components usually referred to as Naphtha and Base. 3. The dyed and printed azoic colors have very good to excellent light fastness. 4. The dyed azoic colors have good washing fastness. 5. Textile materials dyed with azoic dyes suffer from poor Rubbing  – fastness. This occurs because of the formation of the insoluble azoic dye on the surface of the fibre which is not removed during the final stage of dyeing, which is not removed during the final stage of dyeing. This rinsing stage is referred to as Soaping  – off  and involves a through treatment of the dyed textile material with a detergent. If  all stages of azoic dyeing are carefully controlled and followed by thorough soaping – off, poor rub-fastness is unlikely to occur.

3.7. Reactive Dyes

Reactive dyes are so called because their molecules react chemically with the fire polymers of some fibres to form a covalent bond between the dye molecule and fibre polymer. The fibres most readily colored with reactive dyes are cellulose fibres, wool, silk  and nylon. Reactive dyes are also called as Procion dyes When direct dyestuff is applied to cotton and to viscose rayon the process is one of Physical absorption there is no covalent union between dye and fibres. DH Direct dye

+

H O – cell cellulose

Dyes, Theory of Dyeing, Classification of Dyes and its application

DH……..HO – Cell dyed (not reactively) Cellulose

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Direct dye, DH, applied to cellulose, there is no chemical reaction and no covalent union, there is, as indicated by the dotted bond, hydrogen bonding and attachment thorough Vander walls forces. The nature of the union between bye and fibre, commonly referred to absorption, may be difficult to analyze precisely; it may have been mechanical, physical or chemical sorption, hydrogen bonding ands so no, but it was certainly not covalent bond. Drcl

+

Reactive Dye

HO - cell Cellulose

DH

O cell + HCl

reactively (covalently) Dyed cellulose

With the old direct dye DH we obtained dyed rayon DH …..HO-cell. With the reactive dye DRcl we have obtained reactively dyed rayon Dr  – O cell. All that we have gained is covalent union (i.e. Chemical combination) between dye and fibre. As a result of this, fastness to washing and wet processing generally should be much better and so in reactively dyed cellulose DR-O Cell, the dye is part of the fibre; it is impossible to wash it out or to extract it even with such powerful agents as aqueous pyridine. The porcine dyes, on account of the sulphonic acid groups in their molecules, are readily soluble in water. In neutral solution, they have substantively towards cellulose similar to that of very low affinity direct dyes, a wet-fastness of a low order, and they exhaust better in the presence of an electrolyte (salt). In the neutral solution physical adsorption and possibly some hydrogen bonding take place, but there is no formation of  covalent bonds until alkali has been added. The application of reactive dyes to cotton materials involves two distinct steps 1) Dyeing with the dye in the presence of common salt to effect as much exhaustion as possible and 2) Chemically reaching the dye with the fibre (fixation) in the presence of an alkali like soda ash. In the first stage of dyeing, the reactive dye resembles like direct dyes in that its exhaustion can be brought about by adding common salt or Glauber‟s salt. However, it has much lower affinity to cotton than direct d yes. During the second stage of application (fixation) the alkali is added to the dye bath, when the dye reacts with the fibres, however the dye also reacts with water (only after the addition of alkali) and when this rakes place, the dye gets deactivated (hydrolyzed) and then it cannot react with the cotton fibre. In the dyeing and fixing of  reactive dyes, 5 to 30% of the dye used for dyeing and the remaining is deactivated and hence this is a waste. The deactivated dye has some affinity for cotton and hence is absorbed and retained by cotton. Because of the lower affinity of the deactivated dye (compared to direct dyes on cotton) the washing fastness of this form of the dye present, on cotton is very poor and hence it gets washed out progressively during the washing of  the garments made from such fabrics. Therefore, as part of the dyeing process the fabrics Dyes, Theory of Dyeing, Classification of Dyes and its application

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are boiled with a soap solution after the fixation step, when most of the deactivated dye is removed from the dyed fabric. The other form of the dye present in the fibre in a chemically reacted form is not removed during the soaping step, since it is firmly bound to the fibre by a covalent bond. 3.7.1. Cold Brand & Hot Brand Reactive Dyes

The reactivity of these dyes is due to the chlorine atoms attached to the triazine ring. When two chlorine atoms are present in the dye molecule are called Dichloride Procions. Dichloride procions are referred to as M-type procions and their characteristic is that they will combine with alkaline cellulose at room temperature (20ºC to 30ºC) and hence they are called cold brand reactive dyes when only one chlorine atom is present in the dyestuff molecule, the reactivity of the dye decreases considerably and the dyeing has to be carried out at a higher temperature (65ºC to 80ºC). Hence these dyes are called hot   brand reactive dyes. Mono chloride procions are referred to as „H‟ type procions.  Normally „M‟ Brands are suitable for dyeing and H brands are suitable for printing. The instability of the solutions of the cold-dyeing procion colors was a serious disadvantage in their application to textile printing. The stock solution for printing must be kept and used for several hours. The reactive dyes having only one chlorine atom in their molecule are less reactive. Their aqueous, therefore, are more stable and very suitable for printing. 3.7.2. Types of Reactive Dyes

1. 2. 3. 4. 5. 6.

Cold brand reactive dye Hot brand reactive dye High exhaust reactive dye High exhaust reactive dye Vinyl Sulphone reactive dye Low salt reactive dye

-

„M‟ brand „H‟ brand (or „X‟ brand) „HE‟ brand „ME‟ brand for dyeing and printing LS dyes

3.7.3. Properties of Reactive Dyes

1. The Procion dyes, on account of the sulphuric acid groups in their molecule, are readily soluble in water. 2. These dyes, unlike any other class of dye stuffs, react and combine chemically (covalently) with cellulose and this leading to excellent wash-fastness. 3. These dyes give very bright shades such as orange, pink, magenta etc, which were not possible with other class of dyes. 4. They do not react with water nearly as readily as with cellulosic hydroxyl in alkaline conditions, so that they can be applied from an aqueous solution. 5. Reactivity of the dyestuffs can be reduced when desirable by blocking one of the reactive chlorine atoms giving H-type Procions. Dyes, Theory of Dyeing, Classification of Dyes and its application

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6. Procion dyes are dyes with small molecules; their molecules do not have to be very long as those of direct dyes to match the distance between absorption sites on the fibre. Short molecules bring two advantages (a) Clarity and brightness of hue and (b) easy penetration and therefore good leveling. 7. Because there is some, even although not very much reaction between procion dyestuffs and water it is very important to wash the dyes fibre thoroughly clean and free from the reaction product with water. 8. Textile materials colored with reactive dyes have very good light fastness. 9. Textile materials colored with reactive dyed has very good wash-fastness. 10. Textile materials which are colored with reactive dyes have to be thoroughly rinsed and scoured. Reactive dyes can react with the hydroxyl groups of the water molecule to produce dye molecules to produce dye molecules with poor substantively for the fiber. In fact it is these molecules which have to be removed by a washing-off process, involving soaping and rinsing. If these molecules of dye are not removed, poor rub-fastness may result. 11. The formation of the covalent bond between dye and fiber occurs under alkaline conditions. The presence of acids may reverse this process. Perspiration and atmospheric pollution which are both slightly acid may affect textile materials colored with reactive dyes and result in some fading. 3.7.4. Application of Cold Brand Reactive Dyes on Cotton

(Dichlorotriazinyl Reactive dyes (or) Procion  – M brand) 3.7.4.1. Preparation of Dye Solution

The dyestuff is dissolved by making them into paste with cold water, followed by dilution with more water, the temperature of which must not exceed 50ºC, A stock  solution will not remain stable for more than about 4 hours, after which it will begin to lose strength due to hydrolysis. 3.7.4.2. Dyeing

The goods are loaded into the machine and 30 and 60 parts per 1000 of common salt are added, the quantity varying according to the depth of the shade. The liquor is then raised to the required temperature either 40ºC or 60ºC and the pre dissolved dye is added in the machine is then allowed to run for 20 to 30 minutes and the necessary amount of  Soda ash is added over a period of 10 to 30 minutes. Dyeing is continued for further 20 to 40 minutes after which the goods are rinsed to remove the salt and the alkali, and they are then washed off at the boil for 15 to 30 minutes to extract any of the products of hydrolyzed dye.

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Considerable importance must be attached to the final washing of goods dyed with procion colors. The exhaustion is often not good and much dyestuff will be in retained in the liquor, but of greater significance is the fact that cellulose has some affinity for the hydrolyzed dye which is having lost its chlorine atoms, has not entered into chemical combination. The load is first rinsed thoroughly in as great a volume of  cold water as the machine permits. The goods should then be rinsed in hot water nearly at the boil, after which they are soured at the boil, for 15 to 30 minutes with a synthetic detergent or soap and finally rinsed, first in hot and then in cold water . 3.7.5. APPLICATION OF HOT BRAND DYES ON COTTON

(MONOCHLOROTRIAZINYL, REACTIVE DYES (OR) PROCION + H brand) The mono chlorotriazinyl dyes or hot brand reactive dyes are less reactive. Their aqueous solutions are more stable but they do not react with cellulose so readily and the temperature of dyeing must be increased to 60ºC to 70ºC and in some cases, as high as 90ºC to 95ºC. The dyestuffs are dissolved by making them into a paste with cold water, followed by dilution with more water. The dye bath is made by dissolving sufficient common salt to give a concentration of 40 to 80 parts per 1000 according to the depth of the shade, the goods already having been entered. The temperature is brought up to 40ºC and the machine is run for five to ten minutes in order that the fabric can be uniformly impregnated. The pre dissolved dye is then added in two portions at five minute intervals followed by the alkali which should be 20 parts per 1000 of soda ash. The alkali should be added in two portions at five minute intervals and the temperature then raised to between 60 to 90ºC according to that which is recommended for the dye selected. Dyeing is continued for a period of 20 to 40 minutes and then continued for 30 to 60 minutes when soda ash (alkali) is used. After dyeing, the materials must be rinsed and soap boiled to remove hydrolyzed and unfixed dye. 3.7.5.1. After treatment

Treat the dyed material with 1 to 2 g/l of neutral soap at boil for 15 minutes and wash it. Treat the soaped material with 2 to 3 g/l of cationic dye fixing agent at 40ºC for 20 to 30 minutes and dry it.

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3.8. Vat Dyes

The name Vat was derived from the large wooden vessel from which the Vat dyes were first applied. Vat dyes provide textile materials with the best color fastness of all the dyes in common use. The fiber most readily colored with Vat dyes are the natural and man made cellulose fibres of cotton, viscose rayon. 3.8.1. Properties of Vat Dyes

1. Vat dyes are insoluble in water and hence cannot be used directly for dyeing but when treated with the reducing agent, they leuco compounds are soluble in alkaline solutions in which cotton and other textile fibres have a considerable affinity on them. When cotton containing these, is exposed to air, the leuco compounds are oxidized and the insoluble coloring matters are produced on the fibres. 2. Vat dyes fabrics have excellent light fastness. 3. Vat dyes fabrics have excellent washing fastness. This is attributed to the large vat dye molecule as well as its aqueous insolubility. The large vat dye molecules is trapped with the polymer system of the fibre, because of its size and aqueous insolubility and is absorbed with in the fibre polymer system by Vander wail‟s forces. 4. Vat dyes have always been very expensive compares with other dye classes. 5. Vat dyes are mainly used for coloring of cellulose fibres, but these dyes dyed at low temperature and with small amount of alkali for dyeing wool and silk. Vat dyes being insoluble in water cannot be directly applied to textile materials. They have to be converted into water soluble form having affinity for textile fibres such as cellulose fibres. This conversion is usually brought about in two steps: 1. Reduction of the dye into the weakly acidic leuco vat form and 2. Salt formation by neutralizing these acidic leuco vat dyes by sodium hydroxide to give a water-soluble product. Since the second the step results in the formation of water-soluble sodium salt of  leuco vat dye, it may be called as the solubilizing step. Reduction followed by solubilizing is called the vatting of the dye. For this   purpose sodium hydrosulphite, (Na2S2O4) (Usually called “hydrous”) is used as the reducing agent and sodium hydroxide (NaOH) as the solubilizing (Neutralizing) agent.

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The different steps involve in the vatting of the dye are shown below: Vat dye, Insoluble in water and soluble in caustic soda solution (Na2S2O4

Reducing

Reduced Vat Dye or Leuco vat Dye. Also called Vat acid which is insoluble in Water, but Soluble in NAOH solution

Solubilizing (NaoH)

Sodium salt of the Leuco dye. Soluble in water

3.8.2. Classification of VAT dyes

Vat dyes are classified based on chemical constitution of the dyes or based on the method of application.  Based on the chemical constitution, vat dyes are divided into two main classes

(1) Indigoid vat dye. & (2) Anthraquinone vat dye. 3.8.2.1. Indigoid Vat Dye

The indigoids are usually derivatives of indigo tin. The indigoids include natural and synthetic Indigo and substituted Indigoes. These are characterized by forming pale yellow leuco compounds which dissolve in week solutions of sodium hydroxide (NaoH). The leuco compounds are oxidized readily when exposed to air. They are used in neural or slightly alkaline bath and are suitable both for animal and vegetables fibres. These Indigoid colors sublime when heated and are soluble in boiling pyridine. 3.8.2.2. Anthraquinone Vat Dyes

The Anthraquinone vat dyes are derived basically from Anthraquinone. The Anthraquinone vat dyes give colored leuco compounds which are soluble only in Strong alkaline solution and therefore not suitable for animal fibres or protein fibres. The dyestuffs do not (with few exceptions) sublime when heated and are often insoluble in boiling pyridine.

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3.8.3. Principles of application of Vat Dyes

Generally, the application of vat dyes to textile materials involves four distinct steps. a)

Vatting in which the insoluble commercial dye is reduced and solidities (vatted) by using Sodium hydrosulphite (hydrose) and sodium hydroxide (NaoH).

b)  Dyeing, in which the soluble sodium salt of the leuco vat dye is absorbed by the textile material from an alkaline reducing medium in the presence of either a retarding agent or an exhausting agent depending on the rate of dyeing. c)

Oxidation, in which the soluble form of the dye absorbed by the fibre, is reconverted into the original insoluble dye by atmospheric oxygen (Airing) or by the use of  “chemical oxidation.” (i.e. involving the use of a chemical like sodium per borate or potassium dichromate or Hydrogen per oxide).

d)   After treatment, Soaping  –  off , in which the dyed material is subjected to a treatment either boiling soap or other detergent solution in order to get the proper tone by way of aggregation of smaller dye particles into bigger ones and also to get the optimum fastness, especially rubbing fastness by removing the surface deposited dye particles. 3.8.4. Application of Vat Dyes on Cotton 3.8.4.1. Preparation of leuco Vat dye solution

The Vat dyestuff powder is taken in a separate vessel and made into a paste with Turkey red oil (the some weight of dyestuff to be taken) and add some hot water (50º 60ºC). The caustic soda is first added and then sodium hydro sulphate is added, and allows standing for 10-20 minutes with occasional stirring, the complete vatting taking place. In above 10-20 minutes the dyestuff will be reduced completely and going to solution. This can be seen by the clearness of the solution and characteristics of the vat color. The vatting stage temporarily alters the original color of the dye (Reduced color). 3.8.4.2. Dyeing

The required water for dyeing is taken in the dye bath and it is maintain at proper temperature (50º- 60 ºC) the reducing and dyeing temperatures vary from dyestuffs to dyestuff. The vatted dye solution may than be added to the dye bath containing the required amount of caustic soda sodium hydro sulphate, kept at recommended temperature. Dyes, Theory of Dyeing, Classification of Dyes and its application

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The well scoured wet yarn is entered in the dye bath and turned several times, so that the affinity of the color may be uniform. The yarn is then kept completely immersed under the dye liquor and the dyeing is continued for one hour. The yarn is turned from time to time… Care should be taken to keep the bath at required temperature and also to keep the yarn thoroughly immersed under the liquor. The exhaustion agents or retarding agents are added to the dye bath depending upon the dyestuffs taken, during the entire dyeing period. Excess quantities of both sodium hydroxide (NaoH) and sodium hydro sulphate (Na 2s2O4) should be present in the dye bath in order to keep the dye in the soluble form. At the end of the dyeing the partly or completely exhausted dye bath must be kept in a distinctly reduced condition; otherwise oxidation of the residual vatted dye takes place in the dye bath itself leading to the appearance of turbidity. This is ensured by adding sufficient sodium hydro sulphate. The dyed goods may then be removed from the dye bath and excess liquor which contains the unexhausted vat dye, sodium hydroxide, sodium hydro sulphate is removed as for as possible from the goods. The dyed goods are rinsed with cold water and then subjected to an oxidation treatment  by exposure to atmospheric oxygen. This is called “air oxidation” or “airing” but the oxidation may be accelerated by using stronger oxidizing agent such as sodium per borate or hydrogen peroxide or sodium dichromate in the presence of acetic acid. This process is usually referred to as chemical oxidation. During the oxidation step the sodium salt of leuco vat dye absorbed by the fibre is oxidized and converted into insoluble dye in the fibre. At the same time the vatted dye contained in the residual liquor in the goods being dyed also gets converted into the insoluble form which is loosely deposited on the fibre surface. This loosely deposited dye on the surface of the fiber has to be removed for achieving optimum fastness properties especially rubbing and washing fastness properties. This is achieved by soaping process. The dyed material is treated in hot soap solution or a synthetic detergent solution for 15  –  30 minutes. After the soaping treatment the dyed goods should be rinsed thoroughly and finally the dyed material is dried. Important manufacturers of vat dyes in India are Indian Dyestuff Industries (I.D.I) and ATIC Industries which market them under the trade names of  NAVINON and NOVATIC respectively.

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3.8.5. SOLUBILISED VAT DYES (INDIGOSOLS)

It is realized that the vatting process requires great care. To simplify the application, solubilized vat dyes were developed. Solubilized forms of Vat dyes are the leuco ester part of the dye molecule that is responsible for the aqueous solubility of vat dyes. This has made vat dyes easier to handle and results in more level dyeing. 3.8.5.1. Properties of Solubilized Vat Dyes:

1. Soluble in Water, 2. Vatting operation is not necessary and hence can be applied directly in the bath. 3. Solubilised vat dye have less affinity for the fibres and they exhausted by addition of salt. 4. Suitable for light and medium depths. 5. Because of their low affinity, they are usually applied by padding process, followed by a developing bath (an oxidizing treatment). 6. Indigo sols process a good coverage and leveling properties. Soluble vat dyes are mainly applied to viscose rayon, cotton, wool, and silk  fabrics. The solubilized leuco compounds are known as the Indigo sols. Another range called the Solidness is prepared mainly from anothroquine vat dyes. Their application is comparatively simple. Cellulosic fibres are dyed in neutral dye liquor and slightly acid baths are used for protein fibres. They exhaust well at 20º to 40ºC although there are some requiring temperatures ranging from 60º to 80ºC. Their affinity for cellulose is not great and high percentages of electoral are often necessary and for this reason they have only found favor in dyeing pale shades where color cost is not so important. The general method of application is to dissolve the dye in hot but not boiling water and added it to the dye liquor through a strainer, together with the required amount of electrolyte. The goods are entered and the temperature is raised to that at which maximum affinity is developed, which varies from one dye to another. The goods are dyed at the appropriate for a period of 30 minutes.

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3.9. Acid Dyes

The Acid dye stuff is so called mainly due to two reasons. In the first place these classes of dyestuff were applied in a bath containing mineral or organic acids like sulphuric, acetic or formic acid and secondly most of them are sodium salts of organics acids. 3.9.1. Properties of Acid Dyes:

1. Acid dyestuff is soluble in water. 2. These dyes are easily applied on wool, silk and nylon fibres, 3. These dyes are generally applied in the presence of acids like sulphuric, acetic or formic acid. 4. They are in much case soluble in alcohol. 5. When acid dyestuffs are treated with a reducing agent they are generally decolorized. 6. They are usually combined with basic dyes. 7. The dyed acid colors have good light fastness and moderate washing fastness. And leveling characteristics:

3.9.2. Classification of Acid Dyes

Acid dyes are divided into three Groups according to the leveling characteristics 3.9.2.1. Acid dyes with Good leveling characteristics

This type of acid dye is responsible for their good leveling characteristics. As the dye molecules have less attraction for the fibre they will migrate only slowly into the polymer systems of wool or nylon fibres. However to obtain sufficient substantive and to ensure, adequate exhausting agent (sulphuric acid) is added to the dye liquor, their lack of  substantive is evidence by their poor wash fastness. However the light fastness is very good to excellent. 3.9.2.2. Acid dyes with average leveling characteristics

The moderate substantive of this type of acid dye is responsible for average leveling characteristics. To obtain sufficient substantive and to and ensure it, adequate exhausting agent, a week acid (Acetic acid or Formic acid) is added to the dye both. The washing fastness of these dyes is fair, whilst their light  – fastness is good to very good. 3.9.2.3. Acid dyes with poor leveling characteristics

These dyes are also known as fast acid dyes, and milling dyes or Natural dyeing acid dyeing acid dyes. They have the best substantive of all the acid dyes, but have Dyes, Theory of Dyeing, Classification of Dyes and its application

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relatively poor leveling characteristics. Unless care is taken during, their relatively good substantive for the fibre may result in too rapid uptake and consequently unleveled dyeing The excellent substantive of these dyes require neutral bath in order to obtain slower exhaustion and more level dyeing. The wash fastnesses of these dyes are good to very good, while their light fastness is fair to good. The better wash-fastness, compared with the other two type of acid dyes, is due to the greater number of sodium sulphate groups. 3.9.3. Application of acid dyes on wool:

The application of acid dyes to protein fibers results in an ionic or salt link  between the dye molecule and the fibre polymer. The point of the fibre polymer at which the dye is attached is termed the dye site. In wool, the dye sites are of many amino group of the fibre. Under dyeing conditions, the amino group becomes positively charged and attracts the negatively charged dye anion. There are a large number of amino groups are present in the wool fibre. As a guide, there are approximately twenty times as many amino groups on wool as on nylon and five times as many amino groups on wool as on silk. Dark shades can be readily be obtained on wool because of the highly amorphous nature of the fibre, which results in relatively easy penetration of the fibre polymer by the dye molecule and because of the presence of minor groups. 3.9.3.1. Preparation of dye solution

The acid dyes are easy to dissolve, but care is necessary to avoid the possibility of a dissolved particular becoming deposited on the goods. The requisite amount of dyestuff is made into a smooth paste, preferably with a small amount of an anionic or non ionic wetting agent, and sufficient boiling water is added to dissolve it completely. It is advisable to strain the dye solution before adding it to the dye bath. 3.9.4. Method of dyeing with acid dyes on NYLON

The dyeing properties of acid dyes with regard to nylon and wool are similar. The shades are very similar to the corresponding colors on wool, but the saturation point is lower with nylon. When the pH of the dye solution is 2 or lower, nylon has greatly increased affinity for acid dyes. In practice, dyeing cannot be carried out in the pH region of 2 to 2.5 because the degradation of the nylon would be excessive. Acid dyes requiring strong acid are applied from a dye liquor containing 3 to 5% of formic acid. Sulphuric acid should not be used because it can cause degradation of the Dyes, Theory of Dyeing, Classification of Dyes and its application

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nylon, and the addition of Glauber‟s salt is omitted because it has no beneficial effect. Non-ionic leveling agent, either alone or mixed with cationic products, are used. The goods are entered cold and the dye bath is brought to the boil and dyeing continued at this temperature for ¾ to 1 hour. With these acid dyes exhaustion takes place well with weaker acid, 1 to 3% acetic acid (80%), may be substituted for the formic acid or, alternatively, 1 to 3% of ammonium acetate may be used. The application of acid dyes to nylon also results in ionic bonds or salt links between the dye molecules and the polymer. The point at which the ionic is formed is the terminal amino groups of nylon. The greater crystalline fibre structure of nylon compared with wool as well as the relatively lower number of amino groups means that dark shades on nylon cannot be obtained with acid dyes. 3.9.5. Stripping / leveling uneven Dyeing of Acid Dyes

a) With the molecularly  –  dispersed acid dyes, on account of their good migrating properties, continued boiling in the same liquor is often effective. It must, how ever be borne in mind that wool felts if it so boiled form too long. b) Boiling in fresh liquor with 20% of Glauber‟s salt will strip some of the color, and this can be exhausted again by cautious addition of acid or, preferably, ammonium salt. c) If treatment with Glauber‟s salt is not successful, more of the color can be stripped by boiling with 0.5% ammonia, or in liquor containing 2% pyridine. d) Another method is to boil the unevenly-dyed material with 3 to 5% of a cationic, non-ionic mixture such as Tine gal W or Lyogen SMK. When sufficient color has been removed by any of these compounds the wool is rinsed and redeye.

3.9.6. Application of Acid dyes on silk

Although silk has an affinity for acid dyes the colors tend to be less fast than on wool. Silk will exert its affinity for acid dyes at lower temperature than is the case with wool, and dyeing is usually commenced at 40ºC and the temperature is not allowed to rise above 85ºC. Glauber‟s salt is not suitable for use with silk as it diminishes its luster. Sulfuric acid damages the silk. Acid used should be acetic acid. While using boiled off  liquor the bath must be neutral or only faintly acidic.

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3.10. Basic Dyes

Basic dyes are called so since they are salts of organic bases. Basic dyes are also called cationic dyes because in solution the basic dye molecule ionizes, causing its colored component to become an action of positively charged radical. Basic dyes are used for dyeing wool, silk, and acrylic and mod-acrylic fibres. 3.10.1. Properties of Basic Dyes

1. The outstanding characteristics of the basic are brilliance and intensity of their colors. 2. The bright colors achieved from basic dyes do not usually occur with other dye classes. 3. Many of the basic dyes are sparingly soluble in water. 4. The addition of glacial acetic acid helps to dissolve the basic dye quickly in water. 5. Basic dyes are readily soluble in alcohol or mentholated spirit. 6. The basic dyes are poor fastness to light and vary with regard to washing fastness from poor to moderate. 7. An important property of basic dyes is that they will combine with tannic acid to form an insoluble compound provided mineral acid is absent. 8. The wet fastness of the basic dyes on protein fibres can also be improved by back  tanning. This consists of after treating the dyed material with tannic acid in order to form the insoluble complex thereby reducing the tendency to migrate. 9. The basic dyestuff will combine with direct or sulphur or some acid dyestuffs. So they cannot be used together in the same bath. But basic dyestuffs are used in after treating cotton or other materials dyed with direct colors. Here the direct dyestuff acts as mordant. 10. When treated with a reducing agent most of the basic dyes get converted into their colors less leuco compounds, return to their original color by oxidizing agents or even by exposure to air. 11. Basic dyes can be removed from the material by boiling it with dilute acetic acid or hydrochloric acid. 12. Basic dyes are used for woolen goods when particularly bright shades are required which cannot be obtained with an acid dyes. 13. Basic dyes do not have affinity for cellulosic fibres like cotton. The use of basic dyes on cotton involves the troublesome process of mandating with tannic acid. But, sometimes, bright shades are demanded on cotton which can only be obtained with them. 14. Special cationic dyes are available for dyeing acrylic fibres. 15. Basic dyes are also used for making inks, typewriter ribbons and dyeing leather 3.10.2. Preparation of Dye Solution:

Owing to the relative insolubility special precautions are necessary when dissolving basic dyes. The dyestuff is first made into a paste with about its own weight of  30% acetic acid. Sufficient boiling water is then added with constant stirring to dissolve Dyes, Theory of Dyeing, Classification of Dyes and its application

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the dye. The basic dyes have such a great affinity for wool fibres the presence of a retarding agent is often desirable. The Acetic acid acts as a retarding agent. The excess of hydrogen ions in the liquor counter acts the attracting of the electro negative sites in the fibre and slows down the rate of absorption. When acid has been used, the addition of a small amount alkali may be necessary towards the end of the dyeing to complete exhaustion. 3.10.3. Dyeing:

The dye bath is made up containing 1 to 3 % of 40% acetic on the weight of the wool, the dye solution, after being strained through a filter is added, and the goods, which have previously been scoured, are entered. The dye bath temperature is slowly raised to the boil and dyeing is continued for ½ to ¾ hour. After dyeing the goods are rinsed, hydro-extracted and dried.

3.11. Sulphur Dyes

These dyes are so called because they contain sulphur atoms in their molecules. The fibres most readily colored with sulphur dyes are the natural and man-made cellulosic fibres. (Cotton, Viscose rayon) The Characteristics feature of the dyes of this class is that they all contain sulphur linkages within their molecules. They are usually insoluble in water but dissolve in a solution of sodium sulphate to which sodium carbonate may or may not be added. The sodium sulphate acts a reducing agent severing the sulphur linkage and breaking down the molecules into simpler components which are soluble in water and substantive towards cellulose. 3.11.1. General Properties of Sulphur Dyes

The sulphur dyes are cheap and easy to apply. Their wet fastness is good and the light-fastness-satisfactory. They therefore provide a cheap method of dyeing cellulosic fibres with a wet-fastness better than the direct dyes. The sulphur dyes have poor fastness to chlorine and are no use for effect in merchandise which must be bleached with hypochlorite, but they will withstand the conditions in an acid dye bath and can be incorporated in woolen goods intended for subsequent dyeing, as will be referred to latter, however, the after-treatments which improve the fastness of these dyes. In their reduced state, their dyeing properties resemble in any respects those of the direct dyes. They exhaust better in the presence of electrolytes and vary considerably with regard to the temperature at which maximum exhaustion takes place. They are decomposed with acids usually with the liberation of hydrogen sulphate and the Dyes, Theory of Dyeing, Classification of Dyes and its application

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precipitation of insoluble decomposition products. On exposure to air or when acted upon by mild oxidizing agents, a part of the sulphur is oxidized to sulphuric acid. The sulphur dyes resemble the vat dyes in that they are insoluble in water but reduce to a soluble form, which readily converts to the accompanied by an alteration of  color. Sodium sulphate is the reducing agent commonly used but in some cases sodium hydro sulphate may be substituted making it possible to dye selected vat and sulphur dyes together.

3.12. Disperse Dyes

These dyes derive their name from the fact that they are insoluble in water and are, for the purpose of dyeing, dispersed in the dye bath by means of dispersing agents. The fibres most readily colored by disperse dyes are the acetate fibres, polyester, acrylic and nylon. 3.12.1. General Properties of Disperse Dyes

1. Generally these dyes are insoluble in water. 2. However they are soluble in hot water to some extent, the solubility increasing with temperature. 3. A feature of disperse dye molecules is their lack of polar groups, evidenced by the insolubility of disperse dyes. 4. Textile materials which have been colored with disperse dyes have a fair to good light-fastness. 5. Textile materials colored with disperse dyes have a moderate to good washfastness. 6. Some of the disperse dyes are, however, sensitive to nitrogenous fumes, such as may arise from gas, electric or other fibres, suffering serious discoloration, referred to as gas-fading. 7. Disperse dyes have the ability to undergo sublimation: i.e. they can be vaporized without a significant change in their color, i.e. light-fastness or wash-fastness. 3.12.2. Dyeing with Disperse Dyes

Disperse dyes are applied from an aqueous dispersion, not form solution, and which, having a greater affinity for the organic fibre than for the water of the dye bath, eventually migrate to the fibre and form a solid solution in it. The application of heat to the dye liquor increase the energy of the dye molecules and accelerate the dyeing of the textile fibre. Heating the dye liquor swells the fibre to some extent and assists the dye to penetrate the fibre polymer system resulting in the dye being located in the amorphous Dyes, Theory of Dyeing, Classification of Dyes and its application

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regions of the fibre. Once within the fibre polymer system, the dye molecules are held by hydrogen bonds and Vander walls forces. Polyester fibres are extremely crystalline and hydrophobic, lack of reactive groups and much more closely packed polymer chains and there are no gaps which molecule are very close to change their position to suitably accommodate they dyestuff  molecule, and further more the chain molecules are very reluctant to change their positions i.e. to close their orientation. This result, the dyestuff particles do not penetrate to the fibre easily and in fact the process is so slow that it takes a matter of days or even weeks to dye a Terelene fibre at a dyeing temperate of 85ºC. It is difficult to obtain medium or dark shades even by dyeing at the boil. In order to obtain medium to dark shades, polyester fibre is dyed using carries or by using high temperature dyeing techniques.

4.0. INTRODUCTION TO DIFFERENT DYEING MACHINES

There are several dyeing machines used for dyeing of fibre, yarn, fabric and garments. Some of the important of them are (1) Jigger Dyeing Machine (2) Winch Dyeing Machine (3) Jet Dyeing Machine (4) Padding Mangle (5) Package Dyeing Machine (6) High Pressure High Temperature Dyeing Machine. (Beam Dyeing Machine)

4.1. Jigger Dyeing Machine

Jigger dyeing machine is the most commonly used for dyeing all kinds of cotton fabric. There are mainly two types of jigger dyeing machine. One is open jigger dyeing machine and other is closed jigger dyeing machine. The open jigger dyeing machine is shown in the figure. This machine consists of V shaped stainless steel vessel. Two rollers are fitted above the vessel called as cloth rollers. These rollers are rotated by power. Out of these two rollers one roller is driven by a motor which is called take up roller and the other roller from which the cloth is delivered is called let off roller. When all the cloth Dyes, Theory of Dyeing, Classification of Dyes and its application

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is passed from the let off roller to the take up roller, it is called as one end or one turn. The number of ends or turns depends upon the type of the fabric and also the percentage of the shade. Initially, a large length of (50 kg) cloth is wound on the let off roller and take up roller is then driven by the power. After one end is taken, the take up becomes let off roller. These backward and forward movements of cloth through the dye liquor absorb more and more dye. The capacity of the jigger is 100 to 150 gallons. In the modern jigger, automatic devices are fitted along with the timing switch by using reversing will take place automatically. When dyeing all the dye liquor should not be added at one time. The dye liquor should be added in batch wise, in order to get even shade on the cloth. In the present scenario, closed types of jiggers are used. The main advantage is to prevent heat loss and chemical loses by evaporation. This type of jigger is very important for dyeing vat, Sulphur etc.

4.1.1. Advantages of Jigger Dyeing Machine

1. The cloth can be dyed in open width form of full width form. 2. Chemical and heat loses are less when compared to winch dyeing machine 3. The material to liquor ratio is 1:3 (or) 1:4 which saves considerable amount of  chemical cost and steam cost. 4.1.2. Disadvantages of Jigger Dyeing Machine

It exerts lot of tension in the warp direction and because of this normally woolen, knitted fabrics, silk etc are not dyed in jigger dyeing machine. Dyes, Theory of Dyeing, Classification of Dyes and its application

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4.2. Winch Dyeing Machine

Winch dyeing machine is normally used for dyeing light weight fabrics like knitted fabrics as well as woven, silk etc. The winch dyeing machine is different in construction from the jigger. The machine consists of elliptical winch (or) circular winch which is driven by hand or motor. Elliptical winches are most widely used. It has a perforated portion dividing the machine in to two compartments. One is small and the other one is bigger in size. Dye- liquor pipe, steam pipe, water inlet are provided in small compartment. Dyeing is carried out in the larger compartment. During working, one end of the fabric is passed over the guide rollers and winch and under the dye liquor and passed in between the pegs. After the sufficient amount of cloth is fed the ends are stitched and making a long continuous loop formation. Many such loops run together separately by a series of pegs, to avoid entanglements. The loops are drawn in and out of the bath by rotating the winch. After dyeing is over the pieces are separated. The winch is made up of stainless steel. Now-a-days closed type of winch is also used to prevent the temperature loss and pressure loss.

4.2.1. Advantages

Thin and light weight fabrics like knitted fabrics, voile cloth etc, can be dyed successfully in winch dyeing machine without exerting any tension. Embroidery fabrics may be dyed in winch dyeing machine without affecting the embroidery designs. Dyes, Theory of Dyeing, Classification of Dyes and its application

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4.2.2. Disadvantages

Fabrics are dyed in rope form, so there are more chances for uneven dyeing. Therefore, we will get even dyeing only when retarding / leveling agent is added to the dye liquor. The material to liquor ratio is very high i.e. 1:30 or 1:40. Therefore the heat and the additional chemicals are provided more when compared to jigger. Heat and chemical losses are more because of the wider open tank.

4.3. Padding Mangle

Continuous dyeing methods depend upon the impregnation with the padding mangles. The padding mangles are equipped with two, three or even four mangles. The rollers are arranged one above the other. Three bowl padding mangle are usually prepared for dyeing of cloth. The padding mangle consists of two ebonite rollers and one rubber covered roller. To reduce the material to liquor ratio, low capacity troughs are generally used with the different shapes. Some of the machines are provided with jacket troughs for maintaining the temperature of pad liquor. An over head tank is connected to the mangle for feeding the stock solution through the perforated pipe. The supply of the dye-liquor is controlled automatically to maintain a constant level. The pressure on the padding mangle is applied by hydraulic or pneumatic system which enables heavier and uniform pressure. The trough is fitted with dye-liquor and the cloth passes through the dye solution, which is heated by steam. After that the cloth is passed between the ebonite and rubber covered roller to give uniform pressure throughout the fabric. The pressure can be altered depends upon the type of the fabric. The speed is 200 yards/minute. It is used for dyeing vat, Sulphur, Naphthol etc. The solution used in the trough is divided in two equal portions to avoid uneven dyeing. The padding mangles may also be used for desizing purposes.

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4.4. Jet Dyeing Machine

This is the most modern machine used for the dyeing of polyester using disperse dyes. In this machine the cloth is dyed in rope form which is the main disadvantage of the machine. In this machine, the dye tank contains disperse dye, dispersing agent, leveling agent and acetic acid. The solution is filled up in the dye tank and it reaches the heat exchanger where the solution will be heated which then passed on to the centrifugal pump and then to the filter chamber. The solution will be filtered and reaches the tubular chamber. Here the material to be dyed will be loaded and the winch is rotated, so that the material is also rotated. Again the dye liquor reaches the heat exchanger and the operation is repeated for 20 to 30 o minutes at 135 C. Then the dye bath is cooled down, after the material is taken out. Metering wheel is also fixed on winch by external electronic unit. Its purpose is to record the speed of the fabric. The thermometer, pressure gauge is also fixed in the side of the machine to note the temperature and pressure under working. A simple device is also fixed to note the shade under working.

4.4.1. Advantages 

Dyeing time is short compared to beam dyeing.  Material to liquor ratio is 1:5 (or) 1:6  Production is high compared to beam dyeing machine. 4.4.2. Disadvantages   

Cloth is dyed in rope form Risk of entanglement Chance for crease formation.

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4.5. Package Dyeing Machine

A series of technical developments in the recent years has resulted into package dyeing being developed into a highly sophisticated as well as an economic process. Latest design Package Dyeing machines are amenable to accurate control and automation. These features would likely to lead to increases in the application of package dyeing. The term package dyeing usually denotes for dyeing of yarn that has been wound on perforated cores. This helps in forcing the dye liquor through the package. With the start of dyeing cycle, the dye liquor goes on circulating throughout the vessel and tank. This happens till all the dye is used up or fully exhausted. The dye flows through to the yarn package with the help of the deliberate perforations in the tube package. Once full exhaustion is brought about, the carrier of  coloured yarn is consequently removed from the vessel. A large centrifuge removes excess water from the packages. Finally the yarn is dried using an infra red drying oven. The image shows the process working of a Package dyeing machine. 4.5.1. Advantages of Package Dyeing machine

Package dyeing methodologies have been subjected to intensive research and development. As a result package dyeing machine has evolved into a very sophisticated apparatus. It offers a number of advantages .       

Considerable reduction in yarn handling. Compatible to automatic control, in the process leading to reproducible dyeing‟s. Open to large batches. High temperature dyeing a possibility. Low liquor ratios, giving savings in water, effluent and energy. Uniform and High rates of liquor circulation, that leads to level application of  dyes. Machinery totally enclosed resulting in good working conditions at the dye-house.

4.6. Beam Dyeing Machine

The beam dyeing machine operates with the same principle as that of package dyeing machine. It can be effectively used to dye yarn or fabric. The process works like this, fabric or yarn in open width is rolled on to a perforated beam. The beam then subsequently slid into a vessel that is closed and pressurized. The colour impregnates the Dyes, Theory of Dyeing, Classification of Dyes and its application