Cellulosic Dyeing

Colorants
A colorant is a substance capable of imparting its colour to a given substrate, such as paper or cotton, in which it is present Not all colorants are dyes A dye must be
Soluble Substantive Absorbable (at fiber level)

Pigments are colorants composed of particles that are

Insoluble not substantive Pigment particles are large and do not penetrate into fiber

Dyes
The four major characteristics of dyes are:
intense colour solubility in water at some point during the dyeing cycle some substantivity for the fibre being dyed reasonable fastness properties of the dyeing produced.

Classification of dyes
Classification of dyes according to chemical constitution and usage

Chemical Structure of Direct Dyes

Basic Parts
Chromophores Auxochromes

Chromophores contain unsaturated molecules. Most dye molecules contain a number of aromatic rings forming a chromophore (color producing portion Approximately 50% are disazo, 33% are polyazo, and the remainder are monoazo, copper-complex azo or based on other chromophores Sulphonated azo dyes constitute the predominant group of direct dyes These are usually bis-, tris-, or tetra-azo compounds

Chemical Structure of Direct Dyes

Auxochrome modify the color of chromophores by influencing the electronic orbits and causing to absorb or emit certain light wavelengths They also intensify the color Additionally act as solublizing agents b/c of polarity Improve the color fastness (due to polarity) Direct dyes attach with fiber by hydrogen bonding or vander waals forces (weaker bonds) Higher molecular weights increase this attraction thus direct dyes have higher molecular weight

Theory of Direct Dyeing

Exhaustion
Proportion of dye taken up by the fiber at any stage of the process relative to the amount originally available

Substantivity
The affinity of a dye for a given substrate

Fixation
Proportion of dye remaining on the fiber at the end of the process relative to the amount originally available

Fastness
Resistance to fading due to washing, light, etc

Configuration of Dye Molecule

Based on configuration the following behavior of dye molecule is governed
Penetration into the fiber Depth of Penetration; determines color fastness Trapping and bond forming capability ; determines color fastness

Dye molecules enter only the amorphous regions Average distance between molecules in amorphous regions is almost 0.5-0.2 nm Linear and coplanar molecules enter much easily

Behaviour of Dye Molecule in Dyebath

Stages of Dyeing
Adsorption: The first stage in dyeing cellulosic fibres with direct dyes is initial uptake of the dye on the fibre surface, known as strike Absorption: The second stage is diffusion of the dye into the fibre to approach an equilibrium distribution of dye between fibre and dyebath. Fixation or retention (polar or ionic attractions, hydrogen bonding, Van der Waals forces, and solubilities)

Take place due to repulsive forces (water) and attractive forces (fiber)
Depends on ionic nature of dye

Dye molecule repel the fiber initially due to ive charge on both Most dyes exist as aggregates of several dye molecules Important factors affecting the absorption of direct dyes by cellulosic fibres include
time and temperature of dyeing, liquor ratio, salt concentration, and the solubility and aggregation behaviour of individual dyes.

Interaction of Dye Molecule with Water

Water is a medium for dyeing (transport dye and temperature) Water may swell the fiber thus helping diffusion Most dyes exist as aggregates of several dye molecules Dye has affinity both for water and fiber Dye molecule attracts water due to polarity This has to be overcomed, the rate however is important This can be accomplished by heating which makes water more polar resulting in repulsion Lower the liquor ratio better is exhaustion

Interaction of Dye Molecule with fiber

Dyes have natural attraction to fiber (Chemical Attraction) This attraction can attract the dye molecule and can even lead to a bond between the two. Attraction may be due to weak polar forces or hydrogen bond, Ionic or covalent bond For covalent bond first dyes are attracted by longer distance polar forces Larger molecule have larger polar attraction When cellulosic fibres are immersed in a solution of a direct dye, they absorb dye from the solution until equilibrium is approached; at this stage most of the dye is taken up by the fibres.

Effect of Electrolytes
Direct dyes are applied to cellulosic fibres in the presence of an electrolyte at or near the boil Helps exhaustion By Common ion effect Decrease in Zeta potential Increased dissociation An increase in the dye or electrolyte concentration increases aggregation Nonionic dyes are not affected. They exist as dispersions. Here exhaustion occurs due to small particle size

Effect of Temperature
Strike and fibre penetration are temperature-dependent and are accelerated by an increase in temperature An increase in the temperature of dyeing raises the rate of dye absorption, but decreases the equilibrium exhaustion Increases the molecular energy Decreases aggragation Increases the dyeing rate (due to smaller aggregate size) i-e exhaustion & Fixation however reduces extent of dyeing Increases penetration into the fiber Fiber also swells at higher temperature Swells the fiber thus resulting in better entrapped molecules on cooling Many direct dyes tend to decompose during dyeing at or above the boil (attributable to reduction of an azo linkage)

Effect of Time and Liquor ratio

The production of level and well penetrated dyeings is favoured by an increase in the time of dyeing Dyebath exhaustion is highly dependent on liquor ratio, but other factors such as solubility, levelling properties and strike have to be taken into account

HOW WE DYE COTTON WITH DIRECT DYES?

Reactive Dyes
Mostly used for cellulosics Good Fastness properties Contains functional group that react with OH group in fibre Results in a covalent bond Some of them form the bond at room temperature while others do that at higher temperatures May also react with water (in that case it is said to be hydrolysed; opposite case is termed as fixed dye) Alkali is added to increase the reactivity of Electron Rich Oxygen atom on cellulose thus increasing its affinity to react with electron difficient reactive group on dye

Reactive Dyes
Hydrolysed dye may also attach to fiber due to weak forces and lead to lower wash fastness. Low substantive dye may be designed to avoid this Chemical Structure (Molecular configuration)
Chromophore------NH------Reactive group Since bonding is done by reactive group molecular size of chromopore may be small

Cellulosic Dyeing with Reactive Dyes

Dye liquor is prepared similar to direct dye liquor. Reactive dye is dissolved in water and an electrolyte is added to it for exhaustion of the dye onto the surface of the textile material as it is introduced to the dye liquor. For the reaction between dye and cellulosic textile material, alkali must be added to the dye liquor.

Cellulosic Dyeing with Reactive Dyes

For some dyes this reaction take place at room temperatures and for some dyes the temperatures must be increased (in some cases to the boil). As a result the covalent bond is formed between the reactive dye molecule and the hydroxyl groups of the cellulosic fiber.

Properties of Reactive Dyes

Washing fastness properties of reactive dyes are very good Light fastness properties of reactive dyes are fair to good