1.

CHAPTER 1: INTRODUCTION

1.1. General discussion

Silk is a famous name in the domain of clothing and apparels. It is a delicate, soft textured and
very smooth fibre originates from the cocoons of silkworms as a continuous filament of
proteinaceous polymer closely resembles synthetic fibres. Among many of the varieties, Mulberry
silk (Bombyx Mori) is the finest quality and therefore worths high price. Although silk has been
in use for centuries globally, some area associated with dyeing of Bombyx Mori silk is still not
researched.

In recent times, silk has received significant attention and hence attempts have been made to
improve various physical properties [1, 2, 3, 4, 5, 6, 7] as well as dyeability, colourfastness with
different classes of dyes like natural dyes, acid dyes, basic dyes, metal complex, reactive dyes [8,
9, 10, 11, 12, 13] . Research on adsorption, kinetics and thermodynamics on silk with a very few
dyes [14, 15, 16] have been made.

Although reactive dyes are very popular and have been successfully applied to the silk,
investigations on adsorption isotherm, dyeing kinetics, physico-chemical aspects on silk with these
dyes are not well established. Some investigations were based on the effect of process variables
on fixation or influence of dye reactivity on exhaustion or reaction mechanism with reactive dyes
on silk [17, 18]. Level dyeing properties and effluent contributions of reactive dyes while applied
to silk may be an area of excellent interest of study according to industrial point of view.

The introduction of reactive dyes on 1956 by ICI was an important milestone in the history of
textile coloration. That was the first time dyeing which was achieved by direct chemical linkage
between dye and fiber [19].

Before that, the dye applications to textile were involved by three ways. Firstly, physical
adsorption of water soluble dyestuffs from an aqueous medium by the fiber, Secondly, by
mechanical retention of water insoluble dyes in the fiber substances, and thirdly, by suspension of
the dyestuff in the fiber.

Reactive dye was the fourth principle of dyeing and printing. This dye chemically reacts with fiber
and forms a covalent bond between the dye and the fiber.

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Exhaust dyeing of silk with reactive dyes requires salt as electrolyte, which holds back negative
charge build-upat the fiber surface and promotes an increased dye uptake.

The detail idea about the chemistry of vinyl sulphone dyes are described in different literatures
[19]. Common salt and alkali plays the vital role in exhaustion and fixation and addition of salt to
the dye bath before adding the alkali is essential, as with the case with other classes of reactive
dyes. But not only is the salt, the dye substantivity also another major factor in exhaustion process
[20].

Water being the competitor for reaction with the dye, but cellulose fiber takes partin the reaction
maximum time. It is because of the substantivity of the dye to the fiber which is greater than that
to water [21]. But all the reactive dyes do not have the same range of substantivity and reactivity.
Higher reactivity of a dye can spoil the dyeing due to hydrolysis. Reactive dye gets reactivity in
presence of alkali. Reactivity is compulsory for these dyeing, but for a perfect dyeing it should
have a limit.

One of the key problems in dyeing with many reactive dyes is their low fixation level, often which
is less than 70% of the original dye that reacts with fiber. This results huge dye concentrations in
effluent. Newer ranges of reactive dyes, those with more than one reactive group generally give
higher fixation if the parameters are all right [20].

This research aims to focus on the analysis of adsorption isotherm, dyeing kinetics and
thermodynamic aspects of three homo-bifunctional reactive dyes on silk woven fabric and also
enumeration of a factor expressing/assuming level dyeing performance based upon exhaustion-
fixation-migration profile along with an estimation of the effluent level contributed by the reactive
dyes.

1.2. Objective of this research

1.2.1. To study on color build-up and level dyeing performance of reactive dyes
on silk
Color build up were studied to find out the saturation limit of dyes from the k/s values at various
concentration of dyes. Level dyeing performance of each reactive dye on silk has been quantified
by a parameter called Level Dyeing Factor (LDF) which depends on the substantivity exhaustion
in presence of electrolyte, equilibrium exhaustion by fixation alkali and migration behavior of dye.

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 1.2.2. To find out the exhaustion, fixation, loss and effluent percentages of dyes on silk
Dye exhaustion percent indicates how much the dye had been exhausted to the substrate. This
depends upon dye substantivity and the environment of the dye bath. The presence of an
electrolyte, temperature of the dye bath, pH of dyeing can affect the exhaustion percentage.
Washing is obvious after dyeing as not all the dyes become fixed with the fabric. The unfixed dyes
are then washed off. To calculate the percent of dye lost in washing procedures was one of the
objectives of this research.There is a certain amount of dyes which had been fixed in the fabric.
This is the actual percent of dye which was not left in liquor neither washed off. To calculate this
percent of fixation of the three dyes was one of the objectives of this research.The more a dye goes
to effluent the more the chance of environment pollution, especially water pollution. In effluent
treatment plant the water also needs more treatment to be cured. The calculation of dye amounts
participated to the effluents was another goal of this research.

1.2.3. Analysis of the adsorption isotherm and adsorption mechanism of dyes on

silk
The adsorption isotherm of any dye helps to understand its interaction behavior to the substrate.
Nernst, Langmuir and Freundlich adsorption isotherms were considered here for analysis of these
three dyes. Adsorption mechanism were analyzed by using Weber-Morris equation to describe the
diffusion of dye molecules into the substrates and to determine whether the intraparticle diffusion
was only rate controlling step.

1.2.4. To Study the dyeing kinetics on silk

Rate of exhaustion for each dye was investigated and different kinetic approaches such as pseudo-
first-order and pseudo-second-order model were adopted to find out the rate constants and other
kinetic parameters.

1.2.5. To find out thermodynamic parameters of dyeing silk with reactive dyes
The laws of thermodynamics describe the relationships between thermal energy, or heat, and other
forms of energy, and how energy affects matter. Thermodynamic variables such as activation
energy, enthalpy, entropy and free energy are calculated using diffusion constant applying
Arrhenius and Eyring equations.

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 1.3. Outline of this thesis
The outline of this thesis is described in Table 1.1.

Table 1.1: Outline of the thesis

Chapter number Chapter name Description

The introduction chapter includes general discussion

1 Introduction
upon the research work with its objectives.

This chapter contains the review of recent research work

2 Literature review
conducted related to this work.

This chapter includes all theoretical background of this

Theoretical
3 work. These are the theory upon which the research has
background
been conducted.

This chapter gives the description of the materials used

Materials and
4 in this research work and also the methods of the total
methods
experimental work.

Results and The results are discussed here with related table and
5
discussion graphs.

The all over findings and outcomes and the suggestions

6 Conclusion
for the future works are put on here.

In this portion of this dissertation the journals, books and

7 References
websites helped this thesis are referred.

The appendix part includes the curves and data tables

8 Appendix obtained from the instruments from which all the
analysis are done.