TEXTILE DYEING (November 2018)

 The application and fixing of a dye to a substrate, normally with

the intention of obtaining an even distribution throughout the
substrate
 The objective of dyeing is the uniform coloration of the mass of
fibres constituting the material, usually to match a pre-specified
colour.
Colorant & Classification of Colorants

colorants

dyes pigments

 A colorant is a substance capable of imparting its colour to a given

substrate, such as paint, paper or cotton, in which it is present.
 Not all colorants are dyes.
 A dye must be soluble in the application medium, usually water, at
some point during the coloration process.
 It will also usually exhibit some substantivity for the material being
dyed and be absorbed from the aqueous solution.
 On the other hand, pigments are colorants composed of particles that
are insoluble in the application medium.
  They have no substantivity for the material. Since the particles are
too large to penetrate into the substrate, they are usually present on
the substrate surface. The pigment is therefore easily removed
unless fixed with an adhesive.
Natural dyes
 Although finely ground, coloured minerals, dispersed in water, were
used inpaints over 30 000 years ago, they easily washed off any
material coloured with them.
 Fabric was dyed by soaking it in the aqueous extract and drying.
 These dyes had only a limited range of dull colours and the dyeings
invariably had poor fastness to washing and sunlight. The fastness
of a dyeing is a measure of its resistance to fading, or colour change,
on exposure to a given agency or treatment.
 Most natural dyes also lacked substantivity for fibres such as wool
and cotton.
 Substantivity implies some attraction of the dye for the fibre, so that
the dye in the solution gradually becomes depleted as it is absorbed
by the fibres.
 The poor substantivity and fastness properties of natural dyes often
improved if the fabric was first treated with a solution containing a
salt of, for example, iron, copper or tin.
 These metal salts were called mordants
  When the pre-mordanted fabric was soaked in a bath of a suitable
natural dye, the dye penetrated into the fibres and reacted with the
metal ions present. This reaction decreased the water solubility of
the dye so the colour was less likely to bleed out on washing.
 Indigo, extracted from leaves of the plant Indigofera tinctoria, and
Tyrian Purple from Mediterranean sea snails are water insoluble
pigments called vat dyes. These do not require mordants
 For dyeing with Indigo, a water-soluble, reduced form of the dye
was first obtained by extraction and fermentation. The process
became known as vatting, from the name of the vessels used – hence
the term ‘vat dye’.
 The soluble, reduced form of the dye is called a leuco derivative.
Leuco Indigo has substantivity for wool and cotton fibres.
 After dyeing, air oxidation of the pale yellow leuco dye, absorbed in
the fibres, regenerates the dark blue, insoluble pigment trapped
inside them. Because of this, the fastness to washing is very good in
comparison to most natural dyes.
SYNTHETIC DYES
 In 1856, William H Perkin reacted aniline with acidic potassium
dichromate
 From the dark, tarry reaction mixture, he isolated a purple, water-
soluble compound that dyed both wool and silk directly when
immersed in its solution.
 No mordant was required.
 Mauveine (proposed structure 1, Figure 1.1) is a cationic dye since
each of its molecules has a positive ionic charge
 Such cationic dyes are often called basic dyes since many, like
Mauveine, have free amino groups capable of salt formation with
acids.
 Perkin even developed a method for dyeing cotton with Mauveine
using tannic acid as a mordant.

 Two years after the isolation of Mauveine, Peter Greiss discovered

the diazotisation reaction of primary aromatic amines, which
produces diazonium ions, and later, in 1864, their coupling reaction
with phenols or aromatic amines to give
 azo compounds.
  Primary aromatic amines such as aniline (C6H5NH2) are often
diazotised by treatment with sodium nitrite (NaNO2) in acidic
aqueous solution at temperatures around 0–5 °C (Scheme 1.3).

COLOUR AND CHEMISTRY

Unlike most organic compounds, dyes possess colour because they
1) absorb light in the visible spectrum (400–700 nm),
2) have at least one chromophore (color-bearing group),
3) have a conjugated system, i.e. a structure with alternating double and
single bonds, and
4) exhibit resonance of electrons, which is a stabilizing force in organic
compounds

When any one of these features is lacking from the molecular

structure the colour is lost.
Figure 1: Chromophoric system examples
Regarding the requirement of a chromophore generating colour in
organic compounds, it is important to note that the chromophore must be
part of a conjugated system.
This is illustrated through the examples in figure 2 where it can be seen
that placement of an azo group between methyl groups produces a
colourless compound, while a yellow-orange colour is obtained when the
azo group is placed between aromatic rings.

Figure 2: effect of conjugation

In addition to chromophores, most dyes also contain groups known as
auxochromes (colour helpers), examples of which are carboxylic acid,
sulfonic acid, amino, and hydroxyl groups. While these are not
responsible for colour, their presence can shift the colour of a colourant
and they are most often used to influence dye solubility.

Figure 3: auxochrome effect on colour

 Adding groups of increasing electron-donating ability to the

azobenzene structure has a bathochromic effect (cf. OH vs NH2).
 Electron-donating (NH2) and electron-accepting (NO2) groups
placed in conjugation provide a bathochromic effect. In this regard,
nitro groups are especially beneficial, contributing to their
prevalence in disperse dye structures.
  Increasing the number of electron-attracting groups conjugated
with the electron-donor has a bathochromic effect.
 The electron-donating effects of an amino group are enhanced by
adding alkyl groups to the N-atom.

Examples of activating groups in the relative order from the most

activating group to the least activating:

-NH2, -NR2 > -OH, -OR> -NHCOR> -CH3 and other alkyl groups

with R as alkyl groups (CnH2n+1)

Examples of deactivating groups in the relative order from the most

deactivating to the least deactivating:

-NO2, -CF3> -COR, -CN, -CO2R, -SO3H > Halogens

with R as alkyl groups (CnH2n+1)

The order of reactivity among Halogens from the more reactive (least
deactivating substituent) to the least reactive (most deactivating
substituent) halogen is:

F> Cl > Br > I

Classification of dyes

Classification based upon application

Table 1: Fibre specific classes of dyes

 Classification based upon chemical constitution

(1) Nitro Dyes:
Nitro dyes are polynitro derivatives of phenols containing at least
one nitro group ortho or para to the hydroxyl group.

(2) Azo Dyes:

 The azo dyes represent the largest and the most important group of
dyes. They are characterized by the presence of one or more azo
groups (–N=N–), which form bridges between two or more aromatic
rings.
 Following steps are involved in the manufacturing of azo dyes.
(3) Xanthene Dyes:
Xanthene dyes can be identified by a common structural feature shown
below.

(7) Indigoid and Thioindigoid Dyes:

Indigoid. It is the parent compound of indigoid dyes and has been used in
this country from times immemorial.
Thioindigo is used to dye cotton, wool and polyesters
(8) Anthraquinoid Dyes:
Anthraquinoid dyes can be identified by a common structural feature
shown below.
Dye Selection
(1)The types of fibres present; (dyes are fibre specific)
(2)The form of the textile material and the degree of levelness
required level dyeing is less critical for loose fibres, which are
subsequently blended, than it is for fabric;
(3)The fastness properties required for any subsequent
manufacturing processes and for the particular end-use;
(4)The dyeing method to be used, the overall cost, and the
machinery available;
(5)The actual colour requested by the customer

Composition Of Commercial Dyes

 Powder
 Granular
 Aqueous paste

Commercial dye powders also contain various other chemicals

besides the principal dyestuff. These include diluents such as salts
or starch, wetting agents, dispersants, impurities from manufacture
such as residual intermediate chemicals, anti-dusting agents (oils),
buffers (sodium carbonate or phosphates), and shading dyes.
Naming dyes
1) Commercial name
• given by the manufacturer. It conveys some information
e.g., Dispersol Fast Red RN150
red disperse dye, good fastness properties, 150% strength

2) Colour Index name

• The Colour Index is a reference source of technical
information on commercial dyes and pigments
• produced by the Society of Dyers and Colourists, Bradford.
All dyes are given a name of the form
• CI (Application Type) (Colour) (Number)
e.g., CI Reactive Red 43

Dyeing Methods
(1) Direct dyeing, in which the dye in the aqueous solution in
contact with the material is gradually absorbed into the fibres
because of its inherent substantivity;
(2) Dyeing with a soluble precursor of the dye, which forms an
insoluble pigment deep within the fibres on treatment after dyeing;
(3) direct dyeing followed by chemical reaction of the dye with
appropriate groups in the fibre;
(4) Adhesion of the dye or pigment to the surface of the fibres
using an appropriate binder.
Pre-treated Fabric Requirement for Dyeing

Degree of size 6 onward Tegawa scale

rating
Absorbency 1-4sec drop test AATCC
Whiteness 70-75 CIE Whiteness
Damage
pH Neutral

Water for a dye house

Component Permissible conc.
mg/l
Hardness 0-25
Iron 0.02-0.1
Manganese 0.02
Silica 0.5-3.0
Alkalinity to PH 35-65 CaCO3
4
Dissolved solids 65-150

TERMS USED IN DIRECT EXHAUST DYEING

Dyeing is either a batch exhaustion process, or a continuous

impregnation and fixation process. Careful control of the dyeing
temperature, pH and auxiliary chemical concentrations is often
necessary to obtain level, well-penetrated dyeings in exhaust
process.
Amounts of dye and colour yield
 The amounts of dyes used to produce the colour desired are
usually expressed as a percentage of the weight of the dry
material, and abbreviated as % owf, or % dye on the weight
of fibre. Thus, 1.00 kg of dye used to colour 100 kg of cloth
corresponds to a 1.00% dyeing.

 The colour yield is the depth of colour of a dyeing per unit

amount of dye in the material. Quantitative assessment is
possible from measurement of the reflection spectrum of a
sample of the dyeing and the percentage of the dye

Exhaustion
 For a single dye, the exhaustion is defined as the mass
of dye taken up by the material divided by the total
initial mass of dye in the bath, but for a bath of constant
volume:

% E = ((CO – CS) / CO) *100

where C0 and Cs are the concentrations of dye in the

dyebath initially and at some time during the process,
respectively.
Rate Of Dyeing

 The slope of a dyeing exhaustion curve (Figure 1) defines the rate of

dyeing at any instant during the process.
 The degree of exhaustion of a dye at equilibrium is higher the greater
the substantivity of the dye for the fibre being dyed.
 Substantivity is the ‘attraction’ between dye and fibre whereby the dye
is selectively absorbed by the fibre and the bath becomes less
concentrated.
 The initial rate of dyeing (the initial slope of exhaustion versus time) is
called the strike. Rapid strike by a dye often results in initial
unlevelness and must be avoided for those dyes that cannot
subsequently migrate from heavily to lightly dyed areas of the fabric.
 The strike depends on the dyeing temperature, the dyeing pH, and the
addition of
 chemicals.

Effect of temperature on exhaustion and dyeing rate

The rate of dyeing increases with an increase in temperature but the final
exhaustion may increase or decrease depending upon the particular dyeing system.
Dyeing is usually an exothermic process (heat releasing); the interaction between
the dye and fibre molecules is stronger than between the dye and water molecules in
solution.
DYEING EQUILIBRIA
In the study of dyeing equilibria, the fibre and dye solution are heated at
constant temperature until a state of equilibrium is reached. After the
initial increase in the degree of exhaustion, it eventually becomes
constant, but a true equilibrium implies that the dye is also uniformly
distributed throughout the fibres. On heating for the extended period
required to reach a true equilibrium, there is always a risk of some
decomposition of the fibre, or of the dye.

ADSORPTION ISOTHERM
An adsorption isotherm gives the concentration of a substance adsorbed
on a solid surface in relation to its concentration in the surrounding fluid
when the system is at equilibrium at a constant temperature. The graph
representing a dyeing adsorption isotherm has the adsorbed dye
concentration (Cf in g kg–1 or mol kg–1) plotted against the solution
concentration (Cs in g l–1 or mol l–1).
There are three main types of dyeing adsorption isotherm, usually
referred to as the:

 Nernst,
 Langmuir and
 Freundlich isotherms.
NERNST ISOTHERM
The Nernst isotherm is the simplest and is given by the equation:

where k a constant. This is also the equation describing the distribution or

partition of a solute between two immiscible solvents. The graph of Cf
against Cs is linear up to the point corresponding to the dye saturating the
fibre and the water.
The dyeing of many synthetic fibres with disperse dyes follows this type
of isotherm

LANGMUIR ISOTHERM
The Langmuir isotherm applies to adsorption on specific sites in the solid,
of which there are often only a limited number. Such a situation exists in
the dyeing of nylon with simple acid dyes by an ion exchange mechanism.
The counter ion associated with an alkylammonium ion group in the
nylon, under weakly acidic conditions, is exchanged for a dye anion. The
Langmuir adsorption isotherm is easily derived. The rate of desorption
depends only on the fraction of occupied sites (Cf/Cmax).The rate of
adsorption of dye onto the fibre from solution, however, depends upon the
fraction of unoccupied sites (1 – Cf/Cmax) and the concentration of dye
in the solution (Cs). At equilibrium, the two opposing rates
are equal and:
where k1 and k–1 are the rate constants for adsorption and desorption, and
Cmax is
the maximum number of adsorption sites that dye molecules can occupy
in the
fibre. This leads to:

where K is the value of k1/k–1. The graph of Cf versus Cs for the

Langmuir isotherm ((a), in Figure 11.2) clearly shows that the fibre
becomes saturated with
dye when all the available adsorption sites are filled. The maximum
number of sites in the fibre can be determined from the slope of the linear
graph of Cs/Cf versus Cs, according to the equation:

Figure 11.2 shows both forms of the Langmuir isotherm for adsorption of
HCl by
wool fibres. In the graph of Cs/Cf against Cs (b), the value of the slope is
1/Cmax.

FREUNDLICH ISOTHERM
The Freundlich isotherm applies to the situation where dye adsorption
onto the fibre is not limited by a number of specific adsorption sites and
the fibre does not become saturated with dye. The empirical equation
describing this isotherm is:

where k is a constant, and the exponent _ often has a value around 0.5 for
the adsorption of anionic dyes on cellulosic fibres (Figure 11.3). The
amount of dye adsorbed by the cotton fibres depends upon the available
pore surface area. Initially, the dye molecules adsorb on the surfaces of
the most accessible pores, but increasingly the dye must penetrate into the
less accessible areas, so adsorption becomes more difficult. The dye
molecules may even adsorb onto a layer of dye molecules already
adsorbed on the pore surfaces.

MIGRATION
 Migration is the process by which are dye move around the fiber or level itself.
Transfer of dyestuff from heavily dye to light dye portion of the same material
during dyeing is known as migration.
 It can overcome any initial unlevelness resulting from a rapid strike.
Migration of the dye demonstrates that the dye can be desorbed from more
heavily dyed fibres and re-absorbed on more lightly dyed ones.

 Good migration dyes have lower wash fastness and low exhaustion values
Aggregation of dyes
 Dye-dye self-association in solution is called dye aggregation. Dyes
generally remain or tend to remain scattered in powder form but in aqueous
solutions individual dye molecules stack one on top of other e.g. aggregate

 In general, the term aggregation is used for dye-dye interaction and dye
association for interaction of dyes with other compounds e.g. polymers.
  Generally dye molecules form aggregation in aqueous solution at room
temperature and to an extent which depend on

i. Size of dye molecules

ii. No of solubilizing groups in the dye molecules

 Dye aggregation prevents the dye molecules from diffusion into the fiber
pores and hence causes dye wastage as dyes are absorbed in monomeric form
which decreases with dye aggregation.

Prevention of aggregation

 By raising the temperature of dyebath

 Liberation and existence of monomers by circulations or stirring and keep
concentration below 10-5 mole/L of dye