Dyeing Mechanism

Affinity
It is the difference between the chemical potential of dye in its standard state in the fiber & the corresponding
chemical potential in the dye bath i.e. tendency of a dye to move from dye bath into a substance. It is expressed
in Joule or cal (per mole) and quantitative expression of substantivity.

Substantivity
The attraction between a substrate and a dye or other substance under the precise condition of test whereby the
test is selectively extracted from the application medium of substrate. It is the qualitative expression of affinity.
Substantivity depends on temperature, type of fiber, electrolyte concentration. Substantive dyes have affinity
and are soluble.

Reproducibility of Shades
The shade of the dyes should be reproducible when required. Certain dyes have ability to overcome the factors
like liquor ratio, pH, temperature etc. which affect the reproducibility.
Characteristics of highly reproducible dyes are:

Highly soluble

Medium substantivity

Medium reactivity

Good wash off properties

Highly diffusible

Optimization of Dye
The principle is to carry out dyeing in a manner in which the dyestuffs absorbed by substrate almost uniformly
with less dye wastage.
1.Substrate

Affinity

Circulation speed

Action of chemicals before

2.Dyestuff

Depth of shade

Optimum quantity/yield

Diffusion ability and regularity

Color fastness

Combination & mixability

Chromphore percentage

3.Auxiliary Products

Optimum quantity

Compatibility with dyestuff and with each other

Levelness

Control of PH in final exhaustion

Reproducibility

No adverse effect

4. Temperature and time

Low initial temperature to avoid rapid absorption of dye

Control of critical temperature zone for maximum exhaustion

Sufficient time for penetration and fixing

5. Machine

Control of batch

Volume of flow

Temperature regulation

The actual dyeing theory can be obtained mathematically from kinetics of dyeing or dyeing equilibria. The
dyeing phenomena found in principle of dyeing curve. The factors for uniform color & optimization of dye all
are related to kinetic phenomena. Therefore kinetic dyeing is important in the dyeing process.

Functional Groups of fiber

Cotton: OH-, at higher pH it is ionizable
Wool: -COOH, -NH, -CONH2. At pH 3-4 ionized positively so acid dye is used to dyeing
Acrylic: -COOH, -SO3H, -O SO3H
Silk: -NH2, -CONH
Viscose: -OH, -COOH
Polyester: -OH, -COOH. No ionization effect, high temperature used for dyeing with dispersing.
Diacetate: -OH, -COOCH3
Triacetate: -COOCH3

Dyeing Medium
1. Aqueous medium

Water

Solvent

Foam

2. Vapor phase: cationic, anionic, nonionic

Dyeing Mechanism
The sequence of dyeing falls into four stages
1. Transfer of dye onto fiber surface
2. Adsorption
3. Diffusion into the fiber
4. Interaction

Transfer of dye onto fiber surface

The transfer of dye onto the fiber surface depends on:
1. Environment of the dyebath: environment of the bath refers to

Solvent and its type, nature, quantity: solvent may be water and or any other solvents which may be
soft/hard, acidic, alkaline, ionic, nonionic etc.

pH

Dyeing assistants like electrolytes, leveling agents, carrier, dispersing agents etc.

temperature of the dyebath which depends on material type (cotton or polyester), type of dye (hot
brand or cold brand), method of dyeing (padding or exhaust) Suitable environment ensures easy
transference of dye on fiber surface.

2. Substantivity
3. Mechanical and physical force

Adsorption
The distribution process is called adsorption, if the substance which is to be distributed is retained by a surface.
The assembly of dye molecules at the fiber surface is governed by:
Electropotential forces: All fiber when immersed into water or aqueous solution acquires an electric potential
known as zeta potential. Cellulosic fiber bears a negative charge while protein fibers at higher pH than its
isoelectric point bears are negatively charged and at lower pH than isoelectric point is positively charged.
Temperature: most dyes in solution are either in molecular and partially ionized state or exist in the form of
ionic micelles; increase in temperature tends to breakdown micelles into less aggregated units. Increase of
temperature promotes vibrational activity accelerates the migration of the surface of the fiber.
Agitation: when a fiber is immersed in the dye a large no of molecules tend to enter the fabric at once, thus
creating a layer called Barrier. If the dye molecules are to reach the fiber surface then the barrier should be
broken which is done by agitation.
Dye adsorption has affect on fastness properties.

heory of Dyeing

Aggregation of dyes
Dye-dye self association in solution is called dye aggregation, which is important phenomenon where dye
molecules or ion takes part. 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
Size of dye molecules No of solubilizing groups in the dye molecules
In dye aggregation multiple equilibria need to be considered i.e. diametric, trimetric etc, aggregates are formed
D + D=D2
D2 + D=D3
Dn-1 + D=Dn

Measurement of dye aggregation

1.Conductometry
2.Calorimetry
3.Polarography
4.Solubility
5.Sedimentation
6.Fluorescence
7.X-ray diffraction
8.Measurements of diffusion coefficients
9.Activity of counter (Sodium)

10.Light scattering
11.Evaluation of colligative properties
12.Visible light adsorption
13.H and 19F NMR

Reasons of dye aggregation in dyebath

1.Dyes are consists of
a.Hydrophobic aromatic portion
b.Polar groups (OH, amino etc.) for water solubility and charged groups (sulfonic or positive charged groups)
for rendering molecule water soluble When dye molecules dissolved in water a new interface is created
between the hydrophobic portion and water. Dye can reduce the size of the interfacial water by overlapping of
the hydrophobic areas and there will be a tendency to aggregate.
2.Usually linear and planar dye molecules should tend to stack one molecule upon another with the ionized
groups arranged so as to give minimum free energy condition causes aggregation.
3.Dyes with long aliphatic chains form micelles of a spherical form in which the flexible chains associate in
the interior with the sulfonic acid groups exposed on the surface of sphere.
4.Aggregation of dimer is more obvious as aromatic ring system have maximum overlap (van der waals forces)
because the distance between the anionic charges is larger (minimum electrostatic repulsion).
As dye concentration increases there will be an increased tendency for trimers, tetramers etc. to be formed.
5.Aggregation is also expected from the unusual structure of water. When the interface is formed on
dissolution of the dye molecule, the water molecules adjacent to the hydrophobic portion form an iceberg
type structure accompanied by a reduction in entropy. When the dye molecules aggregate not only will energy
be gained from the reduction on the interfacial energy but also an increase in energy will rise from the melting
of the iceberg structure.
6.Calculation shows that below concentration of 10-5 mole/L various higher aggregates appear, giving a
polyassociated system.
7.Higher ionic strength, ionic dye aggregation becomes more dominant.

Prevention of aggregation
1.By raising the temperature of dyebath
2.Liberation and existence of monomers by circulations or stirring and keep concentration below 10-5 mole/L
of dye.

If you read any modern book on pysanka making, you will find many references to aniline dyes (or
analine if the author hasnt spell-checked). While we call the modern chemical dyes we use aniline
dyes, they could be better described as acid dyes (and are, in the textile community). Why, then, this
name?
It has to do with history. The very first artificially produced chemical dye was a produced from aniline
(akaphenylamine or aminobenzene), and most still use it as a precursor substance. (Then again,
acetaminophen is also produced from aniline, as are polyurethane, herbicides and nanowire for use as a
semiconducting electrode bridge.)

Chemical structure of aniline

Aniline was first isolated from the destructive distillation of indigo, a plant used to produce blue dye, in
1826. In 1834, it was also isolated from coal tar. Further attempts by several scientists yielded aniline by

different processes and, in 1841, C. J. Fritzsche gave this blue oil the name aniline, from the specific
name of one of the indigo-yielding plants, Indigofera anil (anil being derived from the Sanskrit nla, darkblue, and nl, the indigo plant). In 1855 these variously named oils were proved to be identical , and
thenceforth they took their place as one body, under the name aniline or phenylamine.
Its first industrial-scale use was in the manufacture of mauveine, a purple dye discovered in 1856 by an
18 year old chemistry student, William Henry Perkin, who was trying to create artificial quinine (an antimalarial drug). At the time of mauveine's discovery, aniline was an expensive laboratory compound, but it
was soon prepared "by the ton" using a process previously discovered by Antoine Bchamp.

Chemical structure of Mauveine A

The synthetic dye industry grew rapidly as new aniline-based dyes were discovered in the late 1850s and
1860s. These new colors were not only relatively easy to produce, but were quite bright, even
garish. The muted dyestuffs of earlier decades gave way to bright prints. Mauve was found to fade very
easilywhen first applied it is a bright purple, and only after fading is it the light, lavender color that we
associate with the name. And mauve gave its name to an entire decade the 1890s. Purple had once
been the rarest and most difficult dye to prepare; Tyrian purple was prepared from the secretions of a
predatory sea snail, and was incredibly expensive. With mauve, anyone could afford purple, a color once
limited to kings.
Aniline itself is a very toxic substance. The dyes we use today are much less toxic than aniline. The
greatest risk of disease or injury due to modern acid dyes is by ingestion of or exposure to dye
dust. These scenarios are normally confined to textile workers. Whereas the dye itself is normally non
toxic, the molecules are metabolized (usually in the liver) where they may be broken back down to the
original intermediates used in manufacture. Many intermediate chemicals used in dye manufacture have
been identified as toxic and their use restricted.
The chemistry of acid dyes is quite complex. Dyes are normally very large aromatic molecules consisting
of many linked rings. Acid dyes usually have a sulfo or carboxy group on the molecule making them

soluble in water. Water is the medium in which dyeing takes place. Most acid dyes are related in basic
structure to the following:

Anthraquinone type:
Many acid dyes are synthesized from chemical intermediates which form anthraquinone-like structures as
their final state. Many blue dyes have this structure as their basic shape. The structure predominates in
the leveling class of acid dye.

Azo dyes:
The structure of azo dyes is based on azobenzene, Ph-N=N-Ph. Although Azo dyes are a separate class
of dyestuff mainly used in the dyeing of cotton (cellulose) fibers, many acid dyes have a similar structure,
and most are red in color.

Triphenylmethane related:
Acid dyes having structures related to triphenylmethane predominate in the milling class of dye. There are
many yellow and green dyes commercially applied to fibers that are related to triphenylmethane.
Acid dyes are thought to fix to fibers by hydrogen bonding, Van der Waals forces and ionic bonding. They
are normally sold as the sodium salt therefore they are anionic in
solution. Animal protein fibers andsynthetic nylon fibers contain many cationic sites, therefore there is an
attraction of anionic dye (- charge)molecule to a cationic site (+ charge) on the fiber. The strength
(fastness) of this bond is related to the desire of the dye to remain dissolved in water over fixation to the
fiber.