International Standard University

Department of Textile Engineering

B.Sc. in Textile Engineering

Assignment: Recent advancement in

dyeing of synthetic fibers like Polyester

Course Name: Wet processing -1

Course Code: TE 217

Submitted by: Murad Hossan

Rizve
Depart. Name: Textile Engineering
Faculty of Textile Engineering
International Standard University
Batch: 06
ID:0962210014121006
Semester. Level 2 Term 2
Session: 2023
Submitted To:
Md. Hasibul Hossain
Lecturer
Dept of Textile Engineering
International Standard University

Signature and Remarks:

CONTENTS

1.Introduction

2.DYEING OF PLASMA Dyeing of treated polyester,

TREATED TEXTILE Further developments.

3.ULTRASONIC ASSISTED Dyeing of synthetic

DYEING fibres(Polyester), Swelling of
Fibres, Further developments.

4.Electrochemical Dyeing Direct electrochemical dyeing,

Reducing agent for the vat dyes ,
Vat dyeing by electrochemical
method,Electrochemical dyeing
process,Indirect electrochemical
dyeing, Further outlook.
Recent advancements in the dyeing of
synthetic fibers like Polyester

Introduction: Textile wet processing consumes a large amount of

energy. These processes involve the use of chemicals, accelerating their
rates. They must be carried out at elevated temperatures to transfer mass
from the processing liquid medium across to the surface of the textile
substrate in a reasonable time. The present-day scenario in textile
processing calls for the conservation of energy or the usage of low
amounts of energy. This may be achieved by various methods such as the
use of radiofrequency, Electrochemical dyeing, microwaves, infrared
heating, etc.

Various approaches like solvent dyeing with different dyes on several

textile substrates have been experimented with—none of these methods
are commercially viable due to the inherent limitations. The use of
ultrasonic waves and EM radiations is also one of the sources of getting
energy that can be utilized in textile wet processing—usage of water as a
solvent for chemicals mostly because of its abundant availability and low
cost. Problems associated with the usage of water are effluent generation
and additional steps needed to dry the fabrics after each step. The amount
of energy spent to remove the water is also huge adding to the woes of
processors, making processing the weakest link among the entire textile
chain. The unspent dyestuffs remain in liquor, thus polluting the effluent.
It leads to additional pollution of wastewater. To eliminate the
disadvantages it is proposed that certain gases can replace water as a
solvating medium. High pressure and temperature are needed to dissolve
the dyes. Of all the gases being possibly converted into supercritical
fluids, CO2 is the most versatile and prominently used.
DYEING OF PLASMA TREATED TEXTILE

Under appropriate pressure, the interaction of electromagnetic field with

gas produces plasma. It is actually partially ionized gas containing ions,
electrons and neutral particles . It is capable to modify the polymer surface
by etching or polymerization . The type of polymer and the conditions of
plasma treatment results in for activation (radical formation), unsaturation
(double bond formation), chain scission and cross-linking . It is an
environmentally friendly technology. It is preferred over chemical
modification treatments in which acids, alkalis, metals and their
compounds are used . This is a promising surface modification treatment
for natural and synthetic fibers where the bulk of the polymer remains
intact, retaining the properties . It is a water-free or low water
consumption process that enables the treated fiber to absorb dyes or
chemicals easily, specially for coloring the textile goods . Corona and
low-pressure plasma are frequently used . Low pressure plasma treatment
is usually employed for surface modification; it has electrons with high
kinetic energy compared to the gas temperature. Such treatment can
cleave covalent chemical bonds . The presence of impurities and additives
in the substrate can affect the outcome of the plasma treatment . The
apparatus for industrial-scale continuous plasma treatment is not
developed yet . However, it may be inserted “inside” existing textile-
processing machines as an essential component of the machine. This
would result in treatment of the substrate with plasma before the
subsequent actual process.

For low pressure plasma treatment, dried substrate with minimum residual
auxiliaries has been a pre-requisite. Therefore, a vacuum is needed to
demoist the wet substrate before the plasma apparatus. In a commercial
production machine, high volume of fabrics has been processed daily.
Moisture content of the substrate (especially in case of natural fibers) and
the presence of residual chemicals lead to high operating costs of the
plasma treatment. Hence, on a commercial scale the use of low-pressure
plasma technology is not realized yet . Figure 1.1 shows an apparatus for
atmospheric low-temperature plasma treatment.

Fig1.1: Apparatus for atmospheric low pressure plasma treatment

Dyeing of treated polyester:

Disperse dyes are usually applied for dyeing the Polyester (PET) textiles
in the presence of phenol-based carriers commercially. These organic
compounds swell the polyester fiber during dyeing at atmospheric
pressure. However, they are not environment-friendly. In a previous
report, PET fibers were dyed using plasma treatment in the place of
carriers. The results revealed improvement in K/S for samples treated with
plasma. It was due to the reason that surface roughness and surface area
of the treated sample was increased .

Further developments: The use of plasma treatment for applying

indigenous natural dyes on natural fibers is a promising area for research
in the future.
ULTRASONIC ASSISTED DYEING
Conventionally, dyeing of textile material is carried out through
migration of dye molecules from bath to surface of fibre and then
slower diffusion. Ultrasonic assisted dyeing enables same dyeing
process with shorter processing time and save energy. It also reduces
processing cost and consumption of auxiliary chemicals; as a result this
process becomes eco-friendly process .The influence of ultrasonic-
assisted dyeing (UAD) has three aspects on the dyeing system i.e.
dispersion, degassing and accelerating the rate of diffusion of the dye.
Dispersion effect: In this aspect, the micelles and high molecular weight
are broken into uniform dispersion of dyes in dye bath. Degassing effect:
In this aspect, the entrapped air molecules are removed from fibre to
facilitate the dye-fibre contact. Accelerating the rate of diffusion of the
dye: In this aspect, this accelerates the rate of diffusion of dye inside the
fibre.

Dyeing of synthetic fibres(Polyester):

Polyester is a synthetic fiber having long chain of synthetic polymer

composed of ester (85% by weight). It possesses highly crystalline
region which makes it relatively difficult to dye. It is therefore necessary
to swell the fiber first in order to penetrate the dye molecule inside the
inter-molecular space of fiber. The polyester fiber dyed with UAD
method followed below three stages.
1. The dye molecules are dispersed in dye bath.
2. Tiny air bubbles are collapsed by increasing temperature and pressure.
3. After swelling of polyester fiber with UAD method, the dye
molecules moves faster into fiber structure and causes rapid diffusion
which enhances the rate of dyeing.
Swelling of Fibres
The degree of swelling of polyester fiber may be measured by image
analysis technique using following formula.
Swelling% = (d2-d1 / d1) x 100
where, d1 = diameter of fiber before swelling
d2 = diameter of fiber after swelling
The polyester fibres can be pre-swollen in benzyl alcohol or dimethyl
formamide. The pre-swollen processes improve the dyeability, the
opening of fiber structure for an increase of dye penetration. However,
then influence of carrier during dyeing with UAD methods reduces. The
ultrasonic-assisted dyeing makes it possible to color polyester fiber with
compact structure even at lower temperature.

Further developments
The dyeing with UAD method has been carried for several materials
including natural, synthetic and their blends. The UAD method has also
been used for sizing, scouring, bleaching and others. Several researchers
have revealed that the UAD method can be used to save energy,
environment friendly wet-processing, to enhance dye migration.
Following are the key task for future development for UAD method in
order to keep Textile Industry competitive.

 Better design of dyeing process in pilot plant and commercial

scale-up application
 Replace expensive thermal energy with UAD method
 Replace chemicals significantly used in dyeing
 Designing and construction of Ultrasound Tank for UAD method
  Distance between Transducer and Textile substrate
 Testing to determine the power level sensitivity, minimum and
maximum power requirements and bath residence time.
 Cost Vs Benefit investigation

Electrochemical dyeing
The vat and sulphur dyes are insoluble in water; therefore for their
application it is necessary to convert them into water-soluble form using
suitable reducing agent and alkali. Different reducing agents use for vat
and shulphur dyes are briefly reviewed with emphasis on the emerging
technique of electro chemical reduction.

Reducing agent for the vat dyes:

Sodium dye thionite is the universal and mainly used reducing agent for
the vat dyes. It is also known as sodium hydrosulphite, which has
chemical formula Na2S2O4. It reduces the entire vat dye at the temp range
300-600 C and above. Sodium dithionite dissociates properly and
liberates nascent hydrogen.

Na2S2O4 + 4H2O 2NaHSO4 + 6H+

Na2S2O4 + NaOH 2NaSO3 + 2H+

Sodium dithionite is very unstable and get decomposed (oxidative) and

thermally to several byproducts. Some are acidic in nature .The stability
of the alkaline solution of sodium dithionite decreased with increased with
temperature; increased surface exposed to the air and decreased agitation
bath.
Vat dyeing by electrochemical method:
Dyestar has patented an electrochemical dyeing process that it developed
jointly with the textile machinery manufacturer Thies GmbH & Co. and
the institute of textile chemistry and textile physics at the university of
Innsbruck in Dornbirn Austria According to the company, the process
uses an electric current instead of chemical reducing agents, giving it a
number of technical, economic and ecological benefits.Dyestar have
developed a vat dye, Indanthrane blue E-BC, specifically for this
electrochemical dyeing process. The dye liquor used in electrochemical
dyeing with Indanthrane blue E-BC can be reused in an unlimited number
of times and contamination of dye house effluent is close to zero.

Electrochemical dyeing:
As seen earlier, the conventional reducing agents, which reduce the
dyestuff, result in nonregenerable-oxidized byproducts that remain in the
bath. The used dye bath cannot be recycled because the reducing power
of these chemicals cannot be regained. The disposal of the dye bath and
the washing water cause various problems due to the non ecofriendly
nature of the decomposed products. Maximum attention must therefore be
paid from the ecological standpoint to the necessary reducing agent for
these dyes. Electrochemical dyeing is still in the laboratory stage but could
become the dyeing process of the future of the vat, indigo and sulphur
according to BASF, a leading dyestuff manufacturing company. Electrons
from the electric current replace Electrochemical dyeing in which
chemical reducing agents, and effluent contaminating substances can be
dispensed with altogether.

The first attempt although not involving directly the electrochemical

dyeing was made by E.H.Daruwala. He tried to reduce the quantity of
sodium dithionite needed for the reduction of the vat dyes by the
application of a direct voltage this reduction can be traced to the fact that
sodium dithionite at the cathode is converted into a form that exhibits
increased reducing power. By appropriate cathode reduction under
suitable condition (cathode potential, concentration, pH) it is possible to
generate a powerful reducing species from sodium dithionite redox
potential higher than sodium dithionite itself. So due to this behavior
decomposition of hydrosulphide takes place to produce free radical ion
SO2

S2O4-2 2(SO2)

However, these products cannot be regenerated at the applied voltage at

the cathode, making recycling of the bath liquor impossible. In
electrochemical dyeing technique, the same concept is adopted one step
ahead and makes the liquor recycling possible.

There are two methods by means of which electrochemical dyeing can be

carried out, direct electrochemical dyeing and indirect electrochemical
dyeing.

Direct electrochemical dyeing:

In case of direct electrochemical dyeing technique, organic dyestuff has

been directly reduced by contact between dye and electrode. However in
practice, the dyestuff is partially reduced by using conventional reducing
agent and then complete dye reduction is achieved by electrochemical
process for complete reduction which facilitates the improved stability of
the reduced dye.

In order to start the process, an initial amount of the leuco dye has to be
generated by a conventional reaction, i.e. by adding a small amount of a
soluble reducing agent. Once the reaction has set in, it is not needed
anymore and further process is self sustaining. The system is found
successful in case of sulphur dyes. However, concentration of the dye
required to get a specific shade is higher than the conventional reducing
process.

In such a system, a dyestuff particle must come into contact with the
electrode surface in order to get reduced. However, the atmosphere
oxygen present in the dye solution immediately reoxidizes the dyestuff
has no protective capacity. Also, since the dye itself must be reduced at
the surface of the cathode, cathode area should be large which itself is a
constraint.

Indirect electrochemical dyeing:

Thomas Bechtold patented indirect electrochemical dye reduction method
in 1993. Here, the dye is not directly reduced at the electrode. Rather, a
reducing agent is added that reduces the dye in the conventional manner
which in turn gets oxidized after dye reduction. The oxidized reducing
agent is subsequently reduced at the cathode surface, which is then further
available for dye reduction. This cycle is continuously repeated during the
dyeing operation. In electrochemistry, the agent, which under goes
reduction and oxidation cycles, is known as reversible redox system and
is called a mediator.

Thus, in the system, the dye reduction does not take place due to direct
contact of dyestuff with the cathode, like in direct electrochemical
reduction, but it takes place through the mediator which gets repeatedly
reduced due to the contact with the cathode. Therefore this system is
known as indirect electrochemical dyeing.

The object of the reversible redox system primarily in the first place is to
generate a continuous regenerable reduction potential in the dye liquor.
Therefore addition of conventional reducing agent is not essential and
therefore there is no accumulation of decomposition products of the
reducing agents takes place in the indirect electrochemical dyeing. The
electrochemical dyeing appears simple because after dyeing cycle, the
unexhausted dye gets precipitated by air oxidation and can be removed by
filtration. After the dye removal, the color containing the mediator, ligand
and alkali can be recycled for subsequent dyeing operation. This appears
to be most important feature in the terms of the cost and the environment
friendliness of the process.
Future outlook: Electro chemical dyeing
Reducing agents should be dispensed with completely on ecological
grounds. This is the aim of the most recent development, which is still in
the laboratory stage in fact, but could become the dyeing process of the
future in BASFs view.

In electrochemical dyeing the chemical reducing agent is replaced by

electrons from the electric current introduced into the dye bath via. a
special cathode. A distinction drawn here between direct and indirect
electrolysis.

In the case of sulphur dyes direct electrolysis is successful i.e. the

electrons are transferred directly to the dye, reducing it to the active
dyeing species. With vat and indigo, which are present as pigment, and
therefore have inadequate interaction with the electrode surface, indirect
electrolysis is employed, in which a mediator, which is easily soluble and
can be regenerated, transfers the electrons from the cathode to the dye
molecules.

References
1. Rahul Guglani, Article about Development in Textile Dyeing
Techniques, Textile Wet Processing Fibre2fashion.com -
Fibre2Fashion, (https://www.fibre2fashion.com/industry-
article/3419/recent-developments-in-textile-dyeing-techniques).
2. Dr. Shamshad Ali ,Dr. Awais Khatri ,Dr. Mazhar Hussain
Peerzada, EMERGING TECHNOLOGIES FOR TEXTILE
DYEING.pdf
,(https://prr.hec.gov.pk/jspui/bitstream/123456789/9529/1/EM
ERGING%20TECHNOLOGIES%20FOR%20TEXTILE%20
DYEING.pdf )