Lecture 3 and 4

Advancements in Pretreatment
of Textiles- Enzymatic processes
By Dr. M. Irfan Siyal
 Module 2 -Contents
• Advancements in pretreatment of textiles;
enzyme biotechnologies for pretreatment of
textiles; desizing, scouring and bleaching.
• Comparison of conventional and advanced
technologies.
• Application of Plasma Technology in
pretreatment.
 Introduction
• Industrial use of biotechnology is bringing
about new products and processes aimed at
the use of renewable resources, as well as
the application of green technologies with
low energy consumption and
environmentally healthy practices.
• Textile processing is a growing industry that
traditionally has used a lot of water, energy
and harsh chemicals.
 Introduction
• Due to the ever-growing costs for water and
energy worldwide investigations are carried
out to substitute conventional chemical
textile processes by environment-friendly
and economically attractive bioprocesses
using enzymes.
• The combined use of the enzymes allows to
omit the alkaline scouring without a loss of
quality in the finishing result.
 Introduction
• The described enzymatic procedure is
accompanied by a significant lower demand
of energy, water, chemicals, time and
therefore costs.
• So it has advantages as well in terms of
ecology as in economy.
• Enzymes are biological catalysts that mediate
virtually all of the biochemical reactions that
constitute metabolism in living systems.
 Enzymes
• They accelerate the rate of chemical
reaction without themselves undergoing any
permanent chemical change.
• The term ‘enzyme’ was first used by Kühne
in 1878, even though Berzelius had
published a theory of chemical catalysis
some 40 years before this date, and comes
from the Greek enzumé meaning ‘in (en)
yeast (zumé)’.
 What are Enzymes?
• All known enzymes are proteins.
• They therefore consist of one or more polypeptide
chains and display properties that are typical of
proteins.
• The building blocks of proteins are amino acids,
which are small organic molecules that consist of
an alpha (central) carbon atom linked to an amino
group, a carboxyl group, a hydrogen atom, and a
variable component called a side chain (see
below).
Chemistry of proteins
 Chemistry of proteins
• Within a protein, multiple amino acids are
linked together by peptide bonds, thereby
forming a long chain.
• Peptide bonds are formed by a biochemical
reaction that extracts a water molecule as it
joins the amino group of one amino acid to
the carboxyl group of a neighboring amino
acid.
 More about Enzymes?
• Enzymes differ from chemical catalysts in
several important ways:
• 1. Enzyme-catalysed reactions are at least
several orders of magnitude faster than
chemically-catalysed reactions.
• When compared to the corresponding
uncatalysed reactions, enzymes typically
enhance the rates by 106 to 1013 times.
 Difference between enzymes and catalysts

• 2. Enzymes have far greater reaction specificity

than chemically-catalyzed reactions and they
rarely form byproducts.
• 3. Enzymes catalyse reactions under
comparatively mild reaction conditions, such as
temperatures below 100°C, atmospheric pressure
and pH around neutral.
• Conversely, high temperatures and pressures and
extremes of pH are often necessary in chemical
catalysis.
 More about enzymes

• Enzymes are very specific in comparison to

inorganic catalysts such as acids, bases,
metals and metal oxides and are differ in
several important characteristics.
• Enzyme can break down particular
compounds.
• The molecule that an enzyme acts on is
known as its substrate, which is converted
into a product or products.
Enzymes and Textile industry
• Enzymes work only on renewable raw materials.
• Fruit, cereals, milk, fats, cotton, leather and wood
are some typical candidates for enzymatic
conversion in industry.
• Enzymes are used in the textile industry because
they accelerate reactions, act only on specific
substrates, operate under mild conditions, are safe
and easy to control, can replace harsh chemicals
and enzymes are biologically degradable i.e.
biodegradable [Uhlig 1991; Ruttloff 1994].
 Properties of enzymes
• 1. Enzyme accelerates the reaction
An enzyme accelerates the rate of particular reaction by
lowering the activation energy of reaction.
• The enzyme remains intact at the end of reaction by acting
as catalyst.
2. Enzymes operate under milder condition
• Each enzyme have optimum temperature and optimum pH
i.e. activity of enzyme at that pH and temperature is on the
peak.
• For most of the enzyme activity degrades on the both sides
of optimum condition.
 Properties of enzymes
• 3. Alternative for polluting chemicals
• Enzymes can be used as best alternative to toxic, hazardous,
pollution making chemicals.
• Also some pollutant chemicals are even carcinogenic. When
we use enzymes there is no pollution.
• 4. Enzyme acts only on specific substrate
• Most enzymes have high degree of specificity and will
catalyse the reaction with one or few substrates.
• One particular enzyme will only catalyse a specific type of
reaction. Enzymes used in desizing do not affect cellulose
hence there is no loss of strength of cotton.
 Properties of enzymes
• 5. Enzyme are easy to control
• Enzymes are easy to control because their activity
depends upon optimum condition.

• 6. Enzymes are biodegradable

• At the end of reaction in which enzymes used we can
simply drain the remaining solution because
enzymes are biodegradable and do not produce toxic
waste on degradation hence there is no pollution.
Microorganisms producing
enzymes are listed in Table
Enzyme applications in textile preparatory process

• The fabric should be free from natural and

added impurities before it goes colouration.
• Some of the chemicals like caustic soda,
soda ash, hydrogen peroxide, hydrochloric
acid, detergent and auxiliaries that are used
at different stages preparatory process to
remove such an impurities are found to be
harmful to the environment.
 Environmental and health effects of chemicals used textile
pretreatment

• NaOH: Sodium hydroxide is very corrosive.

• It can cause irritation to the eyes, skin, and mucous
membrane; an allergic reaction; eye and skin burns; and
temporary loss of hair.
• Workers may be harmed from exposure to sodium hydroxide.
• The level of harm depends upon the dose, duration, and work
being done.
• A high concentration in water will result in toxic effects for
aquatic organisms e.g. fish.
• However, dissolved carbon dioxide and thus the pH will not
increase.
 Environmental and health effects of chemicals used textile
pretreatment

• Soda Ash (Na2CO3)

• may cause severe side effects if swallowed, inhaled or
exposed to the skin.
• If you develop symptoms of sodium carbonate
poisoning, seek emergency medical care.
• Health effects include;
• Difficulty Breathing,
• Stomach upset,
• Skin or eye irritation,
• Abdominal pain etc.
 Environmental and health effects of chemicals used textile
pretreatment

• Hydrogen peroxide H2O2

• Exposure to hydrogen peroxide can cause 
• irritation of the eyes,
• throat,
• respiratory airway, and
• skin.
• Drinking concentrated liquid can cause mild to
severe gastrointestinal effects. 
 Environmental and health effects of chemicals used textile
pretreatment

• Hydrochloric acid
• The HCl in the atmosphere may be a much bigger driver of pollution
and damage to the environment than previously thought, effecting
water and land ecosystems.
• The increased acidity in soil disables some organisms from growing.
• This has a chain effect on entire ecosystems, as species lose their
habitat, and food. 
• Hydrochloric acid is corrosive to the eyes, skin, and mucous
membranes. 
• Inhalation exposure may cause coughing, hoarseness, inflammation
and ulceration of the respiratory tract, chest pain, and pulmonary
edema in humans. 
 Environmental and health effects of chemicals used textile
pretreatment

• Detergents
• Often contain harmful chemicals which lead to negative
health effects, ranging from skin and throat irritation to
carcinogenicity, and negative effects on the environment.
• Researchers have found that dryer vents can emit more
than 7 hazardous air pollutants. This is even more
concerning when dealing with dryers that don’t vent
outside or are blocked, causing indoor air pollution.
• One of the most harmful chemicals found in laundry
detergent is 1,4-Dioxane. he EPA considers this solvent a
human carcinogen
Enzyme applications in textile preparatory process

• Modern wet processing industries should use

enzymes in the preparatory process instead of
using harmful chemical because enzyme are more
convenient, effective and environment friendly.
• The application of enzymes has many advantages
compared to conventional, non-enzymatic
processes.
• Enzymes can be used at low temperatures and at
pH-values near to neutral.
Enzyme applications in textile preparatory process

• Especially in textile manufacturing the use

of enzymes has a long tradition.
• Enzymes used in textile processing and
their effects are shown in Table 2.
Enzymes used in textile processing and their effects
 Enzymes used in textile processing
• Cellulase enzymes were first introduced after decades
of amylase usage as an industry standard for desizing
processes.
• Today, efforts within the textile industry seem to focus
on replacing traditional natural-fiber scouring
processes with enzyme-based solutions.
• As the purpose of scouring is to remove natural
impurities such as polymeric substances like pectins,
and waxes, among others from cotton or other natural
fibers, there are plenty of enzyme that can act on such
impurities.
 Enzymes used in textile processing
• Alkaline pectinases, which loosens fiber
structure by removing pectins between cellulose
fibrils and eases the wash-off of waxy
impurities, is the key enzyme for a bioscouring
process.
• Other enzymes including cellulases,
hemicellulases, proteases and lipases have been
tested, but at present, the only commercial
bioscouring enzyme products are based on
pectinases.
 Enzymes used in textile processing
• In conventional pre-treatment these
substances are removed by a strong alkaline
treatment at high temperatures after the
enzymatic desizing of raw cotton fabrics
with α-amylases.
• This inspecific alkaline scouring process
has a high energy, water and alkali
consumption and can also cause a damage
of the cellulosic material.
 Enzymes used in textile processing
• The group of enzymes called laccases, or
phenol oxidases, possesses the ability to
catalyze the oxidation of a wide range of
phenolic substances, including indigo.
• The first commercial use of laccases in the
textile industry has been in the denim
washing process, where laccases enhance
abrasion levels and bleach indigo.
 Enzymatic scouring
• Bioscouring is a process by which alkaline stable
pectinase is used to remove pectin and waxes
selectively from the cotton fibre.
• Unlike the traditional alkaline scouring, this process
is substrate-specific and does not alter the cellulose
component.
• The treatment here is also rather lower than that of
the high-temperature alkaline scouring.
• The bioscouring however does not swell or remove
the seed coat fragments called motes.
 Enzymatic scouring
• This can be beneficial when scouring for the "natural
look", because of the mote and colour retention in the
cotton fabrics scoured with this process, pastel or light
shades need to be bleached prior to dyeing, but medium
to dark shades can be dyed directly after bioscouring.
• During the pectinase treatment the pectin content of
cotton fibre can be decreased by about 30 %.
• Removal of pectin results in lower amounts of waxes on
the cotton surface and subsequently in improved water
absorbency of the fabric, which supports the hypothesis
of chemical linkage between pectin and waxes.
 Enzymatic scouring
• Pectin acts as a sort of cement or matrix that
stabilizes the primary cell wall of the cotton
fibres.
• Waxes have a melting point about 70 C,
therefore during pretreatment they melt and
disperse into the treatment bath or they are
redistributed on the fibre surface and the
thickness of the fabrics increases.
 Enzymatic scouring
• Novozymes, Bayer and Dexter Chemical Corporation
have introduced an enzymatic alternative for scouring
woven and knitted cotton fabrics in the textile industry
on the basis of an alkaline pectinase (Dextrol Bioscour
3000) produces by a genetically modified Bacillus
strain.
• For cotton knits, enzyme is added in this step. The
temperature is brought to 57 ᵒC and held for 10 minutes.
• This is the actual bioscour part of the procedure. The
bath is then heated to 95 ᵒC to melt and emulsify waxes
and held for 5 minutes.
 Enzymatic scouring
• The scour is followed by at least one 80 ᵒC rince before
proceeding for dyeing. The later modifications include
reducing the time used for rinsing by skipping the drain step
and going directly to another flow wash.
• Among other modifications, at 50 ᵒC rinse prior to the
bioscour process has proved to be effective in helping remove
knitting oils and reducing foam levels.
• For cotton woven fabrics, batch process, pad-batch bioscour
as well as continuous bioscouring have also been suggested.
• The bioscouring process results in textiles being softer than
those scoured in the conventional sodium hydroxide process
[Nierstrasz and Warmoeskerken 2003].
 Enzymatic Bleaching

• Scouring is regularly followed by a bleaching process,

which removes the natural pigments of cotton fibres.
• Mainly flavonoids are responsible for the colour of
cotton [Hedin et al. 1992; Ardon et al., 1996].
• The most common industrial bleaching agent is
hydrogen peroxide. Cellulose fibres are most
frequently bleached with hydrogen peroxide resulting
in high and uniform degrees of whiteness.
• Namely, the bleaching process is conducted in an
alkaline bath at pH 10 to 12 and at
 Enzymatic Bleaching
• Tzanov et al. (2001) reported for the first time the
enhancement of the bleaching effect achieved on
cotton fabrics using laccases in low concentrations.
• In addition, the short time of the enzymatic pre-
treatment sufficient to enhance fabric whiteness
makes this bio-process suitable for continuous
operations.
• Also, Pereira et al. (2005) showed that a laccase from
a newly isolated strain of T. hirsuta was responsible
for whiteness improvement of cotton most likely due
to oxidation of flavonoids.
 Enzymatic Bleaching
• More recently, Basto et al. (2007) proposed a
combined ultrasound-laccase treatment for
cotton bleaching.
• They found that the supply of low ultrasound
energy(7W) enhanced the bleaching
efficiency of laccase on cotton fabrics.
• Natural fabrics such as cotton are normally
bleached with hydrogen peroxide before
dyeing.
 Enzymatic Bleaching
• Catalase enzyme is used to break down
hydrogen peroxide bleaching liquor into
water molecules and less reactive gaseous
oxygen Compared with the traditional
clean-up methods, the enzymatic process
results in cleaner waste water or reduced
water consumption, a reduction of energy
and time.
 References
• https://psa-hydrochloric-acid.weebly.com/ef
fects-on-health--
environment.html
• https://
healthfully.com/side-effects-of-sodium-carb
onate-6166685.html
• https://
www.cleancult.com/blog/is-laundry-deterge
nt-actually-toxic
 Plasma Technology
• Plasma is a charged gas, with strong Coulomb [or
electrostatic] interactions,".
• Atoms or molecules can acquire a positive or
negative electrical charge when they gain or lose
electrons. This process is called ionization. 
• Plasma, as an emerging/green/water-free
technology, can be utilized for development of
nano-scale surface modification of treated textile
materials to impart value added new functionalities
without adversely affecting their bulk properties.
 Plasma Technology
• The generations of plasma active species like ions,
energetic electrons, radicals, photons, UV-light etc.
and their interaction with fabric surface result in
surface activation modification and functionalization
• Plasma can be generated by using low frequency
(50–450 kHz), radio frequency (13 - 27 MHz) or
microwave (0.915 or 2.45 GHz) power supply.
• Additionally, the required power range (10–500 W)
is selected based on both the reactor size as well as
the demanded surface treatment.
 Plasma Technology
• In particular, atmospheric non-thermal plasmas are
suited because most textile materials are heat
sensitive polymers and applicable in a continuous
processes.
• Plasma, provides an alternative tools of
• pretreatment and finishing treatments of
cellulose based textiles, which in turn enable
surface modification and functionalization of
treated substrates in an environmentally sound
manner for wide potential applications.
4 effects of Plasma Technology
• Is used for
• (i) removal of surface contaminants,
• (ii) etching and creation of surface
roughness,
• (iii) thin film deposition and coating,
• (iv) creation of new active sites and
functional groups
 4 effects of Plasma Technology
• (i) Cleaning effect. Mainly associated with changes in
wettability and surface texture of the material may increase
dye or finishing agents absorption;
• (ii) Increased microroughness. This can improve the adhesion
of finishing agents, stamping and the behaviour of anti-felting
finishing agents;
• (iii) Generation of free radicals. May induce secondary
reactions such as crosslinking thus allowing graft
polymerization and the reaction with oxygen or other gases to
generate hydrophobic or hydrophilic surfaces;
• (iv) Plasma Polymerization. Allows the deposition of solid
polymer with desired properties.
 Gases used in plasma
• The commonly used gasses for cold plasma
treatment include:
• chemically inert,
• e.g. argon, neon, helium…etc.,
• reactive/non-polymerisable,
• e.g. air, nitrogen, ammonia etc.,
• reactive/polymerisable,
• e.g. tetrafluoroethylene, hexamethyldisiloxane etc
 Plasma processing basics
• Plasmas are generated by applying electromagnetic
power across a gas volume.
• At sufficiently high power, the field has the power to
strip electrons from some of the gas molecules/atoms
and a highly reactive dynamic mixture consisting of
electrons, ions, radicals, etc., is obtained.
 Plasma processing basics
• The action of the plasma on a substrate
surface can lead to the chemical and
physical modification of the top layers of
the textile material (<100 nm thickness).
• UHF (Ultrahigh frequency)
Application of Plasma Technology in Textile Pretreatments

• For example, reactive sites can be generated

on an inert surface.
• Longer treatment may lead to material
removal by volatilization.
• Cleaning of surfaces by removal of surface
dirt/contamination is another aspect which
has been in use for some time now for
improving ink adhesion on polymer
surfaces.
Application of Plasma Technology in Textile Pretreatments

• Plasma are rays/ionized gas are composed

of ions, charged particles, neutrons,
electrons, and excited species.
• When the material surface is irradiated, it
leads to physicochemical changes of the
surface at the nanometer level.
• As a result of this, dyeing and the other wet
processing of the material become easier.
Plasma uses for textile surfaces
• Plasma treatment can be used as an effective
technique for:
• surface cleaning,
• surface activation and
• functionalization,
• improving adhesion to ensure effective coating,
• enabling, and imparting hydrophilicity or
hydrophobicity, to the treated textile materials.
Application of Plasma Technology in Textile Pretreatments

• Plasma technology also helps to reduce the

dyeing cycle and increase the rate of dye
uptake.
• Additionally, plasma has been used to make
cotton fabric hydrophobic by using plasma-
assisted in situ/post polymerization of
hydrocarbon or fluorocarbon precursors
(Samanta et al., 2016).
Application of Plasma Technology in Textile Pretreatments

• The textile industry uses plasma to make

textile surfaces hydrophobic, hydrophilic, or
dirt-repellent.
• By creating additional functions for a textile
surface e.g. by means of a fire protecting or
self-cleaning coat, plasma treatment can
equip fabrics with new material properties.
• Furthermore, plasma treatment improves the
wettability, and dyeing properties of textiles.
 Comparison of conventional textile processing with Plasma
Technology

• In the textile industry, it is still common

practice today to treat fabrics with wet
chemicals, some of which are harmful to the
environment.
• This is true for the whole manufacturing
range, from the yarns for T-shirts up to
fabric for space suits designed to protect
astronauts from radiation or cold.
 Comparison of conventional textile processing with Plasma
Technology

• Another environmental issue is the wide scope

of colourants and pigments for dyeing fibres and textiles,
as well as the consumption of vast amounts of water in the
production of textiles.
• The waste water primarily comes from the following four
production phases:
• Textile pretreatment (washing, desizing, boiling, bleaching,
mercerising, causticizing)
• Dyeing (continuous/discontinuous)
• Printing
• Finishing
 Comparison of conventional textile processing with Plasma
Technology

• In the course of finishing, the chemicals that are

used in the manufacture of the fibres, yarns and
fabrics and that are removed from the textile
substrate during pre-treatment get into the waste
water, as well as the chemicals used in the finishing
processes.
• With a plasma treatment, the surfaces of fibres and
processed textiles can be modified in many different
ways completely free of hazardous chemicals.
 Plasma Treatment Technology for pretreatments of
Cellulosic Fabrics
Working Cellulosic Main Task Positive impacts
Gas substrate
Air Grey Upgradation • Removal of various impurities which
cotton surface in turn positively affects the subsequent
fabric properties bleaching and
dyeing processes along with reduction
in chemical and energy
Consumption
Air/Argo Grey Upgradation Enhancing wettability as well as
n cotton surface modification and
fabric properties functionalization of the treated fibers
surfaces via removal of impurities,
etchings as well as
generation of new functional groups as
–COOH, –OH …etc
 Plasma Treatment Technology for
pretreatments of Cellulosic Fabrics
Working Cellulosic Main Task Positive impacts
Gas substrate
Helium/ Grey Pretreatment- Enhancing wettability
Air cotton desizing/scouring and desizability of sizing
fabric agent via etching and
introducing new
functional groups.
Air/O2/H Grey Desizing Facilitate the removal of
e and air cotton size with cold after wash
fabric
Air Grey Scouring Improving wettability of
cotton treated substrate via
fabric removal of non
cellulosic impurities.
 Plasma Treatment Technology for pretreatments
of Cellulosic Fabrics
Working Cellulosic Main Task Positive impacts
Gas substrate
O2 Grey desizing/scouring Size and non-cellulosic
cotton impurities removal in
fabric one step, positively
affects the subsequent
dyeing process.
Air Grey Bleaching of grey To achieve high degree
cotton cotton fabric of whiteness,
fabric recommended with two
steps. Plasma
pretreatment followed by
H2O2 bleaching.
Air Grey Mercerization without Plasma treatment
cotton using wetting agent followed by
fabric mercerization brings low
cost, environmentally
friendly process etc.
Limitations of plasma treatment
• Three main drawbacks may be reported:
• (i) Surface cleanliness. Since plasma
treatment only influences the top layer,
contaminations or different surface
conditions (e.g. weft and warp direction) of
the textile could have significant negative
effects.
Limitations of plasma treatment
• (ii) Three dimensional structure of
textiles. Textiles are porous three
dimensional structure and plasma species
could not penetrate deep enough into
fabric structure to ensure proper treatment
as the wet processes do. In this context,
the pressure at which the plasma treatment
is performed is a crucial variable.
Limitations of plasma treatment
• However, the major disadvantages of this
irradiation process are the uniformity in
dyeing and other functional finishing.
• Additionally, the fastness of dyed samples is
always unsatisfactory, as most of the dye
molecules get deposited/reacted on the outer
layer of the substrate.
 References
• Water in textiles and fashion, Consumption, footprint, and life cycle
assessment, Edited by: Edited by Subramanian Senthilkannan Muthu
• Advances in the dyeing and finishing of technical textiles, Edited by M. L.
Gulrajani
• Plasma Treatment Technology for Surface Modification and
Functionalization of Cellulosic Fabrics, By: Nabil A. Ibrahim and Basma M.
Eid
• Advances in Functional Finishing of Textiles, By: Mohammad Shahid,
Ravindra Adivarekar Editors
• https://www.plasma.com/en/plasma-in-textile-technology/
• https://www.plasmatreat.com/industrial-applications/plasma-treatment-in-
textile-manufacturing.html#:~:text=Durable%20colors%2C%20functional
%20surfaces%2C%20high,treatment%3A%20plasma%20in%20textile
%20manufacturing&text=Openair%2DPlasma%C2%AE%20pretreatment
%20significantly,hydrophobic%20and%20dirt%2Drepellent%20finishes.