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Chemical Routes for Energy Conservation in Textile Processing

Conference Paper · March 2014

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Ali Ali Hebeish Mohammed A. Ramadan

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 Chemical Routes for Energy Conservation
In Textile Processing
------------------------
Ali Hebeish & M.A.Ramadan

National Research Center, Textile Research Division

Dokki, Cairo, Egypt
-----------------

Abstract
A great deal of our research activities were directed towards
establishment of conditions and /or development of techniques as well as
synthesis of new auxiliaries with a view to reduce energy, labour , time, and
cost in the wet processing of textiles . In addition to their original targets,
our efforts may form the basis of a potential means for environmentally
sustainable industrial technologies. For convenience, these activities may be
classified into six main categories. The first comprises combination of two
or more of the textile wet processes. The second covers those concerned
with chemical modification of cotton to enhance its susceptibility to dyeing
and finishing. The third category deals with enhancements of reactive dye
fixation via after treatment of the dyed fabrics with environment – friendly
compounds. The fourth calls for synthesis and application of reactive
polymeric products based on starch, dextrin, carboxymethyl cellulose and
polyvinyl alcohol which can react with cotton and become an integral part of
fabrics thereby eliminating their pollution impact when used as temporary
finishes or sizes. The fifth category encompasses low temperature synthesis
and application of new reclaimable sizes for improved high speed weaving
and reduced pollution. The sixth category is concerned with
multifunctionalization of cotton with special reference to nanotechnology.
 1. Introduction

Egyptian textile industry emerged thousands of years ago. However, it

was founded on scientific basis in the year 1927. Egypt became an exporter
rather than importer of textile yarns in 1949. In the early nineties of the last
century the public business sector was established to undertake the
responsibility of privatization of 31 public companies.

At present, this sector after privatization of five companies acquires

26 affiliated companies belonging to the holding company for cotton
spinning and weaving of Textile and Clothes. Production of the 26 affiliated
companies cover spinning, weaving, dyeing, printing, finishing, knitting and
ready – made garments.

Companies concerned with cotton trade and cotton ginning are also
affiliated to the holding company. In addition to the public sector companies,
there are more than 4500 (four thousand and five hundred) companies
belong to the investment and private sectors.

There are also private companies for manufacturing carpets and flour
covers in addition to hundreds of small factories specialized in hand made
carpets. Moreover, the activities of 7 small and medium size enterprises are
directed for manufacturing of technical textiles, in particular, geotextiles and
filters.

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 Very recent information delivered by H.E.Eng. Rashid Mohamed
Rashid, Minister of trade and industry (Al Ahram 21 April 2010) signify the
following. The textile industry and ready-made garments witnessed a
remarkable development during the last five years. This was the reason
behind the breakthrough in the exports of textile products. Textile exports
display an increase of more than 250%. The exports increased to USD 2.5
million in the last year and, efforts are being paid to achieve USD 10 billion
during next periods. These information clarified also that there are more
than 5 thousand companies working in the different fields of textiles with
total investment of L.E 32 billion, and annual production of L.E 47 billion
and, provide 442 thousand working opportunities with total salaries of
L.E.2.5 billion.

Several research, development, technology and innovation institutions

were established in ministries, universities and large companies to assist
development and upgrade the Egyptian textile industry. Among these
institutes is the Textile Research Division (TRD) at the National Research
Centre (NRC), Cairo. A great deal of our research and development work at
TRD was devoted for conservation of energy and improving the quality of
environment over the last three decades. Major findings and conclusions
arrived at from these research efforts are given below.

1. Combined processes
1.1 Combined pretreatments
Traditionally, linen fabric is usually bleached by first scouring in
aqueous solution containing sodium hydroxide along with reducing
agent. Thereafter, it is subjected to three successive bleaching agents,

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 viz., sodium hypochlorite, sodium chlorite and hydrogen peroxide to
effect bleaching.
In our study, unscoured linen fabrics were bleached using H2O2/urea
system under different conditions. Based on results obtained a bleaching
formulation was devised. It is believed that H2O2 / urea system functions
through a free radical mechanism involving hydroxyl free radicals,
perhydroxyl free radicals besides nascent oxygen and perhydroxyl ions,
depending upon pH of the bleaching bath.
Regulation (stabilization) of hydrogen peroxide in strongly alkaline
solutions as well as the effect of these solutions on degradation of starch and
polyvinyl alcohol was studied. Information gained from these studies form
the basis for establishing conditions and developing a desizing – scouring –
bleaching process for starch sized cotton fabric and polyvinyl alcohol sized
polyester/cotton. Treatment of loomstate cotton fabric with a devised
treating bath formulation results in complete size removal, satisfactory
whiteness and absorbency without serious degradation of fibre. The same
holds good for polyester/cotton blend fabric but under milder conditions.
A novel preparatory process has been devised for cotton fabrics using
urea-activated hydrogen peroxide. Laboratory experiments were conducted
to investigate factors controlling the hydrogen peroxide decomposition in the
presence and absence of urea, and the subsequent outcome on the bleaching
of the urea-activated hydrogen peroxide. The bleaching effect was assassed
by monitoring the treated fabrics for whiteness index, loss in fabric weight,
wettability, copper number, carboxyl groups, and tensile strength. Results
obtained form the technical basis for conducting simultaneous desizing,
scouring, and bleaching of cotton fabric.

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1.2 Other combined pretreatments
These include combined desizing and scouring, combined desizing and
merecerizing, combined desizing scouring and bleaching.
1.3 Combined Dyeing and Finishing
In common practice, dyeing and easy care or permanent press of
cellulosics are carried out separately and in succession. Research in this
connection was performed to obtain the necessary basic information required
for establishing one step process for dyeing and finishing.

Preparation of methylolated dye that could react with cotton cellulose

under acidic conditions was described and the mechanism of the reaction
given. This dye was applied to cotton fabric by continuous and semi-
continuous methods. Optimal conditions for application were examined.
Incorporation of N-methylol finishing agents in the dyeing bath to establish
a one step process for dyeing and finishing was investigated. Evaluation of
dyeings and dyed finished goods were assessed by determination of dye
fixation, crease recovery, tensile strength and the over all fastness properties
Three N-methylol compounds, viz., monomethylol urea, dimethylol
urea and N-methylolacrylmaide were independently incorporated in a dyeing
bath containing reactive dye, urea and alkaline catalyst. Cotton fabric was
treated with these solutions by applying the pad-dry-cure method or pad-
cure method. The simultaneously dyed and finished fabric showed
considerable improvement in conditioned crease recovery and outstanding
enhancement in wet crease recovery. Their losses in tensile strength and
elongation were not so striking and their fastness to washing and to light
were comparable with those of dyed fabric.

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 In addition to the foregoing, a new approach for simultaneous dyeing
and wash-wear finishing of textile materials by using acrylamidomethylated
cellulose has been reported. Excellent dye fixation and wash wear properties
could be achieved with dyestuffs containing nucleophilic groups as well as
reactive dyes. In alkaline medium, presence of acrylamidomethyl groups
allowed fixation of dyes containing nucleophilic groups as well crosslinking
of cellulose.
2. Improving Chemical Reactivity of Cotton
This area of research was undertaken with the primary objective of
creating active centers in the cellulose molecule to make it more reactive and
to modify the basic properties of cotton cellulose. By way of example
mention is made of the following:
2.1. Acrylamidomethylated Cotton (AMC)
The pad-dry-cure method and the pad-wet-batch method have been
applied for preparation of AMC by reacting cotton cellulose with N-
methylolacrylamide under acid condition. Dyeing of AMC with dyestuffs
containing nucleophilic groups was studied. Presence of the pendent double
bond of AMC was found advantageous in effecting concurrent dyeing and
wash-and-wear finishing.
2.2. Cotton Cellulose Bearing Aromatic Amino Groups
This modified cotton was prepared by reacting cotton cellulose with
2,4-dichloro-6-p-nitroaniline s-triazine in presence of alkali and subsequent
reduction of the nitro groups to amino groups. Presence of the latter in the
molecular structure of cotton cellulose was disclosed to enhance the
susceptibility of cotton towards reaction with tetrakis (hydroxymethyl)
phosphonium chloride (THPC), N-methylol compounds and/or urea. In this

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way, it is possible to import flame resistance and easy care properties to the
cotton fabric without excessive loss in fabric strength.
2.3. Cellulose Carbamate
Cellulose carbamate was prepared by reacting urea with cotton
cellulose. This was followed by reacting cellulose carbamate with p-
nitroaniline. The reaction product so obtained could be used to bring about a
set of different colors by subjecting it to reduction, diazotization and
coupling with different coupling agents.
2.4 Other Modified Cottons
These include methylolated cellulose carbamate, methylolated
carbamoylethylated cellulose, diethylaminoethylated-cotton,
(polymethylvinyl pyridine)-cotton graft copolymers, poly (glycidyl
methacrylate)-containing cotton and acetylation of the cotton component
in polyester/cotton blend.
2.5 Heat Transfer Printing
In order to render cotton cellulose amenable for heat transfer printing,
cotton either alone or in conjunction with polyester was subjected to the
following chemical modification :( a) it was reacted with various
crosslinking agents, based on N-methylol Compounds, (b) it was reacted
with acrylonitrile in presence of alkali under different conditions to yield
cyanoethylated products having different amounts of cyanoethyl groups,
(c) it was first cyanoethylated followed by crosslinking and (d) it was
graft copolymerized with various vinyl polymers. Cyanoethylated cotton
and polystyrene cotton graft copolymers were found to be the best
substrate amenable for heat transfer printing. Prints with very good
fastness properties could be obtained with these substrates.

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3. Enhancement of Reactive Dye Fixation
Reactive dyes owe their good wash fastness to the covalent bond
formed between the dye and the cellulose during the dyeing process. This
occurs by reaction of a dissociated hydroxyl group of the cellulose with the
dye molecule by either nucleophilic substitution of a reactive chlorine atom
or nucleophilic addition to an activated double bond.
Over the last two decades, a number of major changes have taken
place, primarily aimed at minimizing the major weakness of reactive dyes or
facilitating new application conditions. With the growth in the usage of
reactive dyes, many problems with the qualities of reactive dyes were raised
in respect of lower degree of exhaustion and fixation in exhaust dyeing, poor
levelness and reproducibility, much water, energy and long time required for
washing-off operation. The serious problem is related to wet fastness of dyes
textiles due to incomplete removal of hydrolyzed dyes in washing. Unfixed
hydrolyzed dyes left in dyed textile stain cellulosics in course of domestic
washing. At the same time, shade depth of dyed textiles falls.
Minimisation of dye liquor westage is a major environmental
consideration in continuous dyeing. Computer methods for minimizing
residual liquor have been developed. When applying reactive dyes in full
depth, difficulties may arise in removing the unfixed dyes. In these
circumstances it may be found necessary to after treat the dyeings with a
cationic fixing agent of the type often used on direct dyeing.
Our study had two-fold objective: a) To study the technical feasibility
of utilization of environment friendly compounds in enhancing the
exhaustion properties of the reactive dye, these compounds include chitosan
and poly-acrylamide dextrin hybrid, and b) To establish the optimum
conditions for application of these compounds through detailed investigation

8
into major factors affecting this application such as fixing agent
concentration, aftertreatment time and temperature as well as alkali
concentration of the dyeing process.
Given below are summaries of these studies:
Aftertreatment of reactive dyeing with chitosan or polyacrylamide-
dextrin hybrid was studied. Presence of the amine groups in chitosan and the
amide groups in the hybrid would permit formation of salt linkages. The
latter involves the cotton cellulose, the chitosan or the hybrid and the dye in
addition to covalent bond formation between the reactive dye and the
cellulose hydroxyls. As a result enhancement in dye fixation could be
achieved. The magnitude of such enhancement was found to rely on three
main groups of factors. The first comprises factors affecting the dyeing
process, namely, concentration of sodium carbonate, concentration of
sodium chloride, dyeing time and dyeing temperature. The second includes
factors affecting the aftertreatment, viz., concentration of chitosan or the
hybrid, time of aftertreatment and temperature of aftertreatment. The third
encompasses nature of the dye. The aftertreatments offers a potentially
powerful means for ecological dyeing since it is possible to obtain the same
dyeing performance of traditional dyeing but at reduced concentration of
sodium chloride, reduced concentration of sodium carbonate and lower
temperature. Furthermore the chitosan and the hybrid are biodegradable and,
therefore, they are environment friendly compounds.

4. Reactive Polymeric Products

Carbohydrate materials such as strach and strach derivatives as well as
water-soluble cellulose derivatives are used in textile finishing. Their
attachment to textile fabrics is based on physical forces – mainly hydrogen

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bonding – and, therefore, these materials are considered as temporary
finishes. Removal of the latter from the fabrics during washing increases the
pollution load.
Our research activities have been directed towards synthesis and
application of reactive carbohydrates. Results obtained indicated the
possibility of converting starch and carboxymethyl starch as well as
compounds derived thereof to reactive carbohydrates capable of reacting
with cellulose. Evaluation of these finishes on cotton fabric revealed that
they are permanent finishes. Similar reactive finishes based on
carboxymethyl cellulose could also be achieved as outlined under.
Carboxymethyl cellulose (CMC) and hydrolyzed CMC samples
were graft copolymerized with acrylamide using K2S2O8 as initiator.
Methylolation of the polyacrylamide-CMC graft copolymers results in
reactive finishes. When the latter were applied to cotton fabric according to
the conventional pad-dry-cure method followed by a thorough washing, the
fabric retained ca. 86% of the finish derived from the copolymer of CMC
and 92% of finishes derived from the copolymers of hydrolyzed CMC.

Native starch and hydrolyzed starches were converted to reactive

carbohydrates via graft polymerization with acrylamide followed by
methylolation with formaldehyde. The reactive carbohydrates so obtained
were applied to cotton fabric according to the conventional pad-dry-cure.
The pad-cure and the pad- batch methods were also applied. Examination of
the treated fabrics for nitrogen content as a measure of the extent of reaction,
occurring between the methylolated groups of the reactive carbohydrate and
the hydroxyl groups of cotton cellulose as well as durability of the finish on

10
the fabric indicated the dependence of the reaction and durability on nature
of both reactive carbohydrate and catalyst as well as curing conditions.
Reactive pendant double bonds were introduced in the molecular
structure of carboxymethyl cellulose (CMC) and hydrolyzed CMC via their
reaction with N-methylolacrylamide in the presence of an acid catalyst. The
reaction was carried out under different conditions including type and
concentration of catalyst, concentration of N- methylolacrylamide and time
and temperature of the reaction. This was done to discover the most
appropriate conditions for preparation of these reactive cellulose derivatives.
In other investigations, reactive size could be achieved as follows.
Dextrin was first polymerized with acrylamide. Thus obtained polymeric
hybrid was converted to reactive hybrid through methylolation of its amide
groups by reacting the latter with formaldehyde. On the other hand, poly
(vinyl alcohol) was converted to a reactive form via its reaction with N-
methylolacrylamide in alkaline medium. The two polymeric materials were
applied to cotton fabric with a view to achieve two objectives. The first was
to prepare cotton fabric bearing permanent size. The second was to make
use of these polymeric molecules in chemical finishing of cotton. In both
cases the application involves acid catalyst.

5. New Reclaimable sizes for improved high speed weaving and

reduced pollution
High speed weaving must be considered as an integrated manufacturing
system. All the steps prior to weaving and those following weaving, as well
as the end use of the finished fabric, should be considered in making
decisions concerning any processing steps. One should be aware of the
impact of those decisions on the entire sequence and not only on the one

11
process being changed. Sizing has long been regarded as a ciritical step in
preparing warps for weaving. With the increase in loom speeds, sizing has
become even more critical to good weaving performance, and, hence to the
economics of woven fabric production.
Several processes are applied to fabrics after weaving. Typical sequence
of these is desizing, scouring, bleaching, mercerizing, dyeing, printing and
finish application. The sizing agent that is removed during de-sizing is one
of the major causes of water pollution. If the sizing agent could reclaim and
reused, pollution due to desizing can be eliminated. The reclaimed size
agent, however, must maintain good quality as the original size agent.
Current practice of desizing is the use of enzymes or chemical degradation
of size agent so washing and scouring can remove it. Reclaiming such
degraded sizing agent is almost impossible, unless it is converted to water
soluble through chemical modification. The aim of our research was to
produce such reclaimable sizing agents to minimize pollution.
The ultimate goal of our research was to accomplish the following two
objectives:
- To improve the quality of the environment through minimize
pollution by removing for reuse the sizing agent from finishing
plants’ waste water, and
- To enhance the technical properties of the textile warps for superior
weaving performance on modern high speed weaving machines.
Experimental investigation was conducted to compare between cotton
yarns sized with two commercial and three reclaimable sizes. The five
sizing agents were:
(1) Starch styrene/butadiene copolymer from Phil-chem Inc. the sizing
agent is designed for use at room temperature;(2) PhilBind L-1375S liquid

12
PVA from Phil-chem Inc which is also designed for use at room
temperature; (3) polyacrylamide-starch composite (in paste form) was
prepared at NRC Cairo; (4) carboxyl –containing starch such i.e.
polycarboxylic starch (in liquid form) was prepared by grafting and
etherfication at NRC and (5) carboxyethyl starch along with its ester
adduct(in powder form) was prepared at NRC. Different cotton yarns with
the same twist multiplier were treated with the five sizing agents to evaluate
their weavability. The results indicate that the weavability of the yarns
treated with the reclaimable sizing agent was comparable to the weavability
of the yarns treated with commercial size agents. However, sizing agent (5)
overperformed all other agents. This will make size agent (5) the best
candidate for industrial application.
5.1. Recycling of Water \soluble Starch Sizes
The pollution of environment raised from textile industry contributes
much to the total industrial pollution. The major part of the textile pollution
is mainly caused from discharging the wastewater which is produced during
the different textile wet processes. On the other hand, air pollution caused
from spinning, weaving and some finishing processes constitute the minor
part.
From the typical wet processes used in cotton fabric manufacturing,
the desizing alone causes more than 50% of the textile pollution load. To
minimize this percent of pollution, different methods have been proposed,
one of them is recovering the sizing agents from water. The latter can be
achieved by mean of the ultra filtration method.
The ultrafiltration operation is a pressure driven membrane process by
which macromolecular solutes (sizing agent) are concentrated by means of
transferring the solvent (water) through the membrane pores while the sizing

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molecules (macromolecules) retained. The separation of the sizing agents
molecules from water molecules by the ultrafiltration (UF) process depends
on many parameters such as:
a) The nature and the data of the membrane (molecular weight cut
off, material, water flux, pH and thermal stability)
b) The size and physico-chemical properties of the sizing agent
(solute).
c) Operating conditions (applied pressures, temperature, the
concentration of the feed solution, the operating time and the
Reynolds number of the feed flow).
The main factors which can be measured during the process are the
permeate flux and the rejection, because the understanding of the
mechanism involved in the ultra filtration of the macromolecular solution
is complicated.
Textile sizes are high molecular weight polymers. If these polymers
can be removed from the fabric in the same form as they were applied to
the warp, then the recovery of the size from desizing effluent by means of
ultrafiltration becomes feasible. In this process, a semipermeable
micropores membrane performs the separation. Water and low molecular
weight solutes pass through the membrane surface discharging of permeate
leads to raising up the concentration of the charge "desizing effluent". The
regenerated (concentrate) will be reused as sizing agent and the purified
effluent (permeate) will be used in the desizing process. These changes
depend on the stability of the sizing gents at the operating conditions of the
ultra filtration process.
The ultrafiltration has successfully recovered polyvinyl alcohol,
carboxymethyl cellulose, polyacrylate. Polyvinyl alcohol is the preferred

14
size for reuse due to its high stability because the others suffer from
degradations during the ultra filtration recovery. With starch sizes the
problem is great. Normally starch sizes are not recoverable because of the
need for degradation prior to removal in desizing. The trend now is
modifying the starch to recoverable from the sized yarns. The
modification of starch can be achieved via etherification, esterfication,
oxidation, graft copolymerization and water soluble composite formation.
The latter is the subject of the work, outlined under .
Hence poly (acrylic acid)-starch composite sized cotton fabric was
desized and recovery of the composite was undertaken. The recovery of
composite from the desize effluent was done by making use of the
ultrafiltration technique (UF). In the latter, factors studied were process
time (hr) and regenerate and permeate concentrations, the rate of flux
(1/h.m2) and the rejection%. The effect of the different process (sizing,
desizing, UF recovery) on the viscosity of composite was studied in
comparison with the virgin solution. Results obtained indicated that the
desizing effluent can be recovered successfully by means of the UF
technique.

6. Multifunctionalization of cotton
At present, we adopt a nanotechnology- based research programme
aiming at the multifunctionalization of cotton. Nano-smart/ emerging
technology opens the way to: (a) achieve saving resources and energy
consumption, (b) decline in emission of pollutants, (c) develops
innovative textile products with higher value added and functional
performance properties and ;(d) satisfy the unlimited demand and

15
requirements of the textile consumer as well as to enhance and extend the
appeal, the market and the end –uses of textiles.
Within the framework of this programme, reactive copolymers
containing the moieties of β-cyclodextrin (CD) are synthesized through
grafting the latter with different vinyl monomers. These copolymers are
then applied to cotton along with nano metal particles whereby the
function of thus obtained cotton graft copolymer speaks of the effect of
the supramolecular inclusion complexes with numerous nano-sized metal
particles, as well as of the nature of vinyl polymer.
To start with, we have extensively studied the chemistry of grafting of
cotton with reactive copolymer, namely, monochlorotriazinyl β -
cyclodextrin grafted with poly(butyl acrylate). The importance of such
work and its scope in the realm of textile finishing were reported.
As a continuity of the above work, the impact of grafting of the
reactive copolymer to cotton fabrics when applied to the latter alone as
well as together with ZnO nanoparticles and/or epichlorohydrin was
presented. Application of the reactive copolymer in question was
performed as per the conventional pad-dry thermofixation method and
the onset of this on nitrogen content, wrinkle recovery angle, tensile
strength, elongation break as well as antimicrobial and air permeability
properties were examined. Fabrics so treated exhibit antibacterial
activity which withstands 20 times washing cycle while keeping 70% of
this activity. These grafted fabrics acquire improved air permeability
indicating better breathability and comfortability of garments made
thereof. Also reported was characterization of the grafted fabrics using
IR spectral analysis and scanning electron microscopy. ZnO
nanoparticles was also characterized using Uv-Vis spectrophotometer.

16
 Bibliography:
1- A.Hebeish, in Development in textile chemistry and chemical
technology(special contribution), chapter VII: “ environment protection
via energy and material saving”, pages 177-190 and references therein,
published by Academy of Scientific Research and Technology A.R.E.
(July 1994)
2- M.Hashem and A.Hebeish, Synthesis of reactive polymers and their
applications to cotton fabrics as permanent size”, molecular crystal and
liquid crystals 333, 109-126 (2000).
3- A. Hebeish, A.El Shafei and S.Shaarawy ,Synthesis and
Characterization of Multifunctional Cotton Containing Cyclodextrin
and Butylacrylate Moieties
Polymer-Plastics Technology and Engineering, Volume 48, Issue 8
August 2009 , pages 839 – 850
4- A. El-Shafei, S. Sharaawy, A. Hebeish, Aplication of Reactive
Cyclodextrin poly butyl acrylate preformed polymer containing nano
ZnO to cotton fabric and their impact on fabric performance
Carbohydrate Polymers 79 (2010) 852–857

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