Thesis 10

WOLLO UNIVERSITY
KOMBOLCHA INSTITUTE OF TECHNOLOGY

SCHOOL OF FASHION, GARMENT, LEATHER AND TEXTILE ENGINEERING
DEPARTMENT OF TEXTILE AND LEATHER ENGINEERING
TITLE: SALT FREE DYEING OF COTTON FABRIC WITH REACTIVE DYE BY

TREATMENT WITH FIBRION WASTE
Prepared by: ID/NO

1. ERMIAS FENTAW ..................................................0585/08
2. MOHAMMED ALI ..................................................1186/08
3. MENGISTU TEGEGNE ..........................................1111/08
December 2020
Kombolcha, Ethiopia
SALT FREE DYEING OF COTTON FABRIC WITH REACTIVE DYE BY
A dissertation submitted to
Kombolcha Institute of Technology

Wollo University
Kombolcha, Wollo, Ethiopia
Final Year Project

Bachelor’s Degree in Textile Engineering
By
ERMIAS FENTAW
MOHAMMED ALI
MENGISTU TEGEGNE
Under the Supervision of

ASSAYE DESSIE WOLELA
Date
December 2020
Department of Textile Engineering Page i

Abstract
The coloration of cotton textiles is an important process for ornamenting the textile to emphasize
the appearances and marketing potential. Cotton dyeing requires more amounts of common salt
as an exhausting agent so as to penetrate the dye molecules into the interior structure of cotton
and therefore the used common salt is not fully consumed within the process and drained as
waste and makes more load within the effluent treatment process. Hence an idea has been made
to reduce the load of effluent treatment and the problem to the environment use of an enormous
amount of sodium chloride is replaced with the fibroin Hydrolysate solution extracted from the
silk cocoon. The fibroin Hydrolysate protein was extracted from the thrown away wastes of
fibroin using the hydrolysis reaction process. The extracted fibroin Hydrolysate protein was used
as for the modification of cellulose structure of cotton, dyed with cotton material, and compared
with conventional reactive dyeing using common salt as an exhausting agent. The effect of the
use of extracted fibroin Hydrolysate protein in reactive dyeing as the exhausting agent was
studied by testing washing fastness, rubbing fastness, light fastness, and environment testes
BOD, COD, TDS and TSS values. It was found that the dye uptake was excellent and therefore
the fastness properties were also excellent. The impact of dye effluent to the environment also
found marginally by using extracted fibroin Hydrolysate protein was less as compared to sodium
chloride load to the environment. It had been determined that the utilization of extracted in
fibroin Hydrolysate protein cotton reactive dyeing was more active.
Department of Textile Engineering Page ii

Declaration
We declare that our thesis is original and compiled according to the Bachelor’s degree in textile
engineering and that all contributions from any other persons or sources are properly and duly
cited. All paragraphs and sentences, except those which are taken from reference are our own.
We further certify that the material has not been submitted either in whole or in part, for a degree
program at Wollo or any other university.
Department of Textile Engineering Page iii

Advisors’ Approval Sheet

This is to certify that the thesis entitled “salt free dyeing of cotton fabric with reactive dye by
treatment with fibroin waste: submitted in partial fulfilment of the requirements for the degree
Bachelor’s in Textile Engineering, the Graduate Program and has been carried out by Ermias
Fentaw ID.No WOUR/0585/08, Mohammed Ali WOUR/1186/08 and Mengstu Tegegne ID.No
WOUR/1111/08 under my supervision. Therefore I recommend that the student has fulfilled the
requirements and hence hereby can submit the thesis to the Institute.
____________ ____________ ____________

Name of Advisor Signature Date
Department of Textile Engineering Page iv

Acknowledgment
Primarily, we would like to give quite Glory to God who had contributed to the successful
completion of this thesis. We would like to express our gratitude to our thesis advisor, M/r
Assaye Dessie for his invaluable advice, guidance and his enormous patience throughout the
development of the project. We would also like to give credits to the laboratory assistants Dawit
for helping us during the experiment and pouring valuable knowledge and giving us wonderful
memories while us was in the laboratory.
We want to extend our thanks to M/r Ahmed Mohammed for full support and motivation
throughout our thesis work. Besides, we would also like to express our gratitude to thank our
loving brother, M/r Mulugeta Belayneh and friends who helped us and encouraged us to finish
this project. And last we would like to thank everyone who had contributed to the successful
completion of this thesis.
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Tables Contents
Abstract ........................................................................................................................................... ii
Declaration ..................................................................................................................................... iii
Acknowledgment ............................................................................................................................ v
List of Tables ................................................................................................................................. ix
List of Figures ................................................................................................................................. x
CHAPTER ONE ............................................................................................................................. 1
1. INTRODUCTION ................................................................................................................... 1
1.1 Background ........................................................................................................................... 1
1.3 Objective ............................................................................................................................... 5
1.3.2 Specific Objective........................................................................................................... 5
1.4 Benefit and Beneficiaries ...................................................................................................... 5
1.4.1 Benefit ............................................................................................................................ 5
1.4.2 Beneficiaries ................................................................................................................... 5
1.5 Significance of Project .......................................................................................................... 6
1.6 Scope of the Study................................................................................................................. 6
CHAPTER TWO ............................................................................................................................ 7
LITRETURE REVIEW............................................................................................................... 7
2.2 Cotton Cellulose Fiber .......................................................................................................... 7
2.3Treatment of cotton by cationization ..................................................................................... 9
2.3.1Why Treating or Cationization of Cotton Fabrics? ....................................................... 10
2.3.2 Treatment Reagents ...................................................................................................... 10
2.4 Silk Fibroin.......................................................................................................................... 11
2.4.1 Availability of Silk ....................................................................................................... 12
2.4.2 Production of Silk ......................................................................................................... 12
2.4.3 Chemistry of Amino Acid ............................................................................................ 14
2.4.4 Composition of Fibroin ................................................................................................ 15
2.4.5 Analysis of Amino Acid ............................................................................................... 15
2.4.6 Hydrolysis of Proteins .................................................................................................. 16
2.5 Reactive Dye ....................................................................................................................... 17
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2.5.1 Chemistry behind Reactive Dyeing .............................................................................. 17

2.5.2 Environmental Problem Associated with Reactive dye ............................................... 20
2.5.3 The Reason for Salt Free Dyeing of Cotton Fabric? .................................................... 20
2.6. Extraction Methods ............................................................................................................ 21
2.7. Dyeing Methods ................................................................................................................. 21
2.7.1Exhaust Technique ........................................................................................................ 21
2.7.2 Cold Exhaust Dyeing .................................................................................................... 21
2.7.3Warm, Hot Exhaust Dyeing Dyes ................................................................................. 22
2.7.4 Migration Exhaust Technique ...................................................................................... 22
2.7.5 All-in Method ............................................................................................................... 22
2.7.6 Padding Technique ....................................................................................................... 22
2.8 Performance Evaluation ...................................................................................................... 23
2.8.1 Colour Fastness Tests ................................................................................................... 23
2.8.2Color Strength (k/s) ....................................................................................................... 27
2.8.3 Color Absorption .......................................................................................................... 28
2.9 Research Gap....................................................................................................................... 28
CHAPTER THREE ...................................................................................................................... 30
3. MATERIALS AND METHODS .............................................................................................. 30
3.1 Materials and Chemicals ..................................................................................................... 30
3.1.1 Materials ....................................................................................................................... 30
3.2. Chemicals and Auxiliaries ................................................................................................. 30
3.3 Equipment and Apparatus ................................................................................................... 30
3.4 Experimental Procedure ...................................................................................................... 30
3.4.1 Sample Collection and Sample Preparation ................................................................. 31
3.4.2 Optimization of Extraction Conditions......................................................................... 32
3.4.3 Analysis of Fibroin Protein Hydrolysate ...................................................................... 33
3.4.4Optimization of Treatment Conditions .......................................................................... 33
3.4.5 Dyeing Procedure for Conventional Method................................................................ 34
3.4.6 Dyeing Procedurefor Pretreated or cationized cotton fabric ........................................ 34
3.4.7 Dyeing Procedurefor Pretreated or cationized cotton fabric with half salt .................. 35
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3.5 Evaluation Parameters ......................................................................................................... 36

3.5.1 Evaluation of Dye Uptake ............................................................................................ 36
3.5.2 Determination of Colour Measurement ........................................................................ 36
3.5.3. Washing Fastness Test................................................................................................. 37
3.5.4 Rubbing Fastness Test .................................................................................................. 37
3.5.5. Light Fastness Test ...................................................................................................... 38
CHAPTER FOUR ......................................................................................................................... 39
RESULT AND DISCUSSION.................................................................................................. 39
4.1. Optimization of Extraction Parameter................................................................................ 39
4.2 Optimization Treatment or Cationization Parameters ......................................................... 40
4.3 Dyeing of Treated and Untreated Cotton Fabric with Cold Brand DCT Blue Reactive Dye
................................................................................................................................................... 42
4.4. Effect of Treatment on Dye Fixation ................................................................................. 43
4.5. Effect of Treatment or Cationization on Colour Fastness .................................................. 44
4.5.1. Colourfastness to Washing .......................................................................................... 44
CHAPTER FIVE .......................................................................................................................... 46
CONCLUSION AND RECOMMENDATION ............................................................................ 46
5.1 Conclusion........................................................................................................................... 46
5.2. Recommendation ................................................................................................................ 46
References ..................................................................................................................................... 47
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List of Tables
Table 2. 1: Global Silk Production (in metric tons) ...................................................................... 13
Table 2. 2: Amino acid composition of silk fibroins .................................................................... 15
Table 3. 1: optimization of fibroin Hydrolysate from silk waste .................................................. 32

Table 3. 2: Optimization of fibroin Hydrolysate from fibroin waste (acid hydrolysis) ................ 32
Table 3. 3: optimization of treatment condition for cotton fabric (base hydrolysis) .................... 33
Table 3. 4: Optimization of fibroin Hydrolysate from fibroin waste (acid hydrolysis) ................ 34
Table 4. 1: Optimization of extraction conditions (Base hydrolysis) ......................................................... 39

Table 4. 2: Optimization of extraction conditions (Acid hydrolysis) ......................................................... 40
Table 4. 3: Optimization of treatment condition of cotton by fibroin hydrolysate (base hydrolysis) ......... 41
Table 4. 4: Optimization of treatment condition of cotton by fibroin hydrolysate (acid hydrolysis) ......... 41
Table 4. 5: Percentage fixation of treated cotton, treated cotton with half salt and conventional .............. 43
Table 4. 6: Washing fastness of untreated, treated and half salt, treated cotton fabric with fibroin
Hydrolysate extracted silk waste and dyed with DCT reactive dye ............................................................ 44
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List of Figures
Figure 2. 1: schematic representation of cotton fiber showing its various layers ........................... 8
Figure 2. 2: Chemical structure of cellulose ................................................................................... 9
Figure 2. 3: Chemical Structure of amino acid ............................................................................. 14
Figure 2. 4: Peptide bond formations between two amino acids .................................................. 14
Figure 2. 5: Hydrolysis of protein by hydrochloric acid ............................................................... 16
Figure 2. 6: alkaline hydrolysis of protein .................................................................................... 17
Figure 2. 7: General form of reactive dye ..................................................................................... 18
Figure 2. 8: Nucleophilic substitution reactions of DCT type reactive dyes ................................ 19
Figure 2. 9: Nucleophilic addition reactions of VS type reactive dyes ........................................ 19
Figure 2. 10: Colour change grey scales of British Standards Institution .................................... 24
Figure 2. 11: Degree of staining grey scales of British Standards Institution .............................. 24
Figure 2. 12: Depth of shade effect on light fastness .................................................................... 25
Figure 2. 13: CIELAB color system ............................................................................................. 28
Figure 3. 1: experimental procedure ........................................................................................................... 31

Figure 3. 2: fibroin waste ............................................................................................................................ 31
Figure 3. 3: extraction of fibroin Hydrolysate from fibroin waste .............................................................. 33
Figure 3. 4: applications of fibroin Hydrolysate solutions to cotton fabric in the laboratory ..................... 33
Figure 3. 5: dyeing of treated cotton fabric and conventional dyeing in the laboratory ............................. 35
Figure 4. 1: fibroin Hydrolysate solutions extracted from fibroin waste by base and acid hydrolysis
respectively ................................................................................................................................................. 39
Figure 4. 2: treatment of cotton fabric by fibroin Hydrolysate ................................................................... 41
Figure 4. 3: a: Dyed cotton fabric both treated and untreated ..................................................................... 42
Figure 4. 4: Dyed cotton fabric both treated and untreated......................................................................... 43
Figure 4. 5: dyed fabric during rubbing fastness test .................................................................................. 45
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List of Abbreviations
AOX Absorbable Organic halide

ASTM American society for Testing and Material
BOD Biological Oxygen Demand
C.I Color Index
COD Chemical Oxygen Deman
CSA Central statistical Agency
DCT Dichlorotriazine Reactive Dye
DMDHEU Dimethylol Dihydroxy Ethylene Urea
EPTAC Epoxypropyl Trimethyl ammonium Chloride
GSM Gram per Square Mete
ISO International Organization for Standardizatio
MCT Monochlorotriazine Reactive Dye
MLR Material to Liquor Ratio
TDS Total Dissolved Solid
VS Vinyl Sulphone Reactive Dye
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CHAPTER ONE
INTRODUCTION
1.1 Background
Cotton is the purest natural form of cellulose. The polymer chain of cotton consists of several
hundred to many thousands of β (1-4) D-glucose units linked to each other [1]. Cotton fibers are
commonly used in the textile industry because of their outstanding hygroscopic characteristics,
air permeability, biodegradability, no static electricity, and this fiber is well known for its
comfort, good absorption of moisture and good wicking properties etc [2].Ethiopia is rich of
cotton with a suitable growing conditions and vast land for investment in cotton production.
Dyes may be defined as substances that, when applied to a substrate provides color by a process
that alters, at least temporarily, any crystal structure of the colored substances. Such substances
with considerable coloring capacity are widely employed in the textile, pharmaceutical, food,
cosmetics, plastics, photographic and paper industries [3].
Dyeing is the aqueous application of color to the textile substrates, mainly using synthetic
organic dyes and frequently at elevated temperatures and pressures in some of the steps [4-5].
Reactive dyes are a category of dyes, which may covalently react with cellulose under suitable
conditions to make strong and stable bonds. These dyes are desirable for cotton fabrics with
appreciations to the excellent wash fastness arising from chemical bond formation between dye
and cellulose under alkaline conditions. The reactive dyes provide a full range of bright shades,
good wet fastness, and good light fastness, which is very desirable in textile applications [6].
In recent years, reactive dyes maintain the largest annual consumption in the world among the
dyes used for which establishes its important status in the dye manufacture industry. But some
problems, such as low dye utilization, large amount of electrolyte used and high volume of
wastewater discharged, always exist in the application of reactive dyes [7].
Department of Textile Engineering Page 1

The congenial of reactive dyes for dyeing of cotton, environmental problems associated with
their use have received attention [8].
Cotton is negatively charged in aqueous medium hence it will repel anion dye during dyeing.
Due to its repulsion, a large amount of salts is used to offset the repulsion in a dye bath. Because
cotton has only moderate affinity for most reactive dyes, big amounts of electrolytes such as
sodium chloride, NaCl or sodium sulphate, Na2SO4 are usually needed for exhaustion. Hence
dye bath exhaustion and fixation can still be as low as 50% for some dyes Therefore a significant
quantity of dye and salt, leading to serious environmental problems [2]. In conventional dyeing
process, the dyeing of one kilogram of cotton with reactive dyes demands from 70 to 150 liter
water, 0.6-0.8 Kg NaC1 and from 30 to 60 g dyestuffs. In industrial process more than 80,000
tons of reactive dyes are produced and consumed each year. After dyeing those electrolytes are
neither exhausted nor destroyed and only 60-65% dye utilization is attainable [9]. The residual
dyes and electrolyte was discharged as effluents have caused severe environmental problem and
disorders in living organisms [10].
Higher electrolyte concentration in the effluent causes worst effect such as; impairing the
delicate biochemistry of aquatic organism, destructive attack on pipes if sodium sulphate is used
as electrolyte due to the formation of alumino-sulphate complexes which swell and crack
concretes with considerable alumina content. This may lead to emission of hydrogen sulphide
gas under anaerobic conditions, dissolution of such sulfides and subsequent bacterial oxidation,
which may form the corrosive sulphuric acid. The aforementioned process will lead to higher
Biological Oxygen Demand (BOD), Chemical Oxygen Demand (COD) and Total dissolved
Solid (TDS) [11].
Many researchers in different countries worked with the need for cleaner, cost-effective, and
colorfast textile products, innovative technologies and improved processes for cotton coloration.
Different approaches, such as modification of the dye structure to make it more substantive to
cellulose, cationization of cellulose through chemical reaction with compounds containing
cationic groups or controlled dosing of dye and salt during the exhaustion process, have been
recommended to minimize or eliminate the above effluent problem [12].

The approach of producing fabric from yarns of cationic and normal cotton has been
commercialized by Japanese companies such as Kurabo Industries, Kanab Textiles and Toyobo.
On subsequent dyeing, these fabrics give a differential color and cross-dye effect. Cottum, Colo-
Coto and Viewline are some of the brand names of cationic cotton sold in international market
by the Japanese manufacturers [13].
Most of the techniques developed so far for reducing salt concentration in cotton dyeing are
complicated in nature. Modifying the cotton fiber to increase dye-fiber interaction is therefore
the best route to overcome the lack of affinity for cotton to reactive dyes making salt-free or low-
salt reactive dyeing to become an important research subject in recent years [14].
Different types of cationic reagents such as, choline chloride, biopolymers-chitosan starch and
their derivative, polyepichlorohydrinedimethyleaminetraizin(DCPEAT), synthetic polymer,
epoxy compound,polyamidepichlorohydrine(PECH) polymer, chlorotrize type quaternary
compounds, N methyloacrylamide, miscellaneous approach used for cationization and
modification of cotton fiber [12].
Chemicals or reagent used for cationization of cotton fiber have their limitations. Monomeric
cationic agents, such as EPTAC, often suffer from relatively low substantively, poor thermal
stability, and unpleasant odor. Polymeric cationic agents, ring dyeing, poor light fastness, and
change of hue are the major issues. But generally speaking, the more complicated the reagent,
the more synthesis steps are required resulting in high costs for the reagents. Additionally, vinyl
reagents must be free radical polymerized in situ with an initiator. Finally, reagents such as
chlorine chloride with no reactive group require a cross-linker such as DMDHEU and the
complications associated with cross-linking such as formaldehyde release and breaking strength
of the treated fabric. Most of chemicals or reagents can causes irritation to eye, skin and
respiratory organs which may result in headache, dizziness, nausea, shorten and vomiting.
Moreover, the minimization of Biological Oxygen Demand (BOD), Chemical Oxygen Demand
(COD) and Total Dissolved Solid (TDS) is incommensurate [14].

Finally, if the effluent must be treated, i.e. desalinated, the additional cost of the process renders
desalination unattractive just from an economical point of view. Therefore, an alternative
approach to eliminate or reduce on salt consumption and improve dye utilization and minimize
environmental problems is important.
Having this in mind, the aim of this paper is to study the use of amine group of fibroin
Hydrolysate extracted from fibroin waste as a sustainable material, which can be used in the
modification of cotton during the dyeing of cotton using reactive dyes.
1.2. Statement of Problem
In conventional dyeing process of cotton with reactive dyes, generally, 20-100 grams per liter of
an exhausting agent like sodium sulphate or common salt to overcome the static repulsion
between cotton surface charge and anionic reactive dyes so as to reinforce the substantively and
to enhance the dye adsorption and dying process. In the absence of adequate salt concentration,
reactive dye bath exhaustion is poor. Therefore, the main a part of the dye remains within the
bath and subsequently gets hydrolyzed within the dye bath within the presence of alkali. A part
of these hydrolyzed dyes gets exhausted on the material but remains unfixed. To get rid of the
hydrolyzed/unfixed dye, time-consuming, energy intensive and expensive washing off
procedures is required.
The application process of reactive dye for cotton writhes from the disadvantages of poor
exhaustion of dye into the fiber, and therefore the use of massive amounts of electrolytes that
ultimately create effluent containing high concentration of salt and poor use of reactive dye
fixation can causes worst effect such as impairing the delicate biochemistry of aquatic organism,
destructive attack on pipes if sodium sulphate is used as electrolyte due to the formation of
alumino-sulhato complexes which swell and crack concretes with considerable alumina content
and contribute to environmental issues such as highly colored effluent with high salt content. A
tiny part of electrolytes is discarded during effluent treatment, the residual result in increased
river salinity, marine life disturbance, freshwater scarcity, groundwater infertility, and elevated
values of BOD / COD (Biological Oxygen Demand / Chemical Oxygen Demand).

Having this in mind, the aim of this project is that the dyeing of cotton with reactive dyes using
eco-friendly naturally synthesized fibroin hydrolysate solution which is extracted from fibroin
waste for modification of cotton structure to reinforce dye uptake of cotton fiber in reactive
dyeing and to device different fastness properties and cost effective dyeing.
1.3 Objective
1.3.1 General Objective
 To dye cotton fabric using reactive dye without salt by treating cotton fabric using
fibroin waste.
1.3.2 Specific Objective
 To extract fibroin protein from fibroin waste
 To apply the extracted fibroin protein on cotton fabric
 To dye the treated cotton fabric with reactive dye without salt
 To dye cotton with reactive dye conventional dyeing method
 To investigate tests like dyeing properties and fastness properties to the dyed cotton.
 To analyze and compare the test results
1.4 Benefit and Beneficiaries
1.4.1 Benefit
It gives environmental and economical benefit by elimination of salt from reactive dyeing of
cotton. From ecological and environmental aspects, it eliminates or reduces the discharge of
huge amount of dye, salt and alkali with the waste water to the environment. In the economical
aspects, it minimizes cost of dyestuff, cost of salt, cost of waste water and effluent treatment.
1.4.2 Beneficiaries
This project plays crucial role in dyeing of cellulosic materials with reactive dye in textile
industries. Since reactive dye is more important for dyeing process this project plays significant
role in elimination of salt during dyeing process. So from the beneficiaries of this project,
For Textile company
 It increase profit by reducing cost of salt, dye stuff, cost of effluent treatment.
 It increases the quality of product by improving fastness properties of cotton.
 It reduces cost by reducing cost of salt, dye stuff, cost of effluent treatment.
For Textile student

 It will help them to think beyond this and to work further.

For community
 It will not get environmental pollution from disposed waste of fibroin.
For researcher
 from different disciplines like agriculture, environmental, engineering and others
1.5 Significance of Project

This project plays crucial role in dyeing of cellulosic materials with reactive dye in textile
industries. Since reactive dye is more important for dyeing process. So from the significance of
this project, this provides elimination of salt from reactive dyeing of cotton and improves dye
utilization; so it gives an economical and environmental benefit. From economical point of view,
it minimizes cost of dyestuff, cost of salt, cost of waste water and effluent treatment. In the
environmental aspects, it eliminates or reduces the discharge of huge amount of dye, salt and
alkali with the waste water to the environment. The cationizing/modifying agent also provides
eco-friendly benefit since it is completely bio-degradable as compared to the synthetic
chemicals.
1.6 Scope of the Study

The scope of this research work includes the collection of fibroin waste, investigation of
optimum extraction conditions of protein Hydrolysate obtained from fibroin waste, modification
of cotton by treatment with the extracted fibroin Hydrolysate protein, salt free reactive dyeing of
cotton, carrying out performance tests to the dyed cotton, analyzing the test results, and finally
summarizing the investigations and provide an appropriate recommendation.

CHAPTER TWO
LITRETURE REVIEW
2.1 Introduction
In recent years there has been an increasing awareness about environmental friendliness in all
human activities. The textile industry is a water intensive industry with water being used in every
stage of wet processing from sizing, desizing, scouring and bleaching of fibers to the dyeing,
finishing and printing of fabrics. In the textile industry, ecology and economy are the two
important aspects in the today’s worldwide scenario. This demands the minimization of pollution
load for the textile effluents, particularly in the dye-houses. With advantages in wet fastness
properties and a wide range of hue, reactive dyes are one of the most commonly used dyes for
cotton coloration. However, the conventional reactive dyeing process is plagued with a high
degree of salt utilization and colored effluent due to unexhausted, unfixed, and hydrolyzed
dyestuffs. This is caused by the same anionic charges of both reactive dyes and cotton in water,
resulting in poor affinity of most reactive dyes for cotton. With the need for cleaner, cost-
effective, and colorfast textile products, innovative technologies and improved processes have
been developed for cotton coloration. As an important root to obtaining the desired dyeing
performance with existing dyes, chemical modification of cotton fiber to impart cationic charges
have been widely researched in recent years. By introducing cationic groups into cotton fibers,
the affinity of anionic dyes for cotton was significantly improved, which allows the dyeing of
cotton fabrics without salt and to improve reactive dye utilization. With less chemical, water, and
energy consumption, the dyeing of cationized cotton is a potentially environmentally responsible
process [2].
2.2 Cotton Cellulose Fiber
Cellulose is a renewable, biodegradable and cheap raw material with appealing characteristics as
a biomaterial. It becomes a high-strength and durable wood material in conjunction with lignin
and hemicelluloses. Cellulose has been used as a building material in the form of wood and
clothing for thousands of years, as well as an energy source [15].
Cotton is the purest natural form of cellulose. Cotton fibers are one of the most important types
of fibers in the world even though there are a growing amount of synthetic fiber types available

and a high quantity of wood cellulose in the market. Because of its excellent characteristics
including regeneration, biodegradation, softness, skin affinity, hygroscopic properties, strength
and dye ability, cotton is widely used in clothing fields [16].
Cotton fibers have a structure of febrile as seen in Figure 2.1. The entire cotton fiber contains 88
to 96.5 % of cellulose, while the rest are non-cellulosic polysaccharides, up to 10 % of the total
fiber weight. Non-cellulosic components are made up of pectin, fats and waxes, proteins and
natural colorants. The main wall is only 0.5 - 1 μm dense in mature fibers and includes about
50% cellulose. The secondary wall, which contains approximately 92 - 95 % cellulose, consists
of concentrated layers with alternative shaped twists [17].
Figure 2. 1: schematic representation of cotton fiber showing its various layers
Cellulose's chemical structure is simple, composed of anhydroglucose units (AGU) joined to

form linear polymeric chains by β-1,4-glucosidic bonds, see Figure 2. A cotton cellulose
molecule's chain length, or degree of polymerization (DP), represents the number of
anhydroglucose units connected to form the chain molecule. Cotton DP may be as big as 14 000,
but various purification procedures with alkali can readily reduce it to 1000–2000. Probably the
crystalline regions have a DP of between 200 and 300. Accordingly, cotton's molecular weight
(MW) generally ranges from 50,000 to 1,500,000 depending on the cellulose source [18].
Through hydrogen bonding and Van der Waals forces, the individual chains conform to each
other along their lengths. The cotton fiber’s physical characteristics as a textile material, as well
as its chemical behavior and reactivity, are determined by cellulose molecules' arrangements
with regard to each other and the fiber axis [18,20].

Figure 2. 2: Chemical structure of cellulose
2.3Treatment of cotton by cationization

The process of modifying cotton by developing cat ion site on its surface without affecting its
bulk property is called cationization. Modifying the cotton fiber to increase dye-fiber interactions
is thus, best route to overcome the lack of affinity for cotton to commercial reactive dyes, so that
it can be dyed without salt. It was found that during cationization of cotton, etherification of
primary hydroxyl groups on cellulose takes place [14].
The introduction of cationic sites within the cellulose is the most expected technique to increase
the dye adsorption. Cationic sites can be introduced either by ammonization or cationization.
Cationization is one of the most important modifications for cellulose. The cationization is
mainly carried out to improve affinity toward anionic substances, such as dyes in conventional
textile processing and metal ions or unfixed dyes in effluent treatment. Cationic modification is
the method that has been employed in order to change the surface charge of cellulosic fibers [14,
22].
Cellulosic materials are commonly cationized in three ways: firstly, a direct cationization of
cellulose using a chemical compound with suitable functional groups that react with cellulose
hydroxyl groups. The second approach involves the addition of binding agent, such as
dimethyloldihydroxyethylene urea (DMDHEU), which reacts both with cellulose hydroxyl and
the functional group of cationic agent. This process is mainly used for textile application since
the common textile pad-dry-cure process can be employed. The third approach utilizes graft
polymerization to introduce monomeric or polymeric cationizing agents within the cellulose, but

it is not commercially applicable. Each process has advantages and disadvantages, but none of
these processes has been commercially adopted yet [14, 22].
2.3.1Why Treating or Cationization of Cotton Fabrics?

As previously mentioned, cellulose is the major component of cotton. While in contact with
water, negative charges build up on the surface of cotton due to the partial ionization of hydroxyl
groups on cellulose. Thus, cotton fibers have electrostatic repulsion to reactive and direct dyes,
which are sulfonated and negatively charged. Anionic dyes have to overcome a significant
adverse charge barrier before they are adsorbed on cotton fibers. High concentrations of
electrolytes, such as sodium chloride and sodium sulfate, are used in the conventional dyeing
procedure of cotton with reactive dyes to suppress the negative charge build-up and reduce the
solubility of dyes. Even with electrolytes added, the fixation rate of reactive dyes is still
relatively low, especially when high concentrations of dyes are applied. As a result, the dye bath
wastewater typically contains high concentrations of both salt and unexhausted dye, which
causes serious environmental problems [22].
By introduction of cationic groups into cotton fibers, the affinity of reactive dyes for cotton can
be significantly improved. The ionic attractions between cationized cotton and reactive dyes can
result in increased dye uptake, reduced or no electrolyte use, less dye washing off and less water
and energy consumption. The environmental problems caused by dye and salt in effluent can be
potentially mitigated by cationization pretreatment of cotton [22].
2.3.2 Treatment Reagents
Many researchers have investigated different kinds of treatment reagents for the cationization of
cotton. Based on the molecular weight; the cationic reagents can be divided into two groups,
monomeric reagents and polymeric reagents. Epoxy compounds, chlorotriazine type quaternary
compounds, N methylolacrylamide, chorine chlorideetc.are the monomers commonly used in
modification of cotton fiber.Synthetic polymers polyepichlorohydrindimethylamine, polyamide
epichlorohydri n type polymers, poly-(4-vinylpyridine) quaternary ammonium compounds and
dendritic polymers, and biopolymers-chitosan, starch and their derivatives are typical compounds
commonly used in modification of cotton [14,22].

All agents used for cationization, both monomeric and polymeric, have their limitations, but
generally speaking, the more complicated the reagent, the more synthesis steps are required
resulting in high costs for the reagents. Additionally, vinyl reagents must be free radical
polymerized in situ with an initiator. Finally, reagents such as choline chloride with no reactive
group require a cross linker such as DMDHEU and the complications associated with cross
linking such as formaldehyde release and reduced breaking strength of the treated fabric.
Moreover, all the above chemicals are non-biodegradable as well as non-renewable [14, 22].
Since most synthetic chemicals used for pre-treating of cotton are not safe environmentally,
having this in mind, fibroin, the natural waste product, has been used as a substitute for
improving g cotton dye-ability in this project.
2.4 Silk Fibroin
Silks are commonly defined as protein polymers, which are present in the glands of arthropods
such as silkworms, spiders, scorpions, mites, and then spun into fibers during their
metamorphosis. Silkworm silk has been used in the traditional textile industries for more than
400 years; it is admired for its soft, pearly luster and good mechanical properties. All silk
produced by the worm is composed of two substances: fibroin, the true thread, and sericine,
which are a hard, gummy coating of the fibroin [26].
Silk fibroin is a protein synthesized in large quantity by the silk gland of the caterpillar as two
polypeptide chains linked by a disulfide bridge and stored in the lumen of silk gland. The larger
heavy chain is glycine rich, and most of its sequence is a repeat of Gly-Ala/Ser dipeptides.It is
the raw material for producing precious fabrics, parachutes, tire lining materials, artificial blood
vessels and surgical sutures [27].
Silk fibroin from the domesticated silkworm Bombyxmori is a naturally occurring biopolymer
with charged hydrophilic terminal regions that end-cap a hydrophobic core consisting of
repeating sequences of glycine, alanine, and serine residues.Fibroin consists of non- crystalline
and crystalline regions. The crystalline region tends to be oriented along the fiber axis because
the fiber is drawn as it is extruded from the spinnerets of the silkworm [26].

2.4.1 Availability of Silk

Ethiopia’s bimodal rainfall pattern, ambient temperature, and other agro-ecological factor
provide a fertile ground for mulberry and caster seed cultivation and silk worm production.
InAwassa, Awash Melkassa, Nazareth, Addis Ababa, Debrezeit, Bahirdar,and Kombolcha silk
rearing is started with good progress [28].
The major silk producing countries in the world are; China, India, Uzbekistan, Brazil, Japan,
Republic of Korea, Thailand, Vietnam, DPR Korea, Iran, etc. Few other countries are also
engaged in the production of cocoons and raw silk in negligible quantities; Kenya, Botswana,
Nigeria, Zambia, Zimbabwe, Bangladesh, Colombia, Egypt, Japan, Nepal, Bulgaria, Turkey,
Uganda, Malaysia, Romania, Bolivia, etc [29].
2.4.2 Production of Silk

Cultivation of caster and cassava is quite easy and requires only two months of growing period
before first leaf harvest. Furthermore, Eri silkworm cocoons can be harvested 6 - 7 times within a
year, ensuring continual revenue even at times of variable weather to secure income and
livelihoods [30].
In Ethiopia, according to sericulture training guide report (2005), considerable quantity of dried
cocoons over 3000kg was produced both by farmers and investors from which 95% was
marketed to Addis. According to Sabahar yearly report, currently the silk production in Ethiopia
has increased by almost 200% since 2014 [28].
It is estimated that out of about 1 million tons (fresh weight) of cocoons produced worldwide
approximately 4, 00,000 tons of dry cocoon are generated, that have 350,000 tons of fibroin and
50,000 tons of recoverable sericine [27].

Table 2. 1: Global Silk Production (in metric tons)
No Countries 2014 2015 2016 2017 2018

1 Bangladesh 44.5 44 44 41 41
2 Brazil 560 600 650 600 650
3 Bulgaria 8 8 9 10 10
4 China 146,000 170,000 158,400 142,000 120,000
5 Colombia 0.5 0.5 - - -
6 Egypt 0.8 0.8 1.2 1.1 1.25
7 India 28,708 28,523 30,348 31,906 35,261
8 Indonesia 10 8 4 2.5 2.5
9 Iran 110 120 125 120 110
10 Japan 30 30 32 20 20
11 North 320 350 365 360 350
Korea
12 South 1.2 1 1 1 1
Korea
13 Philippines 1.1 1.2 1.82 1.5 2
14 Syria 0.5 0.3 0.25 0.25 0.25
15 Thailand 692 698 712 680 680
16 Tunisia 4 3 2 2 2
17 Turkey 32 30 32 30 30
18 Uzbekistan 1,100 1,200 1,256 1,200 1,800
19 Vietnam 420 450 523 520 680
20 Madagascar 15 5 6 7 7
Total 178,057.62 202,072.83 192,512.27 177,507.35 159,648.00

2.4.3 Chemistry of Amino Acid

Amino acids are the monomers that make up proteins. Specifically, a protein is made up of one
or more linear chains of amino acids, each of which is called a polypeptide. Amino acid, any of a
group of organic molecules that consist of a basic amino group (−NH2), an acidic carboxyl group
(−COOH), and an organic R group (or side chain) that is unique to each amino acid. The term
amino acid is short for α-amino [alpha-amino] carboxylic acid. Each molecule contains a central
carbon (C) atom, called the α-carbon, to which both an amino and a carboxyl group are attached.
The remaining two bonds of the α-carbon atom are generally satisfied by a hydrogen (H) atom
and the R group. All amino acids have a similar basic structure like that in Figure 2.6 with
different amino acids differing only in the specific structure that lies in the chemical group or
side carbon chain labeled “R” [14,31].
.
Figure 2. 3: Chemical Structure of amino acid
Peptides are a molecule composed of two or more amino acids. The bond that holds together the
two amino acids is a peptide bond or a covalent chemical bond between two compounds (in
figure 2.7, two amino acids). It occurs when the carboxylic group of one molecule reacts with the
amino group of the other molecule, linking the two molecules and releasing a water molecule
[27].
Figure 2. 4: Peptide bond formations between two amino acids

2.4.4 Composition of Fibroin

Table 2. 2: Amino acid composition of silk fibroins
No Name of amino acid Residue (%)

1 Glycine 44.7
2 Alanine 25.7
3 Valine 2.4
4 Leucine 0.53
5 Isoleucine 0.6
6 Serine 11.9
7 Threonine 1.0
8 Aspartic acid 1.6
9 Glutamic acid 1.1
10 Lysine 0.4
11 Arginine 0.5
12 Histidine 0.2
13 Tyrosine 5.4
14 Tryptophan 1.1
15 Methionine 0.1
16 Cysteine 0.2
17 Proline 0.5
18 Phenylananine 1.6
2.4.5 Analysis of Amino Acid

Amino acid analysis is a fundamental biochemical technique used to determine the amino acid
content of amino acid, peptide and protein containing samples. Different methods are available
for the separation and analysis of amino acids and proteins. These methods exploit the chemical
differences of amino acids and in particular their ionization and solubility behaviour. The first
step of amino acid analysis involves hydrolyzing these peptide bonds. The liberated amino acids
are then separated, detected, and the last step is quantification of the individual amino acids [31].

2.4.6 Hydrolysis of Proteins

Hydrolysis is important to destroy fat and carbohydrate. hydrolysis is accomplished by treatment
of a purified protein with a concentrated acid, base or salt solution at a very high temperature.
These conditions cleave the peptide bond between each and every amino acid residues.
Thehydrolyzed protein sample is then separated into its constituent amino acids. Methods
important for amino acid separations include ion exchange chromatography, gas
chromatography, high-performance liquid chromatography, and most recently, capillary zone
electrophoresis [14].
Currently, the most common analytical method to quantify amino acids is based on ion exchange
chromatography using post-column derivatization with ninhydrin and Spectrophotometric
detection. Newer methodologies are based on liquid chromatographic separation with detection
by mass spectrometry or spectrophotometry [31].
Figure 2. 5: Hydrolysis of protein by hydrochloric acid

Figure 2. 6: alkaline hydrolysis of protein
2.5 Reactive Dye

In 1956 Rattee + Stephen (ICI) introduced “first” reactive dyes– chlorotriazines. Reactive dyes
are chemically react with cotton fiber and form covalent bond between carbon atoms of dye
reactive group and oxygen atoms of cotton hydroxyl groups under alkaline conditions and
become a part of the fiber [2,19].
Reactive dyes are best as they can be applied by various methods and give better fastness
properties. The exhaustion of the dye onto the fiber requires large quantity of salt. The salt used
is not exhausted onto the fiber and remains in the dye-bath. Also the dye exhaustion onto the
fiber is only around 60% to 70%. The left over unexhausted dye solution is discharged as
effluent, thereby polluting the environment [14].
2.5.1 Chemistry behind Reactive Dyeing

The dyeing principle is based on fiber reactivity and involves the reaction of a functional group
of the dyestuff with a site on the fiber to form a covalent link between the dye molecule and the
substance.
The Four structural feature of typical reactive dyes molecule are: chromophoric group(C) is a
conjugated system which contributing the color, the reactive system(x), enabling the dye to react
with hydroxyl group in cellulose by addition or substitution reactions In between the two

functional groups, A bridging group(B) that links the reactive system to the chromophore but
also insulates the chromogen from the reactive group to prevent the color generated by the
chromogen from changing and the last one is One or more solublising group(S), usually
sulphuric acid substituent attached to the chromophoric group which provide characteristics such
as water solubility, substantivity, migration and wash-off [2,14].
Figure 2. 7: General form of reactive dye
Reactive dyes are classified depending on the type of reaction with cellulosethrough,dyes
reacting through Nucleophilic substitution reactions and dyes reacting through
Nucleophilicaddition reactions.Dyes reacting through Nucleophilic substitution reactions are
haloheterocycle based dyes and dyes reacting through Nucleophilic addition reactions are vinyl
sulfone based dyes.halogenic heterocyclic derivatives such as MCT, the reaction mechanism
with cellulose is a nucleophilic substitution of a labile chlorine, fluorine, or nicotinyl leaving
group activated by an adjacent nitrogen atom in the heterocyclic ringas shown in figure 2.4.The
vinyl sulfone group reacts with cellulose by0nucleophilic addition to the carbon-carbon double
bond activated by the adjacent electron-attracting sulfone group. As shown in Figure 2.5, the
vinyl sulfone is not present in the dye molecule initially and should be generated in the dyebath
by elimination of sulfate ion from a sulfatoethylsulfone group under basic conditions [22,14].

Figure 2. 8: Nucleophilic substitution reactions of DCT type reactive dyes
Figure 2. 9: Nucleophilic addition reactions of VS type reactive dyes
However, for both reaction mechanisms, alkaline conditions are required to enable the reaction
and there are competing hydrolysis reactions of the dye as shown in figure 2.4 and figure 2.5.
Thus, many reactive dyes applied with exhaustion methods, especially with high liquor ratio,
have relatively low fixation rates. To obtain a higher fixation rate, many of the newer reactive

dyes have more than one reactive group. Those bifunctional reactive dyes can have two identical
or different reactive groups in the dye molecule [20,22].
2.5.2 Environmental Problem Associated with Reactive dye

The large amount of unfixed and hydrolyzed reactive dyes in wastewater may cause serious
environmental problems since they are water-soluble and cannot be easily removed by
conventional treatment systems [23]. Also, the affinity for cotton of most commercially available
reactive dyes is poor since both reactive dyes and cotton carry anionic charges in water. High
concentrations of electrolytes are required to help exhaust the reactive dyes. For dark shades with
conventional reactive dyeing, the concentrations of electrolytes added can be as high as 100
g/L17. Most of the electrolytes remain in the effluent after dyeing and they may also cause an
environmental problem if dye house effluent is discharged without treatment. The substantial
level of unfixed and hydrolyzed dyes is also a major reason for the heavy water consumption for
rinsing. Even though reactive dyes are known for their excellent wet fastness properties, multiple
soaping and rinsing are commonly needed to remove unfixed dyes and ensure acceptable wash
fastness of dyed cotton fabrics. The rinsing cycles required for removing hydrolyzed reactive
dyes greatly extended the entire dyeing process [22,23].
2.5.3 The Reason for Salt Free Dyeing of Cotton Fabric?
In recent years there has been an increasing awareness about environmental friendliness in all
human activities. The textile industry is a water intensive industry with water being used in every
stage of wet processing from sizing, desizing, scouring and bleaching of fibers to the dyeing,
finishing and printing of fabrics. Every textile plant requires large volumes of water and
produces high volumes of effluent wastewater. The typical textile dye wastewater composition is
quite complex. The demand for environmental friendly dyes and application processes is
therefore very strong [22,2].
Reactive dyes have become very popular for cotton due to its brilliancy, variety of hue, high wet
fastness, convenient usage and high applicability [22].
The textile substrate and reactive dye molecule, not necessarily should have of homogeneous
characteristics to combine with each other. In such case, we require some catalyst to facilitate

dyeing action on fabric. Salt plays this crucial role of catalyst. Salt has an extremely high affinity
for water. Broadly speaking, Salt is necessary in three ways, firstly, to drive dye into textile
during the dyeing process in textile. Secondly, use of salt leads to maximum exhaustion of dye
molecules during dyeing process in textiles. Thirdly it is used as an electrolyte for migration,
adsorption and fixation of the dyestuff to the cellulose material [24].
One of the major problem of reactive dyeing is the large amount of electrolyte required for
exhaust and pad application which leads to environmental problem. In addition, inadequate dye
exhaustion and fixation result in colored effluents. As environmental problems arising from
dyeing with reactive dyes have become critical, many studies have been devoted to improving
the substantivity of cotton fiber for reactive dyes, thus reducing or eliminating the amount of
electrolyte used [24,25].
2.6. Extraction Methods
The dry and wet processing methods are methods used to convert proteins into free amino acids,
films, coating and thermoplastics. Dry processing which is thermomechanical process, involves
blending of the reagents, such as plasticizers, and cross-linkers, with proteins without the use of
solvent. The thermomechanical energy is used to activate the reaction and form the final product.
Wet processing involves the proteins being dissolved in solution by mixing it with the
appropriate solvent and reagents. This process allows for more varied modification of the protein
through copolymerization and functional group modification [31].
2.7. Dyeing Methods

2.7.1Exhaust Technique
The exhaust technique is the most used method for application of reactive dyes as it is resistant
to small changes of system variables. It has two steps; exhaustion and fixation. During
exhaustion the dyes are exhausted from the dye bath and come into the fiber phase. High
electrolyte concentration is required to have adequate exhaustion of the dye [31].
2.7.2 Cold Exhaust Dyeing
In this method dyeing begins at 25–30°C and maintained while dye is added. Salt is added in 3–
4 portions over 30–60 min, the size of the addition is increased each time. The amount of salt

used depends on the depth of shade. Dyeing continues for 15 min after the final addition of salt,
then soda ash is added portion wise over 15 min. Dyeing continues for 30–45 min [31].
2.7.3Warm, Hot Exhaust Dyeing Dyes
This is an isothermal technique for depths of shade above 0.5 % of the weight of the fabric(owf).
The process begins at 40°C with salt at pH 7.0. The temperature is brought rapidly up to the
dyeing temperature of 60–80°C depending on the dye. The dye is added over 10–15 min and the
dyeing run for 30 min before adding alkali portion wise over 10–20 min. Dyeing continues for
45–60 min before dropping the dye bath and starting the wash-off sequence [31].
2.7.4 Migration Exhaust Technique
This method is preferred for pale shades below 0.5 % of the weight of the fabric. Dyeing starts at
50°C with salt at pH 7.0. Dye is added over 20 min and the temperature is raised to the
temperature of 95°C. After 20 min of this temperature, the dye bath is cooled to 60–80°C and
alkali is added portion wise over 20 min. After another 30 min, the dyebath is drained and the
washing sequence is started [31].
2.7.5 All-in Method
Dyeing starts at 25°C with salt and alkali which is mixed soda ash and caustic soda and runs for
15 min, before adding dyes over 10 min. After a further 15 min, the temperature is brought up to
80°C and maintained at this temperature for 30–60 min before draining the dye bath and starting
the washing process [31].
2.7.6 Padding Technique
One of the padding techniques is continuous dyeing, where the fabric is passed through bath
containing dye solution and then squeezed through a padding nip at controlled pressure. This
process of squeezing applies dyestuff to the fabric by physical means. The alkali is added to the
dye solution in a second padding treatment. The fabric is dried to a moisture content below that
at which migration can occur and then steamed followed by a washing-off process [32].

2.8 Performance Evaluation

2.8.1 Colour Fastness Tests
Colour fastness is the resistance of a material to change in any of its colour characteristics or
extent of transfer of its colourants to adjacent white fabrics or Color fastness refers to the
resistance of a color to fade or bleed of dyed or printed textile material to various types of
influences e.g. water, light, rubbing washing, perspiration etc. The colour fastness is usually
rated either by loss of depth of colour in original sample or it is also expressed by staining scale
and is evaluated using grey scales and chromatic transference scales. In this study, the samples
were evaluated for colour fastness tests such as colour fastness to washing, light. Also the
samples were subjected to evaluation after 15 washes to assess the wash fastness [36].
Visual assessment of colour fastness
The most well-known and used system of visual assessment is the grey scale. There are two
types of grey scales. One set measures the change in shade of a coloured textile and the other
measures the degree of staining in an adjacent fabric. Grey scales have a rating of 1 to 5 with 1
being the worst colour performance and 5 being the best [34, 36].
Colour change grey scales; these scales consist of five pairs of grey coloured material numbered
from 1 to 5. Number 5 has two identical greys, number 1 grey scale shows the greatest contrast,
and numbers 2, 3 and 4 have intermediate contrasts. After appropriate treatment the specimen is
compared with the original untreated material and any loss in colour is graded with reference to
the grey scale. When there is no change in the colour of a test specimen it would be classified as
'5'; if there is a change it is then classified with the number of the scale that shows the same
contrast as that between the treated and untreated specimens [36].

Figure 2. 10: Colour change grey scales of British Standards Institution
Degree of staining grey scales; A different set of grey scales is used for measuring staining.
Fastness rating 5 is shown by two identical white samples (that is no staining) and rating 1 shows
a white and a grey sample. The other numbers show geometrical steps of contrast between white
and a series of greys. A piece of untreated, unstained, undyed cloth is compared with the treated
sample that has been in contact with the test specimen during the staining test and a numerical
assessment of staining is given.
Figure 2. 11: Degree of staining grey scales of British Standards Institution

2.8.1.1 Colour Fastness to Light

This test measures the resistance to fading of dyed textiles when exposed to daylight.A fabric
exposed to light is influenced by its depth of shade, the intensity of the light, the wavelength
profile of the light, the temperature of the fabric, contaminants within the fabric, and the
moisture content of the fabric [34, 37].
Depth of shade;the depth of shade of a colour has a significant effect on the light fastness of a
product. Light fastness is the degradation of a fixed number of dye molecules per exposure to a
fixed intensity of light. A deeper shade is affected less than a pale shade, as a smaller percentage
of the overall dye molecules are degraded per light exposure.
Figure 2. 12: Depth of shade effect on light fastness
Wavelength; The wavelength of the incident light on the dye bonds significantly influences
the rate of degradation of those bonds . A wavelength profile different from natural daylight
could show an increased or decreased fastness rating, depending on the dye tested. Moisture; the
level of moisture in the fabric can influence the rate of colour degradation. The presence of
moisture during a light fastness test can lead to the generation of peroxide radicals that
significantly influence the results of the test. Contaminates; some fabrics are exposed to chemical
contaminates when they are in use. These contaminates can include salt and chlorine. Tests have
been developed to intermittently spray the fabric with chemical-contaminated water during the
test. Like water, chemical contaminates can become involved in the chemical degradation of the
dye molecules [34, 37].

2.8.1.2 Colour Fastness to Washing

This method used for assessing the resistance of the color of the dyed fabric to all kinds of
washing in water with soap and detergent. A fabric fastness to washing is influenced Soaps and
detergents, agitation time and Temperature. Soaps and detergents; in a wash fastness test the
soap or detergent is used to remove unfixed dye from the fabric. The use of a soap or detergent
can also cause a breakage of bonds that hold the dye on the fiber. The pH of the soap or
detergent has a major influence on the movement of dye from the fabric into the wash liquor and
from the wash liquor to adjacent fabrics. Agitation time; the agitation time of a laundering test
can significantly affect the test results. Short test times limit the dissolution of unfixed or poorly
fixed dye into the liquid or onto the adjacent fabric. Longer test times can allow the dye to
deposit on and migrate into the fibers of adjacent fabrics following a mechanism similar to
dyeing, leading to an increase in the level of staining. Temperature; Low test temperatures limit
the migration of dye from the fabric surface and generally cause low levels of staining on
adjacent fabrics. Higher test temperatures provide the energy required to swell fibers and migrate
dyes. At higher temperatures adjacent fabrics are more likely to be stained by any free dyes in
the wash liquor [34].
2.8.1.3 Rubbing Fastness

Rubbing of two different coloured fabrics or one coloured and another white fabric may cause
transfer of colour from one to the other. This is caused by the presence of; superficial dyes,
inadequate washing at the end of dyeing, formation of few coloured molecules at the textile air
interface, water solubility of dyes or weak dye fiber attachment on the surface layer. Wet rubbing
fastness produces a lower result when compared to dry rubbing. This may be due to
solubilisation of a part of the dye and its migration to the surface of coloured fabric [35].
2.8.1.4 Grading of Fastness Properties

The extent of change in colour change and staining is assessed with two different grey scales
graded from 1 to 5, where 1 is very poor and 5 is excellent. Generally, a grade of 4 or above is
deemed acceptable for commercial use [34].
Light fastness is graded on a system from 1 to 8, where 1 is very poor and 8 is excellent.

2.8.2Color Strength (k/s)

Colorimeter is the science element that deals with colour measurement. Colour is the
consequence of colorants physically modifying light as identified by the human eye called a
response process and expressed in the brain as a perceptual process that induces psychology.
The color strength of the dye is a measure of its ability to impart color to other materials. This
property is characterized by the absorption in the visible region of the spectrum and can be
expressed as a color strength value [37].
The colour strength (K/S) is used to express the reflectance-based reduction ratio of the light
owning to the absorption and dispersion achieved. The higher the colour strength the more dye is
fixed on the fabric and the effect of low dye variation will be on the fabric because light is more
reflected in a uniform surface [17, 37].
CIELAB system has become the universally accepted colorimetric reference system for
quantifying and communicating color. CIELAB is the reference color model used by the paper
making and graphic arts industries. CIELAB forms the foundation of color management and is
generally the ICC profile connection space used for gamut mapping. The basic architecture and
operating premise of CIELAB is based on scientific theory demonstrating that the brain
translates retinal color stimuli into distinctions between light and dark (lightness), and between
mutually exclusive zones of opposing colors: red/green, and blue/yellow.The CIELAB color
system contains one “channel” for lightness (L*) and two channels for color (a* and b*). In the
three dimensional model, the chromatic a* axis extends from green (-a*) to red (+a*), and the
chromatic b* axis extends from blue (-b*) to yellow (+b*). The lightness dimension, represented
by L*, ranges from 0 (pure black) to 100 (diffuse white). The point at which the a* and b* axes
cross, at the L* value of 50, is pure, balanced, neutral gray [35, 37].

Figure 2. 13: CIELAB color system
2.8.3 Color Absorption

When atoms or compounds absorb light of the proper frequency, their electrons are excited to
higher energy levels. Colored compounds absorb visible light and this absorption is responsible
for their color. A material absorbs all wavelengths of visible light appears black [37].
2.9 Research Gap

Salt free dyeing of cellulosic fiber by using cat-ionizing agent such as synthetic chemicals of
ammonium salts has been carried out by many researchers, but which are non-biodegradable.
These chemicals become a permanent part of the fiber and can cause skin irritation and health
problems like cancer and mutagen. Most of the amines are highly toxic in nature and they cause
irritation to eyes, skin and respiratory organs which may result in headache, dizziness, shortness
of breathing, nausea and vomiting. Some chemicals need cross linking agents which in turn
facilitate or release toxic chemicals. Some of these chemicals are expensive and difficult to
manufacture. The various routes for cationization of cellulose have therefore to be modified to
make them free from hazards.
This project provides an alternative approach since most synthetic chemicals used for treatment
or cationization of cotton is not safe environmentally. Here of the treatment of cotton by using
biodegradable natural waste-products of fibroin hydrolysate solution extracted from silk fibroin

is a possible substitute for various hazardous chemicals used for the treatment of cotton. Thus, an
agreeable treatment and dyeing of cotton to the environment is investigated in this research.

CHAPTER THREE
MATERIALS AND METHODS
3.1 Materials and Chemicals

3.1.1 Materials
Waste of silk fibroin was collected from Antsohiya. Full bleached 100% cotton fabric with count
21 Ne warp and weft count with 74 ends per inch and 66 picks per inch was obtained from Wollo
University Laboratory.
3.2. Chemicals and Auxiliaries
Sodium hydroxide (NaOH), Sodium carbonate (Na2CO3), Sodium chloride (NaCl), Blue DCT
reactive dye, detergent and leveling agent were used throughout this research work to carry out
the extraction, modification and dyeing processes. All those listed chemicals auxiliaries were
obtained from and Wollo University Laboratory.
3.3 Equipment and Apparatus
Digital electronic balance, The pH meter, COLOR-EYE 3100, , wash fastness tester, auto dryer,
Beakers, were mainly used throughout this research work and found from Kombolcha Textile
Share Company (KTSC) Laboratory.
3.4 Experimental Procedure
In this research, fibroin Hydrolysate was extracted from fibroin waste. The pre-treated cotton
fabric was pre-treated with fibroin Hydrolysate to introduce positive sites on the surface for
dyeing with cold brand reactive dyeing. The effect of dyeing temperature and time on dye
exhaustion was studied on the reactive dyes. Colourfastness properties of dyed fabrics were also
studied.

Figure 3. 1: experimental procedure
3.4.1 Sample Collection and Sample Preparation

Waste of silk fibroin was collected from Antsohiya washed thoroughly with hot water and
detergent to remove impurities and dirt on the surface of the fibroin. The cleaned cocoon was
exposed to sunlight for drying and then converted into small pieces.
Figure 3. 2: fibroin waste

3.4.2 Optimization of Extraction Conditions

The grounded silk fibroin was dissolved at different concentration of sodium hydroxide and
hydrochloric acid for a constant treatment time and temperature in order to determine the
optimum extraction parameters and the pH of the solution was brought to 11-13 and 5-6
respectively. The resultant solution was filtered and its absorption was determined by UV-
Visible spectroscopy. The temperature, concentration, pH and time combination yielding the
maximum absorption were taken as optimum condition for fibroin Hydrolysate solution
extraction from fibroin waste.
Fibroin Hydrolysate solution was extracted at different combinations of Concentration of NaOH
(20, 30g/l), Concentration of hydrochloric acid (20, 30g/l) with a constant Temperature (80°C),
pH levels of (11 and 5), Time (1:30 Hr.).
Table 3. 1: optimization of fibroin Hydrolysate solution from fibroin waste

Number of Concentration Temperature Time in hr pH MLR
trials of NaOH (oc)
1 20 80 1:30 11 1:20
2 30 80 1:30 11 1:20
Table 3. 2: Optimization of fibroin Hydrolysate from fibroin waste (acid hydrolysis)
Number of Concentration Temperature Time in hr pH MLR

trials of HCL (oc)
1 20 90 1:30 5 1:20
2 30 80 1:30 5 1:20

Figure 3. 3: extraction of fibroin Hydrolysate from fibroin waste

3.4.3 Analysis of Fibroin Protein Hydrolysate
The percentage dissolution (yield) was calculated using equation (1) by drying the residual after
treatment.
(𝑊1−𝑊2)
Fibroin extracted yield (%) = ..................................................Equation 1
𝑊1
Where, W1 = Original weight of silk, W2 = Residual Weight of silk after treatment in gram
3.4.4Optimization of Treatment Conditions
The application of fibroin Hydrolysate solution on bleached cotton was done by batch process at
different combinations of Temperature, treatment Time, at neutral pH and concentrations of
fibroin Hydrolysate solution. Cationization parameters were optimized based on minimum
scorching of fabric, dyeing evenness and maximum K/S values.
Figure 3. 4: applications of fibroin Hydrolysate solutions to cotton fabric in the laboratory
Table 3. 3: optimization of treatment condition for cotton fabric (base hydrolysis)

Number of Concentration of Tempe Treatment pH MLR

trials fibroin hydrolysate rature Time in hr
solutions (oc)
1 20 90 15 Neutral 1:20
2 30 80 30 Neutral 1:20
Table 3. 4: Optimization of fibroin Hydrolysate from fibroin waste (acid hydrolysis)

solutions (oc)
1 20 80 25 Neutral 1:20
2 20 60 45 Neutral 1:20
3.4.5 Dyeing Procedure for Conventional Method

The full bleached cotton fabric was dyed withcold brand blue DCT reactive dye solution for 2%
shade and the material to liquor ratio of 1:20. The fabric was entered at 300C to the dye bath with
a dye and 1g/l levelling agent. After 20 minutes half of 30g/l sodium chloride salt was added.
The dyeing was continued while raising the temperature to 40oC in 25 minutes and the remaining
30 g/l sodium chloride salt was added in the intermediate. The dyeing was continued at 400C for
10 minutes and 15 g/l soda ash was added to the solution and dyeing was continued for 15
minutes. After dyeing was completed soaping was carried out at boiling temperature for 20
minutes by using 2gpl standard soap. The dyed fabric was rinsed by carried out washing with
warm water (60 0C) for 5min and with cold water for 5 min.
3.4.6 Dyeing Procedure for Pre-treated or cationized cotton fabric

The pretreated (cationized) cotton fabric with silk extracted fibroin was immersed in 2% (o.w.f,
weight percent of dye relative to fiber) of cold brand blue DCT reactive dye solution with a
liquor ratio of 1:20. The dyeing temperature was kept at 30ºC constantly for 60 min and the pH

of the dye solution maintained at 11. Later, 5 g/L Na2CO3 was added to the dye solution after 45
min and continue dyeing at 30ºC for 15 min. Dyed fabric was rinsed with cold water and finally
washed with hot water using detergent at room temperature and allowed to air dry.
3.4.7 Dyeing Procedure for Pre-treated or cationized cotton fabric with half
salt
The pretreated (cationized) cotton fabric with silk extracted fibroin was immersed in 2% (o.w.f,
weight percent of dye relative to fiber) of cold brand blue DCT reactive dye solution with a
liquor ratio of 1:20. The dyeing temperature was kept at 30ºC constantly for 60 min, the dye bath
with a dye and 1g/l levelling agent. After 20 minutes half of 30g/l sodium chloride salt was
added and the pH of the dye solution maintained at 11. Later, 5 g/L Na2CO3 was added to the
dye solution after 25 min and continue dyeing at 30ºC for 15 min. Dyed fabric was rinsed with
cold water and finally washed with hot water using detergent at room temperature and allowed to
air dry.
Figure 3. 5: dyeing of treated cotton fabric and conventional dyeing in the laboratory

3.5 Evaluation Parameters

3.5.1 Evaluation of Dye Uptake
3.5.1.1 Determination of Dye Exhaustion (% E)
The percentage dye exhaustion for DCT reactive dye was determined by comparing
concentration of dye in dye bath before and after dyeing. This was done with the help of a
UV/Vis spectrophotometer at the maximum wavelength of absorbency and a calibration curve.
The percentage dye exhaustion was calculated using equation (1):
(𝐴0−𝐴1)
%E = ∗ 100.............................................................. Equation 1
𝐴0
Where, A0 and A1 indicate the absorbencies at maximum wavelength (λmax) of the dye
originally in the dye bath and of residual dye after dyeing respectively.
3.5.1.2 Determination of Fixation (% F)

The reflectance (R) values at all wavelengths were measured. The maximum K/S value of dyed
fabric at the certain wavelength was measured by using Colour Eye 1500 before and after
soaping. The percentage of dye fixation was calculated using equation (2).
(𝐾/𝑆)a
%F = (𝐾/𝑆)𝑏 ∗ 100........................................................................ Equation 2
Where, (K/S)b and (K/S)a are the colour strength before soaping and after soaping respectively.
3.5.1.3 Determination of Total Dye Utilization (%T)

The total dye utilization percentage (%T) of the fabric was calculated by using equation (3).
(𝐸∗𝐹)
%T = ............................................................................... Equation 3
100
Where, E and F are the dye exhaustion and dye fixation respectively
3.5.2 Determination of Colour Measurement
Spectrophotometric readings were carried out using Minolta CM3600 spectrophotometer under
standard CIE illuminant D 65. Measurements were performed for a diameter area of 30 mm and
a 10° observer. Colour measurements were performed in 4 repetitions for each sample, with the
final results calculated as an arithmetic mean and recorded in terms of CIE colorimetric values

(L* a* b* C* and h) as well as spectral reflectance varying from 400 nm to 700 nm at 10 nm

intervals.
The dyed fabric samples were measured in reflectance (%). The strength of any colorant has to
do with the absorption property. The Kubelka – Munk theory gives us the relationship between
reflection and absorption:
(1−𝑅)2
K/S = ......................................................................................... Equation 4
2𝑅
Where R is the reflectance, K is absorbance and S is the scattering. By using the above equation
colour strength of different samples were measured.
3.5.3. Washing Fastness Test

Washing fastness test characterizes colour's resistance to fading or running of material following
ISO 105-C06: 2010.Dyed cotton fiber sample is cut in a dimension of 4 x 10 cm was sandwiched
between a cotton fabric and polyester fabric and sewn along all four sides to from a composite
specimen. Washing solution containing 5gpl soap and 2gpl sodium carbonate was taken in the
launder -O- meter with a liquor ratio of 1:150. The specimen was treated for 45 minutes at 60 oC
at the speed of 22 revolutions per minute.
The specimen was removed and rinsed in running water without applying friction in cold water.
The stitch was opened on three sides and dried in room temperature. The change in color and
degree of staining was evaluated using grey scales.
3.5.4 Rubbing Fastness Test

Rubbing fastness is a basic test used to determine the quality of coloured fabric. The purpose of
this test is to determine the amount of colour transferred by rubbing from the surface of coloured
textile materials to the other surface. Rubbing fastness was tested according to ISO 105 F09 2009
standard. A specimen of 22cm X 8cm was prepared which is equivalent to the size of the plate of
the crock meter. Two specimens were taken-one for dry state and one for wet state for one
sample. A rubbing cloth 5cm x 5cm was prepared and one rubbing cloth is wet out with water for
wet rubbing.
The specimen was mounted on the base board of the crock meter, putting the long direction of
the specimen parallel to truck of rubbing. The white rubbing cloth was mounted flat over the end

of the peg on the crock-meter and holds it taught by means of the spring clip provided. The
finger was rest on the specimen ensuring that the spring clip is not in contact with the test
specimen. The specimen was then rub back and forth over a straight truck for 10 complete cycles
at a rate of 1 second for each cycle. Finally, the white rubbing test cloth was removed and the
degree of staining on the undyed fabric was evaluated with grey scales.
3.5.5. Light Fastness Test
Light fastness was tested according to ISO 105 B02 standard. A fabric sample which is cut and
half of its part is exposed and half of its part is covered was mounted in a frame together with a
standard blue scale reference fabric and it was placed in a testing chamber. This blue scale wool
fabric consisting of eight dark to light blue shades used to record the color change of a fabric.
The test sample is exposed to a continuous light of xenon-arc lump at a radiant of 5 for about 48
hours. The change was compared with the original unexposed sample, which is assessed by blue
scales 1-8.

CHAPTER FOUR
RESULT AND DISCUSSION
4.1. Optimization of Extraction Parameter

The extraction of fibroin Hydrolysate solution from silk waste was carried out at different
extraction conditions. For extraction of solution fibroin Hydrolysate solution from silk waste the
extraction parameters which were optimized includes concentration of NaOH and HCl with a
constant treatment temperature, treatment time and material to liquor ratio.
Figure 4. 1: fibroin Hydrolysate solutions extracted from fibroin waste by base and acid
hydrolysis respectively
Table 4. 1: Optimization of extraction conditions (Base hydrolysis)
No. Concentration Temperature Time MLR Original Residual Efficiency

Experiment of NaOH (oc) in hr. Weight(g) Weight(g) (%)
1 20 80 1:30 1:20 50 11.23 77.54
2 30 80 1:30 1:20 50 6.58 86.84
The above table 4.1 showed that the efficiency of extraction of fibroin Hydrolysate was
maximum (86.84%) at experiment number 2 of base hydrolysis. Therefore, the optimized
extraction conditions were 30% NaOH, 1:30 hours’ treatment time and 1:20 material to liquor

ratio. The extraction was carried out at temperature (80 oc). This means that the treatment of the
fibroin Hydrolysate solution with NaOH at this optimized extraction conditions gives maximum
efficiency of extraction fibroin Hydrolysate of solution.
Table 4. 2: Optimization of extraction conditions (Acid hydrolysis)
No of Concentration Temperature Time MLR Original Residual Efficiency

experiment of HCl (oc) in hr. Weight(g) Weight(g) (%)
1 20 80 1:30 1:20 50 10.47 79.06
2 30 80 1:30 1:20 50 8.63 82.74
The above table 4.2 showed that the efficiency of extraction of fibroin Hydrolysate was
maximum (82.74%) at experiment number 2 of acid hydrolysis. Therefore, the optimized
extraction conditions were 30% HCl, 1:30 hours’ treatment time and 1:20 material to liquor ratio.
The extraction was carried out at temperature (80 oc). This means that the treatment of the fibroin
Hydrolysate solution with HClat this optimized extraction conditions gives maximum efficiency
of extraction fibroin Hydrolysate of solution.
4.2 Optimization Treatment or Cationization Parameters
The application of fibroin hydrolysate solution on bleached cotton was done by batch process at
different combinations of Temperature, treatment Time, at neutral pH and concentrations of
fibroin hydrolysate solution. Cationization parameters were optimized based on minimum
scorching of fabric, dyeing evenness and maximum K/S values.

Figure 4. 2: treatment of cotton fabric by fibroin Hydrolysate
Table 4. 3: Optimization of treatment condition of cotton by fibroin hydrolysate (base

hydrolysis)

solutions (oc)
1 20 90 15 Neutral 1:20
2 30 80 30 Neutral 1:20
Table 4. 4: Optimization of treatment condition of cotton by fibroin hydrolysate (acid hydrolysis)

solutions (oc)
1 15 80 25 Neutral 1:20
2 25 60 45 Neutral 1:20
The above two tables showed that treatment of cotton fabric as we observe the treatment or
cationization increase with increasing temperature and treatment time.

4.3 Dyeing of Treated and Untreated Cotton Fabric with Cold Brand DCT
Blue Reactive Dye
Dyeing was carried out as per the conventional dyeing procedure at room temperature for 60
min. washing and soaping was done for both treated and untreated cotton fabrics. The visual
actual color yield of treated fabric(base hydrolyzed) by exhausted method was higher than
treated by fibroin Hydrolysate solution(acid hydrolyzed) and untreated fabric samples clearly as
shown in Figure 4.3 a and 4.3 b.
Figure 4. 3: a: Dyed cotton fabric both treated and untreated

Figure 4. 4: Dyed cotton fabric both treated and untreated
4.4. Effect of Treatment on Dye Fixation

The color strength of the dyed fabric sample before and after soaping was measured using color
eye 3100. The percentage of dye fixation was calculated using the above equation (3.4).
The reflectance of treated and with half salt 0.81and 0.82 before and after soaping respectively.
The reflectance of treated and salt free has 0.83 and 0.84 before and after soaping respectively.
The reflectance of conventional has 0.85 and 0.86 before and after soaping respectively.
Table 4. 5: Percentage fixation of treated cotton, treated cotton with half salt and conventional
Sample Maximum K/S Maximum K/S after Percent of Fixation (%F)

before soaping soaping at 540 nm
at 540 nm
Treated and with half 4.45 3.95 88.76
salt
Treated and salt free 3.48 3.04 87.35
Conventional 2.64 2.27 85.75
The result of the above Table 4.5 showed that the treated or cationized cotton with half salt
provided higher fixation percentage than the conventional or untreated cotton dyed with salt. The
improvement of fixation percentage was around 3 % from the untreated cotton fabric dyed with

salt and treated or cationized and salt free cotton provided higher fixation percentage than the
conventional or untreated cotton dyed with salt. The improvement of fixation percentage was
around 2 % from the untreated cotton fabric dyed. The reason behind the improvement in the dye
fixation was because there is less chance for hydrolysis of dyes. The improvement in fixation
was also reflected in the washing fastness ratings shown in Table 4.5.
Alkali addition, during fixation, encourages the reaction of the dye with the fiber or with the
water present in the system. The rate of the reaction depends on the reactivity of the dye. The
dyes exhausted by the fiber preferentially react with the fiber, therefore higher exhaustion results
in higher degree of fixation also. The fixation of dyes was also found to be improved greatly on
the cationized cotton. Such treatment was, therefore, adequate in hiding the negative surface
charge of the fiber and thus enabling appreciable exhaustion and fixation of reactive dye even in
the absence of salt. The fixation of reactive dyes appears to be dependent on the initial
absorption of reactive dyes on fibroin Hydrolysate treated cotton.
4.5. Effect of Treatment or Cationization on Colour Fastness
4.5.1. Colourfastness to Washing
Color fastness to washing of the treated cotton fabric with fibroin Hydrolysate solution was
compared with conventionally dyed cotton fabric. It was assessed in respect of color change and
staining as shown in Table 4.6.
Table 4. 6: Washing fastness of untreated, treated and half salt, treated cotton fabric with fibroin
Hydrolysate extracted silk waste and dyed with DCT reactive dye
Sample Colour change Staining

Cotton Polyester
Treated and with half salt 4/5 4/5 5
Treated and salt free 4/5 4/5 5
Untreated 4/5 5 5
The above table shows that the wash fastness of the cationized cotton fabric was almost similar
to the conventional dyed cotton fabric and there was no staining in all cases. Both dyeing

methods scored very good grade by assessment with the standard grey scale reading. This may
be due to the formation of strong ionic bond between the fiber and the dye because it is equally
good as the covalent bond that normally links the dye and fiber. In addition to this, it also
confirms the effectiveness of dye fixation due to pretreatment with fibroin hydrolysate extract
from fibroin waste for salt free dyeing. Wash fatness of the dye would depend on the bonding
between the fibroin (NH3+) and cellulose.
Figure 4. 5: dyed fabric during rubbing fastness test

CHAPTER FIVE
CONCLUSION AND RECOMMENDATION

5.1 Conclusion
The present investigation revealed that application of extracted fibroin Hydrolysate from silk
waste on full bleached cotton fabric for salt free dyeing with reactive dye. The extracted fibroin
Hydrolysate was applied on full bleached cotton fabric by exhaust method and the fabric was
tested its color fastness, color strength, dye exhaustion, Dye exhaustion as well as color fastness
of the dyed samples was improved after the treatment. Since silk waste was widely disposed to
the environment and accumulated in mass, there was an opportunity and possibility of converting
this waste in to valuable purpose such as used as natural biodegradable cationic agent for cotton
fabric to improve the dye ability and dye exhaustion of cotton with reactive dye without addition
of any electrolyte (salt). The result of this research gives three main advantages:- one, by
converting to usable product the waste of silk will be minimized and the environment keep clean.
Secondly, the dye ability, percentage of exhaustion and wash fatness of the reactive dye will be
improved after treatment which leads to reduce the effluent of untreated dye disposed to the
environment. Thirdly, addition of salt in the dye bath during dyeing of cotton with reactive dye
was eliminated and protect environment from this effluent. Therefore, finally it is possible to
propose that extracted fibroin Hydrolysate from silk waste can be used as bio -degradable eco-
friendly cationic agent applied on cotton fabric for salt free reactive dyeing.
5.2. Recommendation
From this thesis work it is recommended that for mass production of fibroin Hydrolysate extract
it should be implemented at investment level. As it was concluded from this thesis work, dyeing
of cotton after cationization provided improved dyeability and dyeing performance, reduced cost
of dyeing and cost of effluent treatment plant, minimized the environmental pollution discharged
to the environment. Bearing this in mind it is better to substitute the conventional dyeing method
with the new approach.

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WOLLO UNIVERSITY

KOMBOLCHA INSTITUTE OF TECHNOLOGY

DEPARTMENT OF TEXTILE AND LEATHER ENGINEERING

TITLE: SALT FREE DYEING OF COTTON FABRIC WITH REACTIVE DYE BY

Prepared by: ID/NO

Kombolcha Institute of Technology

Final Year Project

Under the Supervision of

Department of Textile Engineering Page i

Department of Textile Engineering Page ii

Department of Textile Engineering Page iii

Advisors’ Approval Sheet

____________ ____________ ____________

Department of Textile Engineering Page iv

Department of Textile Engineering Page v

Department of Textile Engineering Page vi

2.5.1 Chemistry behind Reactive Dyeing .............................................................................. 17

Department of Textile Engineering Page vii

3.5 Evaluation Parameters ......................................................................................................... 36

Department of Textile Engineering Page viii

Table 3. 1: optimization of fibroin Hydrolysate from silk waste .................................................. 32

Table 4. 1: Optimization of extraction conditions (Base hydrolysis) ......................................................... 39

Department of Textile Engineering Page ix

Figure 3. 1: experimental procedure ........................................................................................................... 31

Department of Textile Engineering Page x

AOX Absorbable Organic halide

Department of Textile Engineering Page xi

Department of Textile Engineering Page 1

Department of Textile Engineering Page 2

Department of Textile Engineering Page 3

Department of Textile Engineering Page 4

Department of Textile Engineering Page 5

 It will help them to think beyond this and to work further.

1.5 Significance of Project

1.6 Scope of the Study

Department of Textile Engineering Page 6

Department of Textile Engineering Page 7

Figure 2. 1: schematic representation of cotton fiber showing its various layers

Cellulose's chemical structure is simple, composed of anhydroglucose units (AGU) joined to

Department of Textile Engineering Page 8

Figure 2. 2: Chemical structure of cellulose

2.3Treatment of cotton by cationization

Department of Textile Engineering Page 9

2.3.1Why Treating or Cationization of Cotton Fabrics?

Department of Textile Engineering Page 10

Department of Textile Engineering Page 11

2.4.1 Availability of Silk

2.4.2 Production of Silk

Department of Textile Engineering Page 12

Table 2. 1: Global Silk Production (in metric tons)

No Countries 2014 2015 2016 2017 2018

Department of Textile Engineering Page 13

2.4.3 Chemistry of Amino Acid

Figure 2. 4: Peptide bond formations between two amino acids

Department of Textile Engineering Page 14

2.4.4 Composition of Fibroin

No Name of amino acid Residue (%)

2.4.5 Analysis of Amino Acid

Department of Textile Engineering Page 15

2.4.6 Hydrolysis of Proteins

Figure 2. 5: Hydrolysis of protein by hydrochloric acid

Department of Textile Engineering Page 16

Figure 2. 6: alkaline hydrolysis of protein