A Journey towards

RFT (Right First Time) Processing

in Exhaust Dyeing

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 Aiming at Blind Dyeing in Dye-houses
Industry Trends
Garment Manufacturers and Retailers Consumers

Increasing
Number of fashion Trends
Increasing Decreasing

Choice
Range of fabrics Fabric performance
Colour changes
Colour fastness
Environmental pressure
Colour Fastness Requirements Value for money
Order size
Repeat orders
Lead times
Which ultimately trends in increasing Production Cost and reducing Profit margins
Effects on Dyehouse
Energy costs
Increasing

Water and effluent costs

Labour costs
Number of Competitors
Retailer’s knowledge of process costs
Create additional pressure on Production Costs
‘Performance for Profit’
q How much is performance affecting the profitability?
-Impact of Right First Time performance
-Benefits of true dyestuffs & user friendly Processes
-Achieving high standards of process control
q Can we meet retailer needs with cost-effective approaches?
-Optimize dyestuffs Selection to meet exactly customer needs
Main Focus of Standard Operating Procedures
1. Review Industry Trends
2. Impact of RFT
3. Dyeing Performance
4. Optimizing dye selection
5. Process Technology for different Substrates
6. Process Selection
7. Process Control
8. Control Parameters
9. Test procedures
10. Determine effectiveness with ‘on-line’ control
11. Usage of software to make technology user friendly

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 Control Options
q Assignable variables
Measurable factors that influence dye performance can be controlled:
1. Liquor ratio
2. Internal fabric pH
3. Fixation temperature
4. Specific gravity (salt concentration)
5. Addition profile
6. Fixation pH
7. Time
q Random variables
Factors that require intervention of management to effect control of Impurities in:
1. Cotton
2. Water supply
3. Chemicals eg QC of raw materials
4. Controlled Coloration concept
RFT (Right First Time) Performance & Setting Specifications
q Measures of performance
Shade Reproducibility
- Lab to bulk CMC 2:1 delta E 1.0
- Bulk to bulk CMC 2:1 delta E 1.0
Level Dyeing
- Average throughout batch, piece to piece CMC 2:1 delta E 0.3
Colour Fastness
- Customer specific
- Washing, Repeat Washing, Rubbing, Light
q Non-conformance
- Off shade-Lab to Bulk-needs shading addition
- Off shade-Bulk to Bulk-needs shading addition
- Unleveled-side to side variation, shading or patchy
- Fails in Q.C Test-staining, fading
- Combinations of the above

The Benefits Of Right-first-time

Financial Non-financial
Lower Costs per Batch Enhanced Customer Service
Increased Output Improved Quality of Goods
Improved Profit Margin Reduced Effluent Load

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 Cost Management in Dye-houses
Cost control comes from optimization & profit comes from improved performance

Model of costing for average colour Cotton Knit Processing

1. Dyes 25%
2. Chemicals 15%
3. Wage & Salary 15%
4. Capital Investment
& Other Overhead 13% Capacity : 2 batches/day working 7 days a week

5. Energy 15%
6. Water 10%
7. Depreciation 7%

Cost of Non-conformance-for Cotton Exhaust Processing

Process Cost Productivity Profit

Blind Dyeing 100 100 100
Small Addition 110 80 48
Large Addition 135 64 -45
Stripping & Re-dying 206 48 -375

Cost of Shading (30% of original batch cost)

RFT Rate % 50 70 80 90 100
Cost 167 143 125 111 100
Additional Cost 12 9 6 3 0
Total Cost 179 152 131 114 100
Batches 7.0 8.4 9.8 11.2 14

Increasing Productivity
Increase in Productivity 10% 20% 30% 40%
Reduction in total cost % 9 17 23 29
Additional batches/week 1.4 2.8 4.2 5.6

Reducing dye costs

% dye costs -10 -20 -30 -40
Saving on total cost % 2.5 5.0 7.5 10

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 70% Plant Utilization @ 90% RFT
Number of batches/week at % utilization 9.8
New Total Cost at % utilization 80.5
Actual number of RFT batches 8.8
Additional cost at 90% RFT rate 9.0
Total cost 89.3%

70% Plant Utilization @ 70% RFT

Number of batches/week at % utilization 9.8
New Total Cost at % utilization 80.5
Actual number of RFT batches 6.9
Additional cost at 70% RFT rate 12.0
Total cost 92.5%

Reducing dye costs and lower RFT (70 to 60%)

%Cost Reduction 10 20 30 40
Saving on total cost % 2.5 5.0 7.5 10
Additional cost at 60% RFT 24 25 28 29

Summary
q Increasing RFT from 70 to 90 % reduces costs by 32%
q Increasing Productivity by 30% reduces cost by 23%
q Reducing dye costs by 30% only saves 7%
q Combined effect of increasing RFT from 70 to 90% with increase in Productivity of 30%,
even with 30% higher dye costs reduces total cost of production by 44%
q As a bonus additional ‘opportunity’ margin can be generated from increase in productivity.
Impact of RFT on Cost
250

200
Effect on Cost

150

S e r ie s 1
100

50

0
50 55 60 65 70 75 80 85 90 95 100

R F T P e r f o r m a n ce
Conclusions
q Performance of dyestuff combinations is critical to cost and profitability of dyeing operation.
q Selection of the most suitable combination is essential for success.

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 Scouring and Bleaching Process
30’
95-105°C 10’ 10’ 80°C X 10’
80°C

10’ Acetic Acid overflow

40°C
Peroxide Killer-Enzymatic (Catalase based)

Chemicals Pre-dyeing Check:

1.0 g/l Anionic Detergent ( Remove dirt ) Ø Fabric temperature should be lower than
0.5 g/l Nonionic Detergent ( Remove Oil & Fat ) dyeing temperature.
Ø No H2O2 is left in fabric.
1.0 g/l Sequestrant-High alkali stable
Ø pH of fabric should be within 5.0-6.0.
1.0g/l H2O2 Stabilizer-Organic
3.0 g/l Hydrogen Peroxide(50%)
3.0 g/l Caustic Soda 38°Bé ( NaOH 38°Bé )

Audit and Trials Equipment

1. Hardness Test Papers
2. pH Meter or pH Papers
3. Thermometer preferably an Infra Red one.
4. Peroxide Test Papers
5. Hydrometer 1.000-1.100
6. Universal Indicator Solution

Fibre pH
A simple & quick spotting test with pH indicator solution is done. A slightly acidic state avoids
premature fixation during migration phase of dye application. So, Ideal pH of fibre after
neutralization is to be 5.0-6.0

Residual Hydrogen Peroxide

Hydrogen Peroxide in dyebath can reduce dye yields and result in poor shade reproducibility. So,
carry over of residual Hydrogen Peroxide to Zero.

Fibre absorbency
Simple drop test with any temporary colouring liquid (i.e Potassium Permanganate Solution) can
confirm fibre absorbency property.

Salt Concentration
Confirm Salt concentration with a Hydrometer & SG Charts. Specific gravity is influenced by
temperature, so always confirm with a thermometer with Tolerance +/- 5% from target SG
Note: ‘portion-wise’ salt process does not allow this test

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 Liquor Ratio
Confirming Liquor Ratio
Assumed volume X Expected salt Concentration
Actual Volume = ---------------------------------------------
Measured Salt Concentration
Controlling Liquor Ratio and Salt concentration optimizes shade reproducibilty ensuring highest
RFT production performance.
Dye-bath Temperature
Accurate control of dyebath temperature ensures best possible shade reproducibility. Every after
certain period calibrate controller, adjustment needed with an Infra-red one if required.
Reproducibility between lab and bulk
q Same fabric ?
q Same pretreatment (weight loss, ...) ?
q Same liquor ratio ?
q Same salt quality and concentration at same temperature ?
q Soda ash quality ok ?
q Same caustic soda concentration ?
q Temperature indicator at lab equipment and dyeing machine ok or regularly calibrated?
q Right lab method for simulating the bulk process
As per different impurities content in greige cotton, scouring recipe to be adjusted to achieve
required scoured fabric. For this reason, depending on shade depth, required specification for
scoured fabrics (ready for dyeing) to be numerically pre-determined. Such as:
a) Fabric GSM
b) Whiteness value of Scoured fabric depending on shade depth.
c) Absorbency grade of Scoured fabric of specific GSM.
d) Different metal ions contents & total hardness.

Water quality & Standard Textile Process water

Water contamination is constantly varying, so check it timely. Is water treatment effective? Is
water free from vegetable, suspended solids & other mineral impurities? Hardness contaminants in
dyehouse water can adversely effect level dyeing, shade reproducibility & wash off performance.
Ø pH: 6-8
Ø Hardness: max. 5 °dH
Ø Suspended matter: <1 mg/l
Ø Organic load: < 20 mg/l
Ø Residue on ignition: < 50 mg/l
Ø Iron: < 0.1 mg/l
Ø Manganese: < 0.05 mg/l
Ø Copper: < 0.01 mg/l
Ø Nitrate: < 50 mg/l
Ø Nitrite: <5 mg/l
Ø Free CO2 0 if possible (risk of corrosion)

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 Common Observations in Bangladeshi Dye-houses:
Usual phenomena :
qCold water temperature about 40°C-50°C
=All in method needs 25°C-30°C
q Bicarbonates in water about 0.3-0.5 g/l up to 1.0 g/l
=Bad reproducibility in Exhaust method
=Alteration of final shade after wash-off (Chromophore sentitivity)
q Poor quality Common & Glauber’s salt : high presence of impurity and Ca, Mg :
=Bad reproducibility in Exhaust method
=Big problems with Turquoise (Phthalocyanine) & Royal Blue (Anthra-quinone)
q Low quality auxiliaries with insufficient Wetting & Cleaning property
In pretreatment phases :
=Incomplete oil, fat, dirt elimination, consequently lead to bad leveled dyeing
q No controls after bleaching :
=Peroxide residuals destroy dyestuffs
=Out of right pH range (=6.5-8) gives bad reproducibility
=Hardness neutralize alkali (NaOH)
q Large use of non-ionic auxiliaries agents in high amount :
=These kinds of auxiliaries are difficult to be washed out.
=Levelling problem especially with Phthalo-cyanine dyestuffs(Turquoise type)
q Insufficient knowledge about microprocessors in dye machinery :
=People often have new technologies but do not accurately know how to use.
=A program mistake means a bad dyeing e.g. during alkali dosing.

Check List in Exhaust Dyeing-Reactive

1. Water Hardness Test : With Hardness Test-strips.
2. Bicarbonate in dye-bath : Can be tested with Methyl-Orange + HCI Test. Sodium
bicarbonate presence in dye-bath water can work as a buffer; increase caustic soda 38°Bé at
0.1 ml/l for each 0.1 g/l sodium bicarbonate.
3. Salt Hardness Test : With Hardness Test-strips and NaOH Test
If total amount of hardness from water, salt & material is more than 10°dH, try to reduce.
For water : Increase Sequestrant
For salt : Change salt to good quality
For material : Demineralization can solve it.
If not possible, try to dye with Only Soda ash method.
4. Residual Peroxide : With Peroxide test-strips ( if just bleached material )
5. Alkali Concentration : Correct concentration to be used ( if different, convert it)
6. Recipe Calculation : Should be done for dyes & auxiliaries, Control workman
-To measure weight, he has to use a balance.
-To measure volume, he has to to use a cylinder or pipette.
7. Material quality Checking :
- pH with pH test paper
-Hardness with Hardness test-strips
8. Machine parameters :
-Dependability of thermometer
-Circulation pump’s pressure (in package dyeing of yarn)
-Winch speed (in rope dyeing for knit goods)
9. Dyeing Liquor Ratio :The amount of water in Dyeing machine,
=Total amount of water - Water needed for (dyestuffs + Alkali) Solution

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 Determination of Fibre contamination
Simple extraction technique enables fibre hardness level can be determined after pretreatment.
Effective pretreatment reduces carrying over of alkaline earth element contamination of dye-bath.
Ø Extract fibre sample at liquor ratio 20:1, 95°C for 30mins in 100g/l Analytical Salt (Pure NaCl)
Ø Cool solution and test with hardness paper
Ø Calculate approximate hardness level:
1°German Hardness = 17ppm Calcium/Magnesium
So, 5° German Hardness = 85ppm Calcium/Magnesium
Fabric contamination = 85 X 20 ( LR 20:1 )
= 1700ppm
Being a natural fibre, cotton’s contamination levels can vary. So, check regular basis & accordingly
dematerialize, if needed & adjust Sequestrant dosing in pretreatment.

Determination of hardness from salt

Ø Make a solution about 80 g/l Salt( Salt dosing that is used in dye-bath)
Ø Check solution hardness with Hardness Test strip or by titration.
Ø To confirm, add some ml. of NaOH 38°Bé to solution. If there is any hardness in salt, an opal
white snow of Mg(OH)2 Ca(OH)2 can be seen.
Ø Consequently in dye bath from 1/2 to approximately same hardness is found from salt.
Determination of total amount of Bicarbonate in water
Ø Put 100 ml of water (the same water to be used in dyeing) in a beaker.
Ø Add 1-2 drops of Methyl-orange and mix.
Ø The water will turn to a pale yellow solution.
Ø Start adding drops of 0.1 N of HCl (never stop shaking) till last drop that changes solution
colour from yellow to orange-red.
Ø Stop immediately
Ø Write down the amount of HCl solution used and put it in the calculation bellow:
Ø Bicarbonate in water(gm/l) =(ml) of 0.1N HCl X0.084
Check Soda Ash Quality
Soda Ash pH to be able to reach pH 10.8 to 11.2 in salt solution to reach optimum fixation conditions.
Hardness contamination
q Hardness adversely effects level dyeing, shade reproducibility and wash off
q Fibre, salt and water contamination all contribute to dyebath hardness
q Measuring levels of contamination of the above allows us to determine required sequestrant
concentration to protect & overcome it’s adverse effects

Calculating required concentration of dye-bath Sequestrants

Hardness from prepared Fabric
+ Required Amount of Dye-bath
Hardness from process Water Total dyebath
Hardness Sequestering agent
+
Hardness fro Salt

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 Conversion of Caustic soda soln. with Sodium Bicarbonate
Temporary hardness and it’s neutralization :
NaHCO3 + NaoH = Na2CO3 + H2O
Mg 84 40 106 18
1° dH = 0.03 g/l NaHCO3
10° dH = 0.30 g/l NaHCO3
16.7° dH = 0.50 g/l NaHCO3
20° dH = 0.60 g/l NaHCO3
33.4° dH = 1.00 g/l NaHCO3

+ 0.48 g/l Caustic soda

1 g/l NaHCO3 + 1.09 g/l Caustic soda 1.26 g/lNa2CO3
+ 0.62 g/l Caustic soda
Note: Sodium Bicarbonate is generated only by the components in water that cause temporary
hardness, not by total hardness of water.
1°dH = 10 mg/l CaO
= 22.5 mg/l Ca(HCO3)2
= 30 mg/l NaHCO3

Scouring & Bleaching chemicals:

q Anionic detergent - To remove dirt
q Nonionic detergent - To remove FAT & OIL
Caustic soda:
q Proper amount of caustic soda should be used aiming at avoiding oxycellulose
Hydrogen Peroxide:
q Cotton should not be over bleached
Hydrogenperoxide Killer:
q Good Peroxide killer to be selected that has no effect on both dyestuffs & environment.
Fabric condition to be ensured before dyeing that:
q pH on fabric is about be 5.0-6.0 & must be bellow 7.
q No Hydrogen peroxide left in the fabric.
q Fabric temperature is lower than dyeing temperature.
Pre-treatment processing time should not be over 2 hours.

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 Trichromatic View of Colourants

A brief idea about different types of Textile Colourants

Many years of research have been put into the development and synthesis of dyes. Based on
research, there are eight general classes of dyes used to colour different textile fibres. As per their
chemical structures & application, they’re described shortly as in the following ways:
1. Acid dyes:
It is referred to as anionic dyes, are applied under acidic conditions. Acid dyes are typically used
for polyamides (nylon), wool, and silk.
2. Azoic dyes:
They are known as developed dyes because they are built from two smaller molecules. They are
used for dyeing and printing cellulose fibres.
3. Basic dyes:
Due to a net positive ion that is active anchoring portion of dye, they are referred to as cationic
dyes. Acrylic and cationic-dye-able polyester fibres are main targets for these dyes, but they were
originally designed for silk and wool.
4. Direct dyes:
The first dyes to color fibres directly, used without a mordant. They are used for cellulose fibres.
5. Disperse dyes:
Disperse dye class does not contain water-solublizing groups & so remains as finely-dispersed
particles, were developed for synthetic fibres & are used mainly for polyester, but are also used
for acetate, polyamide & acrylic fibres.
6. Reactive dyes:
Fibre-reactive dyes are the only dyes that form a covalent bond with fibre. Are primarily used for
cellulose fibres, but some of them can also be used for polyamide and wool.

7. Sulfur dyes:
These are sulfur-containing dyes with high molecular weights. They are normally insoluble dyes
but become soluble & form leuco compound by reduction. Once applied to the fibre, they are
oxidized to become insoluble again. They are used for cellulose fibres.

8. Vat dyes:
Vat dyes are similar to sulfur dyes as they start as insoluble, become soluble upon reduction, &
are oxidized to become insoluble after application. They are used for cellulose dyeing & printing.
9. Pigment
One additional colourant class for fibres is pigments-are not soluble & do not dye fibres; are
normally applied in printing process along with a binder which fix the pigment particles on the
fabrics & show colour effects. Used on all fibre types, but are only attached to the surface of fibre.

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 Reactive Dyestuffs Details-with it’s major historical landmarks

Group Type Name Brand Company Year

BIS-MCT Mono-functional Monochlorotriazine Procion H-E ICI 1950

VS Mono-functional Vinylsulfone Remazol Hoechst 1960

DCC Mono-functional Dichloroquinoxaline Levafix E Bayer 1960

Bayer
DFCP Mono-functional Diflourochlorpyrimidine Levafix E-A
& 1970
Drimarene K Sandoz
Monochlorotriazine
MCT/VS Bi-functional & Sumifix Supra Sumitomo 1970
Vinyl sulfone
MFT Mono-functional Monofluorotriazine Cibacron F Ciba Geigy 1970
Monofluorotriazine
MFT/VS Bi-functional & Cibacron FN Ciba Geigy 1990
Vinylsulfone
Monofluorotriazine
MFT/MFT Bi-functional & Cibacron L-S Ciba Geigy 2000
Monofluorotriazine
Monofluorotriazine
+
MFT/MCT/VS Multi-functional Monochlorotriazine Cibacron S Ciba Geigy 2000
+
Vinylsulfone

New Chemical Structure Leading to Higher Colour Value & Fastness

Insertion of two Chromophores & more than two Functional Groups in Dye molecular
structures leads to increasing of both Colour value & all round fastness.

Multi-functional Cibacron S 2000

C (Chromophores) : 2-3
R (Reactive group) : 3 R C R C R
Features of new structure
q High fixation rate (>90%)
q Medium-high affinity
q Flexible molecules
q Good wash-off property
q Excellent build-up ability

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 Chemical structure of Cellulose & Dyestuffs-Fibre bonding
H OH C H2O H H OH CH2O H
O H H O O H H O
OH H H OH H H
H OH H H OH H
H O O H H O O H
C H2 O H H OH C H2O H H OH

C6H10O5

Mechanisms of Reactive Dye Fixation

Vinyl Sulphone Based: Chloro Triazine Based:
Ether Bond Additions mech. Ester Bond Substitutions mech.

Resistant to Acid Resistant to Alkali

Sensitive to Alkali Sensitive to Acid

VS Dyes MCT Dyes
N
F -SO2-CH2-CH2 -OSO3Na F -HN- -NH-R
N N
+ Alkali Cl + Alkali
F -SO2-CH=CH2 + HO-Cellulose
+ H2O
N
+ HO-Cellulose N FF- HN- - NH-R
F -HN- -NH-R N N
+ H2O FF -SO2-CH2-CH2-O-Cell N N O
O
Cell
F -SO2-CH2-CH2-OH H
Hydrolysis Hydrolysis
Fibre Reaction 70-95% Hydrolysis 5-30%
Reactive Dyes-Cellulose Reaction in brief

F -SO2-CH2-CH2-O-Cell
+ Alkali Fibre Reaction
-SO2-CH2-CH2-OSO3Na
F -SO2-CH=CH2
ß-sulphato ethyl sulphone Reactive vinyl sulphone
F Hydrolysis
F -SO2-CH2-CH2-OH

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 Reactive Red: Cellulose- dyestuff bonding
O
O OH

HOH2C
OH
O
Cl
HO O N
O N SO3Na
CH2 N
HO HN
O
HO
O OH
N SO3Na
HOH2C NaO3S N

Light Perspiration Fastness of Reactive Dyestuffs

Destruction of Chromophores group (Azo Group) resulting in affecting Light or Light
Perspiration Fastness of Reactive Dyestuffs in following two ways:
i) Photo Oxidation O
O O

O O
O H
O O
O
N H N
N H
N
N
+
N

l Singulet-O2 reacts with Hydrazone-tautomer of Azo Dye

ii) Photo Reduction

N H 2

N + H - D o n o r H N
H N . N H
N N H 2
N •

Griffiths & Hawkins

JCS Perkin II 1977, 747
Reactive Dyestuffs Fixation Parameters

Temperature

Reactive dyes Fixation

Time pH value

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 Temperature Sensitivity of Different Functional Groups
Dependence of Colour Strength on Different Dyeing Parameters for Different Anchor Systems

Lower Temperature Sensitivity

Rel a t ive C olou r S t r en g t h in %

110 MCT-VS
100

90

80
MCT

70 VS
60

50

40
30 40 50 60 70 80

Dyeing Temperature in °C

Stability of dye- MCT/MFT

fibre bond Bi-functional
VS

Acid pH Alkali

Temperature Sensitivity of different Functional Groups

Relative Fixing Rate
Relative Fixing Rate SYSTEM - BALANCE VS
MCT Dyeing-Temperature
Dyeing-Temperature MCT / VS

65 °C

65 °C

60 °C

60 °C

55 °C

55 °C

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 Correct Profile Reactive dyestuffs aiming at better dyeability
Dyeing Parameters in Reactive Dyeing Dy
ei n
g te
mp
Alkali Concerntration e ra
r a ti o E lectr o
tur
e
u or ly te C o
Liq n c er n tr
at ion

All reactive dyestuffs are sensible to the above parameters & show differences, more or
less. Dyestuffs selection of showing same behaviour can reduce sensitivity to different dye
parameters, but decisive for a good reproducibility is a conscientious working method !
Influence of diffusion, substantivity as a function of temperature in fastness washing
Substantivity Rel. diffusion

S D

40 50 60 70 ° 80 90 100
Temperature
C
Standard Requirements for Selection of Dyestuff:
Lower Substantivity + Moderate Reactivity + Lower dye-hydrolysate & Rapid washing-off
Ø The ‘right profile’ represents the best balance of cost and performance
Ø Preservation of Standardized dye quality
Ø Protection from decomposition Reactions
Ø Reasonable recipe cost according to buyers price
Ø Higher Solubility
Ø Higher Acid & Alkali stability
Ø Excellent dyebath stability
Ø Shade, tinctorial strength, viscosity
Ø Good technical performance to meet the most tailor made requirements
Target Profiles for Dyestuffs Selection
1. Substantivity in neutral electrolyte 70 – 80%
2. Exhaustion after the addition of alkali Above 90%
3. Fixation efficiency 80 - 90%
4. Migration Index Above 90%
5. Level Dyeing Factor Above 70%
6. Unfixed dye to be removed in the first hot rinse bath Above 60%

Influence of dye compatibility

Level dyeing factor : LDF = S/E X MI

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 Compatibility Study a Trichromate Dyestuffs
Reactive Orange 107
Reactive Red 198
Reactive Blue 220 Yellow component very low substantivity
Yellow very high secondary exhaustion – unlevel risk
Exhaustion in alkali ‘on tone’
Rapid fixation of yellow and slow of blue
Reactive Yellow 176
Reactive Red 238
Reactive Black 5
Yellow and red medium substantivity, blue low
Red slow to fix
Exhaustion in alkali ‘on tone’
Final fixation of yellow low, fixation greener paler when
compared to final exhaustion
An Ideal Orange
Combination

Increased compatibility during salt exhaustion

Exceptional ‘on tone’ exhaustion and fixation in alkali
Final exhaustion and fixation ‘on tone’
Reactive Orange 107 Reactive Yellow 176 An Ideal Orange
Robustness Study
Reactive Red 198 Reactive Red 238 Combination
Change in Hue Reactive Blue 220 Reactive Black 5

20% Underfill/20% Overfill Yellower Redder Less Blue Redder Little Stable
Redder

-10% Salt/+10% Salt Stable Yellower Less Blue Bluer Stable Stable

Stable Stable Stable Less Blue Stable Stable

-10% Alkali/+10% Alkali

45 mins Fix/75 mins Fix Yellower Stable Bluer Yellower Stable Stable

-Temperature/+Temperature V.Yellow Bluer Bluer V.Yellow Stable Stable

-2:1 Liquor Ratio/+2:1Liquor Ratio V.Yellower Redder

Redder Bluer Stable Stable

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 Compatibility Study a Trichromate Dyestuffs
Migration and Compatibility studies : Orange – Red - Navy
Orange : 1.41%
15’ 15’ 5’ 5’ 5’ 5’ 20’ 20’ 20’
Red : 0.60% 60°C
Navy : 0.65%
3 4 5 6 7 8 9 10 11 12
Salt : 80 g/l
Soda ash : 15 g/l 50°C 2
LR : 10 : 1
Fixation temperature : 60°C 40°C 1
10% Alkali 20% Alkali 70% Alkali
15’
30°C
Migration
D1 D2 B1 Final

Migration index 93.4%

Compatibility

Compatibility Study a Trichromate Dyestuffs

Combinations in Ternary Shade (Olive)

CIELab Color Difference DE*

C.I. Yellow 145

C.I. Red 195
C.I. Blue 222
Exhaustion

STD. A B C D E F G H
Fixation
Standard. Recipe
A : Alkali -20% E : Temp. 50 Chemicals Requirement : Glauber’s salt 60g/l, Soda ash 20g/l
B : Alkali +20% F : Temp. 70 Liquor ratio : 1:10
C : Salt -20% G : L.R. 1:8 Dyeing Temp. : 60
D : Salt +20% H : L.R. 1:12 Exhaustion time 20min., Fixation time 60min.

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 Performance of a Standard Trichromatic Dyestuffs
Compatibility
Ø‘On Tone’ exhaustion in salt
Ø Medium substantivity with high migration in neutral exhaustion conditions
Ø Good levelling ability
Ø Lower E-S leading to better levelling on alkali addition
Ø Exhaustion remains ‘on tone’ after alkali add
Ø Exhaustion and fixation are the same shade through out
Robustness
Ø Most stable only small variations in hue and depth

Conclusion
Traditional combinations are sensitive with large changes in hue, especially to time & temperature
Influence of Chemicals, Processes & Substrates:
For Production of Deep and Color fast Blacks
q Mixture of Soda Ash/Caustic Soda gives highest fixation
q 60’C application ensures good diffusion and penetration
q Highest fixation and diffusion reduce ‘bronzing’ effect
q Best process for fixation and reproducibility is automet
For Production of Bright Greens and Turquoise
q Best preparation – fibre hardness contamination needs to be minimized
q Migration (Temperature raising) Method would give better levelling.
q Avoid using non-ionic chemicals in dyebath
q Good anticreasant with emulsifying properties
q Best quality (pH lower than 8 & zero hardness) Glauber’s Salt
q Use clean Machine
For Production of ready for dis-charge print fabric
q Required dischargeable plus highly pure Reactive dyes to be selected
q Cationic Finishes to be avoided for white dis-chargeability
q Careful usage of Activator: to be added to ink just before printing-should not be pre-mixed earlier
Possible problems and causes
Potential problems
Ø Unlevelness, Shade Variation-Long variation/Short Variations
Ø Poor penetration
Ø Surface deposition
Possible causes
Ø Wrong or poor quality ancillary equipment (e. g. pumps)
Ø Problems due to improper synchronization of winch speed & fabric string speed
Ø Sub-optimized dyeing process
Ø Incorrect dye selection
Ø Improper Auxiliaries selection & Inefficient pretreatment

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 Possible Problems with hardness

Rubbing fastness affected by the following factors:

q Substrate
q Dye concentration
q Water hardness
q Improper finishing of the dyeing
q Inadequate liquor flow rate
q Lower colour yield
q Poor reproducibility of the dyeings
q Dusting of the yarn, particularly when rewinding onto another bobbin
q Poor fastness properties
q Harsh handle
q Poor wettability
q Deposits on the machines
q Poor levelling-out properties, particularly with wound packages
q Formation of spots
These
These problems
problems can
can be
be avoided
avoided by
by
Good
Good pretreatment
pretreatment of
of the
the fabric
fabric
Proper
Proper usage of sequestering and
usage of sequestering and complexing
complexing agents
agents in
in the
the dyeing
dyeing process
process

By Dyeing Machine
Potential Problems-In Processing
q Poor liquor circulation-Too low circulation results in-Unlevelness due to insufficient liquor flow
q Poor temperature control
q Contaminated addition tanks or dyeing equipments (dyes, O.B.A, Softeners, oligomer)
q Flooded seals at reduced liquor levels
In Reactive Dyeing
q Inefficient pretreatment.
q Inefficient rinsing after pretreatment.
q Inappropriate dosing cycle times for the dyes used.
q Inefficient rinsing after dyeing.
q Unleveled application of cationic products to the goods (especially in pale shades).
q Inappropriate dye selection for down-stream processes (eg., post-bleach, post-merc.).

In Polyester Dyeing
q Lack of heat-setting of Yarn or fabric leads to shrinkage on dyeing
q Unevenly heat set of the substrate
q Poor temperature control
- Dispersion stability problems
- Unleveled dyeing
q Incorrect dye selection
q Insufficient dispersing agent with highly concentrated dyestuffs
q Too much auxiliary (less is better)
q Waxes, oils, hydrocarbons on the substrates.

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 Check-list before starting a Winch/Batch dyeing machine
Main items before start
ü Is the dyeing process ok?
ü Is the dyestuff properly desolved?
ü Is the dyeing machine & other used vessels clean or free from any technical problem?

Main elements of a Winch/Batch Dyeing machine

Main vessel
Ø Inside or outside lying pump with engine control or not.
Ø Different kind of level control making variable kind of liquor levels possible or not.
Ø Overpressure devices.
Ø Overpressure devices, different kind of valves, heating & cooling device.
Ø Different kind of sealings.
Peripheral vessels
Ø Expansion vessel with heating, automatic dosing system to regulate pH & stirrer.
Ø Preparation vessel with heating and stirrer.
Ø Dosing system for solid material.
Ø Dosing or cycle pump.
Ø Connection to an automatic dosing system for bulk chemical and auxiliaries.

Wash Off

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 Conclusion
Precautions for Finishing of different shades to achieve required quality
Dark Shades:
Carefulness to be needed to ensure for achieving better wet rubbing, staining or wash
fastness of the darkest Shades:
Cotton:
Ø As required Dye amount is very high, dye selection is to be optimized between Quality & Prices.
Ø Total Shade depth should not exceed total standard depth of it’s different dye components. i.e
try to use as less dyestuffs% as possible.
Ø Any sort of “Micro or Nano” Silicon finish adversely affect wet rubbing, staining or wash
fastness of the finished RMG.
Ø Be sure of removing maximum hydrolyzed dyes from the substrates with efficient wash off
process. Specially for dischargeable dyeing as hydrolyzed dyes do not leave white ground.
Polyester:
Ø Proper Pre-heat set needed to evenly rearrange the fibre structure.
Ø For polyester-filament, lower filament no. containing substrates give better wash, sublimation
& other fastness.
Ø A non-ionic wetting agent to be used with other reduction cleaning recipe.
Ø A post-heat set with subsequent further reduction cleaning may ensure the best wash,
sublimation & other fastness of polyester apart from dyestuffs quality.

Pale Shades:
Pre-cautions to be ensured for achieving required light fastness, shades changes
possibilities & other pale shade related fastness:
Cotton:
Ø As dyestuffs amount is very low, usually the best quality dyestuffs to be chosen.
Ø Avoid matching any light shades without dyestuffs-mostly by scouring as colour fastness of
natural Chromophores & different contamination of scoured fabrics change in time & do not give
permanent effect.
Ø Select equal light & other fast dyes components for on tone fading.
Ø Avoid using any “Cationic finish” or Fixatives as they adversely affect Light fastness
Ø Removal of maximum hydrolyzed dyestuffs from substrates with efficient wash off process.
Polyester:
Ø Proper Pre-heat set needed to evenly rearrange the fibre structure.
Ø For polyester-filament, applicable dyes energy level is inversely proportionate to filament no.
Ø A non-ionic wetting agent to be used with other reduction cleaning recipe.
Ø A post-heat set is not always necessary.

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 Details for Silicon Based Product application-with Types
Silicon emulsion is of three kinds according to its molecular size:

Ø Nano Type :
Amino Silicon Nano-emulsion, having particle size up to 10nm, is physically water like
transparent. Because of their finest particle size, they can easily penetrate right in to the core of
fibre very easily and after cross-linking; they make the fabrics soft handled and elastomeric.
Due to their penetration in side the core of fibres & cross-linking there, they push out the rest
hydrolyzed dyestuffs particles resulting in negatively affect the rubbing, staining, washing &
other fastness properties of fabrics. So, it is advisable to avoid using comparatively loser
particles sized silicone emulsion in darker shaded fabrics.

Ø Micro Types:
Amino Silicon Micro Emulsion, containing particle size above 10nm & up to 50-100nm, is also
physically transparent looking. Because of their smaller particle size, they can penetrate into
the inner parts of the fabrics and with the effect of the temperature; the silicon particles cross-
link themselves with the presence of amino-based emulsifier and hence impart permanent
elastomeric type softness. This type of silicone particle sized emulsion also contributes to the
deteriorations of rubbing, staining, washing & other fastness properties due to the same reason
as nano type silicones sized particles do.

Ø Semi-Micro Types:
Silicon Emulsion containing particle size above 100nm & up to 150nm, are physically
translucent looking. Because of their comparatively smaller particle size than the macro
emulsion but larger than the nano & micro-emulsion, they cannot fully penetrate into the
inner part of the substrate and hence remain submerged in the fabric surface and get cross-
linked there. That’s why they impart both elastomeric and slippery type softness on the surface
of the fabrics. They deteriorate the fastness of dyed fabrics to a few extent.

Ø Macro Type:
Amino Silicon Macro Emulsion, containing particle size above 150nm, is physically opaque
looking. Usually, they’re less shear force stable and emulsion can easily break. So, they can’t be
applied in exhaust process. Because of their comparatively larger particle size, they cannot
penetrate into the inner parts of the fabrics and remain on the surface of the fabrics and then
during drying they cross-link and impart permanent slippery type smooth softness effect on
the surface of the fabrics. So, it also helps in developing rubbing fastness of the substrate.

Ionic Characteristics:
Silicon Emulsions are made by Silicon particles with amine-based emulsifiers and are given
either Anionic or Cationic or Non-ionic nature during manufacturing. So, all kinds of silicon
can be usually of two kinds according to the ionic nature:

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 q Cationic:
Has more affinity towards the substrate and thus more reactive to the fabrics. It leaves some
yellowing effect after application and so is not suitable for use in the white/light shades.
q Non-ionic:
Has less affinity towards the substrate and thus are less reactive to the fabrics. Leaves no
yellowing effect after application and thus does not make any change in white/light shades
application.
q Besides, there are some other silicones of different kind, which impart cotton like hydrophilic
nature of different hydrophobic fabrics, creating some capillary pores on the surface of the
fabrics. There are also some other silicones which are more robust towards alkali i.e remains
active in pH of above 7 and thus make it user friendly.

Carefulness in Silicon based product application:

Ø Because of lower stability of Silicon emulsion i.e, easily breakable emulsion, they should not be
given high sheer-force which might result in breaking of silicone emulsion & thus it is usually
not suitable for use in Exhaust application but in Padding application. While using in Padding,
the concentration of pad-liquor is to be kept constant to avoid “Tailing effect”. If it is used in
Winch, the nozzle pressure is to be reduced remarkably to avoid silicon emulsion breakage.
Ø As it is very sensitive to alkali, specially cationic one, here padding liquor pH should never
exceed 6.5.
Ø As cationic silicone emulsion reacts with different radicals like Ca++, Mg++ and specially
Fe+++, the presence of any kind of the above radicals might make some precipitation & so
water to be softened carefully before applying silicon.
Ø Usually the Cross-linking Temperature of Silicone emulsion is about 45-50° C so, to avoid Pre-
mature cross-linking, the cross linking of silicone emulsion is to let happen in the next
subsequent processes, i.e.. Drying/Calendaring period, not during application.

Over-coming problems of Silicon Spot (pre-matured cross-linking of Silicones):

If accidentally any premature cross-linking happens, there creates some silicon spot on the
fabrics surface & it is very hard to remove. Only some Organic solvent type emulsions (mostly
organic solvent based) can dissolve these spot. So, if these types of problems occur accidentally
during application, some AEPO/NEPO free organic solvent-based detergent can be applied (with
temp. 80-90° C) to overcome it.

Using of both silicon emulsion and fatty acid based softener:

For special softness, combination of both silicon & fatty acid softener can be applied. Some
manufacturers have developed some products of this kind readily usable for this purpose. But
while using combination, it is suitable to use them in padding application:
q Making combination of Fatty acid stock solution+ Silicon Emulsion→Applying in padding
q Silicon Emulsion to be applied first and then Fatty acid softener but because of coating &
washibility nature, fatty acid softener should not be used first.

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