Exhaust Dyeing With Reactive Dyes

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Exhaust Dyeing with Reactive Dyes

Dr. Tanveer Hussain
Dean Faculty of Engineering & Technology
National Textile University Faisalabad.
4/20/2012 Dr. Tanveer Hussain 1
Variables in Reactive Dyeing
Dye variables
System/process variables
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Dye variables in Reactive Dyeing
Dye chemistry
Substantivity
Reactivity
Diffusion coefficient
Solubility

Reactive Dye Chemistry
Chromophore
Affects colour gamut, light fastness, chlorine/ bleach
fastness, solubility, affinity, and diffusion
Azo dyes are dischargeable. Disazo dyes have the
disadvantage of being much more sensitive to
reduction and many of them are difficult to wash-off.
Anthraquinone dyes exhibit relatively low
substantivity and are easier to wash-off. Most of them
possess excellent fastness to light and to crease-
resistant finishes, but they are not dischargeable.
Phthalocyanine dyes diffuse slowly and are difficult to
wash-off
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Reactive Group
Affects
affinity
efficiency of reaction with the fibre,
dyefibre bond stability,
Determines
Sat requirement
Alkali requirement
Temperature requirement
S-triazine dyes
Do not have good wet fastness properties in acidic
media
Due to their high substantivity, have poor wash-off
properties.
Monochlorotriazines have good fastness to light,
perspiration and chlorine.
The fluorotriazine groups form linkages with
cellulose that are stable to alkaline media
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Reactive dyes of dichloroquinoxaline,
monochlorotriazine and monofluorotriazine
types show a tendency for lower resistance to
peroxide washing and dyefibre bond stability
A lower sensitivity to changes in dyeing
conditions (particularly temperature) is the
most important characteristic feature of the
monochlorotriazine-vinyl sulphone
heterobifunctional dyes

Vinyl sulphone reactive system
have poor alkaline fastness.
chemical bond between the vinyl sulphone and the
cellulosic fibre is very stable to acid hydrolysis.
The substantivity of hydrolysed byproducts of vinyl
sulphone is low, so washing off is easy
The turquoise reactive dye shows an optimum
dyeing temperature that is generally about 20 C
higher than that of other dyes with the same
reactive group
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Dye Substantivity
Substantivity is more dependent on the
chromophore as compared to the reactive
system.
A higher dye substantivity may result in:
a lower dye solubility
a higher primary exhaustion
a higher reaction rate for a given reactivity
less diffusion, migration and levelness
a higher risk of unlevel dyeing,
more difficult removal of unfixed dye
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Dye Substantivity
An increase in the dye substantivity may be
affected by:
higher concentration of electrolyte,
lower temperature,
higher pH (up to 11)
lower liquor to goods ratio
Half dyeing time
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Dye Reactivity
Dye Reactivity
A high dye reactivity entails a lower dyeing
time and a lower efficiency of fixation.
Reactivity of a dye can be modified by altering
the pH or temperature, or both.
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Diffusion Coefficient
Dyes with higher diffusion-coefficients usually result in better
levelling and more rapid dyeing.
Diffusion is hindered by the dye that has reacted with the fibre and
the absorption of active dye is restrained by the presence of
hydrolysed dye.
Different types of dyes have different diffusion characteristics.
For example, the order of decreasing diffusion is: unmetallised
dyes, 1:1 metal-complex dyes, 1:2 metal complex dyes;
phthalocyanine dyes.
An increase in the diffusion is affected by:
increasing temperature,
decreasing electrolyte concentration,
adding urea in the bath
using dyes of low substantivity.
Dye Solubility
Dyes of better solubility can diffuse easily and
rapidly into the fibres, resulting in better
migration and levelling.
An increase in dye solubility may be affected
by:
increasing the temperature,
adding urea
decreasing the use of electrolytes.
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System Variables in Reactive Dyeing
Temperature
pH
Electrolyte
Liquor ratio
Surfactants & other auxiliaries
Effect of Temperature
A higher temperature in dyeing with reactive
dyes results in:
a higher rate of dyeing
lower colour yield
better dye penetration
rapid diffusion
better leveling
a higher risk of dye hydrolysis
lower substantivity
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Effect of pH
pH influences primarily the concentration of
the cellusate sites on the fibre.
Raising the pH value by 1 unit corresponds to
a temperature rise of 20 C.
The dyeing rate is best improved by raising the
dyeing temperature once a pH of 1112 is
reached.
Further increase in pH will reduce the reaction
rate as well as the efficiency of fixation
Type of Alkali
Different types of alkalis, such as caustic soda,
soda ash, sodium silicate or a combination of
these alkalis, are used in order to attain the
required dyeing pH.
The choice of alkali usually depends upon the
dye used, the dyeing method as well as other
economic and technical factors
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Effect of Electrolyte
The addition of electrolyte results in:
increase in the rate and extent of exhaustion,
increase in dye aggregation
decrease in diffusion.
The electrolyte efficiency increases in the order:
KCl < Na2SO4 < NaCl
There may be impurities present in the salt to be
used, such as calcium sulphate, magnesium
sulphate, iron, copper and alkalinity, that can be a
source of many dyeing problems
Effect of Liquor Ratio
At lower liquor ratios, there is:
Higher exhaustion, and
Higher colour strength
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Effect of surfactants & auxiliaries
Some anionics may enhance colour yield
Some non-ionics may decrease exhaustion
and colour yield
Some non-ionics may slow down dye
hydrolysis
Triethanolamine (TEA) is known to enhance
colour strength by enhancing the swellability
and accessibility of the cellulose structure
Reactive Dye Exhaustion
Primary exhaustion
Occurs before addition of alkali
Secondary exhaustion
Occurs after addition of alkali
Rate of exhaustion can be increased by selecting dyes
of high substantivity, increasing the temperature and
increasing the electrolyte concentration.
Degree of exhaustion can be increased by selecting
dyes of high substantivity, lowering a bit the
equilibrium temperature and increasing the electrolyte
concentration and dyeing time.
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Reactive Dye Migration
The intrinsic properties of a reactive dye that affect
migration are:
substantivity,
molecular structure,
physical chemistry and stereochemistry.
The higher the dye substantivity, the lower is the migration.
The external factors that affect migration are:
concentration of the dye,
temperature, time,
liquor ratio,
liquor circulation
the form of the textile material
Reactive Dye Levelness
Levelness of dyeing may be inhibited by:
high substantivity,
lower dye migration
too much salt in the dyebath
too high rate of exhaustion
too high concentration of alkali
a rapid shift of dyebath pH,
too high rate of fixation
too high rate of rise of temperature
poor liquor agitation.
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Approaches to Obtain Level Dyeing
Controlled absorption can be obtained by salt dosing, alkali dosing,
and/or controlling the rate of heating.
Obtaining Level Dyeing in Light Shades
During the primary exhaustion, the dye is free to migrate.
During the secondary exhaustion stage, dye migration is
poor.
For light dyeing shades (less than 1 % o.w.f.) the degree of
primary exhaustion is over 80% and the degree of
secondary exhaustion is very small.
Therefore control of the primary exhaustion stage is very
important if level dyeing is to be obtained.
The rate of primary exhaustion is dependent on the
amount of electrolyte used.
Dosing or split addition of salt is recommended to obtain
level dyeing.
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Obtaining Level Dyeing in Medium & Dark Shades
For medium shades, both primary and
secondary exhaustion steps are important for
obtaining level dyeing.
Both controlled salt and alkali addition are
important in this case.
In the case of deep shades, the all-in salt
addition may be possible, but during the
secondary exhaustion, alkali dosing is
important
Obtaining level dyeing in general
Dyes with high substantivity, low secondary
exhaustion, and low MI (Migration Index)
values require controlled addition of
electrolyte after the addition of the dye.
In contrast, dyes with low substantivity, high
secondary exhaustion, and medium to high
migration index values require precise control
of liquor ratio, concentration of electrolyte,
and addition profile of the fixation alkali
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Ways to Enhance Dye Fixation & Colour Yield
Use of fixation accelerators
Use of shorter liquor ratio
Dyeing at low temperature (with decreasing
temperature the substantivity for fibre increases,
causing increased exhaustion)
Modification of chromophore and reactive group
Use of dyes with high substantivity and high reactivity
Treating cellulosic fibres with swelling agents
Modification in appearance techniques
Changing the morphology of fibre by chemical
modification.
Approaches for Uniform Rise in Rate of Fixation
Controlling the temperature of the dyeing process
suitably (possible for hot dyeing dyes only);
Adding alkali in stages (it is virtually impossible,
however, to prevent a sharp rise in fixation rate
whenever alkali is added);
Starting with a weaker alkali such as soda ash, and
following this with a stronger alkali, but only after a
higher degree of fixation has been achieved;
Progressive metering of alkali (such as the Remazol
automet process);
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Exhaust dyeing method example 1
Exhaust dyeing method example 2
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Washing-off of Hydrolyzed Dye
Phases
dilution of dye and chemicals (salt, alkali) in
solution and on the surface of the cellulose;
diffusion of the deeply-penetrated, unfixed,
hydrolysed dye to the fibre surface; and
dilution and removal of the diffused-out dye
Washing-off of Hydrolyzed Dye
Goods are rinsed cold twice to remove
electrolyte & alkali
then rinsed hot to desorb some hydrolysed
dye from the fibre, prior to a
soaping process at or near the boil.
A subsequent cold rinse completes the task of
removing un-reacted and hydrolysed dye
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Washing-off Factors
Dye substantivity
Diffusion behaviour
Liquor ratio
Washing temperature
Electrolyte concentration
pH
Presence of calcium and magnesium ions in the boiling
soap/hardness of water
Amount of unfixed dye
Washing time
Number of washing cycles/washing baths/Filling and draining
Washing auxiliary employed
Mechanical action
Dye-fiber Bond Stability
Dyes that react by a nuceophilic displacement
mechanism show good stability to alkali and, to
different degrees, less stability to acid.
Dyes that react by nucleophilic addition give dye
fibre bonds with good stability to acid, but are
less stable to alkali.
The triazinecellulose bond is generally resistant
to oxidative breakdown in the presence of
perborate, whereas this is a serious defect of
some of the pyrimidine based systems
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Fastness of Reactive Dyes
Factors
The chromophoric group,
the stability of the dyefibre bond
the completeness of the removal of the unfixed
dye.
To maximise wet fastness, particularly in deep
shades, it is advisable to apply cationic after-
treatments.
Sustainable Reactive Dyeing
Shorter/more robust dyeing procedures
Reduced water consumption
Reduced energy consumption
Reduced effluent discharge
Improved ecological image
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BASF has developed a new polymer which combines with a reactive dye hydrolysate to
eliminate its substantivity for the substrate in the presence of salt.

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4/20/2012

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