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CHEMICAL
PROESSING
DYEING
www.textilerun.blogspot.in
Dye
Coloured compounds (organic)
Soluble in water or can be solubilized
Posses affinity for the substrate
Penetrate / diffuse in fiber X-section during dyeing
Depending on nature of fiber & nature of dye, suitable dye fiber bonds are formed which retain the dye on the fiber
Nature & strength of dye fiber bonds determines the fastness of the dye
H- bond energy: 7 – 10 Kcal/mole
Van der Waals: 4 Kcal/ mole
Covalent bond: 80 – 100 Kcal/mole
TR
Pigment
Colouring compounds (organic/ inorganic)
Insoluble in water
No affinity to the substrate
No interaction with fiber
Used in mass colouration
Auxochromes:
Chromophores
(provides colour –
unsaturated grps.)
Chromogens:
(To which chromophore
is attached)
(Modify the hue / solubility –
conjugated system)
Phenyl, Naphthyl, etc.
-NH2
-NHR
-NR2
-OH
Saturated functional groups attached to -OR
-SO3
Chromophore
Chromogen
Auxochrome
Cellulosic fibres
Protein Fibres
Polyamide Fibres
Synthetic fibres
Synthetic fibres
Direct dyes
As anionic dye which has affinity for cellulosic fibre and are generally
dyed with water in presence of salt.
These sulphonate groups molecules are soluble in water
Dyes with a high affinity for cellulose fibres
Substantive dyes: dye molecules are attracted by physical forces at the
molecular level to the textile substrates
Cheap
Electrolyte (SALT):
Salt Sensitive dye
Durazol Fast Blue 4GS
40%
20%
0%
Temperature
Dyeing (exothermic) – lesser exhaustion at higher temp
Temperature
increases
the rate of
diffusion of
dyes in the
fibre
Temperature
lowers
the
equilibrium
dye uptake
of the fibre
Temperature: 900 – 100 0C, for 1 – 2 hrs.
Time
Liquor
M:L
BATCH DYEING
Dye should have very high affinity
Partition co-efficient should be high
CONTINUOUS: Pad – Fixation
Fixation – dry heat / steam
If high affinity, - tailing effect
SEMI-CONTINUOUS: Pad– Batch
Pad is continuous, for 1 – 2 sec.
Fixation is in batch process, for 30 min – 1 hr.
Dye of low affinity should be used
Diazotization and Development
Coupling with Diazonium salt
Treatment with Metal Salts
Treatment with Formaldehyde
Treatment with cationic fixing agent
Reactive dye
Reactive Dyes are coloured compounds that contain groups
capable of forming covalent bonds to a given substrate.
Overall affinity for cotton is poor, necessitating dyeing
for prolonged time along with excess of salt
Dyeing temp. 30 – 40 0C (Cold brand dye, M),
pH: 10-11
60 -70% dyes react with cotton
30-40% of dyes react with H2O
•Dyeing temperature: 60 – 700 / 80 -90 oC
•pH: 11
6
5
4
3
2
1
0
1312109
20
10
30
40
11
Dye Variables : Substantivity
Exhaustion Profile of a Reactive Dyes
50
0
100
80
0.5 h
Time h
1.5 h
100
50
0
0
Dye on Fibre
Dye in Bath
30 60 90 120 180
Time, min
0
100
50
0 30 60 90 120 180
Time, min
Dye on Fibre
Dye Fixation
Mobile Dye on Fibre
Hydrolyzed Dye
100
50
0
0 30 60 90 120 180
Time, min
Exh.
% Dye on Fibre
Dye Fixation
Rate of Fixation
4% per 6 min
100
50
0
0 18030 60 90 120
Time, min
Exh.
%
Dye on Fibre
Dye Fixation
Rate of Fixation
30 % per 6 min
Two bath pad steam process
Two bath pad batch process
Two bath wet fixation process
One bath pad dry process
One bath pad dry steam process
One bath pad steam process
One bath silicate pad batch process
Vat dyes
Indigoid
Indigo on reduction – colourless or light yellow (Leuco form)
Poor fastness property
Oxidation of –C=C- happens easily
Anthraquinoid
Best washing fastness and light fastness prop.
Resistant to alkaline wash / oxidation
Dyeing with vat dyes is based on the principle of converting
a water-insoluble keto-substituted colorant by reduction to
a water-soluble enolate leuco compound that is substantive
to cellulose.
Vatting:
Dissolving the dye under alkaline reducing condition,
mostly with sodium hydrosulphite or sodium dithionite
(Na2S2O4) and caustic soda (NaOH).
Dyeing:
Impregnation of the materials with the dissolved dye.
Oxidation:
The insolubilisation of dye to the original insoluble, non-
substantive pigment form inside the fibre.
Soaping: Removal of Superficial dyes, Dye aggregation
After treatment- Oxidation
Skying in air
Hydrogen Peroxide (H2O2)
Sodium Perborate (NaBO3·H2O)
Sodium m - nitrobenzenesuphonate (Ludigol)
Potassium Dichromate (K2Cr2O7)
Acid dyes
2 8 10
0.25
0.20
0.15
0.10
0.05
4 6
pH of the Dyebath
Aciddyesorbed/meqkg-1
Zone-1 → a regular titration region with an anion of high
affinity;
Zone-2 → a region of electrostatic saturation where there is a
reasonable correlation between amine end group content and
amount of sulphonic acid dye bound;
Zone-3→ a region where electrostatic saturation is exceeded
and where dye uptake has no apparent maximum.
Nylon: 2.7
Wool: 4.6
Silk: 3.5
Hydrolysis of amide groups to primary amine and carboxylic
groups at low pH
Reduction in DP
More accessible fibre (more dye sites)
Applied from acidic pH and also the dye contains acidic
group in their structure
- +
CO-NH COOHH+
3N
DSO3
-
Barre effect
Physical variations’‐ could be:
Fine – difference introduced drawing, heat setting,, etc. of the
filament yarns.
Gross – due to variations in the count or the crimp of the
yarns or Fibres.
Chemical variations’
During polymer spinning or blending of yarns of
different AEG (amino end grp.) content.
Interactions
1 Electrostatic Interaction: This interaction is between the protonated amino
groups of the fibre and the negatively charges anionic dyes.
HOOC ------------NHCO----------------
NH + DYE –
SO3
3
2. Hydrogen Bonding: This interaction is between the amino, amido and
carboxlic acid groups of the fibre and the azo and other hydrogen bonding
groups of the anionic dyes.
3
HOOC ------------NHCO----------------
NH +
3
N = N Ph – SO
2 2- 2 2
2
HOOC ------------NHCO-CH -CHCH -CH -CH
-NH
3
3. Hydrophobic Interactions: This interaction is between the aliphatic groups
of the fibre and the hydrophobic groups of the anionic dyes.
+
2 2
-CH -CH -CH -Ph-N = N-Ph -
3
Metal complex dyes
Reaction of 1 atom of metal with molecule of dye produces 1:1
metal–complex dye.
Very low affinity
Thus Conc. H2SO4 is used in dyeing (it degrades the wool ,
becomes rough).
Reaction of1 atom of metal with 2 molecules of dye produces
1:2 metal– complex dyes.
Dye has high affinity (Neutral Dyeing Metal Complex dye)
Like acid dyes, these anionic dyes form ionic bond
with protonated amino groups (Dye– +H3N-Wool)
Powerful Van der Waals’ forces may act between the big dye
molecules and the fibre.
Dye-SO3 – +H3N-Wool
Dye-Cr+ –OOC-Wool
Dye-Cr ←NH-Wool
Basic dyes
Cationic dyes are basic dyes. They are so-named because they
are derived from organic bases. They are also called cationic
dyes as they ionise in water producing coloured cations
Brilliance and colour intensity
With alkali, these dyes become colourless bases.
Temperature effect
Temperature, 0C TD = 95.60C
Df(mmolkg-1)
With retarding agent
pH effect
4
SO - groups only
Fibre with COO–
groups
End of dyeing
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Chemical Processing Dyeing

  • 2. Dye Coloured compounds (organic) Soluble in water or can be solubilized Posses affinity for the substrate Penetrate / diffuse in fiber X-section during dyeing Depending on nature of fiber & nature of dye, suitable dye fiber bonds are formed which retain the dye on the fiber Nature & strength of dye fiber bonds determines the fastness of the dye H- bond energy: 7 – 10 Kcal/mole Van der Waals: 4 Kcal/ mole Covalent bond: 80 – 100 Kcal/mole TR
  • 3. Pigment Colouring compounds (organic/ inorganic) Insoluble in water No affinity to the substrate No interaction with fiber Used in mass colouration
  • 4. Auxochromes: Chromophores (provides colour – unsaturated grps.) Chromogens: (To which chromophore is attached) (Modify the hue / solubility – conjugated system) Phenyl, Naphthyl, etc. -NH2 -NHR -NR2 -OH Saturated functional groups attached to -OR -SO3
  • 6.
  • 7.
  • 12. Direct dyes As anionic dye which has affinity for cellulosic fibre and are generally dyed with water in presence of salt. These sulphonate groups molecules are soluble in water Dyes with a high affinity for cellulose fibres Substantive dyes: dye molecules are attracted by physical forces at the molecular level to the textile substrates Cheap
  • 13. Electrolyte (SALT): Salt Sensitive dye Durazol Fast Blue 4GS 40% 20% 0%
  • 14. Temperature Dyeing (exothermic) – lesser exhaustion at higher temp Temperature increases the rate of diffusion of dyes in the fibre Temperature lowers the equilibrium dye uptake of the fibre Temperature: 900 – 100 0C, for 1 – 2 hrs.
  • 15. Time
  • 17. BATCH DYEING Dye should have very high affinity Partition co-efficient should be high CONTINUOUS: Pad – Fixation Fixation – dry heat / steam If high affinity, - tailing effect SEMI-CONTINUOUS: Pad– Batch Pad is continuous, for 1 – 2 sec. Fixation is in batch process, for 30 min – 1 hr. Dye of low affinity should be used
  • 18. Diazotization and Development Coupling with Diazonium salt Treatment with Metal Salts Treatment with Formaldehyde Treatment with cationic fixing agent
  • 19. Reactive dye Reactive Dyes are coloured compounds that contain groups capable of forming covalent bonds to a given substrate. Overall affinity for cotton is poor, necessitating dyeing for prolonged time along with excess of salt
  • 20.
  • 21. Dyeing temp. 30 – 40 0C (Cold brand dye, M), pH: 10-11 60 -70% dyes react with cotton 30-40% of dyes react with H2O •Dyeing temperature: 60 – 700 / 80 -90 oC •pH: 11
  • 23. Dye Variables : Substantivity Exhaustion Profile of a Reactive Dyes 50 0 100 80 0.5 h Time h 1.5 h
  • 24.
  • 25. 100 50 0 0 Dye on Fibre Dye in Bath 30 60 90 120 180 Time, min 0 100 50 0 30 60 90 120 180 Time, min Dye on Fibre Dye Fixation Mobile Dye on Fibre Hydrolyzed Dye
  • 26. 100 50 0 0 30 60 90 120 180 Time, min Exh. % Dye on Fibre Dye Fixation Rate of Fixation 4% per 6 min 100 50 0 0 18030 60 90 120 Time, min Exh. % Dye on Fibre Dye Fixation Rate of Fixation 30 % per 6 min
  • 27. Two bath pad steam process Two bath pad batch process Two bath wet fixation process One bath pad dry process One bath pad dry steam process One bath pad steam process One bath silicate pad batch process
  • 28. Vat dyes Indigoid Indigo on reduction – colourless or light yellow (Leuco form) Poor fastness property Oxidation of –C=C- happens easily Anthraquinoid Best washing fastness and light fastness prop. Resistant to alkaline wash / oxidation Dyeing with vat dyes is based on the principle of converting a water-insoluble keto-substituted colorant by reduction to a water-soluble enolate leuco compound that is substantive to cellulose.
  • 29. Vatting: Dissolving the dye under alkaline reducing condition, mostly with sodium hydrosulphite or sodium dithionite (Na2S2O4) and caustic soda (NaOH). Dyeing: Impregnation of the materials with the dissolved dye. Oxidation: The insolubilisation of dye to the original insoluble, non- substantive pigment form inside the fibre. Soaping: Removal of Superficial dyes, Dye aggregation
  • 30.
  • 31. After treatment- Oxidation Skying in air Hydrogen Peroxide (H2O2) Sodium Perborate (NaBO3·H2O) Sodium m - nitrobenzenesuphonate (Ludigol) Potassium Dichromate (K2Cr2O7)
  • 32. Acid dyes 2 8 10 0.25 0.20 0.15 0.10 0.05 4 6 pH of the Dyebath Aciddyesorbed/meqkg-1
  • 33. Zone-1 → a regular titration region with an anion of high affinity; Zone-2 → a region of electrostatic saturation where there is a reasonable correlation between amine end group content and amount of sulphonic acid dye bound; Zone-3→ a region where electrostatic saturation is exceeded and where dye uptake has no apparent maximum.
  • 34. Nylon: 2.7 Wool: 4.6 Silk: 3.5 Hydrolysis of amide groups to primary amine and carboxylic groups at low pH Reduction in DP More accessible fibre (more dye sites) Applied from acidic pH and also the dye contains acidic group in their structure - + CO-NH COOHH+ 3N DSO3 -
  • 35.
  • 36. Barre effect Physical variations’‐ could be: Fine – difference introduced drawing, heat setting,, etc. of the filament yarns. Gross – due to variations in the count or the crimp of the yarns or Fibres. Chemical variations’ During polymer spinning or blending of yarns of different AEG (amino end grp.) content.
  • 37. Interactions 1 Electrostatic Interaction: This interaction is between the protonated amino groups of the fibre and the negatively charges anionic dyes. HOOC ------------NHCO---------------- NH + DYE – SO3 3 2. Hydrogen Bonding: This interaction is between the amino, amido and carboxlic acid groups of the fibre and the azo and other hydrogen bonding groups of the anionic dyes. 3 HOOC ------------NHCO---------------- NH + 3 N = N Ph – SO 2 2- 2 2 2 HOOC ------------NHCO-CH -CHCH -CH -CH -NH 3 3. Hydrophobic Interactions: This interaction is between the aliphatic groups of the fibre and the hydrophobic groups of the anionic dyes. + 2 2 -CH -CH -CH -Ph-N = N-Ph - 3
  • 38. Metal complex dyes Reaction of 1 atom of metal with molecule of dye produces 1:1 metal–complex dye. Very low affinity Thus Conc. H2SO4 is used in dyeing (it degrades the wool , becomes rough). Reaction of1 atom of metal with 2 molecules of dye produces 1:2 metal– complex dyes. Dye has high affinity (Neutral Dyeing Metal Complex dye)
  • 39. Like acid dyes, these anionic dyes form ionic bond with protonated amino groups (Dye– +H3N-Wool) Powerful Van der Waals’ forces may act between the big dye molecules and the fibre. Dye-SO3 – +H3N-Wool Dye-Cr+ –OOC-Wool Dye-Cr ←NH-Wool
  • 40. Basic dyes Cationic dyes are basic dyes. They are so-named because they are derived from organic bases. They are also called cationic dyes as they ionise in water producing coloured cations Brilliance and colour intensity With alkali, these dyes become colourless bases.
  • 41. Temperature effect Temperature, 0C TD = 95.60C Df(mmolkg-1)
  • 43. pH effect 4 SO - groups only Fibre with COO– groups