Sulphur Dye
• Sulphur dyes are one of the most used for producing
bright and brown/black shade on cellulosic fiber
products.
• The chemistry of sulphur dyes dyeing is near similar to
vat dyes dyeing. In both case, final color is developed by
the oxidation process. Although, reactive dyes, azoic
color is available but sulphur dyes is preferable for black
shade production.
• Sulphur dyes contain di-sulphide (S-S) linkage in their
chemical structure. The dyeing process is carried out in
an alkaline condition. Sulphur dyes used for both dyeing
and printing.
General Chemical Structure
Dye-S-S-Dye
Chromophore Chromophore
Di-Sulphide Linkage
Properties of Sulphur Dyes
• Water insoluble
• It needs solubilization for application (with reducing agent)
• Oxidation is needed for final color development
• Applicable in alkaline condition
• Electrolyte can be added in the dye to enhance exhaustion of
dyes
• Average Fastness properties
• Suitable for black and brown shade on the textile materials
• It is mainly applied on cotton, viscose and staple fiber
• Its exhaustion properties are good
• Dyeing is carried out in 80-95oc
• Comparatively cheap
Mechanism of Dyeing
[Na2S + Na2CO3]
Dye-S-S-Dye +
Dye-S-H + H-S-Dye
2[H ] Leuco/Thiol
(Insoluble Stage)
(Soluble Stage)
[O-]
Dye-S-S-Dye + H2O
(Oxidation)
(Insoluble Form)
Classification of Sulphur Dyes
• CI sulphur dyes
• CI leuco sulphur dyes
• CI solublized sulphur dyes
• CI condensed sulphur dyes
CI sulphur dyes
• Water-insoluble
• Contains sulphur both as an integral part of the
chromophore and in attached polysulphide chains.
• Normally applied in the alkaline reduced (leuco) form
from a sodium sulphide solution and subsequently
oxidised to the insoluble form on the fibre.
• Sulphur dyes differ from the vat dyes in being easier to
reduce but more difficult to re-oxidise, different
oxidants producing variations in hue and fastness
properties.
CI leuco sulphur dyes
• Has the same CI constitution number as
the parent sulphur dye but exists as the
soluble leuco form of the parent dye
together with a reducing agent in
sufficient quantity to make it suitable for
application either directly or with only a
small addition of extra reducing agent.
CI solubilized sulphur dyes
• Has a different constitution number
because it is a chemical derivative of
the parent dye, non-substantive to
cellulose but converted to the
substantive form during dyeing.
CI condensed sulphur dyes
• Although containing sulphur, bear
little resemblance to traditional
sulphur dyes in their constitution
and method of manufacture.
Commercial forms of sulphur dyes
• Powders
• Grains
• Dispersed powders
• Dispersed pastes and
• Water soluble-brands
Application method
• Sulfur dyes are water-insoluble. In the presence of a
reducing agent and at alkali pH's at elevated
temperature of around 80°C, the dye particles
disintegrate, which then becomes water-soluble and
hence can be absorbed by the fabric.
• Sodium sulfide or sodium hydrosulfide are suitable
reducing agents. Common salt facilitates the absorption.
After the fabric is removed from the dye solution, it is
allowed to stand in air whereupon the dye is
regenerated by oxidation. The regenerated parent dye is
insoluble in water.
• Oxidation can also be effected in air or by hydrogen
peroxide or sodium bromate in a mildly acidic solution.
Application method
• The low water solubility is the basis of the good
wash-fastness of these dyed fabrics. These dyes
have good all round fastness except to chlorine
bleaches.
• Because the dye is water-insoluble, it will not
bleed when washed in water and will not stain
other clothes. The dye, however, may have poor
fastness to rubbing. The dyes are bleached by
hypochlorite bleach.
Common auxiliaries used in sulphur dyeing
• Reducing agents
• Alkali
• Antioxidants
• Sequestering agents
• Wetting agents
• Neutral electrolyte/salt
• Oxidising agents
Reducing agents
• Types
–Sodium sulphide (Na2S) (commonly used)
–Sodium hydrosulphide (NaHS)
NaOH/ Na S O
–Ammonium sulphide (NH4)2S system may be too
2 2 4
strong & reduce
–Sodium dithionite (Na2S2O4) the dye
chromophore in
–Glucose (C6H12O6) addition to the
sulphide linkage
• Amount of sodium sulphide varies from 2-3
times of the amount of dye
Reducing agents
• Dye solubility may be hindered if sodium
sulphide contains iron sulphide impurities
or if calcium or magnesium is present in
the substrate or liquor
• A well-solublized dye solution drop on
filter paper shows no particles
Alkali
• Functions
–To help solubilize the sulphur dye
–To neutralize any acid produced
-To ph value
• Types
–Caustic soda
–Caustic soda/sodium carbonate mixture
Anti-oxidants
• Function
–inhibit premature oxidation
–promote better dye-bath stability
–lessen the risk of bronzing, poor rubbing
fastness and dark selvedges.
• Types
–Sodium polysulphide
–Sodium borohydride
Sequestering agents
• Function
– to avoid poor rubbing fastness or
un-levelness in the presence of
multivalent ions in the dye liquor or
in the substrate.
Wetting agents
• Function
–To improve the wettability of the substrate.
–To improve liquor penetration
• Although the majority of sulphur dyes are
unaffected by most wetting agents, some
non-ionic wetting agents may inhibit the dye
uptake in exhaust dyeing or precipitate the dye.
Neutral electrolyte/salt
• Function
–To promote dye exhaustion
• Amount may vary from 20-50% o.w.f.
depending on shade %
• Too high amount may cause bronziness
Oxidising agents
• Oxygen in water
• Oxygen in air
• Hydrogen peroxide
• Sodium dichromate (Na2Cr2O7) in acetic
acid solution
• Sodium bromate (NaBrO3)
Main steps in dyeing with sulphur dyes
• Reduction
–whereby the water-insoluble dye is converted into water-soluble form
• Application
–whereby the solubilised dye is applied onto the substrate by a suitable
exhaust or continuous method
• Rinsing
–whereby all loose colour is removed before the oxidation stage
• Oxidation
–whereby the dye absorbed by the substrate is oxidised back into
water-insoluble form, and
• Soaping
–which results in an increase in brightness as well as improved fastness
of the final shade
Exhaust dyeing with sulphur dyes
A 2g/l sequestrant
5g/l soda ash
5ml/l caustic
2g/l sodium sulphide
B X% o.w.f. dye dissolved
in 1.5 times sodium
sulphide at boil
C 30g/l common salt
D 2ml/l H2O2 35%
E 1g/l detergent
Pad dyeing with sulphur dyes
• Padder • Steaming
–2 g/l sequestrant =102 °C
–2 g/l wetting agent saturated steam,
–30 ml/l caustic 38 °Be 60 seconds
–5 g/l soda ash
–20-30 g/l sodium sulphide
–X g/l dye
–Temperature 40-50 °C
–Pick-up 60-80%
Continuous washing after sulphur dyeing
Cold rinse with water
Rinsing 40°C
Oxidation 60°C with 3 ml/l (hydrogen peroxide 35%)
Soaping with 2 g/l detergent
Rinsing 60°C
Neutralisation with acetic acid / sodium acetate
After-treatments
• After-treatments with H2O2
• ” with CuSO4 + CH3COOH
• ” with CuSO4 + CH3COOH + Na2/K2Cr2O7
• ” with NaOCO3
Stripping
• With Reducing Agent at high temperature
• A blank of containing 4.5 – 9g/l sodium
hydrosulphide, 2-3 g/l sequestering agent at
90 – 95oC will strip off 10-20% of dye, while
addition of a stripping agent such as polyvinyl
pyrolidine will remove a further 10-20%. It is
advisable to redye from fresh bath.
Advantages Dis-advantages
• Cheaper • Bronziness of shade:
For this defect some
• Availability white spot can be
• Satisfactory Color Fastness appeared in the
• Suitable for dark shades fabric.
• Tendering of
cellulose on storage
• Poor Rubbing
Fastness.
Environmental issues
• Due to the highly polluting nature of the dye-bath
effluent, sulfur dyes are being slowly phased out in the
West but they are used on a large scale in South Asian
Textile Manufacturers.
• Recent advances in dyeing technologies have allowed
the substitution of toxic sulfide reducing agents. Glucose
in basic solution is now used and both low sulfide and
zero sulfide products are available.
• Future developments in the field of reducing dye levels
by means of electro-chemical processes are promising.
Thank you!
