Direct Dyes

Lecture #2
Textile Dyes and Dyeing
Dr. Rehan Abbasi
Content
• Introduction of Direct Dyes
• Chemical Structures
• Properties
• Classification
• Mechanism of Dyeing
• Effect of Electrolyte, Temperature and L:R
• General procedure of dyeing
• After Treatment
• Disadvantages and Uses
Introduction to Direct Dyes
• Also known as substantive dyes
– Have excellent substantivity for cellulosic textile materials (Cotton,
Viscose etc.)
• Have direct affinity for cellulosic fibres when applied from an aqueous
solution
• Direct dyes are sodium salts of aromatic sulphonic acids and most of them
contain azo group as the main chromophore
– Can be denoted as DSO3Na
– (Many of the direct dyes are based on direct amines)
• These dyes are Sodium salts of aromatic sulphonic acids
Common Chromophores
• Azo • J-Acid

• Biphenyl • H-Acid

• Stilbene
• Thiazole
Direct Dye Chemical Structure
• Bottiger synthesis the 1st Direct Dye in 1884.

Congo Red (Banned nowadays due to the presence of

Benzidine/substituted Benzidine)
Direct Dye Chemical Structure

DIRECT PURE YELLOW 5G Direct Black 38

DIRECT SCARLET B Direct Blue 86

Properties of Direct Dyes
• Direct dyes are soluble in water
• Have affinity for cellulose and protein fibres specially wool
• Chemically the dyes are represented as sodium salts of sulphonic
acids (DSO3Na)
• When dissolved in water, dye molecules get dissociated into ions
DSO3Na → DSO3- + Na+
• During dyeing the textile material absorbs coloured anions from the
dye solution. This is followed by the diffusion of molecules into the
fibres where they are finally anchored by means of physical forces
Properties of Direct Dyes
• Owing to their water solubility, the dye possess poor wash
fastness
• Light fastness is, however, poor to moderate, even good in
some cases
• The fastness properties of these dyes can be improved slightly
by means of certain after treatments
Classification of Direct Dyes
• Class A: Self-levelling Dyes
– Dyeing may be uneven in the initial stages but they get levelled
on prolonged dyeing because of better migration properties
– Do not require salt for exhaustion
• Class B: Salt-controllable Dyes
– Do not migrate well
– Require salt addition for increased exhaustion
– If uneven dyeing takes place initially, it is very difficult to correct
the dyeing
Classification of Direct Dyes
• Class C: Temperature –controllable dyes
– Similar to Class B type
– Levelling properties is poor
– Sensitive to salt and exhaustion cannot be controlled with
salt alone
– Exhaustion is controlled by controlled rise of dye bath
temperature
Mechanism of Dyeing
When cotton is immersed in a solution of a direct dye the following mechanism takes place
• Adsorption
– Dye molecules move towards the fibre
– Get adsorbed on the fibre surface
• Absorption or penetration
– Adsorbed dye penetrate inside the fibre structure
– Gradually penetrate or ‘diffuse’ inside the structure
– Rate of penetration depends on the molecular structure of the dye and dyeing
condition
– Greater the penetration of the dye in the fibre, better and brighter is the dyeing
Mechanism of Dyeing
• Fixation
– Fixation takes place by means of hydrogen bonds and vanderwaals forces of
attraction
Effect of Electrolytes
• Addition of salt in dyeing promotes exhaustion
• When cellulose are immersed in water they acquire a small
negative charge known as ‘zeta potential’
• In an aqueous bath containing both fibre and direct dye, the
latter being anionic will be repelled by the negative surface
charge on the fibre
• Little or no exhaustion will take place
• When electrolyte such as Sodium Chloride (NaCl) is added to the
bath, it ionizes into sodium cations and chloride anions
Effect of Electrolytes
• The sodium cations neutralize or reduce the negative charge
on the fibre surface and the dye anion in the bath, repelled
by the chloride anions move to the fibre where they are
adsorbed
• The dye anion are much larger than
the chloride anions, but they have a
greater substantivity for the cellulose
fibre and therefore quickly absorbed
by the almost neutral fibre surface
Effect of Temperature
• The amount of dye taken by the fibre depends on the
temperature of dyeing
• The rate of dyeing increases with rise in temperature
• So, uneven dyeing can take place at elevated
temperature
• Therefore, it is always advised to start the dyeing at room
temperature and then the temperature is raised to
maximum dyeing temperature
Effect of Temperature
• As the temperature rises, the rate at which equilibrium
is attained increases until it reaches the maximum
– Affinity however decreases with further increase in
temperature
Effect of Liquor Ratio
• As the initial concentration of the dye in the dye bath
increases, the dye uptake also increases
• Therefore, a deeper shade is obtained by using more
concentrated bath of dyeing
Dyeing of Cotton
General Recipe
• Direct dye x% (o.w.m)
• Common salt 5% , 10%, 20% o.w.m (for light,
medium and dark shades respectively)
• Temperature 90°C ~ 100°C
• Time 45 ~60 minutes
• Machines like winch and jigger for fabric and
hank dyeing machine for yarn are generally
used for cotton goods with direct dyes

A typical dyeing process for a Class B direct dye on cotton

After Treatment
• “After Treatment” is done to improve the fastness property
– By increasing the molecular weight and thus decreasing the
solubility in water after dyeing
– But cannot be applicable for all the dyes as colour of the final
product changes
1. Treatment with Metallic salts
– Treatment with copper salts
– Treatment with chromium compounds
2. Treatment with formaldehyde
After Treatment
• Treatment with Copper salts
• The light fastness of certain dyes can be improved by Copper
salts
• The dyed material is treated in a bath containing
Copper sulphate 0.5 % to 2% (owm)
Acetic Acid 0.5% to 2% (owm)
Temperature 80 °C
Time 30 ~ 45 minutes
• The material is then rinsed and dried
After Treatment
• Treatment with Chromium salts
• Chromium atoms can be introduced in the molecular structure of certain direct
dyes resulting in more complex structures
– Washing fastness is improved
– This treatment, however, does not alter their light fastness properties
– The dyed material is treated in a bath containing
Pottasium di-chromate 2 - 3% (owm)
Acetic Acid 2% to 3% (owm)
Temperature 90 °C
Time 30 ~ 45 minutes
• The material is then rinsed and dried
After Treatment
• A combination of the treatments with copper and chromium
compounds can be employed to get improvements in washing as well
as light fastness properties
• The dyed material is treated in a bath containing
Pottasium di-chromate 0.5% (owm)
Copper sulphate 0.5 – 2% (owm)
Acetic Acid 1% to 5% (owm)
Temperature 80 °C
Time 30 ~ 45 minutes
• The material is then rinsed and dried
After Treatment
• Treatment with formaldehyde
– Increasing the relative size of the dye molecules of some direct dyes can
also be achieved by treatment with formaldehyde
– Washing fastness is enhanced
• The dyed material are treated in a bath containing
– Formaldehyde 2 – 3% (owm)
– Acetic Acid 1% (owm)
– Temperature 60 – 70 °C
– Time 30 minutes
• The material is then rinsed and dried
Disadvantages of Direct Dyes
• Many Direct Dyes are bland and dull in color.
• Direct Dyes provide duller color than the color
provided by the fiber reactive dyes.
• The wash fastness quality is also low.
• Few Direct Dyes have low light fastness.
Uses
• Direct dyes dye all cellulosic fibers, including viscose
rayon, and most of them also dye wool and silk.
• They do not dye acetate rayon and synthetic fibers.
Direct dyes can be applied well at low temperatures
and are therefore suitable for tie-dyeing and batik work.
• Generally, these dyes are used where high wash
fastness is not required
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