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Bleaching

Objectives
• To produce white fabrics by destroying (oxidize/reduce) the colouring
matter using bleaching agents ----with minimum degradation of the fibre
• Sources of colouring matters :
Colouring matter (flavone pigments).
Yellowness of various degrees --- due to climate, soil, drought and frost
Tips of leaves or stalks coming in contact with the moist ball after opening
will cause dark spots and discolouration
Dirt, dust, insects or harvesting/processing equipment in the form of oils
and greases.
• Bleached cotton
Pure and permanent white
Level dyeing
No tendering/degradation

Bleaching agents
• Oxidative bleaching agents
Peroxide system: Hydrogen peroxide, peracetic acid, etc.
Chlorine system: Bleaching powder, sodium hypochlorite, sodium
chlorite, etc.

• Reductive bleaching agents: sulphur dioxide, sodium hydrosulphite,

sodium bisulphites, etc.

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Bleaching using hypochlorites (Sodium/calcium)

• Bleaching Powder
Solution of bleaching powder contains calcium hypochlorite
(Ca(OCl)2), calcium chloride (CaCl2), lime Ca(OH)2, hypochlorous acid
(HOCl), free chlorine, etc.
Not preferred in Textile Industry (Solid residue, harsh feel to fabric,
additional treatment to remove calcium salts, need of pH accuracy)
• Sodium hypochlorite (NaOCl)
Sodium salt of hypochlorous acid (HOCl).
Sodium hypochlorite solution is strongly alkaline (pH ~ 11.55) and the
free caustic present in the solution acts as a stabiliser

Factors affecting in hypochlorite bleaching

• Bleaching of cotton—
Hypochlorite solution containing 1-3 gpl available chlorine at room
temperature at pH range of 9.5 to 11.
• pH- self or by adding alkali
• After-treatments: Fabric is treated with dilute acids (souring) to
neutralise any alkali present in the cloth. CaCO3 formed during
bleaching with bleaching powder (deposited on fabric) is also
removed.
• An antichlor treatment with sodium thiosulphate or bisulphite is also
recommended to remove any residual chlorine from the cloth.
• Further washing with water to rinse out acid

Concentration

• Available chlorine
Titration method
Hypochlorite solution + distilled water + 20 ml of KI solution (10%) + 10
ml of glacial acetic acid. The liberated iodine is titrated against N/10
sodium thiosulphate solution --- starch solution as indicator
1 ml of 0.1 N Na2S2O3 = 0.00355 g available chlorine
• Commercial solution of sodium hypochlorite contains 14-15%
available chlorine, compared to 35-36% in bleaching powder.
• Generally 1-3gpl available chlorine
• The optimum bleaching conditions– can vary with the extent of
impurities in fabric-- and final product (dyed/ full white product)

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Effect of pH

• Hypochlorite ionises differently under different pH conditions

• As the pH falls below 5, the liberation of chlorine begins to take place
and pH below 1.5, the whole of hypochlorous acid is converted into
chlorine.
• In the pH range 9 to 11, a plateu occurs at which little change occurs
and is the normal use range for bleaching with hypochlorite solution.
The active species appear to be OCl - ion, or a complex of HOCl and
OCl-

Effect of temperature

• Generally 40°C for 1 h.

• Higher temperature ---higher rate of bleaching ---higher degradation
of cotton
• Hypochlorite solutions by themselves are quite stable at the boil at
pH values 11 or higher, but decomposes at lower pH values
• Cotton may be bleached (pH-11) at 60°C in 7 min--difficult to control
the degradation of cotton in such short period of bleaching

Limitations of sodium hypochlorite bleaching

• Stabilisation of sodium hypochlorite is difficult to achieve

• Cannot be used on natural animal fibres.
• Cannot be used for the bleaching of synthetic fibres as it produces greater
damage to such fibres.
• Does not produce completely satisfactory whites
• Slight damage to cellulosic fibres.
• Produces harsh handle on fabric
• Requires corrosion resistant equipment.
• Unpleasant odour in working environment.
• Harmful to skin in concentrated form.
• Formation of highly toxic chlorinated organic by-products (AOX) during the
bleaching process

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Bleaching with Hydrogen Peroxide (H2O2)

• H2O2 -- stable in acidic medium
• For bleaching –destabilize by addition of alkali /increased
temperature.
• Liberates perhydroxyl ion (HO2-) in aqueous medium and chemically
behaves like a weak dibasic acid.
• HO2- -- highly unstable and in the presence of oxidisable substance
(coloured impurities in cotton), it is decomposed --bleaching
• Sodium hydroxide ---activates H2O2 --- H+ ion is neutralised by alkali --
favourable for liberation of HO2-.
• Liberation of HO2- ion to be controlled

Parameters in peroxide bleaching—1.pH

• At pH 1 to 3 it is stable ; Least stability in pH 11.5-13
• pH 10.5 --accumulation of perhydroxyl ions in the bleaching bath--
bleaching takes place
• At neutral or weak alkaline media, hydrogen peroxide may not
provide whitening effect

2. Temperature
• Cotton bleaching--at 90-100°C --may be increased to 120°C for
pressurised equipment with a corresponding reduction in process
time.
• The rate of bleaching increases with the increase in temperature---
solution becomes unstable and degradation of cotton increases
• Below 80°C --evolution of perhydroxyl ion is very slow – slower rate of
bleaching.

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3. Concentration
• The optimum concentration-- depends on number of factors namely
temperature, time, fibre type, extent of coloured impurities, and
liquor ratio
• Batch process --- 2-4% (o.w.f.) hydrogen peroxide is sufficient for
cotton fabrics with a liquor ratio of 1:10 to 1:20.
• Continuous process--10-30gpl hydrogen peroxide used for saturation
• Very high concentration may damage the fibre.

4.Time
• Time --- depends on temperature, class of fibre and equipment used
for bleaching
• Time of bleaching is inversely proportional to the temperature of the
bleaching bath
• Batch process--At 95-100°C, 1hr is sufficient

Stabilisers for peroxide bleaching

• Stabilisation?
• Regulation or control of perhydroxyl ion to prevent rapid decomposition of
bleach and to minimise fibre degradation
• Stabilisers --function by controlling the formation of free radicals.
Alkalies: Sodium silicate (Na2SiO3forms a complex compound with perhydroxyl
ions which are liberated slowly at higher temperature during bleaching process.
--oxidation and thermal resistant--offer buffering effect--not greatly effected by
the presence of ionic iron. Works well in presence of hard water (MgSO4 may be
added)
Sequestering agents: eliminate heavy metal ions that are responsible for free
radical formation. Anti-catalytic reaction
Other organic stabilisers --copolymers of maleic acid, vinyl acetate, methoxy
PEG, methacrylate, etc.

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After-treatments
• Peroxide killing from fabric
• Neutralize
• Wash

Advantages of Peroxide bleaching

• Universal bleaching agent

• Milder reagent (than hypochlorite), less degradation of cellulose
• Single stage combined scouring and bleaching or a continuous
method is possible using hydrogen peroxide
• White effect is permanent, no yellowing
• Short rinsing (No souring and antichlor required)
• No AOX (adsorbable organic halides)

Limitations
• Costlier
• Requires stabilizer
• 'Catalytic damage' - results in small spots of unevenly dyed fabric or
even, in severe cases, the formation of small holes.

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Bleaching with Sodium Chlorite (NaClO2)

• Bleaching in acidic pH -- Any advantage?

• Stable in alkali. On decomposition produces chlorine dioxide (active species for
bleaching ) a strong oxidising gas
• More ClO2 with higher concentration, lower pH and higher temperature
• Addition of formic acid/acetic acid/phosphoric acid –maintain pH between 3 to 5.
• pH below 3.0, weak acid (HClO2) and strong acids (HCl and HClO3) are formed which
hydrolyse the cellulose--severe damage to cotton
• Slow release : slow building of acidity, use of acid liberating agents like NaH2PO4,
diethyl tartarate

Bleaching of cotton with sodium chlorite

• Batch process
Sodium chlorite (1-2%), pH 3-5, sodium dihydrogen phosphate (0.2-
0.5%), stable wetting agent (0.1-0.25%), nitrogenous chlorine
absorber (Sodium nitrate) and formic acid to maintain the pH.
Temperature --82-90°C, 1-3 h depending on the machine

• Continuous process
Sodium chlorite alone (10-20gpl, pH-3-5, wetting agent 1-3gpl, 18-
20min at 100-105°C)
Accelerated bleaching

Bleaching with Peracetic Acid

• Peracetic acid --equilibrium solution consisting of hydrogen peroxide, acetic acid
and peracetic acid.

• Preferred for synthetic fibres

• Cotton bleaching-- 4-6% owf, pH 6-7, 50-80°C for 20- 60 min depending on the
temperature.

• Environmentally safer than chlorine-based bleaching agents, decomposes to

oxygen and acetic acid
• Expensive, less stable than hydrogen peroxide