Yellowing of Wool In Dye

Bath

BY : Hemant GhanGhor
&
Patanjal Kumar
1.Introduction
2.
3.Types of yellowing
4.
5.Causes of yellowing
6.
7.Mechanism
8.
9.Effect of various parameter
pH
temperature
time
6.Effect of bleaching and whitening
7.
8.Prevention of yellowing
9.
10.Measurement of yellowing
 Introduction
Wool dyeing

It is carried out at boil

Ph=2-7
For prolonged time

Due to which wool fibre is modified in several ways

Modification or damage results in unacceptable level of yellowing

During bleaching and whitening process also the strength of wool fibre
is lost . When bleached and whitened fibres are dyed at boil,due to dye
bath heat wool fibre are
further damaged and result in yellowing of wool . Yellowing of wool
also occurs during sun drying .
 Types of yellowing
Yellowing of wool

Hydrothermal yellowing
photo yellowing

Occurs during dyeing(hydrolysis of peptide bonds)

depanding on the condition
exposure,sunlight
may either yellow wool or
bleach it

254 nm UV light 331 nm UV light

398 nm UV light

Irradiation in ambient conditions UV below 331 nm increases

visible light above
Causes wool to appear green . Wool yellowness
398 nm induces Thermal yellowing
(due to formation of two chromophores)
photobleaching
occurs during:-
•Extended dyeing at boil
Fade rapidly in post irradiation reactions •In setting with superheated steam
To leave a residual yellow colour •Drying for extended time(Ph>7)
 Causes of yellowing

Damage of wool fibre

1.Photo oxidation of CYS(cystine) is the most damaging reaction
2.Hydrolysis of peptide bonds in hot acidic liquors (particularly at aspartic
acid residues)
3.Few carbonyl groups are detachable when wool is wet show pronounced
yellowing
4.In dry state due to irradiation of wool minor amount of α-keto acids becomes
detachable
Wool

Protein fibres containing cystine bonds

Protein are long polymers of amino acids bonded by peptide linkage

amino acids peptide bonds

cystinebonds cell membrane complex
And other non keratinous

region
cleavage of the peptide
N-Cαbond
produces soluble proteins
fibrestrength loss
known as wool gelatins
 Amino acids of wool

Acidic amino acids and their ω-amides (eg. Aspartic acid,glutamic

acid etc)

Lysine
Basic amino acids Histidine
Tryptophan
Serine

Amino acids with hydroxyl groups in the side chain

Threonine

Tyrosine

sulphur containing amino acids (cystine,cysteine,methionine

etc.)

Amino acids without reactive groups in the side chain

Proline

Isoleucine
The residues of amino acids extensively damaged by prolonged exposure to
sunlight are
TRP,PHE,THR,MET,ILEU,LEU,PRO,HIS etc.
Mechanism

R R’
R R’
hΰ
CH C NH CH C CH
C NH2 + C C

O O
O O O

This reaction is implicated both with fibre strenght loss and

subsequent susceptibility to hydrothermal yellowing .
 Effect of various parameters

Effect of
pH Yellowness Index

pH
 Effect of various parameters

ffect of temperature
Yellowness
Index

Temperature
 Effect of various parameters

Effect of
time
At ph 3
Yellowness index

Time/h
 Photostability of wool

Natural wool:- more photo stability

Ox datively bleached with H2O2 :-stability further

reduced

FWA treated wool :- it yellows wool rapidly in sunlight

Principal factors which influences the observed colourchange of wool when exposed to
radiation :-
• Wavelength distribution of incident light
• Presence of oxygen
• presence of water
• processing history the wool
 Effect of bleaching and whitening

WET
DRY
20 20 whitened
Change in yellowness index

Change in yellowness index

whitened bleached
10 10

bleached natural

0
0 natural

0 2 4 0 2 4
Exposure time (days) Exposure time(days)

1.Decreasing order or strength of wool fibre natural > bleached >

whitened
2.Disappointing aspect of wool bleaching and whitening :the products are less
stable in colour than before
 Effect of bleaching and whitening
Commercial bleaching of wool

Oxidative process Double bleaching process Reductive

(Using alkaline (First oxidative H2O2 process
H2O2) bleaching then reductive (using hydros or
sodium dithionite thiourea di
bleaching) oxide)
Whitest wool is
obtained
To further improve whiteness
FWA treatment
(it is carried out either after oxidative bleaching or after reductive
bleaching )
It absorbs UV light and emits blue fluorescence
(Wool appears much brighter)

Yellow rapidly when expose to sunlight,specially in wet

Cause:-superoxide generation via photo induced electron transfer

Example FWA:-Sulphonated stilbene

 Effect of wool processing on colour

Greasy wool
wool
Long garment
processing chain
(either by worsted or by woolen system)

Several of these has many stages and can affect

wool colour
Photo yellowing , yellowing can also occur when it is treated under alkaline
conditions or exposed to heat e.g.

•shrink - resist treatment --- use of chlorine or DCCA leads to

significant yellowing .
•Flame retardant treatment --- use of titanium compound leads to
yellowing
 Prevention of wool dye bath yellowing
Methods of prevention
1.Pretreatment with HA
2.By adding sodium bisulphite to dyebath
3.Addition of H2O2 to dyebath after exhaustion
Pretreatment with HA
(In mildly acidic dye bath)

Add HA ( 0.2 % )
50% - 70% reduction
HA + carbonyl gr. Aldoximes + ketoximes
•Pretreatment of wool with HA - only transient protection
•
•Pretreatment with HA – neutral medium dyeing – no yellowing
•
•Acidic conditions predominate in wool dyeing so HA must be present at an
adequate amount to minimize hydrothermal yellowing .
 Measurement of yellowness
It is measured in the term of (Y-Z) value .
To summarize (Y-Z) yellowness measurements will usually rank between 0( very
good whiteness) to 8-12 (very yellow) and

LOT Clean wt . Yellowness (Y-

(tonnes) Z)
A 2 3.5
B 3 6.2
C 1 5.5
D 4 4.5
WA 10 4.9

Weighted average of yellowness = 3.5×2+6.2×3+5.5×1+4.5×4

10
=4.9
 KS
AN
TH