Phenolic Yellowing

Abstract:
Yellowing is the discoloration of textiles developed during production, processing, usage&
storage. It is one of the most common quality problems in natural and synthetic fibers. About
20% of textiles are finished in full white. Yellowing is mostly encountered in white and pastel
colors, Even dark shades are also affected and it is not prominent. So it is necessary to know the
chemistry behind, various causes and preventive measures of yellowing. In this article the
various potential causes of yellowing like fiber ageing, yellowing due to gaseous pollutant in the
atmosphere, chemical auxiliary used in processing and finishing, contaminant present in the
storage materials & the preventive measures are studied.

Yellowing as name called on very pale to full white fabric (Knit/Woven). Recently, had
chance to visit a towel facility who is facing yellow streaks on towels.When full white OBA
treated towels were tested for core ph. it was fount that ph is above 8.5 and present of Nitrogen
dioxide in air has triggered the reaction.The wet storage for long period further catalyzed the
yellowing.

A good definition of phenolic yellowing is expressed as "Yellowing is caused due to the

presence of phenolic compounds on the textile material, reacting with the oxides of nitrogen in
an alkaline medium. "

Oxides of nitrogen are generated in warehouses/households from direct heating systems or from
automobile emissions in the urban environment. Neither the oxides of nitrogen nor the phenolic
compounds by themselves cause yellowing, but when united, form the yellowing products.

BHT (Butyl Hydroxy Toulene) is added in polyethylene bags as anti oxidant to increase life of
packaging bags and avoid air oxidation/Aging. It is good as for packaging material but, when
this BHT reacts with textile material it caused yellowing. So, textile materials are often advised
to not be placed in poly bags which have anti oxidents like BHT.This chemistry of BHT is low in
cost and highly effective. Due to its low vapor pressure it is volatile and can be transferred to
textile goods easily.

Polyamide (Nylon) is more prone to yellowing than cotton. This is due to the cationic amino
groups present which react with anti oxidants.

Archroma product UMIDOL APY reacts with these cationic amino groups and block them to
react with Anti oxidant and hence chances of yellowing minimizes.

Another reason of yellowing can be OBA itself. Major of the OBAs are not stable to Acidic phs
and appear yellower to greener in acidic ph. so proper choice of OBA is compulsory especially
when Non volatile acids are used.

Precautions which can be carried out are.

Keep fabric core ph to acidic.
keep in dry form
Avoid direct sun light.
Don't pack in BHT containing Poly bags.
Apply Umidol APY as pre caution when packaging material is not confirmed.

Why white garments tend to yellow?

In general a substance appears to white when it reflects red, blue and green light. On usage due
to fiber ageing and environmental factors the substance absorbs blue light and it reflects red and
green light. By theory of light a substance appears to be white when it reflects red, blue and
green light. If it absorbs blue light then it reflects red and green light. The combination of red and
green gives yellow light. That’s why the white garments shows Yellowing.

Yellowing of Textiles
Causes of Yellowing:
1. Fiber ageing
Fiber ageing is one of the primary causes of yellowing. The environmental impact on the textile
fibers leads to fiber ageing. The continuous exposure of sunlight leads to photo degradation of
the textile fibers in particular natural fibers like cotton, viscose, linen etc. In the photo
degradation process there is breakage of bond occurs within the polymeric structure of the fibers
and leads to strength and color loss etc.. Usually natural fibers like cotton by its origin it is slight
yellowish in color. On further photo oxidation it yellowness increase. Manmade fibers like
nylon, spandex and polyester are more prone to yellowing.

 We can avoid the fiber ageing by proper storing of fibers.

 Avoid exposure to direct sunlight and high humidity.

2. Environmental pollutants
Yellowing issues due to the atmospheric pollutants play a vital role. The various environmental
pollutants are ozone, NOX, SOX etc..

2.1 Yellowing by ozone

Ozone is a tri-atomic molecule of oxygen. It is a strong oxidizing agent.

2.1.1 Ozone Formation

Ozone is one of the primary pollutants which found naturally in atmosphere. In addition to this,
ozone is produced by the combined action of sunlight, oxides of nitrogen and oxygen.

Under the sun ultraviolet radiation of shorter wavelength (<420nm), nitrogen dioxide undergoes
photolysis process to form nitrogen oxide and atomic oxygen. This atomic oxygen combines
with molecular oxygen to form ozone molecule. Again this ozone reacts with nitric oxide to form
molecular oxygen and nitrogen dioxide and this cycle continues.

2.1.2 Yellowing of denims

The ozone molecules present in the surface of the earth interact with the denim garments. Ozone
oxidizes the Indigo dye into Isatin and Antranalic acid and the complex of the two products.
Isatin is yellow in color, so indigo dyed blue garment turns to yellow.
2.1.2.1 Factors affecting the yellowing of denims

Unfixed dyes
Indigo dyeing is ring dyeing technique in which dyes are not allowed to diffuse into yarn
structure. On usage the dyes present at the surface of the yarn get abraded and gives faded look.
The yellowing of Indigo dyes depends on the unfixed dye particles present on the surface of the
yarn. The unfixed dyes are mainly due to back staining occurring during the washing process.
Back staining is the re deposition of the loose dyes discharged in to the wash bath.

 Unfixed dyes should be removed at the end of the dyeing process.

 Prevent back staining during de sizing & washing process by using proper anti back
staining agents.

Humidity
Yellowing of denim depend on the humidity of the garment in which it is present. Water film
formation occurs at the surface of the fibers and causes swelling. The swelled fibers absorb
ozone easily and results in yellowing.

 Avoid storing the garment in humid condition.

 Don’t leave the garment in wet condition for longer period.

Anti ozone softeners

For a short term protection we can go by antioxidants like sodium bisulfate and ethylene diamine
etc.. These agents undergo decomposition process and protect Indigo dyes from yellowing. For a
long term period we can use anti ozone softeners & these are amine based softeners.

How Anti ozone softener works?

The main steps involved are

a. Film formation
The anti ozone softener forms a film over fabric surface thus preventing the Indigo dye from
reaction with atmospheric ozone.

b. Self degradation
The anti ozone film will react with atmospheric pollutants and undergoes self degradation
process and breakdown in to its colorless compounds. Thus the anti ozone softener undergoes
self scarification process in the prevention of indigo dyes from the oxidation.
2.2 Oxides of nitrogen
Oxides of nitrogen are one of the main causes of yellowing. In the combustion process when the
temperature of air exceeds 538˚C, nitrogen and oxygen combine to form nitrogen oxide. These
nitrogen oxides are released from automobiles, trucks and industrial equipments. These nitrogen
oxides react with the residues present on the surface of the fabric. At higher concentration these
oxides of nitrogen directly affect the nylon fiber.

 Ware houses and factories should be properly ventilated to avoid the accumulation of
oxides of nitrogen.
 Avoid use of diesel trucks instead use electrical trucks in ware houses and storage areas.

3. Transferred contaminants
One of the main causes of yellowing of white and pastel shades is phenols. BHT (Butyl
Hydroxyl Toluene) is an antioxidant used in polythene and polypropylene bags to prevent ageing
of olefin. It is used in shoulder pads and interlining materials

3.1 Mechanism of yellowing

BHT undergo oxidation process in the presence of NOX to form quinone and nitrophenol. 2,6 di-
tert butyl p-cresol undergoes nitration in the presence of NOX to form 2, 6 di-tert-4-nitrophenol.
In the presence of nitration it forms quinone. These products are yellow in color. Even at the
room temperature it can be transferred to the textile materials These kind of yellowing occur in
the form of yellow streaks or patches while the garments are stored in poly bags in retail shops.
This reaction is base catalyzed and takes place in slightly alkaline medium. These nitro phenols
and quinines are colorless in acidic medium and become bright yellow in alkaline medium.

It is found that polyamide fibers shows severe yellowing with BHT. This yellowing is reversible
and it can be removed by acid scouring or washing with hot water and methanol.

 It can be prevented by avoiding the usage of BHT poly bags for storage purpose. 

 The pH of the final stage of the garment should be slightly acidic to neutral (5.5 to 6.5).
Neutralize with non volatile organic acid (Citric and oxalic acid) to achieve core
neutralization. Avoid using volatile acid for neutralization process because only ring
neutralization can be achieved. 

 Avoid the accumulation of exhaust gases to control the reaction between BHT and
nitrogen oxides. 

 To avoid the reaction between BHT and nitrogen oxides we can use Anti phenolic
yellowing agent. 

 These agents blocks the reactive sites of BHT ,thus the reaction between the BHT &
Atmospheric nitrogen oxides are prevented.
4. Chemical additives
By improper use of chemical additives during processing and finishing like softeners, OBA and
salts leads to yellowing.

a. Softener
Softeners are used to impart soft handle to the fabric. Among softeners most commonly used is
the cationic and silicone softeners. These are amine based softeners (N-H) and reacts with free
chlorine present in the commercial detergents containing chlorine bleaches and also with
municipal water containing chlorine as a disinfectant. The chlorine reacts with these amines to
form chloramines (yellow in color). So it imparts yellow color to textile garments.

In addition these amines undergo oxidation process at temperature over 140˚C to form oxides of
nitrogen. These oxides are yellow in color at lower concentrations.

 Use softeners with low amine value.

 Wash with detergents containing non chlorine bleaches and enzymes.

b. Optical Brightening Agents

OBA is used to enhance the whiteness of the fabric. The unsaturated structure of OBA absorbs
uv light and violet light at 340-370nm and it re-emits the absorbed uv light (short wavelength) in
to visible blue light (longer wavelength) at 420-470nm. The emitted blue light changes the hue of
the yellowness in the fabric to whiter. These unsaturations are very sensitive to sunlight and loss
its ability to work & leads to yellowing

 OBA used for cellulosic fibers not stable at low pH so it leads to yellowing.
  Unfavorable conditions like excessive heat and high humidity leads to oxidation of OBA
and it loses its whiteness.
 Over usage of OBA beyond the saturation limits leads to yellowing and it can be
controlled by stripping.
 Proper selection of OBA to avoid ionic interactions of anionic brightener with cationic
finishes leads to deterioration of brightener.

5. Conclusion
From the above study it can be concluded that yellowing of textiles is mainly due to fiber ageing,
atmospheric pollutants, chemical additives and storage contaminants. The below precautionary
measures should be taken at each stage of the garment production until it reaches the final
customer.

 pH of the garments should be slightly acidic to neutral.

 Avoid storing in place contain atmospheric pollutants like NOX and SOX.
 Avoid use of poly bags containing BHT.
 Proper selection and usage of OBA.

6. References
1. “Yellowing of white fabric and garments” by Dr. Naresh M Saraf and Deepak V. Alat,
International dyer, page no: 23-25
2. “Yellowing of textiles” by Rajesh koul at http://articles.fibre2fashion.com
3. “Jack ‘n’ Jill and their Jaded Jeans” by Dr. Naresh M Saraf and Deepak V. Alat,
International dyer, page no: 28-30
4. “Yellowing of textiles on storage” by David T Parkes at http://articles.fibre2fashion.com
5. Denim garment processing by Dr. Ravichandran.L, Fabric Care