IIT Delhi2013ME20795

Introduction
With new innovations and better technologies touching our door step
every day, there has been a shift in the way we perceive world. There has
been an increasing demand of functional fibrous material which other than
basic characteristics also has environment friendly and useful features like
self cleaning, anti pollution and anti microbal material. A lot of research is
going in the field of self cleaning fibers seeing its usefulness and demand.
Nano sized photosensitive particles are being researched upon which can
decompose undesireable contaminents.
Cellulose is the most abundant naturally occurring organic substance. It is
found in cell walls of higher plants and is water insoluble. Cotton contains
98% cellulose, flax is upto 80% made of cellulose, wood composes 4050% cellulose. Cellulose is made up of 5000 to 10,000 glucose units. The
glucose units in cellulose are beta 1-4 linked allowing an extended rigid
conformation with extensive H-bonding between chains.
There are 2 types of self cleaning surfaces: Hydrophobic and Hydrophilic.

Hydrophobic Self Cleaning: It can be achieved bychemical or

geometrical surface modification. It is also known as Lotus Effect.
The surface natural features of lotus leaves or butterfly wings are
mimicked. The surface attached dirt or micro debries can be
removed by rolling water over the hydrophobic surface, which
carries them away maintaining the cleanliness of surface.
Hydrophilic Self Cleaning: It is also known as Photo catalytic
effect. It is a chemical surface modification that uses photoactive
substances which in the presence of light through photooxidation
and photoreduction induces catalytic purification functions on a
substrate surface which decomposes the dirt, microorganisms etc
present. It also provides additional properties such as antimicrobial
and deordorization.

Use of TiO2
In recent years crystalline Titanium oxide(TiO2) has received much
attention due to its photocatalyst properties. Nano-sized TiO2 particles
show high photoactivity due to their large surface area per unit mass and
diffusion of the electron/holes before recombination. There is widespread
commercial use of TiO2 in the field of water purification, air purification,

disinfection, sterilisation etc. A lot of work has been done on depositing

TiO2 on heat resistant surfaces like glass, silica using sol-gel method.
When TiO2 is illuminated, degradation of various organic compounds could
be achieved. This activity is attributed to the fact that upon exposure to
ultraviolet (UV) radiation (wavelength less than 385 nm) the photon
energy generates an electron hole pair on the TiO2 surface. The hole in the
valence band can react with H2O or hydroxyl ions adsorbed on the surface
to produce hydroxyl radicals, and the electron in the conduction band can
reduce O2 to produce superperoxide ions (O2-). Both hydroxyl radicals and
superoxide ions are extremely reactive particles, and they can decompose
organic compounds upon contact with them. Therefore, functionalization
of the cotton fabric surface with titania nanosols may have efficient
antibacterial properties and may exhibit self-cleaning and disinfecting
properties.
Titania coating on cotton fabric also imparts UV-protection properties. This
property is largely attributed to the scattering effect of UV radiation by the
TiO2 particles. Cotton fabrics when treated with titania nanosols or titaniasilica nanosols which were prepared from tetraethyl orthotitanate
[Ti(OC2H5)4] and tetraethyl orthosilicate [Si(OC2H5)4], the resulting
titaniananosol- treated cotton fabric exhibited excellent and durable UVradiation protection.

Objective
The study intend to show the bonability of TiO2 with fibers like cotton,
wool, polyesteramides etc. by surface modification using RF Plasma, MWplasma and UV irradiation. These pretreatments donot affect bulk of
material, being at low air pressure it only modifies the upper surface from
1 to 20 Ao. The surface pretreatment of the fabric can be carried out using
etching, plasma and corona discharge. Japanese and Chinese workers
have been using emulsions containg TiO2 which are then sprayed on
fabric, then the textile is heated to 100oC for several minutes. In this study
a different approach has been used modifying structure using variable
density negative groups like COO-, OO- by RF plasma, MW plasma and
UV irradiation.

Experimental Methods
1.

RF Plasma

The cotton samples were pretreated in a conventional RFplasma cavity. A variety of functional groups like: C O, O C O,
COH, COOH, CH2 OH were introduced on the fabric surface
through the reaction between the active O species induced by
the plasma activation of the gas phase on the carbon textile
surface. These oxygen functionalities obtained in the 0.1 mbar
cavity of the RF-plasma attained a higher concentration with
longer treatment times up to 30 min. The experimental
conditions used during the RFplasma pretreatment were:
plasma generator at 13.56 MHz; plasma power 100W and a
residual gas pressure of 0.1 mbar.

2.

MW Plasma

The C2 and E cotton samples were also pretreated in a MWplasma cavity. Experiments were performed at 2.45 GHz. The
power was varied from 100 to 600W, the reaction times were
changed from 10 to 180 s, the gas flow was between 20 and
100 ml/min, and the gas pressure varied from 0.02 to 2 mbar.
Before the sample treatments the plasma MW-chamber was
evacuated for 2 h up to 0.01 mbar. MW-plasma in air was used
to oxidize the cotton surface. The ionized gas is composed
atomic oxygen, ionic forms of oxygen (negative and positive),
radicals formed due to the interaction of O-excited species
and residual water vapour.

3.

Vacuum UV Irradiation

The cotton fabrics were also pretreated using the 185 nm line
of a low pressure mercury source having a power of 25W.
Since the vacuumUV activation proceeds with a lower energy
than the plasma activation, no cationic or anionic oxygen
species are formed in the gas phase. Only atomic and excited
oxygen species are formed and this is the difference with the
plasma methods described in sections above. This leads to a
more defined and uniform modification of the textile surfaces
with an increased polarity because it contains a variety of
oxygen functional groups formed by the reactions of free
radicals with the O2 in the gas phase. The upper textile layers
are excited by the incoming UV light up to 100 A.

Result

Production of CO2 during photodegradation of wine

and coffee stains on TiO2 coated fiber.
The mineralisation of coffee and wine stains on fiber due to
presence of activated TiO2 leads to release of CO2 along with
small cations and anions. To make sure this CO2 released is
not from the textile but from the mineralisation of the stains,
the amount of CO2 released was measured from a non loaded
decomposition of textile sample. Further the self cleaning
action was better for wool-polyamide compared to polyester
loaded with TiO2. Further the wine stains were more easily
mineralised compared to coffee stains.
Three types of light sources were tested to irradiate the wool
polyamide stained with wine or coffee:
(a) a Suntest solar simulator with a light intensity of 50
mW/cm2;
(b) a neon room emitting light in the range 350560 nm with
2.2 mW/cm2, and
(c) a mercury blue light emitting at l = 366 nm with 3.5
mW/cm2.
Both the neon and mercury blue lights yielded a very poor
photo-catalytic discoloration of stains compared to the Suntest
simulator. Using the neon light, about 120 h irradiation were
necessary to achieve a discoloration equivalent to that
obtained after 24 h with the Suntest simulator. No significant
discoloration was observed when the mercury lamp was
employed to remove wine or coffee stains. This suggests that
absorption by wine or coffee stains of the visible light emitted
by the Suntest simulator is essential for the discoloration of
these stains. The colored pigments of grease, wine and coffee
seem to sensitize this discoloration by the mechanism
suggested in Fig below

Mechanism for the discoloration of wine stains by light in air on the TiO2 loaded
textiles

Mechanism for the production of oxidative radicals on TiO2 with a stain absorbing
simulated sunlight

Schematic of the generation of highly oxidative

radicals under light irradiation at the surface of
the TiO2 deposited on textiles

The availability of suitable spacer material to

bind TiO2 with the textile fiber

Analysis
A cotton fabric surface was successfully modified with titania nanosols
prepared from TiO2 showed the formation of a film on the fiber surface at
relatively low treatment temperature (150 C). The photocatalytic
properties of the film deposited on the fabric surface imparted selfcleaning properties to the cotton fabric. Indeed, stains of coffee and red
wine on the treated cotton fabric were decomposed by exposure to UV
radiation. Furthermore, the treatment imparted excellent UV-radiation
protection to the cotton fabric especially in the region of the UVB (290-315
nm).
When light is harvested directly by the TiO2, an increased CO2 evolution
was observed with respect to wine and coffee stains under similar
experimental conditions on the same TiO2 loaded textile. The surface
pretreatment of the cotton textile used in this study allows to attach TiO2
directly on the textile by functionalization of the cotton textile with a
variable density of functional groups negatively charged. This
pretreatment seems not to degrade the cotton surface. The pretreatment
is applied in dry conditions in the absence of solvents.

Epilouge

Functions of photocatalytic self-cleaning fibers and application

thereof:
Self-cleaning daily apparels- Anti-fouling, anti-odor and anti-mold.
Protective clothing- UV protection, Medical protection during surgical
operation.

Limitations:
Health and environmental concerns in the production and use of
nano-structured titanium dioxide surface coating. risk of exposure
during manufacture and application.
Earthworms can absorb nanoparticles from the contaminated soil
and move up to the food chain.

Future Prospects:
Visible light-driven photocatalysts
Modification of application process as uneven distribution of the
photocatalyst and non-sustainable coating are common problems
encountered
Need to establish a series of universal empirical testing standards
for objectively characterizing and evaluating the performance of
newly developed self-cleaning fibrous products

Bibliography
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ii.

Synthesis, activity and characterization of textiles showing selfcleaning activity under daylight irradiation by T. Yuranova a, D. Laub
b, J. Kiwi
Enhanced Self-cleaning, Antibacterial and UV Protection Properties
of Nano TiO2 Treated Textile through Enzymatic Pretreatment by
Majid Montazer and Samira Seifollahzadeh

iii.
iv.

v.

Self-cleaning fibers via nanotechnology: a virtual reality by Wing Sze

Tung and Walid A. Daoud
Self-cleaning of modified cotton textiles by TiO2 at low temperatures
under daylight irradiation by A. Bozzi, T. Yuranova , I. Guasaquillo ,
D. Laubb, J. Kiwi
Self-cleaning cotton textiles surfaces modified by photoactive
SiO2/TiO2 coating by T. Yuranova, R. Mosteo, J. Bandara , D. Laubb, J.
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