13

CHAPTER 2
LITERATURE REVIEW

2.1 NANO TECHNOLOGY AN INTRODUCTION
Nano technology deals with small structures (or) small sized materials
of nano meter scale. This chapter of research thesis is dedicated to deal with
the published literature on multifunctional finishing of fabrics, various
processes of functionalization and the concept and application of using Ti
!

and "n nano#particles for functional finishing and the concept and
mechanism of photo catalytic o$idation. The methods of synthesis of Ti
!

and "n nano#particles and the re%uired functional properties which can be
added to the te$tiles by way of treatment with nano#particles are discussed.
Te$tile finishing encompasses all the operation involved in (or) applied
in treatment of fabrics from grey fabric stage to final finished fabric stage
with the ultimate aim of improving the appearance and handle value of the
fabrics. &n this research thesis the term is employed to include all the
processes that usually applied after coloration and improvise certain %ualities
of the fabrics. 'uch improved fabric characteristics may include appearance,
fashion aspects and high performance properties for both personal needs and
industrial applications.
The fundamental difference between finishing and functional finishing
lies in the area of improvement in functional re%uirement of fabrics. (hile
finishing applies to general nature of added properties the functional finishing
has a focused specific enhancement of the fabric properties and performance.
1)
The nature of te$tile fabric substrate, whether woven, *nitted (or) non +
woven (or) the type of yarn used in fabric li*e staple yarn (or) continuous
filament yarns plays a ma,or role in deciding the means and methods of
applying functional finish to fabrics. -athirvelu et al (!../). gave a detailed
account on functional finish of te$tiles by using traditional and conventional
type of chemicals.
'everal research attempts were made to combine various finishes in
one bath. The economical advantages are that the main ob,ectives are met in
one application and drying process. 0owever the technological problem
encountered during such one bath finishing are many li*e similar nature of
effects help each other processes for e$ample silicone elastomers impart water
repellency and softness enhance antistatic properties and finally the antistatic
finishes are made with softening. The finishes that are contradictory in nature
are counteracting each others, for e$ample, hydrophobic finishes and
hydrophilic antistatic finishes (or) stiffening and elastomeric finishes (or)
stiffening and softening finishes.
The properties of final finished products are decided by the chemical
nature and the structure of natural, artificial and synthetic fibre. There are
several characteristics of fibres, both positive and negative properties, which
deserves due consideration in deciding the final applications for e$ample,
some fibres easily burn (cellulose), some burn slowly and self + e$tinguish
(wool, sil*) (or) some burn and melt ('ynthetic fibres).
1otton is *nown to possess the advantages of being imparted with a
wide variety of functional properties. 1ellulosic fibres are chemically reactive
and similarly the natural protein fibres such as wool. 'ynthetic fibres are not
very reactive and many are inert. The cotton molecule has reactive groups
which permit permanent attachment of these functional compounds.
12
2.2 FUNCTIONAL FINISHES FOR TEXTILES
The recent advances in functional te$tiles have been in the direction of
adding features to the basic product and also to address the new emerging
problem that are associated with functions of te$tiles. The process of
imparting the desired functional properties to te$tile and clothing materials is
better *nown as functionalization (3urniston et al !..)). Three different
approaches are thought of in the area of developing functional te$tiles.
New fibres 4 yarns
New type of te$tile construction 4 production technology
New types of te$tile finishing
&n all cases the ob,ective is to develop specific properties which enable
them to perform a particular function in the final product in a better way.
They are e$pected to be high + tech products with additional novel functions.
5any of them are used with the aim of improving wear, contour, safety and
health protection.
The use of specialized fibres that have re%uired characteristics for
performing special functions, either by the characteristics of the polymer (or)
by additives before fibre spinning, can be a possible method for achieving
functional properties in te$tiles. The functional te$tiles are e$plained with
help of a schematic diagram given below6

1/

Figure 2.1 Sce!"#ic $i"gr"!% &' (u'c#i&'") #e*#i)e%
&n alternate method, yarn (or) fabric engineering with different fibres (or)
different layers can also be employed.
2.+ O,-ECTIVES OF FUNCTIONAL TEXTILE FINISHES
The versatility of te$tile fibres offers many avenues for functional
finishes that can add their own form of functionality, modify e$isting
properties of fibres (or) create new benefits that are uni%ue. Te$tile industry
and researchers have developed increasingly many types of functional
finishes. The ob,ective is to enhance comfort feeling to the consumers. There
are two broad divisions of functional finishes namely, physical based finishes
and chemical based finishes. 7t the present scenario of stricter regulations
being imposed on chemical substances, the phases of developments in
physical based finishes have gained momentum. 7 bird8s eye view of the
applications of nano technology in te$tile fabrics is give below6
19

Figure 2.2 N"'&.#ec'&)&g/ i' Fi0er "'$ Te*#i)e 1"'u("c#uri'g
&n chemical based finishes, conventional methods of finishing can be
employed such as e$haustion, padding, low add#on processes, foam
application, printing, coating etc. :ecently newer and alternatives methods of
finish applications li*e micro encapsulation etc have been developed. 1ertain
newer functional capabilities li*e slow and long term release of chemicals
during usage of fabric can be achieved from new methods. Nano technology
has emerged out to open new possibilities in functional finishes. 'urface
modification by means of chemical modification, by the application of a
surface layer (or) by more environmental friendly treatment li*e enzymes (or)
physical modification with plasma technology are few techni%ues to mention
here.
N"'&#ec'&)&g/
i' #e*#i)e%
N"'& (i0er%
"'$ /"r'%
N"'& (i'i%e$
#e*#i)e%
;evelopment of 'ingle and
5ulti # walled nano fibers,
such as 1arbon Nano + Tube
(1NT) composite fibers.
<roduction of nano fibers,
using electro#spinning
process.

Nanotechnology can also
improve surface properties
and functionality of cotton
fabrics.
7 variety of chemical
finishes and coatings can be
developed.
1=
1onsumers demand newer and improved functional properties in
te$tiles. >lobally the demands for technical te$tiles have increased as their
high performance properties are enhanced.
2.2 APPLICATION OF FUNCTIONAL FINISHES AND NANO
TECHNOLOGY
Nano te$tile finishing deals with application of ultra fine particles
produced using nano technology. &n recent times, nanotechnology is
increasingly attracting global attention. &t has a huge potential in a wide range
of end uses (3eringer et al !..)). The new and uni%ue properties of nano
materials have attracted scientists, researches and business persons because of
their economical advantages. &t is interdisciplinary and emerging field which
fundamentally manipulates structural materials to the nano level (or)
molecular level. Nanotechnology encompasses a wide range of technologies
concerned with structures on the nano meter scale. &t has revolutionized
material science and led to the development and evolution of a range of new
improved materials.
3y way of controlling atoms and molecule, one can generate functional
materials, devices and systems of nano meter scale by precisely placing the
individual atoms thereby creating e$cellent properties hither to un*nown and
une$plored (-athirvelu et al !..=e).
7 glimpse through literature offers facts about many nanotechnology
based innovations that has great promise to the future. Nanotechnology has
already ta*en an important part of our daily life in one form (or) the other.


1?
2.2.1 E((ec# &( P"r#ic)e Si3e
Nanotechnology is based on the fact that the properties of materials
can change drastically when the particle size falls below 1..nm. The size of
nano#particles matters a lot with respect to the deciding of its importance nano
technology encompasses the structures whose thic*ness is smaller than 1..
nm in one dimension. &t e$ploits the characteristics of material that are in the
transitional zone between the atomic and microscopic level. The manufacture
and amputation of such nano level structures are also covered under this
umbrella. (hen the particle size is below 1..nm there happens a drastic
change in the properties of materials. 'urprisingly it may result in novel and
significantly improved physical, chemical and biological properties. They
e$hibit fundamentally new behavior, when the size falls below a critical level.
The performance characteristics and functionalities that are previously
thought to be not possible are now made available for e$ploitation. &t is a
convergent technology where the interdisciplinary interaction of sciences
mostly li*es chemistry and physics play a vital role.
Nano#particles may either be natural (or) incidental (or) engineered and
may be amorphous (or) crystalline (or) polymeric (or) composites. They may
be of non metal metallic, semiconductor (or) a combination. The shape of
nano#particles may be spheres, tubes, rods, horns and placeless.
-athirvelu et al (!..=d) reported the size and chemical composition
decides their physical properties. Their reactivity depends on the surface
chemistries including surface defect and impurities. The decreasing size of
nano#particles results in fundamental changes in properties of material. (hen
the particle size is reduced there is an enormous increase in the specific
surface area. The two different approaches generally thought of in nano#
particles production are top down and bottom up types. 'chematic
representations of particle size and surface area at nano scale given below6
!.
P"r#ic)e %i3e
14 c! 1 !! 15! 1'!
Sur("ce "re"
1 144 16 446444 1464446444

Figure 2.+ Sce!"#ic re7re%e'#"#i&'% &( 7"r#ic)e %i3e "'$ %ur("ce "re"
"# '"'& %c")e

The top down approach is li*e precision engineering which starts from
the micro level structure and the components are gradually miniaturized. They
are primarily featured in physics. &t involves enlarging the surface and
separation of the particles. &t results in increase in free energy ma*ing the
system less stable. The second type of bottom + up approach is basically
assembling from atomic (or) molecular components which results in comple$
structures. &t is e$ploited well in chemistry and biology. &n sol gel techni%ue
colloidal particles are produced which ensures the particle size to be of nano
and no energy is re%uired to enlarge the specific surface area.


!1
2.2.2 A$8"'#"ge% &( T9& Di((ere'# A77r&"ce%
&n the @top downA approach of brea*ing down the bigger particles into
smaller nano#particles, the disadvantages are less precision, production of
waste and pollution and more energy consumption. &n the @bottom upA
approach where the sub nano level particles are assembled to nano#particles,
they pose certain advantages li*e absolute precision, no wastage, positive
control on process, less energy re%uired and more eco friendly nature.
2.2.+ N"'&#ec'&)&g/ i' Te*#i)e%
Nanotechnology has been playing are important role in recent
te$tile application (-athirvelu !..3). The very first commercial application of
nanotechnology in te$tiles was in lifestyle applications. 'urprisingly te$tiles
and cosmetics were among the first disciplines to use nano materials. &t is
believed that te$tile fabrics gives one of the safest platform for the application
of nano#particles. There has been an underlying synergy between te$tiles
industry and nanotechnology which ma*e it possible for large potential of
commercial e$ploitation. &t is understood that the large amount of interfacial
area of both nano size particles and fibres in fabrics could be employed in a
more purposeful way that augers well for commercial te$tile potential
(spar*le news !../). ;ue to their large surface area to volume ratio and high
surface energy, nano#particles can provide high durability of finish on fabrics.
This presents better affinity on fabrics and leading to better durability of the
function ((ong et al !../). &t is obvious that this coating of nano#particles
results in negligible and insignificant danger in physical and mechanical
properties li*e handle value, strength, air permeability and wetting properties
(Bin !../). Cery low consumption levels of chemicals and energy are the
advantages of using nano#particles in te$tile finishing.
!!
'urface coating of te$tiles with nano sized particles of metal o$ides
has gained more importance presently due to their specific advantages. 5ulti
functional properties li*e DC bloc*ing, antibacterial, soil release and self
cleaning are achieved through nano coating. 3oth Ti
!
and "n in nano#
particles form are capable of imparting self cleaning property to te$tiles. Nano
silver particles are very effective in imparting antibacterial property to
te$tiles. 0owever its high cost is the ma,or disadvantage. Nano#particles
coating influences the other fabric properties li*e Tensile strength, bursting
strength, 3ending rigidity and air permeability. Ti
!
is a wide band gap and
non to$ic semiconductor. &t has got a high degree of photo catalytic and self
cleaning properties. The catalytic activity of Ti
!
is based on the electron 4
hole pair formation due to photo e$citation. ;ue to large surface area per unit
mass and volume, nano Ti
!
particles show high degree of photo + catalytic
activities. The photo catalytic activity of Ti
!
nano particle coatings depends
on the phase, the crystallite size and porosity of the coatings and the particle
size. <reparation of single phase a%ueous solution of nano crystalline anatase
Ti
!
at a low temperature of 3=E1 by using sol gel method was reported by
(;aoud et al !..)). 3y using chemical co precipitation + peptisation method
preparation of Ti
!
solution at 9!E1 was reported by (Bing et al !..)).
<reparation of Ti
!
sol with surface protective agent was reported. They also
reported characteristics of sol particles and evaluated the photo catalytic
activity. 3oth Ti
!
and "n are bio + safe, bio compatible and can be used
for biomedical application without coating. Cigneshwaran et al (!../)
reported their wor* on "n soluble starch nano composites and synthesis of
nano "n using water as a solvent and soluble starch as a stabilizer. Fadav
et al (!../) studied and reported the performance of nano "n by wet
chemical method using "inc nitrate and 'odium hydro$ide as precursors and
soluble starch as stabilizing agent. 7lessio 3echeri et al (!..9) reported their
wor* on synthesis and characterization of nano "n particles and their
application on cotton and wool fabric resulting in DC shielding. -athirvelu et
!3
al (!..=a,b) reported their findings on nano "n using "inc nitrate and
'odium 0ydro$ide. Nanotechnology in te$tile applications general overview
are given below6

Figure 2.2 Ge'er") &8er8ie9 &( '"'&#ec'&)&g/ i' #e*#i)e "77)ic"#i&'%
The present day applications of nano technology in te$tile industry are
in fibres, yarns, fabrics, nonwovens, finishing li*e dyeing and coating,
electronic te$tile and fibre modification.
2.2.2 N"'&#ec'&)&g/ i' Fi0re%6 F"0ric% A'$ D/ei'g
<roduction of nano#sealed synthetic fibres li*e <olyester, <olyamide
and <olypropylene is a promising application in fibres. The thermal,
electrical, mechanical and chemical properties of fibres can be improved by
!)
using nanotechnology. New products li*e breathable te$tile laminates and
super absorbency fibres with open pore structure are possible in a variety of
polymers. 0igh specific surface area of nano#particles ma*es it attractive for
usage in medical te$tiles. <olymeric nano fibres with nano#sealed diameters
are more suitable to such applications.
0uang (!..2) reported that the decreasing fibre diameter reduces the
contact angle between fibres resulting in e$cellent wetting behavior of final
product. Nanotechnology is applied in production of light weight fibres which
e$hibit greater strength. (Nyati !..2) reported that nano fibre e$hibit high
surface area, small fibre diameter, good filtration properties, thin layers and
high permeability.
The @die swellA effect is *nown as swelling of polymer when passing
through the capillary tube in electro spinning process. This could be
eliminated by addition of carbon nano tube to commercial polymer. &n result,
the improvement strength of fibre against the high voltage between capillary
tube and collector. This helps in increasing the spinning speed in fibre
production. &n an another interesting area of development, the hygroscopic
nature of polyester fibre can be increased by 3. times by coating it with a 2.
nanometer film made up of !. layers on the outside of fibre.
(ang et al (!..)) reported a nylon filament yarn with the double
moisture upta*e of conventional yarn in medical te$tile cardio vascular graft
made of woven and *nitted structure are used to replace arteries in by#pass
surgery. 5achine embroidered implants are used for connecting nerves during
reconstruction shoulder surgery. (ound healing dressings are another area of
developments in medical fields opening up new une$plored characteristics of
nano fibres.
!2
;yeing is another important area where nanotechnology finds
applications. <olypropylene is *nown to be a fibre most difficult to dye
because of absence of dye fi$ation sites. &n polypropylene fibre dye site can
be created with nano die particles with modified %uaternary ammonium salt.
The dyeing cost is also reduced .'ince nano#particles have large surface area
they can be used as solvent for non#ionic, anionic, cationic dyes by using
nano clay and modified nano#clays. 'uch sorbent can be added to the polymer
matri$ in polypropylene to improve the dyeability. 'par*le news (!../)
reported that nano clay te$tile composition have good dyeability, colour
fastness and less cost in dyeing and less waste water treatment problems. 7lso
report that they result in additional functional property improvement li*e
strength, DC absorbance and fire resistance. 5echanical blending of nano
clays can be added to the polypropylene matri$ by using heat, in melting or
dissolving process
2.2.: N"'& Fi'i%i'g Pr&ce%%
<erhaps the finishing of te$tiles is the most interesting area of
application for :ussel (!..!) reported the first wor* on nanotechnology in
te$tile called nano#te$. The e$ploitation of nanotechnology in te$tile finishing
was later ta*en up by an increased number of companies. 7mong the
techni%ues used to apply nano#particles onto te$tiles, coating is employed
ma,oritly. 1ramer et al (!..3) reported that the composition of coating
usually composed of nano#particles, a surfactant, ingredients and a carrier
medium for applying coating onto fabrics. 'everal methods li*e spraying,
transfer printing brushing, washing, rinsing and padding may be employed
Fen et al (!..3) report that padding is the most widely used one.
7 <adder is employed to apply nano#particles onto the fabric followed
by drying and curing. The functional properties that can be imparted to te$tile
by this method may include water repellences, soil resistance, wrin*le
!/
resistance, anti#bacterial, anti#static, DC protection, flame retardation and
improvement of dyeability. &t may also be used to impart new functional
properties li*e energy storage and communication.
Nano te$ : was another commercial te$tile finish developed. 'chulte
(!..2) reported on the application of Ti
!
nano#particles for te$tile finishing.
Nano#care : is reported to impart a new carefree wrin*le resistance finish
with minimum stains offering e$cellent li%uid repellency and wrin*le
resistance. 7nother commercial finish nano#dry : was able to transport
perpiration away from the body and drying it %uic*ly. Nano#fresh : is -nown
to capture body odour giving the wearer an odurs free feeling. 'chulenburg
et al (!..=) reported about nano#pel : which ma*es the fabric breathable at
the same time being li%uid and stain repellent.
2.2.; Pri'ci7)e% &( Cer#"i' C&!!erci") T/7e% &( N"'& Te*#i)e Fi'i%e%
Nano#pel, a water and oil repellent treatment, can be applied to cotton,
wool, polyester, nylon, rayon and blended te$tiles. Nano#care, a wrin*le
resistant and oil repellency finish, is for pure cotton fabrics. Genno$ -err
et al (!..3) reported that both the above finishes have set a benchmar* in
water and stain repellent performance of te$tiles.
5onomers containing methacrylate and per# fluoroal*yl group
producing a copolymer which e$hibits water and oil repellency, where as a
fluorine# free monomer gives improved adhesivenes to fibre. 'imilarly 'ahin
(1??/) reported a monomer capable of improving durability through self#
crosslin*ing or reaction with reactive groups. 7ccording to 'ello et al (1?=))
these copolymer when treated with te$tiles liberate formaldehyde which is
detrimental to environmental safety.
!9
The basic principles of nano#whis*ers, according to Hain (!..)),
consists of oligomeric or polymeric side branches attached to a fle$ible spine.
The branches stand outward from the surface to give a protection against
water or oil particles. 7nother variant of such a finish which does not produce
formaldehyde is called Nano#Te$ 3an*s et al (1??)) reports that the
formulation is capable of providing formaldehyde# free wrin*le resistance and
water and oil repellence when combined with a formaldehyde free resin such
as dimethyl urea glyo$al (;5D>) or butane tetra carbo$ylic acid (3T17).
-athirvelu et al (!../) reported the commercial application called
Nano#;ry a three + dimensional molecular networ* is created surrounding a
fibre , that is nano#net architecture made with nano fibres. 'ynthetic fibres
li*e Nylon and <olyester e$hibit hydrophobic nature.
&n Nano# dry treatment, a hydrophilic networ* of nano net of durable
absorbent nano fibre is created on the hydrophobic substrate fibre of synthetic
fibre. This leads to a durable hydrophilic treatment. 0owever the other
properties of synthetic material such as strength, colour fastness and hand
value are not affected. Hain (!..)) reported that the Nano#;ry treatment
imparts durability by the combination of covalent attachment to the fibre
surface and the use of nano molecules. 7ppro$imately the percentage of
solids loading onto the fabric surface is ..1#..12I by weight of the fabrics.
The problem of build#up of static charges occurs in synthetic fibres
even at high :0 levels. Nano#Te$ is a treatment developed to impart the
positive %ualities of cotton and synthetic.
!=

Figure 2.: Te %ce!"#ic re7re%e'#"#i&' &( #e +.D !&)ecu)"r '"'&.'e#
&( N"'&.Dr/
This finish is aiming to create a permanently attached carbohydrate
sheath around each synthetic fibre of the web. This gives the dual advantages
of utilizing the most desirable characteristics of both synthetic core and of the
natural sheath.

Figure 2.; Sce!"#ic re7re%e'#"#i&' &( " N"'&.T&uc #re"#e$ (i0re
7bsorbent net of
Nano# material
5anmade material

5anmade fibre
Nano#Touch sheath
!?
&n another development a permanent attachment of the carbohydrate
sheath is created around synthetic fibre, commercially *nown as Nano#
Touch. &t consists of Nano# (rap artchitecture which is hydrophilic in nature
with increased moisture regain. &t also e$hibits a durable antistatic nature,
according to (Hain !..)).
2.: THE ,ASIC OF PHOTO.CATALYSIS
Ju,ishima et al (1?9!) describe photo#catalysis as a reaction which uses
light to activate a substance which modifies the rate of a chemical reaction
without being involved itself.

Figure 2.< Sce!"#ic $i"gr"! &( &7er"#i&' &( " 7&#&.ce!ic"))/
e*ci#e$ TiO
2
7"r#ic)e
'ubstances which promote reactions in the presence of light are
generally photo catalists. ;eshpande et al (!../) reported that "inc o$ide,
Titanium di o$ide, "incsulphide, Tungsten o$ide, 'trontium titanate and
0ematite are photo catalysis materials. &n a heterogenous photo#catalytic
system, semiconductor particles which are in close contact with a li%uid or
gaseous reaction medium, when e$posed to light gets to e$cited state and
initate subse%uent reaction li*e redo$ and molecular transformations. Ti
!
is
one such a material which e$ists in three crystalline formsK rutile, anatase and
3.
broo*ite. Ju,ishma et al (1?9!) reported the photocatalystic splitting of water
on Ti
!
electrodes.

Figure 2.= Sce!"#ic $i"gr"!% %&9i'g #e "c#i&'% &( " 7&#&.c"#")/%#
>N"'&TiO
2
.#&7? "'$ #e re%u)#"'# 0e'e(i#% >0&##&!?
Teichner (!..=) reported that Ti
!
is a semi conductive material that
can be chemically activated by light, even though it absorbs only 2I of the
solar light reaching the earth. Ti
!
produces pairs of electrons and holes when
DC radiation is absorbed by it. The electrons of valence band become e$cited
P&#&c"#")/%#
TiO
2

1
0
!

DC Gamp
Dltraviolet :ay
rganic 1ompound
L 0
!
L
!

TiO
2

P&#&c"#")/#ic Re"c#i&'
VOC
"'$
O$&ur
,"c#eri" Ger!%
Fu'gu%



L
i
g

#




L
i
g

#


O$&ur
re!&8")
Se)(.C)e"'i'g
"c#i&'
Air
Puri(ic"#i&'
S#eri)i3"#i&'
31
when light falls on it with the e$cess energy the electron is moved to the
conduction band. Therefore thus the negative electron (e
#
) and the positive
holes (h
L
) pair is created. The energy difference between the valance and
conduction bands is called the 3and >ap. The wave length of the light
necessary for photo e$citation is given by the formulaK
1!). (plane*s constant, h) 4 3.! eC (band gap energy) M 3==7m
The positive hole reacts with water molecule to form hydrogen gas and
hydro$yl radical. The negative electron reacts with o$ygen molecule to form
o$ide union. This reaction is fast at room temperature and atmospheric
pressure.
2.:.1 N"'& TiO
2
i' Te*#i)e%
Nver since the introduction of nano#particles in te$tiles, efforts were on to
produce finished fabrics with multiple functional performances. Gee et al
(!..3) reported the use of nano silver particles for imparting antibacterial
properties. Fadav et al (!../) published the research wor* on the use of "n
nano#particles for anti#bacterial and uv bloc*ing properties. "nO Ti
!
have
the advantages of being non#to$ic and chemically stable. 1olemana et al
(!..2) reported that Ti
!
has strong $idising power of its holes, high photo
stability and redo$ selectivity. &ts commercial availability and ease of lab
preparation ma*es it more advantageous. &t has three types of crystal structure
Ciz, anatase, rutile and broo*ite. 7natase structure of Ti
!
nano#particles are
the most active in photo catalysis. Ti
!
nano#particles are generally produced
by using three methods Ciz. wet synthesis, dry synthesis and milling. The
3ottom#Dp approach is employed in both wet and dry synthesis where as the
Top#;own approach is used in the milling method (-athirvelu et al !..=c).
'ol#gel and precipitation methods are *nown as wet approaches. ;ry
3!
synthesis includes combustion, furnace and plasma synthesis according to
(;aoud et al !..)).
0owever the matter of great difficulty is achieving the uniformity of
size distribution of the nano#particles in all these methods. To less e$tent the
degree of agglomeration is another factor of concern. 1ertain degree of spread
in nano particle size is inevitable. The process parameter employed in
synthesis has influence over the size distribution. The particle size distribution
uniformity can be improved by adopting additional separation steps. 0owever
the drawbac* in this case is that the process yield parcentage is affected.
3urniston et al (!..)) revealed that nano#particles agglomerate together even
at lower temperature than their bul* size counter parts. 0igh energy inputs or
temperature during synthesis may lead to more agglomeration by coaleseing
together of particles.
The band gap value is 3.. eC for the rutile type Ti
!
and 3.! eC for
anatase type. 3oth of this structure absorbs only DC rays. ;aoud et al (!..))
reported that the rutile type can absorb rays that are closer to the visible light
rays. 7ccording to 3ozzi et al (!..2), the anatase type of Ti
!
e$hibits higher
photo catalytic activity than the rutile type.
2.; SYNTHESIS OF TiO
2
NANOPARTICLES
'ynthesis of Nano#particles in general involves the manipulation of
inorganic, organic and biological systems. 5any new methods and devices
are being constantly brought into the field by various researchers. ver the
past decade, nano#particles have evolved as a separate class of materials.
'urprisingly various science disciplines have come together in the ma*ing and
synthesis of nano#particles. Nano#particles of "n in one end, find
application in hygiene products li*e diapers and on the other end used to alter
the characteristics of solid roc*et propellents by addition.
33
The techni%ues of synthesis of nano#particles are divided into three
types Ciz, DC Capour#<hase, 'olution <recipitation and the 'olid#state
process. 'ometimes two or more of these types are combined for synthesis.
;uring the early stages of development the Capour#phase method was in use.
<resently the solid state processer is most widely used for micron sized
particles. 7ccording to the published literature, Jerro corporation, one of the
leading nano powder manufacturer, uses the solid state synthesis method.
0undreds of form of lithium cobalt o$ide nano powder is being produced by
using solid# state synthesis.
Gee et al (!../) reported that Ti
!
nano#particles should fulfil a wide
range of re%uirements such as particle size, size distribution, morphology,
crystallinity and phase etc. so as to become useful and suitable for application.
5anufacture or synthesis of Ti
!
nano#particles with well defined physical
and chemical properties has been a challenging tas*. 5any researches have
published this wor*s related to a variety of methods used for synthesis of
Ti
!
nano#particles. Trunga et al (!..)) reported the sol#gel process, (u
et al (!../) about hydrothermal method and -im etal (!..3) reported on
solvothermal and emulsion precpitation methods.
7ccording to Gee et al (!..3) photo assisted sol#gel method was yet
another variant of the sol#gel techni%ue. The other newer techni%ues reported
in the literature include o$idation of titanium tetrachloride in a modified
diffusion flame reactor, crystallization in reverse micelles or in the
supercritical 1
!
and polymer templating method. Nano#particle synthesized
through different methods e$hibit distinct physiochemical properties. 1ertain
wet chemical methods have been developed to synthesis powder with
spherical shape and uniform size. 7rami et al (!..9) reported that sol#gel
process, emulsion and pyrolysis have been used to prepare mono dispersed
3)
spherical Ti
!
nano#particle. &t is important that the nano#particle e$hibits
crystallinity and narrower size distribution. 'ol#gel synthesized Ti
!
nano#
particle are amorphous and re%uire further calcinations steps to improve
crystallization such heat treatment lead to particle agglomentation and change
in size, sol#gel method for Ti
!
nano#particle has another disadvantage of the
use of costly organic solvents. 'imilarly methods li*e forced hydrolysis and
homogeneous precipitation have the disadvantages of very low reaction time
due to very long concentration of the reacting formulations. 7natase Ti
!

nano#particle can be synthesized hydrothermal methods using amorphous
Ti
!
. 1hang et al (1??2) reported a techni%ue by using Ti1l
)
. ;eshpande
et al (!../) reported a method by using Ti1l
!
a%ueous solution :iv et al
(!../) reported sol#gel method using titanium al*o$ides. Jang et al (!..3)
reported hydrothermal methods amorphous Ti
!
, Ti1l
)
or Ti1l
!
or Ti
!

a%ueous solution and sol#gel method using titanium al*o$ides.
&n order to regulate the physiochemical properties of Ti
!
nano#
particle, organic modifiers are used in synthesis. 'uch modifiers include
hydro$yl group containing, carbo$ylate group and amine group containing
organics. 7s discussed earlier a variety of methodologies for synthesizing
Ti
!
nano#particle have been invertigated by researchers. The commonly
used starting materials (<recusors) in the above methods are Titanium &so#
propo$ide, titanium tetra chloride, titanium (&C) sulphate and amorphous
titanium di o$ide.
7nother important technical aspect in Ti
!
nano#particle is the
arrangements of nano#particle into well define structures or assemblies or
porous aggregates. 'uch nano structure e$hibits uni%ue properties li*e pore
size, thermal stability and their reproducibility. Fang et al (!../) reported
32
that the interaction between the primary building bloc* is controlled in such a
way that at ambient conditions the nanostructure with useful properties is
formed. 'umio (!..2) reported a large no .of such nano structure, their
synthesis and their uni%ue properties.
2.;.1 S&).Ge) 1e#&$ (&r S/'#e%i% O( Ti&
2
N"'&.P"r#ic)e%
ne of the most widely used and successful techni%ue for preparing
Ti
!
nano#particle is sol#gel techni%ue. 3y careful control of the process
parameter and the chemical structure of the starting precursor, the nano#
particle properties can be altered. 3esse*houad et al (!..3) reported the sol#
gel based method by hydrolysis and polycondensation of titanium al*o$ide ,
Ti(:) n to form $opolymers, which are then transformed into an o$ide
networ*. :istic et al (!..2) reported that the microstructure of Ti
!
nano#
particle (anatase O rutile) decide its photo catalytic activity.
;hage et al (!..)) reported a method consisting of using titanium (iv)
n#buto$ide (Tico#bu) )) in isoprophl alcohol (i#<r0) 7cetylaceton (acac)
was used as a chemical addition to moderate the reaction speed. ;eionised
water was used for hydrolysis in solution with i#<r0 under mechanical
stirring. (hite precipitate of titanium o$y hydro$ide was obtained and
washed with water for several times. The molar ratio of these reactants
Ti(#3D)
)
6 0!6 &# <rop. 06 acacM161..6 !6 ...1. Then 0N
3
was added to
the final solution and reflu$ing at =2
.
1 for = hrs was found to influence the
size of Ti
!
nano#particle. Then the sol was gelled by drying at 1..
.
1 for
3hours and then calcined in vaccum ()..#9..
.
1) to give Ti
!
nano#particle.

3/
2.;.2 F)"!e S7r"/ P/r&)/%i%
<rocesses that are yielding high production rate, continuous production
and relatively low cost li*e flame spray pyrolysis are of more commercial
importance. This method yields fine, pure and single#phase particles. 1hang
et al (!..9) reported the properties li*e phase composition and particle sizes
of nano#particle obtained by flame spray pyrolysis. The process is basically
evaporating through pyrolysis the li%uid droplet of precursor to obtain Ti
!

nano#particle. The precursor solution was obtained by dissolving titanium
tetra isopropo$ide (TT&<) in solvent. These prepared nano#particle e$hibit
high purity and clear crystallinity.
The e$perimental set up consists of an ultrasonic atomizer, a diffusion
flame burner and a thermo phoretic sampler. 7 li%uid droplet of precursor was
generated by ultrasonic atomizer, at 1.950z Jre%uency. The argon gas burner
evaporates solvent and precipitates the nano#particle. 0ydrogen gas was used
as a fuel while o$ygen and air were used as o$idants. ;roplets of precursor
were supplied to the flame zone through the central tube. The argon gas flow
rate was !lit4min. in the central tube. Through the second tube the gas was
passed at 1lit4min to *eep the straight path way of the li%uid droplets in the
flame region. Through the outer tube, hydrogen, o$ygen and air were passed
at certain flow rate. 7 cold glass tube cooled at 1!
o
1 by cooling water flow is
used to collect nano#particle finally. The concentration of precursor li%uid and
flame temperature influence particle size.
7 new method called one#pot synthesis used trichloroethylene as
reaction medium. Trunga et al (!..)) discussed that the method has
advantage over multicomponent solution system when Ti
!
is used as a
reinforcement for polymer dissolved in trichloroethylene.
39
Trichloroethylene /.ml was mi$ed with !ml of Titanium &sopropo$ide
with water and stirred rigorously at room temperature. 0ydrolysis and
condensation reaction occured. The prepared powder was washed by ethanol
and acetone for several times, dried at 1..
.
1 in vaccum for 3days and heated
at )..
.
1 for 1. hrs in air.
-im et al (!..3) reported a method by hydrolysis of TNT (tetra
ethylor thotitanate) in two stage mi$ing process. They attempted further to
ma*e a continuous process by small reactor which controlled the rate of
nucleation. 7n ageing tube was employed for controlling the growth of nano#
particle. The hydrolysis rate is controlled by water vapourization and feed rate
of TNT solution. The apparatus has a small reactor for two feed reagents
water and TNT, a syringe pump a heating tape for vapouring 0
!
and a long
silicon tube for ageing the particles. The small reactor is continuously fed
with the two feeds.
Ti
!
<rimary nuclear is generated by the polymerization of the
hydrolysis product. 7ccording to 0ong et al (!..3), a part of them is grown to
fine nano#particle while passing through the ageing tube. &n this part of
literature survey a review has been made over the various methods developed
for synthesis of nano#particles. Nach method has it own merits and demerits.
The choice of method and precursor depend on the end use
re%uirement of nano#particle. 7ccording to 3esse*houad et al (!..3) in
future, these methods could be suitably changed to meet the specific
functional needs of nano#particle.


3=
2.< SYNTHESIS OF @'O NANO.PARTICLES
"inc o$ide is a semiconductor of n type and with direct band gap. 1hen
et al (!..3) reported various techni%ues used to synthesize "n nano#particle
both chemical and physical methods. The chemical method include thermal
hydrolysis techni%ue, hydrothermal processing and sol#gel method. <hysical
methods are spray pyrolysis, vapour condensation and thermo chemical
decomposition of precursor. <resently the vapour phase and sol#gel methods
are widely used. &n case of vapour phase method the drawbac* is that the
powder is in the agglomerate form due to difficulty in control of reaction
condition. 7lso it is slow process and more energy consuming.
The sol#gel method though producing uniform "n nano#particles,
re%uires stricter control on reaction condition. ;ue to high costs it is not
commercialized but suitable for research only. ;iscussed the problem
associated with the poor yield efficiency of "n nano#particles and the
difficulity associated with particle size control. New and other methods were
tried in recent years li*e thermal decomposition, supercritical precipitation
and colloidal synthesis. 5a et al (!..=) discussed a method by thermolysis of
"inc o$ide propionate as a precursor and trioctyl phosphine o$ide at a high
temp of 1/.
o
c. >uo et al (!...) reported various methods of "n nano#
particle synthesis under the broad section namely physical , thermal and
chemical methods. Dm et al (!..9) reported a method called the levitational
gas condensation (G>1) method. Dm et al (!..9) reported a modified method
of G>1 and phase evolution.
The main parts of such an apparatus are high fre%uency induction
generator, levitation and evaporation chamber and o$ygen concentration
3?
control unit. (ang et al (!..)) reported a new combustion method, in which
the mi$ture of "inc nitrate and fuel powder is ignited to form ceramic o$ides.
:apid heat conduction ta*es place resulting in %uic* reduction of temperature.
Jine "n nano#particles can be produced without agglomeration. >lycine was
used as fuel for this purpose due its ine$pensiveness and its heat of
combustion being more on the negative side when compared with urea or
citric acid.
&n another study reported, "inc nitrate was used as the precursor. &t has
the dual function of being a precursor and an o$idant. "inc Nitrate of
analytical grade and glycine were mi$ed at a desired molar ratio. The mi$ture
became li*e transparent slurry matter. Cigourous stirring was carried out to
ma*e a homogenous mi$ture. Then it was heated to 1..
o
1 using a hotplate to
dry it. The dired up precursor is now having combustibility. 7 mini gas
burner was employed for combustion of precursor. 7 large volume of gases
evolved during combustion. This method has the advantages of simplicity,
less cost and speed.
7nother method was reported by -o et al (!../) for synthesis of "n
nano powder. This rapid method is based on ;1 thermal plasma synthesis
yielding a high production rate.
3y changing the plasma gas combination and flow rate it was possible
to control the shape of "n nano#particle .The new type of ;1 plasma reactor
operated at 9. -w and atmospheric pressure. "inc powder with impurities
less than 2. ppm was used in this process. The "inc powders were passed
through nitrogen gas and made to fall on plasma flame. Then it was
vapourised, o$idized and finally %uenched.
).
2.= STRUCTURAL CHARACTERI@ATION OF NANO .PARTICLES
7ccording to (ang (!...), there are several methods used for
characterization of the nano#particle.
B#ray powder ;iffraction method (B:;) for studying the crystal
structure of nano particles, Jourier Transform &nfrared 'pectroscopy (JT&:)
for identifying the name of chemical groups and bonds, Transmission
Nlectron 5icroscope (TN5) for identifying the nano#particle diameter,
<article 'ize 7nalyser (<'7) for measuring the range of size of nano#particles
and 'canning Nlectron 5icroscopy ('N5) for capturing the images capturing
the images containing topological information of fabrics.
2.=.1 X.R"/ P&9$er Di((r"c#i&' 1e#&$ >XRD?
&t is a very useful e$perimental techni%ue to study the crystal structure
of solids. 'tructural parameters li*e lattice constant and geometry, orientation
of single crystals, preferred orientation of polycrystals, defects and stresses
can be studied using this techni%ue (Hen*ins et al 1??/). &dentification of
un*nown materials are also a possibility by using this techni%ue. &n this
method a collimated $#ray beam is made incident on a specimen and
diffracted by the crystalline phases is the specimen. The wave length ranges
from ..9 to !P. 7ccording to 3ragg8s law.
! sin A d = (!.1)
whereK
d M the spacing between atomic planes in the crystalline phase and
7 M the B#ray wavelength.
)1
The intensity of the diffracted $ ray is measured. This is a function of
the diffraction angle !Q and the specimen8s orientation.
7ccording to Hen*ins and 'nydes the specimen8s crystalline phases and
its structural properties are identified by using the diffraction pattern.
7ccording to scherer8s e%uation the crystalline domain diameter ;, is given
by the following e%uationK
..=?
cos
D
W

=

(!.!)
whereK
R M the wavelength of the incident B#ray beam, (1.2) 7S for the 1u -T)
Q M the 3ragg8s diffraction angle
U( M the full width of the B#ray pattern line at half pea*#height in radians
and
- M ..=? (constant)
2.=.2 F&urier Tr"'%(&r! I'(r"re$ S7ec#r&%c&7/ >FTIR?
This techni%ue is based on the assumption that molecules and crystals
can be considered as system of balls (atoms or ions) connected by springs
(chemical bonds). &n such system the fre%uency of vibration depends on the
mass of the balls (atomic weight) and the stiffness of the springs (bond
strength). They can be set into vibration. The mechanical molecular and
crystal vibrations are at very high fre%uencies in the order of 1.
1!
to 1.
1)
0z
(3#3.. Vm wave length) which is in the &nfrared :egion. &t is a useful
techni%ue for identifying the nature of chemicals (organic or inorganic
nature). 7lso the components of an un*nown mi$ture can be %uantified. The
)!
chemical bonds can be determined by the analysis and interpretation of the
infrared absorption spectrum. The JT&: spectra are uni%ue for a compound
and generally accepted as the finger print of the chemical nature of
compound. The JT&: spectra of organic compounds are generally very rich
and detailed where as that of inorganic compounds are much simpler.
&n this instrument the infrared beam radiation intensity is measured
before and after it interacts with the sample as a function of light fre%uency.
&nfrared spectrum is a plot of relative intensity time output of the
interferometer is sub,ected to a Jourier Transform to convert it to the familiar
infrared spectrum (&ntensity fre%uency). This helps to identify the atomic
arrangements and the concentrations of the chemical bonds present in the
sample.
2.=.+ Tr"'%!i%%i&' E)ec#r&' 1icr&%c&7e >TE1?
TN5 is a techni%ue in which the electrons are accelerated to 1..*ev or
higher (up to 15eC). 7 thin specimen (less than !..nm) is used to capture
the pro,ection by mean of the condenser lens system. The electron beam
penetrates the sample thic*ness either un deflected or deflected. TN5 offers
very high magnification ranging from 2. to 1.
/
and has the advantage of
image production with diffraction information from a single sump. The shape
and size of nano#particles can be characterized using TN5 apparatus
operating at =.-v. TN5 samples were placed on carbon coated copper grids.
They are prepared from diluted dispersion of nano#particles in ! + propanol.


)3
2.=.2 PARTICLE SI@E ANALY@ER >PSA?
The <'7 testing instruments wor*ing under dynamic light scattering
principle. The scattering angle is ?.W. The <'7 is an innovative photon cross
correlation sensor allowing for simultaneous measurement of particle size and
stability of opa%ue emulsions and suspensions in the nanometer reign. The
observation of the diffraction pattern at finite distance is done through a lens
(G) placed between the laser source and the detector. The diffraction patterns
of particles having the same size converge at the same point whatever them
location with respect to the lens. This theory is applicable for large particles
compared to the wavelength. The first zero on the detector is 1.!! lf4d, laser
as a source of coherent intense light of fi$ed wavelength. 0e#Ne gas lasers
(RM../3Xm) are the most common as they offer the best stability (especially
with respect to temperature) and better signal to noise than the higher
wavelength laser diodes. &t is to be e$pected when smaller laser diodes can
reach /..nm and below and become more reliable that these will begin to
replace the bul*ier gas lasers. Dsually this is a slice of photosensitive silicon
with a number of discrete detectors. &t can be shown that there are an
optimum number of detectors (1/#3!) increased numbers do not mean
increased resolution. Jor the photon correlation spectroscopy techni%ue (<1')
used in the range 1nm 1Xm appro$imately, the intensity of light scattered is so
low that a photomultiplier tube, together with a signal correlate is needed to
ma*e sense of the information. 'ome means of passing the sample through
the laser beam. The 7gilent N))).7 <'7 high#performance spectrum
analyzer measures and monitors comple$ :J and microwave signals up to
!/.2 >0z. (ith optional e$ternal mi$ing, the fre%uency coverage e$pands to
11. >0z by 7gilent e$ternal mi$er and to 3!2 >0z by other vendorsY mi$er.
The shape and size of the nanoparticles were obtained through <'7, using a
N7N<0B (.1)3 <) <article 'ize 7nalysis.
))
2.=.: Sc"''i'g E)ec#r&' 1icr&%c&7/ >SE1?
'N5 produces images containing topographical information. &t can
also provide details of the chemical composition near the surface of the
material. &t is the most widely used techni%ue for characterization of nano
materials (0oward et al 1?=.). The 'N5 image provides details in the
morphology and microstructures of nano meters. The instrument has
magnification in the range of 1. to 3, ..,.... The samples were *ept on
specimen structure with double sided adhesive tape. >old was coated on
sample by sputtering techni%ue and e$amined with 'N5 ma*e Heol 5odel
H'5 + /3/..
2.A ANTI,ACTERIAL ACTIVITY
The functional performance in te$tiles re%uired by consumer include6
7ntibacterial activity, DC protection, self cleaning and stain releasing.
5icrobes li*e bacteria, virus, and fungi etc are posing a lot of hazards to
human beings ('awai, !..3). The system of immunity bestowed to human
beings by the nature saves us to protect from micro organisms. Te$tile fabrics
are *nown to be potential infusions and odours. They can adhere to te$tile
substrates and grow very rapidly. 0umidity, dirt and sweat offer best
environment for them to grow. 'ometimes they can cause stains under warm
and damp condition. 'uch offensive odours and discoloration on te$tiles
renders them unusable. The tensile strength and water permeability are also
affected. Jabrics li*e leisure wear, sportswear, mattresses, carpets etc are
more prone to bacterial growth. :amachandran et al (!..)) reported that
during fabric finishing and wet storage attac* by bacterial organism are more
severe. 7ntibacterial finish is a re%uirement on the te$tile substrate for the
protection of the wearer.
)2
'ilver is a well *nown anti#bacterial material. 'ilver ions e$hibit a
broad spectrum of antibacterial activity. 5icro encapsulation of sliver
compound and coating on to te$tile is one among the methods for imparting
antibacterial finish to te$tiles. &n another possible method nano#particles of
silver can be added to fibre polymers li*e polystyrene co#malefic anhydride
(-i et al !..9).
Te$tiles generally do not e$hibit resistance to bacterial growth.
Therefore such a functional finish is developed with nano silver, titanium
dio$ide and zinc o$ide solutions (-amal >upta et al !..9). 'tudies reveal that
both nano#particles of Ti
!
O "n are very effective in imparting bacterial
resistance to te$tiles besides nano silver particles. ;uran et al (!..9) reported
that nano sized particles render a better antibacterial effect due to more
number of particles. The photo catalysis reaction of the metal o$ide ions is
responsible for creating a sterilizing effect on te$tiles due to liberation of
active o$ygen molecules.
2.A.1 UV Pr&#ec#i&'
:ecent research studies reveal that it is essential that human s*in is
protected by te$tiles from the harmful DC rays from the sun. DC rays have
wavelength ranging from 12. to )..nm. Gong term e$posure of human s*in
to DC rays results in damages li*e s*in ageing, photo dermatitis, erythema,
(s*in reddening), sun burn, s*in cancer, eye damage and ;N7 damage 4
alteration. The National &nstitutes of 0ealth, D'7 reported that the main
cause of s*in cancer is DC radiation from the sun. 0atchb reported that ?.I
of s*in cancer cases can be prevented by way of sun protection.
Te$tile is an e$cellent medium to protect the s*in from the incident DC
rays. Te$tiles can absorb, reflect and scatter DC rays. (hen dyed, the DC
protection ability is improved further. The fibre type or composition, moisture
)/
content, type and concentration of dye particles, presence of optical whiteners
etc have influence over the degree of DC protection ability of te$tiles. DC
protection finish is the single ma,or influencing factor that decides the ability
of te$tiles to bloc* DC rays. (hen DC rays are incident over a fabric surface,
absorption, transmittance and reflection occurs. These three aspects depend
up on surface smoothness, fabric cover factor and the presence of delustrants,
dyes and DC absorbers. &t is essential to mention here that DC absorbers
deflect DC rays thus protecting the s*in. The intensity and distribution of DC
radiation depends on geographical location, time of day and season. The
wavelength of DC radiation decides the degree of damage to the human s*in
for e$ampleK wavelength less than 3..nm do the most of s*in damage.
7ccording to 0ilfi*er et al (1??/) the wavelengths of DC: of ma$imum
danger to s*in are 3.2 + 31. nm. The erythemal effect is multiplied by the
intensity of sunlight. Now it becomes clear that te$tiles must possess the
ability to protect the wearer from DC: of wavelength in the range of 3.. +
3!.nm. 'un <rotection Jactor ('<J) is an inde$ %uantifying the effectiveness
of such protection. &t is the ratio of the potential erythemal effect to the actual
erythemal effect transmitted through the fabric by the radiation (>ambichler
et al !..1).
&ncase of te$tiles it is more appropriate to call '<J as Dltraviolet
<rotection Jactor (D<J). The term '<J is more often used in cosmetics
e$ample sun protection lotions, creams etc. &t gives a relative measure of how
much longer a person can be e$posed to sunlight continuously before a s*in
irritation occurs. &t is generally accepted that a te$tile fabric with D<J Z). is
e$cellent in protection of human s*in against DC rays. 7ccording to 5entera
et al (!..3) the ma$imum theoretical value for D<J is !.. and in practice
=.I of this value for D<J can be realized.
)9
&ncident radiation
:eflected radiation
7bsorbed radiation
Transmitted r'uper fine
Jibres
&n general, summer wear te$tiles li*e shirts, blouse, T#shirt, swimwear,
beach wear, sportswear etc deserve DC protective finishes. &ndustrial te$tiles
li*e awnings, tents and blinds may also be treated for such a finish (0atchb
et al !../).









Figure 2.A Sce!"#ic re7re%e'#"#i&' &( #e !ec"'i%! &( UV 7r&#ec#i&'
7 te$tile fabric of sufficient weight per s%uare meter provides a
good degree DC protection even with no finishing. The type of fibre
influences the D<J of fabrics. (ool and <olyester e$hibit significantly higher
value of D<J while 1otton and 'il* showing lower values. Nylon is placed in
between. Nylon O <olyester are coated with delustrants which is Ti
!
and
hence strongly protects from DC :adiation.
)=
&f it is assumed that the only possibility of transmission of DC rays
through fabric is the spacing between the yarns then the ma$imum value of
D<J theoretically is,
1
D<J
ma$
M ########################## (!.3)
1 + 1over factor
7ccording to :aleigh8s scattering theory the scattering of light is
inversely proportional to the fourth power of wave length. The optimum
particle size for scattering the radiation is !. to ).nm according to (3urniston
et al !..)). bviously, nano#particles of above size does scatter DC rays
more effectively. Bing et al (!..)) reported that Ti
!
O "n nano#particles
often increased surface area and e$hibits more absorption properties in the
DC region.
2.A.2 Se)(.C)e"'i'g Ac#i&'
Nano#sized silver, titanium dio$ide and zinc o$ide are used for
imparting self#cleaning and antibacterial <roperties. 5etallic ions and
metallic compounds display a certain degree of sterilizing effect. &t is
considered that part of the o$ygen in the air or water is turned into active
o$ygen by a catalyst containing the metallic ion, thereby destroying the
organic substance to create a sterilizing effect. Nano#materials possess
enhanced catalytic abilities due to their highly stressed surface atoms which
are very reactive. (ith the use of nano#sized particles, the number of particles
per unit area is enormously increased.
Thus, the photocatalyst is the substance which can modify the rate of
chemical reaction using light irradiation without being altered or consumed in
the end. The process of photo catalysis can be better e$plained with the help
)?
of a schematic diagram comparing the actions of a man#made photocatalyst
(nano#Ti
!
) with a natural one (chlorophyll).1hlorophyll of plants is a typical
natural photocatalyst (Ju,ishima et al 1???). The difference between
chlorophyll photocatalyst to man#made nano Ti
!
photo catalyst is, usually
chlorophyll captures sunlight to turn water and carbon dio$ide into o$ygen
and glucose, but on the contrary photocatalyst creates strong o$idation agent
and electronic holes to brea*down the organic matter to carbon dio$ide and
water in the presence of photocatalyst, light and water (Ju,ishima et al !...).
(hen it is illuminated by light of energy higher than its band gap, electrons in
Ti
!
will ,ump from the valence band to the conduction band, and the
electron (e+) and electric whole (hL) pairs will form on the surface of the
photocatalyst. The negative electrons and o$ygen will combine to form
!
+
radical ions where as the positive electric holes and water will generate
hydro$yl radicals 0 (-athirvelu et al !..=).
'ince both products are unstable chemical entities, when the organic
compound falls on the surface of the photocatalyst it will combine with
!
#
and 0# and turn into carbon dio$ide (1
!
) and water. This cascade reaction
belongs to the o$idation reduction class and its action is schematically
illustrated. ;uring the reaction, photocatalyst is able to decompose common
organic matter in the air, such as molecules causing odour, bacteria and
viruses or organic stain and dirt.
Jurthermore, when photocatalytic titanium dio$ide is e$posed to
sunlight, it e$hibits super#hydrophilic behavior, which allows partially
decomposed stain4dirt residues on the surface to be washed away easily.


2.

Figure 2.14 Ti#"'iu! $i&*i$e i' " 7&#&c"#")/%# "c#i&'
;ifferent types of chemical are also used to convert nano particles
li*e "inc o$ide, titanium dio$ide, titanium iso#propo$ide, "inc nitrate, silver
nitrate etc., to convert into nano particles.
2.A.+ S&i) Re)e"%e Fi'i%i'g
The ability of fabrics that facilitate the removal of soil during
laundering and other common household condition is a desirable re%uirement.
-issa et al (1?=)) reported several methods of removal of soil from fabrics.
&n first method, adsorption of detergent and absorption of water
remove soil by penetration of soil by wash li%uid, emulsification of soil and
roll up of oily soil. The second method involves mechanical wor* by means
of hydrodynamic flow to remove soil, fle$ing of fibres to free out soil trapped
in between fibres, surface abrasion and swelling of fibres to enhance (1oo*e
21
1?=9). Through te$tile chemical finishing the actions li*e roll up of oily soil,
penetration of soil#fibre interface and finish swelling can be controlled.
7ccording to -issa et al (1?=)), there are the two steps involved in the
soil release process in te$tiles. &n the first step the wash li%uid is penetrated
between the soil particles and the te$tile surface and then the soil is removed
away by the mechanical action. &n the second step soil removal is determined
by the detergent nature type and mechanical action.
'elf cleaning te$tiles are the new developments in this direction. They
are based on the fact that the te$tiles are capable of cleaning themselves to
some e$tent under certain conditions. They are able to free themselves from
dirt and stains. No detergents or chemicals are needed in such cleaning
process. &n the modern day living, consumers prefer such self cleaning
te$tiles.
2.14 1ETHODS OF APPLYING NANO.PARTICLES ON TEXTILES
7ccording to 5iles (!..3) three methods are available to apply nano
particle finish to te$tiles such as 'imple dip and dry method, <ad#dry#cure
method and 'praying method
&n simple dip and dry method the nano#particles are used in the
colloidal state with dispersing agent. The fabric is dipped for 1. minutes and
ta*en out and dried by means of sun drying or hot air or microwave oven
drying. &n pad#dry#cure method, a padding mangle is used to apply nano#
particles in the form of a suspension. The nano#particles are pressed inside the
te$tiles by pressure of padding rollers. The fabric is then dried and cured to
ensure fi$ation. 7 binder is employed to bind the nano#particles to fabric
surface. 7 dispersing agent is used to ma*e a suspension solution of nano#
particles. &n the spraying method, a spray gun is employed to spray the
2!
colloidal suspension of nano#particles on fabrics. 7 hand held spray gun with
compressed air supply and feed tan* is used for this purpose. 7 binder may or
may not be used to bind the nano#particles on the fabric surface.
2.11 TESTING OF FUNCTIONAL PROPERTIES
The fabric samples treated with nano#particles are tested for four
special functional properties namely 7ntimcrobial activity, DC protection
factor, 'oil release characteristics and the self# cleaning action.
2.11.1 E8")u"#i&' &( A'#i0"c#eri") Ac#i8i#/
The antibacterial activity was tested by adopting the %uantitative
assessment method as per 77T11 test method 1.. + !..) (77T11 !..9).
'taphylococcus 7ureus 7merican type 1ulture 1ollection No./23= was used
for >ram positive bacteria and -lebsiella <neumoniae, 7merican type culture
collection no.)32! for >ram negative bacteria. The reduction of bacteria was
calculated in percentage by using the formula,
: M 1.. (3 + 7) 4 3 (!.))
whereK
: M <ercentage reduction in bacteria
7 M the number of bacteria recovered from the inoculated treated test
specimen swatches in the ,ar incubator over !) hours.
3 M the number of bacteria recovered from the incubated treated test
specimen swatches on the ,ar immediately after inoculation (at
"ero contact time)

23
2.11.2 E8")u"#i&' &( U)#r".Vi&)e# Pr&#ec#i&' F"c#&r
The instrumental or in#vitro method is used for evaluating the
ultraviolet protection factor of the fabric. &t is done as per the 77T11 test
method 1=3 (77T11 !..2). DC#Cis spectrophotometer is used to measure
the bloc*ing of erythemal weighted DC: through fabrics. 7fter collecting
transmittance data8 the D<J is calculated by using a formula. The DC#Cis
spectrophotometer has an integrating sphere on which the fabric sample is
placed. 7 direct beam of DC radiation of one wavelength and of *nown
%uantity is made to fall perpendicular to the fabric sample. The amount of DC
radiation transmitted through the fabric is measured. The beams of DC
radiation are chosen at all wave length in the DC range at ! (or) 2nm
intervals.
The transmittance data is collected at all wave lengths. The data is used
to calculate the DC protection factor and the percent transmittance values.
The relative power data of different DC wavelengths to cause s*in redness are
collected using human sub,ects and are given in the erythemal action spectra.
D<J can be calculated by using the formulaK




=

S
S
UPF
nm
nm
nm
nm
)..
!=.
)..
!=.
(!.2)
where6
M :elative Nrythemal spectral effectiveness
S M 'olar spectral irrradiance in wm
#!
nm
#1
M 7verage 'pectral transmittance of fabrics


2)
M The band width in nm
M The wave length in nm
2.11.+ E8")u"#i&' &( S&i) Re)e"%e C"r"c#eri%#ic%
The soil release property was assessed by adopting a modified stain
release test. The stain profiles of the untreated samples were compared to that
of treated samples. The effectiveness of stain release was compared with the
77T11 ratings as per Test method 1926 !..3 (77T11 !..9).
2.11.2 E8")u"#i&' &( Se)( C)e"'i'g Ac#i&'
The self#cleaning activity was assessed with respect to following
parameters6
Nffect of method of preparation and hence the characteristics of
nano#particles
Time of e$posure
;urability of finish
;amage to te$tile
The self#cleaning action 4 photoactivity of the Ti
!
coated cotton
fabric was investigated by e$posing the samples containing adsorbed coffee
stain to visible irradiation. The measured %uantity of /I coffee solution was
introduced on the cotton fabric and was allowed to spread. ne half of each
stain on the fabric was e$posed to the sunlight for 1! + )=h, while the other
half was covered with a blac* paper to prevent its irradiation from sunlight.
The e$posed part of the stain was compared with that of the covered part for
self + cleaning action. >retag 5acbeth, 1olor eye 9...P spectrophotometer
was used to follow the photodegration of coffee stain. The self + cleaning
action was %uantified by comparing -4' values (absorption to scattering
coefficient) of the e$posed and une$posed portions of the same stain. The -4'
22
value of une$posed part of the stain was ta*en as 1.. and relative decrease in
-4' value of e$posed part was calculated using the following relationship
(-amal >upta et al !..=)

(-4')
une$posed
+ (-4')
e$posed

I decrease in -4' of e$posed M ##################################$ 1.. (!./)
(-4')
une$posed
whereK
- is the absorption co#efficient and
' is the scattering co#efficient.
The durability of finish was assessed by sub,ecting the nano#particles
coated te$tile to five wash cycles, and the self#cleaning activity of the coating
was assessed after every wash cycle.
The following aspects are yet to be addressed and very hard to find
research wor* by in these aspects. The present research wor* include the
following aspects6
i) 5ultifunctional finishing of te$tiles by using different precursors using
sol#gel and wet chemical methods on cotton fabric.
ii) 7 comparative performance of Ti
!
O "n nano particle coating on
fabrics made of cotton.
iii) 7 comparative performance of functional testing of Ti
!
O "n nano#
particles with special reference to physical characteristics. The plan of
research wor* has been thoughtfully designed to include these aspects
in this research wor*.