APPLICATION OF NANO-TiO2 2013

A. INTRODUCTION
1. About Titanium Dioxide
Titanium dioxide (TiO2) is a white solid inorganic substance that is
thermally stable, non-flammable, poorly soluble, and not classified as
hazardous according to the United Nations (UN) Globally Harmonized
System of Classification and Labeling of Chemicals (GHS). TiO2, the
oxide of the metal titanium, occurs naturally in several kinds of rock and
mineral sands. Titanium is the ninth most common element in the earths
crust. TiO2 is typically thought of as being chemically inert.
Nanocrystalline semiconductor TiO2 particles are of interest due to
their unique properties and several potential technological applications
such as photocatalysis, sensors, solar cells and self coating glass. TiO2
exists in three polymorphic phases: rutile (tetragonal density, 4.25 g/cm3),
anatase (tetragonal, 3.894 g/cm3) and brookite (orthorhombic, 4.12 g/cm3).
Both anatase and rutile have tetragonal crystal structures but belong to
different space groups. Anatase has the space group I41/amd with four
formula units in one unit cell and rutile has the space group P42/mnm with
two TiO2 formula units in one unit cell. The low-density solid phases are
less stable and under go transition rutile in the solidstate. The
transformation is accelerated by heat treatment and occurs at temperatures
between 450 and 1200 C. This transformation is dependent on several
parameters such as initial particle size, initial phase, dopant concentration,
reaction atmosphere and annealing temperature, etc.

2. CRYSTAL STRUCTURE OF TiO2

Among the three above mentioned crystal structures of TiO2,
anatase owingto its higher photocatalytic activity is commonly used for
photocatalysis. Thishigher photocatalytic activity is related to its lattice
1 structure. Each Ti atom iscoordinated to six oxygen atoms in anatase
tetragonal unit cell. Yong et.el. have reported a significant degree of
buckling associated with O-Ti-O bonds inanatase compared to rutile TiO2.

TiO2 TEAM | NANOTECHNOLOGY

 APPLICATION OF NANO-TiO2 2013

Crystal symmetry is reduced due to this bucklingand in turn it results a

larger unit cell dimensions in the (001) direction. Thekinetics of phase
transformations in TiO2 is extensively reviewed by Zhang & Banfield et
al. Fig.1 shows the unit cell structures of the anatase and rutile crystals.
The titanium and oxygen atoms are more tightly packed in the
rutilecrystal. Both structures can be described in terms of chains of TiO2
octahedra.
Each Ti+4 ion is surrounded by an octahedron of six O-2ions. The
octahedron inrutile is not regular, showing a slight orthorhombic
distortion. The octahedron inanatase is significantly distorted so that its
symmetry is lower than orthorhombic. The Ti-Ti distance in anatase is
greater whereas the Ti-O distances are shorterthan in rutile. In the rutile
structures each octahedron is in contact with 10 neighbor octahedrons (two
sharing edge oxygen pairs and eight sharing corneroxygen atoms) while in
the anatase structure each octahedron is in contact witheight neighbors
(four sharing an edge and four sharing a corner).
These differencesin lattice structures cause different mass densities
and electronic band structures between the two forms of TiO2 as indicated
in Fig.1. Anatase can be conceived asan arrangement of parallel
octahedral, while in case of rutile some octahedral arerotated by 90.
There is a symmetry change from I41/amd to P42/mnm space groupin
terms of reconstructive polymorphism during conversion from anatase to
rutile. As a consequence, the ionic mobility that occurs during phase
transition results in increased densification and coarsening of the TiO2
nanoparticles.

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 APPLICATION OF NANO-TiO2 2013

Fig. 1 Structure of anatase and Rutile TiO2 (a) anatase (b) rutile

TiO2 is stable in aqueous media and is tolerant of both acidic and alkaline
solutions. It is inexpensive, recyclable, reusable and relatively simple to produce.
Itcan also be synthesized in nanostructure forms more readily than many
othercatalysts. Furthermore, its bandgap is appropriate to initiate a variety of
organicreactions.
Semiconductor photocatalysis uses sunlight to activate
nanoparticlescatalysts to break down these chemicals. Photocatalysis works on the
principle thatlight falling on a semiconductor with an appropriate bandgap, or
energy differencebetween the conduction and the valance bands will create
positive (holes) andnegative (electrons) charge carriers, which can in turn be used
to initiate reduction(electrons) and oxidation (holes) reactions at the catalyst
surface. Severalcompeting effects inherently limit catalyst efficiency. The
positively charged holesand negatively charged electrons tend, by nature, to
recombine to yield a neutralstate, through reemission of a photon (light) or a
phonon (heat). This can occur viavolumetric and surface recombination.
Nanostructured (~20-30nm) particlesprovide the optimal balance between these
effects and are thus best suited to photocatalysis. An additional advantage
3
obtained in nanoparticles in the few tensof nm size regime is that the large surface
/volume ratio makes possible the timely utilization of photogenerated carriers in
interfacial processes.

TiO2 TEAM | NANOTECHNOLOGY

 APPLICATION OF NANO-TiO2 2013

TiO2 nanoparticles can be synthesized using various methods such

as sulfate process, chloride process, impregnation, coprecipitation,
hydrothermal method, direct oxidation of TiCl4, metal organic chemical
vapor deposition method, etc. Sol-gel method is one of the mostconvenient
ways to synthesize various metal oxides due to low cost, ease offabrication
and low processing temperatures. It is widely used to prepare TiO 2
forfilms, particles or monoliths. In general, the sol gel process involves
the transition of a system from a liquid sol (mostly colloidal) into a solid
gel phase. The homogeneity of the gels depends on the solubility of
reagents in the solvent, thesequence of addition of reactants, the
temperature and the pH. The precursorsnormally used for the synthesis
and doping of nanoparticles are organic alkoxides,acetates or
acetylacetonates as well as inorganic salts such as chlorides. Among
theclasses of solvents, alcohols are largely used but other solvents such as
benzene mayalso be used for some alkoxides.
3. Products contain TiO2
Titanium dioxide has been used for many years (ca. 90 years) in a
vast range of industrial and consumer goods including paints, coatings,
adhesives, paper and paperboard, plastics and rubber, printing inks, coated
fabrics and textiles, catalyst systems, ceramics, floor coverings, roofing
materials, cosmetics and pharmaceuticals, water treatment agents, food
colorants and in automotive products.

TiO2 TEAM | NANOTECHNOLOGY

 APPLICATION OF NANO-TiO2 2013

B. APPLICATION OF NANO-TiO2
1. TRANSPARENT NANOHYBRIDS OF NANOCRYSTALLINE TiO2
IN PMMA WITH UNIQUE NONLINEAR OPTICAL BEHAVIOR
PMMA is one of the most versatile polymeric materials for
applications in various technological areasincluding optics and electro-
optics. While the current applications of PMMA in optics and electro-
optics arelimited by their linear optical behavior, we report here in this
paper the unique nonlinear optical behavior ofnanohybrids consisting of
nanocrystalline TiO2 in PMMA. Transparent thin films of TiO2PMMA
nanohybridon substrates were synthesized by in-situ solgel and
polymerisation, assisted by spin coating. Using titaniumisoproproxide (Ti-
iP) as the starting material for nanocrystalline titania, together with methyl
methacrylate and3-(trimethoxysilyl)propyl methacrylate, nanohybrids
containing up to 80% Ti-iP in PMMA were successfullyrealized. The
resulting nanohybrid thin films coated on quartz substrates are optically
transparent anddemonstrate large nonlinear optical behavior
Preparation of Nanohybrid TiO2PMMA
Materials
The starting materials in this work were methyl methacrylate(MMA,
99%, Acros), 3-(trimethoxysilyl)propyl methacrylate(MSMA, 98%,
Acros), tetrahydrofuran (THF, 99%, Acros),benzoyl peroxide (BPO, 98%,
Acros), de-ionized water,ethyl alcohol (EtOH, 95%, Merck), hydrochloric
acid(HCL, 36%, Ajax) and titanium isopropoxide (Ti-iP, 98%,Acros).
Process
Where the monomers, MMA and MSMA, and initiator BPO in
THFwere added into a reaction flask and polymerized at 60 oC for1 hour.
The molar ratio of MSMA to MMA 1 MSMA wascontrolled at 0.25 and
the amount of BPO added to the mixturewas fixed at 3.75 mol%. At the
5 same time, a TiO2 based solsolution was prepared using titanium
isopropoxide (Ti-iP),de-ionized water, ethanol and hydrochloric acid.

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 APPLICATION OF NANO-TiO2 2013

Titanium isopropoxide(Ti-iP) was first mixed with ethanol in a

container and stirredfor 30 minutes. A mixture of de-ionized water and
HCl wasthen added under stirring into the transparent solution topromote
hydrolysis. The Ti-iP concentration in the solutionwas controlled at 0.4 M
with an understoichiometric ratioof water to Ti-iP of 0.82 and pH value of
1.3 for obtaining astable solution.
Finally, this homogeneous mixture was addeddropwise over a duration
of 30 minutes into the partiallypolymerized monomers with rigorous
stirring to avoid localinhomogeneities. The reaction was allowed to
proceed at 60 oCfor another 2 hours. Following this procedure, four
transparentsolutions, with the weight percentage of titanium
isopropoxideof 20, 40, 60 and 80 wt% in PMMA, respectively,
wereprepared.
2. APPLICATION OF TiO2 SELF CLEANING IN WATER BASED
PAINT WITH POLYETHYLENE GLYCOL (PEG) AS
DISPERSANT
Paint is mostly used to cover a surface of building as decorative.
Environmental pollution like dust, mud, and bacteria could make the
surface become dirty. Therefore, paint with self cleaning properties is
required to solvethose problems.
One of the technologies that are being developed for applications
in self-cleaning photocatalytic paint is to use semiconductor materials.
Photocatalytic is a chemical reaction process aided by the energy of
ultraviolet light energy.
Almost all semiconductor material can be used in photocatalytic
reactions. But some are less suitable semiconductor used as a catalyst
because it is less favorable.TiO2 semiconductor suitable for photocatalytic
process because it is the most suitable catalyst for biologically inert, stable
6 against chemical corrosion and relatively cheapAnatase crystal wasused as
photocatalytic effect for self cleaning application and rutile crystal was
used as an UV stabilizing to protectthe organic binder. Self cleaning in the

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 APPLICATION OF NANO-TiO2 2013

paint can be made by coating the surface of the paint with TiO2
photocatalyst. Besides TiO2 as a photocatalyst is also amphiphilic, which
become superhidrofilik when UV irradiated and returned to hydrophobic
when no UV rays.At superhidrofilik surface water tends to spread evenly
over the surface of the material on forming particle granules (anti-fogging)
due to the contact angle of water with a low level (<100) that has a high
wet.
Mechanism of photocatalytic
If TiO2 irradiated with UV light will be formed electron-hole pair
(e-and h +) on the surface of the coating.Positive hole (hole) that is formed
will interact with water or OH-ions, producing hydroxyl radical (
OH).The hydroxyl radical is a highly reactive that attack organic
molecules and degrade it toCO2and H2O (and halide ions if organic
molecules containing halogen)(Linsebigler, 1995).This is causes
particulates attached to the ceramic surface will degrade and fall off easily
by water, such as rain. Photocatalytic activity of the catalyst TiO2 films
depends on the crystal structure and good porosity (Ollis, 1993). However,
the catalyst in the form of films have limitations on the extent of the
surface is small, thus reducing the activity of the catalyst.Attempt to
overcome this deficiency is to develop a catalyst TiO2 films with the
addition of other substances such as polyethylene glycol (PEG) and PEG
addition meant to increasing porosity can also assist in the process of
formation of nano-sized catalysts.Moreover, the addition of PEG can also
reduce the possibility of cracks on the surface of the film when the
calcination process can reduce the activity of the catalyst.
Producing of TiO2/PEGs Photocatalyst Film
A solution is prepared by mixing Ti (Opr) 4 Acac 75% with
ethanol and form a homogeneous solution. Solution B was made by
7 mixing with HCl and H2O Mixing ethanol solution A with solution B for
30 min and then added to the PEG (BM 2000) by varying the wt% TiO2
addition is based on a heavy base. Ready mixed paint used to coat.

TiO2 TEAM | NANOTECHNOLOGY

 APPLICATION OF NANO-TiO2 2013

3. Application of Nano-TiO2 in Plastics

Plastics added with nano-TiO2 catalyst will become
photocatalytically degradable plastics. Composite films added with nano-
TiO2 catalyst will exhibit highly enhanced photo-degradability. The final
products of photocatalysis are mainly CO2 and H2O, and the reaction
process causes no pollution to the environment. Nano-TiO2 is nontoxic
and tasteless, with excellent stability and durability. Polymers such as PP
added with nano-TiO2 will become composite materials with high
strength, high toughness and good comprehensive performance. When
PPR (Polypropylen random) is added with nano-TiO2, its HDT (Heat
Deflection Temperature) will rise from 72 to 96 . Besides, under the
effect of light, nano-TiO2 can effectively dispel odors of plastics, and
bestow them with self-cleaning and antifouling effects.
Nano-TiO2 is an inorganic antiseptic widely used in our daily life.
Plastics and composite fiber packing materials, added with nano-TiO2, will
become functional materials with lasting wide-spectrum antibiotic effects
and safe and stable properties. They can be made into food bags, food
packaging films, toys, tableware and engineering plastics for the purpose
of preserving food quality and prolonging the food preservation period,
and improving the toughness and strength of engineering plastics, as well
as their anti-UV and anti-aging properties.
According to statistics, nano-TiO2 is a photocatalyst widely used in
plastics industry for the production of special plastics. It can not only
improve the physical properties of plastics but also induce such effects as
sterilization, antifouling and self-cleaning. Considering plastics industry is
a fundamental industry, the application of nano-TiO2 will have good
prospects. There is a potential market. To satisfy peoples increasing
8 demands for better living conditions, the research and development of
germproof degradable plastics based on nano-technology will be an
important research direction. Plastics are one of the most widely used

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 APPLICATION OF NANO-TiO2 2013

materials today. In 1998, the global output of plastics hit 150 million tons,
and Chinas output of plastics reached 16 million tons, becoming the
second largest producer of plastics in the world. However, plastics are
usually discarded as wastes after use. The quantity of waste plastics is
rapidly increasing with the growth of economic consumptions. According
to statistics, unrecoverable plastic wastes exceeded 2 million tons in 1998.
Due to the nondegradability of plastic wastes, white pollution has
become a difficult problem worldwide. Presently, treated plastic wastes
are still not fully degraded, resulting in secondary pollution. To address
the high treatment costs, the study of degradable plastics has become an
important task in the plastics industry. In 2006, Tsinghua University
launched a research program for photocatalytic degradable plastics.
Polymer nanocomposites are already a part of many important of
worldwide businesses: automotive (molded part in cars), electronics and
electrical engineering, household products, packaging industry, aircraft
interiors, appliance components, security equipments. Among many
nanocomposite precursors, TiO2 nanopowder is increasingly being
investigated due to its special properties. Nanocomposites with
polystyrene chains chemically linked to the surface of TiO2 nanopowders.
Thermogravimetric analysis (TGA) and differential scanning calorimetry
(DSC) indicated that the resulting nanocomposites displayed higher
thermal stability and maintained similar glass transition temperatures (Tg)
compared with pure PS. Ultravioletvisible spectroscopy (UV-Vis)
investigated that these nanocomposites have improved optical properties
potentially acting as visually transparent UV filters. Such incremented
properties were attributed to the nancoscale dispersion (20-50 nm size) of
TiO2 into polystyrene matrix, which morphology was observed by
scanning electron microscopy (SEM).
9 4. SELF CLEANING GLASS
In practice, surface cleaning of building materials like tiles, facades
and glass panescauses considerable trouble, high consumption of energy

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 APPLICATION OF NANO-TiO2 2013

and chemical detergents and,consequently, high costs. To realize self-

cleaning material surfaces there are two principalways: the development of
so-called superhydrophobic or super-hydrophilic surfaces.
What is hydrophobicity? Also termed hydrophobic, materials
possessing this characteristichave the opposite response to water
interaction compared to hydrophilic materials.Hydrophobic materials
("water hating") have little or no tendency to adsorb water andwater tends
to "bead" on their surfaces (i.e., discrete droplets). Hydrophobic
materialspossess low surface tension values and lack active groups in their
surface chemistry forformation of "hydrogen-bonds" with water.
The wetting of a solid with water, where air is the surrounding
medium, is dependent onthe relation between the interfacial tensions
(water/air, water/solid and solid/air). The ratiobetween these tensions
determines the contact angle between a water droplet on a givensurface. A
contact angle of 0 means complete wetting, and a contact angle of
180corresponds to complete non-wetting. Hydrophobic surfaces with low
wettability andcontact angles of about 100 are known for a long time. The
higher this angle the lower isthe value of the adhesion work. Decreasing of
the contact angle leads to enlarged valuesof the adhesion work
(hydrophilic surfaces).
By transferring the microstructure of selected plant surfaces to
practical materials, superhydrophobicsurfaces could be developed. The
water repellency of plant surfaces hasbeen known for many years. That
water-repellent surfaces also indicate self-cleaningproperties has been
completely overlooked. Recently, Barthlott et al. investigated andproved
the correlation between the microstructure, wettability and contaminants in
detailusing lotus leaves. This was called the Lotus Effect because it can be
demonstrated beautifully with the great leaves of the lotus plant. The
10 microrough surfaces show contactangles higher than 130. That means, the
adhesion of water, as well as particles isextremely reduced. Water which
contacts such surfaces will be immediately contracted todroplets. The

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 APPLICATION OF NANO-TiO2 2013

particles of contaminants adhere to the droplet surfaces and are

removedfrom the rough surface when the droplets roll of in figure below.

If TiO2 of the Anatase type is exposed to UV light very low contact

angles are obtained(<1). These materials have the unique property of
attracting rather than repelling water(super-hydrophilicity). The water
lies flat on the surface in sheets instead of formingdroplets. If the
illumination is stopped, the super-hydrophilic behaviour of the TiO2
surfaceis retained for approximately two days. Furthermore, UV
illumination of titanium dioxideleads to the formation of powerful agents
with the ability to oxidize and decompose manytypes of bacteria, organic
and inorganic materials. In the following, the principles andpotential
applications of TiO2 photocatalysis are discussed.
Titanium dioxide (TiO2) is a well-known coating for hydrophilic
self-cleaning surfaces due to its favorable physical and chemicalproperties.
It is non-toxic, chemically inert when there is no lightpresent, inexpensive,
easy to handle and already well-knownin household chemicals (pigment in
cosmetics and paint). Thestrong oxidation power and superhydrophilic
properties of titanium dioxide make it a good material to be used as a self-
cleaning coating especially for outdoor purposes.
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 APPLICATION OF NANO-TiO2 2013

5. DYE-SENSITIZED SOLAR CELL (DSSC)

TiO2 is used as a semiconductor in DSSC. Semiconductor in DSSC
used as a dye molecule adsorption and photocatalist, in which the dye
molecules to generate photon flow and absorb of light spectrum. TiO2 is
used because it is one of the semiconductor bandgep wide areas suitable
for dye adsorption and can absorb a wider spectrum of light, in addition to
the TiO2 is inert, harmless, cheap and have good optical characteristics .
The use of oxide semiconductors in photoelectrochemical stability
due fotocorosion face. In addition a large energy bandwidth ( > 3EV ),
required in DSSC for transparency semiconductor in most solar light
spectrum. In addition to semiconductor TiO2, which is used in this study,
other semiconductor used is ZnO, CdSe, CdS, WO3, Fe2O3, SnO2, Nb2O5,
and Ta2O5. However, TiO2 is a material that is often used because of the
efficiency of DSSC using TiO2 is still unmatched.
In nature generally have three phases namely TiO2 rutile , anatase ,
and brookite crystal structure as shown. Rutile phase of TiO2 is a common
phase and a phase that is synthesized from the mineral ilmenite through
Becher process. In the Becher process, iron oxide contained in the ilmenite
separated by high temperatures and also with the help of sulfate or
chlorine gas to produce rutile TiO2 with purity of 91-93%. Titania in the
anatase phase is generally stable at particle sizes less than 11 nm , brookite
phase pad particle size 11-35 nm, and 35 nm above the rutile phase. For
application in DSSC, TiO2 anatase phase generally used because it has a
high ability of photoactive. In addition to the structure of TiO2 nanopori
the pore size in the nanoscale will increase the system performance
because nanopori structure has the characteristics of high surface area that
will increase the amount of dye that teradsorp the implications will
increase the amount of light that absorbed. And the titanium dioxide
12 particles must be in the size range of 10-40 nm so that the resulting
sintered layer is highly porous. This layer, at the center of the operation
principle, will ultimately act as a light-sponge in the solar cell.

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 APPLICATION OF NANO-TiO2 2013

TiO2 here will be attached to the TCO glass and soaked with dye
molecule, which will dye molecules adsorbed on the TiO2 porous and act
as photon flow and absorb the light spectrum that will be going on the
electron transfer process and generate electricity.
6. SUNSCREEN AND UV-BLOCKING
Titanium dioxide accounts for 70% of the total production volume
of pigments worldwide. It is widely used to provide whiteness and opacity
to products such as paints, plastics, papers, inks, foods, and toothpastes. It
is also used in cosmetic and skin care products, and it is present in almost
every sunblock, where it helps protect the skin from ultraviolet light. It is
also used as a tattoo pigment and in styptic pencils. Titanium dioxide is
produced in varying particle sizes, oil and water dispersible, and in certain
grades for the cosmetic industry.
Titanium dioxide is found in almost every sunscreen with a
physical blocker because of its high refractive index, its strong UV light
absorbing capabilities and its resistance to discoloration under ultraviolet
light. This advantage enhances its stability and ability to protect the skin
from ultraviolet light. Nano-scaled titanium dioxide particles are primarily
used in sun screen lotion because they scatter visible light less than
titanium dioxide pigments while still providing UV protection. Sunscreens
designed for infants or people with sensitive skin are often based on
titanium dioxide, as these mineral UV blockers are believed to cause less
skin irritation than other UV absorbing chemicals.
The titanium dioxide pigment in construction industry also used
extensively in plastics and other applications not only as a white pigment
or an opacifier but also for its UV resistant properties where the powder
disperses the light unlike organic UV absorbers and reduces UV
damage, due mostly to the extremely high refractive index of the particles.
13 Certain polymers used in coatings for concrete or those used to impregnate
concrete as a reinforcement are sometimes charged with titanium white
pigment for UV shielding, but it only delays the oxidative

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 APPLICATION OF NANO-TiO2 2013

photodegradation of the polymer in question, which is said to "chalk" as it

flakes off due to lowered impact strength and may crumble after years of
exposure in direct sunlight if UV stabilizers have not been included .
In furthermore research, titanium dioxide (TiO2) nanoparticles,
found in everything from cosmetics to sunscreen to paint to vitamins,
caused systemic genetic damage in mice, according to a comprehensive
study conducted by researchers at UCLA's Jonsson Comprehensive Cancer
Center. In the past, these TiO2 nanoparticles have been considered non-
toxic in that they do not incite a chemical reaction. Instead, it is surface
interactions that the nanoparticles have within their environment- in this
case inside a mouse -- that is causing the genetic damage. They wander
throughout the body causing oxidative stress, which can lead to cell death.
As recommendation we suggest that manufacturers and suppliers
of titanium dioxide are advised to review and update their material safety
data sheets (MSDS) and product labels based on this new information as
soon as possible. Employers should review their occupational hygiene
programs to ensure that exposure to titanium dioxide dust is eliminated or
reduced to the minimum possible. Workers should be educated concerning
this potential newly recognized risk to their health and trained in proper
work procedures.

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TiO2 TEAM | NANOTECHNOLOGY