Professional Documents
Culture Documents
DOI 10.1007/s11164-009-0032-x
Received: 12 January 2008 / Accepted: 16 May 2008 / Published online: 5 March 2009
Springer Science+Business Media B.V. 2009
Abstract Synthesized and commercial titanium dioxide (TiO2) were coated onto
household curtain fabrics for anti-microbial and ultraviolet (UV) shielding func-
tions. The coating was performed by inducing a deposition of the TiO2 layer from
the Ti precursor onto the fabric surface. A silane adhesive agent was employed to
improve the adhesion between the coating and the fabric. Ag nanoparticles were
also incorporated into some samples to further improve the anti-bacterial activity,
which was evaluated by a standard qualitative test (AATCC 147). Efficiency for UV
shielding was evaluated by measuring a UV–visible reflection of the coated fabrics
both before and after subjecting it to several washing cycles. The results showed
that the TiO2-coated fabrics had potential as both anti-bacterial and UV shielding
for the curtain industry.
Introduction
Since the discovery of the water splitting capability of titanium dioxide (TiO2) in
the late 1960s [1, 2], the subject of interest has shifted into the area of environmental
purification. The use of TiO2 either in the form of particles, films, or coatings has
been widely investigated during the past several decades as an active substance for
the destruction of organic pollutants [3–7] and the growth inhibition of microor-
ganisms [8–10], and as an ultraviolet (UV) absorber in cosmetics or modified
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272 O.-U. Nimittrakoolchai, S. Supothina
textiles [11–13]. So far, TiO2 has been known as the photocatalytic material that
possesses high activity, strong oxidizing power, and long-term stability. Upon
irradiation by light of sufficient energy (k \ 400 nm), electrons are promoted from
a valence band to a conduction band and react with adsorbed oxygen to produce
superoxide ions (O- 2 ), while holes which are produced in a valence band react with
adsorbed water or hydroxyl at the surface to produce hydroxyl radicals (OH•). Both
types of radicals are extremely reactive towards organic compounds or living cells
that come into contact with it. In addition, because of its capability of absorbing UV
light and transmitting visible light, TiO2 has also been used as a UV-filtering
substance in sunscreen cosmetics [14].
To make it suitable for applications such as water purification, it is more common
to coat the TiO2 onto supporting porous materials, such as silica gel, alumina,
activated carbon, and zeolite. The coating can be achieved by using several
techniques, but dip coating is by far the most common [15–17]. This wet process
requires simple apparatus and, more importantly, had less limitations on the
dimension and complexity of articles to be coated compared to physical methods,
which have line-of-sight limitation. The advantage of the dip coating method is a
capability of treating both sides of the substrate in one single step. Moreover,
surface properties of the coating can be easily manipulated by modifying the
component and concentration of the coating precursors.
In this present work, TiO2 was coated onto curtain fabric by a sol–gel dip coating
to filter UV light entering the building, and, at the same time, to inhibit the growth
of microbials which are significant for tropical climate. The coated fabrics would
require fewer sessions of cleaning, which is inconvenient due to their large size. To
further improve the anti-bacterial property, a small amount of commercial P25 TiO2
or Ag nanoparticles were also added into the synthesized TiO2 solution. Since the
efficiency of the coated fabrics depends largely on the ability of the TiO2 to attach
onto the fabric, adhesion of the coating was improved by adding a suitable amount
of an adhesive agent.
Experimental
The curtain fabrics were ultrasonically cleaned in methanol and acetone and then
dried at 100C to remove the residual solvent. A Ti starting precursor was prepared
by dissolving tetrabutyl orthotitanate (97%, Fluka) in absolute ethanol (99.9%,
Mallinckrodt) containing a small amount of de-ionized water and nitric acid
(65%, Scharlau). To improve the adhesion between the TiO2 and the fabrics, bis(3-
triethoxy silyl) propyl tetrasulfide (also known as ‘‘silane-69,’’ Degussa) adhesive
agent (5 vol% in ethanol) was added into the Ti precursor at a volume ratio of 2:5.
The silane-69 was chosen because the silane-coupling agents are bifunctional
organosilane, therefore, permitting chemical cross-linking between the fabrics and
the TiO2 particles, which contain surface hydroxyl groups. The resulting precursor
was vigorously stirred at room temperature for 3 h. The cleaned fabrics were soaked
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Bactericidal activity and UV-filtering property of TiO2-based photocatalysts 273
into the precursor at room temperature for 1 h. Then, the coated fabrics were ironed
at approximately 80C, so that cross-linking reaction between the TiO2 particles and
molecules of the silane-69 were formed. A separate coating method was also
conducted by soaking the clean fabrics in the Ti precursor (without the silane-69) at
80C for 24 h. The coated fabrics were then dried at 50C for 30 min. The adhesion
efficiency of the TiO2-coated fabrics was evaluated by washing them in detergent
solution 20 times.
The samples for bactericidal activity assessment were prepared slightly
differently from the method described above. The cleaned fabrics were dipped
into a silane-69 solution for 6 h, followed by dipping into the Ti precursor (without
the addition of silane-69) for 1 h. Then, the coated fabrics were ironed at
approximately 80C. The sample prepared according to this method is referred to as
a ‘‘TiO2 sol.’’ In some experiments, P25 TiO2 powder or Ag nanoparticles were
added into the Ti precursor at the amount of 0.02 g and 1 mL (*100 ppm) per
100 mL of the solution, respectively. The samples prepared from these precursors
are referred to as ‘‘TiO2 sol_P25’’ and ‘‘TiO2 sol_Ag’’, respectively.
Characterizations
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274 O.-U. Nimittrakoolchai, S. Supothina
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Bactericidal activity and UV-filtering property of TiO2-based photocatalysts 275
Figure 1a is an SEM image of the bare cotton fabric showing the smooth surface.
The EDS spectrum (inset) indicates the absence of any inorganic coating, as only C,
O, and Au (deposited during sample preparation) were detected. Figure 1b is an
SEM image of the as-prepared TiO2-coated fabric prepared by soaking the clean
fabric in the Ti precursor containing the silane-69 adhesive at room temperature for
1 h. The coating is continuous and had a smooth surface, although cracking was
observed at the contact areas between adjacent fibers. The EDS analysis result
(inset) shows strong Ti peaks, confirming the presence of the TiO2 coating. An SEM
image of the washed fabric (Fig. 1c) reveals similar features as those noted from the
sample before washing. That is, the coating layer was continuous and smooth. The
EDS result (inset) shows that intensity ratio of Ti:C peaks is comparable to that
taken from the sample before washing, indicating good adhesion between the TiO2
coating and the fabric surface, due to cross-linking between the hydroxyl group of
the TiO2 and the silanol group of the silane-69.
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276 O.-U. Nimittrakoolchai, S. Supothina
Fig. 3 Transmission electron microscope (TEM) image of the TiO2 taken from the coated fabric. It
consisted of 6 ± 3-nm anatase crystals, as identified by a selected-area electron diffraction pattern
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Bactericidal activity and UV-filtering property of TiO2-based photocatalysts 277
(a) 3500
3000
2500
Reflection intensity
2000
1500
1000
(b) 3500
3000
2500
Reflection intensity
2000
1500
1000
Fig. 4 Reflection spectra of the TiO2-coated fabrics before and after washing. The specimens were
prepared from the Ti precursor a containing the silane-69 and b not containing the silane-69
crystallinity. The presence of the amorphous phase is common for the sample
prepared by the sol–gel process without post-heat treatment. The amorphous phase
might be a hydrated titanium oxide or a residual organic alkyl component.
Figure 4a shows a reflection spectra of the TiO2-coated fabric prepared from the
Ti precursor containing silane-69. The spectra of the uncoated fabric were also
shown for reference. It is apparent that light reflection from the TiO2-coated fabric
is lower than that from the uncoated fabric, especially in the range of 200–350 nm,
which is in the UV region, while the reflectance in the visible-light region is
comparable. As lower reflection implies higher absorption (transmittance was close
to zero for these samples), the results of this reflectance measurement indicates that
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278 O.-U. Nimittrakoolchai, S. Supothina
the TiO2-coated fabric had better UV absorption than the uncoated fabric, and,
therefore, is capable of shielding the UV light. The results of the reflection
measurement are in good agreement with microstructural observations by SEM that
the sample had good adhesion between the TiO2 layer and the fiber, and did not
detach upon washing. Therefore, the UV-shielding efficiency was not decreased.
However, for the TiO2-coated fabric obtained from the precursor without the silane-
69 and subjected to washing (Fig. 4b), its reflection spectrum was higher than that
taken from the same sample before washing, meaning that its UV-shielding
efficiency was decreased after washing.
Figure 5 shows SEM images of the TiO2-coated fabrics prepared from the TiO2
sol containing P25 (TiO2 sol_P25) and Ag nanoparticles (TiO2 sol_Ag). In both
specimens, cracked and thick TiO2 films were obtained as a result of the more
concentrated precursor. The EDS spectrum (inset) showed very strong Ti peaks. The
effect of coated fabrics on growth inhibition of the S. aureus is shown in Fig. 6,
which illustrates the survival of the S. aureus that was in contact with the specimens
(underneath), as well as in the vicinity of the specimen periphery. The bare and TiO2
sol-coated fabrics had no bactericidal effect, as no inhibition area was observed both
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Bactericidal activity and UV-filtering property of TiO2-based photocatalysts 279
Fig. 6 Photographs showing the bactericidal effect of: a bare fabric, b TiO2 sol-coated, c TiO2 sol_P25-
coated, and d TiO2 sol_Ag-coated fabrics
underneath and at the periphery of the specimens (i.e., W = 0). Poor bactericidal
activity of the TiO2 sol-coated fabric could be related to low crystallinity of the
TiO2 sol, which contained a considerable amount of the amorphous phase, as seen in
the TEM image. With the addition of 0.02 g mL-1 of P25 TiO2 and *1 ppm of Ag
particles in the solution (specimens ‘‘TiO2 sol_P25’’ and ‘‘TiO2 sol_Ag’’,
respectively), the coated fabrics had growth inhibition activity, as no S. aureus
was observed both underneath and at the specimen’s periphery. They both had
comparable clear zones of 1.4 ± 0.1 mm and 1.6 ± 0.1 mm, respectively. It was
anticipated that the effect would be more pronounced if a larger quantity of the Ag
or P25 TiO2 was added into the solution. It has been proposed that the bacteria-
killing effect was caused by the destruction of cell membrane and cell wall by free
radicals generated by the TiO2 or dissolved Ag? [9, 18, 19]. The Ag? can also act as
electron traps, which reduce the rate of electron–hole recombination and, therefore,
enhance the efficiency of the Ag–TiO2 catalyst.
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280 O.-U. Nimittrakoolchai, S. Supothina
Conclusions
TiO2 and Ag-doped TiO2 as anti-bacterial and UV shielding coatings were success-
fully deposited onto curtain fabrics by a dip coating method. The coated fabrics had
better UV shielding efficiency than the uncoated fabrics. For the case of TiO2 coating
from the precursor without the addition of adhesive agent, the coating had less
durability upon washing, and, therefore, its UV-shielding efficiency was decreased.
By using the silane adhesive agent, the TiO2 coating had better features—it was
continuous and had good adhesion. The UV-shielding efficiency was not degraded
after being subjected to many washing cycles.
Acknowledgments This research was financially supported by the National Metal and Materials
Technology Center under the National Science and Technology Development Agency, Thailand (grant
no. MT-B-50-CER-13-200-G).
References
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