Accepted Manuscript

Title: Functionalization of textile materials with TiO2

nanoparticles

Author: <ce:author id="aut0005" biographyid="vt0005">

Maja Radetić

PII: S1389-5567(13)00006-3
DOI: http://dx.doi.org/doi:10.1016/j.jphotochemrev.2013.04.002
Reference: JPR 186

To appear in: Journal of Photochemistry and Photobiology C: Photochemistry

Reviews

Received date: 17-10-2012

Revised date: 17-4-2013
Accepted date: 19-4-2013

Please cite this article as: M. Radetić, Functionalization of textile materials with TiO2
nanoparticles, Journal of Photochemistry and Photobiology C:Photochemistry Reviews
(2013), http://dx.doi.org/10.1016/j.jphotochemrev.2013.04.002

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 Functionalization of textile materials with TiO2 nanoparticles

Maja Radetić*

Textile Engineering Department, Faculty of Technology and Metallurgy,

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University of Belgrade, Belgrade, Serbia

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Highlights

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The potential applications of TiO2 nanoparticles to various textile materials are

summarized.
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Self-cleaning textile materials.

Textile materials with UV protection and antibacterial activity.

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The influence of silver on photocatalytic activity of TiO2 nanoparticles

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deposited onto textile materials.

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ABSTRACT

Extraordinary photocatalytic activity, non-toxicity, high availability, biocompatibility,

and low price make TiO2 nanoparticles particularly attractive for manufacturing of

different high value-added products. During the past several years, many efforts have

been made to immobilize TiO2 nanoparticles onto textile materials with an aim to
*
Corresponding author. Tel.: +381 11 3303 857; fax: +381 11 3370 387.
E-mail address: maja@tmf.bg.ac.rs (M. Radetić).

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Page 1 of 63
produce goods with multifunctional properties such as UV protective, self-cleaning and

antibacterial. The processing of textile materials with TiO2 nanoparticles is relatively

simple, but insufficient binding efficiency between certain fibers and TiO2 nanoparticles

imposes a problem concerning the stability and durability of nanocomposite systems

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during their exploitation. Therefore, recent studies were more oriented towards chemical

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and physico-chemical modification of fiber surfaces that may enhance the binding

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efficiency of TiO2 nanoparticles. This article looks at some latest advances in finishing

of different textile materials with TiO2 nanoparticles.

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Keywords: TiO2 nanoparticles, textile materials, plasma, UV protection, photocatalytic

activity
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1. Introduction
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Recent advances in nanoscience and nanotechnology have tremendous impact on

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almost all industries and many segments of daily life. The huge investments in funding

of research and rapid feedback from laboratories made nanotechnology securely

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embedded in the global market. Although enormous progress in this field has been
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already made, nanotechnologies still pose many questions and challenges including

their industrial scale implementation that would enable commercial manufacturing of

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nanomaterials and corresponding products, environmental, safety and health concern,

etc [1-4]. A large number (more than thousand) of labeled commercial products

(electronic, automotive, medical, cosmetics, optics, etc.) contain different nanoparticles

(NPs) [1-2, 5-6]. Ag NPs are currently the most commonly used nano-engineered

material due to their outstanding antimicrobial activity [1]. However, the potentials of

metal oxide nanoparticles, in particular TiO2 NPs, offer broader application [7-8]. This

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Page 2 of 63
photocatalyst can be efficiently utilized for self-cleaning of surfaces [9-11], water and

air purification [12-16], anti-fogging surfaces [17-18], photovoltaics [19-22], etc.

The positive experience in familiar fields and the prospects of good technical

and economical success were promptly recognized by textile industry and thus, the

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finishing of textile materials with Ag, TiO2 and ZnO NPs became the focus of many

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research groups worldwide during the last decade. Numerous studies on Ag NPs

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application to textile surfaces and increasing microbial resistance to various available

antibiotics facilitated the commercial manufacturing of textile goods with antimicrobial

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properties which were readily accepted by consumers [23-33]. At the same time, the

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interest for TiO2 NPs immobilization onto textile materials is continually growing due

to their extraordinary photocatalytic activity, non-toxicity, high availability,

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biocompatibility, and low price [34-35]. Actually, the crucial point is that TiO2 NPs

simultaneously impart antibacterial, UV protective and self-cleaning properties to textile

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materials. Taking into account ever growing consumer demands, the fact that small
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amount of TiO2 NPs provides desirable effects as well as relatively simple routes for

their synthesis and further processing, it becomes clear why such multifunctional
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nanocomposite textile materials are of interest for textile industry. However, unlike
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textile goods with incorporated Ag NPs that are already available in the market, textiles

modified with TiO2 NPs are still on the level of exploration. In spite of their numerous
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potential applications and evident benefits, there are several concerns which inhibit

commercialization of such products requiring further research. The problematic issues

are primarily related to exploitation and maintenance of textile goods containing TiO2

NPs. Namely, unsatisfactory durability of obtained effects due to insufficient stability of

TiO2 NPs on textile materials demands improvement of binding efficiency between NPs

and fibers. This can be achieved with more or less success by certain functionalization

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Page 3 of 63
of fibers prior to deposition of TiO2 NPs. On the other hand, the fate of fibers

impregnated with TiO2 NPs exposed to longer UV irradiation i.e. their integrity and

possible degradation due to the contact with photocatalyst has not been evaluated to a

great extent yet.

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Montazer and Pakdel recently published a review paper focused on the

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functionalization of wool fibers with TiO2 NPs [36]. Current review was intended to

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give broader insight into advances in finishing of different textile materials with TiO2

NPs. The major effects (antibacterial activity, UV protection, self-cleaning properties)

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imparted to textile materials by impregnation with TiO2 NPs have been described in

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detail. Special emphasis has been given to various chemical and physico-chemical

modifications of textile surfaces which result in functionalization of fibers and hence,

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facilitate the binding of TiO2 NPs. In addition, the effect of silver on TiO2 NPs

photocatalytic activity has been considered.

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2. The mechanism of TiO2 NPs action

Before describing the beneficial effects provided by TiO2 NPs deposited on

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textile materials, I find useful briefly to explain how these NPs actually act. The size,
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shape, crystalline structure and specific surface area determine the chemical, optical,

and electrical properties as well as photocatalytic activity of TiO2 NPs [37]. These
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characteristics mainly depend on the method applied for their synthesis [38-39].

Although three common crystalline structures of TiO2 (anatase, rutile and brookite) are

well described in literature, the major practical work has been accomplished with

anatase and rutile [8]. It is reported that anatase is the most stable phase for NPs with

sizes bellow 11 nm whereas rutile is the most stable in the NPs with sizes above 35 nm

[40]. Anatase is generally considered as a more active photocatlyst compared to rutile

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Page 4 of 63
[41]. This is due to lower surface affinity of rutile to many organic compounds as well

as to higher rates of recombination of electron/hole pairs [42-43]. However, there are

several reports which state that certain mixtures of anatase (70-75%) and rutile (30-

25%) are more efficient photocatalysts than anatase alone [44-46]. Widely used

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commercial Degussa P25 TiO2 NPs, in addition to anatase and rutile mixed in

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approximate proportion of 80/20, contain some amount of amorphous TiO2 [38]. Such

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formulation is shown to be more efficient than pure anatase or rutile phases likely

because of the efficient charge separation arising from the presence of multiphase

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particles i.e. lower recombination rates, high surface areas and high adsorption affinity

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to organic compounds [38, 41]. Therefore, such formulations are extensively used in

many different products including textile materials.

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Unlike metals which possess a continuum of electronic states, TiO2 as a

semiconductor has a band structure. Such structure is characterized by the existence of

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energy gap that extends from the top of the occupied valence band to the bottom of the
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unoccupied conduction band [35, 47]. The exposure of TiO2 NP to UV light with an

energy that matches or exceeds its band gap energy (E(anatase) ≥3.2 eV; E(rutile) ≥3.0
p

eV) leads to an excitation of electron from valence band into conduction band while the
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positive hole is left behind (Fig. 1) [8, 35, 46]. Photogenerated charge carriers can be

exploited in different processes at the particle surface. In fact, photogenerated electrons

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and holes migrate to the particle surface inducing the charge transfer to adsorbed

molecules (organic or inorganic, solution). Namely, TiO2 NP surface may donate

electrons reducing an electron acceptor [47]. In contrast, positive holes may accept

electrons from donors oxidizing them. However, the most of the excited electrons and

holes immediately recombine in the bulk or at the surface of the particle dissipating the

heat [46-47]. Hence, in order to obtain efficient charge transfer at the particle surface,

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Page 5 of 63
recombination has to be suppressed. Some of electrons and holes on their way to the

particle surface get trapped at the surface or bulk trapping sites. The charges trapped at

the TiO2 NPs surface react with electron acceptors or donors adsorbed at the particle

surface. In fact, the electrons that reach the conduction band can be trapped at NP

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surface if any defect site exists or they can shortly live as free electrons until they react

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with electron-acceptors that are strongly associated with a particle surface or O2. The

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reactions between free conduction electrons, trapped electrons at the particle surface or

valence band positive holes and surrounding molecules, in particular H2O and O2, result

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in generation of extremely reactive species (OH., O2.-, 1O2, etc) that are initiators of

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photocatalytic processes [8, 35, 44]. Any defect in crystalline lattice negatively affects

the photocatalytic processes favoring the charge recombination. Therefore unlike

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anatase and rutile, amorphous TiO2 NPs exhibit very poor photocatalytic activity. To

conclude, efficient photocatalytic process can only be accomplished if oxidation and

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reduction processes win over the competition with recombination of charge carriers
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[38].
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2.1. Self-cleaning action of TiO2 NPs

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The capability of TiO2 NPs to degrade surrounding molecules under UV light

was exploited for imparting self-cleaning properties to textile materials. The mechanism
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of photocatalytic degradation by TiO2 NPs immobilized on textile materials was

examined on coffee, wine, juice and make-up stains. Bozzi et al. proposed the

mechanism of degradation of pigments originating from coffee and wine [48-49]. When

the stain gets illuminated with visible light, the excited electron from organic molecule

of stain is injected into conduction band of TiO2 NPs. Consequently, unstable pigment

cation is formed, which further decomposes to CO2 (Fig.1.). On the other hand, the

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Page 6 of 63
electrons from the conduction band of TiO2 NPs reduce oxygen generating very reactive

superoxide radicals (eq. 1) which along with the other extreme reactive radicals (HO2.-,

OH., RO., RO2.) degrade the stain. In addition, excited pigment of the organic

compound (R.) could be directly degraded by photo-induced holes (hVB+) (eq. 2 and 3).

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
eCB  O2( ads )  O2 (1)

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
R *  hVB  R  → degradation products (2)

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
RCOO   hVB  R   CO2 (3)

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Grease stain which absorbs the irradiation <290 nm degrades in different way

[49-50]. In this case, TiO2 NPs absorb the incoming UV light and peroxides as well as

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highly oxidative radicals HO2.-, OH., RO. and RO2. are capable to decompose the grease

stain (Fig. 1).

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2.2. Bactericidal action of TiO2 NPs

Photogenerated reactive species are shown to be detrimental for various

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microorganisms (bacteria, fungi, algea, viruses, etc.) [51]. Hence, this can be utilized for
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imparting antibacterial properties to textile materials. The exact mechanism of

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bactericidal activity of TiO2 NPs has not been established yet.

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Early work of Matsuga et al. revealed that coenzyme A (intracellular enzyme)

mediates an electron transfer between the bacteria cells and semiconductor [52]. It was
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assumed that photogenerated hole receives an electron from coenzyme as an electron

donor, inducing the formation of dimeric coenzyme A. Oxidation of coenzyme A leads

to a decrease in respiratory action and consequently to bacteria cell death.

Saito et al. investigated bactericidal photocatalytic action of powdered TiO2 on

bacteria Streptoccocus sobrinus AHT [53]. They suggested that rapid leakage of

potassium ions runs simultaneously with decrease in bacteria viability. In addition,

bacterial cells slowly release proteins and RNA. TEM analysis of bacteria revealed that

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Page 7 of 63
complete destruction of bacteria cells occurred after 1-2 hours of photocatalytic action

of TiO2, indicating that cell death resulted as a consequence of disorders in cell

membrane and further decomposition of cell wall.

Sunada et al. discovered that TiO2 exposed to UV irradiation, not only causes the

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bacteria cell death but also degradation of endotoxin i.e. lipopolysaccharide cell wall

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constituent of Gram-negative bacterium E. coli [54]. It was shown that destruction of

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lipid A layer of endotoxin leads to its inactivation in the presence of TiO2 illuminated

with UV light. Such decomposition implies that TiO2 as a photocatalyst destroys outer

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membrane of the E. coli cell. Later work of these authors confirmed these conclusions

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[55]. They proposed the mechanism of killing the bacteria E. coli by TiO2 film. For

better understanding of suggested mechanism, it is worth emphasizing that cell

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envelope of E. coli consists of outer membrane, peptidoglycan monolayer and

cytoplasmic membrane. Outer membrane together with peptidoglycan layer ensures

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mechanical protection necessary to keep the cell morphology intact [56]. Initially,
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photogenerated reactive radicals slowly react with outer membrane causing its partial

decomposition (Fig. 2). During this initial period of photocatalytic action of TiO2, the
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release of lipopolysaccharides as one of the major components of outer membrane

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occurs. Longer times are needed for changes in peptidoglycan layer. These changes in

outer membrane result in increase of its permeability enabling the reactive species to
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reach the cytoplasmic membrane. The attack of cytoplasmic membrane by reactive

species is followed by peroxidation of membrane lipids, leading to a loss of cell

viability and eventually to cell death.

The peroxidation of membrane lipids using Degussa P25 TiO2 NPs in the

presence of UV light was also studied by Maness et al. [57]. The formation of

malondialdehyde (MDA) was used as a measure of the lipid peroxidation. The lipid

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Page 8 of 63
peroxidation of polyunsaturated phospholipids in E. coli resulted from oxidative actions

exerted by TiO2 NPs. It was suggested that reactive oxygen species (OH., O2-, H2O2)

photogenerated on the TiO2 NPs surface attack the polyunsaturated phospholipids

causing the breakdown of cell membrane and failure of vital functions such as

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respiratory activity.

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Kiwi and Nadtochenko used ATR-FTIR spectroscopy for investigation of E. coli

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cell, lipopolysaccharides, phosphatidyl-ethanolcholine and peptidoglycan peroxidation

by porous film containing Degussa P25 TiO2 NPS [56]. The decay of the

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polysaccharide bands, acyl bands, >CH2 bands, -CH3 bands, and amide bands as well as

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the quick disappearance of oligosaccharide bands of E. coli and lipopolysaccharide

bilayer have been observed along with the formation of peroxidation products
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(aldehydes, ketones and carboxylic acids) [56, 58]. It is interesting to note that the rate

of peroxidation of lipopolysaccharides of E. coli and the lipopolysaccharide sample

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deposited on porous TiO2 membrane was not the same. Although in both cases the
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disorder in lipid layer of lipopolysaccharide occurred during the photocatalysis, this

peroxidation was much more prominent on the lipopolysaccharide deposited on porous

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TiO2 membrane. This implies that the order of the lipopolysaccharide bilayer structure
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in E. coli highly influences the rate of photocatalytic peroxidation process. This study

also proved that peptidoglycane layer was the most resistant to photocatalytic
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peroxidation. These authors also tried to answer the question whether photogenerated

charge carriers directly react with E. coli and lipopolysaccharides or they produce

reactive species (OH., HO2., O2-.radicals) which further react with bacteria cells. Laser

photolysis experiments pointed out that positive holes trapped on the TiO2 surface are

scavenged by E. coli and lipopolysaccharides. Namely, it is suggested that E. coli and

lipopolysaccharides compete in the scavenging of holes with the recombination of holes

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Page 9 of 63
with photogenerated electrons within time intervals > 50 ns. Scavenging of holes by

organic matter results in the formation of organic radicals (R.) and this process is

regarded as an initial stage in the radical chain oxidation processes in the cell

membrane.

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Lu et al. evaluated the morphological changes of the E. coli cell caused by

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photocatalytic action of illuminated TiO2 thin film directly by AFM [59]. AFM analysis

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clearly showed that prolongation of illumination time brought about significant surface

structure changes which after 60 min long illumination ended in the complete

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transformation of the bacterium shape from rod-like to ellipse-like. Observed changes

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undoubtedly reflect the cell wall decomposition stages and cell membrane destruction.

As expected, increase in permeability of the bacteria cells along with the leakage of
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intracellular molecules led to a cell death. Elliptical shape of E. coli after the exposure

to TiO2 and UV light was also observed by SEM [60].

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Recent findings indicated that TiO2 NPs induce considerable oxidative stress
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causing the DNA damage and E. coli cell death [61]. This group of authors assumed

that generated OH., H2O2 and O2- reactive species are responsible for the oxidation of
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polyunsaturated phospholipids. Further peroxidation of lipids induces DNA damage and

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disruption of cell membrane morphology as well as the electron transport chain.

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4.3. UV blocking function of TiO2 NPs

The ability of TiO2 NPs to act as an UV blocker is particularly important for

textile industry since the requirements for UV protective garments are rapidly growing

due to excessive UV irradiation caused by depletion of ozone layer. There are several

approaches for understanding the UV blocking mechanism of TiO2 NPs. Although one

of the approaches relies on an assumption that TiO2 possess the ability to refract and/or

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scatter the most of the incoming UV rays through high refractive index, it is widely

accepted that absorption of UV light by TiO2 NPs provide desirable protection [62].

Numerous studies, as will be described in more detail later, demonstrated that

TiO2 NPs immobilized onto textile materials provide desirable level of UV protection.

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The UV blocking efficiency of garments is judged by UV protection factor (UPF) [63].

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It has been originally established by Australian/New Zealand standard AS/NZS 4399

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[64]. In the meantime many other related standards became available [65-68]. The UPF

is determined by measuring the direct and diffuse transmission of a fabric across the

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wavelength range 290-400 nm which include UVB (290-315 nm) and UVA (315-380

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nm) regions. The UPF is calculated in accordance with the following equation [69]:
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400

 E S dλ λ λ

UPF  290
400
(4)
 E S T dλ
d
λ λ λ
290
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where:  - the wavelength (nm), E - relative erythemal effectiveness, S - solar UV

spectral irradiance (W·m-2·nm-1), T - spectral transmittance of the fabric, and d - the
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wavelength increment (nm).

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Although UPF value gives an accurate data on UV protection of clothing, single

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measured number is rarely used for expression of the UV protection efficiency of

textiles. Instead, tested fabrics are classified into three categories that are presented in

Table 1 [64]. UPF rating 50+ denotes maximum UV protection. In order to make the

meaning of UPF clearer, let’s explain what for instance UPF rating of 50 means. It

indicates that only 1/50 of the UV radiation falling onto the fabric surface passes

through it and reaches the skin. In other words, 98 % of UV radiation is blocked.

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Page 11 of 63
Therefore, the higher the UPF value the better the UV protection. It is recommended

that garments should provide at least UPF rating of 40 to 50+ [70].

3. The application of TiO2 NPs to textile materials

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The impregnation of textile materials with TiO2 NPs is typically conducted by

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dip-coating method. After being immersed in TiO2 NPs colloid or suspension for certain

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time, the fabrics are padded, dried and cured. Afterwards, they are usually rinsed with

water and dried. This procedure is described here in rough outline. Although the times

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of immersion in the colloid, padding pressures, temperatures and times of drying and

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curing as well as rinsing methodologies vary from author to author, the methods of

coating are principally the same.

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TiO2 NPs are applied to different sorts of textile fibers so far with much success.

The following chapters will show that more attention has been paid on effects that can
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be imparted to textile materials than on mechanism of interaction between TiO2 NPs

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and different fibers. The most of the studies relay on the known fact that carboxylic

group is the best anchoring group for TiO2 and this is the reason why it was insisted on
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introduction of new carboxyl groups to different fibers. It is well known that Ti atoms
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can be bound to carboxyl groups through different modes which are shown in Fig. 3

[71-72]. Carboxyl groups can be bound in a monodentate mode to form an ester-like

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linkage or they can bind with each of their two oxygen atoms either to one Ti atom

(bidentate chelating) or to two of them (bidentate bridging). In addition, they can

interact with the TiO2 surface through hydrogen bonding either with a surface-bound

hydroxyl group and/or a lattice oxygen atom [72].

3.1. Cotton

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Page 12 of 63
 The major research so far on the application of TiO2 NPs to textile materials has

been performed on cotton (Co) fabrics. Significant contribution to this field has been

given by Daoud et al. [70, 73-78]. The sol-gel method at room temperature has been

used for the synthesis of TiO2 NPs employing titanium tetraisopropoxide as a precursor.

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SEM analysis applied for the characterization of Co fibers morphology revealed the

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existence of uniform continuous layer of nearly spherical TiO2 NPs with an average size

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of about 20 nm (Fig. 4) [73]. XRD analysis indicated that the coating was

predominantly amorphous with a small content of anatase crystallities. This implies that

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nucleation of anatase crystallities may have occurred during the sol preparation [74].

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However, the sharper peaks associated with anatase form in the XRD pattern and

Raman spectrum appeared after hydrothermal treatment of samples [74].

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TiO2 NPs provided maximum UPF rating of 50+ to Co fabrics since the

complete UV blocking from 332-280 nm has been obtained. Such a high UPF rating
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illustrates the remarkable contribution of TiO2 NPs to UV protective properties taking

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into account that the untreated Co fabric is classified as a nonratable (UPF rating 10)

[72]. Despite a slight increase in UV transmission, maximum UPF rating was preserved
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even after 20 to 55 home launderings indicating the excellent wash fastness which is
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one of the major requirements for textile materials (Fig. 5) [70,-73, 75]. This is

suggested to be due to the formation of covalent bonding resulting from a dehydration

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reaction between the hydroxyl groups of TiO2 and hydroxyl groups of cotton [73, 75].

They also reported that Co fabrics coated with TiO2 NPs exhibited bactericidal

properties against Gram-negative bacteria K. pneumoniae and Gram-positive bacteria S.

aureus [73, 75]. In addition, bursting strength of fabrics was slightly enhanced in the

presence of TiO2 NPs [70].

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Page 13 of 63
 The same group of authors explored the influence of temperature of sol

preparation (25oC (S25), 40oC (S40), 60oC (S60)) on TiO2 NPs structure and their

activity on Co fabrics [76]. XRD analysis revealed that the S25 was predominantly

amorphous while the S40 and S60 had peaks corresponding to anatase crystallities. As

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expected, S60 showed the strongest photocatalytic activity because of the highest

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crystallinity. The Co fabrics impregnated with TiO2 NPs and illuminated with UV lamp

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provided discoloration of Neolan Blue 2G and Cibacron Blue F-R dye solutions. The

decrease in dye concentration with illumination time was the most pronounced in the

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case of S60 due to highest photocatalytic activity. Self-cleaning properties of TiO2 NPs

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(S60) deposited on Co fabrics were assessed on coffee and red wine stains. Stained Co

fabrics were illuminated with the light that simulates the solar light. Unlike untreated
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fabrics, the fabrics containing TiO2 NPs were completely decolorized after 20 h of

illumination. In fact, the side of the fabric exposed to light was decolorized already after
d

8 h, but for cleaning of the back side more time was required. It is interesting to observe
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that antibacterial activity against S. aureus was the most prominent on the Co fabric

treated with S25. Such behavior was attributed to the largest surface area of S25 coating
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arising from its smallest NPs size.

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Latest studies of this group gave better insight into mechanical properties of Co

fabrics treated with TiO2 NPs [78]. It was shown that bending rigidity increased by 13%
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after impregnation with TiO2 NPs indicating that Co fabrics after treatment with TiO2

NPs became slightly stiffer. In contrast, air permeability was not altered. Tensile and

tearing strength as well as TiO2 NPs photocatalytic decomposition of Co fibers were

evaluated under light irradiation in Xenotest Alpha LM light exposure and weathering

test instrument. According to results related to tearing and tensile strength of Co fabrics

modified with TiO2 NPs (slight decrease compared to untreated sample), it was

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Page 14 of 63
concluded that photocatalytic decomposition of the cellulosic chains was limited within

20 h of irradiation.

Another group of pioneers in this field led by Kiwi made efforts to enhance the

binding efficiency of TiO2 NPs to Co fibers [79-83]. Their research was primarily

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oriented towards self-cleaning properties of Co fabrics. In their early work, they

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proposed the application of succinic acid, 1, 2, 3-propanetricarboxylic acid and 1, 2, 3,

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4-butanetetracarboxylic acid as chemical spacers which can be bound to both TiO2 and

Co fiber [79]. Thus, spacers should have at least two carboxylic groups. Ester bond was

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established between one carboxylic group of spacer and hydroxyl group of cellulose as

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proved by ATR-IR spectroscopy. Other carboxylic groups of spacer could anchor TiO2

by electrostatic interaction [84]. The proposed simplified mechanism of binding of

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spacers to cellulose and TiO2 NPs is shown in Fig. 6 [79]. The results indicated that the

amount of spacer bound to the fiber increased with elevation of curing temperature.
d

Self-cleaning properties of Co fabrics modified with Degussa P25 TiO2 NPs were
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evaluated by measuring the volume of released CO2. Namely, the release of CO2 is

proportional to the oxidative decomposition of organic stains. Wine, coffee, make-up

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and perspiration stains on Co fabrics were irradiated for 24 h by a Sunset solar light
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simulator and the release of CO2 during this time interval was quantified by gas

chromatography. The fabrics exhibited excellent self-cleaning properties. Unlike coffee

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and wine stains, make-up stains were the most difficult to clean likely because of the

presence of inorganic dyes in the make-up which could not be photocatalyticaly

degraded. However, the release of CO2 was not proportional to the amount of deposited

TiO2 NPs likely due to non-homogeneity in the distribution of TiO2 NPs agglomerates

on Co fabric. The samples modified only with TiO2 NPs without the use of spacers did

not provide almost any discoloration of coffee and wine stains.

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Page 15 of 63
 Bozzi et al. modified Co and mercerized Co samples by RF-plasma, MW-plasma

and UV-irradiation prior to deposition of Degussa P25 NPs and TiO2 NPs synthesized

employing the different precursors [80]. It was shown that discoloration of wine and

coffee stains was the most efficient on Co fabrics which were exposed to RF-plasma

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before loading of TiO2 NPs synthesized by acidic hydrolysis of TiCl4. On the other

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hand, the highest degree of stains discoloration on mercerized Co sample was achieved

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after activation of sample by MW-plasma and deposition of TiO2 NPs from colloid

solution based on the titanium tetra-isopropoxide as a precursor.

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Further research proved that both air RF-plasma and UVC–light (185 nm) pre-

an
treatments of Co fabrics positively affect the loading of TiO2 NPs from 3 g/L Degussa

P25 suspension [82-83]. XPS analysis revealed that detected signal corresponding to Co
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fiber was attenuated after the TiO2 NPs deposition, indicating that Co fabric was evenly

covered with thin layer of TiO2 NPs [82]. XPS analysis of Co fabrics modified with
d

TiO2 NPs and stained with red wine makes these articles particularly interesting (Fig. 7
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[82]). It was shown that a drop of wine considerably changed the XPS spectra of

functionalized Co fabrics. Wine drop formed 30-40 nm thick layer which attenuated the
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signal of the Ti2p peak. Irradiation of stained samples with Suntest light brought about
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the degradation of wine and the Ti2p peak grew continually with an increase of

irradiation time. In addition, Ti2p3/2 peak was shifted from binding energy of 458.91 eV
Ac

at the beginning to 458.65 eV after 24 h long irradiation. This small shift implied that

discoloration included redox catalysis involving two oxidation states Ti4+/Ti3+.

Fei et al. reported that the share of rutile nanorods dispersed in granular anatase

and brookite phases increased with prolongation of peptization time [85]. Such peptized

colloid applied to Co fabrics ensured satisfactory antibacterial activity against Gram-

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Page 16 of 63
positive bacteria S. areus. UPF value increased from 12 to 200 confirming that TiO2

NPs provided maximum UV protection.

Liuxue et al. applied microwave assisted liquid phase deposition method for the

synthesis of TiO2 NPs [86]. TiO2 NPs in anatase crystalline form have been synthesized

t
by microwave irradiation of mixed solution of (NH4)2TiF6 and H3BO3. The inclusion of

ip
microwaves facilitated the hydrolysis of (NH4)2TiF6. TiO2 NPs film imparted UV

cr
protective and photocatalytic properties to Co fibers. Oppositely to the other literature

sources, the decrease in transmission was not that significant and no cut off appeared

us
neither in UV-A nor in UV-B region. However, photocatalytic activity of TiO2 NPs was

an
more prominent as already after 3 h of UV irradiation, complete discoloration of 20

mg/L methylene blue solution was achieved. The photocatalytic activity of such
M
nanocomposite system lost approximately 10 % of its initial efficiency after five

repeated photodegradation cycles.

d

Comprehensive characterization of Co fibers loaded with TiO2 NPs synthesized

te

by sol-gel method has been reported by Uddin et al. [87]. The aim of their study was to

develop simple method for synthesis of colloidal solution of TiO2 NPs that would be
p

sufficiently stable for longer times, allowing its practical application in industrial
ce

conditions. Titanium isopropoxide was used as a precursor. TiO2 NPs were stabilized by

triethyl amine. SEM analysis revealed that Co fibers were covered with continuous and
Ac

homogeneous thin film comprising of TiO2 NPs. HRTEM analysis of scratched thin

film surface proved that it consisted of uniformly sized TiO2 NPs (3-5 nm). The authors

expected that grafting mechanism involved esterfication of alcoholic groups located on

the external surface of the Co fibers and they used FTIR spectroscopy to check these

assumptions. All detected groups were located inside the fibers. Because of the fiber

diameter (~10 m) the contribution of external alcoholic groups that are supposed to

17
Page 17 of 63
take part in anchoring of TiO2 NPs and thus, to be consumed by the grafting process,

was negligible. In fact, the spectrum of Co fibers grafted with TiO2 NPs was unaltered

compared to pure Co fiber, indicating that FTIR spectroscopy is not informative method

in this case. In other words, the signal of Co fiber dominates in the spectrum of

t
modified fiber while the TiO2 phase is negligible. Unlike FTIR analysis, Raman

ip
spectroscopy measurements confirmed the presence of TiO2 NPs on the surface of Co

cr
fibers in anatase form. The existence of anatase crystallites on the Co fibers was also

confirmed by XRD analysis. On the basis of these results, an average particle diameter

us
of about 5 nm has been calculated. This result is in an excellent correlation with SEM,

an
HRTEM, UV-VIS and Raman spectroscopy results. In addition, TGA analysis showed

that residual amount of 13.5% left after the combustion of organic part corresponds to
M
TiO2. The practical potential of developed system was evaluated by following the

photodegradation of dye methylene blue and bitumen fraction extracted with heptane
d

under artificial solar irradiation. Extraordinary photocatalytic activity of deposited TiO2

te

NPs was preserved after three cycles of irradiation (Fig. 8).

TiO2 NPs synthesized by hydrolysis and condensation of tetrabutyl titanate in

p

water seem to be also a viable solution for the application to Co fabrics [88]. TEM and
ce

XRD analyses revealed the presence of uniformly sized TiO2 NPs with dimensions

between 3-5 nm. Again, XRD pattern contained the peaks that were assigned to anatase
Ac

form of TiO2. However, a weak peak at 230.66osuggested the presence of small

amount of brookite. ATR-IR analysis demonstrated the decrease in the content of

hydroxyl groups on the surface of Co fibers after the deposition of TiO2 NPs. They

assumed that observed changes in ATR spectra could be attributed to high affinity of

TiO2 towards hydroxyl groups and anchoring of TiO2 NPs exactly to these sites. It was

also shown that spectrum of Co fiber loaded with TiO2 NPs remained unchanged after

18
Page 18 of 63
UV irradiation and photocatalytic reactions. This time, photochatalytic activity of TiO2

NPs was tested on dye methylene orange. Excellent photocatalytic activity of TiO2 NPs

was not significantly altered after washing (the number of washing cycles was not

defined).

t
As could be noticed, commonly different dyes have been used as test compounds

ip
for the evaluation of photocatalytic activity of TiO2 NPs deposited on Co fabrics.

cr
Therefore, it is worth mentioning the work of Dong et al. who pointed out that Co

fabrics modified with Degussa P25 TiO2 NPs can efficiently degrade ammonia in the air

us
under UV irradiation [89].

an
A group led by Montazer published several papers dealing with effect of TiO2

NPs on differently Co fabrics properties [90-94]. Their major work was focused on the
M
application of TiO2 NPs stabilized by polycarboxylic acids in the presence of sodium

hypophosphite under different curing conditions (UV irradiation, heating, etc). They
d

also examined the possibility of treatment of Co fabric with sodium hypophosphite,

te

maleic acid, triethanol amine and TiO2 NPs for gaining flame retardancy and self-

cleaning properties. Thorough discussion on all their results would require more space.
p

Since rare data on the effect of TiO2 NPs on creasing could be found in literature, paper
ce

discussing this issue was selected to be presented in current review. In order to finish

bleached Co fabric against creasing, Nazari et al. used polycarboxylic acids BTCA or
Ac

CA as cross-linking agents in the presence of Degussa P25 TiO2 and sodium

hypophosphite [90]. Treated samples were exposed to UVA irradiation or heated at high

temperatures (150-180oC). Combined post-treatments have been also conducted.

Exactly the combination of UVA irradiation and heating resulted in the most efficient

cross-linking. Co fabrics treated with BTCA had higher values of dry crease recovery

angle compared to Co fabrics treated with CA under the same conditions. It was

19
Page 19 of 63
suggested that this could be due to one more carboxylic group existing in BTCA. In

addition, the increase in TiO2 load let to an increase of dry crease recovery angle.

However, at concentrations higher than 2.6%, the decrease of dry crease recovery angle

occurred.

t
More extensive research on mechanical properties and wrinkle recovery of Co

ip
fabrics treated by RF-plasma at atmospheric pressure and commercial TiO2 NPs has

cr
been done by Lam et al. [95]. Kawabata Evaluation System for Fabrics was employed

for this research. It was shown that modification with TiO2 NPs negatively affected

us
tensile properties, compression properties and surface friction. In contrast, it resulted in

an
improvement of shearing and bending properties.

Mihailović et al. employed different forms of plasma for the activation of Co

M
fabrics prior to deposition of colloidal TiO2 NPs synthesized by acid hydrolysis of TiCl4

[96]. Corona discharge treatment at atmospheric pressure and air RF-plasma treatment
d

at low pressure were performed in order to enhance the binding efficiency between Co
te

fibers and TiO2 NPs. XPS analysis indicated that corona/plasma treatments as well as

subsequent TiO2 NPs deposition caused the decrease in the content of C-OH, C-O-C
p

and O-C-O groups on the substrate. The presence of Ti2p1/2 and Ti2p3/2 spin-orbital
ce

splitting electrons located at 464.2 and 458.5 eV as well as deconvoluted O1s spectra

proved the presence of TiO2 NPs. TiO2 mapping indicated that unlike RF-plasma treated
Ac

Co fabric modified with TiO2 NPs, Co fabrics modified with TiO2 NPs and corona

treated Co fabrics modified with TiO2 NPs were uniformly covered with NPs (Fig. 9).

This difference was attributed to distinguished morphological changes induced by

corona/plasma treatments which were confirmed by SEM analysis. AAS measurements

showed that both corona and RF-plasma pretreatments led to an equal increase (by

31%) of deposited amount of TiO2 NPs. Co fabrics without any activation had to be

20
Page 20 of 63
double loaded with TiO2 NPs to achieve equivalent antibacterial effect against E. coli.

Corona/RF-plasma treated samples only once loaded with TiO2 NPs ensured maximum

bacteria reduction which remained unchanged after five washing cycles. Similarly,

maximum UV-protection was preserved after repetitive washing. Such nanocomposites

t
also provided extraordinary self-cleaning properties that were evaluated on blueberry

ip
juice stains. Finally, deposited TiO2 NPs exhibited excellent photocatalytic properties

cr
enabling complete discoloration of methylene blue solutions under UV illumination.

Layer-by-layer deposition of TiO2 has been also proposed as a promising

us
method for imparting UV-protective properties to Co fabric [97]. Namely, layers of

an
different anionic polymers with TiO2 NPs were deposited onto previously cationized Co

fabrics providing satisfactory UV protective properties. It was concluded that the higher
M
the number of layers the larger the UV protection.

One of the essential features of UV-blockers is to shield the skin from UV

d

irradiation, but also it should not initiate the degradation of textile material or skin.
te

Taking into account excellent photocatalytic activity of TiO2 NPs that are deposited

onto Co fabrics as well as their possible harmful effect to Co fabric and skin, Chen et al.
p

proposed the mechanism how to lower the photoactivity of TiO2 NPs by capturing of
ce

OH· and O2·- using the carboxymethyl chitosan (CMCH) [98]. Prepared mixture of TiO2

NPs and CMCH was applied to Co fabric by dip-pad-dry-cure process. Generated

Ac

nanocomposite system consisting of a core of TiO2 and a shell of CMCH, lowered the

photocatalytic activity of TiO2 NPs. On the other hand, antibacterial and UV-protective

properties were not considerably changed compared to the Co fabric that was only

treated with TiO2 NPs.

It was reported that application of SiO2/TiO2 colloid coating to Co fabrics

provides excellent photocatalytic performance, while maintaining Co fiber intrinsic

21
Page 21 of 63
property [81]. Namely, SiO2 was chosen as a binder since it cannot be decomposed due

to the strong action of TiO2 NPs. The nanocomposite SiO2/TiO2 layer protects Co fibers

from the attack of positive holes generated by the TiO2 NPs under sunlight irradiation.

However, it is important to emphasize that SiO2 NPs layers should cover the textile

t
material before the topmost layer of TiO2 NPs. Such nanocomposite systems exhibited

ip
better self-cleaning properties tested on red wine stains compared to the samples that

cr
were only coated with TiO2 NPs. IR spectroscopy analysis indicated that no

modification of the Co could be detected after photo-discoloration process with

us
SiO2/TiO2 NPs.

an
M
3.2. Wool
d

As already mentioned, Montazer and Pakdel recently published review paper

te

dealing with wool/TiO2 nanocomposites and hence, less attention will be paid to this

issue here despite its importance [36]. Undoubtedly, the greatest contribution in this
p

field has been given by two separate groups led by Daoud [99-102] and Montazer [103-
ce

108]. In spite of their unique chemical structure and properties (excellent insulating

ability, biodegradability, durability etc), wool fibers are difficult for maintenance and
Ac

care because of low thermal and chemical resistance, poor photostability under UV light

and weak resistance to microorganisms [102]. Some of these problems can be

efficiently overcome by modification with TiO2 NPs.

Tung et al. investigated the influence of precursor (titanium tetraisopropoxide)

concentration in the coating formulation on self-cleaning, UV-protective and

mechanical properties of wool fabric [102]. Peaks in the XRD pattern corresponding to

22
Page 22 of 63
anatase form of TiO2 synthesized by sol-gel method have been found independently on

the concentration of the colloids. Broader particle distribution has been found in more

concentrated colloids. XRD analysis indicated that average size of TiO2 NPs was

around 4 nm independently of concentration. Therefore, it was suggested that

t
concentration did not affect the size of single unit cell of TiO2 nanocrystallite, but it

ip
strongly influenced the tendency of NPs to aggregate. Although wool fibers modified

cr
with higher concentrated colloids exhibited stronger photacatalytic activity (self-

cleaning effect on coffee and red wine stains, discoloration of methylene blue solution),

us
UV-protection, tensile strength and air permeability, concentrations of colloid over 15%

an
should be avoided as their application caused deterioration of tearing strength. This was

in accordance with SEM images which revealed existence of severe peel-off effect on
M
wool fibers. This research clearly show that processing conditions should be strictly

controlled in order to obtain desired UV-protective and self-cleaning properties without

d

deterioration of fiber stability and its mechanical properties.

te

Keeping in mind that TiO2 is predominantly bound to carboxylic and hydroxyl

groups, this group of authors proposed to coat the wool fibers with succinic anhydride
p

and in such a way introduce new carboxylic groups by acylation [99]. Hence, the
ce

binding efficiency of TiO2 NPs can be enhanced. An intention to detect the coordination

between oxygen atoms of carboxylic groups and titanium atom by ATR-IR technique
Ac

was not successful due to overlapping with bands corresponding to other functional

groups of the fibers. However, XPS analysis demonstrated that Ti content increased by

70% on succinylated wool fibers (Table 2). In addition, uniform distribution of TiO2

NPs was observed by SEM. Self-cleaning properties evaluated on red wine stain were

satisfactory (Fig. 10). The contribution of introduction of additional carboxylic groups

to wool fibers was particularly prominent during the discoloration of methylene blue

23
Page 23 of 63
solution under UV light as this sample provided faster degradation rate compared to one

that was only treated by TiO2 NPs by 33%.

Montazer and colleagues based their work on the application of TiO2 NPs

stabilized with polycarboxylic acids CA and BTCA in the presence of sodium

t
hypophosphite to wool fibers. They thoroughly analyzed the influence of formulation

ip
composition on different wool properties. Particular attention has been paid on decrease

cr
of problematic photo-yellowing of wool under UV light due to TiO2 NPs ability to

absorb UV light [103]. As expected, higher amounts of deposited TiO2 NPs positively

us
influenced the retardation of photo-yellowing. KMnO4 was often used in their work for

an
the wool surface oxidation which provided generation of additional carboxylic groups

valuable for better binding of TiO2 NPs. The presence of larger amounts of TiO2 NPs
M
induced by oxidation of wool fibers brought better antifelting and antibacterial

properties [108]. Particularly important finding was that alkali solubility of wool as an
d

indicator of fiber damage decreased in the presence of TiO2 NPs and BTCA in the
te

impregnation bath [106]. In contrast, hydrophilicity of naturally hydrophobic wool fiber

dramatically increased and hence, water absorption time decreased.

p
ce

3.3. Synthetic fibers

The application of TiO2 NPs to synthetic fibers was the most extensively studied
Ac

on polyester (PET) and polyamide (PA) fibers. PA and particularly PET fibers are

hydrophobic in nature. Poor wetting properties highly affect their processability i.e.

dyeing and finishing are more difficult. Many efforts have been made to modify the

surface of synthetic fibers with an aim to introduce new carboxylic and hydroxyl groups

to fiber surface in order to enhance the binding efficiency of TiO2 NPs. Several

chemical and physico-chemical methods are proposed for the functionalization of PA

24
Page 24 of 63
and PET fibers so far. Treatment of fabrics with various forms of plasma seem to be a

viable method for the superficial modification of fibers as it is confined to a thin layer

on the fiber surface, leaving the bulk properties unaltered. In addition to chemical

changes, plasma treatment causes morphological changes, resulting in increased active

t
surface area and roughness. Topographical changes are favorable for deposition of TiO2

ip
NPs. For this purpose plasmas operating at low pressures and atmospheric pressure have

cr
been employed.

Self-cleaning properties of wool/PA blends and PET fabrics activated by RF-

us
and MW-plasma prior to application of suspensions of TiO2 Degussa P25 and/or

an
differently prepared colloidal solutions of TiO2 NPs were evaluated by measuring the

volume of generated CO2 during the mineralization of organic matter as described in

M
section 3.1 [109]. Coffee and red wine stains were successfully decomposed in all cases,

but the most efficient self-cleaning effect was obtained on the sample with basic layer
d

consisted of hydrothermally treated colloidal TiO2 NPs and second coating of TiO2
te

Degussa P25 NPs. This was likely due to small colloidal TiO2 NPs deposited on

substrates, which provided sites for better anchoring of bigger TiO2 Degussa P25
p

crystallites. It was also evident that blend exhibited better self-cleaning properties in
ce

comparison with PET fabrics as well as that wine stains were more easily removed than

coffee stains. Although TiO2 NPs could be observed on the fiber surfaces after dry-
Ac

cleaning of samples, the rate of photodegradation decreased due to organic and

chloride-ions residues originating from perchloroethylene used for dry-cleaning.

Mejía et al. modified PA fabrics by RF-plasma at atmospheric pressure and

UVC light (185 nm) in air before the deposition of colloidal TiO2 NPs with dimensions

ranging from 8-20 nm [111]. RF-plasma treatment was not conventionally conducted in

vacuum, but at atmospheric pressure and low power (100 W) resulting in the heating of

25
Page 25 of 63
PA and breaking of intermolecular bonds (hydrogen bonds) as well as partial

segmenting of textile fibers. Consequently, new C-O, -COO and –O-O- anionic groups

were generated. Namely, TiO2 NPs are bound to the PA fibers by electrostatic

attraction/chelation between slightly positive Ti4+ of TiO2 and –COO and –O-O- groups

t
of PA and via N-H bonds, amine/amide groups generated by local heating of PA. In

ip
contrast, UVC activation, possessing lower energy compared to RF-plasma, initiated

cr
formation only of atomic and excited oxygen species. The absence of other anionic and

cationic oxygen species caused more even distribution of activated sites on PA,

us
resulting in more uniform deposition of TiO2 NPs on the fabric. Both treatments

an
significantly enhanced the deposition of TiO2 NPs, implying that desired

functionalization can be reached in the absence of vacuum. Self-cleaning properties

M
were evaluated as in previous papers. The most superior self-cleaning effect appeared

on the sample that was pretreated by UVC for 10 min before loading of TiO2 NPs.
d

Qi et al. employed oxygen glow discharge at low pressure for the

te

functionalization of PET fabric before loading of TiO2 NPs synthesized using the

titanium tetraisopropoxide as a precursor [112]. As could be predicted, XPS analysis

p

revealed an increase in oxygen content and decrease in carbon content after plasma
ce

treatment. More precisely, new polar anionic groups were formed (-CO-, COO-) on the

fiber surface. It was also found that the content of Ti on the PET fabric that was plasma
Ac

treated was larger than on the one that was not. An introduction of new polar groups and

increased roughness induced by plasma etching obviously enhanced the binding of TiO2

NPs. Raman spectroscopy measurements also confirmed the presence of TiO2 NPs in

the form of anatase crystallites (Fig. 11). The increased amount of TiO2 NPs deposited

on PET fibers pretreated by plasma was reflected on end-use properties. UPF value of

this sample was 347.5 whereas of the sample only modified with TiO2 NPs 259.7 (Fig.

26
Page 26 of 63
12). Equivalently, antibacterial activity against Gram-positive bacterium S. aureus of

this sample was higher probably due to larger amount of deposited TiO2 NPs.

Photocatalytic activity of TiO2 NPs was investigated in the solution of Neolan Blue 2G

under UV illumination. Washing slightly diminished this effect.

t
Mihailović et al. made comprehensive studies on potential of functionalization

ip
of PET fabrics with RF-plasma at low pressures and corona discharge at atmospheric

cr
pressure prior to loading of colloidal TiO2 NPs [113-116]. Initially, colloidal TiO2 NPs

were synthesized by acid hydrolysis of TiCl4 in manner analogues to the procedure

us
proposed by Reich et al. [116, 117]. The results of TEM characterization demonstrated

an
the presence of the agglomerates of Ti-based NPs with individual size ranging from 5-

10 nm. However, neither diffraction pattern nor HREM imaging revealed the existence
M
of the crystalline phase indicating the amorphous structure of TiO2. Untreated and

corona treated PET fabrics were coated with colloidal TiO2 NPs. The results of XPS
d

analysis showed that corona treatment caused an increase in O/C atomic ratio by
te

approximately 36%, indicating the formation of new oxygen-containing functionalities.

Evident decrease in the carbon content is a characteristic feature of plasma treatment of

p

polymers which primarily appears due to chain scission induced by plasma active
ce

species [118]. On the other hand, rise of oxygen content can be attributed to the

presence of atomic oxygen in the discharge during the sample processing and/or post-
Ac

plasma reactions of activated fiber surface with environment species [118]. Even though

numerous active species (ozone, nitrogen, oxides, radicals, etc.) are generated in corona

discharge in the air, it is believed that atomic oxygen is the most responsible for the

chemical changes on the fiber surface [119-120]. The deconvolution of high-resolution

C1s spectra clearly revealed an increase of content of C-O and C=O groups after corona

treatment of PET. It was also found that corona treatment brought about an increase in

27
Page 27 of 63
Ti content. It was suggested that newly formed polar groups on the PET fiber surface

improved the hydrophilicity of fibers which became more accessible to TiO2 NPs. The

presence of TiO2 NPs on the surface of PET fibers provided excellent UV-protective

properties as well as photacatalytic activity tested by following the self-cleaning effect

t
on blueberry juice stain and discoloration of the solution of methylene blue under UV

ip
light. However, desired level of antibacterial activity against Gram-negative bacterium

cr
E. coli was not reached. Therefore, further step in the preparation of colloid had to be

made. Additional thermal treatment of the colloid synthesized in accordance with

us
previous procedure resulted in the generation of TiO2 NPs with average size of 6 nm in

an
anatase form which was confirmed by HREM and Raman spectroscopy [113-116]. Such

colloid was applied to the same PET fabrics pre-treated by corona at atmospheric
M
pressure and air, oxygen and argon RF plasma at low pressures. All forms of plasma

caused the similar chemical changes on the PET fiber surfaces and equivalent
d

functionalities have been formed. However, Ti content on the pretreated samples

te

increased in the following order Ar plasma<Corona<Air plasma<O2 plasma. Actually,

Ti content in the O2 and air plasma treated samples was almost the same. This time the
p

amount of deposited TiO2 NPs was sufficient to provide maximum reduction of E. coli.
ce

Excellent antibacterial activity was preserved after five washing cycles except in the

case of Ar plasma pretreated sample. These nanocomposite systems ensured maximum

Ac

(50+) UV protection. Although UPF values slightly dropped down after washing,

maximum UV rating was kept. Obtained self-cleaning effect tested on blueberry juice

stains (Fig. 13) along with fast discoloration of methylene blue solution under UV light

proved excellent photocatalytic efficiency of anatase TiO2 crystallites. Photocatalytic

activity of TiO2 NPs remained the same if not better in repeated procedures.

28
Page 28 of 63
 The same group of authors also reported that chemical modification of PET fiber

with biopolymer alginate can provide additional carboxyl groups which enhanced the

deposition of TiO2 NPs [113]. AAS measurements showed that pretreatment with

alginate caused an increase in TiO2 content by about 38% compared to sample that was

t
only loaded with TiO2 NPs. Thin layer of biopolymer (around 300 nm) was detected by

ip
SEM as well as unevenly deposited TiO2 NPs. The same effects (UV protection, self-

cr
cleaning, antibacterial activity) have been evaluated and it was concluded that proposed

treatment can be a viable alternative to other mentioned treatments.

us
Recently, Hashemizad et al. reported the possibility of utilizing the conventional

an
alkaline hydrolysis of PET fibers for enhancement of the binding efficiency of TiO2

NPs [121]. It is well established that alkaline hydrolysis of PET fibers leads to a
M
considerable chemical and topographical changes of fibers where scission of polymer

chains takes place [122-124]. Namely, the carboxylic and hydroxyl groups are
d

anticipated to be introduced and this can be utilized for the improvement of binding of
te

TiO2 NPs. This treatment provided better uniformity of the TiO2 NPs deposition that

was observed by SEM analysis. The presence of TiO2 NPs caused an increase in surface
p

hydrophilicity and thus, vertical wicking properties. Self-cleaning efficiency tested on

ce

methylene blue stains was evaluated by determining of CIE L*a*b* coordinates. It was

evident that the higher the concentration of applied TiO2 NPs suspension the higher the
Ac

color difference after certain periods of UV illumination. In fact, lightness coordinate

(L*) increased rapidly indicating the photocatalytic degradation of methylene blue.

Although obtained effects were durable after 10 washing cycles, the release of TiO2 NPs

has been detected and this was more pronounced on the samples that were loaded with

higher concentrated TiO2 suspensions. However, TiO2 NPs release was less introduced

on the PET fabrics that were exposed to alkaline treatment than on those that were not.

29
Page 29 of 63
It was also emphasized that in addition to alkaline pretreatment, curing of samples

modified with TiO2 NPs at 200oC positively influenced the stability of modified PET

fabrics.

Martinova et al. opened new possibilities in a view of PET fabric preparation for

t
deposition of TiO2 NPs [125]. Enzymatic treatment of PET fabrics with esterase

ip
resulted in more uniform deposition of larger amount of TiO2 NPs. A particular value of

cr
this paper lies in application of non-standard pollutants (ammonia and formaldehyde)

for testing of TiO2 NPs photocatalytic activity.

us
Some recent works by Zhang et al. indicated that TiO2 NPs can be in situ

an
immobilized on the PA and PET fabrics using titanium sulfate and urea by

hydrothermal method [126-127]. It is interesting to note that the shape and the sizes of
M
generated TiO2 NPs were not the same on different substrates. Short rod or spindle

shaped NPs were found on the surface of PA fibers whereas granular structures
d

appeared on PET fibers. In both cases agglomerated particles evenly covered the surface
te

of fibers. XRD and HREM analyses revealed the presence of anatase crystallites. TGA

and DSC results indicated that thermal stability of PET fibers decreased after
p

hydrothermal processing. Photocatalytic activity of deposited TiO2 NPs tested on

ce

methylene blue and methylene orange solutions under UV illumination was acceptable.

However, quite small difference in degradation rate between these samples and control
Ac

samples raises doubts on photodegradation and pure adsorption contribution to removal

of dye from solution. In addition, hydrothermal processing of these fibers results in

significant shrinkage of fabrics what is unacceptable from technological point of view.

Recent study highlights the environmental impact of TiO2 NPs loaded on textile

materials [128]. Windler et al. investigated the release of TiO2 NPs during washing of

different commercial textile materials mainly made of PET and PA fibers. Size

30
Page 30 of 63
fractionation demonstrated that almost equal quantities were released as particles below

and above 0.45 m. TEM analysis revealed that TiO2 particles released into the washing

bath were spherical with sizes ranging from 60 to 350 nm. The overall suggested that

release of TiO2 particles from tested materials appeared during washing but not in a

t
large extant and not in the nanoparticulate range. Namely, TiO2 cannot dissolve in water

ip
and hence, the release of ionic metals is not possible. The release of particles depends

cr
on the manner how the particles are attached to fibers.

us
3.4. The influence of Ag deposits on photocatalytic activity of TiO2 NPs

an
This review paper undoubtedly showed that TiO2 NPs may impart versatile

properties to various textile materials. Although TiO2 NPs exhibit high photocatalytic
M
activity, the problem of high rate of the electron-hole recombination on TiO2 NPs is one

of the major limitations of this photocatalyst. Doping of metal ions into the TiO2 lattice
d

and dye photosensitization as well as a noble metal deposition on TiO2 NPs may
te

provide charge separation and subsequent electron transfer [8, 129-132]. Particularly

Ag-TiO2 systems gained much scientific and industrial interest. Deposition of Ag NPs
p

on TiO2 NPs results in electronic interaction between them. Namely, photo-excited

ce

electrons from the conduction band of TiO2 NPs are transferred to the vicinity of Ag

NPs. In fact, Ag acts as an electron trap [132]. Consequently, the charge separation
Ac

occurs and hence, recombination of electron-hole pairs is inhibited. Therefore, positive

holes in valence band become free to react with pollutants or adsorbed water molecules,

producing the hydroxyl radicals that are well known as extremely powerful oxidants. In

addition, Ag deposited on TiO2 NPs extends the light absorption into the visible

spectrum [132].

31
Page 31 of 63
 Taking into account all benefits that offer both Ag and TiO2 NPs to textile

materials i.e. antimicrobial activity, self-cleaning properties and UV protection, it was

worth trying to combine Ag and TiO2 NPs deposition. The first attempts to apply Ag-

TiO2 NPs to Co fabric seemed to be unsatisfactory as detrimental effect of TiO2 NPs on

t
the Ag-clusters deposited on the Co fibers, during E. coli inactivation in the dark and

ip
under solar simulated light occurred [133].

cr
Later study of Messaoud et al. demonstrated that photoreduction of Ag ions in

the suspension consisting of TiO2 NPs under UV illumination led to a formation of

us
mixed Ag-TiO2 suspension that can be applied to Co/PET blend [134]. Ethanol

an
employed as a diluting agent was also utilized for scavenging of positive holes

promoting the Ag ions photoreduction. Comprehensive study on the influence of TiO2

M
NPs and AgNO3 concentrations on metallization rate implied that increase in both

concentrations resulted in enhanced metallization rate to the one point when this rate
d

even dropped down. Above certain concentrations UV light absorption by Ag and TiO2
te

NPs becomes dominant in the solution and UV light penetration through the solution is

reduced, inhibiting the metallization. FEG-SEM analysis of Co/PET demonstrated that

p

Ag-TiO2 NPs not continually coat the fibers but are uniformly distributed over the fiber
ce

surface. EDX analysis suggested that Ti/Ag atomic ratio was around 5. Unlike control

sample and sample treated only with TiO2 NPs, the sample impregnated with Ag-TiO2
Ac

NPs suspension exhibited excellent antibacterial activity against E. coli and L. innocua.

Montazer et al. also conducted photoreduction of Ag ions in the presence of

TiO2 nanoparticles [135]. Such nanocomposite TiO2-Ag system was applied to wool

fabric in the presence of citric acid as a crosslinking agent under sonication. The

increase in the concentration of TiO2-Ag nanocomposite and citric acid in impregnation

32
Page 32 of 63
bath resulted in improved self-cleaning efficiency of wool fabrics which was tested on

methylene blue and saffron stains.

Mihajlović et al. investigated the influence of order of colloidal Ag and TiO2

NPs deposition on different properties of PET fabric [136]. For this purpose, uniform,

t
nearly spherical colloidal Ag NPs with an average diameter of approximately 10 nm

ip
have been used [32-33] as well as TiO2 NPs with average dimensions of 6 nm in anatase

cr
form [113-116]. The concentrations of Ag NPs colloids were 10 and 50 ppm. PET

fabrics were dip-coated with TiO2 NPs and afterwards with Ag NPs and vice versa. The

us
results showed that such combined treatment can simultaneously provide antimicrobial,

an
UV protective and self-cleaning properties to PET fabrics. It was also concluded that

both concentration of applied Ag NPs colloid and order of Ag and TiO2 NPs loading
M
play important role in obtaining desired effects. AAS measurements demonstrated that

six times higher Ag content was found in the PET fabric treated with 50 ppm colloid
d

compared to the fabrics treated with Ag NPs from 10 ppm colloid. TiO2 content in PET
te

fabric already loaded with Ag NPs was by 25 % higher compared to the samples that

were modified in opposite order implying that TiO2 NPs have greater affinity towards
p

Ag NPs than bare PET fibers. The application of 50 ppm colloid ensured not only
ce

superior antimicrobial activity but also desired level of UV protection and

photodegradation of methylene blue in aqueous solution (Fig.14). However, it was

Ac

found out that antimicrobial activity against bacteria E. coli and S. aureus and fungi C.

albicans can be preserved after five washing cycles only if loading of Ag NPs was

carried out after loading of TiO2 NPs. The photocatalytic activity of TiO2 NPs was

considerably enhanced in the presence of Ag NPs likely due to decrease of

recombination rate of TiO2 photo-excited charge carriers.

33
Page 33 of 63
4. Conclusions

This review clearly indicates that huge potential of TiO2 nanoparticles could be

efficiently utilized for imparting antibacterial, self-cleaning and UV-protective

properties to various textile materials. Simple routs for processing of textile materials

t
with TiO2 nanoparticles and the fact that small amount of this cheap, chemically and

ip
physically stable photocatalyst provide desired effects make TiO2 nanoparticles

cr
particularly attractive finishing agent which can find a broad application in textile

industry. However, unlike in some other industries, their stronger implementation into

us
textile industry has not been established yet since this technology still poses many

an
problems requiring multidisciplinary approach.

Self-cleaning effect could considerably reduce water and energy consumption

M
necessary for washing of textile goods. On the other hand, washing process can be a

serious source of pollution where detachment of single TiO2 nanoparticles or fibers with
d

deposited nanoparticles from textile goods may appear. Such undesirable release would
te

be more pronounced in the case of textile nanocomposite systems where TiO2

nanoparticles are not chemically bound but only weakly physically anchored to fibers.
p

The investigation on environmental impact and potential risks of TiO2 nanoparticles

ce

release into environment is running. Although it is generally assumed that TiO2

nanoparticles are non-toxic and thus, safe, it should be kept in mind that behavior of
Ac

nano-sized TiO2 significantly differs from the bulk TiO2. Therefore, the development of

adequate nanotoxicology tests is urgent.

Another group of problems concerns the nature of TiO2 nanoparticles and fibers.

TiO2 nanoparticles are activated by UV light constituting only about 5 % of sunlight.

Even smaller share of UV light in indoor lightening limits the action of goods with TiO2

nanoparticles indoors. Therefore, further research on modification of TiO2 nanoparticles

34
Page 34 of 63
which will ensure extension of the light absorption into the visible spectrum is needed.

At the same time, uneven distribution of TiO2 nanoparticles on fiber surface and poor

binding efficiency are essential issues to be solved as they affect efficiency,

reproducibility and durability of products. Appropriate activation of textile fibers i.e.

t
introduction of functional groups as potential sites for binding of TiO2 nanoparticles

ip
would provide not only enhanced efficiency, but better stability of the textile

cr
nanocomposite. This would further ensure long-term durability and reduce possible

environmental problems concerning the release of TiO2 nanoparticles during

us
exploitation and maintenance.

an
Undoubtedly finishing of textile materials with TiO2 nanoparticles brings many

valuable benefits in a view of end-use properties, but many aspects must be covered in
M
order to meet functional, economical, health safety and environmental demands.
d
te

Acknowledgements

This work was supported by the Ministry of education, science and technological
p

development, Republic of Serbia, projects no. 45020 and 172056.

ce

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Table and figure captions

Ac

Table 1. UPF rating for textile fabrics [64]

Table 2. Surface elemental composition of samples (pristine wool fiber (PO), wool

fiber coated with TiO2 NPs (TO) and succinylated wool fibers coated with TiO2 NPs

(TS)) [99].

44
Page 44 of 63
Fig. 1. (a) Suggested scheme for the discoloration of grease stains under Suntest light

irradiation mediated by TiO2 photocatalyis. (b) Suggested scheme for the discoloration

of wine and coffee stains under Suntest light irradiation by TiO2 photocatalyis [49].

Fig. 2. (a-c) Schematic illustration of the process of E. coli photokilling on TiO2 film. In

t
lower row, the part of cell envelope is magnified [55].

ip
Fig. 3. Possible binding mode of a COOH group to TiO2 [71-72].

cr
Fig. 4. SEM images of (a) cotton fiber, (b) titania coated cotton fiber, showing the

morphological change in the surface structure, (c) expansion of the cracks region

us
showing the thickness of the coating to be about 100 nm, (d) higher magnification

an
image of titania coated cotton, revealing the nanostructure and particles size of titania

coating (SEM images are original, but the scale bars are added) [73].
M
Fig. 5. UV blocking characterization of untreated cotton fabric and treated cotton fabric

before and after 10, 25, 35, and 55 cycles of accelerated home laundering: ○ untreated,
d

● treated before wash, ∆ 10 launderings, ▲ 25 launderings, □ 35 launderings, ■ 55

te

launderings [70].

Fig. 6. Simplified mechanism of binding of spacers to cellulose and TiO2 NPs [79].
p

Fig. 7. XPS spectrum of Ti2p peaks of TiO2-cotton stained with wine pretreated for 10
ce

min, no vacuum and irradiated with Suntest light for (a) 0 h, (b) 3 h, (c) 6 h, (d) 24 h
Ac

and (e) TiO2-coated cotton pretreated in the same way without wine at 0 h [82].

Fig. 8. (a) Photocatalytic activity of TiO2-covered cellulose fiber upon repeated

methylene blue adsorption-illumination cycles. (b) Photocatalytic activity of TiO2-

covered cellulose fiber upon repeated bitumen fraction extracted with heptane

adsorption-illumination cycles [87].

45
Page 45 of 63
Fig. 9. TiO2 mapping of the surfaces of (a) Co fabric impregnated with TiO2 NPs, (b)

corona pretreated Co fabric impregnated with TiO2 NPs and (c) air RF plasma pretreated

Co fabric impregnated with TiO2 NPs [96].

Fig. 10. Degradation of red wine stains on pristine wool fiber (PO), wool fiber coated

t
with TiO2 NPs (TO) and succinylated wool fibers coated with TiO2 NPs (TS) after 0, 8,

ip
and 20 h of light irradiation by a solar light simulator with light intensity of 45

cr
m·W·cm-2 [99].

Fig. 11. Raman spectra of (a) original polyester and (b) TiO2-coated polyester

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pretreated with oxygen plasma (A, anatase) [112].

an
Fig. 12. UV absorption of (a) oxygen plasma-pretreated polyester without TiO2 coating,

(b) TiO2-coated polyester without oxygen plasma pretreatment, and (c) TiO2-coated
M
polyester pretreated with oxygen plasma [112].

Fig. 13. Blueberry juice stains on the untreated PET (UPES) fabric, untreated PET
d

fabric and PET fabrics pretreated with oxygen and argon plasma loaded with TiO2 NPs
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(UPES+TiO2, O2PES+TiO2, ArPES+TiO2) before and after 24 h of UV illumination

[114].
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Fig. 14. Methylene blue photodegradation by TiO2 nanoparticles on differently

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modified PET fabrics under UV illumination [136].

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Author’s biography

Maja Radetić was born in 1971 in Belgrade, Serbia. She received her BSc (1995) in

chemical engineering from the Faculty of Technology and Metallurgy, University of

Belgrade, Serbia. She received her MSc (1998) and PhD (2003) in textile engineering

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from the Faculty of Technology and Metallurgy, University of Belgrade, Serbia.

Currently, she is an associate professor at Textile Engineering Department at the same

institution. She has also been a visiting associate professor at the Ghent University

(Belgium) in September 2012. She is a member of editorial board of International

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Journal of Textile Science and Technology and editorial advisory board of Journal of

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Textile & Engineer. Her research interests include plasma modification of textile

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materials, modification of textile materials with biopolymers and nanoparticles, textile

sorbents.

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Table 1
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M
UPF values UPF ratings UV protection category
< 15 / not labeled
d

15-24 15 and 20 good protection

25-39 25, 30 and 35 very good protection
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40-50 40, 45, 50 and 50+ excellent protection

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Table 2
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Sample Chemical composition % Atomic ratio

C N O S Ti Ti/C Ti/N
PO 73.0 15.8 8.7 2.5 0.0
TO 59.9 4.6 34.0 1.6 5.7 0.09 1.24
TS 47.2 4.9 37.8 0.5 9.6 0.20 1.94

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