Pretreatment of wool/polyester blended fabrics to enhance

titanium dioxide nanoparticle adsorption and self-cleaning

properties
Authors
Majid Montazer,
1.

Samira Seifollahzadeh
1.

First published: 24 August 2011Full publication history

DOI: 10.1111/j.1478-4408.2011.00316.xView/save citation
Cited by: 10 articles
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Abstract
This research aims to enhance the self-cleaning properties of fibre-
blended fabric using surface pretreatment prior to the application of
titanium dioxide nanoparticles. To this end, the polyester/wool fabric was
modified, in that the wool fibres were oxidised with potassium
permanganate and the polyester fibres were hydrolysed with lipase before
nano processing. Butane tetracarboxylic acid was also used to enhance
the adsorption of the nanoparticles and also to stabilise them on the fabric
surface. The self-cleaning properties of the fabric were examined through
staining of the fabric with CI Basic Blue 9 and then discolouring by
exposing to ultraviolet and daylight irradiation. Some other properties of
the treated fabrics, such as water drop absorption, crease recovery angle
and bending were investigated and are discussed in detail. The colour
changes of different samples indicated an appropriate discoloration on the
titanium dioxide-treated fabrics after ultraviolet and daylight irradiation.
Overall, the surface pretreatment of the wool and polyester fibres
improved the self-cleaning properties of the fabric significantly.
Introduction
In recent years, considerable effort has been devoted to the subject of
textile self-cleaning [110]. Nowadays, titanium dioxide (TiO2)
nanoparticles are increasingly being used for the discoloration of coffee
and for coloured pigments on the surface of fabrics [1]. Titanium dioxide
was shown to be the best candidate for photocatalytic applications [2].
Because of its relatively large surface area per unit mass and volume,
titanium dioxide has oxidation activity under sun irradiation. It has also
attracted considerable attention in the textile industry [37]. In order to
proceed with the photocatalysis process, semiconductors such as titanium
dioxide need to absorb energy equal to or more than its energy gap to
shift electrons from the valence band to the conduction band to generate
negatively charged electrons and positively charged holes [2]. The
electron reacts with atmospheric oxygen and the hole reacts with water
vapour, resulting in a superoxide anion and hydroxyl radical, respectively
[2]. Recently, several techniques have been applied for fixing nano
titanium dioxide on a fabric surface and the self-cleaning properties that
are obtained [310]. Bozzi et al. modified the structure of the textile
surface by introducing a variable density of negative groups COO, O
O, by pretreatment with radio frequency-plasma, microwave-plasma and
vacuum-ultraviolet (UV) irradiation [1]. They found that applying titanium
dioxide (Degussa P-25; Evonik, Germany), consisting of 80% anatase and
20% rutile with a 30 to 40 nm crystallite size, led to the best discoloration
of stains.
Yuranova et al. examined the preparation of photocatalytic active titanium
dioxidesilicon dioxide layers [11]. A more efficient discoloration and
carbon dioxide production was observed for the titanium dioxidesilicon
dioxide coated cotton compared with samples coated only with titanium
dioxide. The surface organic compounds were degraded by the
photoactive titanium dioxide in close contact with the surrounding layers
of silicon dioxide.
Others presented radio frequency plasma, microwave plasma and
vacuum-UV light irradiation as pretreatment on synthetic textile surfaces
to load titanium dioxide by wet chemical techniques [12]. These treated
textiles showed a significant photo-oxidative activity under visible light in
air that discoloured and mineralised persistent pigment stains.
Different approaches provided the means to attach titanium dioxide on to
the cotton surface using chemical spacers. Meilert et al. [13] focused on
the introduction of a spacer with at least two free carboxylic groups to be
able to link both the cotton and the titanium dioxide. It was found that the
acylation of wool allows for increasing functionality and reactivity of fibres
towards nano titanium dioxide, which in turn resulted in enhanced self-
cleaning functionality [14].
Zhang et al. assessed the role of photocatalytic nano crystalline titanium
dioxide (P-25) in the photo-yellowing of wool [15]. They showed that nano
crystalline titanium dioxide could effectively reduce the rate of photo-
yellowing particularly at higher concentrations. Therefore, nano crystalline
titanium dioxide acts primarily as a UV absorber on wool in dry conditions
and not as a photocatalyst.
The major concerns with polyester are the highly crystalline structure, the
lack of reactant groups and the inaccessible polymeric chain as a
consequent low scale of linking on the fibre [16]. Enzymes are biological
compounds with protein structures that accelerate chemical reactions
[1719]. Enzyme processes were performed at a low temperature and at
small time intervals [20]. Enzymes were unable to leak into the structure
and their activities were limited only to the surface of the fabrics. Lipases
are capable of hydrolysing carboxylic esters that can be used for the
surface hydrolysis of polyester [2123].
To our knowledge, the self-cleaning properties of the blend of
wool/polyester fabric have not been reported in the published literature. In
addition, the pretreatment on the fabric was carried out on both wool and
polyester fibres to enhance the fabric functional groups, leading to higher
nanoparticle adsorption. Further, the crosslinking agent was used to
stabilise the nanoparticles on the fabric surface and increase nano
titanium dioxide adsorption. The self-cleaning properties of the
wool/polyester fabric, as the main objective of this work, and the influence
of the pretreatment on this property and other characterisation of the
fabric were investigated and are discussed in detail.
Experimental
Materials
Raw wool/polyester fabric (45:55%) with 29 yarns/cm in the warp and
17 yarns/cm in the weft direction was used. Nano titanium dioxide
Degussa P-25, size 21 nm, and Brunauer Emmett Teller (BET; specific
surface area 50 15 m2/g) from Evonik (Germany) was applied. Also,
lipase (Lipex; Novazyme, Denmark), butane tetracarboxylic acid (BTCA;
Merck, Germany), sodium hypophosphite (SHP; Merck), sodium chloride
(Merck), potassium permanganate (Merck), sodium hydrosulphite (Merck),
sulphoric acid (Merck), distilled water and CI Basic Blue 9 was used.
In addition, an ultrasonic bath (50-W with 50 kHz), spectrophotometer
(Datacolor 98; Datacolor, USA), scanning electron microscope (SEM)
(XL30; Philips, USA), energy-dispersive X-ray spectrometer (EDX), Shirley
crease recovery angle tester, Shirley bending length tester (Shirley, UK)
and UV-C region 8-W lamp (Philips) were employed.
Preparation of nano titanium dioxide dispersion and fabric treatment
The dispersion was prepared with 01% titanium dioxide, 020% butane
tetracarboxylic acid, 010% sodium hypophosphite in distilled water and
then sonicated for 10 min in the ultrasonic bath. The fabric samples were
5 5 cm. First, the samples were oxidised with 3% (w/w) potassium
permanganate and 10 g/l sodium chloride by sonication in an ultrasonic
bath for 30 min. This led to the production of more negative groups such
as COO and OO on the fabric surface. The fabric samples were then
treated with 5% (w/w) sodium hydrosulphite in an acidic media, along with
sulphuric acid at pH 4 to remove the remaining manganese (Mn) from the
fabric surface. To modify the polyester fibres, the fabrics were treated with
1% (w/w) Lipex for 30 min at 30 C in a bath with a liquor-to-goods ratio of
50:1 along with stirring. The fabrics were then washed with cold water.
The pretreated fabrics were soaked in the pre-dispersed solution of nano
titanium dioxide for 1530 min and then dried at 70 C, followed by curing
at 180 C for 90 s. Finally, the nano titanium dioxide-treated samples were
sonicated for 5 min in an aqueous bath to remove the unbonded titanium
dioxide nanoparticles from the fabric surface.
Characterisation techniques
The fabric samples were stained with 0.1% solution of CI Basic Blue 9 and
were then irradiated by UV-C lamp at an intensity of 345 W cm2 at 8 W,
290100 nm for 12 h at 10 cm distance for discoloration. In addition, some
samples were exposed to daylight for 24 h for discolouring. These samples
were exposed to sunlight in summer (July) from 07.00 to 19.00 h for 2
consecutive days in Tehran. The colour data for the samples stained with
CI Basic Blue 9 and the irradiated samples were measured by
spectrophotometer in order to provide the colour difference according
to Eqn 1 and to give an indication of the self-cleaning properties. The
recoded data were based on D65 illuminant and 10 observer.
(1)

The three coordinates of CIELab represent the lightness of the colour

(L* = 0 yields black and L* = 100 indicates diffuse white), its position
between red and green (a*, negative values indicate green, while positive
values indicate red) and its position between yellow and blue (b*, negative
values indicate blue and positive values indicate yellow).
SEM analysis was carried out on the modified samples and the titanium
dioxide-treated fabric. The samples were prepared by coating with a gold
(Au) layer to obtain a clearer picture. The SEM pictures were taken at
16 kV at a magnification of 1000. Energy dispersive X-ray microanalysis
was also performed to verify the elemental composition of the deposited
materials on the fibre surface.
Results and Discussion
The effective factors of the experiments, including the amount of titanium
dioxide, butane tetracarboxylic acid, sodium hypophosphite and sonicated
time, are given in Table 1. The prepared samples were compared with the
blank, oxidised and oxidised/enzyme-treated samples.

Sample no. TiO2 (%) BTCA (%) SHP (%) Time

1 0.50 10 0.0 30

2 0.50 0 5.0 30

3 0.00 10 5.0 30

4 0.75 15 2.5 15

5 0.50 10 5.0 30

6 0.50 20 5.0 30

7 1.00 10 5.0 30

Table 1. Variable values used for the dispersions

Scanning electron microscopy and energy dispersive X-ray analysis

 Figure 1 shows the SEM micrograph of the wool/polyester fibre surface
before and after pretreatment with oxidant and hydrolysis with enzyme,
and also the modified fibre after titanium dioxide loading. It can be seen
that the pretreatment process leads to a change in the surface of wool
and polyester after oxidisation and enzymatic hydrolysis (Figure 1b). The
removal of the surface layers from the fibres increases the roughness of
the surface. The surface roughness is far more accentuated than that of
the original fibre surface. The formation of titanium dioxide layers on the
fibre surfaces (Figure 1c) can be clearly seen on the pretreated fabric, in
that wool fibres oxidised with potassium permanganate and polyester
fibres hydrolysed with lipases.

Figure 1.
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SEM image of different samples (a) blank, (b) modified and (c) treated
with TiO2
The titania on the textiles can be identified by the EDX spectrum. On the
basis of the results, the existence of titanium and gold can be observed. It
is known that gold is used on the fabric surface to obtain a better-quality
picture. The EDX pattern of the blank sample, the sample treated with
0.5% titanium dioxide and the sample treated with 0.75% titanium dioxide
are shown in Figure 2. The amount of titanium is higher for the fabric
sample treated with the higher amount of titanium dioxide.

Figure 2.
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EDX spectrums of various samples (a) blank, (b) treated with 0.5%
TiO2 and (c) treated with 0.75% TiO2. ka, kb, La, Lb and Ma are electron
shells of the element
Water absorbance, crease recovery angle and bending length
The water absorbance, crease recovery angle and bending length of the
samples after being treated with titanium dioxide were measured
according to BS4554, BS3056 and BS3356 [24], respectively, and the
results are reported in Table 2. A small reduction can be seen in the crease
recovery angles of the treated samples compared with the blank sample.
This can be attributed to the formation of new bonds within the protein
chains, which disturbs the former arrangement and results in a decrease
in the crease recovery angle. The breaking of the disulphide (SS) bonds
through the pretreatment processing of wool could be responsible for this
adverse effect.
 Crease Bending Wat
Sample BTCA SHP
TiO2(%) recovery length abso
no. (%) (%)
angle () (cm) (min

1 0.50 10 0.0 148 2.2 0

2 0.50 0 5.0 152 2.5 6

3 0.00 10 5.0 150 2.4 90

4 0.75 15 2.5 152 2.2 0

5 0.50 10 5.0 150 2.4 0

6 0.50 20 5.0 148 2.2 0

7 1.00 10 5.0 152 2.3 0

Blank 0.00 0 0.0 162 1.8 120

Oxidised 0.00 0 0.0 161 2.1 2

Oxidised 0.00 0 0.0 161 2.0 0

and
treated
with
enzyme

Table 2. Water absorbance, crease recovery angle and bending length of various sa

The bending length is considered as a good factor to indicate the handling

characteristic, as an increase in the bending length causes a hard handle.
The bending length of all the treated samples increased. Application of
nano titanium dioxide, along with the cross-linking agent on the fabric
surface, formed a non-uniform layer. This increased the bending length of
the fabrics with the increase of the cross-linking agent.

In the presence of titanium dioxide on the fabric, the water absorption

property increases and the time for water adsorption decreases. The
hydrophilic property of the titanium dioxide is made under UV irradiation.
This property, forces the water drops to stand at a very low angle on the
surfaces covered by titanium dioxide and spread on the fabric surfaces
and finally wet the surfaces. One of the mechanisms discussed in the
process of hydrophilicity of titanium dioxide is that electrons gain enough
energy through UV irradiation with wavelengths under 388 nm, shifting
from the valance band to the conduction band and generating the
electron-hole pair [2527]. The electrons tend to convert the Ti4+ to Ti3+.
The generated Ti3+reacts with the oxygen molecules of the air, changing
them to O2, which is adsorbed by the surface. Ti3+cations switch to the
Ti4+cations through this reaction [2527]. The adsorbed anions of O2 were
oxidised by the holes and, as a consequence, the titanium dioxide
molecules come out to their original state and the oxygen molecules rise
from the surface. This generates empty spaces that can be filled by the
water molecules, which then leads to the hydrophilic property of the
surface [2527]. With this property, a thin layer of water lies on the
surface instead of the water drops with the high angles [2527]. The
results obtained for increasing the hydrophilicity of titanium dioxide were
in good agreement with those published in the literature regarding the
application of Degussa P-25 [28].
Self-cleaning measurements
The colour difference results of the treated and stained samples after
irradiation, along with blank and oxidised/enzyme-treated samples, are
shown in Table 3. E1 is the difference between colour indices before and
after 12-h UV irradiation and E2 is the difference between colour indices
before and after 24-h daylight irradiation.

Sample no. E1 E2

1 20.0 23.1

2 18.6 19.2

3 18.0 18.7

4 21.1 22.3

5 24.5 26.1

6 25.1 26.6

7 41.2 47.5

Blank 12.1 14.7

 Sample no. E1 E2

1 20.0 23.1

Oxidised 17.0 18.0

Oxidised and treated with enzyme 17.1 18.3

Table 3. Colour difference of samples after UV and daylight irradiation

The self-cleaning properties of the titanium dioxide-treated textiles were

based upon the highly oxidative intermediates generated on the surface
of the fabric [1]. The decomposition of the CI Basic Blue 9 (BB) is
performed also based on this mechanism. The oxidisation reactions after
irradiation were as following [29]:
(2)

(3)

(4)

(5)

(6)

The discoloration of stains is affected by variables such as the amounts of

titanium dioxide and butane tetracarboxylic acid and the soaking time in
the ultrasonic bath. As mentioned before, it is necessary to chemically
modify the wool with 50% of functional groups and polyester with high
crystallinity in order to stabilise the titanium dioxide on the surface of the
wool/polyester fabric. Therefore, the oxidised samples, and also the
modified samples with the enzyme and oxidation, show a better colour
difference against the oxidised and unmodified samples, respectively. This
is attributable to the generation of strong functional groups further to the
amine, hydroxyl, thiol and phenol functional groups of the wool [14]. The
oxidised and enzyme-modified samples demonstrate the appropriate
colour differences, because these fabric surfaces were prepared to attract
a higher amount of the titanium dioxide nanoparticles. The discoloration
of different fabric samples is illustrated and compared in Figure 3. It can
be considered that the self-cleaning properties of the samples under the
 daylight irradiations have been improved. This can be attributed to the
modification of titanium dioxide with other compounds in the finishing
bath, including butane tetracarboxylic acid and sodium hypophosphite,
and/or the intensity of the daylight compared with UV-C lamps.

Figure 3.
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Self-cleaning of the blank, pretreated and treated sample with 1%

TiO2 [Colour figure can be viewed in the online issue, which is available at
wileyonlinelibrary.com.]
The attachment of titanium dioxide to the fabric surface is naturally
electrostatic. This means that the charges of the titanium dioxide and the
fabric surface were positive and negative, respectively. Because of having
four functional groups, butane tetracarboxylic acid is a strong cross-linking
agent that can help to adsorb more nano titanium dioxide to the fabric
surface. Also, the photocatalytic decomposition results for butane
tetracarboxylic acid-treated fabrics give better results than that of the
blank sample. Titanium dioxide can be attracted by functional groups of
wool and polyester, such as carboxyl and hydroxyl, resulting in
electrostatic linkages. This phenomenon has already been confirmed for
cellulose [13]. Some of the reactions occurred, such as wooltitanium
dioxide and woolbutane tetracarboxylic acidtitanium dioxide, which
show the role of the hydroxyl and carboxylic groups of wool in the ionic
attractions of nano titanium dioxide. Also, reactions between butane
tetracarboxylic acid and the amine and hydroxyl groups of wool introduce
more carboxylic acids on the wool surface, hence leading to the ionic
attraction of titanium dioxide. Similar reactions occurred between
polyester and nano titanium dioxide, which exhibit the ionic attraction of
titanium dioxide toward the hydroxyl and carboxyl groups of polyester.
Also, butane tetracarboxylic acid can react with those groups of polyester
and introduce the more carboxylic groups on the polyester surface. The
ionic linkages emerge between the carboxylic groups and nano titanium
dioxide.
Washing fastness
To evaluate the washing fastness of the treated samples, sample 4 was
selected and washed with 1 g/l nonionic detergent at 60 C for 20 min for
five cycles. After each cycle of washing, the sample was stained with CI
Basic Blue 9 and irradiated with UV for 12 h. Three approaches were used
to evaluate the washing fastness including: (i) estimation of the colour
difference of the samples before and after UV irradiation using a
greyscale. The results after each washing cycle are shown in Table 4; (ii)
indicating the titanium dioxide particles by the SEM image of the washed
sample (Figure 4); and (iii) confirming the presence of titanium by the EDX
spectrum of the washed sample (Figure 5). The results exhibit the
existence of titanium dioxide on the fibre after five washing cycles. Also,
 the photocatalytic reactions were occurring with the UV irradiation, while
the photocatalytic properties were reduced by consecutive washing.

Number of washing stages Fastness

Before washing 45

1 4

2 4

3 4

4 4

5 3

6 3

7 32

Table 4. Greyscale of washed sample in each stage

Figure 4.
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SEM image of the sample after seven cycles of washing

Figure 5.
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EDX spectrum of the sample after seven cycles of washing

Conclusion
This study aimed to modify the wool/polyester surface to enhance the
nano titanium dioxide adsorption and stabilise it on the fabric surface by
using butane tetracarboxylic acid as a cross-linking agent to produce a
fabric with enhanced self-cleaning properties. Adequate absorbability has
been provided via fabric pretreatment. Also, using butane tetracarboxylic
acid as a cross-linking agent in the ultrasonic bath helped to achieve a
stable self-cleaning property on the titanium dioxide-treated
wool/polyester textiles. Partial discoloration of the CI Basic Blue 9 as a
stain on the fabric surface under UV and daylight irradiation presented a
long-term stable performance. The experimental results show an
improvement in water absorbance of the titanium dioxide-treated fabric.
Also, the crease recovery angle of the treated fabrics decreased a little,
while the bending length increased.