DEPOSITION OF TITANIUM DIOXIDE LAYERS UPON POLYESTER

TEXTILE MATERIALS: CHECKING THE ADHERENCE

BY ULTRA-SONICATION*

IRINA ZGURA, STEFAN FRUNZA, MONICA ENCULESCU,

CAMELIA FLORICA, FLORIN COTOROBAI
National Institute of Materials Physics, PO Box MG 07, 077125 Magurele, Romania
E-mail: irina.zgura@infim.ro, E-mail: frunza@infim.ro
Receiver October 10, 2014

An important parameter of deposited thin films is their adhesion to the substrate

materials. we focused on the adhesion of TiO2 layer by sol-gel or sputtering onto textile
substrate as checked by an ultra-sonication method. The characterization made prior
and after the tests have shown a good adherence of the nanoparticles, despite the low
deposition temperature.
Key words: Adhesion, ultra-sonication, coatings, textiles, polyesters, fibers.

1. INTRODUCTION

Titanium dioxide TiO2 is a transition metal oxide with UV absorbing

properties, which are very interesting from a scientific standpoint and also due to
technological applications in many fields. It is used either as bulk or as thin layer.
Thus, TiO2 layers were deposited for UV blocking, antibacterial or/and photo
catalytic properties. The TiO2 layers can be obtained using many techniques like:
sol-gel [1], sputtering [2–4], ion beam evaporation [5] or plasma enhanced
chemical vapor deposition [6–9].
Each coating is very important in live organism, because if it happens a
detachment of the thin layers from basic materials, then the deposition does not
serve to the purpose, more then that the remains of the layer could cause additional
damage to surrounding tissue. Adhesion is an important parameter for every
coating. There are several methods for its determination, but one of the most used
methods is scratch test. Nowadays, micro and nano-scratch tests supplement the
classic (macroscopic) scratch test, which is well described in literature [10].
*
Paper presented at the 14th International Balkan Workshop on Applied Physics, July 2–4,
2014, Constanta, Romania.

Rom. Journ. Phys., Vol. 60, Nos. 3–4, P. 488–494, Bucharest, 2015
2 Deposition of titanium dioxide layers on polyester textile materials 489

Testing the adhesion of a film onto substrate by sonication (or ultra-

sonication as well) was already used [11]. On the other hand, in the textile field,
sonication was used for enhanced dye degradation (see some recent applications in
ref. [12–14]), leading up to ultrasonic cleaning [15], for dispersion stabilization
[16], etc.
The aim of this work was to check of the functionalization of the polyester
textile surface with TiO2 nanoparticles from the adherence point of view. Polyester
is known as less chemically active but needs mild deposition conditions because of
the rather easy thermal degradation. That is why checking the adherence becomes
an important task. TiO2 deposition was thus applied onto polyester textile materials
[17] at low temperature by sol-gel or sputtering techniques. The composite systems
thus obtained were submitted to a sonication treatment either for short time (3 min)
or for 1h. The main investigation method of the deposited layers was by scanning
electron microscopy. We found a very good adherence of the TiO2 nanoparticles as
deposited upon polyester fabric by the used techniques.

2. EXPERIMENTAL

Fabric samples
The investigated textile substrate is a fabric of polyester having the following
formula

and further labeled PES2. From the point of view of the textile elements, the
samples were knitted/ interlock and the white thread has Nm 70/1.
Prior to functionalization the plain commercial weave was cut at the
dimensions of ~20×20 mm and washed in n-propylic alcohol by 5 min sonication
to remove the impurities. The drying was performed at room temperature with
caution against the dust in a laminar flow hood.

Surface functionalization
Textile surface was modified with TiO2 by two deposition techniques,
sputtering and sol-gel. This modification leading to changed surface properties was
further called functionalization.
490 Irina Zgura et al. 3

• Sputtering (SP) deposition used a Sputter-Coater (Tectra GmbH)

installation and a TiO2 target (99.9% oxide, K.J. Lesker). Deposition time (kept in
all the experiments) was 6 h at 4x10-3 bar. The distance sample-target was kept
constant for all the experiments. The incident beam was obtained at 200 W
constant power under argon plasma. The sample was at room temperature.
• Sol-gel (SG) deposition was performed by covering the fabrics with
TiO2 by dip coating from a TiO2 sol in a homemade installation at a drawing rate of
10 mm/min. As precursor for TiO2 sol synthesis was used titanium (IV)
tetraisopropoxide (TIP). TiO2 sol was prepared by stirring for 2h at room
temperature, the following reaction mixture: ethylic alcohol (abs.); acetic acid
(glacial); TIP; chlorhydric acid (conc.) [17].

Adherence tests
Once obtained the deposited surfaces, the adherence of the layer were
checked by submitting the deposited samples to a sonication treatment for 3 min or
for 1h in an equipment UIS250V (Hilscher Ultrasound Technology) of max. 250 W
in a continuous mode at 70% amplitude. The sample immersed in water was very
close to the resonant horn.

Characterization
The deposited fabrics were characterized by applying the following
techniques:
Scanning Electron Microscopy (SEM) was performed with a Zeiss Evo 50
XVP instrument after conventional gold metallization of the samples. The
morphology of TiO2 particles grown on the investigated textiles were thus
obtained.
The thickness of the layer deposited by sputtering was determined with a
profilometer Ambios Xp100. The thickness of the TiO2 layer formed by sol gel can
be estimated looking at one crack along the fiber: it turns to be 150-180 nm as
determined from SEM images.

3. RESULTS AND DISCUSSION

First of all we make a short SEM characterization of the TiO2 deposited

materials and then we focus on the results of adhesion tests.
SEM images (Fig. 1) suggest the formation of nanoparticles, which are not
singularly distinguishable. The sputtering layers consist in aggregates of
nanoparticles with less than 20 nm diameter touching each other. In the case of the
4 Deposition of titanium dioxide layers on polyester textile materials 491

sol-gel layer, there are bridge-aggregated nanoparticles leading to a mosaic-like

structure but also to cracks and interfiber bonds. The bridges formation can be
explained by the anchoring TiO2 nanoparticles on the strong polar ester groups
existent along the polymer fibers: onto cotton fibers such carboxylic groups were
specially introduced to anchor TiO2 nanoparticles [18].
The formation of spherical structures (possibly by a particle superposition
effect) is peculiar of the sputtering deposited films, titania spherodization being
already observed [19] the formed nucleation centers might grow to bigger (~100 nm)
formations.

a) b)

Fig. 1 – SEM images of TiO2 layer obtained by: a) sputtering deposition; b) sol-gel.
The magnification is mentioned on the images.

The adhesion of the deposited layer to the textile substrates was normally
affected by the roughness and cleanness of the substrate, by the chemical affinity
between the coating layer and the substrate, and by the presence of cracks and
other defects. As resulted from above, the treatment of PES samples was carried
out under conditions allowing modification of the top fiber layer without damage to
the fabric. Moreover, the sporadic cracks occur in the point of crossing of fibers of
fabrics, only seldom there was found disengaging of TiO2 layer from the substrate.
The adherence of the TiO2 layer to the textile materials was checked by
submitting the composite systems to an sonication process, in a water bath, the
sample being close to the sonication horn. It is known that cavitation generated
during the sonication produces (for very short time) high pressure and temperature
and liquid jet streams so that the samples were submitted to extreme conditions.
The adherence of the layer were checked by submitting the deposited samples to a
sonication treatment for 3 min, Figure 2 shows SEM images obtained on samples
deposited with TiO2 by sputtering deposition (Fig. 2a, after sonication and Fig. 2b,
without sonication).
492 Irina Zgura et al. 5

a) b)

Fig. 2 – SEM images of TiO2 obtained by sputtering deposition, after sonication (a) in comparison
with the image of original deposited sample (b).

Moreover, the adherence test was successfully performed on the samples

additionally deposited with gold. In Fig. 3, the SEM images were similar to that
without sonication as in the previous case. The appearance of the deposited fibers
is quite similar to that without sonication showing that the deposited layer is quite
adherent.

a) b)

Fig. 3 – SEM images of TiO2 layer, submitted for 3 min to sonication process: a) TiO2 obtained
by sputtering deposition; b) TiO2 layer obtained by sol-gel.

The samples were sonicated also a longer time (1h); however, by increasing
the duration of sonication, the deposited layer was not detached, but only bridges
between fibers were destroyed, as can be seen from Figure 4. SEM images of these
composite systems after sonication (Fig. 4a, Fig. 4c) have indicated that the
deposited fibers are quite similar to that without sonication (Fig. 4b, Fig. 4d)
showing that the deposited layer is quite adherent.
6 Deposition of titanium dioxide layers on polyester textile materials 493

a) c)

b) d)

Fig. 4 – SEM images of TiO2 nanostructures obtained by sol-gel, at different magnifications:

a), c) TiO2 layer submitted for 1h to sonication process; b), d) TiO2 layer without
sonication for comparison.

From all these SEM images one can see that the ultrasonic tests do not
influence the TiO2 deposition. Moreover, it might be the case that sonication
treatment might improve the adhesion as it was shown in the literature for carbon
nanotubes to a substrate [20]. In addition, there is an analogy of the deposition onto
our textile materials by ultrasound dip coating and the deposition onto nylon and
cotton-blended fabric by using the microwave-assisted cross-linking [21] which is
already known to result in a micro and nano-scale rough surface on the fibers. Our
present research has shown that binding of the nanoparticles is quite possible by
the chosen deposition methods in line with some recent review [22, 23].

4. CONCLUSIONS

One of the important parameters of thin films made on various types of

substrates is adhesion of these films to substrate material. We studied the adhesion
of TiO2 layer on polyester textiles. TiO2 layer is quite adherent as checked by an
sonication method. The method is nondestructive and it is used for adhesion testing
of a coating on a component surface through ultrasonic cavitation.
494 Irina Zgura et al. 7

SEM images of these composite systems after sonication have indicated that
the deposited fibers are quite similar to that without sonication showing that the
deposited layer is quite adherent. Increasing the duration of ultra sonication up to 1
h does not detach the deposited layer but destroys only the interfiber bridges.

Acknowledgements. The authors gratefully thank the Romanian Authority of the Education
Ministry for the financial support under the project IDEI 281/2011.

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