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Synthesis, Activity

and Characterization
of Textiles Showing
Self-cleaning Activity
Under Ultraviolet

Franz Rossben A. Managuit
Synthesis, Activity and Characterization of Textiles
Showing Self-cleaning Activity Under Ultraviolet
CHAPTER I purposes. The attachment of a TiO2 through a
chemically stable spacer is also possible and is the
(Introduction) object of our recent studies.

Background of the Study:

Statement of the Problem:
This study intends to show the bondability of TiO2
on artificial fibers like wool–polyamide and polyester This study aims to distinguish/identify the
textiles and also in natural fibers like cotton by synthesis, activity and characterization of UV-
surface textile modifications induced by and UV- Vacuum Irradiation to textiles.
irradiation. These pretreatments at low pressure in
air leave the bulk of the textile intact and only
modify the upper surface layers from 1 to 20 A ˚ [1]. 1. How is UV-Vacuum Treatment and Titanium
Surface pretreatments of fabrics and polymers have Oxide reacts and results upon to putting in textile?
been carried out by etching, plasma, and corona
2. Using the UV-Vacuum Irraditaion Treatment to
discharge. Japanese workers have coated TiO2 on
fabrics, what were the activities present in it?
textiles by using emulsions containing acrylate,
additives, fluidizers and TiO2. The emulsion is then 3. How effective was UV-Vacuum Irradiation
sprayed on the textile fabric. Then the textile is Treatment to apply into textile?
heated to around 100 8C for a few minutes to
produce the polymer on the textile containing the
TiO2. Recent
Chinese work uses a similar approach with some
To distinguish the capability of sing UV-Vacuum
variations as cited in reference. Our work uses a
irradiation for textiles to show self-cleaning activity.
different approach. It consists in modifying the
structure of the textile surface introducing a variable
density of negative groups –COO, –O–O, by
Vacuum-UV irradiation. Then, the TiO2 is attached 1. To know the capability of UV-Vacuum Irradiation
to the modified textile surface by exchange with the Treatment for textiles.
positively loaded Ti4+ of TiO2. The surplus charge is 2. To evaluate the properties of UV-Vacuum
3+, which is quite considerable in electrostatic terms. Irradiation Treatment for Textiles.
Deposition of TiO2 clusters on natural cotton textiles
has recently been reported showing the formation of 3. To know the effectiveness of UV-Vacuum
anatase crystals of small dimensions stably grafted Irradiation Treatment for textile’s self-cleaning
onto cotton fabrics and using other oxide/ composites activity.
on different supports. Also, in our work we intend to
optimize the formulation of colloids to produce
efficient discoloration of some persistent stains on Hypothesis:
synthetic textiles. These TiO2 modified textiles will be
stained with organic dyes, pigments and grease and This study hypothesizes the following:
the discoloration or degradation of these stains will
be tested under daylight (and other weak light
sources) at room temperature for self-cleaning
1. If there is a strong indication of Self-Cleaning find that ratio. However, at most the instrument will
Activity, then UV-Vacuum Irradiation Treatment only probe 20nm into a sample.
was a great thing to be used on fabricating textile
XPS spectra are obtained by irradiating a
material with a beam of X-rays while simultaneously
2. If there are UV-Vacuum Irradiation Treatment measuring the kinetic energy and number of
present in textiles or fabrics, then it might be a good electrons that escape from the top 0 to 10 nm of the
used for textile factories. material being analyzed. XPS requires high vacuum
(P ~ 10−8 millibar) or ultra-high vacuum (UHV; P <
10−9 millibar) conditions, although a current area of
Scope and Limitations: development is ambient-pressure XPS, in which
samples are analyzed at pressures of a few tens of
CHAPTER II millibar.

(Review of Related Literature and Studies)

Infrared spectroscopy (IR spectroscopy
Variable/s: or vibrational spectroscopy)
Titanium Dioxide Infrared spectroscopy (IR spectroscopy or
vibrational spectroscopy) involves the interaction of
Titanium dioxide, also known as titanium (IV)
infrared radiation with matter. It covers a range of
oxide or titania, is the naturally occurring oxide of
techniques, mostly based on absorption spectroscopy.
titanium, chemical formula TiO When used as a
As with all spectroscopic techniques, it can be used to
pigment, it is called titanium white, Pigment White 6
identify and study chemicals. Samples may be solid,
(PW6), or CI 77891. Generally, it is sourced from
liquid, or gas. The method or technique of infrared
ilmenite, rutile and anatase. It has a wide range of
spectroscopy is conducted with an instrument called
applications, including paint, sunscreen and food
an infrared spectrometer (or spectrophotometer) to
coloring. When used as a food coloring, it has E
produce an infrared spectrum. An IR spectrum can
number E171. World production in 2014 exceeded 9
be visualized in a graph of infrared light absorbance
million metric tons.It has been estimated that
(or transmittance) on the vertical axis vs. frequency
titanium dioxide is used in two-thirds of all pigments,
or wavelength on the horizontal axis. Typical units of
and the oxide has been valued at $13.2 billion.
frequency used in IR spectra are reciprocal
centimeters (sometimes called wave numbers), with
the symbol cm−1. Units of IR wavelength are
Materials and Apparatus: commonly given in micrometers (formerly called
X-Ray Photoelectron Spectroscopy "microns"), symbol μm, which are related to wave
numbers in a reciprocal way. A common laboratory
(XPS) instrument that uses this technique is a Fourier
X-ray photoelectron spectroscopy (XPS) is a transform infrared (FTIR) spectrometer. Two-
surface-sensitive quantitative spectroscopic dimensional IR is also possible as discussed below.
technique that measures the elemental composition
at the parts per thousand range, empirical formula,
chemical state and electronic state of the elements Transmission Electron Microscopy
that exist within a material. Put more simply, XPS is (TEM)
a useful measurement technique because it not only
shows what elements are within a film but also what Transmission electron microscopy (TEM), also
other elements they are bonded to. This means if you sometimes conventional transmission electron
have a metal oxide and you want to know if the microscopy or CTEM) is a microscopy technique in
metal is in a +1 or +2 state, using XPS will allow you to which a beam of electrons is transmitted through a
specimen to form an image. The specimen is most
often an ultrathin section less than 100 nm thick or a
suspension on a grid. An image is formed from the crystallography is still the primary method for
interaction of the electrons with the sample as the characterizing the atomic structure of new materials
beam is transmitted through the specimen. The and in discerning materials that appear similar by
image is then magnified and focused onto an other experiments. X-ray crystal structures can also
imaging device, such as a fluorescent screen, a layer account for unusual electronic or elastic properties of
of photographic film, or a sensor such as a charge- a material, shed light on chemical interactions and
coupled device. processes, or serve as the basis for designing
pharmaceuticals against diseases.
Transmission electron microscopes are capable of
imaging at a significantly higher resolution than light
microscopes, owing to the smaller de Broglie
wavelength of electrons. This enables the instrument Related Studies:
to capture fine detail—even as small as a single Synthesis, Activity and Characterization of textiles
column of atoms, which is thousands of times smaller showing Self-cleaning Activity under RF-Plasma
than a resolvable object seen in a light microscope. Irradiation
Transmission electron microscopy is a major
(J. Kiwi, et al, 2007)
analytical method in the physical, chemical and
biological sciences. TEMs find application in cancer The preparation, activity and characterization of
research, virology, and materials science as well as TiO2 clusters on several of textiles are presented
pollution, nanotechnology and semiconductor having a self-cleaning effect under RF-Plasma
research. irradiation. The textile upper layers are modified in
such a way that negatively charged TiO2 chelating
groups such as carboxylic groups are introduced by
Literary Words: the pretreatment methods used. The pretreatments
used in this study were applied in dry conditions in
X-Ray Crystallography (XRC)
the absence of solvents. Also, the times employed for
X-ray crystallography (XRC) is a technique used the cotton surface modification were short and
for determining the atomic and molecular structure involved reduced energy requirements. The
of a crystal, in which the crystalline structure causes a quantitative results obtained during the discoloring
beam of incident X-rays to diffract into many specific of spots of wine, coffee, make up and grease indicate
directions. By measuring the angles and intensities of that the photoactivity observed on the TiO2
these diffracted beams, a crystallographer can modified textiles upper layers strongly depends on
produce a three-dimensional picture of the density of the nature of the TiO2 used and on the procedure
electrons within the crystal. From this electron used to apply the TiO2 on the textile. When light is
density, the mean positions of the atoms in the crystal harvested directly by the TiO2, like in the case of
can be determined, as well as their chemical bonds, grease stains an increased CO2 evolution was
their crystallographic disorder, and various other observed with respect to wine and coffee stains under
information. similar experimental conditions on the same TiO2
loaded textile. Also, chemical spacers able to graft
Since many materials can form crystals—such as TiO2 on suitable functional groups of the textile and
salts, metals, minerals, semiconductors, as well as through a second link bond to the TiO2 clusters have
various inorganic, organic, and biological molecules— been studied with promising results in
X-ray crystallography has been fundamental in the photoactivated light induced discoloration processes.
development of many scientific fields. In its first The TiO2 loaded textiles were characterized by
decades of use, this method determined the size of transmission electron microscopy (TEM), by
atoms, the lengths and types of chemical bonds, and elemental analysis (EA), by X-ray photoelectron
the atomic-scale differences among various spectroscopy (XPS), by infrared spectroscopy (IR), X-
materials, especially minerals and alloys. The method ray diffraction (XRD) and by gas adsorption studies
also revealed the structure and function of many (BET).
biological molecules, including vitamins, drugs,
proteins and nucleic acids such as DNA. X-ray
CHAPTER III air, slowly deactivating the radicals induced on the
pretreated fabrics. The textile samples were then
(Methodology) washed with distilled water under sonication to
remove TiO2 particles that did not attach to the
fabric surface. During this study, we found that only
Pretreatment of synthetic textiles fabrics:
pretreated surfaces were able to fix TiO2 from
The textile polymer surface was also pretreated colloidal solutions or suspensions or the combination
using the 185 nm line of a 25 W low pressure mercury of both. Samples exhibited comparable amount of
lamp (Ebara Corp., Iwasaki Electric Co., Shiba, TiO2 around 1.5– 2.5% (w/w).
Japan). The lamp wall consisted of synthetic silica
able to transmit the 184 nm light. This wavelength
comprises 25% of the total lamp output. The other Irradiation Procedure and Evaluation of the
75% of the lamp output consisted of a 254 nm Textile Cleaning Action:
radiation. Since the vacuum-UV activation proceeds
with a lower energy than the plasma activation, no The photochemical reactor consisted of 80 mL
cationic or anionic oxygen species can be produced in cylindrical Pyrex flasks containing a strip of textile of
the gas phase. Only atomic and excited oxygen 48 cm2 positioned immediately against thewall of
species are formed. This leads to a more controlled the reactor. Except when mentioned in the text,
and uniform modification of the textile surfaces with irradiation of the samples was carried out in the
an increased polarity which is related to the variety cavity of a Suntest solar simulator (Hanau,
of oxygen functional groups formed by the reactions Germany) air-cooled at
of free radicals with O2 in the gas phase. At the 458.TheSuntestlampemitted7%of the photons in the
pressures used for plasma or vacuum-UV 290 and 400 nm range. The profile of the photons
pretreatment, the residual oxygen was sufficient to emitted between 400 and 800 nm followed the solar
modify the textile surfaces owing to the absorption spectrum with a light intensity of 50 mW/cm2
cross section of O2 for plasma radiation or ultraviolet corresponding to 50% of AM1 (AM1 corresponding to
light. the light intensity of the midday equatorial solar
radiation). The CO2 produced during irradiation was
measured in a gas chromatograph (Carlo Erba,
Preparation of TiO2 Suspensions and Colloids Milano) provided with a Poropak S column. The
quantitative test for the self-cleaning action of the
and Mixtures of Both:
TiO2 loaded textiles is shown in Fig. 1. The textile strip
Many TiO2 formulations are tried to impregnate without TiO2 loading did not evolve any significant
the textiles based on powders, colloids or amounts of CO2. By visual inspection the
combination of both. The photodiscoloration results discoloration of the sample was observed to be in
give the data of the best starting formulation to use relation with the amount of CO2 evolved under light
for each particular textile. irradiation. An increase in specular reflectance taken
in a spectrophotometer for tissues before and after
irradiation was also observed.
Preparation of TiO2 Coated Textiles:
Plasma or UV pretreated textiles samples were Transmission Electron Microscopy (TEM):
immersed in the selected TiO2 suspension/ colloidal
solutions for 30 min. Then, the samples were dried in A field emission TEM microscope (CM 300FE-UT,
air at 22 8C (laboratory temperature) for 24 h then 300 kV, Cs 0.7 mm point-to-point resolution at
heated at 100 8C for 15 min. The exchange operation scherzer defocus 0.17 nm) and a Philips EM 430 (300
was carried out immediately after the pretreatment kV, source LaB6 resolution point 2 A ˚ ) were used to
using any of the three techniques mentioned above. measure the particle size of titania clusters on the
The reason for this is that the radicals formed at the textile surface. The Philips CM 300 was equipped
fabric surface react with humidity and oxygen of the with energy dispersive X-ray analysis (EDS)
spectrometer allowing the identification of the Ti-
clusters deposited on the textile fabrics. The textiles
were coated with an epoxy resin and the fabric was
cut with a microtome to a thin layer of 50 nm for
experimental observations at a 908 angle. Probes
having a 10 mm diameter were examined to monitor
the supported TiO2 cluster size and distribution. After
a dry cleaning cycle, transmission electron microscopy
was carried out to investigate whether or not the
TiO2 was present and resisted dry cleaning.

X-Ray Diffraction Measurements Of Tio2

Loaded Textiles:
The amount of crystallinity and phase of the
titanium oxide loaded on the textile surface was
studied with a Siemens X-ray diffractometer using Cu
Ka radiation.