CHAPTER THREE

RESEARCH METHODOLOGY

3.1 Introduction

The experimental works of the study are illustrated in Figure 3.1. The cotton yarn
initially went through the scouring process. The zinc oxide (ZnO) suspension and 1,2,3,4-
butanetetracarboxylic acid (BTCA) solution were prepared for the ZnO coating and crosslinking.
After the crosslinking and coating process, the ZnO coated yarn underwent 5 washing cycles,
which were 1, 5, 10, 15, and 20, respectively. The yarn from each cycle was tested for the
morphological structure, elemental composition of the sample, changes in functional groups, UV
resistance, and anti-microbial. Any inconsistent result needs to go through the process involved.

3.2 Materials

Two metres of cotton yarn with the size of 30 tex were used in the current study. The
yarn underwent a scouring process by washing the yarn with water and detergent at 80 oC
for 30 minutes and was rinsed several times with deionized water (Vihodceva & Kukle,
2013). The scouring process was able to remove any dirt or impurities on the yarn. The
yarn was then washed in acetone, followed by ethanol for 30 minutes at 60 oC (Mai et al.,
2018). Then, the yarn was dried at room temperature for 24 hours before proceeding to
the next process.

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 Start

Scouring
=
process

Scoured cotton
yarn

Crosslinking process

Coating process

ZnO coated cotton

yarn No

Uniformity of
ZnO coating

Yes
Washing for 1, 5, 10, 15 & 20
cycles

Washed ZnO coated cotton

yarn

Washing durability of ZnO coated yarn at different washing

cycles based on SEM, EDX and FTIR analysis

UV resistance test using UV-Vis spectra

Data analysis

End

Figure 3.1: Flowchart of the study.

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3.3 Chemicals

The chemicals used were 1,2,3,4-butanetetracarboxylic acid (BTCA) (Sigma Aldrich),

zinc oxide (ZnO) (Sigma Aldrich), acetone (Merck Millipore), and ethanol (Merck
Millipore) and these chemicals were laboratory grade. All the chemicals were used
without further purification.

3.4 Preparation of ZnO Solution

In the study, two concentrations of ZnO were used to coat the cotton yarn. In Plate
3.1, a round neck bottom flask was used to dilute 0.5 g and 0.25 g of ZnO powder in
100 ml of distilled water, respectively, in order to achieve 0.5% and 0.25% w/v
concentration of ZnO suspension. The ZnO suspension was stirred using a magnetic
stirrer for 24 hours at room temperature to obtain a homogenous solution before the
coating process was done (Farouk et al., 2009). The coating process must be done within
12 hours after the ZnO was stirred because the ZnO tended to accumulate at the bottom
of the flask. As shown in Plate 3.2, before the coating process, the ZnO suspension was
sonicated using a probe sonicator at room temperature for 30 minutes to ensure that the
solution was in a homogenous state.

3.5 Crosslinking of Cotton Yarn With 1,2,3,4-Butanetetracarboxylic Acid

(BTCA)

The preparation of crosslinking solution and crosslinking method were based on

Farouk et al. (2009). 0.5% w/v and 1.5% w/v were two different concentrations of BTCA
used to crosslink the fibre within the cotton yarn. The BTCA powder was initially mixed
with 100 ml of distilled water and was further sonicated using a probe sonicator for 1
hour. 2 metres of the cotton yarn was impregnated in the prepared solutions of BTCA.
The yarn was then dried at 80 oC for 10 minutes.

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3.6 Coating of Cotton Yarn with ZnO

Dip-coating method with aid of sonochemical treatment was used to coat ZnO on the
cotton yarn. This method has been reported as a simple and effective process for the
surface treatment of fibrous materials, such as cotton (Tang et al., 2018). As suggested
by El-Hady et al. (2013), the cotton yarn should be immersed in 0.25% and 0.5% w/v
of ZnO suspension, respectively, for 1 hour at 70 oC in the sonication bath. The resultant
ZnO coated cotton yarn is illustrated in Figure 3.2. The coated yarn was dried at 80 oC
for 10 minutes and was further cured at 130 oC for 3 minutes. The coated yarn was
rinsed in a hot water, followed by the cold water, to remove any unfixed ZnO particles
on the surface of the yarn. The yarn was then washed for 1, 5, 10, 15, and 20 washing
cycles. The effects of washing cycles on the yarn morphological structures, and UV
protection were investigated in the study.

Plate 3.1: A picture of stirring of ZnO solution for 24 hours

Plate 3.2: A picture of sonication of ZnO solution before dip-coating process of cotton
yarn

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 Figure 3.2: Typical SEM image of ZnO coated cotton yarn

3.7 Washing Durability of ZnO Coated Cotton Yarn

Based on the ISO 105-C10:2006, the washing durability of ZnO coated cotton yarn
under simulated laundering conditions was used as the guideline procedures in the study.
The washing durability of the ZnO coated yarn was tested at 1, 5, 10, 15 and 20 washing
cycles. The weight of the yarn was taken before and after washing for each cycle in order
to determine the weight loss of the coated yarn using equation (1) (Mai et al., 2018).

Weight loss (%) = w1 – w2 x 100

w1 (1)

where w1 is the weight of ZnO coated yarn before washing, whereas w2 is the weight of
ZnO coated yarn after washing.

In addition, the effect of washing the ZnO/cotton yarn after each cycle of laundering
determines the ability of the ZnO to retain its UV protection and anti-microbial properties
even after washing. The sample was prepared in the length of 2 metres and was weighed
before the washing process. The yarn was washed using a laundering machine,
WASHTEC-P, Roaches International Ltd., England at 60 oC for 30 minutes. The yarn
samples were placed in a steel jar with a standard reference detergent and the liquor ratio
of 1:50. The yarn sample was washed, dried, and weighed. The process represents one
washing cycle and it was repeated until 20 times to represent 20 washing cycles.

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3.8 Scanning Electron Microscopy (SEM)

A scanning electron microscope (SEM) is a microscope that works with electrons,

which are particles with a negative charge. These electrons are liberated by a field
emission source. With SEM, small graphic details on the surface of the sample can be
visualized. SEM is often used to observe the structure of the sample as small as 1
nanometre (Stanley et al., 2000).
The morphology of the coated yarn was observed before and after incorporating ZnO
using SEM. SEM studies were performed by Hitachi TM3030Plus. All the yarn samples
including the coated cotton yarn, unwashed ZnO coated yarn, and ZnO coated yarn after
1, 5, 10, 15, and 20 washing cycles were prepared by cutting each sample into the length
of 1 cm and was observed under 100, 500, and 1000 magnifications with an accelerating
voltage of 15.0 kV. All the samples were mounted on stabs and sputter coated with
gold before the analysis to prevent any charging from the samples (El-Hady et al., 2013).

3.9 Energy Disperse X-Ray (EDX) -Mapping

EDX by Oxford Instrument, INCA, is used to observe the elements present on the
sample and investigate the accumulation of metal on the surface of the yarn (Scimeca
et al., 2018). EDX uses X-ray spectrum to obtain a localized chemical analysis (Scimeca
et al., 2018). It is an X-ray microanalysis that can also be used as a mapping similar to
SEM.
The uncoated cotton yarn and ZnO coated yarn from each washing cycle was tested
for the EDX analysis. All the samples were mounted on stabs and were sputter coated
with gold before analyzing the sample to prevent any charging from the samples (El-
Hady et al., 2013). The EDX data are usually in the form of percentage of weight value
of elements exist on the sample. The possible elements of the ZnO coated yarn were C,
O, and Zn. The estimated percentage of weight for each sample from a different washing
cycle was recorded and compared.

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3.10 Fourier-Transform Infrared Spectroscopy (FTIR)

FTIR is a method used to obtain infrared spectrum of absorption or transmittance of a

solid, liquid or gas. In addition, the FTIR determines the bonding mechanisms in solids and
on surfaces, and the molecular vibrations that can be related directly to the symmetry of
molecules (Peak, 2005). It is also possible to determine precisely how a molecule is bonding
on surfaces or as a component in a solid phase from its infrared spectrum (Peak, 2005).
The FTIR spectra of uncoated cotton yarn and coated ZnO cotton yarn were recorded
using Perkin Elmer, Spectrum 3 FT-IR Spectrometer, by using the diffuse reflectance
assembly in the spectral range of 4000-800 cm-1. The use of FTIR was based upon
Arphutaraj et al. (2018), where the samples were placed on the surface of zinc selenide prism
and pressure was exerted to ensure that the crystal and the sample were in a good contact for
assessment (Arphutaraj et al., 2018). The spectra for each sample were at resolution 2 cm -1
and an average of 64 scans (Arphutaraj et al., 2018). The uncoated cotton yarn acted as a
control sample. The BTCA and ZnO raw materials were used to determine the presence of
these materials on the coated yarn. An analysis of the data was conducted by observing the
shift of the spectra of the coated cotton yarn and the control sample in order to observe any
crosslinking between the cotton yarn, BTCA, and ZnO.

3.11 UV Filtration

The responses of the ZnO coated cotton yarn towards the UV were measured by the
absorbance and transmittance values. The UV absorbance and transmittance spectra of
uncoated and ZnO coated yarns were measured using the UV-VIS spectroscopy (Perkin
Elmer) in the wavelength range of 200 – 800 nm. Based on a research done by Yu (2015),
the single yarn was parallelly assembled to the vertical frame edge until it was partially or
fully obscured at the open area of the hole. As for the blank reference, air was set as the
reference. The UV spectra of the uncoated cotton yarn was compared with the ZnO coated
cotton yarn based on the effectiveness of the UV absorbance. Apart from that, the percentage
of transmission (T%) was also collected. The T% of all the samples at wavelength of UVA
and UVB was calculated and compared based on the AS/NZS 4399: 1996 standard method
using equation (2) (Belay et al. 2020).

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 (2)
where T is the transmittance value, λ1 is the wavelength started and λ2 is the wavelength
ended.

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