Journal of Natural Fibers

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Eco-Friendly Bleaching of Cotton Fabrics Without

Heating Using Direct Process Water in the
Presence of Sodium Chlorite and Phosphonate

Sami Dursun & Salih Z. Yıldız

To cite this article: Sami Dursun & Salih Z. Yıldız (2023) Eco-Friendly Bleaching of Cotton
Fabrics Without Heating Using Direct Process Water in the Presence of Sodium Chlorite and
Phosphonate, Journal of Natural Fibers, 20:1, 2146248, DOI: 10.1080/15440478.2022.2146248

To link to this article: https://doi.org/10.1080/15440478.2022.2146248

© 2022 The Author(s). Published with

license by Taylor & Francis Group, LLC.

Published online: 15 Nov 2022.

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JOURNAL OF NATURAL FIBERS
2023, VOL. 20, NO. 1, 2146248
https://doi.org/10.1080/15440478.2022.2146248

Eco-Friendly Bleaching of Cotton Fabrics Without Heating Using

Direct Process Water in the Presence of Sodium Chlorite and
Phosphonate
Sami Dursuna and Salih Z. Yıldızb
a
Faculty of Engineering and Natural Sciences, Department of Metallurgical and Materials Engineering, Konya Technical
University, Konya, Turkey; bFaculty of Arts and Sciences, Department of Chemistry, Sakarya University, Sakarya, Turkey

ABSTRACT KEYWORDS
A large amount of chemicals, water and energy are used during the bleaching NaClO2; HEDP; green;
of raw cotton fabrics. For this reason, it is extremely important for economic budget-friendly; cotton
and ecological aspect to develop eco-friendlier bleaching technology that fabric-friendly
eliminates the need for heat energy, process water, and wetting agent in the 关键词
bleaching of these fabrics. Here, we report on green approach for industrial- 绿色; 预算友好; 棉织物友
scale bleaching with sodium chlorite (NaClO2) in presence of phosphonates 好型
(HEDP), which is used as both wetting agent and pH regulator and contri­
butes to the high whiteness of fabrics. In bleaching, the process water was
used in ambiant temperature as flote without any heating process, thus
reducing the energy requirement significantly. In the measurements, it was
observed that the whiteness value (W.I. = 72.6) obtained after 8.0 h bleaching
at 20°C which was very close to the whiteness value (W.I. = 74.2) of reference
W-1 fabric. Also, it has been confirmed that cotton fabrics bleached with
NaClO2 have higher strength values, less damage, and residue on the fabric
compared to reference fabrics, as well. This study showed that cotton fabrics
can generate a small amount of wastewater and can be successfully bleached
in the presence of NaClO2 without the need for any heating energy.

摘要
原棉织物漂白过程中需要大量的化学物质、水和能量. 因此, 从经济和生态
方面来说, 开发更环保的漂白技术是极其重要的, 该技术消除了这些织物漂
白过程中对热能、工艺水和润湿剂的需求. 在这里, 我们报道了在膦酸盐
(HEDP) 存在下用亚氯酸钠 (NaClO2) 进行工业规模漂白的绿色方法, 该方法
既用作润湿剂又用作pH调节剂, 有助于织物的高白度. 在漂白过程中, 工艺
水在环境温度下作为浮石使用, 无需任何加热过程, 从而显著降低了能量需
求. 在测量中, 观察到在20°C下漂白8.0小时后获得的白度值 (W.I. = 72.6) 非

CONTACT Salih Z. Yıldız [email protected] Sakarya University, Department of chemistry, Serdivan, Sakarya 54050, Turkey
© 2022 The Author(s). Published with license by Taylor & Francis Group, LLC.
This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/4.0/),
which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
2 S. DURSUN AND S. Z. YILDIZ

常接近参考W-1织物的白度 (W.I = 74.2). 此外, 已经证实, 与参考织物相比,

用NaClO2漂白的棉织物具有更高的强度值、更少的损伤和织物上的残留
物. 这项研究表明, 棉织物可以产生少量废水, 并且可以在NaClO2存在下成
功漂白, 而不需要任何热能.

Introduction
The world’s population is expected to increase by around 30% by 2050. This population growth will
lead to a significant increase in textile production and consumption, which will significantly increase
the textile industry’s energy and water use and emissions of carbon dioxide and other harmful
emissions to the environment (CO2) (Atav et al. 2021; Hasanbeigi and Price 2015). Due to the
increasing demand for textile products, reducing energy use and CO2 emissions requires innovation
in addition to existing technologies.
Cotton fabric, which is the most popular of the cellulosic textile materials, constitutes about half of
the fabric sector in recent years (Liu, Liu, and Fang 2022; Peng et al. 2018). The main reasons why
cotton fabrics are so preferred are their sustainability, low environmental concerns, and biocompat­
ibility (Andra et al. 2021; Kim et al. 2017). While 90% of cotton fabrics consist of cellulose, 10%
consists of impurities such as protein, pectin, minerals, and wax (Bogard et al. 2021; Farrell, De
Boskey, and Ankeny 2016). Even though pectin and wax have positive effects on cotton, it significantly
reduces the wettability of cotton by preventing water adsorption (Xia et al. 2021). Considering these
results, dyeing fabrics without removing impurities present in cotton fabric is difficult for the dyeing
industry. In commercial bleaching processes, bleaching processes are usually carried out at high
alkalinity at high temperatures to achieve the required whiteness of the fabrics. This can cause
significant damage to cotton fibers as well as significant energy consumption (Wang et al. 2020).
Bleaching of cellulose material with hydrogen peroxide is generally carried out under alkaline condi­
tions at extreme temperatures, resulting in greater energy consumption and fiber damage (Liu, Zhang,
and Yan 2018). The processes to remove these impurities in cotton fabrics are very important in order
not to damage the cotton structure and to ensure its whiteness. The hydrogen peroxide bleaching
process, which is the most used to remove the natural pigments from cotton and cotton blends,
requires high water consumption and energy input, as well as an alkaline environment, stabilizer, and
long incubation time at high temperatures. This process results in damage to the cotton fibers and
decreases product quality, as well. For this reason, enzyme-mediated systems are considered better
alternatives, and there are remarkable studies on the bleaching of cotton fabric by enzymatic methods
in the literature. Tülek et al. worked with MmLac cloned and heterologously expressed in P. pastoris
for the removal of specific synthetic dyes and in the treatment of textile effluent (Tülek et al. 2021).
Subsequently, they investigated their performance in bleaching cotton fabrics by using the materials
MmLac, silica@MmLac/ZIF-8 and silica@Glu-MmLac/ZIF-8 produced by them. As a result of these
studies, silica@MmLac/ZIF-8 and silica@Glu MmLac/ZIF-8 concluded that laccase-based biocatalysts
are promising for biotechnology (Tülek et al. 2021). In the Mojsov study, treatment of cotton terry
fabrics with alkaline pectinase enzyme and properties such as whiteness and weight loss after abrasion
were investigated. It was determined that cotton fabrics treated with enzymatic treatment were less
damaged and needed less energy and water (Mojsov 2018). These processes consist of two pre-
treatment processes, namely scrubbing and bleaching (Wang et al. 2020). However, natural fibers
and fabrics are still yellowish and brownish in color even after scrubbing. The reason for these colors
may be various environmental factors such as climate, soil, drought, and frost (Amutha et al. 2022;
Vörösmarty et al. 2010). The purpose of the bleaching step is to remove the coloring matter via
bleaching chemicals and as a result, to obtain white fabrics.
Sodium chlorite is one of the most important bleaching chemicals, as it ensures that the textile
material it is treated with exhibits low loss of strength and a high degree of whiteness (Forte-Tavčer
 JOURNAL OF NATURAL FIBERS 3

2010; Kramar, Ivanovska, and Kostić 2021). In addition, sodium chlorite is easily obtained and is
relatively stable in storage. In addition, sodium chlorite is a stable free radical that acts as a one-electron
oxidant in reactions with reducing substrates such as amines, sulfites, and phenols (Jangam and
Richardson 2010; Kawata et al. 2021). However, sodium chlorite, like other bleaching agents, is either
relatively environmentally harmful or shows high energy use during bleaching (Hasanbeigi and Price
2015). For instance, when bleaching cotton fabric with the aid of sodium chlorite, the higher the
ambient temperature, the higher the rate of decomposition of sodium chlorite as a strong oxidizer
(Toshikj et al. 2019). However, this results in relatively high energy use in the bleaching process.
In this study, an approach that can minimize energy consumption by performing the bleaching
process of cotton fabrics at process water temperature (20 ± 5°C) without the need for additional heat
is presented. In addition, the chemical consumption in the bleaching process was tried to be reduced by
using HEDP chemical as both pH regulator and wetting agent. It was observed that the whiteness value
obtained as a result of bleaching using sodium chlorite at 20 ± 5°C was close to the whiteness value
obtained using hydrogen peroxide in a high temperature environment. The study is also remarkable in
terms of obtaining high quality and tenacity cotton fabrics with sufficient whiteness value.

Experimental
Equipment and materials
Orbital shaker of LBX Orb-Pro was used for bleaching. The orbital shaker descriptions were as follow:
timer function (1 min–19 h 59 min), The speed is adjustable between 100 and 500 rpm, an orbital
diameter of 10 mm and a load capacity of 7.5 kg. The whiteness of the bleached samples was measured
as reflectance by the Konica Minolta Spectrophotometer, CM-3600d. Mettler Toledo S220-K table top
pH meter was used for pH measurements. Cotton samples were examined using a scanning electron
microscope (SEM, Hitachi S-4700). A Shimadzu brand analytical balance (AUX320 Analytical
Balance, 320 g/0.1 mg) was used to calculate the weight loss of fabrics as a result of bleaching.
Cotton fabric was coated with a sputter machine (cressington 108 auto sputter coater). Fourier
transform infrared spectroscopy (FT-IR, VERTEX-70 Bruker) was used to determine the chemical
bonds of the fabrics and whether the impurities contained in the fabrics were successfully removed by
bleaching. Measurements were made at a resolution of 4 cm−1 in the range of 4000–400 cm−1. The
100% cotton fabric used in the studies was supplied by NUR Textile Co., Turkey. The fabric has 150 g/
m2 weight, 30 yarn/cm weft, and 36 yarn/cm warp properties.

Chemicals
Phosphoric acid (H3PO4, 85% pure), citric acid (C₆H₈O₇, 99% pure), acetic acid (C2H4O2, 99% pure),
and formic acid (CH₂O₂ reagent grade, ≥96%) used for pH adjustment were obtained from Merck
Chemical Company. Potassium iodide (KI, reagent grade, ≥99%), sulfuric acid (H2SO4, 96%), sodium
thiosulfate (Na2S2O3, reagent grade, ≥99%), and hydrogen peroxide solution (H2O2, 30%) were
obtained from Sigma Aldrich Chemical Company. Sodium chlorite was supplied as a 31% solution
in water by Turoksi Chemical Co. 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) used for
wetting agent and pH adjustment and Nonylphenol (NP-10) used for wetting agent were supplied by
the Turkish domestic market as technical grade.

Bleaching
Process conditions
An average of 10 g was cut from a roll of raw cotton fabric for each bleaching experiment. The cut
fabric was soaked in a liquor solution. Liquids consist of sodium chlorite, a wetting agent (optional),
and different acids. The fabric/liquor ratio specified in the recipes is 1/10. 5.25 g/L NaClO2, (0–1 g/L)
4 S. DURSUN AND S. Z. YILDIZ

wetting agent was used in the experiments. NP-10 was used as a wetting agent. The pH of the liquids
was adjusted (2.5–11.0) by adding phosphoric acid (PA), citric acid (CA), acetic acid (AA), formic acid
(FA), and 1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP) acids. HEDP is used as both a pH
regulator and a wetting agent. The resulting solution and cotton fabric were transferred into a 200 mL
beaker. Beakers were fixed on the orbital shaker. Then, the orbital shaker rotation speed of 100 rpm
was adjusted and fabric bleaching was carried out at different times (Figure 1). At the end of the
period, the fabrics taken from the beaker were rinsed with tap water. Then, the fabric was left to dry at
ambient temperature. Further research has been carried out with bleached fabrics and their process
waste.

Preparation of reference fabrics

In this study, experimental fabrics bleached with NaClO2 were compared with reference fabrics
bleached with H2O2 under two different conditions. With the approach of the textile industry,
Witness-1 (W-1) and Witness-2 (W-2) reference cotton fabrics were given, respectively, for the
reference of bleached fabric before dyeing and the reference of fabric showing exact whiteness.
6 g/L H2O2 was used for bleaching the W-1 fabrics. NaOH was used to adjust the pH in bleaching
performed at pH = 10.5. Non-ionic NP-10 was used as a wetting agent and bleaching duration was
determined as 2 h. In the bleaching of the W-2 fabrics, unlike in the bleaching process of the W-1
fabric, 4 g/L H2O2 was used and the bleaching time was determined as 1 h.

Measurements and analysis

Sodium chlorite (NaCIO2) analysis
A sample of 0.25 g was taken into the erlenmeyer with a pipette for sodium chlorite analysis. 50 mL of
distilled water was added to the substance. Then, 20 mL of KI (100 g/L) and 10 mL of H2SO4 (50 g/L)
were added, respectively. The Erlenmeyer containing the sample to be analyzed was kept in the dark
for 10 min. Titration was performed with 0.1 M sodium thiosulfate after adding a few drops of starch
indicator. The point at which the solution turned a light blue-black color was recorded as a turning
point. C8 is the sodium chlorite (NaClO2) content, as a percentage by mass given by the formula:
C8 ¼ V1 :c:ð2:262Þ
(1)
m
where V1 is the spent sodium thiosulfate (mL), c is the concentration of sodium thiosulfate solution
(M) and m is the test sample weight (g).

Figure 1. Schematic representation of the cotton fabric bleaching process at process water temperature (20±5°C).
 JOURNAL OF NATURAL FIBERS 5

Weight loss
The weight loss of the fabric after the bleaching process was calculated on a dry weight basis using the
following formula:
W1 W2
Weight Lossð%Þ ¼ � 100 (2)
W1
where W1 and W2 are the dry weights of the cotton fabric before and after bleaching treatment,
respectively.

Degree of whiteness
In the whiteness measurements, the whiteness degrees of the reference samples (W-1 and W-2)
bleached with H2O2 and the samples bleached with NaClO2 using different combinations in this
study were investigated. The whiteness indexes (W.I.) of bleached cotton fabrics were measured using
a Konica Minolta spectrophotometer (CM-3600d). Whiteness indexes were calculated in terms of CIE
Y (green) and (blue) reflectance components using the ASTM Method E31373 equation.
4Z
W:I: ¼ 3Y (3)
1:18
where Y and Z are the readings of the device.

Tensile strength (RT)

Tensile strength of cotton samples was determined by the strip method according to ASTM procedure
D 2256-66T.

SEM analysis of cotton samples

Scanning electron microscopy (SEM, Hitachi S-4700) was used to obtain information about the
microstructures of the raw cotton fabric, the reference (W-1) sample bleached with H2O2 and the
cotton fabric with the highest whiteness index bleached with NaClO2, and to observe the differences
before and after bleaching. Before SEM analysis, the samples were coated with a Cressington 108
automatic spray coater device. The diameter and size distribution of cotton fibers were determined
using Image J software.

Results and discussion

Since it is known that NaClO2 shows better bleaching properties under acidic conditions, the effect of
acid species on whiteness was first investigated at different pH values (pH = 2.5, 3.0, 3.5, 4.0 and 4.5).
The acid types used are phosphoric acid (PA), citric acid (CA), acetic acid (AA), formic acid (FA), and
1-hydroxy ethylidene-1,1-diphosphonic acid (HEDP). The results of these examinations are given in
Figure 2a.
Among these acid types, HEDP acid gave the best results, and the rest of the study was carried out
on this acid. After determining the acid to be used, bleaching studies were carried out at different pH
values (2.5, 3.0, 3.5, 4.0, 4.5, 5.0, 7.0, and 11.0) to determine the optimum pH and the results were given
in the Figure 2b. It was determined that the pH value giving the best whiteness value (W.I. = 72.6) was
3.0. Used during the bleaching process; Information such as the amount of bleach, the name of the pH
regulator, the liquor ratio, and the temperature value was given in Table 1 in detail. One of the most
important advantages of this study is that no wetting agent is used in bleaching, and HEDP acts as both
an acid regulator and a wetting agent.
6 S. DURSUN AND S. Z. YILDIZ

Figure 2. (a) The effect of different pH values and different acid types on the whiteness of cotton fabric, and (b) Comparison of the
whiteness index of the bleaching processes using HEDP at different pH values with the reference (W-1 and W-2) fabrics.

Table 1. Determination of optimum pH in cotton bleaching.

(NaClO2) pH Wetting Temperature Whiteness
Code (g/L) Regulatior Agent (g/L) Ratio (°C) pH Index (%)
1 5.25 HEDP - 1/10 20 11.0 11.2
2 5.25 HEDP - 1/10 20 7.0 20.4
3 5.25 HEDP - 1/10 20 5.0 36.0
4 5.25 HEDP - 1/10 20 4.5 42.9
5 5.25 HEDP - 1/10 20 4.0 55.6
6 5.25 HEDP - 1/10 20 3.5 69.1
7 5.25 HEDP - 1/10 20 3.0 72.6
8 5.25 HEDP - 1/10 20 2.5 72.4
W-1 6.00 (H2O2) NaOH NP-10 1/20 90 10.5 74.2
W-2 4.00 (H2O2) NaOH NP-10 1/20 70 10.5 59.4
Raw Cotton - - - - - 6.4
Duration: 8 h.

While there was an increase in the whiteness value as the pH value decreased, this acceleration
deviated only at pH = 2.5. The lower the pH value in bleaching processes, the higher the bleaching
success (Hubbell and Ragauskas 2010). Chloric acid (HClO2) used in bleaching is an unstable acid.
 JOURNAL OF NATURAL FIBERS 7

Therefore, it decomposes into chlorine dioxide (ClO2), which is the active species during bleaching.
However, when a pH below 3.0 is used, it causes a decrease in the whiteness value as it will cause
a decrease in oxygen formation in the chlorite, which plays an active role in bleaching. This explains
the decrease in whiteness value at pH = 2.5. In order to better understand the effect of pH on
bleaching, changes in sodium chlorite concentration in the presence of different pH values were
investigated using a UV-visible spectrophotometer (Figure 3a). The absorption peaks at 260 nm and
360 nm in the figure belong to NaClO2 and ClO2, respectively (Yang et al. 2017). It is observed that as
the pH value decreases, the concentration of NaClO2 decreases and the formation of ClO2 increases.
This can be explained by the higher oxidation performance of the system with the increase of H+ in the
bleaching process. However, as the pH decreases, NaClO2 can turn into toxic and corrosive chlorine
dioxide gas. For this reason, it was desired to determine the optimum pH value that gives the
appropriate whiteness value at different pH values (Hao et al. 2017). When the pH value drops to
2.5 and below, it turns into the above-mentioned undesirable gas. In addition, low pH values can
damage cotton fabric. Considering these results, it was decided not to drop below pH = 3 in the
bleaching process, and Figure 3b supports this situation. In this figure, the remaining NaClO2 content

Figure 3. Investigation of (a) the effect of pH change on sodium chlorite concentration by means of UV-visible spectrophotometer,
and (b) the change in sodium chlorite content at different pH values in the presence of HEDP.
8 S. DURSUN AND S. Z. YILDIZ

in the medium after bleaching at different pH values is given. It was determined that as the pH value
decreased, the amount of NaClO2 decreased in direct proportion. While there was no significant
change in NaClO2 concentration at high pH values, it was observed that NaClO2 decreased as the pH
value decreased, that is, as the system became acidic (Gong and Li 2019).
After the optimum pH value for bleaching was determined as 3.0, bleaching studies were carried
out to determine the optimum duration. For this, bleaching studies were carried out at different times
(0.5, 1.0, 2.0, 4.0, 8.0, 12.0, and 24.0 h) while keeping other conditions such as pH = 3, temperature =
20 ± 5°C constant (Figure 4a).
For this, bleaching studies were carried out at different times while keeping other conditions
constant. It has been observed that fabrics produced after 0.5-h bleaching exhibit a low whiteness
value (W.I. = 43.4). It was determined that there was a significant increase in the whiteness value of the
fabric in bleaching from 1.0 h to 4.0 h. However, it was determined that there was no significant
change in the whiteness value of the cotton fabric as a result of 8.0-h bleaching and 24.0-h bleaching
time. The reaction of sodium chlorite with yellowish and brownish colored groups caused by different

Figure 4. (a) Effect of different durations of bleaching on whiteness, and (b) Comparison of the weight loss of the fabric as a result of
different bleaching times with the weight loss of the W-1 fabrics.
 JOURNAL OF NATURAL FIBERS 9

physical, chemical, and environmental factors in cotton fabric is similar to chemical reactions. For this
reason, the bleaching process is almost completed within 8 h. Considering the measured whiteness
values, it was decided that 8.0-h of bleaching time would be sufficient for bleaching cotton fabrics. The
whiteness value (W.I. = 71.7) obtained after 8.0 h of bleaching is very close to the reference value (W.I.
= 74.2) of the fabric used as a W-1 after bleaching with H2O2 at 90°C. In addition, the whiteness value
of the cotton fabric bleached for 1.0 and 2.0 h is close to the reference value of the W-2 fabric bleached
with H2O2 at 70°C, and it can be used easily in under dye fabrics. The parameters used to determine
the optimum time in the bleaching process and the whiteness values at different times are given in
Table 2.
One of the points to be considered in the bleaching process is the weight loss of the fabric after
bleaching. For this reason, the weight losses that occur as a result of the bleaching processes carried out
at different times are calculated and given in Figure 4b. As seen from the figure, it is seen that the
weight loss of the fabric increases as the bleaching time increases. This can be explained by the removal
of unwanted parts such as waxes, pectins, proteins, pigments, hemicelluloses, and other organic and
inorganic impurities from the fabric as the bleaching process continues. In addition, the weight loss in
the cotton fabric as a result of bleaching in the presence of NaClO2 is 1/3 of the weight loss in the
presence of it. It is noteworthy that the weight loss when the whiteness values are close to each other is
considerably lower than the weight loss with H2O2. The bleaching process performed with NaClO2
also provides an advantage with less weight loss on the fabric.
In Figure 5, FE-SEM and high resolution FE-SEM images of unbleached raw cotton fabric and
cotton fabrics bleached with H2O2 and NaClO2 were given. The FE-SEM image in Figure 5a belongs to
the raw cotton fabric, and it is seen from the image that the fibers have homogeneous diameters. As
a result of the measurements made from 40 different points on the FE-SEM image with the ImageJ
program, the average diameter of the fibers was calculated to be 18 ± 6 µm. The size distribution
diagram of the fibers was given in Figure 5a as an inset in figure. A high resolution FE-SEM image of
the same fabric was given in Figure 5d. When looking at the image, it is observed that there are
residues that can consist of waxes, pectin, proteins, pigments, hemicelluloses, and other organic and
inorganic impurities, which are also indicated by pink arrows among the cotton fibers. Figure 5b
shows the FE-SEM image of cotton fabric bleached with H2O2 to be used as a reference sample. After
bleaching, the cotton fabric appears to be damaged, and there are some tears in the fibers (indicated by
pink circles in the image). In addition, as a result of the measurement performed on the FE-SEM
image, it was determined that the average fiber diameters were 13 ± 5 µm (the size distribution
diagram of the fibers is given as an inside picture in Figure 5a). This decrease in fiber diameters can be
explained by the removal of organic and inorganic impurities in cotton fibers as a result of bleaching.
High resolution FE-SEM image of the reference cotton fabric sample was given in Figure 5e. Looking
at the image, it is observed that there are residues in the cotton fibers, which are also indicated by the
pink arrows. It is observed that the residues cannot be removed to a large extent after bleaching with

Table 2. Determination of optimum duration in cotton bleaching.

(NaClO2) pH Wetting Temperature Duration Whiteness
Code (g/L) Regulatior Agent (g/L) Ratio (°C) (hour) Index (%)
1 5.25 HEDP - 1/10 20 0.5 43.4
2 5.25 HEDP - 1/10 20 1.0 54.4
3 5.25 HEDP - 1/10 20 2.0 58.8
4 5.25 HEDP - 1/10 20 4.0 64.9
5 5.25 HEDP - 1/10 20 8.0 72.6
6 5.25 HEDP - 1/10 20 12.0 73.2
7 5.25 HEDP - 1/10 20 24.0 73.7
W-1 6.00 (H2O2) NaOH NP-10 1/20 90 1.5 74.2
W-2 4.00 (H2O2) NaOH NP-10 1/20 70 1.0 59.4
Raw Cotton - - - - - 6.4
Bleaching with NaClO2, pH: 3.0, Bleaching with H2O2, pH: 10.5.
10 S. DURSUN AND S. Z. YILDIZ

Figure 5. FE-SEM images of samples of (a) raw fabric, (b) W-1 fabric bleached with H2O2, (c) experimental fabric bleached with NaClO2
(fiber size distribution histograms were given as inset in each figure) and high-magnification FE-SEM images of samples (d) raw
fabric, (e) W-1 fabric bleached with H2O2, and (f) experimental fabric bleached with NaClO2.

H2O2. In Figure 5c, the FE-SEM image of the experimental cotton fabric bleached with NaClO2 was
given. Looking at the image, it is seen that the fibers have homogeneous diameters. As a result of the
measurements made on the image, the average diameter of the fibers was found to be 16 ± 5 µm and
the size distribution diagram was given in Figure 5c as an inside graph. While this value is smaller than
the average diameter of raw cotton fibers, it is larger than the diameter of cotton fabric fibers bleached
with H2O2. A slight reduction in fiber diameters may mean that the cotton fibers may not have suffered
any damage as a result of bleaching. The high-resolution FE-SEM image in Figure 5F also supports this
situation. In this figure, it is seen that the surface of the fibers is smoother than the reference fiber. In
addition, it was observed that there was much less residue in the fabric bleached with NaClO2
compared to the FE-SEM images of raw and H2O2-bleached cotton fabrics. The results from all of
the FE-SEM images match the results in the weight loss graph in Figure 4b.
The FTIR spectra of cotton fabric raw and bleached with NaClO2 at 20 ± 5°C are given in Figure 6.
The peaks at 1594 and 1592 cm−1 in the spectra of both samples can be attributed to the stretching
vibration of the conjugated carbonyl group. Likewise, the peaks at 1325 and 1321 cm−1 in both samples
express the bending vibrations of the C-H groups. The peaks of raw cotton fabric at 1027 and 885 cm−1
and bleached cotton fabric at 1024 and 882 cm−1 are related to the ether bonds of cellulose (Bulut 2016;
Zhao et al. 2010). The peak corresponds to the C=O stretching vibration of the aryl group in pectin.
However, this peak is not in the spectrum of cotton fabric bleached with NaClO2. This can be
explained by the removal of pectin from the fabric during bleaching. A similar situation can be said
for the peak at 1155 cm−1 of the raw cotton sample. The fact that the peak at this frequency is not
observed in the bleached sample can be explained by the deformation of the anti-symmetric
C-O-C bond as a result of the bleaching process (Sangeetha, Varghese, and Nayak 2019).
The mechanical properties of fabrics are very important for their purposes and areas of use.
For this reason, it is desirable that the bleached fabrics show sufficient strength. Considering this
situation, the strengths of pure, H2O2 and NaClO2 bleached fabrics were measured and it is
given in Figure 7. In Figure 7a, how pH and time parameters affect the tenacity of the fabric is
 JOURNAL OF NATURAL FIBERS 11

Figure 6. FTIR spectra of raw cotton, and bleached cotton fabric at process water temperature.

Figure 7. (a) The effect of different pH values and duration on tenacity of cotton fabric, and (b) Whiteness and tenacity values of
fabrics bleached at different pH values via HEDP and NaClO2.
12 S. DURSUN AND S. Z. YILDIZ

Table 3. Effect of pH on the physical properties and whiteness index of the bleached cotton fabric.
W.I Tenacity
Code (NaClO2) (g/L) pH pH Regulatior (%) (kg f) Elongation (%)
1 5.25 2.5 HEDP 72.4 59.4 31.2
2 5.25 3.0 HEDP 72.6 61.6 31.2
3 5.25 3.5 HEDP 69.1 63.2 30.4
4 5.25 4.0 HEDP 55.6 65.1 29.1
5 5.25 4.5 HEDP 42.9 66.2 27.8
6 5.25 5.0 HEDP 36.0 67.5 25.3
7 5.25 7.0 HEDP 20.4 68.1 24.4
8 5.25 11.0 HEDP 11.2 69.0 23.6
W-1 6.00 H2O2 10.5 NaOH 74.2 51.3 32.6
W-2 4.00 H2O2 10.5 NaOH 59.4 58.2 28.7
Raw Cotton - - - 6.4 71.3 21.1
Duration: 8 h.

examined. As seen from the figure, it was observed that tenacity increased with the increase in
pH, but decreased as the bleaching time increased. The sample with the highest tenacity was the
unbleached raw cotton fabric sample, while the sample with the lowest tenacity was the W-1
sample, which was bleached with H2O2. It was determined that the tenacity value of the fabric
sample exhibiting optimum bleaching with NaClO2 was significantly higher than the tenacity
value of the W-1 sample. For a better understanding of the above, in Figure 7b, the relationship
between whiteness value and tenacity is discussed in the graph. When the graph was examined,
it was observed that there was an inverse proportion between the whiteness value and tenacity,
and the tenacity decreased as the whiteness increased. The results of the measurements made to
determine the physical properties of raw, reference and experimental fabrics bleached at different
pH values (tenacity and percentage elongation at break) are given in Table 3. As seen from the
table, fabrics that were bleached at low pH values and exhibited high whiteness gave relatively
better percentage elongation results. It is seen that all these results obtained in the determination
of physical properties coincide with the results of FE-SEM and FT-IR. It is an expected result
that components such as cellulose and pectin in raw fabric fibers are removed from the fiber by
the bleaching process and cause a decrease in fiber diameters, resulting in a decrease in tenacity
and a relatively increase in percent elongation (Bulut 2016).

Conclusion
In this study, the effects of parameters such as pH regulator, pH, time, and bleach concentration on the
bleaching of raw cotton fabric were investigated. HEDP gave the best whiteness value among the acids,
and the rest of the study was carried out on this acid. HEDP acts as a wetting agent as well as being
used as a pH regulator. After determining the acid to be used, bleaching studies were carried out at
different pH values to determine the optimum pH, and the best whiteness value was obtained at pH =
3.0. In addition, the effect of pH on NaClO2 was investigated, and it was determined that as the pH
value decreased, the percentage of NaClO2 decomposed by bleaching increased. Also, bleaching was
done at different times to determine the optimum bleaching time. In the bleaching experiments
carried out up to 8.0 h, it has been determined that the whitening speed of cotton fabrics is high, and
the bleaching rate decreases significantly as the time gets longer, i.e., 24 h. Considering the whiteness
values of the bleached fabrics, it was decided that 8.0 h of bleaching time would be sufficient for
bleaching the cotton fabrics. The whiteness value (W.I. = 72.6) obtained at this bleaching time was
found to be close to the whiteness value (W.I. = 74.2) of the reference W-1 fabric. In addition, it has
been calculated that the weight loss of the fabric as a result of bleaching with NaClO2 is only 1/3 of that
of the fabric bleached with H2O2. From the FE-SEM images, it was seen that the experimental fabric
bleached with NaClO2 had larger fiber diameters, less residue, and caused less damage to cotton fibers
than the reference fabric bleached with H2O2. In addition, the mechanical properties of the fabrics
 JOURNAL OF NATURAL FIBERS 13

were examined, and it was determined that the strength of the fabric bleached with NaClO2 was better
than the reference fabrics bleached with H2O2. In future studies, it is considered that biocomposite
catalysts will be produced and used in the bleaching of cotton fabrics. In this way, it is aimed to obtain
fabrics that are less damaged, have a higher whiteness value, and are more durable.

Highlights
(a) The bleaching process used in the study is economical and ecological.
(b) Since no heating process is applied, minimum energy is consumed.
(c) Less chemicals are used thanks to functional phosphonate (HEDP).
(d) Bleached fabrics exhibit high tenacity, whiteness and low residue formation.

Acknowledgements
The authors extend their appreciation to the TUROKSI Chemical Co. Ltd. for providing the cotton fabric and some
chemicals.

Disclosure statement
No potential conflict of interest was reported by the author(s).

Funding
There are no funding and benefits.

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