coatings

Article
Green Application of Isolated Colorant from Neem Bark for
Mordant-Coated Wool: Optimization of Dyeing and
Mordanting for Shade Development
Shahid Adeel 1, * , Muhammad Zuber 2 , Mustafa Kınık 3 , Aydın Zor 4 , Semih Büyükkol 5 ,
Ayşe Derya Kahraman 6, * , Meral Ozomay 7 , Attila Döl 8 , Zafer Lehimler 9 and Shahnaz Parveen Khattak 10

1 Department of Applied Chemistry, Government College University Faisalabad, Faisalabad 38000, Pakistan
2 Department of Chemistry, Riphah International University, Faisalabad Campus, Faisalabad 38000, Pakistan;
m.zuber@riphahfsd.edu.pk
3 Department of Graphics, Faculty of Fine Arts and Architecture, Necmettin Erbakan University,
42310 Konya, Turkey
4 Department of Graphics, Faculty of Fine Arts, Akdeniz University, 07050 Antalya, Turkey;
aydinzor@akdeniz.edu.tr
5 Painting Department, Faculty of Fine Arts, Akdeniz University, 07050 Antalya, Turkey
6 Vocational School of Technical Sciences, Istanbul University-Cerrahpaşa, 34320 İstanbul, Turkey
7 Department of Textile Engineering, Marmara University, 34854 İstanbul, Turkey;
meral.akkaya@marmara.edu.tr
8 Department of Painting, Faculty of Fine Arts, Niğde Ömer Halisdemir University, 51240 Niğde, Turkey
9 Department of Graphics, Faculty of Fine Arts, Atatürk University, 25240 Erzurum, Turkey
10 College of Home Economics, University of Peshawar, Peshawar 25130, Pakistan
* Correspondence: shahidadeel@gcuf.edu.pk (S.A.); a.kahraman@iuc.edu.tr (A.D.K.)

Abstract: This study aimed to assess the effectiveness of utilizing a tannin-based natural brown
colorant from neem bark for dyeing wool under microwave treatment, specifically evaluating its
coloring efficiency. The colorant was extracted in a methanol solution that had been acidified both
Citation: Adeel, S.; Zuber, M.; Kınık,
before and after being subjected to microwave treatment for up to 6 min. The dyeing variables were
M.; Zor, A.; Büyükkol, S.; Kahraman,
A.D.; Ozomay, M.; Döl, A.; Lehimler,
optimized to create new shades of dye with desirable fastness properties, and sustainable chemical
Z.; Khattak, S.P. Green Application of and bio-mordants ranging from 1 to 10 g/100 mL were employed. Through experimentation, it was
Isolated Colorant from Neem Bark determined that when an unirradiated acidic methanolic extract (AME) with a salt concentration of
for Mordant-Coated Wool: 3 g/100 mL was applied onto wool fabric (RWF) and subjected to microwave treatment for 4 min,
Optimization of Dyeing and it resulted in a high color yield. This was achieved by heating the solution to 65 ◦ C and allowing it
Mordanting for Shade Development. to remain in contact with the fabric for a duration of 65 min. Favorable color characteristics were
Coatings 2023, 13, 1639. https:// achieved when utilizing a pre-chemical mordant of 5% Fe and a post-chemical mordant of 5% Fe.
doi.org/10.3390/coatings13091639 In contrast, the utilization of 7% henna as a pre-bio-mordant in combination with 3% turmeric
Academic Editor: Maria Vittoria extract as a meta-bio-mordant resulted in favorable color characteristics. The study concludes
Diamanti that microwave treatment exhibits outstanding sustainable efficacy in isolating colorants from
neem bark powder for wool dyeing. Incorporating bio-mordants further enhanced the process’s
Received: 23 July 2023
sustainability and eco-friendliness.
Revised: 2 September 2023
Accepted: 13 September 2023
Keywords: bio-anchors; green extraction; microwave radiation; neem; sustainability; tannin
Published: 18 September 2023

Copyright: © 2023 by the authors. 1. Introduction

Licensee MDPI, Basel, Switzerland. Synthetic dyes are organic substances synthesized from coal tar, benzene, toluene, and
This article is an open access article their other derivatives [1]. These dyes are considered cheaper, brighter, and colorfast and
distributed under the terms and
can be applied easily onto a matrix [2]. Direct dyes, reactive, azo dyes, basic dyes, acidic
conditions of the Creative Commons
dyes, etc., are the common synthetic dyes applied in the paper, leather, food, wood, and
Attribution (CC BY) license (https://
textile industries [3]. In addition to these benefits, these dyes have numerous disadvantages,
creativecommons.org/licenses/by/
such as water pollution, the production of carcinogenic chemicals, and hazardous waste as
4.0/).

Coatings 2023, 13, 1639. https://doi.org/10.3390/coatings13091639 https://www.mdpi.com/journal/coatings

Coatings 2023, 13, 1639 2 of 12

industrial effluents [4]. From an application point of view (color range, low cost, and bright
shading), these dyes are widely available and exhibit beautiful properties, yet they may
cause dermatologic and genotoxic effects on humans and other living beings [5,6]. Hence,
due to such acute and lethal effects of these synthetic dyes, the revival of natural dyes in all
fields is underway around the globe.
Several advantages make natural dyes an excellent choice and a better alternative to
synthetic dyes. The benefits of using natural dyes have attracted people to their frequent use
in all fields. These dyes are readily biodegradable and compatible with the environment [7].
These dyes are non-toxic, non-carcinogenic, and non-allergic to the skin. Most natural dyes
are also sustainable and Ayurvedic [8]. These dyes produce a variety of soothing colors with
or without the aid of different types of mordants [9,10]. These dyes play a vital role in the
environment’s cleanliness and help maintain the eco-balance of the globe. These dyes are
considered antioxidant, insect repellent, flame retardant, deodorant, antibacterial, etc. [11].
These dyes are not only used in the textile industry but also have wide applications in food,
flavors, cosmetics, electronic industries (dye-sanitized solar cells, DSSC), etc. [12]. It is also
seen that natural dyes used in dyeing techniques in various fields of art maintain their
vitality for many years. It is a fact that the natural dyes used in wall paintings, ceramics,
and fabrics obtained in ancient excavations have survived to the present day by preserving
their clarity as that of the first day. Today, the use of natural dyes, which has started to be
preferred especially in artistic printing techniques, is becoming more and more widespread
day by day. Especially in the last 10–15 years, theories about the use of natural dyes in
the coloring of textiles have significantly changed the view of natural dyeing methods
and techniques, leading to the emergence of different perspectives. Today, there are more
advanced and versatile natural screening methods using advanced protection.
From a sustainable point of view, textile researchers, traders, and other associated
companies are trying to standardize the extraction process to obtain stable and strong
shades with high extraction yields [13,14]. These methods involve traditional and modern
tools for extracting colorants from plant sources [15]. Previously, researchers tried to
employ two methods, i.e., either to improve the extraction process by using the Soxhlet
method, immersion method, supercritical method [16], acidic and alkali extraction, soaking
method [17], adsorption methods, etc., or to modify the fabric surface by using techniques
such as cationization, mercerization, and bio-polishing [18]. These tools either cause
degradation of the colorant’s ability to interact firmly with fabric or are expensive in terms
of the solvent, energy, and money required to give acceptable results [17]. However, the role
of novel tools such as gamma radiation, ultrasonic radiation, and microwave irradiation
is receiving more attention because of their high treatment speed and energy- and cost-
effective nature in the field of isolation of natural products and their application in various
fields such as textiles, cosmetics, pharmaceuticals, leather, food, and flavors [19–21].
Being a clean, rapid, and even heating source, the microwave (MW) is one of the
modern tools in synthetic chemistry, particularly in the field of dye synthesis and its appli-
cation [22]. Because of its time-, cost-, chemical-, and energy-effective nature, it is one of the
best tools for this application in natural dye industries [23]. This radiation works through
the charges in the liquid or the conducting ions in the solid to shift the energy into heat,
driving the process compared to conventional heating [24]. During dyeing, microwave ra-
diation uniformly heats the substrate from core to surface, which causes uniform coloration
in a very efficient manner, giving excellent results [21,25]. Microwave radiation (MW), the
commercially viable heating source, is found everywhere at the domestic and industrial
levels. In the world of natural products, this conventional heating source adds value to the
isolation yield without any damage to the actual nature of a potent molecule [26–28]. Hence
this unique mode of action requires less solvent consumption, time, labor, and money and
lower temperatures [29].
Bio-mordants are another type of anchor where the functional biological isolate acts
as the bridging agent between the fabric and the dye. Their application involves extra
H-bonding to develop a new and firm tint when applied onto the fabric before, after, and
Coatings 2023, 13, 1639 3 of 12

during the dyeing [30]. The application of biological anchors is a newly introduced novel
technique to obtain excellent tint with the desired fastness properties and make the process
cleaner, sustainable, and soothing [31]. Another advantage is that these potent molecules
exhibit excellent therapeutic, Ayurvedic, and attractive characteristics such as antibacterial,
antiviral, anti-inflammatory, and antioxidant properties, which upon the dyeing, make
the dyed fabric more beneficial to the global community [32,33]. Bio-mordants are part
of medication systems in Greece, China, India, etc., so these are natural blessings that
add value to sustainability and give new dimensions to the eco-friendly approach of the
natural dyeing process [34]. Chemical mordanting is an old conventional art of fixing color
onto fabrics. The salts of Al+3 (Alum) and Fe+2 (FeSO4 ) are commonly used as sustainable
anchors for this purpose, while the salts of Cu+2 , Cr+3 , Co+2 , and Sn+2 are also used [35].
However, due to toxicity, using Cr+3 , Co+2 , Sn+2 , and Cu+2 salts is under strict observation.
Mordants cause either the brightening of the shades or the darkening of the tint, depending
upon the nature of the fabrics and the dye [36]. Among all mordants, aluminum (Al) is the
safest to use and cheapest to buy, whereas chrome (Cr) and Tin (Sn) are the most expensive
mordants. However, mordants can reduce the fabric’s tenacity [6].
Neem bark (Azadirachta indica) is a source of a natural red-brown dye belonging to the
Meliaceae family. It is one of nature’s blessings and is a powerful home remedy for many
health-related problems [37]. Its bark extracts have excellent antifungal, antiviral, antibac-
terial, anti-inflammatory, antimalarial, antidiabetic, and antiallergic characteristics [38]. Its
extract also exhibits anti-UV, insect repellent, antiarthritic, antipyretic, hypoglycemic, and
antistress characteristics. Due to such excellent benefits, it has a good place in Ayurvedic,
Greek, and Chinese systems of medicine [39–41]. Proteinous wool fiber has keratin as its
significant functional moiety [42,43]. In its helical structure, the amino acids are linked
through peptide linkage to form different proteins. Wool fiber, being amorphous, is more
sorbent and hypoallergenic. The amido linkage of the wool keratin is responsible for the
bonding with the functional sites of the dye [44–46].
The aim of the current study was to use microwave treatment for the isolation of
colorant (tannin) from neem bark and surface scaling of wool for maximum sorption.
Additionally, plant-derived biomolecules were included as eco-mordants to develop new
colorfast tints.

2. Materials and Methods

2.1. Collection of Materials
Neem bark powder, in conjunction with various bio-mordants, including pomegranate
(Punica granatum L.) peels, Acacia nilotica bark, turmeric (Curcumaa longa) rhizomes, and
henna (Lawsonia inermis) leaves, were procured from the local market in Faisalabad. The
aforementioned samples were subjected to fine grinding to achieve powders of uniform
particle size via a 25-mesh sieve. Chemical mordants, including Al+3 (SO4 )3 , Fe+2 (FeSO4 ),
Cu+2 (CuSO4 ), Co+2 (CoCl2 ), tannic acid (T.A.), Ni (NiSO4 ), Sn (SnCl2 ), and Cr (CrCl2 ),
were acquired from Paragon Dyes and Chemicals, Faisalabad.

2.2. Extraction and Irradiation Process

The present study utilized an acidified methanol extraction medium to isolate natural
dye from neem bark powder effectively. Specifically, 4 g of finely prepared neem bark
powder was heated with 100 mL of distilled water at the boiling point for 45 min, filtered,
and stored. A methanolic extract from an acidic medium, utilizing a 1% HCl solution
(v/v%), was obtained using the same procedure. One part of the acidified methanol
extracts and woolen fabric were exposed to a domestic M.W. irradiator and heated for
6 min at high power. In the first series, the unirradiated woolen fabric (NRWF) was dyed
with unirradiated neem bark extract (NRE) at a temperature of 65 ◦ C. For comparative
purposes, irradiated woolen fabric (RWF) was dyed with irradiated neem bark extracts
(RE) at 65 ◦ C for a duration of 45 min.
Coatings 2023, 13, 1639 4 of 12

2.3. Optimization of Dyeing and Mordanting Conditions

Response surface methodology was employed as a statistical approach to create a
central composite design consisting of 32 experiments. Various parameters, as listed in
Table 1, were utilized for computer simulation to generate the design for the different trials.

Table 1. Levels for optimization of dyeing conditions.

Powder Amount Volume Dyeing Temperature Dyeing Time Table Salt

Radiation Used
(g) (mL) (◦ C) (min) (g/100 mL)
2 10 25 25 0
4 20 35 35 1
6 30 45 45 3
Microwave 8 40 55 55 5
50 65 65 7
10 60 75 75 9
70 85 85 10

2.4. Mordanting Process

The demand for colorfast gamuts has led to a global interest in utilizing eco-friendly
chemicals in natural dyeing. The present study utilized the electrolytes of Al, Fe, Cu, Co,
Sn, and tannic acid. To prepare the Al-mordant solution, 1, 3, 5, 7, 9, and 10 g of Al2 (SO4 )3
were dissolved in 100 mL of water and utilized at a temperature of 65 ◦ C for a duration of
65 min, with the fabric to acidified methanolic extract value maintained at 1:25. The same
process was carried out before and after dyeing, utilizing iron, Cu, Sn, Co salt, and tannic
acid at predetermined concentrations. In order to carry out comparative studies, plant
extracts were utilized as a natural source of biomolecules. Pomegranate peels, acacia bark,
turmeric rhizomes, and henna leaves were ground and sieved up to 25 mesh. The resulting
extracts were used to prepare bio-mordants by boiling 1–10 g with 100 mL of water for
65 min. The resulting filtrates were utilized before and after dyeing at a temperature of
65 ◦ C for a duration of 65 min, with the bio-mordant to fabric ratio maintained at 25:1.

2.5. Evaluation of Color Characteristics of Dyed Fabrics

Subsequently, the color attributes of the dyed fabrics were evaluated utilizing the
Spectra flash SF 600 at the Department of Applied Chemistry, Government University
Faisalabad, Pakistan. The dyed fabrics’ colorfastness properties were examined per ISO
standards to determine the efficacy of the bio-mordants compared to the chemical mordants.
The ISO 105 CO3 method was used for washing fastness evaluation in a Rota wash, while
ISO 105 BO2 was employed for light fastness evaluation in a fadometer. The ISO 105 X-12
method was used for crocking (rubbing) fastness evaluation, and the ISO 105 E04 method
was employed for perspiration fastness evaluation in a perspirometer. Lastly, dry cleaning
fastness was evaluated utilizing the ISO 105 D01 method at the Department of Chemistry,
Government College University Faisalabad, Pakistan.

3. Result and Discussion

Sustainable technologies are now attracting people, research organizations, and indus-
trial sectors due to their cost-, energy-, and time-effectiveness in nature [47]. Their role in
natural products is much appreciated [25]. Their rapid action and use of less time, solvent,
and energy have improved their yield of natural products (colorants) from crude materials
with suitable results [48,49]. The same role of sustainable technologies, i.e., microwave
radiation, was observed in our studies when neem bark was used to isolate reddish-brown
natural pigment (tannin) for wool dyeing. The results obtained after treatment with radia-
tion, as shown in Figure 1, show that the treatment of both the fabric and the extract should
Coatings 2023, 13, 1639 5 of 12

be conducted for 4 min before dyeing, whereas after dyeing, the highest yield has been
observed. Three factors play their roles side by side, i.e., (i) name of the fabric, (ii) name
of extract, and (iii) medium selected. These rays are eco-friendly and act uniformly on
plant material by creating solvent polymerization [24]. The energy referring to solvent
molecules when they collide with the plant’s outer wall causes its rupture and the evolu-
tion of functional materials due to rapid mass transfer kinetics [25,26]. Upon treatment, at
4 min, the maximum bioactive mass (tannin) from neem bark was developed, and upon
application, tannin imparts dark shades onto wool (Figure 1). The solvent role is also
much appreciable because acidified methanol can quickly produce the maximum tannin
level through the solid–solvent interaction (SSI) up to a high extract level (K/S = 4.1165).
Also, wool, a natural protein, contains amido linkage for interaction with dye-binding
sites, hence the addition of acid to organic molecules to obtain an excellent yield. The third
factor is the irradiation of fabric, which has been found to be significant for its surface
tuning. Chemically, these rays do not disturb its nature, but physically, they scratch the
fiber surface, and where the peeled surface is used for the sorption of colorant, a high
yield is obtained [50,51]. Our previous studies have confirmed that MW irradiation has no
potential to alter the chemistry of fiber but only modifies the wool surface physically to
obtain maximum yield [52,53]. Hence, it was concluded that extracts and fabric should be
subjected to MW irradiation for up to 4 min.

Figure 1. Influence of microwave radiation for isolation of colorant from neem bark in acidified
methanolic extract for isolation of colorant in an aqueous medium (c) and its dyeing of wool.

Two-way ANOVA was applied to observe the radiation rate on the extract and fabric
together or alone. The results revealed in Table 2 show that the model used is fit (p = 0.04),
the choice to use MW treatment (MWT) for both fabric and extract is also significant, and
treatment time (MW = 4 min) (p = 0.012) is of higher significance (p = 0.002).
The extract obtained from the selected powder amount was subjected to MW treatment
for up to 4 min after utilization, furnishing a high yield. Low powder amounts (2 g/100 mL)
do not give a high colorant yield, whereas above 4 g/100 mL, other molecules present in
the extract play their role and, during dyeing, disturb the shade strength. The maximum
yield with level shade is obtained when 4 g of neem powder is subjected to extraction
with 100 mL of acidic methanol medium (AMM) followed by treatment for up to 4 min.
Similarly, 40 mL of extract obtained from 4 g/100 mL of acidified methanol also developed
a dark shade upon treatment for up to 4 min. Thus, it is clear that 40 mL of AAM from 4 g
Coatings 2023, 13, 1639 6 of 12

powder after 4 min of MW heating can be used to obtain a high yield. The utilization of
4 g powder for extract and the value for dyeing revealed that the MW is a cost-effective
tool. In wool dyeing, the nature of the extract is essential because wool contains amido
units, which work well under acidic conditions to interact with the extract. Under acidic
conditions, the wool’s amino group is positively charged, so the -OH from the dye should
attach firmly to yield a high yield [54].

Table 2. Two-way ANOVA design for optimization of irradiation and extraction of colorant from
neem bark for wool dyeing under microwave radiation.

Type III Sum of

Source Df Mean Square F p-Value
Squares
Corrected Model 13.185 9 1.465 4.217 0.004
Intercept 126.958 1 126.958 365.478 0.000
Sample course 5.909 4 1.477 4.252 0.012
Time 7.276 5 1.455 4.189 0.009
Error 6.948 20 0.347
Total 147.091 30
Corrected Total 20.133 29

The results in Figure 2 show that applying an acidified methanolic extract with a pH
of 3 to fabric yields a high yield. Above that (pH > 3), the nature of the colorant is also
disturbed, as is the acidic group of wool amido linkage, which also loses its affinity to bind
firmly [55]. Adding salt is also beneficial for wool dyeing because the salt adds value by
exhausting the colorant from the medium toward the fabric [19]. A low amount cannot
perform the activity, whereas a high amount creates exhaustion, resulting in aggregation
or poor fixation upon the finishing process. Many colorants are stripped, and low yield is
observed. Hence, acidified methanol is extracted at pH 3 with 3 g/100 mL of salt (OWF).
After treatment with MW rays for up to 4 min, it yields excellent color strength when
employed onto surface-tuned fabric. Adding auxiliaries has always been helpful because
these additives reduce the dyeing time of wool and the dyeing temperature during the
natural dyeing process. It has been found that dyeing of MW-treated fabric at 65 ◦ C for
65 min, using 40 mL of an acidified methanol extract (3 pH) containing 3 g/NaCl of sodium
sulfate, gave a high yield. For low contact levels, the dyeing rate is low, whereas the
above-selected (65 ◦ C/65 min) desorption rate is favorably rated, and in both cases, after
washing, a low yield is found [56]. Hence, the results displayed in Figure 2 show that MWT
of the fabric and extract also reduced contact levels, which are the properties of the energy-
and time-effective nature of MW treatment.
Mordanting is the art of developing colorfast shades using plant colorants. Previously,
chemical mordants such as a salt of Al, Fe, Cu, Ni, Sn, and tannic acid have been used [45].
However, owing to toxicity, salts of Cu, Ni, Sn, and Co are under strict observation, and
only low amounts are allowed to be used to develop colorfast shades. Microwave treatment
of fabrics and extracts before mordanting has made it possible to use less toxic anchors to
develop colorfast shades [24]. The results in Table 3 show that 40 mL of 7 g/100 mL Cu,
3 g/100 mL of Sn, and 1 g/100 mL T.A. salt developed a colorfast shade with a reddish-
yellow hue. However, 5 g/100 mL of Al, Co, and Fe developed high strength before dyeing
with a dark reddish-yellow hue.
Similarly, after dyeing with 5 g/100 mL of Fe and T.A., the dye developed an excellent
shade, whereas during dyeing with 5% T.A. and 3% Fe salt, the dye developed a dark
reddish shade (Table 3). Hence, using all chemical anchors for tannin from neem bark, only
salt of Al, Fe, and T.A. is suitable to develop dark reddish-brown shades on the wool fabric
surface. The metal develops a coordinate bond when interacting with dye as a bridging
agent on fabric [57,58]. The particular type of binding creates new shades with excellent
fastness. Low amounts of mordants do not form stable complexes on fabric, whereas too
much anchoring forms dye complexes in the form of aggregates, hence failing to sorb onto
Coatings 2023, 13, 1639 7 of 12

fabric evenly [59]. It is only the optimal amount of metal (5 g/100 mL) depending upon
its reduction power that adds value in coloration by furnishing a dark colorfast gamut.
Hence, the overall salt of Al, Fe, and tannic acid has an excellent affinity for neem-bark-
based tannin for wool to furnish colorfast shades under the selected dyeing and radiation
conditions. Despite the use of toxic salt as a fixer, the concept of using a plant extract is now
gaining fame [31]. The reasons behind using pollution-free fixers are as follows: one is that
a plant extract has excellent biological characteristics, and the other is that new shooting
shades with excellent fastness are obtained [19]. Most plants have phenolics that utilize the
-OH group to bind with the -OH of the colorant and -CONH of wool; their extra H-bonding
develops a colorfast gamut [8]. The results reveal that among bio-mordants used, henna
after dyeing, and a 5% turmeric extract was notable; during dyeing, a 3% turmeric extract
developed dark reddish-yellow shades. Compared to chemical fixers, plant extracts have
the highest yields with dark reddish-yellow hues.

Figure 2. Optimization of dyeing variables such as contact level (a), salt (b), volume (c), and powder
(d) under the influence of microwave radiation for dyeing of wool with optimal extract of neem.
Coatings 2023, 13, 1639 8 of 12

Table 3. Color characteristics of chemical and bio-mordanted wool fabrics dyed before, after, and
during dyeing with microwave-treated neem bark extract.

Mordant Concentration K/S L* a* b* Mordant Concentration K/S L* a* b*

Al 5% (Pre) 4.0798 61.81 12.24 27.21 T. A 1% (Pre) 2.9228 58.86 5.35 17.47
Al 7% (Post) 1.9339 68.03 6.52 21.02 T. A 5% (Post) 3.7146 52.79 7.00 17.47
Al 5% (Meta) 1.8577 73.18 10.67 28.03 T. A 5% (Meta) 3.7450 50.01 6.58 14.07
Fe 5% (Pre) 4.1340 62.51 8.06 27.04 Acacia 5% (Pre) 3.6193 56.11 13.99 20.24
Fe 5% (Post) 3.8795 69.23 8.89 33.98 Acacia 5% (Post) 3.2125 57.08 14.24 19.97
Fe 3% (Meta) 2.5213 66.19 5.32 21.52 Acacia 3% (Meta) 3.8085 56.89 15.24 22.91
Co 5% (Pre) 3.7763 63.70 11.52 27.81 Pomegranate 7% (Pre) 4.6298 67.59 8.21 25.79
Co 3% (Post) 2.5504 65.54 9.69 22.08 Pomegranate 5% (Post) 5.6319 60.26 10.56 25.08
Co 5% (Meta) 3.1093 60.75 9.99 21.29 Pomegranate 3% (Meta) 7.0519 59.37 10.88 27.55
Sn 3% (Pre) 2.0064 56.32 7.76 12.20 Henna 7% (Pre) 6.2985 55.38 11.12 27.46
Sn 3% (Post) 1.6422 62.14 9.73 15.22 Henna 5% (Post) 4.2884 61.60 11.41 27.85
Sn 5% (Meta) 0.4971 84.86 2.48 10.41 Henna 7% (Meta) 10.427 46.63 6.05 22.01
Cu 7% (Pre) 0.6167 80.49 0.46 7.88 Turmeric 7% (Pre) 6.0265 59.25 9.25 28.02
Cu 3% (Post) 0.5680 80.83 0.21 7.64 Turmeric 5% (Post) 13.285 57.52 11.30 47.29
Cu 3% (Meta) 1.2408 69.96 5.56 12.69 Turmeric 3%(Meta) 15.567 56.52 9.53 50.41

Poor fastness ratings are a big issue in using natural dyes for all fields. To overcome
this issue, sustainable chemicals and bio-extracts have been used [24]. The rating given
in Table 4 reveals that using the selected amount of mordants before and after dyeing
has given a colorfast gamut. The proposed mechanism in Figure 3 shows that the stable
metal dye complex formed on surface-modified wool and extract H-bonding formed using
biomolecules have developed shades and are resistant to light, washing, crocking, cleaning,
and perspiration [31,32]. Hence, the problem of poor fastness can be overcome by using
optimal amounts of chemicals and bio-mordants in the surface tuning of fabrics and using
Coatings 2023, 13, x FOR PEER REVIEW 9 of 13
pollution-free tools. The variation in shades described in Figure 4 shows that tannin isolated
from neem bark is effective for wool when used under MWT before and after mordanting.

Figure
Figure 3.
3. Proposed
Proposedinteraction ofof
interaction metal (a)(a)
metal andand
mordants (b) with
mordants functional
(b) with group
functional of dyeofand
group dyebind-
and
ing site of wool fabric.
binding site of wool fabric.

Control Al 5%Pre Al 7%Post Al 5%Meta Fe 5%Pre

Coatings 2023, 13, 1639 9 of 12
Figure 3. Proposed interaction of metal (a) and mordants (b) with functional group of dye and bind-
ing site of wool fabric.

Control Al 5%Pre Al 7%Post Al 5%Meta Fe 5%Pre

Fe 5%Post Fe 3%Meta Co 5%Pre Co 3%Post Co 5%Meta

Sn 3%Pre Sn 3%Post Sn 5%Meta Cu 7%Pre Cu 3%Post

Cu 3%Meta T.A 1%Pre T.A 5%Post T.A 5%Meta Acacia 5%Pre

Acacia 5%Post Acacia 3%Meta Pomegranate 7%Pre Pomegranate 5%Post Pomegranate 3%Meta

Henna 7%Pre Henna 5%Post Henna 7%Meta Turmeric 7%Pre Turmeric5%Post

Turmeric 3%Meta
Figure4.4.Tonal
Figure Tonal variation
variation of
ofmicrowave-treated
microwave-treateddyed and
dyed mordanted
and wool
mordanted fabrics
wool usingusing
fabrics neemneem
bark
extract.
bark extract.

Table 4. Colorfastness rating of mordanted and dyed microwave-treated wool fabric using neem
bark extract.

WF RF PF
Mordant Concentration LF DCF
c.s c.c DRF WRF Acidic Alkaline
Control 3/4 3 3/4 3/4 3/4 3/4 3/4 3/4
Al 5% (Pre) 5 4/5 4/5 5 4 5 5 5
Al 7% (Post) 5 4/5 4/5 5 4/5 4/5 5 5
Al 5% (Meta) 5 4/5 4/5 5 4/5 4/5 5 5
Fe 5% (Pre) 5 4/5 4/5 5 4/5 5 4/5 5
Fe 5% (Post) 5 4/5 4/5 5 4/5 5 4/5 5
Fe 3% (Meta) 5 4/5 4/5 5 4/5 5 4/5 5
Co 5% (Pre) 4/5 4 4 4/5 4 4/5 4/5 5
Co 3% (Post) 4/5 4 4 4/5 4 4/5 5 4/5
Co 5% (Meta) 4/5 4 4 4/5 4 4/5 5 4/5
Sn 3% (Pre) 4/5 4 4 4/5 4 5 5 4/5
Sn 3% (Post) 4/5 4 4 4/5 4 5 5 4/5
Sn 5% (Meta) 5 4 4 4/5 4 5 5 4/5
Cu 7% (Pre) 4/5 4 4 4/5 4 4/5 5 5
Cu 3% (Post) 5 4 4 4/5 4 4/5 5 5
Cu 3% (Meta) 5 4 4 4/5 4 4/5 4/5 4/5
T. A 1% (Pre) 5 4/5 4/5 5 4/5 5 4/5 4/5
T. A 5% (post) 5 4/5 4/5 5 4/5 5 4/5 4/5
T. A 5% (Meta) 5 4/5 4/5 5 4/5 5 5 5
Acacia 5% (Pre) 5 4/5 4/5 5 4/5 4/5 5 5
Acacia 5% (Post) 5 4/5 4/5 5 4/5 4/5 5 5
Acacia 3% (Meta) 4/5 4/5 4/5 5 4/5 4/5 5 5
Coatings 2023, 13, 1639 10 of 12

Table 4. Cont.

WF RF PF
Mordant Concentration LF DCF
c.s c.c DRF WRF Acidic Alkaline
Pomegranate 7% (Pre) 4/5 4/5 4/5 5 4/5 4/5 5 4/5
Pomegranate 5%(Post) 5 4/5 4/5 5 4/5 5 5 4/5
Pomegranate 3%(Meta) 5 4/5 4/5 5 4/5 5 5 4/5
Henna 7% (Pre) 4/5 4/5 4/5 5 4/5 5 5 5
Henna 5% (Post) 5 4/5 4/5 5 4/5 5 5 5
Henna 7% (Meta) 5 4/5 4/5 5 4/5 4/5 5 5
Turmeric 7% (Pre) 4/5 4/5 4/5 4/5 4 4/5 4/5 4/5
Turmeric 5% (Post) 4/5 4/5 4/5 4/5 4/5 4/5 4/5 4/5
Turmeric 3%(Meta) 4/5 4/5 4/5 4/5 4/5 4/5 4/5 4/5
LF = light fastness, WF = wash fastness, c.s = color stain, c.c = color change, RF = rub fastness, DRF = dry rub
fastness, WRF = wet rub fastness, DCF = dry clean fastness, PF = perspiration fastness.

4. Conclusions
The awareness spread by research organizations has compelled the use of pollution-
free green technologies in textile processing. Sustainable products such as natural dyes
for all fields are now catching the eye of the global market due to their versatile health
benefits such as antiviral, antioxidant, antibacterial, and antiallergic actions. Neem bark is a
natural blessing having an excellent effect for almost all diseases. MW treatment as a green
pollution-free heating source has helped to isolate colorants in high yields. The inclusion of
plant extracts has provided a benefit in the development of a colorfast shade. These results
were statistically analyzed to reveal that this fast and consistent tool is cost-, energy-, and
time-effective for textiles. It is concluded that this technology should be used to explore
new sources of bio-colorants and their applications under mild conditions. Additionally,
herbal plant extracts as alternatives to toxic chemicals should be used to overcome the issue
of poor fastness.

Author Contributions: S.A. has conducted the experiments, M.Z. has supervised the work, M.O. and
S.P.K. and M.K. has helped in analysis of data. A.D.K., A.D. and Z.L. has made formal analysis in
content writing. A.Z. and S.B. has helped in writing, editing of manuscript. All authors have read
and agreed to the published version of the manuscript.
Funding: This research received no external funding.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: All authors give consent to publish work.
Data Availability Statement: Not applicable.
Conflicts of Interest: The authors declare no conflict of interest.

References
1. Khobrani, S.H.A. Synthesis and characteristics of Some organic dyes. Adv. Appl. Sci. Res. 2023, 14, 109.
2. Al–Etaibi, A.M.; El–Apasery, M.A. Microwave–Assisted synthesis of azo disperse dyes for dyeing polyester fabrics: Our
contributions over the past decade. Polymers 2022, 14, 1703. [CrossRef]
3. Hassan, E.A.; Mashaly, H.M.; Hashem, Z.M.; Zayed, S.E.; Abo–Bakr, A.M. Eco–friendly synthesis of new polyfunctional azo dyes
using shrimp chitin as a catalyst: Application on polyester fabrics and their biological activities. Fibers Polym. 2022, 23, 2373–2383.
[CrossRef]
4. Talib, A.; Adeel, S.; Ali, A.; Ahmad, T.; Hussaan, M.; Qayyum, M.A. Sustainable isolation and application of plant extract–based
natural dye for bio–dyeing of silk fabric. Coatings 2023, 13, 112. [CrossRef]
5. Mohamed, A.L.; Shaarawy, S.; Elshemy, N.; Hebeish, A.; Hassabo, A.G. Treatment of cotton fabrics using polyamines for improved
coloration with natural dyes extracted from plant and insect sources. Egypt. J. Chem. 2023, 66, 1–19. [CrossRef]
6. Özomay, M. Sustainable and environmental dyeing with maut method comparative selection of the dyeing recipe. Sustainability
2023, 15, 2738. [CrossRef]
Coatings 2023, 13, 1639 11 of 12

7. Al–Tohamy, R.; Ali, S.S.; Li, F.; Okasha, K.M.; Mahmoud, Y.A.G.; Elsamahy, T.; Sun, J. A critical review on the treatment of
dye–containing wastewater: Ecotoxicological and health concerns of textile dyes and possible remediation approaches for
environmental safety. Ecotoxicol. Environ. Saf. 2022, 231, 113160. [CrossRef]
8. Rahman, M.M.; Kim, M.; Youm, K.; Kumar, S.; Koh, J.; Hong, K.H. Sustainable one–bath natural dyeing of cotton fabric using
turmeric root extract and chitosan bio–mordant. J. Clean. Prod. 2023, 382, 135303. [CrossRef]
9. Sharma, N.; Sheikh, Z.N.; Alamri, S.; Singh, B.; Kesawat, M.S.; Guleria, S. Chemical Composition, Antibacterial and Combinatorial
Effects of the Essential Oils from Cymbopogon spp. and Mentha arvensis with Conventional Antibiotics. Agronomy 2023, 13, 1091.
[CrossRef]
10. Thakker, A.M.; Sun, D. Sustainable application of novel herbs on cotton fabrics as bio–mordants and colourants. Environ. Sci.
Pollut. Res. 2022, 29, 47598–47616. [CrossRef]
11. Otaviano, B.T.H.; Sannomiya, M.; de Queiroz, R.S.; Sánchez, A.A.C.; Freeman, H.S.; Mendoza, L.E.R.; da Costa, S.M. Natural dye
extracted from pomegranate peel: Physicochemical characterization, dyeing of cotton fabric, color fastness, and photoprotective
properties. Fibers Polym. 2023, 24, 1321–1332. [CrossRef]
12. Shaban, S.; Vats, A.K.; Pandey, S.S. Bifacial dye–sensitized solar cells utilizing visible and nir dyes: Implications of dye adsorption
behaviour. Molecules 2023, 28, 2784. [CrossRef]
13. Ali, N.F.; El–Khatib, E.M.; Bassyouni, F.A. Utilization and characterization of natural products pretreatment and dyeing wool
fabric by natural dyes with economical methods. J. Text. Eng. Fash. Technol. 2022, 8, 178–183. [CrossRef]
14. Geetha, P.; Dhanya, M.; Sankaralingam, S.; Sugapriya, M.P.; Vasthi, G.R.; Mahendran, S.; Balasundaram, H. Extraction and
applications of natural dye from the flower of Tagetes erecta. L in different fabrics and focus on antimicrobial activity. Res. J. Pharm.
Technol. 2022, 15, 1287.
15. Sutlović, A.; Brlek, I.; Ljubić, V.; Glogar, M.I. Optimization of dyeing process of cotton fabric with cochineal dye. Fibers Polym.
2020, 21, 555–563. [CrossRef]
16. Naik, N.M.; Krishnaveni, M.; Mahadevswamy, M.; Bheemanna, M.; Nidoni, U.; Kumar, V.; Tejashri, K. Characterization of
phyto–components with antimicrobial traits in supercritical carbon dioxide and soxhlet Prosopis juliflora leaves extract using
GC–MS. Sci. Rep. 2023, 13, 4064. [CrossRef]
17. Asghar, A.; Tajammal, A.; Ashiq, S.; Hussain, S.; Ahmad, M.; Sian, K.; Bodlah, M.A. Eco–friendly dye of olive fruit peel and its
color fastness applications on wool/silk fabrics. Pol. J. Environ. Stud. 2023, 32, 1995–1999. [CrossRef]
18. Kabish, A.K.; Abate, M.T.; Alemar, Z.A.; Girmay, S. The importance of natural indigo dye and its revitalization and ethiopian
potential for indigo growing. Adv. Mater. Sci. Eng. 2023, 2023, 2135014. [CrossRef]
19. Bhouri, N.; Ltaief, S.; Bhouri, N.; Ben Abdessalem, S. Optimization of a green dyeing process using natural dyes extracted from
corchorus olitorius leaves. J. Nat. Fibers. 2023, 20, 2170946. [CrossRef]
20. Castillo–Suárez, L.A.; Sierra–Sánchez, A.G.; Linares–Hernández, I.; Martínez–Miranda, V.; Teutli–Sequeira, E.A. A critical review of
textile industry wastewater: Green technologies for the removal of indigo dyes. Int. J. Environ. Sci. Technol. 2023, 20, 10553–10590.
[CrossRef] [PubMed]
21. Periyasamy, A.P.; Periyasami, S. Critical review on sustainability in denim: A step toward sustainable production and consumption
of denim. ACS Omega 2023, 8, 4472–4490. [CrossRef]
22. Yadav, S.; Tiwari, K.S.; Gupta, C.; Tiwari, M.K.; Khan, A.; Sonkar, S.P. A brief review on natural dyes, pigments: Recent advances
and future perspectives. Results Chem. 2023, 5, 100733. [CrossRef]
23. Khajeh Mehrizi, M.; Jokar, M.; Shahi, Z. The coloration of polyester fabric with Prangos ferulacea natural dye: New approaches
toward a cleaner production. Pigm. Resin Technol. 2023, 52, 377–382. [CrossRef]
24. El Sayed, N.A.; El–Bendary, M.A.; Ahmed, O.K. A sustainable approach for linen dyeing and finishing with natural lac dye
through chitosan bio–mordanting and microwave heating. J. Eng. Fibers Fabr. 2023, 18, 15589250231155882. [CrossRef]
25. Mahboob, M.; Adeel, S.; Bakraat, S.; Ahamd, T.; Ahamd, T.; Ozomay, M.; Mia, R.; Mirnezhad, S.; Zuber, M. Assisted santalin
extraction from Pterocarpus santalinus for mordanted woolen yarn dyeing. Sustain. Chem. Pharm. 2023, 35, 101224. [CrossRef]
26. Syafaatullah, A.Q.; Mahfud, M. Optimization extraction of Indigofera tinctoria L. using microwave–assisted extraction. Conf. Ser.
Mater. Sci. Eng. 2021, 1053, 012131. [CrossRef]
27. Ji, X.; Zhao, Z.; Ren, Y.; Xu, F.; Liu, J. Dyeing properties, color gamut, and color evaluation of cotton fabrics dyed with Phellodendron
amurense rupr.(amur cork tree bark). Molecules 2023, 28, 2220. [CrossRef]
28. Phan, P.T.; Hong, J.; Tran, N.; Le, T.H. The properties of microwave–assisted synthesis of metal–organic frameworks and their
applications. Nanomaterials 2023, 13, 352. [CrossRef]
29. Jabar, J.M.; Ogunsade, A.F.; Odusote, Y.A.; Yılmaz, M. Utilization of nigerian mango (Mangifera indica L) leaves dye extract for silk
fabric coloration: Influence of extraction technique, mordant and mordanting type on the fabric color attributes. Indus. Crop. Prod.
2023, 193, 116235. [CrossRef]
30. Haji, A.; Shahmoradi Ghaheh, F.; Indrie, L. Pomegranate fallen leaves as a source of natural dye for mordant-free dyeing of wool.
Color. Technol. 2022, 139, 165–170. [CrossRef]
31. Hosseinnezhad, M.; Gharanjig, K.; Iamin, H.; Rouhani, S.; Adeel, S. Environmentally dyeing of wool yarns using of combination
of myrobalan and walnut husk as bio–mordants. Prog. Color Color. Coat. 2023, 16, 197–205.
32. Phromphen, P. Optimization of marigold flower dye using banana peel as a biomordant. J. Nat. Fibers 2023, 20, 2153193. [CrossRef]
Coatings 2023, 13, 1639 12 of 12

33. Nazir, F.; Siddique, A.; Nazir, A.; Javed, S.; Hussain, T.; Abid, S. Eco-friendly dyeing of cotton using waste-derived natural dyes
and mordants. Color. Technol. 2022, 138, 684–692. [CrossRef]
34. Shahmoradi Ghaheh, F.; Moghaddam, M.K.; Tehrani, M. Comparison of the effect of metal mordants and bio-mordants on the
colorimetric and antibacterial properties of natural dyes on cotton fabric. Color. Technol. 2021, 137, 689–698. [CrossRef]
35. Baaka, N.; Khiari, R.; Haji, A. Ecofriendly dyeing of textile materials with natural colorants from date palm fiber Fibrillium.
Sustainability 2023, 15, 1688. [CrossRef]
36. Islam, M.R.; Khan, A.N.N.; Mahmud, R.U.; Haque, S.M.N.; Khan, M.M.I. Sustainable dyeing of jute–cotton union fabrics with
onion skin (Allium cepa) dye using banana peel (Musa) and guava leaves (Psidium guajava) extract as biomordants. Pigm. Resin
Technol. 2022. [CrossRef]
37. El–Khatib, E.M.; Ali, N.F.; El–Mohamedy, R.S.R. Influence of Neem oil pretreatment on the dyeing and antimicrobial properties of
wool and silk fibers with some natural dyes. Arab. J. Chem. 2020, 13, 1094–1104. [CrossRef]
38. Wylie, M.R.; Scott Merrell, D. The antimicrobial potential of the neem tree Azadirachta indica. Front. Pharmacol. 2022, 13, 891535.
[CrossRef]
39. Baby, A.R.; Freire, T.B.; Marques, G.D.A.; Rijo, P.; Lima, F.V.; Carvalho, J.C.M.D.; Morocho–Jácome, A.L. Azadirachta indica (Neem)
as a Potential natural active for dermocosmetic and topical products: A narrative review. Cosmetics 2022, 9, 58. [CrossRef]
40. Altayb, H.N.; Yassin, N.F.; Hosawi, S.; Kazmi, I. In–vitro and in–silico antibacterial activity of Azadirachta indica (Neem), methanolic
extract, and identification of Beta. d–Mannofuranoside as a promising antibacterial agent. BMC Plant Bio. 2022, 22, 1–14.
41. Chrysargyris, A.; Goumenos, C.; Tzortzakis, N. Use of medicinal and aromatic plant residues for partial peat substitution in
growing media for Sonchus oleraceus production. Agronomy 2023, 13, 1074. [CrossRef]
42. Gomaa, S.K.; Zaki, R.A.; Wahba, M.I.; Taleb, M.A.; El–Refai, H.A.; El–Fiky, A.F.; El–Sayed, H. Green method for improving
performance attributes of wool fibres using immobilized proteolytic thermozyme. 3 Biotech. 2022, 12, 254. [CrossRef] [PubMed]
43. Sanchez Ramirez, D.O.; Vineis, C.; Cruz–Maya, I.; Tonetti, C.; Guarino, V.; Varesano, A. Wool keratin nanofibers for bioinspired
and sustainable use in biomedical field. J. Funct. Biomater. 2022, 14, 5. [CrossRef] [PubMed]
44. Aazou, N.; Nadi, A.; Cherkaoui, O.; Gmouh, S. Study and characterization of Moroccan wool fibers for the development of
non–woven products. Conf. Ser. Mater. Sci. Eng. 2023, 1266, 012016. [CrossRef]
45. Adeel, S.; Anjum, F.; Zuber, M.; Hussaan, M.; Amin, N.; Ozomay, M. Sustainable extraction of colourant from harmal seeds
(Peganum harmala) for dyeing of bio–mordanted wool fabric. Sustainability 2023, 14, 12226. [CrossRef]
46. Wang, M.; Yi, N.; Fang, K.; Zhao, Z.; Xie, R.; Chen, W. Deep colorful antibacterial wool fabrics by high–efficiency pad dyeing with
insoluble curcumin. Chem. Eng. J. 2023, 452, 139121. [CrossRef]
47. Průša, D.; Šuhajda, K.; Žajdlík, T.; Svobodová, K.; Št’astník, S.; Hobzova, K.; Venkrbec, V. Effect of microwave radiation on the
compressive strength of solid ceramic brick. Buildings 2023, 13, 1018. [CrossRef]
48. Elmahaishi, M.F.; Ismail, I.; Muhammad, F.D. A review on electromagnetic microwave absorption properties: Their materials and
performance. J. Mater. Res. Technol. 2022, 20, 2188–2220. [CrossRef]
49. Stanfield, L.D.; Powell, A.W.; Horsley, S.A.R.; Sambles, J.R.; Hibbins, A.P. Microwave demonstration of Purcell effect enhanced
radiation efficiency. Sci. Rep. 2023, 13, 5065. [CrossRef]
50. Ibrahim, N.A.; Hala, A.; Mohamed, A.; Abdel–Aziz, S.; Basma, M.E. A green approach for modification and functionalization of
wool fabric using bio–and nano–technologies. Clean Technol. Environ. Policy 2022, 24, 3287–3302. [CrossRef]
51. Xue, Z. Effect of microwave pretreatment on dyeing performance of wool fabric. J. Text. Eng. Fash. Technol. 2017, 1, 217–222.
[CrossRef]
52. Norambuena–Contreras, J.; Garcia, A. Self–healing of asphalt mixture by microwave and induction heating. Mater. Des. 2016,
106, 404–414. [CrossRef]
53. Zhang, Y.; Rather, L.J.; Li, Q. Recent advances in the surface modification strategies to improve functional finishing of cotton with
natural colourants—A review. J. Clean. Prod. 2022, 335, 130313. [CrossRef]
54. AL–Khateeb, D.S.M. Extraction dyes from two natural plants olive leaves and beta vulgaris and the uses in dyeing textile. J. Phys.
Conf. Ser. 2019, 1294, 062109. [CrossRef]
55. Mulder, R.; Morshed, M.N.; Seipel, S.; Norén, U.; Niit, E.; Nierstrasz, V. Study on hydraulic spray atomizing system as a new
resource–efficient dyeing–finishing method for wool fabric. Sci. Rep. 2022, 12, 21814. [CrossRef] [PubMed]
56. Rehman, A.; Irfan, M.; Hameed, A.; Saif, M.J.; Qayyum, M.A.; Farooq, T. Chemical–free dyeing of cotton with functional natural
dye: A pollution–free and cleaner production approach. Front. Environ. Sci. 2022, 115, 848245. [CrossRef]
57. Adeel, S.; Habiba, M.; Kiran, S.; Iqbal, S.; Abrar, S.; Hassan, C.M. Utilization of colored extracts for the formulation of ecological
friendly plant–based green products. Sustainability 2022, 14, 11758. [CrossRef]
58. Mesrar, F.E.; Tachallait, H.; Cherkaoui, O.; Bougrin, K.; Benhida, R. Green and sustainable dyeing of wool with madder plant of
the Moroccan flora. IOP Conf. Ser. Mater. Sci. Eng. 2023, 1266, 012015. [CrossRef]
59. Vankar, P.S.; Gangwar, A. Natural dyeing mediated by atmospheric air pressure plasma treatment of polyester. Pigm. Resin
Technol. 2023. [CrossRef]

Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual
author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to
people or property resulting from any ideas, methods, instructions or products referred to in the content.