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Arabian Journal of Chemistry (2020) 13, 1094–1104

King Saud University

Arabian Journal of Chemistry


www.ksu.edu.sa
www.sciencedirect.com

ORIGINAL ARTICLE

Influence of Neen oil pretreatment on the dyeing


and antimicrobial properties of wool and silk fibers
with some natural dyes
E.M. El-Khatib *, N.F. Ali, R.S.R. El-Mohamedy

National Research Centre, El Buhouth St., Dokki, Cairo 12622, Egypt

Received 27 May 2017; accepted 19 September 2017


Available online 27 September 2017

KEYWORDS Abstract Wool and silk fibers pretreated with neem oil and dyed with chlorophyll, saffron red and
Wool fibers; yellow natural dyes using economic methods such as microwave heating and ultrasonic energy. The
Silk fibers; effect of neem oil concentrations on color strength (K/S) was measured. The results indicated that,
Neem oil; wool and silk fibers pretreated with neem oil recorded higher color strength values than the
Chlorophyll; untreated fibers. Fastness properties and the color yield of the dyes under investigation on wool
Saffron red; and silk fibers were evaluated. The results indicated that, color fastness to rubbing, washing and
Saffron yellow natural dyes; perspiration of all dyes are excellent to good and are approximately the same in microwave and
Antimicrobial activity ultrasonic method. The antimicrobial activity against bacteria and fungi were tested, and the results
indicated that the samples pretreated exhibited higher inhibition percent than the untreated fibers.
The morphologies structure of the untreated and treated wool fibers were examined by scanning
electron microscopy (SEM). The untreated samples have a rough surface. The pretreated samples
of wool fibers were swelling compared to the untreated fibers .The diameter of the fibers increased
and have smooth and even surfaces. The changes in the surface morphology due to the effect of
active ingredients of treatment with neem oil. This behavior as swelling and increase in diameter
of the fibers leads to high penetration of the dyes in the fibers.
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article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

1. Introduction

The rapid growth in technical fibers and their end-uses leads to


many requirements for the application of innovative modifica-
* Corresponding author. tion in dyeing and finishing in textile industry. Novel treat-
E-mail address: dreman411@yahoo.com (E.M. El-Khatib). ments finishes of high added value for apparel fibers are also
Peer review under responsibility of King Saud University. greatly appreciated by demanding consumer market. Antimi-
crobial textiles with improved functionality find a variety of
applications such as health, hygiene products and several med-
ical applications (Joshi, 2009a, 2009b).
Production and hosting by Elsevier

https://doi.org/10.1016/j.arabjc.2017.09.012
1878-5352 Ó 2017 Production and hosting by Elsevier B.V. on behalf of King Saud University.
This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).
Influence of Neen oil pretreatment on the dyeing and antimicrobial properties 1095

In the last few years, the increase in new antimicrobial attack (Ramachandran et al., 2004). In recent years antimicro-
fibers technologies and the growing awareness about cleaner bial textiles have gained interest from both academic research
surroundings and healthy lifestyle. Textile products based on and industry because of their potential to provide high-quality
synthetic antimicrobial agents such as triclosan, metal and life and safety benefits to people (Purwar and Joshi, 2004).
their salts, organo metallics, phenols and quaternary ammo- Textile products are prone to host micro-organisms responsible
nium compounds, have been developed. Although, the syn- for diseases, unpleasant odors, color degradation and deterio-
thetic antimicrobial compounds are very effective against ration of textiles. Antimicrobial textiles can be used to produce
microbes and give a durable effect on fibers, but it caused many goods such as sportswear, outdoor apparels, undergar-
water pollution. Consequently, there is a great demand for nat- ments, shoes, furnishings, upholstery, hospital linens, wound
ural antimicrobial textiles based on eco-friendly compounds care wraps, towels and wipes. Self-sterilizing fabrics could have
which not only help to reduce health hazards associated due potential benefits to reduce disease transfers among hospital
to microbial growth on textile material but also improve the populations, bio warfare protection and other applications.
environment (Hebeish et al., 2012; Joshi, 2009a, 2009b). The Neem (Azadira chtaindica), an evergreen tree of India,
use of natural products such as chitosan (Shin et al., 2010) belongs to the plant family Meliaceae (mahogany). It has been
and natural dyes for antimicrobial finishing of textile fibers recognized as one of the most sources of compounds with
has been reported (El-Khatib et al., 2016, 2014; Ali et al., insect control, antibacterial and medicinal properties
2014). Other natural herbal products, such as Aloe Vera, tea (Rajendran, 2012).
tree oil extracts, can also be used for this purpose (Sanjay, Neem has been used as a traditional medicine against vari-
2013). There is a large source of medicinal plants has active ous human ailments from ancient times in Egypt. However,
antimicrobial ingredients. The study on natural products rich Neem has also received a lot of attention worldwide for its
in antimicrobial agents, is very limited and not well docu- potential use as a herbal pesticide and other healthcare formu-
mented. The reactions of herbal products as compared to mod- lations in countries such as India, China, USA, France, Ger-
ern synthetic pharmaceuticals, with their reduced cost, can be many and Italy. The active ingredients of Neem are found in
exploited as an effective eco friendly alternative to synthetic all parts of the tree but in general, seed, bark, leaves and roots
antimicrobial agents for textile applications. Recent develop- are used for extraction purpose. The most important limonoids
ments on plant based bioactive agents have opened up new are azadirachtin and salannin. The Neem extracts have been
opportunities in research. Most of the papers in this area con- widely used in herbal pesticide formulation because of its pest
centrate on the technical details of applying individual natural repellent properties has a potential to inhibit growth of bacte-
products. The review on the natural product based on antimi- ria both Gram positive and Gram negative (Kut et al., 2005).
crobial finishing agents for application on textiles has been From the point of view, the neem seed is the most impor-
reported (Kwong et al., 2006, Thilagavathi et al., 2007). tant part of the plant given its content in oil and its many
The consumers are now aware of the hygienic life style and active molecules. That is why special attention is paid to the
there is a necessity for textile products finished with antimicro- seed. However, research on the seeds has increased since the
bial properties by natural /products. The inherent properties of isolation of azadirachtin as a natural insecticide. It has multi-
the textile fibers provide environment for the growth of ple uses mainly for the soap, pesticide and pharmaceutical
microorganisms. Also, the structure of the substrates and the (Sidhu et al., 2003). It also has antibacterial, antifungal and
chemical processes may initiate the growth of microbes. medicinal properties (Imam et al., 2012).
Humid and warm environment increase the problem. The aim of this work is the pretreatments for wool and silk
Infestation by microbes causes cross infection by pathogens fibers by neem oil to enhance dyeing and the antimicrobial
and produce odor. In addition, the staining and loss of the per- activity. It is necessary to avoid cross infection by pathogenic
formance properties of textile fibers are the results of microbial microorganisms. These treatments control the infestation by

Fig. 1 Neem oil extract (pretreatment agent).


1096 E.M. El-Khatib et al.

2. Experimental

2.1. Materials

2.1.1. Wool fibers


Wool fibers10/2, and silk fibers supplied by El Mahalla
company-Egypt. Neem oil extract was purchased from
ELGmhoria company, Egypt.

2.1.2. Dyestuffs
– Chlorophyll (a) dye (Chlorophyll-100-WSP: A commercial
product by HANSEN‘S Company.
– Saffron yellow and red dyes (Saffron is the dried stigma of
Fig. 2 Chemical structure of effective constituent of neem oil flowers of Crocus sativus L. Saffron red and yellow).
extract.
2.2. Apparatus

microbes. They also interrupt metabolism in microbes in order 2.2.1. Microwave


to reduce the formation of odor and to safeguard the fibers
products from staining discoloration and quality deterioration. The microwave equipment used in this experiment was the
On the other hand, the aim of this research to use extracted Samsung M 245 with an output of 1550 Watt operating at
natural pigments which extracted from plants such as chloro- 2450 MHz (see Figs. 1–5).
phyll, saffron red and yellow dyes for dyeing wool and silk
fibers. Natural dyes have been used for coloring fibers to pro- 2.2.2. Ultrasonic
tect the environment and prevent pollution caused by indus- Thermostated CREST benchtop 575 HT ultrasonic cleaner of
tries. The dyeing was carried out by using economic methods capacity 5.75 L, frequency 38.5 kHz and with a maximum 500
such as ultrasonic energy and microwave heating. These Watt output was used. The output power levels are from 100
methods are economic and better but not be used in industry. up 500 Watt.

Fig. 3 Chlorophyll plant, Chemical Structure of Chlorophyll (a).

Fig. 4 Saffron yellow and red dyes (Saffron is the dried stigma of flowers of Crocus sativus L. Saffron red and yellow dyes).
Influence of Neen oil pretreatment on the dyeing and antimicrobial properties 1097

Fig. 5 Structures of the chemical constituents of saffron.

2.3. Pretreatment of wool and silk fibers by neem oil pretreated wool and silk fibers with neem oil extract dyed with
Chlorophyll, saffron red and yellow dyes was evaluated.
Wool and silk fibers treated by pad-dry-cure techniques. The
wool fibers treated by neem oil extract at different concentra- 2.5.2. Color data CIE LAB space
tions (20–50%)and silk fibers treated by neem oil extract at Color-difference formula CIE (L*, a*, b*): The total difference
concentrations (2–10%), then padded to 100% wet pick up, CIE (L*, a*, b*) was measured using the Hunter-Lab spec-
dried at 80 °C for 5 min. then cured at 120 °C for 3 min. trophotometer (model: Hunter Lab DP-9000). CIE (L*, a*, b*)
between two colors each given in terms of L*, a*, b* is calcu-
2.4. Dyeing procedure lated from: L* value: indicates lightness, (+) if sample is
lighter than standard, if darker than standard, a* and b* val-
2.4.1. Dyeing wool and silk fibers using microwave method ues: indicate the relative positions in CIE Lab space of the
sample and the standard, from which some indication of the
In a dye bath containing 2 g/l of chlorophyll dye, saffron yel- nature of the difference can be seen. Treated and untreated
low and saffron red dye with a liquor ratio 1:50, the wool and dyed wool and silk fibers were assessed, by measuring the color
silk fibers were dyed by microwave heating at pH 5, time for differences with each sample at five separate points and the
5 min. The dyed samples were rinsed by warm water and then average color difference (DE) between these points was
cold water, washed in a bath containing 5 g/l non-ionic deter- determined.
gent at 50 °C for 30 min, then rinsed and dried in air at room
temperature. 2.5.3. Fastness properties
According to ISO standard methods. The specific tests were
2.4.2. Dyeing wool and silk fibers using ultrasonic method ISO 105-X12 (1987), ISO 105-C02 (1989) and ISO 105-E04
Wool and Silk fibers were dyed with (2 g/L) chlorophyll, saf- (1989), corresponding to color fastness to rubbing, washing
fron red and yellow dyes using ultrasonic energy at L.R 1:50, and perspiration, respectively. The color changes of the sam-
pH 5. The samples were dyed at temperature 50 °C for ples were assessed against an accurate Gray scale.
30 min, the power energy of ultrasonic 500 Watt then the sam-
ples rinsed with cold water, washed in a bath containing 5 g/l 2.5.4. Measurements of antimicrobial activity
non-ionic detergent, at 50 °C for 30 min then rinsed and dried The antimicrobial activities of wool and silk fibers dyed with
in air at room temperature. chlorophyll, saffron red and yellow natural dyes and pre-
treated with neem oil was evaluated by using standard meth-
2.5. Measurements ods(serial dilution and plate count method according to Alen
(1962). Experiment on soil bacteriology Burges Publishing
2.5.1. Measurements of color strength (K/S value) Co. Minneapolis Minnesota USA.
An Ultra Scan PRO spectrophotometer was used to measure The serial dilution blanks were prepared in bottles contain-
the reflectance of the samples and hence, the K/S was mea- ing 99 ml distilled water and marked sequentially starting from
sured spectrophotometrically at wave lengths (Chlorophyll 10 1 to 10 5 dilution and autoclave sterilized. 1.0 gm of each
dye: kmax 440, Saffron red dye: kmax 520 and Saffron yellow fabric sample was added in 99 ml solution i.e. 10–1 dilution.
dye: kmax 385 nm). The color strength K/S of untreated and 1 ml from this was then transferred to 9 ml of the 10 2labeled
1098 E.M. El-Khatib et al.

test tube i.e. 10 2 dilution, using a fresh sterile pipette; and this (SEM), with a JSMT-20, JEOL-Japan. Before examination,
was repeated for each succeeding step till 10 5. Nutrient pep- wool fibers surface was prepared on an appropriate disk and
tone Agar media was used for counting of bacterial strains randomly coated with a spray of gold. SEM was carried out
and for the counting of fungal strains potato dextrose agar at the National Research Centre (Egypt).
(PDA) media was used. From 10 3, 10 4, and 10–5 dilution
tubes, 0.1 ml of dilution fluid was then spread on sterilized pet-
riplates in triplicates using the standard spread plate technique, 3. Results and discussion
for both bacterial and fungal strain isolation .The LB agar
plates were then incubated at 37 °C for 24 h and the PDA 3.1. Effect of concentrations of neem oil extract on wool fibers
plates were incubated at 27 °C for 72 h. After successful dyed with chlorophyll dye
growth of microorganisms, characteristics of each distinct col-
ony, e.g., shapes, color, transparency, etc. were determined. The results obtained indicated that, the pretreatment using
Gram stain was performed to observe the cellular morphology 30% concentration of neem oil extract gave the highest value
and gram reaction of the bacteria. The number of bacterial and of color strength (K/S) for wool fibers dyed with chlorophyll
fungal colonies in the fiber samples was counted and the den- dye by microwave and ultrasonic methods as shown in
sity was expressed as Colony Forming Units (CFU). The Fig. 6, Fig. 7 illustrate samples of wool fibers untreated and
antimicrobial activity was estimated and expressed as reduc- pretreated with neem oil and dyed with chlorophyll dye by
tion in total count of fungi and bacteria in each treatment. microwave method.
The Effect of Microwave heating mechanism is through
2.5.5. Scanning Electron Microscopy (SEM) ionic conduction, which is a type of resistance heating.
The surface morphology of untreated and pretreated wool Depending on the acceleration of the ions through the dye
fibers were investigated by using scanning electron microscopy solution, it results in collision of dye molecules with the mole-
cules of the fiber (Zhao and He, 2011).
Microwave dyeing takes into account the dielectric and
the thermal properties of matter. The dielectric property
refers to the intrinsic electrical properties that affect the dye-
ing by dipolar rotation of the dye and influences the micro-
wave field upon the dipoles. The aqueous solution of dye
has two components which are polar, in the high frequency
microwave field. It influences the vibration energy in the
water molecules and the dye molecules (Zhan and Zhao,
2009).
There are many hypotheses explaining the possible action
of ultrasonic energy on the dyeing system. Theoretical explana-
tions have been presented which attribute this effect to wave’s
high energy influencing the dyeing system by means of
mechanical or hydrodynamic forces associated with cavita-
Fig. 6 Effect of conc. of neem oil extract on the K/S of dyed wool tions which affected on the structure of dye (Shokry et al.,
fibers with chlorophyll dye by microwave and ultrasonic methods. 2010).

Fig. 7 Samples of wool fibers untreated and pretreated with neem oil and dyed with chlorophyll dye by microwave method.
Influence of Neen oil pretreatment on the dyeing and antimicrobial properties 1099

Fig. 10 Effect of conc. of neem oil extract on silk fibers dyed


with saffron red dye by microwave and ultrasonic methods.
Fig. 8 Effect of conc. of neem oil on silk fibers dyed with saffron
red dye by microwave and ultrasonic methods.
3.3. Fastness properties and the color yield of chlorophyll,
saffron red and yellow dyes on wool and silk fibers
3.2. Effect of conc. of neem oil on silk fibers dyed with saffron
red dye and yellow by microwave and ultrasonic methods Fastness properties and the color yield of the dyes under inves-
tigation on wool and silk fibers were evaluated. Table 6 indi-
The results obtained indicated that dyeing silk fibers with cate that color fastness to rubbing, washing and perspiration
saffron red and yellow dye by microwave and ultrasonic of all dyes are excellent to good and are approximately the
methods. The samples pretreated with 4% neem oil exhibited same in microwave and ultrasonic methods, because the dye
highest value of color strength (K/S). Generally the was fixed due to the treatment with neem oil.
pretreated silk fibers gave higher results than the untreated
as shown in Figs. 8 and 10. Figs. 9 and 11 illustrate samples 3.4. Antimicrobial activities of wool and silk fibers
of silk fibers untreated and pretreated with neem oil
and dyed with saffron red and yellow dyes by microwave The antimicrobial activities of dyed wool and silk fibers dyed
method. with chlorophyll, saffron red and yellow dyes and pretreated
In addition, the colorimetric CIE L*a *b*C*h data were with different concentrations of neem oil were expressed as
evaluated for dyed wool and silk fibers were shown in Tables reduction percents in total count of fungi and bacteria associ-
1–5. The color strength changes remarkably as different con- ated with 1 gram of treated fibers as shown in Figs. 12–14
centrations of neem oil were used while the Lab values show (El-Mohamedy and Abdalla, 2014a, 2014b).
that samples treated with 4% are darker in shades. The results Antimicrobial activity, expressed as growth reduction of the
obtained revealed that, the pretreatment with neem oil extract microorganisms, could be explained as follows, the hydroxyl
enhanced the leveling properties. groups in neem oil structure interfere with the bacterial

Fig. 9 Samples of silk fibers untreated and pretreated with neem oil and dyed with saffron red dye by microwave method.
1100 E.M. El-Khatib et al.

Fig. 11 Samples of silk fibers untreated and treated with neem oil and dyed with saffron yellow dye by microwave method.

Table 1 Effect of conc. of neem oil extract on wool fibers dyed with chlorophyll dye by ultrasonic method.
Sample No. K/S L* a* b* C* H DE
0% 6.00 42.59 6.97 16.69 18.08 112.66 46.27
20% 7.31 54.62 6.78 18.35 19.56 110.29 58.01
30% 10.6 49.96 7.63 17.76 19.33 113.24 53.48
40% 9.71 49.14 6.39 16.87 18.04 110.74 52.34
50% 10.0 48.52 8.46 16.85 18.85 116.65 52.06

Table 2 Effect of conc. of neem oil on silk fibers dyed with saffron red dye by microwave method.
Sample No. K/S L* a* b* C* H DE
0% 20.00 39.44 65.93 27.89 63.39 26.10 74.66
2% 25.35 39.43 57.48 28.83 64.30 26.64 75.43
4% 31.83 37.77 56.46 28.02 63.03 26.39 73.48
6% 29.54 38.15 65.80 27.94 63.30 26.19 73.91
8% 21.84 37.18 50.52 20.19 54.41 21.78 65.90
10% 20.80 35.18 40.52 20.89 52.41 20.78 64.90

Table 3 Effect of conc. of neem oil extract on silk fibers dyed with saffron red dye by ultrasonic method.
Conc. of neem oil extract K/S L* a* b* C* H DE
0 2.69 63.30 43.91 4.83 44.17 6.27 56.76
2% 4.27 44.75 43.92 10.15 45.08 13.02 51.10
4% 23.32 60.66 56.92 20.05 60.35 19.41 71.24
6% 7.83 42.51 52.79 14.10 54.64 14.95 63.89
8% 5.17 49.65 49.93 14.85 52.02 16.28 59.08
10% 2.42 45.03 45.88 15.10 48.00 17.08 51.12

metabolism by stacking at the cell surface and binding with 3.5. Surface morphology
DNA to inhibit m-RNA synthesis. The increasing of concen-
tration of neem oil shows more tendencies to deposit on the The morphologies structure of the untreated and pretreated
surface of the fibers resulting in hydroxyl groups more easily wool fibers were examined by scanning electron microscopy
accessible to microorganisms. Wool fibers treated with neem (SEM). Effect of treatment with 30% conc. of neem oil using
oil and dyed with the chlorophyll natural dye display high scanning electron microscope (SEM) for wool fibers,
growth reduction of microbes.
Influence of Neen oil pretreatment on the dyeing and antimicrobial properties 1101

Table 4 Effect of conc. of neem oil extract on silk fibers dyed with saffron yellow dye by microwave method.
Conc. of neem oil extract K/S L* a* b* C* H DE
0% 12.96 73.53 16.19 81.92 83.51 78.82 112.27
2% 22.27 71.29 20.64 88.93 91.29 76.93 115.82
4% 15.02 75.13 15.42 86.51 87.87 79.89 115.61
6% 17.40 70.97 17.43 83.30 85.11 78.18 110.81
8% 13.56 71.56 23.77 79.47 82.95 73.35 109.55
10% 12.56 70.56 23.75 76.42 81.90 71.35 107.53

Table 5 Effect of conc. of neem oil extract on silk fibers dyed with saffron yellow dye by ultrasonic method.
Conc. of neem oil extract K/S L* a* b* C* H DE
0 1.66 84.32 5.35 69.28 69.48 85.58 56.71
2% 3.05 79.76 9.00 56.28 56.99 80.02 41.66
4% 12.33 87.28 2.53 56.44 56.49 87.44 41.66
6% 10.23 73.75 10.90 82.80 83.51 82.50 88.36
8% 5.75 82.12 7.12 81.92 82.23 85.03 66.73
10% 3.86 79.97 6.08 5.86 66.14 84.73 50.63

Table 6 Fastness properties of dyed wool and silk fibers pretreated with neem oil extract and dyed with chlorophyll, saffron red and
yellow dyes.
Dye Fastness to rubbing Wash fastness Fastness to Perspiration
Alkaline Acidic
Dry Wet Alt SC SW Alt SC SW Alt SC SW
Chlorophyll dye 5 5 4–5 4–5 4–5 5 4–5 4–5 4–5 5 5
Saffron yellow 4–5 4–5 5 5 4–5 5 4–5 4–5 5 4–5 4–5
Saffron red 4–5 5 5 5 4–5 5 4–5 4–5 5 4–5 4–5
Untreated 4 3 3 4 4 4 3 3 3 4 4
Alt = change in color, SC = staining on cotton, SW = staining on wool.

Fig. 12 Antimicrobial activities of wool fibers untreated and treated with neem oil extract and dyed with chlorophyll natural dye.

Fig. 15a, Fig. 15b represent the SEM images of untreated and swelling compared to the untreated fibers, the diameter of
treated wool fibers respectively. The untreated samples have a the fibers increase and have smooth and even surfaces. The
rough surface as shown in Fig. 15a, the treated samples as changes in the surface morphology due to the effect of active
shown in Fig. 15b indicate that the treated wool fibers were ingredients of treatment with neem oil.
1102 E.M. El-Khatib et al.

Fig. 13 Antimicrobial activities of silk fibers untreated and treated with neem oil extract and dyed with saffron red natural dye.

Fig. 14 Antimicrobial activities of silk fibers untreated and treated with neem oil extract and dyed with saffron yellow natural dye.

Fig. 15a SEM for untreated wool fibers.


Influence of Neen oil pretreatment on the dyeing and antimicrobial properties 1103

Fig. 15b SEM for pretreated wool fibers with 30% conc. of neem oil extract.

4. Conclusion References

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This project was supported financially by the Science and El-Mohamedy, Riad S.R., Abdalla, Aboelfetoh M., 2014a. Evaluation
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