Progress in Organic Coatings 163 (2022) 106627

Contents lists available at ScienceDirect

Progress in Organic Coatings

journal homepage: www.elsevier.com/locate/porgcoat

Preparation of highly efficient chitosan-based flame retardant coatings with

good antibacterial properties for cotton fabrics
Ghada Makhlouf a, Aksam Abdelkhalik a, *, Heba Ameen b
a
Fire and explosion protection Lab, National Institute of Standards, NIS, El-Sadaat street, El-Haram, P.O.Box 136, El-Giza 12211, Egypt
b
Textile Metrology Lab, National Institute of Standards, NIS, El-Sadaat street, El-Haram, P.O.Box 136, El-Giza 12211, Egypt

A R T I C L E I N F O A B S T R A C T

Keywords: Improving the flame retardancy, thermal stability and antibacterial properties of cotton fabric are necessary for
Chitosan-based flame retardants using it safely. To achieve this goal, melamine phosphate (MP) was added to nanochitosan (nCH) and polyvinyl
Cotton fabric alcohol (PVA) solution to prepare flame retardant coatings for cotton fabric. In addition, melamine salt of chi­
Antibacterial activity
tosan phosphate (MCHP) was prepared, mixed with PVA and used as a coating for cotton fabric. Limiting oxygen
Water wettability
index (LOI) data indicated that PVA/nCH/MP and PVA/MCHP coatings increased LOI of cotton fabric from
17.2% to 57.9% and 58.2%, respectively. Horizontal burning rate and vertical flame spread measurements
manifested, that the flame did not propagate in all treated samples. SEM images of char residue after the vertical
flame spread test showed the formation of an intumescent char layer on the fabric surface that protected cotton
fabric from heat and flame. The antibacterial properties against both pathogenic gram-positive (S. aureus) and
gram-negative (E-coli) bacteria presented that treated samples demonstrate large inhibition zone diameters (IZD)
relative to the control sample. Furthermore, the flame retardant coatings enhanced the control sample thermal
stability and char residue at high temperatures. The tensile strength, water wettability, air permeability and
stiffness of treated samples were measured. Durability study exhibited that treated samples were able to preserve
high flame retardancy properties after the washing process.

1. Introduction Therefore, it can be used in environmentally friendly flame retardant

formulations. Chitosan alone is not an effective flame retardant; how­
Cotton fabrics are vastly used in different applications such as health ever, it can be utilized with other flame retardant additives to make
care and medical clothes due to their fascinating properties which efficient flame retardant formulations that are suitable for various
include air permeability, flexibility, comfortability and water absorp­ polymeric materials. In addition, the functional groups in chitosan (NH2,
tivity. However, cotton fabrics show certain drawbacks such as they can OH) can react with phosphorus-containing compounds to design a
ignite easily at an ambient condition where the LOI value of cotton highly efficient flame retardant materials [18,19]. The application of
fabrics is in the range of 16–18% [9,10,38,51]. In addition, cotton can chitosan-based flame retardants to enhance the flammability properties
give an appropriate environment for the growth of microorganisms of cotton fabrics was investigated by many researchers in the literature
because of its hydrophilic nature detaining oxygen, nutrients and [14,18,19,30,31,39,40,47,50]. Pan et al. [39] applied layer by layer
moisture [44]. Therefore, much research work is directed to improve the technique to coat cotton fabrics with chitosan and phosphorylated
flame retardancy and antibacterial properties of cotton fabrics. chitin; especially 5, 10 and 20 bi-layers were settled on cotton fabrics.
Chitosan, a natural and biodegradable polymer, is composed of Cone calorimeter test data showed that all treated samples had lower
β-(1–4)-linked d-glucosamine and N-acetyl-d-glucosamine which are values for the peak of heat release rate (pHRR) and total heat release
distributed randomly within the polymer structure. It is obtained by (THR) relative to the control sample. In addition, the vertical flamma­
partial deacetylation of chitin under alkaline conditions. When the de­ bility test indicated that the assemblies containing 20 bi-layers (where
gree of deacetylation of chitin reaches nearly 50%, the acidic medium phosphorylated chitin concentration was 2 wt%) made cotton fabric
becomes able to dissolve the chitosan obtained [18,37]. The chemical self- extinction. Liu et al. [31] used layer by layer method to coat cotton
structure of chitosan contains the reactive OH and NH2 groups. fabrics with chitosan, sodium phytate and 3-aminopropyl

* Corresponding author.
E-mail address: [email protected] (A. Abdelkhalik).

https://doi.org/10.1016/j.porgcoat.2021.106627
Received 15 September 2021; Received in revised form 7 November 2021; Accepted 16 November 2021
Available online 2 December 2021
0300-9440/© 2021 Elsevier B.V. All rights reserved.
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

triethoxysilane (APTES). The first layer included sodium phytate and +

NH3 groups of chitosan can interact with the DNA of microorganisms
hydrolysed (APTES) and the second layer included sodium phytate and and prevent DNA transcription, synthesis of RNA and protein
chitosan. The final assemblies consisted of 5, 10 and 15 bi-layers. Cotton [6,17,42,52]. Because chitosan is a polymer with a large molecular
fabrics with 15 bi-layers realized the LOI value of about 29%, while the weight, converting it to nanochitosan can provide a greater chance for
LOI of untreated cotton was 18.1%. Moreover, these samples attained binding with microbes and enhancing its antimicrobial activity [42,52].
self-extinction in the vertical flame spread test. Zhang et al. [50] coated In this work, nCH and MCHP were synthesized and characterized.
cotton fabrics with chitosan/phytic acid /Ba2+ using the dip-pad-dry Then, PVA/MCHP and PVA/nCH/MP coatings were prepared and used
method. The horizontal flame spread test showed that the treated to improve the flame retardancy and antibacterial properties of cotton
samples failed to achieve self-extinction. However, the coatings suc­ fabrics. The flammability, thermal stability, antibacterial and durability
ceeded in decreasing the pHRR and THR values relative to the control properties of the treated fabrics were studied. The flame retardancy
sample in pyrolysis-combustion flow calorimetry measurements. El- mechanism was suggested and confirmed by FTIR, SEM and EDXS
Tahlawy [14] added chitosan /citric acid solution to phosphorylation analysis of char residue formed after the vertical flammability test.
bath including sodium hypophosphite/diammonium hydrogen phos­ Tensile strength, water wettability, stiffness, and air permeability
phate/ butane tetracarboxylic acid. Vertical flammability test showed properties of treated samples were measured and compared.
that the addition of chitosan (even at low concentrations; 1% and 2%) to
phosphorylation bath enabled cotton fabrics to achieve self-extinction 2. Experimental
and the char length was greatly decreased. Pan et al. [40] applied the
layer-by-layer procedure to prepare a robust flame-retardant coating on 2.1. Materials
the surface of cotton fabrics. To achieve this aim, the fabrics were
treated with bi-layers of polyethyleneimine (that has a positive charge) Cotton fabric (100%) with surface density 142 g/m2 was obtained
and chitosan modified with hypophosphorous acid (that has a negative from Texmar Company, Egypt. Poly (vinyl alcohol) with a degree of
charge), then crosslinked by genipin. Finally, 5 or 10 bi-layers were polymerization 1700–1800 was supplied by Oxford Lab Chem, India.
deposited on the cotton fabrics. Horizontal flame spread test showed The molecular weight (MW) of Poly (vinyl alcohol) was 115,000 g/mol.
that fabrics treated with 10 bi-layers were able to achieve self- Melamine (99%) was acquired from Alfa Aesar Company, Germany.
extinction, irrespective using of genipin as a cross-linker. In addition, Phosphoric acid (85%), methanol (99%), Low molecular weight chito­
pHRR and THR of the control sample were decreased by (up to 73%) and san (MW: 50 kDa, degree of acetylation >75%, viscosity 20 cps) and
(up to 80%) in the micro cone calorimeter test. Analysis of char residue high molecular weight chitosan (MW: 310 kDa, degree of acetylation
after flammability tests showed the formation of an intumescent char >75%, viscosity 800 cps) were obtained from Sigma-Aldrich Company,
layer that was able to protect the cotton fabrics from heat and flame. Li Germany. Sodium tripolyphosphate (85%) and acetic acid (99%) was
et al. [30] prepared bio-based layer-by–layer flame retardant coating for purchased from Sigma-Aldrich Company, Germany. All chemicals were
cotton fabric based on chitosan and ammonium phytate. In addition, the utilized as they were received without further purification. Deionized
authors treated the cotton fabrics with chitosan or ammonium phytate water was obtained from the water purification unit (purite select fusion
only to compare the results with the coating prepared by the layer- unit).
by–layer method. The results indicated that chitosan alone was not able
to make good enhancement in LOI test. Δ LOI is used to express the 2.2. Preparation of nCH, MP and MCHP
improvement in the LOI value and it is calculated following Eq. (1).
Chitosan nanoparticles (nCH) were prepared according to the pro­
Δ LOI% = LOI%of treated sample–LOI%of control sample (1)
cedure in Salamata et al. [41] and Kuo-Shien et al. [28] with some
When applying chitosan alone on cotton fabrics, Δ LOI value was 3%. modifications. Low molecular weight chitosan (1.5 g) was dissolved in
In contrast, samples treated with ammonium phytate showed Δ LOI 300 mL of 1% acetic acid solution and stirred for 1 h. Then, a solution of
value of 9%. The specimens treated with chitosan/ ammonium phytate sodium tripolyphosphate (0.7 g in 300 mL deionized water) was added
presented Δ LOI value of 7%. Cone calorimeter data indicated that slowly to the chitosan solution. The nanoparticles were formed under
chitosan, ammonium phytate and chitosan/ammonium phytate continuous stirring for 2 h at room temperature.
decreased the pHRR of the control sample by 10%, 49% and 56%, Melamine salt of chitosan phosphate (MCHP) was synthesized by the
respectively. Xie et al. [47] applied carboxymethyl chitosan and an same method which was reported in our previous work [19]. High
epoxy-silane modified montmorillonite coating to cotton fabric using a molecular weight chitosan (3 g) was added to 59 g of phosphoric acid in
dip-coating technique. The results showed that cotton fabric achieved a 250 mL glass beaker. The solution was stirred for 30 min using a hot
self-extinction in vertical flame spread test when carboxymethyl chito­ plate with a stirrer and the temperature was increased gradually from
san /montmorillonite system contained 50% modified montmorillonite 23 ◦ C to 150 ◦ C. The intermediate compound, chitosan phosphate (CHP)
in treating bath at four repetitions of the dip-coating procedure. El- with yellowish colour, was obtained and it was added gradually to a
Shafei et al. [13] coated cotton fabric with TiO2 nanoparticles and chi­ three-necked flask containing 63 g of melamine dispersed in 500 mL
tosan phosphate (Chit-P) in the presence of [1,2,3,4-butane tetra­ methanol. The temperature of the hot plate was adjusted at 120 ◦ C and
carboxylic acid (BTCA)] and sodium hypophosphite (SHP) as a catalyst. the reaction continued for 4 h. Then, the solution containing MCHP was
The results showed that the maximum value of Δ LOI was 5.6% and it filtered and washed with methanol several times to remove the excess
was achieved in cotton fabric treated with a coating formulation con­ phosphoric acid. The final product was dried at room temperature and it
taining BTCA (4%)/SHP (4%)/ Chit-P (6%)/TiO2 nanoparticles (9%). was crushed to be smooth powder. FTIR analysis of MCHP shows ab­
Chitosan also is widely used in biomedical and pharmaceutical ap­ sorption peaks at 3400 cm− 1, 3158 cm− 1, 1250 cm− 1, 1180 cm− 1, 1108
plications. This is due to its fascinating properties which include anti­ cm− 1and 1050 cm− 1 for NH2, +NH3, P– – O, P–O, P-O-C and P-OH. These
microbial activity, biocompatibility, non-toxicity, biodegradability, low peaks agree with literature data for MCHP [19–21,46]. 1H NMR analysis
immunogenicity and anti tumer properties [3,6,17,18,42,52]. The of MCHP shows peaks at 2.5 ppm (for NH2 of melamine), 6.8 ppm (for H
antimicrobial activity of chitosan refers to its polycationic structure atoms of chitosan ring), and 8.3 ppm for H atoms of the phosphate ester
where the amino groups (+NH3) with positive charges can bind with the group. These peaks are harmonized with the results in Hassan et al. [19].
surface of bacteria which has negative substances such as proteins and Melamine phosphate (MP) was prepared through the reaction be­
lipopolysaccharides. The binding between +NH3 and the surface of tween phosphoric acid and melamine. The reaction was carried out in a
bacteria assists in destroying the cell membrane, increasing perme­ 500 mL round bottom flask with a condenser placed on a hot plate with a
ability and hence destroying the cell. In addition, it was also stated that magnetic stirrer. 30 g of melamine were dispersed in 250 mL of

2
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

methanol for 30 min. Then, 25 g of phosphoric acid were put into the (DMSO‑d6).
previous solution. The hot plate temperature was increased from room Thermogravimetric analysis (TGA) measurements between room
temperature to 120 ◦ C and the reaction went on for 3 h. The solid temperature and 750 ◦ C were carried out on a Shimadzu TGA50 with a
product (MP) was refined, rinsed with methanol several times till the linear heating rate 10 ◦ C/min, under nitrogen atmosphere with a flow
excess phosphoric acid was removed, and left to be dry for 72 h at room rate 30 mL/min. Each sample was placed in a platinum crucible and
temperature. FTIR analysis of MP shows absorption peaks at 3400 cm− 1 specimens' weights were between 7 and 8 mg.
(P-OH and NH2), 1250 cm− 1 (P=O) and 1670 cm− 1 (triazine ring of Vertical flame spread test was conducted by the UL94 flame chamber
melamine), 1406 cm− 1 and 3149 cm− 1 (+NH3) [1,33–35]. following ASTM D 6413 [4]. Control and treated fabric specimens with
dimensions 250 mm × 90 mm were exposed vertically (for 12 s) to a
2.3. Preparation of coated cotton fabrics flame with 38 mm height.
Horizontal flame spread test was carried out by the UL94 flame
In the beginning, cotton fabric was washed with deionized water and chamber according to ISO 3795 [24]. The samples with dimensions 365
dried at 60 ◦ C for 1 h. PVA was used as a binder for improving coating mm × 90 mm were subjected horizontally (for 15 s) to a flame with 38
durability [27]. Eight samples of PVA solution were prepared where mm height. The rate of burning of each sample was calculated following
each sample contained 10 g of PVA that were dissolved in 100 mL of Eq. (3).
deionized water using a hot plate (at 150 ◦ C) with a mechanical stirrer distance (in mm)
(at 700 rpm). Then, 0, 10, 20 and 30 g of MCHP were added to PVA Rate of burning = (3)
time (in min)
solutions at 70 ◦ C to prepare C/PVA, MCHP10, MCHP20 and MCHP30
coatings. MP30 coating was prepared in the same way where 30 g of MP LOI test was conducted by an oxygen index instrument which was
were added to the PVA solution. For coatings containing nCH/MP, 40 g purchased from Reohmetric Scientific Ltd., UK. The test was performed
of nCH solution were added to the PVA solution. Then, 10, 20 and 30 g of at ambient conditions, according to ISO 4589-2 [25]. The samples' di­
MP were added to PVA/nCH solution at 70 ◦ C to prepare nCH10, nCH20 mensions were 120 mm × 50 mm.
and nCH30 coatings. After that, cotton fabric samples were soaked in Small ignition source (SIS) instrument (manufactured by FTT-
these coatings at 70 ◦ C for 10 min and nearly 100% pick-up was ach­ Company, UK) was used to define the ignitability of materials. The
ieved within three pads. The coated samples were dried at 100 ◦ C for 6 samples were subjected to a flame with 20 mm height, for 30 s following
min and cured at 150 ◦ C for 2 min. The data in Table 1 shows the for­ the standard test method ISO 11925-2 [22]. The final results of all
mulations of coatings that were applied on cotton fabrics. The weight flammability tests are the average of three test specimens' results.
gain (WG %) of coated samples was calculated following Eq. (2). Scanning electron microscope (SEM) investigations were carried out
to watch the morphology of cotton fabrics and the char residue after the
W1 − W2
WG% = × 100 (2) flammability tests. Images were collected using Quanta 250 FEG (Field
W2
Emission Gun) supplied by FEI Company, the Netherlands.
Where, W1 and W2 were the weight of control and coated samples, Elemental analysis of char residue was performed using energy-
respectively. The values of WG % are presented in Table 1. In addition, dispersive X-ray spectroscopy (EDXS) which was connected to the
Fig. 1 shows a schematic diagram for preparing cotton fabrics coated SEM instrument and had 30 kV as accelerating voltage.
with chitosan-based flame retardant coatings. TEM images of chitosan nanoparticles were obtained by high-
resolution TEM (Tecnai G20, FEI Company, Netherlands). A droplet of
2.4. Characterization liquid containing chitosan nanoparticles suspension was positioned on a
carbon-supported copper grid. The surplus of liquid was eliminated and
FTIR measurements were executed on Nicolet 380 spectrophotom­ the sample was air-dried before imaging using TEM.
eter (supplied by Thermo Scientific) in the optical range 400–4000 The mean particle size (Z-average) of the chitosan nanoparticles was
cm− 1. Each sample (0.002 g) was mixed with KBr to reach (0.2 g) and determined by Zetasizer Nano ZS instrument (supplied by the Malvern
pressed with a hand press unit to form a round disk suitable for Panalytical Company, UK). The measurements were carried out at a
measurements. temperature of 24.6 ◦ C in triplicate.
1
H NMR spectra were collected on a varian mercury VX-300 NMR Evaluation of antibacterial activity against Gram-positive (G + ve,
spectrometer, which operated at 300 MHz in dimethylsulphoxide S. aureus) and Gram-negative (G-ve, E. coli) pathogenic bacteria was
defined qualitatively according to the AATCC test method (147-1988)
and it was expressed by the zone of growth inhibition (in mm).
Table 1
Formulations of coatings that applied on cotton fabric samples. Furthermore, the antimicrobial activity against the selected bacteria was
marked quantitatively according to AATCC 100 test method. The
Sample code Coating composition Pick up Weight
reduction of colonies was calculated using Eq. (4).
% gain %
PVA nCHa MP MCHP [ ]
g g g g B− A
R = 100 (4)
Cotton (control 0 0 0 0 – –
B
sample)
C/PVA 10 0 0 0 99.5 17.5 Where (R) is the reduction %, (A) is the number of bacterial colonies that
MCHP10 10 0 0 10 99.8 27.3 survived after contacting with the treated sample, and (B) is the number
MCHP20 10 0 0 20 100 35.2 of colonies present in the control sample.
MCHP30 10 0 0 30 100 46.4
The air permeability of the samples was carried out according to
nCH10 10 40 10 0 99.7 26.1
nCH20 10 40 20 0 100 33.9 standard test method EN ISO 9237 [15], using FX 3300 (SDL Interna­
nCH30 10 40 30 0 100 44.7 tional Limited) air permeability tester. The water wettability of the
MP30 10 0 30 0 100 44.4 control and treated samples was measured with water contact angle
MCHP30/alone 0 0 0 30 100 25.5
(WCA) method using compact video microscope (SDL international
nCH30/alone 0 40 30 0 100 24.1
LTD). A water droplet of 5 μl was dropped on the surface of the coated
MCHP30/alone: is cotton fabric treated with MCHP without addition of PVA. and uncoated fabrics and images were taken after 60 s to measure the
nCH30/alone: is cotton fabric treated with nCH and MP without addition of CA. Five measurements were taken for each sample and the average
PVA. value of WCA was reported. The stiffness of the different samples was
a
nCH: the weight of nanochitosan solution used in coatings formulations.

3
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

Fig. 1. A schematic diagram for preparing cotton fabrics coated with chitosan-based flame retardant coatings.

measured following to the ASTM D1388 [5] standard test method.

Tensile strength was measured in the strip method by using a universal
testing machine (Tinlus Olsen, model H5KT) according to the standard
test method ISO 13934–1 [23].
The durability study was carried out in a small washing machine at
30 ◦ C using tape water without the addition of any detergent. Each
sample was subjected to 10 washing cycles and each cycle continued for
5 min. Then, the samples were placed in an oven for 1 h at 60 ◦ C to be
ready for further tests.

3. Results and discussion

3.1. Characterization of nCH

Transmission electron microscope (TEM) image in Fig. 2(a) shows

the formation of spherical and smooth chitosan nanoparticles. The
particle size distribution profile was studied by Zetasizer NanoZS90
instrument. The profile of particle size distribution is presented in Fig. 2
Fig. 3. FTIR analysis of control, MCHP30 and nCH30 samples.
(b) and it indicates the formation of nanoparticles with a mean diameter
48.6 nm and polydispersity index < 1.
3443 cm− 1 which refers to H bonded OH groups. The peak at 2920 cm− 1
is assigned to CH2 of long alkyl chain. The peaks at 1120, 1044 and 894
3.2. FTIR analysis of control, MCHP30 and nCH30 samples
cm− 1 are referred to C-O-C bridge, C–O stretch and out-of-phase ring
stretch: C1–O–C4; β glucosidic bond [11]. FTIR spectra of MCHP30 and
FTIR spectra of cotton fabric, MCHP30 and nCH30 samples are dis­
nCH30 present nearly the same absorption peaks as control sample.
played in Fig. 3. Control sample spectrum shows an absorption peak at

Fig. 2. (a) TEM image, and (b) the size distribution profile of chitosan nanoparticles.

4
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

However, there are some differences where a new peak appears at 1511 Table 2
and 480 cm− 1 (in MCHP30) and 1508 and 490 cm− 1 (in nCH30) for a LOI, horizontal burning rate and vertical flammability test data for control and
triazine ring of melamine and O-P-O group [2,12]. treated samples.
Sample code LOI % Rate of burning Vertical flammability test
(mm/min)
3.3. SEM images of control, MPCH30 and nCH30 taf tag Char length
(s) (s) (cm)
Fig. 4(a-e) shows SEM images of cotton fabric, MPCH30 and nCH30 Control 17.2 212.8 10 38 No chara
samples. SEM image of control sample presents that the surface is clean sample
and smooth because there is no coating on it, Fig. 4(a). In contrast, C/PVA 19.5 209.7 15 0 No chara
MCHP10 26.6 0 0 0 11.5
images of MPCH30 and nCH30 in Fig. 4(b-e) show the flame retardant
(9.4)
materials on the surface and inside the fabrics. Fig. 4(d,e) indicates that MCHP20 34.1 0 0 0 9.5
the density of nCH/MP on the surface of the cotton fabrics is higher than (16.9)
MCHP. This is attributed to the coating formulation in nCH30 sample MCHP30 58.2 (41) 0 0 0 7
contains 40 g of chitosan nanoparticle solution and 30 g as a flame nCH10 26.4 0 0 0 12
(9.2)
retardant meanwhile the coating formulation of MCHP30 includes 30 g nCH20 33.8 0 0 0 11
of MCHP. (16.6)
nCH30 57.9 0 0 0 8.5
(40.7)
3.4. Flammability properties of control and treated samples MP30 36.3 0 0 0 12
(19.1)
3.4.1. LOI data MCHP30/ 41.5 0 0 0 8.9
The data in Table 2 shows the LOI of control and treated samples. LOI alone (24.3)
nCH30/ 38.4 0 0 0 9.2
values of cotton fabric and C/PVA are 17.2% and 19.5%, respectively.
alone (21.2)
The addition of PVA/MCHP, PVA/nCH/MP, MCHP30/alone and
a
nCH30/alone coatings to cotton fabrics succeed in increasing the LOI No char means the sample burnt completely without leaving char residue
value of cotton fabric and as the loading levels of MCHP and nCH/MP after test.
boost in the coating formulation, LOI values are enhanced. According to
the data in Table 2, the oxygen concentration necessary to support flame
propagation in cotton fabric increases by (Δ LOI) 9.4%, 16.9% and 41%

Fig. 4. SEM images of (a) control, (b,c) MCHP30, and (d,e) nCH30 samples.

5
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

in MCHP10, MCHP20 and MCHP30, respectively. Furthermore, the LOI Table 3

of the control sample is enhanced by 9.2%, 16.6% and 40.7% in nCH10, Results of single flame source test.
nCH20 and nCH30, respectively. Also, MCHP30/alone and nCH30/ Sample Parameters
alone samples increased LOI value of cotton by 24.3% and 21.2%, code
Occurrence Whether Time to Ignition Classification
respectively. In contrast, PVA/MP coating in MP30 sample promotes LOI of ignition flame exceed of filter
of the control sample by 19.1%. This means that the single molecule exceed 150 mm paper
intumescent flame retardant (MCHP) and the traditional intumescent 150 mm (t150, s)
flame retardant system (nCH/MP) are more efficient as a flame retardant Control Yes Yes 35a, 37b No F
than MP alone. In addition, the data in Table 2 indicates that MCHP sample
samples have LOI values that are slightly higher than LOI values of nCH/ C/PVA Yes Yes 43a, 45b No F
MCHP10 No No 0 No B,C,D,E
MP samples. The improvement in LOI values refers to the formation of
MCHP20 No No 0 No B,C,D,E
an intact char layer on the cotton fabric surface which prevents flame MCHP30 No No 0 No B,C,D,E
propagation in treated samples. nCH10 No No 0 No B,C,D,E
nCH20 No No 0 No B,C,D,E
3.4.2. Horizontal and vertical flammability tests data nCH30 No No 0 No B,C,D,E
MP30 No No 0 No B,C,D,E
The horizontal burning rate results of control and treated samples are MCHP30/ No No 0 No B,C,D,E
presented in Table 2. The control and C/PVA samples have burning rates alone
212.8 and 209.7 mm/min. In contrast, all MCHP, nCH/MP and MP nCH30/ No No 0 No B,C,D,E
containing samples show a high degree of flame retardancy. The rates of alone
burning of all these samples are 0 mm/min where the flame did not pass a
Result in the case of surface exposure.
the reference mark at 38 mm and did not propagate in samples. b
Results in the case of bottom edged exposure.
Vertical flame spread test data are displayed in Table 2. Control
sample shows after flame time (taf) 10 s, afterglow time (tag) 38 s and the samples after the vertical flame spread test. Fig. 5(a) presents that the
sample burnt completely without leaving char residue. In addition, C/ flame propagated in the control sample from the lower end to the upper
PVA sample shows (15 s) as taf, (0 s) as tag and the sample burnt end and there isn't char residue remaining. In contrast, Fig. 5(b-g) in­
completely. MCHP, nCH/MP and MP containing samples have taf and tag dicates that PVA/MCHP, PVA/nCH/MP and PVA/MP coatings were able
equal to 0 s. This means that after removing the ignition source, the to save cotton fabric from the effect of the ignition source. MCHP con­
flame did not spread in samples. The char length is decreasing with taining coatings form an intact and a coherent char layer on cotton
increasing the flame retardant concentration in the coating formulation. fabrics surfaces, Fig. 5(b-d). On the contrary, nCH/MP system leads to
In addition, char lengths of MCHP containing samples are shorter than the formation of a discontinuous char layer on the fabric surface, Fig. 5
char lengths of nCH/MP and MP containing samples, see Table 2. In (e-g). The same behavior is observed in MP30 sample, Fig. 5(h). The
general, the char formed on treated samples surfaces was able to prevent high quality of char residue formed in the case of MCHP containing
flame propagation in the samples. coatings leads to a higher degree in flame retardancy (higher LOI results
and lower char length values in vertical flame spread test) compared
3.4.3. Single flame source test with nCH/MP containing coatings.
The single flame source test was executed according to ISO 11925-2 SEM images in Fig. 6(a-d) show the char residue of MCHP30 and
[22]. Following the standard test method, the flame can be applied to nCH30 samples after the vertical flame spread test. On one hand, images
the samples for 15 s and the total test duration is 20 s or the flame of the MCHP30 sample, Fig. 6(a,b), shows that the flame retardant
applied for 30 s and the total test duration is 60 s. In this work, the succeeded in protecting the fibers without damage during the combus­
samples were subjected to a direct flame for 30 s and were watched for tion process which means excellent flame retardancy action. Also, an
30 s after removing the ignition source (total test duration was 60 s). The intumescent char layer on the fabric surface was formed. On the other
flame was applied at the midpoint of the bottom edge of samples and hand, SEM images of nCH30 samples, Fig. 6(c,d), display that nCH/MP
also at the surface (40 mm) above the bottom end of samples. For all formed an intumescent char layer above the sample surface. The char
samples, a reference line was drawn at 150 mm from the bottom end. layers in MCHP30 and nCH30 samples were able to protect the samples
The specimen is considered to pass the test if the flame front did not pass from flame and heat, and fibers were maintained without damage after
the reference line at 150 mm within the test duration which is 30 s for the combustion process.
flame application and 30 s after removing the flame source away from EDXS analysis of char of MCHP30 and nCH30 samples appears in
specimens. All samples were tested at the bottom edge and the surface, Fig. 6(e-f). It can be seen that the char of both samples consist of C, P, N
however the data reported in Table 3 is for surface flame exposure. The and O atoms which are interacted during combustion to form the char
results for bottom edges exposure are nearly the same as surface flame layer.
exposure results and the minor differences in results are mentioned at FTIR analysis of char residue of MCHP30 and nCH30 samples after
the end of Table 3. It can be seen in Table 3 that the cotton fabric and C/ vertical flammability test is presented in Fig. 7. MCHP30 spectrum
PVA ignited and the flame front reached the line at 150 mm at 35 and 43 displays absorption peaks at 1727 cm− 1 (for C– – O), 1648 cm− 1 (for C–
–C
s. Therefore, cotton fabrics and C/PVA sample fail to pass this test. In − 1
aromatic), 1408 cm (for C–N), 1246 cm (for P– − 1 – O), 1102 cm− 1 (for
contrast, all flame retardant treated samples did not ignite and pass the P – O – C), 989 cm− 1 (for pyrophosphate and/or polyphosphate), 725
test. According to BS EN 13501-1 [7], the specimen which passes this cm− 1 (for aromatic C–H), and 494 cm− 1 (for O – P – O). The FTIR
test achieves the requirements of classes (B, C, D, and E) concerning the spectrum of nCH30 manifests nearly the same peaks as MCHP30 where
single flame source test. But there are other large scale tests such as the peaks at 1724 cm− 1 (for C– – O), 1631 cm− 1 (for C– – C aromatic), 1406
single burning item test will be necessary for samples to obtain final cm (for C–N), 1255 cm 1 for (P=O), 1092 cm− 1 (for P – O – C), 992
− 1 −
classification as (B, C, and D). cm− 1 (for pyrophosphate and/or polyphosphate), 721 cm− 1 (for aro­
matic C–H) and 484 cm− 1 (for O – P – O) [1,2,35,36].
3.4.4. Flame retardant mechanism Based on char residue analyses, MCHP30 and nCH30 were decom­
The possible flame retardant mechanism for MCHP and nCH/MP posed during combustion and gave out water vapor, CO, CO2 and
containing samples is organized based on analysis of char residue after ammonia in the gas phase. In the condensed phase, MCHP and nCH/MP
the vertical flammability test by digital photos, SEM images, EDXS and decomposed to form polyphosphate which interacted with cellulose
FTIR. The digital photographs in Fig. 5 show the control and treated

6
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

Fig. 5. Digital photographs for (a) control, (b) MCHP10, (c) MCHP20, (d) MCHP30, (e) nCH10, (f) nCH20, (g) nCH30 and (h) MP30 samples after vertical flame
spread test.

structure to form a coherent and compact char layer on samples surfaces. activity). In addition, the treated samples display more activity (larger
FTIR and EDXS analysis of char residue indicated that it contained IZD and higher reduction %) against S. aureus than E. coli. It is expected
polyaromatic structure, pyrophosphate and/or polyphosphate, P-O-C, that the antimicrobial behavior of our coatings is due to the presence of
C–N and C–O bonds. The char layer char was able to protect the fibers +
NH3 groups in MP, nCH/MP and MCHP. These functional groups have
from heat and flame. In addition, it was able to stop flame propagating in positive charges which can interact electrostatically with the negative
the samples regardless of the flame application time (which was 12 s as charges on the cell membrane of bacteria. As a result, they can penetrate
stated by ASTM D 6413 [4]; 15 s according to ISO 3795 [24] and 30 s through bacteria walls and inhibit their growing process
following to ISO 11925-2 [22]. It was reported that the single molecule ([3,6,17,42,52];-21). According to the data in Table 4, the sample
intumescent flame retardants are more efficient than the traditional nCH30 shows the best growth inhibition of bacteria. This may be
intumescent flame retardant system [1,36]. Therefore, samples include referred to that nano-sized chitosan in nCH3 sample can bind more
MCHP show higher LOI value relative to nCH/MP samples. easily with bacterial cell membrane than MP and MCHP compounds [3].
The higher antimicrobial activity of MCHP compared to MP may be
attributed to that MCHP contains a large number of +NH3 (and in
3.5. Antimicrobial activity consequence higher activity) compared to MP. It can be concluded that
the selected chitosan-based flame retardants have good antibacterial
The antibacterial behavior of cotton fabrics coated with chitosan- properties and can be widely used in biomedical and environmental
based flame retardants against S. aureus and E. coli was estimated applications.
using the disk diffusion approach. The data obtained are expressed by
inhibition zone diameter (IZD) and reduction percent methods; and are
presented in Table 4 and Fig. 8(a,b). It is obvious in Table 4 that there is 3.6. TGA data
no antibacterial activity for control and C/PVA samples. Fig. 8(a,b)
shows that the selected flame retardant coatings present antibacterial Thermogravimetric analysis of control and treated samples was
activities against S. aureus and E. coli. IZD values in the case of S. aureus studied by TGA under nitrogen atmosphere. Fig. 9(a,b) shows TGA and
are 17.3, 26.8 and 30.5 mm in MP30, MCHP30 and nCH30 samples Dr.TGA curves of control, MP30, nCH30 and MCHP30 samples and the
meanwhile IZD results in the case of E. coli are 15.5, 24.3 and 27.6 mm in corresponding data are in Table 5. In general, when the cotton fabric is
MP30, MCHP30 and nCH30 samples, respectively. According to the data subjected to intense heat, the degradation reaction of cellulose occurs
in Table 4 and Fig. 8(a,b), the samples can be ordered according to their through two competing reactions: (1) cellulose dehydration and for­
activity in inhibiting the growth of G (+ve) and G (–ve) bacteria as mation of CO2, water vapor and char residue. (2) Cellulose depoly­
follow: nCH30 > MCHP30 > MP30 > C/PVA and control sample (no merization to form levoglucosan that is also degrading to low molecular

7
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

Fig. 6. SEM images of char residue of MCHP30 (a,b), nCH30 (c,d); and EDXS analysis of MCHP30 (e), and nCH30 (f) samples after vertical flame spread test.

Table 4
Antibacterial activity of control and coated samples against S. aureus and E. coli.
Antibacterial activity Control C/ MP30 MCHP30 nCH30
PVA

IZD (mm) S. aureus (G 0 0 17.3 26.8 30.5

Reduction +ve) 0 0 70.6 91.0 96.8
(%)
IZD (mm) E.coli (G-ve) 0 0 15.5 24.3 27.6
Reduction 0 0 62.5 87.6 95.4
(%)

weight compounds and char [8,45]. TGA and Dr.TGA data show that
treated samples start degradation earlier than the control sample. T10%
(the temperature at which 10% weight loss takes place) of the control
sample is 300 ◦ C and it decreased to 298, 291 and 237 ◦ C in MP30,
nCH30 and MCHP30 samples, respectively. The reduction in T10% values
of treated samples agrees with the Dr.TGA curves of these samples that
show a small decomposition step (with a slight weight loss rate) in the
temperature range 180–332 ◦ C. This step of degradation starts and ends
at 295–332 ◦ C, 290–332 ◦ C and 180–280 ◦ C in MP30, nCH30 and
MCHP30 samples, respectively. It is expected that the decrease in T10%
Fig. 7. FTIR analysis of char residue of nCH30 and MCHP30 samples. of treated samples may be attributed to the decomposition of less ther­
mally stable C–N and P–O bonds [29,33,34]. The control and treated
samples show the main decomposition step in the temperature range
290–450 ◦ C. In the control sample, this step starts and ends at

8
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

Fig. 8. Digital photos for antibacterial activity of control, MCHP30, nCH30 and MP30 samples against (a) S. aureus and (b) E. coli bacteria.

Table 5
TGA and Dr.TGA data of control, MP30, nCH30 and MCHP30 samples.
Sample T10% Tmax Maximum weight loss Char residue at
code (◦ C) (◦ C) rate (mg.min− 1) 750 (◦ C)

Control 300 348 1.13 0.3

sample
MP30 298 375 0.78 20.9
nCH30 291 378 0.58 19.8
MCHP30 237 383 0.47 27.5

T10%: the temperature at which 10% weight loss takes place.

290–365 ◦ C. All the flame retardant coatings succeed in shifting this

degradation step to higher temperatures where it starts and ends at
344–415 ◦ C, 346–441 ◦ C and 330–450 ◦ C, in MP30, nCH30 and
MCHP30 samples, respectively. The temperatures at the peaks (Tmax)
and maximum weight loss rates (mg. min− 1) within this decomposition
step are presented in Table 5. It can be seen that Tmax of the control
sample enhances by 27, 30 and 35 ◦ C in MP30, nCH30 and MCHP30
samples, respectively. In addition, the maximum weight loss rate of the
cotton sample is reduced by the addition of the flame retardant coatings,
see Table 5. This improvement in thermal stability is referred to that the
flame retardants decomposed to form polyphosphoric acid, which
interacted with cellulose products to form thermally stable char residue
that was able to protect cotton fabrics from the effect of heat. As the
temperature increases to reach 750 ◦ C, a slight degradation in the
treated samples is observed in TGA curves. The char residue of the
control sample at 750 ◦ C is 0.3% and it is increased to 20.9%, 19.8% and
27.5% in MP30, nCH30 and MCHP30 samples, respectively. The
enhancement in thermal stability and char residue of treated samples
gives a primary indication that the different coatings will have good
flame retardancy action on cotton fabrics.

Table 6
Physical and mechanical properties of control and treated samples.
Sample Stiffness Air permeability WCA Tensile
code (bending length, (cm3/cm2/s) after 60 strength (N)
mm) s

Control 35.8 25.5 0 330.1

sample
C/PVA 48.6 24.1 0 316.2
MCHP10 49.1 23.6 114 315.6
MCHP20 57.4 22.3 125 297.2
Fig. 9. (a) TGA and (b) Dr.TGA data of control and treated samples. MCHP30 68.2 20.9 142 285.1
nCH10 59.7 14.9 0 309.9
nCH20 77.5 11.7 0 284.3
nCH30 85.8 10.0 0 273.5
MP30 86.3 9.6 0 267.1

9
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

3.7. Stiffness, air permeability, surface wettability, tensile strength and Table 7
water/oil separation LOI, horizontal burning rate and vertical flammability test data for control and
treated samples after washing process.
The bending properties of control and coated samples are presented Sample code LOI % Rate of burning Vertical flammability test
in Table 6. The stiffness of the control sample is lower than treated mm/min
taf tag Char length
samples. It is clear in Table 6 that as the concentration of flame retardant (s) (s) (cm)
in coating formulation is growing up, stiffness value is enhanced. MCHP
Cotton 17.2 212.8 10 38 No char
containing samples have lower stiffness values than the samples contain MCHP10 18.3 185.6 0 0 25
nCH/MP and MP. In general, the higher values of stiffness for treated (1.1)
samples may be referred to the augmentation in friction between fibers MCHP20 24.6 0 0 0 18.5
or yarns as a result of the presence of coatings over cotton fabric [16]. (7.4)
MCHP30 37.5 0 0 0 12.3
The increase in stiffness values is considered an indication on a slight (20.3)
opposite effect of the flame retardant coatings on the softness of the nCH10 17.7 200.4 29 0 25
cotton fabric [32]. (0.5)
It is obvious in Table 6 that the air permeability of control sample is nCH20 25.6 0 0 0 13.4
(8.4)
changing with the addition of flame retardant coatings. It was reported
nCH30 38.1 0 0 0 10.8
that the thickness of coating plays an important role in air permeability. (20.9)
When the thickness of coating increases, air permeability decreases MP30 23.5 0 42 0 25
because the coating reduces the air space between fibers [26]. The (6.3)
samples including MCHP shows a slight reduction in air permeability MCHP30/ 17.9 199.9 0 0 25
alone (0.7)
compared to the untreated cotton fabric. SEM images in Fig. 4(b,c) for nCH30/alone 17.7 205.1 0 0 25
MCHP30 show that the surface of the fabric is not crowded with MCHP (0.5)
particles. This structure permits the flow of air through the fabrics. In
The values in brackets are referred to Δ LOI.
contrast, the samples containing nCH/MP as a flame retardant display
higher reductions in air permeability relative to untreated sample. This
behavior can be referred to that nCH/MP particles were dense at the 3.8. Durability study
surface of cotton fabric. SEM images in Fig. 4(d,e) for nCH30 sample
present that many particles of flame retardants (nCH/MP) are found on To evaluate the durability of coated samples, LOI, horizontal and
the surface of cotton and this hinders the air flow through the fabric. The vertical flammability tests were carried out after the washing process
presence of nCH particles may also lead to slight thickening of coating and the results are presented in Table 7. The washing process decreases
which can cause reduction in air permeability of the sample [26]. the concentration of flame retardants on cotton fabrics surfaces.
The wettability of fabric surface is determined by the CA of a liquid Therefore, LOI values of treated samples are reduced but it still better
(water) on the solid fabric surface. In case of cotton fabrics, it is than the control sample especially at high concentrations of flame re­
impossible to have base line for CA measurement because the macro­ tardants. For example, LOI values of MCHP20 and MCHP30 specimens
scopic weave structure of the fabric and the existence of notable fibers are greater than the control sample by 7.4% and 20.3%. Also, LOI results
[49]. The data in Table 6 presents that the control sample has WCA equal of nCH20 and nCH30 samples are higher than blank by 8.4% and 20.9%.
to 0◦ which indicates excellent hydrophilic properties of cotton. The The sample MP30 shows Δ LOI value equal to 6.3%. In general, coated
samples treated with MCHP flame retardant show hydrophobic prop­ samples (MCHP20, MCHP30, nCH20, nCH30 and MP30) are still having
erties where the WCA > 90◦ after 60 s. It is clear in Table 6 that as the good flame retardancy action after the washing process. In addition,
concentration of MCHP grows up in coating formulations; WCA values of nCH20 and MCHP20 samples are more flame resistant than MP30. The
samples are enhanced. The maximum WCA value is 142◦ and it is data in Table 7 shows that MCHP30/alone and nCH30/alone samples
observed in MCHP30 sample after 60 s, see Fig. S1(a) in supplementary have LOI values very close to the LOI value of the control sample. This
data. The samples treated with PVA, PVA/nCH/MP and PVA/MP have means that most of coating leaves the cotton fabric during washing
WCA < 90◦ after 60 s which infers the hydrophilic properties of these process when PVA is not found in coating formulation.
samples. It was reported that the WCA values are depending on the The rates of burning of MCHP10, nCH10, MCHP30/alone and
chemical structure of the coating on fabric surface [43]. The traditional nCH30/alone samples after the washing process are 185.6, 200.4, 199.9
intumescent flame retardants systems are characterized by water and 205.1 mm/min, respectively, see Table 7. These values are still
leaching meanwhile single molecule intumescent flame retardants are lower than the rate of burning of the control sample (212.8 mm/min).
distinguished by the reduced polarity and water repellent properties The rest of the treated samples have a burning rate 0 mm/min. This
[33,35]. Therefore, addition of MCHP (which is a single molecule means that samples MP30, MCHP20, MCHP30, nCH20 and nCH30 still
intumescent flame retardant) to coating improves the hydrophobic have a high degree of flame retardancy after the washing process where
properties of coated fabrics. In contrast, samples coated with nCH/MP the flame did not propagate in the samples and wasn't able to pass the
(which is considered as traditional intumescent flame retardant) show reference mark at 38 mm.
hydrophilic properties. Vertical flame spread test data after washing, display that the sample
To investigate the hydrophobic and superoleophilic properties of MCHP10 burns during the application time of ignition source (12 s) and
MCHP30 sample, water and oil droplets were scattered on the surface of the char residue length is 25 cm. As the concentration of MCHP grows up
MCHP30 samples, Fig. S1(b) in supplementary data. The sample is in coating formulation, good flame retardancy is achieved where the
considered superoleophilic where the oil droplets were absorbed by the char lengths results are reduced to 18.5 and 12.3 cm in MCHP20 and
MCHP30 sample after 1 s. In contrary, the water droplets continued for MCHP30, respectively. The same behavior is observed in nCH/MP
at least 10 min without spreading on the sample surface. This indicates containing samples. The sample nCH10 presents taf 29 s and it leaves
that MCHP30 can be applied in water/oil separation processes. char with 25 cm length. nCH20 and nCH30 samples manifest a higher
Tensile strength of control and coated samples are presented in degree of flame retardancy compared with nCH10 sample where taf
Table 6. Pretreated samples show a slight reduction in tensile strength values are 0 s. The char length results are 13.4 and 10.2 cm in nCH20
relative to untreated sample. The decrease in tensile strength may be and nCH30 samples, respectively. MP30 sample shows taf equal to 42 s
referred to the high temperature of the curing process [48]. and char length 25 cm. This indicates that after washing the samples
nCH20, nCH30, MCHP20 and MCHP30 are more flame resistant than

10
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

Fig. 10. Digital photographs for (a) MCHP10, (b) MCHP20, (c) MCHP30, (d) nCH10, (e) nCH20, (f) nCH30 and (g) MP30 after washing process and vertical flame
spread test.

MP30. Fig. 10(a-f) presents digital photographs of the treated cotton

fabrics after the washing process. It is clearly seen in Fig. 10(a,d,g) that
Table 8 the flame spread to the far end of MCHP10, nCH10 and MP30 samples.
Results of single flame source test after washing process. In contrast, Fig. 10(b,c,e,f) shows that MCHP20, MCHP30, nCH20 and
Sample Parameters nCH30 still have good flame retardancy action after washing where the
code
Occurrence Whether Time to Ignition Classification flame failed to propagate and to reach the upper end of samples.
of ignition flame exceed of filter Single flame source test results data in Table 8 presents that after
exceed 150 mm paper washing the samples MCHP20, MCHP30, nCH20 and nCH30 passed the
150 mm (t150, s) test where the flame did not spread in samples. On the contrary, samples
Cotton Yes Yes 35a, 37b No F MCHP10, nCH10 and MP30 ignited and the flame attained the reference
MCHP10 Yes Yes 44a, 45b No F mark at 150 mm within test duration. This indicates that at high con­
MCHP20 No No 0 No B,C,D,E
centrations from nCH/MP and MCHP, the samples still have good flame
MCHP30 No No 0 No B,C,D,E
nCH10 Yes Yes 43a, 46b No F retardancy action after washing.
nCH20 No No 0 No B,C,D,E The antimicrobial activity of MCHP30 and nCH30 samples after
nCH30 No No 0 No B,C,D,E washing process is presented in Table S1. The data in Table S1 infers that
MP30 Yes Yes 33a, 34b No F the values of IZD of the samples are decreased after washing process.
a
Result in the case of surface exposure. This may be attributed to that some of coating leaves the fabric during
b
Results in the case of bottom edged exposure. washing process.

11
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

4. Conclusions [5] ASTM D1388, Standard Test Method for Stiffness of Fabrics, 2018.
[6] S. Benltoufa, W. Miled, M. Trad, R.B. Slama, F. Fayala, Chitosan hydrogel-coated
cellulosic fabric for medical end-use: antibacterial properties, basic mechanical and
In this work, PVA/MCHP and PVA/nCH/MP were used as coatings comfort properties, Carbohydr. Polym. 227 (2020), 115352, https://doi.org/
for the cotton fabric to improve its flammability, thermal stability and 10.1016/j.carbpol.2019.115352.
antibacterial properties. The results indicated that the prepared coatings [7] BS EN 13501-1, Fire classification of construction products and building elements,
in: Classification Using Data From Reaction to Fire Tests, 2018.
are highly efficient flame retardants with good antibacterial properties. [8] F. Carosio, C. Negrell-Guirao, A.D. Blasio, J. Alongi, G. David, G. Camino, Tunable
MCHP coating enhanced LOI of the control sample by 9.4%, 16.9% and thermal and flame response of phosphonated oligoallylamines layer by layer
41% in MCHP10, MCHP20 and MCHP30 samples, respectively. In assemblies on cotton, Carbohydr. Polym. 115 (2015) 752–759, https://doi.org/
10.1016/j.carbpol.2014.06.066.
addition, nCH/MP coating increased LOI of cotton by 9.2%, 16.6% and [9] Y. Chen, D. Wang, S. Liu, Y. Lu, G. Zhang, F. Zhang, A novel P–N-based flame
40.7% in nCH10, nCH20 and nCH30 samples, respectively. Horizontal retardant with multi-reactive groups for treatment of cotton fabrics, Cellulose 27
burning rate and vertical flame spread data showed that the flame failed (2020) 9075–9089, https://doi.org/10.1007/s10570-020-03387-0.
[10] Y. Chen, C. Wan, S. Liu, P. Wang, G. Zhang, A novel flame retardant based on
to propagate in all MCHP and nCH/MP containing samples. According to polyhydric alcohols and P–N synergy for treatment of cotton fabrics, Cellulose 28
BS EN13501–1, cotton fabrics coated with MCHP and nCH/MP suc­ (2021) 1781–1793, https://doi.org/10.1007/s10570-020-03615-7.
ceeded in fulfilling the requirements of classes B, C, D and E concerning [11] C. Chung, M. Lee, E.K. Choe, Characterization of cotton fabric scouring by FT-IR
ATR spectroscopy, Carbohydr. Polym. 58 (2004) 417–420, https://doi.org/
the single flame source test. IZD data showed that the selected chitosan- 10.1016/j.carbpol.2004.08.005.
based flame retardants coatings had good antibacterial properties [12] C. Dayanand, G. Bhikshamaiah, V.J. Tyagaraju, M. Salagram, A.S.R.K. Murthy,
against S. aureus and E. coli bacteria. The activity of samples against the Structural investigations of phosphate glasses: a detailed infrared study of the x
(PbO)-(1-x)P2O5 vitreous system, J. Mater. Sci. 31 (1996) 1945–1967, https://doi.
selected types of bacteria can be ordered as follow: nCH30 > MCHP30 >
org/10.1007/BF00356615.
MP30 > C/PVA and control sample. In addition, the coated samples [13] A. El-Shafei, M. ElShemy, A. Abou-Okeil, Eco-friendly finishing agent for cotton
presented higher growth inhibition zones for S. aureus bacteria fabrics to improve flame retardant and antibacterial properties, Carbohydr. Polym.
compared to E. coli. TGA data manifested, that MCHP and nCH/MP 118 (2015) 83–90, https://doi.org/10.1016/j.carbpol.2014.11.007.
[14] K. El-Tahlawy, Chitosan phosphate: a new way for production of eco-friendly flame
enhanced the thermal stability of cotton fabrics at high temperatures retardant cotton textiles, J. Text I 99 (2008) 185–191, https://doi.org/10.1080/
and increased the char residue at 750 ◦ C relative to the control sample. 00405000701584311.
The stiffness of treated samples was increased relative to blank while [15] EN ISO 9237, Textiles – Determination of the Permeability of Fabrics to Air, 1995.
[16] S. Faheem, V. Baheti, M. Tunak, J. Wiener, J. Militky, Flame resistance behavior of
tensile strength values slightly decreased by increasing flame retardants cotton fabrics coated with bilayer assemblies of ammonium polyphosphate and
concentrations in coatings formulations. The air permeability value of casein, Cellulose 26 (2019) 3557–3574, https://doi.org/10.1007/s10570-019-
control sample was slightly decreased by addition of MCHP in coating 02296-1.
[17] X. Fu, Y. Shen, X. Jiang, D. Huang, Y. Yan, Chitosan derivatives with dual-
formulation. WCA data indicated that C/PVA, nCH10, nCH20 and antibacterial functional groups for antimicrobial finishing of cotton fabrics,
nCH30 coatings had hydrophilic properties. In contrast, MCHP10, Carbohydr. Polym. 85 (2011) 221–227, https://doi.org/10.1016/j.
MCHP20 and MCHP30 samples showed hydrophobic properties and carbpol.2011.02.019.
[18] R.R. Gadkari, A. Gupta, U. Teke, A. Awadhiya, M. Shahadat, W. Ali, A. Das,
superoleophilic characteristics. The durability study showed that R. Alagirusamy, A sustainable way for surface functionalisation of PET nonwoven
MCHP20, MCHP30, nCH20 and nCH30 samples maintained antibacte­ with novel chitosan-cinnamaldehyde cross-linked nanoparticles, J. Ind. Eng. Chem.
rial and a high degree of flame retardancy after washing process. 99 (2021) 214–223, https://doi.org/10.1016/j.jiec.2021.04.031.
[19] M. Hassan, M. Nour, Y. Abdelmonem, G. Makhlouf, A. Abdelkhalik, Synergistic
effect of chitosan-based flame retardant and modified clay on the flammability
CRediT authorship contribution statement properties of LLDPE, Polym. Degrad. Stab. 133 (2016) 8–15, https://doi.org/
10.1016/j.polymdegradstab. 2016.07.011.
[20] S. Hu, L. Song, Y. Hu, Preparation and characterization of chitosan-based flame
Ghada Makhlouf: Conceptualization, Methodology, Data curation, retardant and its thermal and combustible behavior on polyvinyl alcohol, Polym.-
Investigation, Validation, Visualization, Writing – review & editing. Plast. Technol. Eng. 52 (2013) 393–399, https://doi.org/10.1080/
Aksam Abdelkhalik: Conceptualization, Investigation, Visualization, 03602559.2012.754465.
[21] S. Hu, L. Song, H. Pan, Y. Hu, Effect of a novel chitosan-based flame retardant on
Writing – original draft, Data curation. Heba Ameen: Conceptualiza­
thermal and flammability properties of polyvinyl alcohol, J. Therm. Anal. Calorim.
tion, Data curation, Investigation, Validation, Visualization, Writing – 112 (2013) 859–864, https://doi.org/10.1007/s10973-012-2686-7.
review & editing. [22] ISO 11925-2, Reaction to Fire Tests - Ignitability of Products Subjected to Direct
Impingement of Flame - Part 2: Single-flame Source Test, 2020.
[23] ISO 13934–1, Textiles – Tensile Properties of Fabrics – Part 1: Determination of
Declaration of competing interest Maximum Force and Elongation at Maximum Force Using the Strip Method, 2013.
[24] ISO 3795, Road Vehicles, and Tractors and Machinery for Agriculture and Forestry
- Determination of Burning Behaviour of Interior Materials, 1989.
There is no conflict of interest concerning our manuscript. [25] ISO 4589-2, Plastics - Determination of Burning Behaviour by Oxygen Index - Part
2: Ambient-temperature Test, 2017.
[26] K. Kaliyamoorthi, R. Thangavelu, Union dyeing of cotton/nylon blended fabric by
Appendix A. Supplementary data plasma-nano chitosan treatment, Fash Text 2 (2015) 2–10, https://doi.org/
10.1186/s40691-015-0035-8.
Supplementary data to this article can be found online at https://doi. [27] M.M. Khin, Y. Bao, Y.N. Liang, M.I. Setyawati, H. Gnayem, K.W. Ng, Y. Sasson,
X. Hu, BiOClBr-coated fabrics with enhanced antimicrobial properties under
org/10.1016/j.porgcoat.2021.106627.
ambient light, J. Mater. Chem. B 9 (2021) 3079–3087, https://doi.org/10.1039/
D0TB02835E.
References [28] H. Kuo-Shien, S. Yea-Ru, C. In-Chun, Preparation and properties of nanochitosan,
Polym.-Plast. Technol. Eng. 48 (12) (2009) 1239–1243, https://doi.org/10.1080/
03602550903159069.
[1] A. Abdelkhalik, A. Abdel-Hakim, G. Makhlouf, A.A. El-Gamal, Effect of iron poly
[29] X. Lai, J. Qiu, H. Li, X. Zeng, S. Tang, Y. Chen, Z. Chen, Flame retardant and
(acrylic acid-co-acrylamide) and melamine polyphosphate on the flammability
thermal degradation mechanism of caged phosphate charring agent with melamine
properties of linear low-density polyethylene, J. Therm. Anal. Calorim. 138 (2019)
pyrophosphate for polypropylene, Int. J. Polym. Sci. 2015 (2015) 1–11, https://
1021–1031, https://doi.org/10.1007/s10973-019-08293-7.
doi.org/10.1155/2015/360274.
[2] A. Abdelkhalik, G. Makhlouf, M.A. Hassan, Manufacturing, thermal stability, and
[30] P. Li, B. Wang, Y. Liu, Y. Xu, Z. Jiang, C. Dong, L. Zhang, Y. Liu, P. Zhu, Fully bio-
flammability properties of polypropylene containing new single molecule
based coating from chitosan and phytate for fire-safety and antibacterial cotton
intumescent flame retardant, Polym. Adv. Technol. 30 (2019) 1403–1414, https://
fabrics, Carbohydr. Polym. 237 (2020), 116173, https://doi.org/10.1016/j.
doi.org/10.1002/pat.4573.
carbpol.2020.116173.
[3] R.M. Abdel-Rahman, A.M. Abdel-Mohsen, R. Hrdina, L. Burgert, Z. Fohlerova,
[31] Y. Liu, Q. Wang, Z. Jiang, C. Zhang, Z. Li, H. Chen, P. Zhu, Effect of chitosan on the
D. Pavliňák, O.N. Sayed, J. Jancar, Wound dressing based on chitosan/hyaluronan/
fire retardancy and thermal degradation properties of coated cotton fabrics with
nonwoven fabrics: preparation, characterization and medical applications, Int. J.
sodium phytate and APTES by LBL assembly, J. Anal. Appl. Pyrolysis 135 (2018)
Biol. Macromol. 89 (2016) 725–736, https://doi.org/10.1016/j.
289–298, https://doi.org/10.1016/j.jaap.2018.08.024.
ijbiomac.2016.04.087.
[4] ASTM D 6413, Standard Test Method for Flame Resistance of Textile (Vertical
Test), 2015.

12
G. Makhlouf et al. Progress in Organic Coatings 163 (2022) 106627

[32] M. Liu, S. Huang, G. Zhang, F. Zhang, Synthesis of P–N–Si synergistic flame hybrid coating of copper/chitosan nanocomposites loaded polymer blends via
retardant based on a cyclodiphosphazane derivative for use on cotton fabric, gamma irradiation, Int. J. Biol. Macromol. 183 (2021) 23–34, https://doi.org/
Cellulose 26 (2019) 7553–7567, https://doi.org/10.1007/s10570-019-02608-5. 10.1016/j.ijbiomac.2021.04.059.
[33] G. Makhlouf, M. Hassan, M. Nour, Y. Abdelmonem, A. Abdelkhalik, Evaluation of [43] A.K. Singh, J.K. Singh, An efficient use of waste PE for hydrophobic surface coating
fire performance of linear low-density polyethylene containing novel intumescent and its application on cotton fibers for oil-water separator, Prog. Org. Coat. 131
flame retardant, J. Therm. Anal. Calorim. 130 (2) (2017) 1031–1041, https://doi. (2019) 301–310, https://doi.org/10.1016/j.porgcoat.2019.02.025.
org/10.1007/s10973-017-6418-x. [44] P. Taheri, A. Khajeh-Amiri, Antibacterial cotton fabrics via immobilizing silver
[34] G. Makhlouf, M. Hassan, M. Nour, Y. Abdelmonem, A. Abdelkhalik, A novel phosphate nanoparticles onto the chitosan nanofiber coating, Int. J. Biol.
intumescent flame retardant: synthesis and its application for linear low-density Macromol. 158 (2020) 282–289, https://doi.org/10.1016/j.ijbiomac.2020.04.258.
polyethylene, Arab. J. Sci. Eng. 42 (10) (2017) 4339–4349, https://doi.org/ [45] C. Wan, M. Liu, P. Tian, G. Zhang, F. Zhang, Renewable vitamin B5 reactive N–P
10.1007/s13369-017-2443-0. flame retardant endows cotton with excellent fire resistance and durability,
[35] G. Makhlouf, A. Abdelkhalik, M.A. Hassan, Combustion toxicity of polypropylene Cellulose 27 (2020) 1745–1761, https://doi.org/10.1007/s10570-019-02886-z.
containing melamine salt of pentaerythritol phosphate with high efficiency and [46] Y. Xiao, Y. Zheng, X. Wang, Z. Chen, Z. Xu, Preparation of a chitosan-based flame-
stable flame retardancy performance, Process. Saf. Environ. Prot. 138 (2020) retardant synergist and its application in flame-retardant polypropylene, J. Appl.
300–311, https://doi.org/10.1016/j.psep.2020.04.012. Polym. Sci. 131 (2014) 40845–40852, https://doi.org/10.1002/app.40845.
[36] G. Makhlouf, A. Abdelkhalik, H. Ameen, Synthesis of a novel highly efficient flame- [47] H. Xie, X. Lai, Y. Wang, H. Li, X. Zeng, A green approach to fabricating nacre-
retardant coating for cotton fabrics with low combustion toxicity and antibacterial inspired nanocoating for super efficiently fire-safe polymers via one-step self-
properties, Cellulose 28 (2021) 8785–8806, https://doi.org/10.1007/s10570-021- assembly, J. Hazard. Mater. 365 (2019) 125–136, https://doi.org/10.1016/j.
04076-2. jhazmat.2018.10.099.
[37] G. Malucelli, Flame-retardant systems based on chitosan and its derivatives: state [48] D. Xu, S. Wang, Y. Wang, Y. Liu, C. Dong, Z. Jiang, P. Zhu, Preparation and
of the art and perspectives, Molecules 25 (18) (2020) 4046, https://doi.org/ mechanism of flame-retardant cotton fabric with phosphoramidate siloxane
10.3390/molecules25184046. polymer through multistep coating, Polymers 12 (2020) 1538, https://doi.org/
[38] H. Nabipour, X. Wang, M.Z. Rahman, L. Song, Y. Hu, An environmentally friendly 10.3390/polym12071538.
approach to fabricating flame retardant, antibacterial and antifungal cotton fabrics [49] M. Zhang, S. Wang, C. Wang, J. Li, A facile method to fabricate super hydrophobic
via self-assembly of guanazole-metal complex, J. Clean. Prod. 273 (2020) (2020), cotton fabrics, Appl. Surf. Sci. 261 (2012) 561–566, https://doi.org/10.1016/j.
122832, https://doi.org/10.1016/j.jclepro.2020.122832. apsusc.2012.08.055.
[39] H. Pan, W. Wang, Y. Pan, L. Song, Y. Hu, K.M. Liew, Formation of self- [50] Z. Zhang, Z. Ma, Q. Leng, Y. Wang, Eco-friendly flame retardant coating deposited
extinguishing flame retardant bio-based coating on cotton fabrics via Layer-by- on cotton fabrics from bio-based chitosan, phytic acid and divalent metal ions, Int.
Layer assembly of chitin derivatives, Carbohydr. Polym. 115 (2015) 516–524, J. Biol. Macromol. 140 (2019) 303–310, https://doi.org/10.1016/j.
https://doi.org/10.1016/j.carbpol.2014.08.084. ijbiomac.2019.08.049.
[40] Y. Pan, L. Liu, Y. Zhang, L. Song, Y. Hu, S. Jiang, H. Zhao, Effect of genipin [51] W.J. Zhu, M.Y. Yang, H. Huang, Z. Dai, B.W. Cheng, S.S. Hao, A phytic acid-based
crosslinked layer-by-layer self-assembled coating on the thermal stability, chelating coordination embedding structure of phosphorus-boron-nitride
flammability and wash durability of cotton fabric, Carbohydr. Polym. 206 (2019) synergistic flame retardant to enhance durability and flame retardancy of cotton,
396–402, https://doi.org/10.1016/j.carbpol.2018.11.037. Cellulose 27 (2020) 4817–4829, https://doi.org/10.1007/s10570-020-03063-3.
[41] S. Salamata, M. Hadavifar, H. Rezaei, Preparation of nanochitosan-STP from [52] D.Z. Zmejkoski, Z.M. Marković, M.D. Budimir, N.M. Zdravković, D.D. Trišić,
shrimp shell and its application in removing of malachite green from aqueous N. Bugárová, M. Danko, N.O. Kozyrovska, Z. Špitalský, A. Kleinová, S.B. Kuzman,
solutions, J. Environ. Chem. Eng. 7 (2019), 103328, https://doi.org/10.1016/j. V.B. Pavlović, B.M.T. Marković, Photoactive and antioxidant nanochitosan dots/
jece.2019.103328. biocellulose hydrogels for wound healing treatment, Mater. Sci. Eng. C 122 (2021),
[42] S.N. Saleh, M.M. Khaffaga, N.M. Ali, M.S. Hassan, A.M. El-Naggar, A.M. Rabie, 111925, https://doi.org/10.1016/j.msec.2021.111925.
Antibacterial functionalization of cotton and cotton/polyester fabrics applying

13