Article

2016, Vol. 46(4) 1003–1023

! The Author(s) 2015

Banana pseudostem sap: Reprints and permissions:

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DOI: 10.1177/1528083715591580
A waste plant resource for jit.sagepub.com

making thermally stable

cellulosic substrate

S Basak, S Saxena, SK Chattopadhyay, R Narkar

and R Mahangade

Abstract
The flame retardant functionality was imparted in cellulosic textile using banana pseu-
dostem sap, an eco-friendly waste plant product. The extracted sap was applied in three
different pH conditions, viz. acidic, neutral and alkaline to the pre-mordanted bleached
and mercerized cotton fabrics. Flame retardant characteristics of both the control and
the treated fabrics were analysed in terms of limiting oxygen index, vertical flammability
and heat release related properties using a cone calorimeter. The thermal degradation
and pyrolysis mechanism were studied using thermogravimetric analysis and differential
scanning calorimetry. The elemental analysis was carried out with X-ray fluorescence,
and the quantification of phosphorus and nitrogen was also done. Besides, the charring
mechanism of both the control and the treated fabric was analysed in detail, and a char
structure model has been proposed. The treated fabrics were also evaluated in terms of
colour and other physical properties.

Keywords
Banana pseudostem sap, cellulose, char, cone calorimeter, flame retardant, pH

Introduction
Cellulosic cotton textile catches flame readily that is quite difficult to extinguish.
This poses a serious risk to health and life of a living being and damages potential
to textile products. Significant efforts have been made in the past to improve the

Chemical, Biochemical and Mechanical Processing Division, Central Institute for Research on Cotton
Technology, Mumbai, India

Corresponding author:
S Basak, Chemical, Biochemical and Mechanical Processing Division, Central Institute for Research on Cotton
Technology, Adenwala Road, Matunga, Mumbai 400019, India.
Email: shantanubasak@gmail.com
1004 Journal of Industrial Textiles 46(4)

flame retardant property of cotton textiles using various synthetic chemicals, and
many of them are available in the market. The most simple and common chemical
is borax and boric acid mixture [1]. Phosphorus-based flame retardants along with
nitrogenous compound are the most effective formulation reported so far, due to
their synergistic effect. Consequently, for the past 50 years, flame retardants based
on the composition of phosphorus, nitrogen and halogen, such as Tetrakis phos-
phonium salt and N-alkyl phosphopropionamide derivatives, are widely dominat-
ing the commercial scenario [2]. However, as such formulations need to be applied
in an acidic condition, the cotton fabric loses its tensile strength and become stiffer.
Besides, such a treatment is expensive, non-eco-friendly due to the involvement of a
large amount of chemicals, high temperature curing process and for toxic formal-
dehyde emission during treatment [3]. Although antimony in combination with
halogen could impart good flame retardant property, it is still not very successful
due to the negative impact of halogen compounds in the environment [2]. Although
some intumescent-based flame retardants, such as silicate [4], composition of the
nano zinc-oxide and polycarboxylic acid [5], have been developed to make the
process environmentally friendly, such treatment cannot satisfy the handle,
strength and the fire resistant durability requirements of the fabric. Recently,
researchers have also used plasma treatment with various polymerization gases
to impart the fire retardancy property to the cellulosic fabric. Plasma process is
water free and eco-friendly, but it is very costlier and the imparted flame retardant
property is not durable to washing and ageing [6]. Hence, there is a need to develop
more cost-effective, environmentally friendly and sustainable fire retardant prod-
ucts, which when applied to cotton fabrics will maintain its quality and flame
retardant durability to a great extent. This apart, the increased awareness on
human health and hygiene in recent years is also driving the demand of those
cellulosic textiles, which are finished with natural products, such as natural dyes
for colouration, enzyme for bio-polishing, neem and aloe vera extract for anti-
microbial finishing [7,8]. A very few researches have so far been reported on
imparting fire retardancy to cellulosic fabric using natural products [9–11].
Recently, the researchers have reported that DNA from herring sperm and solo-
mon fishes can be applied to the cotton fabric to make it thermally stable [9].
Attempts have also been made to impart fire retardant to cotton fabrics with
whey proteins, casein and hydrophobins due to their phosphate, disulphide and
protein content, as they can influence the pyrolysis by an early char formation [10,
11]. However, a limited application of waste plant bio-molecules has been made for
imparting flame retardant finishing to any textile and/or polymeric material till
date to the best of our knowledge. As some of the plants contain phosphorus,
silicate and other minerals and mineral salts, they offer immense potential to be
utilized to impart flame retardancy to cellulosic and non-cellulosic textiles. In our
earlier publications, we have reported a detailed study of imparting fire retardant to
cellulosic cotton fabric, using spinach juice [12] and wastage banana pseudostem
sap (BPS) [13]. BPS is a 100% pure liquid extracted from the pseudostem of banana
plants. It is stable up to a wide range of pH. However, it turns to colourless at an
Basak et al. 1005

acidic pH, at alkaline pH it remains with khaki colour. When BPS was applied on
the mordanted cotton fabric at alkaline pH, treated fabric showed uniform khaki
colour and BPS treatment does not appear as a stain on the fabric. Our previous
publication [13] provided information on the application of BPS in alkaline condi-
tion to the cotton fabric and data on the fire retardant durability and the elemental
composition of sap and treated fabric by Energy dispersive X-ray (EDX) and
Secondary ion mass spectrometry (SIMS) analysis. It showed the presence of
sodium, magnesium, silicate, iron, proteinaceous nitrogen, nitrate, organophosphate
and other metallic constituents in the BPS responsible for imparting fire retardant
property. Further, as far as the wash durability is concerned, oxygen index value of
the BPS-treated fabric reduced from 30 to 24 after single ISO 2 washing. As the wash
durability of the end product is low, it can be used only for the textiles which are not
washed regularly. In the present study, an attempt has been made to apply the BPS
in different pH, and the fire retardant properties, heat, temperature generation and
pyrolysis mechanism have also been assessed in detail by multiple thermal charac-
terization techniques. Besides, the charring mechanism has been proposed in detail,
whichalso provides knowledge regarding the total phosphorus, nitrogen content of
the treated fabric, colour and strength parameters. This developed process could use
flame retardant finishing of home furnishing products such as home window curtain,
railway curtain, hospital curtain, table lamp and as a covering material of non-
permanent structure, such as in book fair, festival and religious purpose, where
large quantity of textile is used and has chance of fire hazards. BPS is abundantly
available in India as well as in other countries, and it is normally considered as waste
material. It is eco-friendly and produced from renewable source. Therefore, the
application of BPS in cotton textile for colouration and functionalization will give
the advantages of value addition using natural product.

Materials and methods

Material and BPS application
A 200 GSM (areal density) plain woven bleach cotton fabric of 30 EPI (ends/inch)
and 40 PPI (picks/inch) was procured from the local market and was used for the
flame retardant finishing. BPS was supplied by Navsari Agricultural University,
Gujarat, India, for the treatment. Supplied BPS was characterized by atomic
absorption spectroscopy analysis, which showed the presence of 0.2 ppm phos-
phorus, 7.4 ppm potassium (outside the range limit of the machine), 0.9 ppm mag-
nesium, 4.5 ppm manganese and 4.9 ppm iron. The supplied sap had a pH of 7.5
(neutral), which was made both alkaline (pH 10) and also acidic (pH 5) with the
addition of soda ash and acetic acid, respectively. The bleached cotton fabric was
first mordanted with 5% tannic acid and 10% alum. Thereafter, the mordanted
fabrics were impregnated separately in the BPS solution of three different pH, viz.
acidic, neutral and alkaline, maintaining material to liquor ratio of 1:10. The fabric
was then treated for 30 min followed by drying at 110 C for 5 min.
1006 Journal of Industrial Textiles 46(4)

Determination of percent add-on

Before any physical and chemical characterization, both the treated and the control
cotton fabrics were conditioned at 65% RH and 27 C for 48 h. After the applica-
tion of BPS on cellulosic cotton textile, the add-on, i. e. the increase in sample
weight, was determined by gravimetric principle from the bone dry weights of the
sample before and after the treatments, and the results have been expressed in
percentage over the initial weight of the sample.
Percentadd  on ¼ ½M2  M1 =M1 0 100
where M1 and M2 are the oven dried weights of the control and the BPS-treated
samples, respectively. The reported results are average of five readings.

Thermal characterization
Flammability assessment: The burning behaviour of both the control and the treated
samples was evaluated by standard methods. For the limiting oxygen index (LOI)
analysis, IS 13501 test method was used. For LOI analysis, sample size was
140  52 mm, with an ignition time of 30 s was maintained as per BIS method
[14] which is equivalent to ASTMD 2863-13 test method. In vertical flammability,
the different parameters were measured as per IS: 1871 method A (equivalent to the
ASTM D6413), where a fabric sample was ignited by 38 mm flame for 12 s [15]. The
maximum temperature produced during the burning of a sample was measured
using infrared thermometer, Fisher Scientific made (Model No. 15077968 FB61354
225PE) in non-contact mode. Based on the data, the temperature generation profile
curve was plotted for both the control and the treated fabric.

Cone calorimeter analysis of treated fabric: The cone calorimeter available at the
Laboratory of Ahmedabad Textile Industries Research Association, India, was
used to test the 100  100 mm cellulosic cotton specimens in accordance with the
procedure of ASTM international test method, E 1354-10 a. The specimens were
tested at horizontal orientation with heat flux of 35 kW/m2. Three replicates of each
sample of 2 g weight were tested. Before testing, all the samples were conditioned at
65% RH and 27 C. The data recorded included those specified in the ISO5660-1
standard. The parameters reported in the paper included the following measure-
ments, consisting of total heat release (MJ/m2), effective heat of combustion
(MJ/kg), heat release rate (kW/m2), average mass loss rate for the period of
10–90% mass loss (g/s-m2), average mass loss rate (g/m2s), specific extinction
area (m2/kg), total smoke production (m2/m2), carbon monoxide and carbon diox-
ide generated (kg/kg) during the burning.

Thermogravimetric analysis in N2 atmosphere: Thermogravimetric (TG) curves of both

the control and the treated fabrics were obtained by using a Thermo Gravimetric
Analyser, METTLER TOLEDO TG-50/MT5 at a heating rate of 10 C/min at N2
atmosphere.
Basak et al. 1007

Differential scanning calorimetry analysis in N2 atmosphere: The differential scanning

calorimetry (DSC) of both the control and the BPS-treated cotton fabric was
measured by using METTLER TOLEDO DSC30 thermal analyser, where the
temperature was maintained at 10 C/min.

Scanning electron microscope analysis

The char analysis of both the control and the treated samples was analysed using
scanning electron microscope (SEM) PHILIPS- XL30. The samples were coated
with a thin layer of conducting material (gold/palladium) by using a sputter coater,
and the same were examined under the SEM with an accelerating voltage of 12 kV.

X-ray fluorescence analysis

X-ray fluorescence (XRF) analysers from Bruker were used to qualify and quantify
the presence of elemental substituents in the material. Here, BPS has been dried
first and then used for the evaluation of elemental analysis of BPS.

P and N content analysis

The amount of Phosphorous (P) in the treated fabrics was measured according to
the soil chemical analysis method by using stannous chloride [16] and the amount
of nitrogen (N) by Kjeldahl method [17]. As far the phosphorus analysis is con-
cerned, one stock solution was prepared by potassium dihydrogen phosphate and
sulphuric acid. Besides, a specific weight of treated cotton fabric dissolved in the
mixture of sulphuric acid, nitric acid and perchloric acid. Then, Chlor molybdic
acid was added in different concentration of stock solutions and also in the solution
containing the above dissolved fabric. All the solutions are reduced by stannous
chloride. Then, a curve of the absorbance, vis-à-vis the wavelength, was plotted,
from which the concentration of phosphorus was determined.
As far as the N2 analysis is concerned, initially 0.3 g fabric sample mixed with
10 ml 98% concentrated H2SO4 and 3 g catalyst (1 part CuSO4 þ 5 part K2SO4).
The mixture was digested at 420 C for 2 h till it reduced to a clear solution. Then,
mixture was then cooled in room temperature and thereafter mixed with alkali and
boiled. During the boiling, the released NH3 was trapped in boric acid, which was
back titrated against 0.1 N HCl. The concentration noted in the titration was taken
as a measure of nitrogen.

Colour parameters
It was observed that after application of the BPS in the cotton textile, its colour
changed from white to khaki at alkaline pH and turned to colourless at acidic pH.
Here, colour parameters such as K/S, L.a and b were measured using a Perkin–
Elmer double-beam spectrophotometer, Lambda (35 model) equipped with an
1008 Journal of Industrial Textiles 46(4)

integrating sphere. The colour depth of the BPS-treated fabric was determined in
terms of K/S from the reflectance data using the Kubelka–Munk equation as
follows

K=S ¼ ð1  R2 Þ=2R

where K is the absorption coefficient, S the scattering coefficient and R is the

reflectance of the treated fabric. Here, K/S was determined at 213 nm (maximum
wavelength) of the respective dye. Other colour parameters such as L* (lightness-
darkness), a* (red-green) and b* (blue-yellow component) were measured using the
Win lab software, delta-E 1976.

Strength parameters
Tensile and tear strength were evaluated according to the ASTM D5035 and
ASTM D1004, respectively.

Results and discussion

LOI and vertical flammability
The mordanted cotton fabrics were treated separately in three different pH of the
BPS as discussed in Materials and Methods. The results of the flammability testing
including LOI of the control and the treated samples are presented in Table 1. The
LOI, a measure of flammability of a sample, is defined as the minimum amount of
oxygen in the oxygen/nitrogen mixture required to support the combustion [14].
A textile material having the LOI value of 21 or below ignite easily and burn
rapidly in the open atmosphere, whereas one that has the LOI value equal to or
more than 26 may be considered as flame retardant [14]. The LOI values of the
control, mordanted and BPS-treated cotton fabrics with different pH values are
given in Table 1.
Being pure cellulosic in nature, the cotton fabric showed a lower LOI value of 18
that catches flame readily with flashing. It was observed from Table 1 that there
was no change in the LOI value of the mordanted sample. After application of BPS
at different pH, the LOI value of cotton textile was found to increase. Regarding
the mordanted fabric treated with acidic BPS solution (pH 5), the LOI value was
found to increase to 28, which is almost 1.5 times higher than that of the control
sample. As the pH shifted towards the neutral, the LOI also remained unchanged
like in the acidic condition with a value of 28. As far as the alkaline pH (pH 10) was
concerned, the LOI value increased to 30, and in the vertical flammability meas-
urement, the fabric showed flame for only 4 s and then self-extinguished. The
sample took 900 s for the complete burning, whereas the control sample caught
the flame readily in 1 s and burnt fully within 60 s. The fabric C showed a slow
thermal decomposition without any flame, and the amount of temperature
Table 1. Flammability parameters of the control only mordanted and mordanted followed BPS-treated cotton fabrics.

Sample pH level
Basak et al.

Flammability parameters Control (D) Mordanted pH 5 (A) pH 7.5 (B) pH 10 (C)

Add-on (%) – 0.4 4 4.50 5

LOI 18 18 28 28 30
Add-on(%) = X, LOI = Y, R2 = 0.9909, Y = 2.46X þ 17.5
Vertical flammability (sample length – 250  40 mm)
Occurring of flashing Yes Yes No No No
over the surface
Burning with flame time (s) 60 60 15 b 8b 4
Add-on (%) = X, Burning with flame time = Y, R2 = 0.9959, Y =  11.8X þ 62.20
Burning with afterglow time (s) 0 (as completely 0 (as completely – – 900
after flame stop burnt with flame) burnt with flame)
Total burning timea 60 s þ 0 s 60 s þ 0 s 250 s þ 15 s 400 s þ 8 s 4 s þ 900 s
Char length (mm) nil Nil nil nil nil
Observed burning rate 250 250 56.6 36.8 16.6
(mm/min)
Add-on (%) = X, Burning rate = Y, R2 = 0.9957, Y =  49.227X þ 258.82
State of the fabric in Completely Completely Completely Completely Burnt initially
contact of flame burnt with flame burnt with flame burnt with flame burnt with flame with flame followed
by afterglow
a
Total burning time = Burning with flame time þ burning with afterglow time (after flame stopped).
b
Sample catches flame after 6–7 s of continuous contact with flame.
1009
1010 Journal of Industrial Textiles 46(4)

Figure 1. Vertical burning model of the control (D) and the BPS-treated fabric (C).

generated during the thermal decomposition was also less (200 C). This will
required a serious hazard to happen several hours. It may be the presence of
alkali in the treatment formulation had provided more thermal stability and also
helped to pick up more amount (5% add-on) of the BPS in the treated sample
compared to the fabrics A and B. To represent the vertical burning phenomena of
the BPS-treated sample C, the control sample D, we have proposed a model pre-
sented at Figure 1. As far as the vertical flammability of the sample A and B is
concerned, they catch flame quickly than fabric C. However, all the samples take
more than 4 min for the complete burning. Another interesting phenomenon was
observed that although the LOI value of fabric C is higher than those of the sam-
ples A and B, the extent of afterglow, smouldering and smoke formation in fabric
C was more than that noted with the sample A and B. We have also tried the BPS
treatment without mordant at different pH on the cotton fabric; however, they
showed lower add-on (1–2.3%) and lower oxygen index value of 23–25.

Thermogravimetric analysis
Figure 2 represents the thermal stability curves of the control and the BPS-treated
(at different pH) cellulosic cotton fabric in N2 atmosphere. Curve D showed a
sharp fall at 350 C, signifying cellulosic degradation, i.e. the pyrolysis occurred
at that temperature. The amount of char remained after the pyrolysis is also very
less. In contrast, TG and derivative thermogravimetric (DTG) curves of only BPS
showed steep humps at temperature below 100 C represent the evaporation of
moisture from the extracted BPS. After that main degradation had occurred at
200 C, so that less flammable gas was produced. With addition the amount of
carbonaceous char remained at high temperature 500 C is also 38%. It may be
due to the presence of more inorganics (such as sodium, potassium, silicon,
Basak et al. 1011

Figure 2. Thermogravimetric analysis plots of control (D), BPS-treated cotton fabric in acidic
pH (A), alkaline pH (C) and only BPS. BPS: banana pseudostem sap.

magnesium, iron) in the extracted BPS [13]. Connected to it, curve A and C (BPS-
treated cotton fabric) showed initial humps at below 100 C, which may be due to
the evaporation of moisture [18]. DTG of curve A showed an earlier pyrolysis at
310 C (shifted 40 from control), which signifies that the BPS treatment has aided
to dehydrate the cellulosic fraction of the fabric earlier, so that the less flammable
1012 Journal of Industrial Textiles 46(4)

gas will be evolved and also, the amount of the char mass remained at higher
temperature will be more compared to the control one. As far as the DTG of
the curve C is concerned, it has also showed an early cellulosic degradation like
curve A. However here, the amount of char mass production is more compared to
the curve A. In addition, mass loss rate is also lower compared to the curve A. Both
of these phenomena proved the fact that the alkaline pH BPS-treated cotton fabric
is thermally more stable compared to the acidic pH BPS-treated cotton fabric.
It may be due to more pick up of the BPS by the cotton fabric at alkaline PH.
The additional alkali used during the treatment might have helped to improve the
thermal stability of the fabric [19]. The char production observed from the TG
curves can also be correlated with the real life vertical burning pictures as shown in
Figure 2. Curve D and the vertical burning series D showed negligible amount of
residual char after complete burning, whereas the vertical burning series C showed
more amount of residual carbonaceous char after the burning, which can be
correlated with the TG and DTG curve of C.

DSC analysis
The TG analysis has showed an early pyrolysis and extensive char formation of the
BPS-treated fabrics. To support the same, DSC analysis was also carried out for
both the control and the treated cotton fabric (Figure 3). It can be observed from
the figure that initially at below 100 C, both the control and the treated fabric
showed steep endotherm corresponding to the evaporation of water from the fabric
samples [18]. It was also observed from the figure that curve A exhibited an
exotherm with the peak at 374 C [20, 21]. On the other hand, curve B showed
an exothermic peak observed at 340 C. It means that similar to that in the TG
analysis, the exothermic peak of BPS-treated cellulose B, which was also accom-
panied by an endothermic shoulder, shifted towards lower temperature

Figure 3. DSC analysis of the control cotton fabric (A) and the alkaline pH BPS-treated (B)
fabric.
Basak et al. 1013

(peak shifted by 34 C) compared to the control one (A). The same phenomenon
was also observed in the DSC curve of cellulosic fabric finished with different fire
retardant agent [20].

Temperature generation analysis

As far as the vertical flammability is concerned, we have reported that the alkaline
BPS-treated fabric showed flame for 4 s and then self-extinguished, and the
observed afterglow burnt the total fabric in a much slower rate compared to the
control fabric. Here, the temperature data have been noted during flaming as well
as during afterglow. Associated with it, Figure 4 showed the temperature gener-
ation curves of the control and the BPS-treated fabric during vertical burning of
the samples in the real life situation. In case of the control cotton fabric, the initial
temperature generation was high around 400–450 C as the fabric was burnt with
flame and flashed, whereas in case of the treated fabric, only 300 C temperature
was generated during the first 20 s of ignition due to the presence of the flame for
4 s. In the second phase, the control fabric showed an afterglow for 30 s with a
temperature around 350 C. Thereafter, the temperature of the fabric was gradually
dropped due to the complete damage of the fabric and ash formation after burning.
In contrast, the BPS-treated fabric showed a very slow rate of damage and a
decrease in temperature of afterglow with the increase in burning time. This less
amount of temperature generation is very much beneficial for the end users in
practical real life situation, as it will generate less heat and fire hazards. The less
temperature generation may be due to the fact that the BPS treatment forms a thick
insulated, coated layer on the treated fabric surface as seen in the SEM micro-
graphs [13], which acts as an intumescent that may have thickened on heating and
absorbing the heat energy through endothermic reaction.

Figure 4. Temperature generation profile during burning of control and alkaline pH BPS-treated
cotton fabric. BPS: banana pseudostem sap.
1014 Journal of Industrial Textiles 46(4)

Cone calorimeter analysis

The cone calorimeter test was used to determine the reaction of fire to the material
surface. The test apparatus consisted of an electric heater, an ignition source and a
gas collection system. The three replicates test specimen measuring 100  100 mm
has the thickness of 10 mm. The fabric test specimen was mounted horizontally,
and it was exposed to a heat flux of 35 kW/m2 from the electric heater. This amount
of heat flux was similar to the amount of heat generated during in house burning of
the home textile. Before testing, the control and the treated samples were condi-
tioned at 23 C and 50% relative humidity and ambient pressure of 101.45 kPa.
Many heat-related variables are measured by using this testing machine. Among
the testing results, mass loss rate, heat release rate, amount of heat generation are
having major importance. Here in Table 2 all the data reported, are the mean
values of the three replicates tested in the cone calorimeter machine.
Table 2 showed that the length of time observed for ignition of the control and
the treated sample is 7 s and 14 s, respectively. In addition, flame came from the
control and the treated sample after 20 s and 33 s, respectively. It showed that the
BPS treatment on the cellulosic cotton fabric increased the sample ignition time as
well as delayed the flame out time. Further as far as the treated fabric is concerned,
the amount of mass remain at the flame out condition is 26.05% higher than the
control fabric. Heat release related results showed that the mean heat release rate
and the total amount of heat release of the control cotton fabric are 31% and 29%
higher compared to the BPS-treated cotton fabric. These phenomena also have
been represented in the Figure 5. From the figure, it was clearly observed that
BPS treatment lowers the heat release rate. Figure 7 showed that even after 80 s,
the rate of heat release has been continually increasing for the control fabric,
whereas for the treated fabric, the rate of heat release has been constant after
80 s. Similar phenomena also have been observed in the temperature generation
profile curve of the treated fabric. Curve showed that after 80 s of burning, tem-
perature generated from the BPS-treated fabric remains almost constant 160 C,
which may indirectly support the constant heat generation during burning in cone
calorimeter after 80 s. Heat stability after 80 s might be because of the more
amount of carbonaceous insulated char mass formation as observed from the
DSC and the TG curves. Here, char mass may help to absorb the generated heat
during the burning cycle in cone calorimeter. BPS treatment also reduced the aver-
age effective heat of combustion as shown in Figure 6. Regarding the heat of
combustion, control fabric generates average combustion heat of 21.45 MJ/kg,
whereas BPS-treated fabric generates only 12.24 MJ/kg heat which is almost half
of the control fabric. In addition, heat of combustion peak observed for the control
fabric is 40.44 MJ/kg, whereas it was 27.12 MJ/kg for the BPS-treated fabric.
Maximum average rate of the heat emission is also 17.81% less for the treated
fabric compared to the control fabric. Connected to the heat release results, total
fuel load, i.e. the amount of energy released by complete combustion of per unit
mass of oxygen consumed, is 11.79 MJ/kg for the BPS-treated fabric, whereas for
the control fabric, fuel load is more than 25.77 MJ/kg (54.2% more). Like TG
 Basak et al.

Table 2. Summary of cone calorimeter results at heat flux of 35 kW/m2.

Heat release related results

Test series no. Treatment HRR (kW/m2) THR (MJ/m2) EHC Peak (MJ/kg) EHC (MJ/kg) MARHE

1 Control 34.08 5.24 40.44 21.45 133.24

2 Treated (C) 23.45 3.72 27.12 12.25 109.50

Mass loss and smoke related results

Test series no. Treatment Average specific mass Initial mass (g) Sample mass Total smoke CO2 release (kg/kg)
loss rate (10% to loss (g/m2) release(m2/m2)
90%) g/m2s
1 Control 10.17 2.00 229.82 4.83 1.08
2 Treated (C) 5.59 3.16 296.21 7.33 0.76

Ignition-related results
Test series no. Treatment Time to ignition (s) Time to flameout (s) Mass at flameout (g)
1 Control 4.72
7.00 20.00
2 Treated (C) 5.95
14.00 33.00
HRR: heat release rate; THR: total heat release; EHC: effective heat of combustion; MARHE: maximum average rate of heat emission.
1015
1016 Journal of Industrial Textiles 46(4)

Figure 5. Total heat release of BPS treated (A) and the control (B) cotton fabric.

Figure 6. Effective heat of combustion of control (A) and BPS-treated (B) cotton fabric.

analysis, here also the average specific mass loss rate of the BPS-treated fabric is
45% lower in contrast to the control cotton fabric. However, the BPS treatment
causes an increase in total average smoke, carbon monoxide and decrease in the
carbon dioxide formation during burning. Connected to the smoke production
average surface extinction area (m2/kg) observed for the control fabric is 5.18,
whereas for the treated fabric, it was reported 19.78. It might be due to the fact
that in case of treated fabric, delayed ignition was observed and also sample takes
longer time for total ignition. This phenomena might also be correlated with the
observed afterglow during the vertical burning of alkaline pH BPS-treated fabric,
after self-extinguishing of flame. Regarding the smoke formation, it has been
reported in the literature that phosphate-based flame retardants increase in
smoke emission and also rise in carbon monoxide with decrease in carbon dioxide
formation [22]. Connected to it, researchers recently reported that the cotton fabric
treated with the mixed formulation of diammonium phosphate (15%) and urea
(5%) delivered 144 m2/kg smoke in contrast to the 73 m2/kg smoke generated after
burning of cotton fabric [23]. As some amount of halogens such as chlorine are
present in the BPS, it may also tends to increase the amount of smoke formation as
reported in the literature [24].
Basak et al. 1017

Figure 7. SEM micrographs of char residues of the control (B) and the treated (A) fabric after
vertical flammability test.

Char analysis
The char residue of the samples after combustion was further investigated, and
their SEM micrographs are presented in Figure 7. It was already noted that the
residual remains were negligible for the control fabric (B) after the complete burn-
ing, whereas in case of alkaline BPS-treated fabric (A), both the weight and the
volume of the residuals were much higher. The same has clearly been shown by the
black colour insulated carbonaceous char mass formation. Further, structural
integrity of the fabric (A) was found to be maintained after the complete burning,
in contrast with the complete lightweight white ash formation noted in the SEM
micrograph of the control fabric (B). As far as the char morphology is concerned,
from the SEM pictures of the char residues and from the char models (Figure 8), it
has been proposed that the treated fabric had an intact char structure of closed cells
containing gas pockets, gas bubbles, while freezing into the gas pockets, expands
and thickens the alkaline BPS coating that quickly solidifies. The solidified struc-
ture of the residual mass of the treated fabric looked like an ant nest or honeycomb
(as seen in SEM micrograph, Figure 8(A)) which restricts the formation of the
flammable liquids by forming a heat insulating foam-like layer on the polymer
substrate. On the other hand, as far as the char structure of the control fabric is
concerned, it showed an open dry leaf net like channels by which gas and flam-
mable volatiles can easily escape by capillary action into the hotter flammable
1018 Journal of Industrial Textiles 46(4)

Figure 8. Model char structure of the control (A) and the BPS-treated cotton fabric (B).
BPS: banana pseudostem sap.

region resulting in the burning of the cellulosic cotton polymer continuously, with
high temperature and heat generation.

XRF analysis
The SEM pictures of the treated fabric showed a thick insulated BPS coating on the
fibre surface as shown from our earlier reported work [13]. To determine the pres-
ence of different elements responsible for the fire retardant behaviour of the treated
fabric, EDX analysis was carried out. The analysis showed the presence of different
elements such as calcium, phosphorus, chlorine, potassium, aluminium [13]. EDX
analysis showed the percent weights of magnesium, 5.8; phosphorus, 0.7; chlorine,
1.9; potassium, 1.7 and aluminum, 0.2 in the surface of the alkaline pH BPS-treated
fabric [13]. In the present study, to reconfirm the results of the EDX analysis, XRF
studies of both the extracted BPS and alkaline pH BPS-treated fabric were carried
out and reported in Figure 9. The results showed that the BPS contain elements
such as phosphorus, chlorine, silicon and trace amount of aluminium, whereas the
BPS-treated fabric contains elements such as chlorine, phosphorus, silicon, calcium
and aluminium with chlorine and phosphorus being predominant. From the EDX
analysis, it was found that in the treated fabric, the amount of the aluminium
present is 0.2%. However, extracted BPS contains very less amount (0.04%) alu-
minium [13]. It may be due to the addition of aluminium by the mordanting process
in the fabric before the treatment.

P and N content analysis

In our previous study from the mass spectroscopy analysis, it was observed that the
presence of phosphate, phosphite, chlorine and other metal constituents are present
in the crude BPS, responsible for the fire retardant property [13]. In the present
study, the total amount of phosphorus and nitrogenous matter present in the control
Basak et al. 1019

Figure 9. XRF analysis of alkaline BPS-treated cotton fabric (A) and only BPS (B).

Table 3. Content of nitrogen and phosphorus in control and treated fabrics.

N (%)
Fabric treatment condition Add-on (%) N (%) P (%) þ P (%) LOI

Control – 0.15 0.15 0.30 18

BPS (pH 4.5) 4 1.00 0.10 1.10 28
BPS (pH 7) 4 1.15 0.25 1.40 28
BPS (pH 10) 4.5 1.40 0.30 1.70 30
LOI: limiting oxygen index; BPS: banana pseudostem sap.

and in the treated fabric samples were analysed by using stannous chloride and
Kjeldahl method, respectively, and the data obtained are presented in Table 3.
It can be observed from the Table 3 that with the increase in pH with the same
concentration of BPS, there was a gradual improvement of add-on resulting in an
increase in the quantity of nitrogen and phosphorus on the fabric surface also.
Besides the total amount of phosphorus and nitrogen content, the LOI of the treated
fabric was also found to increase. The alkaline pH BPS-treated fabric with 5%
add-on showed the total amount of phosphorus and nitrogen present on the
fabric being 1.70%, which translated into a higher LOI value of 30. It has again
substantiated the fact that the thermal stability of the treated fabric was increased
with the increasing presence of phosphorus and nitrogen on the fabric surface at an
alkaline pH (pH 10) in the application of BPS. It may be noted that an earlier
research have reported that 3% add-on of phosphorus-nitrogen-based eco-friendly
4 methylpiperazin-1-yl phosphoramidate provided a total nitrogen, phosphorus per-
centage content of 2.15, and the cotton fabric treated with this composition provided
a char length of more than 30 cm with an after-flame of 14–19 s.
1020 Journal of Industrial Textiles 46(4)

Mechanism of imparted flame retardancy

Cotton being pure cellulosic in nature has a low LOI value of 18 and does not show
any protection from flame. Prior to bleaching and mercerization of cotton fabric
followed by mordanting, applications of BPS varying in pH condition ensured a
good add-on (4–5% uptake). This implies that cotton is exhibiting flame retard-
ancy mainly because of the chemicals present in the BPS. More explicitly, the effect
of flame retardancy imparted by BPS may be attributed to the presence of various
mineral salts in it in the form of chloride, phosphate and silicate, such as sodium
silicate, magnesium chloride, sodium chloride. The presence of these inorganic salt
molecules was roughly observed in the Fourier transform infrared spectroscopy
analysis and by the peaks of the elements in the EDX analysis of BPS [13]. The
surface ion mass spectroscopy analysis has also confirmed and quantified the
amount of phosphate, phosphite, chloride, potassium chloride and other metal
elements in the pure BPS, which is responsible for fire retardant property [13].
Besides, in this paper, we have analysed the presence of different elements in the
BPS and the alkaline pH BPS-treated fabric by XRF. We have also quantified the
total amount of nitrogen and phosphorus in the control and the BPS-treated fabric
at different pH. It has been found that the amount of phosphorus and nitrogen is
more in the alkaline BPS-treated fabric, and it is showing more thermal stability
rather than the acidic BPS-treated fabric. As these phosphates and chlorinated
products can act as fire retardants for the cellulosic substrate, the flame retardancy
effect in the BPS-treated cotton fabric is attributed to the combined effect of the
presence of metal salts, silicate, phosphate, nitrate and bound and unbound water
molecules. Their presence has helped in the formation of more char and non-
flammable gases like CO2, H2O, etc. As far as the flame retardancy mechanism
is concerned, BPS mainly acts in the condensed phase mechanism, possibly due to
phosphate and other metallic constituent contents, which are aiding the pyrolysis
of the treated fabric by forming a char at an earlier stage, as observed from the
thermogravimetric analysis and DSC curves. SEM pictures of the treated fabric
showed that when this treated cotton fabric is exposed to heat or flame, it favours
the formation of a stable and protective char and the char model shows the pres-
ence of closed cells, which limits the exchange of oxygen and combustible volatile
products, thus adding towards the flame retardancy of the BPS-treated textile. It is
possible that the BPS coating also might have acted as an intumescent that swells
on heating and increase its volume, thus protecting the underlying polymeric
material from heat or flame action by char insulation and foaming.

Physical properties and colour parameters

It can be seen from Table 4 that the application of the flame retardant finish at
different pH has no significant adverse effect on either tensile or tear strength of the
treated sample. Most of the conventional flame retardant finishes cause a high loss
of tensile strength in the range of 10–30% [25]. As indicated in the earlier literature,
Basak et al. 1021

Table 4. Strength and the colour parameters of the treated fabric.

Physical properties of treated fabric

Tensile strength (N) Tear strength (N)

Cotton fabric Warp Weft Warp Weft

Control 300 310 610 638

Sap treated (pH 10) sample 293 305 605 630
Sap treated (pH 5) sample 280 300 575 610

Colorimetric data of treated cotton fabric

Cotton fabric K/S L* a* b*

Control 0.04 92.11 0.43 2.58

Mordanted 0.25 85.52 0.25 6.23
BPS treated (pH 5) 0.42 89.15 0.64 21.28
BPS treated (pH 7) 0.63 83.04 1.10 19.36
BPS treated (pH 10) 0.87 77.25 2.67 21.08
BPS: banana pseudostem sap.

after application of alkaline BPS in the pre-mordanted cotton fabric, the sample
changed its colour from white to khaki [13]. However, when the application pH
shifted towards the neutral condition, the colour of the treated fabric changed from
khaki to colourless. It might be because of the degradation of natural colour of the
BPS chromophore by acidic condition. Colour strength values are represented in
the Table 1.

Conclusion
The present study has investigated the flame retardancy effect of BPS on cellulosic
cotton textiles at different pH. After application of BPS, the thermal stability of the
fabric was found to increase and it also delivered more safety time either to extin-
guish the fire or to escape from fire hazards zone. Not only more time could be
available, but also the total heat production and temperature generation in
BPS-treated sample were lower. It was found that the BPS solution is more effective
for thermal stability at alkaline pH. Flame retardancy property in the BPS-treated
cotton fabric might have been attributed to the presence of (i) phosphate com-
pounds and (ii) metal salts especially sodium and potassium chloride. Also the
presence of approximately 14% inorganic materials in the BPS-treated cellulose
textile might have helped in production of more char and non-flammable gases. TG
curves showed the dehydration and char formation phenomena in the BPS-treated
cotton fabrics.
1022 Journal of Industrial Textiles 46(4)

Declaration of Conflicting Interests

The author(s) declared no potential conflicts of interest with respect to the research, author-
ship, and/or publication of this article.

Funding
The author(s) disclosed receipt of the following financial support for the research, author-
ship, and/or publication of this article: This research received no specific grant from any
funding agency in the public, commercial, or not-for-profit sectors.

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