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REFERENCES
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as natural dyes for colouration, enzyme for bio-polishing10, was characterized by atomic absorption sp
neem and aloe-vera extract for antimicrobial finishing, the presence of traces of metals in it. It
etc. are receiving greater attention in research and deve- contained high amounts of potassium (
lopment11. Only limited work has been reported recently the maximum detectable range the of the in
on the fire retardancy of cellulosic fabrics with bio- manganese (4.55 ppm), followed by iron
macromolecules. DNA from herring sperm has been copper (0.043 ppm). No chromium an
applied to cotton fabric to make it thermally stable. DNA were detected. The grey jute fabric wa
consists of phosphate, deoxyribose units, nitrogen contain- with 5% tannic acid and 10% alum. T
ing bases and blowing agents, which help in carbona- nated with different concentrations of B
ceous char formation and ammonia release, thus making as pure BPS (1:0) and solutions made
the cellulosic cotton thermally stable12. Researchers have pure BPS to half (1 :2) and quarter (1 :4
also tried to make fire-retardant cotton fabric using milk applying temperature. The material
protein, a by-product of the cheese industry, due to their kept at 1:15. This implies that the B
phosphate, disulphide and protein content that can influ- times that of the jute fabric by weig
ence the pyrolysis by early char formation13'14. then dipped in the alkaline (maintaine
However, till date, the application of plant extracts ash) BPS solution for 30 min at 90°C. Th
(e.g. plant biomolecules) for flame-retardant finishing of samples were subsequently dried at 110
any textile and/or polymeric material has not been
reported to the best of our knowledge. As some of the „ , . ,
. . . . . ... , . Determination of per cent add-on
plants contain potassium, phosphorus, silicon and other
minerals and their salts, there exists good scope of
Before conducting any physical and chemical characteri
research for their effective utilization to improve the
zation tests, the treated and control jute fabrics were con
flame-retardant properties of cellulosic and non-cellulosic
ditioned at 65% RH and 27°C for 48 h. After the
textiles. In this direction, we have already studied the
application of BPS on jute fabric samples, the add-on, i.e.
flame retardancy of cellulosic cotton fabric treated with
increase in the sample weight was determined using t
alkaline solution of spinach juice (SJ)15. Continuing the
gravimetric principle from the bone dry weights of the
effort, we have now attempted to improve the flame re
sample before and after the treatments. The per cent ad
tardancy of ligno-cellulosic jute textiles using BPS, as it on of BPS was calculated as follows:
contains elements like potassium, magnesium, silicate,
phosphorus, chlorine and other metallic constituents16 and
Per cent add-on = [M2 - MJM\\ x 100,
salts of magnesium nitrate and potassium nitrate17, potas
sium chloride, sodium chloride and metal phosphate18.
where M\ and M2 are the oven-dried weight of the control
Further, BPS is abundantly available in India and nor
and the alkaline BPS-treated samples respectively. The
mally considered as a waste material. The present study
reported results are the average of five readings.
reports an extensive investigation conducted to assess the
effect of different concentration of BPS on the flame
retardant properties of jute textile in terms of limiting Thermal characterization
oxygen index (LOI), burning rate and total heat produc
tion. The possible mechanism of imparting flame retar- LOI, Horizontal and vertical flammability: The burn
dancy to jute textiles by application of BPS has been behaviour of the control and treated samples was eva
postulated based on the inferences made from thermogra- ated using standard methods. For LOI analysis, IS 1
vimetry analysis (TGA), differential scanning calorimetry test method was used19. In the horizontal flammab
(DSC), Fourier transform infrared spectroscopy (FTIR), test, the flame time and propagation rate were meas
scanning electron microscopy (SEM), energy dispersive according to the FMVSS302N standard20. In the ve
X-ray analysis (EDX) and wash durability studies. flammability test, different parameters were mea
according to the 1871 method A21). The maximum tem
perature produced during the burning of the sample was
Materials and methods
measured using an IR thermometer in non-contact mode.
Material and BPS application Gross calorific value analysis: An oxygen bomb
meter was used to measure the gross calorific value
A plain woven loom-state jute fabric (Greige state with (GCV) of the control and BPS-treated samples
natural golden colour) of 0.2 kg/m2 areal density with dynamic 25°C measuring mode.
12 ends/cm and 13 picks/cm and having 200 tex warp and
240 tex weft yarn counts was used in the study. The BPS Thermogravimetry analysis: Thermogravim
supplied by the Navsari Agricultural University, Gujarat measures the gradual weight loss of a sample wi
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tc time at a constant heating rate. It also indicates the Results and discussion
effect of flame-retardant chemical on the pyrolysis of the
polymer substrate22. The TG curves of the control and LOI, horizontal and vertical flammabilit
treated fabrics were drawn using a thermo gravimetric
analyser in a nitrogen atmosphere with 2 ml/min flow rate The pre-mordanted jute fabrics were treate
and at a constant heating rate of 10°C/min. ent concentrations of BPS as discussed earlier
the flammability test are presented in Table 1. The LOI,
Differential scanning calorimetry (DSC): DSC of the measure of flammability of a sample, i
control and alkaline, BPS-treated jute fabric was carried minimum amount of oxygen required
out using a DSC thermal analyser. The heating rate was combustion in the oxygen/nitrogen mixtur
maintained at 10°C/min in the N2 atmosphere. LOI of 21 or below ignites easily and burns
open atmosphere, whereas a sample with LOI above 2
FTIR analysis ignites but burns slowly. A sample with LOI of 26 or
more may be considered as flame-retardant1.
FTIR analysis of the control and BPS-treated samples As indicated above- jute beinë a ligno-cellulosic fi
was carried out m an IR analyser over the wavelength of catches flame readlly> as cellulose is its major com
500-4500 cm"1 using the KBr disc sample preparation nent' Its L01 18 as low as 21 ■ In the Present study'the Ju
method. Here, the ATR transmittance mode with DLaTGS samPle was pre-mordanted with tannic acid and alum
detector, 49 scans and four resolutions was used to per- increase the uptake of BPS. It was observed that the
form the FTIR analysis was no cban8e 'n LOI of the sample due to mordantin
After application at different concentrations of BPS in the
mordanted jute samples, LOI was found to increase signi
SEM and EDX analysis ficantly. In the mordanted fabrics treated with 1 : 2 B
solution, the LOI value was found to increase to 36,
The surface of both the control and BPS-treated samples which ,s almost , ? times higher than that of the control
was analysed using a scanning electron microscope. The sample with further mcrease in the concentration of BPS
samples were coated with a thin layer of conducting (1 . 4)> the per cent add.on increased t0 8 from 5 7> result.
material (gold/palladium) using a sputter coater and exam- ing in a linear increasg jn L0I from 36 t0 40 Because of
ined under SEM with an accelerating voltage of 12 kV. tbe increased LOI, the BPS-treated samples did not catch
The EDX analysis of these samples was carried out using flame easüy whereas jn the yertica| flammabillty meas.
a field emission gun scanning electron microscope (FEG- urement5 the control sample was found t0 catch flame
S EM) to determine the quantity of the elements present reaciily and the entire sample burnt with flame within
on the surface, and the same was expressed in atomic and 60 gec The Bps_treated (1:2) sample showed no after
weight per cent. The time of flight secondary ion mass flame, followed by combustion with an afterglow in
spectroscopy (TOF-SIMS) was carried out using gallium 8qq sec ^jtb furtber increase in the add-on percentage,
as the primary ion surface. the burning with afterglow also stopped within 40 sec,
making the fabric a self-extinguishable one (Figure 1).
Wash durability of the finish Only this sample produced a 30 mm char length, indicat
ing its superior flame retardancy.
The flame-retardant activity of the finished samples was It is interesting to note that in the 1:0 BPS-treat
evaluated after washing them in a laundrometer using a sample, the total burning time could be increased
standard detergent of 5 g/1 at 40°C for 40 min. The fabric 605 sec, from 60 sec merely found with the control samp
was then rinsed in freshwater for 5 min, followed by dry- Similarly, for the BPS-treated (1:2) sample, the t
ing at 100°C for another 5 min. The samples were then burning time was 800 sec, which is approximately 13
conditioned in a desiccator for 24 h, before conducting more than that found with the control sample. By inc
LOI and flammability tests. ing the concentration of BPS, the burning flame time was
reduced to nil, thus turning the fabric self-extinguishable
Mechanical strength within 40 sec. In a practical scenario of burning micro
climate, burning with afterglow is not so severe in corn
Tensile strength and tear strength, the two most important parison to burning with the flame. This is because the
properties of any textile, were evaluated in an instron burning flame happens at a much higher temperature
tensile tester according to standards ASTM D5035 and compared to the burning with afterglow in a realistic ver
ASTM D1004 respectively23'24. The values of the control tical burning. In our experiment with vertical burning, a
and treated samples were compared to study the effect maximum temperature of 380°C was observed in the con
of BPS on the mechanical properties of the treated trol sample, while in the BPS-treated (1:0) sample, it
samples. was reduced to 300°C. This indicates that the presence of
374 CURRENT SCIENCE, VOL. 108, NO. 3, 10 FEBRUARY 2015
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Table
Table 1. Results
1. Results
of the flammability
of the tests
flammability tests
Alkaline BPS-treated
BPS concentration
Horizontal flammabi
Warp way burn rate (mm/min) 55 53 15 11.5 -
Vertical flammability
Occurrence of flashing over the surface Yes Yes No No No
After flame (sec) 60 60 5 Nil Nil
Burning with afterglow time (sec) 0 (as completely 0 (as completely 600 800 40
burnt with flame) burnt with flame)
State of the fabric Completely burnt Completely burnt Burnt initially with Burnt only with Partially burnt with
in contact with flame with flame with flame flame followed by afterglow afterglow and
afterglow char length observed
*Total burning time of the fabric = burning with flame time + burning with afterglow time (after the
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BPS in the jute fabric could reduce the burning tempera- burning rate, and more afterglow
ture by 80°C. It is interesting to note that the 1:2 BPS that BPS could be considered as an
treatment not only reduced the maximum burning with dant green-chemical for the ligno-
flame temperature, but also the afterglow temperature,
which reduced gradually from 320°C to 280°C, 250°C
Thermogravimetry
and finally to 120°C at intervals of approximately 60 sec.
In any flame-retardant finishing of a textile substrate,
Figure 2 shows the TG curves of the control (Al) and
three time-periods, namely (i) burning with flame, (ii)
1 :4 BPS-treated (Bl) jute fabrics in N2 atmospher
burning with afterglow and (iii) total burning time are
heating rate of 10°C/min. The TG curve of the c
important, as they determine either the escape time or the
(Al) jute samples depicts three stages of mass loss. In
time available to extinguish the flame. It will be benefi
initial stage at temperature below 200°C, mass loss
cial if the burning with flame time could be reduced and
occurred mainly due to the removal of bound and unbound
the burning with afterglow time could be increased from
absorbed moisture from the cellulose polymer26. How
the angle of fire hazards. In all the BSP-treated samples,
ever, the main pyrolysis occurred in the temperature
the flame time was found almost negligible compared
range 260-500°C. In this range, the major mass loss
to the control sample with 60 sec flame time. Also, the
happened at around 330°C due to pyrolysis of cellulose27.
afterglow time in the BPS-treated samples was much more,
Above 400°C, dehydration and char formation
600-800 sec, from practically nil in the control sample.
occurred. In the case of dehydration, the non-oxidizable
In real-life situations, this longer afterglow time will help
water and C02 might have been released22. It could be
e ither to escape from the fire hazard zone or to extinguish
seen that the control sample (Al) lost approximately 98%
the flame, which is not possible with the control sample
of its mass at below 500°C. A similar phenomenon was
w ith nil afterglow. The BPS-treated sample mostly burnt
observed in the vertical flammability measurement,
w ith afterglow and the burning rate was reduced signifi
where the control and mordanted fabric burnt completely
cantly from 250 mm/min in the control sample to
with a maximum temperature of 380°C and burning rate
18.75 mm/min in the 1:2 BPS-treated sample. Similar
as high as 250 mm/min. In the BPS-treated jute fabric
tiends were also observed in the horizontal flammability , , , . .. ,
, , , , . _ (B1 ), more weight loss (10%) was observed at the initial
measurement, where the burning rate reduced from ° .
stage (50-150°C) of the TG curve compared to the 5%
55 mm/min in the control sample to 11.5 mm/min in the
weight loss in the control fabric. This may be due to the
1 : 2 BPS-treated sample.
presence of more bound or unbound moisture in the BPS
treated fabric due to the presence of various inorganic
Gross calorific value analysis salts and their hydrates, as discussed below. In the second
stage, the curve B1 started to lose its mass with the onset
In the oxygen bomb calorimeter, the specimen sample of thermal degradation at 215°C, which is 45°C below the
was inserted in a steel cylinder (i.e. the bomb) and près- degradation temperature (260°C) of the control sample
surized with the excess of pure oxygen. The cylinder was with a shift in temperature from 330°C to 300°C (i.e.
then inserted in a bucket filled with water, and the sur- 30°C lower) at which the peak in the main loss occurred,
rounding jacket was kept at a constant temperature. The As 60% of the mass loss was observed, hence it can be
burning of the specimen caused a rise in temperature of deduced that the BPS treatment reduced the amount of
the bomb and that of water in the bucket. An ignition cir- mass loss in the second degradation range only. Further,
cuit was used to ignite the specimen. After allowing an it reduced the combustion temperature of the cellulosic
appropriate correction factor, the rise in temperature of substrate with dilution of the flammable volatiles by the
water in the bucket was measured to determine the GCV generation of non-oxidizable C02, H20 at a compara
of the sample. It has been observed that the control cellu- tively low temperature. It can also be observed from the
losic jute sample showed a GCV of 16,299 J/g, however, TG curve that in the third stage, the treated fabric Bl
the 1 :4 BPS-treated sample produced much less heat of started forming char and the quantity of char residue
12,848 J/g, which was almost 21% lower than the control remained higher than the control fabric at any higher tem
fabric as shown in Table 2. The total heat produced by perature and at 500°C, it increased from 15% to 30%. It
the BPS-treated fabric could be compared with the com- shows that the alkaline BPS also has a positive effect on
mercially available flame-retardant chemical formulation prior dehydration and char formation. With regard to
(10% diammonium phosphate (DAP) + 5% urea) for the alkalinity the thermal stability of uniaxial natural ligno
cellulosic substrate, as reported in the literature25. It was cellulosic fabric increased when it was treated with alkali,
observed that the residues obtained after the GCV experi- This might be because alkali treatment increases the crys
ment had no calorific values, as it is mostly a non- tallinity of the treated fabric. The TG curve shows that
combustible inorganic material. Therefore, the lesser heat for both untreated and 3% alkali treated ligno-cellulosic
production along with a lower burning temperature and fibre pyrolysis started from 250°C. However, the rate of
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Table
Table 2. Gross
2. calorific
Grossvalue
calorific
(GCV) of jute
value
fabric (GCV) of jute fab
Fabric
Fabric parameters
parametersSample massmass
Sample (g) Temperature (AT) (A7*)
(g)Temperature (K) GCV
(K) (H) (J/g)
GCV (H) (J/g)
Control
Control jute jute 0.4279 0.783
0.4279 0.783 16,29916,299
BPS-treated
BPS-treated (1 :4) jute (1:4)
0.696 jute 0.696 1.000 12,848
1.000 12,848
100 at around 365°C, which is lower than the control jute fab
80
ric. Therefore, the curve in Figure 3 b reveals that the en
dothermic peak related to the degradation of cellulose has
60
to
to
shifted to a lower temperature (from 387°C to 365°C),
° 40 with the BPS add-on increased to 8%. Like TG analysis,
O)
20
DSC interpretation also showed that BPS treatment low
0
ered the pyrolysis temperature and diluted the formation
0
of flammable gases, resulting in an increase in LOI and
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750 decrease in flame time and the burning rate. Besides, the
50 100 150 200 250 300 350 400 450 500 550 600 650 700 750
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® .
O
ü ^t10
10
E
Q)
8
JZ
4
o
'E 2
<D
-C 0
O
"O
*-2
c
LU
-4
1a5
1
CD
.£
Oo
-O
T3
10 100 160
160
220
220 280
280
Temperature
Temperature (°C)
(°C)
Figure
Figure 3.3.
DSC
DSC
curves
curves
of the
of control
the cont
(a)
Wavenumber
Wavenumber (cm-1)
(cm-1)
Figure
Figure 4.4.
FTIR
FTIR
analysis
analysis
of control
of control
fabric
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Figure
Figure S. SEM
S. SEM images
images of(a),
of control control (a), (1:4)
BPS-treated BPS-treated (1 pure
fabric (ft), and
12 3 4
Table
Table 3. 3.
Atomic
Atomic
percentage
percentage
of control of
(A) control
and BPS-treated
(A) and
(1 : 4)BPS-treated
jute fabric measured
(1 : 4)
byjute
EDX fabric
Elements Weight (%) Atomic (%) Weight (%) Atomic (%) Weight (%) Atomic (%)
calcium. It can be seen that in the BPS-treated jute fabric, K2S04, 24H20) and sodium from alkali Na2C03 and BPS
the magnesium percentage is more followed by sodium used during the experiments. The presence of magnesium
compared to the other atoms. Also, compared to the con- is due to BPS (possibly in the form of MgCl2 salt, magne
trol sample, the per cent weight of carbon is significantly sium phosphate or MgO), phosphorus in the form of
lower (by 20) in the BPS-treated sample. However, 15% phosphate salt and silicon present in the form of silicate
more oxygen might be due to the presence of various (Si02 or Na2Si03).
metal chlorides and oxides. The other elements, except
sulphur and aluminium, present in pure BPS as well in
the BPS-treated samples might be in the form of metal Surface ion mass spectroscopy analysis
oxide, metal chloride or metal phosphate. Aluminium,
potassium and sulpur were found in the BPS-treated As indicated in Figure 7 and Table 4, the negative TOF
sample, mainly due to the mordant (alum: A12(S04)3, SIMS of BPS showed the presence of H, C, N, O, OH ,
CURRENT SCIENCE, VOL. 108, NO. 3, 10 FEBRUARY 2015 379
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7.0E*6- m,
6.0E*6
» 5.0E«6
§ 4 0E*6:
O 3.0E*6:
.»•P»
2.0E*6
1.0E*6
1200
80
0 4 30 36
25 30 35 40
40
50 55 60 65
Figure
Figure 7. 7.
TOFTOF
SIMSSIMS
of BPS.
of BPS.
Table4.
Table 4.Mass
Mass spectroscopy
spectroscopy peaks
peaks and their
and their quantifications
quantifications Mechanism of imparting fla
Molecular Mass/charge Intensity/ application of BPS
Molecule formula (MIX) ratio
(M/Z) count
Phosphate po;
po2 62, 63 3000 observed that the uptake/exhaustion of BPS by cellulose
Phosphite P05 79 2000 textile was very low, when the samples were treated with
Potassium chloride KCl"
Kcr 74,
74, 76,
76,78
78 2000 out any mordanting agent. However, prior mordanting of
Pottasium K+ 40,41 5.0E + 6
jute followed by application of BPS in alkaline condition
Magnesium Mg+ 24, 25, 26 1.0E + 6
Aluminium Al+
27 1.0E + 6
ensured a good add-on with 3-8% uptake of BPS. This
Calcium Ca+
43 3.0E + 5 implies that jute has become flame-retardant mainly
because of BPS, and partially due to the interaction of
BPS and the mordant. The effect of flame retardancy
imparted by BPS may be attributed to the presence of
F-, CL, PO2, PO3, KCL, KF , Cl2, etc. and the positive phosphate, silicate and other mineral salts and metal
TOF-SIMS showed the presence of Mg+, K+, Mn+, Fe+ ides in the sap. The phosphate and silicate in th
ions. Therefore, the flame retardancy (i.e. more amount treated sample were present mainly in the form of
of char formation and higher LOI) of the cellulosic cotton cium, magnesium. Similarly, other metals are pres
fabric might be attributed to the free metal ions present in the treated jute in the form of chloride, such as magn
BPS, in addition to the presence of salts like potassium sium chloride, calcium chloride, potassium chlorid
chloride, potassium fluoride, calcium chloride, phos- The presence of these molecules, i.e. chloride and pho
phate, phosphite, etc. which also help impart fire retar- phate was also observed in the FT1R analysis and by
dancy to the BPS-treated fabric. Therefore, the mass peaks of the elements in the EDX analysis. In this re
spectroscopy results of BPS also support the conclusion recently, researchers have reported that 10.5 g inorg
drawn from the analysis of FTIR and EDX. An earlier salts was obtained from the evaporation of 500 ml a
study on GC-MS analysis of BPS has also reported that ous ash extract collected by burning the air-dried BP
magnesium nitrate and potassium nitrate are the two has also been reported that potassium chloride, sodiu
major active compounds present in it17. chloride and metal phosphate are the main compone
380 CURRENT SCIENCE, VOL. 108, NO. 3, 10 FEBRUARY 2015
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Tabic
Tabic 5. Flammabi
5. Flammabi
lity parameters
lityof treated
parameters
and washed of
fabric
treated and was
Fabric
Fabric parameters
parameters
BPS-treated
BPS-treated (1: 4) sample
(1: 4) sample
Flammability
parameters Control sample After washing Before washing
LOI 21 30 40
Horizontal flamm
Warp way burn rate (mm/min) 55 20 -
Jute
Jutefabric fabric Warp
Warp Weft
Weft Warp
Warp Weft
Weft
Control
Control 300
300 310
310 610
610 638
638
BPS-treated
BPS-treated (1:4) sample (1 :4)
293 sample
305 293 305
605 605 630
630
of the salt substitute18. It has also been reported that ba- calorific value, while reducing the formation of flamma
nana roots are able to induce silicate dissolution, thereby ble gases as seen in the TGA analysis,
increasing the availability of silicon37. In the present
study, it has been deduced that not only the BPS alone,
Wash durability
but also the formation of some complex with the mor
dants has helped the jute textile substrate to be a better
The test on the durability of the imparted flame-retardant
flame retardant, as a high uptake of BPS was possible
finish on jute textile was carried out with a soap solution
only due to prior mordanting of the fabric. From the vari
to study the after-wash effectiveness of the finish. The
ous characterizations made in the present study, it is pre
changes in LOI and burning rate are presented in Table 5.
sumed that phosphate, silicate and other mineral salts
It can be seen that the LOI value of the washed fabric de
might have retarded the thermal decomposition of cellu
creased from 40 for the 1 :4 unwashed fabric to 30 in the
lose and contributed to the dehydration process by increas
washed fabric sample, which is, significantly (by 1.4
ing the amount of char formation, as shown in the TG
times) higher than that noted with the control sample.
curve. Phosphate-containing molecules are known to be
„ _ , After washing the sample, as LOI decreased its burning
name retardant . Metal chloride has also been reported as . ° , _ , , ■ , ,
„ . , . c ,, . , . . 3g x , , rate also increased. The measured horizontal burning rate
a nre-retardant lor cellulosic substrate . Silicate has been , . . . , , , „ , , „ ,
. , . , • r- . j , 639 t, (20 mm/min) in the washed sample was found to be 2.5
reported to have passive tire-retardant properties ' . Be
• . r it- .-.rte i times slower than that of the control sample, and the
sides, the presence of water molecules in BPS as shown , , , " ,
™TT1 _ a\ ■ .. . i . decrease in the flame-retardant properties in the BPS
m the FTIR curve C (Figure 4), might have also contrib- , , , . , , , ,
, j ~ j , treated sample after washing may be attributed to the par
uted in preventing the rise in temperature of the sample . , ; . , ° J _
, , , . c .. ,,.A tial removal of the active component of BPS molecules
by absorbing the heat of evaporation (540 cal/g). The , , . , , ,
^ ... . . ■ ,. such as metal salts, phosphate and silicates,
presence of moisture peak has been observed in the FTIR r r
spectra and the TGA curves. Therefore, the flame retar
dancy exhibited by the BPS-treated jute fabric might be Physical properties
possibly due to the combined effect of (i) phosphate
compounds, (ii) metal salts (iii) silicate, and (iv) bound It can be seen from Table 6 that the a
and unbound water molecules. These have helped in more retardant finish has no significant ad
char and non-flammable gas formation, such as like C02, tensile and tear strength of the 1:4
H20, etc. Besides, researchers have also noted the près- In contrast, it may be noted that of
ence of organometallic additives in the cellulosic cotton flame-retardant finish generally ca
fabric that increased the char formation and also de- tensile strength of the jute fabric
creased the tar formation40. In addition, the presence of in acidic condition41. In our case, sin
approximately 20% of the inorganic material and reduc- in alkaline condition, the changes in e
tion of organic material (cellulose) in similar quantum, strength were non-significant. Here in
might have helped in the production of more char with no been reported that alkaline trea
CURRENT SCIENCE, VOL. 108, NO. 3, 10 FEBRUARY 2015 381
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RESEARCH ARTICLES
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