Cellulose (2017) 24:4069–4081
DOI 10.1007/s10570-017-1391-x
ORIGINAL PAPER
A novel durable flame retardant cotton fabric produced
by surface chemical grafting of phosphorus- and nitrogen-
containing compounds
Ziyi Liu . Miaojun Xu . Qi Wang . Bin Li
Received: 30 November 2016 / Accepted: 30 June 2017 / Published online: 10 July 2017
Ó Springer Science+Business Media B.V. 2017
Abstract Phosphorus- and nitrogen-containing
compounds were grafted on a cotton fabric surface
by three steps. Firstly, the cotton fabric was oxidized
by sodium periodate to form aldehyde groups, and
then the aldehyde groups were reacted with the
organic amine to generate Schiff bases. Finally, the
Schiff bases were reacted with dimethyl phosphate by
the phosphine hydride addition reaction. The chemical
structure of grafted cotton fabric was characterized
and confirmed. The results demonstrated that the
limiting oxygen index (LOI) value of the modified
cotton fabric dramatically increased from 19.5% for
pure cotton fabric to 28.1% due to the chemical grafted
on the cotton surface. After washing, the LOI value
slightly decreased to 27.4%, which indicated that the
prepared cotton fabric possessed superior washing
durability. Thermogravimetry and cone calorimetry
results demonstrated that the grafted flame retardant
stimulated the thermal degradation and charring of
cotton fabric ahead of time and formed sufficient char
residue at high temperature, which efficiently pre-
vented the underlying cotton fabric from degradation
and combustion. Consequently, the flame retardancy
of the cotton fabric was enhanced.
Z. Liu  M. Xu  Q. Wang  B. Li (&)
Heilongjiang Key Laboratory of Molecular Design and
Preparation of Flame Retarded Materials, College of
Science, Northeast Forestry University, Harbin 150040,
People’s Republic of China
e-mail: libinzh62@163.com
Keywords Flame retardant cotton fabric  Chemical
grafted  Washing durable
Introduction
Cellulose is one of the most common and most widely
distributed polysaccharides in the world. It has been
widely used in clothing, accessories, industrial appli-
cation, aerospace and military industry due to its
superior merits, such as renewability, breathability
and so on (Dong et al. 2016; Sirvio et al. 2011).
Despite its attractive properties, the use of cellulose is
still restricted in many applications which require high
flame retardant grade, because the cellulose possesses
a low limiting oxygen index of 18% and it can be
ignited easily (Cheema et al. 2013). Consequently,
improving the flame retardancy of cellulose is becom-
ing an urgent problem and has attracted much attention
in recent decades.
Traditionally, halogen-based flame retardants have
been effective for cellulose retardancy; however, their
application has been restricted in recent years due to
release of corrosive and toxic gases and black smoke
during the combustion process (Alongi et al. 2011). In
this context, the development and application of
halogen-free flame retardant has become a subject of
extensive investigation for cellulose. Up to now, a
wide variety of halogen-free flame retardants have
been proposed for cellulose, mainly including flame
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4070
retardants containing phosphonate and phosphonium
salts (Gaan and Sun 2007), phosphorus-nitrogen
(Zhang et al. 2015), phosphorus-silicon (Jelena Vasil-
jević et al. 2015), nitrogen-silicon (Boukhriss et al.
2016), and nitrogen-boron (Xie et al. 2013). Among
them, the phosphorus-nitrogen-containing system is
the most effective flame retardant for cotton fabric and
has attracted much attention in recent decades. Shari-
atinia et al. (2015) synthesized five novel nanosized
phosphoramide compounds and used them in flame
retardant cotton fabric; the results indicated that the
char lengths of the flame retardant cotton fabrics
ranged from 3 to 14 mm compared with nothing left
for the pure cotton after combustion. Gao et al. (2015)
synthesized an organic phosphorus-based ammonium
salt flame retardant (AHDTMPA) and introduced it
into cotton fabric; the limiting oxygen index (LOI)
value was greatly enhanced from 18% for pure cotton
to 36.0%.
The permanence and durability of flame retardant
cotton fabric is critical and has been became a focus of
research. In recent decades, significant methods have
been proposed for improving the flame retardancy of
cotton, including chemical treatment (Lecoeur et al.
2001), pad-dry curing (Lessan et al. 2011), graft
polymerization (Tsafack and Levalois-Grützmacher
2006), nanoparticle adsorption (Alongi et al. 2014),
sol–gel process (Alongi et al. 2013a), layer-by-layer
assembly (Yang et al. 2016), and ultraviolet polymer-
ization (Wang et al. 2016a, b). In most of these
methods, the flame retardants are physically adsorbed
on the cellulose surface or weak covalent bonds are
formed with the cellulose, which leads to the less than
ideal durability and permanence of the prepared flame
retardant cotton fabrics. Li et al. (2015) synthesized a
phosphorus-nitrogen-containing flame retardant
(DTCTNG) and incorporated it in the cotton fabric
by the pad-dry cure method; the results indicated that
the LOI value of the flame retardant cotton fabric
declined from 28.4 to 20.7% before and after 10
washings. Zhang et al. (2015) prepared flame-retarded
cotton fabric with a novel ammonium salt
(AEDTMPA) utilizing the covalent bonds effect
between AEDTMPA and the cellulose surface; the
LOI value of cotton fabric dramatically decreased
from 48.0 to 31.2%, and decreased by 35% after 50
laundering cycles. The results demonstrated that the
permanence and durability of the prepared flame
retardant cotton fabric by above methods should be
123
Cellulose (2017) 24:4069–4081
further improved. The flame retardant compounds
reacted with the cellulose surface and formed a
stable chemical bond; this was a promising method
for preparing flame retardant cotton fabric with
permanent and durable properties. Consequently, we
tended to integrate the phosphorus and nitrogen
compounds on the surface of cotton fabric by surface
chemical grafted method for preparing cotton fabric
with effective flame retardancy and excellent
durability.
In this work, the flame retardant cotton fabric was
prepared by surface chemical grafting of ethylenedi-
amine (or methylamine) and dimethyl phosphate on
the oxidized cotton fabric which was firstly oxidized
by sodium periodate. The chemical structure of the
obtained flame retardant cotton fabric was character-
ized and the fire retardancy, thermal degradation
behavior, flame retardant mechanism and the washing
durability were investigated and disclosed.
Experimental
Materials
Undyed cotton fabrics (357 g/m2) were purchased
from Rainbow Knitting Factory (Hebei, China).
Sodium periodate, methylamine (MY), ethylenedi-
amine (EDA), and dimethyl phosphate (DMP) were
purchased from Aladdin Reagent Co. Ltd. (Shanghai,
China). All solvents and chemicals were used without
further purification.
Preparation of the surface chemical grafted cotton
fabric
The preparation route of the surface chemical grafted
cotton fabrics is shown in Scheme 2. Firstly, the
original cotton fabrics were cut into reasonable size
and soaked in boiling water for 30 min, then washed
three times with a great deal of deionized water and
hung in the ventilation place to dry. The treated cotton
fabrics and a certain amount of sodium periodate
solutions (ratio, 20:1, v/w) with the concentration of
0.6 moL/L were put into a 1000-mL glass vessel and
reacted for 2 h in a dark environment at 40 °C. After
reaction, the oxidized cotton fabrics were taken out
and soaked into 0.1 moL/L ethanediol solution for
30 min to remove the extra sodium periodate and then
Cellulose (2017) 24:4069–4081
washed with plenty of deionized water for three times.
The obtained oxidized cotton fabrics were used in the
following reaction without further drying. Secondly,
the prepared oxidized cotton fabrics were immersed
into 0.15 moL/L methylamine (MY) or ethylenedi-
amine (EDA) methanol solution (ratio, 10:1, v/w) for
2 h at 30 °C as revealed in Scheme 2, and then the
cotton fabrics were taken out and washed with
excessive deionized water for several times to remove
the extra MY (or EDA) and the Schiff-base formed on
the cotton fabrics surface. Finally, the cotton fabrics
with Schiff-base were respectively dipped into the
dimethyl phosphate (DMP) methanol solution for 1, 2,
3, 4 and 5 h at 40, 50 and 60 °C in order for the P–H
bonds of dimethyl phosphate to react with Schiff base.
Consequently, the flame retardant elements of nitro-
gen and phosphorus were grafted by chemical reaction
on the surface of cotton fabrics. The treated cotton
fabrics were washed with excessive deionized water
for several times and dried in the ventilation place. The
cotton fabrics were then cut into the standard size for
property tests.
Determination of the aldehyde group content
The determination of aldehyde group content of the
oxidized cotton fabric was based on oxime reaction
between th aldehyde group and NH2OHHCl
(Scheme 1). The hydrochloric acid released from
hydroxylamine hydrochloride was titrated by
0.03 moL/L NaOH methanol solution (Liu and Xu
2014). The aldehyde group content was calculated
based on Eq. (1)
30V
CHO ¼ ð1Þ
w0
where CHO is the aldehyde group content, mmoL/g;
V is the consumption volume of 0.03 moL/L sodium
hydroxide methanol solution, L; w0 is the sample
weight, g.
Scheme 1 is the reaction OH
mechanism between the
oxidized cotton fabric and
NH2OHHCl * O
HO-NH2.HCl
* * +2HCl + 2H 2O
O O
O O
4071
The results show the aldehyde group content of the
oxidized cotton fabrics was 1.36 mmoL/g.
Fourier transform infrared analysis (FTIR)
The Fourier transform infrared (FTIR) spectra were
obtained with a spectrophotometer (PerkinElmer 400)
in the range of 400 to 4000 cm-1, and using the KBr
pellet technique.
Determination of the phosphorus content
The quimociac method was used to determine the
phosphorus content of surface-modified cotton fabrics
(Shaver 2008), and the phosphorus content was
calculated based on Eq. (2)
ðwA  wB Þ  0:07
P% ¼  100% ð2Þ
w0
where P is the phosphorus content, %; wA is the weight
of the surface-modified cotton fabrics solution gener-
ated by the quinoline phosphomolybdic acid precip-
itation, g; wB is the weight of the blank solution
generated by the quinoline phosphomolybdic acid
precipitation, g; w0 is the sample weight, g; 0.07 is the
conversion factor between quinoline phosphomolyb-
dic acid and phosphorus.
Determination of the nitrogen content
The Kjeldahl method was used to determine the
nitrogen content of surface-modified cotton fabrics
(Hou et al. 2008), and the nitrogen content was
calculated based on Eq. (3)
ðV  V0 Þ  c  14:01
N% ¼  100% ð3Þ
w0
where N is the nitrogen content, %; V is the
consumption volume of 0.05 moL/L hydrochloric
acid solution for the surface-modified cotton fabrics,
OH
O
*
N
N
OH
HO
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4072
mL; V0 is the consumption volume of hydrochloric
acid solution for pure cotton, mL; c is the concentrate
of hydrochloric acid solution; w0 is the weight of
sample, mg.
Grafting yield of organic amine and dimethyl
phosphate
The grafting yield of organic amine and dimethyl
phosphate for surface-modified cotton fabrics was
calculated as follows per Eq. (4):
w  w0
G% ¼  100 ð4Þ
w0
where G is the grafted yield, %; w is the weight of the
surface-modified cotton fabrics, g; w0 is the weight of
the oxidized cotton fabric, g.
Tensile strength mechanical properties tests
Tests of tensile strength of surface-modified cotton
fabrics were performed using a Regeer computer-
controlled mechanical instrument (Shenzhen, China),
according to GB/T3923.1-1997 standards. The dimen-
sions of the fabrics were 280 mm 9 60 mm. At least
five specimens were tested for each fabric.
Flame retardant tests
LOI values of flame retardant cotton fabrics were
determined using a JF-3 oxygen index instrument
(Jiangning Analysis Instrument Company, China)
with specimen dimensions of 58 9 150 mm accord-
ing to GB/T5454-1997 standard.
Thermal analysis
Thermogravimetric analysis (TGA) was carried out
using a Perkin Elmer Pyris 1 thermal gravimetric
analyzer (MA, USA) at a heating rate of 10 °C/min
and heating from 50 to 800 °C under nitrogen with a
flow rate of 20 mL/min. All thermal degradation data
were obtained from the TGA and differential thermo-
gravimetry analysis (DTG) curves.
Cone test
The combustion behavior under ventilated conditions
was conducted using a cone calorimeter (West Sussex,
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Cellulose (2017) 24:4069–4081
UK), according to ISO 5660-1 standard. The specimen
dimensions were 100 9 100 mm and they were
exposed to the cone at a heat flux of 35 kW m2.
Scanning electron microscopy (SEM)
Scanning electron microscopy (SEM) was conducted
using an FEI QuanTa-200 (Eindhoven, Netherlands)
instrument in order to research the surface morphol-
ogy of the flame retardant cotton fabrics before and
after burning. All the samples were sputter-coated
with a conductive gold layer before SEM analysis.
Washing durability test
In order to evaluate the washing durability of flame
retardant cotton fabrics, the samples were washed
repeatedly at 40 °C for 2 min in soap water (4 g/L)
with no rubbing for one time. The samples were taken
out and dried in a ventilation environment after being
washed 10 times. The washing durability of the flame
retardant cotton fabric was evaluated by the change of
LOI values, and N and P contents.
Results and discussion
The preparation route of surface chemical grafted cotton
fabric was shown in Scheme 2. Firstly, the cotton
fabrics were oxidized with sodium periodate. Then, the
aldehyde groups on the oxidized cotton fabrics surface
respectively reacted with methylamine (MY) and
ethylenediamine (EDA), forming the Schiff base struc-
ture on cotton fabrics. Finally, the dimethyl phosphate
(DMP) reacted with the Schiff base by phosphine
hydride addition reaction, and the flame retardant
elements of nitrogen and phosphorus were grafted on
the cotton fabric surface (the products respectively
defined as MY/DMP-cot and EDA/DMP-cot).
Effect of reaction temperature and time on grafting
yield, flame retardancy and tensile strength
Figure 1 shows the relationship between the reaction
temperature, time and the grafting yield of cotton
fabric. As revealed in Fig. 1a for MY/DMP-cot, the
grafting yield gradually increased with the increasing
of reaction time. At the same reaction time, the
grafting yield of MY/DMP-cot at 50 °C was obviously
Cellulose (2017) 24:4069–4081 4073

Scheme 2 Preparation routes of MY/DMP-cot and EDA/DMP-cot

18 19
(a) (b)
18
17

17
16
Grafting yeild/%
Grafting yeild/%

16
o
15 40 C
o
o
40 C 15 50 C
o
o
50 C 60 C
14
14

13 13

12 12
1 2 3 4 5 1 2 3 4 5
Time/h Time/h

Fig. 1 Effect of reaction time and temperature on grafting of MY/DMP-cot (a) and EDA/DMP-cot (b)

higher than that at 40 °C, which indicated that the
reaction temperature could enhance the reactive
activity. However, the MY/DMP-cot materials were
seriously damaged and cracked when the reaction
temperature was enhanced to 60 °C. Figure 1b gives
the relationship between the reaction temperature,
time and the grafting yield of EDA/DMP-cot, and the
tendency was similar with that of MY/DMP-cot. The
EDA/DMP-cot could endure the reaction at 60 °C due
to the incorporation of EDA resulting in the formation
of crosslinking structure; also, the strength of EDA/
DMP-cot was higher than that of MY/DMP-cot, but
the EDA/DMP-cot became hard and yellow after
reaction at 60 °C.
The relationship between the reaction temperature,
time and the flame retardancy of MY/DMP-cot
(Fig. 2a) and EDA/DMP-cot (Fig. 2b) are presented.
As revealed in Fig. 2, the flame retardancy for both
MY/DMP-cot and EDA/DMP-cot correspondingly
increased with the enhancement of reaction tempera-
ture and time. The phenomenon is attributed to the fact
that the grafting yield and flame retardant component
were also increased with the enhancement of reaction
time and temperature, and the content of flame

123
4074 Cellulose (2017) 24:4069–4081

36 (a) 40 C
o
36 (b) 40 C
o

o
o
50 C 50 C
o
60 C
30 30

24 24
LOI/%

LOI/%
18 18

12 12

6 6

0 0
1 2 3 4 5 1 2 3 4 5
Time/h Time/h

Fig. 2 Effect of reaction time and temperature on LOI values of MY/DMP-cot (a) and EDA/DMP-cot (b)

retardant elements was critical for the flame retar-
dancy of cotton fabric.
The relationship and data between the reaction
temperature, time and the tensile strength of cotton
fabric are shown in Fig. 3. The tensile strength of pure
cotton fabric was 13.56 MPa. When the MY/DMP-cot
materials reacted with DMP for 1 h at 40 °C, the
tensile strength was decreased to 11.03 MPa, as shown
in Fig. 3a. With the increase of reaction time, the
tensile strength gradually decreased. When the reac-
tion time was enhanced to 5 h, the tensile strength was
only 5.68 MPa. As revealed in Fig. 3a, the tensile
strength obviously decreased when the reaction tem-
perature increased to 50 °C. The tensile strength was
only 2.89 MPa when the reaction time was 5 h. It
could be deduced that the increase of reaction time and
temperature damage the mechanical properties of
cotton fabric materials. For the EDA/DMP-cot, the
changing tendency of tensile strength was similar with
that of MY/DMP-cot materials, as revealed in Fig. 3b.
Comparing with Fig. 3a, it can be seen that the tensile
strength of EDA/DMP-cot was higher than that of
MY/DMP-cot at the same reaction temperature and
time, meanwhile, the extent of decline for EDA/DMP-
cot was acceptable compared with that of pure cotton
fabric. This could correspond to the introduction of
EDA into EDA/DMP-cot materials benefitting to the
formation of the crosslinking structure between the
cellulose fabrics, thus enhancing the tensile strength of
EDA/DMP-cot materials.
Taking into account the comprehensive perfor-
mance of flame retardant cotton fabric materials, the

14 14
(a) (b) o
40 C
o
12 40 C 12 o
50 C
o
50 C o
60 C
Tensile strength/MPa

Tensile strength/MPa

10 10

8 8

6 6

4 4

2 2

0 0
1 2 3 4 5 1 2 3 4 5
Time/h Time/h

Fig. 3 Effect of reaction time and temperature on tensile strength of MY/DMP-cot (a) and EDA/DMP-cot (b)

123
Cellulose (2017) 24:4069–4081
reaction temperature and time between DMP and
Schiff base cotton fabrics were fixed at 50 °C and 3 h
in the next research work, and we correspondingly
defined the MY/DMP-cot and EDA/DMP-cot pre-
pared under this condition as FR-cot-1 and FR-cot-2
for the further properties tests, respectively.
FTIR analysis of the surface-modified cotton
fabric
The chemical structures of the cotton fabrics were
characterized by FTIR, as shown in Fig. 4. From the
spectrum of line (a) for pure cotton fabric, the broad
peak at 3400 cm-1 is attributed to O–H stretching
vibration and the hydrogen bond association effect of
hydroxyl groups, the peak at 2900 cm-1 assigned to
C–H stretching vibration, the peak at 1650 cm-1
corresponds to O–H bending vibration, the peaks at
1060 and 1020 cm-1 are assigned to stretching
vibration of C–O bonds, and the peak at 897 cm-1 is
attributed to the glucosidic ring in the cellulose
structure (Nikolic et al. 2014).
Comparing with line (a) of pure cotton fabric, the
novel characteristic peaks appearing in line (b) for the
oxidized cotton fabric at 1740 and 796 cm-1 is
respectively assigned to C=O stretching vibration
and hemiacetal bonds between an aldehyde group and
a neighboring hydroxyl group (Azzam et al. 2015),
which indicates that the aldehyde groups formed after
the cotton fabrics were oxidized by sodium periodate.
The spectrum of lines (c) and (d) correspond to FR-
(a)
(b)
Transmittance/%
(c)
1740
(d)
4000 3500 3000 2500 2000
Wavenumber/cm-1
Fig. 4 FTIR spectra of pure-cot (a), oxidized-cot (b), FR-cot-
1(c), FR-cot-2 (d)
4075
cot-1 and FR-cot-2, respectively, and the lines were
similar. Compared with the spectrum of line (b), the
characteristic peak assigned to the aldehyde group
disappeared in lines (c) and (d), and the novel peaks
appearing at 712 cm-1, 1060 and 1170 cm-1 are
assigned to P–C, P–O–C and P=O stretching vibration,
respectively. It could be deduced that the organic
amine reacted with aldehyde groups and then DMP
was connected by phosphine hydride addition
reaction.
Flame retardancy elements contents
To further verify the successful grafting of organic
amine and DMP on the surface of cotton fabrics,
quimociac and Kjeldahl methods were used to deter-
mine the phosphorus and nitrogen contents of surface-
modified cotton fabrics. P and N contents of flame
retardant cotton fabrics before and after washing were
shown in Table 1. It could be observed that the
contents of N and P for FR-cot-1 were, respectively,
1.71 and 3.57%, and after 10 washings, N and P
contents correspondingly decreased to 1.67 and
3.49%. It could be deduced that a small amount of
flame retardant composition was removed during
repeated washings. Meanwhile, it also could be seen
that the contents of N and P for FR-cot-2 declined from
1.82 and 3.83% to 1.78 and 3.74%, respectively,
before and after 10 washings. The results indicated
that the flame retardant compositions on FR-cot-2
were less extracted by water than that of FR-cot-1,
which might be attributed to the incorporation of EDA
in FR-cot-2 stimulating the formation of crosslinking
structure and made FR-cot-2 possess more durability
during the washing process.
Flammability of the surface-modified cotton
796
fabrics
In order to evaluate the effects of the surface chemical
grafted modification on the flame retardancy for cotton
fabrics, LOI tests were conducted and the related data
of FR-cot-1 and FR-cot-2 before and after washing are
712 summarized in Table 1. It could be observed that the
11701060
LOI value of the pure cotton fabric was only 19.5%,
1500 1000 500
which indicated the pure cotton fabric was easily
flammable. After the pure cotton fabric was oxidized
and then grafted with MY and DMP (FR-cot-1), the
LOI value increased from 19.5% for pure cotton fabric
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4076
Table 1 Contents of grafting yield, flame retardant elements and LOI values of cotton fabrics before and after washing
Samples Grafting yield (%) N (%) P (%)
Pure-cot 0 0 0 19.5
FR-cot-1 16.59 1.71 3.57
FR-cot-2 17.54 1.82 3.83
to 26.3%, an increase of 34.8%. The phenomenon
revealed that the surface chemical grafted modifica-
tion enhanced the flame retardancy for cotton fabric. It
could be attributed to the grafted DMP decomposing
and producing phosphoric and polyphosphoric acid,
which stimulated the cotton fabric to form a protective
char layer and protected the cotton fabrics from further
burning (Alongi et al. 2013a, b). On the other hand, the
nitrogen element also acted as a flame retardant in the
gas phase, and the phosphorus and nitrogen elements
played a synergistic flame retardant effect (Bogdanova
et al. 2016). As a result, the flame retardancy of the
cotton fabric was enhanced. When MY was replaced
by EDA during the modified process, the LOI value of
the FR-cot-2 was 28.1% and the grafting yield was
17.54%, which presented much higher LOI values and
grafting yield than FR-cot-1. This fact could be mainly
assigned to the higher P content, and the incorporation
of EDA in FR-cot-2 benefited the formation of the
thick and crosslinked char layer on the cotton fabric,
and effectively inhibited the translation of the com-
bustible gas, oxygen and heat between the cotton
fabric and combustible zone.
The permanence and washing durability is critical
for flame retardant cotton fabrics. In order to evaluate
the washing durability of the prepared FR-cot-1 and
FR-cot-2, the LOI tests was carried out after the
samples were washed, and the relative data are
summarized in Table 1. As revealed in Table 1, the
LOI value of FR-cot-1 decreased from 26.3 to 24.6%
after washing, which indicated the prepared FR-cot-1
retained good flame retardancy, and the LOI value was
merely reduced 1.7% before and after 10 washings. As
the results revealed in past years, Li et al. (2015)
prepared a novel phosphorus-nitrogen-containing
flame retardant cotton fabric by the pad-dry cure
method, and the LOI value of the flame retardant
cotton fabric declined from 28.4 to 20.7% before and
after 10 washings. Moreover, Deh and Gähr (2016)
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Cellulose (2017) 24:4069–4081
LOI (%) After washing treated 4LOI (%)
N (%) P (%) LOI (%)
0 0 19.2 -0.3
26.3 1.67 3.49 24.6 -1.7
28.1 1.78 3.74 27.4 -0.7
modified the cotton fabric with H3PO4 and urea, and
the LOI value of the obtained cotton fabric decline
from 26.8 to 24.4% after 10 washings. Compared with
the results of previously reported work, the prepared
FR-cot-1 possessed more outstanding washing dura-
bility due to the flame retardant compound being
grafted on the cotton fabric surface by chemical
reaction, and the formed P–C bonds possessing
excellent hydrolysis resistance; thus, the flame retar-
dant elements could firmly remain atached during the
washing process, leading to the retention of good
flame retardancy by FR-cot-1 after washing. When
FR-cot-2 was subjected to washing, as shown in
Table 1, the LOI value for FR-cot-2 without washing
only decreased from 28.1% to 27.4%, a reduction of
0.7%. The results demonstrated that FR-cot-2 pre-
sented more excellent water durability. This fact might
be attributed to the introduction of EDA, thereby
prompting the FR-cot-2 to form the cross linking
structure, which enhanced the firmness of the grafted
compound on cotton fabric surface and prevented the
flame retardant composition from being extracted by
water during washing. As a result, the water durability
of FR-cot-2 was further enhanced.
Thermal degradation behavior of flame retardant
cotton fabrics
A degree to which a sample loses mass with increasing
temperature can be measured by TGA, which provides
direct information about the thermal stability, char
formation and the degradation behavior of samples.
The initial decompose temperature is defined as the
temperature at which 5% weight loss occurs and Tmax
is defined as the temperature at the maximum weight
loss rate. TGA and DTG curves of the flame retardant
cotton fabrics under nitrogen atmosphere are pre-
sented in Fig. 5, and the relative thermal degradation
data are summarized in Table 2.
Cellulose (2017) 24:4069–4081 4077

100 0

(a) Pure-cot (b) Pure-cot

80 FR-cot-1
FR-cot-1

Derivative Weight /%
FR-cot-2 -5 FR-cot-2
60
Weight/ %

40 -10

20

-15
0

100 200 300 400 500 600 700 800 100 200 300 400 500 600 700 800
O O
Temperature / C Temperature/ C

Fig. 5 TGA (a) and DTG (b) curves of pure and flame retardant cotton fabrics

Table 2 Thermal Samples T-5% (°C) Rpeak1/Tpeak1 Rpeak2/Tpeak2 Residues

degradation data of pure (% min-1/°C) (% min-1/°C) (% at 800 °C)
and flame retardant cotton
fabrics Pure-cot 301.8 15.8/379.1 – 12.1
FR-cot-1 214.9 1.6/221.6 10.9/324.9 29.4
FR-cot-2 182.6 1.9/221.9 7.5/327.8 31.9

The pure cotton fabric started to decompose at
301.8 °C and the char yield was 12.1% at 800 °C. As
per the DTG curves of Fig. 5b, there was only one
peak appearing at 379.1 °C with the weight loss rate of
15.8% min-1/°C during the thermal degradation
course; this was caused by the depolymerization and
dehydration of cotton through inducing levoglucosan
reactions and char formation (Alongi et al. 2013a).
After the surface chemical grafting for cotton fabric,
the initial thermal decomposition temperature of FR-
cot-1 decreased from 379.1 °C for pure cotton fabric
to 214.9 °C due to the incorporation of the phospho-
rus-nitrogen-containing compounds on the cotton
fabric surface. This stimulated the thermal degradation
and char formation of cotton fabric ahead of time.
Consequently, the residual char of FR-cot-1 was
enhanced from 12.1% for pure cotton fabric to
29.4% at 800 °C. From the DTG curves revealed in
Fig. 5b, it could be seen that the whole thermal
degradation process of FR-cot-1 could be divided into
two stages; the peak maximum thermal decomposition
rate for step one appeared at 221.6 °C with the loss
weight rate of 1.6% min-1/°C, which might be
attributed to DMP firstly decomposing to phosphoric
and polyphosphoric acid and then catalyzing the
dehydration process, thereby phosphorylating the C6
primary hydroxyl groups (Zhao et al. 2016). The
second stage happened in the range from 280 to
350 °C and the peak appeared at 324.9 °C, with a
weight loss rate of 10.9% min-1/°C; this occurred
earlier and the peak strength was lower than that of the
pure cotton fabric. The phenomenon might be
attributed to the produced phosphoric and polyphos-
phoric acid in first stage promoting the dehydration
and degradation of the cotton fabric and then forming a
protective char layer ahead of time, which protected
the underlying cotton fabric from further degradation.
Compared with the DTG curve of FR-cot-1, the
tendency of the thermal degradation course for FR-
cot-2 was similar with FR-cot-1, as revealed in
Fig. 5b, and the peak strength for the second stage of
FR-cot-2 was decreased from 10.9% min-1/°C for
FR-cot-1 to 7.5% min-1/°C, a decrease of 31.2%. This
might be assigned to incorporation of

123
4078
ethylenediamine, which benefited the formation of the
crosslinking structure and retention of more sufficient
flame retardant on the FR-cot-2 surface, which
stimulated the formation of the char layer with high
thermal stability, firmness and strength. As a result, the
residual char for FR-cot-2 was enhanced from 12.1%
for pure cotton fabric and 29.4% for FR-cot-1 to
31.9%. The higher char yield will enhance the flame
retardancy of cotton fabric, and the thermal degrada-
tion results coincided with the flame retardancy tests
discussed above.
Cone calorimetric measurement
To investigate the effect of the surface chemical
grafted modification on the combustion performance
of cotton fabric, the cone calorimeter was exploited.
The parameters including time to ignition (TTI), the
heat release rate (HRR), the peak heat release rate
(PHRR) and the total heat release (THR) were
determined. Figure 6 and Table 3 present the plots
and the detailed information of combustion behavior
for pure cotton fabric, FR-cot-1 and FR-cot-2 obtained
from the cone calorimeter test at a heat flux of
35 kW m-2.
TTI represents the ignitability of materials. As
shown in Table 3, the TTI of FR-cot-1 decreased from
16 s for pure cotton fabric to 9 s, which might be
attributed to the decomposition products of DMP
grafted on the FR-cot-1 surface stimulating degrada-
tion of cotton fabric at a relative low temperature. In
certain conditions, the degradation behaviors ahead of
time contributed to charring earlier during combustion
(a)
300 Pure-cot
FR-cot-1
FR-cot-2
200
HRR/kW m-2
THR/MJ m-2
100
0
0 40 80 120 160
Times/s
Fig. 6 HRR (a) and THR (b) curves of pure and flame retardant cotton fabrics
123
Cellulose (2017) 24:4069–4081
and this benefited the better flame retardancy for
cotton fabric. It could be observed that the TTI for FR-
cot-2 was 7 s and ahead that of FR-cot-1, as revealed
in Table 3. The fact corresponded that more flame
retardant elements were grafted on FR-cot-2 and
stimulated the degradation of cotton fabric, which led
to more sufficient combustible gas gathering on the
FR-cot-2 surface and igniting earlier than that of FR-
cot-1.
HRR is one of the parameters for quantifying the
effectiveness of a flame retardant system, and a lower
HRR represents better flame retardancy. Figure 6a
shows the HRR curves of pure cotton fabric, FR-cot-1
and FR-cot-2. The results revealed that there was only
one peak during combustion after the pure cotton
fabric was ignited and the HRR peak appeared at 26 s
with a peak heat release rate (PHRR) of
349.9 kW m-2. When the cotton fabric surface was
chemically grafted with methylamine and DMP, the
HRR peak of FR-cot-1 appeared at 16 s with a PHRR
value of 248.7 kW m-2, as revealed in Fig. 6a and
Table 3, which was earlier and the lower than that of
pure cotton fabric. The phenomenon might be
attributed to the grafted flame retardants on the cotton
fabric surface decomposing themselves at the initial
stage on heating and stimulating the degradation and
charring of the cotton fabric at a relative low
temperature. Correspondingly, the combustible gas
was produced ahead of time and gathered on the
surface of FR-cot-1, which led to the HRR peak
occurring earlier than that of pure cotton fabric.
However, the previously formed char layer prevented
the transfer of heat from the samples during the
(b)
6
4
Pure-cot
2
FR-cot-1
FR-cot-2
0
0 40 80 120 160 200
Time/s
Cellulose (2017) 24:4069–4081 4079

Table 3 Cone calorimeter Samples TTI/s Peak-HRR/kW m-2 tPeak-HRR/s THR/kJ m-2
data of pure and flame
retardant cotton fabrics Pure-cot 16 349.9 26 6.2
FR-cot-1 9 248.7 16 4.8
FR-cot-2 7 189.6 15 4.5

combustion process; meanwhile, the nitrogen com-
pound grafted on the FR-cot-1 surface released the
nonflammable gas and diluted the combustible gas,
thus degrading the intensity of combustion pyrolysis
reactions and decreasing the quantity of heat released.
Consequently, the THR for FR-cot-1 decreased from
6.2 kJ m-2 for pure cotton fabric to 4.8 kJ m-2 , a
decrease of 22.6%. For the FR-cot-2, the HRR curve
trend was similar to that of FR-cot-1, and it indicated
that the PHRR value was decreased from
248.7 kW m-2 to 189.6 kW m-2 for FR-cot-1, a
decrease of 23.8%. This might be attributed to the
introduction of ethylenediamine promoting the for-
mation of a crosslinking structure, whereby more
flame retardant elements wrer grafted on the surface of
FR-cot-2 which acted both in condensed and gas
phases, thus further reducing the intensity of combus-
tion for FR-cot-2. Correspondingly, the THR value for
FR-cot-2 (4.8 kJ m-2 ) was lower than that of FR-cot-
1 (4.5 kJ m-2).
Morphology analysis of the cotton fabric
The surface morphologies of the pure and flame
retardant cotton fabrics were measured by SEM
magnified 50 and 3000 times, as shown in Fig. 7. It
could be observed that the pure fabric cotton exhibited
an applanate and smooth surface morphology, as
revealed in Fig. 7a1, a2. However, the surface mor-
phology of FR-cot-1 turned plump and wrinkled with a
sparse fabric structure (Fig. 7b1, b2), which was
attributed to the oxidation and chemical grafting

a1
(a1) 500um b1
(b1) 500um C1
(C1) 500um

a2
(a2) 20um b2
(b2) 10um C2
(C2) 10um

Fig. 7 SEM images of pure fabric (a1, a2), FR-cot-1(b1, b2) and FR-cot-2 (c1, c2)

123
4080
a1
(a1) 400um
b1
(b1)
a2
(a2) 20um b2
(b2)
Fig. 8 SEM images of the char residue for pure fabric (a1, a2), FR-cot-1 (b1, b2) and FR-cot-2 (c1, c2)
reaction on the cotton fabric surface. Compared with
the surface morphology of FR-cot-1, the surface of
FR-cot-2 was more corrugated and the fabric structure
was tighter, as shown in Fig. 7c1, c2. This corresponds
with the two terminal amino groups of ethylenedi-
amine reacting with the formed aldehyde groups on
the cotton surface and then forming the crosslinking
structure.
The residual char of the pure and flame retardant
cotton fabrics obtained from cone tests were measured
by SEM magnified 50 and 3000 times, as presented in
Fig. 8. It could be seen that there were small amounts
of flimsy and tenuous char residue left after the cone
tests were carried out on pure cotton fabric (Fig. 8a1,
a2). It was noteworthy that the residual char of the two
flame retardant cotton fabrics still retained the fabric
structure integrity after the cone tests, and the bulged
and dense char layer acted as a physical barrier which
inhibited the oxygen and heat transfer into the surface
of the cotton fabrics (Wang et al. 2016a, b). In this
way, further degradation and combustion were sup-
pressed and the FR-cot-1 and FR-cot-2 samples
achieved superior flame retardancy. Moreover, the
residual char for FR-cot-2 (Fig. 8b1, b2) was much
123
Cellulose (2017) 24:4069–4081
500um c1
(c1) 500um
20um c2
(c2) 20um
more compact and intumescent than that of FR-cot-1
(Fig. 8c1, c2). This is attributed to the phosphorus and
nitrogen content in FR-cot-2 being higher than that of
FR-cot-1, as revealed in Table 1. Rich phosphorus
promotes the formation of sufficient char and more
nitrogen can release abundant inflammable gas during
combustion; thus, more intumescent residual char is
produced.
Conclusions
In this paper, cotton fabric with superior flame
retardant performance and excellent washing durabil-
ity was prepared by surface chemical grafted modifi-
cation on the cotton fabric surface. The surface
modification stimulated the cotton fabric degradation
and charring ahead of time, the grafted phosphorus and
nitrogen composition benefited the formation of
sufficient, compact and intumescent char residue,
which efficiently prevented the heat transmission and
diffusion, inhibited the production of combustible
gases, then led to the reduction of the heat release rate
and the enhancement of the flame retardancy for
Cellulose (2017) 24:4069–4081
cotton fabric. The flame retardant compositions were
grafted by chemical bonds and connected firmly on the
cotton fabric surface; thus, the obtained flame retar-
dant cotton fabric possessed excellent washing
durability.
Acknowledgments We are grateful for funding supported by
National Natural Science Foundation of China (grant no.
31370709), and Heilongjiang Major Research Projects
(GA12A102, GA15A101).
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